WO2019030090A1 - Herbicidal mixtures comprising l-glufosinate and their use in rice cultures - Google Patents

Herbicidal mixtures comprising l-glufosinate and their use in rice cultures Download PDF

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Publication number
WO2019030090A1
WO2019030090A1 PCT/EP2018/070932 EP2018070932W WO2019030090A1 WO 2019030090 A1 WO2019030090 A1 WO 2019030090A1 EP 2018070932 W EP2018070932 W EP 2018070932W WO 2019030090 A1 WO2019030090 A1 WO 2019030090A1
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methyl
ethyl
quizalofop
salts
esters
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PCT/EP2018/070932
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French (fr)
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Christian Winter
Markus Gewehr
Ryan Louis NIELSON
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Basf Se
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    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives 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
    • A01N43/14—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 six-membered rings
    • A01N43/18—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 six-membered rings with sulfur as the ring hetero 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • Herbicidal mixtures comprising L-glufosinate and their use in rice cultures
  • the present invention relates to herbicidal mixture comprising L-glufosinate and and a herbicidal compound II selected from clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop- ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop- P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfu- ron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, fluce- tos
  • the invention also relates to methods and uses for controlling undesirable vegetation in glufosinate-tolerant rice.
  • Tolerant or resistant rice varieties e.g. transgenic rice varieties
  • herbicides which are originally not selective in respective tolerant or resistant rice in addition to conventional weed control system.
  • glufosinate which can not only be used for pre- plant burn-down both in conventional rice and rice that is tolerant against herbicides including glufosinate; but which can also achieve effective weed control by post-emergence application in glufosinate tolerant rice.
  • Glufosinate is a broad-spectrum herbicide that controls most grass and broadleaf herbicide species; however, there are a few tough to control species or resistant bio- types that it does not fully control.
  • One possibility for improving the use profile of a herbicide is the combination of the herbicide in question with one or more other active compounds which have the desired additional properties.
  • the combined use of a plurality of active compounds may lead to phenomena of a chemical, physical and biological incompatibility (e.g. instability of a coformulation, decomposition of an active compound or antagonism in the biological action of the active compounds).
  • finding effective glufosinate combinations with an additional herbicide faces the challenge that in many instances the effectiveness of such combinations is not satisfactory and high appli- cation rates are still required to achieve an acceptable weed control.
  • glufosinate is a racemate of two enantiomers, out of which only one shows sufficient herbicidal activity (see e.g. US 4265654 and JP92448/83).
  • mixtures of L-glufosinate or its salt and the herbicidal compound II show enhanced herbicide action against undesirable vegetation in pre-plant burn-down prior to planting of conventional rice and rice that is tolerant against herbicides including glufosinate and in post-emergence use in glufosinate tolerant rice and/or show superior compat- ibility with rice, i.e. their use leads to a reduced damage of the rice plants and/or does not result in increased damage of the rice plants, if compared to mixtures of racemic glufosinate and the herbicidal compound II, or if compared to L-glufosinate or its salts alone.
  • the present invention relates to herbicidal mixtures of
  • a herbicidal compound II selected from clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, halox- yfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, flucetosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfu- ron, iodosulfuron-methyl
  • Glufosinate [common name of DL-4-[hydroxyl(methyl)phosphinoyl]-DL-homoalaninate] and its salts such as glufosinate ammonium and its herbicidal acitivity have been described e.g. by F. Schwerdtle et al. Z. convincedr. Wunsch, 1981 , Sonderheft IX, pp. 431 -440. Racemic glufosinate and its salts are commercially available, e.g. from Bayer CropScience under the tradenames BastaTM and LibertyTM.
  • L-Glufosinate also called glufosinate-P
  • (2S)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid (CAS Reg. No. 35597-44-5).
  • Relevant salts of L-glufosinate are L-glufosinate-ammonium (also called glufosinate-P-ammonium), which is ammonium (2S)-2-amino-4- (methylphosphinato)butyric acid (CAS Reg. No.
  • L-glufosinate-sodium also called glufosinate-P-sodium
  • (2S)-2-amino-4-(methylphosphinato)butyric acid CAS Reg. No. 70033-13-5
  • L-glufosinate-potassium also called glufosinate-P-potassium
  • L-Glufosinate as used in the present invention comprises more than 70% by weight of the L- enantiomer; preferably more than 80% by weight of the L-enantiomer; more preferably more than 90% of the L-enantiomer, most preferably more than 95% of the L-enantiomer and can be prepared as referred to above.
  • the abovementioned invention relates to herbicidal mixtures as described above, wherein L-glufosinate comprises more than 70% by weight of the L-enantiomer.
  • L-glufosinate can be prepared according to methods known in the art, e.g. as described in WO2006/104120, US5530142, EP0127429 and J. Chem. Soc. Perkin Trans. 1 , 1992, 1525- 1529.
  • the weight ratio of compound I to compound II is preferably from 1000: 1 to 1 : 500, 400:1 to 1 :40, more preferably 500:1 to 1 :250, in particular from 200:1 to 1 :20, even more preferably from 100:1 to 1 :10, most preferably 50:1 to 1 :5..
  • mixtures are preferred, which contain L-glufosinate-ammonium or L-glufosinate- sodium as L-glufosinate salts or L-glufosinate as free acid.
  • mixtures which contain L-glufosinate-ammonium as L-glufosinate salt.
  • Preferred compounds II are clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop- ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop- P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfu- ron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, fluce- tosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, metazo
  • preferred mixtures of the present invention are mixtures of L-glufosinate-ammonium or L- glufosinate-sodium as L-glufosinate salts or L-glufosinate as free acid and a herbicidal com- pound II selected from the group consisting of clethodim, cyhalofop, cyhalofop-butyl, fenoxa- prop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, halox- yfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cino
  • More preferred mixtures of the present invention are mixtures of L-glufosinate-ammonium or L- glufosinate-sodium as L-glufosinate salts or L-glufosinate as free acid and at least one compound II selected from the group consisting of cyhalofop, cyhalofop-butyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, profoxydim, benfuresate, molinate, thiobencarb, bensulfuron, bensulfuron- methyl, chlorimuron, chlorimuron-ethyl, ethoxysulfuron, halosulfuron, halosulfuron-methyl, met- sulfuron, metsulfuron-methyl, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, ,mazamox, imazamox ammonium, imazapic
  • the inventive mixtures can further contain one or more insecticides, fungicides, herbicides.
  • the inventive mixtures can be converted into customary types of agrochemical mixtures, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • agrochemical mixtures e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • mixture types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wetable powders or dusts (e.g.
  • WP WP
  • SP WS
  • DP DS
  • pressings e.g. BR, TB, DT
  • gran- ules e.g. WG, SG, GR, FG, GG, MG
  • insecticidal articles e.g. LN
  • gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • the mixtures are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkylated
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con- densed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • Exam- pies of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the inventive mixtures on the tar- get.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • 10-60 wt% of an inventive mixture and 5-15 wt% wetting agent e.g. alcohol alkoxylates
  • a wetting agent e.g. alcohol alkoxylates
  • the active substance dissolves upon dilution with water.
  • an inventive mixture and 1 -10 wt% dispersant e. g. polyvinylpyrrolidone
  • organic solvent e.g. cyclohexanone
  • emulsifiers e.g. calcium dodecylben- zenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzene- sulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • 20-60 wt% of an inventive mixture are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1 - 2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance sus- pension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1 - 2 wt% thickener e.g. xanthan gum
  • water ad 100 wt% to give a fine active substance sus- pension.
  • Dilution with water gives a stable suspension of the active substance.
  • binder e.g. polyvinylalcohol
  • an inventive mixture 50-80 wt% of an inventive mixture are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • Water-dispersible powders and water-soluble powders (WP, SP, WS) 50-80 wt% of an inventive mixture are ground in a rotor-stator mill with addition of 1 -5 wt% dis- persants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dis- persants e.g. sodium lignosulfonate
  • wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • an inventive mixture In an agitated ball mill, 5-25 wt% of an inventive mixture are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. carboxymethylcellulose
  • an inventive mixture 5-20 wt% are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamicallystable microemulsion.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of an inventive mixture, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of an inventive mixture according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.
  • diphenylmethene-4,4'- diisocyanatae are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol).
  • a protective colloid e.g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of pol- yurea microcapsules.
  • the monomers amount to 1-10 wt%. The wt% relate to the total CS mixture.
  • Dustable powders (DP, DS)
  • an inventive mixture are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
  • solid carrier e.g. finely divided kaolin
  • an inventive mixture is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%.
  • solid carrier e.g. silicate
  • organic solvent e.g. aromatic hydrocarbon
  • the mixtures types i) to xii) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
  • the resulting agrochemical mixtures generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the mixtures in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations.
  • Application can be carried out before or during sowing.
  • Methods for applying the inventive mixtures and mixtures thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propaga- tion material.
  • the inventive mixtures or the mixtures thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the inventive mixtures comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the inventive mixtures in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the user applies the mixture according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemi- cal mixture is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical mixture according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to- use spray liquor are applied per hectare of agricultural useful area.
  • the inventive mixtures provide excellent pre-plant burn-down, pre- and post-emergence control of weeds in rice, including rice that is tolerant to herbicides including glufosinate.
  • the compounds present in the inventive mixtures can be applied for pre-plant burn-down (to control emerged weeds prior to planting), pre-emergence (before the emergence of undesirable vegetation) or post-emergence (i.e., during and/or after emergence of the undesirable vegetation).
  • the invention relates to a method of an inventive mixture for controlling undesirable vegetation in rice, including rice that is tolerant to herbicides including glufosinate, which comprises applying the compounds present in the inventive mixtures to a locus of planted crops where undesirable vegetation occurs or might occur.
  • the application is done before the emergence of undesirable vegetation or during and/or after emergence of the undesirable vegetation.
  • locus means the area in which the vegetation or plants are growing or will grow, typically a field.
  • controlling and “combating” are synonyms.
  • undesirable vegetation As used herein, the terms “undesirable vegetation”, “undesirable species”, “undesirable plants”, “harmful plants”, “undesirable weeds”, or “harmfull weeds” are synonyms.
  • the active com- pounds present in the inventive mixtures can be applied simultaneously or in succession, where undesirable vegetation may occur.
  • compounds present in the inventive mixtures are formulated jointly or separately and applied jointly or separately, and, in the case of separate application, in which order the application takes place. It is only necessary, that the compounds present in the inventive mixtures are applied in a time frame, which allows simultaneous action of the active ingredients on the undesirable plants.
  • the inventive mixtures have an outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants.
  • the inventive mix- tures also act efficiently on perennial weeds which produce shoots from rhizomes, rootstocks or other perennial organs and which are difficult to control.
  • the inventive mixtures are suitable for controlling a large number of harmful plants in agricultural crops, including monocotyledonous weeds, in particular annual weeds such as gramineous weeds (grasses) including Echinochloa species such as barnyardgrass (Echinochloa crusgalli var.
  • Poa species such as Poa annua or Poa trivialis L., Puccinellia distans, Rottboellia cochinchinensis, Sclerochloa kengiana (Ohwi) Tzvel., Trichloris crinita, Urochloa or Brachiaria species such as Brachiaria decumbens, Brachiaria plantaginea, Brachiaria platyphylla, Urochloa panicoides, Urochloa ramosa and the like.
  • Both L-glufosinate alone as well as the inventive mixtures are also suitable for controlling a large number of dicotyledonous weeds, in particular broad leaf weeds including Polygonum species such as wild buckwheat (Polygonum convolvolus), Polygonum pensilvanicum, Polygo- num persicaria or prostrate knotweed (Polygonum aviculare), Amaranthus species such as pigweed (Amaranthus retroflexus), Palmer amaranth (Amaranthus palmeri), tall waterhemp (Amaranthus tuberculatus or Amaranthus rudis), redroot pigweed (Amaranthus retroflexus), green amaranth (Amaranthus hybridus), purple amaranth (Amaranthus lividus), prickly amaranth (Amaranthus spinosus) or Amaranthus quitensis, Chenopodium species such as common lambsquarters (Chenopodium album L.), Chenopodium serotin
  • Both L-glufosinate alone as well as the inventive mixtures are also suitable for controlling a large number of annual and perennial sedge weeds including Cyperus species such as purple nutsedge (Cyperus rotundus L), yellow nutsedge (Cyperus esculentus L), hime-kugu (Cyperus brevifolius H.), sedge weed (Cyperus microiria Steud), rice flatsedge (Cyperus iria L), Cyperus difformis, Cyperus difformis L, Cyperus esculentus, Cyperus ferax, Cyperus flavus, Cyperus iria, Cyperus lanceolatus, Cyperus odoratus, Cyperus rotundus, Cyperus serotinus Rottb., Eleo- charis acicularis, Eleocharis kuroguwai, Fimbristylis dichotoma, Fimbristylis miliace
  • Both L-glufosinate alone as well as the inventive mixtures are also suitable for controlling weeds that are resistant to commonly used herbicides such as, for example, weeds that are resistant to glyphosate, weeds that are resistant to auxin inhibitor herbicides such as e. g. 2,4-D or dicam- ba, weeds that are resistant to photosynthesis inhibitors such as e. g. atrazine, weeds that are resistant to ALS inhibitors such as e. g. sulfonylureas, imidazolinones or triazolopyrimidines, weeds that are resistant to ACCase inhibitors such as e. g.
  • clodinafop clethodim or pinoxaden or weeds that are resistant to protoporphyrinogen-IX-oxidase inhibitors such as e. g. sulfentra- zone, flumioxazine, fomesafen or acifluorfen, for example the weeds that are listed in the International Survey of Resistant Weeds
  • Rapistrum rugosum Rorippa indica, Rotala indica, Rotala pusilla, Rumex dentatus, Sagittaria guayensis, Sagittaria pygmaea, Sagittaria trifolia
  • Schoenoplectus fluviatilis Schoenoplectus juncoides
  • Schoenoplectus wallichii Sida spinosa, Silene gallica, Sinapis alba, Sisymbrium thel- lungii, Sorghum bicolor
  • mice Micranthos, Cirsium arvense, Commelina diffusa, Echinochloa crus-pavonis, Soliva sessilis and Sphenoclea zeylanica, HPPD inhibitor resistant Amaranthus palmeri and Amaranthus rudis, PPO inhibitor resistant Acalypha australis, Amaranthus hybridus, Amaranthus palmeri, Amaranthus retroflexus, Amaranthus rudis, Ambrosia artemisifolia, Avena fatua, Conyza sumatrensis, Descurainia sophia, Euphorbia heterophylla and Senecio vernalis, carotenoid biosynthesis in- hibitor resistant Hydrilla verticillata, Raphanus raphanistrum, Senecio vernalis and Sisymbrium orientale, VLCFA inhibitor resistant Alopecurus myosuroides, Avena fatua and Echinochloa crus-galli.
  • the compounds of the inventive mixtures are applied to the soil surface before germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have reached the cotyledon stage but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
  • the active compounds of the inventive mixtures and further herbicides can be used in any of the treatment combinations outlined below that consist of pre-plant burn down, pre-emergence and post-emergence treatments.
  • These treatment combinations can be particularly suitable if the rice is tolerant to the action of one or more herbicides present in the treatment combination, including tolerance that is a result of breeding and/or genetic modification.
  • tolerant plants include glufosinate tolerant rice, glyphosate tolerant rice, rice that is tolerant to AHAS inhibitors (e. g. imidazolinone herbicides such as imazamox, imazapyr, ima- zapic or imazethapyr) and rice that is tolerant to PPO herbicides.
  • the following active compounds of the inventive mixtures and further herbicides are particularly suitable as pre-plant burn-down weed control components in such treatment combinations: L- Glufosinate, L-glufosinate ammonium, L-glufosinate sodium, glyphosate, glyphosate dime- thylammonium, glyphosate potassium, glyphosate isopropylammonium, paraquat, trifludimoxa- zin, saflufenacil.
  • the following active compounds of the inventive mixtures and further herbicides are particularly suitable as pre-emergence weed control components in such treatment combinations: Ben- furesate, molinate, thiobencarb, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, clomazone, oryzalin, pendimethalin, acetochlor, bu- tachlor, pretilachlor, thenylchlor, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, quinclorac, quinclorac dimethylammonium, cinmethylin, dymron (daimuron), etobenzanid, inda- nofan, methyldymron (methyl-daimuron), oxaciclome
  • the following active compounds of the inventive mixtures and further herbicides are particularly suitable for post-emergence weed control components in such treatment combinations: L- Glufosinate, L-glufosinate ammonium, L-glufosinate sodium, glyphosate, glyphosate dimethylammonium, glyphosate potassium, glyphosate isopropylammonium, clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, profoxydim, azimsulfuron, ben- sulfuron, bensulfuron-methyl, cinosulfuron, ethoxysulfuron, fluceto
  • inventive mixtures are suitable for controlling a large number of harm- ful plants in glufosinate tolerant rice
  • glufosinate tolerant rice includes also (rice) plants which have been modified by mutagenesis, genetic engineering or breeding and mutation selection techniques in order to provide a new trait to a plant or to modify an already present trait.
  • Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome.
  • Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
  • Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination.
  • one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait.
  • transgenic plants These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants.
  • the process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific "event", which is referred to by a specific event name.
  • Glufosinate tolerance has been created by using mutagenesis as well as using genetic engineering.
  • Transgenic rice events comprising glufosinate tolerance genes are for example, but not excluding others, LLRICE06 (event code: ACS-OS001 -4, e.g.
  • LLRICE601 event code: BCS-OS003-7, e.g. commercially available as Liberty LinkTM rice
  • LLRICE62 event code: ACS-OS002-5, e.g. commercially available as Liberty LinkTM rice.
  • the inventive mixtures can be applied in conventional manner by using techniques as skilled person is familiar with.
  • Suita- ble techniques include spraying, atomizing, dusting, spreading or watering.
  • the type of application depends on the intended purpose in a well known manner; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
  • the inventive mixtures are applied to locus mainly by spraying, in particular foliar spraying of an aqueous dilution of the active ingredients of the mixture.
  • Application can be carried out by customary spraying techniques using, for example, water as carrier and spray liquor rates of from about 10 to 2000 l/ha or 50 to 1000 l/ha (for example from 100 to 500 l/ha).
  • Application of the inventive mixtures by the low-volume and the ultra-low-volume method is possible, as is their application in the form of microgranules.
  • the required application rate of the mixture of the pure active compounds depends on the density of the undesired vegetation, on the development stage of the plants, on the climatic conditions of the location where the mixture is used and on the application method.
  • the rate of application of L-glufosinate is usually from 50 g/ha to 3000 g/ha and preferably in the range from 100 g/ha to 2000 g/ha or from 200 g/ha to 1500 g/ha of active substance (a.i.), and the rate of application of the secod herbicida compound II is from 1 g/ha to 2000 g/ha and preferably in the range from 5 g/ha to 1500 g/ha, more preferably from 25 g/ha to 900 g/ha of active substance (a.i.).
  • Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds.
  • the presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 21 -22):
  • the culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate.
  • the seeds of the test plants were sown separately for each species and/or resistant biotype.
  • the active ingredients which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
  • the containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
  • the plants were kept at 10 - 25°C or 20 - 35°C, respectively.
  • the test period extended to 20 days after treatment. During this time, the plants were tended, and their response to the individual treatments was evaluated. The evaluation was carried out by using a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth. Data shown are the mean of two replications.
  • Trifludimoxazin 500 g/l SC formulation
  • Methiozolin 250 g/l SC formulation
  • Example 1 Post emergence treatment with the mixture of L-glufosinate with saflufenacil

Abstract

The present invention relates to herbicidal mixtures and their methods and uses for controlling undesirable vegetation in rice, e.g. glufosinate-tolerantrice, wherein theherbicidal mixture comprises L-glufosinate and and a herbicidal compound II selected from clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron- ethyl, cinosulfuron, ethoxysulfuron, flucetosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox ammonium,imazapic,imazapic ammonium,imazapyr, imazapyr isopropylammonium,imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, pyrimisulfan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, thiencarbazone, thiencarbazone-methyl, triafamone, bentazone, bentazone-sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, picolinafen, benzobicyclon, benzofenap, bicyclopyrone, clomazone, pyrazolynate, sulcotrione, tefuryltrione, topramezone, fenquinotrione, lancotrione, lancotrione-sodium, glyphosate, glyphosate dimethylammmonium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sulfosate), oryzalin, pendimethalin, acetochlor, butachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, pyroxasulfone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifenand its salts and esters, quinclorac, quinclorac dimethylammonium, quinmerac, triclopyr and its salts and esters, diflufenzopyr, diflufenzopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), etobenzanid, indanofan, methyl-dymron (methyl-daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P, cycloxydim and cyclosulfamuron.

Description

Herbicidal mixtures comprising L-glufosinate and their use in rice cultures Description The present invention relates to herbicidal mixture comprising L-glufosinate and and a herbicidal compound II selected from clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop- ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop- P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfu- ron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, fluce- tosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, ox- asulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, pyrimisulfan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, thiencarbazone, thiencarbazone-methyl, triafamone, benta- zone, bentazone-sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, picolinafen, ben- zobicyclon, benzofenap, bicyclopyrone, clomazone, pyrazolynate, sulcotrione, tefuryltrione, to- pramezone, fenquinotrione, lancotrione, lancotrione-sodium, glyphosate, glyphosate dime- thylammmonium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sulfosate), oryzalin, pendimethalin, acetochlor, butachlor, metazachlor, metolachlor, S- metolachlor, pretilachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, pyroxasulfone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, quinclorac, quinclorac dimethylammonium, quinmerac, triclopyr and its salts and esters, diflufenzopyr, diflufenzopyr- sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), etobenzanid, indanofan, methyl-dymron (methyl-daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P, cycloxydim and cyclosulfamuron.
The invention also relates to methods and uses for controlling undesirable vegetation in glufosinate-tolerant rice. Tolerant or resistant rice varieties (e.g. transgenic rice varieties) provide the option to use herbicides, which are originally not selective in respective tolerant or resistant rice in addition to conventional weed control system. One example is glufosinate, which can not only be used for pre- plant burn-down both in conventional rice and rice that is tolerant against herbicides including glufosinate; but which can also achieve effective weed control by post-emergence application in glufosinate tolerant rice. Glufosinate is a broad-spectrum herbicide that controls most grass and broadleaf herbicide species; however, there are a few tough to control species or resistant bio- types that it does not fully control. Another challenge is the duration of action, or the degradation rate of the herbicide. Furthermore, changes in the sensitivity of harmful plants, which may occur upon prolonged use of the herbicides or within a geographical limited area, must also be taken into consideration. The resulting loss of action against individual plants can sometimes compensated for to a certain extent by higher application rates of the herbicides. However, there is always a demand for methods to achieve the herbicidal effect with lower application rates of active compounds to reduce not only the amount of an active compound required for applica- tion, but also the amount of formulation auxiliaries. Thus, low application rates are for economic and environmental reasons an object eco-friendliness of the herbicide treatment.
One possibility for improving the use profile of a herbicide is the combination of the herbicide in question with one or more other active compounds which have the desired additional properties. However, the combined use of a plurality of active compounds may lead to phenomena of a chemical, physical and biological incompatibility (e.g. instability of a coformulation, decomposition of an active compound or antagonism in the biological action of the active compounds). Thus, finding effective glufosinate combinations with an additional herbicide faces the challenge that in many instances the effectiveness of such combinations is not satisfactory and high appli- cation rates are still required to achieve an acceptable weed control.
Thus, it is an object of the present invention to find combinations of active compounds with a favorable profile of action, high stability and, ideally, synergistically enhanced activity for application in glufosinate tolerant rice, which allows the application rate to be reduced in comparison with solutions provided by prior art mixtures. Moreover, the persistence of the herbicidal activity of the mixture should be sufficiently long in order to achieve control of the weeds over a sufficient long time period thus allowing a more flexible application. The mixtures should also show an accelerated action on harmful plants and not affect the growth of the rice plant. Glufosinate is a racemate of two enantiomers, out of which only one shows sufficient herbicidal activity (see e.g. US 4265654 and JP92448/83). Even though are various methods to prepare L- glufosinate (and respective salts) are known, the mixtures known in the art do not point at the stereochemistry, meaning that the racemate is present (e.g. WO 2003024221 , WO2009141367, WO2013154396, DE 19815820).
Surprisingly, it has been found that mixtures of L-glufosinate or its salt and the herbicidal compound II show enhanced herbicide action against undesirable vegetation in pre-plant burn-down prior to planting of conventional rice and rice that is tolerant against herbicides including glufosinate and in post-emergence use in glufosinate tolerant rice and/or show superior compat- ibility with rice, i.e. their use leads to a reduced damage of the rice plants and/or does not result in increased damage of the rice plants, if compared to mixtures of racemic glufosinate and the herbicidal compound II, or if compared to L-glufosinate or its salts alone.
Thus, the present invention relates to herbicidal mixtures of
1 ) L-glufosinate or its salt as compound I and
2) a herbicidal compound II selected from clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, halox- yfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, flucetosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosul- furon, orthosulfamuron, oxasulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, ima- zethapyr, imazethapyr ammonium, penoxsulam, pyrimisulfan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, thiencarba- zone, thiencarbazone-methyl, triafamone, bentazone, bentazone-sodium, propanil, carfen- trazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, picolinafen, benzobicyclon, benzofenap, bicyclopy- rone, clomazone, pyrazolynate, sulcotrione, tefuryltrione, topramezone, fenquinotrione, lan- cotrione, lancotrione-sodium, glyphosate, glyphosate dimethylammmonium, glyphosate- isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sulfosate), oryzalin, pendimethalin, acetochlor, butachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfen- carbazone, pyroxasulfone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, quinclorac, quinclorac dimethylammoni- um, quinmerac, triclopyr and its salts and esters, diflufenzopyr, diflufenzopyr-sodium, cinme- thylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), etobenzanid, indanofan, methyl-dymron (methyl-daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop- tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P, cycloxydim and cyclosulfamuron. Glufosinate [common name of DL-4-[hydroxyl(methyl)phosphinoyl]-DL-homoalaninate] and its salts such as glufosinate ammonium and its herbicidal acitivity have been described e.g. by F. Schwerdtle et al. Z. Pflanzenkr. Pflanzenschutz, 1981 , Sonderheft IX, pp. 431 -440. Racemic glufosinate and its salts are commercially available, e.g. from Bayer CropScience under the tradenames Basta™ and Liberty™.
L-Glufosinate, also called glufosinate-P, is (2S)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid (CAS Reg. No. 35597-44-5). Relevant salts of L-glufosinate are L-glufosinate-ammonium (also called glufosinate-P-ammonium), which is ammonium (2S)-2-amino-4- (methylphosphinato)butyric acid (CAS Reg. No. 73777-50-1 ); L-glufosinate-sodium (also called glufosinate-P-sodium), which is sodium (2S)-2-amino-4-(methylphosphinato)butyric acid (CAS Reg. No. 70033-13-5) and L-glufosinate-potassium (also called glufosinate-P-potassium), which is potassium (2S)-2-amino-4-(methylphosphinato)butyric acid.
L-Glufosinate as used in the present invention comprises more than 70% by weight of the L- enantiomer; preferably more than 80% by weight of the L-enantiomer; more preferably more than 90% of the L-enantiomer, most preferably more than 95% of the L-enantiomer and can be prepared as referred to above.
In a preferred embodiment, the abovementioned invention relates to herbicidal mixtures as described above, wherein L-glufosinate comprises more than 70% by weight of the L-enantiomer. L-glufosinate can be prepared according to methods known in the art, e.g. as described in WO2006/104120, US5530142, EP0127429 and J. Chem. Soc. Perkin Trans. 1 , 1992, 1525- 1529.
Compounds II as well as their pesticidal action and methods for producing them are generally known, for example in the Pesticide Manual V5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ) amongst other sources.
In the inventive mixtures the weight ratio of compound I to compound II is preferably from 1000: 1 to 1 : 500, 400:1 to 1 :40, more preferably 500:1 to 1 :250, in particular from 200:1 to 1 :20, even more preferably from 100:1 to 1 :10, most preferably 50:1 to 1 :5..
Furthermore, mixtures are preferred, which contain L-glufosinate-ammonium or L-glufosinate- sodium as L-glufosinate salts or L-glufosinate as free acid. Especially preferred are mixtures, which contain L-glufosinate-ammonium as L-glufosinate salt.
Preferred compounds II are clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop- ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop- P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfu- ron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, fluce- tosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, ox- asulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamox, ima- zamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, pyrimisulfan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, thien- carbazone, thiencarbazone-methyl, triafamone, bentazone, bentazone-sodium, propanil, carfen- trazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cy- clopyranil, saflufenacil, trifludimoxazin, benzobicyclon, benzofenap, bicyclopyrone, clomazone, pyrazolynate, sulcotrione, tefuryltrione, fenquinotrione, lancotrione, lancotrione-sodium, glypho- sate, glyphosate dimethylammmonium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sulfosate), oryzalin, pendimethalin, acetochlor, butachlor, metolachlor, S- metolachlor, pretilachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, MCPA and its salts and esters, quin- clorac, quinclorac dimethylammonium, triclopyr and its salts and esters, diflufenzopyr, diflufen- zopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), etoben- zanid, indanofan, methyl-dymron (methyl-daimuron), oxaziclomefone, quizalofop, quizalofop- ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P, cycloxydim and cyclosulfamuron.
Thus, preferred mixtures of the present invention are mixtures of L-glufosinate-ammonium or L- glufosinate-sodium as L-glufosinate salts or L-glufosinate as free acid and a herbicidal com- pound II selected from the group consisting of clethodim, cyhalofop, cyhalofop-butyl, fenoxa- prop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, halox- yfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, flucetosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfu- ron, imazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, pyrimisul- fan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyrimino- bac-methyl, thiencarbazone, thiencarbazone-methyl, triafamone, bentazone, bentazone- sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pent- oxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, benzobicyclon, benzofenap, bicy- clopyrone, clomazone, pyrazolynate, sulcotrione, tefuryltrione, fenquinotrione, lancotrione, lan- cotrione-sodium, glyphosate, glyphosate dimethylammmonium, glyphosate- isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sulfosate), oryzalin, pendi- methalin, acetochlor, butachlor, metolachlor, S-metolachlor, pretilachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, MCPA and its salts and esters, quinclorac, quinclorac dimethylammonium, triclopyr and its salts and esters, diflufenzopyr, diflufenzopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), etobenzanid, indanofan, methyl-dymron (methyl-daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P- ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P, cy- cloxydim and cyclosulfamuron.
All preferred mixtures are listed in table 2, wherein the following abbreviations are used in table 1 :
Table 1
Compound Abbreviation Compound Abbreviation
L-glufosinate-ammonium -1 chlorimuron 11-1 1
L-glufosinate-sodium -2 chlorimuron-ethyl 11-12
L-glufosinate as free acid -3 ethoxysulfuron 11-13 cyhalofop 1-1 halosulfuron 11-14 cyhalofop-butyl I-2 halosulfuron-methyl 11-15 fenoxaprop-ethyl I-3 metsulfuron 11-16 fenoxaprop-P-ethyl I-4 metsulfuron-methyl 11-17 profoxydim I-5 pyrazosulfuron 11-18 benfuresate I-6 pyrazosulfuron-ethyl 11-19 molinate I -7 tritosulfuron II-20 thiobencarb I-8 imazamox 11-21 bensulfuron I-9 imazamox ammonium, 11-21 a bensulfuron-methyl 1-10 imazapic II-22 Compound Abbreviation Compound Abbreviation imazapic ammonium, ll-22a thylammonium,
imazapyr 11-23 diflufenzopyr II-57 imazapyr isopropylammo- ll-23a diflufenzopyr-sodium II-58 nium cinmethylin II-59 imazaquin 11-24 cyclopyrimorate II-60 imazethapyr 11-25 dymron (daimuron) 11-61 imazethapyr ammonium ll-25a quizalofop II-62 penoxsulam 11-26 quizalofop-ethyl II-63 bispyribac 11-27 quizalofop-tefuryl II-64 bispyribac-sodium 11-28 quizalofop-P II-65 bentazone 11-29 quizalofop-P-ethyl II-66 bentazone-sodium 11-30 quizalofop-P-tefuryl II-67 propanil 11-31 MCPA and its salts and II-68 carfentrazone II-32 esters
carfentrazone-ethyl II-33 dimethenamid II-69 flumioxazin II-34 dimethenamid-P II-70 oxadiazon II-35 cycloxydim 11-71 pyraclonil II-36 cyclosulfamuron II-72 saflufenacil II-37 clethodim II-73 trifludimoxazin II-38 fenoxaprop II-74 clomazone II-39 fenoxaprop-P II-75 tefuryltrione II-40 haloxyfop II-76 fenquinotrione 11-41 haloxyfop-methyl II-77 lancotrione II-42 haloxyfop-P II-78 lancotrione-sodium II-43 haloxyfop-P-methyl II-79 pendimethalin II-44 metamifop II-80 acetochlor II-45 azimsulfuron 11-81 butachlor II-46 cinosulfuron II-82 metolachlor II-47 flucetosulfuron II-83
S-metolachlor II-48 imazosulfuron II-84 pretilachlor mefenacet II-49 iodosulfuron II-85 fentrazamide II-50 iodosulfuron-methyl- II-86 anilofos 11-51 sodium
2,4-D and its salts and II-52 metazosulfuron II-87 esters nicosulfuron II-88 clomeprop II-53 orthosulfamuron II-89 dicamba and its salts and II-54 oxasulfuron II-90 esters propyrisulfuron 11-91 florpyrauxifen II-55 pyrimisulfan II-92 quinclorac II-56 pyroxsulam II-93 quinclorac dime- ll-56a pyribenzoxim II-94 Compound Abbreviation Compound Abbreviation pyriftalid 11-95 glyphosate-trimesium (sul- 11-1 1 1 pyriminobac 11-96 fosate)
pyriminobac-methyl 11-97 oryzalin 11-1 12 thiencarbazone 11-98 thenylchlor 11-1 13 thiencarbazone-methyl 11-99 flufenacet 11-1 14 triafamone, 11-100 cafenstrole 11-1 15 oxadiargyl 11-101 fenoxasulfone 11-1 16 pentoxazone 11-102 ipfencarbazone 11-1 17 benzobicyclon 11-103 MCPA and its salts and 11-1 18 benzofenap 11-104 esters
bicyclopyrone 11-105 triclopyr and its salts and 11-1 19 pyrazolynate 11-106 esters
sulcotrione 11-107 etobenzanid 11-120 glyphosate 11-108 indanofan 11-121 glyphosate dimethyl- l l-108a methyl-dymron (methyl- 11-122 ammmonium daimuron)
glyphosate- 11-109 oxaziclomefone 11-123 isopropylammonium cyclopyranil 11-124 glyphosate-potassium 11-1 10
Table 2
No I I I No I I I
M-1 1-1 11-1 M-20 1-1 M-20
M-2 1-1 M-2 M-21 1-1 11-21
M-3 1-1 M-3 M-22 1-1 M-22
M-4 1-1 M-4 M-23 1-1 M-23
M-5 1-1 M-5 M-24 1-1 M-24
M-6 1-1 M-6 M-25 1-1 M-25
M-7 1-1 M-7 M-26 1-1 M-26
M-8 1-1 M-8 M-27 1-1 M-27
M-9 1-1 M-9 M-28 1-1 M-28
M-10 1-1 11-10 M-29 1-1 M-29
M-1 1 1-1 11-1 1 M-30 1-1 M-30
M-12 1-1 11-12 M-31 1-1 11-31
M-13 1-1 11-13 M-32 1-1 M-32
M-14 1-1 11-14 M-33 1-1 M-33
M-15 1-1 11-15 M-34 1-1 M-34
M-16 1-1 11-16 M-35 1-1 M-35
M-17 1-1 11-17 M-36 1-1 M-36
M-18 1-1 11-18 M-37 1-1 M-37
M-19 1-1 11-19 M-38 1-1 M-38 No I I I No I I I
M-39 1-1 M-39 M-80 1-1 M-80
M-40 1-1 M-40 M-81 1-1 11-81
M-41 1-1 11-41 M-82 1-1 M-82
M-42 1-1 M-42 M-83 1-1 M-83
M-43 1-1 M-43 M-84 1-1 M-84
M-44 1-1 M-44 M-85 1-1 M-85
M-45 1-1 M-45 M-86 1-1 M-86
M-46 1-1 M-46 M-87 1-1 M-87
M-47 1-1 M-47 M-88 1-1 M-88
M-48 1-1 M-48 M-89 1-1 M-89
M-49 1-1 M-49 M-90 1-1 M-90
M-50 1-1 M-50 M-91 1-1 11-91
M-51 1-1 11-51 M-92 1-1 M-92
M-52 1-1 M-52 M-93 1-1 M-93
M-53 1-1 M-53 M-94 1-1 M-94
M-54 1-1 M-54 M-95 1-1 M-95
M-55 1-1 M-55 M-96 1-1 M-96
M-56 1-1 M-56 M-97 1-1 M-97
M-57 1-1 M-57 M-98 1-1 M-98
M-58 1-1 M-58 M-99 1-1 M-99
M-59 1-1 M-59 M-100 1-1 11-100
M-60 1-1 M-60 M-101 1-1 11-101
M-61 1-1 11-61 M-102 1-1 11-102
M-62 1-1 M-62 M-103 1-1 11-103
M-63 1-1 M-63 M-104 1-1 11-104
M-64 1-1 M-64 M-105 1-1 M-105
M-65 1-1 M-65 M-106 1-1 11-106
M-66 1-1 M-66 M-107 1-1 11-107
M-67 1-1 M-67 M-108 1-1 11-108
M-68 1-1 M-68 M-109 1-1 11-109
M-69 1-1 M-69 M-1 10 1-1 11-1 10
M-70 1-1 M-70 M-1 1 1 1-1 11-1 1 1
M-71 1-1 11-71 M-1 12 1-1 11-1 12
M-72 1-1 M-72 M-1 13 1-1 11-1 13
M-73 1-1 M-73 M-1 14 1-1 11-1 14
M-74 1-1 M-74 M-1 15 1-1 11-1 15
M-75 1-1 M-75 M-1 16 1-1 11-1 16
M-76 1-1 M-76 M-1 17 1-1 11-1 17
M-77 1-1 M-77 M-1 18 1-1 M-1 18
M-78 1-1 M-78 M-1 19 1-1 11-1 19
M-79 1-1 M-79 M-120 1-1 11-120 No I II No I II
M-121 1-1 11-121 M-162 I-2 II-39
M-122 1-1 11-122 M-163 I-2 II-40
M-123 1-1 11-123 M-164 I-2 11-41
M-124 I-2 11-1 M-165 I-2 II-42
M-125 I-2 II-2 M-166 I-2 II-43
M-126 I-2 II-3 M-167 I-2 II-44
M-127 I-2 II-4 M-168 I-2 II-45
M-128 I-2 II-5 M-169 I-2 II-46
M-129 I-2 II-6 M-170 I-2 II-47
M-130 I-2 II-7 M-171 I-2 II-48
M-131 I-2 II-8 M-172 I-2 II-49
M-132 I-2 II-9 M-173 I-2 II-50
M-133 I-2 11-10 M-174 I-2 11-51
M-134 I-2 11-1 1 M-175 I-2 II-52
M-135 I-2 11-12 M-176 I-2 II-53
M-136 I-2 11-13 M-177 I-2 II-54
M-137 I-2 11-14 M-178 I-2 II-55
M-138 I-2 11-15 M-179 I-2 II-56
M-139 I-2 11-16 M-180 I-2 II-57
M-140 I-2 11-17 M-181 I-2 II-58
M-141 I-2 11-18 M-182 I-2 II-59
M-142 I-2 11-19 M-183 I-2 II-60
M-143 I-2 II-20 M-184 I-2 11-61
M-144 I-2 11-21 M-185 I-2 II-62
M-145 I-2 II-22 M-186 I-2 II-63
M-146 I-2 II-23 M-187 I-2 II-64
M-147 I-2 II-24 M-188 I-2 II-65
M-148 I-2 II-25 M-189 I-2 II-66
M-149 I-2 II-26 M-190 I-2 II-67
M-150 I-2 II-27 M-191 I-2 II-68
M-151 I-2 II-28 M-192 I-2 II-69
M-152 I-2 II-29 M-193 I-2 II-70
M-153 I-2 II-30 M-194 I-2 11-71
M-154 I-2 11-31 M-195 I-2 II-72
M-155 I-2 II-32 M-196 I-2 II-73
M-156 I-2 II-33 M-197 I-2 II-74
M-157 I-2 II-34 M-198 I-2 II-75
M-158 I-2 II-35 M-199 I-2 II-76
M-159 I-2 II-36 M-200 I-2 II-77
M-160 I-2 11-37 M-201 I-2 II-78
M-161 I-2 11-38 M-202 I-2 II-79 No I II No I II
M-203 I-2 II-80 M-244 I-2 11-121
M-204 I-2 11-81 M-245 I-2 11-122
M-205 I-2 II-82 M-246 I-2 11-123
M-206 I-2 II-83 M-247 I-3 11-1
M-207 I-2 II-84 M-248 I-3 II-2
M-208 I-2 II-85 M-249 I-3 II-3
M-209 I-2 II-86 M-250 I-3 II-4
M-210 I-2 11-87 M-251 I-3 II-5
M-211 I-2 11-88 M-252 I-3 II-6
M-212 I-2 11-89 M-253 I-3 II-7
M-213 I-2 11-90 M-254 I-3 II-8
M-214 I-2 11-91 M-255 I-3 II-9
M-215 I-2 II-92 M-256 I-3 11-10
M-216 I-2 II-93 M-257 I-3 11-11
M-217 I-2 II-94 M-258 I-3 11-12
M-218 I-2 II-95 M-259 I-3 11-13
M-219 I-2 II-96 M-260 I-3 11-14
M-220 I-2 II-97 M-261 I-3 11-15
M-221 I-2 II-98 M-262 I-3 11-16
M-222 I-2 II-99 M-263 I-3 11-17
M-223 I-2 11-100 M-264 I-3 11-18
M-224 I-2 11-101 M-265 I-3 11-19
M-225 I-2 11-102 M-266 I-3 II-20
M-226 I-2 11-103 M-267 I-3 11-21
M-227 I-2 11-104 M-268 I-3 II-22
M-228 I-2 11-105 M-269 I-3 II-23
M-229 I-2 11-106 M-270 I-3 II-24
M-230 I-2 11-107 M-271 I-3 II-25
M-231 I-2 11-108 M-272 I-3 II-26
M-232 I-2 11-109 M-273 I-3 II-27
M-233 I-2 11-110 M-274 I-3 II-28
M-234 I-2 11-111 M-275 I-3 II-29
M-235 I-2 11-112 M-276 I-3 II-30
M-236 I-2 11-113 M-277 I-3 11-31
M-237 I-2 11-114 M-278 I-3 II-32
M-238 I-2 11-115 M-279 I-3 II-33
M-239 I-2 11-116 M-280 I-3 II-34
M-240 I-2 11-117 M-281 I-3 II-35
M-241 I-2 11-118 M-282 I-3 II-36
M-242 I-2 11-119 M-283 I-3 II-37
M-243 I-2 11-120 M-284 I-3 II-38 No I II No I II
M-285 I-3 II-39 M-326 I-3 II-80
M-286 I-3 II-40 M-327 I-3 11-81
M-287 I-3 11-41 M-328 I-3 II-82
M-288 I-3 II-42 M-329 I-3 II-83
M-289 I-3 II-43 M-330 I-3 II-84
M-290 I-3 II-44 M-331 I-3 II-85
M-291 I-3 II-45 M-332 I-3 II-86
M-292 I-3 II-46 M-333 I-3 II-87
M-293 I-3 II-47 M-334 I-3 II-88
M-294 I-3 II-48 M-335 I-3 II-89
M-295 I-3 II-49 M-336 I-3 II-90
M-296 I-3 II-50 M-337 I-3 11-91
M-297 I-3 11-51 M-338 I-3 II-92
M-298 I-3 II-52 M-339 I-3 II-93
M-299 I-3 II-53 M-340 I-3 II-94
M-300 I-3 II-54 M-341 I-3 II-95
M-301 I-3 II-55 M-342 I-3 II-96
M-302 I-3 II-56 M-343 I-3 II-97
M-303 I-3 11-57 M-344 I-3 II-98
M-304 I-3 11-58 M-345 I-3 II-99
M-305 I-3 11-59 M-346 I-3 11-100
M-306 I-3 11-60 M-347 I-3 11-101
M-307 I-3 11-61 M-348 I-3 11-102
M-308 I-3 II-62 M-349 I-3 11-103
M-309 I-3 II-63 M-350 I-3 11-104
M-310 I-3 II-64 M-351 I-3 11-105
M-31 1 I-3 II-65 M-352 I-3 11-106
M-312 I-3 II-66 M-353 I-3 11-107
M-313 I-3 II-67 M-354 I-3 11-108
M-314 I-3 II-68 M-355 I-3 11-109
M-315 I-3 II-69 M-356 I-3 11-1 10
M-316 I-3 II-70 M-357 I-3 11-1 1 1
M-317 I-3 11-71 M-358 I-3 11-1 12
M-318 I-3 II-72 M-359 I-3 11-1 13
M-319 I-3 II-73 M-360 I-3 11-1 14
M-320 I-3 II-74 M-361 I-3 11-1 15
M-321 I-3 II-75 M-362 I-3 11-1 16
M-322 I-3 II-76 M-363 I-3 11-1 17
M-323 I-3 II-77 M-364 I-3 11-1 18
M-324 I-3 II-78 M-365 I-3 11-1 19
M-325 I-3 II-79 M-366 I-3 11-120 No I II No I II
M-367 I-3 11-121 M-379 I-2 ll-25a
M-368 I-3 11-122 M-380 I-2 ll-56a
M-369 I-3 11-123 M-381 I-2 ll-108a
M-370 1-1 11-21 a M-382 I-3 ll-21 a
M-371 1-1 ll-22a M-383 I-3 ll-22a
M-372 1-1 ll-23a M-384 I-3 ll-23a
M-373 1-1 ll-25a M-385 I-3 ll-25a
M-374 1-1 ll-56a M-386 I-3 ll-56a
M-375 1-1 ll-108a M-387 I-3 ll-108a
M-376 I-2 11-21 a M-388 1-1 11-124
M-377 I-2 ll-22a M-389 I-2 11-124
M-378 I-2 ll-23a M-390 I-3 11-124
More preferred mixtures of the present invention are mixtures of L-glufosinate-ammonium or L- glufosinate-sodium as L-glufosinate salts or L-glufosinate as free acid and at least one compound II selected from the group consisting of cyhalofop, cyhalofop-butyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, profoxydim, benfuresate, molinate, thiobencarb, bensulfuron, bensulfuron- methyl, chlorimuron, chlorimuron-ethyl, ethoxysulfuron, halosulfuron, halosulfuron-methyl, met- sulfuron, metsulfuron-methyl, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, ,mazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammoni- um, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, bispyribac, bispyribac- sodium, bentazone, bentazone-sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxa- zin, oxadiazon, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, clomazone, tefuryltrione, fenquinotrione, lancotrione, lancotrione-sodium, pendimethalin, acetochlor, butachlor, metolachlor, S-metolachlor, pretilachlor, mefenacet, fentrazamide, anilofos, 2,4-D and its salts and esters, domeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, quinclorac, quinclorac dimethylammonium, diflufenzopyr, diflufenzopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), oxaziclomefone, quizalofop, quizalo- fop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P and cycloxydim. Thus, more preferred are mixtures M-1 , M-2, M-3, M-4, M-5, M-6, M-7, M-8, M-9, M-10, M-1 1 , M-12, M-13, M-14, M-15, M-16, M-17, M-18, M-19, M-20, M-21 , M-22, M-23, M-24, M-25, M-26, M-27, M-28, M-29, M-30, M-31 , M-32, M-33, M-34, M-35, M-36, M-37, M-38, M-39, M-40, M-41 , M-42, M-43, M-44, M-45, M-46, M-47, M-48, M-49, M-50, M-51 , M-52, M-53, M-54, M-55, M-56, M-57, M-58, M-59, M-60, M-61 , M-62, M-63, M-64, M-65, M-66, M-67, M-68, M-69, M-70, M-71 , M-122, M-124, M-125, M-126, M-127, M-128, M-129, M-130, M-131 , M-132, M-133, M-134, M- 135, M-136, M-137, M-138, M-139, M-140, M-141 , M-142, M-143, M-144, M-145, M-146, M- 147, M-148, M-149, M-150, M-151 , M-152, M-153, M-154, M-155, M-156, M-157, M-158, M- 159, M-160, M-161 , M-162, M-163, M-164, M-165, M-166, M-167, M-168, M-169, M-170, M- 171 , M-172, M-173, M-174, M-175, M-176, M-177, M-178, M-179, M-180, M-181 , M-182, M- 183, M-184, M-185, M-186, M-187, M-188, M-189, M-190, M-191 , M-192, M-193, M-194, M- 246, M-247, M-248, M-249, M-250, M-251 , M-252, M-253, M-254, M-255, M-256, M-257, M- 258, M-259, M-260, M-261 , M-262, M-263, M-264, M-265, M-266, M-267, M-268, M-269, M- 270, M-271 , M-272, M-273, M-274, M-275, M-276, M-277, M-278, M-279, M-280, M-281 , M- 282, M-283, M-284, M-285, M-286, M-287, M-288, M-289, M-290, M-291 , M-292, M-293, M- 294, M-295, M-296, M-297, M-298, M-299, M-300, M-301 , M-302, M-303, M-304, M-305, M- 306, M-307, M-308, M-309, M-310, M-31 1 , M-312, M-313, M-314, M-315, M-316, M-317 and M-369.
Most preferred are mixtures M-1 , M-2, M-3, M-4, M-5, M-6, M-7, M-8, M-9, M-10, M-1 1 , M-12, M-13, M-14, M-15, M-16, M-17, M-18, M-19, M-20, M-21 , M-22, M-23, M-24, M-25, M-26, M-27, M-28, M-29, M-30, M-31 , M-32, M-33, M-34, M-35, M-36, M-37, M-38, M-39, M-40, M-41 , M-42, M-43, M-44, M-45, M-46, M-47, M-48, M-49, M-50, M-51 , M-52, M-53, M-54, M-55, M-56, M-57, M-58, M-59, M-60, M-61 , M-62, M-63, M-64, M-65, M-66, M-67, M-68, M-69, M-70, M-71 and M- 1229.
All above-referred mixtures are herein below referred to as "inventive mixtures".
The inventive mixtures can further contain one or more insecticides, fungicides, herbicides. The inventive mixtures can be converted into customary types of agrochemical mixtures, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for mixture types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wetable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), gran- ules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further mixtures types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The mixtures are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con- densed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam- pies of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the inventive mixtures on the tar- get. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for mixture types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of an inventive mixture and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of an inventive mixture and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt%. Dilution with water gives a disper- sion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of an inventive mixture and 5-10 wt% emulsifiers (e.g. calcium dodecylben- zenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of an inventive mixture and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzene- sulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of an inventive mixture are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1 - 2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance sus- pension. Dilution with water gives a stable suspension of the active substance. For FS type mixture up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of an inventive mixture are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS) 50-80 wt% of an inventive mixture are ground in a rotor-stator mill with addition of 1 -5 wt% dis- persants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of an inventive mixture are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of an inventive mixture are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamicallystable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of an inventive mixture, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of an inventive mixture according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4'- diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of pol- yurea microcapsules. The monomers amount to 1-10 wt%. The wt% relate to the total CS mixture.
xi) Dustable powders (DP, DS)
1 -10 wt% of an inventive mixture are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
x) Granules (GR, FG)
0.5-30 wt% of an inventive mixture is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xii) Ultra-low volume liquids (UL)
1 -50 wt% of an inventive mixture are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
The mixtures types i) to xii) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants. The resulting agrochemical mixtures generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
The mixtures in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying the inventive mixtures and mixtures thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propaga- tion material. Preferably, the inventive mixtures or the mixtures thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the inventive mixtures comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the inventive mixtures in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the mixture according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemi- cal mixture is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical mixture according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to- use spray liquor are applied per hectare of agricultural useful area. The inventive mixtures provide excellent pre-plant burn-down, pre- and post-emergence control of weeds in rice, including rice that is tolerant to herbicides including glufosinate. Thus, in the methods and uses of the invention, the compounds present in the inventive mixtures can be applied for pre-plant burn-down (to control emerged weeds prior to planting), pre-emergence (before the emergence of undesirable vegetation) or post-emergence (i.e., during and/or after emergence of the undesirable vegetation).
Thus, the invention relates to a method of an inventive mixture for controlling undesirable vegetation in rice, including rice that is tolerant to herbicides including glufosinate, which comprises applying the compounds present in the inventive mixtures to a locus of planted crops where undesirable vegetation occurs or might occur. The application is done before the emergence of undesirable vegetation or during and/or after emergence of the undesirable vegetation.
The application can be done after seeding of the rice or during and/or after emergence of the rice. The term "locus", as used herein, means the area in which the vegetation or plants are growing or will grow, typically a field.
As used herein, the terms "controlling" and "combating" are synonyms. As used herein, the terms "undesirable vegetation", "undesirable species", "undesirable plants", "harmful plants", "undesirable weeds", or "harmfull weeds" are synonyms.
When using the inventive mixtures in the methods of the present invention, the active com- pounds present in the inventive mixtures can be applied simultaneously or in succession, where undesirable vegetation may occur. Herein, it is immaterial whether compounds present in the inventive mixtures are formulated jointly or separately and applied jointly or separately, and, in the case of separate application, in which order the application takes place. It is only necessary, that the compounds present in the inventive mixtures are applied in a time frame, which allows simultaneous action of the active ingredients on the undesirable plants.
In the above-mentioned methods of controlling weeds by application of the inventive mixtures, the inventive mixtures have an outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. The inventive mix- tures also act efficiently on perennial weeds which produce shoots from rhizomes, rootstocks or other perennial organs and which are difficult to control. In this context, it does not matter whether the compounds of the inventive mixtures are applied before sowing, pre-emergence or post-emergence. Post-emergence application, or early pre-sowing or pre-emergence application, is preferred.
Both L-glufosinate alone as well as, in the methods of the present invention, the inventive mixtures are suitable for controlling a large number of harmful plants in agricultural crops, including monocotyledonous weeds, in particular annual weeds such as gramineous weeds (grasses) including Echinochloa species such as barnyardgrass (Echinochloa crusgalli var. crus-galli), Echinchloa walteri (Pursh) Heller, jungle rice (Echinochloa colona), Echinochloa crus-pavonis, Echinochloa oryzicola, Digitaria species such as crabgrass (Digitaria sanguinalis), Digitaria hor- izontalis, sourgrass (Digitaria insularis) or naked crabgrass (Digitaria nuda), Setaria species such as green foxtail (Setaria viridis), giant foxtail (Setaria faberii), yellow foxtail (Setaria glauca or Setaria pumila) or Setaria verticillata, Sorghum species such as johnsongrass (Sorghum halepense Pers.), Avena species such as wild oats (Avena fatua), Avena sterillis or Avena stri- gosa, Cenchrus species such as Cenchrus species such as field sandbur (Cenchrus pauciflo- rus) or Cenchrus echinatus, Bromus species such as Bromus japonicus Thunb, Bromus sterilis or Bromus tectorum, Lolium species, Phalaris species such as Phalaris brachystachys, Phalaris minor or Phalaris persicaria, Eriochloa species, Panicum species such as fall panicum (Panicum dichotomiflorum), Panicum fasciculatum or Panicum maximum, Brachiaria species, annual bluegrass (Poa annua), Alopecurus species such as blackgrass (Alopecurus myosuroides), Al- opecurus aequalis Sobol or Alopecurus japonicus Steud, Aegilops species such as Aegilops cylindrica or Aegylops tauschii, Apera spica-venti, Eleusine indica, Cynodon dactylon, couch grass (Agropyron repens or Elymus repens), Agrostis alba, Beckmannia syzigachne (Steud.) Fernald, Chloris species such as Chloris virgata, Commelina species such as Commelina ben- ghalensis, Commelina communis, Commelina diffusa or Commelina erecta, Dactyloctenium aegyptium, Hordeum jubatum, Hordeum leporinum, Imperata cylindrica, Ischaemum rogusum, Ixophorus unisetus, Leerisa hexandra, Leersia japonica, Leptochloa species such as Lepto- chloa chinensis, Leptochloa fascicularis, Leptochloa filiformis or Leptochloa panicoides, Lolium species such as Lolium multiflorum, Lolium perenne, Lolium persicum or rigid ryegrass (Lolium rigidum), Luziola subintegra, Murdannia nudiflora (L.) Brenan, Oryza latifolia, Oryza rufipogon, Paspalum distichum, Paspalum species, Pennisetum americanum, Pennisetum purpureum, Phleum paniculatum, Phragmites australia, Ploypogon fugax. N., Poa species such as Poa annua or Poa trivialis L., Puccinellia distans, Rottboellia cochinchinensis, Sclerochloa kengiana (Ohwi) Tzvel., Trichloris crinita, Urochloa or Brachiaria species such as Brachiaria decumbens, Brachiaria plantaginea, Brachiaria platyphylla, Urochloa panicoides, Urochloa ramosa and the like.
Both L-glufosinate alone as well as the inventive mixtures are also suitable for controlling a large number of dicotyledonous weeds, in particular broad leaf weeds including Polygonum species such as wild buckwheat (Polygonum convolvolus), Polygonum pensilvanicum, Polygo- num persicaria or prostrate knotweed (Polygonum aviculare), Amaranthus species such as pigweed (Amaranthus retroflexus), Palmer amaranth (Amaranthus palmeri), tall waterhemp (Amaranthus tuberculatus or Amaranthus rudis), redroot pigweed (Amaranthus retroflexus), green amaranth (Amaranthus hybridus), purple amaranth (Amaranthus lividus), prickly amaranth (Amaranthus spinosus) or Amaranthus quitensis, Chenopodium species such as common lambsquarters (Chenopodium album L.), Chenopodium serotinum or Quinoa (Chenopodium quinoa), Sida species such as prickly sida (Sida spinosa L.), Ambrosia species such as common ragweed (Ambrosia artemisiifolia) or giant ragweed (Ambrosia trifida), Acanthospermum species, Anthemis species such as Anthemis arvensis or Anthemis cotula, Atriplex species, Cirsium species such as Cirsium arvense, Convolvulus species such as field bindweed (Con- volvulus arvensis), Conyza species such as horseweed (Conyza canadensis, Erigeron canadensis) or hairy fleabane (Conyza bonariensis, Erigeron bonariensis), Cassia species, Datura species such as jimsonweed (Datura stramonium), Euphorbia species such as toothed spurge (Euphorbia dentata), Euphorbia hirta, Euphorbia helioscopia or fireplant (Euphorbia heterophyl- la), Geranium species such as Geranium donianum or Geranium pusillum, Galinsoga species, morningglory (Ipomoea species), Lamium species such as henbit dead-nettle (Lamium amplexi- caule), Malva species such as dwarf mallow (Malva neglecta) or cheeseweed (Malwa parviflo- ra), Matricaria species such as chamomile (Matricaria chamomilla) or Matricaria inodora, Sysimbrium species, Solanum species such as black nightshade (Solanum nigrum), Xanthium species, Veronica species such as Veronica polita, Viola species, common chickweed (Stellaria media), velvetleaf (Abutilon theophrasti), Sesbania species such as Sesbania exaltata, Ses- bania herbacea or hemp sesbania (Sesbania exaltata Cory), Anoda cristata, Bidens species such as Bidens frondosa or Bidens pilosa, Brassica kaber, Capsella species such as Capsella media or Capsella bursa-pastoris, Centaurea cyanus, Galeopsis tetrahit, Galium aparine, Heli- anthus annuus, Desmodium tortuosum, Kochia scoparia, Mercurialis annua, Myosotis arvensis, Papaver rhoeas, Raphanus species such as wild radish (Raphanus raphanistrum), Salsola species such as Salsola tragus or Salsola kali, Sinapis arvensis, Sonchus species sucha Sonchus asper, Sonchus arvensis or Sonchus oleraceus, Thlaspi arvense, Tagetes minuta, Richardia species such as Richardia scabra or Richardia brasiliensis, Aeschynomeme species such as Aeschynomene denticulata, Aeschynomene indica orAeschynomene rudis, Alisma species such as Alisma canaliculatum orAlisma plantago-aquatica, Borreria species such as Borreria verticil- lata, Brassica rapa, Carduus acanthoides, Parietaria debilis, Portulaca oleracea, Ipomoea species such as Ipomoea grandifolia, Ipomoea hederacea, Ipomoea indivisa, Ipomoea lacunose, Ipomoea lonchophylla or Ipomoea wrightii,, Senna obtusifolia, Sida species such as arrowleaf sida (Sida rhombifolia) or prickly sida (Sida spinosa), Spermacoce latifolia, Tridax procumbens, Trianthema portulacastrum, Parthenium hysterophorus, Portulaca oleracea, Acalypha australis, Ammi majus, Atriplex species, Orobanche species, Mercurialis annua, Cirsium arvense, Calys- tegia sepium, Stellaria media, Lamium species, Viola species, Celosia argentea, Melampodium divaricatum, Cleome viscosa, Molugo verticilatus, Borhevia erecta, Gomphrena species, Nican- dra physalodes, Ricinus communis, Geranium dissectum, Alternanthera species such as Al- thernanthera philoxeroides or Alternanthera tenella, Ammannia species such as Ammania coc- cinea, Anacamtodon fortunei Mitt., Anagallis arvensis, Aneilema keisak, Arenaria serpyllifolia, Argemone mexicana, Asphodelus tenuifolius, Atriplex patula, Bacopa rotundifolia, Brassica na- pus, Caperonia species sucha as Caperonia castaneifolia or Caperonia palustris, Cephalano- plos segetum, Corynopus didymus, Crepis capillaris, Crepis tectorum, Croton lobatus, Descu- minia sophia (L), Descurainia pinnata, Echinodorus grandiflorus, Eclipta alba, Eclipta prostrata, Eichhornia crassipes, Eleocharis species, Equisetum arvense, Fallopia convolvulus, Fallopia convolvulus, Heteranthera limosa, Jussiaea species, Kallstroemia maxima, Lactuca serriola, Lathyrus aphaca, Launea mudicaulis, Leucas chinensis, Limnocharis flava, Lindernia dubia, Lindernia pyxidaria, Litospermum arvense, Ludwigia species such as Ludwigia octovallis, Mac- roptilium lathyroides, Malachium aquaticum (L), Melilotus species, Merremia aegyptia, Momor- dica charantia, Monochoria hastate, Monochoria vaginalis, Mucuna species, Murdannia nudiflo- ra, Oxalis neaei, Phylanthus species, Physalis species, Pistia stratiotes, Potamogeton distinc- tus, Rorippa islandica, Rotala indica, Rotala ramosior, Rumex dentatus, Rumex obtusifolius, Sagittaria montevidensis, Sagittaria pygmaea Miq., Sagittaria sagittifolia, Sagittaria trifolia L, Senecio vulgaris, Sicyos polyacanthus, Silene gallica, chenopoSisymbrium species such as Sisymbrium oficinale, Solanum species, Spergula arvensis, Sphenoclea zeylanica, Trianthema spp., Tripleurospermum inodorum, Veronica species such as Veronica persica orVeronica polita Vicia sativa and the like.
Both L-glufosinate alone as well as the inventive mixtures are also suitable for controlling a large number of annual and perennial sedge weeds including Cyperus species such as purple nutsedge (Cyperus rotundus L), yellow nutsedge (Cyperus esculentus L), hime-kugu (Cyperus brevifolius H.), sedge weed (Cyperus microiria Steud), rice flatsedge (Cyperus iria L), Cyperus difformis, Cyperus difformis L, Cyperus esculentus, Cyperus ferax, Cyperus flavus, Cyperus iria, Cyperus lanceolatus, Cyperus odoratus, Cyperus rotundus, Cyperus serotinus Rottb., Eleo- charis acicularis, Eleocharis kuroguwai, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus grossus, Scirpus juncoides, Scirpus juncoides Roxb, Scirpus or Bolboschoenus maritimus, Scirpus or Schoenoplectus mucronatus, Scirpus planiculmis Fr. Schmidt and the like.
Both L-glufosinate alone as well as the inventive mixtures are also suitable for controlling weeds that are resistant to commonly used herbicides such as, for example, weeds that are resistant to glyphosate, weeds that are resistant to auxin inhibitor herbicides such as e. g. 2,4-D or dicam- ba, weeds that are resistant to photosynthesis inhibitors such as e. g. atrazine, weeds that are resistant to ALS inhibitors such as e. g. sulfonylureas, imidazolinones or triazolopyrimidines, weeds that are resistant to ACCase inhibitors such as e. g. clodinafop, clethodim or pinoxaden or weeds that are resistant to protoporphyrinogen-IX-oxidase inhibitors such as e. g. sulfentra- zone, flumioxazine, fomesafen or acifluorfen, for example the weeds that are listed in the International Survey of Resistant Weeds
(http://www.weedscience.org/Summary/SpeciesbySOATable.aspx). In particular, they are suitable for controlling the resistant weeds that are listed in the International Survey of Resistant Weeds, for example ACCase resistant Echinochloa crus-galli, Avena fatua, Alopecurus myosu- roides, Echinochloa colona, Alopecurus japonicus, Bromus tectorum, Hordeum murinum, Is- chaemum rugosum, Setaria viridis, Sorghum halepense, Alopecurus aequalis, Apera spica- venti, Avena sterilis, Beckmannia szygachne, Bromus diandrus, Digitaria sanguinalis, Echi- nocloa oryzoides, Echinochloa phyllopogon, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Brachypodium distachyon, Bromus diandrus, Bromus sterilis, Cynosurus echina- tus, Digitaria insularis, Digitaria ischaemum, Leptochloa chinensis, Phalaris brachystachis, Rot- boellia cochinchinensis, Digitaria ciliaris, Ehrharta longiflora, Eriochloa punctata, Leptochloa panicoides, Lolium persicum, Polypogon fugax, Sclerochloa kengiana, Snowdenia polystacha, Sorghum Sudanese and Brachiaria plantaginea, ALS inhibitor resistant Echinochloa crus-galli, Poa annua, Avena fatua, Alopecurus myosuroides, Echinochloa colona, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Amaranthus retroflexus, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Senecio ver- nalis, Alopecurus japonicus, Bidens pilosa, Bromus tectorum, Chenopodium album, Conyza bonariensis, Hordeum murinum, Ischaemum rugosum, Senecio vulgaris, Setaria viridis, Sisym- brium orientale, Sorghum halepense, Alopecurus aequalis, Amaranthus blitum, Amaranthus powellii, Apera spica-venti, Avena sterilis, Brassica rapa, Bromus diandrus, Descurainia sophia, Digitaria sanguinalis, Echinochloa oryzoides, Echinochloa phyllopogon, Euphorbia heterophylla, Lactuca serriola, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Sinapis arvensis, Solanum ptycanthum, Sonchus oleraceus, Stellaria media, Amaranthus blitoides, Am- aranthus spinosus, Amaranthus viridis, Ambrosia trifida, Bidens subalternans, Bromus diandrus, Bromus sterilis, Capsella bursa-pastoris, Centaurea cyanus, Cynosurus echinatus, Cyperus difformis, Fimbristilis miliacea, Galeopsis tetrahit, Galium aparine, Galium spurium, Helianthus annuus, Hirschfeldia incana, Limnocharis flava, Limnophila erecta, Papaver rhoeas, Parthenium hysterophorus, Phalaris brachystachis, Polygonum convolvulus, Polygonum lapathifolium, Po- lygonum persicaria, Ranunculus acris, Rottboellia cochinchinensis, Sagittaria montevidensis, Salsola tragus, Schoenoplectus mucronatus, Setaria pumila, Sonchus asper, Xanthium stru- marium, Ageratum conyzoides, Alisma canaliculatum, Alisma plantago-aquatica, Ammannia auriculata, Ammannia coccinea, Ammannia arvensis, Anthemis cotula, Bacopa rotundifolia, Bi- fora radians, Blyxa aubertii, Brassica tournefortii, Bromus japonicus, Bromus secalinus, Litho- spermum arvense, Camelina microcarpa, Chamaesyce maculata, Chrysanthemum coronarium, Clidemia hirta, Crepis tectorum, Cuscuta pentagona, Cyperus brevifolis, Cyperus compressus, Cyperus esculentus, Cyperus iria, Cyperus odoratus, Damasonium minus, Diplotaxis erucoides, Diplotaxis tenuifolia, Dopatrum junceum, Echium plantagineum, Elatine triandra, Eleocharis acicularis, Erucaria hispanica, Erysimum repandum, Galium tricornutum, Iva xanthifolia, Ixopho- rus unisetus, Lamium amplexicaule, Limnophilia sessiliflora, Lindernia dubia, Lindernia micran- tha, Lindernia procumbens, Ludwigia prostrata, Matricaria recutita, Mesembryanthemum crystal- linum, Monochoria korsakowii, Monochoria vaginalis, Myosoton aquaticum, Neslia paniculata, Oryza sativa var. sylvatica, Pentzia suffruticosa, Picris hieracioides, Raphanus sativus,
Rapistrum rugosum, Rorippa indica, Rotala indica, Rotala pusilla, Rumex dentatus, Sagittaria guayensis, Sagittaria pygmaea, Sagittaria trifolia, Schoenoplectus fluviatilis, Schoenoplectus juncoides, Schoenoplectus wallichii, Sida spinosa, Silene gallica, Sinapis alba, Sisymbrium thel- lungii, Sorghum bicolor, Spergula arvensis, Thlaspi arvense, Tripleurospermum perforatum, Vaccaria hispanica and Vicia sativa, photosynthesis inhibitor resistant Echinochloa crus-galli, Poa annua, Alopecurus myosuroides, Echinochloa colona, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Amaranthus retroflexus, Ambrosia artemisifo- lia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Senecio vernalis, Alopecurus japonicus, Bidens pilosa, Bromus tectorum, Chenopodium album, Conyza bonariensis, Is- chaemum rugosum, Senecio vulgaris, Setaria viridis, Sisymbrium orientale, Amaranthus blitum, Amaranthus powellii, Apera spica-venti, Beckmannia syzigachne, Brassica rapa, Digitaria san- guinalis, Euphorbia heterophylla, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Sinapis arvensis, Solanum ptycanthum, Stellaria media, Amaranthus blitoides, Amaranthus viridis, Bidens subalternans, Brachypodium distachyon, Capsella bursa-pastoris, Chloris bar- bata, Cyperus difformis, Echinochloa erecta, Epilobium ciliatum, Polygonum aviculare, Polygonum convolvulus, Polygonum lapathifolium, Polygonum persicaria, Portulaca oleracea, Schoenoplectus mucronatus, Setaria pumila, Solanum nigrum, Sonchus asper, Urochloa panicoides, Vulpia bromoides, Abutilon theophrasti, Amaranthus albus, Amaranthus cruentus, Arabidopsis thaliana, Arenaria serpyllifolia, Bidens tripartita, Chenopodium album, Chenopodium ficifolium, Chenopodium polyspermum, Crypsis schoenoides, Datura stramonium, Epilobium tetragonum, Galinsoga ciliata, Matricaria discoidea, Panicum capillare, Panicum dichotomiflorum, Plantago lagopus, Polygonum hydopiper, Polygonum pensylvanicum, Polygonum monspeliensis, Ros- traria, smyrnacea, Rumex acetosella, Setaria verticillata and Urtica urens, PS-l-electron diversion inhibitor resistant Poa annua, Conyza sumatrensis, Conyza canadensis, Alopecurus japon- icus, Bidens pilosa, Conyza bonariensis, Hordeum murinum, Ischaemum rugosum, Amaranthus blitum, Solanum ptycanthum, Arctotheca calendula, Epilobium ciliatum, Hedyotis verticillata, Solanum nigrum, Vulpia bromoides, Convolvulus arvensis, Crassocephalum crepidioides, Cuphea carthagensis, Erigeron philadelphicus, Gamochaeta pensylvanica, Landoltia punctata, Lepidium virginicum, Mazus fauriei, Mazus pumilus, Mitracarpus hirtus, Sclerochloa dura, Sola- num americanum and Youngia japonica, glyphosate resistant Poa annua, Echinochloa colona, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Bidens pilosa, Conyza bonariensis, Hordeum murinum, Sorghum halepense, Brassica rapa, Bromus diandrus, Lactuca serriola, Sonchus oleraceus, Amaranthus spinosus, Ambrosia trifida, Digitaria insularis, Hedyotis verticillata, Helianthus annuus, Parthenium hysterophorus, Plantago lanceolata, Salso- la tragus, Urochloa panicoides, Brachiaria eruciformis, Bromus rubens, Chloris elata, Chloris truncata, Chloris virgata, Cynodon hirsutus, Lactuca saligna, Leptochloa virgata, Paspalum pa- niculatum and Tridax procumbens, microtubule assembly inhibitor resistant Echinochloa crus- galli, Poa annua, Avena fatua, Alopecurus myosuroides, Amaranthus palmeri, Setaria viridis, Sorghum halepense, Alopecurus aequalis, Beckmannia syzigachne and Fumaria densifloria, auxin herbicide resistant Echinochloa crus-galli, Echinochloa colona, Amaranthus hybridus, Amaranthus rudis, Conyza sumatrensis, Kochia scoparia, Raphanus raphanistrum, Cheno- podim album, Sisymbrium orientale, Descurainia sophia, Lactuca serriola, Sinapis arvensis, Sonchus oleraceus, Stellaria media, Arctotheca calendula, Centaurea cyanus, Digitaria ischae- mum, Fimbristylis miliacea, Galeopsis tetrahit, Galium aparine, Galium spurium, Hirschfeldia incana, Limnocharis flava, Limnocharis erecta, Papaver rhoeas, Plantago lanceolata, Ranunculus acris, Carduus nutans, Carduus pycnocephalus, Centaurea soltitialis, Centaurea stoebe ssp. Micranthos, Cirsium arvense, Commelina diffusa, Echinochloa crus-pavonis, Soliva sessilis and Sphenoclea zeylanica, HPPD inhibitor resistant Amaranthus palmeri and Amaranthus rudis, PPO inhibitor resistant Acalypha australis, Amaranthus hybridus, Amaranthus palmeri, Amaranthus retroflexus, Amaranthus rudis, Ambrosia artemisifolia, Avena fatua, Conyza sumatrensis, Descurainia sophia, Euphorbia heterophylla and Senecio vernalis, carotenoid biosynthesis in- hibitor resistant Hydrilla verticillata, Raphanus raphanistrum, Senecio vernalis and Sisymbrium orientale, VLCFA inhibitor resistant Alopecurus myosuroides, Avena fatua and Echinochloa crus-galli.
If the compounds of the inventive mixtures are applied to the soil surface before germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have reached the cotyledon stage but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
If the active compounds of the inventive mixtures are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the rice plants, is eliminated at a very early point in time and in a sustained manner. When the active compounds of the inventive mixtures are used jointly, superadditive
(=synergistic) effects are observed. This means that the effect in the combinations exceeds the expected total of the effects of the individual herbicides employed. The synergistic effects allow the application rate to be reduced, a broader spectrum of broad-leaved weeds and weed grasses to be controlled, the herbicidal effect to take place more rapidly, the duration of action to be longer, the harmful plants to be controlled better while using only one, or few, applications, and the application period which is possible to be extended. In some cases, uptake of the compositions also reduces the amount of harmful constituents in the crop plant, such as nitrogen or oleic acid. The active compounds of the inventive mixtures can be used jointly or in succession. They can also conveniently be combined with further herbicide treatments to treatment combinations that ensure a more complete or long-lasting weed control, or to ensure control of weeds that are resistant against certain herbicides through combined action of mutiple herbicides with different modes of action. In particular, the active compounds of the inventive mixtures and further herbicides can be used in any of the treatment combinations outlined below that consist of pre-plant burn down, pre-emergence and post-emergence treatments. These treatment combinations can be particularly suitable if the rice is tolerant to the action of one or more herbicides present in the treatment combination, including tolerance that is a result of breeding and/or genetic modification. Such tolerant plants include glufosinate tolerant rice, glyphosate tolerant rice, rice that is tolerant to AHAS inhibitors (e. g. imidazolinone herbicides such as imazamox, imazapyr, ima- zapic or imazethapyr) and rice that is tolerant to PPO herbicides.
The following active compounds of the inventive mixtures and further herbicides are particularly suitable as pre-plant burn-down weed control components in such treatment combinations: L- Glufosinate, L-glufosinate ammonium, L-glufosinate sodium, glyphosate, glyphosate dime- thylammonium, glyphosate potassium, glyphosate isopropylammonium, paraquat, trifludimoxa- zin, saflufenacil.
The following active compounds of the inventive mixtures and further herbicides are particularly suitable as pre-emergence weed control components in such treatment combinations: Ben- furesate, molinate, thiobencarb, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, clomazone, oryzalin, pendimethalin, acetochlor, bu- tachlor, pretilachlor, thenylchlor, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, quinclorac, quinclorac dimethylammonium, cinmethylin, dymron (daimuron), etobenzanid, inda- nofan, methyldymron (methyl-daimuron), oxaciclomefone.
The following active compounds of the inventive mixtures and further herbicides are particularly suitable for post-emergence weed control components in such treatment combinations: L- Glufosinate, L-glufosinate ammonium, L-glufosinate sodium, glyphosate, glyphosate dimethylammonium, glyphosate potassium, glyphosate isopropylammonium, clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, profoxydim, azimsulfuron, ben- sulfuron, bensulfuron-methyl, cinosulfuron, ethoxysulfuron, flucetosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, orthosul- famuron, oxasulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, imazamox, imaza- mox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazethapyr, imazethapyr ammonium, penoxsulam, pyrimisulfan, pyroxsulam, bispyribac, bispyri- bac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, triafamone, bentazone, bentazone-sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, benzobicyclon, ben- zofenap, pyrazolynate, tefuryltrione, topramezone, fenquinotrione, lancotrione, lancotrione- sodium, ipfencarbazone, 2,4-D and its salts and esters, clomeprop, florpyrauxifen and its salts and esters, quinclorac, quinclorac dimethylammonium, triclopyr and its salts and esters, quizalo- fop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, cycloxydim and cyclosulfamuron. The abovementioned properties and advantages are necessary under practical weed control conditions to keep the rice free from undesired competing plants and thus to guarantee and/or increase the yields from the qualitative and quantitative point of view. These novel combinations markedly exceed the technical state of the art with a view to the properties described. While the active compounds of the inventive mixtures have an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, the tolerant, or cross-tolerant, glufosinate tolerant rice are damaged only to a minor extent, or not at all.
As mentioned above, the inventive mixtures are suitable for controlling a large number of harm- ful plants in glufosinate tolerant rice
Thus, the term " glufosinate tolerant rice" as used herein includes also (rice) plants which have been modified by mutagenesis, genetic engineering or breeding and mutation selection techniques in order to provide a new trait to a plant or to modify an already present trait.
Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific "event", which is referred to by a specific event name. Glufosinate tolerance has been created by using mutagenesis as well as using genetic engineering. Transgenic rice events comprising glufosinate tolerance genes are for example, but not excluding others, LLRICE06 (event code: ACS-OS001 -4, e.g. commercially available as Liberty Link™ rice), LLRICE601 (event code: BCS-OS003-7, e.g. commercially available as Liberty Link™ rice) and LLRICE62 (event code: ACS-OS002-5, e.g. commercially available as Liberty Link™ rice).
In all treatments according to the methods of the present invention, the inventive mixtures can be applied in conventional manner by using techniques as skilled person is familiar with. Suita- ble techniques include spraying, atomizing, dusting, spreading or watering. The type of application depends on the intended purpose in a well known manner; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention. In one embodiment, the inventive mixtures are applied to locus mainly by spraying, in particular foliar spraying of an aqueous dilution of the active ingredients of the mixture. Application can be carried out by customary spraying techniques using, for example, water as carrier and spray liquor rates of from about 10 to 2000 l/ha or 50 to 1000 l/ha (for example from 100 to 500 l/ha). Application of the inventive mixtures by the low-volume and the ultra-low-volume method is possible, as is their application in the form of microgranules.
The required application rate of the mixture of the pure active compounds depends on the density of the undesired vegetation, on the development stage of the plants, on the climatic conditions of the location where the mixture is used and on the application method.
In general, the rate of application of L-glufosinate is usually from 50 g/ha to 3000 g/ha and preferably in the range from 100 g/ha to 2000 g/ha or from 200 g/ha to 1500 g/ha of active substance (a.i.), and the rate of application of the secod herbicida compound II is from 1 g/ha to 2000 g/ha and preferably in the range from 5 g/ha to 1500 g/ha, more preferably from 25 g/ha to 900 g/ha of active substance (a.i.).
The examples which follow illustrate the invention without imposing any limitation.
Biological examples
Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 21 -22):
Figure imgf000028_0001
When the observed combined control effect is greater than the expected (calculated) combined control effect (E), then the combined effect is synergistic.
The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific weeds. However, the weed control afforded by the compounds, mixtures or compositions is not limited to these species. The analysis of synergism or antagonism between the mixtures or compositions was determined using Colby's equation.
Test method:
The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species and/or resistant biotype. For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. Depending on the species, the plants were kept at 10 - 25°C or 20 - 35°C, respectively. The test period extended to 20 days after treatment. During this time, the plants were tended, and their response to the individual treatments was evaluated. The evaluation was carried out by using a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth. Data shown are the mean of two replications.
Products:
L-Glufosinate: 5 % EC formulation
Saflufenacil: 342 g/l SC formulation
Trifludimoxazin: 500 g/l SC formulation
Methiozolin: 250 g/l SC formulation
Weeds in the study:
Figure imgf000029_0001
Example 1 : Post emergence treatment with the mixture of L-glufosinate with saflufenacil
Herbicidal activity against
Application rate in g ai/ha
ECHCG
L-Glufosinate Saflufenacil Found Calculated
400 — 65 —
— 0.5 0 —
400 0.5 97 65
200 — 0 —
— 0.5 0 —
200 0.5 35 0 Example 2: Post emergence treatment with the mixture of L-glufosinate with trifludimoxazin
Figure imgf000030_0001
Example 3: Post emergence treatment with the mixture of L-glufosinate with methiozolin
Herbicidal activity against
Application rate in g ai/ha
LOLMU
L-Glufosinate methiozoline Found Calculated
75 — 0 —
— 250 25 —
75 250 40 25
75 — 0 —
— 125 0 —
75 125 10 0

Claims

Claims
Use of a herbicidal mixture for controlling undesirable vegetation in rice, wherein the herbicidal mixture comprises
a) L- glufosinate and its salts, and
b) a herbicidal compound II selected from the group consisting of clethodim, cyhalofop, cyhalofop-butyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensul- furon-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, fluce- tosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfu- ron-methyl-sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammoni- um, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, pyrimisulfan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, thiencarbazone, thiencarbazone-methyl, triafamone, benta- zone, bentazone-sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludi- moxazin, picolinafen, benzobicyclon, benzofenap, bicyclopyrone, clomazone, pyra- zolynate, sulcotrione, tefuryltrione, topramezone, fenquinotrione, lancotrione, lanco- trione-sodium, glyphosate, glyphosate dimethylammmonium, glyphosate- isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sulfosate), oryzalin, pendimethalin, acetochlor, butachlor, metazachlor, metolachlor, S- metolachlor, pretilachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, pyroxasulfone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, quinclorac, quinclorac dimethylammonium, quinmerac, triclopyr and its salts and esters, diflufenzopyr, diflufenzopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), etobenzanid, indanofan, methyl-dymron (methyl- daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalo- fop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dime- thenamid, dimethenamid-P, cycloxydim and cyclosulfamuron.
wherein L-glufosinate comprises more than 70% by weight of the L-enantiomer.
The use as claimed in claim 1 , wherein compound I in the herbicidal mixture is selected from the group consisting of L-glufosinate-ammonium or L-glufosinate-sodium as L- glufosinate salts and L-glufosinate as free acid.
The use as claimed in claim 1 , wherein compound I in the herbicidal mixture is L- glufosinate-ammonium.
The use as claimed in any of claims 1 to 3, wherein L-glufosinate in the herbicidal mixture comprises more than 80% by weight, preferably more than 90% by weight, even more preferably 95% by weight of the L-enantiomer.
The use as claimed in any of claims 1 to 4, wherein compound II is selected from the group consisting of ethyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, profoxydim, benfuresate, molinate, thiobencarb, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, cinosulfuron, ethoxysulfuron, fluce- tosulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron- methyl-sodium, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosul- famuron, oxasulfuron, propyrisulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, py- rimisulfan, pyroxsulam, bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyrimino- bac, pyriminobac-methyl, thiencarbazone, thiencarbazone-methyl, triafamone, bentazone, bentazone-sodium, propanil, carfentrazone, carfentrazone-ethyl, flumioxazin, oxadiargyl, oxadiazon, pentoxazone, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, benzobicy- clon, benzofenap, bicyclopyrone, clomazone, pyrazolynate, sulcotrione, tefuryltrione, fenquinotrione, lancotrione, lancotrione-sodium, glyphosate, glyphosate dimethylammmo- nium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-trimesium (sul- fosate), oryzalin, pendimethalin, acetochlor, butachlor, metolachlor, S-metolachlor, preti- lachlor, thenylchlor, flufenacet, mefenacet, fentrazamide, anilofos, cafenstrole, fenoxasul- fone, ipfencarbazone, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, MCPA and its salts and esters, quinclorac, quinclorac dimethylammonium, triclopyr and its salts and esters, diflufenzopyr, diflufen- zopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), eto- benzanid, indanofan, methyl-dymron (methyl-daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, dimethenamid-P, cycloxydim and cyclosul- famuron.
The use as claimed as claimed in any of claims 1 to 4, wherein compound II is selected from the group consisting of cyhalofop, cyhalofop-butyl, fenoxaprop-ethyl, fenoxaprop-P- ethyl, profoxydim, benfuresate, molinate, thiobencarb, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, ethoxysulfuron, halosulfuron, halosulfuron-methyl, metsulfuron, metsulfuron-methyl, pyrazosulfuron, pyrazosulfuron-ethyl, tritosulfuron, imazamox, imazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, imazethapyr, imazethapyr ammonium, penoxsulam, bispyribac, bispyribac-sodium, bentazone, bentazone-sodium, propanil, carfentrazone, carfentrazone- ethyl, flumioxazin, oxadiazon, pyraclonil, cyclopyranil, saflufenacil, trifludimoxazin, clomazone, tefuryltrione, fenquinotrione, lancotrione, lancotrione-sodium, pendimethalin, aceto- chlor, butachlor, metolachlor, S-metolachlor, pretilachlor, mefenacet, fentrazamide, anilo- fos, 2,4-D and its salts and esters, clomeprop, dicamba and its salts and esters, florpyrauxifen and its salts and esters, quinclorac, quinclorac dimethylammonium, diflufen- zopyr, diflufenzopyr-sodium, cinmethylin, cyclopyrimorate (CAS 499223-49-3), dymron (daimuron), oxaziclomefone, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, MCPA and its salts and esters, dimethenamid, di- methenamid-P and cycloxydim.
7. The use as claimed in any of claims 1 to 6, wherein the weight ratio of compound I to com- pound 11 is from 1000: 1 to 1 :500.
8. The use as claimed as claimed in any of claims 1 to 6, wherein the weight ratio of compound I to compound II is from 500:1 to 1 :250.
9. A pesticidal mixture, wherein the compounds I and II are as defined in any of claims 1 to 8.
10. A pesticidal composition, comprising a liquid or solid carrier and a mixture as defined in any of claims 1 to 8.
1 1 . A method for controlling undesirable vegetation in glufosinate tolerant rice, which method comprises applying a mixture according to claims 1 to 8 to the undesirable vegetation or the locus thereof or applying to the soil or water.
12. The method as claimed in claim 1 1 , wherein the glufosinate tolerant rice is a transgenic rice plant.
13. The method as claimed in any of claims 1 1 to 12, wherein compounds I and II of the mixture as defined in any of claims 1 to 8 are applied simultaneously, that is jointly or separately, or in succession.
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