WO2021036251A1 - Composition herbicide contenant des dérivés d'acide pyridyloxycarboxylique de type r et son application - Google Patents

Composition herbicide contenant des dérivés d'acide pyridyloxycarboxylique de type r et son application Download PDF

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Publication number
WO2021036251A1
WO2021036251A1 PCT/CN2020/081644 CN2020081644W WO2021036251A1 WO 2021036251 A1 WO2021036251 A1 WO 2021036251A1 CN 2020081644 W CN2020081644 W CN 2020081644W WO 2021036251 A1 WO2021036251 A1 WO 2021036251A1
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salt
alkyl
polyoxyethylene ether
methyl
evaluation
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PCT/CN2020/081644
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English (en)
Chinese (zh)
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彭学岗
赵德
金涛
张景远
刘娜
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青岛清原化合物有限公司
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Publication of WO2021036251A1 publication Critical patent/WO2021036251A1/fr

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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
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-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
    • A01N43/72—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
    • A01N43/84—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/18—Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • R" each independently represents a C1-C16 alkyl group, and is selected from one or more groups of halogen, hydroxy, C1-C6 alkoxy, C1-C6 alkylthio, and hydroxy C1-C6 alkoxy.
  • Substituted C1-C16 alkyl preferably C1-C6 alkyl
  • C2-C12 alkenyl preferably C2-C6 alkenyl
  • C2-C12 alkynyl preferably C2-C6 alkynyl
  • C3-C12 cycloalkane Group unsubstituted or substituted by C1-C6 alkyl phenyl or benzyl
  • C1-C6 alkyl phenyl or benzyl preferably C1-C6 alkyl group, and is selected from one or more groups of halogen, hydroxy, C1-C6 alkoxy, C1-C6 alkylthio, and hydroxy C1-C6 alkoxy.
  • Z stands for And unsubstituted or substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, halogenated C1-C6 alkyl, cyano and halogen Phenyl, tetrahydrofuranyl, pyridyl, pyrazolyl, thienyl, furanyl or naphthyl;
  • R 7 represents C1-C6 alkyl, C2-C6 alkenyl,
  • the active ingredient B is selected from one or more of the following compounds and their salts/esters:
  • ALS inhibitors Penoxsulam (CAS Number: 219714-96-2), Bispyrifen (CAS Number: 125401-92-5), Pyrimsulfuron (CAS Number: 93697-74-6) ), Nicosulfuron (CAS Number: 111991-09-4), Fenoxsulam (CAS Number: 145701-23-1), Susulfuron-methyl (CAS Number: 122931-48-0), Imazethapyr Tobacco (CAS Number: 81335-77-5), Imazethapyr (CAS Number: 104098-48-8), Imazethapyr (CAS Number: 114311-32-9), Metsulfuron (CAS No.: 74222-97-2), Chlorfentrazone (CAS No.: 147150-35-4);
  • HPPD inhibitors ciclofenac (CAS number: 1855929-45-1), fentrazone (CAS number: 1622908-18-2), flufentrazone (CAS number: 1992017-55) -6), mesotrione (CAS number: 1911613-97-2), fursotrione (CAS number: 473278-76-1), mesotrione (CAS number: 104206-82-8), Cyclosulfone (CAS number: 335104-84-2), oxaflutole (CAS number: 210631-68-8), isoxaflutole (CAS number: 141112-29-0), bicyclazone ( CAS number: 156963-66-5);
  • Q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, Methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, hydroxymethyl, Benzyl, naphthyl Furanyl Pyridyl Pyrimidinyl And unsubstituted or chloro-substituted thiazolyl Thienyl unsubstituted or substituted by fluorine Unsubstituted or substituted by methyl or fluorine Unsubstituted or substituted by at least one of methyl, trifluoromethyl, chlorine and methoxy;
  • M represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ten Monoalkyl, dodecyl, octadecyl, trifluoromethyl, pentafluoroethyl, 3-chlorobutyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2, 2-Difluoroethyl, 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoropropyl, cyclopropyl, cyclobutyl Group, cyclopentyl, cyclohexyl, allyl, 2-propynyl, meth
  • the preparation method of the active ingredient A includes the following steps:
  • W represents hydrogen or alkali metal, preferably K, Na;
  • Hal represents halogen, preferably Br, Cl;
  • the reaction is carried out in the presence of a catalyst and a solvent, preferably, the catalyst is TBAB, and the solvent is DCM, One or more combinations of DCE, ACN, THF, and DMF.
  • the solvent is selected from one or more combinations of methanol, ethanol, and isopropanol.
  • the reaction is carried out in the presence of a dehydrating agent and a solvent.
  • the dehydrating agent is DCC
  • the solvent is selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, and N,N-dimethylformamide , N,N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, toluene, xylene, one or more combinations.
  • the halogenated compound is preferably a chlorinated compound or a brominated compound; the reaction is carried out in the presence of a base and a solvent, and the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate.
  • the solvent is selected from one of THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane and chloroform
  • a catalyst can also be added during the reaction process, preferably DMAP.
  • the salt is a pesticide acceptable salt, preferably the R-type pyridyloxy carboxylic acid compound of the present invention is formed by reacting with a chemically acceptable basic compound.
  • the above-mentioned pharmaceutically acceptable salts are easy to separate and can be purified by conventional separation methods, such as solvent extraction, dilution, recrystallization, column chromatography and preparative thin layer chromatography.
  • the mass percentage of A and B in the herbicidal composition accounts for 1-95%, preferably 10-80% of the total.
  • the herbicidal composition also contains conventional adjuvants, and the conventional adjuvants include carriers and surfactants.
  • carrier refers to an organic or inorganic, natural or synthetic substance. They facilitate the application of the active ingredient.
  • the carrier is generally inert and must be agriculturally acceptable, especially acceptable to the plants being treated.
  • the carrier can be solid, such as clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or wax hydrocarbons, chlorine Hydrocarbon, liquefied gas, etc.
  • the surfactant may include an emulsifier, dispersant or wetting agent, and it may be ionic or non-ionic. Examples that may be mentioned are the salts of polyacrylic acid, lignosulfonate, phenolsulfonic acid or naphthalenesulfonic acid, ethylene oxide with aliphatic alcohols or with aliphatic acids or with aliphatic amines and substituted phenols (in particular Alkylphenol or arylphenol) polymers, sulfosuccinates, taurine derivatives (especially taurine alkane esters) and alcohol phosphate esters or polyhydroxyethylated phenol phosphate esters, Alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated cetyl, heptadecyl and stearyl alcohols and sulf
  • composition may also contain various other components, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents, dyes, colorants and polymers.
  • composition of the present invention can be mixed with the following active substances, such as "Encyclopedia of World Pesticide New Variety Technologies", China Agricultural Science and Technology Press, 2010.9 and known substances in the literature cited here.
  • the herbicide active substances mentioned below (note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, and the code when appropriate): acetochlor, butachlor, Alachlor, Propolachlor, Metolachlor, Refined Metolachlor, Pretilachlor, Tetrachlor, Metochlor, Napropionate, R-Naphtochlor, Propanochlor , Mefenacet, difenacet, diflufenican, chlorfenazone, flubutazone, bromobutyrazamide, dimethenamid, high-efficiency dimethenamid, ethoxylate Apifenacet, flufenacet, metolachlor, metazachlor,
  • the herbicidal composition further includes at least one safener selected from:
  • Dichlorophenylpyrazoline-3-carboxylic acid (S1) compounds the preferred compound is, for example, 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl Ethyl-2-pyrazoline-3-carboxylate (S1-1, mefenpyr-diethyl, PM, p. 594-595), and described in, for example, WO91/07874 and PM (p. 594-595) 594-595 pages) related compounds.
  • Dichlorophenylpyrazole carboxylic acid derivatives the preferred compound is, for example, 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylic acid ethyl ester (S1-2), 1-(2,4-Dichlorophenyl)-5-isopropylpyrazole-3-carboxylic acid ethyl ester (S1-3), 1-(2,4-Dichlorophenyl)-5-(1 ,1-Dimethyl-ethyl)pyrazole-3-carboxylic acid ethyl ester (S1-4), 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylic acid ethyl Esters (S1-5), and related compounds described in EP-A-333131 and EP-A-269806.
  • 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid compound preferably
  • the compound is, for example, 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylic acid ethyl ester (S1-7) or 5-phenyl-2-isoxazoline-3-carboxylic acid Ethyl acid (S1-8) and related compounds described in WO91/08202, or 5,5-diphenyl-2-isoxazoline described in patent application (WO-A-95/07897) Ethyl 3-carboxylate (S1-9, isoxadifen-ethyl) or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid n-propyl ester (S1-10) Or 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline
  • S2 8-quinolinoxyacetic acid (S2) compounds, preferably 1-methylhex-1-yl (5-chloro-8-quinolinoxy) acetate (S2-1, cloquintocet- mexyl), such as PM (pages 195-196), (1,3-dimethylbut-1-yl)(5-chloro-8-quinolinoxy)acetate (S2-2), 4- Allyloxybutyl (5-chloro-8-quinolinoxy) acetate (S2-3), 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy) Yl) acetate (S2-4), (5-chloro-8-quinolinoxy) ethyl acetate (S2-5), (5-chloro-8-quinolinoxy) methyl acetate (S2- 6), (5-chloro-8-quinolinoxy) allyl acetate (S2-7), 2-(2-propylene iminooxy)-1-ethyl (5-chloro-8-
  • Phenoxyacetic acid, phenoxypropionic acid or aromatic carboxylic acid active compounds such as 2,4-dichlorophenoxyacetic acid (and ester) (2,4-D), 4-chloro-2- Methylphenoxypropionate (2-methyl-4-chloropropionic acid (mecoprop)), MCPA or 3,6-dichloro-2-methoxybenzoic acid (and ester) (dicamba) .
  • the safener is preferably dibenzoxazole acid (CAS: 163520-33-0), cyprosulfamide (CAS: 221667-31-8), pyrazolone (CAS: 135590-91-9), detox quinine (CAS : 99607-70-2), one or more of gibberellic acid (CAS: 7-06-5), furilazole (CAS: 121776-33-8), metcamifen (CAS: 129531-12-0).
  • the abbreviated form of the common name of the active compound all conventional derivatives, such as esters and salts, as well as isomers, especially optical isomers, especially One or more commercially available forms.
  • the generic name indicates an ester or salt, it also includes all other conventional derivatives in each case, such as other esters and salts, free acids and neutral compounds, as well as isomers, especially optical isomers, especially Is one or more commercially available forms.
  • the chemical name of the given compound indicates at least one compound covered by the generic name, and is usually the preferred compound.
  • salts also include salts formed by the exchange of cations with hydrogen atoms in the sulfonamide group.
  • 2 methyl 4 chloro derivatives include but are not limited to: 2 methyl 4 chloride sodium salt, potassium salt, dimethyl ammonium salt, isopropylamine salt, etc., and 2 methyl 4 chloro methyl, ethyl, isooctyl ester, ethyl sulfide Esters, etc.
  • 2,4-D derivatives include but are not limited to: 2,4-D salts such as sodium salt, potassium salt, dimethylammonium salt, triethanolammonium salt, isopropylamine salt, choline, etc., and 2,4 -D esters such as methyl ester, ethyl ester, butyl ester, isooctyl ester, etc.
  • the salt of the compound is preferably in the form of the respective alkali metal salt, alkaline earth metal salt or ammonium salt, preferably in the form of the respective alkali metal salt, more preferably in the form of the respective sodium salt or potassium salt, It is most preferably in the form of the respective sodium salt.
  • composition of the present invention can be diluted or used directly by the user before use.
  • the formulation can be prepared by the usual processing methods, that is, after mixing the active substance with a liquid solvent or a solid carrier, then adding one or more of surfactants such as dispersing agents, stabilizers, wetting agents, adhesives, defoamers, etc. kind.
  • the specific formulations of the herbicidal composition are dispersible oil suspensions, water suspensions, suspoemulsions, wettable powders, emulsifiable concentrates, water dispersible granules (dry suspensions), water emulsions, and microemulsions.
  • composition of the present invention can be mixed with solid and liquid additives conventionally used in prior art formulations.
  • composition of the present invention can be applied to the leaves of plants to be treated by spraying, that is, applied to weeds, especially on the surfaces that are infested or easily affected by weeds.
  • the present invention also provides an application of the herbicidal composition for controlling weeds; and a method for controlling the growth of unwanted plants, which includes applying the herbicidal composition to plants, plant parts, and plants.
  • the herbicidal composition is used to selectively control weeds in useful crops. More preferably, the useful crops are transgenic crops or crops processed by genome editing technology.
  • the compounds of the invention can be used to treat all plants and plant parts.
  • Plant varieties and cultivated lines can be obtained through conventional propagation and breeding methods or through genetic engineering methods.
  • Genetically modified plants are those in which a heterologous gene (transgene) has been stably integrated into the genome of the plant.
  • the transgene defined by its specific position in the plant genome is called a transformation event or a transgenic event.
  • the genetically modified plant cultivars that can be treated according to the present invention include those resistant to one or more biotic stresses (pests, such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization) Etc.), or it contains other desired features. Plants can be genetically modified to exhibit traits, such as herbicide tolerance, insect tolerance, modified oil characteristics, or drought tolerance. Available genetically modified plants containing a single genetic transformation event or a combination of transformation events are listed in Table 1. Additional information about the genetic modifications listed in Table 1 can be obtained from publicly available databases maintained, for example, through the United States Department of Agriculture.
  • T1 to T37 are used for the traits in Table 1. "-" means that the entry is not available.
  • the herbicidal composition of the present invention When the herbicidal composition of the present invention is applied, an unexpected synergistic effect is obtained, and the herbicidal activity is more significant than the expected sum of the activities of a single herbicide and the activity of a single herbicide.
  • the synergistic effect is manifested by reduced application rate, wider weed control spectrum, faster and longer weeding action, these characteristics are required in the process of weed control practice.
  • these new compositions are significantly superior to existing herbicides, achieve reduced usage, and are more environmentally friendly.
  • composition of the present invention is environmentally friendly and is easily degraded in the environment.
  • the herbicidal composition of the present invention has low cost and convenient use, and its popularization and application have huge economic and social benefits.
  • dispersible oil suspension agent processing equipment mixing kettle, colloid mill, sand mill, shearing machine, etc.
  • the above-mentioned dispersible oil suspension agent processing process put all the materials into the mixing kettle, stir and mix, pass through the colloid mill, then enter the three-stage sand mill of the sand mill, and finally shear evenly in the shearing machine. After the test is qualified, transfer To the storage tank for filling.
  • the above-mentioned water suspension agent processing equipment mixing kettle, colloid mill, sand mill, shearing machine, etc.
  • the above-mentioned water suspension agent processing process put all the materials into the mixing kettle, stir and mix, pass through the colloid mill, then enter the three-stage sand mill of the sand mill, and finally cut uniformly in the shearing machine, and transfer to the storage after the test is qualified. Can filling.
  • suspoemulsion processing equipment mixing kettle, colloid mill, sand mill, shearing machine, etc.
  • suspoemulsion processing process put part of the materials and additives into the mixing kettle, stir and mix, pass through the colloid mill, then enter the three-stage sand mill of the sand mill, and transfer to the intermediate tank as the water phase after the sand mill is completed; Put part of the original medicine and cosolvent into the batching kettle, stir and dissolve until it is completely transparent, and stir evenly into the oil phase; finally, open the shear in the shearing kettle, and slowly drip the oil phase into the water phase, after all the materials are dripped , Continue to cut for 1 hour, after passing the test, transfer to the storage tank for filling.
  • the above-mentioned water emulsion processing equipment vacuum pump, batching kettle, storage tank, shearing kettle.
  • the above-mentioned water emulsion processing process Put the original medicine and solvent into the batching kettle, stir to dissolve until completely transparent, then add the emulsifier, stir evenly into the oil phase, and then pump the glycol, defoamer and deionized water into the shear In the kettle, finally, under the shearing state, the oil phase is slowly drawn into the shearing kettle. After all the materials are drawn in, continue to shear for 1 hour. After passing the test, transfer to the storage tank for filling.
  • microemulsion processing equipment vacuum pump, batching kettle, storage tank.
  • microemulsion processing process put the original drug and solvent into the batching kettle, stir and dissolve until completely transparent, then add the emulsifier, stir evenly, finally add deionized water, stir until the solution is completely transparent, and transfer to the storage tank after the test Filling.
  • the above-mentioned emulsifiable concentrate processing process put the original medicine and solvent into the batching kettle, stir to dissolve until completely transparent, then add the emulsifier, stir evenly until the solution is completely transparent, and transfer to the storage tank for filling after passing the test.
  • liquid processing equipment vacuum pump, batching kettle, storage tank.
  • the above-mentioned water preparation process put the original medicine and deionized in the batching kettle, stir to dissolve until completely transparent, then add the emulsifier, stir until the solution is completely transparent, and transfer to the storage tank for filling after passing the test.
  • the above-mentioned weeds are cultivated in pots. They are placed in an enamel tray in a 180 ⁇ 140mm plastic nutrient bowl, containing the top soil (4/5) collected from the farmland and air-dried and sieved. The soil moisture is initially controlled at 20%. Select Weed seeds with full and uniform grains, soaked in warm water at 25°C for 6 hours, incubate germination in a biochemical incubator (dark) at 28°C, evenly place the white weed seeds on the soil surface, and cover with 0.5 soil according to the size of the seed. -1cm.
  • 3WP-2000 walking spray tower Nanjing Agricultural Machinery Research Institute, Ministry of Agriculture. GA10 one-tenth electronic balance (Germany); ZDR2000 intelligent data recorder (Hangzhou Zeda Instrument Co., Ltd.); SPX type intelligent biochemical incubator (Ningbo Jiangnan Instrument Factory).
  • the required active ingredient A comes from the patent CN201911321469.4.
  • the preparation examples of representative compounds are as follows, and the synthesis methods of other compounds are similar, so they will not be repeated.
  • the required active ingredients B, cicloflurzone, carfentrazone, flufentrazone, and trifentrazone are produced by the company, and the others are purchased by the reagent company.
  • the original medicines all use acetone as the solvent, diluted with 0.1% emulsifier Tween-80 aqueous solution, and are now diluted.
  • the action characteristics and toxicities of the two agents should be measured, and the main purpose of the formulation should also be considered.
  • the single and mixed dosages of A and B active ingredients are shown in the table respectively. Use water without medicament and with the same solvent and emulsifier as a blank control.
  • Each treatment was repeated 4 times, 3 pots per treatment each time, 20 weed seeds were sown in each pot, and a total of 60 plants per treatment.
  • the whole seedling of the surviving weed was cut along the soil surface with a blade, and the fresh weight of the weed was weighed with an analytical balance. For weeds that have died, the fresh weight is zero.
  • E-E0 value greater than 10% is synergistic effect, less than -10% is antagonistic effect, and between -10% and 10% is additive effect.
  • X is the fresh weight inhibition rate when the amount of active ingredient A is P
  • Y is the fresh weight inhibition rate when the amount of active ingredient B is Q.
  • the test soil is quantitatively filled to 3/4 of the pot, and then watered from the bottom of the pot to make the soil completely wet to a saturated state. Spread the pretreated weed seeds evenly and quantitatively on the surface, cover 0.5-2cm of soil according to the seed size, and reserve 24 hours after sowing.
  • GA10 one-tenth electronic balance (Germany); ZDR2000 intelligent data recorder (Hangzhou Zeda Instrument Co., Ltd.); SPX type intelligent biochemical incubator (Ningbo Jiangnan Instrument Factory), pipettes, etc.
  • Table 17 The actual control effect and joint effect evaluation of A2 mixed quizalofop-p-ethyl on barnyardgrass
  • Table 128 The actual control effect and joint effect evaluation of A3 mixed pyrenpyrazone on wild rape
  • Table 130 The actual control effect and joint effect evaluation of A4 mixed triazole sulcotrione on paddy field barnyardgrass
  • Table 135 The actual control effect and joint effect evaluation of A4 mixed isoxaflutole on paddy field barnyardgrass
  • the herbicide composition prepared in Examples 1-150 was used to conduct field weed effect tests.
  • Stem and leaf treatment When the weeds are in the 3-5 leaf stage, use a manual sprayer, with a water volume of 30 kg/667m 2 , and use stem and leaf spray treatment.
  • Table 151 The specific test agents and doses are shown in Table 151.
  • the plot area is 50 square meters, and each treatment is repeated 4 times. See Table 151 for the investigation of the control effect 45 days after application.
  • Example number Dosage (g a.i./ha) Fresh weight control effect (%) 1 150 97.8 2 180 95.6 3 210 93.8 4 150 98.3 5 180 95.2 6 210 94.6 7 150 97.5 8 180 96.7 9 210 94.9 10 180 96.6 11 210 96.7 12 240 94.1 13 124.5 97.1 14 154.5 96.3 15 184.5 94.9 16 150 96.3 17 180 97.8 18 210 95.2 19 210 95.4 20 240 97.8 twenty one 270 94.4 twenty two 270 95.9 twenty three 300 97.4 twenty four 330 95.2 25 180 95.1 26 210 98.9 27 240 95.5 28 270 94.2
  • the present invention unexpectedly discovered that the composition is used for the prevention and control of Amaranthus amaranthus, Amaranthus retroflexus, Amaranthus amaranthus, Solanum vulgaris, Channa intestines, Pork Salmon, Eleutherococcus sp Mother-in-law, Arabian mother-in-law, cow chickweed, chickweed, wild rape, Polygonum clove, Moshangcai, cocory, sorrel, chinensis, cocklebur, artemisia sowing, quinoa, dayflower, round Leaf morning glory and other broad-leaved weeds, Kan Mai Niang, Japanese Mai Niang, Chrysanthemum japonicum, Western barnyardgrass, Paddy barnyardgrass, Echinochloa crusgalli, Setaria viridis, Green Setaria, Golden Setaria, Crabgrass, gooseweed, Sawgrass Grasses and other gramineous weeds have surprising and unexpected synergistic effects

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

Abstract

La présente invention se rapporte au domaine des pesticides et concerne plus précisément une composition herbicide contenant des dérivés d'acide pyridyloxycarboxylique de type R et son application. La composition comprend un ingrédient actif A et un ingrédient actif B qui ont une quantité efficace d'herbicide, l'ingrédient actif A étant choisi parmi un ou plusieurs éléments parmi un acide pyridyloxycarboxylique de type R tel que représenté dans la formule I ainsi que des sels et des dérivés d'ester correspondants : (I) dans laquelle R1 et R2 représentent indépendamment un atome d'halogène, un alkyle en C1-C6, un halogénoalkyle en C1-C6 et un cycloalkyle en C3-C6 respectivement ; R3 représente un atome d'hydrogène, un halogène, un alkyle en C1-C6 et un alkyle en C1-C6 halogéné ; Q représente un alkyle en C1-C6 ou similaire ; et Y représente un amino ou similaire. Le principe actif B est choisi parmi un ou plusieurs des composés suivants et des sels/esters correspondants : un inhibiteur d'ALS, un inhibiteur d'ACCase, un inhibiteur de PSII, un inhibiteur de HPPD, un inhibiteur de PDS, un inhibiteur de DOXP et un inhibiteur de PPO. La composition décrite peut lutter efficacement contre divers problèmes de mauvaises herbes tels que des graminées ou des dicotylédones dans des champs de culture, et a les caractéristiques d'expansion du spectre d'élimination des mauvaises herbes, de réduction de la quantité à appliquer, d'aptitude à produire des effets synergiques et d'élimination de mauvaises herbes résistantes.
PCT/CN2020/081644 2019-08-27 2020-03-27 Composition herbicide contenant des dérivés d'acide pyridyloxycarboxylique de type r et son application WO2021036251A1 (fr)

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