WO2019090818A1 - Composé de 4-benzoylpyrazole, procédé de préparation s'y rapportant et utilisation de ce dernier - Google Patents

Composé de 4-benzoylpyrazole, procédé de préparation s'y rapportant et utilisation de ce dernier Download PDF

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WO2019090818A1
WO2019090818A1 PCT/CN2017/112020 CN2017112020W WO2019090818A1 WO 2019090818 A1 WO2019090818 A1 WO 2019090818A1 CN 2017112020 W CN2017112020 W CN 2017112020W WO 2019090818 A1 WO2019090818 A1 WO 2019090818A1
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group
alkyl
acyl
aryl
halogen
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Chinese (zh)
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连磊
征玉荣
何彬
彭学岗
金涛
崔琦
刘娜
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Qingdao Kingagroot Chemical Compound Co Ltd
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Qingdao Kingagroot Chemical Compound Co Ltd
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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
    • A01N43/48—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
    • 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
    • C07D401/14—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 three or more hetero rings
    • 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
    • C07D405/14—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 three or more hetero rings

Definitions

  • the invention belongs to the technical field of pesticides, and in particular relates to a 4-benzoylpyrazole compound and a preparation method and application thereof.
  • Patent CN103980202A discloses a 4-benzoylpyrazole compound with herbicidal activity.
  • the object of the present invention is to provide a 4-benzoylpyrazole compound with high herbicidal activity and good crop compatibility, and a preparation method and application thereof.
  • R 1 is selected from the group consisting of methyl, ethyl, propyl, isopropyl or cyclopropyl;
  • R 2 is selected from alkylsulfonyl, alkoxy, alkylthio, fluoro, chloro or cyano;
  • R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl or trifluoromethyl;
  • R 4 is selected from the group consisting of hydrogen, cyano, nitro, halogen, carboxyl, hydroxy, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, cycloalkane with or without halogen Oxyl, alkylthio, alkenylthio, cycloalkylthio, alkylacyl, alkylacyloxy, alkylsulfonyl, alkyl, haloalkyl, alkenyl, alkynyl, nitro, Hydroxy, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkyl acyl, alkyl acyloxy, alkylcarbamoyl, trialkylsilyl, dialkylphosphonyl and unsubstituted or substituted Aromatic or heteroaryl substituted amino group, and unsubstituted or substituted aryl, aryl acyl
  • R is selected from among them
  • X and Y are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, carboxyl, hydroxy, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy with or without halogen Alkyl, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkylacyl, alkylacyloxy, alkylsulfonyl, alkyl, haloalkyl, alkenyl, alkynyl , nitro, hydroxy, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkyl acyl, alkyl acyloxy, alkylcarbamoyl, trialkylsilyl, dialkylphosphonyl and Unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl,
  • Z is selected from the group consisting of hydrogen, amino, nitro, cyano, halogen, carboxyl, hydroxy, alkylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyl groups with or without halogen Oxyl, alkoxyalkyl, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkylacyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylalkyl, alkoxy Carbonylalkyl, alkylaminocarbonylalkyl, alkylcarbamoyl, alkylacyloxy, alkylsulfonyl, trialkylsilyl, dialkylphosphonyl, and unsubstituted or substituted aryl, aromatic Alkanoyl group, aryloxy group, arylalkyl group, arylalkyl acy
  • substituted means selected from halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, alkenyloxy, alkylthio, aryl, aryloxy a group, a benzyl group, a benzyloxy group, an acyl group, an acyloxy group, an alkenyl group, and one or more groups of amino groups substituted with an alkyl group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, and an alkenyl group Replaced by the regiment.
  • R 1 is selected from the group consisting of methyl, ethyl, propyl, isopropyl or cyclopropyl;
  • R 2 is selected from a C 1 -C 8 alkylsulfonyl group, a C 1 -C 8 alkoxy group, a C 1 -C 8 alkylthio group, a fluorine, a chlorine or a cyano group;
  • R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl or trifluoromethyl;
  • R 4 is selected from the group consisting of hydrogen, cyano, nitro, halogen, carboxyl, hydroxy, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C3-C8 cycloalkoxy, C1-C8 alkylthio, C2-C8 alkenylthio, C3-C8 cycloalkylthio, C1- a C8 alkyl acyl group, a C1-C8 alkyl acyloxy group, a C1-C8 alkylsulfonyl group, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, Nitro, hydroxy, amino, C1
  • R is selected from among them
  • X and Y are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, carboxyl, hydroxy, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 alkenyl, C2- C8 alkynyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C3-C8 cycloalkoxy, C1-C8 alkylthio, C2-C8 alkenylthio, C3-C8 cycloalkane a C1-C8 alkyl acyl group, a C1-C8 alkyl acyloxy group, a C1-C8 alkylsulfonyl group, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C2-C8 alkenyl group, a C1- C8 alkynyl, nitro, hydroxy, amino
  • Z is selected from the group consisting of hydrogen, amino, nitro, cyano, halogen, carboxyl, hydroxy, C1-C8 alkylamino, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 olefin , C2-C8 alkynyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C1-C8 alkoxy C1-C8 alkyl, C3-C8 cycloalkoxy, C1-C8 alkylthio , C2-C8 alkenylthio, C3-C8 cycloalkylthio, C1-C8 alkyl acyl, C1-C8 alkoxycarbonyl, C1-C8 alkylaminocarbonyl, C1-C8 alkylcarbonyl C1-C8 alkyl , C1-C8 alkoxycarbonyl C1-C8 alkyl,
  • substituted means selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2 -C8 alkenyloxy, C1-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, C1-C8 acyl, C1-C8 acyloxy, C2-C8 alkenyl and available C1 Substituting one or more of the -C8 alkyl, aryl, aryloxy, C1-C8 acyl, C1-C8 acyloxy and C2-C8 alkenyl substituted amino groups.
  • R 1 is selected from the group consisting of methyl, ethyl, isopropyl
  • R 2 is selected from the group consisting of methylsulfonyl and ethylsulfonyl;
  • R 3 is selected from the group consisting of hydrogen, methyl, ethyl, cyclopropyl
  • R 4 is selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkane Oxy, C2-C6 alkenyloxy, C3-C6 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C3-C6 cycloalkylthio, C1-C6 alkyl acyl a C1-C6 alkyl acyloxy group, a C1-C6 alkylsulfonyl group, an amino group which may be substituted by a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxy group, an aryl group or a heteroaryl group. And an unsubstituted or
  • R is selected from among them
  • X and Y are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkyl acyl, C1-C6 alkyl acyloxy, C1-C6 alkylsulfonyl, using C1-C6 alkane Alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl acyl, aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, heteroaryl, aryl acyl Heteroaryl acyl;
  • Z is selected from the group consisting of hydrogen, halogen, C1-C6 alkylamino, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkane
  • substituted means selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1 Substituting one or more groups of -C6 acyl, C1-C6 acyloxy, C1-C6 alkylamino, or amino.
  • R 1 is selected from the group consisting of methyl, ethyl, isopropyl
  • R 2 is selected from methylsulfonyl
  • R 3 is selected from the group consisting of hydrogen, methyl, ethyl, cyclopropyl
  • R 4 is selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkyl acyl, C1-C6 An alkylsulfonyl group, an amino group which may be substituted by a C1-C6 alkyl group or a halogenated C1-C6 alkyl group;
  • R is selected from among them
  • X and Y are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl a C1-C6 alkylthio group, a C1-C6 alkyl acyl group, a C1-C6 alkylsulfonyl group, an amino group substituted with a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, and an unsubstituted or substituted aryl group, Heteroaryl
  • Z is selected from the group consisting of hydrogen, halogen, C1-C6 alkylamino, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkyl acyl, and unsubstituted or substituted aryl, hetero Aryl;
  • substituted means substituted with one or more groups selected from the group consisting of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, and C1-C6 alkoxy.
  • R 1 is selected from the group consisting of methyl, ethyl, isopropyl
  • R 2 is selected from methylsulfonyl
  • R 3 is selected from the group consisting of hydrogen, methyl, ethyl, cyclopropyl
  • R 4 is selected from the group consisting of hydrogen, cyano, nitro, chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, trifluoromethyl, difluoromethyl, Trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl;
  • R is selected from among them
  • X and Y are each independently selected from the group consisting of hydrogen, cyano, nitro, chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, methoxycarbonyl, three Fluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl;
  • Z is selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, Fluoromethoxy, methoxy, ethoxy, phenyl, pyridyl.
  • the aryl group includes a phenyl group, a 2,3-indanyl group or a naphthyl group; and the heteroaryl group includes a 5-10 membered heteroaryl group having 1 to 3 O, S, and N hetero atoms.
  • a method for synthesizing a 4-benzoylpyrazole compound comprising the steps of:
  • M is selected from the group consisting of hydrogen, potassium, sodium or lithium; and compound (IV) is Or an acid anhydride such as (RCO) 2 O, RCOO-Ts, RCOO-Ms, and X is selected from chlorine, bromine or iodine.
  • the transposition product can be directly reacted with the compound of the formula (IV), and the organic layer is separated, and the impurity is separated to obtain the compound of the formula (I); or a reaction method for catalyzing the ester formation by a conventional dehydrating agent such as DCC or CDI can also be used.
  • a compound of formula (I) is prepared.
  • the acid binding agent is selected from one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide and potassium hydroxide. Acid agent.
  • the reaction temperature is -50 to 180 ° C, preferably -10 to 60 ° C.
  • the compounds of the formula (II), the formula (III) and the formula (IV) are each dissolved in a solvent to form a solution, and the solvent is selected from the group consisting of acetonitrile, N,N-dimethylformamide, N,N- One or more mixed solvents of dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, toluene, xylene, and dichloroethane.
  • a herbicidal composition comprising at least one of a herbicidally effective amount of said 4-benzoylpyrazole compound.
  • a plant growth regulator comprising at least one of an effective amount of the 4-benzoylpyrazole compound.
  • a method for controlling harmful plants or regulating plant growth applying at least one of the 4-benzoylpyrazoles or the herbicidal composition or plant growth regulator to a seed of a harmful plant or On the plant growing area.
  • the compounds of formula I of the present invention have outstanding herbicidal activity.
  • the active substances of the present invention are also effective for perennial weeds which grow from rhizomes, rhizomes, or other perennial organs and are difficult to control. In this regard, it is generally not important to use the substance before, before, or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the invention, without limiting the identified species.
  • weed species in which the active substance is effective include monocotyledons: annual oats, rye, grasses, maiden, ferraris, medlar, genus, foxtail, and sedge, and perennial ice. Genus, Bermudagrass, Rhizoma and sorghum, and perennial sedge.
  • dicotyledonous weed species species whose effects can be extended to, for example, the annual genus Polyporus, Amaranth, Pomna, Wild Sesame, Stellaria, Amaranthus, White Mustard, Ipomoea, and Yellow Flower Genus, Matricaria and genus, and perennial weeds, genus, genus and genus.
  • the active substance of the present invention effectively controls harmful plants under the conditions of rice sowing, such as cockroaches, genus, genus, genus, genus, cane, and sedge.
  • the compound of the present invention is applied to the surface of the soil before germination, the weeds of the weeds can be completely prevented before the weeds grow, or when the weeds grow out of the cotyledons, and finally completely die after three to four weeks.
  • the compound of the present invention is particularly resistant to the following plants, and is active in the following plants, such as Apila, Xiaoye Sesame, Rolling Stalk, Poria, Ivy, Herba, Arabian, Pansy, Pansy, Poria and Kochia. .
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no damage to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. Or the damage is trivial. In particular, it is well compatible with cereal crops such as wheat, barley and corn, especially wheat. Thus, the compounds of the invention are highly suitable for the selective control of unwanted plants in agricultural or ornamental plants.
  • Transgenic plants Due to their herbicidal nature, these active substances can be used to control harmful plants in genetically engineered plant cultivation that is known or to be present.
  • Transgenic plants generally have superior traits, such as resistance to specific insecticides, particularly specific herbicides, resistance to pathogenic microorganisms of plant diseases or plant diseases, such as specific insect or fungal, bacterial or viral microorganisms.
  • Other specific traits are related to the following conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients.
  • the obtained transgenic plant product has an increased starch content or an improved starch quality or a different fatty acid composition.
  • the compounds of the formula I according to the invention or their salts are preferably used in economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or for beets, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of the formula I are preferably used as herbicides for the cultivation of useful plants which are resistant or resistant to the toxic effects of the herbicide by genetic engineering.
  • transgenic crop plant such as cotton which is capable of producing Bacillus thuringiensis toxin (Bt toxin) which protects against specific pests against plants (EP-0142924A, EP-0193259A);
  • Plant cells of the activity-reducing gene product can be prepared by, for example, expressing at least one appropriate antisense-RNA, sense-RNA to achieve co-suppression, or by expressing at least one appropriately constructed ribozyme, It specifically cleaves the transcription product of the above gene product.
  • DNA molecules comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and the use of DNA molecules comprising only a portion of the coding sequence, which must be sufficiently long to achieve antisense in the cell Effect. Sequences that are highly homologous but not identical to the gene product coding sequence can also be used.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • These sequences are known to those skilled in the art (see, for example, Braun et al, EMBO J. 11 (1992) 3219-3227; Wolter et al, Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).
  • Transgenic plant cells can be recombined into whole plants using known techniques.
  • the control can be improved or expanded.
  • the range of weeds, the application rate at the time of application is preferably a combination of the resistance of the transgenic crops and the performance of the herbicide, and the effects of the growth and yield of the transgenic crop plants.
  • the invention therefore also provides the use of said compounds as herbicides to control harmful plants in plants of transgenic crops.
  • the compounds of the invention can significantly modulate the growth of crop plants. By modulating the involvement of plant metabolism, these compounds are used to orient the components of the plant and promote harvesting, such as drying and dwarfing the plants. Moreover, they are also suitable for regulating and inhibiting unwanted plant growth without destroying the growth of the crop. Inhibition of plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, as this reduces or completely prevents lodging.
  • the compound of the present invention can be applied using a general formulation, and a wettable powder, a concentrated emulsion, a sprayable solution, a powder or granules can be used.
  • a herbicidal composition comprising a compound of formula I.
  • the compounds of formula I can be formulated in a variety of ways, depending on the usual biological and/or chemical physical parameters.
  • suitable formulations are: wettable powders (WP), water soluble powders (SP), water soluble concentrates, concentrated emulsions (EC), emulsions such as oil dispersed in water and water dispersed in oil (EW) , sprayable solution, suspension concentrate (SC), dispersible oil suspension (OD), oil or water diluent, solution of miscible oil, powder (DP), capsule suspension (CS) ), seed dressing composition, particles for spreading and soil application, sprayed particles, coated particles and absorbent particles, water dispersible particles (WG), water soluble particles (SG), ULV (super Low volume) formula, microcapsules and wax products.
  • WP wettable powders
  • SP water soluble powders
  • EC concentrated emulsions
  • EW oil dispersed in water and water dispersed in oil
  • SC sprayable solution, suspension concentrate
  • OD dispersible oil suspension
  • DP powder
  • Wettable powders can be uniformly dispersed in water, in addition to active substances, including diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersing agents), such as polyethoxylated alkylphenols, poly Ethoxylated fatty alcohol, polyoxyethyl aliphatic amine, fatty alcohol polyglycol ether sulfate, alkyl sulfonate, alkyl phenyl sulfonate, sodium lignosulfonate, 2, 2'- dinaphthylmethane Sodium 6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate.
  • the herbicide active substance is finely ground, for example, using a conventional apparatus such as a hammer mill, a fan mill and a jet mill, and an auxiliary agent is simultaneously or sequentially mixed.
  • a concentrated emulsion such as butanol, cyclohexanone, dimethylformamide, xylene or a higher boiling aromatic compound or a mixture of hydrocarbons or solvents, and adding one more One or more ionic and/or nonionic surfactants (emulsifiers).
  • emulsifiers which can be used are, for example, calcium alkylaryl sulfonates of calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A glycan ester.
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A gly
  • the active substance and the finely divided solid matter are ground to obtain a powder, a solid substance such as talc, a natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • a water or oil based suspension can be prepared by, for example, wet milling using a commercially available bead mill with or without the addition of a surfactant of the other formulation type described above.
  • an aqueous organic solvent may be used, using a stirrer, a colloid mill and/or a static mixer, and if necessary, a surfactant of another formulation type as described above may be added.
  • the granules are prepared by spraying the active material onto the adsorbate, granulating with an inert material, or concentrating the active material onto the surface of, for example, a sand or kaolinite carrier, granulating the inert material by a binder, and adhering Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • the appropriate active can be plasmidized by the method of preparing fertilizer granules, if necessary Mixed with fertilizer.
  • the water-suspended granules are prepared by a usual method such as spray-drying, fluidized bed granulation, disc granulation, mixing using a high speed mixer, and extrusion without a solid inert material.
  • the agrochemical formulations usually comprise from 0.1 to 99% by weight, in particular from 0.1 to 95%, of the active substance I.
  • the concentration of the active substance in the wettable powder is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remaining amount by weight to 100%.
  • the concentration of the active substance in the concentrated emulsion may range from about 1 to 90%, preferably from 5 to 80% by weight.
  • the powder formulation comprises from 1 to 30% by weight of active substance, usually from 5 to 20% by weight of active substance, whereas the sprayable solution comprises from about 0.05 to 80%, preferably from 2 to 50% by weight of active substance. .
  • the content of the active material in the water-suspended granules mainly depending on whether the active material is liquid or solid, and auxiliaries, fillers and the like used in granulation.
  • the content of the active substance in the aqueous suspension granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the preparation of the active substance may include a tackifier, a wetting agent, a dispersing agent, an emulsifier, a penetrating agent, a preservative, an antifreezing agent, a solvent, a filler, a carrier, a coloring agent, an antifoaming agent, an evaporation inhibitor, and pH and viscosity modifiers commonly used in all cases.
  • insecticide active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and/or plant growth regulators.
  • safeners for premixed or filled mix.
  • Suitable active substances which can be mixed with the active substance of the present invention in a mixed preparation or a tank mix are, for example, "World Pesticide New Variety Technology Encyclopedia", China Agricultural Science and Technology Press, 2010.9 and the literature cited herein.
  • the herbicide active substance mentioned below may be mixed with the mixture of the formula I (note: the name of the compound, or a common name according to the International Organization for Standardization (ISO), or a chemical name, if appropriate, a code): Amine, butachlor, alachlor, propisochlor, metolachlor, stilben, acetochlor, chlorfenapyr, acetochlor, naproxen, R-levoperin Acetochlor, dipivoxil, thiaceuramide, dibenzoylamine, piracetamide, herbicide, flufenic acid, bromobutyramide, dimethoprim, high-efficiency dimethyl Thiamethoxazole, acetophene, flufenacet,
  • the commercially available formulations are diluted in a conventional manner, for example, in wettable powders, concentrated emulsions, suspensions, and granules suspended in water, diluted with water. Granules for powder or soil application or for spreading and spraying
  • the solution is generally not required to be further diluted with an inert substance prior to use.
  • the amount of the compound of formula I required varies with external conditions, such as temperature, humidity, the nature of the herbicide used, and the like. It can have a large range of variation, for example between 0.001 and 1.0 kg/ha, or more active substance, but preferably between 0.005 and 750 g/ha, in particular between 0.005 and 250 g/ha.
  • the activity level criteria for harmful plant damage are as follows:
  • Grade 9 growth control rate is above 95%
  • Level 7 growth control rate is above 80%
  • Level 5 The growth control rate is above 60%
  • Level 2 growth control rate is 5-20%
  • Level 1 The growth control rate is below 5%
  • the above growth control rate is the fresh weight control rate.
  • Post-emergence test Place monocotyledonous and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, canola, millet, sorghum) in a plastic pot containing soil, then cover 0.5-2 Cm soil, so that it grows in a good greenhouse environment, after 2-3 weeks of sowing, the test plants are treated in the 4-5 leaf stage, and the tested compound of the present invention is dissolved in acetone, and then Tween 80 is added, with a certain amount. The water is diluted to a concentration of the solution and sprayed onto the plants using a spray tower. After the application, the cells were cultured for 3 weeks in the greenhouse, and the experimental effects of the weeds after 3 weeks are shown in Table 3.
  • the compound of the present invention to be tested was dissolved in acetone, and then Tween 80 was added thereto, and diluted to a certain concentration with a certain amount of water, and sprayed immediately after sowing. After the application, the cells were cultured for 4 weeks in the greenhouse, and after 3 weeks, the results of the experiment were observed, and it was found that most of the agents of the present invention were excellent in the measurement at 250 g/ha, especially for weeds such as valerian, ginseng, and ramie. Many compounds have good selectivity for corn, wheat, rice, soybean, and rape.
  • the compounds of the present invention generally have better weed control effects, especially for major grasses such as weeds, crabgrass, and foxtail, which are widely occurring in corn fields, paddy fields, and wheat fields, and nettles.
  • the main broadleaf weeds such as amaranth and sinensis have good effects and have good commercial value.
  • the broad-leaved weeds such as amaranth, sage, amaranth, maijiagong, piglet, and sorghum, which are resistant to ALS inhibitors, have extremely high activity.
  • the paddy soil After filling the paddy soil in a 1/1,000,000 hectare tank, seeds of valerian, flamingo, wolf grass, and wild sage were planted, and the soil was gently covered thereon. Thereafter, it was placed in a greenhouse at a depth of 0.5 to 1 cm, and the tubers of the wild sage were implanted the next day or two days later. Thereafter, the water retention depth is 3-4 cm, and the wettability of the compound of the present invention is prepared according to the usual preparation method at the time when the grass, the firefly, the wolf grass reaches 0.5 leaf, and the wild sage reaches the primary leaf stage. A water dilution of a powder or a suspension is uniformly dripped with a pipette to achieve a prescribed amount of active ingredient.
  • the transplanting depth was 3 cm to transplant the rice (japan) in the 3 leaf stage.
  • the compound of the present invention was treated in the same manner as above on the fifth day after transplantation.
  • the fertility status of valerian, sputum, wolf grass and wild sage was treated with the naked eye on the 14th day after treatment. On the 21st day after the growth status of rice, the herbicidal effect was evaluated at an activity standard level of 1-10. According to the experimental conditions, we found that many of the compounds of the present invention are selective for transplanting rice and have excellent effects on weeds such as valerian, sorghum, and wild sage.
  • many of the compounds of the present invention have good selectivity against grasses such as Zoysia, Bermudagrass, tall fescue, bluegrass, ryegrass, seashore gar, etc., and can prevent many key grasses. Weeds and broadleaf weeds. Tests on wheat fields, corn fields, sorghum fields, soybeans, cotton, oil sunflowers, potatoes, fruit trees, peanuts, sugar cane, millet, rapeseed, vegetables, etc. under different application methods also showed excellent selectivity and commercial value.
  • grasses such as Zoysia, Bermudagrass, tall fescue, bluegrass, ryegrass, seashore gar, etc.

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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)
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Abstract

L'invention appartient au domaine technique des pesticides et concerne en particulier un composé de 4-benzoylpyrazole et un procédé de préparation s'y rapportant et l'utilisation de ce dernier. La structure chimique du composé de 4-benzoylpyrazole est représentée par la formule (I), dans laquelle R1 est choisi parmi le méthyle, l'éthyle, etc. ; R2 est choisi parmi l'alkylsulfonyle, etc. ; R3 est choisi parmi l'hydrogène, le méthyle, etc. ; R4 est choisi parmi l'hydrogène, etc. ; et R est choisi parmi (1). Le composé présente une activité herbicide élevée et une compatibilité avec les cultures satisfaisante.
PCT/CN2017/112020 2017-11-10 2017-11-21 Composé de 4-benzoylpyrazole, procédé de préparation s'y rapportant et utilisation de ce dernier Ceased WO2019090818A1 (fr)

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WO2021000736A1 (fr) * 2019-07-04 2021-01-07 东莞市东阳光农药研发有限公司 Composés benzoyle-pyrazole substitués et utilisation de ces derniers dans l'agriculture
CN113387942B (zh) 2020-03-13 2025-08-01 沈阳中化农药化工研发有限公司 一种吡唑羧酸酯类化合物及其应用
CN113387926B (zh) * 2020-03-13 2023-12-12 沈阳中化农药化工研发有限公司 一种杂环羧酸酯类化合物及其作为除草剂的用途

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CN103980202A (zh) * 2014-05-27 2014-08-13 青岛清原化合物有限公司 一种具有除草活性的4-苯甲酰吡唑类化合物
CN105218449A (zh) * 2015-11-06 2016-01-06 青岛清原化合物有限公司 吡唑酮类化合物或其盐、制备方法、除草剂组合物及用途
CN105503728A (zh) * 2015-12-31 2016-04-20 青岛清原化合物有限公司 吡唑类化合物或其盐、制备方法、除草剂组合物及用途

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US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles

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CN103980202A (zh) * 2014-05-27 2014-08-13 青岛清原化合物有限公司 一种具有除草活性的4-苯甲酰吡唑类化合物
CN105218449A (zh) * 2015-11-06 2016-01-06 青岛清原化合物有限公司 吡唑酮类化合物或其盐、制备方法、除草剂组合物及用途
CN105503728A (zh) * 2015-12-31 2016-04-20 青岛清原化合物有限公司 吡唑类化合物或其盐、制备方法、除草剂组合物及用途

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