CN107674025A - A kind of 4 benzoylpyrazole class compounds and its preparation method and application - Google Patents

A kind of 4 benzoylpyrazole class compounds and its preparation method and application Download PDF

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CN107674025A
CN107674025A CN201711108041.2A CN201711108041A CN107674025A CN 107674025 A CN107674025 A CN 107674025A CN 201711108041 A CN201711108041 A CN 201711108041A CN 107674025 A CN107674025 A CN 107674025A
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alkyl
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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 Qing Yuan 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
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    • 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
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    • 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
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    • 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
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    • 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

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  • Organic Chemistry (AREA)
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Abstract

The invention belongs to technical field of pesticide, and in particular to a kind of 4 benzoylpyrazole class compounds and its preparation method and application.The chemical constitution such as formula (I) of the 4 benzoylpyrazole class compound：Wherein, R1Selected from methyl, ethyl etc.；R2Selected from alkyl sulphonyl etc.；R3Selected from hydrogen, methyl etc.；R4Selected from hydrogen etc.；R is selected fromOr

Description

4-benzoyl pyrazole compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a 4-benzoyl pyrazole compound and a preparation method and application thereof.
Background
The weed control is an important link in the process of realizing high-efficiency agriculture, and a patent CN103980202A discloses a 4-benzoyl pyrazole compound with herbicidal activityDespite the diversity of herbicides on the market, due to the growing market, the problems of weed resistance, the life span of the drugs and the economic efficiency of the drugs, and the increasing environmental importance, scientists are required to continuously research and develop new herbicide varieties with high efficiency, safety, economy and different modes of action.
Disclosure of Invention
The invention aims to provide a 4-benzoyl pyrazole compound with high herbicidal activity and good crop compatibility, and a preparation method and application thereof.
A4-benzoyl pyrazole compound with a chemical structure shown in formula (I):
wherein:
R1selected from methyl, ethyl, propyl, isopropyl or cyclopropyl;
R2selected from alkylsulfonyl, alkoxy, alkylthio, fluoro, chloro or cyano;
R3selected from hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl or trifluoromethyl;
R4selected from the group consisting of hydrogen, cyano, nitro, halogen, carboxyl, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkanoyl, alkanoyloxy, alkylsulfonyl, amino which may be substituted with alkyl, haloalkyl, alkenyl, alkynyl, nitro, hydroxyl, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkanoyl, alkanoyloxy, alkylcarbamoyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl or heteroaryl, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylalkyl, arylalkylacyl, arylalkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
r is selected fromWherein,
x, Y are each independently selected from hydrogen, cyano, nitro, halogen, carboxy, hydroxy, alkyl with or without halogen, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkanoyl, alkanoyloxy, alkylsulfonyl, amino substitutable with alkyl, haloalkyl, alkenyl, alkynyl, nitro, hydroxy, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkanoyl, alkanoyloxy, alkylcarbamoyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl or heteroaryl, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylalkyl, arylalkylacyl, arylalkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
z is selected from the group consisting of hydrogen, amino, nitro, cyano, halogen, carboxyl, hydroxyl, alkylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkoxyalkyl, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkanoyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, alkylcarbamoyl, alkanoyloxy, alkylsulfonyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylalkyl, arylalkylacyl, arylalkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
wherein, the "substituted" means substituted with one or more groups selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, alkenyloxy, alkylthio, aryl, aryloxy, benzyl, benzyloxy, acyl, acyloxy, alkenyl, and amino which may be substituted with alkyl, aryl, aryloxy, acyl, acyloxy, and alkenyl.
Preferably, the first and second electrodes are formed of a metal,
R1selected from methyl, ethyl, propyl, isopropyl or cyclopropyl;
R2selected from C1-C8 alkylsulfonyl, C1-C8 alkoxy, C1-C8 alkylthio, fluoro, chloro or cyano;
R3selected from hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl or trifluoromethyl;
R4selected from hydrogen, cyano, nitro, halogen, carboxyl, hydroxyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C8-C8 alkoxy, C8-C8 alkenyloxy, C8-C8 cycloalkoxy, C8-C8 alkylthio, C8-C8 alkenylthio, C8-C8 cycloalkylthio, C8-C8 alkanoyl, C8-C8 alkylacyloxy, C8-C8 alkylsulfonyl, C8-C8 alkyl, halogenated C8-C8 alkyl, C8-C8 alkenyl, C8-C8 alkynyl, nitro, hydroxyl, amino, C8-C8 alkoxy, C8-C8 alkoxycarbonyl, C8-C8 alkylsulfonyl, C8-C8 alkylcarboxyl, C8-C8 alkyl 8 acylamino, C8 alkyl 8, C8-C8 alkyl 8, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono and unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, arylacyl, aryloxy, aryl C1-C8 alkyl, aryl C1-C8 alkylacyl, aryl C1-C8 alkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
r is selected fromWherein,
x, Y is independently selected from hydrogen, cyano, nitro, halogen, carboxyl, hydroxyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C1 alkoxy, C1-C1 alkenyloxy, C1-C1 cycloalkoxy, C1-C1 alkylthio, C1-C1 alkenylthio, C1-C1 cycloalkylthio, C1-C1 alkanoyl, C1-C1 alkylacyloxy, C1-C1 alkylsulfonyl, C1-C1 alkyl, halogenated C1-C1 alkyl, C1-C1 alkenyl, C1-C1 alkynyl, nitro, hydroxyl, amino, C1-C1 alkoxy, C1 alkoxycarbonyl, C1-C1 alkylsulfonyl, C1-C1 alkyl, C1-C1 alkanoyl, C1-C1 alkyl 1-C1 alkoxy, C1-C1 alkoxy, C, C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono and unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylC 1-C8 alkyl, arylC 1-C8 alkylacyl, arylC 1-C8 alkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
z is selected from hydrogen, amino, nitro, cyano, halogen, carboxyl, hydroxyl, C1-C8 alkylamino, C1-C8 alkyl with or without halogen, C8-C8 cycloalkyl, C8-C8 alkenyl, C8-C8 alkynyl, C8-C8 alkoxy, C8-C8 alkenyloxy, C8-C8 alkoxy C8-C8 alkyl, C8-C8 cycloalkoxy, C8-C8 alkylthio, C8-C8 alkenylthio, C8-C8 cycloalkylthio, C8-C8 alkanoyl, C8-C8 alkoxycarbonyl, C8-C8 alkylaminocarbonyl, C8-C8 alkylcarbonyl C8-C8 alkyl, C8-C8 alkoxycarbonyl C8-C8 alkyl, C8-C8 alkyl, C1-C8 alkylsulfonyl, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono, and unsubstituted or substituted aryl, arylacyl, aryloxy, aryl C1-C8 alkyl, aryl C1-C8 alkylacyl, aryl C1-C8 alkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
wherein, said "substituted" means substituted with one or more groups selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo 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 amino which may be substituted with C1-C8 alkyl, aryl, aryloxy, C1-C8 acyl, C1-C8 acyloxy, and C2-C8 alkenyl.
More preferably still, the first and second liquid crystal compositions are,
R1selected from methyl, ethyl, isopropyl;
R2selected from methylsulfonyl, ethylsulfonyl;
R3selected from hydrogen, methyl, ethyl, cyclopropyl;
R4selected from hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C3-C6 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C3-C6 cycloalkylthioC1-C6 alkanoyl, C1-C6 alkanoyloxy, C1-C6 alkylsulfonyl, amino which may be substituted with C1-C6 alkyl, haloC 1-C6 alkyl, C1-C6 alkoxy, aryl or heteroaryl, and unsubstituted or substituted aryl, heteroaryl, arylacyl, heteroarylacyl;
r is selected fromWherein,
x, Y are each independently selected from 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 alkanoyl, C1-C6 alkanoyloxy, C1-C6 alkylsulfonyl, amino substituted with C1-C6 alkyl, haloC 1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkanoyl, aryl or heteroaryl, and unsubstituted or substituted aryl, heteroaryl, arylacyl, heteroarylacyl;
z is selected from hydrogen, halogen, C1-C6 alkylamino, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkanoyl, and unsubstituted or substituted aryl, heteroaryl, arylacyl, heteroarylacyl;
wherein, the substituted refers to being substituted by one or more groups selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 acyl, C1-C6 acyloxy, C1-C6 alkylamino and amino.
It is further preferred that the first and second liquid crystal compositions,
R1selected from methyl, ethyl, isopropyl;
R2selected from methylsulfonyl;
R3selected from hydrogen, methyl, ethyl, cyclopropyl;
R4selected from hydrogenCyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkanoyl, C1-C6 alkylsulfonyl, amino which may be substituted with C1-C6 alkyl, halo-C1-C6 alkyl;
r is selected fromWherein,
x, Y are each independently selected from hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkanoyl, C1-C6 alkylsulfonyl, amino substituted with C1-C6 alkyl, halogenated C1-C6 alkyl, and unsubstituted or substituted aryl, heteroaryl;
z is selected from hydrogen, halogen, C1-C6 alkylamino, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkylacyl, and unsubstituted or substituted aryl, heteroaryl;
wherein, the substituted is substituted by one or more groups selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl and C1-C6 alkoxy.
Most preferably, the first and second substrates are,
R1selected from methyl, ethyl, isopropyl;
R2selected from methylsulfonyl;
R3selected from hydrogen, methyl, ethyl, cyclopropyl;
R4selected from hydrogen, cyano, nitro, chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl;
r is selected fromWherein,
x, Y are each independently selected from hydrogen, cyano, nitro, chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, methoxycarbonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl;
z is selected from hydrogen, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl.
In the definitions of the compounds of the general formula given above, the terms used are collectively defined as follows:
the aryl group includes phenyl, 2, 3-indanyl or naphthyl, etc.; the heteroaryl group includes 5-to 10-membered heteroaryl groups containing 1 to 3O, S, N heteroatoms, such as pyridyl, pyrimidinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridazinyl, triazinyl, quinolyl, quinoxalyl, indolyl, benzotriazolyl, benzothienyl, benzofuryl, isoquinolyl, tetrahydroquinolyl and the like.
A synthetic method of a 4-benzoyl pyrazole compound comprises the following steps:
carrying out esterification reaction on a compound of a formula (II) and a compound of a formula (III) under the action of an acid-binding agent, adding sodium cyanide, potassium cyanide or acetone cyanohydrin for transposition, and directly reacting with a compound of a formula (IV) to obtain a compound of a formula (I); the chemical reaction equation is as follows:
wherein M is selected from hydrogen, potassium, sodium or lithium; the compound (IV) isOr (RCO)2O, RCOO-Ts, RCOO-Ms and the like, and X is selected from chlorine, bromine or iodine.
The transposition product can directly react with the compound shown in the formula (IV), an organic layer is separated, and impurities are removed through separation to obtain the compound shown in the formula (I); the compounds of formula (I) can also be prepared by reaction catalyzed to esters using conventional dehydrating agents such as DCC, CDI, and the like.
The acid-binding agent is one or more mixed acid-binding agents selected from triethylamine, diisopropylethylamine, pyridine, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide.
The reaction temperature is-50-180 ℃, preferably-10-60 ℃.
The compounds of the formula (II), the formula (III) and the formula (IV) are respectively dissolved into solution by a solvent and then participate in the reaction, wherein the solvent is one or more mixed solvents selected from acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, toluene, xylene and dichloroethane.
A herbicide composition comprising a herbicidally effective amount of at least one of said 4-benzoylpyrazoles.
A plant growth regulator comprises an effective amount of at least one of the 4-benzoyl pyrazole compounds.
A method for controlling harmful plants or regulating plant growth, wherein at least one of said 4-benzoylpyrazoles or said herbicide composition or plant growth regulator is applied to the seeds of harmful plants or the area where plants grow.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous and dicotyledonous harmful plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substance is used before sowing, before germination or after germination. Mention is made in particular of representative examples of the monocotyledonous and dicotyledonous weed groups which the compounds of the invention can control, without being restricted to a defined species. Examples of weed species for which the active substance acts effectively include monocotyledons: annual avena, rye, grass, alopecurus, farris, barnyard grass, digitaria, setaria and sedge, and perennial agropyron, bermudagrass, cogongrass and sorghum, and perennial sedge.
With regard to dicotyledonous weed species, the action can be extended to species such as the annual cleavers, viola, veronica, picea, chickweed, amaranthus, sinapis, ipomoea, sida, matricaria and abutilon species, and the perennial weeds cyclocarya, thistle, sorrel and artemisia. The active substances according to the invention are effective in controlling harmful plants, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, in this particular condition of sowing of rice. If the compounds of the present invention are applied to the soil surface before germination, seedlings of weeds can be completely prevented before the weeds grow out, or the weeds stop growing when they grow out of cotyledons and finally die completely after three to four weeks. The compounds of the invention are particularly active against plants such as, for example, alpinia, sesamum indicum, polygonum convolvulus, chickweed, veronica vinifera, veronica albo, viola tricolor and amaranth, cleavers and kochia.
Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not at all harmful or only insignificantly harmful to the important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. Especially good compatibility with cereal crops such as wheat, barley and maize, especially wheat. The compounds according to the invention are therefore very suitable for selectively controlling unwanted vegetation in agricultural crops or ornamental plants.
Due to their herbicidal properties, these active substances can be used for controlling harmful plants in the cultivation of genetically engineered plants which are known or are to occur. Transgenic plants often have advantageous traits, such as resistance to specific insecticides, particularly to specific herbicides, resistance to plant diseases or to microorganisms pathogenic to plant diseases, such as specific insects or microorganisms of fungi, bacteria or viruses. Other specific traits are related to the conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients. Thus, it is known that the resulting transgenic plant products have 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 for economically important transgenic crops and ornamentals, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or for the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable plants. The compounds of the formula I are preferably used as herbicides for cultivating useful plants which are resistant to the action of the herbicide or which are resistant to the toxic action of the herbicide by genetic engineering.
Conventional methods for breeding plants having improved shape over known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits may be obtained by means of methods of genetic engineering (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:
to improve starch synthesis in plants, crop plants are modified by genetic engineering (e.g. WO 92/11376, WO92/14827, WO 91/19806);
transgenic crop plants which are resistant to particular herbicides, to glufosinate herbicides (e.g. EP-0242236A, EP-0242246A) or to glyphosate-type herbicides (WO 92/00377), or to sulfonylurea-type herbicides (EP-0257993A, US-5013659A);
transgenic crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) which protect against attack on plants by specific pests (EP-0142924A, EP-0193259A);
-transgenic crop plants with improved fatty acid composition (WO 91/13972).
A number of molecular biotechnologies are known which enable the production of transgenic plants with improved traits (see, for example, Sambrook et al, 1989, molecular amplification, second edition of the laboratory Manual, Cold spring harbor laboratory publications in USA, Cold spring harbor, New York; or Winnacker "Gene und Klone" [ genes and clones ], VCH Weinheim, second edition 1996 or Christou, "trends in plant science" 1(1996)423- "431)). In order to carry out the manipulation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, which undergo mutations or sequence changes by recombination of DNA sequences. Using standard methods as described above, it is possible, for example, to exchange substrates, remove partial sequences or add natural or synthetic sequences. In order to ligate the DNA fragments to each other, it is possible to attach a binder or a linker to the fragments.
Plant cells of reduced activity gene products can be prepared, for example, by expressing at least one suitable antisense-RNA, sense-RNA to achieve a cosuppression effect, or by expressing at least one suitably configured ribozyme which specifically cleaves transcripts of the gene products.
For this purpose, it is possible to use DNA molecules which contain the entire coding sequence of the gene product, including any flanking sequences which may be present, and to use DNA molecules which contain only a part of the coding sequence which has to be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous but not identical to the coding sequence of the gene product may also be used.
When expressing the nucleic acid molecule in a plant, the synthetic protein can be localized in any desired plant cell compartment. However, for localization in a specific chamber, it is possible, for example, to link the coding region to a DNA sequence in order to ensure localization in a specific location. 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. USA85(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 transgenic plant may be of any desired plant variety, i.e., monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (═ natural) genes or gene sequences, or by expressing heterologous (═ external) genes or gene sequences.
When the active substances according to the invention are used on transgenic crops, in addition to the harmful-plant-inhibiting effects observed on other crops, special effects are often observed on the corresponding transgenic crops, for example an improved or enlarged spectrum of weed control, improved application rates in the application, preferably a good combination of resistance of the transgenic crop and herbicide performance, and an influence on the growth and yield of the transgenic crop plants. The invention therefore also provides for the use of the compounds as herbicides for controlling harmful plants in transgenic crop plants.
In addition, the compound of the invention can obviously regulate the growth of crop plants. These compounds are used to target the control of plant components and to promote harvesting, such as desiccation and stunting of plants, by regulating the metabolism of plants involved. They are also suitable for regulating and inhibiting undesirable vegetation without destroying the growth of the crop plants. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crop plants, since this reduces or completely prevents lodging.
The compounds of the present invention may be applied using a general formulation, wettable powders, concentrated emulsions, sprayable solutions, powders or granules may be used, so the present invention also provides herbicidal compositions comprising compounds of formula I. depending on the general biological and/or chemical physical parameters, the compounds of formula I may be formulated in a variety of ways. examples of suitable formulation choices 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 solutions, Suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, miscible oil solutions, powders (DP), Capsule Suspensions (CS), core encapsulated (casing) compositions, granules for broadcasting and soil application, Spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), water soluble granules (formula), microcapsules and wax preparations, these individual formulations are known in the literature, published as "mineral, published under" market, 9, published ", published by" company.
The necessary formulation auxiliaries, such as inerts, surfactants, solvents and other additives, are likewise known and are described in the documents mentioned below, for example in Watkins, "handbook of powdered diluents pesticides and carriers", second edition, Darland book Caldwell n.j.; h.v.01phen, "entry to clay colloid chemistry," second edition, j.wiley and Sons, n.y.; marsden, second edition "solvent guide", Interscience, n.y.1963; "annual report of detergents and emulsifiers" by McCutcheon, MC issues, Ridgewood n.j.; sisley and Wood, "surfactant encyclopedia", chemical publishing company, n.y.1964;is/are as follows[ ethylene oxide adduct surfactant]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-"Chemische technology" [ chemical Process]Volume 7, c.hauser Verlag Munich, 4 th edition 1986.
Wettable powders can be uniformly dispersed in water and, in addition to the active substance, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonates, sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substances of the herbicides are finely ground, for example using customary instruments, such as hammer mills, fan mills and jet mills, with simultaneous or sequential incorporation of the adjuvants.
Emulsions are prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or higher boiling aromatics or hydrocarbons or mixtures of solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are calcium alkylarylsulfonates, for example calcium dodecylbenzenesulfonate, or nonionic emulsifiers, for example polyglycol esters of fatty acids, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
The active substance and finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to give a powder. Water or oil based suspensions may be prepared, for example, by wet milling using a commercially available bead mill, with or without the addition of a surfactant of the other formulation type described above.
For preparing emulsions, for example oil-in-water Emulsions (EW), it is possible to use aqueous organic solvents, using stirrers, colloid mills and/or static mixers, and, if desired, to add surfactants of another formulation type as described above.
Granules are prepared by spraying the active substance onto the adsorbate, granulating with inert material, or concentrating the active substance onto the surface of a carrier, for example sand, kaolinite, and granulating the inert material with a binder, for example polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the process for preparing fertilizer granules, if desired mixed with fertilizers. The preparation of water-suspendable granules is carried out by customary methods, for example spray-drying, fluidized-bed granulation, millstone granulation, mixing using high-speed mixers and extrusion without solid inert materials.
For the preparation of granules using a millstone, a fluidized bed, an extruder and Spray coating, see the following processes, for example "Spray Drying handbook", third edition 1979, g.goodwin ltd, london; browning, "Agglomeration", chemical and engineering 1967, page 147 ff; "Perry's handbook of Engineers of chemistry", fifth edition, McGraw-Hill, New York 1973, pages 8-57. If preparations for crop protection products are to be known, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, New York, pages 196181-96 and J.D. Freyer, S.A. Evans "Weed Control Manual", fifth edition, Blackwell scientific rules, Oxford university 1968, page 101-.
Agrochemical formulations generally comprise from 0.1 to 99%, in particular from 0.1 to 95% by weight of active substance of formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, with usual formulation components making up the remainder to 100% by weight. The concentration of the active substance in the emulsion concentrate may be about 1 to 90%, preferably 5 to 80% by weight. Powder formulations contain from 1 to 30% by weight of active, usually preferably from 5 to 20% by weight of active, whereas sprayable solutions contain from about 0.05 to 80%, preferably from 2 to 50% by weight of active. The content of active substance in the aqueous suspension granules depends primarily on whether the active substance is liquid or solid, and the auxiliaries, fillers and the like used in granulation. The content of active substance in the water-suspendable granule formulation is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
The active substance formulations mentioned may additionally comprise tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and generally customary pH and viscosity regulators in all cases.
On the basis of these formulations, it is also possible to mix them with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, either premixed or mixed in containers.
Suitable active substances which can be mixed with the active substances according to the invention in a compounded or tank-mixed formulation are, for example, the substances known from "the world Wide Specification of New agricultural chemical products", from the national agricultural science and technology Press, 2010.9 and the documents cited therein. For example, the herbicidal active substances mentioned below may be mixed with the mixtures of the formula I (remarks: name of the compound, either by common name according to the International organization for standardization (ISO), or by chemical name, where appropriate with a code number): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, mefenacet, metazachlor, isoxaflutole, ryegrass methyl ester, loflutolane, diacrylamide, pethoxamide, butachlor, propisochlor, cyprosulfamide, flumetsulam, heptanoyl, isobutramine, propyzamide, terbutamid, dimethenamid, larvamide, trimethylcyclam, clofenamid, propyzamide, penoxulamide, carpronide, diflormid, trinitrol, butachlor, butafenacet, butachlor, benfluralin, bencarbzamide, pencyhalonil, metolachlor, bencarbzamide, pencyhalonil, buta, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naphazel, thiachlor, pyraflufen, bensulfuron-methyl, prochloraz, clofenamide, butamidam, flupiram, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, triazineone-flumetsulam, ciprofloxacin, glycazine, pradapazine, prometryn, simatong, azidezin, diuron, isopentetryn, cycloprozine, ametryn, terbuthylazine, terbuton, metocloprid, cyanazine, bentazon, clonazine, atrazine, metribuzin, cyanuric acid, indaziflazaflam, chlorsulfuron, meturon, bensulfuron, chlorimuron, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl, sulfometuron, Cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, primisulfuron-methyl, flusulfuron-methyl, flupyrsulfuron-methyl, epoxysulfuron, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, metsulfuron-methyl sodium, flupyrazosulfuron, methisulfuron-methyl, primisulfuron, propysilfuron (Propyrisulfuron), metribusulfuron, acifluorfen-methyl, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfen, prosulfuron, benfuresafen, trifloxysulfuron, metofen-ethyl, metofen, trifloxysulfuron, fluroxypyr, fluridone, benfop, benfluridone, benfurazolin, benfluridone, benfurbenflur, Dimethofen, oxyfluorfen, clofenflurate, Halosafen, chlortoluron, isoproturon, linuron, diuron, sifenuron, fluometuron, benzthiauron, methabenzuron, prosulfuron, sulfosulfuron, clomauron, clodinafuron, clofensulfuron, metoxuron, bromuron, metoxuron, meturon, fensulfuron, prosulfuron, subtilon, cuarone, metolachlor, cycloaroron, cyclouron, thifluuron, buthiuron, kuron, cumuron, metoxuron, methamidothion, metominosulfuron, trifolium, isoxafluron, isoxauron, moneuronon, aniron, methicuron, chloretron, clotururon, teuron, benuron, pennison, phenmedibensulfuron, bensulfuron, benazolin, propham, buthan, thiuron, buthan, benazolin, buthan, benazolin, buthan, benazol, Thiobencarb, merthiolane, diclofop, triallate, penoxsulam, pyributicarb, dichlorfon, edifenphos, ethiofen, prosulfocarb, clenbuterol, prosulfocarb, dichotomene, thiobencarb, promethazine, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-chlorobutyric acid, 2,4, 5-d nasal discharge, 2,4, 5-d propionic acid, 2,4, 5-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-d propionic acid, 2-d propionic acid, 2-cloroprionic acid, triclocarb, triclopyr, triclop, Aminodiclofenac, metocloprofenac, diclofop-methyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-p-butyl, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, fenoxaprop-ethyl, clodinafop-ethyl, benazolin, clodinafop-ethyl, haloxyfop-methyl, benazolin, propalaxyl, butyfen-ethyl, chloroethafloxacin, aminofluanid, benazolin, dichlofop-ethyl, methamphetalin, propamocarb-ethyl, benfop-methyl, thiophosphine, pirimiphos-methyl, benfop-ethyl, benazolin, benfop-methyl, imax-methyl, mefenofos, mefeno, Imazamox ammonium salt, imazapic acid, imazamethabenz ester, fluroxypyr, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyril, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Clodinate, sethoxydim, clethodim, cycloxydim, clethodim, topramezone, Buthidazole, metribuzin, hexazinone, metamitron, metribuzin, amitridione, Amibuzin, bromoxynil, octanoyl ioxynil, dichlobenitrile, pyraclonil, hydroxybensulam, Iodobonil, flumetsulam, penoxsulam, clofenapyr, pyraclonil, pyraflufen-ethyl, pyraoxystrobin, flumetsulam, pyraclonil, pyraoxystrobin, isoxathion, pyriftalid, pyriminobac-methyl, pyrithiobac-methyl, benzobicylon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketodradox, isoxaflutole, isoxaclomazone, fenoxasulfofone, methiozoline, isopyrafen, pyraflufen, pyrazote, difenzoquat, pyrazoxazole, pyroxaflutole, pyroxsulam, pyraclofos, pyraclonil, amicarbazone, carfentrazone, flumiclone, sulfentrazone, bencarane, bisphenomezone, butafenacil, isoxaflutole, cyclam, triclopyr, fluroxypyr, flumethazine, parnaprox, flumiclone, flumethol, carfentrazone, carzone, carfentrazone, car, Fluazifop-methyl, pyriminostrobin, bromopicrin, didaphylm, pyridaben, Pyridafol, quinclorac, chloroquine, bentazon, pyridate, oxaziclomefone, benazolin, clomazone, isoprox, isoproxypyrim, propyribac, cumylfen, clomazone, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, mequat, bromophenol oxime, triazasulam, imazazole, flurtamone, mesotrione, ethofumesate, pyrimethanil, clodinafop-methyl, clodinium, pyributaine, benfurazolin, meton, metamitron, metolachlor, dichlorvofen, triclopyr, aloac, Dietmquat, Etpronil, ipriflam, iprimazam, iprodione, Trizopyr, Thiaclonifen, chlorpyrifos, pyradifquat, chlorpyrifos, propiram, pyradifurone, pyradifon, pyradifurone, pyrazone, thion, pyrazone, clomazone, fenclorim, cloquintocet-mexyl, mefenpyr-diethyl, DOWFAUC, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.
When used, the commercially available formulations are diluted in the usual manner, if desired, for example in wettable powders, concentrated emulsions, suspensions and granules suspended in water, using water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The required amount of the compound of formula I to be used varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 250 g/ha.
Detailed Description
The following examples are intended to illustrate the invention and should not be construed as limiting it in any way. The scope of the invention is indicated by the appended claims.
In view of the economic and diversity of the compounds, we prefer to synthesize some of the compounds, a selection of which are listed in table 1 below. Specific compound structures and corresponding compound information are shown in tables 1-2. The compounds in table 1 are only for better illustrating the present invention, but not for limiting the present invention, and it should not be understood to limit the scope of the above-mentioned subject matter of the present invention to the following compounds for those skilled in the art.
Table 1 Structure of the Compounds
TABLE 2 Compounds1HNMR data
Several methods for preparing the compounds of the present invention are illustrated in the schemes and examples below. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic route are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.
The following process examples are provided to facilitate a further understanding of the methods of preparation of the present invention, and the particular materials, species and conditions used are intended to be further illustrative of the invention and are not intended to limit the reasonable scope thereof. The reagents used in the synthesis of the compounds indicated in the following table are either commercially available or can be readily prepared by one of ordinary skill in the art.
Examples of representative compounds are as follows:
preparation of compound 003:
1.0g of 1-methyl-5-hydroxypyrazole, 3.3g of triethylamine and 30mL of toluene are mixed, cooled to 5-10 ℃ in an ice bath, 2.8g of toluene solution of 2-methanesulfonyl-4-trifluoromethylbenzoyl chloride is added dropwise under stirring, the reaction temperature is controlled not to exceed 15 ℃, the external bath is removed after the dropwise addition is finished, and the mixture is stirred and reacted for 30min at room temperature. After the reaction is completely monitored by HPLC, 0.2g of acetone cyanohydrin is added, the temperature is slowly raised to 45-50 ℃, the mixture is stirred and reacted for 1 hour, the mixture is cooled to the room temperature, and 1.6g of 1, 5-dimethylpyrazole-3-formyl chloride is slowly dropped. After the dropwise addition, the reaction was carried out at room temperature for 1 hour. To the reaction solution, 50mL of water was added, followed by liquid separation, and the organic phase was washed with a saturated sodium chloride solution, dried and concentrated. The residue was purified by column chromatography to give 3.3g of the desired product in 70% yield.
Evaluation of biological Activity:
the activity level criteria for harmful plant destruction (i.e. growth control rate) are as follows:
10 level: death is complete;
and 9, stage: the growth control rate is more than 95 percent;
and 8, stage: the growth control rate is more than 90%;
and 7, stage: the growth control rate is more than 80 percent;
and 6, level: the growth control rate is more than 70%;
and 5, stage: the growth control rate is more than 60 percent;
4, level: the growth control rate is more than 50%;
and 3, level: the growth control rate is more than 20 percent;
and 2, stage: the growth control rate is 5-20%;
level 1: the growth control rate is below 5%;
level 0: no effect is produced.
The growth control rate is the fresh weight control rate.
Post-emergence test experiments: placing monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil to make the plastic pot grow in a good greenhouse environment, treating test plants in a 4-5 leaf period after sowing for 2-3 weeks, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with certain water to a certain concentration, and spraying the solution onto the plants by a spray tower. The weeds were cultured in the greenhouse for 3 weeks after application, and the experimental effects of the weeds after 3 weeks are shown in Table 3.
TABLE 3 post-emergence weed test
Note: 1) blank spaces represent untested data; 2) the application dose is 50 g/hectare of effective components, and the water adding amount is 450 kg/hectare; 3) control compound B:
pre-emergence test experiment:
placing the monocotyledon and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into solution with a certain concentration by using a certain amount of water, and immediately spraying the solution after sowing. After application, the mixture is cultured in a greenhouse for 4 weeks, and after 3 weeks, experimental results are observed, so that the medicament has a superior effect under the measurement of 250 g/hectare, and particularly has a superior effect on weeds such as cockspur grass, moleplant seed, abutilon and the like. Many compounds have good selectivity to corn, wheat, rice, soybean and rape.
Experiments show that the compound has better weed control effect generally, has good effect on main gramineous weeds such as cockspur grass, digitaria sanguinalis and setaria viridis and main broadleaf weeds such as piemarker, rorippa rorifolia and sponish needles herb which are widely generated in corn fields, paddy fields and wheat fields, and has good commercial value. Particularly, the broadleaf weeds such as rorippa rorifolia, descurainia sophia, capsella bursa-pastoris, ophiopogon japonicus, cleavers and chickweed which have resistance to ALS inhibitors have extremely high activity.
Evaluating the safety of transplanted rice and the weed control effect of paddy field:
after the paddy field soil was filled in a tank of 1/1,000,000 hectare, seeds of barnyard grass, japanese iris, bidens tripartita and edible tulip were sown, and soil was lightly covered thereon. Standing in a state of water storage depth of 0.5-1 cm in a greenhouse, and implanting tuber of Pseudobulbus Cremastrae seu pleiones in the next or 2 days. Thereafter, the water storage depth was maintained at 3 to 4 cm, and an aqueous dilution of a wettable powder or a suspension, which was prepared by a usual formulation method, was dropped uniformly by a pipette at a time point when barnyard grass, japanese iris, or burley reached 0.5 leaf and the bulb reached the primary leaf stage to obtain a predetermined amount of active ingredient.
In addition, after filling the 1/1,000,000 hectare pot with paddy field soil, leveling is carried out to ensure that the water storage depth is 3-4 cm, and the rice (japonica rice) at the 3-leaf stage is transplanted with the transplanting depth of 3 cm on the next day. The compound of the present invention was treated on the 5 th day after transplantation in the same manner as described above.
The growth state of barnyard grass, japanese iris, bidens tripartita and edible tulip on 14 th day after the treatment with the agent is observed by naked eyes, and the growth state of rice on 21 th day after the treatment with the agent is evaluated by the activity standard grade of 1-10. According to experimental conditions, many of the compounds of the present invention were found to be selective for transplanted rice and excellent in effect against weeds such as barnyard grass, japanese iris, and edible tulip.
Note: the seeds of barnyard grass, Chinese iris, edible tulip and bidens tripartita are all collected from Heilongjiang in China, and are detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.
Comparative experiment (post-emergence test conditions are as above):
control compound a:
TABLE 4 comparative experimental results (30 g/hectare)
Serial number All-grass of Japanese stephania Abutilon Maijiagong (a Chinese character of Maijiagong)
Compound 3 10 9 10
Compound 4 10 10 10
Control Compound A 8 7 7
Control Compound B 5 5 3
Meanwhile, a plurality of tests show that the compound has good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, tall fescue, blue grass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on wheat fields, corn fields, sorghum fields, soybeans, cotton, sunflower, potatoes, fruit trees, peanuts, sugarcane, millet, rape, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims (10)

1. A4-benzoyl pyrazole compound with a chemical structure shown in formula (I):
wherein:
R1selected from methyl, ethyl, propyl, isopropyl or cyclopropyl;
R2selected from alkylsulfonyl, alkoxy, alkylthio, fluoro, chloro or cyano;
R3selected from hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl or trifluoromethyl;
R4selected from the group consisting of hydrogen, cyano, nitro, halogen, carboxyl, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkanoyl, alkanoyloxy, alkylsulfonyl, amino which may be substituted with alkyl, haloalkyl, alkenyl, alkynyl, nitro, hydroxyl, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkanoyl, alkanoyloxy, alkylcarbamoyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl or heteroaryl, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylalkyl, arylalkylacyl, arylalkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
r is selected fromWherein,
x, Y are each independently selected from hydrogen, cyano, nitro, halogen, carboxy, hydroxy, alkyl with or without halogen, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkanoyl, alkanoyloxy, alkylsulfonyl, amino substitutable with alkyl, haloalkyl, alkenyl, alkynyl, nitro, hydroxy, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkanoyl, alkanoyloxy, alkylcarbamoyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl or heteroaryl, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylalkyl, arylalkylacyl, arylalkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
z is selected from the group consisting of hydrogen, amino, nitro, cyano, halogen, carboxyl, hydroxyl, alkylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkoxyalkyl, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkanoyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, alkylcarbamoyl, alkanoyloxy, alkylsulfonyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylalkyl, arylalkylacyl, arylalkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
wherein, the "substituted" means substituted with one or more groups selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, alkenyloxy, alkylthio, aryl, aryloxy, benzyl, benzyloxy, acyl, acyloxy, alkenyl, and amino which may be substituted with alkyl, aryl, aryloxy, acyl, acyloxy, and alkenyl.
2. The 4-benzoylpyrazole compound according to claim 1,
R1selected from methyl, ethyl, propyl, isopropyl or cyclopropyl;
R2selected from C1-C8 alkylsulfonyl, C1-C8 alkoxy, C1-C8 alkylthio, fluoro, chloro or cyano;
R3selected from hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl or trifluoromethyl;
R4selected from hydrogen, cyano, nitro, halogen, carboxyl, hydroxyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C8-C8 alkoxy, C8-C8 alkenyloxy, C8-C8 cycloalkoxy, C8-C8 alkylthio, C8-C8 alkenylthio, C8-C8 cycloalkylthio, C8-C8 alkanoyl, C8-C8 alkylacyloxy, C8-C8 alkylsulfonyl, C8-C8 alkyl, halogenated C8-C8 alkyl, C8-C8 alkenyl, C8-C8 alkynyl, nitro, hydroxyl, amino, C8-C8 alkoxy, C8-C8 alkoxycarbonyl, C8-C8 alkylsulfonyl, C8-C8 alkylcarboxyl, C8-C8 alkyl 8 acylamino, C8 alkyl 8, C8-C8 alkyl 8, IIIC1-C8 alkylsilyl, di-C1-C8 alkylphosphono and unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, arylacyl, aryloxy, aryl C1-C8 alkyl, aryl C1-C8 alkylacyl, aryl C1-C8 alkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
r is selected fromWherein,
x, Y is independently selected from hydrogen, cyano, nitro, halogen, carboxyl, hydroxyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C1 alkoxy, C1-C1 alkenyloxy, C1-C1 cycloalkoxy, C1-C1 alkylthio, C1-C1 alkenylthio, C1-C1 cycloalkylthio, C1-C1 alkanoyl, C1-C1 alkylacyloxy, C1-C1 alkylsulfonyl, C1-C1 alkyl, halogenated C1-C1 alkyl, C1-C1 alkenyl, C1-C1 alkynyl, nitro, hydroxyl, amino, C1-C1 alkoxy, C1 alkoxycarbonyl, C1-C1 alkylsulfonyl, C1-C1 alkyl, C1-C1 alkanoyl, C1-C1 alkyl 1-C1 alkoxy, C1-C1 alkoxy, C, C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono and unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, arylacyl, aryloxy, arylC 1-C8 alkyl, arylC 1-C8 alkylacyl, arylC 1-C8 alkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
z is selected from hydrogen, amino, nitro, cyano, halogen, carboxyl, hydroxyl, C1-C8 alkylamino, C1-C8 alkyl with or without halogen, C8-C8 cycloalkyl, C8-C8 alkenyl, C8-C8 alkynyl, C8-C8 alkoxy, C8-C8 alkenyloxy, C8-C8 alkoxy C8-C8 alkyl, C8-C8 cycloalkoxy, C8-C8 alkylthio, C8-C8 alkenylthio, C8-C8 cycloalkylthio, C8-C8 alkanoyl, C8-C8 alkoxycarbonyl, C8-C8 alkylaminocarbonyl, C8-C8 alkylcarbonyl C8-C8 alkyl, C8-C8 alkoxycarbonyl C8-C8 alkyl, C8-C8 alkyl, C1-C8 alkylsulfonyl, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono, and unsubstituted or substituted aryl, arylacyl, aryloxy, aryl C1-C8 alkyl, aryl C1-C8 alkylacyl, aryl C1-C8 alkyloxy, heteroaryl, heteroarylacyl, heteroaryloxy;
wherein, said "substituted" means substituted with one or more groups selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo 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 amino which may be substituted with C1-C8 alkyl, aryl, aryloxy, C1-C8 acyl, C1-C8 acyloxy, and C2-C8 alkenyl.
3. The 4-benzoylpyrazole compound according to claim 1,
R1selected from methyl, ethyl, isopropyl;
R2selected from methylsulfonyl, ethylsulfonyl;
R3selected from hydrogen, methyl, ethyl, cyclopropyl;
R4selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C3-C6 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C3-C6 cycloalkylthio, C1-C6 alkanoyl, C1-C6 alkanoyloxy, C1-C6 alkylsulfonyl, amino which may be substituted with C1-C6 alkyl, haloC 1-C6 alkyl, C1-C6 alkoxy, aryl or heteroaryl, and unsubstituted or substituted aryl, heteroaryl, arylacyl, heteroarylacyl;
r is selected fromWherein,
x, Y are each independently selected from 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 alkanoyl, C1-C6 alkanoyloxy, C1-C6 alkylsulfonyl, amino substituted with C1-C6 alkyl, haloC 1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkanoyl, aryl or heteroaryl, and unsubstituted or substituted aryl, heteroaryl, arylacyl, heteroarylacyl;
z is selected from hydrogen, halogen, C1-C6 alkylamino, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkanoyl, and unsubstituted or substituted aryl, heteroaryl, arylacyl, heteroarylacyl;
wherein, the substituted refers to being substituted by one or more groups selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 acyl, C1-C6 acyloxy, C1-C6 alkylamino and amino.
4. The 4-benzoylpyrazole compound according to claim 1,
R1selected from methyl, ethyl, isopropyl;
R2selected from methylsulfonyl;
R3selected from hydrogen, methyl, ethyl, cyclopropyl;
R4selected from hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylacyl, C1-C6 alkylsulfonyl, amino which can be substituted by C1-C6 alkyl, halogenated C1-C6 alkyl;
r is selected fromWherein,
x, Y are each independently selected from hydrogen, cyano, nitro, halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkanoyl, C1-C6 alkylsulfonyl, amino substituted with C1-C6 alkyl, halogenated C1-C6 alkyl, and unsubstituted or substituted aryl, heteroaryl;
z is selected from hydrogen, halogen, C1-C6 alkylamino, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C1-C6 alkylacyl, and unsubstituted or substituted aryl, heteroaryl;
wherein, the substituted is substituted by one or more groups selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl and C1-C6 alkoxy.
5. The 4-benzoylpyrazole compound according to claim 1,
R1selected from methyl, ethyl, isopropyl;
R2selected from methylsulfonyl;
R3selected from hydrogen, methyl, ethyl, cyclopropyl;
R4selected from hydrogen, cyano, nitro, chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl;
r is selected fromWherein,
x, Y are each independently selected from hydrogen, cyano, nitro, chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, methoxycarbonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl;
z is selected from hydrogen, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, phenyl, pyridyl.
6. A method for the synthesis of 4-benzoylpyrazoles according to any of claims 1 to 5, comprising the steps of:
carrying out esterification reaction on a compound of a formula (II) and a compound of a formula (III) under the action of an acid-binding agent, adding sodium cyanide, potassium cyanide or acetone cyanohydrin for transposition, and directly reacting with a compound of a formula (IV) to obtain a compound of a formula (I); the chemical reaction equation is as follows:
wherein M is selected from hydrogen, potassium, sodium or lithium; the compound (IV) isOr (RCO)2O, RCOO-Ts and RCOO-Ms, X is selected from chlorine, bromine or iodine.
7. The method for synthesizing the 4-benzoylpyrazole compounds according to claim 6, wherein the acid-binding agent is one or more mixed acid-binding agents selected from triethylamine, diisopropylethylamine, pyridine, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide; the reaction temperature is-50-180 ℃, preferably-10-60 ℃; the compounds of the formula (II), the formula (III) and the formula (IV) are respectively dissolved into solution by a solvent and then participate in the reaction, wherein the solvent is one or more mixed solvents selected from acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, toluene, xylene and dichloroethane.
8. A herbicidal composition comprising a herbicidally effective amount of at least one of the 4-benzoylpyrazoles according to any one of claims 1 to 5.
9. A plant growth regulator comprising an effective amount of at least one of the 4-benzoylpyrazoles of any of claims 1-5.
10. A method for controlling harmful plants or regulating plant growth, characterized in that at least one of the 4-benzoylpyrazoles according to any one of claims 1 to 5 or the herbicide composition according to claim 8 or the plant growth regulator according to claim 9 is applied to seeds of harmful plants or to a plant growth area.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112689626A (en) * 2019-07-04 2021-04-20 东莞市东阳光农药研发有限公司 Substituted benzoyl-pyrazole compounds and application thereof in agriculture
CN113387926A (en) * 2020-03-13 2021-09-14 沈阳中化农药化工研发有限公司 Heterocyclic carboxylic ester compound and application thereof as herbicide
CN113387942A (en) * 2020-03-13 2021-09-14 沈阳中化农药化工研发有限公司 Pyrazole carboxylic ester compound and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles
CN103980202A (en) * 2014-05-27 2014-08-13 青岛清原化合物有限公司 4-benzoyl pyrazole compound with herbicidal activity
CN105503728A (en) * 2015-12-31 2016-04-20 青岛清原化合物有限公司 Pyrazole compounds or salts thereof and preparation method thereof, and weedicide composition and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105218449B (en) * 2015-11-06 2017-08-11 青岛清原化合物有限公司 Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles
CN103980202A (en) * 2014-05-27 2014-08-13 青岛清原化合物有限公司 4-benzoyl pyrazole compound with herbicidal activity
CN105503728A (en) * 2015-12-31 2016-04-20 青岛清原化合物有限公司 Pyrazole compounds or salts thereof and preparation method thereof, and weedicide composition and application thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112689626A (en) * 2019-07-04 2021-04-20 东莞市东阳光农药研发有限公司 Substituted benzoyl-pyrazole compounds and application thereof in agriculture
CN112689626B (en) * 2019-07-04 2022-08-12 东莞市东阳光农药研发有限公司 Substituted benzoyl-pyrazole compounds and application thereof in agriculture
CN113387926A (en) * 2020-03-13 2021-09-14 沈阳中化农药化工研发有限公司 Heterocyclic carboxylic ester compound and application thereof as herbicide
CN113387942A (en) * 2020-03-13 2021-09-14 沈阳中化农药化工研发有限公司 Pyrazole carboxylic ester compound and application thereof
WO2021180193A1 (en) 2020-03-13 2021-09-16 沈阳中化农药化工研发有限公司 Pyrazole carboxylate compound and use thereof
CN115279738A (en) * 2020-03-13 2022-11-01 沈阳中化农药化工研发有限公司 Pyrazole carboxylic ester compound and application thereof
AU2021234584B2 (en) * 2020-03-13 2023-05-18 Jiangsu Yangnong Chemical Co., Ltd. Pyrazole carboxylate ester compound and use thereof
CN113387926B (en) * 2020-03-13 2023-12-12 沈阳中化农药化工研发有限公司 Heterocyclic carboxylic ester compound and application thereof as herbicide
CN115279738B (en) * 2020-03-13 2023-12-19 沈阳中化农药化工研发有限公司 Pyrazole carboxylic ester compound and application thereof

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