CN111285863A - 4- (3-heterocyclyl-1-benzoyl) pyrazole compound or salt thereof, preparation method, herbicide composition and application - Google Patents

4- (3-heterocyclyl-1-benzoyl) pyrazole compound or salt thereof, preparation method, herbicide composition and application Download PDF

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CN111285863A
CN111285863A CN201911105871.9A CN201911105871A CN111285863A CN 111285863 A CN111285863 A CN 111285863A CN 201911105871 A CN201911105871 A CN 201911105871A CN 111285863 A CN111285863 A CN 111285863A
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连磊
华荣保
蒋其柏
彭学岗
崔琦
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Qingdao Kingagroot Chemical Compound Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms

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Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a 4- (3-heterocyclic-1-benzoyl) pyrazole compound or a salt thereof, a preparation method, a herbicide composition and an application. The structure of the compound is shown as a formula I:

Description

4- (3-heterocyclyl-1-benzoyl) pyrazole compound or salt thereof, preparation method, herbicide composition and application
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a 4- (3-heterocyclic-1-benzoyl) pyrazole compound or a salt thereof, a preparation method, a herbicide composition and an application.
Technical Field
The control of weeds is a crucial link in the process of realizing high-efficiency agriculture, and although the types of herbicides in the market are various, the research on pyrazole herbicides is numerous, for example, CN1250447A and CN1104429C introduce a series of pyrazole compounds with a pyrazole ring in the general structural formula. However, due to the expanding market, the resistance of weeds, the life span of the drugs, and the economic nature of the drugs, and the growing environmental importance, scientists are required to research and develop new herbicide varieties with high efficiency, safety, economy, and different modes of action.
Disclosure of Invention
In order to design and synthesize a herbicide compound with higher drug property, wider active spectrum and better safety, on the basis of researching pyrazole herbicide compounds, through molecular design and optimization, the invention synthesizes a novel 4- (3-heterocyclic-1-benzoyl) pyrazole compound which contains two pyrazole rings in a novel structure and can be used as an active component of the herbicide, and the compound has more outstanding activity and crop safety.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a4- (3-heterocyclyl-1-benzoyl) pyrazole compound having the structure of formula I:
Figure BDA0002271272620000011
wherein the content of the first and second substances,
x represents alkyl or cycloalkyl;
y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an unsubstituted or alkyl-substituted cycloalkyl group, which may be free of halogen;
z represents alkyl, halogen, cyano, alkoxy, alkylthio, alkylsulfonyl;
q represents unsubstituted or substituted pyrazolyl.
Preferably, X represents C1-8Alkyl radical, C3-8A cycloalkyl group;
y represents a hydrogen atom, C containing no or halogen1-8Alkyl radical, C2-8Alkenyl radical, C2-8Alkynyl, unsubstituted or with C1-8Alkyl substituted C3-8A cycloalkyl group;
z represents C1-8Alkyl, halogen, cyano, C1-8Alkoxy radical, C1-8Alkylthio radical, C1-8An alkylsulfonyl group;
q represents
Figure BDA0002271272620000021
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen, cyano, thiocyano, cyanoalkyl, nitro, halogen, mercapto, OR4，R5，SOm-R5，SO2-O-R4，NR6-SO2-R5，O-SO2-R5，NR6-(C＝O)-R4，NR6-(C＝O)-O-R4，-(C＝O)-NR6-OR4，NR7R8，SO2-NR7R8，-(C＝O)-NR7R8，O-(C＝O)-O-R4，NR6-(C＝O)-NR7R8，O-(C＝O)-NR7R8-alkyl-NR6-(C＝O)-R4-alkyl-SO2-O-R4-alkyl-NR6-SO2-R5-alkyl-O-SO2-R5-alkyl-SO2-NR7R8，SO2-NR7alkyl-S (O)n-R5-alkyl-OR4，(C＝O)-R4，(C＝O)-O-R4，O-(C＝O)-R4-alkyl- (C ═ O) -R4-alkyl- (C ═ O) -O-R4-alkyl-O- (C ═ O) -R4，(C＝S)-R4，(C＝S)-O-R4，(C＝S)-S-R5，(C＝O)-S-R5，S-(C＝O)-R4，S-(C＝S)-R4，O-(C＝S)-R4-alkyl- (C ═ S) -R4-alkyl- (C ═ S) -O-R4-alkyl- (C ═ O) -S-R5-alkyl- (C ═ S) -S-R5-alkyl-S- (C ═ O) -R4-alkyl-O- (C ═ S) -R4-alkyl-S- (C ═ S) -R4-alkyl-SOm-R5-O-alkyl-NR7R8-S-alkyl-NR7R8-alkyl-O-alkyl-NR7R8-alkyl-S-alkyl-NR7R8-alkyl- (C ═ O)n-NR7R8-alkyl- (C ═ S)n-NR7R8-NH-alkyl-NR7R8，P(O)(OR9)2，CH2P(O)(OR9)2；
R3、R6、R7、R8Each independently represents hydrogen, amino, nitro, cyano, mercapto, halogen, alkylamino, dialkylamino, OR11-alkyl-OR11，SOq-R10-alkyl-SOq-R10，(C＝O)-R11，(C＝O)-O-R11，R10Alkylthio, alkylaminocarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, alkylcarbamoyl, alkoxyaminocarbonyl, alkanoyloxy, alkylthiocarbonyl, trialkylsilyl, dialkylphosphono; or R7R8N-represents a six-membered heterocyclic group
Figure BDA0002271272620000022
R9Each independently represents an alkyl group;
R5、R10each independently represents an unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, cycloalkenyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, cycloalkenylalkyl, heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl, and whereinHeterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: halogen-free OR halogen-containing alkyl, alkenyl, alkynyl OR cycloalkyl, cyano, cyanoalkyl, halogen, mercapto, nitro, thiocyanato, OR12-alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And an alkoxyalkoxycarbonyl group;
R4、R11each independently represents hydrogen, unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, cycloalkenyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, cycloalkenylalkyl, heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl, and wherein the heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: halogen-free OR halogen-containing alkyl, alkenyl, alkynyl OR cycloalkyl, cyano, cyanoalkyl, halogen, mercapto, nitro, thiocyanato, OR12-alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And an alkoxyalkoxycarbonyl group;
R12、R13each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, or halogen-free alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl;
R14each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, or a mixture thereof, which is free or contains halogen;
m and q independently represent 0, 1 or 2, and n represents 0 or 1.
More preferably, X represents C1-6Alkyl radical, C3-6A cycloalkyl group;
y represents a hydrogen atom, C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, unsubstituted or with C1-6Alkyl substituted C3-6A cycloalkyl group;
z represents C1-6Alkyl, halogen, cyano, C1-6Alkoxy radical, C1-6Alkylthio radical, C1-6An alkylsulfonyl group;
q represents
Figure BDA0002271272620000031
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen, cyano, thiocyano, cyano-C1-6Alkyl, nitro, halogen, mercapto, OR4，R5，SOm-R5，SO2-O-R4，NR6-SO2-R5，O-SO2-R5，NR6-(C＝O)-R4，NR6-(C＝O)-O-R4，-(C＝O)-NR6-OR4，NR7R8，SO2-NR7R8，-(C＝O)-NR7R8，O-(C＝O)-O-R4，NR6-(C＝O)-NR7R8，O-(C＝O)-NR7R8，-C1-6alkyl-NR6-(C＝O)-R4，-C1-6alkyl-SO2-O-R4，-C1-6alkyl-NR6-SO2-R5，-C1-6alkyl-O-SO2-R5，-C1-6alkyl-SO2-NR7R8，SO2-NR7-C1-6alkyl-S (O)n-R5，-C1-6alkyl-OR4，(C＝O)-R4，(C＝O)-O-R4，O-(C＝O)-R4，-C1-6Alkyl- (C ═ O) -R4，-C1-6Alkyl- (C ═ O) -O-R4，-C1-6alkyl-O- (C ═ O) -R4，(C＝S)-R4，(C＝S)-O-R4，(C＝S)-S-R5，(C＝O)-S-R5，S-(C＝O)-R4，S-(C＝S)-R4，O-(C＝S)-R4，-C1-6Alkyl- (C ═ S) -R4，-C1-6Alkyl- (C ═ S) -O-R4，-C1-6Alkyl- (C ═ O) -S-R5，-C1-6Alkyl- (C ═ S) -S-R5，-C1-6alkyl-S- (C ═ O) -R4，-C1-6alkyl-O- (C ═ S) -R4，-C1-6alkyl-S- (C ═ S) -R4，-C1-6alkyl-SOm-R5，-O-C1-6alkyl-NR7R8，-S-C1-6alkyl-NR7R8，-C1-6alkyl-O-C1-6alkyl-NR7R8，-C1-6alkyl-S-C1-6alkyl-NR7R8，-C1-6Alkyl- (C ═ O)n-NR7R8，-C1-6Alkyl- (C ═ S)n-NR7R8，-NH-C1-6alkyl-NR7R8，P(O)(OR9)2，CH2P(O)(OR9)2；
R3、R6、R7、R8Each independently represents hydrogen, amino, nitro, cyano, mercapto, halogen, C1-6Alkylamino, di-C1-6Alkylamino radical, OR11，-C1-6alkyl-OR11，SOq-R10，-C1-6alkyl-SOq-R10，(C＝O)-R11，(C＝O)-O-R11，R10，C1-6Alkylthio radical, C1-6Alkylamino carbonyl radical, C1-6Alkyl carbonyl radical C1-6Alkyl radical, C1-6Alkoxycarbonyl radical C1-6Alkyl radical, C1-6Alkylamino carbonyl group C1-6Alkyl radical, C1-6Alkylcarbamoyl, C1-6Alkoxyaminocarbonyl group, C1-6Alkanoyloxy of C1-6Alkylthio carbonyl, tri-C1-6Alkylsilyl, di-C1-6Alkyl radicalPhosphono; or R7R8N-represents a six-membered heterocyclic group
Figure BDA0002271272620000041
Figure BDA0002271272620000042
R9Each independently represents C1-6An alkyl group;
R5、R10each independently represents unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-6Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-6Alkyl radical, C2-6Alkynyl C1-6Alkyl radical, C3-6Cycloalkyl radical C1-6Alkyl radical, C3-6Cycloalkenyl radical C1-6Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-6Alkyl, aryl C1-6Alkyl, heteroaryl C1-6Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-6Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-6alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-6An alkoxycarbonyl group;
R4、R11each independently represents hydrogen, unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-6Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-6Alkyl radical, C2-6Alkynyl C1-6Alkyl radical, C3-6Cycloalkyl radical C1-6Alkyl radical, C3-6Cycloalkenyl radical C1-6Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-6Alkyl, aryl C1-6Alkyl, heteroaryl C1-6Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-6Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-6alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-6An alkoxycarbonyl group;
R12、R13each independently represents hydrogen, C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
R14each independently represents C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
m and q independently represent 0, 1 or 2, and n represents 0 or 1.
Further preferably, X represents C1-6Alkyl radical, C3-6A cycloalkyl group;
y represents a hydrogen atom, C1-6Alkyl, halo C1-6Alkyl radical, C3-6A cycloalkyl group;
z represents C1-6Alkyl, halogen, cyanoBase, C1-6An alkylsulfonyl group;
q represents
Figure BDA0002271272620000051
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen, cyano, thiocyano, cyano-C1-2Alkyl, nitro, halogen, mercapto, OR4，R5，SOm-R5，SO2-O-R4，NR6-SO2-R5，O-SO2-R5，NR6-(C＝O)-R4，NR6-(C＝O)-O-R4，-(C＝O)-NR6-OR4，NR7R8，SO2-NR7R8，-(C＝O)-NR7R8，O-(C＝O)-O-R4，NR6-(C＝O)-NR7R8，O-(C＝O)-NR7R8，-C1-2alkyl-NR6-(C＝O)-R4，-C1-2alkyl-SO2-O-R4，-C1-2alkyl-NR6-SO2-R5，-C1-2alkyl-O-SO2-R5，-C1-2alkyl-SO2-NR7R8，SO2-NR7-C1-2alkyl-S (O)n-R5，-C1-2alkyl-OR4，(C＝O)-R4，(C＝O)-O-R4，O-(C＝O)-R4，-C1-2Alkyl- (C ═ O) -R4，-C1-2Alkyl- (C ═ O) -O-R4，-C1-2alkyl-O- (C ═ O) -R4，(C＝S)-R4，(C＝S)-O-R4，(C＝S)-S-R5，(C＝O)-S-R5，S-(C＝O)-R4，S-(C＝S)-R4，O-(C＝S)-R4，-C1-2Alkyl- (C ═ S) -R4，-C1-2Alkyl- (C ═ S) -O-R4，-C1-2Alkyl- (C ═ O) -S-R5，-C1-2Alkyl- (C ═ S) -S-R5，-C1-2alkyl-S- (C ═ O) -R4，-C1-2alkyl-O- (C ═ S) -R4，-C1-2alkyl-S- (C ═ S) -R4，-C1-2alkyl-SOm-R5，-O-C1-2alkyl-NR7R8，-S-C1-2alkyl-NR7R8，-C1-2alkyl-O-C1-2alkyl-NR7R8，-C1-2alkyl-S-C1-2alkyl-NR7R8，-C1-2Alkyl- (C ═ O)n-NR7R8，-C1-2Alkyl- (C ═ S)n-NR7R8，-NH-C1-2alkyl-NR7R8，P(O)(OR9)2，CH2P(O)(OR9)2；
R3、R6、R7、R8Each independently represents hydrogen, amino, nitro, cyano, mercapto, halogen, C1-6Alkylamino, di-C1-6Alkylamino radical, OR11，-C1-2alkyl-OR11，SOq-R10，-C1-2alkyl-SOq-R10，(C＝O)-R11，(C＝O)-O-R11，R10，C1-6Alkylthio radical, C1-6Alkylamino carbonyl radical, C1-6Alkyl carbonyl radical C1-2Alkyl radical, C1-6Alkoxycarbonyl radical C1-2Alkyl radical, C1-6Alkylamino carbonyl group C1-2Alkyl radical, C1-6Alkylcarbamoyl, C1-6Alkoxyaminocarbonyl group, C1-6Alkanoyloxy of C1-6Alkylthio carbonyl, tri-C1-6Alkylsilyl, di-C1-6An alkylphosphonyl group; or R7R8N-represents a six-membered heterocyclic group
Figure BDA0002271272620000052
Figure BDA0002271272620000053
R9Each independently represents methyl, ethyl;
R5、R10each independently of the other represents unsubstitutedOr substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-2Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-2Alkyl radical, C2-6Alkynyl C1-2Alkyl radical, C3-6Cycloalkyl radical C1-2Alkyl radical, C3-6Cycloalkenyl radical C1-2Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-2Alkyl, aryl C1-2Alkyl, heteroaryl C1-2Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by 1 to 2 groups selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-2Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-2alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-2An alkoxycarbonyl group;
R4、R11each independently represents hydrogen, unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-2Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-2Alkyl radical, C2-6Alkynyl C1-2Alkyl radical, C3-6Cycloalkyl radical C1-2Alkyl radical, C3-6Cycloalkenyl radical C1-2Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-2Alkyl, aryl C1-2Alkyl, heteroaryl C1-2Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by 1 to 2 groups selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-2Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-2alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-2An alkoxycarbonyl group;
R12、R13each independently represents hydrogen, C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
R14each independently represents C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
m and q independently represent 0, 1 or 2, and n represents 0 or 1.
Even more preferably, X represents methyl, ethyl, isopropyl, cyclopropyl;
y represents a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, a cyclopropyl group;
z represents methyl, chlorine, fluorine, cyano, methylsulfonyl;
q represents
Figure BDA0002271272620000061
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen or C1-6Alkyl, halo C1-6Alkyl, halogen, C3-6Cycloalkyl radical, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkoxycarbonyl, phenyl, pyridyl;
R3represents methyl or ethyl.
The synthesis method of the 4- (3-heterocyclic-1-benzoyl) pyrazole compound comprises the following steps: firstly, the compound is
Figure BDA0002271272620000062
Performing acyl halogenation reaction to obtain a compound III, and performing esterification reaction with a compound IV to obtain a compound shown as a general formula I; the reaction equation is as follows:
Figure BDA0002271272620000063
wherein Hal represents halogen, preferably chlorine;
the acid halogenation reaction is carried out in the presence of a halogenating agent and a solvent, the reaction temperature is 0-100 ℃, preferably, the halogenating agent is thionyl chloride, and the solvent is one or more of acetonitrile, DMF, THF, dichloromethane and dichloroethane; the esterification reaction is carried out in the presence of a solvent and a base, wherein the reaction temperature is 0-100 ℃, preferably, the solvent is one or more of acetonitrile, DMF, THF, dichloromethane and dichloroethane, and the base is triethylamine, NMM or DIPEA.
In the definition of the above compound formula, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: refers to fluorine, chlorine, bromine, iodine.
Alkyl groups: refers to straight-chain OR branched alkyl radicals, e.g. the compound "-alkyl-OR4"the alkyl group may be-CH2-、-CH2CH2-、-CH(CH3) -and the like. Alkyl groups are, for example, C1 alkyl-methyl; c2 alkyl-ethyl; c3 alkyl-propyl such as n-propyl or isopropyl; c4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; c5 alkyl-pentyl such as n-pentyl; c6 alkyl-hexyl radicals such as the n-hexyl, isohexyl and 1, 3-dimethylbutyl radical. Similarly, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl isFor example propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds may be at any position per unsaturated group. Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is monocyclic alkenyl having, for example, three to six carbocyclic members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein the double bond can be in any position.
Halogenated alkyl groups: means that on a straight or branched alkyl group all or part of the hydrogen atoms are substituted by halogen atoms.
Alkoxy groups: refers to a functional group in which an alkyl group is bonded to an oxygen atom.
Unless otherwise specified, the term "aryl" as used herein includes, but is not limited to, phenyl, naphthyl,
Figure BDA0002271272620000071
Figure BDA0002271272620000072
The "heterocyclyl" includes but is not limited to those having 0, 1 or 2 oxo groups
Figure BDA0002271272620000073
Figure BDA0002271272620000074
Figure BDA0002271272620000075
The "heteroaryl" is an aromatic cyclic group containing, for example, 3 to 6 ring atoms, 1 to 4 of which (e.g., 1, 2, 3 or 4) are heteroatoms (e.g., oxygen, nitrogen and/or sulfur), e.g., oxygen, nitrogen and/or sulfur, and optionally also benzo ring fused
Figure BDA0002271272620000076
Figure BDA0002271272620000077
Figure BDA0002271272620000081
If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different radicals selected from those mentioned. In addition, the same or different substituent characters contained in the same or different substituents are each independently selected, e.g. "R5And SOm-R5Two of R in `5The radicals are independently selected from R5Those radicals mentioned, which may be identical OR different, "P (O) (OR)9)2Two of R in `9The radicals are independently selected from R9Those mentioned may be the same or different. The same applies to ring systems formed from different atoms and units. Also, the scope of the claims will exclude those compounds known to those skilled in the art to be chemically unstable under standard conditions.
In addition, unless otherwise specified, the foregoing qualifiers for a plurality of juxtaposed substituents (either "or" apart ") in the present invention have a limiting effect on each substituent thereafter, e.g.," halogen-free or halogen-containing alkyl, alkenyl, alkynyl or cycloalkyl "wherein" halogen-free or halogen-containing "has a limiting effect on each group" alkyl "," alkenyl "," alkynyl "or" cycloalkyl "thereafter. Groups not labeled for a particular attachment position (including heterocyclyl, aryl, etc.) may be attached at any position, including the position attached to C or N; if it is substituted, the substituents can likewise be substituted in any position, provided that the bond rules are complied with. Heteroaryl as substituted by 1 methyl group
Figure BDA0002271272620000082
Can represent
Figure BDA0002271272620000083
And the like.
The pyrazole compound having the structure of formula I may be formed into a corresponding salt by a conventional method if necessary, and the salt may be in any form as long as it is agriculturally applicable, for example, an alkali metal salt (e.g., sodium salt or potassium salt), an alkaline earth metal salt (e.g., magnesium salt or calcium salt), or an ammonium salt (e.g., dimethylamine salt or triethylamine salt).
Solvates of the compounds of the invention are also encompassed by the invention.
The compounds to which the present invention relates may exist in the form of one or more stereoisomers. The various isomers include enantiomers, diastereomers, geometric isomers. It is within the scope of the present invention for these isomers to include mixtures of these isomers.
A herbicidal composition comprising a herbicidally effective amount of at least one of said 4- (3-heterocyclyl-1-benzoyl) pyrazole compound or a salt thereof.
The herbicide composition also comprises a preparation auxiliary agent.
A method for controlling weeds, which comprises applying a herbicidally effective amount of at least one of said 4- (3-heterocyclyl-1-benzoyl) pyrazole compounds or salts thereof or said herbicide composition to a plant or a weed area.
The application of at least one of the 4- (3-heterocyclic-1-benzoyl) pyrazole compounds or salts thereof or the herbicide composition in weed control, preferably the 4- (3-heterocyclic-1-benzoyl) pyrazole compounds or salts thereof is used for controlling weeds in useful crops, wherein the useful crops are transgenic crops or crops treated by genome editing technology.
The compounds of formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous and dicotyledonous weeds. 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 weeds, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, in this particular condition of sowing 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 weeds in the cultivation of genetically engineered plants which are known or will emerge. 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-ammonium 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. 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 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 weed-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 performance of the herbicide, and an influence on the growth and yield of the transgenic crop plants. The invention therefore also provides for the use of said compounds as herbicides for controlling weeds 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;
Figure BDA0002271272620000121
is/are as follows
Figure BDA0002271272620000122
[ ethylene oxide adduct surfactant]"Chemische Technologie" of Wiss.Verlagagesell.Stuttgart 1976, Winnacker-K ü chler [ 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
In view of the economy, diversity and biological activity of the compounds, we prefer to synthesize compounds, a selection of which are listed in the following table. Specific compound structures and corresponding compound information are shown in table 1. 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 Compounds and methods of use thereof1H NMR data
Figure BDA0002271272620000161
Figure BDA0002271272620000171
Figure BDA0002271272620000181
Figure BDA0002271272620000191
Figure BDA0002271272620000201
Figure BDA0002271272620000211
Figure BDA0002271272620000221
Figure BDA0002271272620000231
Figure BDA0002271272620000241
Figure BDA0002271272620000251
Figure BDA0002271272620000261
Figure BDA0002271272620000271
Figure BDA0002271272620000281
Figure BDA0002271272620000291
The foregoing aspects of the present invention are further illustrated by the specific embodiments provided in the following examples, which should not be construed as limiting the scope of the above-described subject matter of the present invention to the following examples by those skilled in the art; all the technologies realized based on the above contents of the present invention belong to the scope of the present invention. The process parameters and product yields in the following examples were not optimized.
Examples of representative compounds are given below, and the synthesis of other compounds is similar and will not be described in detail herein.
1. Synthesis of Compound 1
Figure BDA0002271272620000292
Adding pyrazole acid (1.05eq), dichloroethane (50ml) and DMF (3 drops), dropwise adding thionyl chloride (1.5eq) at 65 ℃, stirring for 1h after dropwise adding, controlling no pyrazole acid residue, and removing half of dichloroethane for later use (cooling to 55 ℃); and (3) adding a (1g), dichloroethane (50ml) and triethylamine (1.05eq) into the other reaction bottle, cooling to 15 ℃, dropwise adding 55-degree heat-preservation pyrazole acid chloride, reacting for 1h at 15 ℃, after the controlled reaction is finished, adding water to adjust the pH to be about 3, heating to 50 ℃, preserving heat for 0.5h, separating an organic layer, washing with water once again, removing the solvent, pulping with ethanol, and drying to obtain a product 1, wherein the yield is 80%.
2. Synthesis of Compound 10
Figure BDA0002271272620000301
B (1g) and dichloroethane (50ml) are added, the temperature is reduced to 20 ℃, a few drops of DMF are added for catalysis, oxalyl chloride (1.1eq) is added dropwise, the temperature is controlled to 20 ℃, stirring is carried out for 1h after the dropwise addition is finished, the reaction is finished until b is less than 1%, and dichloroethane solution c is obtained and directly used as the next step;
Figure BDA0002271272620000302
adding dichloroethane (50ml), sodium carbonate (1.2eq), water (50ml) and pyrazole alcohol (1.05eq), cooling to below 10 ℃, dropwise adding the c dichloroethane solution obtained in the previous step at 10 ℃, keeping the temperature for 1h after dropwise adding, heating to 50 ℃, keeping the temperature for 1h, carrying out hot liquid separation, taking an organic layer, washing with 2 times of mass of cold water once, and separating the organic layer; refluxing the organic layer with water, removing water, cooling to 30 ℃, adding triethylamine (10ml) and acetone cyanohydrin (1ml), heating to 50 ℃, and keeping the temperature for two hours, wherein the central control raw material c is less than 1%. Cooling to less than 10 ℃, adjusting the pH value to about 2 by hydrochloric acid, separating liquid to obtain an organic layer, removing half of the solvent after washing once again, cooling to separate out a solid, and performing suction filtration to obtain the product e.
Figure BDA0002271272620000303
Adding pyrazole acid (1.05eq), dichloroethane (50ml) and DMF (3 drops), dropwise adding thionyl chloride (1.5eq) at 60 ℃, stirring for 1h after dropwise adding, controlling no pyrazole acid residue, and removing half of dichloroethane for later use (cooling to 50 ℃); adding e (1eq), dichloroethane (50ml) and triethylamine (1.05eq) into another reaction bottle, cooling to 10 ℃, dropwise adding pyrazole acid chloride with 50 ℃ heat preservation, reacting for 1h at 10 ℃, after the middle control reaction is finished, adding water to adjust the pH to be about 3, heating to 50 ℃, preserving heat for 0.5h, separating out an organic layer, washing once again, removing the solvent, pulping with ethanol, and drying to obtain a product 10 with the total yield of 65%.
3. Synthesis of Compound 103
Figure BDA0002271272620000311
Adding pyrazole acid (1.05eq), dichloroethane (50ml) and DMF (3 drops), dropwise adding thionyl chloride (1.5eq) at 60 ℃, stirring for 1h after dropwise adding, controlling no pyrazole acid residue, and removing half of dichloroethane for later use (cooling to 60 ℃); and (3) adding a (1g), dichloroethane (50ml) and triethylamine (1.05eq) into the other reaction bottle, cooling to 20 ℃, dropwise adding 60-degree heat-preservation pyrazole acid chloride, reacting for 1h at 10 ℃, after the middle-control reaction is finished, adding water to adjust the pH to be about 3, heating to 50 ℃, preserving heat for 0.5h, separating an organic layer, washing with water once again, removing the solvent, pulping with ethanol, and drying to obtain a product 103, wherein the yield is 85%.
4. Synthesis of Compound 141
Figure BDA0002271272620000312
Adding pyrazole acid (1.05eq), dichloroethane (50ml) and DMF (3 drops), dripping thionyl chloride (1.5eq) at 70 ℃, stirring for 1h after dripping, controlling no pyrazole acid residue, and removing half of dichloroethane for later use (cooling to 50 ℃); and (3) adding a (1g), dichloroethane (50ml) and triethylamine (1.05eq) into the other reaction bottle, cooling to 10 ℃, dropwise adding 50-degree heat-preservation pyrazole acid chloride, reacting for 1h at 20 ℃, after the middle control reaction is finished, adding water to adjust the pH to be about 3, heating to 50 ℃, preserving heat for 0.5h, separating an organic layer, washing with water once again, removing the solvent, pulping with ethanol, and drying to obtain a product 141 with the yield of 82%.
Evaluation of biological Activity:
the activity level criteria for weed destruction (i.e., growth control rate) are as follows:
and 5, stage: the growth control rate is more than 85 percent;
4, level: the growth control rate is more than or equal to 60 percent and less than 85 percent;
and 3, level: the growth control rate is more than or equal to 40% and less than 60%;
and 2, stage: the growth control rate is more than or equal to 20% and less than 40%;
level 1: the growth control rate is more than or equal to 5% and less than 20%;
level 0: the growth control rate is less than 5%.
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 2-3 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 2.
TABLE 2 post-emergence weed test
Figure BDA0002271272620000321
Figure BDA0002271272620000331
Note: the application dose was 5 g/ha.
Control compound a:
Figure BDA0002271272620000332
control compound B: topramezone.
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, and the medicament has a remarkable effect under the metering of 250 g/hectare for most of the medicaments, particularly on weeds such as cockspur grass, crab grass, piemarker and the like. Many compounds have good selectivity to corn, wheat, rice, soybean and rape.
Evaluating the safety of transplanted rice and the weed control effect of paddy field:
after the soil in the paddy field was filled in a pot of 1/1,000,000 hectare, seeds of barnyard grass, bidens tripartita, edible tulip, monochoria vaginalis, etc. were sown and covered with soil gently. 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 prepared by formulating the compound of the present invention according to a usual formulation method was dropped uniformly by a pipette at a time point when barnyard grass, bidens tripartite, or monochoria vaginalis reached 0.5 leaf stage and the edible tulip reached 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, edible tulip, bidens tripartita and monochoria vaginalis at day 14 after the treatment with the agent was observed with the naked eye, and the herbicidal effect was evaluated at the activity standard level of 1 to 5 described above, thereby obtaining the results of table 3.
TABLE 3 results of the activity test (15 g/ha active ingredient)
Number of Compounds Barnyard grass Edible tulip Herb of Bidens tripartita Herba Monochoriae
1 5 4 5 5
3 5 4 5 5
5 5 4 5 5
7 5 4 5 5
14 5 4 5 5
Note: the seeds of barnyard grass, edible tulip, bidens tripartita and monochoria vaginalis are all collected from Heilongjiang and Jiangsu in China, and are detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.
Meanwhile, a plurality of tests show that the compound and the composition thereof have good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, festuca arundinacea, bluegrass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, sunflower, potato, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims (10)

1. A4- (3-heterocyclyl-1-benzoyl) pyrazole compound having the structure of formula I:
Figure FDA0002271272610000011
wherein the content of the first and second substances,
x represents alkyl or cycloalkyl;
y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an unsubstituted or alkyl-substituted cycloalkyl group, which may be free of halogen;
z represents alkyl, halogen, cyano, alkoxy, alkylthio, alkylsulfonyl;
q represents unsubstituted or substituted pyrazolyl.
2. The 4- (3-heterocyclyl-1-benzoyl) pyrazole compound according to claim 1, wherein:
x represents C1-8Alkyl radical, C3-8A cycloalkyl group;
y represents a hydrogen atom, C containing no or halogen1-8Alkyl radical, C2-8Alkenyl radical, C2-8Alkynyl, unsubstituted or with C1-8Alkyl substituted C3-8A cycloalkyl group;
z represents C1-8Alkyl, halogen, cyano, C1-8Alkoxy radical, C1-8Alkylthio radical, C1-8An alkylsulfonyl group;
q represents
Figure FDA0002271272610000012
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen, cyano, thiocyano, cyanoalkyl, nitro, halogen, mercapto, OR4，R5，SOm-R5，SO2-O-R4，NR6-SO2-R5，O-SO2-R5，NR6-(C＝O)-R4，NR6-(C＝O)-O-R4，-(C＝O)-NR6-OR4，NR7R8，SO2-NR7R8，-(C＝O)-NR7R8，O-(C＝O)-O-R4，NR6-(C＝O)-NR7R8，O-(C＝O)-NR7R8-alkyl-NR6-(C＝O)-R4-alkyl-SO2-O-R4-alkyl-NR6-SO2-R5-alkyl-O-SO2-R5-alkyl-SO2-NR7R8，SO2-NR7alkyl-S (O)n-R5-alkyl-OR4，(C＝O)-R4，(C＝O)-O-R4，O-(C＝O)-R4-alkyl- (C ═ O) -R4-alkyl- (C ═ O) -O-R4-alkyl-O- (C ═ O) -R4，(C＝S)-R4，(C＝S)-O-R4，(C＝S)-S-R5，(C＝O)-S-R5，S-(C＝O)-R4，S-(C＝S)-R4，O-(C＝S)-R4-alkyl- (C ═ S) -R4-alkyl- (C ═ S) -O-R4-alkyl- (C ═ O) -S-R5-alkyl- (C ═ S) -S-R5-alkyl-S- (C ═ O) -R4-alkyl-O- (C ═ S) -R4-alkyl-S- (C ═ S) -R4-alkyl-SOm-R5-O-alkyl-NR7R8-S-alkyl-NR7R8-alkyl-O-alkyl-NR7R8-alkyl-S-alkyl-NR7R8-alkyl- (C ═ O)n-NR7R8-alkyl- (C ═ S)n-NR7R8-NH-alkyl-NR7R8，P(O)(OR9)2，CH2P(O)(OR9)2；
R3、R6、R7、R8Each independently represents hydrogen, amino, nitro, cyano, mercapto, halogen, alkylamino, dialkylamino, OR11-alkyl-OR11，SOq-R10-alkyl-SOq-R10，(C＝O)-R11，(C＝O)-O-R11，R10Alkylthio, alkylaminocarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, alkylcarbamoyl, alkoxyaminocarbonyl, alkanoyloxy, alkylthiocarbonyl, trialkylsilyl, dialkylphosphono; or R7R8N-represents a six-membered heterocyclic group
Figure FDA0002271272610000021
R9Each independently represents an alkyl group;
R5、R10each independently represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, cycloalkenyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, cycloalkenylalkyl, heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl, and wherein the heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: halogen-free OR halogen-containing alkyl, alkenyl, alkynyl OR cycloalkyl, cyano, cyanoalkyl, halogen, mercapto, nitro, thiocyanato, OR12-alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And an alkoxyalkoxycarbonyl group;
R4、R11each independently represents hydrogen, unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, cycloalkenyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, cycloalkenylalkyl, heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl, and wherein the heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: halogen-free OR halogen-containing alkyl, alkenyl, alkynyl OR cycloalkyl, cyano, cyanoalkyl, halogen, mercapto, nitro, thiocyanato, OR12-alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And an alkoxyalkoxycarbonyl group;
R12、R13each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, or halogen-free alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl;
R14each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, or a mixture thereof, which is free or contains halogen;
m and q independently represent 0, 1 or 2, and n represents 0 or 1.
3. The 4- (3-heterocyclyl-1-benzoyl) pyrazole compound according to claim 1, wherein:
x represents C1-6Alkyl radical, C3-6A cycloalkyl group;
y represents a hydrogen atom, C containing no or halogen1-6Alkyl radical, C2-6An alkenyl group,C2-6Alkynyl, unsubstituted or with C1-6Alkyl substituted C3-6A cycloalkyl group;
z represents C1-6Alkyl, halogen, cyano, C1-6Alkoxy radical, C1-6Alkylthio radical, C1-6An alkylsulfonyl group;
q represents
Figure FDA0002271272610000031
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen, cyano, thiocyano, cyano-C1-6Alkyl, nitro, halogen, mercapto, OR4，R5，SOm-R5，SO2-O-R4，NR6-SO2-R5，O-SO2-R5，NR6-(C＝O)-R4，NR6-(C＝O)-O-R4，-(C＝O)-NR6-OR4，NR7R8，SO2-NR7R8，-(C＝O)-NR7R8，O-(C＝O)-O-R4，NR6-(C＝O)-NR7R8，O-(C＝O)-NR7R8，-C1-6alkyl-NR6-(C＝O)-R4，-C1-6alkyl-SO2-O-R4，-C1-6alkyl-NR6-SO2-R5，-C1-6alkyl-O-SO2-R5，-C1-6alkyl-SO2-NR7R8，SO2-NR7-C1-6alkyl-S (O)n-R5，-C1-6alkyl-OR4，(C＝O)-R4，(C＝O)-O-R4，O-(C＝O)-R4，-C1-6Alkyl- (C ═ O) -R4，-C1-6Alkyl- (C ═ O) -O-R4，-C1-6alkyl-O- (C ═ O) -R4，(C＝S)-R4，(C＝S)-O-R4，(C＝S)-S-R5，(C＝O)-S-R5，S-(C＝O)-R4，S-(C＝S)-R4，O-(C＝S)-R4，-C1-6Alkyl- (C ═ S) -R4，-C1-6Alkyl- (C ═ S) -O-R4，-C1-6Alkyl- (C ═ O) -S-R5，-C1-6Alkyl- (C ═ S) -S-R5，-C1-6alkyl-S- (C ═ O) -R4，-C1-6alkyl-O- (C ═ S) -R4，-C1-6alkyl-S- (C ═ S) -R4，-C1-6alkyl-SOm-R5，-O-C1-6alkyl-NR7R8，-S-C1-6alkyl-NR7R8，-C1-6alkyl-O-C1-6alkyl-NR7R8，-C1-6alkyl-S-C1-6alkyl-NR7R8，-C1-6Alkyl- (C ═ O)n-NR7R8，-C1-6Alkyl- (C ═ S)n-NR7R8，-NH-C1-6alkyl-NR7R8，P(O)(OR9)2，CH2P(O)(OR9)2；
R3、R6、R7、R8Each independently represents hydrogen, amino, nitro, cyano, mercapto, halogen, C1-6Alkylamino, di-C1-6Alkylamino radical, OR11，-C1-6alkyl-OR11，SOq-R10，-C1-6alkyl-SOq-R10，(C＝O)-R11，(C＝O)-O-R11，R10，C1-6Alkylthio radical, C1-6Alkylamino carbonyl radical, C1-6Alkyl carbonyl radical C1-6Alkyl radical, C1-6Alkoxycarbonyl radical C1-6Alkyl radical, C1-6Alkylamino carbonyl group C1-6Alkyl radical, C1-6Alkylcarbamoyl, C1-6Alkoxyaminocarbonyl group, C1-6Alkanoyloxy of C1-6Alkylthio carbonyl, tri-C1-6Alkylsilyl, di-C1-6An alkylphosphonyl group; or R7R8N-represents a six-membered heterocyclic group
Figure FDA0002271272610000032
Figure FDA0002271272610000033
R9Each independently represents C1-6An alkyl group;
R5、R10each independently represents unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-6Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-6Alkyl radical, C2-6Alkynyl C1-6Alkyl radical, C3-6Cycloalkyl radical C1-6Alkyl radical, C3-6Cycloalkenyl radical C1-6Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-6Alkyl, aryl C1-6Alkyl, heteroaryl C1-6Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-6Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-6alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-6An alkoxycarbonyl group;
R4、R11each independently represents hydrogen, unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-6Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-6Alkyl radical, C2-6Alkynyl C1-6Alkyl radical, C3-6Cycloalkyl radical C1-6Alkyl radical, C3-6Cycloalkenyl radical C1-6Alkyl, heterocyclic, arylRadicals, heteroaryl radicals, heterocyclic radicals C1-6Alkyl, aryl C1-6Alkyl, heteroaryl C1-6Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by at least one group selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-6Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-6alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-6An alkoxycarbonyl group;
R12、R13each independently represents hydrogen, C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
R14each independently represents C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
m and q independently represent 0, 1 or 2, and n represents 0 or 1.
4. The 4- (3-heterocyclyl-1-benzoyl) pyrazole compound according to claim 1, wherein:
x represents C1-6Alkyl radical, C3-6A cycloalkyl group;
y represents a hydrogen atom, C1-6Alkyl, halo C1-6Alkyl radical, C3-6A cycloalkyl group;
z represents C1-6Alkyl, halogen, cyano, C1-6An alkylsulfonyl group;
q represents
Figure FDA0002271272610000041
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen, cyano, thiocyano, cyano-C1-2Alkyl, nitro, halogen, mercapto, OR4，R5，SOm-R5，SO2-O-R4，NR6-SO2-R5，O-SO2-R5，NR6-(C＝O)-R4，NR6-(C＝O)-O-R4，-(C＝O)-NR6-OR4，NR7R8，SO2-NR7R8，-(C＝O)-NR7R8，O-(C＝O)-O-R4，NR6-(C＝O)-NR7R8，O-(C＝O)-NR7R8，-C1-2alkyl-NR6-(C＝O)-R4，-C1-2alkyl-SO2-O-R4，-C1-2alkyl-NR6-SO2-R5，-C1-2alkyl-O-SO2-R5，-C1-2alkyl-SO2-NR7R8，SO2-NR7-C1-2alkyl-S (O)n-R5，-C1-2alkyl-OR4，(C＝O)-R4，(C＝O)-O-R4，O-(C＝O)-R4，-C1-2Alkyl- (C ═ O) -R4，-C1-2Alkyl- (C ═ O) -O-R4，-C1-2alkyl-O- (C ═ O) -R4，(C＝S)-R4，(C＝S)-O-R4，(C＝S)-S-R5，(C＝O)-S-R5，S-(C＝O)-R4，S-(C＝S)-R4，O-(C＝S)-R4，-C1-2Alkyl- (C ═ S) -R4，-C1-2Alkyl- (C ═ S) -O-R4，-C1-2Alkyl- (C ═ O) -S-R5，-C1-2Alkyl- (C ═ S) -S-R5，-C1-2alkyl-S- (C ═ O) -R4，-C1-2alkyl-O- (C ═ S) -R4，-C1-2alkyl-S- (C ═ S) -R4，-C1-2alkyl-SOm-R5，-O-C1-2alkyl-NR7R8，-S-C1-2alkyl-NR7R8，-C1-2alkyl-O-C1-2alkyl-NR7R8，-C1-2alkyl-S-C1-2alkyl-NR7R8，-C1-2Alkyl- (C ═ O)n-NR7R8，-C1-2Alkyl- (C ═ S)n-NR7R8，-NH-C1-2alkyl-NR7R8，P(O)(OR9)2，CH2P(O)(OR9)2；
R3、R6、R7、R8Each independently represents hydrogen, amino, nitro, cyano, mercapto, halogen, C1-6Alkylamino, di-C1-6Alkylamino radical, OR11，-C1-2alkyl-OR11，SOq-R10，-C1-2alkyl-SOq-R10，(C＝O)-R11，(C＝O)-O-R11，R10，C1-6Alkylthio radical, C1-6Alkylamino carbonyl radical, C1-6Alkyl carbonyl radical C1-2Alkyl radical, C1-6Alkoxycarbonyl radical C1-2Alkyl radical, C1-6Alkylamino carbonyl group C1-2Alkyl radical, C1-6Alkylcarbamoyl, C1-6Alkoxyaminocarbonyl group, C1-6Alkanoyloxy of C1-6Alkylthio carbonyl, tri-C1-6Alkylsilyl, di-C1-6An alkylphosphonyl group; or R7R8N-represents a six-membered heterocyclic group
Figure FDA0002271272610000051
Figure FDA0002271272610000052
R9Each independently represents methyl, ethyl;
R5、R10each independently represents unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-2Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-2Alkyl radical, C2-6Alkynyl C1-2Alkyl radical, C3-6Cycloalkyl radical C1-2Alkyl radical, C3-6Cycloalkenyl radical C1-2Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-2Alkyl, aryl C1-2Alkyl, heteroaryl C1-2Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by 1 to 2 groups selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-2Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-2alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-2An alkoxycarbonyl group;
R4、R11each independently represents hydrogen, unsubstituted or substituted C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C1-6Alkoxy radical C1-2Alkyl radical, C3-6Cycloalkenyl radical, C2-6Alkenyl radical C1-2Alkyl radical, C2-6Alkynyl C1-2Alkyl radical, C3-6Cycloalkyl radical C1-2Alkyl radical, C3-6Cycloalkenyl radical C1-2Alkyl, heterocyclyl, aryl, heteroaryl, heterocyclyl C1-2Alkyl, aryl C1-2Alkyl, heteroaryl C1-2Alkyl, and wherein heterocyclyl has 0, 1 or 2 oxo groups; the term "substituted" refers to substitution by 1 to 2 groups selected from: c containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6Cycloalkyl, cyano C1-2Alkyl, halogen, mercapto, nitro, thiocyanato, OR12，-C1-2alkyl-OR12，S(O)mR14，NR12R13，NR13OR12，COR12，OCOR12，SCOR12，NR13COR12，NR13COOR12，NR13SO2R14，CO2R12，COSR12，CONR12R13And C1-6Alkoxy radical C1-2An alkoxycarbonyl group;
R12、R13each independently represents hydrogen, C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
R14each independently represents C containing no or halogen1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl, phenyl, benzyl;
m and q independently represent 0, 1 or 2, and n represents 0 or 1.
5. The 4- (3-heterocyclyl-1-benzoyl) pyrazole compound according to claim 1, wherein:
x represents methyl, ethyl, isopropyl or cyclopropyl;
y represents a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, a cyclopropyl group;
z represents methyl, chlorine, fluorine, cyano, methylsulfonyl;
q represents
Figure FDA0002271272610000061
Wherein the content of the first and second substances,
R1、R2each independently represents hydrogen or C1-6Alkyl, halo C1-6Alkyl, halogen, C3-6Cycloalkyl radical, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkoxycarbonyl, phenyl, pyridineA group;
R3represents methyl or ethyl.
6. A process for producing a 4- (3-heterocyclyl-1-benzoyl) pyrazole compound or its salt according to any one of claims 1 to 5, which comprises the steps of: firstly, the compound is
Figure FDA0002271272610000062
Performing acyl halogenation reaction to obtain a compound III, and performing esterification reaction with a compound IV to obtain a compound shown as a general formula I; the reaction equation is as follows:
Figure FDA0002271272610000063
wherein Hal represents halogen, preferably chlorine;
the acid halogenation reaction is carried out in the presence of a halogenating agent and a solvent, the reaction temperature is 0-100 ℃, preferably, the halogenating agent is thionyl chloride, and the solvent is one or more of acetonitrile, DMF, THF, dichloromethane and dichloroethane; the esterification reaction is carried out in the presence of a solvent and a base, wherein the reaction temperature is 0-100 ℃, preferably, the solvent is one or more of acetonitrile, DMF, THF, dichloromethane and dichloroethane, and the base is triethylamine, NMM or DIPEA.
7. A herbicidal composition comprising a herbicidally effective amount of at least one of the 4- (3-heterocyclyl-1-benzoyl) pyrazoles or salts thereof according to any one of claims 1 to 5.
8. A herbicidal composition according to claim 7, which further comprises formulation adjuvants.
9. A method for controlling weeds, which comprises applying a herbicidally effective amount of at least one of the 4- (3-heterocyclyl-1-benzoyl) pyrazole compounds or salts thereof according to any one of claims 1 to 5 or the herbicidal composition according to claim 7 or 8 to plants or to a weed region.
10. Use of at least one of the 4- (3-heterocyclyl-1-benzoyl) pyrazole compounds or salts thereof according to any one of claims 1 to 5 or the herbicidal composition according to claim 7 or 8 for controlling weeds, preferably for controlling weeds in crops of useful plants, such as transgenic or genome editing-treated plants.
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