CN107629046A - Pyrazolone compound or its salt, herbicidal composition and purposes - Google Patents

Pyrazolone compound or its salt, herbicidal composition and purposes Download PDF

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CN107629046A
CN107629046A CN201711002458.0A CN201711002458A CN107629046A CN 107629046 A CN107629046 A CN 107629046A CN 201711002458 A CN201711002458 A CN 201711002458A CN 107629046 A CN107629046 A CN 107629046A
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alkyl
alkoxy
group
amino
carbonyl
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CN107629046B (en
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连磊
征玉荣
何彬
彭学岗
金涛
崔琦
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Qingdao Qing Yuan Compound Co Ltd
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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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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    • 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
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
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    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
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    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

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  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Environmental Sciences (AREA)
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  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The application belongs to pesticide field, and in particular to a kind of pyrazolone compound or its salt, herbicidal composition and purposes.The pyrazolone compound is as shown in formula I：In formula, R1R2N is representedHet is selected from five or hexa-member heterocycle, in addition to the N atoms and 1 or 2 C=O on the ring on containing C, 1, also contains the part of less than 13 atoms or group as ring：O、NRb、S、SO、SO2, when Het is hexa-member heterocycle, and the C=O on the ring has and only 1 and at 2, and 4 can not be O, NRbOr S；R3Represent hydrogen, C1~4Alkyl etc.；R4Represent methyl, ethyl etc.；X represents hydrogen, R5、‑S(O)nR6、‑CH2R7, (C=O) R8、‑PO(OR9)2、‑Si(OR9)3Deng.The pharmaceutical actives good drug efficacy of the present invention, easy to use, cost is cheap, possesses good commercial value.

Description

Pyrazolone compound or its salt, herbicidal composition and purposes
Technical field
The application belongs to pesticide field, and in particular to a kind of pyrazolone compound or its salt, herbicidal composition and use On the way.
Background technology
Exploitation turns into one of vital task for ensureing agricultural production with efficient, safe, economic pesticide herbicide, wherein Pyrazole compound has the characteristics that efficient, low toxicity and various structures, and it is its most important application field to be used as herbicide.
Patent CN105218449A etc. disclose a series of pyrazolone herbicidal compounds with activity of weeding and its Synthetic method.To design and synthesize out more efficient, the wider array of herbicidal compounds of activity profile, on this Research foundation, this Invention has synthesized class formation novelty, has had the pyrazolone compound of activity of weeding.
The content of the invention
Led it is an object of the invention to provide a kind of pyrazolone compound or its salt, herbicidal composition, and in agricultural chemicals Weeding application in domain.Pharmaceutical actives good drug efficacy provided by the invention, easy to use, cost is cheap.
To reach above-mentioned purpose, the technical scheme that the present invention takes is as follows：
A kind of pyrazolone compound or its salt as shown in formula I：
In formula,
R1R2N is representedWherein,
Het is selected from five or hexa-member heterocycle, in addition to the N atoms and 1 or 2 C=O on the ring on containing C, 1- position, also contains The 1-3 parts of following atom or group as ring：O、NRb、S、SO、SO2, when Het is hexa-member heterocycle, and the C on the ring =O has and only 1 and at 2- positions, and 4- positions can not be O, NRbOr S；
RaSelected from one or more of following group group：Hydrogen, halogen, cyano group, nitro, hydroxyl, carboxyl, amino, C1- C6Alkyl sulphonyl, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy, halo C1~6Alcoxyl Base, C1~6Alkylamino, C2~6Alkenyloxy group, halo C2~6Alkenyloxy group, C2~6Enamino, halo C2~6Enamino, C1~6Alkyl-carbonyl, halogen For C1~6Alkyl-carbonyl, C1~6Alkoxy carbonyl, C1~6Alkyl amino-carbonyl, C1~6Alkoxy C1~6Alkyl, halo C1~6Alkoxy C1~6 Alkyl, C1~6Alkyl carbonyl epoxide C1~6Alkyl, C1~6Alkoxy C1~6Alkoxy, halo C1~6Alkoxy C1~6Alkoxy, C1~6Alkane Epoxide carbonyl C1~6Alkoxy, C1~6Alkyl carbonyl epoxide, halo C1~6Alkyl carbonyl epoxide, C1~6Alkyl-carbonyl-amino, C1~6Alkane Base sulfonyl epoxide, C1~6Alkyl sulfonyl-amino, C1~6Alkyl-carbonyl C1~6It is alkoxy, unsubstituted or independent selected by 1-3 From halogen, nitro, cyano group, C1~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, C1~6The virtue that group in alkyl-carbonyl is substituted Base, heteroaryl, aryl carbonyl epoxide, aryl sulfonyl epoxide, arylmethyl epoxide, hetervaromatic methyl epoxide, aryl-amino-carbonyl, Arlysulfonylamino, arylmethyl amino or hetervaromatic methyl amino；
RbSelected from hydrogen, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy C1~6Alkyl, Halo C1~6Alkoxy C1~6Alkyl, C1~6Alkyl-carbonyl, halo C1~6Alkyl-carbonyl, C1~6Alkyl sulphonyl, C1~6Alkoxy carbonyl Base, C1~6Alkyl amino-carbonyl, C1~6Alkyl-carbonyl C1~6Alkyl, C1~6Alkoxy carbonyl C1~6Alkyl, C1~6Alkyl amino-carbonyl C1~6Alkane It is base, unsubstituted or halogen, nitro, cyano group, C are independently selected from by 1-31~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, halogen For C1~6Alkoxy, C1~6Aryl that group in alkyl-carbonyl is substituted, heteroaryl, aryl carbonyl, Heteroarylcarbonyl, aryl Sulfonyl, arylmethyl, hetervaromatic methyl；
R3Represent hydrogen, C1~4Alkyl, C2~4Alkenyl, C2~4It is alkynyl, unsubstituted or use C1~4Alkyl-substituted C3~6Cycloalkyl；
R4Represent methyl, ethyl, n-propyl, isopropyl, cyclopropyl；
X represents hydrogen ,-R5、-S(O)nR6、-CH2R7,-(C=O) R8、-PO(OR9)2、-Si(OR9)3, wherein,
R5、R6Represent substituted or unsubstituted C1~6Alkyl, aryl or heterocyclic radical, n represent 1,2,3；
R7Represent substituted or unsubstituted aryl or heterocyclic radical, halogen, C1~6Alkyl amino, C2~4Alkynyl, C2~4Alkenyl, C1~6Alkoxy, nitro, cyano group, C3~6Cycloalkyl, amino, C1~6Alkylthio group；
R8Represent C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, C1~6Alkyl amino C1~6Alkyl, C1~6Alkylthio group C1~6Alkyl, halogen, amino, cyano group, nitro, C1~6Alkoxy C1~6Alkyl, substituted or unsubstituted phenyl, benzene Base C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl or heterocyclic radical；
R9Represent hydrogen, C1~6Alkyl, C3~6Cycloalkyl, substituted or unsubstituted phenyl or heterocyclic radical.
Preferably, R5、R6Represent unsubstituted C1~6Alkyl, phenyl are heteroatomic selected from O, N and S containing 1~4 3~10 circle heterocycles bases, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6 Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6The C that one or more of cycloalkyl group is substituted1~6Alkyl, phenyl Or represent 1,2,3 containing 1~4 heteroatomic 3~10 circle heterocycles base for being selected from O, N and S, n；
R7Represent unsubstituted phenyl or containing 1~4 heteroatomic 3~10 circle heterocycles base for being selected from O, N and S, be chosen From C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, Cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6Alkyl, C1~6Alkylthio group sulphonyl Base C1~6Alkyl, C3~6The phenyl or miscellaneous selected from O, N and S containing 1~4 that one or more of cycloalkyl group is substituted 3~10 circle heterocycles bases of atom, halogen, C1~6Alkyl amino, C2~4Alkynyl, C2~4Alkenyl, C1~6Alkoxy, nitro, cyano group, C3~6Cycloalkyl, amino, C1~6Alkylthio group；
R8Represent C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, C1~6Alkyl amino C1~6Alkyl, C1~6Alkylthio group C1~6Alkyl, halogen, amino, cyano group, nitro, C1~6Alkoxy C1~6Alkyl, phenyl, phenyl C1~6Alkyl, benzene oxygen Base, phenoxy group C1~6Alkyl or heteroatomic 3~10 circle heterocycles base selected from O, N and S containing 1~4, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6Phenyl that one or more of cycloalkyl group is substituted, phenyl C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl contains There is 1~4 heteroatomic 3~10 circle heterocycles base for being selected from O, N and S；
R9Represent hydrogen, C1~6Alkyl, C3~6Cycloalkyl, unsubstituted phenyl or contain 1~4 be selected from O, N and S hetero atom 3~10 circle heterocycles bases, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6 Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6Phenyl that one or more of cycloalkyl group is substituted or containing 1~ 4 heteroatomic 3~10 circle heterocycles bases for being selected from O, N and S.
It is highly preferred that Het is selected from
R3Represent hydrogen, methyl, ethyl, cyclopropyl；
R4Represent methyl, ethyl, isopropyl；
X represents hydrogen ,-R5、-S(O)nR6、-CH2R7,-(C=O) R8、-PO(OR9)2、-Si(OR9)3, wherein,
R5、R6Represent unsubstituted C1~6Alkyl, phenyl contain 1~4 be selected from O, N and S heteroatomic 3~10 yuan Aromatic heterocyclic, by selected from C1~6Alkyl, C1~6The C that one or more of alkoxy, halogen group is substituted1~6Alkyl, phenyl Or represent 2 containing 1~4 heteroatomic 3~10 yuan of aromatic heterocyclic for being selected from O, N and S, n；
R7Represent unsubstituted phenyl or containing 1~4 heteroatomic 3~10 yuan of aromatic heterocyclic for being selected from O, N and S, quilt Selected from C1~6Alkyl, C1~6The phenyl or be selected from O, N containing 1~4 that one or more of alkoxy, halogen group is substituted With S heteroatomic 3~10 yuan of aromatic heterocyclics, C1~6Alkyl amino, C2~4Alkynyl, C2~4Alkenyl, C1~6Alkoxy, C1~6Alkane sulphur Base；
R8Represent C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, C1~6Alkyl amino C1~6Alkyl, C1~6Alkylthio group C1~6Alkyl, phenyl, phenyl C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl or containing 1~4 selected from O, N and S heteroatomic 3~10 yuan of aromatic heterocyclics, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen Element, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6 Alkyl sulphonyl C1~6Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6One or more of cycloalkyl group is substituted Phenyl, phenyl C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl is selected from heteroatomic the 3~10 of O, N and S containing 1~4 First aromatic heterocyclic；
R9Represent hydrogen, C1~6Alkyl, C3~6Cycloalkyl, unsubstituted phenyl or contain 1~4 be selected from O, N and S hetero atom 3~10 yuan of aromatic heterocyclics, by selected from C1~6Alkyl, C1~6The phenyl that one or more of alkoxy, halogen group is substituted Or contain 1~4 heteroatomic 3~10 yuan of aromatic heterocyclic for being selected from O, N and S.
Term " heterocycle " or " heterocyclic radical " represent containing 1~4 heteroatomic 3~10 yuan of fragrance selected from O, N and S or Person's nonaromatic heterocycles and with lactone, cyclic ethers, 4~10 membered cyclic compounds of lactam structure, and including bicyclic groups. Therefore, " heterocyclic radical " includes " aromatic heterocyclic " and its dihydro or tetrahydrochysene analog.Heterocyclyl substituent can be through carbon atom Or hetero atom is attached.What term " aromatic heterocyclic " represented in each ring up to 7 atoms stablizes monocyclic or two rings, its In may include an aromatic rings and containing 1~4 be selected from O, N and S hetero atom.Aromatic heterocyclic bag within the range defined herein Include but be not limited to：Acridinyl, carbazyl, cinnolines base, quinoxalinyl, pyrazolyl, indyl, BTA base, thienyl, furans Base, benzothienyl, benzofuranyl, quinolyl, isoquinolyl, oxazolyl, isoxazolyls, indyl, pyrazinyl, pyridazine Base, pyridine radicals, pyrimidine radicals, pyrrole radicals, tetrahydric quinoline group, thiazolyl, imidazole radicals, triazolyl, oxadiazoles base, thiadiazolyl group, three Piperazine base, as the definition of heterocycle, the N- oxides that " aromatic heterocyclic " is also understood as including any nitrogenous aromatic heterocyclic spread out Biology.
The salt is acceptable salt in Pesticide Science, is preferably that this class compound and chemically acceptable acid progress are anti- Obtained acid-addition salts are answered, or wherein there is the hydroxypyrazoles of acidic-group and alkali compounds to react generation Salt.Wherein, described acid preferably selected from inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid) and organic acid (such as oxalic acid, Maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid etc.)；Described alkali compounds is preferably selected from hydrogen-oxygen Change sodium, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate or saleratus etc..It is above-mentioned pharmaceutically acceptable Salt can be easily separated, and conventional separation methods can be used to purify, such as solvent extraction, dilution, recrystallization, column chromatography and prepare thin-layer chromatography Deng.
A kind of method for preparing the pyrazolone compound or its salt, it comprises the following steps：
(1) using the compound as shown in formula II and excessive compound R1R2NH is reacted, and prepares such as general formula III Shown compound；
(2) compound as shown in general formula III and compound X-A are reacted, the chemical combination as shown in formula I is made Thing；
Wherein, A represents hydroxyl, halogen, mesyl or p-toluenesulfonyl, and reaction equation is as follows：
The step (1) and (2) are carried out in non-protonic solvent, in the presence of alkali；Reaction temperature is -30 DEG C - 180 DEG C, preferably -5 DEG C -90 DEG C.
The solvent is acetonitrile, ether, tetrahydrofuran, DMF or DMSO, preferably acetonitrile, tetrahydrofuran or DMF；The alkali For sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, triethylamine, DIPEA or DBU, preferably NaH, triethylamine or potassium carbonate.
Wherein, the compound as shown in formula II can be made through following reactions：
Or the compound that the step (1) is prepared shown in general formula III can also use following reaction：
Also the compound shown in formula I can be prepared in the step (2) as following methods：
Wherein, B represents halogen, and M represents alkali metal, alkaline-earth metal etc..
For containing SO, SO in Het2Compound, its oxygen can be controlled through oxidation procedures by compound containing S accordingly Change degree is made, and oxidant used includes but is not limited to the peroxide such as NaClO and mCPBA, Peracetic acid.
A kind of herbicidal composition, it is included in the described pyrazolone compound of herbicidally effective amount or its salt at least It is a kind of.
The herbicidal composition also includes formulation auxiliary agents.
A kind of method for controlling noxious plant, it is included the described pyrazolone compound or its salt of herbicidally effective amount At least one of or described herbicidal composition use on plant or noxious plant region.
At least one of described pyrazolone compound or its salt or described herbicidal composition are harmful in control Purposes on plant, it is preferable that described pyrazolone compound or its salt are used to prevent and kill off the noxious plant in useful crop, The crop that the useful crop is genetically modified crops or genome editing technique treats.
For many economically important unifacial leaves and dicotyledonous harmful plants, compound of formula I of the invention, which has, to be protruded Activity of herbicide.The active material of the present invention is effective also for perennial weeds, and these weeds are from rhizome, root-like stock or other Perennial organ on grow out, it is difficult to control.On this point, if prior to seeding, sprout before or sprout after using should Material is typically inessential.The controllable unifacial leaf of specifically mentioned the compounds of this invention and the representation example of broadleaf weed group, The species for the determination being not limited to.The example of the weed species of active material useful effect includes monocotyledon：It is annual In Avena, rye, careless category, amur foxtail category, farad this, barnyard grass, knotgrass, setaria and Cyperus, and perennial wheatgrass Category, Cynodon, cogon and sorghum and perennial Cyperus.
On dicotyldenous weed species, its act on for example annual Bedstraw of species that can be expanded to, Viola, Veronica, lamium, Stellaria, Amaranthus, sinapsis alba category, Ipomoea, chrysanthemum harvest spp, Matricaria and abutilon, and it is perennial Weeds japanese bearbind genus, Cirsium, Rumex and artemisia.Active material of the present invention rice growing it is this it is undetermined under the conditions of effectively control have Evil plant, such as barnyard grass, Sagittaria, Waterplantain, Eleocharis, sugarcane grass and Cyperus.If the compounds of this invention is applied before rudiment For soil surface, the rice shoot of weeds can be prevented completely before weeds grow, or just be stopped growing when weeds grow cotyledon, It is finally completely dead after three to four weeks.The compounds of this invention especially resists the good activity of following plants, and A Pila is careless, small White dead nettle, volume stem smartweed, chickweed, Changchun cane leaves Veronica, Veronica persica, heartsease and amaranth, Bedstraw and summer cypress.
Although the compounds of this invention has excellent activity of herbicide for unifacial leaf and dicots weeds, for important Economy class crop plants, such as wheat, barley, rye, rice, corn, beet, cotton and soybean do not damage but at all, Either infringement is inappreciable.It is compatible particularly with cereal crops very well, such as wheat, barley and corn, particularly Wheat.Therefore, the compounds of this invention is very suitable for the useless plant being selectively controlled in agricultural crop or ornamental plant.
Due to their deweeding property, in the plant cultivation of genetic engineering that is known or will occurring, these active matters Matter can be used for controlling noxious plant.Genetically modified plants generally have superior character, such as particularly special to specific insecticide The resistance of herbicide is determined, to plant disease or the resistance of the pathogenic microorganisms of plant disease, such as specific insect or true The microorganism of bacterium, bacterium or virus.Other especially characters are relevant with following conditions of product, for example, quantity, quality, storage Stability, component and special composition.So, it is known that the transgenic plant product of acquisition have increased content of starch or Improved starch quality or different Fatty acid components.
The compound of formula I or its salt of the present invention is preferred for, the crop and ornamental plant of economically important transgenosis, example Such as cereal, such as wheat, barley, rye, oat, grain, rice, cassava and corn or for beet, cotton, soybean, rape Seed, the cultivation of potato, tomato, pea and other vegetable plants.Compound of formula I is preferred for the weeding of useful plant cultivation Agent, these plants are with the resistance to the action of a drug or by toxic action of the genetic engineering to herbicide with the resistance to the action of a drug.
It is traditional to breed with including than known plants with the method for improving shape plant, such as traditional mating method Bred with mutant strain.In other words, can be by means of the method for genetic engineering (see, e.g. EP-0221044 A, EP- 0131624 A) come obtain with improve character new plant.Such as, it has been described that several methods：
- in order to improve the Starch synthesis in plant, change crop plants (such as WO 92/11376, WO using genetic engineering 92/14827, WO 91/19806)；
- the transgenic crop plant resistant to specific herbicide, to careless fourth phosphine herbicide (such as EP-0242236 A, EP-0242246 A) or to glyphosate-class herbicides (WO 92/00377), or to sulfonylurea herbicide (EP-0257993 A, US-5013659 A)；
The transgenic crop plant of-such as cotton, it can produce bacillus thuringiensis toxin (Bt toxin), and this toxin can To defend the infringement of specific pests on plants (EP-0142924 A, EP-0193259 A)；
- the transgenic crop plant (WO91/13972) with improved Fatty acid component.
Known many can prepare with improve character genetically modified plants molecular biotechnologies (see, e.g. Sambrook etc., 1989, molecule amplification, the laboratory manual second edition, Cold Spring Harbor Laboratory publication, Cold SpringHarbor, New York；Or Winnacker " Gene und Klone " [gene and clone], VCH Weinheim, the second edition 1996 or Christou, " plants The trend of thing science " 1 (1996) 423-431)).In order to realize the operation of genetic engineering, nucleic acid molecules may be introduced plasmid, By the restructuring of DNA sequence dna, undergo mutation or sequence changes.Using above-mentioned standard method, such as substrate can be exchanged, removed Partial sequence increases the sequence naturally or synthesized.In order to which DNA fragmentation is interconnected, it is possible to be accompanied with knot in fragment Fit or connector.
The plant cell for the gene prod for reducing activity can be prepared with following methods, for example, it is at least one suitable by expressing When antisense-RNA, justice-RNA reach the effect of co-suppression, or by expressing the ribozyme of at least one appropriate structuring, it The transcription product of specific cleavage said gene product.
For this purpose, it is possible to use including the DNA molecular of gene outcome whole coded sequence, include that may be present Any flanking sequence, and using including the DNA molecular of only only a part coded sequence, these parts must long enough to reach The effect of antisense in cell.Can also use has high homology but incomplete same sequence with gene outcome coded sequence Row.
When the express nucleic acid molecule in plant, the protein of synthesis can be determined in any desired plant cell room Position.But in order to be positioned in specific room, it is possible to for example connect code area with DNA sequence dna, to ensure to determine in ad-hoc location Position.These sequences be known to those skilled in the art (see, e.g. Braun etc., EMBO J.11 (1992) 3219- 3227；Wolter etc., Proc.Natl.Acad.Sci.USA 85 (1988), 846-850；The Plant such as Sonnewald are J.1 (1991), 95-106).
Transgenic plant cells can be recombinated using known technology onto whole plant.Genetically modified plants can be to appoint What desired plant variety, i.e. unifacial leaf and dicotyledon.In such a way, by overexpressing, forbidding or suppress homologous (=naturally) gene or gene order, or pass through (=outside) gene or the expression of gene order of xenogenesis, it is possible to Obtain the genetically modified plants for improving character.
When using the active material of the present invention on the crop in transgenosis, except with can be observed on other crops Suppression noxious plant effect outside, special effect is often had on corresponding genetically modified crops, for example, can improve or Expand the scope of control weeds, improve amount of application during application, the preferably resistance to the action of a drug of genetically modified crops and the performance of herbicide very Good combination, and the growth of the crop plants of transgenosis and the influence of yield.Therefore present invention provides the compound Purposes, as herbicide control transgenic crop plant in noxious plant.
Other the compounds of this invention can substantially adjust the growth of crop plants.Plant metabolism is participated in by adjusting, is used The component of these compound oriented control plants and promotion harvest, such as make plant desiccation and stunted growth.And they are also fitted In adjusting and suppressing undesirable plant growth, the growth without destroying crop.The many unifacial leaves that are grown in for suppressing plant are planted Play very important effect in thing and dicotyledon crop because can so reduce or completely pre- lodging-prevention.
The compound of the present invention can be applied using in general preparation, wettable powder, emulsifiable concentrates can be used, can spray Solution, powder or the particle spilt.So present invention provides the herbicidal composition including compound of formula I.According to common The physical parameter of biology and/or chemistry, compound of formula I can be prepared with various ways.Suitable preparation selection example for：Can WP (WP), water miscible powder (SP), water miscible concentrate, emulsifiable concentrates (EC), for example oil in water disperse and Water in oil disperse emulsion (EW), sprayable solution, suspending agent concentrate (SC), dispersible oil-suspending agent (OD), with oil or Water is suspension, miscible oily solution, powder (DP), capsule suspension liquid (CS), the bag core (seeddressing) of diluent Composition, for broadcasting sowing with the particle of soil pesticide, injection particle, coated particle and absorbing particles, dispersible particle in water (WG), water miscible particle (SG), ULV (ultra-low volume) formulas, micro-capsule and wax work.These single preparation types are known , it is described in the following references, for example, Winnacker-K ü chler, " Chemische Techonologie " [chemical works Skill], volume 7, C.Hauser Verlag Munich, the 4th edition 1986；Wade van Valkenburg, " Pesticide Formulations ", Marcel Dekker, N.Y., 1973；K.Martens, " Spray Drying " handbooks, the 3rd edition 1979, G.Goodwin Ltd.London。
Necessary formulation auxiliary agents, such as inert substance, surfactant, solvent and other additives are similarly known, And described in following files, such as Watkins " powder diluent insecticide and carrier handbook ", the second edition, Darland books Caldwell N.J.；H.v.01phen " introduction of Clay Colloids chemistry ", the second edition, J.Wiley and Sons, N.Y.； C.Marsden " solvent guide " second edition, Interscience, N.Y.1963；McCutcheon " detergent and emulsifying agent Annual report ", MC distributing and releasing corporations, Ridgewood N.J.；Sisley and Wood, " surfactant encyclopedia ", chemistry is published public Department, N.Y.1964；'s[ethylene oxide adduct surface Activating agent], Wiss. Verlagagesell.Stuttgart 1976；Winnacker-K ü chler " Chemische Technologie " [chemical technology], volume 7, C.Hauser Verlag Munich, the 4th edition 1986.
Wettable powder equably can be dispersed in water, except active material, in addition to diluent or inert substance, from Son and nonionic surface active agent (wetting agent, dispersant), such as polyethoxy alkylphenol, polyethoxy fatty alcohol, polyoxy Ethyl fatty race amine, poly alkyl alcohol ether sulfates, alkylsulfonate, alkyl benzene sulfonate, wooden sodium sulfonate, 2,2 '- Dinaphthyl methane -6,6 '-sodium disulfonate, nekal or oleoyl N-methyltaurine sodium., will in order to prepare wettable powder The active material fine grinding of herbicide, such as using conventional instrument, hammer-mill, fan grater and jet-propelled grater such as are used, Simultaneously or sequentially it is mixed into auxiliary agent.
Active material dissolving is prepared into emulsifiable concentrates, solvent such as butanol, cyclohexanone, dimethyl formyl in organic solvent Amine, the aromatic compounds of dimethylbenzene or higher or the mixture of hydrocarbon or solvent, and add one or more Ion and/or nonionic surface active agent (emulsifying agent).The example for the emulsifying agent that can be used is such as detergent alkylate The alkyl aryl sulphonic acid calcium of sulfoacid calcium, or nonionic emulsifier, for example, fatty acid polyglycol diol ester, alkylaryl polyglycol ether, Poly alkyl alcohol glycol ethers, propylene oxide-oxirane condensation product, alkyl, polyether, the mountain of such as sorbitan fatty acid ester Pears glycan ester, or the polyoxyethylene sorbitan ester of such as Polyoxyethylene sorbitan fatty ester.
Active material and solid matter in small, broken bits are ground to obtain powder, such as solid matter such as talcum, kaolin, bentonite With the natural clay or diatomite of pyrophyllite.It can be prepared with water or oil for the suspension of substrate by following methods, such as profit Wet-milling is carried out with commercial general bead mill, adds or be added without the surfactant of another above-mentioned preparation type.
The emulsion of such as oil-water emulsifiers (EW) is prepared, aqueous organic solvent can be used, use agitator, colloid Mill and/or static mixer, if it is desired, add the surfactant of another preparation type as described above.
Granule is prepared with following methods, active material is sprayed onto on adsorbate, using inert material particle, or will be living Property material be concentrated to for example husky, surface of kaolinite carrier, inert material is granulated by adhesive, adhesive such as polyethylene Alcohol, Sodium Polyacrylate or mineral oil.Suitable active material can be granulated with the method for preparing fertiliser granulates agent, if desired Fertilizer can be mixed with.Aqueous suspension granule is prepared using usual way, such as sprinkling-drying, fluidized bed prilling, mill are made Grain, mixed using high-speed mixer, and extruded in the case of without solid, inert material.
On using mill, fluid bed, extruder and the preparation method of sprayed particle agent, referring to following techniques, such as " Spray Drying handbooks " third edition 1979, G.Goodwin Co., Ltds, London；J.E.Browning, " Agglomeration ", chemistry and engineering 1967,147ff pages；" engineer's handbook of Perry ' s chemistry ", the 5th edition, McGraw-Hill, New York 1973,8-57 pages.If it is to be understood that the preparation on crop protection products, see, for example, G.C.Klingman, " Weed Control as a Science ", John Wiley and Sons companies, New York, 1961 81-96 Page and J.D.Freyer, S.A.Evans " weed control handbook ", the 5th edition, Blackwell Scientific Rublications, Oxford University 1968,101-103 pages.
Agrochemical formulation generally comprises the active material Formulas I of by weight 0.1 to 99%, particularly 0.1 to 95%. The concentration of active material is in wettable powder, and by weight for example from about 10 to 99%, common formulation components are formed and pressed Weight meter surplus is to 100%.Concentration by weight of the active material in emulsifiable concentrates can be about 1 to 90%, preferably 5 To 80%.Powder formulation includes by weight 1 to 30% active material, it is usually preferred to by weight 5 to 20% active matter Matter, but sprayable solution includes by weight about 0.05 to 80%, preferably 2 to 50% active material.Hanged on water The content of active material in floating particles agent, be mainly liquid or solid-state according to active material, and use when being granulated auxiliary agent, fill out Material etc..The content of active material is for example by weight between 1 to 95% in aqueous suspension granule, preferably by weight 10 To between 80%.
The preparation of described active material can include tackifier, wetting agent, dispersant, emulsifying agent, bleeding agent, anti-in addition Rotten agent, antifreezing agent, solvent, filler, carrier, colouring agent, defoamer, evaporation suppressor and generally all conventional in all cases PH and viscosity modifier.
Based on these preparations, it is also possible to and other biocidal activity materials for example insecticide, acaricide, herbicide and Bactericide mixes, and can also be mixed with safener, fertilizer and/or plant growth regulator, hybrid mode can be to be pre-mixed Good or filling mixing.
In mixture preparation or bucket mix formulation, can be with the suitable active material of the active material mixing of the present invention, Such as《World pesticide new varieties technology is complete works of》, Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in Known substance.Such as herbicidal activity material mentioned below can mix with Formulas I mixture, (remarks：The name of compound Claim, be either according to the common name of International Organization for standardization (ISO) or be chemical name, there is code name when appropriate)： Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, S-metolachlor, pretilachlor, propachlor, kecaoan, naphthalene Propionyl grass amine, the left-handed naphthalene propionyl grass amines of R-, propanil, mefenacet, diphenamide, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, fluorine butyryl Careless amine, bromobutide, dimethenamid, dimethenamidP, ethobenzanid, flufenacet, thenylchlor, pyrrole grass Amine, isoxaben, flampropMmethyl, flampropMisopropyl, allidochlor, pethoxamid, chloranocryl, the grass of ring third Amine, mefluidide, monalide, delachlor, prynachlor, terbuchlor, xylachlor, dimethachlor, amine of taking to the greenwood, Front three ring grass amine, clomeprop, propyzamide, valeryl benzene grass amine, the careless amine of card, suffer, three rings match careless amine, butylene grass Amine, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, acetyl alachlor, quinclorac, fenacet, pyrrole cyanogen grass amine, benzene More grams of grass is dead, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, atrazine, Simanex, prometryn, cyanatryn, symetryne, Ametryn, propazine, dipropetryn, SSH-108, terbutryn, Garagard, triaziflam, cyprazine, proglinazine, trietazine, flutter Go out net logical, Gesadrual, nitrine, desmetryn, dimethametryn, third blue or green Tianjin of ring, green bristlegrass of going out Tianjin, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy Third is net, cyanatryn, ipazine, chlorazine, atraton, weed eradication are logical, radix glycyrrhizae Tianjin, cyanuric acid, Indaziflam, green sulphur are grand, first Sulphur is grand, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, pyrazosulfuron, mesosulfuron, iodosulfuron-methyl-sodium, formyl Amino Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, ring Third Sulfometuron Methyl, rimsulfuron, azimsulfuron, pyridine ethyl methyl, monosulfmeturon, single phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, Fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, procarbazone, prosulfuron, Sulfosulfuron, trifluoro pyridine Sulphur is grand, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, flucetosulfuron, Sulfonylurea, orthosulfamuron, Propyrisulfuron (promazine Sulfometuron Methyl), piperazine pyrazosulfuron, acifluorfen, fomesafen, lactofen, second carboxylic AKH7088, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, bifenox, fluoroform grass ether, methoxy weeding Ether, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass ether, fluorine lactazone grass ether, AKH7088 ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, Ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, phenobenzuron, methoxy daimuron, metobromuron, first Oxygen is grand, afesin, telvar, Tupersan, fenuron, fluorine sulphur are grand, neburea, chloroxifenidium, herban, isonoruron, Alipur-O, Thiazfluron, tebuthiuron, difenoxuron, to fluon, methylamine methabenz thiazuron, Long Caote, front three isourea, dimefuron, Monisouron, Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-ethyl ester, desmedipham, the spirit of sulphur grass, special grass Spirit, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Ding Caote, benthiocarb, vernolate, molinate, tri-allate, dimepiperate, standing grain Careless fear, pyributicarb, cycloate, Avadex, bactericide, the careless spy of second sulphur, orbencarb, pebulate, prosulfocarb, tiocarbazil, sulphur alkene grass Pellet, dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, the chlorine sodium of 2 first 4, the different monooctyl ester of 2,4- drops, the chlorine of 2 first 4 are different Monooctyl ester, 2,4- drops sodium salt, 2,4- drops dimethylamine salt, the chloroethene thioesters of 2 first 4, the chlorine of 2 first 4,2,4- drops propionic acid, high 2,4- drops propionate, 2,4- Embutoxs, Vi par, Vi par salt, Thistrol, 2,4,5- tears, 2,4,5- tears propionic acid, 2,4,5- tears Butyric acid, the chloramines salt of 2 first 4, Mediben, erbon, Fenac, match pine, trichlorobenzoic acid, chloramben, methoxy trichlorobenzoic acid, standing grain Careless spirit, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient haloxyfop, quizalofop-ethyl, Quizalotop-ethyl, oxazole standing grain Careless spirit, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, diclofop-methyl thiazole, chloroazifoppropynyl, the standing grain of hydroxyl penta Spirit, trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, ethalfluralin, isopropalin, nitralin, ring third Fluorine spirit, prodiamine, benfluralin, fluchloraline, the spirit of amino second fluorine, dipropalin, chloroethene dipropalin, Methalpropalin, the third nitre phenol, glyphosate, Sha barnyard grass phosphine, glufosinate-ammonium, amiprophos-methyl, sulphosate, piperazine grass phosphine, bialaphos, Bensulide, butamifos, creeping weed phosphorus, cut down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr, imazethapyr, imazaquin, Imazamox, imazamox ammonium salt, AC 263222, miaow grass ester, fluroxypyr, the different monooctyl ester of fluroxypyr, Clopyralid, picloram, trichlopyr, dithiopyr, halogen grass are fixed, phenolate trichloropyridine, thiazopyr, halozydine Ketone, chlorine Fampridine acid, diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate, sethoxydim, clethodim, thiophene grass Ketone, alloxydimsodium, clefoxidim, butroxydim, tralkoxydim, tepraloxydim, Buthidazole, metribuzin, hexazinone, benzene piperazine grass Ketone, ethiozin, Ametridione, Amibuzin, Brominal, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, Diphenatril, pyraclonil, chloroxynil, Iodobonil, Flumetsulam, florasulam, penoxsuam, sulphur grass azoles It is amine, cloransulammethyl, diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyribenzoxim, pyriftalid, KIH 6127, phonetic Sulphur grass ether, benzobicylon, mesotrione, sulphur humulone, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxaflutole, isoxachlorotole, Fenoxasulfone, Methiozolin, fluazolate, pyrrole grass Ether, pyrazolate, difenzoquat, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine, Pyrasulfotole, topramezone, Pyroxasulfone, Cafenstrole, flupoxam, Amrol, amicarbazone, azafenidin, profluazone, sulfentrazone, Bencarbazone, double benzene Phonetic humulone, butafenacil, bromacil, isoprocil, lenacil, terbacil, Flupropacil, cinidon-ethyl, fluorine alkene grass Acid, flumioxazin, alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachlorophenol (sodium), dinoseb, dinoterb, dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol, medinoterb acetate, Di Lete, oxadiargyl, oxadiazon, pentoxazone, profluazol, fluthiacet, Fentrazamide, flufenpyrethyl, pyrazon, brompyrazon, diformazan reach careless volt, Kusakira, careless pyridazone, grass rattle away pine, norflurazon, Pyridafol, dichloro quinolinic acid, quinmerac, Bentazon, pyridate, oxaziclomefone, benazolin, clomazone, cycloheptyl grass Ether, iso-propyl-ester nitrofen, propyl-ester nitorfen, indanofan, sodium chlorate, Dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoro third Acid, herbage are fast, bromofenoxim, triazole sulphur, kill azoles, flurtamone, benfuresate, ethofumesate, phonetic careless amine, chlorine phthalandione, fluorochloridone, The phonetic sulphur grass of barnyard grass, methacrylaldehyde, bentranil, tridiphane, Bidisin, thiadiazoles grass amine, phenisopham, hydroxyl humulone, dioxybenzone, benzene Amine, chlorine acyl grass phosphine, chloropon, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl、 Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、 First sulphur nitralin, Cambendichlor, the pyrimidine acid of ring third, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, solution grass Quinoline, oxabetrinil, MG191, cyometrinil, DKA_24, mefenpyrdiethyl, furilazole, fluxofenim, isoxadifen, dichloro Allylamine, fluorine chloropyridine ester, DOW chlorine fluorine pyridine ester, 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- 9201st, ET-751, KIH-6127 and KIH-2023.
When deployed, if it is desired, commercially available preparation is diluted in a manner of common, such as in wettable powder, concentration When emulsion, suspension and the particle to suspend in water, make to be diluted with water.Granule used in powder, soil pesticide or broadcast sowing and The solution of sprinkling, further it need not be diluted typically before use with inert substance.With the change of external condition, it is desirable to formula The usage amount of I is also different, and external condition is, such as temperature, humidity, property of herbicide for using etc..It can be with Have a big amplitude of variation, such as 0.001 between 1.0kg/ha, or more active material, but preferably arrived 0.005 Between 750g/ha, particularly 0.005 between 250g/ha.
Embodiment
Following examples are used to illustrate the present invention, should not regard it as limiting the invention in any way.The present invention Claimed interest field is illustrated by claims.
The several methods for preparing the compounds of this invention are illustrated in following scheme and embodiment.Raw material can be bought through market To or can be prepared by known in the literature method.It will be appreciated by those skilled in the art that it can also utilize other The compound of the synthetic route synthesis present invention.Although hereinafter the specific raw material in synthetic route and condition are carried out Illustrate, however, it is possible to be easily replaced with other similar raw materials and condition, these changes to preparation method of the present invention Type or variant and various isomeries of caused compound etc. are included within the scope of the present invention.In addition, system as described below Preparation Method can further be repaiied according to the disclosure of invention, using conventional chemical processes well known to those skilled in the art Decorations.For example, during the course of the reaction appropriate group protect etc..
In view of the economy and diversity of compound, embodiment of the method presented below is used to promote the preparation to the present invention Method further appreciates that specific material, species and the condition used is determined as the further explanation to the present invention, is not Limitation to its zone of reasonableness.The reagent that is used in the synthesis compound shown in the following table can be bought with market, or Person can be prepared easily by those of ordinary skill in the art.Wherein hydrogen nuclear magnetic resonance spectral condition is as follows：1HNMR is by AVANCE AV-500 nmr determinations, TMS are internal standard, and mass spectrum is determined by Shimadzu-2010A mass spectrographs.
Table 1 below gives a series of compounds with following structural formula of the present invention：
The compound structure of table 1 and its1HNMR data
The embodiment of representative compound is as follows：
1. the preparation of compound 001
The fluoro- 4- trifluoromethylbenzoic acids (A0) of the chloro- 3- of 120g 2- and 100mL thionyl chlorides Hybrid Heating backflow 1h, decompression Excessive thionyl chloride is reclaimed, not purified be directly used in of residue is reacted in next step.
54.0g 1,3- dimethyl -5- pyrazoles alcohol, 160g triethylamines and 350mL 1,2- dichloroethanes mix, ice bath cooling To 0 DEG C, the fluoro- 4- trifluoromethyl benzoyl chlorides of the chloro- 3- of 120g 2- and 100mL 1, the chloroethenes of 2- bis- is slowly added dropwise under stirring thereto Alkane mixed solution.Drip off and be slowly warmed to room temperature, continue stirring reaction 1h, then add 5mL acetone cyanohydrins, be warming up to 60 DEG C of stirrings Reaction is overnight.Watery hydrochloric acid is added into reaction solution and adjusts pH to 3 or so, liquid separation, aqueous phase is extracted with ethyl acetate.Merge organic phase, Washed, anhydrous sodium sulfate drying, be concentrated under reduced pressure with water, saturated nacl aqueous solution successively, obtain 160g pale pink solids, compound A1。
1.8g thiomorpholine ketone is dissolved in 10mL DMF, and lower addition 1.0g 60% sodium hydrides reaction is stirred at room temperature 30min, 3.4g compound A1 are then added, be warming up to 60 DEG C of reaction 3.5h, be down to room temperature.It is dilute that 60mL water is added into reaction solution Release, watery hydrochloric acid adjusts pH value, and to 3 or so, ethyl acetate extracts.Organic phase washed with water, saturated nacl aqueous solution washing, anhydrous sulphur Sour sodium is dried, and concentration, obtains 4.0g faint yellow solids, compound A2.
2.2g compounds A2 is dissolved in 10mL acetonitriles, is stirred at room temperature down and the liquor natrii hypochloritises of 5mL 6% are slowly added dropwise, instead It should stay overnight.Next day adds 5mL liquor natrii hypochloritises, continues stirring 4 hours.Watery hydrochloric acid is slowly added dropwise and adjusts pH to 3, separates out yellow and consolidates Body.Filter, filter cake is fully washed with water, is dried, is obtained 1.5g faint yellow solids, HPLC purity>92%.
The synthetic method of compound 003 is similar to Example 1, no longer describes in detail herein.
2. the preparation of compound 009
3.4g compound A-13s are dissolved in 10mL dichloromethane, and 5mL oxalyl chlorides are slowly added dropwise, and reaction solution is heated to reflux 2h, Then excessive oxalyl chloride is removed under reduced pressure.Residue is diluted with 5mL 1,2- dichloroethanes.
1.2g 1,3- dimethyl pyrazole -5- alcohol, 3.2g triethylamines and 10mL 1,2- dichloroethanes are mixed, and ice bath is cooled to 0 DEG C, the solution of acid chloride of above-mentioned preparation is slowly added dropwise under stirring, control temperature is no more than 5 DEG C, drips off follow-up 0 DEG C of reaction of continuation of insurance temperature 1h.0.5mL acetone cyanohydrins are added dropwise into reaction solution, is warming up to 60 DEG C of stirring reaction 3h, is then down to room temperature, add watery hydrochloric acid to adjust pH To 3, liquid separation, aqueous phase is extracted with ethyl acetate.Merge organic phase and washed successively with water, saturated nacl aqueous solution, anhydrous slufuric acid Sodium is dried, and concentration, obtains 3.9g yellow solids, compound A4.
2.1g compounds A4,1.5g triethylamine is mixed with 10mL acetonitriles, ice bath is cooled to 0 DEG C, is slowly added dropwise under stirring The solution of 0.7g N- methylpyrazole -4- formyl chlorides and 2mL acetonitriles composition, control temperature are no more than 5 DEG C, drip off follow-up continuation of insurance temperature 0 DEG C reaction 1h.Then the dilution of 30mL water is added, separates out faint yellow solid, is filtered, filter cake is fully washed, and obtains 2.0g pale yellow colored solids Body, HPLC purity>90%.
The synthetic method of compound 011 and 012 is similar with embodiment 1-2, no longer describes in detail herein.
3. the preparation of compound 014
4.5g mercaptoacetylglycines, 3.1g triethylamines mix with 250mL dichloromethane, and ice bath is cooled to 0 DEG C, stirring Under the solution of 3.4g ethyl chloroformates and 25mL dichloromethane is slowly added dropwise, drip off to be warmed to room temperature and continue stirring reaction 2.5h, so Afterwards plus 100mL water dilutes, liquid separation.Organic phase washed with water, saturated nacl aqueous solution washing, anhydrous sodium sulfate drying, concentration, is obtained To yellow oily liquid crude product obtain 1.5g off-white powder compounds B2 through silica gel column chromatography.
1.3g compounds B2 is dissolved in 6mL DMF, lower addition 0.6g 60% sodium hydrides reaction 30min is stirred at room temperature, so 2.0g compound A-45s are added afterwards, are warming up to 60 DEG C of reaction 3.5h, are down to room temperature.The dilution of 60mL water, dilute salt are added into reaction solution Acid adjusts pH value, and to 3 or so, ethyl acetate extracts.Organic phase washed with water, saturated nacl aqueous solution washing, anhydrous sodium sulfate are done It is dry, concentration, obtain 2.0g faint yellow solids, compound A6.
1.8g compounds A6 is mixed with 5mL POCl3s, 2h is heated to reflux, is then poured on trash ice, separates out yellow Solid, fully washing, dry, obtain 1.6g compounds A7.
1.5g compounds A7 is dissolved in 5mL acetonitriles, is stirred lower addition 1.0g 2- methyl 4- hydroxymethylfurans sodium salts, is stirred Backflow is mixed, reaction is overnight.Reaction solution is concentrated under reduced pressure, the purifying of residue column chromatography, obtains 1.0g yellow solids, HPLC purity> 92%.
4. the preparation of compound 038
2.3g compound A-28s, 1.5g triethylamines mix with 10mL acetonitriles, and ice bath is cooled to 0 DEG C, are slowly added into 0~5 DEG C 0.4g chloroacetic chlorides, are stirred overnight at room temperature.50mL water is added into reaction solution, watery hydrochloric acid adjusts pH value ethyl acetate extraction, to have to 6 Machine is mutually washed, anhydrous sodium sulfate drying, and concentration, obtained crude product purifies through column chromatography, obtains the faint yellow color solids of 2.0g, yield 80%, HPLC purity 97%.
Biological evaluation：
The active class criteria that noxious plant destroys (growing control rate) is as follows：
10 grades：It is completely dead；
9 grades：Control rate is grown more than 95%；
8 grades：Control rate is grown more than 90%；
7 grades：Control rate is grown more than 80%；
6 grades：Control rate is grown more than 70%；
5 grades：Control rate is grown more than 60%；
4 grades：Control rate is grown more than 50%；
3 grades：Control rate is grown more than 20%；
2 grades：Control rate is grown in 5-20%；
1 grade：Control rate is grown below 5%；
0 grade：To no effect.
Growth control rate is fresh weight control rate above.
By unifacial leaf and broadleaf weed seed and chief crop seed (wheat, corn, rice, soybean, cotton, oil Dish, millet, sorghum) it is placed in the plastic tub equipped with soil, 0.5-2 centimetres of soil is then covered, makes it in good greenhouse Grown in environment, sowing in the 4-5 leaf phases handle test plants after 2-3 weeks, respectively will for examination the compounds of this invention acetone it is molten Solution, then adds Tween 80, is diluted to certain density solution with certain water, is sprayed application to spray tower on plant.After dispenser The experiment effect of weeds is listed in table 2 after being cultivated 3 weeks, 3 weeks in greenhouse.
The after seedling weeds of table 2 are tested
Note：Application dosage is 250 grams/ha of active ingredient, and the amount of being watered is 450 kilograms/hectare.
Transplanting rice safety evaluatio is evaluated with paddy land weed preventive effect：
After loading paddy field soil in 1/1,000,000 hectare of tank, sowing barnyard grass, moleplant seed, the seed of Monochoria vaginalis, at it On lightly overburden soil.Thereafter it is statically placed in the state of 0.5-1 centimetres of water storage depth in greenhouse, 3-4 centimetres of water storage depth is kept, in barnyard grass Grass, moleplant seed, Monochoria vaginalis reach 1.5 leaves, the wettable powder that will be formed according to common formulation method modulation the compounds of this invention Agent or the water diluent of suspending agent, with pipette uniformly drip is handled to reach defined active ingredient amount.
In addition, after loading paddy field soil in 1/1,000,000 hectare of tank, progress is smooth, makes 3-4 centimetres of water storage depth, the The rice (japonica rice) of 3 leaf phases was transplanted with 3 centimetres of transplanting depth in two days.The present invention is handled as described above within the 5th day after transplanting Compound.
14th day barnyard grass, moleplant seed, the fertility status of Monochoria vaginalis after the chemicals treatment that detects by an unaided eye respectively, after chemicals treatment The fertility status of 21st day rice, with 0-10 activity criteria's level evaluation herbicidal effect, so as to obtain the result of table 3.
The transplanting rice field experimental result of table 3 (250 grams/ha of active ingredient)
Sequence number Barnyard grass Moleplant seed Monochoria vaginalis Rice
001 10 10 10 0
002 10 10 9 0
003 10 10 10 0
004 10 10 10 0
015 10 10 10 0
019 10 9 10 0
020 10 10 10 0
021 10 10 10 0
025 10 10 10 0
032 10 10 9 0
036 10 10 10 0
Note：Barnyard grass, moleplant seed, Monochoria vaginalis seed are gathered from Chinese Heilungkiang, phonetic to the pyrrole of routine dose by detection Sulphur is grand the resistance to the action of a drug.
Contrast test：
Test method step is consistent with the experiment of foregoing after seedling weeds, and each compound comparative test result see the table below 4-7, wherein Comparative example a-h comes from patent CN105218449A.
The comparative test result of table 4
The comparative test result of table 5
The comparative test result of table 6
The comparative test result of table 7
Find that compound of the present invention is much to Korea lawn grass, Bermuda grass, Festuca Arundinacea, precocity by many tests simultaneously The Gramineae lawns such as standing grain, rye grass, seashore paspalum have good selectivity, can prevent and kill off many crucial grassy weeds and broad-leaved Weeds.Fabulous choosing is also showed that to tests such as the soybean under different insecticide-applying way, cotton, oily certain herbaceous plants with big flowers, potato, fruit tree, vegetables Selecting property and commercial value.

Claims (9)

  1. A kind of 1. pyrazolone compound or its salt as shown in formula I：
    In formula,
    R1R2N is representedWherein,
    Het is selected from five or hexa-member heterocycle, in addition to the N atoms and 1 or 2 C=O on the ring on containing C, 1- position, also containing 1-3 The part of following atom or group as ring：O、NRb、S、SO、SO2, when Het is hexa-member heterocycle, and the C=O on the ring has And only 1 and at 2- positions, 4- positions can not be O, NRbOr S；
    RaSelected from one or more of following group group：Hydrogen, halogen, cyano group, nitro, hydroxyl, carboxyl, amino, C1-C6Alkane Base sulfonyl, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy, halo C1~6Alkoxy, C1~6Alkylamino, C2~6Alkenyloxy group, halo C2~6Alkenyloxy group, C2~6Enamino, halo C2~6Enamino, C1~6Alkyl-carbonyl, halo C1~6Alkyl-carbonyl, C1~6Alkoxy carbonyl, C1~6Alkyl amino-carbonyl, C1~6Alkoxy C1~6Alkyl, halo C1~6Alkoxy C1~6Alkane Base, C1~6Alkyl carbonyl epoxide C1~6Alkyl, C1~6Alkoxy C1~6Alkoxy, halo C1~6Alkoxy C1~6Alkoxy, C1~6Alcoxyl Base carbonyl C1~6Alkoxy, C1~6Alkyl carbonyl epoxide, halo C1~6Alkyl carbonyl epoxide, C1~6Alkyl-carbonyl-amino, C1~6Alkyl Sulfonyl epoxide, C1~6Alkyl sulfonyl-amino, C1~6Alkyl-carbonyl C1~6It is alkoxy, unsubstituted or be independently selected from by 1-3 Halogen, nitro, cyano group, C1~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, C1~6The virtue that group in alkyl-carbonyl is substituted Base, heteroaryl, aryl carbonyl epoxide, aryl sulfonyl epoxide, arylmethyl epoxide, hetervaromatic methyl epoxide, aryl-amino-carbonyl, Arlysulfonylamino, arylmethyl amino or hetervaromatic methyl amino；
    RbSelected from hydrogen, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy C1~6Alkyl, halo C1~6Alkoxy C1~6Alkyl, C1~6Alkyl-carbonyl, halo C1~6Alkyl-carbonyl, C1~6Alkyl sulphonyl, C1~6Alkoxy carbonyl, C1~6Alkyl amino-carbonyl, C1~6Alkyl-carbonyl C1~6Alkyl, C1~6Alkoxy carbonyl C1~6Alkyl, C1~6Alkyl amino-carbonyl C1~6Alkyl, It is unsubstituted or halogen, nitro, cyano group, C are independently selected from by 1-31~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, halo C1~6Alkoxy, C1~6Aryl that group in alkyl-carbonyl is substituted, heteroaryl, aryl carbonyl, Heteroarylcarbonyl, aryl sulphur Acyl group, arylmethyl, hetervaromatic methyl；
    R3Represent hydrogen, C1~4Alkyl, C2~4Alkenyl, C2~4It is alkynyl, unsubstituted or use C1~4Alkyl-substituted C3~6Cycloalkyl；
    R4Represent methyl, ethyl, n-propyl, isopropyl, cyclopropyl；
    X represents hydrogen ,-R5、-S(O)nR6、-CH2R7,-(C=O) R8、-PO(OR9)2、-Si(OR9)3, wherein,
    R5、R6Represent substituted or unsubstituted C1~6Alkyl, aryl or heterocyclic radical, n represent 1,2,3；
    R7Represent substituted or unsubstituted aryl or heterocyclic radical, halogen, C1~6Alkyl amino, C2~4Alkynyl, C2~4Alkenyl, C1~6Alkane Epoxide, nitro, cyano group, C3~6Cycloalkyl, amino, C1~6Alkylthio group；
    R8Represent C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, C1~6Alkyl amino C1~6Alkyl, C1~6Alkane Sulfenyl C1~6Alkyl, halogen, amino, cyano group, nitro, C1~6Alkoxy C1~6Alkyl, substituted or unsubstituted phenyl, phenyl C1~6 Alkyl, phenoxy group, phenoxy group C1~6Alkyl or heterocyclic radical；
    R9Represent hydrogen, C1~6Alkyl, C3~6Cycloalkyl, substituted or unsubstituted phenyl or heterocyclic radical.
  2. 2. pyrazolone compound according to claim 1 or its salt, it is characterised in that
    R5、R6Represent unsubstituted C1~6Alkyl, phenyl contain 1~4 heteroatomic 3~10 circle heterocycles for being selected from O, N and S Base, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, Nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6Alkyl, C1~6Alkane sulphur Base sulfonyl C1~6Alkyl, C3~6The C that one or more of cycloalkyl group is substituted1~6Alkyl, phenyl contain 1~4 Heteroatomic 3~10 circle heterocycles base selected from O, N and S, n represent 1,2,3；
    R7Unsubstituted phenyl is represented or containing 1~4 heteroatomic 3~10 circle heterocycles base for being selected from O, N and S, by selected from C1~6 Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxylic Base, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkane Base, C3~6Phenyl that one or more of cycloalkyl group is substituted or containing 1~4 selected from O, N and S heteroatomic 3~ 10 circle heterocycles bases, halogen, C1~6Alkyl amino, C2~4Alkynyl, C2~4Alkenyl, C1~6Alkoxy, nitro, cyano group, C3~6Cycloalkyl, Amino, C1~6Alkylthio group；
    R8Represent C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, C1~6Alkyl amino C1~6Alkyl, C1~6Alkane Sulfenyl C1~6Alkyl, halogen, amino, cyano group, nitro, C1~6Alkoxy C1~6Alkyl, phenyl, phenyl C1~6Alkyl, phenoxy group, benzene Epoxide C1~6Alkyl or heteroatomic 3~10 circle heterocycles base selected from O, N and S containing 1~4, by selected from C1~6Alkyl, C1~6Alkane Epoxide, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alcoxyl Base carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6Cycloalkanes Phenyl that one or more of base group is substituted, phenyl C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl contains 1~4 Individual heteroatomic 3~10 circle heterocycles base selected from O, N and S；
    R9Represent hydrogen, C1~6Alkyl, C3~6Cycloalkyl, unsubstituted phenyl or containing 1~4 be selected from O, N and S heteroatomic 3 ~10 circle heterocycles bases, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4 Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl sulphonyl C1~6Alkane Base, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6Phenyl that one or more of cycloalkyl group is substituted or containing 1~4 Individual heteroatomic 3~10 circle heterocycles base selected from O, N and S.
  3. 3. pyrazolone compound according to claim 1 or 2 or its salt, it is characterised in that
    Het is selected from
    R3Represent hydrogen, methyl, ethyl, cyclopropyl；
    R4Represent methyl, ethyl, isopropyl；
    X represents hydrogen ,-R5、-S(O)nR6、-CH2R7,-(C=O) R8、-PO(OR9)2、-Si(OR9)3, wherein,
    R5、R6Represent unsubstituted C1~6Alkyl, phenyl contain 1~4 heteroatomic 3~10 yuan of heteroaromatic for being selected from O, N and S Base, by selected from C1~6Alkyl, C1~6The C that one or more of alkoxy, halogen group is substituted1~6Alkyl, phenyl contain 1 ~4 heteroatomic 3~10 yuan of aromatic heterocyclics for being selected from O, N and S, n represent 2；
    R7Represent unsubstituted phenyl or containing 1~4 be selected from O, N and S heteroatomic 3~10 yuan of aromatic heterocyclics, by selected from C1~6Alkyl, C1~6The phenyl or be selected from O, N and S containing 1~4 that one or more of alkoxy, halogen group is substituted Heteroatomic 3~10 yuan of aromatic heterocyclics, C1~6Alkyl amino, C2~4Alkynyl, C2~4Alkenyl, C1~6Alkoxy, C1~6Alkylthio group；
    R8Represent C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, C1~6Alkyl amino C1~6Alkyl, C1~6Alkane Sulfenyl C1~6Alkyl, phenyl, phenyl C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl is miscellaneous selected from O, N and S containing 1~4 3~10 yuan of aromatic heterocyclics of atom, by selected from C1~6Alkyl, C1~6Alkoxy, C1~6Alkyl amino, C1~6Alkylthio group, halogen, C2~4Alkenyl, C2~4Alkynyl, amino, nitro, cyano group, carboxyl, C1~6Alkoxy carbonyl, C1~6Alkoxy C1~6Alkyl, C1~6Alkyl Sulfonyl C1~6Alkyl, C1~6Alkylthio group sulfonyl C1~6Alkyl, C3~6The benzene that one or more of cycloalkyl group is substituted Base, phenyl C1~6Alkyl, phenoxy group, phenoxy group C1~6Alkyl contains 1~4 heteroatomic 3~10 yuan of virtue for being selected from O, N and S Heterocyclic radical；
    R9Represent hydrogen, C1~6Alkyl, C3~6Cycloalkyl, unsubstituted phenyl or containing 1~4 be selected from O, N and S heteroatomic 3 ~10 yuan of aromatic heterocyclics, by selected from C1~6Alkyl, C1~6Phenyl that one or more of alkoxy, halogen group is substituted or Contain 1~4 heteroatomic 3~10 yuan of aromatic heterocyclic for being selected from O, N and S.
  4. A kind of 4. herbicidal composition, it is characterised in that the pyrrole described in the claim 1-3 any one including herbicidally effective amount At least one of sulfinpyrazone compound or its salt.
  5. 5. herbicidal composition according to claim 4, it is characterised in that also including formulation auxiliary agents.
  6. A kind of 6. method for controlling noxious plant, it is characterised in that including by the claim 1-3 any one of herbicidally effective amount Herbicidal composition described at least one of described pyrazolone compound or its salt or claim 4-5 any one Using on plant or noxious plant region.
  7. 7. at least one of pyrazolone compound or its salt as described in claim 1-3 any one or claim 4- Purposes of the herbicidal composition on control noxious plant described in 5 any one.
  8. 8. purposes according to claim 7, it is characterised in that be used to prevent and kill off by described pyrazolone compound or its salt Noxious plant in useful crop.
  9. 9. purposes according to claim 8, it is characterised in that the useful crop is that genetically modified crops or genome are compiled Collect the crop of technical finesse.
CN201711002458.0A 2017-10-24 2017-10-24 Pyrazolone compound or salt thereof, herbicide composition and application Active CN107629046B (en)

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WO1999007697A1 (en) * 1997-08-07 1999-02-18 Basf Aktiengesellschaft Substituted 4-benzoyl-pyrazoles
CN1409710A (en) * 1999-12-02 2003-04-09 巴斯福股份公司 Cyclopropyl-anellated 3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles
KR100393500B1 (en) * 1995-02-24 2003-10-17 바스프 악티엔게젤샤프트 Pyrazol-4-yl-benzoyl derivatives and their use as herbicides
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
CN105218449A (en) * 2015-11-06 2016-01-06 青岛清原化合物有限公司 Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes

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KR100393500B1 (en) * 1995-02-24 2003-10-17 바스프 악티엔게젤샤프트 Pyrazol-4-yl-benzoyl derivatives and their use as herbicides
WO1998031682A1 (en) * 1997-01-17 1998-07-23 Basf Aktiengesellschaft 4-(3-heterocyclyl-1-benzoyl)pyrazoles and their use as herbicides
WO1999007697A1 (en) * 1997-08-07 1999-02-18 Basf Aktiengesellschaft Substituted 4-benzoyl-pyrazoles
CN1409710A (en) * 1999-12-02 2003-04-09 巴斯福股份公司 Cyclopropyl-anellated 3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles
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
CN105218449A (en) * 2015-11-06 2016-01-06 青岛清原化合物有限公司 Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes

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