WO2019233372A1 - Substituted pyrazolyl pyrazole sulfonamide compound or pesticidally acceptable salt thereof, composition and use thereof - Google Patents

Substituted pyrazolyl pyrazole sulfonamide compound or pesticidally acceptable salt thereof, composition and use thereof Download PDF

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WO2019233372A1
WO2019233372A1 PCT/CN2019/089798 CN2019089798W WO2019233372A1 WO 2019233372 A1 WO2019233372 A1 WO 2019233372A1 CN 2019089798 W CN2019089798 W CN 2019089798W WO 2019233372 A1 WO2019233372 A1 WO 2019233372A1
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alkoxy
alkyl
halo
substituted
compound
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PCT/CN2019/089798
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French (fr)
Chinese (zh)
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杨春河
李建国
邢阳阳
王旭
刘明东
马娥
耿丽文
葛家成
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海利尔药业集团股份有限公司
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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
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00

Definitions

  • the present invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrazolylpyrazolesulfonamide compound or a salt and composition acceptable as a pesticide, and to these compounds or a salt and composition acceptable as a pesticide.
  • Substituted pyrazole derivatives are known to have herbicidal activity. Related pyrazole derivatives and their herbicidal activity are described in patents published as CN1087342A, CN1161956A, and CN105492443A; a pyridine is described in patent published as CN1073440A The azole-pyrazole compound has herbicidal activity; and sulfonamide-based herbicides are known to have good herbicidal activity, such as the herbicide compounds having a sulfonamide structure described in the patent publications CN1073679A and the publication number CN101485320A.
  • the present invention provides a substituted pyrazolylpyrazolesulfonamide compound or an acceptable salt, composition, and use thereof as a pesticide.
  • the compounds of the above-mentioned pyrazolylpyrazolesulfonamide structure or their acceptable salts as pesticides have higher herbicidal activity than known compounds, and especially have very good herbicidal activity against common weeds in paddy fields.
  • Y represents NH, CH 2 , O, SO 2 or S
  • R 1 represents H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 1 -C 6 alkoxy Radical, halo C 1 -C 6 alkoxy;
  • R 2 represents H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 1 -C 6 alkoxy Radical, halo C 1 -C 6 alkoxy;
  • R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 1-6;
  • R 3 represents H or halogen
  • R 4 represents H, CN, halogen, NO 2 , CONR 1 R 2 ;
  • R 5 represents H or halogen
  • R 6 represents C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halo C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkenyl Thio, either unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy Alky
  • R 6 may be selected from C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl.
  • R 1 represents H, C 1 -C 4 alkyl
  • R 2 represents H, C 1 -C 4 alkyl
  • R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 2-4;
  • R 3 represents H or halogen
  • R 4 represents H, CN, halogen, NO 2 , COOR 1 , CONR 1 R 2 ;
  • R 5 represents H or halogen
  • R 6 represents C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl, halo C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, or unsubstituted or 1-5 independently selected from halogen , Nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 Alkylcarbonyl
  • R 1 and R 2 together form a group-(CH 2 ) m- , m represents 1-4, and Y represents NH and CH 2 .
  • the aryl group is phenyl and naphthyl
  • the heteroaryl group is thiazole, furan, pyrrole, thiophene, imidazole, pyran, pyridine, pyrazole, pyrimidine, indole, purine , Pyrimidine, pyrazine, pyridazine, triazine, benzothiazole, benzofuran, quinoline, or oxazole.
  • R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 3 or 4;
  • R 3 represents H or halogen
  • R 4 represents H, halogen, CONH 2 or CN
  • R 5 represents H or halogen
  • R 6 represents C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl Aminocarbonyl, carboxyl, aldehyde, hydroxyl, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycl
  • Y represents NH
  • R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 3 or 4;
  • R 3 represents H, chlorine or bromine
  • R 4 represents H, CN
  • R 5 represents H
  • R 6 represents C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, or phenyl, thiazolyl, pyrimidinyl, or is independently selected from halogen , Nitro, cyano, C 1 -C 4 alkyl, halo C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl substituted phenyl, thiazolyl, Pyrimidinyl.
  • Y represents NH
  • R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 4;
  • R 3 represents chlorine or bromine
  • R 4 represents CN
  • R 5 represents H
  • R 6 represents methyl, ethyl, propyl, cyclopropanyl, cyclohexane, piperidinyl, or phenyl, pyrimidinyl, or is independently selected from fluorine, chlorine, bromine, methyl, 1-3, Ethyl, propyl, trifluoromethyl, trichloromethyl, methoxycarbonyl, acetyl substituted phenyl groups or 1-3 groups independently selected from fluorine, chlorine, bromine Of pyrimidinyl.
  • C 1 -C 6 alkyl a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or tert-butyl.
  • Halogen or halogen refers to fluorine, chlorine, bromine, and iodine.
  • Halo C 1 -C 6 alkyl straight or branched alkyl groups having 1 to 6 carbon atoms.
  • the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogens.
  • C 1 -C 6 alkoxy a linear or branched alkyl group having 1 to 6 carbon atoms, connected to the structure via an oxygen atom bond.
  • Halo C 1 -C 6 alkoxy straight or branched chain alkoxy groups having 1 to 6 carbon atoms.
  • the hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogens, for example, chloroform Oxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
  • C 1 -C 6 alkylthio A straight or branched alkyl group having 1 to 6 carbon atoms, which is connected to the structure via a sulfur atom bond.
  • Halo C 1 -C 6 alkylthio Linear or branched alkylthio groups having 1 to 6 carbon atoms.
  • the hydrogen atoms on these alkylthio groups may be partially or completely replaced by halogen atoms, for example, chlorine Methylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, and the like.
  • C 1 -C 6 alkoxy-substituted C 1 -C 6 alkoxy a group in which an alkoxy group having 1 to 6 carbon atoms is substituted by an alkoxy group having 1 to 6 carbon atoms Mission, such as
  • C 3 -C 6 heterocyclylamine carbonyl a group formed by linking an amine group obtained by substituting an amino group with a heterocyclic group having 3 to 6 carbon atoms as a substituent, such as
  • C 1 -C 6 alkylcarbonyl A group formed by linking an alkyl group having 1 to 6 carbon atoms with a carbonyl group, such as
  • C 1 -C 6 alkylsulfonyl A group formed by linking an alkyl group having 1 to 6 carbon atoms with a sulfonyl group, such as
  • C 3 -C 6 cycloalkyloxycarbonyl group A group formed by a cycloalkyl group having 3-6 carbon atoms, an oxygen atom, and a carbonyl group connected in sequence, such as
  • Aryl Any functional group or substituent derived from a simple aromatic ring.
  • Heteroaryl a five- or six-membered ring containing one or more N, O, and S heteroatoms, such as pyridine, furan, thiophene, pyrazole, pyrimidine, pyrazine, pyridazine, triazine, quinoline, Thiazole, benzothiazole, benzofuran and the like.
  • Arylamino group An amine group obtained by substituting an amino group with an aryl group as a substituent.
  • Heteroaralkyl An alkyl obtained by substituting a hydrogen of an alkyl group with a heteroaryl group as a substituent.
  • Heteroaryloxy Heteroaryl is connected to an oxygen atom and is connected to the structure via an oxygen atom bond.
  • Paracyclic group a group in which a bicyclic or tricyclic ring is joined together, such as
  • a method for synthesizing a compound described by the general formula I is characterized in that a compound of the general formula II and a compound of the general formula III (in the chemical formulae listed below, unless otherwise defined, the substituents and symbols are the same as those defined in the general formula I And symbol have the same meaning)
  • the product is obtained after the reaction is performed with or without a solvent.
  • the compound represented by general formula II can be synthesized by referring to the method described in patent CN200910092609.5
  • the compound represented by general formula III can be synthesized by referring to the method described in patent CN96116762.9:
  • the solvent is selected from acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, One or more solvents among one or more solvents of methyl chloride, dichloroethane, chloroform, carbon tetrachloride, toluene, xylene and the like.
  • the reaction can be performed in the presence or absence of a basic reagent
  • the base may be selected from alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium or potassium hydroxide; alkali metal carbonates such as sodium bicarbonate, sodium carbonate or potassium carbonate; organic bases Class, such as pyridine, sodium methoxide, sodium ethoxide, potassium t-butoxide or sodium t-butoxide, 4-dimethylaminopyridine, triethylamine, N-methylpyrrole or diisopropylethylamine, etc .;
  • the reaction temperature can be between minus 20 degrees and the boiling point of the solvent, usually -20 to 150 ° C; the reaction time is 30 minutes to 24 hours, usually 1 to 10 hours.
  • the pesticide acceptable salt may be a salt prepared by reacting a substituted pyrazolyl pyrazole sulfonamide compound of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid may be an inorganic acid ( (Such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) or organic acids (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the acceptable salts of the pesticides can also be It is a salt prepared by reacting a substituted pyrazolyl pyrazole sulfonamide compound with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base (such as sodium hydroxide, potassium hydroxide, Calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or organic bases (such as trimethylamine, triethylamine, etc.).
  • the acceptable salt of the pesticide may be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridine salt, or a choline salt.
  • the present invention also discloses a herbicidal composition
  • a herbicidal composition comprising a herbicidally effective amount of at least one of the substituted pyrazolylpyrazolesulfonamide compounds as described above or an acceptable salt thereof as a pesticide.
  • a formulation carrier or a formulation auxiliary is also included.
  • the present invention also discloses a method for controlling unwanted plants, which comprises applying a herbicidally effective amount of at least one of the substituted pyrazolyl pyrazole sulfonamide compounds as described above or an acceptable salt thereof as a pesticide or The herbicidal composition as described above is used on unwanted plants.
  • the invention also discloses the use of the substituted pyrazolyl pyrazole sulfonamide compound as described above or at least one of the salts acceptable as pesticides or the herbicidal composition as described above for controlling harmful plants.
  • the compounds of formula I according to the invention have outstanding herbicidal activity.
  • the active substances of the invention are also effective against perennial weeds, which grow from rhizomes, rhizomes, or other perennial organs.
  • the use timing of the active substance of the present invention it may be before sowing, before germination or after germination.
  • weed species in which the active substance of the present invention can effectively include grass weeds: wild oats, brome, Festival wheat, watching Mai Niang, Japanese watching Mai Niang, yarrow, bluegrass, foxtail and so on.
  • broadleaf weeds the species whose effects can be extended to, for example, Artemisia sphaerocephala, Amaranth, Pomfret, Zeqi, Poona, Chenopodium, Firefly, Herba, Cyperus, etc.
  • the active substance of the present invention can still effectively control harmful plants, such as yarrow, firefly, quailgrass, sedge, etc. under the specific conditions of rice seeding.
  • the compound of the present invention is applied to the soil surface before germination, the seedlings of weeds can be completely prevented before weeds grow, or the weeds can stop growing when weeds develop cotyledons, and finally die completely after three to four weeks.
  • the compound of the present invention has excellent herbicidal activity against grass weeds and broadleaf weeds, it does not cause damage to important economic crop plants, such as rice, or the damage is minimal. Therefore, the compounds of the present invention are very suitable for selectively controlling unwanted plants in agricultural or ornamental plants.
  • the compounds of the present invention can significantly regulate the growth of crop plants. By regulating participation in plant metabolism, these compounds are used to orient the control of plant components and promote harvesting, such as drying and dwarfing plants. They are also suitable for regulating and inhibiting unwanted plant growth without disrupting crop growth.
  • the compounds of the present invention can be applied using general formulations, and wettable powders, soluble powders, emulsifiable concentrates, aqueous emulsions, suspensions, dispersible oil suspensions, powders, microcapsule suspensions, water-dispersible granules, water-soluble granules Agent.
  • the invention thus also provides a herbicide composition comprising a compound of formula I.
  • the compounds of formula I can be formulated in a variety of ways depending on the usual biological and / or chemical physical parameters.
  • Suitable formulation choices are: wettable powder (WP), wettable liquid (SL), soluble powder (SP), dispersible liquid (DC), aqueous (AS), microemulsion (ME), emulsifiable concentrate (EC), water emulsion (EW), sprayable solution, suspension (SC), dispersible oil suspension (OD), powder (DP), microcapsule suspension (CS), water dispersible granule (WG), water soluble Granules (SG), large granules (GG), granules (GR) for seeding and soil application, aerosols (AE), ultra-low-volume agents (ULV), and wax products.
  • Necessary formulation aids such as inert substances, surfactants, solvents and other additives.
  • suitable active substances that can be mixed with the active substance of the present invention are, for example, known substances in the "World Encyclopedia of New Pesticide Technology” (China Agricultural Science and Technology Press, 2010.9).
  • the herbicide actives mentioned below can be mixed with compounds of the formula I: acetochlor, butachlor, alachlor, isopropylchlor, mesochloramine, acetochlor, propachlor, Chlorpyramid, chlorpyramid, naproxyl, R-L-naphthoxyl, diazepam, fenpropifen, difenoxypyr, fenpyr, chlorfenapyr, fluorobutyryl Salachlor, Bromobutachlor, Metformamide, Metformamide, Acetochlor, Fluoxamid, Methiopyramide, Pomechlor, Clomazone, Efficient Straw Fluoromethyl methyl, triclopyr, dipropachlor, dimethachlor, butyramide,
  • the method for preparing the compounds of the present invention is illustrated in the following technical schemes and examples.
  • the starting materials can be purchased on the market or can be prepared by methods known in the literature or as shown in the detailed description.
  • Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention.
  • the specific raw materials and conditions in the synthetic route have been described below, they can be easily replaced with other similar raw materials and conditions, such as the compounds produced by the modification or variation of the preparation method of the present invention.
  • Various isomers and the like are included in the scope of the present invention.
  • the preparation method described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, and the like.
  • the compound was purified to obtain 3.99 g of the target compound as a milky white powder with a melting point of 127-129 ° C; 1 H-NMR (CDCl 3 -d 6 , 500MHz) ⁇ : 8.00-7.98 (m, 1H), 7.76-7.73 (m, 2H), 7.58-7.55 (m, 1H), 7.42-7.40 (m, 1H) , 4.00-3.98 (s, 3H), 3.84-3.82 (m, 2H), 2.74-2.73 (m, 2H), 2.13-2.11 (m, 2H), 188-1.86 (m, 2H) ppm.
  • Powder 20% by mass of the compound of the general formula (I) and 80% of kaolin are mixed uniformly and pulverized to obtain a product powder.
  • Wettable powder 20% by mass of the compound of the general formula (I), 8% of calcium ligninsulfonate, 2% of sodium lauryl sulfate, 3% of white carbon black, and kaolin are added to 100%. %. After mixing, the product is wettable powder after being pulverized by air flow.
  • Water-dispersible granules 60% by mass of the compound of the general formula (I), 6% of sodium ligninsulfonate, 4% of NNO (alkylnaphthalenesulfonate formaldehyde condensate), and 2% of BX (sodium dibutylnaphthalene sulfonate), 3% sodium lauryl sulfate, 5% carboxymethyl ethyl cellulose, 5% diatomaceous earth, 5% glucose, kaolin. %. Mix uniformly, pulverize by airflow, weigh the good powder, add water and mix, granulate in a granulator, then dry and sieve to obtain the product water dispersible granule.
  • test compound is dissolved in a small amount of acetone in the original medicine, and then diluted with water containing 0.1% Tween 80 to the required concentration.
  • Sprinkle a certain amount of weed seeds into a flowerpot press the seeds into the soil, and place them in a greenhouse to manage them according to conventional methods (the water layer is always kept at about 2cm). Set the dosage to 30g / ha.
  • the firefly grows to the 2-leaf stage
  • the elder plant grows to the 2-3 leaf stage
  • the sedge grows to the 2-3 leaf stage.
  • the application rate was 30 g / ha
  • the specific application amount of the flower pot was converted to the specific area of the flower pot, and two treatments were set for each treatment.) After the application, it was continued to be placed in the greenhouse to regularly observe the growth and development of the test material.
  • Level 4 equivalent to 5.1-10% of the weeds in the blank control area
  • Level 3 equivalent to 2.6-5% of weeds in the blank control area
  • Level 2 equivalent to 0-2.5% of weeds in the blank control area
  • the compounds protected by the present invention have excellent biological activity in paddy field weeds, and have very good effects on common weeds in paddy fields, especially against broad-leaved weeds common in paddy fields.
  • the biological activity has good commercial application prospects.
  • test compound is dissolved in a small amount of acetone in the original medicine, and then diluted with water containing 0.1% Tween 80 to the required concentration.
  • Quantitative rice seeds are sprinkled into flower pots, the seeds are pressed into the soil, placed in a greenhouse and managed according to conventional methods (the water layer is always maintained at about 2 cm). After sowing, the soil is sprayed through the Potter spray tower according to the experimental design dose.
  • Class a no phytotoxicity
  • Grade b the degree of phytotoxicity is 1-10%, without obvious phytotoxicity
  • the compounds protected by the present invention are basically no phytotoxicity or obvious phytotoxicity to the rice by visual inspection under the current dosage. Therefore, the compound has good safety at a suitable dosage.
  • the compounds of the present invention can be used as selective herbicides for paddy field broadleaf weeds.

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Abstract

Disclosed is a substituted pyrazolyl pyrazole sulfonamide compound or a pesticidally acceptable salt thereof, a composition, and a use thereof. The compound has a structure represented by formula (I). The definition of each group in the formula is given in the specification. The substituted pyrazolyl pyrazole sulfonamide compound has higher herbicidal activity than known compounds, and has excellent herbicidal activity against common weeds in rice paddy, especially broad-leaved weeds.

Description

一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐、组合物及其用途Substituted pyrazolyl pyrazole sulfonamide compound or its acceptable salt, composition and application as pesticide 技术领域Technical field
本发明属于农药技术领域，具体涉及一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐、组合物，并涉及这些化合物或其作为农药可接受的盐、组合物作为除草剂的用途。The present invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrazolylpyrazolesulfonamide compound or a salt and composition acceptable as a pesticide, and to these compounds or a salt and composition acceptable as a pesticide. The use of herbicides.
背景技术Background technique
已知取代的吡唑衍生物具有除草活性，在公开号为CN1087342A、CN1161956A及CN105492443A的专利中描述了相关的吡唑衍生物和其除草活性；在公开号为CN1073440A的专利中描述了一种吡唑基吡唑化合物的除草活性；而已知磺酰胺类除草剂具有很好的除草活性，例如在公开号为CN1073679A以及公开号为CN101485320A的专利中所描述的具有磺酰胺类结构的除草剂化合物。但是，这些化合物的活性可能不够高或者存在选择性问题；以及在现有技术中，并未具体公开在吡唑环的吡唑环上结合了取代基的吡唑磺酰胺类化合物。Substituted pyrazole derivatives are known to have herbicidal activity. Related pyrazole derivatives and their herbicidal activity are described in patents published as CN1087342A, CN1161956A, and CN105492443A; a pyridine is described in patent published as CN1073440A The azole-pyrazole compound has herbicidal activity; and sulfonamide-based herbicides are known to have good herbicidal activity, such as the herbicide compounds having a sulfonamide structure described in the patent publications CN1073679A and the publication number CN101485320A. However, the activity of these compounds may not be high enough or there is a problem of selectivity; and in the prior art, pyrazolesulfonamide compounds in which a substituent is bonded to the pyrazole ring of the pyrazole ring are not specifically disclosed.
技术问题technical problem
为解决现有技术中存在的上述问题，本发明提供了一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐、组合物及其用途。令人惊喜的是上述吡唑基吡唑磺酰胺类结构的化合物或其作为农药可接受的盐具有比已知化合物更高的除草活性尤其是针对水田常见杂草具有非常优异的除草活性。In order to solve the above problems in the prior art, the present invention provides a substituted pyrazolylpyrazolesulfonamide compound or an acceptable salt, composition, and use thereof as a pesticide. Surprisingly, the compounds of the above-mentioned pyrazolylpyrazolesulfonamide structure or their acceptable salts as pesticides have higher herbicidal activity than known compounds, and especially have very good herbicidal activity against common weeds in paddy fields.
技术解决方案Technical solutions
本发明为实现上述目的采用的技术方案是：一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其结构式如下：The technical solution adopted by the present invention to achieve the above objective is: a substituted pyrazolyl pyrazole sulfonamide compound or an acceptable salt thereof as a pesticide, and its structural formula is as follows:
式中，
Figure PCTCN2019089798-appb-000001
Where
Figure PCTCN2019089798-appb-000001
Y表示NH、CH 2、O、SO 2或S； Y represents NH, CH 2 , O, SO 2 or S;
R 1表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基； R 1 represents H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 1 -C 6 alkoxy Radical, halo C 1 -C 6 alkoxy;
R 2表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基； R 2 represents H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 1 -C 6 alkoxy Radical, halo C 1 -C 6 alkoxy;
或者，R 1和R 2一起形成基团-(CH 2) m-，m表示1-6； Alternatively, R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 1-6;
R 3表示H或者卤素； R 3 represents H or halogen;
R 4表示H、
Figure PCTCN2019089798-appb-000002
CN、卤素、NO 2、CONR 1R 2； R 4 represents H,
Figure PCTCN2019089798-appb-000002
CN, halogen, NO 2 , CONR 1 R 2 ;
R 5表示H或者卤素； R 5 represents H or halogen;
R 6表示C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基取代的C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 2-C 6烯氧基、C 2-C 6烯硫基，或者未取代的、或被1-5个独立选自卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、卤代C 1-C 6烷羰基、C 1-C 6烷基磺酰基、卤代C 1-C 6烷基磺酰基、C 1-C 6烷氧基羰基、卤代C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、卤代C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、卤代C 3-C 6环烷基、C 3-C 6环烷基氧基、C 3-C 6环烷基氧羰基、C 3-C 6环烷基胺羰基、C 3-C 6杂环基、C 3-C 6杂环基氧基、C 3-C 6杂环基氧羰基、C 3-C 6杂环基胺羰基、C 1-C 6烷基取代的C 3-C 6杂环基或C 1-C 6烷氧基取代的C 1-C 6烷氧基中的基团所取代的芳基、杂芳基、芳胺基、杂芳胺基、芳烷基、杂芳烷基、芳氧基、杂芳氧基或并环基； R 6 represents C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halo C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkenyl Thio, either unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy Alkyl, halo C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, halo C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl, halo C 1 -C 6 alkyl Sulfonyl, C 1 -C 6 alkoxycarbonyl, halo C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, halo C 1 -C 6 alkylaminocarbonyl, carboxyl, aldehyde Group, hydroxy, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, halo C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkane Alkoxy, C 3 -C 6 cycloalkyloxycarbonyl, C 3 -C 6 cycloalkylaminecarbonyl, C 3 -C 6 heterocyclyl, C 3 -C 6 heterocyclyloxy, C 3 -C a heterocyclic 6-yloxy Carbonyl, C 3 -C 6 heterocyclylamine carbonyl, C 1 -C 6 alkyl substituted C 3 -C 6 heterocyclyl or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy Aryl, heteroaryl, arylamino, heteroarylamino, aralkyl, heteroarylalkyl, aryloxy, heteroaryloxy, or cyclic ring groups substituted by
即R 6可以选自C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷硫基取代的C 1-C 6烷基、卤代C 1-C 6烷硫基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 2-C 6烯硫基、C 2-C 6烯氧基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 1-C 6烷氧基取代的C 1-C 6烷氧基中任一种基团，或者R 6可以选自未取代的芳基、杂芳基、芳胺基、杂芳胺基、芳烷基、杂芳烷基、芳氧基、杂芳氧基或并环基，或者R 6可以选自由1-5个取代基取代的芳基、杂芳基、芳胺基、杂芳胺基、芳烷基、杂芳烷基、芳氧基、杂芳氧基或并环基，前述取代基可自由地选自卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、卤代C 1-C 6烷羰基、C 1-C 6烷基磺酰基、卤代C 1-C 6烷基磺酰基、C 1-C 6烷氧基羰基、卤代C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、卤代C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、卤代C 3-C 6环烷基、C 3-C 6环烷基氧基、C 3-C 6环烷基氧羰基、C 3-C 6环烷基胺羰基、C 3-C 6杂环基、C 3-C 6杂环基氧基、C 3-C 6杂环基氧羰基、C 3-C 6杂环基胺羰基、C 1-C 6烷基取代的C 3-C 6杂环基或C 1-C 6烷氧基取代的C 1-C 6烷氧基中的基团。 That is, R 6 may be selected from C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl. , Halogenated C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 2 -C 6 alkenylthio, C 2 -C 6 alkenyloxy, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1- Any of C 6 alkoxy groups, or R 6 may be selected from unsubstituted aryl, heteroaryl, arylamino, heteroarylamino, aralkyl, heteroaralkyl, aryloxy, Heteroaryloxy or cyclic ring, or R 6 may be selected from aryl, heteroaryl, arylamino, heteroarylamino, aralkyl, heteroaralkyl, aryloxy substituted by 1-5 substituents Group, heteroaryloxy group or cyclic group, the aforementioned substituent may be freely selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, halo C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl, C 1 -C 6 alkoxycarbonyl, halo C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, halogenated C 1 -C 6 alkylaminocarbonyl, carboxyl, aldehyde, hydroxyl, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, halogenated C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkyloxycarbonyl, C 3 -C 6 cycloalkylamine carbonyl, C 3 -C 6 heterocyclyl, C 3 -C 6 heterocyclyloxy, C 3 -C 6 heterocyclyloxycarbonyl, C 3 -C 6 heterocyclylamine carbonyl, C 1 -C 6 alkyl substituted C 3 -C 6 heterocyclyl or a C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy group.
进一步地，式(I)中，R 1表示H、C 1-C 4烷基； Further, in formula (I), R 1 represents H, C 1 -C 4 alkyl;
R 2表示H、C 1-C 4烷基； R 2 represents H, C 1 -C 4 alkyl;
或者，R 1和R 2一起形成基团-(CH 2) m-，m表示2-4； Alternatively, R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 2-4;
R 3表示H或者卤素； R 3 represents H or halogen;
R 4表示H、CN、卤素、NO 2、COOR 1、CONR 1R 2； R 4 represents H, CN, halogen, NO 2 , COOR 1 , CONR 1 R 2 ;
R 5表示H或者卤素； R 5 represents H or halogen;
R 6表示C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷硫基取代的C 1-C 6烷基、卤代C 1-C 6烷硫基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 1-C 6烷氧基取代的C 1-C 6烷氧基，或者未取代的、或被1-5个独立选自卤素、硝基、氰基、C 1-C 6 烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、C 1-C 6烷基磺酰基、C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、C 3-C 6环烷基氧基、C 3-C 6环烷基氧羰基、C 3-C 6环烷基胺羰基、C 3-C 6杂环基、C 3-C 6杂环基氧基、C 3-C 6杂环基氧羰基或C 1-C 6烷基取代的C 3-C 6杂环基中的基团所取代的芳基或杂芳基。 R 6 represents C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl, halo C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, or unsubstituted or 1-5 independently selected from halogen , Nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, carboxyl, aldehyde, hydroxyl, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkyloxycarbonyl, C 3 -C 6 cycloalkylamine carbonyl , C 3 -C 6 heterocyclyl, C 3 -C 6 heterocyclyloxy, C 3 -C 6 heterocyclyloxycarbonyl or C 1 -C 6 alkyl substituted C 3 -C 6 heterocyclyl Is substituted by an aryl or heteroaryl group.
进一步地，式(I)中，R 1和R 2一起形成基团-(CH 2) m-，m表示1-4，Y表示NH、CH 2。 Further, in formula (I), R 1 and R 2 together form a group-(CH 2 ) m- , m represents 1-4, and Y represents NH and CH 2 .
进一步地，式(I)中，所述芳基为苯基、萘基，所述杂芳基为噻唑、呋喃、吡咯、噻吩、咪唑、吡喃、吡啶、吡唑、嘧啶、吲哚、嘌呤、嘧啶、吡嗪、哒嗪、三嗪、苯并噻唑、苯并呋喃、喹啉或噁唑。Further, in formula (I), the aryl group is phenyl and naphthyl, and the heteroaryl group is thiazole, furan, pyrrole, thiophene, imidazole, pyran, pyridine, pyrazole, pyrimidine, indole, purine , Pyrimidine, pyrazine, pyridazine, triazine, benzothiazole, benzofuran, quinoline, or oxazole.
进一步地，式(I)中，Y表示NH，Further, in formula (I), Y represents NH,
R 1和R 2一起形成基团-(CH 2) m-，m表示3或4； R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 3 or 4;
R 3表示H或者卤素； R 3 represents H or halogen;
R 4表示H、卤素、CONH 2或CN； R 4 represents H, halogen, CONH 2 or CN;
R 5表示H或者卤素； R 5 represents H or halogen;
R 6表示C 1-C 6烷基、卤代C 1-C 6烷基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基，未取代的或被1-5个独立选自卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、C 3-C 6杂环基中的基团取代的苯基、噻唑基、嘧啶基、吡啶基。 R 6 represents C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl Aminocarbonyl, carboxyl, aldehyde, hydroxyl, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocyclyl groups Group substituted phenyl, thiazolyl, pyrimidinyl, pyridyl.
进一步地，Y表示NH；Further, Y represents NH;
R 1和R 2一起形成基团-(CH 2) m-，m表示3或4； R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 3 or 4;
R 3表示H、氯或溴； R 3 represents H, chlorine or bromine;
R 4表示H、CN； R 4 represents H, CN;
R 5表示H； R 5 represents H;
R 6表示C 1-C 4烷基、C 3-C 6环烷基、C 3-C 6杂环烷基，或苯基、噻唑基、嘧啶基，或被1-3个独立选自卤素、硝基、氰基、C 1-C 4烷基、卤代C 1-C 4烷基、C 1-C 4烷羰基、C 1-C 4烷氧基羰基取代的苯基、噻唑基、嘧啶基。 R 6 represents C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, or phenyl, thiazolyl, pyrimidinyl, or is independently selected from halogen , Nitro, cyano, C 1 -C 4 alkyl, halo C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl substituted phenyl, thiazolyl, Pyrimidinyl.
进一步地，式(I)中，Y表示NH；Further, in formula (I), Y represents NH;
R 1和R 2一起形成基团-(CH 2) m-，m表示4； R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 4;
R 3表示氯或溴； R 3 represents chlorine or bromine;
R 4表示CN； R 4 represents CN;
R 5表示H； R 5 represents H;
R 6表示甲基、乙基、丙基、环丙烷基、环己烷基、哌啶基，或苯基、嘧啶基，或被1-3个独立选自氟、氯、溴、甲基、乙基、丙基、三氟甲基、三氯甲基、甲氧基羰基、乙酰基中的基团取代的苯基或被1-3个独立选自氟、氯、溴中的基团取代的嘧啶基。 R 6 represents methyl, ethyl, propyl, cyclopropanyl, cyclohexane, piperidinyl, or phenyl, pyrimidinyl, or is independently selected from fluorine, chlorine, bromine, methyl, 1-3, Ethyl, propyl, trifluoromethyl, trichloromethyl, methoxycarbonyl, acetyl substituted phenyl groups or 1-3 groups independently selected from fluorine, chlorine, bromine Of pyrimidinyl.
在上述化合物结构式的定义中，所使用的专业术语均具有如下含义：In the definitions of the above compound structural formulas, the professional terms used have the following meanings:
C 1-C 6烷基：碳原子数为1-6的直链或支链烷基，例如甲基、乙基、丙基、异丙基或叔丁基。 C 1 -C 6 alkyl: a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or tert-butyl.
卤或卤素：指氟、氯、溴、碘。Halogen or halogen: Refers to fluorine, chlorine, bromine, and iodine.
卤代C 1-C 6烷基：碳原子数为1-6的直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤素所取代，例如，氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基等。 Halo C 1 -C 6 alkyl: straight or branched alkyl groups having 1 to 6 carbon atoms. The hydrogen atoms on these alkyl groups may be partially or completely replaced by halogens. For example, chloromethyl, di Chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
C 1-C 6烷氧基：碳原子数为1-6的直链或支链烷基，经氧原子键连接到结构上。 C 1 -C 6 alkoxy: a linear or branched alkyl group having 1 to 6 carbon atoms, connected to the structure via an oxygen atom bond.
卤代C 1-C 6烷氧基：碳原子数为1-6的直链或支链烷氧基，在这些烷氧基上的氢原子可部分或全部被卤素所取代，例如，氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基等。 Halo C 1 -C 6 alkoxy: straight or branched chain alkoxy groups having 1 to 6 carbon atoms. The hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogens, for example, chloroform Oxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
C 1-C 6烷硫基：碳原子数为1-6的直链或支链烷基，经硫原子键连接到结构上。 C 1 -C 6 alkylthio: A straight or branched alkyl group having 1 to 6 carbon atoms, which is connected to the structure via a sulfur atom bond.
卤代C 1-C 6烷硫基：碳原子数为1-6的直链或支链烷硫基，在这些烷硫基上的氢原子可部分或全部被卤原子所取代，例如，氯甲硫基、二氯甲硫基、三氯甲硫基、氟甲硫基、二氟甲硫基、三氟甲硫基、氯氟甲硫基等。 Halo C 1 -C 6 alkylthio: Linear or branched alkylthio groups having 1 to 6 carbon atoms. The hydrogen atoms on these alkylthio groups may be partially or completely replaced by halogen atoms, for example, chlorine Methylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, and the like.
C 1-C 6烷氧基取代的C 1-C 6烷氧基：由碳原子数为1-6的烷氧基作为取代基对碳原子数为1-6的烷氧基进行取代的基团，如
Figure PCTCN2019089798-appb-000003
C 1 -C 6 alkoxy-substituted C 1 -C 6 alkoxy: a group in which an alkoxy group having 1 to 6 carbon atoms is substituted by an alkoxy group having 1 to 6 carbon atoms Mission, such as
Figure PCTCN2019089798-appb-000003
C 3-C 6杂环基胺羰基：由碳原子数为3-6的杂环基作为取代基对氨基进行取代得到的胺基与羰基连接形成的基团，如
Figure PCTCN2019089798-appb-000004
C 3 -C 6 heterocyclylamine carbonyl: a group formed by linking an amine group obtained by substituting an amino group with a heterocyclic group having 3 to 6 carbon atoms as a substituent, such as
Figure PCTCN2019089798-appb-000004
C 1-C 6烷羰基：由碳原子数为1-6的烷基与羰基连接形成的基团，如
Figure PCTCN2019089798-appb-000005
C 1 -C 6 alkylcarbonyl: A group formed by linking an alkyl group having 1 to 6 carbon atoms with a carbonyl group, such as
Figure PCTCN2019089798-appb-000005
C 1-C 6烷基磺酰基：由碳原子数为1-6的烷基与磺酰基连接形成的基团，如
Figure PCTCN2019089798-appb-000006
C 1 -C 6 alkylsulfonyl: A group formed by linking an alkyl group having 1 to 6 carbon atoms with a sulfonyl group, such as
Figure PCTCN2019089798-appb-000006
C 3-C 6环烷基氧羰基：由碳原子数为3-6的环烷基与氧原子、羰基依次连接形成的基团，如
Figure PCTCN2019089798-appb-000007
C 3 -C 6 cycloalkyloxycarbonyl group: A group formed by a cycloalkyl group having 3-6 carbon atoms, an oxygen atom, and a carbonyl group connected in sequence, such as
Figure PCTCN2019089798-appb-000007
芳基：任何从简单芳香环衍生出的官能团或取代基。Aryl: Any functional group or substituent derived from a simple aromatic ring.
杂芳基：含1个或多个N、O、S杂原子的五元环或六元环，例如吡啶、呋喃、噻吩、吡唑、嘧啶、吡嗪、哒嗪、三嗪、喹啉、噻唑、苯并噻唑、苯并呋喃等。Heteroaryl: a five- or six-membered ring containing one or more N, O, and S heteroatoms, such as pyridine, furan, thiophene, pyrazole, pyrimidine, pyrazine, pyridazine, triazine, quinoline, Thiazole, benzothiazole, benzofuran and the like.
芳胺基：芳基作为取代基对氨基进行取代得到的胺基。Arylamino group: An amine group obtained by substituting an amino group with an aryl group as a substituent.
杂芳烷基：杂芳基作为取代基对烷基的氢进行取代得到的烷基。Heteroaralkyl: An alkyl obtained by substituting a hydrogen of an alkyl group with a heteroaryl group as a substituent.
杂芳氧基：杂芳基与氧原子相连、经氧原子键连接到结构上。Heteroaryloxy: Heteroaryl is connected to an oxygen atom and is connected to the structure via an oxygen atom bond.
并环基：双环或者三环并在一起的基团，如
Figure PCTCN2019089798-appb-000008
Paracyclic group: a group in which a bicyclic or tricyclic ring is joined together, such as
Figure PCTCN2019089798-appb-000008
通式Ⅰ所述化合物的合成方法，其特征是将通式Ⅱ化合物与通式Ⅲ化合物(在下列列举的化学式中，只要未另外进行定义，取代基和符号与通式Ⅰ中定义的取代基和符号具有相同的意义)在有或无溶 剂的条件下进行反应后得到产物。通式Ⅱ所代表的化合物可参考专利CN200910092609.5所述的方法合成，通式Ⅲ所代表的化合物可参考专利CN96116762.9所述的方法合成：A method for synthesizing a compound described by the general formula I is characterized in that a compound of the general formula II and a compound of the general formula III (in the chemical formulae listed below, unless otherwise defined, the substituents and symbols are the same as those defined in the general formula I And symbol have the same meaning) The product is obtained after the reaction is performed with or without a solvent. The compound represented by general formula II can be synthesized by referring to the method described in patent CN200910092609.5, and the compound represented by general formula III can be synthesized by referring to the method described in patent CN96116762.9:
Figure PCTCN2019089798-appb-000009
Figure PCTCN2019089798-appb-000009
其中，溶剂选自乙腈、丙酮、丁酮、四氢呋喃、乙酸乙酯、N-甲基吡咯烷酮、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二甲亚砜、二氯甲烷、二氯乙烷、氯仿、四氯化碳、甲苯、二甲苯等其中的一种或多种溶剂中的一种或多种溶剂。Wherein, the solvent is selected from acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, One or more solvents among one or more solvents of methyl chloride, dichloroethane, chloroform, carbon tetrachloride, toluene, xylene and the like.
反应可以在有碱性试剂存在或无碱性试剂存在的情况下进行；The reaction can be performed in the presence or absence of a basic reagent;
所述的碱可以选自碱金属氢化物，如氢化钠；碱金属氢氧化物，如氢氧化钠或氢氧化钾；碱金属碳酸盐，如碳酸氢钠、碳酸钠或碳酸钾；有机碱类，如吡啶、甲醇钠、乙醇钠、叔丁醇钾或叔丁醇钠、4-二甲氨基吡啶、三乙胺、N-甲基吡咯或二异丙基乙基胺等；The base may be selected from alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium or potassium hydroxide; alkali metal carbonates such as sodium bicarbonate, sodium carbonate or potassium carbonate; organic bases Class, such as pyridine, sodium methoxide, sodium ethoxide, potassium t-butoxide or sodium t-butoxide, 4-dimethylaminopyridine, triethylamine, N-methylpyrrole or diisopropylethylamine, etc .;
反应温度可在零下20度至溶剂沸点温度之间，通常为-20～150℃；反应时间为30分钟至24小时，通常1～10小时。The reaction temperature can be between minus 20 degrees and the boiling point of the solvent, usually -20 to 150 ° C; the reaction time is 30 minutes to 24 hours, usually 1 to 10 hours.
所述的农药可接受的盐可以为本发明的取代的吡唑基吡唑磺酰胺类化合物与化学上可接受的酸进行反应制得的盐，其中化学上可接受的酸可以是无机酸(如盐酸、硫酸、磷酸或氢溴酸等)或有机酸(如草酸、马来酸、富马酸、苹果酸、酒石酸、柠檬酸或苯甲酸等)；所述的农药可接受的盐也可以为本发明的取代的吡唑基吡唑磺酰胺类化合物与化学上可接受的碱进行反应制得的盐，其中化学上可接受的碱可以是无机碱(如氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠或碳酸氢钾)或有机碱(如三甲胺、三乙胺等)。The pesticide acceptable salt may be a salt prepared by reacting a substituted pyrazolyl pyrazole sulfonamide compound of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid may be an inorganic acid ( (Such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) or organic acids (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the acceptable salts of the pesticides can also be It is a salt prepared by reacting a substituted pyrazolyl pyrazole sulfonamide compound with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base (such as sodium hydroxide, potassium hydroxide, Calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or organic bases (such as trimethylamine, triethylamine, etc.).
进一步地，所述的农药可接受的盐可以为钾盐、钠盐、铵盐、钙盐、吡啶盐或胆碱盐。Further, the acceptable salt of the pesticide may be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridine salt, or a choline salt.
本发明还公开了一种除草组合物，包括除草有效量的如上所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐中的至少一种。The present invention also discloses a herbicidal composition comprising a herbicidally effective amount of at least one of the substituted pyrazolylpyrazolesulfonamide compounds as described above or an acceptable salt thereof as a pesticide.
优选的，还包括制剂载体或制剂助剂。Preferably, a formulation carrier or a formulation auxiliary is also included.
本发明还公开了一种控制不想要的植物的方法，包括将除草有效量的如上所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐中的至少一种或如上所述的除草组合物使用在不想要的植物上。The present invention also discloses a method for controlling unwanted plants, which comprises applying a herbicidally effective amount of at least one of the substituted pyrazolyl pyrazole sulfonamide compounds as described above or an acceptable salt thereof as a pesticide or The herbicidal composition as described above is used on unwanted plants.
本发明还公开了如上所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐中的至少一种或如上所述的除草组合物在控制有害植物上的用途。The invention also discloses the use of the substituted pyrazolyl pyrazole sulfonamide compound as described above or at least one of the salts acceptable as pesticides or the herbicidal composition as described above for controlling harmful plants.
对于许多一年生的禾本科杂草、阔叶杂草，本发明的式I化合物具有突出的除草活性。本发明的活性物质也对于多年生杂草有效，这些杂草从根茎、根状茎、或其它的多年生的器官上生长出来。至于本发明的活性物质的使用时机，可以是在播种前、萌发前或萌发后。特别提及本发明化合物可以控制的 禾本科杂草、阔叶杂草的代表例，本发明的活性物质能起到有效作用的杂草物种代表例包括禾本科杂草：野燕麦、雀麦、节节麦、看麦娘、日本看麦娘、稗草、早熟禾、狗尾草等。关于阔叶杂草，其作用可以扩展到的物种例如播娘蒿、荠菜、猪殃殃、泽漆、婆婆纳、藜、萤蔺、鸭舌草、莎草等。本发明活性物质在水稻播种这种特定条件下依然能有效控制有害植物，例如稗草、萤蔺、鸭舌草、莎草等。如果将本发明化合物在萌芽前施用于土壤表面，可以在杂草长出前完全预防杂草的秧苗，或在杂草长出子叶时就停止生长，最后在三到四星期之后完全死亡。虽然本发明化合物对于禾本科杂草和阔叶杂草具有优良的除草活性，但对于重要的经济类作物植物，例如水稻等却没有损害，或者是损害非常微小。因此，本发明化合物非常适于有选择地控制在农用作物或观赏植物中的无用植物。另外本发明化合物可以明显调节作物植物的生长。通过调节参与植物代谢，使用这些化合物定向控制植物的组分和促进收获，例如使植物干化和矮化生长。而且它们也适于调节和抑制不希望的植物生长，而不破坏作物的生长。For many annual grasses, broadleaf weeds, the compounds of formula I according to the invention have outstanding herbicidal activity. The active substances of the invention are also effective against perennial weeds, which grow from rhizomes, rhizomes, or other perennial organs. As for the use timing of the active substance of the present invention, it may be before sowing, before germination or after germination. Special mention is made of representative examples of gramineous weeds and broad-leaved weeds that can be controlled by the compounds of the present invention. Representative examples of weed species in which the active substance of the present invention can effectively include grass weeds: wild oats, brome, Festival wheat, watching Mai Niang, Japanese watching Mai Niang, yarrow, bluegrass, foxtail and so on. Regarding broadleaf weeds, the species whose effects can be extended to, for example, Artemisia sphaerocephala, Amaranth, Pomfret, Zeqi, Poona, Chenopodium, Firefly, Herba, Cyperus, etc. The active substance of the present invention can still effectively control harmful plants, such as yarrow, firefly, quailgrass, sedge, etc. under the specific conditions of rice seeding. If the compound of the present invention is applied to the soil surface before germination, the seedlings of weeds can be completely prevented before weeds grow, or the weeds can stop growing when weeds develop cotyledons, and finally die completely after three to four weeks. Although the compound of the present invention has excellent herbicidal activity against grass weeds and broadleaf weeds, it does not cause damage to important economic crop plants, such as rice, or the damage is minimal. Therefore, the compounds of the present invention are very suitable for selectively controlling unwanted plants in agricultural or ornamental plants. In addition, the compounds of the present invention can significantly regulate the growth of crop plants. By regulating participation in plant metabolism, these compounds are used to orient the control of plant components and promote harvesting, such as drying and dwarfing plants. They are also suitable for regulating and inhibiting unwanted plant growth without disrupting crop growth.
可以使用一般的制剂来应用本发明的化合物，可使用可湿性粉剂、可溶性粉剂、乳油、水乳剂、悬浮剂、可分散油悬浮剂、粉剂、微囊悬浮剂、水分散粒剂、水溶性粒剂等。这样本发明也提供了包括式I化合物的除草剂组合物。根据通常的生物学和/或化学的物理参数，可以用多种方式配制式I化合物。适合的制剂选择实例为：可湿性粉剂(WP)、可湿性液剂(SL)、可溶性粉剂(SP)、可分散液剂(DC)、水剂(AS)、微乳剂(ME)、乳油(EC)、水乳剂(EW)、可喷洒溶液、悬浮剂(SC)、可分散油悬浮剂(OD)、粉剂(DP)、微囊悬浮剂(CS)、水分散粒剂(WG)、水溶性粒剂(SG)、大粒剂(GG)、用于撒播和土壤施药的颗粒剂(GR)、气雾剂(AE)、超低容量剂(ULV)和蜡制品。必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂。The compounds of the present invention can be applied using general formulations, and wettable powders, soluble powders, emulsifiable concentrates, aqueous emulsions, suspensions, dispersible oil suspensions, powders, microcapsule suspensions, water-dispersible granules, water-soluble granules Agent. The invention thus also provides a herbicide composition comprising a compound of formula I. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and / or chemical physical parameters. Examples of suitable formulation choices are: wettable powder (WP), wettable liquid (SL), soluble powder (SP), dispersible liquid (DC), aqueous (AS), microemulsion (ME), emulsifiable concentrate ( EC), water emulsion (EW), sprayable solution, suspension (SC), dispersible oil suspension (OD), powder (DP), microcapsule suspension (CS), water dispersible granule (WG), water soluble Granules (SG), large granules (GG), granules (GR) for seeding and soil application, aerosols (AE), ultra-low-volume agents (ULV), and wax products. Necessary formulation aids, such as inert substances, surfactants, solvents and other additives.
在混配制剂或桶混制剂中，可以和本发明的活性物质混合的合适的活性物质为，例如《世界农药新品种技术大全》(中国农业科学技术出版社，2010.9)中的已知物质。例如以下提到的除草剂活性物质可以和式I化合物混合：乙草胺、丁草胺、甲草胺、异丙草胺、异丙甲草胺、精异丙甲草胺、丙草胺、毒草胺、克草胺、萘丙酰草胺、R-左旋萘丙酰草胺、敌稗、苯噻酰草胺、双苯酰草胺、吡氟酰草胺、杀草胺、氟丁酰草胺、溴丁酰草胺、二甲噻草胺、高效二甲噻草胺、乙氧苯草胺、氟噻草胺、甲氧噻草胺、吡草胺、异噁草胺、高效麦草氟甲酯、高效麦草氟丙酯、二丙烯草胺、烯草胺、丁酰草胺、环丙草胺、氟磺酰草胺、庚酰草胺、异丁草胺、丙炔草胺、特丁草胺、二甲苯草胺、二甲草胺、落草胺、三甲环草胺、氯甲酰草胺、炔苯酰草胺、戊酰苯草胺、卡草胺、新燕灵、三环噻草胺、丁烯草胺、牧草胺、苄草胺、醌萍胺、苯氟磺胺、萘丙胺、乙酰甲草胺、萘草胺、噻草胺、吡氰草胺、苯草多克死、草克乐、氯酞亚胺、丁脒胺、氟吡草胺、莠去津、西玛津、扑草净、氰草净、西草净、莠灭净、扑灭津、异丙净、氟草净、特丁净、特丁津、三嗪氟草胺、环丙津、甘扑津、草达津、扑灭通、西玛通、叠氮净、敌草净、异戊乙净、灭莠津、另丁津、仲丁通、特丁通、甲氧丙净、氰草净、抑草津、可乐津、莠去通、灭草通、甘草津、三聚氰酸、Indaziflam、绿磺隆、甲磺隆、苄嘧磺隆、氯嘧磺隆、苯磺隆、噻磺隆、吡嘧磺隆、甲基二磺隆、甲基碘磺隆钠盐、甲酰氨基嘧磺隆、醚磺隆、醚苯磺隆、甲嘧磺隆、烟嘧磺隆、胺苯磺隆、酰嘧磺隆、乙氧嘧磺隆、环丙嘧磺隆、砜嘧磺隆、四唑嘧磺隆、啶嘧黄隆、单嘧磺隆、单嘧磺酯、氟唑磺隆、氟啶嘧磺隆、氟吡嘧磺隆、环氧嘧磺隆、唑吡嘧磺隆、氟嘧磺隆、丙苯磺隆、三氟丙磺隆、磺酰 磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、甲磺隆钠盐、氟吡磺隆、甲硫嘧磺隆、嘧苯胺磺隆、Propyrisulfuron(丙嗪嘧磺隆)、嗪吡嘧磺隆、三氟羧草醚、氟磺胺草醚、乳氟禾草灵、乙羧氟草醚、乙氧氟草醚、草枯醚、苯草醚、氯氟草醚乙酯、甲羧除草醚、三氟甲草醚、甲氧除草醚、三氟硝草醚、氟化除草醚、氟呋草醚、除草醚、甲草醚、二甲草醚、氟酯肟草醚、氟草醚酯、Halosafen、绿麦隆、异丙隆、利谷隆、敌草隆、莎扑隆、氟草隆、苯噻隆、甲基苯噻隆、苄草隆、磺噻隆、异噁隆、特丁噻草隆、炔草隆、氯溴隆、甲基杀草隆、酰草隆、甲氧杀草隆、溴谷隆、甲氧隆、绿谷隆、灭草隆、环草隆、非草隆、氟硫隆、草不隆、枯草隆、草完隆、异草完隆、环莠隆、噻氟隆、丁噻隆、枯莠隆、对氟隆、甲胺噻唑隆、隆草特、三甲异脲、噁唑隆、Monisouron、Anisuron、Methiuron、Chloreturon、四氟隆、甜菜宁、甜菜宁-乙酯、甜菜安、磺草灵、特草灵、燕麦灵、苯胺灵、氯苯胺灵、二氯苄草酯、灭草灵、氯炔灵、Carboxazole、Chlorprocarb、Fenasulam、BCPC、CPPC、Carbasulam、丁草特、禾草丹、灭草猛、禾草特、野麦畏、哌草丹、禾草畏、稗草丹、环草敌、燕麦敌、菌达灭、乙硫草特、坪草丹、克草猛、苄草丹、仲草丹、硫烯草丹、草灭散、Isopolinate、Methiobencarb、2,4-滴丁酯、2甲4氯钠、2,4-滴异辛酯、2甲4氯异辛酯、2,4-滴钠盐、2,4-滴二甲胺盐、2甲4氯乙硫酯、2甲4氯、2,4-滴丙酸、高2,4-滴丙酸盐、2,4-滴丁酸、2甲4氯丙酸、2甲4氯丙酸盐、2甲4氯丁酸、2,4,5-涕、2,4,5-涕丙酸、2,4,5-涕丁酸、2甲4氯胺盐、麦草畏、抑草蓬、伐草克、赛松、三氯苯酸、氨二氯苯酸、甲氧三氯苯酸、禾草灵、吡氟禾草灵、精吡氟禾草灵、氟吡甲禾灵、高效吡氟氯禾灵、喹禾灵、精喹禾灵、恶唑禾草灵、精恶唑禾草灵、喔草酯、氰氟草酯、恶唑酰草胺、炔草酯、噻唑禾草灵、炔禾灵、羟戊禾灵、三氟禾草肟、异恶草醚、百草枯、敌草快、安磺灵、乙丁烯氟灵、异丙乐灵、甲磺乐灵、环丙氟灵、氨基丙氟灵、乙丁氟灵、氯乙氟灵、氨基乙氟灵、地乐灵、氯乙地乐灵、Methalpropalin、丙硝酚、草甘膦、莎稗膦、草铵膦、甲基胺草磷、草硫膦、哌草膦、双丙氨膦、地散磷、抑草磷、蔓草磷、伐垅磷、双甲胺草磷、草特磷、咪唑烟酸、咪唑乙烟酸、咪唑喹啉酸、甲氧咪草烟、甲氧咪草烟铵盐、甲咪唑烟酸、咪草酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、二氯吡啶酸、氨氯吡啶酸、三氯吡氧乙酸、氟硫草定、卤草定、三氯吡啶酚、噻草啶、氟啶草酮、氯氨吡啶酸、氟吡草腙、三氯吡氧乙酸丁氧基乙酯、Cliodinate、烯禾啶、烯草酮、噻草酮、禾草灭、环苯草酮、丁苯草酮、肟草酮、吡喃草酮、Buthidazole、嗪草酮、环嗪酮、苯嗪草酮、乙嗪草酮、Ametridione、Amibuzin、溴苯腈、辛酰溴苯腈、辛酰碘苯腈、碘苯腈、敌草腈、二苯乙腈、双唑草腈、羟敌草腈、Iodobonil、唑嘧磺草胺、双氟磺草胺、五氟磺草胺、磺草唑胺、氯酯磺草胺、双氯磺草胺、啶磺草胺、呋草黄、双草醚、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚、双环磺草酮、硝磺草酮、磺草酮、Tembotrione、Tefuryltrione、Bicyclopyrone、Ketodpiradox、异噁唑草酮、异噁氯草酮、Fenoxasulfone、Methiozolin、异丙吡草酯、吡草醚、吡唑特、野燕枯、苄草唑、吡草酮、吡氯草胺、Pyrasulfotole、苯唑草酮、Pyroxasulfone、唑草胺、氟胺草唑、杀草强、胺唑草酮、唑啶草酮、氟唑草酮、甲磺草胺、Bencarbazone、双苯嘧草酮、氟丙嘧草酯、除草定、异草定、环草啶、特草定、Flupropacil、吲哚酮草酯、氟烯草酸、丙炔氟草胺、炔草胺、酞苄醚、Flumezin、五氯酚(钠)、地乐酚、特乐酚、特乐酯、戊硝酚、二硝酚、氯硝酚、地乐施、地乐特、丙炔噁草酮、噁草酮、环戊噁草酮、氟唑草胺、嗪草酸甲酯、四唑酰草胺、氟哒嗪草酯、杀草敏、溴莠敏、二甲达草伏、哒草醚、草 哒酮、草哒松、哒草伏、Pyridafol、二氯喹啉酸、氯甲喹啉酸、苯达松、哒草特、噁嗪草酮、草除灵、异噁草酮、环庚草醚、异丙酯草醚、丙酯草醚、茚草酮、氯酸钠、茅草枯、三氯醋酸、一氯醋酸、六氯丙酮、四氟丙酸、牧草快、溴酚肟、三唑磺、灭杀唑、呋草酮、乙呋草磺、嘧草胺、氯酞酸、氟咯草酮、稗草稀、丙烯醛、苯草灭、灭草环、燕麦酯、噻二唑草胺、棉胺宁、羟草酮、甲氧苯酮、苯嘧磺草胺、氯酰草膦、三氯丙酸、Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazonemethyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、甲硫磺乐灵、Cambendichlor、环丙嘧啶酸、硫氰苯胺、肟草安、双苯噁唑酸、二氯丙烯胺、氟氯吡啶酯、氯氟吡啶酯。In the compound formulation or tank mix formulation, suitable active substances that can be mixed with the active substance of the present invention are, for example, known substances in the "World Encyclopedia of New Pesticide Technology" (China Agricultural Science and Technology Press, 2010.9). For example, the herbicide actives mentioned below can be mixed with compounds of the formula I: acetochlor, butachlor, alachlor, isopropylchlor, mesochloramine, acetochlor, propachlor, Chlorpyramid, chlorpyramid, naproxyl, R-L-naphthoxyl, diazepam, fenpropifen, difenoxypyr, fenpyr, chlorfenapyr, fluorobutyryl Salachlor, Bromobutachlor, Metformamide, Metformamide, Acetochlor, Fluoxamid, Methiopyramide, Pomechlor, Clomazone, Efficient Straw Fluoromethyl methyl, triclopyr, dipropachlor, dimethachlor, butyramide, ciprofloxacin, flusulfuron, heptanosin, isobutachlor, propachlor, Terbutachlor, Xyloxamine, Dimethochlor, Paracetamol, Trimethoprim, Chloroform, Acetochlor, Valprofen, Carbamide, Xinyanling, Trimethoprim Ciclosamide, Butachlor, Herbachlor, Bentochlor, Quinachlor, Phenflusulfa, Naphthylamine, Metolachlor, Naptochlor, Thiachlor, Pyridoxamine, Bentochlor Die, grass clon, chlorophthalimide, Allanin, flufenacil, atrazine, simazine, profenazine, cyanuric acid, dicamba, fenpronil, chlorphene, isopropyl, fluroxypyr, terbutin, terbutin , Triazoxystromine, ciprofloxacin, ganprozine, cadazine, chlorphenantamine, ximatone, azide, diazepam, isoprene, fenprotin, fenprotin, chlorbutrazine , Terbutene, Metoprom, Ciclofenac, Inhibin, Colazin, Atrazine, Medicillone, Glycyrrhizin, Cyanuric Acid, Indaziflam, Chlorsulfuron, Metsulfuron, Bensulfuron , Chlorsulfuron-methyl, besulfuron-methyl, sulfsulfuron-methyl, sulfsulfuron-methyl, sulfsulfuron-methyl, sulfsulfuron-methyl, methiosulfuron-methyl, sodium sodium salt Imisulfuron, nicosulfuron, amisulfuron, sulfasulfuron, ethoxysulfuron, ciprosulfuron, sulfasulfuron, tetrazofuron, sulfasulfuron, monosulfuron , Monosulfuronate, fluazosulfuron, flusulfuron-methyl, flusulfuron-methyl, episulfuron-methyl, triazosulfuron-methyl, flusulfuron-methyl, trisulfiraf-methyl Sulphuron, sulfsulfuron, triflusulfuron, flusulfuron, triflusulfuron, Mesosulfuron sodium salt, Flumesulfuron, Methiosulfuron-methyl, Pyrisulfuron-methyl, Propysulfuron, Propylsulfuron-methyl, Pyrisulfuron-methyl, Triflubensulfuron-methyl, Triflufenacil-methyl Herbazone, acetofluoride, ethoxyfluorfen, chlorpyrrol, acetochlor, chloroflufenamate, methylcarboximid, triflufenachlor, methoxyfenacet, triflunitr Chlorfen, fluorinated fenoxyfen, flufenafen, fenoxafen, triclosyl, dimethyl oxafen, fenprofen, chlorfenuron, Halosafen, green wheat, isopropylon, liguron, Diuron, saponuron, fluoxauron, fenthionon, methylphenotholon, bensulfuron, sulfsulfuron, isoxuron, terbuturon, acetyluron, clobron, methyl Chlorfenuron, acylchlorsulfuron, methoxyfensulfuron, bromogluturon, methoxysulfuron, green glutensulfuron, chlorfenuron, cyclosulfuron, non-chlorsulfuron, flusulfuron, chlorprothuron, chlorosulfuron, grass Wanlong, Isotrione, Cyclofronon, Teflon, Butylthionon, Kupferon, Parafluon, Methathiazolone, Longuron, Trimethylisourea, Oxazolone, Monisouron, Anisuron, Methiuron, Chloreturon , Teflon, Betaine, Betanine-ethyl ester, betaan, sulfamethoxam, tricoxadin, oatrin, aniline, chloraniline, dicloxacil, chlorfenazine, carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC , Carbasulam, dicamba, chloracetin, dicamba, dicamba, dicamba, bivalir, chloraceta, dicamba, scopolamine, ringgrass enemies, oat enemies, chlorfendiben, ethalacet, Pingcao Dan, Ke Cao Meng, Benthocarb, Zhong Cao Dan, Thiamethazone, Grass Dispersal, Isopolinate, Methiobencarb, 2,4-Dibutyl Butyl, 2 Methyl Chlorochloride, 2,4-Diisooctyl Ester, 2 methyl 4 chloroisooctyl ester, 2, 4- drop sodium salt, 2, 4- drop dimethylamine salt, 2 methyl 4 chloroethyl thioester, 2 methyl 4 chloro, 2, 4- drop propionic acid, high 2,4-dipropionate, 2,4-dibutyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-chloropropionate, 2 methyl 4-chlorobutyric acid, 2,4,5-dipyridine, 2,4 , 5-Dipropanoic acid, 2,4,5-Dibutyric acid, 2 methyl 4-chloramine salt, dicamba, dicamba, valeric, cedar, trichlorobenzoic acid, aminodichlorobenzoic acid, formazan Oxytrichlorobenzoic acid, grass grass, pilofluazone, fine fluazone, flupirazone, high-efficiency fluafluzone, quinazone, fine quinazone, oxazole grass , Oxadiazine, oxadiazine, cyhalofop, oxadiazol, trimethoate, thiazolynazone, trimethoprim, trimethoprim, clomazone, clomazone Ether, Paraquat, Diquat, Disulfiram, Ebutenylfluoxin, Isoproline, Mesosulfurin, Ciprofloxacin, Amiprofloxacin, Ebutylfluoxin, Chlorethalin, Amino Eflufloxacin, diralin, chloroethalil, Methalpropalin, profenol, glyphosate, salinate, glufosinate, methylglyphosate, glufosinate, piperidin, dipropionin Diphosphine, chlorpyrifos, crocetin, valafos, bismethoxam, glufosinate, imazapyronate, imazapyronate, imidazolinac, azamethoxam, and azamethoxam , Memidazole nicotinic acid, imazamox, fenfluroxyacetic acid, isooctyl clofloxypyroxyacetic acid, dichloropyridic acid, ampicolinic acid, trichloropyroxyacetic acid, flufenadine, difluchlordime, Pyridoxine, Thiapyridine, Fluoxastrone, Chloramphenic Acid, Flufenazone, Trichloropyroxybutoxyethyl, Cliodinate, Diethylpyridine, Dimethyridone, Tetrapyridone, Gramine Chlorfenoxazone , Butazone, oxamethoxone, pyrazone, buthidazole, oxazolidin, cyclazinone, oxazolidin, acetazinone, Ametridione, Amibuzin, bromoxynil, caprylyl bromonitrile, octyl Acyl iodobenzonitrile, iodobenzonitrile, dipropionitrile, diphenylacetonitrile, dioxapyrazole, oxybipropenitrile, Iodobonil, saflufenacil, diflusulfuron, pentosulfur, sulfachlor Amine, mesotripylam, mesotrichlor, saflufenacil, furazol, bispyrifen, pyrimethazone, ciprofen, acetochlor, saflufenacil, dicyclohumidone , Mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxaflutole, clomazone, Fenoxasulfone, Methiozolin, imiproxacil, proxafen, pyrazol, wild swallow Ket, benpropazone, pramifen, mecloxacil, Pyrasulfotole, oxaflutole, Pyroxasulfone, oxaflutole, flufenacil, fenoxazone, amifluben, aflufenazone, flufenazone Keto, mesotrione, Bencarbazone, diflufenazone, flupronil, chlorfendipyr, wesotridin, cyprodin, tetridin, Flupropacil, indole Ketoprost, flufenoxal, propoxyflutosin, flufenoxamine, phthalbenzyl ether, Flumezin, pentachlorophenol (sodium), dinol, terrel, terrexate, pentanol, dinitrophenol , Clonoxyphen, dilaxate, dilotre, propynoxazone, oxadiazon, cyclopentazone, fluoxachlor, methyloxazine, tetrazolyl, fluoxapyron , Herbicidal, bromopyridine, dimethylpyridoxine, pyridazol, pyridone, chlorpyrazine, pyridoxine, Pyridafol, chloroquinolinic acid, chloroquinolinic acid, bentazon, pyrida Special, oxadiazon, herbicide, clomazone, cycloheptazone, isopropyl acetochlor, propyl acetochlor, indicazone, sodium chlorate, dicamba, trichloroacetic acid, monochloroacetic acid , Hexachloroacetone, tetrafluoropropionic acid, forage herb, bromophenol oxime, triazosulfon, metronidazole, furazone, acetofuran, saflufenacil, chlorophthalic acid, fluoxazone, humulone , Acrolein, chlorfenapyr, chlorfenapyr, oat esters, thiadiachlor, nisin, oxytridone, methoxyphenone, saflufenacil, chlorpyrifron, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazon e, Thiencarbazonemethyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methiosulfurin, Cambendichlor, Cypropyranic Acid, Thioaniline, Oxachlor, Dibenoxazate, Dichloropropenylamine, Fluchloropyridine, Chloroflurane Pyridyl ester.
有益效果Beneficial effect
综上所述，由于采用了上述技术方案，本发明的有益效果是：In summary, since the above technical solution is adopted, the beneficial effects of the present invention are:
通过对取代吡唑基吡唑化合物进行化学修饰和分子设计，引入了磺酰胺类结构，得到了一系列更加高效、具有更好的选择性和安全性的可用于农业或林业除草用的具有除草活性的化合物，针对水田常见杂草尤其是阔叶杂草具有很好的活性和选择性。Through chemical modification and molecular design of substituted pyrazolylpyrazole compounds, the introduction of sulfonamide structures has resulted in a series of herbicides with higher efficiency, better selectivity and safety, which can be used for agricultural or forestry weed control. Active compound with good activity and selectivity against common weeds in paddy fields, especially broad-leaved weeds.
本发明的实施方式Embodiments of the invention
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
通过对所合成的化合物的经济性、多样性以及生物活性进行综合考量，优选了部分化合物列于下表中。具体的化合物结构如表1所示、具体的化合物物性数据如表2所示。表1-2中的化合物只是为了更好的说明本发明，并不会对本发明产生限定，本领域的技术人员不应将此理解为本发明上述主题的范围仅限于以下化合物。By comprehensively considering the economics, diversity, and biological activity of the synthesized compounds, some of the compounds are preferably listed in the table below. The specific compound structure is shown in Table 1, and the specific compound physical property data is shown in Table 2. The compounds in Table 1-2 are only for better illustrating the present invention, and do not limit the present invention. Those skilled in the art should not understand that the scope of the above subject matter of the present invention is limited to the following compounds.
Figure PCTCN2019089798-appb-000010
Figure PCTCN2019089798-appb-000010
表1式I化合物结构Table 1 Structure of the compound of formula I
Figure PCTCN2019089798-appb-000011
Figure PCTCN2019089798-appb-000011
Figure PCTCN2019089798-appb-000012
Figure PCTCN2019089798-appb-000012
Figure PCTCN2019089798-appb-000013
Figure PCTCN2019089798-appb-000013
Figure PCTCN2019089798-appb-000014
Figure PCTCN2019089798-appb-000014
Figure PCTCN2019089798-appb-000015
Figure PCTCN2019089798-appb-000015
Figure PCTCN2019089798-appb-000016
Figure PCTCN2019089798-appb-000016
表2  1H NMR数据 Table 2 1 H NMR data
Figure PCTCN2019089798-appb-000017
Figure PCTCN2019089798-appb-000017
Figure PCTCN2019089798-appb-000018
Figure PCTCN2019089798-appb-000018
Figure PCTCN2019089798-appb-000019
Figure PCTCN2019089798-appb-000019
制备本发明化合物的方法在以下技术方案和实施例中进行了说明。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构体等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。The method for preparing the compounds of the present invention is illustrated in the following technical schemes and examples. The starting materials can be purchased on the market or can be prepared by methods known in the literature or as shown in the detailed description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described below, they can be easily replaced with other similar raw materials and conditions, such as the compounds produced by the modification or variation of the preparation method of the present invention. Various isomers and the like are included in the scope of the present invention. In addition, the preparation method described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, and the like.
实施例1Example 1
化合物1的合成：Synthesis of compound 1:
Figure PCTCN2019089798-appb-000020
Figure PCTCN2019089798-appb-000020
将中间体-1(1.51g，10mmol)、乙腈(30ml)加入到反应瓶内，0℃搅拌下加入中间体-2(1.41g，10.1mmol)，0℃下搅拌反应1h，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，再加入中间体Ⅲ-1(2.62g，10mmol)，加入NaH固体250mg，室温反应1h；旋出溶剂，柱层析提纯化合物，得到目标化合物4.45g，淡黄色粉末，熔点135-137℃。 1H-NMR(CDCl 3-d 6,500MHz)δ:7.97-7.95(m,1H),7.55-7.53(m,1H),7.46-7.44(s,1H),7.40-7.38(m,1H),7.24-7.22(m,1H),4.00-3.98(s,3H),3.84-3.82(m,2H),2.74-2.73(m,2H),2.13-2.11(m,2H),188-1.86(m,2H)ppm。 Intermediate-1 (1.51g, 10mmol) and acetonitrile (30ml) were added to the reaction flask. Intermediate-2 (1.41g, 10.1mmol) was added with stirring at 0 ° C, and the reaction was stirred for 1h at 0 ° C. The reaction was followed by TLC ( Ethyl acetate: petroleum ether = 1: 1, GF254, UV coloration), after the reaction is complete, intermediate III-1 (2.62 g, 10 mmol) is added, and 250 mg of NaH solid is added, and the reaction is performed at room temperature for 1 h; The compound was purified by chromatography to obtain 4.45 g of the target compound as a pale yellow powder with a melting point of 135-137 ° C. 1 H-NMR (CDCl 3 -d 6 , 500 MHz) δ: 7.97-7.95 (m, 1H), 7.55-7.53 (m, 1H), 7.46-7.44 (s, 1H), 7.40-7.38 (m, 1H) , 7.24-7.22 (m, 1H), 4.00-3.98 (s, 3H), 3.84-3.82 (m, 2H), 2.74-2.73 (m, 2H), 2.13-2.11 (m, 2H), 188-1.86 ( m, 2H) ppm.
实施例2Example 2
化合物2的合成：Synthesis of compound 2:
Figure PCTCN2019089798-appb-000021
Figure PCTCN2019089798-appb-000021
将中间体-3(1.52g，10mmol)、乙腈30ml加入到反应瓶内，0℃搅拌下加入中间体-2(1.41g，10.1mmol)，0℃下搅拌反应1h，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，再加入中间体Ⅲ-1(2.62g，10mmol)，加入NaH固体250mg，室温反应1h；旋出溶剂，柱层析提纯化合物，得到目标化合物3.99g，乳白色粉末，熔点127-129℃；。 1H-NMR(CDCl 3-d 6,500MHz)δ:8.00-7.98(m,1H),7.76-7.73(m,2H),7.58-7.55(m,1H),7.42-7.40(m,1H),4.00-3.98(s,3H),3.84-3.82(m,2H),2.74-2.73(m,2H),2.13-2.11(m,2H),188-1.86(m,2H)ppm。 Add Intermediate-3 (1.52g, 10mmol) and 30ml of acetonitrile to the reaction flask, add Intermediate-2 (1.41g, 10.1mmol) with stirring at 0 ° C, stir the reaction for 1h at 0 ° C, and follow the reaction with TLC (ethyl acetate Ester: petroleum ether = 1: 1, GF254, UV coloration), after the reaction is completed, intermediate III-1 (2.62 g, 10 mmol) is added, and 250 mg of NaH solid is added, and the reaction is performed at room temperature for 1 h; the solvent is removed, and column chromatography is performed. The compound was purified to obtain 3.99 g of the target compound as a milky white powder with a melting point of 127-129 ° C; 1 H-NMR (CDCl 3 -d 6 , 500MHz) δ: 8.00-7.98 (m, 1H), 7.76-7.73 (m, 2H), 7.58-7.55 (m, 1H), 7.42-7.40 (m, 1H) , 4.00-3.98 (s, 3H), 3.84-3.82 (m, 2H), 2.74-2.73 (m, 2H), 2.13-2.11 (m, 2H), 188-1.86 (m, 2H) ppm.
实施例3Example 3
化合物3的合成：Synthesis of compound 3:
Figure PCTCN2019089798-appb-000022
Figure PCTCN2019089798-appb-000022
将中间体Ⅲ-1(2.62g，10mmol)、乙腈30ml加入到反应瓶内，0℃搅拌下加入中间体Ⅱ-3(2.91g，10mmol)，加入NaH固体250mg，0℃下搅拌反应1h，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，旋出溶剂，柱层析提纯化合物，得到目标化合物4.13g，白色粉末，熔点129-131℃。 1H-NMR(CDCl 3-d 6,500MHz)δ:7.74-7.72(m,1H),7.55-7.53(s,1H),7.48-7.46(m,1H),7.39-7.36(m,2H)4.03-4.01(s,2H),3.94-3.92(s,3H),3.84-3.82(m,2H),2.74-2.73(m,2H),2.13-2.11(m,2H),188-1.86(m,2H)ppm。 Add intermediate III-1 (2.62 g, 10 mmol) and 30 ml of acetonitrile to the reaction flask, add intermediate II-3 (2.91 g, 10 mmol) with stirring at 0 ° C, add 250 mg of solid NaH, and stir the reaction at 0 ° C for 1 h. TLC followed the reaction (ethyl acetate: petroleum ether = 1: 1, GF254, UV color development). After the reaction was completed, the solvent was spun off, and the compound was purified by column chromatography to obtain 4.13 g of the target compound, a white powder, melting point 129-131 ° C. . 1 H-NMR (CDCl 3 -d 6 , 500 MHz) δ: 7.74-7.72 (m, 1H), 7.55-7.53 (s, 1H), 7.48-7.46 (m, 1H), 7.39-7.36 (m, 2H) 4.03-4.01 (s, 2H), 3.94-3.92 (s, 3H), 3.84-3.82 (m, 2H), 2.74-2.73 (m, 2H), 2.13-2.11 (m, 2H), 188-1.86 (m , 2H) ppm.
实施例4Example 4
化合物4的合成：Synthesis of compound 4:
Figure PCTCN2019089798-appb-000023
Figure PCTCN2019089798-appb-000023
将中间体-4(1.68g，10mmol)、乙腈30ml加入到反应瓶内，0℃搅拌下加入中间体-2(1.41g，10.1mmol)，0℃下搅拌反应1h，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，再加入中间体Ⅲ-1(2.62g，10mmol)，加入NaH固体250mg，室温反应1h；旋出溶剂，柱层析提纯化合物，得到目标化合物3.73g，黄色粉末，熔点137-139℃。 1H-NMR(CDCl 3-d 6,500MHz)δ:8.02-8.00(m,1H),7.63-7.60(m,2H),7.51-7.48(m,2H),4.00-3.98(s,3H),3.84-3.82(m,2H),2.74-2.73(m,2H),2.13-2.11(m,2H),188-1.86(m,2H)ppm。 Add Intermediate-4 (1.68g, 10mmol) and 30ml of acetonitrile to the reaction flask, add Intermediate-2 (1.41g, 10.1mmol) with stirring at 0 ° C, stir the reaction for 1h at 0 ° C, and follow the reaction with TLC (ethyl acetate Ester: petroleum ether = 1: 1, GF254, UV coloration), after the reaction is completed, intermediate III-1 (2.62 g, 10 mmol) is added, and 250 mg of NaH solid is added, and the reaction is performed at room temperature for 1 h; the solvent is removed, and column chromatography is performed. The compound was purified to obtain 3.73 g of the target compound as a yellow powder with a melting point of 137-139 ° C. 1 H-NMR (CDCl 3 -d 6 , 500MHz) δ: 8.02-8.00 (m, 1H), 7.63-7.60 (m, 2H), 7.51-7.48 (m, 2H), 4.00-3.98 (s, 3H) , 3.84-3.82 (m, 2H), 2.74-2.73 (m, 2H), 2.13-2.11 (m, 2H), 188-1.86 (m, 2H) ppm.
实施例5Example 5
化合物5的合成：Synthesis of compound 5:
Figure PCTCN2019089798-appb-000024
Figure PCTCN2019089798-appb-000024
向反应瓶内加入化合物1(5.18g，10mmol)、甲醇30ml，搅拌下加入氢氧化钠480mg(12mmol)，1ml H 2O，室温下搅拌反应2h，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，旋出溶剂，调PH＝4；柱层析提纯化合物，得到目标化合物4.63g，淡黄色粉末，熔点129-131℃。 1H-NMR(CDCl 3-d 6,500MHz)δ:7.927.90(m,1H),7.75-7.72(m,2H),7.53-7.52(s,1H),7.25-7.23(m,1H),3.84-3.82(m,2H),2.74-2.73(m,2H),2.13-2.11(m,2H),188-1.86(m,2H)ppm。 Add compound 1 (5.18 g, 10 mmol) and 30 ml of methanol to the reaction flask, add 480 mg (12 mmol) of sodium hydroxide and 1 ml of H 2 O under stirring, and stir the reaction for 2 h at room temperature. TLC followed the reaction (ethyl acetate: petroleum ether = 1: 1, GF254, UV color development), after the reaction is completed, the solvent is spun off and the pH is adjusted to 4; the compound is purified by column chromatography to obtain the target compound 4.63 g, pale yellow powder, melting point 129-131 ° C. 1 H-NMR (CDCl 3 -d 6 , 500MHz) δ: 7.927.90 (m, 1H), 7.75-7.72 (m, 2H), 7.53-7.52 (s, 1H), 7.25-7.23 (m, 1H) , 3.84-3.82 (m, 2H), 2.74-2.73 (m, 2H), 2.13-2.11 (m, 2H), 188-1.86 (m, 2H) ppm.
实施例6Example 6
化合物43的合成：Synthesis of compound 43:
Figure PCTCN2019089798-appb-000025
Figure PCTCN2019089798-appb-000025
将中间体-43(0.93g，10mmol)、乙腈30ml加入到反应瓶内，0℃搅拌下加入中间体-2(1.41g，10.1mmol)，0℃下搅拌反应1h，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，再加入中间体43-2(1.97g，10mmol)，加入NaH固体250mg，室温反应1h；旋出溶剂，柱层析提纯化合物，得到目标化合物3.03g，黄色粉末，熔点127-129℃。 1H-NMR(CDCl 3-d 6,500MHz)δ:7.40-7.38(d,1H),7.33-7.30(m,2H),7.25-7.23(m,2H),7.00-6.98(m,1H),6.83-6.81(s,1H),6.23-6.21(m,1H),3.94-3.92(s,3H)ppm。 Add Intermediate-43 (0.93g, 10mmol) and 30ml of acetonitrile to the reaction flask, add Intermediate-2 (1.41g, 10.1mmol) with stirring at 0 ° C, stir the reaction for 1h at 0 ° C, and follow the reaction with TLC (ethyl acetate Ester: petroleum ether = 1: 1, GF254, UV coloration), after the reaction is completed, intermediate 43-2 (1.97 g, 10 mmol) is added, 250 mg of solid NaH is added, and the reaction is performed at room temperature for 1 h; the solvent is removed, and column chromatography is performed. The compound was purified to obtain 3.03 g of the target compound as a yellow powder with a melting point of 127-129 ° C. 1 H-NMR (CDCl 3 -d 6 , 500MHz) δ: 7.40-7.38 (d, 1H), 7.33-7.30 (m, 2H), 7.25-7.23 (m, 2H), 7.00-6.98 (m, 1H) , 6.83-6.81 (s, 1H), 6.23-6.21 (m, 1H), 3.94-3.92 (s, 3H) ppm.
实施例7Example 7
制剂实施例Formulation examples
1.粉剂：称取质量百分比20％的通式(Ⅰ)化合物、80％的高岭土混合均匀，经粉碎而得到产品粉剂。1. Powder: 20% by mass of the compound of the general formula (I) and 80% of kaolin are mixed uniformly and pulverized to obtain a product powder.
2.可湿性粉剂：称取质量百分比20％的通式(Ⅰ)化合物、8％的木质素磺酸钙、2％的十二烷基硫酸钠、3％的白炭黑、高岭土加至100％。混合均匀，经气流粉碎后得到产品可湿性粉剂。2. Wettable powder: 20% by mass of the compound of the general formula (I), 8% of calcium ligninsulfonate, 2% of sodium lauryl sulfate, 3% of white carbon black, and kaolin are added to 100%. %. After mixing, the product is wettable powder after being pulverized by air flow.
3.水分散粒剂：称取质量百分比60％的通式(Ⅰ)化合物、6％的木质素磺酸钠、4％的NNO(烷基萘磺酸盐甲醛缩合物)、2％的拉开粉BX(二丁基萘磺酸钠)、3％的十二烷基硫酸钠、5％的羧甲基乙基纤维素、5％的硅藻土、5％的葡萄糖、高岭土加至100％。混合均匀，经气流粉碎后，称量好粉剂 加入水混合，在造粒机中进行造粒，然后干燥、筛分，即得到产品水分散粒剂。3. Water-dispersible granules: 60% by mass of the compound of the general formula (I), 6% of sodium ligninsulfonate, 4% of NNO (alkylnaphthalenesulfonate formaldehyde condensate), and 2% of BX (sodium dibutylnaphthalene sulfonate), 3% sodium lauryl sulfate, 5% carboxymethyl ethyl cellulose, 5% diatomaceous earth, 5% glucose, kaolin. %. Mix uniformly, pulverize by airflow, weigh the good powder, add water and mix, granulate in a granulator, then dry and sieve to obtain the product water dispersible granule.
4.乳油：称取质量百分比15％的通式(Ⅰ)化合物，5％的农乳700#、5％的农乳500#、6％的农乳1601#、10％的环已酮、3％的N-甲基吡咯烷酮、溶剂油150加至100％，经溶解完全并混合均匀，得到产品乳油。4. EC: Weigh 15% by mass of the compound of general formula (I), 5% agricultural milk 700 #, 5% agricultural milk 500 #, 6% agricultural milk 1601 #, 10% cyclohexanone, 3 N-methylpyrrolidone and solvent oil 150% to 100%, completely dissolved and mixed uniformly to obtain a product emulsifiable concentrate.
5.悬浮剂：5. Suspending agent:
称取质量百分比15％的通式(Ⅰ)化合物，4％的FS3000(磷酸酯型阴离子表面活性剂)、2％的NS-500LQ(非离子型羟基聚环氧乙烷嵌段共聚物)、0.2％的黄原胶、1％的硅酸镁铝、5％的乙二醇、0.1％的BIT(1,2-苯并异噻唑啉-3-酮)、0.3％的有机改性硅氧烷消泡剂，去离子水加至100％。制成浆料，进行砂磨，得到产品悬浮剂。Weigh 15% by mass of the compound of general formula (I), 4% of FS3000 (phosphate anionic surfactant), 2% of NS-500LQ (non-ionic hydroxypolyethylene oxide block copolymer), 0.2% xanthan gum, 1% magnesium aluminum silicate, 5% ethylene glycol, 0.1% BIT (1,2-benzoisothiazolin-3-one), 0.3% organically modified silicone Defoamer, add deionized water to 100%. The slurry is made and sanded to obtain the product suspension.
以上均为重量百分比。The above are all weight percentages.
实施例8Example 8
水田生物活性评价(苗后)：Evaluation of paddy field biological activity (post-emergence):
待测化合物原药用少量丙酮溶解，再用含有0.1％吐温80的水稀释至所需的浓度。准备水稻田专用土装至花盆3/4处的口径为11cm、底径为7cm、高11cm的塑料不透明花盆，每个花盆加入120mL的水，将土和水混合均匀并保持表面平整。将定量的杂草种子撒入花盆中，将种子压入土中，置于温室内按常规方法管理(水层始终保持为2cm左右)，设置用药量为30g/ha组，待稗草长至2-3叶期、萤蔺长至2叶期、鸭舌草长至2-3叶期、莎草长至2-3叶期时按实验设计剂量通过移液枪点滴施药(按照用药量为30g/ha进行施药，花盆具体施药量以花盆具体面积进行换算，每处理设两个重复)，施药后继续放置于温室内定期观察试材的生长发育情况，并根据实际情况，于处理后定期通过目测法调查供试药剂对杂草的防除效果及对作物的安全性；另设置用药量为60g/ha组，待稗草长至4叶期、萤蔺长至3-4叶期、鸭舌草长至4叶期、莎草长至4叶期时按实验设计剂量通过移液枪点滴施药(按照用药量为60g/ha进行施药，花盆具体施药量以花盆具体面积进行换算，每处理设两个重复)，施药后继续放置于温室内定期观察试材的生长发育情况，并根据实际情况，于处理后定期通过目测法调查供试药剂对杂草的防除效果及对作物的安全性。根据《NY/T1155.5-2006农药室内生物测定试验准则除草剂第5部分：水田除草剂土壤活性测定试验浇灌法》，依据测试靶标杂草的受害症状和严重程度，评价药剂的除草活性，采用统一级别进行调查：The test compound is dissolved in a small amount of acetone in the original medicine, and then diluted with water containing 0.1% Tween 80 to the required concentration. Prepare plastic opaque flower pots for rice fields to 3/4 of the flower pots with a diameter of 11 cm, a base diameter of 7 cm, and a height of 11 cm. Add 120 mL of water to each flower pot, mix the soil and water evenly and keep the surface flat. . Sprinkle a certain amount of weed seeds into a flowerpot, press the seeds into the soil, and place them in a greenhouse to manage them according to conventional methods (the water layer is always kept at about 2cm). Set the dosage to 30g / ha. In the 2-3 leaf stage, the firefly grows to the 2-leaf stage, the elder plant grows to the 2-3 leaf stage, and the sedge grows to the 2-3 leaf stage. The application rate was 30 g / ha, and the specific application amount of the flower pot was converted to the specific area of the flower pot, and two treatments were set for each treatment.) After the application, it was continued to be placed in the greenhouse to regularly observe the growth and development of the test material. Condition, after treatment, regularly inspect the test agent's control effect on weeds and the safety of crops by visual inspection; set a dosage of 60g / ha, and wait for the sedge to grow to the 4-leaf stage and the firefly to 3 -In the 4-leaf stage, the plant grows to the 4-leaf stage, and the sedge grows to the 4-leaf stage according to the experimental design dose by pipette gun application (apply according to the dosage of 60g / ha, and the specific application of the flower pot The amount is converted based on the specific area of the flowerpot, and two treatments are set for each treatment.) After the application, continue to place in the greenhouse to periodically observe the health of the test material. According to the actual situation, after the treatment, the effect of the test agent on the control of weeds and the safety of crops are regularly investigated by visual inspection after treatment. According to "NY / T1155.5-2006 Guidelines for Indoor Bioassay Tests of Pesticides, Herbicides, Part 5: Paddy Field Herbicides, Soil Activity Test, Test Watering Method", according to the damage symptoms and severity of the test target weeds, evaluate the herbicidal activity of the pesticide, Surveys using a uniform level:
效果分级标准：Effect grading standard:
9级：相当于空白对照区杂草的67.6-100％；Level 9: equivalent to 67.6-100% of the weeds in the blank control area;
8级：相当于空白对照区杂草的35.1-67.5％；Level 8: equivalent to 35.1-67.5% of the weeds in the blank control area;
7级：相当于空白对照区杂草的25.1-35％；Level 7: equivalent to 25.1-35% of the weeds in the blank control area;
6级：相当于空白对照区杂草的15.1-25％；Level 6: equivalent to 15.1-25% of the weeds in the blank control area;
5级：相当于空白对照区杂草的10.1-15％；Level 5: equivalent to 10.1-15% of the weeds in the blank control area;
4级：相当于空白对照区杂草的5.1-10％；Level 4: equivalent to 5.1-10% of the weeds in the blank control area;
3级：相当于空白对照区杂草的2.6-5％；Level 3: equivalent to 2.6-5% of weeds in the blank control area;
2级：相当于空白对照区杂草的0-2.5％；Level 2: equivalent to 0-2.5% of weeds in the blank control area;
1级：全部死亡。Level 1: All dead.
按照以上方法，选取部分化合物(化合物编号1-9、化合物16-18、化合物24-27、化合物30、化合物34、化合物36-37、化合物40、化合物56、化合物57)与双唑草腈、乙羧氟草醚进行了除草活性的平行测定。施药3周后的杂草防除活性如下表所示：According to the above method, select some compounds (compound numbers 1-9, compounds 16-18, compounds 24-27, compound 30, compound 34, compound 36-37, compound 40, compound 56, compound 57) and bisoxacillin, Paracetamol was tested in parallel for herbicidal activity. The weed control activity after 3 weeks of application is shown in the following table:
表3水田防效级别Table 3 Paddy field effectiveness levels
Figure PCTCN2019089798-appb-000026
Figure PCTCN2019089798-appb-000026
通过上述实验，可以发现本发明所保护的化合物具有极佳的水田杂草生物活性，对于水田内常见的杂草均有很好的效果，尤其是针对水田内常见的阔叶杂草具有极佳的生物活性，具备较好的商业应用前景。Through the above experiments, it can be found that the compounds protected by the present invention have excellent biological activity in paddy field weeds, and have very good effects on common weeds in paddy fields, especially against broad-leaved weeds common in paddy fields. The biological activity has good commercial application prospects.
实施例9Example 9
作物安全性评价：Crop safety evaluation:
待测化合物原药用少量丙酮溶解，再用含有0.1％吐温80的水稀释至所需的浓度。准备水稻田专用土装至花盆3/4处的口径为11cm、底径为7cm、高11cm的塑料不透明花盆，每个花盆加入120mL的水，将土和水混合均匀并保持表面平整。将定量的水稻种子撒入花盆中，将种子压入土中，置于温室内按常规方法管理(水层始终保持为2cm左右)，播种24h后按实验设计剂量通过Potter喷雾塔对土壤进行喷雾施药，施药后继续放置于温室内定期观察水稻的生长发育情况，并根据实际情况，于处理后定期通过目测法调查供试药剂对作物的安全性。根据《NY/T1155.5-2006农药室内生物测定试验准则除草剂第6部分：对作物的安全性试验土壤喷雾法》，并依据实际情况，于处理后定期通过目测法调查供试药剂对作物的影响，同时描述药害症状，主要症状有：The test compound is dissolved in a small amount of acetone in the original medicine, and then diluted with water containing 0.1% Tween 80 to the required concentration. Prepare plastic opaque flower pots for rice fields to 3/4 of the flower pots with a diameter of 11 cm, a base diameter of 7 cm, and a height of 11 cm. Add 120 mL of water to each flower pot, mix the soil and water evenly and keep the surface flat. . Quantitative rice seeds are sprinkled into flower pots, the seeds are pressed into the soil, placed in a greenhouse and managed according to conventional methods (the water layer is always maintained at about 2 cm). After sowing, the soil is sprayed through the Potter spray tower according to the experimental design dose. After applying the pesticide, continue to place it in a greenhouse to regularly observe the growth and development of the rice, and according to the actual situation, to regularly inspect the safety of the test agent to the crop by visual inspection after treatment. According to "NY / T1155.5-2006 Guidelines for Pesticide Indoor Bioassay Tests, Herbicides, Part 6: Safety Tests on Crops, Soil Spraying Method", and based on the actual situation, regularly inspect the test agents for crops by visual inspection after treatment. And describe the symptoms of drug damage. The main symptoms are:
1)颜色变化(黄化、白化、变紫等)；1) Color change (yellowing, whitening, purple, etc.);
2)形态变化(新叶畸形、扭曲等)；2) Morphological changes (new leaf deformities, distortions, etc.);
3)生长变化(脱水、枯萎、矮化、簇生等)。3) Growth changes (dehydration, wilting, dwarfing, clustering, etc.).
药害评价分级：Evaluation of drug damage:
a级：无药害；Class a: no phytotoxicity;
b级：药害程度为1-10％，无明显药害；Grade b: the degree of phytotoxicity is 1-10%, without obvious phytotoxicity;
c级：药害程度为11-30％，轻微药害；Grade c: 11-30% of phytotoxicity, slight phytotoxicity;
d级：药害程度为31-50％，中度药害；Grade d: 31-50% of phytotoxicity, moderate phytotoxicity;
e级：药害程度为51-100％，严重药害。Grade e: The degree of phytotoxicity is 51-100%, which is serious.
按照以上方法，选取部分化合物(化合物1、化合物6、化合物7、化合物8、化合物17、化合物24、化合物26、化合物28)与双唑草腈进行了作物安全性的平行测定。施药3周后的作物安全性实验效果如下表所示：According to the above method, some compounds (compound 1, compound 6, compound 7, compound 8, compound 17, compound 24, compound 26, compound 28) and bisoxacillin were selected for parallel determination of crop safety. The results of the crop safety experiment after 3 weeks of application are shown in the following table:
表4作物安全性试验Table 4 Crop safety tests
化合物编号Compound number 施药量(g ai/ha)Dosage (g / ai) 水稻Rice
11 6060 bb
66 6060 aa
77 6060 aa
88 6060 aa
1717 6060 aa
24twenty four 6060 aa
2626 6060 bb
2828 6060 aa
双唑草腈Oxadiazole 6060 cc
空白对照Blank 6060 aa
可见，在当前用药量下本发明所保护的化合物对于水稻经目测法观察基本为无药害或无明显药害，因此，在适合的剂量下对于水稻有很好的安全性。It can be seen that the compounds protected by the present invention are basically no phytotoxicity or obvious phytotoxicity to the rice by visual inspection under the current dosage. Therefore, the compound has good safety at a suitable dosage.
上述实施例只是为了说明本发明的技术构思及特点，其目的是在于让本领域内的普通技术人员能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡是根据本发明内容的实质所作出的等效的变化或修饰，都应涵盖在本发明的保护范围内。The above embodiments are only used to explain the technical concept and features of the present invention, and the purpose thereof is to enable a person of ordinary skill in the art to understand and implement the content of the present invention, and shall not limit the protection scope of the present invention. Any equivalent changes or modifications made according to the substance of the present invention should be covered by the protection scope of the present invention.
工业实用性Industrial applicability
本发明的化合物可以作为水田阔叶杂草选择性除草剂。The compounds of the present invention can be used as selective herbicides for paddy field broadleaf weeds.

Claims (10)

  1. 一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其结构式如下：A substituted pyrazolylpyrazolesulfonamide compound or an acceptable salt thereof as a pesticide has a structural formula as follows:
    式中，
    Figure PCTCN2019089798-appb-100001
    Where
    Figure PCTCN2019089798-appb-100001
    Y表示NH、CH 2、O、SO 2或S； Y represents NH, CH 2 , O, SO 2 or S;
    R 1表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基； R 1 represents H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 1 -C 6 alkoxy Radical, halo C 1 -C 6 alkoxy;
    R 2表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基； R 2 represents H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 1 -C 6 alkoxy Radical, halo C 1 -C 6 alkoxy;
    或者，R 1和R 2一起形成基团-(CH 2) m-，m表示1-6； Alternatively, R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 1-6;
    R 3表示H或者卤素； R 3 represents H or halogen;
    R 4表示H、
    Figure PCTCN2019089798-appb-100002
    CN、卤素、NO 2、CONR 1R 2；     R 4 represents H,
    Figure PCTCN2019089798-appb-100002
    CN, halogen, NO 2 , CONR 1 R 2 ;
    R 5表示H或者卤素； R 5 represents H or halogen;
    R 6表示C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基取代的C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 2-C 6烯氧基、C 2-C 6烯硫基，或者未取代的、或被1-5个独立选自卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、卤代C 1-C 6烷羰基、C 1-C 6烷基磺酰基、卤代C 1-C 6烷基磺酰基、C 1-C 6烷氧基羰基、卤代C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、卤代C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、卤代C 3-C 6环烷基、C 3-C 6环烷基氧基、C 3-C 6环烷基氧羰基、C 3-C 6环烷基胺羰基、C 3-C 6杂环基、C 3-C 6杂环基氧基、C 3-C 6杂环基氧羰基、C 3-C 6杂环基胺羰基、C 1-C 6烷基取代的C 3-C 6杂环基或C 1-C 6烷氧基取代的C 1-C 6烷氧基中的基团所取代的芳基、杂芳基、芳胺基、杂芳胺基、芳烷基、杂芳烷基、芳氧基、杂芳氧基或并环基。 R 6 represents C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, halo C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halo C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkenyl Thio, either unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy Alkyl, halo C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, halo C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl, halo C 1 -C 6 alkyl Sulfonyl, C 1 -C 6 alkoxycarbonyl, halo C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, halo C 1 -C 6 alkylaminocarbonyl, carboxyl, aldehyde Group, hydroxy, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, halo C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkane Alkoxy, C 3 -C 6 cycloalkyloxycarbonyl, C 3 -C 6 cycloalkylaminecarbonyl, C 3 -C 6 heterocyclyl, C 3 -C 6 heterocyclyloxy, C 3 -C a heterocyclic 6-yloxy Carbonyl, C 3 -C 6 heterocyclylamine carbonyl, C 1 -C 6 alkyl substituted C 3 -C 6 heterocyclyl or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy Aryl, heteroaryl, arylamino, heteroarylamino, aralkyl, heteroarylalkyl, aryloxy, heteroaryloxy, or cyclic ring substituted by a group of.
  2. 如权利要求1所述的一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其特征在于，式(I)中，R 1表示H、C 1-C 4烷基； The substituted pyrazolylpyrazolesulfonamide compound or an acceptable salt thereof as claimed in claim 1, wherein in the formula (I), R 1 represents H, C 1 -C 4 alkane base;
    R 2表示H、C 1-C 4烷基； R 2 represents H, C 1 -C 4 alkyl;
    或者，R 1和R 2一起形成基团-(CH 2) m-，m表示2-4； Alternatively, R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 2-4;
    R 3表示H或者卤素； R 3 represents H or halogen;
    R 4表示H、CN、卤素、NO 2、COOR 1、CONR 1R 2； R 4 represents H, CN, halogen, NO 2 , COOR 1 , CONR 1 R 2 ;
    R 5表示H或者卤素； R 5 represents H or halogen;
    R 6表示C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷硫基取代的C 1-C 6烷基、卤代C 1-C 6烷硫基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 1-C 6烷氧基取代的C 1-C 6烷氧基，或者未取代的、或被1-5个独立选自卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、C 1-C 6烷基磺酰基、C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、C 3-C 6环烷基氧基、C 3-C 6环烷基氧羰基、C 3-C 6环烷基胺羰基、C 3-C 6杂环基、C 3-C 6杂环基氧基、C 3-C 6杂环基氧羰基或C 1-C 6烷基取代的C 3-C 6杂环基中的基团所取代的芳基或杂芳基。 R 6 represents C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylthio substituted C 1 -C 6 alkyl, halo C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy or C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, or unsubstituted or 1-5 independently selected from halogen , Nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, carboxyl, aldehyde, hydroxyl, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkyloxycarbonyl, C 3 -C 6 cycloalkylamine carbonyl , C 3 -C 6 heterocyclyl, C 3 -C 6 heterocyclyloxy, C 3 -C 6 heterocyclyloxycarbonyl or C 1 -C 6 alkyl substituted C 3 -C 6 heterocyclyl Is substituted by an aryl or heteroaryl group.
  3. 如权利要求1所述的一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其特征在于，式(I)中，R 1和R 2一起形成基团-(CH 2) m-，m表示1-4，Y表示NH、CH 2。 The substituted pyrazolyl pyrazole sulfonamide compound or an acceptable salt thereof as claimed in claim 1, wherein, in formula (I), R 1 and R 2 together form a group-( CH 2 ) m- , m represents 1-4, and Y represents NH and CH 2 .
  4. 如权利要求1-3中任一项所述的一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其特征在于，式(I)中，所述芳基为苯基、萘基，所述杂芳基为噻唑、呋喃、吡咯、噻吩、咪唑、吡喃、吡啶、吡唑、嘧啶、吲哚、嘌呤、嘧啶、吡嗪、哒嗪、三嗪、苯并噻唑、苯并呋喃、喹啉或噁唑。The substituted pyrazolyl pyrazole sulfonamide compound or a salt acceptable as a pesticide according to any one of claims 1-3, wherein in the formula (I), the aryl group is Phenyl and naphthyl, the heteroaryl is thiazole, furan, pyrrole, thiophene, imidazole, pyran, pyridine, pyrazole, pyrimidine, indole, purine, pyrimidine, pyrazine, pyridazine, triazine, benzo Thiazole, benzofuran, quinoline or oxazole.
  5. 如权利要求4所述的一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其特征在于，式(I)中，Y表示NH，A substituted pyrazolylpyrazolesulfonamide compound or a salt acceptable as a pesticide according to claim 4, wherein Y in formula (I) represents NH,
    R 1和R 2一起形成基团-(CH 2) m-，m表示3或4； R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 3 or 4;
    R 3表示H或者卤素； R 3 represents H or halogen;
    R 4表示H、卤素、CONH 2或CN； R 4 represents H, halogen, CONH 2 or CN;
    R 5表示H或者卤素； R 5 represents H or halogen;
    R 6表示C 1-C 6烷基、卤代C 1-C 6烷基、C 3-C 6环烷基、C 3-C 6杂环烷基、C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基，未取代的或被1-5个独立选自卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷羰基、C 1-C 6烷氧基羰基、C 1-C 6烷胺基羰基、羧基、醛基、羟基、C 1-C 6烷氧基取代的C 1-C 6烷氧基、C 3-C 6环烷基、C 3-C 6杂环基中的基团取代的苯基、噻唑基、嘧啶基、吡啶基。 R 6 represents C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl Aminocarbonyl, carboxyl, aldehyde, hydroxyl, C 1 -C 6 alkoxy substituted C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocyclyl groups Group substituted phenyl, thiazolyl, pyrimidinyl, pyridyl.
  6. 如权利要求5所述的一种取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其特征在于，Y表示NH；A substituted pyrazolylpyrazolesulfonamide compound or a salt acceptable as a pesticide according to claim 5, wherein Y represents NH;
    R 1和R 2一起形成基团-(CH 2) m-，m表示3或4； R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 3 or 4;
    R 3表示H、氯或溴； R 3 represents H, chlorine or bromine;
    R 4表示H、CN； R 4 represents H, CN;
    R 5表示H； R 5 represents H;
    R 6表示C 1-C 4烷基、C 3-C 6环烷基、C 3-C 6杂环烷基，或苯基、噻唑基、嘧啶基，或被1-3个独立选自卤素、硝基、氰基、C 1-C 4烷基、卤代C 1-C 4烷基、C 1-C 4烷羰基、C 1-C 4烷氧基羰基取代的苯基、噻唑基、嘧啶基。 R 6 represents C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocycloalkyl, or phenyl, thiazolyl, pyrimidinyl, or is independently selected from halogen , Nitro, cyano, C 1 -C 4 alkyl, halo C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl substituted phenyl, thiazolyl, Pyrimidinyl.
  7. 如权利要求6所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐，其特征在 于，式(I)中，Y表示NH；The substituted pyrazolylpyrazolesulfonamide compound or a salt acceptable as a pesticide according to claim 6, characterized in that in the formula (I), Y represents NH;
    R 1和R 2一起形成基团-(CH 2) m-，m表示4； R 1 and R 2 together form a group-(CH 2 ) m- , where m represents 4;
    R 3表示氯或溴； R 3 represents chlorine or bromine;
    R 4表示CN； R 4 represents CN;
    R 5表示H； R 5 represents H;
    R 6表示甲基、乙基、丙基、环丙烷基、环己烷基、哌啶基，或苯基、嘧啶基，或被1-3个独立选自氟、氯、溴、甲基、乙基、丙基、三氟甲基、三氯甲基、甲氧基羰基、乙酰基中的基团取代的苯基或被1-3个独立选自氟、氯、溴中的基团取代的嘧啶基。 R 6 represents methyl, ethyl, propyl, cyclopropanyl, cyclohexane, piperidinyl, or phenyl, pyrimidinyl, or is independently selected from fluorine, chlorine, bromine, methyl, 1-3, Ethyl, propyl, trifluoromethyl, trichloromethyl, methoxycarbonyl, acetyl substituted phenyl groups or 1-3 groups independently selected from fluorine, chlorine, bromine Of pyrimidinyl.
  8. 一种除草组合物，其特征在于，包括除草有效量的权利要求1-7任意一项所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐中的至少一种；优选的，还包括制剂载体或制剂助剂。A herbicidal composition, comprising at least one of a substituted pyrazolylpyrazolesulfonamide compound according to any one of claims 1 to 7 or a pesticide-acceptable salt thereof in a herbicidally effective amount ; Preferably, a formulation carrier or a formulation auxiliary is also included.
  9. 一种控制不想要的植物的方法，其特征在于，包括将除草有效量的权利要求1-7任一项所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐中的至少一种或如权利要求8所述的除草组合物使用在不想要的植物上。A method for controlling unwanted plants, characterized by comprising a herbicidally effective amount of the substituted pyrazolylpyrazolesulfonamide compound according to any one of claims 1 to 7 or an acceptable salt thereof as a pesticide At least one of them or the herbicidal composition according to claim 8 is used on unwanted plants.
  10. 如权利要求1-7任一项所述的取代的吡唑基吡唑磺酰胺类化合物或其作为农药可接受的盐中的至少一种或如权利要求8所述的除草组合物在控制有害植物上的用途。The substituted pyrazolyl pyrazole sulfonamide compound according to any one of claims 1 to 7 or at least one of the salts acceptable as pesticides or the herbicidal composition according to claim 8 is harmful to control Uses on plants.
PCT/CN2019/089798 2018-06-04 2019-06-03 Substituted pyrazolyl pyrazole sulfonamide compound or pesticidally acceptable salt thereof, composition and use thereof WO2019233372A1 (en)

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GB2110689A (en) * 1981-12-03 1983-06-22 Sandoz Ltd Herbicidal heterocyclic aminosulfonyl ureas and isoureas
WO1991013884A2 (en) * 1990-03-06 1991-09-19 Nissan Chemical Industries Ltd. Sulfamidosulfonamide derivatives and herbicides
CN1073440A (en) * 1991-11-13 1993-06-23 先灵公司 The pyrazolyl-pyrazole of new replacement, its preparation method, and their intermediate and they are as the purposes of weedicide
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CN1195339A (en) * 1995-09-04 1998-10-07 拜尔公司 4-thiocarbamoyl-1-(3-pyrazolyl)-pyrazoles and their use as herbicides
CN1227546A (en) * 1996-08-08 1999-09-01 拜尔公司 Substituted 1-(3-pyrazolyl)-pyrazoles with herbicide activity and intermediate for its preparation
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* Cited by examiner, † Cited by third party
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GB2110689A (en) * 1981-12-03 1983-06-22 Sandoz Ltd Herbicidal heterocyclic aminosulfonyl ureas and isoureas
WO1991013884A2 (en) * 1990-03-06 1991-09-19 Nissan Chemical Industries Ltd. Sulfamidosulfonamide derivatives and herbicides
CN1073440A (en) * 1991-11-13 1993-06-23 先灵公司 The pyrazolyl-pyrazole of new replacement, its preparation method, and their intermediate and they are as the purposes of weedicide
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