WO2020200290A1 - Composé méta-diamide et son utilisation - Google Patents

Composé méta-diamide et son utilisation Download PDF

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Publication number
WO2020200290A1
WO2020200290A1 PCT/CN2020/083032 CN2020083032W WO2020200290A1 WO 2020200290 A1 WO2020200290 A1 WO 2020200290A1 CN 2020083032 W CN2020083032 W CN 2020083032W WO 2020200290 A1 WO2020200290 A1 WO 2020200290A1
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hydrogen
fluorine
compound
cyano
trifluoromethyl
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PCT/CN2020/083032
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English (en)
Chinese (zh)
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张立新
张静
汪杰
康卓
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沈阳化工大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/25—Aminoacetonitriles
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton

Definitions

  • the invention belongs to the field of agricultural pesticides, and specifically relates to a novel meta-diamide compound and its application.
  • Patent CN102112437A discloses compounds CK1 (Compound No. 5-45) and CK2 (Compound No. 5-108), which have insecticidal activity.
  • Patent WO2018194144A1 discloses compounds CK3 (Compound No.: 61) and CK4 (Compound No.: 64), which have insecticidal activity.
  • Patent CN102119143A discloses compounds CK5 (compound number: 7-1104), CK6 (compound number: 7-1107), CK7 (compound number: 7-1574), CK8 (compound number: 7-1577), CK9 (compound number: 7-1595), CK10 (Compound No. 7-1730) and disclose the insecticidal activity of these compounds.
  • CK7 has been commercialized and its English name is Broflanilide.
  • the purpose of the present invention is to provide a novel structure of meta-diamide compound to solve the technical problem that the prior art compound has poor insecticidal effect or insufficient quick effect at a lower dosage.
  • the compounds of the present invention can be used to prepare medicines for controlling pests in agriculture and other fields.
  • a meta-diamide compound as shown in general formula I:
  • R 1 and R 2 are each independently selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyano C 1 -C 6 alkyl, but not from cyanomethyl
  • X 1 is selected from halogen, cyano or C 1 -C 6 alkoxy
  • X 2 , X 3 , and X 4 are each independently selected from hydrogen, halogen, cyano or C 1 -C 6 alkoxy.
  • R 1 and R 2 are each independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyano C 1 -C 4 alkyl, but not from cyanomethyl
  • X 1 is selected from fluorine or methoxy
  • X 2 , X 3 , and X 4 are each independently selected from hydrogen, fluorine or cyano.
  • a further preferred compound in the present invention is: in general formula I,
  • R 1 and R 2 are each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyano C 1 -C 4 alkyl, but not from cyanomethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are each independently selected from hydrogen or fluorine.
  • a further preferred compound in the present invention is: in general formula I,
  • R 1 is selected from halogen
  • R 2 is selected from halogen, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CH 2 CN, -CH(CH 3 )CN, -CH(CH 2 CH 3 )CN,- CH(CH 2 CH 2 CH 3 )CN, -C(CH 3 )(CH 3 )CN or -C(CH 3 )(CH 2 CH 3 )CN;
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • a further preferred compound in the present invention is: in general formula I,
  • R 1 is selected from fluorine, chlorine, bromine or iodine
  • R 2 is selected from fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN;
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • a further preferred compound in the present invention is: in general formula I,
  • R 1 is selected from fluorine, chlorine, bromine or iodine
  • R 2 is selected from fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN;
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • R 1 is selected from bromine
  • R 2 is selected from bromine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from iodine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl Group
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from iodine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl Group
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from bromine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from iodine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl.
  • Fluoromethyl X 1 is selected from fluorine, X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from iodine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoromethyl.
  • Fluoromethyl X 1 is selected from fluorine, X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from bromine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoro Methyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from iodine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano or trifluoro Methyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen
  • R 1 is selected from bromine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano Or trifluoromethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from iodine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CH 2 CH 2 CN
  • R 5 is selected from hydrogen, fluorine, cyano Or trifluoromethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • the present invention also includes an intermediate compound that can be used to prepare compounds of general formula I, as shown in general formula II:
  • R 1 and R 2 are each independently selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyano C 1 -C 6 alkyl, but not from cyanomethyl
  • X 1 is selected from halogen, cyano or C 1 -C 6 alkoxy
  • X 2 , X 3 , and X 4 are each independently selected from hydrogen, halogen, cyano or C 1 -C 6 alkoxy.
  • the more preferred compound in the present invention is: in general formula II
  • R 1 and R 2 are each independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyano C 1 -C 4 alkyl, but not from cyanomethyl
  • X 1 is selected from fluorine or methoxy
  • X 2 , X 3 , and X 4 are each independently selected from hydrogen, fluorine or cyano.
  • R 1 and R 2 are each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyano C 1 -C 4 alkyl, but not from cyanomethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are each independently selected from hydrogen or fluorine.
  • a further preferred compound in the present invention is: in general formula II
  • R 1 is selected from halogen
  • R 2 is selected from halogen, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CH 2 CN, -CH(CH 3 )CN, -CH(CH 2 CH 3 )CN,- CH(CH 2 CH 2 CH 3 )CN, -C(CH 3 )(CH 3 )CN or -C(CH 3 )(CH 2 CH 3 )CN;
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • a further preferred compound in the present invention is: in general formula II
  • R 1 is selected from fluorine, chlorine, bromine or iodine
  • R 2 is selected from fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN;
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • R 1 is selected from bromine
  • R 2 is selected from bromine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from iodine
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from iodine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from heptafluoroisopropyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or
  • R 1 is selected from bromine
  • R 2 is selected from bromine
  • R 3 is selected from nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from iodine
  • R 3 is selected from nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from bromine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen; or,
  • R 1 is selected from iodine
  • R 2 is selected from trifluoromethyl
  • R 3 is selected from nonafluoro-2-butyl
  • R 4 is selected from -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN or -CH 2 CH 2 CH 2 CH 2 CN
  • X 1 is selected from fluorine
  • X 2 , X 3 , and X 4 are selected from hydrogen.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl straight or branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers.
  • Halogenated alkyl groups straight or branched chain alkyl groups, the hydrogen atoms on these alkyl groups can be partially or completely replaced by halogen, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl Group, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl Nonafluoro-2-butyl 1,1,2,2,2-pentafluoroethyl, etc.
  • halogen such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl Group, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl Nonafluoro-2-butyl 1,1,2,2,2-pentafluoroethyl, etc.
  • Alkoxy straight or branched chain alkyl, connected to the structure via an oxygen atom bond, such as methoxy, ethoxy, tert-butoxy, etc.
  • Haloalkoxy The hydrogen atoms on the alkoxy group can be partially or completely replaced by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, tri Fluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
  • Alkylthio straight or branched chain alkyl, connected to the structure via a sulfur atom bond, such as methylthio, ethylthio and the like.
  • Haloalkylthio The hydrogen atoms on the alkylthio group can be partially or fully replaced by halogen, such as difluoromethylthio, trifluoroethylthio and the like.
  • Cyanoalkyl straight or branched chain alkyl, the hydrogen atoms on these alkyl groups can be partially or completely replaced by cyano groups, such as -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CH 2 CN, -CH(CH 3 )CN, -CH(CH 2 CH 3 )CN, -CH(CH 2 CH 2 CH 3 )CN, -C(CH 3 )(CH 3 )CN Or -C(CH 3 )(CH 2 CH 3 )CN.
  • cyano groups such as -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CH 2 CN, -CH(CH 3 )CN, -CH(CH 2 CH 3 )CN, -C(CH 3 )(CH 3 )CN.
  • the compound of general formula III and the halogenated compound R 4 -LG are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain a compound of general formula II.
  • the reaction is carried out in the presence of a base and a catalyst;
  • the compound of formula II and the compound of general formula IV are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain a compound of general formula I.
  • the reaction can be carried out in the presence of a base and a catalyst.
  • Suitable solvents in the above steps can be the same or different: aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; methyl acetate Esters, ethyl acetate and other esters, tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane and other ethers, water, acetonitrile, N,N-dimethylformamide, N-methyl Polar solvents such as pyrrolidone and dimethyl sulfoxide, or mixed solvents of the above solvents.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • the bases that can be the same or different are organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride, potassium hydride, and alkali metals such as sodium hydroxide and potassium hydroxide.
  • the catalysts in each of the above steps may be the same or different: potassium iodide, sodium iodide, potassium fluoride, sodium fluoride, potassium bromide or sodium bromide.
  • the compound of the general formula V and the halogenated compound R 4 -LG are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain a compound of the general formula VI.
  • the reaction is carried out in the presence of a base;
  • the compound and the compound of the general formula IV are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain the compound of the general formula VII.
  • the reaction can be carried out in the presence of a base.
  • the suitable solvents in the above steps can be the same or different.
  • Aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and halogenated hydrocarbons such as chloroform and dichloromethane.
  • Types, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane, water, acetonitrile, N,N-dimethylformamide, Polar solvents such as N-methylpyrrolidone and dimethyl sulfoxide, or mixed solvents of the above solvents.
  • the bases that can be the same or different are organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride, potassium hydride, and alkali metals such as sodium hydroxide and potassium hydroxide.
  • the compound of general formula VII can be reacted at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours in the presence of a base to prepare a compound of general formula VIII;
  • a suitable base can be lithium hydroxide, sodium hydroxide or potassium hydroxide, which is suitable
  • the solvent can be any one or a mixed solvent of at least two of water, methanol, ethanol, tetrahydrofuran or dioxane.
  • the compound of formula VIII is combined with thionyl chloride, oxalyl chloride, phosgene, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, thionyl bromide, triphosgene, phosphorus tribromide or isopropyl chloroformate
  • the compound of general formula IX can be prepared by reacting with halogenating reagent.
  • a compound of general formula IX and a compound of general formula X can be reacted in a suitable solvent at a temperature from -70°C to the boiling point of the solvent for 0.5-48 hours to obtain a compound of general formula I.
  • the reaction is carried out in the presence of a base; a suitable solvent can be Aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; esters such as methyl acetate and ethyl acetate; tetrahydrofuran and dioxins Ethers such as alkane, diethyl ether, 1,2-dimethoxyethane, polar solvents such as water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.
  • the mixed solvent of the above solvents, the base can be organic bases such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-butylamine, pyridine, DBU, 4-dimethylaminopyridine, sodium hydride, Alkali metal hydrides such as potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkalis such as sodium bicarbonate Metal bicarbonate, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, sodium tert-butoxide and other metal alkoxides.
  • organic bases such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-butylamine, pyridine, DBU, 4-dimethylaminopyridine, sodium hydride,
  • the compound of general formula XI can be reacted with the halogenated compound R 4 -LG in the presence of a suitable solvent and a suitable base at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain a compound of general formula I.
  • suitable solvents can be aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; and esters such as methyl acetate and ethyl acetate.
  • Suitable bases can be organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and hydroxides Alkaline earth metal hydroxides such as calcium, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, sodium tert-butoxide, etc. Metal alkoxides.
  • Compounds of general formula III, compounds of general formula X and compounds of general formula XI can be prepared according to known methods, for example with reference to WO20110201687, WO2011093415, WO2005021488, WO2005073165, WO2006137395, JP2007099761, WO2008000438, WO2008074427, WO2008107091, WO2010013567, WO2010018714, WO2010090282, WO2010127926, WO2010127928 JP2011063549, WO2012020483, WO2012020484, WO2012077221, WO2012164698, WO2013050261, WO2014069665, WO2014067838, WO2014161848, WO2014161850, WO2015097091 or WO2015097094 are prepared by methods reported; compounds of general formula IV, compounds of general formula V and halogenated compounds R 4 -LG are generally available in the market It can also be made by conventional methods.
  • the compound of general formula I of the present invention has unexpectedly high insecticidal activity and can be used to control the following pests (the listed objects are only used to illustrate the present invention, but by no means limit the present invention):
  • Lepidopteran pests such as diamondback moth, armyworm, Beet armyworm, Spodoptera litura, Helicoverpa armigera, Paleidia, Chilo suppressalis, Chilo suppressalis, Cnaphalocrocis medinalis, Corn borer, Small heartworm, Helicoverpa armigera, etc.
  • Homoptera pests such as pea aphid, bean Aphid, beet aphid, cotton aphid, apple aphid, green peach aphid, corn aphid, whitefly, leafhopper, planthopper, rice planthopper, mealybug, etc.
  • Hemiptera pests such as corn bug, cotton net bug, tomato bug , Rice green bug, Ailanthus altissima, etc.
  • the compound of general formula I of the present invention also has unexpectedly high insecticidal quick-acting effect, quick onset of effect, high insecticidal activity can be achieved one day after application, and extremely high insecticidal activity can be achieved within 3 days.
  • the preparation method of the compound of the general formula I of the present invention is simple and efficient, easy to large-scale industrial production, and has a wide application prospect. Therefore, the technical scheme of the present invention also includes the use of the compound of general formula I as an insecticide preparation in agriculture or other fields.
  • the above-mentioned compounds can be advantageously used to protect important crops, livestock and breeding animals in agriculture and horticulture, as well as the environment frequently visited by humans from pests.
  • the amount of the compound varies due to various factors, such as the compound used, the crops to be protected, the type of pests, the degree of infection, climatic conditions, the application method, and the dosage form used.
  • a compound dose of 5 g-5 kg per hectare can provide adequate control.
  • the present invention also includes insecticides with the compound of formula I as the active ingredient.
  • the weight percentage of active components in the insecticide is between 0.1-99%.
  • the pesticide also includes agricultural, forestry, and sanitary acceptable carriers and auxiliary agents.
  • the insecticide of the present invention can be applied in the form of a formulation.
  • the compound of general formula I is used as an active ingredient to be dissolved or dispersed in a carrier and/or adjuvant or formulated into a preparation for easier dispersion when used as an insecticide.
  • the compound of general formula I is used as the active component, and the compound of general formula I can be prepared into a variety of formulation types in a manner well known in the art, including water, soluble liquid, emulsifiable concentrate, microemulsion, water emulsion, and suspension.
  • Suspended seed coating agent Suspended seed coating agent, dispersible oil suspension agent, ultra-low volume agent, powder, wettable powder, soluble powder, emulsifiable powder, granule, water dispersible granule, soluble granule, emulsifiable granule, dry suspension , Effervescent granules, floating granules, tablets, soluble tablets, effervescent tablets, microcapsule powders, microcapsule suspensions, in any case, the choice of formulation type depends on the physical and chemical properties of the compound of general formula I And biological characteristics.
  • the insecticidal preparation of the compound of general formula I of the present invention can be prepared by the usual processing method, that is, after the active substance is mixed with a liquid carrier or a solid carrier, one or more surface active agents such as emulsifiers, dispersants, wetting agents, and enhancers are added. Thickener, stabilizer and defoamer, etc. Usually the composition contains at least one carrier and at least one surfactant. In all cases, it should be ensured that the active ingredients of the composition of the present invention are evenly distributed.
  • Aqueous agent is to mix the compound of general formula I, surfactant and water uniformly to form a uniform and transparent liquid. It usually contains 5-50% active ingredient, 5-20% emulsifier, 0-10% other additives such as penetrant, and the balance of water.
  • the soluble liquid agent mixes the compound of general formula I, the surfactant, and the non-aqueous polar solvent uniformly to form a uniform transparent liquid.
  • the soluble liquid usually contains 5-60% of active ingredients, 5-20% of emulsifiers, 0-10% of other additives such as penetrants, and the balance of the liquid carrier.
  • Emulsifiable concentrate mixes the compound of general formula I, the surfactant and the organic solvent uniformly to form a homogeneous oily liquid.
  • Emulsifiable concentrates usually contain 1 to 70% of active ingredients, 5 to 20% of emulsifiers, 0 to 10% of other additives such as penetrants, stabilizers, and the balance of the liquid carrier.
  • microemulsion mixes the compound of general formula I, surfactant, water and organic solvent uniformly to form a uniform transparent liquid.
  • Microemulsions usually contain 1-50% of active ingredients, 5-30% of emulsifiers, 2-10% of antifreeze, 0-10% of other additives such as penetrants, stabilizers, and the balance of the liquid carrier.
  • the compound of general formula I, the surfactant, and the organic solvent are uniformly mixed to form the oil phase; the water and the antifreeze are mixed together to form the water phase.
  • a high-shear emulsifier to shear the oil phase at high speed while slowly adding the water phase to the oil phase to obtain a uniformly dispersed water emulsion. It usually contains 5-50% active ingredient, 5-20% emulsifier, 2-5% antifreeze, and the balance of liquid carrier.
  • the suspending agent mixes the compound of general formula I, dispersant, wetting agent, antifreeze, and water evenly, and is sanded by a sand mill to obtain a stable, non-deposition, flowable liquid.
  • Suspending agents usually contain 5-50% active ingredients, 2-10% dispersant, 2-5% wetting agent, 2-5% antifreeze, 0-10% other additives such as defoamer, thickener, Preservative, and the balance of liquid carrier.
  • the suspension seed coating agent mixes the compound of general formula I, the dispersant, the wetting agent, the film-forming agent, and the water uniformly, and is sanded by a sand mill to obtain a stable non-deposition and flowable liquid.
  • Suspended seed coatings usually contain 1-50% active ingredients, 2-10% dispersing agent, 2-10% wetting agent, 2-5% antifreeze, 2-10% film former, 0-10% others Additives such as defoamers, thickeners, preservatives, warning colors, and liquid carrier balance.
  • the dispersible oil suspension agent mixes the compound of general formula I, the surfactant, and the oil-based carrier uniformly, and is sanded by a sand mill to obtain a stable, non-deposition, flowable liquid.
  • the dispersible oil suspension usually contains 5-50% of active ingredients, 5-30% of surfactants, 0-10% of other additives such as thickeners, stabilizers, and the balance of the liquid carrier.
  • the ultra-low-volume agent mixes the compound of general formula I, the surfactant, and the organic solvent uniformly and processes it into a uniform transparent oil phase. It usually contains 1-30% of active ingredients, 5-30% of emulsifiers, 0-10% of other additives such as stabilizers, and the balance of the liquid carrier.
  • the powder mixes the compound of general formula I, the auxiliary agent, and the carrier, and is pulverized to obtain a powder.
  • the powder usually contains 5-85% of active ingredient, 5-10% of dispersant, 0-10% of other additives such as stabilizer, and the balance of solid carrier.
  • the wettable powder is mixed with a compound of general formula I, a dispersant, a wetting agent, and a carrier, and pulverized to obtain a powder.
  • Wettable powders usually contain 5-85% of active ingredients, 5-10% of dispersants, 1-10% of wetting agents, 0-10% of other additives such as stabilizers, and the balance of solid carriers.
  • the soluble powder is mixed with a compound of general formula I, a dispersant, a wetting agent, and a carrier, and pulverized to obtain a powder.
  • the soluble powder usually contains 5 to 80% of active ingredients, 5 to 10% of dispersant, 1 to 10% of wetting agent, 0 to 10% of other additives such as stabilizers, and the balance of solid carrier.
  • the emulsifiable powder is mixed with a compound of general formula I, a surfactant, and an organic solvent to prepare a uniform transparent oil phase, and then the above oil phase is uniformly sprayed on the pre-pulverized carrier.
  • the emulsifiable powder usually contains 5-50% active ingredient, 5-30% emulsifier, 5-10% wetting and dispersing agent, 0-15% organic solvent, and the balance of solid carrier.
  • the granule is mixed with the compound of general formula I, auxiliary agent and carrier, and then kneaded, granulated, dried and coated.
  • Granules usually contain 0.5-20% active ingredient, 0.1-10% binder, 0-10% other additives such as stabilizers, and the balance of solid carrier.
  • the water dispersible granules are mixed with the compound of general formula I, dispersant, wetting agent, disintegrant and carrier, then kneaded, granulated and dried.
  • Water dispersible granules usually contain 5-85% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, and 0-10% other additives such as disintegrant, stabilizer Agent, and the balance of the solid carrier.
  • the soluble granules are mixed with the compound of general formula I, dispersant, wetting agent, disintegrant and carrier, and then kneaded, granulated and dried.
  • Soluble granules usually contain 5-85% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, 0-10% other additives such as disintegrant and stabilizer , And the balance of the solid carrier.
  • Emulsifiable granules are mixed with the compound of general formula I, the surfactant and the organic solvent to form a uniform transparent oil phase, and then the oil phase is uniformly sprayed on the pre-pulverized carrier, kneaded, granulated and dried.
  • Emulsifiable granules usually contain 5-50% active ingredient, 5-30% emulsifier, 5-10% wetting and dispersing agent, 0-15% organic solvent, 0-10% other additives such as disintegrant, Stabilizer, binder, and solid carrier balance.
  • the dry suspending agent is uniformly mixed with the compound of general formula I, dispersant, wetting agent, carrier, and water, then sanded by a sand mill, and spray dried after sanding.
  • the dry suspension usually contains 5 to 80% of active ingredients, 2 to 20% of dispersant, 2 to 10% of wetting agent, 0 to 10% of other additives such as defoamers, thickeners, and the balance of solid carriers.
  • the effervescent granules are mixed with the compound of general formula I, wetting and dispersing agent, effervescent disintegrant, and carrier, then kneaded and granulated.
  • Effervescent granules usually contain 0.5-30% active ingredient, 2-20% wetting and dispersing agent, 2-20% effervescent disintegrant, 0-10% other additives such as stabilizers, binders, and solids Carrier margin.
  • the floating granules are mixed with the compound of general formula I, wetting and dispersing agent, floating beads, and carrier, then kneaded and granulated.
  • Floating granules usually contain 0.5-30% active ingredients, 2-20% wetting and dispersing agent, 5-20% floating beads, 0-10% other additives such as stabilizers, binders, disintegrants, and solids Carrier margin.
  • the tablet is mixed with the compound of general formula I, dispersant, wetting agent, disintegrant, and carrier, then kneaded, compressed, and dried.
  • Tablets usually contain 5-50% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, 0-10% other additives such as disintegrant, stabilizer, And the solid carrier balance.
  • Soluble tablets usually contain 5-50% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, and 0-10% other additives such as disintegrant and stabilizer , And the balance of the solid carrier.
  • Effervescent tablets are mixed with the compound of general formula I, a wetting and dispersing agent, an effervescent disintegrant, and a carrier, and then kneaded and compressed.
  • Effervescent tablets usually contain 0.5-30% active ingredients, 2-20% wetting and dispersing agents, 2-20% effervescent disintegrants, and 0-10% other additives such as stabilizers, binders, and solids. Carrier margin.
  • Microcapsule powder dissolve the compound of general formula I in a solvent, add emulsifier and wall materials to it, stir evenly to obtain an oil phase; add a dispersant to the water to obtain an aqueous phase; under high-speed stirring, add the oil phase to the water phase, An oil-in-water emulsion is formed; under agitation, a curing agent is added to the emulsion, heated and kept to form a capsule, and then filtered and dried.
  • Microcapsule powders usually contain 0.5-30% active ingredients, 2-10% emulsifiers, 2-10% wetting and dispersing agents, and 5-30% other additives such as wall materials, defoamers, curing agents, stabilizers, And the solid carrier balance.
  • Microcapsule suspending agent dissolve the compound of general formula I in a solvent, add emulsifier and wall materials to it, stir evenly to obtain an oil phase; add a dispersant to water to obtain an aqueous phase; under high-speed stirring, add the oil phase to the water phase , To form an oil-in-water emulsion; under stirring conditions, add a curing agent to the emulsion, heat and keep it to form a capsule to form a microcapsule suspension.
  • Microcapsule suspensions usually contain 0.5-30% active ingredients, 2-10% emulsifiers, 2-10% wetting and dispersing agents, and 5-30% other additives such as wall materials, defoamers, preservatives, thickening Agent, curing agent, stabilizer, and liquid carrier balance.
  • insecticidal preparation of the compound of the general formula I of the present invention can be formulated with carriers and various auxiliary agents known to those skilled in the art (liquid or solid). Examples include but are not limited to the following types of substances.
  • the suitable surfactant in the insecticidal preparation of the compound of general formula I of the present invention can be an emulsifier, a dispersant or a wetting agent; it can be one or more of non-ionic or ionic.
  • the ionic surfactant is selected from sulfonates, sulfates, carboxylates, phosphate salts, succinate salts, lignosulfonates, acrylamide acrylic copolymers and the like.
  • Nonionic surfactants are selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ether, acid alcohol ester and its polyoxyethylene ether, alkyl polyethylene glycol Alcohol ether, alkyl phenyl polyglycol ether, fatty amide and its polyoxyethylene ether, alkanolamide and its polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer, sodium alkyl naphthalene sulfonate Fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, etc.
  • the above-mentioned surfactant can be selected from one or more of the surfactants shown, such as: sodium or calcium lignosulfonate, polyoxyethylene (n20) phenethyl phenol ether oleate, alkyl Aryl polyoxyethylene polyoxypropylene ether, tristyryl phenol polyoxyethylene (n20) ether phosphorylated triethanolamine salt, agricultural milk 0201B, agricultural milk 0203B, agricultural milk 100#, agricultural milk 600#, agricultural milk 700# , Nong Milk 1601#, Nong Milk AEO-3, Nong Milk AEO-5, Nong Milk AEO-7, Nong Milk T-20, Nong Milk T-80, Nong Milk T-85, Nong Milk S-80, Nong Milk S-85, agricultural milk NP-7, agricultural milk NP-10, agricultural milk NP-15, agricultural milk OX-2681, agricultural milk OX-8686, agricultural milk OX-690, agricultural milk 2201#, polycarboxylate dispersion GY-D800, polycar
  • the suitable liquid carrier in the insecticidal preparation of the compound of general formula I of the present invention can be one or more of water, organic solvent, and oily medium.
  • Suitable organic solvents are selected from aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols and their ethers and esters, ketones, etc., such as benzene, xylene, toluene, alkylbenzene, alkylnaphthalene , Chlorobenzene, vinyl chloride, trichloroethane, dichloromethane, chloroform, carbon tetrachloride, polychloroethane, petroleum fractions, cyclohexane, methanol, ethanol, isopropanol, butanol, ethylene glycol , Propylene glycol, glycerol, sorbitol, benzyl alcohol, furfuryl alcohol, cyclohexanol
  • Suitable solid carriers in the insecticidal preparations of compounds of general formula I of the present invention include natural or synthetic ones.
  • Suitable particle carriers include crushed and classified Natural rocks such as sepiolite and dolomite and synthetic particles made of organic and inorganic powders.
  • Suitable binders and thickeners include synthetic or natural water-soluble polymers.
  • Suitable defoamers can be selected from, but not limited to, defoamers SAG1522, silicones, C8-10 fatty alcohols, phosphate esters, C10-20 saturated fatty acids (such as capric acid), amides, and the like.
  • Suitable antifreeze agent can be selected from but not limited to ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, urea Wait.
  • Suitable penetrants can be selected from, but not limited to, silicone, penetrant T, penetrant JFC and the like.
  • Suitable film-forming agents include natural products and their modifications and synthetic polymers.
  • Suitable preservatives can be selected from, but not limited to, sodium benzoate, cassone, potassium sorbate and the like.
  • Suitable disintegrants can be selected from but not limited to sodium carboxymethyl starch, croscarmellose sodium, croscarmellose sodium, modified starch, cross-linked polyvinylpyrrolidone, ammonium sulfate, sodium sulfate, Sodium chloride, ammonium chloride, etc.
  • the effervescent disintegrant can be an acidic component and/or an alkaline component, wherein the acidic component can be selected from organic acids and inorganic acids, such as tartaric acid, citric acid, salicylic acid, phosphoric acid, etc.; the alkaline component can be It is selected from basic carbonate, carbonate, for example: sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate and the like.
  • Suitable warning colors can be selected from, but not limited to, inorganic pigments, such as iron oxide, titanium oxide or Prussian blue; organic dyes, such as alizarin, acid scarlet G, basic rose spirit, azo dyes, metal phthalocyanines and the like.
  • inorganic pigments such as iron oxide, titanium oxide or Prussian blue
  • organic dyes such as alizarin, acid scarlet G, basic rose spirit, azo dyes, metal phthalocyanines and the like.
  • Suitable wall materials include one or more of natural polymer materials, semi-synthetic polymer materials and fully synthetic polymer materials.
  • the natural polymer material can be selected from but not limited to gelatin, acacia, agar, alginate, chitosan, fibrin, zein, etc.
  • the semi-synthetic polymer material can be selected from but not limited to methyl (ethyl) cellulose , Carboxymethyl cellulose (sodium), cellulose acetate and its esters and partial glycerides, etc.
  • fully synthetic polymer materials can be selected from but not limited to polyacrylic resin, urea resin, polyamide, polyester, polymethyl Methyl acrylate, polyurea, polyurethane, etc.
  • Suitable curing agents include one or more of polyols and polyamines.
  • the polyol may be selected from but not limited to ethylene glycol, glycerol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol Alcohol 600, etc.; polyamines can be selected from but not limited to ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, iso Folone diamine and so on.
  • Microcapsule suspending agent stir 5 parts of active compound, 5 parts of 600#, 10 parts of xylene and 1 part of diphenylmethane diisocyanate to make the oil phase, and then add it to the oil phase consisting of 1 part of ethylene diamine and 5 parts In an aqueous phase composed of glycerol, 3 parts Atlox 4913, 2 parts EFW and 1 part SAG1522 with the remaining water, a 5% active compound microcapsule suspension can be prepared after high-speed stirring, solidification and heat preservation.
  • Emulsifiable concentrate add 10 parts of active compound, 5 parts of 0201B, 7 parts of 0203B, solvent naphtha 150 to 100% into the mixing kettle, stir and mix evenly, if necessary, use a hot water bath to heat and dissolve to obtain 10% active compound emulsifiable concentrate.
  • Water emulsion Add 15 parts of active compound, 8 parts of T-20, 4 parts of agricultural milk S-85, 5 parts of tributyl phosphate, and 5 parts of solvent naphtha 200 into the mixing kettle, stir and mix to dissolve into a uniform oil phase, Under high-speed stirring, add the remaining amount of water (to make up to 100%) into the oil phase to obtain a 15% active compound aqueous emulsion with good dispersibility.
  • Dispersible oil suspension agent add 25 parts of active compound, 6 parts of dispersant SP-OF3468, 6 parts of dispersant SP-OF3472, 2 parts of Nongru 1601#, 2 parts of organic bentonite, and methyl oleate to 100%. It is mixed in the mixing tank, firstly subjected to high shear for coarse pulverization and homogenization, and then pumped into the sand mill for fine grinding. The particle size of the sanded material is measured with a particle size distribution meter. When the particle size reaches the standard requirements, it is filtered , You can get 25% active compound dispersible oil suspension.
  • Water dispersible granules 60 parts of active compound, 2 parts of Morwet EFW, 4 parts of dispersant D425, 4 parts of alkyl naphthalene sulfonate formaldehyde condensate, 10 parts of soluble starch, 8 parts of amine sulfate, and diatomaceous earth make up to 100 % Is added together, mixed and crushed, and then kneaded by adding water, then added to a granulator equipped with a certain size of screen for granulation. Then, after drying and sieving (according to the mesh range), 60% active compound water dispersible granules can be obtained.
  • Wettable powder 50 parts of active compound, 3 parts of sodium lauryl sulfate, 4 parts of sodium salt of alkyl naphthalene sulfonic acid condensation polymer, 4 parts of sodium methylene naphthalene sulfonate, 4 parts of sodium lignosulfonate, 5 parts of white carbon black and diatomaceous earth are made up to 100% and fully mixed, and after being pulverized by an ultrafine pulverizer, a wettable powder of 50% active compound is obtained.
  • Microemulsion 10 parts of active compound, 6 parts of agricultural milk 0201B, 2 parts of NP-15, 8 parts of YUS-A51G, 5 parts of methanol,
  • Soluble agent 10 parts of active compound, 6 parts of tristyrylphenol polyoxyethylene (n20) ether phosphorylated triethanolamine salt, 3 parts of agricultural milk T-20, 2 parts of agricultural milk 0201B, 3 parts of N-methyl Pyrrolidone and cyclohexanone are supplemented to 100% and mixed uniformly. If necessary, it can be heated and dissolved in a hot water bath to prepare a 10% active compound solution.
  • Emulsifiable powder Add 15 parts of active compound, 2 parts of agricultural milk 1601#, 3 parts of 500#, 5 parts of agricultural milk 0201B, 5 parts of N-methylpyrrolidone, and 5 parts of Armid FMPC into the mixing kettle. Stir and mix evenly. Use a hot water bath to heat and dissolve. Under agitation, spray the above-mentioned oil base evenly onto a mixture composed of 20 parts of white carbon black and bentonite to make up to 100%. After being pulverized by an ultrafine pulverizer, 15% activity is obtained. Compound emulsifiable powder.
  • Suspending agent 20 parts of active compound, 2 parts of dispersant 4913, 2 parts of wetting agent TXC, 2 parts of Nongru 1601#, 2 parts of white carbon black, 0.2 parts of xanthan gum, 1 part of SAG 1522, 5 parts of ethylene glycol , Water is made up to 100% and then added to the mixing tank to mix, first go through high shear for coarse pulverization and homogenization, then pump into the sand mill for fine grinding, and use the particle size distribution meter to detect the particle size of the sanding material. After the particle size reaches the standard requirement, filter to obtain 20% active compound suspension.
  • Dry suspending agent add 50 parts of active compound, 20 parts of sodium lignosulfonate, 2 parts of wetting agent TXC, 2 parts of white carbon black, and kaolin to 100%, and then add them to the mixing tank and mix with water.
  • the cutting is coarsely pulverized and homogenized, and then pumped into a sand mill for fine grinding, and the particle size of the sanding material is detected by a particle size distribution meter, sprayed, granulated, and dried to obtain a 50% active compound dry suspension.
  • Ultra-low volume agent add 10 parts of active compound, 5 parts of Armid FMPC, 2 parts of agricultural milk 0201B, 1 part of S-80, solvent oil to 100% into the mixing kettle, stir and mix evenly, and heat with a hot water bath if necessary After dissolving, you can get 10% active compound ultra-low volume agent.
  • Suspended seed coating agent 10 parts of active compound, 2 parts of dispersant FS3000, 2 parts of wetting agent TXC, 2 parts of SK-92FS1, 2 parts of white carbon black, 0.2 parts of xanthan gum, 10 parts of 10% polyvinyl alcohol solution , 0.2 parts of alkaline rose essence, 1 part of SAG1522, 5 parts of ethylene glycol, and water to 100% were added to the mixing tank and mixed in sequence, firstly subjected to high shear for coarse crushing and homogenization, and then pumped into the sand mill Fine grinding is carried out in the process, and the particle size of the sanding material is measured with a particle size distribution meter. When the particle size reaches the standard requirement, it is filtered to obtain a 10% active compound suspension seed coating.
  • Powder Mix 30 parts of active compound, 5 parts of sodium methylene naphthalene sulfonate, 6 parts of sodium lignin sulfonate, 8 parts of white carbon black, and diatomaceous earth to 100%, and then pulverize with an ultrafine pulverizer. A 30% active compound powder is obtained.
  • Soluble powder make up 50 parts of active compound, 3 parts of sodium lauryl sulfate, 4 parts of sodium salt of alkyl naphthalene sulfonic acid condensation polymer, 4 parts of EFW, 5 parts of hydroxypropyl cellulose, and ammonium sulfate to 100% After mixing and pulverizing with an ultrafine pulverizer, a 50% active compound soluble powder is obtained.
  • Tablets make up 10 parts of active compound, 2 parts of methyl naphthalene sulfonate sodium formaldehyde condensate, 1 part of sodium lauryl sulfate, 15 parts of soluble starch, 8 parts of sodium sulfate, 5 parts of white carbon black, and diatomaceous earth. It is fully mixed to 100%, pulverized by an ultrafine pulverizer, and then compressed to obtain 10% active compound tablets.
  • Granules add 10 parts of active compound, 3 parts of methyl naphthalene sulfonate sodium formaldehyde condensate, 2 parts of sodium salt of alkyl naphthalene sulfonic acid condensation polymer, 10 parts of sodium sulfate and diatomaceous earth to make up to 100%. After mixing and pulverizing, adding water and kneading, it is added to a granulator equipped with a certain size screen for granulation. Then, it is dried and sieved (according to the mesh range) to obtain 10% active compound granules.
  • Effervescent granules 20 parts of active compound, 4 parts of sodium salt of alkyl naphthalene sulfonic acid condensation polymer, 2 parts of methyl naphthalene sulfonate sodium formaldehyde condensate, 2 parts of sodium lauryl sulfate, 20 parts of soluble starch, 15 parts of sodium citrate, 15 parts of sodium bicarbonate, 10 parts of sodium sulfate, diatomaceous earth make up to 100% fully mixed, pulverized by an ultrafine grinder, and then kneaded and granulated to obtain 20% active compound foam Teng granules.
  • Emulsifiable granules add 20 parts of active compound, 1 part of agricultural milk EL-40, 3 parts of OX-2681, 4 parts of agricultural milk 0201B, 2 parts of agricultural milk 700#, 3 parts of N-methylpyrrolidone, and 3 parts of ArmidFMPC.
  • the mixing kettle stir and mix evenly. If necessary, use a hot water bath to heat to dissolve. Under stirring conditions, spray the above oil base evenly onto the mixture composed of 25 parts of white carbon black and light calcium carbonate to make up to 100%.
  • After being pulverized by an ultrafine pulverizer after adding water and kneading, it is added to a granulator equipped with a certain size of screen for granulation. Then, it is dried and sieved (according to the mesh range) to obtain 20% active compound emulsifiable granules.
  • Soluble tablet Mix 20 parts of active compound, 3 parts of wetting agent TXC, 4 parts of sodium salt of alkyl naphthalene sulfonic acid condensation polymer, 4 parts of EFW, 5 parts of hydroxypropyl cellulose, and ammonium sulfate to 100%. After being crushed by an ultrafine pulverizer and compressed into tablets, 20% active compound soluble tablets are obtained.
  • Microcapsule granules In a 1000ml plastic (with baffle) bottle, add 600ml of 0.5% polyvinyl alcohol aqueous solution, use a tetrafluoroethylene stirrer, add 40 parts of active compound and 9g of ethylene oxide under high-speed stirring Alkyloxypropylene block copolymer, 6 grams of epoxidized soybean oil, 3 grams of diphenylmethane-4,4-diisocyanate, 1.5 grams of ethylene diamine, 5 grams of sodium carbonate and 150 milliliters of water. After the addition is complete, Slow down the speed and continue to stir for 1 hour, stand for 1 hour, filter, and vacuum dry to obtain 40% active compound microcapsule granules.
  • Effervescent tablet 10 parts of active compound, 4 parts of sodium lignosulfonate, 4 parts of NNO, 2 parts of sodium lauryl sulfate, 20 parts of soluble starch, 20 parts of sodium citrate, 20 parts of sodium bicarbonate, 10 parts
  • a portion of sodium sulfate and calcined kaolin are made up to 100% and fully mixed, crushed by an ultrafine pulverizer, then kneaded and compressed to obtain effervescent tablets of 10% active compound.
  • Floating granules 15 parts of active compound, 4 parts of D425, 2 parts of EFW, 2 parts of sodium lauryl sulfate, 20 parts of corn starch, 20 parts of floating beads, 5 parts of white carbon black, 10 parts of sodium sulfate, diatom
  • the soil is supplemented to 100% and fully mixed, after being pulverized by an ultrafine pulverizer, and then kneaded and granulated, 15% active compound floating granules can be obtained.
  • Soluble granules 30 parts of active compound, 3 parts of wetting agent TXC, 4 parts of sodium salt of alkyl naphthalene sulfonic acid condensation polymer, 4 parts of sodium lauryl sulfate, 5 parts of carboxymethyl cellulose, 5 parts of glucose , Ammonium sulfate is made up to 100% and mixed thoroughly, then pulverized by an ultrafine pulverizer, kneaded and granulated to obtain 30% active compound soluble granules.
  • insecticidal preparation of the compound of general formula I of the present invention can be diluted or sprayed directly with water by the user before use, or can be used directly.
  • the technical solution of the present invention also includes a method for controlling pests: applying the pesticide of the present invention to the pests or their growth medium.
  • the more suitable effective amount is selected to be 10 g to 1000 g per hectare, and the effective amount is preferably 10 to 500 g per hectare.
  • the compounds represented by the general formula I and the intermediate general formula II of the present invention can be respectively prepared, which are further specifically described as follows:
  • compound 15 (white solid) was prepared by reacting intermediate compound II.7 with benzoyl chloride.
  • the NMR and MS data of compound 15 are as follows:
  • compound 16 (white solid) was prepared by reacting intermediate compound II.7 with p-fluorobenzoyl chloride.
  • the NMR and MS data of compound 16 are as follows:
  • compound 20 (white solid) was prepared by reacting intermediate compound II.7 with p-cyanobenzoyl chloride.
  • the NMR and MS data of compound 20 are as follows:
  • compound 29 (yellow solid) was prepared by reacting intermediate compound II.2 with benzoyl chloride.
  • the NMR and MS data of compound 29 are as follows:
  • compound 30 (yellow solid) was prepared by reacting intermediate compound II.2 with p-fluorobenzoyl chloride.
  • the NMR and MS data of compound 30 are as follows:
  • compound 57 (yellow solid) was prepared by reacting intermediate compound II.3 with benzoyl chloride.
  • the NMR and MS data of compound 57 are as follows:
  • the compound of the present invention was used to test several insecticidal activities.
  • the measurement method is as follows:
  • test compound After the test compound is dissolved in a mixed solvent of acetone/methanol (1:1), it is diluted with water containing 0.1% (wt) Tween 80 to the desired concentration.
  • Measurement method Cut corn leaves into 2cm leaf segments, the pressure of Airbrush spray treatment is 10psi (approximately 0.7kg/cm 2 ), the front and back sides of each leaf segment are sprayed, and the spray volume is 0.5ml. After drying in the shade, 10 3rd instar larvae were inserted into each treatment, and the treatment was repeated 3 times. After the treatment, it was placed in an observation room at 25°C and a relative humidity of 60-70%, and the number of surviving insects was investigated 1, 2, and 3 days after the treatment, and the mortality was calculated.
  • the lethality of compounds 15, 16, 20, 22, 43, and 71 to Mythimna separata was 100% 3 days after the administration.
  • CK1 and CK2 are selected as control compounds, and compounds 1, 2, 8, 9, 13, 15, 16, 20, 22, 29, 30, 43, 57, 58, and 71 of the present invention are selected for parallel comparison test of insecticidal activity of Mythimna separata (3 days after the drug), the determination method is the same as before; the results are shown in Table 3:
  • Example 25 Determination of the activity against beet armyworm
  • Determination method the activity test was carried out by the leaf-dipping dish feeding method. Immerse the leaf discs in the medicinal solution for 10 seconds, dry them and place them in a petri dish, 4 dishes per dish, and put filter paper in the petri dish for moisture. Test 10 beet armyworms in each dish, repeat 3 times. Place in a light incubator, temperature 25°C, light 14hL:10hD, cultivate. The number of dead beet armyworms was investigated 1 day, 2 days, and 3 days after treatment, and the mortality was calculated.
  • test results of the beet armyworm are as follows:
  • the lethality rate of compounds 15, 16, 20, 22, 43, 71 to beet armyworm was 100% 3 days after the treatment.
  • the compounds of the present invention 1, 2, 8, 9, 13, 15, 16, 20, 22, 29, 30, 43, 57, 58, 71 Compared with the control compounds CK1 and CK2, it has significant insecticidal activity advantages; further, the compound of the present invention has a lethality rate of 100% against Spodoptera exigua at a low dose of 1 mg/L or even 0.5 mg/L. However, the control compounds CK1 and CK2 completely lost their insecticidal activity at the doses of 100, 1, and 0.5 mg/L (the lethality rate was 0).
  • Example 26 Determination of the activity against Plutella xylostella
  • the cabbage leaves were punched into leaf discs with a diameter of 2 cm with a punch.
  • the pressure of Airbrush spray treatment was 10 psi (approximately 0.7 kg/cm 2 ), and the front and back sides of each leaf disc were sprayed, and the spray volume was 0.5 ml.
  • 10 3rd instar larvae were inserted into each treatment, and the treatment was repeated 3 times. After the treatment, it was placed in an observation room at 25°C and a relative humidity of 60-70%, and the number of surviving insects was investigated 1, 2, and 3 days after the treatment, and the mortality was calculated.
  • the lethality rate of compounds 1, 2, 8, 9, 13, 15, 16, 20, 22, 29, 30, 43, 57, 58, 71 to Plutella xylostella was 100%.
  • the lethality of compounds 15, 16, 20, 22, 43, 71 to Plutella xylostella was 100% at 3 days after the treatment.
  • CK3, CK4, CK5, CK6 are selected as control compounds, and compounds 1, 2, 8, 9, 13, 29, 30, 57, and 58 of the present invention are selected for parallel comparison test of insecticidal activity of Plutella xylostella to compare the quick-acting insecticidal effects; The results are shown in Table 5:
  • CK7, CK8, CK9, CK10 were selected as control compounds, and the compounds 15, 16, 20, 22, 43, and 71 of the present invention were selected for the parallel comparison test of insecticidal activity of Plutella xylostella to compare the insecticidal quick effect; the results are shown in Table 6. :
  • Determination method 1) Preparation of rice seedlings: cultivate rice in a constant temperature room (temperature 26-28°C, relative humidity 60-80%, light 16hL:8hD) in a plastic cup with a diameter of 4.5cm and a height of 4cm. At the 4 to 5 leaf stage, select robust and consistent rice seedlings for chemical treatment, with 3 repetitions for each treatment. 2) Preparation for test insects: Chilo suppressalis, 3rd instar larvae continuously reared indoors. 3) The method of spraying insects on rice stems. The spraying method is adopted to uniformly spray the whole plant of the rice seedlings, and 15ml of medicine is used for each treatment.
  • the rice seedlings are sprayed, they are placed in a cool place to dry the liquid, and about 5 cm of the stalk at the base of the stem is cut to feed the test insects.
  • CK3, CK4, CK5, CK6 were selected as control compounds, and the compounds 1, 2, 8, 9, 13, 29, 30, 57, and 58 of the present invention were selected for parallel comparison test of Chilo suppressalis insecticidal activity.
  • the determination method is the same as that described above ; The results are shown in Table 7:
  • CK7, CK8, CK9, CK10 were selected as the control compounds, and the compounds 15, 16, 20, 22, 43, and 71 of the present invention were selected for the parallel comparison test of Chilo suppressalis insecticidal activity.
  • the determination method was the same as that described above; the results are shown in Table 8. Show:
  • the inventors of the present invention through a large number of experiments, on the basis of the molecular skeleton of the existing compound, appropriately introduced a cyanoalkyl group on the amide bond N atom, thereby obtaining the compound of the general formula I of the present invention. It can be seen from the activity comparison test data in Table 3 to Table 10: Compared with the existing compounds, due to the introduction of new appropriate fragments (pharmacophores), the interaction between the molecule and the receptor and the chance of binding are improved.
  • the compound of the present invention has an unexpected effect relative to the existing compounds, that is, the compound of the present invention has higher insecticidal activity and better insecticidal quick-acting (fast onset of action, and can achieve higher Insecticidal activity, extremely high insecticidal activity can be achieved within 3 days).
  • the transport performance of the entire molecule in insects and plants or the binding to the receptor will be very different.
  • the activity difference will also be great, and the transport performance of the molecule and the suitability of binding to the receptor are unpredictable and require a lot of creative work to know. Therefore, the present invention has substantial characteristics and significant progress.

Abstract

La présente invention concerne un composé méta-diamide et son utilisation. La structure du composé est représentée par la formule générale I. La définition de chaque substituant dans la formule est fournie dans la description. Le composé représenté par la formule générale I a une nouvelle structure et une excellente activité insecticide, et peut prévenir de manière efficace des dommages causés par des organismes nuisibles tels que les légionnaires d'automne, les légionnaires de la betterave, la fausse-teigne des crucifères, les foreurs de tiges de riz à rayures, etc. à faibles doses. Le composé représenté par la formule générale I a également une capacité insecticide à action rapide étonnamment élevée, un début rapide, et peut atteindre une activité insecticide élevée après 1 jour d'application et une activité insecticide extrêmement élevée dans 3 jours, présentant ainsi de vastes perspectives d'application.
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CN1926094A (zh) * 2004-01-28 2007-03-07 三井化学株式会社 酰胺衍生物及其制备方法和作为杀虫剂的使用方法
CN102112437A (zh) * 2008-08-01 2011-06-29 三井化学Agro株式会社 酰胺衍生物、含有该酰胺衍生物的有害生物防除剂及有害生物的防除方法
WO2017104838A1 (fr) * 2015-12-18 2017-06-22 三井化学アグロ株式会社 Procédé de production d'un dérivé amide aromatique
CN110194726A (zh) * 2018-05-11 2019-09-03 沈阳化工大学 一种苯甲酰胺类化合物及其应用

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EP2427426B1 (fr) * 2009-05-06 2018-02-07 Syngenta Participations AG Composés insecticides

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Publication number Priority date Publication date Assignee Title
CN1926094A (zh) * 2004-01-28 2007-03-07 三井化学株式会社 酰胺衍生物及其制备方法和作为杀虫剂的使用方法
CN102112437A (zh) * 2008-08-01 2011-06-29 三井化学Agro株式会社 酰胺衍生物、含有该酰胺衍生物的有害生物防除剂及有害生物的防除方法
WO2017104838A1 (fr) * 2015-12-18 2017-06-22 三井化学アグロ株式会社 Procédé de production d'un dérivé amide aromatique
CN110194726A (zh) * 2018-05-11 2019-09-03 沈阳化工大学 一种苯甲酰胺类化合物及其应用

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