WO2023051261A1 - Composé imine et son utilisation - Google Patents

Composé imine et son utilisation Download PDF

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Publication number
WO2023051261A1
WO2023051261A1 PCT/CN2022/118920 CN2022118920W WO2023051261A1 WO 2023051261 A1 WO2023051261 A1 WO 2023051261A1 CN 2022118920 W CN2022118920 W CN 2022118920W WO 2023051261 A1 WO2023051261 A1 WO 2023051261A1
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sch
alkyl
haloalkyl
phenyl
halogen
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PCT/CN2022/118920
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Chinese (zh)
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吴鸿飞
徐靖博
孙俊
韩金龙
刘少武
解喜山
郭春晓
徐利保
程学明
于海波
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沈阳中化农药化工研发有限公司
江苏扬农化工股份有限公司
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Publication of WO2023051261A1 publication Critical patent/WO2023051261A1/fr

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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
    • 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
    • A01N37/36—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • 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
    • A01N37/52—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 groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/56—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C07C237/40—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 the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/02—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by halogen atoms, e.g. imino-halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • the invention belongs to the field of insecticides and acaricides, and in particular relates to an imine compound and its application.
  • WO2005073165A1 and WO2010018714A1 disclose bisamide structure type compounds with insecticidal activity.
  • the imine structure type compound of the present invention has a novel structure and has excellent insecticidal and acaricidal activities.
  • the imine compounds shown in the present invention and their insecticidal and acaricidal activities have not been reported.
  • the object of the present invention is to provide an imine compound and its application as an insecticide or acaricide.
  • a kind of imine compound the structure of imine compound is shown in general formula I:
  • X 1 is selected from halogen, nitro, cyano, CONH 2 , CHO, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl , C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylamino, C 1 -C 6 dialkylamino, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkyl Carbonyl, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Haloalkylsulfonyl, C 1
  • n is selected from 0, 1, 2, 3, 4 or 5;
  • X 2 and X 3 can be the same or different and are selected from H, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 - C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl;
  • R 1 is selected from H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or cyano methylene;
  • R 2 is selected from H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 1 -C 6 alkylamine C 1 -C 6 haloalkylamino group, C 1 -C 6 dialkylamino group, C 1 -C 6 halodialkylamino group, C 1 -C 6 alkoxy group , C 1 -C 6 Haloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkynyloxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 haloalkenylthio, C 2 -
  • Y 1 and Y 2 may be the same or different and are selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio.
  • X 1 is selected from halogen, nitro, cyano, CONH 2 , CHO, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl , C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylamino, C 1 -C 3 dialkylamino, C 1 -C 3 alkoxycarbonyl, C 1 -C 3 alkylcarbonyl, C 1 -C 3 haloalkyl Carbonyl, C 1 -C 3 Alkylsulfonyl, C 1 -C 3 Haloalkylsulfonyl, C 1
  • n is selected from 0, 1, 2, 3, 4 or 5;
  • X 2 and X 3 may be the same or different and are selected from H, halogen, nitro, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, C 2 - C 4 haloalkenyl, C 2 -C 4 alkynyl or C 2 -C 4 haloalkynyl;
  • R 1 is selected from H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or cyano methylene;
  • R 2 is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, halogenated C 2 -C 4 alkenyl, C 1 -C 3 alkylamine C 1 -C 3 haloalkylamino, C 1 -C 3 dialkylamino, C 1 -C 3 halodialkylamino, C 1 -C 3 alkoxy , C 1 -C 3 Haloalkyloxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 2 -C 4 alkynyloxy, C 2 -C 4 haloalkynyloxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 2 -C 4 alkenylthio, C 2 -C 4 haloalkenylthio, C 2 -C 4
  • Y 1 and Y 2 may be the same or different and are selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio or C 1 -C 3 haloalkylthio.
  • X 1 is selected from halogen, nitro, cyano, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy or C 1 -C 3 haloalkylthio;
  • n 0, 1, 2 or 3;
  • X 2 and X 3 can be the same or different and are independently selected from H or halogen;
  • R 1 is selected from H or C 1 -C 3 alkyl
  • R 2 is selected from halogen, C 1 -C 3 alkylamino, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, 1-1H-1,2,4-triazolyl or 4 Piperazin-1-yl substituted by the following groups, wherein the following groups are: C 1 -C 3 alkyl, C 1 -C 3 alkylcarbonyl or phenyl;
  • Y 1 and Y 2 may be the same or different and are selected from halogen, C 1 -C 3 haloalkyl or C 1 -C 3 haloalkoxy.
  • X is selected from F, Cl, Br, I, nitro, cyano, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy or trifluoromethylthio;
  • n is selected from 0, 1 or 2;
  • Both X2 and X3 are selected from F;
  • R is selected from H or methyl
  • R is selected from F, Cl, Br, I, methylamino, ethylamino, propylamino, cyclopropanylamino, methoxy, ethoxy, propoxy, methylthio, ethylthio, propyl Thio, 1-1H-1,2,4-triazolyl or 4-methylpiperazin-1-yl, 4-ethylpiperazin-1-yl, 4-acetylpiperazin-1-yl , 4-phenylpiperazin-1-yl;
  • Y1 and Y2 may be the same or different and are selected from F, Cl, Br, I, trifluoromethyl, trifluoromethoxy or difluoromethoxy.
  • X is selected from F, Cl, nitro, cyano, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy or trifluoromethylthio;
  • n is selected from 0, 1 or 2;
  • Both X2 and X3 are selected from F;
  • R 1 is selected from methyl
  • R is selected from Cl, Br, methylamino, ethoxy, methylthio, ethylthio, 1-1H-1,2,4-triazolyl or 4-ethylpiperazin-1-yl;
  • Y 1 and Y 2 may be the same or different and are selected from Br, trifluoromethyl or difluoromethoxy.
  • R 2 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 1 -C 6 alkoxy Methylene, C 1 -C 6 haloalkoxymethylene, C 1 -C 6 alkylthiomethylene, C 1 -C 6 haloalkylthiomethylene, C 1 -C 6 alkylaminomethylene C 1 -C 6 haloalkylaminomethylene, C 1 -C 6 dialkylaminomethylene, C 1 -C 6 halodialkylaminomethylene, phenyl or cyanomethylene )
  • the specific synthesis method is as follows, the compound of general formula IV reacts with an acid chloride reagent (such as oxalyl chloride and thionyl chloride, etc.) to prepare acid chloride III, the compound of acid chloride III reacts with the compound of general formula V-a to prepare the compound of general formula II, and the compound of general formula II and substituted aniline
  • an acid chloride reagent such as oxalyl chloride and thionyl chloride, etc.
  • the specific synthesis method is as follows, the compound of general formula VIII reacts with an acid chloride reagent (such as oxalyl chloride and thionyl chloride, etc.) to prepare acid chloride VII, the reaction of acid chloride VII and substituted aniline V prepares a compound of general formula VI, and the compound of general formula VI reacts with a halogenating reagent (such as phosphorus oxychloride and phosphorus oxybromide, etc.) dehydration reaction to prepare imines, that is, compounds of general formula I.
  • an acid chloride reagent such as oxalyl chloride and thionyl chloride, etc.
  • a halogenating reagent Such as phosphorus oxychloride and phosphorus oxybromide, etc.
  • the specific synthesis method is as follows, 2-fluoro-3-nitrobenzoic acid reacts with acyl chloride reagents (such as oxalyl chloride and thionyl chloride, etc.) to prepare 2-fluoro-3-nitrobenzoyl chloride, 2-fluoro-3- The reaction of nitrobenzoyl chloride and substituted aniline V to prepare the compound of general formula XI, the reduction reaction of the nitro group of the compound of general formula XI to prepare the compound of general formula X, the alkylation reaction of the compound of general formula X to prepare the compound of general formula IX, the compound of general formula IX and acid chloride III reaction to prepare the compound of general formula VI, the dehydration reaction of the compound of general formula VI with a halogenation reagent (such as phosphorus oxychloride and phosphorus oxybromide, etc.) to prepare imine, that is, the compound of general formula I.
  • acyl chloride reagents such as ox
  • R 2 is C 1 -C 6 alkylamino group, C 1 -C 6 haloalkylamino group, C 1 -C 6 dialkylamino group, C 1 -C 6 halodialkylamino group, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkynyloxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 haloalkenylthio Base, C 2 -C 6 alkynylthio, C 2 -C 6 haloalkynylthio, amino, hydrazino, cyano, 1-pyrrolidinyl, 1-piperidin
  • the specific synthesis method is as follows, the compound of general formula VI is reacted with phosphorus oxybromide to prepare the compound of general formula I-a, and the compound of general formula I-a is further substituted to prepare the compound of general formula I.
  • Intermediate V, intermediate V-1 and intermediate X can be prepared according to the method of US8853440B2.
  • Acid halide reagents other conventional raw materials and reagents are usually commercially available, and can also be self-made according to conventional methods.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl linear, branched or cyclic alkyl, such as methyl, ethyl, n-propyl, isopropyl or cyclopropyl, etc.
  • Haloalkyl Straight chain, branched or cyclic alkyl, the hydrogen atoms on these alkyl groups can be partially or completely replaced by halogen, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluoromethyl, trifluoromethyl, pentafluoroethyl or heptafluoroisopropyl, etc.
  • halogen such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluoromethyl, trifluoromethyl, pentafluoroethyl or heptafluoroisopropyl, etc.
  • Alkenyl straight-chain, branched or cyclic alkenyl groups such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers; alkenyl also includes polyenes Classes such as 1,2-propadienyl and 2,4-hexadienyl, etc.
  • Haloalkenyl an alkenyl group in which at least one or more hydrogen atoms may be replaced by a halogen atom.
  • Alkynyl includes straight or branched chain alkynyl groups such as ethynyl, 1-propynyl and the different butynyl, pentynyl and hexynyl isomers; alkynyl also includes radicals consisting of multiple triple bonds group, such as 2,5-hexadiynyl.
  • Haloalkynyl an alkynyl group in which at least one or more hydrogen atoms may be replaced by halogen atoms.
  • Alkoxy linear, branched or cyclic alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropyloxy or n-butoxy, etc.
  • Halogenated alkoxy straight chain, branched or cyclic alkoxy, the hydrogen atoms on these alkoxy can be partially or completely replaced by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, heptafluoroisopropyloxy, etc.
  • halogen such as chloromethoxy, dichloromethoxy, trichloromethoxy fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, heptafluoroisopropyloxy, etc.
  • Alkylthio Straight-chain, branched or cyclic alkyl, bonded to the structure via a sulfur atom, such as methylthio, ethylthio, etc.
  • Halogenated alkylthio straight chain, branched or cyclic alkylthio, the hydrogen atoms on these alkylthio can be partially or completely replaced by halogen, such as difluoromethylthio, trifluoroethylthio, etc.
  • Alkenylthio straight-chain, branched-chain or cyclic alkenyl, bonded to the structure via a sulfur atom, such as 1-propenyl-3-thio, 2-butenyl-4-thio, etc.
  • Haloalkenylthio straight-chain, branched or cyclic alkenylthio, the hydrogen atoms on these alkenylthio can be partially or fully replaced by halogen.
  • Alkynylthio straight-chain, branched-chain or cyclic alkynyl, bonded to the structure via a sulfur atom, such as 1-propynyl-3-thio, 2-butynyl-4-thio, etc.
  • Haloalkynylthio Straight-chain, branched or cyclic alkynylthio. The hydrogen atoms on these alkynylthio groups can be partially or completely replaced by halogen.
  • Alkylamino Straight-chain, branched-chain, or cyclic alkyl group bonded to the structure via a nitrogen atom bond, such as methylamino, ethylamino, n-propylamino, isopropylamino, or isomeric butyl Amino.
  • Dialkylamino Two identical or different straight-chain, branched-chain or cyclic alkyl groups linked to the structure via a nitrogen atom bond, such as dimethylamino, methylethylamino, dicyclopropylamino, etc.
  • Alkoxycarbonyl alkyl-O-CO-, eg CH 3 OCO-.
  • Alkylcarbonyl alkyl-CO-, such as CH3CO-
  • Alkylsulfonyl alkyl-S(O) 2 -, such as methylsulfonyl.
  • Alkylsulfinyl alkyl-S(O)-, eg methylsulfinyl.
  • Alkylaminocarbonyl alkyl-NH-CO-, eg CH 3 NHCO-.
  • Alkylaminosulfonyl alkyl-NH-S(O) 2 -, eg CH 3 NHS(O) 2 -.
  • the compound of general formula I is a chirality structure compound.
  • the compound can be mixed with a single chiral isomer or two chiral isomers Existing in different forms; the imine structure of the compound of general formula I has geometric isomerism, and the compound can exist in the form of a single geometric isomer or a mixture of two geometric isomers.
  • the compound shown in the general formula I to be protected by the present invention is not protected by the above Isomer structures exist as formal limitations.
  • the novel imine derivatives (compound of general formula I) of the present invention have excellent insecticidal and acaricidal activities, and can control the following pests: Lepidoptera pests, such as armyworm, beet armyworm and diamondback moth, etc.; Homoptera Pests, such as green peach aphid, leaf-chan and planthopper, etc.; Hemiptera pests, such as corn long bug, tomato mirid bug and rice ailanthus, etc.; Thysanoptera pests, such as cotton thrips, alfalfa thrips and soybean thrips, Western Flower thrips, etc.; Coleoptera pests, such as potato beetles and clam beetles; Diptera pests, such as flies and mosquitoes; Hymenoptera pests, such as bees and ants.
  • Lepidoptera pests such as armyworm, beet armyworm and diamondback moth, etc.
  • Homoptera Pests
  • the present invention also includes the use of the compound of general formula I for controlling insect pests and acarids in the fields of agriculture, forestry and hygiene.
  • the technical scheme of the present invention also includes a method for controlling pests: applying the pesticidal compound of the present invention to the pests or their growth medium.
  • the more suitable effective dose is 10 grams to 1000 grams per hectare, and the preferred effective dose is 20 grams to 500 grams per hectare.
  • the technical solution of the present invention also includes a method for controlling harmful mites: applying the insecticidal compound of the present invention to the harmful mites or their growth medium.
  • the more suitable effective dose is 10 grams to 1000 grams per hectare, and the preferred effective dose is 20 grams to 500 grams per hectare.
  • the compound of the invention is novel in structure, has both insecticidal and acaricidal properties, and has wide uses.
  • Embodiment 1 the preparation of compound I-38
  • reaction solution was lowered to room temperature, filtered to remove insoluble matter, added ethyl acetate (100mL) to dissolve, washed with saturated aqueous sodium bicarbonate solution and saturated brine successively, separated the organic phase, dried the organic phase with anhydrous magnesium sulfate, filtered Afterwards, the organic solvent was evaporated under reduced pressure, and the residue was separated and purified by column chromatography to obtain the title product, 1.86 g of a white solid, with a yield of 8% (with 2-bromo-4-heptafluoroisopropyl-6-trifluoromethylaniline count).
  • reaction system was cooled to room temperature, and the reaction solution was slowly poured into ice water (20 mL), fully stirred, and a solid was precipitated, filtered, and the filter cake was separated and purified by column chromatography to obtain the title product, 1.02 g of a white solid, and the yield was 90% ( N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethylphenyl)-2-fluoro-3-aminobenzamide).
  • the reaction system was cooled to room temperature, fully stirred, and the solid was gradually precipitated, filtered, and the filter cake was separated and purified by column chromatography to obtain the title product, 0.57 g of a white solid, and the yield was 85% (based on N-(2-bromo-4-heptafluoro (isopropyl-6-trifluoromethylphenyl)-2-fluoro-3-methylaminobenzamide).
  • reaction system was cooled to room temperature, the reaction solution was slowly poured into a large amount of ice water, fully stirred, dissolved with ethyl acetate (30mL), extracted, and layered, the organic phase was washed successively with saturated aqueous sodium bicarbonate and saturated brine, and separated The organic phase was taken out, and the organic phase was dried with anhydrous magnesium sulfate.
  • Embodiment 2 the preparation of compound I-46
  • Embodiment 3 the preparation of compound I-122
  • reaction system was cooled to room temperature, the reaction solution was slowly poured into a large amount of ice water, fully stirred, dissolved with ethyl acetate (30mL), extracted, and layered, the organic phase was washed successively with saturated aqueous sodium bicarbonate and saturated brine, and separated The organic phase was taken out, and the organic phase was dried with anhydrous magnesium sulfate.
  • Embodiment 4 the preparation of compound I-128
  • reaction system was cooled to room temperature, the reaction solution was slowly poured into a large amount of ice water, fully stirred, dissolved with ethyl acetate (30mL), extracted, and layered, the organic phase was washed successively with saturated aqueous sodium bicarbonate and saturated brine, and separated The organic phase was taken out, and the organic phase was dried with anhydrous magnesium sulfate.
  • Embodiment 5 the preparation of compound I-130
  • reaction system was cooled to room temperature, the reaction solution was slowly poured into a large amount of ice water, fully stirred, dissolved with ethyl acetate (30mL), extracted, and layered, the organic phase was washed successively with saturated aqueous sodium bicarbonate and saturated brine, and separated The organic phase was taken out, and the organic phase was dried with anhydrous magnesium sulfate.
  • Embodiment 6 the preparation of compound I-176
  • Embodiment 7 the preparation of compound I-618
  • Embodiment 8 the preparation of compound I-620
  • the system was lowered to room temperature, quenched with 1N hydrochloric acid, diluted with water, extracted with ethyl acetate, separated into layers, and the organic phase was washed with water and saturated brine successively, and separated The organic phase was taken out, dried with anhydrous magnesium sulfate, filtered, and the organic solvent was distilled off under reduced pressure. The residue was separated and purified by column chromatography to obtain the title compound, 95.5 mg of white solid, with a yield of 63%.
  • Embodiment 9 the preparation of compound I-626
  • the reaction system is cooled to room temperature, the reaction solution is poured into a large amount of water, extracted with ethyl acetate, layered, the organic phase is washed with water and saturated brine successively, and the organic phase is separated. phase, the organic phase was dried with anhydrous magnesium sulfate, filtered, and the organic solvent was distilled off under reduced pressure. The residue was separated and purified by column chromatography to obtain the title compound, 71.0 mg of white solid, with a yield of 48%.
  • Embodiment 10 the preparation of compound I-628
  • reaction system is lowered to room temperature, poured into a large amount of water, extracted with ethyl acetate, layered, organic phase Wash with water and saturated brine for several times, separate the organic phase, dry the organic phase with anhydrous magnesium sulfate, filter and distill off the organic solvent under reduced pressure, and the residue is separated and purified by column chromatography to obtain the title compound, white solid 122.3 mg, yield 85%.
  • Embodiment 11 the preparation of compound I-630
  • the reaction system was cooled to room temperature, and the reaction solution was poured into a large amount of water, extracted with ethyl acetate, layered, and the organic phase was washed with water and saturated brine successively , separated the organic phase, dried the organic phase with anhydrous magnesium sulfate, filtered and evaporated the organic solvent under reduced pressure, and the residue was separated and purified by column chromatography to obtain the title compound, 120.7 mg of white solid, with a yield of 76%.
  • Embodiment 12 Preparation of Compound I-632
  • solubility of the compound to be tested dissolve it with acetone or dimethyl sulfoxide, and then use 0.1% Tween 80 solution to prepare 50 ml of the test solution of the required concentration, acetone or dimethyl sulfoxide in the total solution content of not more than 10%, for use.
  • Select cabbage leaves cultivated at room temperature remove the waxy layer on the surface, use a puncher to make a circular leaf disc with a diameter of 2 cm, put it into the prepared medicinal solution and soak it for 10 seconds, dry it in the shade, and place it in a container with filter paper.
  • neat healthy test insects (2 instars) were inserted, and 10 insects were each treated. The test was repeated 4 times, and the water treatment was set as a blank control. After treatment, put them into a room with 24°C, 60%-70% relative humidity, and natural light for indoor cultivation. After 72 hours, investigate the number of surviving insects and calculate the mortality rate.
  • Embodiment 14 Determination of acaricidal activity

Abstract

La présente invention concerne le domaine des insecticides et des acaricides, et concerne spécifiquement un composé imine et son utilisation. La structure est représentée par la formule générale I, chaque substituant dans la formule étant défini dans la description. Le composé de formule générale I présente d'excellentes propriétés insecticides et acaricides, et peut être utilisé pour prévenir et lutter contre divers insectes nuisibles ou acariens nuisibles.
PCT/CN2022/118920 2021-09-28 2022-09-15 Composé imine et son utilisation WO2023051261A1 (fr)

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JP2006117565A (ja) * 2004-10-20 2006-05-11 Agro Kanesho Co Ltd 有害生物の防除に有効なトリフルオロメチルスルホニルアミジン誘導体
JP2009209090A (ja) * 2008-03-04 2009-09-17 Mitsui Chemicals Inc 殺虫剤及び該殺虫剤に含まれる化合物、並びに該化合物の使用方法
US20120022263A1 (en) * 2009-02-06 2012-01-26 Agro-Kanesho Co., Ltd. 3-aminoxalyl-aminobenzamide derivatives and insecticidal and miticidal agents containing same as active ingredient
US20120149910A1 (en) * 2009-08-14 2012-06-14 Bayer Cropscience Ag Pesticidal Carboxamides
WO2015040405A2 (fr) * 2013-09-18 2015-03-26 Redx Pharma Limited Produits chimiques agricoles
CN106278942A (zh) * 2015-05-20 2017-01-04 沈阳中化农药化工研发有限公司 一种制备肟醚类杀虫活性化合物高效体的方法
CN109206397A (zh) * 2017-06-29 2019-01-15 沈阳中化农药化工研发有限公司 一种胡椒酸衍生物及其制备和应用
CN112457288A (zh) * 2019-09-06 2021-03-09 沈阳中化农药化工研发有限公司 一种胡椒酸衍生物及其应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006117565A (ja) * 2004-10-20 2006-05-11 Agro Kanesho Co Ltd 有害生物の防除に有効なトリフルオロメチルスルホニルアミジン誘導体
JP2009209090A (ja) * 2008-03-04 2009-09-17 Mitsui Chemicals Inc 殺虫剤及び該殺虫剤に含まれる化合物、並びに該化合物の使用方法
US20120022263A1 (en) * 2009-02-06 2012-01-26 Agro-Kanesho Co., Ltd. 3-aminoxalyl-aminobenzamide derivatives and insecticidal and miticidal agents containing same as active ingredient
US20120149910A1 (en) * 2009-08-14 2012-06-14 Bayer Cropscience Ag Pesticidal Carboxamides
WO2015040405A2 (fr) * 2013-09-18 2015-03-26 Redx Pharma Limited Produits chimiques agricoles
CN106278942A (zh) * 2015-05-20 2017-01-04 沈阳中化农药化工研发有限公司 一种制备肟醚类杀虫活性化合物高效体的方法
CN109206397A (zh) * 2017-06-29 2019-01-15 沈阳中化农药化工研发有限公司 一种胡椒酸衍生物及其制备和应用
CN112457288A (zh) * 2019-09-06 2021-03-09 沈阳中化农药化工研发有限公司 一种胡椒酸衍生物及其应用

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