WO2020087694A1 - Substituted nitrogen-containing heterocyclic formamide derivative, weeding composition and uses thereof - Google Patents

Substituted nitrogen-containing heterocyclic formamide derivative, weeding composition and uses thereof Download PDF

Info

Publication number
WO2020087694A1
WO2020087694A1 PCT/CN2018/121998 CN2018121998W WO2020087694A1 WO 2020087694 A1 WO2020087694 A1 WO 2020087694A1 CN 2018121998 W CN2018121998 W CN 2018121998W WO 2020087694 A1 WO2020087694 A1 WO 2020087694A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
alkoxy
halogen
cycloalkyl
substituted
Prior art date
Application number
PCT/CN2018/121998
Other languages
French (fr)
Chinese (zh)
Inventor
连磊
华荣保
崔琦
张辽宁
刘娜
Original Assignee
青岛清原化合物有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 青岛清原化合物有限公司 filed Critical 青岛清原化合物有限公司
Publication of WO2020087694A1 publication Critical patent/WO2020087694A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D403/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/501,3-Diazoles; Hydrogenated 1,3-diazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/501,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/521,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/541,3-Diazines; Hydrogenated 1,3-diazines
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/761,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/781,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D405/00Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D409/00Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D417/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D471/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0834Compounds having one or more O-Si linkage
    • C07F7/0836Compounds with one or more Si-OH or Si-O-metal linkage

Definitions

  • the invention belongs to the technical field of pesticides, and particularly relates to a substituted nitrogen-containing heteroaromatic ring formamide derivative and its herbicidal composition and use.
  • Patent WO2003 / 011853 discloses the use of 6-aryl- 4-Aminopyridine carbamate and its derivatives as herbicides: WO2005 / 063721A1, WO2007 / 082076A1, US7,863,220B2, US7,300,907B2, US7,642,220B2 and US7,786,044B2 disclose certain 6-amino-2-substituted-pyrimidine-4-carboxylic acids and their derivatives and Its use as a herbicide.
  • the present invention provides a substituted nitrogen-containing heteroaromatic ring formamide derivative and its herbicidal composition and use.
  • the substituted nitrogen-containing heteroaromatic ring formamide derivatives and their herbicidal compositions have excellent herbicidal activity and crop selectivity.
  • a substituted nitrogen-containing heteroaromatic ring formamide derivative its structural formula is as follows:
  • M represents Het is selected from a five-membered unsaturated ring, which contains 1-3 atoms or groups in addition to the N atom at the 1-position as a component of the ring: NR b ;
  • R b represents hydrogen, alkyl
  • Q stands for N or CR "; where R” stands for hydrogen, halogen, cyano, alkyl with or without halogen, alkoxy, alkenyl, alkynyl, cycloalkyl, and unsubstituted or substituted aryl , Heteroaryl;
  • X represents halogen, with or without halogen alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, unsubstituted or substituted aryl, heteroaryl;
  • R 11 and R 21 independently represent halogen, hydroxyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted Aryl, heteroaryl;
  • R 12 and R 22 independently represent H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ;
  • R 41 represents H, alkyl or alkoxy;
  • R 42 represents H, alkyl or benzyl;
  • R 14 represents alkyl, haloalkyl
  • R 15 represents H, alkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl;
  • R 16 represents H, alkyl;
  • R 17 represents H, alkyl, unsubstituted or substituted with 1-3 groups in halogen, alkyl, alkoxy;
  • R 18 represents H, alkyl; or
  • N CR 17 R 18 represents
  • R 31 and R 34 independently represent H or alkyl
  • R 32 and R 33 independently represent H or alkyl; or NR 32 R 33 represents a 5- or 6-membered saturated or unsaturated ring that does not contain or contains an oxygen atom, sulfur atom or other nitrogen atom;
  • R 35 represents alkyl
  • M represents Het is selected from a five-membered unsaturated ring, which contains 1, 2 or 3 atoms or groups as part of the ring in addition to the N atom at the 1-position: NR b ;
  • R a is selected from the group of one or more groups: hydrogen, halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, containing or not containing a halogen C1-C8 alkyl, C2 -C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C2-C8 alkenyl C1-C8 alkyl, C2-C8 alkynyl C1-C8 alkyl, C3-C8 cycloalkyl C1-C8 alkyl Group, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkylthio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 Alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 al
  • R b represents hydrogen, C1-C8 alkyl
  • Q stands for N or CR "; where R” stands for hydrogen, halogen, cyano, C1-C8 alkyl with or without halogen, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
  • X represents halogen, with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylamino, di C1-C8 alkylamino, unsubstituted or substituted aryl, heteroaryl;
  • R 11 and R 21 independently represent halogen, hydroxyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 Alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;
  • R 12 and R 22 independently represent H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ;
  • R 41 represents H, C1-C8 alkyl or C1-C8 alkoxy Radical;
  • R 42 represents H, C1-C8 alkyl or benzyl;
  • R 14 represents C1-C8 alkyl, halogenated C1-C8 alkyl
  • R 15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylcarbonyl, halogenated C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl;
  • R 16 represents H, C1-C8 alkyl;
  • R 17 represents H, C1-C8 alkyl, unsubstituted or substituted by 1-3 groups in halogen, C1-C8 alkyl, C1-C8 alkoxy;
  • R 18 represents H, C1- C8 alkyl; or
  • N CR 17 R 18 represents
  • R 31 and R 34 independently represent H or C1-C8 alkyl
  • R 32 and R 33 independently represent H or C1-C8 alkyl; or NR 32 R 33 represents
  • R 35 represents C1-C8 alkyl
  • Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1- C8 alkyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxy C1-C8 alkyl , C1-C8 alkylthio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylacyloxy, C1-C8 alkylsulfinyl, C1-C8 alkyl Sulfonyl, -S-CN, R 51 R 52 R 53 Si- (O
  • R ' represents hydrogen or alkyl; it can be selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, unsubstituted or selected from halogen, alkyl, alkoxy Phenyl, benzyl, phenoxy substituted with at least one group, and alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkylthio with or without halogen , Alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-
  • M represents Het is selected from a five-membered unsaturated ring, which contains 1, 2 or 3 atoms or groups as part of the ring in addition to the N atom at the 1-position: NR b ;
  • R a is selected from one or more of the following groups: hydrogen, halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C6 alkyl with or without halogen, C2 -C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C6 alkenyl C1-C6 alkyl, C2-C6 alkynyl C1-C6 alkyl, C3-C6 cycloalkyl C1-C6 alkyl Group, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 Alkoxycarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkyls
  • R b represents hydrogen, C1-C6 alkyl
  • Q represents N or CR "; where R" represents hydrogen, halogen, cyano, C1-C6 alkyl with or without halogen, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
  • X represents halogen, with or without halogen C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylamino, di C1-C6 alkylamino, unsubstituted or substituted aryl, heteroaryl;
  • R 11 and R 21 independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 Alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;
  • R 12 and R 22 independently represent H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ;
  • R 41 represents H, C1-C6 alkyl or C1-C6 alkoxy Radical;
  • R 42 represents H, C1-C6 alkyl or benzyl;
  • R 14 represents C1-C6 alkyl, halogenated C1-C6 alkyl
  • R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl;
  • R 16 represents H, C1-C6 alkyl;
  • R 17 represents H, C1-C6 alkyl, unsubstituted or substituted by 1-3 groups in halogen, C1-C6 alkyl, C1-C6 alkoxy;
  • R 18 represents H, C1- C6 alkyl; or
  • N CR 17 R 18 represents
  • R 31 and R 34 independently represent H or C1-C6 alkyl
  • R 32 and R 33 independently represent H or C1-C6 alkyl; or NR 32 R 33 represents
  • R 35 represents C1-C6 alkyl
  • Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1- C6 alkyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxy C1-C6 alkyl , C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylacyloxy, C1-C6 alkylsulfinyl, C1-C6 alkyl Sulfonyl, -S-CN, R 51 R 52 R 53 Si- (O
  • R ' represents hydrogen, C1-C8 alkyl; it can be selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, unsubstituted or selected from halogen, C1-C8 alkyl , C1-C8 alkoxy substituted by at least one group of phenyl, benzyl, phenoxy, and with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl , C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkyl Thio C1-
  • M represents unsubstituted or selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, with or without fluorine, chlorine, bromine, iodine C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkenyl C1-C4 alkyl, C2-C6 alkynyl C1-C4 alkyl, C3-C6 ring Alkyl C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkyl Carbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkyl, C
  • Q stands for N or CR "; where R” stands for hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C4 alkyl, C1-C4 alkoxy, with or without fluorine, chlorine, bromine, iodine, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
  • X represents fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 with or without fluorine, chlorine, bromine, iodine Alkoxy, C1-C4 alkylamino, di-C1-C4 alkylamino, unsubstituted or substituted aryl, heteroaryl;
  • Y stands for NH 2 , NHMe, N (Me) 2 ,
  • Z represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C4 alkyl, C3-C6 with or without fluorine, chlorine, bromine, iodine Cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4 alkylamino , C1-C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylacyloxy, C1 -C4 alkylsulfinyl, C1-C4 alkyls
  • R ' represents hydrogen, C1-C6 alkyl; it can be selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, unsubstituted or selected from fluorine , Chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 alkoxy substituted by 1 to 3 groups of phenyl, benzyl, phenoxy, and with or without fluorine, chlorine, bromine , Iodine C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6
  • M represents unsubstituted or selected from fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C4 alkane with or without fluorine, chlorine, bromine Group, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C4 alkenyl C1-C2 alkyl, C2-C4 alkynyl C1-C2 alkyl, C3-C6 cycloalkyl C1 -C2 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxy C1-C2 alkyl, C1-C4 alkylthio C1-C2 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C
  • Q stands for N or CR "; where R” stands for hydrogen, fluorine, chlorine, bromine, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkene with or without fluorine, chlorine, bromine Group, C2-C4 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted phenyl;
  • X represents fluorine, chlorine, bromine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 alkoxy, with or without fluorine, chlorine, bromine C1-C4 alkylamino, di-C1-C4 alkylamino, unsubstituted or substituted phenyl, naphthyl,
  • Y stands for NH 2 , NHMe, N (Me) 2 ,
  • Z represents hydrogen, fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C4 alkyl, C2-C4 alkenyl, C3 with or without fluorine, chlorine, bromine -C6 cycloalkyl, C3-C6 cycloalkyl C1-C2 alkyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4 alkyl Amino, C1-C4 alkoxy C1-C2 alkyl, C1-C4 alkylthio C1-C2 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylacyloxy , C1-C4 alkylsulfinyl, C1-C4 alkylsul
  • substituted means that it is selected from fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, amino, mercapto, formyl, and C1- with or without fluorine, chlorine, or bromine C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1 -C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C1-C4 1, 2, or 3 groups in the alkylsulfonyl group, C1-C4 alkylamino group,
  • halogen refers to fluorine, chlorine, bromine, iodine
  • alkyl refers to straight-chain alkyl or branched Chain alkyl.
  • a herbicidal composition includes (i) a substituted nitrogen-containing heteroaromatic ring formamide derivative represented by general formula I; preferably, it also includes (ii) one or more additional herbicides and / or safeners ; More preferably, (iii) agrochemically acceptable formulation aids.
  • a method for controlling weeds includes using a herbicidally effective amount of at least one of the substituted nitrogen-containing heteroaromatic ring carboxamide derivatives or the herbicidal composition on plants or weed areas.
  • At least one of the substituted nitrogen-containing heteroaromatic ring carboxamide derivatives or the use of the herbicidal composition for controlling weeds preferably, the substituted nitrogen-containing heteroaromatic ring carboxamide Derivatives are used to control weeds in useful crops, which are genetically modified crops or crops treated by genome editing techniques.
  • the present invention also includes a method for preparing the compound of the present invention, which includes the following steps:
  • the reaction in the step (1) is carried out in the presence of a condensing agent and a solvent, the condensing agent is PyBOP, HATU or CDI, and the solvent is selected from one or more of DCM, DCE, ACN, DMF and THF ;
  • Base can be added to the reaction system as needed, the base is selected from TEA, NMM or DIPEA; the reaction temperature is 0-100 °C, preferably 25-50 °C.
  • the acid halogenation reaction temperature is 0-100 ° C, and the acid halogenation reagent used is SOCl 2 ; then the next reaction is carried out in the presence of a base and a solvent, the solvent is selected from DCM, DCE, ACN , DMF, one or more of THF, the base is selected from TEA, NMM or DIPEA, the reaction temperature is 0-25 °C.
  • the compounds of formula I according to the invention have outstanding herbicidal activity.
  • the active substances of the present invention are also effective for perennial weeds, which grow from rhizomes, rhizomes, or other perennial organs, and are difficult to control. In this regard, it is generally not important whether the substance is used before sowing, before germination or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed colonies that can be controlled by the compounds of the present invention, and there is no limitation to certain species.
  • weed species where the active substance works effectively include monocotyledons: annual oats, rye, grass, hordeum, ferraris, barnyardgrass, crabgrass, foxtail and sedge, and perennial ice Grasses, bermudagrass, chrysanthemum and sorghum, and perennial sedges.
  • dicotyledonous weed species the effects of which can be extended to species such as the annual Swine, Viola, Pompona, Wild Sesame, Stellaria, Amaranthus, Sphaeropsis, Ipomoea, Hirsch Genus, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia.
  • the active substance of the present invention can effectively control harmful plants, such as barnyardgrass, Cicus, Alisma, water chestnut, cane grass, and sedge, under such predetermined conditions as rice seeding.
  • the weed seedlings can be completely prevented before the weeds grow, or they can stop growing when the weeds grow cotyledons, and finally die completely after three to four weeks.
  • the compounds of the present invention are particularly active against the following plants, Apila grass, Ono sesame, Polygonum sibiricum, Stellaria, Ivy leaf Pompa, Arab Pompa, Pansy and Amaranthus, Swamp, and Kochia .
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not harmful to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean , Or the damage is negligible. Especially compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compound of the present invention is very suitable for selectively controlling useless plants in agricultural or ornamental plants.
  • Transgenic plants Due to their herbicidal properties, these active substances can be used to control harmful plants in the cultivation of genetically engineered plants that are known or will appear.
  • Transgenic plants generally have superior traits, such as resistance to specific insecticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insect or fungal, bacterial or viral microorganisms.
  • Other special characteristics are related to the following conditions of the product, for example, quantity, quality, storage stability, components and special ingredients. As such, it is known that the obtained transgenic plant products have increased starch content or improved starch quality or different fatty acid compositions.
  • the compounds of the formula I or salts thereof of the present invention are preferably used for economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or for sugar beets, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of formula I are preferably used as herbicides for the cultivation of useful plants, which plants are resistant or resistant to the toxic effects of the herbicides through genetic engineering.
  • Plant cells with reduced activity gene products can be prepared by the following methods, for example, by expressing at least one appropriate antisense-RNA, sense-RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme, It specifically cleaves the transcription products of the above-mentioned gene products.
  • DNA molecules that contain the entire coding sequence of the gene product including any flanking sequences that may be present, and DNA molecules that contain only a portion of the coding sequence, which must be long enough to achieve antisense in the cell Effect. It is also possible to use sequences that have a high degree of homology to the gene product coding sequence but are not completely identical.
  • the synthesized protein When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, in order to locate in a specific chamber, it is possible, for example, to connect the coding region and the DNA sequence to ensure the localization at a specific position. These sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992) 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J.1 (1991), 95-106).
  • Transgenic plant cells can be recombined into whole plants using known techniques.
  • the active substance of the present invention When using the active substance of the present invention on genetically modified crops, in addition to the observable effects on other crops of suppressing harmful plants, there will often be special effects on the corresponding genetically modified crops, for example, to improve or expand control
  • the range of weeds, improved application rates during application preferably a good combination of the resistance of transgenic crops and the performance of herbicides, and the effects of growth and yield of transgenic crop plants. Therefore, the present invention also provides the use of the compound as a herbicide for controlling harmful plants in transgenic crop plants.
  • the compounds of the present invention can significantly regulate the growth of crop plants. By regulating participation in plant metabolism, these compounds are used to directionally control plant components and promote harvesting, such as drying and dwarfing plant growth. And they are also suitable for regulating and inhibiting undesired plant growth without destroying the growth of crops. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, because this can reduce or completely prevent lodging.
  • the present invention has found that the compounds of formula I are useful as pre-emergence and post-emergence herbicides for rice and cereal planting systems and forage management planning.
  • herbicide is used herein to mean killing, controlling, or other active ingredients that adversely alter plant growth.
  • the herbicidal effective amount or vegetation control amount is the amount of active ingredients that cause adverse alteration and include deviation from natural development, killing, conditioning, dehydration, delay, etc.
  • plants and vegetation include germinated seeds, emerged seedlings, aboveground and underground plant parts such as branches, roots, tubers, rhizomes, etc., and grown vegetation.
  • the compound of the present invention exhibits herbicidal activity.
  • the actual measurement effect depends on the plant species to be controlled, the plant growth stage, the application parameters of the dilution and spray droplet size (the application parameters of spraying size), the particle size of the solid components, the environmental conditions at the time of use, the used Specific compounds, specific excipients and carriers used, soil type, water quality, etc., as well as the amount of chemicals applied. It is known in the art that these and other factors can be adjusted to promote selective herbicidal action. Generally, it is preferred to apply the compound of formula I to relatively immature undesirable vegetation via spray or water application after seedling to achieve maximum control of weeds.
  • Foliar application and water application post-emergence operations generally use application rates of 1 to 500 grams per hectare (g / ha).
  • the preferred application rate is 10 to 300 g / ha.
  • an application rate of 5 to 500 g / ha is generally used.
  • the preferred application rate is 30 to 300 g / ha.
  • the higher application rates designed generally produce non-selective control of a wide variety of undesirable vegetation.
  • Lower application rates typically produce selective control and can be used in the locus of the crop.
  • the herbicidal compounds of the present invention are often applied in combination with one or more other herbicides to control a wider variety of undesirable vegetation.
  • the compound claimed in the present invention can be formulated with one or more herbicides, mixed with other one or more herbicide tanks or mixed with other one or more herbicides Apply sequentially.
  • the compounds of the invention can additionally be used to control undesired vegetation in a variety of crops that have been made tolerant or resistant to the compounds of the invention or other herbicides by genetic manipulation or by mutation and selection.
  • the herbicidal compounds of the present invention can also be combined with glyphosate, glufosinate, dicamba, imidazolinones, aryloxyphenoxypropionates or 2,4- Drip (2,4-D) is used in combination with glyphosate, glufosinate, dicamba, imidazolinone, aryloxyphenoxypropionate or 2,4-D crops.
  • the compounds of the present invention can be used in combination with herbicides whose application rates are selective for the crops to be treated, and which complement the spectrum of weeds controlled by these compounds. It is generally further preferred to apply the compound of the present invention and other supplementary herbicides simultaneously as a combined preparation or as a tank mix.
  • the herbicidal compounds of the present invention can be used in combination with acetolactate synthase (ALS) inhibitors for crops resistant to acetolactate synthase inhibitors or in combination with 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors For crops resistant to 4-hydroxyphenylpyruvate dioxygenase inhibitors.
  • ALS acetolactate synthase
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • the compounds of the present invention can generally be used in combination with known herbicide safeners such as benoxacor, benthiocarb, brassinolide to enhance their selectivity Brassinolide, cloquintocet (mexyl), cyometrinil, cyprosulfamide, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietholate , Dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, chlorimide Furilazole, harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxalane (MG191), MON4660, naphthalene Naphthalicanhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoicacidamides.
  • herbicide safeners such as
  • the compounds of the invention can additionally be used to control undesirable vegetation in a variety of crops that have been made tolerant or resistant to the compounds of the invention or to other herbicides through genetic manipulation or through mutation and selection.
  • crops that have been made tolerant or resistant to the compounds of the invention or to other herbicides through genetic manipulation or through mutation and selection.
  • corn, wheat, rice, soybean, sugar beet, cotton, brassica, and other crops that have been tolerated or resistant to compounds that are acetolactate synthase inhibitors in susceptible plants can be treated.
  • a variety of glyphosate-tolerant and glufosinate-tolerant crops can also be treated alone or in combination with these herbicides.
  • auxin herbicides such as 2,4- (dichlorophenoxy) acetic acid (2,4-D) and dicamba and aryloxyphenoxypropionate. These herbicides can be used to treat such resistant crops or other auxin-resistant crops.
  • Some crops are already resistant to herbicides that inhibit 4-hydroxyphenylpyruvate dioxygenase, and these herbicides can be used to treat such resistant crops.
  • the compound of formula I is preferred to use it in the form of a mixture containing the herbicidally effective amount of the compound and at least one agriculturally acceptable adjuvant or carrier.
  • Suitable excipients or carriers should not be phytotoxic to valuable crops, especially in the concentrations used in the application of compositions for selective weed control in the presence of crops, and should not occur with compounds of formula I or other composition ingredients chemical reaction.
  • Such a mixture may be designed to be applied directly to the weed or its locus, or it may be a concentrate or formulation that is usually diluted with additional carriers and adjuvants before application.
  • They can be solids, such as powders, granules, water-dispersible granules or wettable powders, or liquids, such as emulsifiable concentrates, solutions, emulsions or suspensions. They can also be provided as a premix or tank mix.
  • Suitable agricultural excipients and carriers for preparing the herbicidal mixtures of the present invention are well known to those skilled in the art. Some of these excipients include, but are not limited to, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylate; benzyl cocoa alkyl dimethyl quaternary ammonium salt ; Blend of petroleum hydrocarbons, alkyl esters, organic acids and anionic surfactants; C9-C11 alkyl polyglycosides; phosphorylated alcohol ethoxylates; natural primary alcohols (C12-C16) ethoxylates; Di-sec-butylphenol EO-PO block copolymer; methyl-terminated polysiloxane; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl (synthetic) ethyl Oxygenate (8EO); Tallowamine
  • Useful liquid carriers include water and organic solvents.
  • the organic solvents used typically include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oil, etc .; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower oil, coconut oil, corn Oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc .; and esters of the above vegetable oils; monohydric or binary, ternary or other lower polyols (containing 4-6 hydroxyl groups) Esters, such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, dibutyl adipate, diphthalate Octyl esters, etc .; esters of mono-, di- and polycarboxylic acids, etc.
  • organic solvents include toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, tetrachloroethylene, ethyl acetate, amyl acetate, butyl acetate Ester, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, pentanol, ethylene glycol, propylene glycol, glycerin, N-methylpyrrolidone-2-one, N, N-dimethyl Alkyl amide, dimethyl sulfoxide, liquid fertilizer, etc. Water is usually the carrier of choice for dilution of the concentrate.
  • Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgusclay, kaolin, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, bleach Soil (Fuller'searth), cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, etc.
  • surfactants are advantageously used in solid and liquid compositions, especially compositions designed to be diluted with a carrier before application.
  • the nature of the surfactant can be anionic, cationic or nonionic, and can be used as an emulsifier, wetting agent, suspending agent or for other purposes.
  • Surfactants that are commonly used in the field of formulations and can also be used in this formulation are specifically (interalia) in "McCutcheon's Detergents and EmulsifiersAnnual," MC Publishing.Corp., Ridgewood, New Jersey, 1998 and “Encyclopedia of Surfactants” , "Vol.I-III, Chemical Publishing Co., New York, 1980-81.
  • Typical surfactants include alkyl sulfates, such as diethanolammonium laurylsulfate; alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-oxyalkylene addition products, For example, nonylphenol-C18 ethoxylate; alcohol-oxyalkylene addition product, such as tridecyl alcohol-C16 ethoxylate; soap, such as sodium stearate; alkylnaphthalene-sulfonate, such as di Sodium butylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium bis (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium, For example, lauryl trimethyl ammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glyco
  • compositions commonly used in agricultural compositions include compatibilizers, defoamers, sequestering agents, neutralizers and buffers, corrosion inhibitors, dyes, fragrances, spreading agents, penetration aids, adhesives, dispersion Agents, thickeners, antifreeze agents, antimicrobial agents, etc.
  • the composition can also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, insecticides, etc., and can be combined with liquid fertilizers or solid granular fertilizer carriers such as ammonium nitrate, urea, etc. Prepare together.
  • the concentration of the active ingredient in the herbicidal composition of the present invention is usually 0.001 to 98% by weight (weight percent). A concentration of 0.01 to 90% by weight is often used. In compositions designed for use as concentrates, the active ingredient is usually present in a concentration of 5 to 98% by weight, preferably 10 to 90% by weight.
  • the composition is typically diluted with an inert carrier (eg water) before application.
  • the diluted composition which is usually applied to the weeds or locus of the weeds generally contains 0.0001 to 1% by weight of active ingredient, and preferably contains 0.001 to 0.05% by weight of active ingredient.
  • composition of the present invention can be used by adding conventional ground or air dusters, sprayers and granule applicators, by addition to irrigation water or paddy flood water and by others known to those skilled in the art Conventional means are applied to weeds or their locus.
  • the standard of activity level of harmful plant destruction (ie growth control rate) is as follows:
  • Level 5 The growth control rate is above 85%;
  • Level 4 The growth control rate is greater than or equal to 60% and less than 85%;
  • Level 3 Growth control rate is greater than or equal to 40% and less than 60%;
  • Level 2 The growth control rate is greater than or equal to 20% and less than 40%;
  • Level 1 The growth control rate is greater than or equal to 5% and less than 20%;
  • Level 0 The growth control rate is less than 5%.
  • the above growth control rate is the fresh weight control rate.
  • Post-emergence test experiment Place monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) in a plastic pot filled with soil, and then cover 0.5-2 cm soil, let it grow in a good greenhouse environment, treat the test plants at 4-5 leaf stage after sowing for 2-3 weeks, dissolve the tested compound of the invention with acetone, and then add Tween 80, Dilute it with a certain amount of water to a certain concentration, and spray it on the plants with a spray tower. After the application, the plants were cultivated in the greenhouse for 3 weeks. After 3 weeks, the experimental effects of weeds are shown in Table 3.
  • Control Compound A Control Compound B: Control Compound C: Control Compound D:
  • the compound of the present invention has significantly higher control effect or crop selectivity than the control compound.
  • the compound of the present invention to be tested is dissolved in acetone, then Tween 80 is added, diluted with a certain amount of water to a solution of a certain concentration, and sprayed immediately after sowing.
  • the experimental results were observed after 3 weeks, and it was found that most of the agents of the present invention are excellent at 250 g / ha, and many compounds have good choices for corn, wheat, rice, soybean, rape Sex.
  • the compounds of the present invention generally have better weed control effects, especially for the broad-leaved weeds such as velvetleaf, needle needle grass and other weeds that widely occur in corn fields, rice fields and wheat fields
  • the effect has good commercial value.
  • the broadleaf weeds such as Maijiagong, Swamp, and Stellaria which are resistant to ALS inhibitors have extremely high activity.

Abstract

The present invention relates to a substituted nitrogen-containing heterocyclic formamide derivative, a weeding composition and the uses thereof. The substituted nitrogen-containing heteroaromatic ring formamide derivative has a structural formula as shown in the specification, wherein M represents (AA), Q represents N or C-R, X represents halogen and the like, Y represents nitro or NR1R 2, Z represents hydrogen, halogen, cyano, nitro, amino and the like. The substituted nitrogen-containing heterocyclic formamide derivative and the weeding composition thereof show good herbicidal activity and crop selectivity.

Description

一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途Substituted nitrogen-containing heteroaromatic ring formamide derivative and its herbicidal composition and use 技术领域Technical field
本发明属于农药技术领域,具体涉及一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途。The invention belongs to the technical field of pesticides, and particularly relates to a substituted nitrogen-containing heteroaromatic ring formamide derivative and its herbicidal composition and use.
背景技术Background technique
杂草的防治是实现高效农业过程中一个至关重要的环节,目前市场上的吡啶/嘧啶甲酸类除草剂种类多样,专利WO2003/011853公开了采用如下通式Ⅰ所示的6-芳基-4-氨基吡啶甲酸酯及其衍生物作为除草剂:
Figure PCTCN2018121998-appb-000001
WO2005/063721A1、WO2007/082076A1、US7,863,220B2、US7,300,907B2、US7,642,220B2和US7,786,044B2公开了某些6-氨基-2-取代的-嘧啶-4-甲酸和其衍生物及其作为除草剂的用途。
The control of weeds is a crucial link in the process of achieving efficient agriculture. There are various types of pyridine / pyrimidinecarboxylic acid herbicides currently on the market. Patent WO2003 / 011853 discloses the use of 6-aryl- 4-Aminopyridine carbamate and its derivatives as herbicides:
Figure PCTCN2018121998-appb-000001
WO2005 / 063721A1, WO2007 / 082076A1, US7,863,220B2, US7,300,907B2, US7,642,220B2 and US7,786,044B2 disclose certain 6-amino-2-substituted-pyrimidine-4-carboxylic acids and their derivatives and Its use as a herbicide.
由于市场的不断扩大、杂草的抗性、药物的使用寿命以及药物的经济性等问题以及人们对环境的日益重视,需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。Due to the continuous expansion of the market, the resistance of weeds, the service life of drugs and the economics of drugs, and the increasing emphasis on the environment, scientists need to continue to research and develop new high-efficiency, safe, economic, and different Variety of herbicides in different ways.
发明内容Summary of the invention
基于此,本发明提供了一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途。所述取代的含氮杂芳环甲酰胺衍生物及其除草组合物具有优异的除草活性和作物选择性。Based on this, the present invention provides a substituted nitrogen-containing heteroaromatic ring formamide derivative and its herbicidal composition and use. The substituted nitrogen-containing heteroaromatic ring formamide derivatives and their herbicidal compositions have excellent herbicidal activity and crop selectivity.
本发明采用的技术方案如下:The technical scheme adopted by the present invention is as follows:
一种取代的含氮杂芳环甲酰胺衍生物,其结构式如下:A substituted nitrogen-containing heteroaromatic ring formamide derivative, its structural formula is as follows:
Figure PCTCN2018121998-appb-000002
Figure PCTCN2018121998-appb-000002
式中,M代表
Figure PCTCN2018121998-appb-000003
Het选自五元不饱和环,该环上除含有1-位上的N原子外,还含有1-3个以下原子或基团作为环的组成部分:NR b
In the formula, M represents
Figure PCTCN2018121998-appb-000003
Het is selected from a five-membered unsaturated ring, which contains 1-3 atoms or groups in addition to the N atom at the 1-position as a component of the ring: NR b ;
R a选自以下基团中的一个或多个基团:氢,卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的烷基、烯基、炔基、环烷基、烯基烷基、炔基烷基、环烷基烷基、烷氧基、烷硫基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基亚硫酰 基、烷基磺酰基、烷基氨基、二烷基氨基、烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基、芳基氧基、杂芳基氧基;或者相邻两个R a一起形成未取代或取代的-CH=CH-CH=CH-、-CH 2CH 2CH 2CH 2-、-N=CH-CH=CH-、-CH=N-CH=CH-基团; R a is selected from one or more of the following groups: hydrogen, halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, alkyl with or without halogen, alkenyl, alkyne Group, cycloalkyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl , Alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylacyloxy and unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl, Aryloxy, heteroaryloxy; or two adjacent Ra together form unsubstituted or substituted -CH = CH-CH = CH-, -CH 2 CH 2 CH 2 CH 2- , -N = CH -CH = CH-, -CH = N-CH = CH- group;
R b代表氢,烷基; R b represents hydrogen, alkyl;
Q代表N或C-R”;其中,R”代表氢,卤素,氰基,含有或不含有卤素的烷基、烷氧基、烯基、炔基、环烷基,以及未取代或取代的芳基、杂芳基;Q stands for N or CR "; where R" stands for hydrogen, halogen, cyano, alkyl with or without halogen, alkoxy, alkenyl, alkynyl, cycloalkyl, and unsubstituted or substituted aryl , Heteroaryl;
X代表卤素,含有或不含有卤素的烷基、烯基、炔基、环烷基、烷氧基、烷基氨基、二烷基氨基,未取代或取代的芳基、杂芳基;X represents halogen, with or without halogen alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, unsubstituted or substituted aryl, heteroaryl;
Y代表硝基或NR 1R 2,其中R 1代表H,任选地被1-2个R 11取代的烷基、烯基或炔基,未取代或取代的芳基、杂芳基,-COR 12,硝基,OR 13,SO 2R 14,NR 15R 16,N=CR 17R 18,烷基氨基甲酰基,二烷基氨基甲酰基,三烷基甲硅烷基或二烷基膦酰基;R 2代表H,任选地被1-2个R 21取代的烷基或-COR 22;或者NR 1R 2代表N=CR 31NR 32R 33,N=CR 34OR 35,未取代或被1-2个独立选自卤素、烷基、烷氧基、卤代烷氧基、烷硫基、卤代烷硫基、氨基、烷基氨基、二烷基氨基、烷氧基羰基中的基团所取代的不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环; Y represents nitro or NR 1 R 2 , wherein R 1 represents H, alkyl, alkenyl or alkynyl optionally substituted by 1-2 R 11 , unsubstituted or substituted aryl, heteroaryl,- COR 12 , nitro, OR 13 , SO 2 R 14 , NR 15 R 16 , N = CR 17 R 18 , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphine Acyl; R 2 represents H, optionally substituted with 1-2 R 21 alkyl or -COR 22 ; or NR 1 R 2 represents N = CR 31 NR 32 R 33 , N = CR 34 OR 35 , unsubstituted Or by 1-2 groups independently selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl Substituted 5- or 6-membered saturated or unsaturated rings containing no or containing oxygen atoms, sulfur atoms or other nitrogen atoms;
其中R 11、R 21独立地代表卤素,羟基,烷氧基,卤代烷氧基,烷硫基,卤代烷硫基,氨基、烷基氨基,二烷基氨基,烷氧基羰基,未取代或取代的芳基、杂芳基; Where R 11 and R 21 independently represent halogen, hydroxyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted Aryl, heteroaryl;
R 12、R 22独立地代表H、烷基、卤代烷基、烷氧基、苯基、苯氧基或苄氧基; R 12 and R 22 independently represent H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;
R 13代表H、烷基、卤代烷基、苯基、苄基或CHR 41C(O)OR 42;R 41代表H、烷基或烷氧基;R 42代表H、烷基或苄基; R 13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ; R 41 represents H, alkyl or alkoxy; R 42 represents H, alkyl or benzyl;
R 14代表烷基、卤代烷基; R 14 represents alkyl, haloalkyl;
R 15代表H、烷基、甲酰基、烷基羰基、卤代烷基羰基、烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基;R 16代表H、烷基; R 15 represents H, alkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, alkyl;
R 17代表H、烷基、未取代或被卤素、烷基、烷氧基中的1-3个基团所取代的苯基;R 18代表H、烷基;或N=CR 17R 18代表
Figure PCTCN2018121998-appb-000004
R 17 represents H, alkyl, unsubstituted or substituted with 1-3 groups in halogen, alkyl, alkoxy; R 18 represents H, alkyl; or N = CR 17 R 18 represents
Figure PCTCN2018121998-appb-000004
R 31、R 34分别独立地代表H或烷基; R 31 and R 34 independently represent H or alkyl;
R 32、R 33分别独立地代表H或烷基;或者NR 32R 33代表不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环; R 32 and R 33 independently represent H or alkyl; or NR 32 R 33 represents a 5- or 6-membered saturated or unsaturated ring that does not contain or contains an oxygen atom, sulfur atom or other nitrogen atom;
R 35代表烷基; R 35 represents alkyl;
Z代表氢,卤素,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有卤素的烷基、环烷基、环烷基烷基、炔基、烷氧基、烷硫基、烷基氨基、二烷基氨基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基酰氧基、烷基亚硫酰基、烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自卤素、氰基、环烷基、烷基羰基、烷氧基羰基、烷氧基、烷硫基、烷基亚硫酰基、烷基磺酰基中的至少一个基团所取代的烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表烷基、环烷基、卤代烷基、卤代环烷基、未取代或取代的苯基、烷氧基、卤代烷氧基、羟基;R 54代表氢、卤素、烷基、卤代烷基;R 55代表氢、卤素;m代表0或1,n代表0~8之间的整数。 Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, alkyl with or without halogen, cycloalkyl, cycloalkylalkyl, alkynyl, alkoxy, alkyl Thio, alkylamino, dialkylamino, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylacyloxy, alkylsulfinyl, alkylsulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected from halogen, cyanide An alkenyl group substituted with at least one group in the group, cycloalkyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, and epoxide thereof, Unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 independently represent alkyl , Cycloalkyl, haloalkyl, halocycloalkyl, unsubstituted or substituted phenyl, alkoxy, haloalkoxy, hydroxy; R 54 represents hydrogen, halogen, alkyl, haloalkyl; R 55 represents hydrogen, Halogen; m Table 0 or 1, n represents an integer between 0 and 8.
优选地,M代表
Figure PCTCN2018121998-appb-000005
Het选自五元不饱和环,该环上除含有1-位上的N原子外,还含有1、2或3个以下原子或基团作为环的组成部分:NR b
Preferably, M represents
Figure PCTCN2018121998-appb-000005
Het is selected from a five-membered unsaturated ring, which contains 1, 2 or 3 atoms or groups as part of the ring in addition to the N atom at the 1-position: NR b ;
R a选自以下基团中的一个或多个基团:氢,卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C2-C8烯基C1-C8烷基、C2-C8炔基C1-C8烷基、C3-C8环烷基C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基、芳基氧基、杂芳基氧基;或者相邻两个R a一起形成未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的烷基、烯基、炔基、环烷基、环烷基烷基、烷氧基、烷硫基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基亚硫酰基、烷基磺酰基、烷基氨基、二烷基氨基、烷基酰氧基,以及未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基、芳基氧基、杂芳基氧基中的至少一个基团所取代的-CH=CH-CH=CH-、-CH 2CH 2CH 2CH 2-、-N=CH-CH=CH-、-CH=N-CH=CH-基团; R a is selected from the group of one or more groups: hydrogen, halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, containing or not containing a halogen C1-C8 alkyl, C2 -C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C2-C8 alkenyl C1-C8 alkyl, C2-C8 alkynyl C1-C8 alkyl, C3-C8 cycloalkyl C1-C8 alkyl Group, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkylthio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 Alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkylacyloxy and unsubstituted or substituted Aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl, aryloxy, heteroaryloxy; or two adjacent Ra together form unsubstituted or selected From halogen, nitro, cyano, hydroxy, carboxyl, amino, mercapto, formyl, with or without halogen alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkyl Thio, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfinyl, alkyl Acyl, alkylamino, dialkylamino, alkylacyloxy, and unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy, heteroaryloxy -CH = CH-CH = CH-, -CH 2 CH 2 CH 2 CH 2- , -N = CH-CH = CH-, -CH = N-CH = CH- substituted by at least one group in the group Group
R b代表氢,C1-C8烷基; R b represents hydrogen, C1-C8 alkyl;
Q代表N或C-R”;其中,R”代表氢,卤素,氰基,含有或不含有卤素的C1-C8烷基、C1-C8烷氧基、C2-C8烯基、C2-C8炔基、C3-C8环烷基,以及未取代或取代的芳基、杂芳基;Q stands for N or CR "; where R" stands for hydrogen, halogen, cyano, C1-C8 alkyl with or without halogen, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
X代表卤素,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C1-C8烷氧基、C1-C8烷基氨基、二C1-C8烷基氨基,未取代或取代的芳基、杂芳基;X represents halogen, with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylamino, di C1-C8 alkylamino, unsubstituted or substituted aryl, heteroaryl;
Y代表硝基或NR 1R 2,其中R 1代表H,任选地被1-2个R 11取代的C1-C8烷基、C2-C8烯基或C2-C8炔基,未取代或未取代或取代的芳基、杂芳基,-COR 12,硝基,OR 13,SO 2R 14,NR 15R 16,N=CR 17R 18,C1-C8烷基氨基甲酰基,二C1-C8烷基氨基甲酰基,三C1-C8烷基甲硅烷基或二C1-C8烷基膦酰基;R 2代表H,任选地被1-2个R 21取代的C1-C8烷基或-COR 22;或者NR 1R 2代表N=CR 31NR 32R 33,N=CR 34OR 35,未取代或被1-2个独立选自卤素、C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷硫基、卤代C1-C8烷硫基、氨基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷氧基羰基中的基团所取代的
Figure PCTCN2018121998-appb-000006
Figure PCTCN2018121998-appb-000007
Y represents nitro or NR 1 R 2 , where R 1 represents H, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted with 1-2 R 11 , unsubstituted or unsubstituted Substituted or substituted aryl, heteroaryl, -COR 12 , nitro, OR 13 , SO 2 R 14 , NR 15 R 16 , N = CR 17 R 18 , C1-C8 alkylcarbamoyl, di C1- C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphono; R 2 represents H, C1-C8 alkyl optionally substituted by 1-2 R 21 or- COR 22 ; or NR 1 R 2 represents N = CR 31 NR 32 R 33 , N = CR 34 OR 35 , unsubstituted or substituted by 1-2 independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxy , Halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl Substituted by groups in
Figure PCTCN2018121998-appb-000006
Figure PCTCN2018121998-appb-000007
其中R 11、R 21独立地代表卤素,羟基,C1-C8烷氧基,卤代C1-C8烷氧基,C1-C8烷硫基,卤代C1-C8烷硫基,氨基,C1-C8烷基氨基,二C1-C8烷基氨基,C1-C8烷氧基羰基,未取代或取代的芳基、杂芳基; Wherein R 11 and R 21 independently represent halogen, hydroxyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 Alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;
R 12、R 22独立地代表H、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基、苯基、苯氧基或苄氧基; R 12 and R 22 independently represent H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;
R 13代表H、C1-C8烷基、卤代C1-C8烷基、苯基、苄基或CHR 41C(O)OR 42;R 41代表H、C1-C8烷基或C1-C8烷氧基;R 42代表H、C1-C8烷基或苄基; R 13 represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ; R 41 represents H, C1-C8 alkyl or C1-C8 alkoxy Radical; R 42 represents H, C1-C8 alkyl or benzyl;
R 14代表C1-C8烷基、卤代C1-C8烷基; R 14 represents C1-C8 alkyl, halogenated C1-C8 alkyl;
R 15代表H、C1-C8烷基、甲酰基、C1-C8烷基羰基、卤代C1-C8烷基羰基、C1-C8烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基;R 16代表H、C1-C8烷基; R 15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylcarbonyl, halogenated C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R 16 represents H, C1-C8 alkyl;
R 17代表H、C1-C8烷基、未取代或被卤素、C1-C8烷基、C1-C8烷氧基中的1-3个基团所取代的苯基;R 18代表H、C1-C8烷基;或N=CR 17R 18代表
Figure PCTCN2018121998-appb-000008
R 17 represents H, C1-C8 alkyl, unsubstituted or substituted by 1-3 groups in halogen, C1-C8 alkyl, C1-C8 alkoxy; R 18 represents H, C1- C8 alkyl; or N = CR 17 R 18 represents
Figure PCTCN2018121998-appb-000008
R 31、R 34分别独立地代表H或C1-C8烷基; R 31 and R 34 independently represent H or C1-C8 alkyl;
R 32、R 33分别独立地代表H或C1-C8烷基;或者NR 32R 33代表
Figure PCTCN2018121998-appb-000009
Figure PCTCN2018121998-appb-000010
R 32 and R 33 independently represent H or C1-C8 alkyl; or NR 32 R 33 represents
Figure PCTCN2018121998-appb-000009
Figure PCTCN2018121998-appb-000010
R 35代表C1-C8烷基; R 35 represents C1-C8 alkyl;
Z代表氢,卤素,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有卤素的C1-C8烷基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C2-C8炔基、C1-C8烷氧基、C1-C8 烷硫基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基酰氧基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自卤素、氰基、C3-C8环烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基中的至少一个基团所取代的C2-C8烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表C1-C8烷基,C3-C8环烷基,卤代C1-C8烷基,卤代C3-C8环烷基,未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、苯基、苄基、苯氧基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷基酰氧基中的至少一个基团所取代的苯基,烷氧基,卤代C1-C8烷氧基,羟基;R 54代表氢、卤素、C1-C8烷基、卤代C1-C8烷基;R 55代表氢、卤素;m代表0或1,n代表0~6之间的整数; Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1- C8 alkyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxy C1-C8 alkyl , C1-C8 alkylthio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylacyloxy, C1-C8 alkylsulfinyl, C1-C8 alkyl Sulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected From halogen, cyano, C3-C8 cycloalkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl , C2-C8 alkenyl substituted by at least one group in C1-C8 alkylsulfonyl and its epoxide, unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 independently represent C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C1-C8 Alkyl, halogenated C 3-C8 cycloalkyl, unsubstituted or selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, C1-C8 alkyl with or without halogen, C2-C8 alkenyl, C2-C8 Alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, phenyl, benzyl, phenoxy, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkyl Substituted by at least one group of carbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkylacyloxy Phenyl, alkoxy, halogenated C1-C8 alkoxy, hydroxy; R 54 represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl; R 55 represents hydrogen, halogen; m represents 0 Or 1, n represents an integer between 0 and 6;
其中,所述“芳基”是指苯基、萘基,“杂芳基”是指
Figure PCTCN2018121998-appb-000011
Figure PCTCN2018121998-appb-000012
Figure PCTCN2018121998-appb-000013
其中,R’代表氢、烷基;其可被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,未取代或被选自卤素、烷基、烷氧基中的至少一个基团所取代的苯基、苄基、苯氧基,以及含有或不含有卤素的烷基、烯基、炔基、环烷基、环烷基烷基、烷氧基、烷硫基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基亚硫酰基、烷基磺酰基、烷基氨基、二烷基氨基、烷基酰氧基、-OCH 2CH 2-、-OCH 2O-、-OCH 2CH 2O-中的至少一个基团所取代。
Among them, the "aryl" refers to phenyl, naphthyl, "heteroaryl" refers to
Figure PCTCN2018121998-appb-000011
Figure PCTCN2018121998-appb-000012
Figure PCTCN2018121998-appb-000013
Where R 'represents hydrogen or alkyl; it can be selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, unsubstituted or selected from halogen, alkyl, alkoxy Phenyl, benzyl, phenoxy substituted with at least one group, and alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkylthio with or without halogen , Alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-, -OCH 2 CH 2 O- is substituted by at least one group.
更优选地,M代表
Figure PCTCN2018121998-appb-000014
Het选自五元不饱和环,该环上除含有1-位上的N原子外,还含有1、2或3个以下原子或基团作为环的组成部分:NR b
More preferably, M represents
Figure PCTCN2018121998-appb-000014
Het is selected from a five-membered unsaturated ring, which contains 1, 2 or 3 atoms or groups as part of the ring in addition to the N atom at the 1-position: NR b ;
R a选自以下基团中的一个或多个基团:氢,卤素,硝基,氰基,羟基,羧基,氨基,巯 基,甲酰基,含有或不含有卤素的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C2-C6烯基C1-C6烷基、C2-C6炔基C1-C6烷基、C3-C6环烷基C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基C1-C6烷基、杂芳基C1-C6烷基、芳基氧基、杂芳基氧基;或者相邻两个R a一起形成未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二烷C1-C8基氨基、C1-C8烷基酰氧基,以及未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基、芳基氧基、杂芳基氧基中的至少一个基团所取代的-CH=CH-CH=CH-、-CH 2CH 2CH 2CH 2-、-N=CH-CH=CH-、-CH=N-CH=CH-基团; R a is selected from one or more of the following groups: hydrogen, halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C6 alkyl with or without halogen, C2 -C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C6 alkenyl C1-C6 alkyl, C2-C6 alkynyl C1-C6 alkyl, C3-C6 cycloalkyl C1-C6 alkyl Group, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 Alkoxycarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkylacyloxy and unsubstituted or substituted Aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl, aryloxy, heteroaryloxy; or two adjacent Ra together form unsubstituted or selected From halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl with or without halogen , C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkylthio C1-C8 alkyl , C1 -C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, dialkyl C1-C8 amino, C1-C8 alkyl Acyloxy, and at least one of unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl, aryloxy, heteroaryloxy -CH = CH-CH = CH-, -CH 2 CH 2 CH 2 CH 2- , -N = CH-CH = CH-, -CH = N-CH = CH- group substituted by the group;
R b代表氢,C1-C6烷基; R b represents hydrogen, C1-C6 alkyl;
Q代表N或C-R”;其中,R”代表氢,卤素,氰基,含有或不含有卤素的C1-C6烷基、C1-C6烷氧基、C2-C6烯基、C2-C6炔基、C3-C6环烷基,以及未取代或取代的芳基、杂芳基;Q represents N or CR "; where R" represents hydrogen, halogen, cyano, C1-C6 alkyl with or without halogen, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
X代表卤素,含有或不含有卤素的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷基氨基、二C1-C6烷基氨基,未取代或取代的芳基、杂芳基;X represents halogen, with or without halogen C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylamino, di C1-C6 alkylamino, unsubstituted or substituted aryl, heteroaryl;
Y代表硝基或NR 1R 2,其中R 1代表H,任选地被1-2个R 11取代的C1-C6烷基、C2-C6烯基或C2-C6炔基,未取代或未取代或取代的芳基、杂芳基,-COR 12,硝基,OR 13,SO 2R 14,NR 15R 16,N=CR 17R 18,C1-C6烷基氨基甲酰基,二C1-C6烷基氨基甲酰基,三C1-C6烷基甲硅烷基或二C1-C6烷基膦酰基;R 2代表H,任选地被1-2个R 21取代的C1-C6烷基或-COR 22;或者NR 1R 2代表N=CR 31NR 32R 33,N=CR 34OR 35,未取代或被1-2个独立选自卤素、C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、氨基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷氧基羰基中的基团所取代的
Figure PCTCN2018121998-appb-000015
Figure PCTCN2018121998-appb-000016
Y represents nitro or NR 1 R 2 , where R 1 represents H, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl optionally substituted by 1-2 R 11 , unsubstituted or unsubstituted Substituted or substituted aryl, heteroaryl, -COR 12 , nitro, OR 13 , SO 2 R 14 , NR 15 R 16 , N = CR 17 R 18 , C1-C6 alkylcarbamoyl, di C1- C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; R 2 represents H, C1-C6 alkyl optionally substituted by 1-2 R 21 or- COR 22 ; or NR 1 R 2 represents N = CR 31 NR 32 R 33 , N = CR 34 OR 35 , unsubstituted or substituted by 1-2 independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy , Halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl Substituted by groups in
Figure PCTCN2018121998-appb-000015
Figure PCTCN2018121998-appb-000016
其中R 11、R 21独立地代表卤素,羟基,C1-C6烷氧基,卤代C1-C6烷氧基,C1-C6烷硫基,卤代C1-C6烷硫基,氨基,C1-C6烷基氨基,二C1-C6烷基氨基,C1-C6烷氧基羰基,未取代或取代的芳基、杂芳基; Wherein R 11 and R 21 independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 Alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;
R 12、R 22独立地代表H、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、苯基、苯氧基或苄氧基; R 12 and R 22 independently represent H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;
R 13代表H、C1-C6烷基、卤代C1-C6烷基、苯基、苄基或CHR 41C(O)OR 42;R 41代表H、C1-C6烷基或C1-C6烷氧基;R 42代表H、C1-C6烷基或苄基; R 13 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ; R 41 represents H, C1-C6 alkyl or C1-C6 alkoxy Radical; R 42 represents H, C1-C6 alkyl or benzyl;
R 14代表C1-C6烷基、卤代C1-C6烷基; R 14 represents C1-C6 alkyl, halogenated C1-C6 alkyl;
R 15代表H、C1-C6烷基、甲酰基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基;R 16代表H、C1-C6烷基; R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R 16 represents H, C1-C6 alkyl;
R 17代表H、C1-C6烷基、未取代或被卤素、C1-C6烷基、C1-C6烷氧基中的1-3个基团所取代的苯基;R 18代表H、C1-C6烷基;或N=CR 17R 18代表
Figure PCTCN2018121998-appb-000017
R 17 represents H, C1-C6 alkyl, unsubstituted or substituted by 1-3 groups in halogen, C1-C6 alkyl, C1-C6 alkoxy; R 18 represents H, C1- C6 alkyl; or N = CR 17 R 18 represents
Figure PCTCN2018121998-appb-000017
R 31、R 34分别独立地代表H或C1-C6烷基; R 31 and R 34 independently represent H or C1-C6 alkyl;
R 32、R 33分别独立地代表H或C1-C6烷基;或者NR 32R 33代表
Figure PCTCN2018121998-appb-000018
Figure PCTCN2018121998-appb-000019
R 32 and R 33 independently represent H or C1-C6 alkyl; or NR 32 R 33 represents
Figure PCTCN2018121998-appb-000018
Figure PCTCN2018121998-appb-000019
R 35代表C1-C6烷基; R 35 represents C1-C6 alkyl;
Z代表氢,卤素,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有卤素的C1-C6烷基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C2-C6炔基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基酰氧基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自卤素、氰基、C3-C6环烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基中的至少一个基团所取代的C2-C6烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基C1-C6烷基、杂芳基C1-C6烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表C1-C6烷基,C3-C6环烷基,卤代C1-C6烷基,卤代C3-C6环烷基,未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,含有或不含有卤素的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、苯基、苄基、苯氧基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基羰基、 C1-C6烷氧基羰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷基酰氧基中的至少一个基团所取代的苯基,烷氧基,卤代C1-C6烷氧基,羟基;R 54代表氢、卤素、C1-C6烷基、卤代C1-C6烷基;R 55代表氢、卤素;m代表0或1,n代表0~4之间的整数; Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1- C6 alkyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxy C1-C6 alkyl , C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylacyloxy, C1-C6 alkylsulfinyl, C1-C6 alkyl Sulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected From halogen, cyano, C3-C6 cycloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl , C2-C6 alkenyl substituted by at least one group in C1-C6 alkylsulfonyl and its epoxide, unsubstituted or substituted aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 independently represent C1-C6 alkyl, C3-C6 cycloalkyl, halogenated C1-C6 Alkyl, halogenated C3 -C6 cycloalkyl, unsubstituted or selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkyne with or without halogen Group, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, phenyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkyl Substituted by at least one group of carbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkylacyloxy Phenyl, alkoxy, halogenated C1-C6 alkoxy, hydroxy; R 54 represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl; R 55 represents hydrogen, halogen; m represents 0 or 1, n represents an integer between 0 and 4;
其中,所述“芳基”是指苯基、萘基,“杂芳基”是指
Figure PCTCN2018121998-appb-000020
Figure PCTCN2018121998-appb-000021
Figure PCTCN2018121998-appb-000022
其中,R’代表氢、C1-C8烷基;其可被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,未取代或被选自卤素、C1-C8烷基、C1-C8烷氧基中的至少一个基团所取代的苯基、苄基、苯氧基,以及含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷基酰氧基、-OCH 2CH 2-、-OCH 2O-、-OCH 2CH 2O-中的至少一个基团所取代。
Among them, the "aryl" refers to phenyl, naphthyl, "heteroaryl" refers to
Figure PCTCN2018121998-appb-000020
Figure PCTCN2018121998-appb-000021
Figure PCTCN2018121998-appb-000022
Where R 'represents hydrogen, C1-C8 alkyl; it can be selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, unsubstituted or selected from halogen, C1-C8 alkyl , C1-C8 alkoxy substituted by at least one group of phenyl, benzyl, phenoxy, and with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl , C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkyl Thio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, di-C1- At least one group of C8 alkylamino, C1-C8 alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-, -OCH 2 CH 2 O- is substituted.
进一步优选地,M代表未取代或被选自氟,氯,溴,碘,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C2-C6烯基C1-C4烷基、C2-C6炔基C1-C4烷基、C3-C6环烷基C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基C1-C4烷基、杂芳基C1-C4烷基、芳基氧基、杂芳基氧基中的1~3个基团所取代的
Figure PCTCN2018121998-appb-000023
Figure PCTCN2018121998-appb-000024
Further preferably, M represents unsubstituted or selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, with or without fluorine, chlorine, bromine, iodine C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkenyl C1-C4 alkyl, C2-C6 alkynyl C1-C4 alkyl, C3-C6 ring Alkyl C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkyl Carbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkylacyloxy 1 to 3 groups in the group and unsubstituted or substituted aryl, heteroaryl, aryl C1-C4 alkyl, heteroaryl C1-C4 alkyl, aryloxy, heteroaryloxy replaced
Figure PCTCN2018121998-appb-000023
Figure PCTCN2018121998-appb-000024
Q代表N或C-R”;其中,R”代表氢,氟,氯,溴,碘,氰基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C1-C4烷氧基、C2-C4烯基、C2-C4炔基、C3-C6环烷基,以及未取代或取代的芳基、杂芳基;Q stands for N or CR "; where R" stands for hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C4 alkyl, C1-C4 alkoxy, with or without fluorine, chlorine, bromine, iodine, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
X代表氟,氯,溴,碘,含有或不含有氟、氯、溴、碘的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C1-C4烷氧基、C1-C4烷基氨基、二C1-C4烷基氨基,未取代或取代的芳基、杂芳基;X represents fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 with or without fluorine, chlorine, bromine, iodine Alkoxy, C1-C4 alkylamino, di-C1-C4 alkylamino, unsubstituted or substituted aryl, heteroaryl;
Y代表NH 2、NHMe、N(Me) 2
Figure PCTCN2018121998-appb-000025
Figure PCTCN2018121998-appb-000026
Y stands for NH 2 , NHMe, N (Me) 2 ,
Figure PCTCN2018121998-appb-000025
Figure PCTCN2018121998-appb-000026
Z代表氢,氟,氯,溴,碘,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C3-C6环烷基、C3-C6环烷基C1-C4烷基、C2-C4炔基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基酰氧基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自氟、氯、溴、碘、氰基、C3-C6环烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基中的1~3个基团所取代的C2-C4烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基C1-C4烷基、杂芳基C1-C4烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表C1-C4烷基,C3-C6环烷基,卤代C1-C4烷基,卤代C3-C6环烷基,未取代或被选自氟,氯,溴,碘,硝基,氰基,羟基,羧基,氨基,巯基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C3-C6环烷基C1-C4烷基、苯基、苄基、苯氧基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基中的1~3个基团所取代的苯基,烷氧基,卤代C1-C6烷氧基,羟基;R 54代表氢、氟、氯、C1-C4烷基、卤代C1-C4烷基;R 55代表氢、氟、氯;m代表0或1,n代表0、1、2或3; Z represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C4 alkyl, C3-C6 with or without fluorine, chlorine, bromine, iodine Cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4 alkylamino , C1-C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylacyloxy, C1 -C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected from fluorine, chlorine, bromine, iodine, cyano, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkyl C2-C4 alkenyl and its epoxides substituted by 1 to 3 groups in oxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, unsubstituted Or substituted aryl, heteroaryl, aryl C1-C4 alkyl, heteroaryl C1-C4 alkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 are independently Represents C1-C4 alkyl, C3-C 6 cycloalkyl, halogenated C1-C4 alkyl, halogenated C3-C6 cycloalkyl, unsubstituted or selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, benzene with or without fluorine, chlorine, bromine, iodine Group, benzyl, phenoxy, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfonyl, C1-C4 alkyl Phenyl, alkoxy, halogenated C1-C6 alkoxy, hydroxy substituted by 1 to 3 groups in the amino group, di C1-C4 alkylamino group, C1-C4 alkyl acyloxy group; R 54 Represents hydrogen, fluorine, chlorine, C1-C4 alkyl, halogenated C1-C4 alkyl; R 55 represents hydrogen, fluorine, chlorine; m represents 0 or 1, n represents 0, 1, 2 or 3;
其中,所述“芳基”是指苯基、萘基,“杂芳基”是指
Figure PCTCN2018121998-appb-000027
Figure PCTCN2018121998-appb-000028
其中,R’代表氢、C1-C6烷基;其可被选自氟,氯,溴,碘,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,未取代或被选自氟、氯、溴、碘、C1-C6 烷基、C1-C6烷氧基中的1~3个基团所取代的苯基、苄基、苯氧基,以及含有或不含有氟、氯、溴、碘的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷基酰氧基、-OCH 2CH 2-、-OCH 2O-、-OCH 2CH 2O-中的1~4个基团所取代。
Among them, the "aryl" refers to phenyl, naphthyl, "heteroaryl" refers to
Figure PCTCN2018121998-appb-000027
Figure PCTCN2018121998-appb-000028
Where R 'represents hydrogen, C1-C6 alkyl; it can be selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, unsubstituted or selected from fluorine , Chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 alkoxy substituted by 1 to 3 groups of phenyl, benzyl, phenoxy, and with or without fluorine, chlorine, bromine , Iodine C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6 Alkylthio, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfinyl Acyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-, -OCH 2 1 to 4 groups in CH 2 O- are substituted.
更进一步优选地,M代表未取代或被选自氟,氯,溴,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C2-C4烯基C1-C2烷基、C2-C4炔基C1-C2烷基、C3-C6环烷基C1-C2烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧基C1-C2烷基、C1-C4烷硫基C1-C2烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基以及未取代或取代的苯基、苄基、苯氧基中的1、2或3个基团所取代的
Figure PCTCN2018121998-appb-000029
Figure PCTCN2018121998-appb-000030
Even more preferably, M represents unsubstituted or selected from fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C4 alkane with or without fluorine, chlorine, bromine Group, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C4 alkenyl C1-C2 alkyl, C2-C4 alkynyl C1-C2 alkyl, C3-C6 cycloalkyl C1 -C2 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxy C1-C2 alkyl, C1-C4 alkylthio C1-C2 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkylacyloxy and Substituted or substituted by 1, 2 or 3 groups in phenyl, benzyl, phenoxy
Figure PCTCN2018121998-appb-000029
Figure PCTCN2018121998-appb-000030
Q代表N或C-R”;其中,R”代表氢,氟,氯,溴,氰基,含有或不含有氟、氯、溴的C1-C4烷基、C1-C4烷氧基、C2-C4烯基、C2-C4炔基、C3-C6环烷基,以及未取代或取代的苯基;Q stands for N or CR "; where R" stands for hydrogen, fluorine, chlorine, bromine, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkene with or without fluorine, chlorine, bromine Group, C2-C4 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted phenyl;
X代表氟,氯,溴,含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C1-C4烷氧基、C1-C4烷基氨基、二C1-C4烷基氨基,未取代或取代的苯基、萘基、
Figure PCTCN2018121998-appb-000031
X represents fluorine, chlorine, bromine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 alkoxy, with or without fluorine, chlorine, bromine C1-C4 alkylamino, di-C1-C4 alkylamino, unsubstituted or substituted phenyl, naphthyl,
Figure PCTCN2018121998-appb-000031
Y代表NH 2、NHMe、N(Me) 2
Figure PCTCN2018121998-appb-000032
Figure PCTCN2018121998-appb-000033
Y stands for NH 2 , NHMe, N (Me) 2 ,
Figure PCTCN2018121998-appb-000032
Figure PCTCN2018121998-appb-000033
Z代表氢,氟,氯,溴,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C3-C6环烷基、C3-C6环烷基C1-C2烷基、C2-C4 炔基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷氧基C1-C2烷基、C1-C4烷硫基C1-C2烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基酰氧基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基,以及未取代或取代的苯基、萘基、
Figure PCTCN2018121998-appb-000034
Figure PCTCN2018121998-appb-000035
Z represents hydrogen, fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C4 alkyl, C2-C4 alkenyl, C3 with or without fluorine, chlorine, bromine -C6 cycloalkyl, C3-C6 cycloalkyl C1-C2 alkyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4 alkyl Amino, C1-C4 alkoxy C1-C2 alkyl, C1-C4 alkylthio C1-C2 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylacyloxy , C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, and unsubstituted or substituted phenyl, naphthyl,
Figure PCTCN2018121998-appb-000034
Figure PCTCN2018121998-appb-000035
其中,所述“取代的”是指其被选自氟,氯,溴,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,以及含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C3-C6环烷基C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基中的1、2或3个基团所取代。Wherein, the "substituted" means that it is selected from fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, amino, mercapto, formyl, and C1- with or without fluorine, chlorine, or bromine C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1 -C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C1-C4 1, 2, or 3 groups in the alkylsulfonyl group, C1-C4 alkylamino group, di-C1-C4 alkylamino group, C1-C4 alkylacyloxy group.
在上述通式I所示化合物的定义中,所用专业术语不论单独使用或者使用在复合词中,代表如下取代基:卤素:指氟、氯、溴、碘;烷基:指直链烷基或者支链烷基。In the above definition of the compound represented by the general formula I, the technical terms used, whether used alone or in compound words, represent the following substituents: halogen: refers to fluorine, chlorine, bromine, iodine; alkyl: refers to straight-chain alkyl or branched Chain alkyl.
一种除草组合物包括(i)如通式I所示的取代的含氮杂芳环甲酰胺衍生物;优选地,还包括(ii)一种或多种另外的除草剂和/或安全剂;更优选地,还包括(iii)农业化学上可接受的制剂助剂。A herbicidal composition includes (i) a substituted nitrogen-containing heteroaromatic ring formamide derivative represented by general formula I; preferably, it also includes (ii) one or more additional herbicides and / or safeners ; More preferably, (iii) agrochemically acceptable formulation aids.
一种控制杂草的方法包括将除草有效量的所述的取代的含氮杂芳环甲酰胺衍生物中的至少一种或所述的除草组合物使用在植物上或者杂草区域。A method for controlling weeds includes using a herbicidally effective amount of at least one of the substituted nitrogen-containing heteroaromatic ring carboxamide derivatives or the herbicidal composition on plants or weed areas.
所述的取代的含氮杂芳环甲酰胺衍生物中的至少一种或所述的除草组合物在控制杂草上的用途,优选地,将所述的取代的含氮杂芳环甲酰胺衍生物用于防除有用作物中的杂草,所述有用作物为转基因作物或者基因组编辑技术处理过的作物。At least one of the substituted nitrogen-containing heteroaromatic ring carboxamide derivatives or the use of the herbicidal composition for controlling weeds, preferably, the substituted nitrogen-containing heteroaromatic ring carboxamide Derivatives are used to control weeds in useful crops, which are genetically modified crops or crops treated by genome editing techniques.
本发明还包括制备本发明化合物的方法,其包括以下步骤:The present invention also includes a method for preparing the compound of the present invention, which includes the following steps:
(1)使用如通式II所示的化合物与通式III所示的化合物进行反应,制备如通式I所示的化合物,反应方程式如下:(1) The compound represented by the general formula II is reacted with the compound represented by the general formula III to prepare the compound represented by the general formula I, and the reaction equation is as follows:
Figure PCTCN2018121998-appb-000036
Figure PCTCN2018121998-appb-000036
或(2)先将如通式II所示的化合物进行酰卤化反应,然后与通式III所示的化合物进行反应,制备如通式I所示的化合物,反应方程式如下:Or (2) First, the compound represented by the general formula II is subjected to an acid halogenation reaction, and then reacted with the compound represented by the general formula III to prepare the compound represented by the general formula I, and the reaction equation is as follows:
Figure PCTCN2018121998-appb-000037
Figure PCTCN2018121998-appb-000037
所述步骤(1)反应在缩合剂和溶剂的存在下进行,所述缩合剂为PyBOP、HATU或CDI,所述溶剂选自DCM、DCE、ACN、DMF、THF中的一种及一种以上;根据需要可在反应体系中加入碱,所述碱选自TEA、NMM或DIPEA;所述反应温度为0-100℃,优选25-50℃。The reaction in the step (1) is carried out in the presence of a condensing agent and a solvent, the condensing agent is PyBOP, HATU or CDI, and the solvent is selected from one or more of DCM, DCE, ACN, DMF and THF ; Base can be added to the reaction system as needed, the base is selected from TEA, NMM or DIPEA; the reaction temperature is 0-100 ℃, preferably 25-50 ℃.
所述步骤(2)中酰卤化反应温度为0-100℃,采用的酰卤化试剂为SOCl 2;然后在碱和溶剂的存在的下进行下一步反应,所述溶剂选自DCM、DCE、ACN、DMF、THF中的一种及一种以上,所述碱选自TEA、NMM或DIPEA,所述反应温度为0-25℃。 In the step (2), the acid halogenation reaction temperature is 0-100 ° C, and the acid halogenation reagent used is SOCl 2 ; then the next reaction is carried out in the presence of a base and a solvent, the solvent is selected from DCM, DCE, ACN , DMF, one or more of THF, the base is selected from TEA, NMM or DIPEA, the reaction temperature is 0-25 ℃.
对于许多经济上重要的单子叶和双子叶有害植物,本发明的式I化合物具有突出的除莠活性。本发明的活性物质也对于多年生杂草有效,这些杂草从根茎、根状茎、或其它的多年生的器官上生长出来,很难控制。关于这点,是否在播种前、萌发前或萌发后使用该物质一般不重要。特别提及本发明化合物可以控制的单子叶和双子叶杂草群的代表例子,没有限制到的确定的物种。活性物质有效作用的杂草物种的例子包括单子叶植物:一年生燕麦属、黑麦、草属、看麦娘属、法拉里斯、稗、马唐属、狗尾草属和莎草属,和多年生的冰草属、狗牙根属、白茅属和高粱属、以及多年生的莎草属。For many economically important monocotyledonous and dicotyledonous harmful plants, the compounds of formula I according to the invention have outstanding herbicidal activity. The active substances of the present invention are also effective for perennial weeds, which grow from rhizomes, rhizomes, or other perennial organs, and are difficult to control. In this regard, it is generally not important whether the substance is used before sowing, before germination or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed colonies that can be controlled by the compounds of the present invention, and there is no limitation to certain species. Examples of weed species where the active substance works effectively include monocotyledons: annual oats, rye, grass, hordeum, ferraris, barnyardgrass, crabgrass, foxtail and sedge, and perennial ice Grasses, bermudagrass, chrysanthemum and sorghum, and perennial sedges.
关于双子叶杂草物种,其作用可以扩展到的物种例如一年生的猪殃殃属、堇菜属、婆婆纳属、野芝麻属、繁缕属、苋属、白芥属、番薯属、黄花稔属、母菊属和苘麻属,和多年生杂草旋花属、蓟属、酸模属和艾属。本发明活性物质在水稻播种这种待定条件下有效控制有害植物,例如稗、慈姑属、泽泻属、荸荠属、蔗草和莎草属。如果将本发明化合物在萌芽前施用于土壤表面,可以在杂草长出前完全预防杂草的秧苗,或在杂草长出子叶时就停止生长,最后在三到四星期之后完全死亡。本发明化合物特别抗下述植物的活性优良,阿皮拉草、小野芝麻、卷茎蓼、繁缕、长春藤叶婆婆纳、阿拉伯婆婆纳、三色堇和苋、猪殃殃属和地肤。Regarding dicotyledonous weed species, the effects of which can be extended to species such as the annual Swine, Viola, Pompona, Wild Sesame, Stellaria, Amaranthus, Sphaeropsis, Ipomoea, Hirsch Genus, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia. The active substance of the present invention can effectively control harmful plants, such as barnyardgrass, Cicus, Alisma, water chestnut, cane grass, and sedge, under such predetermined conditions as rice seeding. If the compound of the present invention is applied to the soil surface before germination, the weed seedlings can be completely prevented before the weeds grow, or they can stop growing when the weeds grow cotyledons, and finally die completely after three to four weeks. The compounds of the present invention are particularly active against the following plants, Apila grass, Ono sesame, Polygonum sibiricum, Stellaria, Ivy leaf Pompa, Arab Pompa, Pansy and Amaranthus, Swamp, and Kochia .
虽然本发明化合物对于单子叶和双子叶的杂草具有优良的除莠活性,但对于重要的经济类作物植物,例如小麦、大麦、黑麦、稻子、玉米、甜菜、棉花和大豆却根本没有损害,或者是损害是微不足道的。特别是和谷类作物相容得很好,例如小麦、大麦和玉米,特别是小麦。因此,本发明化合物非常适于有选择地控制在农用作物或观赏植物中的无用植物。Although the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not harmful to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean , Or the damage is negligible. Especially compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compound of the present invention is very suitable for selectively controlling useless plants in agricultural or ornamental plants.
由于它们的除莠性质,在已知或将要出现的遗传工程的植物耕种中,这些活性物质可以用于控制有害植物。转基因植物通常具有优越的性状,例如对特定杀虫剂特别是特定除草剂的抵抗力,对植物病害或植物病害的致病微生物的抵抗力,例如特定的昆虫或真菌、细菌或 病毒的微生物。其它的特别性状与产品的下述条件有关,例如,数量、质量、贮存稳定性、组分和特殊的成分。如此,已经知道获得的转基因植物产品具有增加的淀粉含量或改进的淀粉质量或不同的脂肪酸成份。Due to their herbicidal properties, these active substances can be used to control harmful plants in the cultivation of genetically engineered plants that are known or will appear. Transgenic plants generally have superior traits, such as resistance to specific insecticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insect or fungal, bacterial or viral microorganisms. Other special characteristics are related to the following conditions of the product, for example, quantity, quality, storage stability, components and special ingredients. As such, it is known that the obtained transgenic plant products have increased starch content or improved starch quality or different fatty acid compositions.
本发明的式I化合物或其盐优选用于,经济上重要的转基因的作物和观赏植物,例如谷类,例如小麦、大麦、黑麦、燕麦、粟、稻子、木薯和玉米、或用于甜菜、棉花、大豆、油菜籽、马铃薯、番茄、豌豆及其他蔬菜类植物的耕种。式I化合物优选用于有用植物耕种的除草剂,这些植物具有抗药性或通过遗传工程对除草剂的毒害作用具有抗药性。The compounds of the formula I or salts thereof of the present invention are preferably used for economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or for sugar beets, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of formula I are preferably used as herbicides for the cultivation of useful plants, which plants are resistant or resistant to the toxic effects of the herbicides through genetic engineering.
传统的繁育具有比已知植物具有改进形状植物的方法包括,例如传统的交配方法和突变株繁育。换句话说,可以借助于遗传工程的方法(参见,例如EP-0221044 A,EP-0131624 A)来得到具有改进性状的新植物。例如,已经描述了几个方法:Conventional methods for breeding plants with improved shapes compared to known plants include, for example, traditional mating methods and mutant breeding. In other words, new plants with improved traits can be obtained by means of genetic engineering (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:
-为了改进植物中的淀粉合成,利用遗传工程改变作物植物(例如WO 92/11376,WO 92/14827,WO 91/19806);-In order to improve starch synthesis in plants, genetic engineering is used to change crop plants (eg WO 92/11376, WO 92/14827, WO 91/19806);
-对特定的除草剂具有抗性的转基因作物植物,对草丁膦除草剂(例如EP-0242236 A,EP-0242246 A)或对草甘膦类除草剂(WO 92/00377),或对磺酰脲类除草剂(EP-0257993 A,US-5013659 A);-Genetically modified crop plants that are resistant to specific herbicides, glufosinate herbicides (eg EP-0242236 A, EP-0242246 A) or glyphosate herbicides (WO 92/00377), or parasulfonate Acyl urea herbicides (EP-0257993 A, US-5013659 A);
-例如棉花的转基因作物植物,它能够产生苏芸金杆菌毒素(Bt毒素),这种毒素可以防御特定害虫对植物的侵害(EP-0142924 A,EP-0193259 A);-Transgenic crop plants such as cotton, which can produce Bacillus thuringiensis toxin (Bt toxin), this toxin can protect plants against specific pests (EP-0142924A, EP-0193259A);
-具有改进的脂肪酸成份的转基因作物植物(WO91/13972)。-Transgenic crop plants with improved fatty acid composition (WO91 / 13972).
已经知道许多能够制备具有改进性状转基因植物分子生物技术(参见,例如Sambrook等,1989,分子扩增,实验手册第二版,美国冷泉港实验室出版,冷泉港,纽约;或Winnacker“Gene und Klone”[基因和克隆],VCH Weinheim,第二版1996或Christou,“植物科学的趋势”1(1996)423-431))。为了实现遗传工程的操作,可能将核酸分子引入质粒,通过DNA序列的重组,发生突变或序列改变。利用上述的标准方法,例如可以交换底物、除去部分序列或增加自然的或合成的序列。为了将DNA片段互相连接,有可能在片段上附带有结合体或连接体。Many molecular biotechnologies that can produce transgenic plants with improved traits are known (see, for example, Sambrook et al., 1989, Molecular Amplification, Second Handbook of Experiments, Published by Cold Spring Harbor Laboratory, Cold Spring Harbor, New York; or Winnacker "Gene Kunde "[Genes and Cloning], VCH Weinheim, Second Edition 1996 or Christou," Trends in Plant Science "1 (1996) 423-431)). In order to realize the operation of genetic engineering, a nucleic acid molecule may be introduced into a plasmid, and mutation or sequence change may occur through recombination of DNA sequences. Using the standard methods described above, for example, it is possible to exchange substrates, remove partial sequences, or add natural or synthetic sequences. In order to connect DNA fragments to each other, it is possible to attach binders or linkers to the fragments.
可以用下述方法制备降低活性的基因产品的植物细胞,例如通过表达至少一种适当的反义-RNA、正义-RNA来达到共抑制的效果,或通过表达至少一种适当构造的核糖酶,它特定裂解上述基因产品的转录产物。Plant cells with reduced activity gene products can be prepared by the following methods, for example, by expressing at least one appropriate antisense-RNA, sense-RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme, It specifically cleaves the transcription products of the above-mentioned gene products.
为此目的,有可能使用包含基因产物全部编码序列的DNA分子,包括有可能存在的任何旁侧序列,和使用包含仅仅一部分编码序列的DNA分子,这些部分必须足够长以达到在细胞中反义的效果。也可以使用与基因产物编码序列具有高度同源性但不完全相同的序列。For this purpose, it is possible to use DNA molecules that contain the entire coding sequence of the gene product, including any flanking sequences that may be present, and DNA molecules that contain only a portion of the coding sequence, which must be long enough to achieve antisense in the cell Effect. It is also possible to use sequences that have a high degree of homology to the gene product coding sequence but are not completely identical.
当在植物中表达核酸分子时,合成的蛋白质可以在任何期望的植物细胞室中定位。然而为了在特定的室定位,有可能例如将编码区和DNA序列连接,以确保在特定位置定位。这些序列为本领域所属技术人员已知的(参见,例如Braun等,EMBO J.11(1992)3219-3227;Wolter等,Proc.Natl.Acad.Sci.USA 85(1988),846-850;Sonnewald等Plant J.1(1991),95-106)。When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, in order to locate in a specific chamber, it is possible, for example, to connect the coding region and the DNA sequence to ensure the localization at a specific position. These sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992) 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J.1 (1991), 95-106).
利用已知的技术可以将转基因植物细胞重组到整个植物上。转基因植物可以为任何期望的植物品种,即单子叶和双子叶植物。用这样的方式,通过超表达、禁止或抑制同源(=自然的)基因或基因序列,或通过异种的(=外部的)基因或者基因序列的表达,有可能获得改进性状的转基因植物。Transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plant can be any desired plant variety, namely monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (= natural) genes or gene sequences, or by expressing heterogeneous (= external) genes or gene sequences.
当在转基因的作物上使用本发明的活性物质时,除了具有在其它作物上可观察到的抑制有害植物的效果外,经常在相应的转基因作物上会有特殊的效果,例如可以改进或扩大控制杂草的范围,改进应用时的施用量,优选转基因作物的抗药性和除草剂的性能很好的结合,并且转基因的作物植物的生长和产率的影响。因此本发明也提供了所述化合物的用途,作为除草剂控制转基因作物植物中的有害植物。When using the active substance of the present invention on genetically modified crops, in addition to the observable effects on other crops of suppressing harmful plants, there will often be special effects on the corresponding genetically modified crops, for example, to improve or expand control The range of weeds, improved application rates during application, preferably a good combination of the resistance of transgenic crops and the performance of herbicides, and the effects of growth and yield of transgenic crop plants. Therefore, the present invention also provides the use of the compound as a herbicide for controlling harmful plants in transgenic crop plants.
另外本发明化合物可以明显调节作物植物的生长。通过调节参与植物代谢,使用这些化合物定向控制植物的组分和促进收获,例如使植物干化和矮化生长。而且它们也适于调节和抑制不希望的植物生长,而不破坏作物的生长。抑制植物的生长在许多单子叶植物和双子叶植物作物中起着非常重要的作用,因为这样可以减少或完全预防倒伏。In addition, the compounds of the present invention can significantly regulate the growth of crop plants. By regulating participation in plant metabolism, these compounds are used to directionally control plant components and promote harvesting, such as drying and dwarfing plant growth. And they are also suitable for regulating and inhibiting undesired plant growth without destroying the growth of crops. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, because this can reduce or completely prevent lodging.
本发明已经发现,式I的化合物作为稻和谷类种植制度和牧草管理规划的苗前和苗后除草剂是有用的。术语除草剂用在本文中意思是杀死、防治或其它不利地改变植物生长的活性成分。除草有效量或植被防治量是引起不利改变作用和包括从自然发育中偏离、杀死、调节、脱水、延迟等的活性成分的量。术语植物和植被包括发芽的种子、出苗的苗、地上和地下植物部分例如枝条、根、块茎(tubers)、根茎(rhizomes)等和已长成的植被。The present invention has found that the compounds of formula I are useful as pre-emergence and post-emergence herbicides for rice and cereal planting systems and forage management planning. The term herbicide is used herein to mean killing, controlling, or other active ingredients that adversely alter plant growth. The herbicidal effective amount or vegetation control amount is the amount of active ingredients that cause adverse alteration and include deviation from natural development, killing, conditioning, dehydration, delay, etc. The terms plants and vegetation include germinated seeds, emerged seedlings, aboveground and underground plant parts such as branches, roots, tubers, rhizomes, etc., and grown vegetation.
在生长的任何阶段或者在种植或出苗前,当将化合物直接施用于植物或植物的所在地时,本发明的化合物表现出除草活性。实测效果取决于所要防治的植物物种、植物的生长阶段、稀释和喷雾液滴大小的施用参数(the application parameters of dilution and spray drop size)、固体组分的粒度、使用时的环境状况、所用的具体化合物、所用的具体辅料和载体、土壤类型、水质等,以及所施用化学品的量。本领域已知的是,这些及其它因素可进行调整以促进选择性的除草作用。通常,优选在苗后经由喷雾或水施用向相对不成熟的不期望的植被施用式I的化合物以实现对杂草的最大防治。At any stage of growth or before planting or emergence, when the compound is directly applied to the plant or the locus of the plant, the compound of the present invention exhibits herbicidal activity. The actual measurement effect depends on the plant species to be controlled, the plant growth stage, the application parameters of the dilution and spray droplet size (the application parameters of spraying size), the particle size of the solid components, the environmental conditions at the time of use, the used Specific compounds, specific excipients and carriers used, soil type, water quality, etc., as well as the amount of chemicals applied. It is known in the art that these and other factors can be adjusted to promote selective herbicidal action. Generally, it is preferred to apply the compound of formula I to relatively immature undesirable vegetation via spray or water application after seedling to achieve maximum control of weeds.
叶面施用的和水施用的苗后操作通常使用1至500克每公顷(g/ha)的施用率。优选的施用率是10至300g/ha。对于苗前施用,通常使用5至500g/ha的施用率。优选的施用率是30至300g/ha。所设计的较高施用率通常产生宽广种类不期望的植被的非选择性防治。较低的施用率典型地产生选择性防治并且可以在作物的所在地使用。Foliar application and water application post-emergence operations generally use application rates of 1 to 500 grams per hectare (g / ha). The preferred application rate is 10 to 300 g / ha. For pre-emergence application, an application rate of 5 to 500 g / ha is generally used. The preferred application rate is 30 to 300 g / ha. The higher application rates designed generally produce non-selective control of a wide variety of undesirable vegetation. Lower application rates typically produce selective control and can be used in the locus of the crop.
本发明的除草化合物常与一种或更多种其它除草剂联合施用以防治更广种类的不期望的植被。当与其它除草剂联合使用时,可将本发明要求保护的化合物与其它一种或多种除草剂一起配制,与其它一种或多种除草剂罐混合或者与其它一种或多种除草剂先后施用。一些可与本发明的化合物联合使用的除草剂包括:2,4-滴盐、酯和胺(2,4-D salts、esters and amines)、乙草胺(acetochlor)、三氟羧草醚(acifluorfen)、甲草胺(alachlor)、酰嘧磺隆(amidosulfuron)、氯氨基吡啶酸(aminopyralid)、氨基三唑(aminotriazole)、硫氰酸铵(ammoniumthiocyanate)、anilifos、莠去津(atrazine)、四唑嘧磺隆(azimsulfuron)、呋草黄(benfuresate)、苄嘧磺隆(bensulfuron-methyl)、灭草松(bentazon)、禾草丹(benthiocarb)、苯并双环酮(benzobicyclon)、吡草酮(benzofenap)、甲羧除草醚(bifenox)、双草醚-钠(bispyribac-sodium)、溴丁酰草胺(bromobutide)、丁草胺(butachlor)、唑草胺(cafenstrole)、唑草酮-乙基(carfentrazone-ethyl)、chlodinafop-propyrgyl、氯嘧磺隆脱乙基酸(chlorimuron)、氯苯胺灵(chlorpropham)、醚磺隆(cinosulfuron)、烯草酮(clethodim)、异噁草酮(clomazone)、稗草胺(clomeprop)、二氯吡啶酸(clopyralid)、氯酯磺草胺(cloransulam-methyl)、环丙嘧磺隆(cyclosulfamuron)、噻草酮(cycloxydim)、氰氟草酯-丁基(cyhalofop-butyl)、苄草隆(cumyluron)、香草隆(daimuron)、唑嘧磺胺(diclosulam)、吡氟酰草胺(diflufenican)、二氟吡隆(diflufenzopyr)、哌草丹(dimepiperate)、戊草津(dimethametryn)、敌草快(diquat)、氟硫草定(dithiopyr)、EK2612、茵草敌(EPTC)、戊草丹(esprocarb)、ET-751、乙氧嘧磺隆(ethoxysulfuron)、ethbenzanid、噁唑禾草灵(fenoxaprop)、噁唑禾草灵-乙基(fenoxaprop-ethyl)、噁唑禾草灵-乙基(fenoxaprop-ethyl)+isoxadifen-ethyl、四唑草胺(fentrazamide)、啶嘧磺隆(flazasulfuron)、双氟磷草胺(florasulam)、吡氟禾草灵(fluazifop)、精吡氟禾草灵-丁基(fluazifop-P-butyl)、氟吡磺隆(flucetosulfuron)、氟噻草胺(flufenacet)、氟哒嗪草酯-乙基(flufenpyr-ethyl)、唑嘧磺草胺(flumetsulam)、丙炔氟草胺(flumioxazin)、氟啶嘧磺隆脱甲基酸(flupyrsulfuron)、氯氟吡氧乙酸(fluroxypyr)、氟磺胺草醚(fomesafen)、甲酰胺磺隆(foramsulfuron)、草铵膦(glufosinate)、精草铵膦(glufosinate-P)、草甘膦(glyphosate)、氯吡嘧磺隆(halosulfuron-methyl)、氟吡甲禾灵(haloxyfop-methyl)、高效氟吡禾灵(haloxyfop-R)、高效氟吡甲禾灵(haloxyfop-R-methyl)、咪草酯(imazamethabenz)、甲氧咪草烟(imazamox)、甲咪唑烟酸(imazapic)、咪唑烟酸(imazapyr)、咪唑喹啉酸(imazaquin)、咪唑乙烟酸(imazethapyr)、唑吡嘧磺隆(imazosulfuron)、茚草酮(indanofan)、碘苯腈(ioxynil)、卤苯胺唑(ipfencarbazone)、异 噁酰草胺(isoxaben)、2甲4氯(MCPA)、2甲4氯丁酸(MCPB)、苯噻酰草胺(mefenacet)、甲磺胺磺隆脱甲基酸(mesosulfuron)、硝磺草酮(mesotrione)、噁唑酰草胺(metamifop)、双醚氯吡嘧磺隆(metazosulfuron)、异丙甲草胺(metolachlor)、磺草唑胺(metosulam)、甲磺隆脱甲基酸(metsulfuron)、禾草敌(molinate)、单嘧磺隆(monosulfuron)、甲胂一钠(MSMA)、嘧苯胺磺隆(orthosulfamuron)、氨磺乐灵(oryzalin)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、噁嗪草酮(oxazichlomefone)、乙氧呋草醚(oxyfluorfen)、百草枯(paraquat)、二甲戊灵(pendimethalin)、五氟磺草胺(penoxsulam)、戊噁唑草(pentoxazone)、烯草胺(pethoxamid)、氨氯吡啶酸(picloram)、哌草磷(piperophos)、丙草胺(pretilachlor)、环苯草酮(profoxydim)、调环酸-钙(prohexadione-calcium)、毒草胺(propachlor)、敌稗(propanil)、异丙草胺(propisochlor)、炔苯酰草胺(propyzamide)、嗪咪唑嘧磺隆(propyrisulfuron)、氟磺隆(prosulfuron)、pyrabuticarb、双唑草腈(pyraclonil)、双唑草腈(pyrazogyl)、吡唑特(pyrazolynate)、吡嘧磺隆(pyrazosulfuron-ethyl)、苄草唑(pyrazoxyfen)、嘧啶肟草醚(pyribenzoxim)、哒草特(pyridate)、环酯草醚(pyriftalid)、嘧草醚-甲基(pyriminobac-methyl)、pyrimisulfan、氟嘧磺隆脱甲基酸(primisulfuron)、啶磺草胺(pyroxsulam)、灭藻醌(quinoclamine)、二氯喹啉酸(quinclorac)、精喹禾灵-乙基(quizalofop-P-ethyl)、S-3252、烯禾啶(sethoxydim)、西玛津(simazine)、西草净(simetryne)、精异丙甲草胺(s-metolachlor)、磺草酮(sulcotrione)、甲磺草胺(sulfentrazone)、草硫膦(sulfosate)、tefuryltrione、噻吩草胺(thenylchlor)、噻唑烟酸(thiazopyr)、禾草丹(thiobencarb)、绿草定(triclopyr)、三氯吡氧乙酸酯和胺(triclopyr-estersand amines)、氟乐灵(trifluralin)、抗倒酯(trinexapac-ethyl)、三氟甲磺隆(tritosulfuron)及其它4-氨基-6-(取代的苯基)吡啶-2-甲酸和6-氨基-2-(取代的苯基)-嘧啶-4-甲酸及其盐和酯。The herbicidal compounds of the present invention are often applied in combination with one or more other herbicides to control a wider variety of undesirable vegetation. When used in combination with other herbicides, the compound claimed in the present invention can be formulated with one or more herbicides, mixed with other one or more herbicide tanks or mixed with other one or more herbicides Apply sequentially. Some herbicides that can be used in combination with the compounds of the present invention include: 2,4-D salt, esters and amines (2,4-D salts, esters and amines), acetochlor, acetochlor ( acifluorfen), alachlor, amidoxuron, amidosulfuron, aminopyralid, aminotriazole, ammoniumthiocyanate, anilifos, atrazine, Azimsulfuron, benfuresate, bensulfuron-methyl, bentazon, benthiocarb, benzobicyclon, pyraclopyr Benzofenap, bifenox, bispyribac-sodium, bromobutide, butachlor, cafenstrole, alafenone -Ethyl (carfentrazone-ethyl), chlodinafop-propyrgyl, chlorimuron, chlorpropham, chlorpropham, cinosulfuron, clethodim, clomazone (clomazone), clomeprop, clopyralid, cloransulam-methyl ), Cyclosulfamuron, cyclooxydim, cyhalofop-butyl, cyhalofop-butyl, cumyluron, daimuron, diclosulam , Diflufenican, diflufenzopyr, dimefenate, dimepiperate, dimethametryn, diquat, dithiopyr, EK2612, grass EPTC, esprocarb, ET-751, ethoxysulfuron, ethbenzanid, fenoxaprop, fenoxaprop-ethyl, Fenoxaprop-ethyl + isoxadifen-ethyl, fentrazamide, flazasulfuron, florasulam, fluazifop ), Fluazifop-P-butyl, flucetosulfuron, flufentosulfuron, flufenacet, flufenpyr-ethyl, azole Flumetsulam, flumioxazin, flupyrsulfuron, fluroxypyr, fluroxypyr, and fomesafen mesafen), foramsulfuron, glufosinate, glufosinate-P, glyphosate, halosulfuron-methyl, flupiroxon-methyl Haloxyfop-methyl, haloxyfop-R, haloxyfop-R-methyl, imazamethabenz, imazamox, memidazole Niacin (imazapic), imazapyr, imazaquin, imazathapyr, imazosulfuron, indanofan, ioxynil, halogen Ipfencarbazone, isoxaben, isoxaben, MCPA, MCPA, mefenacet, mesulfacetate (mesosulfuron), mesotrione, metamifop, metazosulfuron, metolachlor, metosulam, methyl Metsulfuron, metolin, monosulfuron, monosodium arsulon (MSMA), orthosulfamuron, sulfasulfuron Oryzalin, oxadiargyl, oxadiazon, oxazichlomefone, oxyfluorfen, paraquat, pendimethalin ), Penoxsulam, penoxazone, penthoxamid, picloram, piperophos, pretilachlor, cyclobenzene Profoxydim, prohexadione-calcium, propachlor, propanil, propisochlor, propyzamide, imidazopyrazine Propyrisulfuron, prosulfuron, pyrabuticarb, pyraclonil, pyrazogyl, pyrazoglynate, pyrazolynate, pyrazosulfuron-ethyl, benzalconazole (pyrazoxyfen), pyribenzoxim, pyridate, pyriftalid, pyriminobac-methyl, pyrimsulfan, flusulfuron-methyl primisulfuron), pyroxsulam, quinoclamine, quinclorac, quinquine Quizalofop-P-ethyl, S-3252, sethoxydim, simazine, simetryne, s-metolachlor, sulfonate Sulcotrione, sulfentrazone, sulfosate, tefuryltrione, thenylchlor, thiazopyr, thiobencarb, triclopyr , Triclopyr-esters and amines, trifluralin, trifluralin, trinexapac-ethyl, tritosulfuron and other 4-amino-6- ( Substituted phenyl) pyridine-2-carboxylic acid and 6-amino-2- (substituted phenyl) -pyrimidine-4-carboxylic acid and their salts and esters.
本发明的化合物另外可用来防治多种作物中的不期望的植被,所述作物已经通过遗传操作(geneticmanipulation)或通过突变和选择使其对本发明的化合物或对其它除草剂耐受或耐药。本发明的除草化合物还可以与草甘膦(glyphosate)、草铵膦(glufosinate)、麦草畏(dicamba)、咪唑啉酮(imidazolinones)、芳氧苯氧丙酸酯(aryloxyphenoxypropionates)或2,4-滴(2,4-D)联合用在耐草甘膦、耐草铵膦、耐麦草畏、耐咪唑啉酮、耐芳氧苯氧丙酸酯或耐2,4-滴的作物上。通常优选将本发明的化合物与除草剂联合使用,所述除草剂在所用的施用率对于待处理的作物具有选择性,并且对这些化合物所防治的杂草的谱进行了补充。通常进一步优选同时施用本发明的化合物和其它补充除草剂,作为组合制剂,或者作为罐混合物。类似地,本发明的除草化合物可与乙酰乳酸合酶(ALS)抑制剂联合用于耐乙酰乳酸合酶抑制剂的作物或者与4-羟基苯基丙酮酸双加氧酶(HPPD)抑制剂联合用于耐4-羟基苯基丙酮酸双加氧酶抑制剂的作物。The compounds of the invention can additionally be used to control undesired vegetation in a variety of crops that have been made tolerant or resistant to the compounds of the invention or other herbicides by genetic manipulation or by mutation and selection. The herbicidal compounds of the present invention can also be combined with glyphosate, glufosinate, dicamba, imidazolinones, aryloxyphenoxypropionates or 2,4- Drip (2,4-D) is used in combination with glyphosate, glufosinate, dicamba, imidazolinone, aryloxyphenoxypropionate or 2,4-D crops. It is generally preferred to use the compounds of the present invention in combination with herbicides whose application rates are selective for the crops to be treated, and which complement the spectrum of weeds controlled by these compounds. It is generally further preferred to apply the compound of the present invention and other supplementary herbicides simultaneously as a combined preparation or as a tank mix. Similarly, the herbicidal compounds of the present invention can be used in combination with acetolactate synthase (ALS) inhibitors for crops resistant to acetolactate synthase inhibitors or in combination with 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors For crops resistant to 4-hydroxyphenylpyruvate dioxygenase inhibitors.
本发明的化合物通常可与已知的除草剂安全剂组合使用,以增强其选择性,所述已知的除草剂安全剂例如解草嗪(benoxacor)、禾草丹(benthiocarb)、芸薹素内酯(brassinolide)、解草酯(cloquintocet(mexyl))、解草胺腈(cyometrinil)、环丙磺酰胺(cyprosulfamide)、香草隆(daimuron)、烯丙酰草胺(dichlormid)、dicyclonon、dietholate、哌草丹(dimepiperate)、乙拌磷(disulfoton)、解草唑-乙基(fenchlorazole-ethyl)、解草啶(fenclorim)、解草胺(flurazole)、氟草肟(fluxofenim)、解草噁唑(furilazole)、超敏蛋白(harpin proteins)、双苯噁唑酸乙酯(isoxadifen-ethyl)、吡唑解草酯(mefenpyr-diethyl)、mephenate、解草烷(MG191)、MON4660、萘二甲酸酐(naphthalicanhydride,NA)、解草腈(oxabetrinil)、R29148和N-苯基-磺酰基苯甲酸酰胺(N-phenyl-sulfonylbenzoicacidamides)。本发明的化合物另外可用来防治多种作物中的不期望的植被,所述作物已经通过遗传操作或通过突变和选择使其对本发明的化合物或对其它除草剂耐受或耐药。例如,可以处理玉米、小麦、稻、大豆、甜菜、棉花、芸苔和其它作物,所述作物已经对在易感植物中作为乙酰乳酸合酶抑制剂的化合物耐受或耐药。还可以单独或与这些除草剂组合处理多种耐草甘膦和耐草铵膦的作物。一些作物已经对植物生长素除草剂和ACCase除草剂如2,4-(二氯苯氧基)乙酸(2,4-D)和麦草畏和芳氧苯氧丙酸酯产生耐受。这些除草剂可以用来处理这样的耐药作物或其它耐植物生长素的作物。一些作物已经对抑制4-羟基苯基丙酮酸双加氧酶的除草剂耐受,而这些除草剂可用来处理这样的耐药作物。The compounds of the present invention can generally be used in combination with known herbicide safeners such as benoxacor, benthiocarb, brassinolide to enhance their selectivity Brassinolide, cloquintocet (mexyl), cyometrinil, cyprosulfamide, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietholate , Dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, chlorimide Furilazole, harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxalane (MG191), MON4660, naphthalene Naphthalicanhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoicacidamides. The compounds of the invention can additionally be used to control undesirable vegetation in a variety of crops that have been made tolerant or resistant to the compounds of the invention or to other herbicides through genetic manipulation or through mutation and selection. For example, corn, wheat, rice, soybean, sugar beet, cotton, brassica, and other crops that have been tolerated or resistant to compounds that are acetolactate synthase inhibitors in susceptible plants can be treated. A variety of glyphosate-tolerant and glufosinate-tolerant crops can also be treated alone or in combination with these herbicides. Some crops have developed tolerance to auxin herbicides and ACCase herbicides such as 2,4- (dichlorophenoxy) acetic acid (2,4-D) and dicamba and aryloxyphenoxypropionate. These herbicides can be used to treat such resistant crops or other auxin-resistant crops. Some crops are already resistant to herbicides that inhibit 4-hydroxyphenylpyruvate dioxygenase, and these herbicides can be used to treat such resistant crops.
尽管有可能直接采用式I化合物作为除草剂,但优选的是以混合物的形式使用,所述混合物含有除草有效量的化合物以及至少一种可农用的辅料或载体。适合的辅料或载体不应对有价值作物有植物毒性,特别是在作物存在时在施用用于选择性杂草防治的组合物中所用的浓度,且不应与式I化合物或者其它组合物成分发生化学反应。这样的混合物可以设计成直接施用于杂草或其所在地,或者可以是通常在施用前以另外的载体和辅料来稀释的浓缩物或制剂。它们可以是固体,例如粉剂、颗粒剂、水分散颗粒剂或可湿性粉末剂,或者液体,例如乳油(emulsifiable concentrates)、溶液、乳液或混悬液。它们还可以作为预先混合物或罐混合物来提供。Although it is possible to directly use the compound of formula I as the herbicide, it is preferred to use it in the form of a mixture containing the herbicidally effective amount of the compound and at least one agriculturally acceptable adjuvant or carrier. Suitable excipients or carriers should not be phytotoxic to valuable crops, especially in the concentrations used in the application of compositions for selective weed control in the presence of crops, and should not occur with compounds of formula I or other composition ingredients chemical reaction. Such a mixture may be designed to be applied directly to the weed or its locus, or it may be a concentrate or formulation that is usually diluted with additional carriers and adjuvants before application. They can be solids, such as powders, granules, water-dispersible granules or wettable powders, or liquids, such as emulsifiable concentrates, solutions, emulsions or suspensions. They can also be provided as a premix or tank mix.
用于制备本发明的除草混合物的适合农用辅料和载体为本领域技术人员所熟知。这些辅料中的一些包括,但不限于,作物油浓缩物(矿物油(85%)+乳化剂(15%));壬基苯酚乙氧基化物;苄基可可烷基二甲基季铵盐;石油烃、烷基酯、有机酸和阴离子表面活性剂的共混物;C9-C11烷基多聚糖苷;磷酸化醇乙氧基化物;天然伯醇(C12-C16)乙氧基化物;二仲丁基苯酚EO-PO嵌段共聚物;甲基封端的聚硅氧烷;壬基苯酚乙氧基化物+脲硝酸铵;乳化的甲基化种子油;十三醇(合成的)乙氧基化物(8EO);牛脂胺乙氧基化物(15EO);PEG(400)二油酸酯-99。Suitable agricultural excipients and carriers for preparing the herbicidal mixtures of the present invention are well known to those skilled in the art. Some of these excipients include, but are not limited to, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylate; benzyl cocoa alkyl dimethyl quaternary ammonium salt ; Blend of petroleum hydrocarbons, alkyl esters, organic acids and anionic surfactants; C9-C11 alkyl polyglycosides; phosphorylated alcohol ethoxylates; natural primary alcohols (C12-C16) ethoxylates; Di-sec-butylphenol EO-PO block copolymer; methyl-terminated polysiloxane; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl (synthetic) ethyl Oxygenate (8EO); Tallowamine ethoxylate (15EO); PEG (400) dioleate-99.
可使用的液体载体包括水和有机溶剂。所用的有机溶剂典型地包括,但不限于,石油馏分或烃例如矿物油、芳香族溶剂、石蜡油等;植物油例如大豆油、菜籽油、橄榄油、蓖麻油、葵花子油、椰子油、玉米油、棉籽油、亚麻子油、棕榈油、花生油、红花油、麻油、桐油等;以及上述植物油的酯;一元醇或者二元、三元或者其它低级多元醇(含有4-6个羟基)的酯,例如硬脂酸2-乙基己酯、油酸正丁酯、十四烷酸异丙酯、丙二醇二油酸酯、琥珀酸二辛酯、己二酸二丁酯、酞酸二辛酯等;单、二和多羧酸的酯等。具体的有机溶剂包括甲苯、二甲苯、石脑油(petroleumnaphtha)、作物油、丙酮、甲基乙基酮、环己酮、三氯乙烯、四氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇单甲醚和二甘醇单甲醚、甲醇、乙醇、异丙醇、戊醇、乙二醇、丙二醇、甘油、N-甲基吡咯烷-2-酮、N,N-二甲基烷基酰胺、二甲基亚砜、液体肥料等。水通常是浓缩物稀释所选择的载体。Useful liquid carriers include water and organic solvents. The organic solvents used typically include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oil, etc .; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower oil, coconut oil, corn Oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc .; and esters of the above vegetable oils; monohydric or binary, ternary or other lower polyols (containing 4-6 hydroxyl groups) Esters, such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, dibutyl adipate, diphthalate Octyl esters, etc .; esters of mono-, di- and polycarboxylic acids, etc. Specific organic solvents include toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, tetrachloroethylene, ethyl acetate, amyl acetate, butyl acetate Ester, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, pentanol, ethylene glycol, propylene glycol, glycerin, N-methylpyrrolidone-2-one, N, N-dimethyl Alkyl amide, dimethyl sulfoxide, liquid fertilizer, etc. Water is usually the carrier of choice for dilution of the concentrate.
适合的固体载体包括滑石、叶蜡石粘土(pyrophylliteclay)、硅石、活性白土(attapulgusclay)、高岭土、硅藻土(kieselguhr)、白垩、硅藻土(diatomaceous earth)、石灰、碳酸钙、膨润土、漂白土(Fuller′searth)、棉子壳、小麦粉、大豆粉、浮石粉(pumice)、木粉、胡桃壳粉、木质素等。Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgusclay, kaolin, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, bleach Soil (Fuller'searth), cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, etc.
通常期望的是将一种或更多种表面活性剂引入本发明的组合物中。这种表面活性剂有益地在固体和液体组合物中使用,尤其是设计成在施用前用载体稀释的组合物。所述表面活性剂的性质可以是阴离子的、阳离子的或非离子的,并可用作乳化剂、润湿剂、助悬剂或用于其它目的。通常在制剂领域中使用的且也可在本制剂中使用的表面活性剂特别地(interalia)在“Mc Cutcheon’s Detergents and Emulsifiers Annual,”MC Publishing Corp.,Ridgewood,NewJersey,1998 and in“Encyclopedia of Surfactants,”Vol.I-III,Chemical Publishing Co.,NewYork,1980-81中有述。典型的表面活性剂包括烷基硫酸盐,例如月桂基硫酸二乙醇铵(diethanolammoniumlaurylsulfate);烷基芳基磺酸盐,如十二烷基苯磺酸钙;烷基苯酚-氧化烯加成产物,例如壬基苯酚-C18乙氧基化物;醇-氧化烯加成产物,例如十三烷基醇-C16乙氧基化物;皂,例如硬脂酸钠;烷基萘-磺酸盐,例如二丁基萘磺酸钠;磺基琥珀酸盐的二烷基酯,例如磺基琥珀酸二(2-乙基己基)酯钠;山梨糖醇酯,例如油酸山梨糖醇酯;季铵,例如月桂基三甲基-氯化铵;脂肪酸的聚乙二醇酯,例如硬脂酸聚乙二醇酯;环氧乙烷和环氧丙烷的嵌段共聚物;磷酸单烷基酯的盐和磷酸二烷基酯的盐;植物油或种子油,例如大豆油、菜籽油/芸苔油、橄榄油、蓖麻油、葵花子油、椰子油、玉米油、棉籽油、亚麻子油、棕榈油、花生油、红花油、麻油、桐油等;以及上述植物油的酯,特别是甲酯。It is generally desirable to introduce one or more surfactants into the composition of the present invention. Such surfactants are advantageously used in solid and liquid compositions, especially compositions designed to be diluted with a carrier before application. The nature of the surfactant can be anionic, cationic or nonionic, and can be used as an emulsifier, wetting agent, suspending agent or for other purposes. Surfactants that are commonly used in the field of formulations and can also be used in this formulation are specifically (interalia) in "McCutcheon's Detergents and EmulsifiersAnnual," MC Publishing.Corp., Ridgewood, New Jersey, 1998 and "Encyclopedia of Surfactants" , "Vol.I-III, Chemical Publishing Co., New York, 1980-81. Typical surfactants include alkyl sulfates, such as diethanolammonium laurylsulfate; alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-oxyalkylene addition products, For example, nonylphenol-C18 ethoxylate; alcohol-oxyalkylene addition product, such as tridecyl alcohol-C16 ethoxylate; soap, such as sodium stearate; alkylnaphthalene-sulfonate, such as di Sodium butylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium bis (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium, For example, lauryl trimethyl ammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of monoalkyl phosphates And dialkyl phosphate salts; vegetable or seed oils such as soybean oil, rapeseed oil / canola oil, olive oil, castor oil, sunflower oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil , Peanut oil, safflower oil, sesame oil, tung oil, etc .; and esters of the above vegetable oils, especially methyl esters.
通常,这些物质中的一些,例如植物油或种子油以及其酯,可互换地作为农用辅料、作为液体载体或者作为表面活性剂使用。Generally, some of these substances, such as vegetable or seed oils and their esters, are used interchangeably as agricultural excipients, as a liquid carrier, or as a surfactant.
常用于农用组合物的其它辅料包括相容剂、消泡剂、掩蔽剂(sequesteringagent)、中和剂和缓冲剂、缓蚀剂、染料、芳香剂、铺展剂、渗透助剂、粘着剂、分散剂、增稠剂、防冻剂、抗微生物剂等。所述组合物还可以含有其它相容性组分,例如,其它除草剂、植物生长调节剂、杀真菌剂、杀虫剂等,并可与液体肥料或者固体颗粒肥料载体例如硝酸铵、脲等一起配制。Other excipients commonly used in agricultural compositions include compatibilizers, defoamers, sequestering agents, neutralizers and buffers, corrosion inhibitors, dyes, fragrances, spreading agents, penetration aids, adhesives, dispersion Agents, thickeners, antifreeze agents, antimicrobial agents, etc. The composition can also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, insecticides, etc., and can be combined with liquid fertilizers or solid granular fertilizer carriers such as ammonium nitrate, urea, etc. Prepare together.
本发明除草组合物中活性成分的浓度通常在0.001至98wt%(重量百分数)。常使用0.01至90wt%的浓度。在设计用作浓缩物的组合物中,活性成分通常以5至98wt%,优选以10至90wt%的浓度存在。在施用前将所述组合物典型地用惰性载体(例如水)稀释。通常施用至杂草或杂草所在地的稀释的组合物一般含有0.0001至1wt%活性成分,并优选含有0.001至0.05wt%活性成分。The concentration of the active ingredient in the herbicidal composition of the present invention is usually 0.001 to 98% by weight (weight percent). A concentration of 0.01 to 90% by weight is often used. In compositions designed for use as concentrates, the active ingredient is usually present in a concentration of 5 to 98% by weight, preferably 10 to 90% by weight. The composition is typically diluted with an inert carrier (eg water) before application. The diluted composition which is usually applied to the weeds or locus of the weeds generally contains 0.0001 to 1% by weight of active ingredient, and preferably contains 0.001 to 0.05% by weight of active ingredient.
本发明组合物可通过使用常规的地面或空气撒粉器、喷雾器和颗粒施用器(granule applicators),通过添加至灌溉水或稻田淹灌水(paddy flood water)以及通过本领域技术人员已知的其它常规手段施用于杂草或其所在地。The composition of the present invention can be used by adding conventional ground or air dusters, sprayers and granule applicators, by addition to irrigation water or paddy flood water and by others known to those skilled in the art Conventional means are applied to weeds or their locus.
具体实施方式detailed description
以下实施例用于举例说明本发明,不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。The following examples are used to illustrate the present invention and should not be considered as limiting the present invention in any way. The scope of the claimed rights of the present invention is described by the claims.
鉴于化合物的经济性与多样性,我们优选合成了一些化合物,在合成的诸多化合物中,选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1-2所示。表1中的化合物只是为了更好的说明本发明,但并不限定本发明,对于本领域的技术人员而言,不应将此理解为本发明上述主题的范围仅限于以下化合物。In view of the economics and diversity of compounds, we prefer to synthesize some compounds. Among the many compounds synthesized, selected parts are listed in Table 1 below. The specific compound structure and corresponding compound information are shown in Table 1-2. The compounds in Table 1 are only for better description of the present invention, but do not limit the present invention. Those skilled in the art should not understand this as the scope of the above subject of the present invention is limited to the following compounds.
表1.化合物的结构Table 1. Structure of the compound
Figure PCTCN2018121998-appb-000038
Figure PCTCN2018121998-appb-000038
Figure PCTCN2018121998-appb-000039
Figure PCTCN2018121998-appb-000039
Figure PCTCN2018121998-appb-000040
Figure PCTCN2018121998-appb-000040
Figure PCTCN2018121998-appb-000041
Figure PCTCN2018121998-appb-000041
Figure PCTCN2018121998-appb-000042
Figure PCTCN2018121998-appb-000042
Figure PCTCN2018121998-appb-000043
Figure PCTCN2018121998-appb-000043
Figure PCTCN2018121998-appb-000044
Figure PCTCN2018121998-appb-000044
Figure PCTCN2018121998-appb-000045
Figure PCTCN2018121998-appb-000045
Figure PCTCN2018121998-appb-000046
Figure PCTCN2018121998-appb-000046
Figure PCTCN2018121998-appb-000047
Figure PCTCN2018121998-appb-000047
Figure PCTCN2018121998-appb-000048
Figure PCTCN2018121998-appb-000048
Figure PCTCN2018121998-appb-000049
Figure PCTCN2018121998-appb-000049
Figure PCTCN2018121998-appb-000050
Figure PCTCN2018121998-appb-000050
Figure PCTCN2018121998-appb-000051
Figure PCTCN2018121998-appb-000051
Figure PCTCN2018121998-appb-000052
Figure PCTCN2018121998-appb-000052
Figure PCTCN2018121998-appb-000053
Figure PCTCN2018121998-appb-000053
Figure PCTCN2018121998-appb-000054
Figure PCTCN2018121998-appb-000054
Figure PCTCN2018121998-appb-000055
Figure PCTCN2018121998-appb-000055
Figure PCTCN2018121998-appb-000056
Figure PCTCN2018121998-appb-000056
Figure PCTCN2018121998-appb-000057
Figure PCTCN2018121998-appb-000057
Figure PCTCN2018121998-appb-000058
Figure PCTCN2018121998-appb-000058
Figure PCTCN2018121998-appb-000059
Figure PCTCN2018121998-appb-000059
Figure PCTCN2018121998-appb-000060
Figure PCTCN2018121998-appb-000060
Figure PCTCN2018121998-appb-000061
Figure PCTCN2018121998-appb-000061
Figure PCTCN2018121998-appb-000062
Figure PCTCN2018121998-appb-000062
Figure PCTCN2018121998-appb-000063
Figure PCTCN2018121998-appb-000063
Figure PCTCN2018121998-appb-000064
Figure PCTCN2018121998-appb-000064
Figure PCTCN2018121998-appb-000065
Figure PCTCN2018121998-appb-000065
Figure PCTCN2018121998-appb-000066
Figure PCTCN2018121998-appb-000066
Figure PCTCN2018121998-appb-000067
Figure PCTCN2018121998-appb-000067
Figure PCTCN2018121998-appb-000068
Figure PCTCN2018121998-appb-000068
Figure PCTCN2018121998-appb-000069
Figure PCTCN2018121998-appb-000069
Figure PCTCN2018121998-appb-000070
Figure PCTCN2018121998-appb-000070
Figure PCTCN2018121998-appb-000071
Figure PCTCN2018121998-appb-000071
表2.化合物的 1HNMR数据 Table 2. 1 HNMR data of the compound
Figure PCTCN2018121998-appb-000072
Figure PCTCN2018121998-appb-000072
Figure PCTCN2018121998-appb-000073
Figure PCTCN2018121998-appb-000073
Figure PCTCN2018121998-appb-000074
Figure PCTCN2018121998-appb-000074
Figure PCTCN2018121998-appb-000075
Figure PCTCN2018121998-appb-000075
制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解,也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明,但是,可以很容易地将其替换为其它类似的原料及条件,这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外,如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如,在反应过程中对适当的基团进行保护等等。Several methods for preparing the compounds of the present invention are explained in detail in the following schemes and examples. The raw materials are commercially available or can be prepared by methods known in the literature or as shown in the detailed explanation. Those skilled in the art should understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described in the following, they can be easily replaced with other similar raw materials and conditions, such as those produced by the modification or modification of the preparation method of the present invention, such as compounds Various isomers and the like are included in the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, the protection of appropriate groups during the reaction and so on.
以下提供的方法实施例用于促进对本发明制备方法的进一步了解,使用的具体物质、种类和条件确定为是对本发明的进一步说明,并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到,或者可以由本领域普通技术人员轻易制备得到。The method examples provided below are used to promote a further understanding of the preparation method of the present invention. The specific substances, types and conditions used are determined to be a further illustration of the present invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds indicated in the table below are either commercially available or can be easily prepared by those of ordinary skill in the art.
代表性化合物的实施例如下:Examples of representative compounds are as follows:
1、化合物14的合成1. Synthesis of compound 14
Figure PCTCN2018121998-appb-000076
Figure PCTCN2018121998-appb-000076
在8毫升的DCM中依次加入a(0.35g,1.1mmol,1.0eq),PyBOP(0.62g,1.2mmol,1.1eq),Et 3N(0.14g,1.4mmol,1.3eq),并在室温搅拌30min后加入b(0.16g,1.2mmol,1.1eq),然后反应液搅拌8小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用10毫升DCM萃取三次,有机相干燥,旋干,柱层析分离得到化合物14(0.25g,51%收率)(白色固体)。 In 8 mL of DCM, add a (0.35 g, 1.1 mmol, 1.0 eq), PyBOP (0.62 g, 1.2 mmol, 1.1 eq), Et 3 N (0.14 g, 1.4 mmol, 1.3 eq), and stir at room temperature After 30 min, b (0.16 g, 1.2 mmol, 1.1 eq) was added, and then the reaction solution was stirred for 8 hours. LCMS detected the product. The reaction solution was poured into 10 ml of water, and the layers were separated. The aqueous phase was extracted three times with 10 ml of DCM. The organic phase was dried, spin-dried, and separated by column chromatography to obtain compound 14 (0.25 g, 51% yield) (white solid).
2、化合物16的合成2. Synthesis of Compound 16
Figure PCTCN2018121998-appb-000077
Figure PCTCN2018121998-appb-000077
在8毫升的DMF中依次加入a(0.35g,1.1mmol,1.0eq),HATU(0.45g,1.2mmol,1.1eq),Et 3N(0.14g,1.4mmol,1.3eq)并在室温搅拌30min后加入c(0.11g,1.2mmol,1.1eq),然后反应液搅拌8小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用10毫升乙酸乙酯萃取三次,有机相用饱和食盐水(20ml)洗一次,干燥,旋干,柱层析分离得到化合物16(0.30g,69%收率)(白色固体)。 To 8 ml of DMF, add a (0.35 g, 1.1 mmol, 1.0 eq), HATU (0.45 g, 1.2 mmol, 1.1 eq), Et 3 N (0.14 g, 1.4 mmol, 1.3 eq) and stir at room temperature for 30 min Then c (0.11 g, 1.2 mmol, 1.1 eq) was added, and then the reaction solution was stirred for 8 hours. LCMS detected the product. The reaction solution was poured into 10 ml of water, and the layers were separated. The aqueous phase was extracted three times with 10 ml of ethyl acetate, and the organic phase was washed once with saturated brine (20 ml), dried, spin-dried, and separated by column chromatography to obtain compound 16 (0.30 g , 69% yield) (white solid).
3、化合物54的合成3. Synthesis of Compound 54
Figure PCTCN2018121998-appb-000078
Figure PCTCN2018121998-appb-000078
在10毫升的THF中依次加入a(0.35g,1.1mmol,1.0eq),CDI(0.19g,1.2mmol,1.1eq)然后在50℃条件下搅拌1小时后加入d(0.16g,1.2mmol,1.1eq),然后反应液在50℃条件下搅拌1小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用10毫升乙酸乙酯萃取三次,有机相用饱和食盐水(20ml)洗一次,干燥,旋干,柱层析分离得到化合物54(0.35g,74%收率)(白色固体)。Add a (0.35g, 1.1mmol, 1.0eq), CDI (0.19g, 1.2mmol, 1.1eq) in 10ml of THF, then stir at 50 ℃ for 1 hour, then add d (0.16g, 1.2mmol, 1.1eq), and then the reaction solution was stirred at 50 ° C for 1 hour. LCMS detected the product. The reaction solution was poured into 10 ml of water, and the layers were separated. The aqueous phase was extracted three times with 10 ml of ethyl acetate, and the organic phase was washed once with saturated brine (20 ml), dried, spin-dried, and separated by column chromatography to obtain compound 54 (0.35 g , 74% yield) (white solid).
4、化合物70的合成4. Synthesis of Compound 70
Figure PCTCN2018121998-appb-000079
Figure PCTCN2018121998-appb-000079
在50毫升的圆底单口烧瓶中依次加入a(0.35g,1.1mmol,1.0eq),SOCl 2(10ml),然后在70℃条件下搅拌1小时后浓缩除掉过量的SOCl 2。然后依次加入DCM(10ml),Et 3N(0.14g,1.4mmol,1.3eq)和e(0.14g,1.2mmol,1.1eq),然后反应液在25℃条件下搅拌2小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用10毫升二氯甲烷萃取三次,有机相用饱和食盐水(20ml)洗一次,干燥,旋干,柱层析分离得到化合物70(0.31g,68%收率)(白色固体)。 In a 50 ml round-bottomed single-necked flask, a (0.35 g, 1.1 mmol, 1.0 eq), SOCl 2 (10 ml) were added in sequence, then stirred at 70 ° C for 1 hour, and concentrated to remove excess SOCl 2 . Then, DCM (10 ml), Et 3 N (0.14 g, 1.4 mmol, 1.3 eq) and e (0.14 g, 1.2 mmol, 1.1 eq) were sequentially added, and then the reaction solution was stirred at 25 ° C. for 2 hours. LCMS detected the product. The reaction solution was poured into 10 ml of water and separated. The aqueous phase was extracted three times with 10 ml of dichloromethane. The organic phase was washed once with saturated brine (20 ml), dried, spin-dried and separated by column chromatography to obtain compound 70 (0.31 g , 68% yield) (white solid).
5、化合物173的合成5. Synthesis of Compound 173
Figure PCTCN2018121998-appb-000080
Figure PCTCN2018121998-appb-000080
在8毫升的DCM中依次加入f(0.70g,2.2mmol,1.0eq),PyBOP(1.24g,2.4mmol,1.1eq),Et 3N(0.28g,2.8mmol,1.3eq),并在室温搅拌30min后加入b(0.32g,2.4mmol,1.1eq),然后反应液搅拌8小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用25毫升DCM萃取三次,有机相干燥,旋干,柱层析分离得到化合物173(0.61g,61%收率)(白色固体)。 In 8 mL of DCM, add f (0.70 g, 2.2 mmol, 1.0 eq), PyBOP (1.24 g, 2.4 mmol, 1.1 eq), Et 3 N (0.28 g, 2.8 mmol, 1.3 eq), and stir at room temperature After 30 min, b (0.32 g, 2.4 mmol, 1.1 eq) was added, and then the reaction solution was stirred for 8 hours. LCMS detected the product. The reaction solution was poured into 10 ml of water, and the layers were separated. The aqueous phase was extracted three times with 25 ml of DCM. The organic phase was dried, spin-dried, and separated by column chromatography to obtain compound 173 (0.61 g, 61% yield) (white solid).
6、对照化合物A的合成6. Synthesis of Control Compound A
Figure PCTCN2018121998-appb-000081
Figure PCTCN2018121998-appb-000081
在8毫升的DMF中依次加入a(0.35g,1.1mmol,1.0eq),HATU(0.45g,1.2mmol,1.1eq),Et 3N(0.14g,1.4mmol,1.3eq),并在室温搅拌30min后加入g(0.10g,1.2mmol,1.1eq),然后反应液搅拌8小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用10毫升乙酸乙酯萃取三次,有机相用饱和食盐水(20ml)洗一次,干燥,旋干,柱层析分离得到对照化合物A(0.28g,67%收率)(白色固体)。 To 8 ml of DMF, add a (0.35 g, 1.1 mmol, 1.0 eq), HATU (0.45 g, 1.2 mmol, 1.1 eq), Et 3 N (0.14 g, 1.4 mmol, 1.3 eq), and stir at room temperature After 30 min, g (0.10 g, 1.2 mmol, 1.1 eq) was added, and then the reaction solution was stirred for 8 hours. LCMS detected the product. The reaction solution was poured into 10 ml of water and separated. The aqueous phase was extracted three times with 10 ml of ethyl acetate. The organic phase was washed once with saturated brine (20 ml), dried, spin-dried, and separated by column chromatography to obtain control compound A (0.28 g, 67% yield) (white solid).
7、对照化合物B的合成7. Synthesis of Control Compound B
Figure PCTCN2018121998-appb-000082
Figure PCTCN2018121998-appb-000082
在8毫升的DMF中依次加入a(0.35g,1.1mmol,1.0eq),HATU(0.45g,1.2mmol,1.1eq),Et 3N(0.14g,1.4mmol,1.3eq),并在室温搅拌30min后加入h(0.08g,1.2mmol,1.1eq),然后反应液搅拌8小时。LCMS检测到产品。将反应液倒入10毫升水中,分液,水相用10毫升乙酸乙酯萃取三次,有机相用饱和食盐水(20ml)洗一次,干燥,旋干,柱层析分离得到对照化合物B(0.29g,72%收率)(白色固体)。 To 8 ml of DMF, add a (0.35 g, 1.1 mmol, 1.0 eq), HATU (0.45 g, 1.2 mmol, 1.1 eq), Et 3 N (0.14 g, 1.4 mmol, 1.3 eq), and stir at room temperature After 30 min, h (0.08 g, 1.2 mmol, 1.1 eq) was added, and then the reaction solution was stirred for 8 hours. LCMS detected the product. The reaction solution was poured into 10 ml of water, and the layers were separated. The aqueous phase was extracted three times with 10 ml of ethyl acetate. The organic phase was washed once with saturated brine (20 ml), dried, spin-dried, and separated by column chromatography to obtain control compound B (0.29 g, 72% yield) (white solid).
生物活性评价:Evaluation of biological activity:
有害植物破坏(即生长控制率)的活性级别标准如下:The standard of activity level of harmful plant destruction (ie growth control rate) is as follows:
5级:生长控制率在85%以上;Level 5: The growth control rate is above 85%;
4级:生长控制率大于等于60%且小于85%;Level 4: The growth control rate is greater than or equal to 60% and less than 85%;
3级:生长控制率大于等于40%且小于60%;Level 3: Growth control rate is greater than or equal to 40% and less than 60%;
2级:生长控制率大于等于20%且小于40%;Level 2: The growth control rate is greater than or equal to 20% and less than 40%;
1级:生长控制率大于等于5%且小于20%;Level 1: The growth control rate is greater than or equal to 5% and less than 20%;
0级:生长控制率小于5%。Level 0: The growth control rate is less than 5%.
以上生长控制率为鲜重控制率。The above growth control rate is the fresh weight control rate.
(1)苗后测试实验:将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中,然后覆盖0.5-2厘米土壤,使其在良好的温室环境中生长,播种2-3周后在4-5叶期处理测试植物,分别将供试的本发明化合物用丙酮溶解,然后加入吐温80,用一定的水稀释成一定浓度的溶液,用喷雾塔喷施到植物上。施药后在温室中培养3周,3周后杂草的实验效果列于表3。(1) Post-emergence test experiment: Place monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) in a plastic pot filled with soil, and then cover 0.5-2 cm soil, let it grow in a good greenhouse environment, treat the test plants at 4-5 leaf stage after sowing for 2-3 weeks, dissolve the tested compound of the invention with acetone, and then add Tween 80, Dilute it with a certain amount of water to a certain concentration, and spray it on the plants with a spray tower. After the application, the plants were cultivated in the greenhouse for 3 weeks. After 3 weeks, the experimental effects of weeds are shown in Table 3.
表3.苗后杂草试验(15克/公顷)Table 3. Post-emergence weed test (15 g / ha)
化合物序号Compound number 猪殃殃Pig 荠菜Shepherd's purse 反枝苋Amaranthus retroflexus 野慈姑Ye Cigu 鸭舌草Zantedeschia
77 55 55 55 55 55
1313 55 55 55 55 55
1414 55 55 55 55 55
1515 55 55 55 55 55
1616 55 55 55 55 55
1717 55 55 55 55 55
24twenty four 55 55 55 55 55
2626 55 55 55 55 55
2727 55 55 55 55 55
2828 55 55 55 55 55
3131 55 55 55 55 55
5252 55 55 55 55 55
5353 55 55 55 55 55
5454 55 55 55 55 55
5555 55 55 55 55 55
5656 55 55 55 55 55
5858 55 55 55 55 55
5959 55 55 55 55 55
6060 55 55 55 55 55
6161 55 55 55 55 55
6262 55 55 55 55 55
6464 55 55 55 55 55
6565 55 55 55 55 55
6666 55 55 55 55 55
7070 55 55 55 55 55
7171 55 55 55 55 55
7272 55 55 55 55 55
7474 55 55 55 55 55
7575 55 55 55 55 55
324324 55 44 44 44 55
351351 55 44 55 55 55
363363 44 22 44 33 44
374374 44 44 55 44 55
379379 55 55 55 44 55
380380 44 44 55 44 44
381381 44 44 44 33 44
392392 55 55 55 55 55
455455 55 55 55 44 55
AA 11 00 11 11 00
BB 11 00 00 11 00
CC 11 00 11 11 11
DD 11 00 11 11 11
注:对照化合物A:
Figure PCTCN2018121998-appb-000083
对照化合物B:
Figure PCTCN2018121998-appb-000084
对照化合物C:
Figure PCTCN2018121998-appb-000085
对照化合物D:
Figure PCTCN2018121998-appb-000086
Note: Control Compound A:
Figure PCTCN2018121998-appb-000083
Control Compound B:
Figure PCTCN2018121998-appb-000084
Control Compound C:
Figure PCTCN2018121998-appb-000085
Control Compound D:
Figure PCTCN2018121998-appb-000086
(2)直播水稻2-3叶期,玉米2-3叶期,杂草3叶期茎叶喷雾安全性与活性测试,结果如表4所示。(2) The safety and activity tests of direct seeding rice 2-3 leaf stage, corn 2-3 leaf stage, weed 3 leaf stage stem and leaf spray, the results are shown in Table 4.
表4.安全性与活性测试结果(45克/公顷)Table 4. Safety and activity test results (45 g / ha)
化合物序号Compound number 水稻Rice 玉米corn 马唐Matang 苘麻Velvetleaf
1313 00 11 33 55
1616 11 NTNT 33 55
5252 00 11 33 55
5353 00 00 33 55
6262 00 11 33 55
7171 11 00 33 55
7474 11 11 33 55
455455 00 11 33 55
EE 44 55 33 55
注:NT代表未测试数据,对照化合物E:
Figure PCTCN2018121998-appb-000087
Note: NT stands for untested data, control compound E:
Figure PCTCN2018121998-appb-000087
由以上表格可知,本发明化合物与对照化合物相比,明显具有更高的防效或作物选择性。It can be seen from the above table that the compound of the present invention has significantly higher control effect or crop selectivity than the control compound.
(3)苗前测试实验:(3) Pre-emergence test experiment:
将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中,然后覆盖0.5-2厘米土壤,分别将供试的本发明化合物用丙酮溶解,然后加入吐温80,用一定的水稀释成一定浓度的溶液,播种后立即喷施。施药后在温室中培养4周,3周后观察实验结果,发现本发明的药剂多数在250克/公顷计量下效果出众,且很多化合物对玉米、小麦、水稻、大豆、油菜有良好的选择性。Place monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) in plastic pots filled with soil, and then cover 0.5-2 cm of soil, respectively. The compound of the present invention to be tested is dissolved in acetone, then Tween 80 is added, diluted with a certain amount of water to a solution of a certain concentration, and sprayed immediately after sowing. After 4 weeks of cultivation in the greenhouse after application, the experimental results were observed after 3 weeks, and it was found that most of the agents of the present invention are excellent at 250 g / ha, and many compounds have good choices for corn, wheat, rice, soybean, rape Sex.
通过实验我们发现本发明所述化合物普遍具有较好的杂草防效,尤其对于玉米田、水稻田、小麦田广泛发生的杂草苘麻、鬼针草等主要的阔叶杂草有良好的效果,具备良好的商业价值。尤其是我们注意到对于ALS抑制剂有抗性的麦家公、猪殃殃、繁缕等阔叶杂草有极高的活性。Through experiments, we found that the compounds of the present invention generally have better weed control effects, especially for the broad-leaved weeds such as velvetleaf, needle needle grass and other weeds that widely occur in corn fields, rice fields and wheat fields The effect has good commercial value. In particular, we have noticed that the broadleaf weeds such as Maijiagong, Swamp, and Stellaria which are resistant to ALS inhibitors have extremely high activity.
(4)移栽水稻安全性评价与水田杂草防效评价:(4) Safety evaluation of transplanted rice and evaluation of weed control effectiveness in paddy fields:
在1/1,000,000公顷罐中装入水田土壤后,播种稗草、萤蔺、狼把草、野慈姑的种子,在其上轻轻地覆盖土。其后以蓄水深0.5-1厘米的状态静置于温室内,第二天或者2天后植入野慈姑的块茎。其后保持蓄水深3-4厘米,在稗草、萤蔺、狼把草达到0.5叶,野慈姑达到初生叶期的时间点,将按照通常的制剂方法调制本发明化合物而成的可湿性粉剂或者悬浮剂的水稀释液,用吸液管进行均匀的滴下处理以达到规定的有效成分量。After filling the paddy field soil in a 1 / 1,000,000 hectare pot, sow the seeds of barnyard grass, fireflies, wolfgrass, and wild Cigu, and cover it gently with soil. After that, it was placed in a greenhouse with a water storage depth of 0.5-1 cm, and the tubers of Yecigu were implanted the next day or 2 days later. Afterwards, the water storage depth is 3-4 cm, and the barnyardgrass, firefly, and wolfgrass will reach 0.5 leaves, and the wild Cigu will reach the primary leaf stage. The water dilution of powder or suspending agent is uniformly dropped with a pipette to achieve the specified amount of active ingredients.
另外,在1/1,000,000公顷罐中装入水田土壤后,进行平整,使蓄水深3-4厘米,第二天以移栽深度3厘米来移植3叶期的水稻(粳稻)。移植后第5天与上述同样地处理本发明化合物。In addition, after filling the paddy field soil in a 1 / 1,000,000 hectare pot, it was leveled so that the water storage depth was 3-4 cm, and rice (Japonica) at the 3-leaf stage was transplanted at the transplant depth of 3 cm the next day. On the fifth day after transplantation, the compound of the present invention was treated in the same manner as described above.
分别用肉眼观察药剂处理后第14天稗草、萤蔺、狼把草及野慈姑的生育状态,药剂处理后第21天水稻的生育状态,以1-10的活性标准级别评价除草效果,试验发现很多本发明的化合物有优秀的活性和选择性,尤其对于野慈姑和稗草。Observe the growth status of barnyardgrass, firefly, foxgrass, and wild Cigu on the 14th day after chemical treatment with the naked eye. It has been found that many of the compounds of the present invention have excellent activity and selectivity, especially for wild Cigu and barnyard grass.
注:稗草、萤蔺、野慈姑、狼把草种子均采集自中国黑龙江,经过检测对常规剂量的吡 嘧磺隆有抗药性。Note: Barnyard grass, firefly, wild Cigu, and Wolfgrass seeds are all collected from Heilongjiang, China, and have been tested to be resistant to conventional dosages of pyrasulfuron-methyl.
同时经过很多测试发现,本发明所述化合物及其组合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性,能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的小麦、玉米、水稻、甘蔗、大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。At the same time, after many tests, it was found that many of the compounds and compositions of the present invention have good selectivity to grass lawns such as Zoysia japonica, bermudagrass, tall fescue, bluegrass, ryegrass, seashore paspalum, and can be controlled Many key grass weeds and broad-leaved weeds. Tests on wheat, corn, rice, sugar cane, soybean, cotton, oil sunflower, potato, fruit tree, vegetable, etc. under different application methods also showed excellent selectivity and commercial value.

Claims (10)

  1. 一种取代的含氮杂芳环甲酰胺衍生物,其结构式如下:A substituted nitrogen-containing heteroaromatic ring formamide derivative, its structural formula is as follows:
    Figure PCTCN2018121998-appb-100001
    Figure PCTCN2018121998-appb-100001
    式中,M代表
    Figure PCTCN2018121998-appb-100002
    Het选自五元不饱和环,该环上除含有1-位上的N原子外,还含有1-3个以下原子或基团作为环的组成部分:NR b
    In the formula, M represents
    Figure PCTCN2018121998-appb-100002
    Het is selected from a five-membered unsaturated ring, which contains 1-3 atoms or groups in addition to the N atom at the 1-position as a component of the ring: NR b ;
    R a选自以下基团中的一个或多个基团:氢,卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的烷基、烯基、炔基、环烷基、烯基烷基、炔基烷基、环烷基烷基、烷氧基、烷硫基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基亚硫酰基、烷基磺酰基、烷基氨基、二烷基氨基、烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基、芳基氧基、杂芳基氧基;或者相邻两个R a一起形成未取代或取代的-CH=CH-CH=CH-、-CH 2CH 2CH 2CH 2-、-N=CH-CH=CH-、-CH=N-CH=CH-基团; R a is selected from one or more of the following groups: hydrogen, halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, alkyl with or without halogen, alkenyl, alkyne Group, cycloalkyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl , Alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylacyloxy and unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl, Aryloxy, heteroaryloxy; or two adjacent Ra together form unsubstituted or substituted -CH = CH-CH = CH-, -CH 2 CH 2 CH 2 CH 2- , -N = CH -CH = CH-, -CH = N-CH = CH- group;
    R b代表氢,烷基; R b represents hydrogen, alkyl;
    Q代表N或C-R”;其中,R”代表氢,卤素,氰基,含有或不含有卤素的烷基、烷氧基、烯基、炔基、环烷基,以及未取代或取代的芳基、杂芳基;Q stands for N or CR "; where R" stands for hydrogen, halogen, cyano, alkyl with or without halogen, alkoxy, alkenyl, alkynyl, cycloalkyl, and unsubstituted or substituted aryl , Heteroaryl;
    X代表卤素,含有或不含有卤素的烷基、烯基、炔基、环烷基、烷氧基、烷基氨基、二烷基氨基,未取代或取代的芳基、杂芳基;X represents halogen, with or without halogen alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, unsubstituted or substituted aryl, heteroaryl;
    Y代表硝基或NR 1R 2,其中R 1代表H,任选地被1-2个R 11取代的烷基、烯基或炔基,未取代或取代的芳基、杂芳基,-COR 12,硝基,OR 13,SO 2R 14,NR 15R 16,N=CR 17R 18,烷基氨基甲酰基,二烷基氨基甲酰基,三烷基甲硅烷基或二烷基膦酰基;R 2代表H,任选地被1-2个R 21取代的烷基或-COR 22;或者NR 1R 2代表N=CR 31NR 32R 33,N=CR 34OR 35,未取代或被1-2个独立选自卤素、烷基、烷氧基、卤代烷氧基、烷硫基、卤代烷硫基、氨基、烷基氨基、二烷基氨基、烷氧基羰基中的基团所取代的不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环; Y represents nitro or NR 1 R 2 , wherein R 1 represents H, alkyl, alkenyl or alkynyl optionally substituted by 1-2 R 11 , unsubstituted or substituted aryl, heteroaryl,- COR 12 , nitro, OR 13 , SO 2 R 14 , NR 15 R 16 , N = CR 17 R 18 , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphine Acyl; R 2 represents H, optionally substituted with 1-2 R 21 alkyl or -COR 22 ; or NR 1 R 2 represents N = CR 31 NR 32 R 33 , N = CR 34 OR 35 , unsubstituted Or by 1-2 groups independently selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl Substituted 5- or 6-membered saturated or unsaturated rings containing no or containing oxygen atoms, sulfur atoms or other nitrogen atoms;
    其中R 11、R 21独立地代表卤素,羟基,烷氧基,卤代烷氧基,烷硫基,卤代烷硫基,氨基、烷基氨基,二烷基氨基,烷氧基羰基,未取代或取代的芳基、杂芳基; Where R 11 and R 21 independently represent halogen, hydroxyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted Aryl, heteroaryl;
    R 12、R 22独立地代表H、烷基、卤代烷基、烷氧基、苯基、苯氧基或苄氧基; R 12 and R 22 independently represent H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;
    R 13代表H、烷基、卤代烷基、苯基、苄基或CHR 41C(O)OR 42;R 41代表H、烷基或烷氧基;R 42代表H、烷基或苄基; R 13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ; R 41 represents H, alkyl or alkoxy; R 42 represents H, alkyl or benzyl;
    R 14代表烷基、卤代烷基; R 14 represents alkyl, haloalkyl;
    R 15代表H、烷基、甲酰基、烷基羰基、卤代烷基羰基、烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基;R 16代表H、烷基; R 15 represents H, alkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, alkyl;
    R 17代表H、烷基、未取代或被卤素、烷基、烷氧基中的1-3个基团所取代的苯基;R 18代表H、烷基;或N=CR 17R 18代表
    Figure PCTCN2018121998-appb-100003
    R 17 represents H, alkyl, unsubstituted or substituted with 1-3 groups in halogen, alkyl, alkoxy; R 18 represents H, alkyl; or N = CR 17 R 18 represents
    Figure PCTCN2018121998-appb-100003
    R 31、R 34分别独立地代表H或烷基; R 31 and R 34 independently represent H or alkyl;
    R 32、R 33分别独立地代表H或烷基;或者NR 32R 33代表不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环; R 32 and R 33 independently represent H or alkyl; or NR 32 R 33 represents a 5- or 6-membered saturated or unsaturated ring that does not contain or contains an oxygen atom, sulfur atom or other nitrogen atom;
    R 35代表烷基; R 35 represents alkyl;
    Z代表氢,卤素,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有卤素的烷基、环烷基、环烷基烷基、炔基、烷氧基、烷硫基、烷基氨基、二烷基氨基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基酰氧基、烷基亚硫酰基、烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自卤素、氰基、环烷基、烷基羰基、烷氧基羰基、烷氧基、烷硫基、烷基亚硫酰基、烷基磺酰基中的至少一个基团所取代的烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表烷基、环烷基、卤代烷基、卤代环烷基、未取代或取代的苯基、烷氧基、卤代烷氧基、羟基;R 54代表氢、卤素、烷基、卤代烷基;R 55代表氢、卤素;m代表0或1,n代表0~8之间的整数。 Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, alkyl with or without halogen, cycloalkyl, cycloalkylalkyl, alkynyl, alkoxy, alkyl Thio, alkylamino, dialkylamino, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylacyloxy, alkylsulfinyl, alkylsulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected from halogen, cyanide An alkenyl group substituted with at least one group in the group, cycloalkyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, and epoxide thereof, Unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 independently represent alkyl , Cycloalkyl, haloalkyl, halocycloalkyl, unsubstituted or substituted phenyl, alkoxy, haloalkoxy, hydroxy; R 54 represents hydrogen, halogen, alkyl, haloalkyl; R 55 represents hydrogen, Halogen; m Table 0 or 1, n represents an integer between 0 and 8.
  2. 根据权利要求1所述的一种取代的含氮杂芳环甲酰胺衍生物,其特征在于,A substituted nitrogen-containing heteroaromatic ring formamide derivative according to claim 1, wherein
    M代表
    Figure PCTCN2018121998-appb-100004
    Het选自五元不饱和环,该环上除含有1-位上的N原子外,还含有1、2或3个以下原子或基团作为环的组成部分:NR b
    M stands for
    Figure PCTCN2018121998-appb-100004
    Het is selected from a five-membered unsaturated ring, which contains 1, 2 or 3 atoms or groups as part of the ring in addition to the N atom at the 1-position: NR b ;
    R a选自以下基团中的一个或多个基团:氢,卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C2-C8烯基C1-C8烷基、C2-C8炔基C1-C8烷基、C3-C8环烷基C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基、芳基氧基、杂芳基氧基;或者相邻两个R a一起形成未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的烷基、烯基、炔基、环烷基、环烷 基烷基、烷氧基、烷硫基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基亚硫酰基、烷基磺酰基、烷基氨基、二烷基氨基、烷基酰氧基,以及未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基、芳基氧基、杂芳基氧基中的至少一个基团所取代的-CH=CH-CH=CH-、-CH 2CH 2CH 2CH 2-、-N=CH-CH=CH-、-CH=N-CH=CH-基团; R a is selected from the group of one or more groups: hydrogen, halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, containing or not containing a halogen C1-C8 alkyl, C2 -C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C2-C8 alkenyl C1-C8 alkyl, C2-C8 alkynyl C1-C8 alkyl, C3-C8 cycloalkyl C1-C8 alkyl Group, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkylthio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 Alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkylacyloxy and unsubstituted or substituted Aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl, aryloxy, heteroaryloxy; or two adjacent Ra together form unsubstituted or selected From halogen, nitro, cyano, hydroxy, carboxyl, amino, mercapto, formyl, with or without halogen alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkyl Thio, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfinyl, alkyl Acyl, alkylamino, dialkylamino, alkylacyloxy, and unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy, heteroaryloxy -CH = CH-CH = CH-, -CH 2 CH 2 CH 2 CH 2- , -N = CH-CH = CH-, -CH = N-CH = CH- substituted by at least one group in the group Group
    R b代表氢,C1-C8烷基; R b represents hydrogen, C1-C8 alkyl;
    Q代表N或C-R”;其中,R”代表氢,卤素,氰基,含有或不含有卤素的C1-C8烷基、C1-C8烷氧基、C2-C8烯基、C2-C8炔基、C3-C8环烷基,以及未取代或取代的芳基、杂芳基;Q stands for N or CR "; where R" stands for hydrogen, halogen, cyano, C1-C8 alkyl with or without halogen, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
    X代表卤素,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C1-C8烷氧基、C1-C8烷基氨基、二C1-C8烷基氨基,未取代或取代的芳基、杂芳基;X represents halogen, with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylamino, di C1-C8 alkylamino, unsubstituted or substituted aryl, heteroaryl;
    Y代表硝基或NR 1R 2,其中R 1代表H,任选地被1-2个R 11取代的C1-C8烷基、C2-C8烯基或C2-C8炔基,未取代或未取代或取代的芳基、杂芳基,-COR 12,硝基,OR 13,SO 2R 14,NR 15R 16,N=CR 17R 18,C1-C8烷基氨基甲酰基,二C1-C8烷基氨基甲酰基,三C1-C8烷基甲硅烷基或二C1-C8烷基膦酰基;R 2代表H,任选地被1-2个R 21取代的C1-C8烷基或-COR 22;或者NR 1R 2代表N=CR 31NR 32R 33,N=CR 34OR 35,未取代或被1-2个独立选自卤素、C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷硫基、卤代C1-C8烷硫基、氨基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷氧基羰基中的基团所取代的
    Figure PCTCN2018121998-appb-100005
    Figure PCTCN2018121998-appb-100006
    Y represents nitro or NR 1 R 2 , where R 1 represents H, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted with 1-2 R 11 , unsubstituted or unsubstituted Substituted or substituted aryl, heteroaryl, -COR 12 , nitro, OR 13 , SO 2 R 14 , NR 15 R 16 , N = CR 17 R 18 , C1-C8 alkylcarbamoyl, di C1- C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphono; R 2 represents H, C1-C8 alkyl optionally substituted by 1-2 R 21 or- COR 22 ; or NR 1 R 2 represents N = CR 31 NR 32 R 33 , N = CR 34 OR 35 , unsubstituted or substituted by 1-2 independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxy , Halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl Substituted by groups in
    Figure PCTCN2018121998-appb-100005
    Figure PCTCN2018121998-appb-100006
    其中R 11、R 21独立地代表卤素,羟基,C1-C8烷氧基,卤代C1-C8烷氧基,C1-C8烷硫基,卤代C1-C8烷硫基,氨基,C1-C8烷基氨基,二C1-C8烷基氨基,C1-C8烷氧基羰基,未取代或取代的芳基、杂芳基; Wherein R 11 and R 21 independently represent halogen, hydroxyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 Alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;
    R 12、R 22独立地代表H、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基、苯基、苯氧基或苄氧基; R 12 and R 22 independently represent H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;
    R 13代表H、C1-C8烷基、卤代C1-C8烷基、苯基、苄基或CHR 41C(O)OR 42;R 41代表H、C1-C8烷基或C1-C8烷氧基;R 42代表H、C1-C8烷基或苄基; R 13 represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ; R 41 represents H, C1-C8 alkyl or C1-C8 alkoxy Radical; R 42 represents H, C1-C8 alkyl or benzyl;
    R 14代表C1-C8烷基、卤代C1-C8烷基; R 14 represents C1-C8 alkyl, halogenated C1-C8 alkyl;
    R 15代表H、C1-C8烷基、甲酰基、C1-C8烷基羰基、卤代C1-C8烷基羰基、C1-C8烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基;R 16代表H、C1-C8烷基; R 15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylcarbonyl, halogenated C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R 16 represents H, C1-C8 alkyl;
    R 17代表H、C1-C8烷基、未取代或被卤素、C1-C8烷基、C1-C8烷氧基中的1-3个基团所取代的苯基;R 18代表H、C1-C8烷基;或N=CR 17R 18代表
    Figure PCTCN2018121998-appb-100007
    R 17 represents H, C1-C8 alkyl, unsubstituted or substituted by 1-3 groups in halogen, C1-C8 alkyl, C1-C8 alkoxy; R 18 represents H, C1- C8 alkyl; or N = CR 17 R 18 represents
    Figure PCTCN2018121998-appb-100007
    R 31、R 34分别独立地代表H或C1-C8烷基; R 31 and R 34 independently represent H or C1-C8 alkyl;
    R 32、R 33分别独立地代表H或C1-C8烷基;或者NR 32R 33代表
    Figure PCTCN2018121998-appb-100008
    Figure PCTCN2018121998-appb-100009
    R 32 and R 33 independently represent H or C1-C8 alkyl; or NR 32 R 33 represents
    Figure PCTCN2018121998-appb-100008
    Figure PCTCN2018121998-appb-100009
    R 35代表C1-C8烷基; R 35 represents C1-C8 alkyl;
    Z代表氢,卤素,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有卤素的C1-C8烷基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C2-C8炔基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基酰氧基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自卤素、氰基、C3-C8环烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基中的至少一个基团所取代的C2-C8烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表C1-C8烷基,C3-C8环烷基,卤代C1-C8烷基,卤代C3-C8环烷基,未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、苯基、苄基、苯氧基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷基酰氧基中的至少一个基团所取代的苯基,烷氧基,卤代C1-C8烷氧基,羟基;R 54代表氢、卤素、C1-C8烷基、卤代C1-C8烷基;R 55代表氢、卤素;m代表0或1,n代表0~6之间的整数; Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1- C8 alkyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxy C1-C8 alkyl , C1-C8 alkylthio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylacyloxy, C1-C8 alkylsulfinyl, C1-C8 alkyl Sulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected From halogen, cyano, C3-C8 cycloalkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl , C2-C8 alkenyl substituted by at least one group in C1-C8 alkylsulfonyl and its epoxide, unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 independently represent C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C1-C8 Alkyl, halogenated C3 -C8 cycloalkyl, unsubstituted or selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkyne with or without halogen Group, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, phenyl, benzyl, phenoxy, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkyl Substituted by at least one group of carbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkylacyloxy Phenyl, alkoxy, halogenated C1-C8 alkoxy, hydroxy; R 54 represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl; R 55 represents hydrogen, halogen; m represents 0 or 1, n represents an integer between 0 and 6;
    其中,所述“芳基”是指苯基、萘基,“杂芳基”是指
    Figure PCTCN2018121998-appb-100010
    Figure PCTCN2018121998-appb-100011
    Figure PCTCN2018121998-appb-100012
    其中,R’代表氢、烷基;其可被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,未取代或被选自卤素、烷基、烷氧基中的至少一个基团所取代的苯基、苄基、苯氧基,以及含有或不含有卤素的烷基、烯基、炔基、环烷基、环烷基烷基、烷氧基、烷硫基、烷氧基烷基、烷硫基烷基、烷基羰基、烷氧基羰基、烷基亚硫酰基、烷基磺酰基、烷基氨基、二烷基氨基、烷基酰氧基、-OCH 2CH 2-、-OCH 2O-、-OCH 2CH 2O-中的至少一个基团所取代。
    Among them, the "aryl" refers to phenyl, naphthyl, "heteroaryl" refers to
    Figure PCTCN2018121998-appb-100010
    Figure PCTCN2018121998-appb-100011
    Figure PCTCN2018121998-appb-100012
    Where R 'represents hydrogen or alkyl; it can be selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, unsubstituted or selected from halogen, alkyl, alkoxy Phenyl, benzyl, phenoxy substituted with at least one group, and alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkylthio with or without halogen , Alkoxyalkyl, alkylthioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-, -OCH 2 CH 2 O- is substituted by at least one group.
  3. 根据权利要求1或2所述的一种取代的含氮杂芳环甲酰胺衍生物,其特征在于,A substituted nitrogen-containing heteroaromatic ring formamide derivative according to claim 1 or 2, wherein
    M代表
    Figure PCTCN2018121998-appb-100013
    Het选自五元不饱和环,该环上除含有1-位上的N原子外,还含有1、2或3个以下原子或基团作为环的组成部分:NR b
    M stands for
    Figure PCTCN2018121998-appb-100013
    Het is selected from a five-membered unsaturated ring, which contains 1, 2 or 3 atoms or groups as part of the ring in addition to the N atom at the 1-position: NR b ;
    R a选自以下基团中的一个或多个基团:氢,卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C2-C6烯基C1-C6烷基、C2-C6炔基C1-C6烷基、C3-C6环烷基C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基C1-C6烷基、杂芳基C1-C6烷基、芳基氧基、杂芳基氧基;或者相邻两个R a一起形成未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二烷C1-C8基氨基、C1-C8烷基酰氧基,以及未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基、芳基氧基、杂芳基氧基中的至少一个基团所取代的-CH=CH-CH=CH-、-CH 2CH 2CH 2CH 2-、-N=CH-CH=CH-、-CH=N-CH=CH-基团; R a is selected from one or more of the following groups: hydrogen, halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C6 alkyl with or without halogen, C2 -C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C6 alkenyl C1-C6 alkyl, C2-C6 alkynyl C1-C6 alkyl, C3-C6 cycloalkyl C1-C6 alkyl Group, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 Alkoxycarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkylacyloxy and unsubstituted or substituted Aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl, aryloxy, heteroaryloxy; or two adjacent Ra together form unsubstituted or selected From halogen, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl with or without halogen , C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkylthio C1-C8 alkyl , C1 -C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, dialkyl C1-C8 amino, C1-C8 alkyl Acyloxy, and at least one of unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl, aryloxy, heteroaryloxy -CH = CH-CH = CH-, -CH 2 CH 2 CH 2 CH 2- , -N = CH-CH = CH-, -CH = N-CH = CH- group substituted by the group;
    R b代表氢,C1-C6烷基; R b represents hydrogen, C1-C6 alkyl;
    Q代表N或C-R”;其中,R”代表氢,卤素,氰基,含有或不含有卤素的C1-C6烷基、C1-C6烷氧基、C2-C6烯基、C2-C6炔基、C3-C6环烷基,以及未取代或取代的芳基、杂芳基;Q represents N or CR "; where R" represents hydrogen, halogen, cyano, C1-C6 alkyl with or without halogen, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
    X代表卤素,含有或不含有卤素的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷基氨基、二C1-C6烷基氨基,未取代或取代的芳基、杂芳基;X represents halogen, with or without halogen C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylamino, di C1-C6 alkylamino, unsubstituted or substituted aryl, heteroaryl;
    Y代表硝基或NR 1R 2,其中R 1代表H,任选地被1-2个R 11取代的C1-C6烷基、C2-C6烯基或C2-C6炔基,未取代或未取代或取代的芳基、杂芳基,-COR 12,硝基,OR 13,SO 2R 14,NR 15R 16,N=CR 17R 18,C1-C6烷基氨基甲酰基,二C1-C6烷基氨基甲酰基,三C1-C6烷基甲硅烷基或二C1-C6烷基膦酰基;R 2代表H,任选地被1-2个R 21取代的C1-C6烷基或-COR 22;或者NR 1R 2代表N=CR 31NR 32R 33,N=CR 34OR 35,未取代或被1-2个独立选自卤素、C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、氨基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷氧基羰基中的基团所取代的
    Figure PCTCN2018121998-appb-100014
    Figure PCTCN2018121998-appb-100015
    Y represents nitro or NR 1 R 2 , where R 1 represents H, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl optionally substituted by 1-2 R 11 , unsubstituted or unsubstituted Substituted or substituted aryl, heteroaryl, -COR 12 , nitro, OR 13 , SO 2 R 14 , NR 15 R 16 , N = CR 17 R 18 , C1-C6 alkylcarbamoyl, di C1- C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; R 2 represents H, C1-C6 alkyl optionally substituted by 1-2 R 21 or- COR 22 ; or NR 1 R 2 represents N = CR 31 NR 32 R 33 , N = CR 34 OR 35 , unsubstituted or substituted by 1-2 independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy , Halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl Substituted by groups in
    Figure PCTCN2018121998-appb-100014
    Figure PCTCN2018121998-appb-100015
    其中R 11、R 21独立地代表卤素,羟基,C1-C6烷氧基,卤代C1-C6烷氧基,C1-C6烷硫基,卤代C1-C6烷硫基,氨基,C1-C6烷基氨基,二C1-C6烷基氨基,C1-C6烷氧基羰基,未取代或取代的芳基、杂芳基; Wherein R 11 and R 21 independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 Alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;
    R 12、R 22独立地代表H、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、苯基、苯氧基或苄氧基; R 12 and R 22 independently represent H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;
    R 13代表H、C1-C6烷基、卤代C1-C6烷基、苯基、苄基或CHR 41C(O)OR 42;R 41代表H、C1-C6烷基或C1-C6烷氧基;R 42代表H、C1-C6烷基或苄基; R 13 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR 41 C (O) OR 42 ; R 41 represents H, C1-C6 alkyl or C1-C6 alkoxy Radical; R 42 represents H, C1-C6 alkyl or benzyl;
    R 14代表C1-C6烷基、卤代C1-C6烷基; R 14 represents C1-C6 alkyl, halogenated C1-C6 alkyl;
    R 15代表H、C1-C6烷基、甲酰基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基;R 16代表H、C1-C6烷基; R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R 16 represents H, C1-C6 alkyl;
    R 17代表H、C1-C6烷基、未取代或被卤素、C1-C6烷基、C1-C6烷氧基中的1-3个基团所取代的苯基;R 18代表H、C1-C6烷基;或N=CR 17R 18代表
    Figure PCTCN2018121998-appb-100016
    R 17 represents H, C1-C6 alkyl, unsubstituted or substituted by 1-3 groups in halogen, C1-C6 alkyl, C1-C6 alkoxy; R 18 represents H, C1- C6 alkyl; or N = CR 17 R 18 represents
    Figure PCTCN2018121998-appb-100016
    R 31、R 34分别独立地代表H或C1-C6烷基; R 31 and R 34 independently represent H or C1-C6 alkyl;
    R 32、R 33分别独立地代表H或C1-C6烷基;或者NR 32R 33代表
    Figure PCTCN2018121998-appb-100017
    Figure PCTCN2018121998-appb-100018
    R 32 and R 33 independently represent H or C1-C6 alkyl; or NR 32 R 33 represents
    Figure PCTCN2018121998-appb-100017
    Figure PCTCN2018121998-appb-100018
    R 35代表C1-C6烷基; R 35 represents C1-C6 alkyl;
    Z代表氢,卤素,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有卤素的C1-C6烷基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C2-C6炔基、C1-C6烷氧基、C1-C6 烷硫基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基酰氧基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自卤素、氰基、C3-C6环烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基中的至少一个基团所取代的C2-C6烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基C1-C6烷基、杂芳基C1-C6烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表C1-C6烷基,C3-C6环烷基,卤代C1-C6烷基,卤代C3-C6环烷基,未取代或被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,含有或不含有卤素的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、苯基、苄基、苯氧基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷基酰氧基中的至少一个基团所取代的苯基,烷氧基,卤代C1-C6烷氧基,羟基;R 54代表氢、卤素、C1-C6烷基、卤代C1-C6烷基;R 55代表氢、卤素;m代表0或1,n代表0~4之间的整数; Z represents hydrogen, halogen, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1- C6 alkyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxy C1-C6 alkyl , C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylacyloxy, C1-C6 alkylsulfinyl, C1-C6 alkyl Sulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected From halogen, cyano, C3-C6 cycloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl , C2-C6 alkenyl substituted by at least one group in C1-C6 alkylsulfonyl and its epoxide, unsubstituted or substituted aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 independently represent C1-C6 alkyl, C3-C6 cycloalkyl, halogenated C1-C6 Alkyl, halogenated C 3-C6 cycloalkyl, unsubstituted or selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, C1-C6 alkyl with or without halogen, C2-C6 alkenyl, C2-C6 Alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, phenyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkyl Substituted by at least one group of carbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkylacyloxy Phenyl, alkoxy, halogenated C1-C6 alkoxy, hydroxy; R 54 represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl; R 55 represents hydrogen, halogen; m represents 0 Or 1, n represents an integer between 0 and 4;
    其中,所述“芳基”是指苯基、萘基,“杂芳基”是指
    Figure PCTCN2018121998-appb-100019
    Figure PCTCN2018121998-appb-100020
    Figure PCTCN2018121998-appb-100021
    其中,R’代表氢、C1-C8烷基;其可被选自卤素,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,未取代或被选自卤素、C1-C8烷基、C1-C8烷氧基中的至少一个基团所取代的苯基、苄基、苯氧基,以及含有或不含有卤素的C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧基C1-C8烷基、C1-C8烷硫基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基亚硫酰基、C1-C8烷基磺酰基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷基酰氧基、-OCH 2CH 2-、-OCH 2O-、-OCH 2CH 2O-中的至少一个基团所取代。
    Among them, the "aryl" refers to phenyl, naphthyl, "heteroaryl" refers to
    Figure PCTCN2018121998-appb-100019
    Figure PCTCN2018121998-appb-100020
    Figure PCTCN2018121998-appb-100021
    Where R 'represents hydrogen, C1-C8 alkyl; it can be selected from halogen, nitro, cyano, hydroxy, carboxy, amino, mercapto, formyl, unsubstituted or selected from halogen, C1-C8 alkyl , C1-C8 alkoxy substituted by at least one group of phenyl, benzyl, phenoxy, and with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl , C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkyl Thio C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, di-C1- At least one group of C8 alkylamino, C1-C8 alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-, -OCH 2 CH 2 O- is substituted.
  4. 根据权利要求1-3任意一项所述的一种取代的含氮杂芳环甲酰胺衍生物,其特征在于,A substituted nitrogen-containing heteroaromatic ring formamide derivative according to any one of claims 1-3, characterized in that
    M代表未取代或被选自氟,氯,溴,碘,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C2-C6烯基C1-C4烷基、C2-C6炔基C1-C4烷基、C3-C6环烷基C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基以及未取代或取代的芳基、杂芳基、芳基C1-C4烷基、杂芳基C1-C4烷基、芳基氧基、杂芳基氧基中的1~3个基团所取代的
    Figure PCTCN2018121998-appb-100022
    Figure PCTCN2018121998-appb-100023
    M represents unsubstituted or selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C4 alkyl with or without fluorine, chlorine, bromine, iodine , C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkenyl C1-C4 alkyl, C2-C6 alkynyl C1-C4 alkyl, C3-C6 cycloalkyl C1- C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1 -C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkylacyloxy and unsubstituted Or substituted aryl, heteroaryl, aryl C1-C4 alkyl, heteroaryl C1-C4 alkyl, aryloxy, heteroaryloxy substituted by 1 to 3 groups
    Figure PCTCN2018121998-appb-100022
    Figure PCTCN2018121998-appb-100023
    Q代表N或C-R”;其中,R”代表氢,氟,氯,溴,碘,氰基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C1-C4烷氧基、C2-C4烯基、C2-C4炔基、C3-C6环烷基,以及未取代或取代的芳基、杂芳基;Q stands for N or CR "; where R" stands for hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C4 alkyl, C1-C4 alkoxy, with or without fluorine, chlorine, bromine, iodine, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted aryl and heteroaryl;
    X代表氟,氯,溴,碘,含有或不含有氟、氯、溴、碘的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C1-C4烷氧基、C1-C4烷基氨基、二C1-C4烷基氨基,未取代或取代的芳基、杂芳基;X represents fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 with or without fluorine, chlorine, bromine, iodine Alkoxy, C1-C4 alkylamino, di-C1-C4 alkylamino, unsubstituted or substituted aryl, heteroaryl;
    Y代表NH 2、NHMe、N(Me) 2
    Figure PCTCN2018121998-appb-100024
    Figure PCTCN2018121998-appb-100025
    Y stands for NH 2 , NHMe, N (Me) 2 ,
    Figure PCTCN2018121998-appb-100024
    Figure PCTCN2018121998-appb-100025
    Z代表氢,氟,氯,溴,碘,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C3-C6环烷基、C3-C6环烷基C1-C4烷基、C2-C4炔基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基酰氧基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、-S-CN、R 51R 52R 53Si-(O) m-(CH 2) n-、R 51R 52R 53Si-CR 54=CR 55-,以及未取代或被选自氟、氯、溴、碘、氰基、C3-C6环烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基中的1~3个基团所取代的C2-C4烯基及其环氧化物,未取代或取代的芳基、杂芳基、芳基C1-C4烷基、杂芳基C1-C4烷基、芳基氧基、杂芳基氧基;其中,R 51、R 52、R 53分别独立地代表C1-C4烷基,C3-C6环烷基,卤代C1-C4烷基,卤代C3-C6环烷基,未取代 或被选自氟,氯,溴,碘,硝基,氰基,羟基,羧基,氨基,巯基,含有或不含有氟、氯、溴、碘的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C3-C6环烷基C1-C4烷基、苯基、苄基、苯氧基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基中的1~3个基团所取代的苯基,烷氧基,卤代C1-C6烷氧基,羟基;R 54代表氢、氟、氯、C1-C4烷基、卤代C1-C4烷基;R 55代表氢、氟、氯;m代表0或1,n代表0、1、2或3; Z represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C4 alkyl, C3-C6 with or without fluorine, chlorine, bromine, iodine Cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4 alkylamino , C1-C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylacyloxy, C1 -C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -S-CN, R 51 R 52 R 53 Si- (O) m- (CH 2 ) n- , R 51 R 52 R 53 Si-CR 54 = CR 55- , and unsubstituted or selected from fluorine, chlorine, bromine, iodine, cyano, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkyl C2-C4 alkenyl and its epoxides substituted by 1 to 3 groups in oxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, unsubstituted Or substituted aryl, heteroaryl, aryl C1-C4 alkyl, heteroaryl C1-C4 alkyl, aryloxy, heteroaryloxy; wherein, R 51 , R 52 , R 53 are independently Represents C1-C4 alkyl, C3-C 6 cycloalkyl, halogenated C1-C4 alkyl, halogenated C3-C6 cycloalkyl, unsubstituted or selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, benzene with or without fluorine, chlorine, bromine, iodine Group, benzyl, phenoxy, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfonyl, C1-C4 alkyl Phenyl, alkoxy, halogenated C1-C6 alkoxy, hydroxy substituted by 1 to 3 groups in the amino group, di C1-C4 alkylamino group, C1-C4 alkyl acyloxy group; R 54 Represents hydrogen, fluorine, chlorine, C1-C4 alkyl, halogenated C1-C4 alkyl; R 55 represents hydrogen, fluorine, chlorine; m represents 0 or 1, n represents 0, 1, 2 or 3;
    其中,所述“芳基”是指苯基、萘基,“杂芳基”是指
    Figure PCTCN2018121998-appb-100026
    Figure PCTCN2018121998-appb-100027
    其中,R’代表氢、C1-C6烷基;其可被选自氟,氯,溴,碘,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,未取代或被选自氟、氯、溴、碘、C1-C6烷基、C1-C6烷氧基中的1~3个基团所取代的苯基、苄基、苯氧基,以及含有或不含有氟、氯、溴、碘的C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基亚硫酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C1-C6烷基酰氧基、-OCH 2CH 2-、-OCH 2O-、-OCH 2CH 2O-中的1~4个基团所取代。
    Among them, the "aryl" refers to phenyl, naphthyl, "heteroaryl" refers to
    Figure PCTCN2018121998-appb-100026
    Figure PCTCN2018121998-appb-100027
    Where R 'represents hydrogen, C1-C6 alkyl; it can be selected from fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, unsubstituted or selected from fluorine , Chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 alkoxy substituted by 1 to 3 groups of phenyl, benzyl, phenoxy, and with or without fluorine, chlorine, bromine , Iodine C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6 Alkylthio, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfinyl Acyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkylacyloxy, -OCH 2 CH 2- , -OCH 2 O-, -OCH 2 1 to 4 groups in CH 2 O- are substituted.
  5. 根据权利要求1-4任意一项所述的一种取代的含氮杂芳环甲酰胺衍生物,其特征在于,A substituted nitrogen-containing heteroaromatic ring formamide derivative according to any one of claims 1 to 4, characterized in that
    M代表未取代或被选自氟,氯,溴,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C2-C4烯基C1-C2烷基、C2-C4炔基C1-C2烷基、C3-C6环烷基C1-C2烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧基C1-C2烷基、C1-C4烷硫基C1-C2烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基以及未取代或取代的苯基、苄基、苯氧基中的1、2或3个基团所取代的
    Figure PCTCN2018121998-appb-100028
    M represents unsubstituted or selected from fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, amino, mercapto, formyl, C1-C4 alkyl, C2-C4 with or without fluorine, chlorine, bromine Alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C4 alkenyl C1-C2 alkyl, C2-C4 alkynyl C1-C2 alkyl, C3-C6 cycloalkyl C1-C2 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxy C1-C2 alkyl, C1-C4 alkylthio C1-C2 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxy Carbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkylacyloxy and unsubstituted or substituted benzene Substituted by 1, 2 or 3 groups in the group, benzyl, phenoxy
    Figure PCTCN2018121998-appb-100028
    Q代表N或C-R”;其中,R”代表氢,氟,氯,溴,氰基,含有或不含有氟、氯、溴的C1-C4烷基、C1-C4烷氧基、C2-C4烯基、C2-C4炔基、C3-C6环烷基,以及未取代或取代的苯基;Q stands for N or CR "; where R" stands for hydrogen, fluorine, chlorine, bromine, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkene with or without fluorine, chlorine, bromine Group, C2-C4 alkynyl, C3-C6 cycloalkyl, and unsubstituted or substituted phenyl;
    X代表氟,氯,溴,含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C1-C4烷氧基、C1-C4烷基氨基、二C1-C4烷基氨基,未取代或取代的苯基、萘基、
    Figure PCTCN2018121998-appb-100029
    X represents fluorine, chlorine, bromine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 alkoxy, with or without fluorine, chlorine, bromine C1-C4 alkylamino, di-C1-C4 alkylamino, unsubstituted or substituted phenyl, naphthyl,
    Figure PCTCN2018121998-appb-100029
    Y代表NH 2、NHMe、N(Me) 2
    Figure PCTCN2018121998-appb-100030
    Figure PCTCN2018121998-appb-100031
    Y stands for NH 2 , NHMe, N (Me) 2 ,
    Figure PCTCN2018121998-appb-100030
    Figure PCTCN2018121998-appb-100031
    Z代表氢,氟,氯,溴,氰基,硝基,氨基,羟基,羧基,巯基,甲酰基,含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C3-C6环烷基、C3-C6环烷基C1-C2烷基、C2-C4炔基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷氧基C1-C2烷基、C1-C4烷硫基C1-C2烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基酰氧基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基,以及未取代或取代的苯基、萘基、
    Figure PCTCN2018121998-appb-100032
    Figure PCTCN2018121998-appb-100033
    Z represents hydrogen, fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, carboxyl, mercapto, formyl, C1-C4 alkyl, C2-C4 alkenyl, C3 with or without fluorine, chlorine, bromine -C6 cycloalkyl, C3-C6 cycloalkyl C1-C2 alkyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4 alkyl Amino, C1-C4 alkoxy C1-C2 alkyl, C1-C4 alkylthio C1-C2 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylacyloxy , C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, and unsubstituted or substituted phenyl, naphthyl,
    Figure PCTCN2018121998-appb-100032
    Figure PCTCN2018121998-appb-100033
    其中,所述“取代的”是指其被选自氟,氯,溴,硝基,氰基,羟基,羧基,氨基,巯基,甲酰基,以及含有或不含有氟、氯、溴的C1-C4烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、C3-C6环烷基C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷基酰氧基中的1、2或3个基团所取代。Wherein, the "substituted" means that it is selected from fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, amino, mercapto, formyl, and C1- with or without fluorine, chlorine, or bromine C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1 -C4 alkoxy C1-C4 alkyl, C1-C4 alkylthio C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfinyl, C1-C4 1, 2, or 3 groups in the alkylsulfonyl group, C1-C4 alkylamino group, di-C1-C4 alkylamino group, C1-C4 alkylacyloxy group.
  6. 根据权利要求1-5任意一项所述的一种取代的含氮杂芳环甲酰胺衍生物,其特征在于,结构式为说明书表1中的任意一个。The substituted nitrogen-containing heteroaromatic ring formamide derivative according to any one of claims 1 to 5, wherein the structural formula is any one of Table 1 in the specification.
  7. 一种如权利要求1-6任意一项所述的取代的含氮杂芳环甲酰胺衍生物的制备方法,其特征在于,包括以下步骤:A method for preparing a substituted nitrogen-containing heteroaromatic ring carboxamide derivative according to any one of claims 1-6, characterized in that it comprises the following steps:
    (1)使用如通式II所示的化合物与通式III所示的化合物进行反应,制备如通式I所示的化合物,反应方程式如下:(1) The compound represented by the general formula II is reacted with the compound represented by the general formula III to prepare the compound represented by the general formula I, and the reaction equation is as follows:
    Figure PCTCN2018121998-appb-100034
    Figure PCTCN2018121998-appb-100034
    或(2)先将如通式II所示的化合物进行酰卤化反应,然后与通式III所示的化合物进行反应,制备如通式I所示的化合物,反应方程式如下:Or (2) First, the compound represented by the general formula II is subjected to an acid halogenation reaction, and then reacted with the compound represented by the general formula III to prepare the compound represented by the general formula I, and the reaction equation is as follows:
    Figure PCTCN2018121998-appb-100035
    Figure PCTCN2018121998-appb-100035
    优选地,所述步骤(1)反应在缩合剂和溶剂的存在下进行,所述缩合剂为PyBOP、HATU或CDI,所述溶剂选自DCM、DCE、ACN、DMF、THF中的一种及一种以上;根据需要可在反应体系中加入碱,所述碱选自TEA、NMM或DIPEA;所述反应温度为0-100℃,优选25-50℃;Preferably, the reaction in the step (1) is carried out in the presence of a condensing agent and a solvent, the condensing agent is PyBOP, HATU or CDI, and the solvent is selected from one of DCM, DCE, ACN, DMF, THF and More than one; according to need, a base can be added to the reaction system, the base is selected from TEA, NMM or DIPEA; the reaction temperature is 0-100 ℃, preferably 25-50 ℃;
    所述步骤(2)中酰卤化反应温度为0-100℃,采用的酰卤化试剂为SOCl 2;然后在碱和溶剂的存在的下进行下一步反应,所述溶剂选自DCM、DCE、ACN、DMF、THF中的一种及一种以上,所述碱选自TEA、NMM或DIPEA,所述反应温度为0-25℃。 In the step (2), the acid halogenation reaction temperature is 0-100 ° C, and the acid halogenation reagent used is SOCl 2 ; then the next reaction is carried out in the presence of a base and a solvent, the solvent is selected from DCM, DCE, ACN , DMF, one or more of THF, the base is selected from TEA, NMM or DIPEA, the reaction temperature is 0-25 ℃.
  8. 一种除草组合物,其特征在于,包括(i)权利要求1-6任意一项如通式I所示的取代的含氮杂芳环甲酰胺衍生物;优选地,还包括(ii)一种或多种另外的除草剂和/或安全剂;更优选地,还包括(iii)农业化学上可接受的制剂助剂。A herbicidal composition, characterized in that it comprises (i) the substituted nitrogen-containing heteroaromatic ring formamide derivative represented by general formula I according to any one of claims 1-6; preferably, it further comprises (ii) a One or more additional herbicides and / or safeners; more preferably, (iii) agrochemically acceptable formulation aids.
  9. 一种控制杂草的方法,其特征在于,包括将除草有效量的权利要求1-6任意一项所述的取代的含氮杂芳环甲酰胺衍生物中的至少一种或权利要求8所述的除草组合物使用在植物上或者杂草区域。A method for controlling weeds, characterized by comprising a herbicidally effective amount of at least one of the substituted nitrogen-containing heteroaromatic ring carboxamide derivatives according to any one of claims 1-6 or claim 8 The herbicidal composition described is used on plants or weed areas.
  10. 如权利要求1-6任意一项所述的取代的含氮杂芳环甲酰胺衍生物中的至少一种或权利要求8所述的除草组合物在控制杂草上的用途,优选地,将所述的取代的含氮杂芳环甲酰胺衍生物用于防除有用作物中的杂草,所述有用作物为转基因作物或者基因组编辑技术处理过的作物。The use of at least one of the substituted nitrogen-containing heteroaromatic ring carboxamide derivatives according to any one of claims 1-6 or the herbicidal composition according to claim 8 for controlling weeds, preferably, The substituted nitrogen-containing heteroaromatic ring carboxamide derivatives are used to control weeds in useful crops, and the useful crops are transgenic crops or crops treated by genome editing technology.
PCT/CN2018/121998 2018-10-31 2018-12-19 Substituted nitrogen-containing heterocyclic formamide derivative, weeding composition and uses thereof WO2020087694A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811286571.0 2018-10-31
CN201811286571.0A CN109293640B (en) 2018-10-31 2018-10-31 Substituted nitrogen-containing heteroaromatic formamide derivative and weeding composition and application thereof

Publications (1)

Publication Number Publication Date
WO2020087694A1 true WO2020087694A1 (en) 2020-05-07

Family

ID=65145236

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/121998 WO2020087694A1 (en) 2018-10-31 2018-12-19 Substituted nitrogen-containing heterocyclic formamide derivative, weeding composition and uses thereof

Country Status (2)

Country Link
CN (1) CN109293640B (en)
WO (1) WO2020087694A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023129493A1 (en) * 2021-12-28 2023-07-06 Fmc Corporation Substituted cyclopropylpyrimidne herbicides

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109942498A (en) * 2019-05-07 2019-06-28 湖南省农业生物技术研究所 Phenyl pyrimidine derivative of the structure containing hydrazone and its preparation method and application
MX2022008518A (en) * 2020-01-16 2022-08-08 Qingdao Kingagroot Chemical Compound Co Ltd Fused ring substituted aromatic compound and preparation method therefor, herbicidal composition, and use thereof.
CN114644622B (en) * 2020-12-17 2022-10-18 山东省联合农药工业有限公司 Isoxazoline-containing pyridine biphenyl compound and preparation method and application thereof
CN112898208B (en) * 2021-01-29 2023-06-20 中国医科大学 Phenylpyrimidine amine antitumor compound and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060069132A1 (en) * 2004-04-07 2006-03-30 Armel Gregory R Azolecarboxamide herbicides
WO2007041130A2 (en) * 2005-09-30 2007-04-12 Vertex Pharmaceuticals Incorporated Deazapurines useful as inhibitors of janus kinases
US20090088322A1 (en) * 2007-10-02 2009-04-02 Dow Agrosciences Llc 2-substituted-6-amino-5-alkyl, alkenyl or alkynyl-4-pyrimidinecarboxylic acids and 6-substituted-4-amino-3- alkyl, alkenyl or alkynyl picolinic acids and their use as herbicides

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69837621T2 (en) * 1997-12-03 2007-12-27 Mid-America Commercialization Corp., Manhattan SUBSTITUTED PYRIMIDINES AND PYRIDINES AS WEED CONTROLS
AU2003301443A1 (en) * 2002-10-18 2004-05-04 E.I. Du Pont De Nemours And Company Azolecarboxamide herbicides
WO2004106324A1 (en) * 2003-05-27 2004-12-09 E.I. Dupont De Nemours And Company Azolecarboxamide herbicides
WO2005058037A1 (en) * 2003-12-12 2005-06-30 Syngenta Participations Ag Picolinylpyrazoles as herbicides
TWI355894B (en) * 2003-12-19 2012-01-11 Du Pont Herbicidal pyrimidines
US7300907B2 (en) * 2006-01-13 2007-11-27 Dow Agrosciences Llc 2-(Poly-substituted aryl)-6-amino-5-halo-4-pyrimidinecarboxylic acids and their use as herbicides
GB0617575D0 (en) * 2006-09-06 2006-10-18 Syngenta Ltd Herbicidal compounds and compositions
CA2750539A1 (en) * 2009-02-27 2010-09-02 Dow Agrosciences Llc N-alkoxyamides of 6-(substituted phenyl)-4-aminopicolinates and 2-(substituted phenyl)-6-amino-4-pyrimidinecarboxylates and their use as selective herbicides for crops
CN107759581B (en) * 2017-10-24 2021-05-14 青岛清原化合物有限公司 Substituted benzoyl isoxazole compound or tautomer, salt, preparation method, herbicidal composition and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060069132A1 (en) * 2004-04-07 2006-03-30 Armel Gregory R Azolecarboxamide herbicides
WO2007041130A2 (en) * 2005-09-30 2007-04-12 Vertex Pharmaceuticals Incorporated Deazapurines useful as inhibitors of janus kinases
US20090088322A1 (en) * 2007-10-02 2009-04-02 Dow Agrosciences Llc 2-substituted-6-amino-5-alkyl, alkenyl or alkynyl-4-pyrimidinecarboxylic acids and 6-substituted-4-amino-3- alkyl, alkenyl or alkynyl picolinic acids and their use as herbicides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023129493A1 (en) * 2021-12-28 2023-07-06 Fmc Corporation Substituted cyclopropylpyrimidne herbicides

Also Published As

Publication number Publication date
CN109293640A (en) 2019-02-01
CN109293640B (en) 2020-05-19

Similar Documents

Publication Publication Date Title
CN107629035B (en) Pyrazolone compound or salt thereof, herbicide composition and application
WO2020087694A1 (en) Substituted nitrogen-containing heterocyclic formamide derivative, weeding composition and uses thereof
CN108774179B (en) Substituted pyrimidine-4-formic acid derivative and weeding composition and application thereof
WO2017113509A1 (en) Pyrazole compound or salt thereof, and preparation method, herbicide composition and use thereof
UA121506C2 (en) Pyrazolone compound or salt thereof, preparation method therefor, herbicide composition and use thereof
CN113402510B (en) Condensed ring substituted aromatic compound, preparation method thereof, weeding composition and application
CN108586357B (en) Substituted pyrimidineformyl oxime derivatives, preparation method thereof, herbicidal composition and application
CN112778289B (en) Aromatic compound containing substituted isoxazoline, preparation method thereof, weeding composition and application
CN109438333B (en) Pyridyloxycarboxylate derivative, preparation method thereof, weeding composition and application
KR102276572B1 (en) Pyrazole compounds or salts thereof, and methods for their preparation, herbicide compositions and uses thereof
CN108084108B (en) 5-chlorobenzoxazole derivative and preparation method, herbicidal composition and application thereof
CN115707690B (en) 3-isoxazolidinone compound, preparation method thereof, weeding composition and application
CN107759581B (en) Substituted benzoyl isoxazole compound or tautomer, salt, preparation method, herbicidal composition and application thereof
CN107674025B (en) 4-benzoyl pyrazole compound and preparation method and application thereof
CN113149975B (en) Isoxazoline oxime formate compound, preparation method thereof, weeding composition and application
CN111285863B (en) 4- (3-heterocyclyl-1-benzoyl) pyrazole compound or salt thereof, preparation method, herbicide composition and application
CN109721546B (en) Substituted pyrimidine aryl ester derivative and preparation method, herbicidal composition and application thereof
JP2023139056A (en) R-pyridyloxycarboxylic acid, salt and ester derivative thereof, and preparation method therefor, and herbicidal composition thereof and application thereof
CN110878081B (en) Pyridinyl ring substituted pyridazinol compounds and derivatives thereof, preparation method, weeding composition and application
CN113024531B (en) Isoxazoline-containing compound, preparation method thereof, weeding composition and application
CN112390759B (en) Pyridazinol compound and derivatives thereof, preparation method, weeding composition and application
CN109400526B (en) Pyridyloxy thioester derivative, preparation method thereof, herbicidal composition and application
CN112441993B (en) Substituted thiadiazinon dioxide and preparation method thereof, weeding composition and application
CN109832277B (en) Substituted nitrogen-containing heteroaromatic imine formate derivative, preparation method thereof, herbicidal composition and application
CN107629046B (en) Pyrazolone compound or salt thereof, herbicide composition and application

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18938375

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18938375

Country of ref document: EP

Kind code of ref document: A1