WO2020119612A1 - 一种吡唑酰胺类化合物及其作为除草剂的用途 - Google Patents

一种吡唑酰胺类化合物及其作为除草剂的用途 Download PDF

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WO2020119612A1
WO2020119612A1 PCT/CN2019/123872 CN2019123872W WO2020119612A1 WO 2020119612 A1 WO2020119612 A1 WO 2020119612A1 CN 2019123872 W CN2019123872 W CN 2019123872W WO 2020119612 A1 WO2020119612 A1 WO 2020119612A1
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alkyl
cycloalkyl
haloalkyl
alkoxy
heteroatoms
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PCT/CN2019/123872
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French (fr)
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杨辉斌
英君伍
马宏娟
秦博
崔东亮
程岩
王刚
孙冰
陈霖
李斌
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沈阳中化农药化工研发有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the invention belongs to the field of herbicides. Specifically, it is a pyrazole amide compound and its application as a herbicide.
  • CN108290846A reported that certain benzamide compounds have herbicidal activity, for example, Compound No. 1-28 (KC1) and Compound No. 1-9 (KC2):
  • the pyrazole amide compounds shown in the present invention are not disclosed.
  • the object of the present invention is to provide a pyrazole amide compound with novel structure and safe for crops and its application as a herbicide.
  • a pyrazole amide compound the compound is shown in general formula I:
  • Q is the following group: Q 1 , Q 2 , Q 3
  • X 1 and X 3 may be the same or different from hydrogen, cyano, nitro, halogen, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylene Sulfonyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 1 -C 6 alkoxy C 1 -C 3 alkoxy, C 1 -C 6 alkoxy C 1 -C 3 alkoxy, C 1 -C 6 alkoxy C 1 -C 3 alkoxy C 1 -C 3 alkyl
  • X 2 is selected from hydrogen, cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl, C 3 -C 6 halocycloalkyl C 1 -C 6 alkyl, Y 1 oxy, Y 1 oxy C 1 -C 6 alkyl, Y 1 thio C 1 -C 6 alkyl, Y 1 sulfoxide C 1 -C 6 alkyl,
  • Y 1 and Y 2 are independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl , C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or unsubstituted or substituted with 1-5 substituents described below , 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms C 1 -C 6 alkyl or 5-7 membered aromatic heterocycle C 1 -C 6 alkyl containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C 1 -C 6 alkyl,
  • R 1 is selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 3 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkylsulfonate Acyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkoxy C 1 -C 3 alkyl, C 1 -C 6 haloalkoxy C 1 -C 3 alkyl, C 1 -C 6 alkyl Oxygen C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 1 -C 6 alkylthio C 1 -
  • R 2 is selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
  • R 3 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl, C 3 -C 6 halocycloalkyl C 1 -C 3 alkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl Or unsubstituted or substituted with 1-5 substituents described below, the following substituents are selected from cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy.
  • X 1 and X 3 may be the same or different and are respectively selected from cyano, nitro, halogen, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylsulfinyl Acyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1- C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 1 -C 6 alkoxy C 1 -C 3 alkoxy, C 1 -C 6 alkoxy C 1 -C 3 alkoxy C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 3 -C 6
  • X 2 is selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkyl Sulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkane C 1 -C 6 alkyl, C 3 -C 6 halocycloalkyl C 1 -C 6 alkyl, Y 1 oxy, Y 1 oxy C 1 -C 6 alkyl, Y 1 thio C 1 -C 6 alkyl, Y 1 sulfoxide C 1 -C 6 alkyl, Y 1 sulfone
  • Y 1 and Y 2 are independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl , C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or unsubstituted or substituted with 1-5 substituents described below , 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms C 1 -C 6 alkyl or 5-7 membered aromatic heterocycle C 1 -C 6 alkyl containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C 1 -C 6 alkyl,
  • R 1 is selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 3 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkylsulfonate Acyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkoxy C 1 -C 3 alkyl, C 1 -C 6 haloalkoxy C 1 -C 3 alkyl, C 1 -C 6 alkyl Oxygen C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 1 -C 6 alkylthio C 1 -
  • R 2 is selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
  • R 3 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl, C 3 -C 6 halocycloalkyl C 1 -C 3 alkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl Or unsubstituted or substituted with 1-5 substituents described below, the following substituents are selected from cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy.
  • X 1 and X 3 may be the same or different from hydrogen, nitro, halogen, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
  • X 2 is selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkyl Sulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkane C 1 -C 6 alkyl, C 3 -C 6 halocycloalkyl C 1 -C 6 alkyl, Y 1 oxy, Y 1 oxy C 1 -C 6 alkyl, Y 1 thio C 1 -C 6 alkyl, Y 1 sulfoxide C 1 -C 6 alkyl, Y 1 sulfone
  • Y 1 and Y 2 are independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl , C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or unsubstituted or substituted with 1-5 substituents described below , 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms C 1 -C 6 alkyl, 5-7 membered aromatic heterocycle C 1 -C 6 alkyl containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C 1 -C 6 alkyl,
  • R 1 is selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl C 1 -C 3 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkyne Group, C 1 -C 6 alkylsulfonyl group, C 1 -C 6 alkylthio group C 1 -C 3 alkyl group, C 1 -C 6 alkyl sulfoxide group C 1 -C 3 alkyl group or C 1 -C 6 alkyl sulfone groups C 1 -C 3 alkyl;
  • R 2 is selected from hydrogen, halogen, nitro, cyano, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
  • R 3 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl or unsubstituted or Phenyl substituted with 1-5 substituents selected from cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 ring Alkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy.
  • X 1 and X 3 may be the same or different and are respectively selected from hydrogen, nitro, halogen, C 1 -C 3 alkylsulfonyl, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
  • X 2 is selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkane Group C 1 -C 6 alkyl, Y 1 oxy, Y 1 oxy C 1 -C 3 alkyl, Y 1 thio C 1 -C 3 alkyl, or unsubstituted or substituted by 1-5 of the following Group substituted phenyl, 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, 5-7 membered containing 1-4 heteroatoms Aliphatic heterocyclic C 1 -C 6 alkyl or 5-7 membered aromatic heterocyclic C 1 -C 6 alkyl containing 1-4 heteroatoms, the following substituents are selected from halogen, C 1 -C
  • Y 1 is selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 Alkoxy C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or unsubstituted or substituted with 1-5 of the following substituents, including 1-4 Heteroatom 5-7 membered aliphatic heterocycle, 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, 5-7 membered aliphatic heterocycle C 1 -C 6 alkyl containing 1-4 heteroatoms or 5-7 membered aromatic heterocycle C 1 -C 6 alkyl containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1
  • R 1 is selected from C 1 -C 3 alkyl, C 1 -C 3 alkylsulfonyl or C 1 -C 3 alkylsulfonyl C 1 -C 3 alkyl;
  • R 2 is selected from hydrogen, halogen, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
  • R 3 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 3 -C 6 cycloalkyl.
  • Alkyl refers to straight or branched chain forms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, Groups such as n-hexyl.
  • Cycloalkyl refers to groups including cyclic chains, such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • Alkenyl refers to straight-chain or branched alkenyl, such as 1-propenyl, 2-propenyl, butenyl, pentenyl and hexenyl groups.
  • Alkynyl refers to straight-chain or branched-chain alkynyl groups such as 1-propynyl, 2-propynyl, butynyl, pentynyl and hexynyl.
  • the alkoxy group refers to a group having an oxygen atom attached to the terminal of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and the like.
  • a 5-7 membered heterocyclic ring containing 1-4 heteroatoms refers to a 5-7 membered heterocyclic compound containing 1-4 heteroatoms without aromatic characteristics, such as ethylene oxide, tetrahydrofuran, imidazolinone, caprolactam Wait.
  • a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms refers to a 5-7 membered heterocyclic compound containing 1-4 heteroatoms with aromatic characteristics, such as furan, thiophene, pyrazole, pyridine, and the like.
  • the general formula I of the present invention can be prepared by the following method:
  • the compound of formula II and the compound of formula III are reacted in a suitable solvent at a temperature of -10°C to the boiling point of a suitable solvent for 0.5-48 hours to obtain the target compound I.
  • Suitable solvents are selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N, N -Dimethylformamide or dimethylsulfoxide.
  • Suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, tertiary Sodium butoxide or potassium tert-butoxide etc.
  • the compound of formula IV and the compound of formula V are reacted in a suitable solvent at a temperature of -10°C to the boiling point of a suitable solvent for 0.5-48 hours to prepare the target compound I.
  • Suitable solvents are selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N, N -Dimethylformamide or dimethylsulfoxide.
  • Suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, tertiary Sodium butoxide or potassium tert-butoxide etc.
  • Suitable activators are selected from phosgene, triphosgene, CDI, DCC, dichlorosulfoxide, oxalyl chloride, phosphorus oxychloride or phosphorus pentachloride and the like.
  • Suitable bases are selected from N-methylimidazole or DMAP.
  • the compound of the general formula I of the present invention has herbicidal activity and can be used to control various weeds in agriculture. Compared with the compounds disclosed in the prior art, the pyrazolamide compounds of the present invention not only have excellent herbicidal activity, but are also safe for crops.
  • the present invention also includes herbicidal compositions with the compound of formula I as the active component.
  • the weight percentage of the active ingredient in the herbicidal composition is 1-99%.
  • the herbicidal composition also includes an agriculturally acceptable carrier.
  • the herbicidal composition of the present invention can be applied in the form of various preparations.
  • the compound of the present invention is dissolved or dispersed in a carrier to prepare a formulation so as to be more easily dispersed when used as a herbicide.
  • a carrier for example: These chemical preparations can be made into wettable powders or emulsifiable concentrates. Therefore, in these compositions, at least one liquid or solid carrier is added, and it is usually necessary to add an appropriate surfactant.
  • the present invention also provides an implementation method for controlling weeds, which method comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the surface of the weeds or a place where the weeds grow or a growth medium thereof.
  • a more suitable effective dose is 1 g to 1000 g per hectare, and a preferred effective dose is 10 g to 500 g per hectare.
  • one or more other herbicides can be added to the herbicidal composition of the present invention, thereby providing additional advantages and effects.
  • the compound of the present invention may be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.
  • the general formula compounds of the present invention contain one benzoyl group and one pyrazolyl substitution, the structure is novel, and the pyrazole amide compounds of the present invention have unexpectedly high herbicidal activity, in At lower dosages, it also has high herbicidal activity, which is not only highly efficient, but also reduces the use of pesticides, reduces costs, and reduces environmental pollution.
  • 1,3-Dimethyl-4-pyrazolecarboxylic acid (0.32 g, 2.3 mmol) and toluene (10 mL) were added to the reaction flask, sulfoxide chloride (0.7 g, 5.8 mmol) was slowly added, and the mixture was heated After refluxing for 4 hours, the solvent was distilled off under reduced pressure to obtain 0.36 g of yellow oil, which was directly used in the next step.
  • the compound represented by the general formula I can be obtained after the raw materials are replaced during the reaction.
  • the compounds are shown in Table 1.
  • Q is the following group: Q 1 , Q 2 , Q 3 :
  • Compound 140 8.32 (s, 1H), 8.00 (d, 1H), 7.93 (d, 1H), 4.13 (s, 3H), 3.94 (s, 3H), 3.24 (s, 3H), 2.49 (q, 2H ), 2.17 (s, 3H), 1.16 (t, 3H).
  • the test solution with the required concentration is prepared with 1 ⁇ Tween 80 standing tap water according to the test requirements.
  • spray treatment was carried out on a crawler crop sprayer (designed and produced by British Engineer Research Ltd.) (spray pressure 1.95 kg/cm 2 , spray liquid volume 500 L/hm 2 , crawler speed 1.48 km/h). The test is repeated 3 times. After the materials are processed, they are placed in the operation hall. After the chemicals are naturally dried, they are placed in the greenhouse and managed according to conventional methods. Observe and record the response of the weeds to the medicament. After treatment, periodically check the effect of the test medicament on the weeds. It is represented by 0-100%, with "0" representing no control effect and "100%" representing complete kill.
  • test results show that the compounds of general formula I generally have a higher control effect on broad-leaved weeds and gramineous weeds.
  • Some of the tested compounds such as compounds 9, 10, 15, 19, 20, 21, 22, 23, 24, 29, 30, 61, 66, 80, 82, 94, 102, 104, 131, 142, 164 , 171 has a good control effect on Zinnia, velvetleaf, bristlegrass, and barnyard grass at an application dose of 600 g ai/hm 2 , and the control effect is greater than 75%.
  • the fixed amount of wheat seeds were sown in a paper cup with nutrient soil of 7 cm in diameter, covered with 1 cm of soil after sowing, and cultivated in the greenhouse according to conventional methods after suppression and water spraying.
  • a crawler crop sprayer designed and produced by British Engineer Research Ltd.
  • stem and leaf spray treatment spray pressure 1.95kg/cm 2 , spray volume 50mL/m 2.
  • the crawler speed is 30cm/s
  • the nozzle is a fan-shaped nozzle
  • the test material is placed in the operation hall after treatment, and after the chemical liquid is naturally dried, it is placed in the greenhouse and managed according to conventional methods.
  • After treatment observe the response of wheat to the test compound regularly. Visual inspection was carried out 4 weeks after the treatment.
  • the inhibition rate was various degrees of damage compared with the control, expressed as 0-100%, with "0" representing no damage And "100%" means complete death.
  • the compound of the present invention has herbicidal activity and can be used to control various weeds in agriculture.
  • the pyrazolamide compounds of the present invention not only have excellent herbicidal activity, but are also safe for crops.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

一种吡唑酰胺类化合物及其作为除草剂的应用，所述化合物如通式(I)所示，通式I化合物具有除草活性，可用于防治农业杂草，

Description

一种吡唑酰胺类化合物及其作为除草剂的用途 技术领域
本发明属于除草剂领域。具体地说是一种吡唑酰胺类化合物及其作为除草剂的应用。
背景技术
由于杂草种群的演替、变迁以及对化学农药抗药性的产生和迅速发展，人们对生态环境保护意识的不断加强，对化学农药污染、农药对非靶标生物影响的认识以及在农药生态环境中归宿问题的重视不断提高。随着世界耕地面积的逐渐减少、人口的不断增长及对粮食需求量的增加，迫使人们迅速发展农业生产技术、改进完善耕作制度，并需要不断发明新型的和改进的除草化合物和组合物。
CN108290846A报道了某些苯甲酰胺类化合物具有除草活性，例如其中的1-28号化合物(KC1)和1-9号化合物(KC2)：
Figure PCTCN2019123872-appb-000001
如本发明所示的吡唑酰胺类化合物未见公开。
发明内容
本发明的目的是提供一种结构新颖且对作物安全的吡唑酰胺类化合物及其作为除草剂的应用。
为实现上述目的，本发明的技术方案如下：
一种吡唑酰胺类化合物，化合物如通式I所示：
Figure PCTCN2019123872-appb-000002
Q为如下基团：Q 1、Q 2、Q 3
Figure PCTCN2019123872-appb-000003
式中：
X 1和X 3可相同或不同分别选自氢、氰基、硝基、卤素、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫 基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 3烷基、C 3-C 6环烷基C 1-C 3烷氧基或C 3-C 6环烷基氧基；
X 2选自氢、氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 6烷基、Y 1硫基C 1-C 6烷基、Y 1亚砜基C 1-C 6烷基、Y 1砜基C 1-C 6烷基、Y 1Y 2氨基C 1-C 6烷基、COY 1、COOY 1、OCOOY 1、NY 1COOY 2、C(O)N Y 1Y 2、NY 1C(O)N Y 1Y 2、OC(O)NY 1Y 2、C(O)N(Y 1)OY 2、NY 1SO 2Y 2、NY 1COY 2、OSO 2Y 1、CH＝NOY 1、C 1-C 6烷基-CH＝NOY 1、C 1-C 6烷基-O-N＝CY 1Y 2，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
Y 1、Y 2分别独立的选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
R 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 3烷基、C 2-C 6烯基、C 2-C 6卤代烯基、C 2-C 6炔基、C 2-C 6卤代炔基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷氧基C 1-C 3烷基、C 1-C 6卤代烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷硫基C 1-C 3烷基、C 1-C 6卤代烷硫基C 1-C 3烷基、C 1-C 6烷基亚砜基C 1-C 3烷基、C 1-C 6卤代烷基亚砜基C 1-C 3烷基、C 1-C 6烷基砜基C 1-C 3烷基或C 1-C 6卤代烷基砜基C 1-C 3烷基；
R 2选自氢、卤素、硝基、氰基、C 1-C 6烷基或C 1-C 6卤代烷基；
R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 3烷基、C 1-C 6烷氧基、C 2-C 6烯基、C 2-C 6炔基或未取代或被1-5个下述取代基取代的苯基，下述取代基选自氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基。
所述优选化合物，通式I中：
X 1和X 3可相同或不同的分别选自氰基、硝基、卤素、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 3烷氧基、C 1-C 3卤代烷氧基、C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 3-C 6环烷基或C 3-C 6环烷基氧基；
X 2选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 6烷基、Y 1硫基C 1-C 6烷基、Y 1亚砜基C 1-C 6烷基、Y 1砜基C 1-C 6烷基、Y 1Y 2氨基C 1-C 6烷基、COY 1、COOY 1、OCOOY 1、NY 1COOY 2、C(O)N Y 1Y 2、NY 1C(O)N Y 1Y 2、OC(O)NY 1Y 2、C(O)N(Y 1)OY 2、NY 1SO 2Y 2、NY 1COY 2、OSO 2Y 1、CH＝NOY 1、C 1-C 6烷基-CH＝NOY 1、C 1-C 6 烷基-O-N＝CY 1Y 2，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
Y 1、Y 2分别独立的选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
R 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 3烷基、C 2-C 6烯基、C 2-C 6卤代烯基、C 2-C 6炔基、C 2-C 6卤代炔基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷氧基C 1-C 3烷基、C 1-C 6卤代烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷硫基C 1-C 3烷基、C 1-C 6卤代烷硫基C 1-C 3烷基、C 1-C 6烷基亚砜基C 1-C 3烷基、C 1-C 6卤代烷基亚砜基C 1-C 3烷基、C 1-C 6烷基砜基C 1-C 3烷基或C 1-C 6卤代烷基砜基C 1-C 3烷基；
R 2选自氢、卤素、硝基、氰基、C 1-C 6烷基或C 1-C 6卤代烷基；
R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 3烷基、C 1-C 6烷氧基、C 2-C 6烯基、C 2-C 6炔基或未取代或被1-5个下述取代基取代的苯基，下述取代基选自氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基。
所述进一步优选化合物，通式I中：
X 1和X 3可相同或不同分别选自氢、硝基、卤素、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基或C 1-C 6卤代烷基；
X 2选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 6烷基、Y 1硫基C 1-C 6烷基、Y 1亚砜基C 1-C 6烷基、Y 1砜基C 1-C 6烷基、Y 1Y 2氨基C 1-C 6烷基、COOY 1、C(O)N Y 1Y 2、CH＝NOY 1、C 1-C 6烷基-CH＝NOY 1、C 1-C 6烷基-O-N＝CY 1Y 2，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
Y 1、Y 2分别独立的选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基、含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
R 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基C 1-C 3烷基、C 2-C 6烯基、C 2-C 6炔基、C 1-C 6烷基磺酰基、C 1-C 6烷硫基C 1-C 3烷基、C 1-C 6烷基亚砜基C 1-C 3烷基或C 1-C 6烷基砜基C 1-C 3烷基；
R 2选自氢、卤素、硝基、氰基、C 1-C 3烷基或C 1-C 3卤代烷基；
R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基或未取代或被1-5个下述取代基取代的苯基，下述取代基选自氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基。
所述在进一步优选化合物，通式I中：
X 1和X 3可相同或不同分别选自氢、硝基、卤素、C 1-C 3烷基磺酰基、C 1-C 3烷基或C 1-C 3卤代烷基；
X 2选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 3烷基、Y 1硫基C 1-C 3烷基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
Y 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
R 1选自C 1-C 3烷基、C 1-C 3烷基磺酰基或C 1-C 3烷基砜基C 1-C 3烷基；
R 2选自氢、卤素、C 1-C 3烷基或C 1-C 3卤代烷基；
R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基或C 3-C 6环烷基。
上面给出的通式I化合物的定义中，汇集所用术语定义如下：
烷基是指直链或支链形式，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、特丁基、正戊基、异戊基、正己基等基团。环烷基是指包括环状链形式，例如环丙基、甲基环丙基、环丙基环丙基、环丁基、环戊基、环己基等基团。烯基是指直链或支链烯基，如1-丙烯基、2-丙烯基、丁烯基、戊烯基和已烯基等基团。炔基是指直链或支链炔基，如1-丙炔基、2-丙炔基、丁炔基、戊炔基和己炔基等基团。烷氧基是指烷基末端连有氧原子的基团，例如甲氧基、乙氧基、正丙氧基、异丙氧基、特丁氧基等。含有1-4个杂原子的5-7元脂杂环是指含有1-4个杂原子的5-7元没有芳香特征的杂环化合物，如环氧乙烷、四氢呋喃、咪唑啉酮、己内酰胺等。含有1-4个杂原子的5-7元芳杂环是指含有1-4个杂原子的5-7元具有芳香特征的杂环化合物，如呋喃、噻吩、吡唑、吡啶等。
本发明的通式化合物I可由如下方法制备：
方法一：
Figure PCTCN2019123872-appb-000004
通式II化合物与通式III化合物在适宜的溶剂中、温度为-10℃到适宜的溶剂的沸点下反应0.5-48小时制得目标化合物I。
适宜的溶剂选自二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、乙酸、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
反应体系内加入适宜的碱类物质可对反应有利。适宜的碱选自有机碱如三乙胺、N,N-二甲基苯胺或吡啶等，或无机碱如氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾等。
通式III化合物可由相应的酸制得，酸有市售或参考WO2009123714中的操作制得。
方法二：
Figure PCTCN2019123872-appb-000005
通式IV化合物与通式V化合物在适宜的溶剂中、温度为-10℃到适宜的溶剂的沸点下反应0.5-48小时制得目标化合物I。
适宜的溶剂选自二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、乙酸、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
反应体系内加入适宜的碱类物质可对反应有利。适宜的碱选自有机碱如三乙胺、N,N-二甲基苯胺或吡啶等，或无机碱如氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾等。
通式V化合物可由相应的酸(市售)制得。
通式II化合物的制备方法如下：
Figure PCTCN2019123872-appb-000006
通式VI化合物(有市售)与通式VII化合物(有市售)在适宜的碱和溶剂中，与适宜的活化剂反应，温度为-10℃至适宜的溶剂的沸点下反应0.5-48小时，制得通式II化合物；适宜的溶剂选自石油醚、己烷、苯、甲苯、氯苯、乙酸乙酯、乙腈、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、吡啶、2-甲基吡啶、3-甲基吡啶或4-甲基吡啶等。适宜的活化剂选自光气、三光气、CDI、DCC、二氯亚砜、草酰氯、三氯氧磷或五氯化磷等。适宜的碱选自N-甲基咪唑或DMAP等。
通式IV化合物的制备方法可参考通式II的制备方法。
本发明的通式I化合物具有除草活性，可用于农业上防治多种杂草。与现有技术所公开的化合物相比，本发明的吡唑酰胺类化合物不但具有优异的除草活性，而且对作物安全。
本发明还包括以通式I化合物为活性组分的除草组合物。该除草组合物中活性组分的重量百分含量为1-99％。该除草组合物中还包括农业上可接受的载体。
本发明的除草组合物可以多种制剂的形式施用。通常将本发明的化合物溶解或分散于载体中配制成制剂以便作为除草剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油等。因此，在这些组合物中，至少加入一种液体或固体载体，并且通常需要加入适当的表面活性剂。
本发明还提供了防治杂草的实施方法，该方法包括将除草有效量的本发明的除草组合物施于所述杂草或所述杂草生长的场所或其生长介质的表面上。较为适宜有效剂量为每公顷1克到1000克，优选有效剂量为每公顷10克到500克。对于某些应用，可在本发明的除草组合物中加入一种或多种其它的除草剂，由此可产生附加的优点和效果。
本发明的化合物既可以单独使用也可以和其它已知的杀虫剂、杀菌剂、植物生长调节剂或肥料等一起混合使用。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
本发明所具有的优点：
同已知的吡唑酰胺类化合物相比，本发明通式化合物含有一个苯甲酰基和一个吡唑酰基取代，结构新颖，并且本发明的吡唑酰胺类化合物具有意想不到的高除草活性，在较低剂量下也具有高的除草活性，不仅高效，而且减少了农药的使用量，降低了成本，减少了对环境的污染。
具体实施方式
下列实施例和生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实例
实施例1、化合物9的合成：
(1)、N-(1-甲基-四氮唑-5基)-2-甲磺酰基-4-三氟甲基苯甲酸酰胺的合成
Figure PCTCN2019123872-appb-000007
向反应瓶内加入2-甲磺酰基-4-三氟甲基苯甲酸(19.1克，71.2毫摩尔)、1-甲基-5-氨基四氮唑(8.5克，85.4毫摩尔)、3-甲基吡啶(80克，855毫摩尔)、N-甲基咪唑(11.7克，142毫摩尔)，室温搅拌半小时，冰水浴冷却至10摄氏度以下，缓慢滴入二氯亚砜(13.6克，114毫摩尔)，室温搅拌2小时，升温至50摄氏度保温反应2小时，冰水浴冷却至10摄氏度以下，缓慢滴入冷水，有固体析出，过滤，滤饼用100毫升水洗两次，干燥得到白色固体17.5克，收率70％。
(2)、1-乙基-5-甲基-3-吡唑甲酰氯的合成
Figure PCTCN2019123872-appb-000008
向反应瓶内加入1-乙基-5-甲基-3-吡唑甲酸(20克，130毫摩尔)、甲苯(100毫升)，缓慢加入氯化亚砜(50克，42.4毫摩尔)，混合物加热回流4小时，减压蒸尽溶剂，得黄色油22.3克，直接用于下一步。
(3)、化合物9的合成
Figure PCTCN2019123872-appb-000009
向反应瓶内加入N-(1-甲基-四氮唑-5基)-2-甲磺酰基-4-三氟甲基苯甲酰胺(30克，86毫摩尔)、二氯甲烷(100毫升)、三乙胺(13克，128毫摩尔)，滴加上步1-乙基-5-甲基-3-吡唑甲酰氯的二氯甲烷溶液(50毫升)。室温下搅拌1小时，减压蒸尽溶剂，向残余物中加入乙酸乙酯(500毫升)，水(200毫升)分液萃取，有机相依次用饱和食盐水(100毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，残余物通过柱色谱分离，得22.5克白色固体化合物9，纯度97％，收率52％。
实施例2、化合物19的合成：
(1)、1-乙基-5-甲基-N-(1-甲基-1H-四氮唑-5-基)-1H-吡唑-3-甲酰胺的合成
Figure PCTCN2019123872-appb-000010
向反应瓶内加入1-乙基-5-甲基-1H-吡唑-3-羧酸(2.59克，16.82毫摩尔)、1-甲基-5-氨基四氮唑(2.0克，20.18毫摩尔)、3-甲基吡啶(10毫升)、N-甲基咪唑(2.76克，33.6毫摩尔)，室温搅拌半小时，冰水浴冷却至10摄氏度以下，缓慢滴入二氯亚砜(3.20克，26.9毫摩尔)，室温搅拌2小时，升温至50摄氏度保温反应2小时，冰水浴冷却至10摄氏度以下，缓慢滴入冷水，加入乙酸乙酯萃取，有机层减压脱溶，柱层析提纯，得黄色油2.0克，收率48％。
(2)、2-氯-3-甲氧甲基-4-甲磺酰基苯甲酰氯的合成
Figure PCTCN2019123872-appb-000011
向反应瓶内加入2-氯-3-甲氧甲基-4-甲磺酰基苯甲酸(1克，3.6毫摩尔)、草酰氯(2.3克，17.9毫摩尔)及二氯甲烷(20毫升)于室温下搅拌20分钟，向体系中滴加2滴N,N-二甲基甲酰胺后于室温下继续搅拌40分钟，减压蒸尽溶，直接用于下一步。
(3)、化合物19的合成
Figure PCTCN2019123872-appb-000012
向反应瓶内加入1-乙基-5-甲基-N-(1-甲基-1H-四氮唑-5-基)-1H-吡唑-3-甲酰胺(0.77克，3.27毫摩尔)、三乙胺(0.66克，6.55毫摩尔)及二氯甲烷(20毫升)，室温下搅拌10分钟使固体溶解，冰浴下逐滴滴加上步2-氯-3-甲氧甲基-4-甲磺酰基苯甲酰氯(1.46克，4.91毫摩尔)的二氯甲烷溶液(5毫升)。室温下搅拌30分钟，减压蒸尽溶剂，向残余物中加入乙酸乙酯(50毫升)使其溶解，用饱和碳酸氢钠溶液洗涤3次(50毫升*3)，有机相用饱和食盐水(50毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，残余物通过柱色谱分离，得0.6克黄色油，收率36％。
实施例3、化合物82的合成：
(1)、1,3-二甲基-4-吡唑甲酰氯的合成
Figure PCTCN2019123872-appb-000013
向反应瓶内加入1,3-二甲基-4-吡唑甲酸(0.32克，2.3毫摩尔)、甲苯(10毫升)，缓慢加入氯化亚砜(0.7克，5.8毫摩尔)，混合物加热回流4小时，减压蒸尽溶剂，得黄色油0.36克，直接用于下一步。
(2)、化合物82的合成
Figure PCTCN2019123872-appb-000014
向反应瓶内加入N-(1-甲基-四氮唑-5基)-2-甲磺酰基-4-三氟甲基苯甲酰胺(0.4克，1.15毫摩尔)、二氯甲烷(10毫升)、三乙胺(0.35克，3.4毫摩尔)，滴加上步1,3-二甲基-4-吡唑甲酰氯的二氯甲烷溶液(5毫升)。室温下搅拌1小时，减压蒸尽溶剂，向残余物中加入乙酸乙酯(100毫升)，水(50毫升)分液萃取，有机相依次用饱和食盐水(20毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，残余物通过柱色谱分离，得0.28克白色固体化合物82，纯度99％，收率52％。
实施例4、化合物142的合成：
(1)、1-乙基-3-甲基-5-吡唑甲酰氯的合成
Figure PCTCN2019123872-appb-000015
向反应瓶内加入1-乙基-3-甲基-5-吡唑甲酸(0.35克，2.3毫摩尔)、甲苯(10毫升)，缓慢加入氯化亚砜(0.7克，5.8毫摩尔)，混合物加热回流4小时，减压蒸尽溶剂，得黄色油0.39克，直接用于下一步。
(2)、化合物142的合成
Figure PCTCN2019123872-appb-000016
向反应瓶内加入N-(1-甲基-四氮唑-5基)-2-甲磺酰基-4-三氟甲基苯甲酰胺(0.4克，1.15毫摩尔)、二氯甲烷(10毫升)、三乙胺(0.23克，2.3毫摩尔)，滴加上步1-乙基-3-甲基-5-吡唑甲酰氯的二氯甲烷溶液(5毫升)。室温下搅拌1小时，减压蒸尽溶剂，向残余物中加入乙酸乙酯(100毫升)，水(50毫升)分液萃取，有机相依次用饱和食盐水(20毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，残余物通过柱色谱分离，得0.34克白色固体化合物142，纯度96％，收率58％。
按照上述制备方法的记载，将反应过程中原料进行替换后即可获得通式I所示的化合物，化合物如表1记载。
Figure PCTCN2019123872-appb-000017
Q为如下基团：Q 1、Q 2、Q 3：
Figure PCTCN2019123872-appb-000018
表1 部分通式I化合物的结构和物理性质
Figure PCTCN2019123872-appb-000019
Figure PCTCN2019123872-appb-000020
Figure PCTCN2019123872-appb-000021
Figure PCTCN2019123872-appb-000022
Figure PCTCN2019123872-appb-000023
Figure PCTCN2019123872-appb-000024
Figure PCTCN2019123872-appb-000025
Figure PCTCN2019123872-appb-000026
Figure PCTCN2019123872-appb-000027
部分化合物的 1H NMR(300MHz,CDCl 3)数据如下：
化合物1:8.30(s,1H),8.01(d,1H),7.79(d,1H),6.49(s,1H),4.14(s,3H),3.74(t,2H)3.18(s,3H),2.18(s,3H),1.56-1.62(m,2H),0.76(t,3H)。
化合物2:8.29(s,1H),8.01(d,1H),7.79(d,1H),6.32(s,1H),4.15(s,3H),3.65(s,3H),3.18(s,3H),1.56-1.60(m,1H),0.93-0.98(m,2H),0.57-0.59(m,2H)。
化合物4:8.30(s,1H),8.02(d,1H),7.81(d,1H),6.52(s,1H),5.67-5.72(m,1H),5.22(d,1H),4.88(d,1H),4.41(d,2H),4.13(s,3H),3.19(s,3H),2.17(s,3H)。
化合物5:8.29(s,1H),8.02(d,1H),7.78(d,1H),6.74(t,1H),6.53(s,1H),5.58(d,2H),4.14(s,3H),3.17(s,3H),2.24(s,3H)。
化合物6:8.30(s,1H),8.01(d,1H),7.79(d,1H),6.32(s,1H),4.16(s,3H),3.96-4.00(m,2H),3.19(s,3H),1.57-1.61(m,1H),1.22-1.24(t,3H),0.95-0.96(m,2H),0.57-0.60(m,2H)。
化合物7:8.31(s,1H),8.02(d,1H),7.79(d,1H),6.49(s,1H),4.15(s,3H),3.96-4.02(m,1H),3.19(s,3H),2.18(s,3H),1.53-1.57(m,2H),1.18(d,3H),0.63(t,3H)。
化合物8:8.30(s,1H),8.02(d,1H),7.79(d,1H),6.50(s,1H),4.14(s,3H),3.57(d,2H),3.19(s,3H),2.18(s,3H),1.85-1.90(m,1H),0.77(d,6H)。
化合物9:8.29(s,1H),8.01(d,1H),7.79(d,1H),6.48(s,1H),4.14(s,3H),3.82(q,2H),3.18(s,3H),2.18(s,3H),1.192(t,3H)。
化合物10:8.29(s,1H),8.02(d,1H),7.79(d,1H),6.49(s,1H),4.15(s,3H),3.54(s,3H),3.19(s,3H),2.18(s,3H)。
化合物15:8.30(s,1H),8.02(d,1H),7.79(d,1H),6.48(s,1H),4.14(s,3H),3.78(t,2H),3.18(s,3H),2.18(s,3H),1.51-1.54(m,2H),1.12-1.16(m,2H),0.91(t,3H)。
化合物16:8.83(s,1H),8.38(d,1H),7.83(d,1H),6.45(s,1H),4.23(s,3H),3.84(q,2H),3.19(s,3H),2.19(s,3H),1.21(t,3H)。
化合物17:7.53(d,1H),7.39-7.42(m,2H),6.55(s,1H),4.14(s,3H),3.87(q,2H),2.21(s,3H),1.21(t,3H)。
化合物18:8.22(d,1H),7.68(d,1H),6.54(s,1H),5.08(s,2H),4.16(s,3H),3.58(s,3H),3.48(s,3H),3.27(s,3H),2.21(s,3H)。
化合物19:8.22(d,1H),7.68(d,1H),6.54(s,1H),5.08(s,2H),4.17(s,3H),3.86(q,2H),3.48(s,3H),3.27(s,3H),2.21(s,3H),1.21(t,3H)。
化合物20:8.22(d,1H),7.68(d,1H),6.54(s,1H),5.11(s,2H),4.17(s,3H),3.87(dd,2H),3.68(dd,2H),3.29(s,3H),2.21(s,3H),1.21-1.25(m,6H)。
化合物21:8.24(d,1H),7.72(d,1H),6.54(s,1H),5.34(s,2H),4.17(s,3H),4.01(q,2H),3.87(q,2H),3.24(s,3H),2.21(s,3H),1.21(t,3H)。
化合物22:8.04(d,1H),7.89(d,1H),6.64(s,1H),4.18(s,3H),3.93(q,2H),3.37(s,3H),2.73(s,3H),2.22(s,3H),1.09(t,3H)。
化合物23:8.21(d,1H),7.67(d,1H),6.54(s,1H),5.17(s,2H),4.17(s,3H),3.86(q,2H),3.74-3.77(m,2H),3.54-3.57(m,2H),3.33(s,3H),3.32(s,3H),2.21(s,3H),1.21(t,3H)。
化合物24:8.21(d,1H),7.67(d,1H),6.53(s,1H),5.18(s,2H),4.17(s,3H),4.05-4.08(m,1H),3.86(q,2H),3.71-3.83(m,2H),3.56-3.63(m,2H),3.32(s,3H),2.21(s,3H),1.82-1.97(m,3H),1.45-1.49(m,1H)。
化合物26:8.24(d,1H),7.69(d,1H),6.66(s,1H),6.52(s,1H),5.73(s,2H),4.12(s,3H),3.82-3.86(m,2H),3.08(s,3H),2.35(s,3H),2.19(s,3H),2.03(s,3H),1.16-1.19(t,3H)。
化合物29:7.96-7.98(m,2H),7.77(d,1H),6.54(s,1H),4.16(s,3H),3.87(q,2H),3.11(s,3H),2.21(s,3H),1.19(t,3H)。
化合物30:8.23(d,1H),7.64(d,1H),6.55(s,1H),4.17(s,3H),3.85-3.88(m,2H),3.32(s,3H),2.21(s,3H),1.19-1.22(t,3H)。
化合物61:8.32(s,1H),8.04(d,1H),7.79(d,1H),6.66(s,1H),4.96(s,2H),4.12(s,3H),3.19(s,3H),2.70(s,3H),2.36(s,3H)。
化合物66:8.02(s,1H),7.71(d,1H),7.60(d,1H),6.49(s,1H),4.96(s,2H),4.14(s,3H),3.80-3.84(m,2H),3.17(s,3H),2.18(s,3H),1.18-1.20(t,3H)。
化合物71:8.00(d,1H),7.50(d,1H),6.52(s,1H),4.96(s,2H),4.12(s,3H),3.87-3.89(m,2H),3.51(s,3H),3.20(s,3H),2.59(s,3H),2.21(s,3H),1.21-1.24(t,3H)。
化合物79:8.27(s,1H),8.01-7.79(m,2H),4.11(s,3H),3.92(s,3H),3.22(s,3H)。
化合物80:8.32(s,1H),7.98(d,1H),7.78(d,1H),7.76(s,1H),4.03(s,3H),3.88(s,3H),3.25(s,3H)。
化合物82:8.36(s,1H),7.96(d,1H),7.77(d,1H),7.40(s,1H),4.02(s,3H),3.74(s,3H),3.25(s,3H),2.30(s,3H)。
化合物83:8.36(s,1H),7.96(d,1H),7.77(d,1H),7.45(s,1H),4.02(s,3H),3.99(q,2H),3.26(s,3H),2.31(s,3H),1.39(t,3H)。
化合物88:7.93(s,1H),7.88(d,1H),7.80(d,1H),7.58(dd,1H),4.09(s,3H),3.73(s,3H),2.22(s,3H)。
化合物94:8.00(d,1H),7.96(d,1H),4.14(s,3H),3.73(s,3H),3.35(s,3H),2.72(s,3H),2.20(s,3H)。
化合物96:8.17(d,1H),7.69(d,1H),5.18(d,2H),4.05-4.09(m,1H),4.00(s,3H),3.79-3.83(m,1H),3.77(s,3H),3.71-3.76(m,1H),3.63-3.65(m,1H),3.57-3.61(m,1H),3.32(s,3H),2.33(s,3H),1.92-1.98(m,1H),1.83-1.89(m,2H),1.53-1.59(m,1H),。
化合物102:8.15(d,1H),8.14(d,1H),8.00(s,1H),7.86(s,1H),4.13(s,3H),3.73(s,3H),3.36(s,3H),2.21(s,3H)。
化合物104:8.12(d,1H),8.07(d,1H),7.84(s,1H),4.94(d,2H),4.14(s,3H),3.72(s,3H),3.39(s,3H),3.36(s,3H),2.20(s,3H)。
化合物131:8.06(d,1H),8.00(s,1H),7.98(d,1H),4.12(s,3H),3.75(s,3H),3.45(s,3H),2.55(s,3H),2.21(s,3H)。
化合物140:8.32(s,1H),8.00(d,1H),7.93(d,1H),4.13(s,3H),3.94(s,3H),3.24(s,3H),2.49(q,2H),2.17(s,3H),1.16(t,3H)。
化合物142:8.35(s,1H),8.02(d,1H),7.84(d,1H),5.98(s,1H),4.28(q,2H),4.05(s,3H),3.22(s,3H),2.15(s,3H),1.34(t,3H)。
化合物164:8.10(d,1H),7.60(d,1H),5.93(s,1H),4.29(q,2H),4.06(s,3H),3.11(s,3H),2.74(s,3H),2.12(s,3H),1.32(t,3H)。
化合物171:7.99(d,2H),7.84(d,1H),5.90(s,1H),4.34(q,2H),4.08(s,3H),3.11(s,3H),2.17(s,3H),1.37(t,3H)。
生测实例
实施例5、除草活性的测定
将阔叶杂草(百日草、苘麻)或禾本科杂草(狗尾草、稗草)种子分别播于直径为7cm的装有营养土的纸杯中，播后覆土1cm，镇压、淋水后在温室按常规方法培养，待杂草2-3叶期后茎叶喷雾处理。
原药用丙酮溶解后，按试验要求用1‰的吐温80静置自来水配制所需浓度的待测液。按试验设计剂量，在履带式作物喷雾机(英国Engineer Research Ltd.设计生产)上进行喷雾处理(喷雾压力1.95kg/cm 2，喷液量500L/hm 2，履带速度1.48km/h)。试验设3次重复。试材处理后置于操作大厅，待药液自然阴干后，放于温室内按常规方法管理，观察并记录杂草对药剂的反应情况，处理后定期目测供试药剂对杂草的防除效果，用0～100％来表示，以“0”代表无防效和“100％”代表完全杀死。
试验结果表明，通式I化合物对阔叶杂草和禾本科杂草普遍具有较高防效。部分供试的化合物中，如化合物9、10、15、19、20、21、22、23、24、29、30、61、66、80、82、94、102、104、131、142、164、171在施用剂量为600g a.i./hm 2时对百日草、苘麻、狗尾草和稗草均具有较好防效，防效均大于75％。
按照以上测试方法，选取部分通式I化合物与KC2进行防除百日草的活性试验，结果见表2。
表2：通式I部分化合物与对照化合物KC2防除百日草活性(苗后，防效％)
Figure PCTCN2019123872-appb-000028
按照以上测试方法，选取部分通式I化合物与KC2进行防除苘麻的活性试验，结果见表3。
表3：通式I部分化合物与对照化合物KC2防除苘麻活性(苗后，防效％)
Figure PCTCN2019123872-appb-000029
按照以上测试方法，选取部分通式I化合物与KC1和KC2进行防除稗草的活性试验，结果见表4。
表4：通式I部分化合物与对照化合物KC1和KC2防除稗草活性(苗后，防效％)
Figure PCTCN2019123872-appb-000030
Figure PCTCN2019123872-appb-000031
按照以上测试方法，选取部分通式I化合物与KC1和KC2进行防除狗尾草的活性试验，结果见表5。
表5：通式I部分化合物与对照化合物KC1和KC2防除狗尾草活性(苗后，防效％)
Figure PCTCN2019123872-appb-000032
实施例6、小麦安全性试验
将定量的小麦种子播于直径为7cm的装有营养土的纸杯中，播后覆土1cm，镇压、淋水后在温室按常规方法培养。待小麦长至3叶期，选取生长均匀一致的试材用履带式作物喷雾机(英国Engineer Research Ltd.设计生产)进行茎叶喷雾处理(喷雾压力1.95kg/cm 2，喷液量50mL/m 2，履带速度30cm/s，喷嘴为扇形喷嘴)，试材处理后置于操作大厅，待药液自然风干后，置于温室内按常规方法管理。处理后定期观察小麦对供试化合物的反应情况，于处理后4周进行目测调查，抑制率为与对照相比的各种损伤程度，用0～100％来表示，以“0”代表无损伤和“100％”代表完全死亡。
通式I化合物82同KC1进行了小麦安全性平行对比试验，结果见表6。
表6：通式I中部分化合物对小麦安全性(苗后，损伤率％)
Figure PCTCN2019123872-appb-000033
综上本发明通式化合物具有除草活性，可用于农业上防治多种杂草。同时本发明的吡唑酰胺类化合物不但具有优异的除草活性，而且对作物安全。

Claims (7)

  1. 一种吡唑酰胺类化合物，其特征在于：化合物如通式I所示：
    Figure PCTCN2019123872-appb-100001
    Q为如下基团：Q 1、Q 2、Q 3
    Figure PCTCN2019123872-appb-100002
    式中：
    X 1和X 3可相同或不同分别选自氢、氰基、硝基、卤素、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 3烷基、C 3-C 6环烷基C 1-C 3烷氧基或C 3-C 6环烷基氧基；
    X 2选自氢、氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 6烷基、Y 1硫基C 1-C 6烷基、Y 1亚砜基C 1-C 6烷基、Y 1砜基C 1-C 6烷基、Y 1Y 2氨基C 1-C 6烷基、COY 1、COOY 1、OCOOY 1、NY 1COOY 2、C(O)N Y 1Y 2、NY 1C(O)N Y 1Y 2、OC(O)NY 1Y 2、C(O)N(Y 1)OY 2、NY 1SO 2Y 2、NY 1COY 2、OSO 2Y 1、CH＝NOY 1、C 1-C 6烷基-CH＝NOY 1、C 1-C 6烷基-O-N＝CY 1Y 2，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    Y 1、Y 2分别独立的选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    R 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 3烷基、C 2-C 6烯基、C 2-C 6卤代烯基、C 2-C 6炔基、C 2-C 6卤代炔基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷氧基C 1-C 3烷基、C 1-C 6卤代烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷硫基C 1-C 3烷基、C 1-C 6卤代烷硫基C 1-C 3烷基、C 1-C 6烷基亚砜基C 1-C 3烷基、C 1-C 6卤代烷基亚砜基C 1-C 3烷基、C 1-C 6烷基砜基C 1-C 3烷基或C 1-C 6卤代烷基砜基C 1-C 3烷基；
    R 2选自氢、卤素、硝基、氰基、C 1-C 6烷基或C 1-C 6卤代烷基；
    R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 3烷基、C 1-C 6烷氧基、C 2-C 6烯基、C 2-C 6炔基或未取代或被1-5个下述取代基取代的苯基，下述取代基选自氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基。
  2. 按照权利要求1所述的化合物，其特征在于，通式I中：
    X 1和X 3可相同或不同的分别选自氢、氰基、硝基、卤素、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 3烷氧基、C 1-C 3卤代烷氧基、C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 3-C 6环烷基或C 3-C 6环烷基氧基；
    X 2选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 6烷基、Y 1硫基C 1-C 6烷基、Y 1亚砜基C 1-C 6烷基、Y 1砜基C 1-C 6烷基、Y 1Y 2氨基C 1-C 6烷基、COY 1、COOY 1、OCOOY 1、NY 1COOY 2、C(O)N Y 1Y 2、NY 1C(O)N Y 1Y 2、OC(O)NY 1Y 2、C(O)N(Y 1)OY 2、NY 1SO 2Y 2、NY 1COY 2、OSO 2Y 1、CH＝NOY 1、C 1-C 6烷基-CH＝NOY 1、C 1-C 6烷基-O-N＝CY 1Y 2，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    Y 1、Y 2分别独立的选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    R 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 3烷基、C 2-C 6烯基、C 2-C 6卤代烯基、C 2-C 6炔基、C 2-C 6卤代炔基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷氧基C 1-C 3烷基、C 1-C 6卤代烷氧基C 1-C 3烷基、C 1-C 6烷氧基C 1-C 3烷氧基C 1-C 3烷基、C 1-C 6烷硫基C 1-C 3烷基、C 1-C 6卤代烷硫基C 1-C 3烷基、C 1-C 6烷基亚砜基C 1-C 3烷基、C 1-C 6卤代烷基亚砜基C 1-C 3烷基、C 1-C 6烷基砜基C 1-C 3烷基或C 1-C 6卤代烷基砜基C 1-C 3烷基；
    R 2选自氢、卤素、硝基、氰基、C 1-C 6烷基或C 1-C 6卤代烷基；
    R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6卤代环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 3烷基、C 1-C 6烷氧基、C 2-C 6烯基、C 2-C 6炔基或未取代或被1-5个下述取代基取代的苯基，下述取代基选自氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基。
  3. 按照权利要求2所述的化合物，其特征在于，通式I中：
    X 1和X 3可相同或不同分别选自氢、硝基、卤素、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基或C 1-C 6卤代烷基；
    X 2选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 3-C 6 环烷基、C 3-C 6环烷基C 1-C 6烷基、C 3-C 6卤代环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 6烷基、Y 1硫基C 1-C 6烷基、Y 1亚砜基C 1-C 6烷基、Y 1砜基C 1-C 6烷基、Y 1Y 2氨基C 1-C 6烷基、COOY 1、C(O)N Y 1Y 2、CH＝NOY 1、C 1-C 6烷基-CH＝NOY 1、C 1-C 6烷基-O-N＝CY 1Y 2，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    Y 1、Y 2分别独立的选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基、含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    R 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基C 1-C 3烷基、C 2-C 6烯基、C 2-C 6炔基、C 1-C 6烷基磺酰基、C 1-C 6烷硫基C 1-C 3烷基、C 1-C 6烷基亚砜基C 1-C 3烷基或C 1-C 6烷基砜基C 1-C 3烷基；
    R 2选自氢、卤素、硝基、氰基、C 1-C 3烷基或C 1-C 3卤代烷基；
    R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基或未取代或被1-5个下述取代基取代的苯基，下述取代基选自氰基、硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基。
  4. 按照权利要求3所述的化合物，其特征在于，通式I中：
    X 1和X 3可相同或不同分别选自氢、硝基、卤素、C 1-C 3烷基磺酰基、C 1-C 3烷基或C 1-C 3卤代烷基；
    X 2选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、Y 1氧基、Y 1氧基C 1-C 3烷基、Y 1硫基C 1-C 3烷基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    Y 1选自C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 3-C 6环烷基C 1-C 6烷基、C 1-C 6烷氧基C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基，或未取代或被1-5个下述取代基取代的苯基、含有1-4个杂原子的5-7元脂杂环、含有1-4个杂原子的5-7元芳杂环、含有1-4个杂原子的5-7元脂杂环C 1-C 6烷基或含有1-4个杂原子的5-7元芳杂环C 1-C 6烷基，下述取代基选自硝基、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 3-C 6环烷基或C 3-C 6环烷氧基；
    R 1选自C 1-C 3烷基、C 1-C 3烷基磺酰基或C 1-C 3烷基砜基C 1-C 3烷基；
    R 2选自氢、卤素、C 1-C 3烷基或C 1-C 3卤代烷基；
    R 3选自氢、C 1-C 6烷基、C 1-C 6卤代烷基或C 3-C 6环烷基。
  5. 一种权利要求1所述的通式I化合物在用于控制杂草中的应用。
  6. 一种除草组合物，其特征在于：除草组合物为活性物质和农业上可接受的载体，活性组分为权利要求1所述的通式I化合物，组合物中活性组分的重量百分含量为1-99％。
  7. 一种如权利要求6所述的除草组合物的控制杂草的方法，其特征在于：向杂草或杂草的生长介质或地点上施用除草有效剂量的如权利要求6所述的除草组合物。
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WO2014126070A1 (ja) * 2013-02-15 2014-08-21 石原産業株式会社 トリアジノンカルボキサミド系化合物又はその塩
CN108290846A (zh) * 2015-09-28 2018-07-17 拜耳作物科学股份公司 酰化的n-(1,2,5-噁二唑-3-基)-、n-(1,3,4-噁二唑-2-基)-、n-(四唑-5-基)-和n-(三唑-5-基)-芳基羧酰胺及其作为除草剂的用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014126070A1 (ja) * 2013-02-15 2014-08-21 石原産業株式会社 トリアジノンカルボキサミド系化合物又はその塩
CN108290846A (zh) * 2015-09-28 2018-07-17 拜耳作物科学股份公司 酰化的n-(1,2,5-噁二唑-3-基)-、n-(1,3,4-噁二唑-2-基)-、n-(四唑-5-基)-和n-(三唑-5-基)-芳基羧酰胺及其作为除草剂的用途

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