[go: up one dir, main page]

WO2024099118A1 - 一种氧杂双环烷类化合物及其制备方法、除草组合物和应用 - Google Patents

一种氧杂双环烷类化合物及其制备方法、除草组合物和应用 Download PDF

Info

Publication number
WO2024099118A1
WO2024099118A1 PCT/CN2023/127411 CN2023127411W WO2024099118A1 WO 2024099118 A1 WO2024099118 A1 WO 2024099118A1 CN 2023127411 W CN2023127411 W CN 2023127411W WO 2024099118 A1 WO2024099118 A1 WO 2024099118A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
alkenyl
alkynyl
cycloalkyl
cor
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2023/127411
Other languages
English (en)
French (fr)
Inventor
连磊
华荣保
彭学岗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Kingagroot Chemical Compound Co Ltd
Original Assignee
Qingdao Kingagroot Chemical Compound Co Ltd
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 Qingdao Kingagroot Chemical Compound Co Ltd filed Critical Qingdao Kingagroot Chemical Compound Co Ltd
Priority to AU2023379359A priority Critical patent/AU2023379359A1/en
Priority to EP23887808.6A priority patent/EP4617275A1/en
Priority to JP2025526605A priority patent/JP2025537252A/ja
Publication of WO2024099118A1 publication Critical patent/WO2024099118A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protection of plants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • 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
    • A01N43/82—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 three 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
    • A01N43/90—Biocides, 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention belongs to the technical field of pesticides, and specifically relates to an oxabicycloalkane compound and a preparation method thereof, a herbicidal composition and application thereof.
  • the present invention provides an oxabicycloalkane compound and a preparation method thereof, a herbicidal composition and application thereof.
  • the compound has better crop safety while maintaining equivalent or even better herbicidal activity and can establish better selectivity on crops.
  • a and B each independently represent an alkyl group
  • X, Y and Z each independently represent hydrogen, nitro, halogen, cyano, formyl, thiocyano, mercapto, OR 1 , COR 1 , COOR 1 , OCOR 1 , OCOOR 1 , NR 3 SO 2 R 2 , OSO 2 R 2 , S(O) m R 2 , NR 3 COR 1 , NR 3 COOR 1 , C(O)NR 3 OR 1 , SO 2 OR 1 , C(O)NR 4 R 5 , NR 3 C(O)NR 4 R 5 , OC(O)NR 4 R 5 , SO 2 NR 4 R 5 , C(S)R 1 , C(S)OR 1 , C(S)SR 2 , C(O)SR 2 , SC(O)R 1 , SC(S)R 1 , OC(S)R 1 , -alkyl-C(S)R 1 , -alkyl-C(S)OR 1 , -alky
  • R 1 , R 3 , R 4 , and R 5 each independently represent hydrogen, aryl, arylalkyl, heterocyclyl, heterocyclylalkyl, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, and cycloalkylalkyl, wherein the last 10 groups are substituted by s substituents selected from the group consisting of cyano, halogen, nitro, thiocyanato, OR 7 , S(O) m R 9 , NR 7 R 8 , NR 8 OR 7 , COR 7 , OCOR 7 , SCOR 7 , NR 8 COR 7 , CO 2 R 7 , COSR 7 , CONR 7 R 8 and alkoxyalkoxycarbonyl;
  • R 2 is aryl, arylalkyl, heterocyclyl, heterocyclylalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, wherein the last five groups are substituted by s groups selected from cyano, halogen, nitro, thiocyanato, OR 7 , S(O) m R 9 , NR 7 R 8 , NR 8 OR 7 , COR 7 , OCOR 7 , SCOR 7 , NR 8 COR 7 , CO 2 R 7 , COSR 7 , CONR 7 R 8 and alkoxyalkoxycarbonyl;
  • R6 is methyl or ethyl
  • R 7 and R 8 each independently represent hydrogen, alkyl, alkenyl or alkynyl
  • R 9 is alkyl, alkenyl or alkynyl
  • R10 each independently represents hydrogen, alkyl, haloalkyl, phenyl or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy;
  • n 0, 1 or 2
  • s 0, 1, 2, 3, 4 or 5.
  • a and B each independently represent a C1-C8 alkyl group
  • X, Y and Z each independently represent hydrogen, nitro, halogen, cyano, formyl, thiocyano, mercapto, OR 1 , COR 1 , COOR 1 , OCOR 1 , OCOOR 1 , NR 3 SO 2 R 2 , OSO 2 R 2 , S(O) m R 2 , NR 3 COR 1 , NR 3 COOR 1 , C(O)NR 3 OR 1 , SO 2 OR 1 , C(O)NR 4 R 5 , NR 3 C(O)NR 4 R 5 , OC(O)NR 4 R 5 , SO 2 NR 4 R 5 , C(S)R 1 , C(S)OR 1 , C(S)SR 2 , C(O)SR 2 , SC(O)R 1 , SC(S)R 1 , OC(S)R 1 , -(C1-C8 alkyl)-C(S)R 1 , -(C1-C8 alkyl
  • R 1 , R 3 , R 4 , and R 5 each independently represent hydrogen, aryl, aryl C1-C8 alkyl, heterocyclic group, heterocyclic C1-C8 alkyl, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, halogenated C2-C8 alkenyl, C2-C8 alkynyl, halogenated C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C3-C8 cycloalkyl, C1-C8 alkoxy C1-C8 alkyl, C3-C8 cycloalkyl C1-C8 alkyl, wherein the last 10 groups are selected from cyano, halogen, nitro, thiocyanato, OR 7 , S(O) m R 9 , NR 7 R 8 , NR 8 OR 7 , COR 7 , OCOR 7 , SCOR
  • R 2 is aryl, arylC1-C8 alkyl, heterocyclyl, heterocyclylC1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, wherein the last five groups are substituted by s groups selected from cyano, halogen, nitro, thiocyanato, OR 7 , S(O) m R 9 , NR 7 R 8 , NR 8 OR 7 , COR 7 , OCOR 7 , SCOR 7 , NR 8 COR 7 , CO 2 R 7 , COSR 7 , CONR 7 R 8 and C1-C8 alkoxyC1-C8 alkoxycarbonyl;
  • R6 is methyl or ethyl
  • R 7 and R 8 each independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;
  • R 9 is C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;
  • R10 each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy;
  • n 0, 1 or 2
  • s 0, 1, 2, 3, 4 or 5.
  • a and B each independently represent a C1-C6 alkyl group; preferably, A represents a methyl group or an ethyl group; B represents a methyl group, an ethyl group or an isopropyl group;
  • X, Y and Z each independently represent hydrogen, nitro, halogen, cyano, formyl, thiocyano, mercapto, OR 1 , COR 1 , COOR 1 , OCOR 1 , OCOOR 1 , NR 3 SO 2 R 2 , OSO 2 R 2 , S(O) m R 2 , NR 3 COR 1 , NR 3 COOR 1 , C(O)NR 3 OR 1 , SO 2 OR 1 , C(O)NR 4 R 5 , NR 3 C(O)NR 4 R 5 , OC(O)NR 4 R 5 , SO 2 NR 4 R 5 , C(S)R 1 , C(S)OR 1 , C(S)SR 2 , C(O)SR 2 , SC(O)R 1 , SC(S)R 1 , OC(S)R 1 , -(C1-C6 alkyl)-C(S)R 1 , -(C1-C6 alkyl
  • R 1 , R 3 , R 4 , and R 5 each independently represent hydrogen, aryl, aryl C1-C6 alkyl, heterocyclic group, heterocyclic C1-C6 alkyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, halogenated C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C1-C6 alkoxy C1-C6 alkyl, C3-C6 cycloalkyl C1-C6 alkyl, wherein the last 10 groups are selected from cyano, halogen, nitro, thiocyanato, OR 7 , S(O) m R 9 , NR 7 R 8 , NR 8 OR 7 , COR 7 , OCOR 7 , SCOR
  • R 2 is aryl, arylC1-C6 alkyl, heterocyclyl, heterocyclylC1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, wherein the last five groups are substituted by s groups selected from cyano, halogen, nitro, thiocyanato, OR 7 , S(O) m R 9 , NR 7 R 8 , NR 8 OR 7 , COR 7 , OCOR 7 , SCOR 7 , NR 8 COR 7 , CO 2 R 7 , COSR 7 , CONR 7 R 8 and C1-C6 alkoxyC1-C6 alkoxycarbonyl;
  • R6 is methyl or ethyl
  • R 7 and R 8 each independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl;
  • R 9 is C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl;
  • R10 each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy;
  • n 0, 1 or 2
  • s 0, 1, 2, 3, 4 or 5.
  • Alkyl groups with more than two carbon atoms may be straight-chain or branched.
  • the alkyl group may be -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, etc.
  • Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl.
  • alkenyl is, for example, vinyl, allyl, 1-methylprop-2-ene-1-yl, 2-methylprop-2-ene-1-yl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl.
  • Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be in any position of each unsaturated group.
  • Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cycloalkenyl is a monocyclic alkenyl having, for example, three to six carbocyclic ring members, such as cyclopropenyl, Cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein the double bond may be in any position.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • the "aryl” mentioned in the present invention includes but is not limited to phenyl, naphthyl,
  • the "heterocyclic group” includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., also including but not limited to heteroaryl, i.e. aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms among the ring atoms are selected from oxygen, nitrogen and sulfur, for example
  • a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned.
  • identical or different substitution characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude compounds that are known to the person skilled in the art to be chemically unstable under standard conditions.
  • substituted by at least one group in the present invention means substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without specific connection positions can be connected at any position. Including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl substituted with 1 methyl Can represent wait.
  • Stereoisomers can be obtained from the mixture obtained in the preparation by conventional separation methods, for example by chromatographic separation. Stereoisomers can also be selectively prepared by using stereoselective reactions and using optically active starting materials and/or auxiliaries.
  • the present invention also relates to all stereoisomers and mixtures thereof contained in the general formula I but not specifically defined.
  • the present invention also provides a method for preparing the oxabicycloalkane compound, comprising the following steps:
  • Hal represents halogen, and the other substituents A, B, X, Y, and Z are as defined above;
  • the reaction is carried out in the presence of NaH or anhydrous carbonate (such as potassium salt, sodium salt) and a solvent; more preferably, the solvent is selected from at least one of DMF, dimethylacetamide, THF, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate.
  • NaH or anhydrous carbonate such as potassium salt, sodium salt
  • a solvent is selected from at least one of DMF, dimethylacetamide, THF, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate.
  • the compounds of the present invention can be prepared by referring to the relevant methods described in patent CN1045786A and the like.
  • the present invention also provides a herbicide composition, which comprises (i) a herbicidally effective amount of at least one of the oxabicycloalkane compounds.
  • the herbicidal composition further comprises (ii) a herbicidally effective amount of one or more additional herbicides and/or safeners.
  • the herbicidal composition further comprises (iii) an agrochemically acceptable formulation adjuvant.
  • the present invention also provides a method for controlling unwanted plants, comprising applying a herbicidally effective amount of at least one of the oxabicycloalkane compounds or the herbicide composition to plants or their locations or to soil or water bodies to control the emergence or growth of unwanted plants.
  • the undesirable plants include herbicide resistant or tolerant weed species.
  • the present invention also provides use of at least one of the oxabicycloalkane compounds or the herbicide composition in controlling unwanted plants.
  • the oxabicycloalkane compounds are used to control weeds in useful crops.
  • the useful crops include transgenic crops or crops treated with genome editing technology, and the weeds Includes herbicide-resistant or -tolerant weed species.
  • the compounds of formula I of the present invention have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants.
  • the active substances of the present invention are also effective against perennial weeds, which grow from rhizomes, rootstocks, or other perennial organs and are difficult to control. In this regard, it is generally unimportant whether the substance is used before sowing, before germination, or after germination.
  • Representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention are particularly mentioned, without limiting to certain species.
  • weed species on which the active substances are effective include monocotyledonous plants: annual oats, rye, grass, alopecuroides, phalaris, barnyardgrass, crabgrass, Setaria and sedge, and perennial wheatgrass, bermudagrass, Imperata and sorghum, and perennial sedge.
  • dicotyledonous weed species With regard to dicotyledonous weed species, its effect can be extended to species such as annual Galium, Viola, Veronica, Sesame, Chickweed, Amaranth, Sinapis, Ipomoea, Rhizoma Coptidis, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia.
  • the active substance of the present invention effectively controls harmful plants such as Echinochloa, Sagittaria, Alisma, Eriobotrya, Sugarcane and Cyperus under such undetermined conditions of rice sowing.
  • the seedlings of the weeds can be completely prevented before the weeds grow, or the weeds stop growing when the cotyledons grow, and finally die completely after three to four weeks.
  • the compound of the present invention is particularly good in activity against the following plants, Apila, Sesame, Polygonum, Chickweed, Veronica hedera, Veronica arabica, Pansy and Amaranth, Galium and Kochia.
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they do not damage economically important crop plants such as peanuts, wheat, barley, rye, rice, corn, sugar beet, cotton and soybeans at all, or the damage is negligible. In particular, they are very compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compounds of the present invention are very suitable for selectively controlling unwanted plants in agricultural crops or ornamental plants.
  • Transgenic plants Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetically engineered plant cultivation.
  • Transgenic plants usually have superior properties, such as resistance to specific pesticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insects or fungal, bacterial or viral microorganisms.
  • Other special properties are related to the following conditions of the product, for example, quantity, quality, storage stability, composition and special ingredients. In this way, it is known to obtain transgenic plant products with increased starch content or improved starch quality or different fatty acid compositions.
  • the compounds of formula I of the present invention or their salts are preferably used in economically important genetically modified crops and ornamental plants, for example cereals, for example wheat, barley, rye, oats, millet, rice, cassava and corn, or in the cultivation of beets, 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 are resistant or genetically engineered to the toxic effects of herbicides.
  • glufosinate herbicides e.g. EP-0242236 A, EP-0242246 A
  • glyphosate herbicides WO 92/00377
  • sulfonylurea herbicides EP-0257993 A, US-5013659 A
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins that protect plants against attack by certain pests (EP-0142924 A, EP-0193259 A);
  • Plant cells in which the activity of a gene product is reduced can be prepared by, for example, expressing at least one appropriate antisense RNA, sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme which specifically cleaves the transcript of the above gene product.
  • DNA molecule comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and to use a DNA molecule comprising only a portion of the coding sequence, which portion must be long enough to achieve an antisense effect in the cell. It is also possible to use sequences that have a high degree of homology to the gene product coding sequence, but are not identical.
  • the synthesized protein When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, for localization in a specific compartment, it is possible, for example, to connect the coding region and the DNA sequence to ensure 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).
  • the transgenic plant cells can be recombined into whole plants using known techniques.
  • the active substance of the present invention when used on genetically modified crops, in addition to the effect of inhibiting harmful plants observed on other crops, there are often special effects on the corresponding genetically modified crops, such as improving or expanding the scope of weed control, improving the application rate during application, preferably combining the resistance of genetically modified crops with the performance of herbicides well, and affecting the growth and yield of genetically modified crop plants. Therefore, the present invention also provides the use of the compound as a herbicide to control harmful plants in genetically modified crop plants.
  • the compounds according to the invention can significantly regulate the growth of crop plants.
  • these compounds can be used to control the composition of the plant and promote the harvest, for example to dry out and dwarf the growth of the plant. They are also suitable for regulating and inhibiting undesirable plant growth without destroying the growth of the crop. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, because this can reduce or completely prevent lodging.
  • the compounds of the invention can be applied using conventional formulations, such as wettable powders, concentrated emulsions, sprayable solutions, powders or granules.
  • the invention also provides herbicidal compositions comprising compounds of formula I.
  • the compounds of formula I can be formulated in a variety of ways, depending on the usual biological and/or chemical physical parameters.
  • suitable formulations are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsion concentrates (EC), emulsions such as oil-in-water and water-in-oil emulsions (EW), sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluent, solutions miscible in oil, powders (DP), capsule suspensions (CS), core capsules
  • the invention relates to seeding compositions, granules for broadcasting and soil application, spray granules, coated granules and absorbent granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra-low volume) formulations, microcapsules and wax products.
  • These individual formulation types are known and are described, for example, in Winnacker-Küchler, "Chemische Techonologie” [Chemical Technology], Volume 7, C. Hauser Verlag Kunststoff, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd edition 1979, G. Goodwin Ltd. London.
  • Wettable powders are homogeneously dispersible in water and contain, in addition to the active substance, diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthomethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate.
  • the active substance of the herbicide is finely ground, for example using conventional apparatus such as hammer mills, fan mills and jet mills, and adjuvants are mixed in simultaneously or sequentially.
  • the concentrated emulsion is prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of aromatic compounds or hydrocarbons with a higher boiling point or solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers).
  • organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of aromatic compounds or hydrocarbons with a higher boiling point or solvents.
  • emulsifiers examples include calcium alkylaryl sulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters.
  • calcium alkylaryl sulfonates such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene
  • Powders are obtained by grinding the active substance with finely divided solid materials, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspensions based on water or oil can be prepared, for example, by wet grinding using a commercially available bead mill, with or without the addition of a surfactant of another formulation type as described above.
  • Emulsions such as oil-in-water emulsions (EW) can be prepared using aqueous organic solvents using stirrers, colloid mills and/or static mixers and, if necessary, adding surfactants of another formulation type as described above.
  • EW oil-in-water emulsions
  • Granules are prepared by spraying the active substance onto an adsorbent, granulating with an inert material, or concentrating the active substance on the surface of a carrier such as sand or kaolinite and granulating the inert material with a binder such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • Suitable active substances can be granulated by the method for preparing fertilizer granules, and if necessary, Mixed with fertilizers.
  • Water suspension granules are prepared using conventional methods, such as spray-drying, fluidized bed granulation, disc granulation, mixing using a high-speed mixer, and extrusion in the absence of solid inert materials.
  • Agrochemical formulations usually contain 0.1 to 99% by weight, in particular 0.1 to 95% of active substance formula I.
  • the concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remainder to 100% by weight.
  • the concentration of active substance in concentrated emulsions can be about 1 to 90% by weight, preferably 5 to 80%.
  • Powder formulations contain 1 to 30% by weight of active substance, usually preferably 5 to 20% by weight of active substance, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% of active substance.
  • the content of active substance in water-suspended granules it mainly depends on whether the active substance is liquid or solid, and the adjuvants, fillers, etc. used during granulation.
  • the content of active substance in water-suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the formulations of the active substances may additionally include tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, generally, the pH and viscosity regulators customary in each case.
  • suitable active substances that can be mixed with the compound of formula I of the present invention are, for example, known substances in the World New Pesticide Variety Technology Encyclopedia, China Agricultural Science and Technology Press, 2010.9 and the literature cited herein.
  • the following herbicide active substances can be mixed with compound 1 (Note: the name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with a code when appropriate):
  • HPPD Hydrophenyl Pyruvate Dioxygenase inhibitors: including but not limited to the following types,
  • Triketones for example, Sulcotrione (CAS NO: 99105-77-8); Mesotrione (CAS NO: 104206-82-8); Bicyclopyrone (CAS NO: 352010-68-5); Tembotrione (CAS NO: 335104-84-2); Tefuryltrione (CAS NO: 473278-76-1); Benzobicyclon (CAS NO: 156963-66-5);
  • Isoxaazoles for example, isoxaflutole (CAS NO: 141112-29-0); isoxachlortole (CAS NO: 141112-06-3); clomazone (CAS NO: 81777-89-1);
  • EPSPS Enduvyl Shikimate Phosphate Synthase inhibitors: such as sulphosate, glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium;
  • PPO Protoporphyrinogen Oxidase inhibitors: divided into pyrimidinediones, diphenyl-ethers, phenylpyrazoles, N-phenylphthalimides, thiadiazoles, oxadiazoles, triazolinones, oxazolidinediones and other herbicides with different chemical structures.
  • the pyrimidinedione herbicide includes but is not limited to fluazifop-butyl (CAS NO: 134605-64-4), benzasulfuron (CAS NO: 372137-35-4), bispyribac (CAS NO: 158755-95-4), fluazifop-butyl (CAS NO: 1220411-29-9), [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]ethyl acetate (Epyrifenacil, ...
  • Diphenyl ether herbicides include but are not limited to fomesafen (CAS NO: 72178-02-0), oxyfluorfen (CAS NO: 42874-03-3), benifloxylate (CAS NO: 74070-46-5), fluazifop-butyl (CAS NO: 131086-42-5), lactofen (CAS NO: 77501-63-4), methoxyfenoxam (CAS NO: 32861-85-1), fensulfuron (CAS NO: 1836-77-7), fluazifop-butyl (CAS NO: 77501-90-7), and trifloxystrobin or sodium salt (acifluorfen, CAS NO: 50594-66-6 or 62476-59-9), cypermethrin (CAS NO: 42576-02-3), chlorfenapyr (CAS NO: 188634-90-4), fluoronitrofen (CAS NO: 13738-63-1), furyloxyfen (CAS NO: 80020-41-3), nitro
  • Phenylpyrazole herbicides include but are not limited to pyraclostrobin (CAS NO: 129630-19-9) and fluazolate (CAS NO: 174514-07-9);
  • N-phenylimide herbicides include but are not limited to fluazifop-butyl (CAS NO: 103361-09-7), fenoxaline (CAS NO: 142891-20-1), Flumipropyn (CAS NO: 84478-52-4) and flufenoxate (CAS NO: 87546-18-7);
  • Thiadiazole herbicides include but are not limited to fluthiacet-methyl (CAS NO: 117337-19-6), fluthiacet-methyl (CAS NO: 149253-65-6) and thiamethoxam (CAS NO: 123249-43-4);
  • Oxadiazole herbicides include but are not limited to oxadiazine (CAS NO: 39807-15-3) and oxadiazine (CAS NO: 19666-30-9);
  • Triazolinone herbicides include but are not limited to carfentrazone (CAS NO: 128621-72-7), carfentrazone ethyl (CAS NO: 128639-02-1), sulfentrazone (CAS NO: 122836-35-5), oxazolidinone (CAS NO: 68049-83-2) and bencarbazone (CAS NO: 173980-17-1);
  • Oxazolidinedione herbicides include but are not limited to oxadiazine (CAS NO: 110956-75-7);
  • herbicides include but are not limited to bispyribac (CAS NO: 158353-15-2), fluazifop-butyl (CAS NO: 188489-07-8), flufenacet (CAS NO: 190314-43-3), trifludimoxazin (CAS NO: 1258836-72-4), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 452098-9 2-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 452099-05-7), N-tetrahydrofurfuryl-3-(2-ch
  • ALS Acetolactate Synthase inhibitors
  • herbicides or their mixtures include but are not limited to the following herbicides or their mixtures:
  • Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl hyl), imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicos
  • Imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;
  • triazolopyrimidine herbicides and sulfonanilides such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyroxsulam, pyrimisulfan, and triafamone;
  • Pyrimidinylbenzoic acids such as bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac sodium, 4-[[[2-[(4,6-dimethoxybenzyl)benzoate 1-Methylethyl 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoate (CAS NO: 420138-41-6), 4-[[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoate (CAS NO: 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzylamine (CAS NO: 420138-01-8);
  • Sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl.
  • ACCase (Acetyl CoA Carboxylas) inhibitors such as fenthiaprop, alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, chloranil diclofop), diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl ), haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxy
  • GS (Glutamine Synthetase) inhibitors such as Bialaphos (bilanafos), Bialaphos-natrium, Glufosinate-ammonium, Glufosinate and glufosinate-P;
  • PDS Phytoene Desaturase inhibitors: such as flurochloridone, flurtamone, beflubutamid, norflurazon, fluridone, diflufenican, picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS NO: 180608-33-7);
  • DHPS Dihydropteroate Synthase inhibitors: such as Asulam;
  • DXPS Deoxy-D-Xyulose Phosphate Synthase inhibitors: such as Bixlozone and Clomazone;
  • HST Homogentisate Solanesyltransferase inhibitors: such as Cyclopyrimorate
  • SPS Solanesyl diphosphate synthase inhibitors: such as aclonifen;
  • Cellulose Synthesis Inhibitors such as Indaziflam, Triaziflam, Chlorthiamid, Dichlobenil, Isoxaben, Flupoxam, 1-cyclohexyl-5-pentafluorophenoxy-1 4 -[1,2,4,6]thiatriazine-3-ylamine (CAS NO: 175899-01-1), and azines disclosed in CN109688807A;
  • VLCFAS Very Long-Chain Fatty Acid Synthesis inhibitors: including but not limited to the following types:
  • Chloroacetamides such as acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor;
  • ⁇ -Oxyacetamides such as flufenacet and mefenacet
  • ⁇ -Thioacetamides such as anilofos and piperophos
  • Azolylcarboxamides such as cafenstrole, fentrazamide and ipfencarbazone;
  • Benzofurans such as Benfuresate and Ethofumesate
  • Isoxazolines such as fenoxasulfone and pyroxasulfone
  • Thiocarbamates such as Cycloate, Dimepiperate, S-ethyldipropylthiocarbamate (EPTC), Esprocarb, Molinate, Orbencarb, Prosulfocarb, Thiobencarb/Benthiocarb, Triallate, Vernolate, and isoxazoline compounds of formula II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9, and other isoxazoline compounds mentioned in patents such as WO 2006/024820, WO 2006/037945, WO 2007/071900 and WO 2007/096576.
  • Fatty acid thioesterase inhibitors such as Cinmethylin and Methiozolin;
  • Serine threonine protein phosphatase inhibitors such as Endothall
  • Lycopene cyclase inhibitors such as Amitrole.
  • Microtubule Assembly Inhibitors such as Benefin/benfluralin, Butralin, Dithiopyr, Thiazopyr, Ethalfluralin, Prodiamine, Butamifos, Oryzalin, Pendimethalin, Chlorthaldimethyl/DCPA, Trifluralin, Propyzamide/pronamide, Dinitramine (CAS NO: 29091-05-2);
  • Auxin Mimics such as 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-dichlorophenoxybutyric acid (2,4-DB), 3,4-dichlorophenoxybutyric acid (3,4-DB), 2,4-DEB (CAS NO: 94-83-7), 4-chlorophenoxyacetic acid (4-CPA), 4-CPP (CAS NO: 3307-39-9), cloprop (CAS NO: 101-10-0), clofop (CAS NO: 26129-32-8), Clomeprop, Dichlorprop, MCPA, MCPB, Mecoprop, Aminopyralid, Clopyralid, Aminocyclopyrachlor, Florpyrauxifen, Halauxifen, Quinclorac, Benazolin-ethyl, Picloram, Chloramben, Quinmerac, Fluroxypyr, Triclopyr, Dicamba;
  • D1 Serine 264 binders (and other non-histidine 215 binders): Ametryne, Atrazine, Cyanazine, Dimethametryn, Prometon, Prometryne, Propazine, Simazine, Terbuthylazine, Terbutryne, Chlorotoluron, Diuron, Fluometuron, Isoproturon, Linuron, Metobromuron, Methabenz thiazuron (CAS NO: 18691-97-9), Monuro n, Tebuthiuron, Hexazinone, Metamitron, Metribuzin, Bromacil, Lenacil, Terbacil, Chloridazon/pyrazon, Amicarbazone, Desmedipham, Phenmedipham, Chloranocryl/dicryl (CAS NO: 2164-09-2), Propanil, Chlorazine (CAS NO: 580-48-3), Cyprazine (CAS NO: 22936-86-3), Trietazine (CAS NO
  • D1 Histidine 215 binders such as Bromoxyl, Ioxynil, Pyridate, and Bentazon;
  • Auxin transport inhibitors such as diflufenzopyr (CAS NO: 109293-97-2) and naptalam;
  • PS l Electron Diversion such as Diquat and Paraquat
  • Inhibitors of Microtubule Organization such as Carbetamide (CAS NO: 16118-49-3), Barban (CAS NO: 101-27-9), Chlorpropham;
  • Uncouplers such as Dinoseb, 4,6-dinitro-o-cresol (DNOC);
  • Component A Another herbicide (Component B) mixed with one or more of the following compounds: benzylsulfuron-methyl (CAS No.: 83055-99-6), pyrazosulfuron-methyl (CAS No.: 93697-74-6), penoxsulam (CAS No.: 219714-96-2), thifensulfuron-methyl (CAS No.: 79277-27-3), fluazifop-butyl (CAS No.: 98967-40-9), Oxadiazon (CAS No. 19666-30-9), Oxadiazon propargyl (CAS No. 39807-15-3), Oxyfluorfen (CAS No. 42874-03-3), Bifenthion (CAS No.
  • Clomazone (CAS No.: 81777-89-1), clomazone-1 (CAS No.: 81777-95-9), oxazithromycin (CAS No.: 153197-14-9), cyhalofop-butyl (CAS No.: 122008-85-9), mefenacet (CAS No.: 256412-89-2), cyproconazole (CAS No.: 139001-49-3).
  • the herbicidal compounds as described herein which can be used in the context of the present invention are capable of forming geometrical isomers, for example E/Z isomers, it is possible to use both, pure isomers and mixtures thereof, in the compositions according to the invention.
  • the herbicidal compounds as described herein have one or more chiral centers (compounds of formula I At least three chiral centers C1*, C2* and C4*) are present and thus exist as enantiomers or diastereomers, it is possible to use both, pure enantiomers and diastereomers and mixtures thereof, in the compositions according to the invention.
  • herbicidal compounds as described herein have ionizable functional groups, they can also be used in the form of their agriculturally acceptable salts. Generally, salts of those cations and acid addition salts of those acids are suitable, whose cations and anions, respectively, have no adverse effect on the activity of the active compound.
  • Preferred cations are ions of alkali metals, preferably lithium, sodium and potassium, ions of alkaline earth metals, preferably calcium and magnesium, and ions of transition metals, preferably manganese, copper, zinc and iron, further ammonium and substituted ammonium, in which 1 to 4 hydrogen atoms are replaced by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy - C 1 -C 4 -alkyl, ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, t
  • the anions of the acid addition salts which can be used are mainly chloride, bromide, fluoride, iodide, hydrogen sulfate, methyl sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • the herbicidal compounds having a carboxyl group as described herein can be used in the form of the acid, in the form of the agriculturally suitable salts mentioned above or else in the form of agriculturally acceptable derivatives, for example as amides such as mono- and di-C 1 -C 6 -alkylamides or arylamides, as esters such as allyl esters, propargyl esters, C 1 -C 10 -alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl) methyl) esters and also as thioesters such as C 1 -C 10 -alkylthioesters.
  • amides such as mono- and di-C 1 -C 6 -alkylamides or arylamides
  • esters such as allyl esters, propargyl esters, C 1 -C 10 -alkyl esters, alkoxyalkyl esters, tefury
  • Preferred mono- and di-C 1 -C 6 -alkylamides are methyl and dimethylamides.
  • Preferred arylamides are, for example, N-anilide and 2-chloroanilide.
  • Preferred alkyl esters are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl or isooctyl (2-ethylhexyl) esters.
  • C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl esters are linear or branched C 1 -C 4 -alkoxyethyl esters, such as 2 -methoxyethyl ester, 2-ethoxyethyl ester, 2-butoxyethyl (butotyl) ester, 2-butoxypropyl ester or 3-butoxypropyl ester.
  • An example of a linear or branched C 1 -C 10 -alkyl thioester is ethyl thioester.
  • the commercially available preparations are diluted, if necessary, in the usual manner, for example with water in the case of wettable powders, emulsifiable concentrates, suspensions and granules suspended in water. Powders, granules for soil application or solutions for broadcasting and spraying generally do not require further dilution with inert substances before use.
  • the required amount of the compound of formula I varies with changing external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It can vary greatly
  • the range of activity may vary, for example between 0.001 and 1.0 kg ai/ha, or more, but preferably between 0.005 and 750 g ai/ha
  • Table AH is constructed in the same manner as Table 1 above, except that the chiral center (compound of Formula I) is replaced by The racemic compounds of the compounds in which the carbon atoms at C1*, C2* and C4* are chiral centers are replaced with (1R, 2R, 4R) configuration, (1S, 2R, 4R) configuration, (1R, 2S, 4R) configuration, (1R, 2R, 4S) configuration, (1S, 2S, 4R) configuration, (1R, 2S, 4S) configuration, (1S, 2R, 4S) configuration, and (1S, 2S, 4S) configuration, respectively, and in Table A, the entries under the "Serial Number” column heading are sequentially described as "1(1R, 2R, 4R)-79(1R, 2R, 4R)", and the other tables have the same structure.
  • “1(1R, 2R, 4R)” corresponds to the compound "1" in Table 1 having R configuration at C1* position, R configuration at C2* position
  • the raw materials can be purchased from the market or can be prepared by methods known in the literature or as shown in the detailed description. It will be appreciated by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described below, it can be easily replaced with other similar raw materials and conditions, and these modifications or variations of the preparation method of the present invention such as various isomers of the compound are included within 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, appropriate groups are protected during the reaction, etc.
  • the activity level standards for plant damage i.e., growth control rate are as follows:
  • Level 8 Growth control rate is greater than or equal to 90% and less than 100%
  • Level 7 Growth control rate is greater than or equal to 80% and less than 90%
  • Growth control rate is greater than or equal to 70% and less than 80%;
  • Level 5 Growth control rate is greater than or equal to 50% and less than 70%
  • Level 4 Growth control rate is greater than or equal to 30% and less than 50%;
  • Level 3 Growth control rate is greater than or equal to 20% and less than 30%;
  • Level 2 Growth control rate is greater than or equal to 10% and less than 20%;
  • the above growth control rates are fresh weight control rates.
  • Monocotyledonous and dicotyledonous weed seeds and main crop seeds were placed in a plastic pot filled with soil, and then covered with 0.5-2 cm of soil.
  • the tested compounds of the present invention were dissolved in acetone, and then Tween 80 was added, and diluted with a certain concentration of water to a solution, and sprayed immediately after sowing. After culturing in a greenhouse for 4 weeks after application, the experimental results were observed.
  • the compound dosages used were 3.75, 7.5, 15, 30, 60, and 120 g a.i./ha. Representative data are listed in Table 2.
  • N no data
  • Control compound B right According to compound C:
  • the compounds of the present invention have excellent effects, and their herbicidal activity is significantly higher than that of the control compounds A and B.
  • the control compound C while maintaining high herbicidal activity, the safety of crops is improved, that is, it has good selectivity, especially the use of the control compound C for closed weeding has unacceptable phytotoxicity to wheat.
  • the compounds of the present invention generally have good weed control effects.
  • the compounds of the present invention have extremely high activity against broad-leaved weeds and sedges resistant to ALS inhibitors, such as Dalbergia vaginalis, Cyperus difformis, Polygonum syringae, Lolium perenne, Alopecuroides, and Glechoma longituba, and have very good commercial value.
  • paddy field soil was filled into 1/1,000,000 hectare pots and leveled to a water depth of 2-3 cm.
  • rice japonica rice
  • rice at the 3-leaf stage was transplanted at a transplanting depth of 2-3 cm.
  • the compound of the present invention was treated in the same manner as above on the 3rd day after transplantation.
  • the dosage of the compound used in the above experiment was 3.75, 7.5, 15, 30, 60, and 120 g a.i./ha.
  • the growth status of weeds on the 14th day after treatment with the agent and the growth status of rice on the 7th day after treatment with the agent were observed with the naked eye, and the effect was evaluated according to the above activity standard level. Representative data are listed in Table 3.
  • Echinochloa crusgalli, Echinochloa oryzae, and Duck tongue grass were collected from Heilongjiang, China, and were tested to be resistant to conventional doses of pyrazosulfuron-methyl.
  • the compounds of the present invention have better herbicidal activity and/or rice safety than the reference compounds A, B and C.
  • the required active ingredient B is purchased from a reagent company or synthesized by a known method.
  • the original drug uses acetone as solvent and is diluted with a 0.1% emulsifier Tween-80 aqueous solution, and is diluted before use.
  • Weeds were cultivated in potted plants using 180 ⁇ 140 mm plastic nutrient pots placed in enamel trays filled with air-dried and sieved surface soil (4/5 of the soil) collected from farmland. The soil moisture was initially controlled at 20%. Weed seeds with full and uniform grains were selected, soaked in 25°C warm water for 6 hours, and germinated in a 28°C biochemical incubator (dark). The weed seeds that had just turned white were evenly placed on the soil surface and covered with 0.5-1 cm of soil according to the seed size.
  • the culture was carried out in a controlled sunlight greenhouse at a temperature of 20-30°C, natural light, and a relative humidity of 57%-72%.
  • Each treatment was repeated 4 times, with 4 pots in each treatment and 20 weed seeds sown in each pot.
  • the drug was used once in the experiment. When the weeds reached 1-2 leaves, thinning was performed, and 10 plants were kept for each treatment.
  • the test soil was quantitatively filled to 3/4 of the pot, and then watered from the bottom of the pot to make the soil completely wet to saturation.
  • the weed seeds for the test were germinated until they turned white, and then evenly and quantitatively sown on the surface, covered with 0.5-1cm of soil according to the seed size, and kept ready for use 72 hours after sowing.
  • Each treatment was repeated 4 times, with 4 pots per treatment and 20 weed seeds sown in each pot.
  • the absolute number survey method was used. The whole seedlings of surviving weeds were cut off along the soil surface with a blade and the fresh weight of the weeds was weighed with an analytical balance. For dead weeds, the fresh weight was counted as zero.
  • the survey was conducted 21 days after treatment, for a total of 1 survey.
  • E measured inhibition rate
  • E-E0 value is greater than 10%, it is a synergistic effect, less than -10% is an antagonistic effect, and between -10% and 10% is an additive effect.
  • the best ratio is determined based on factors such as the actual prevention effect, the characteristics of the herbicide, and the balance of the formula.
  • X is the fresh weight inhibition rate when the dosage of active ingredient A is P
  • Y is the fresh weight inhibition rate when the dosage of active ingredient B is Q.

Landscapes

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

Abstract

本发明属于农药技术领域，具体涉及一种氧杂双环烷类化合物及其制备方法、除草组合物和应用。所述化合物如通式I所示：其中，A、B分别独立地代表烷基；X、Y、Z分别独立地代表氢、硝基、卤素等。所述化合物在维持相当甚至更好的除草活性的基础上具有更优异的作物安全性，能够在作物上建立更好的选择性。

Description

一种氧杂双环烷类化合物及其制备方法、除草组合物和应用 技术领域
本发明属于农药技术领域，具体涉及一种氧杂双环烷类化合物及其制备方法、除草组合物和应用。
背景技术
杂草的防治是实现高效农业过程中一个至关重要的环节，尽管市场上的除草剂种类多样，比如专利CN1045786A等公开了一类氧杂双环烷化合物除草剂在水稻田中防除有害植物生长的方法。然而，这些已知化合物对有害植物的除草性能和对作物的选择性并不完全令人满意。且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。
发明内容
为解决现有技术中存在的上述问题，本发明提供了一种氧杂双环烷类化合物及其制备方法、除草组合物和应用，所述化合物在维持相当甚至更好的除草活性的基础上具有更优异的作物安全性，能够在作物上建立更好的选择性。
本发明采用的技术方案如下：
一种氧杂双环烷类化合物，如通式I所示：
其中，A、B分别独立地代表烷基；
X、Y、Z分别独立地代表氢、硝基、卤素、氰基、甲酰基、硫氰基、巯基、OR1、COR1、COOR1、OCOR1、OCOOR1、NR3SO2R2、OSO2R2、S(O)mR2、NR3COR1、NR3COOR1、C(O)NR3OR1、SO2OR1、C(O)NR4R5、NR3C(O)NR4R5、OC(O)NR4R5、SO2NR4R5、C(S)R1、C(S)OR1、C(S)SR2、C(O)SR2、SC(O)R1、SC(S)R1、OC(S)R1、-烷基-C(S)R1、-烷基-C(S)OR1、-烷基-C(O)SR1、-烷基-C(S)SR1、-烷基-SC(O)R1、-烷基-OC(S)R1、-烷基-SC(S)R1、-O-烷基-NR4R5、-S-烷基-NR4R5、-烷基-O-烷基-NR4R5、-烷基-S-烷基-NR4R5、-烷基-(C＝S)n-NR4R5、-NH-烷基-NR4R5、-烷基-OR1、-烷基-COR1、-烷基-CO2R1、-烷基-OCOR1、-烷基-NR3COR1、-烷基-SO2OR1、-烷基-NR3SO2R2、-烷基-OSO2R2、-烷基-S(O)mR2、-烷基-CONR4R5、-烷基-SO2NR4R5、NR4R5、P(O)(OR6)2、CH2P(O)(OR6)2、-烷基-CN、烷基、烯基、炔基、环烷基、环烷基烷基、环烯基、环烯基烷基、杂环基、杂环基烷基、芳基或芳基烷基，其中，所述“烷基”、“烯基”或“炔基”分别独立地是未取代的或被卤素所取代的，所述“环烷基”、“环烷基烷基”、“环烯基”、“环烯基烷基”、“杂环基”、“杂环基烷基”、“芳基”或“芳基烷基”分别独立地是未取代的 或被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-烷基-(CO)OR10中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
R1、R3、R4、R5分别独立地代表氢、芳基、芳基烷基、杂环基、杂环基烷基、烷基、卤代烷基、烯基、卤代烯基、炔基、卤代炔基、环烷基、卤代环烷基、烷氧基烷基、环烷基烷基，其中后10个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和烷氧基烷氧基羰基的取代基取代；
R2为芳基、芳基烷基、杂环基、杂环基烷基、烷基、烯基、炔基、环烷基、环烷基烷基，其中后5个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和烷氧基烷氧基羰基的基团取代；
R6为甲基或乙基；
R7、R8分别独立地代表为氢、烷基、烯基或炔基；
R9为烷基、烯基或炔基；
R10分别独立地代表氢，烷基，卤代烷基，苯基或被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基；
m代表0、1或2，n代表0或1，s代表0、1、2、3、4或5。
在一个具体实施方式中，A、B分别独立地代表C1-C8烷基；
X、Y、Z分别独立地代表氢、硝基、卤素、氰基、甲酰基、硫氰基、巯基、OR1、COR1、COOR1、OCOR1、OCOOR1、NR3SO2R2、OSO2R2、S(O)mR2、NR3COR1、NR3COOR1、C(O)NR3OR1、SO2OR1、C(O)NR4R5、NR3C(O)NR4R5、OC(O)NR4R5、SO2NR4R5、C(S)R1、C(S)OR1、C(S)SR2、C(O)SR2、SC(O)R1、SC(S)R1、OC(S)R1、-(C1-C8烷基)-C(S)R1、-(C1-C8烷基)-C(S)OR1、-(C1-C8烷基)-C(O)SR1、-(C1-C8烷基)-C(S)SR1、-(C1-C8烷基)-SC(O)R1、-(C1-C8烷基)-OC(S)R1、-(C1-C8烷基)-SC(S)R1、-O-(C1-C8烷基)-NR4R5、-S-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-O-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-S-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-(C＝S)n-NR4R5、-NH-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-OR1、-(C1-C8烷基)-COR1、-(C1-C8烷基)-CO2R1、-(C1-C8烷基)-OCOR1、-(C1-C8烷基)-NR3COR1、-(C1-C8烷基)-SO2OR1、-(C1-C8烷基)-NR3SO2R2、-(C1-C8烷基)-OSO2R2、-(C1-C8烷基)-S(O)mR2、-(C1-C8烷基)-CONR4R5、-(C1-C8烷基)-SO2NR4R5、NR4R5、P(O)(OR6)2、CH2P(O)(OR6)2、-(C1-C8烷基)-CN、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、C3-C8环烯基、C3-C8环烯基C1-C8烷基、杂环基、杂环基C1-C8烷基、芳基或芳基C1-C8烷基，其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”分别独立地是未取代的或被卤素所取代的，所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“C3-C8环烯基”、“C3-C8环烯基 C1-C8烷基”、“杂环基”、“杂环基C1-C8烷基”、“芳基”或“芳基C1-C8烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8烷基)-(CO)OR10中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
R1、R3、R4、R5分别独立地代表氢、芳基、芳基C1-C8烷基、杂环基、杂环基C1-C8烷基、C1-C8烷基、卤代C1-C8烷基、C2-C8烯基、卤代C2-C8烯基、C2-C8炔基、卤代C2-C8炔基、C3-C8环烷基、卤代C3-C8环烷基、C1-C8烷氧基C1-C8烷基、C3-C8环烷基C1-C8烷基，其中后10个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C8烷氧基C1-C8烷氧基羰基的取代基取代；
R2为芳基、芳基C1-C8烷基、杂环基、杂环基C1-C8烷基、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，其中后5个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C8烷氧基C1-C8烷氧基羰基的基团取代；
R6为甲基或乙基；
R7、R8分别独立地代表为氢、C1-C8烷基、C2-C8烯基或C2-C8炔基；
R9为C1-C8烷基、C2-C8烯基或C2-C8炔基；
R10分别独立地代表氢，C1-C8烷基，卤代C1-C8烷基，苯基或被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基；
m代表0、1或2，n代表0或1，s代表0、1、2、3、4或5。
在另一个具体实施方式中，A、B分别独立地代表C1-C6烷基；优选地，A代表甲基或乙基；B代表甲基、乙基或异丙基；
X、Y、Z分别独立地代表氢、硝基、卤素、氰基、甲酰基、硫氰基、巯基、OR1、COR1、COOR1、OCOR1、OCOOR1、NR3SO2R2、OSO2R2、S(O)mR2、NR3COR1、NR3COOR1、C(O)NR3OR1、SO2OR1、C(O)NR4R5、NR3C(O)NR4R5、OC(O)NR4R5、SO2NR4R5、C(S)R1、C(S)OR1、C(S)SR2、C(O)SR2、SC(O)R1、SC(S)R1、OC(S)R1、-(C1-C6烷基)-C(S)R1、-(C1-C6烷基)-C(S)OR1、-(C1-C6烷基)-C(O)SR1、-(C1-C6烷基)-C(S)SR1、-(C1-C6烷基)-SC(O)R1、-(C1-C6烷基)-OC(S)R1、-(C1-C6烷基)-SC(S)R1、-O-(C1-C6烷基)-NR4R5、-S-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-O-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-S-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-(C＝S)n-NR4R5、-NH-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-OR1、-(C1-C6烷基)-COR1、-(C1-C6烷基)-CO2R1、-(C1-C6烷基)-OCOR1、-(C1-C6烷基)-NR3COR1、-(C1-C6烷基)-SO2OR1、-(C1-C6烷基)-NR3SO2R2、-(C1-C6烷基)-OSO2R2、-(C1-C6烷基)-S(O)mR2、-(C1-C6烷基)-CONR4R5、-(C1-C6烷基)-SO2NR4R5、NR4R5、P(O)(OR6)2、CH2P(O)(OR6)2、-(C1-C6烷基)-CN、 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、C3-C6环烯基、C3-C6环烯基C1-C6烷基、杂环基、杂环基C1-C6烷基、芳基或芳基C1-C6烷基，其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”分别独立地是未取代的或被卤素所取代的，所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“C3-C6环烯基”、“C3-C6环烯基C1-C6烷基”、“杂环基”、“杂环基C1-C6烷基”、“芳基”或“芳基C1-C6烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6烷基)-(CO)OR10中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
R1、R3、R4、R5分别独立地代表氢、芳基、芳基C1-C6烷基、杂环基、杂环基C1-C6烷基、C1-C6烷基、卤代C1-C6烷基、C2-C6烯基、卤代C2-C6烯基、C2-C6炔基、卤代C2-C6炔基、C3-C6环烷基、卤代C3-C6环烷基、C1-C6烷氧基C1-C6烷基、C3-C6环烷基C1-C6烷基，其中后10个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C6烷氧基C1-C6烷氧基羰基的取代基取代；
R2为芳基、芳基C1-C6烷基、杂环基、杂环基C1-C6烷基、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，其中后5个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C6烷氧基C1-C6烷氧基羰基的基团取代；
R6为甲基或乙基；
R7、R8分别独立地代表为氢、C1-C6烷基、C2-C6烯基或C2-C6炔基；
R9为C1-C6烷基、C2-C6烯基或C2-C6炔基；
R10分别独立地代表氢，C1-C6烷基，卤代C1-C6烷基，苯基或被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的至少一个基团所取代的苯基；
m代表0、1或2，n代表0或1，s代表0、1、2、3、4或5。
在上述通式所示化合物的定义和以下所有结构式中，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：具有多于两个碳原子的烷基基团可为直链或支链的。如复合词“-烷基-C(S)R1”中烷基可为-CH2-、-CH2CH2-、-CH(CH3)-、-C(CH3)2-等。烷基基团为，例如，C1烷基-甲基；C2烷基-乙基；C3烷基-丙基如正丙基或异丙基；C4烷基-丁基如正丁基、异丁基、叔丁基或2-丁基；C5烷基-戊基如正戊基；C6烷基-己基如正己基、异己基和1,3-二甲基丁基。类似地，烯基是例如乙烯基、烯丙基、1-甲基丙-2-烯-1-基、2-甲基丙-2-烯-1-基、丁-2-烯-1-基、丁-3-烯-1-基、1-甲基丁-3-烯-1-基和1-甲基丁-2-烯-1-基。炔基是例如乙炔基、炔丙基、丁-2-炔-1-基、丁-3-炔-1-基、1-甲基丁-3-炔-1-基。多重键可以在每个不饱和基团的任何位置。环烷基是具有例如三至六个碳原子的碳环饱和环体系，例如环丙基、环丁基、环戊基或环己基。类似地，环烯基是具有例如三至六个碳环成员的单环烯基，例如环丙烯基、 环丁烯基、环戊烯基和环己烯基，其中双键可以在任何位置。卤素为氟、氯、溴或碘。
除非有特别说明的，本发明所述“芳基”包括但不限于苯基、萘基、 所述“杂环基”不仅包括但不限于饱和或不饱和的非芳族环状基团 等，还包括但不限于杂芳基，即含有例如3至6个环原子且还任选地有苯并环稠合的芳族环状基团，所述环原子中的1至4个(例如1、2、3或4个)杂原子选自氧、氮和硫，例如
如果一个基团被基团所取代，则这应理解为意指该基团被一个或多个相同或不同的选自所提及的那些基团的基团取代。另外，相同或不同取代基中含有的相同或不同的取代字符均独立地选择，可相同也可不同。这同样适用于由不同原子和单元形成的环体系。同时，权利要求的范围将排除那些为本领域技术人员知晓的在标准条件下化学不稳定的化合物。
另外，除非特别限定地，本发明所述“至少一个基团所取代的”是指被如1、2、3、4或5个基团所取代；未标注具体连接位置的基团(包括杂环基、芳基等)，可在任意位置连接， 包括与C或N相连接的位置；如果其是被取代的，取代基同样可在任何位置取代，只要符合化合键连接规则。如被1个甲基所取代的杂芳基可代表等。
根据取代基的性质和其被连接的方式，通式I的化合物及其衍生物可作为立体异构体存在。立体异构体可通过常规分离方法、例如通过色谱分离法从在制备中获得的混合物中获得。同样可通过使用立体选择性反应且使用光学活性的起始原料和/或助剂来选择性地制备立体异构体。本发明还涉及包含在通式I中但没有具体定义的所有立体异构体及其混合物。
本发明还提供所述氧杂双环烷类化合物的制备方法，包括以下步骤：
将通式Ⅱ所示的化合物和通式Ⅲ所示的化合物进行取代反应，制得通式Ⅰ所述的化合物；其化学反应方程式如下：
其中，Hal代表卤素，其他取代基A、B、X、Y、Z的定义如前所示；
优选地，所述反应在NaH或无水碳酸盐(如钾盐、钠盐)和溶剂的存在下进行；更优选地，所述溶剂选自DMF、二甲基乙酰胺、THF、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种。
本发明所述化合物可参照专利CN1045786A等记载的相关方法制备。
本发明还提供一种除草剂组合物，其包括(i)除草有效量的所述的氧杂双环烷类化合物中的至少一种。
任选地，所述除草剂组合物还包括(ii)一种或多种除草有效量的另外的除草剂和/或安全剂。
优选地，所述除草剂组合物还包括(iii)农业化学上可接受的制剂助剂。
本发明还提供一种防治不希望的植物的方法，包括将除草有效量的所述的氧杂双环烷类化合物中的至少一种或所述的除草剂组合物施用至植物或者其场所或施用至土壤或水体以防治不希望的植物出苗或生长。
优选地，所述不希望的植物包括除草剂抗性或耐受性杂草物种。
本发明还提供所述的氧杂双环烷类化合物中的至少一种或所述的除草剂组合物在控制不希望的植物上的用途。
优选地，将所述的氧杂双环烷类化合物用于防除有用作物中的杂草。
更优选地，所述有用作物包括转基因作物或者基因组编辑技术处理过的作物，所述杂草 包括除草剂抗性或耐受性杂草物种。
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。
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。
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，例如花生、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。
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。
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。
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：
-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)；
-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)；
-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)；
-具有改进的脂肪酸成份的转基因作物植物(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。
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。
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。
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)。
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。
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。
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。
可以使用一般的制剂来应用本发明的化合物，可使用可湿性粉剂、浓缩乳剂、可喷洒的溶液、粉末或颗粒。这样本发明也提供了包括式I化合物的除草剂组合物。根据通常的生物学和/或化学的物理参数，可以用多种方式配制式I化合物。适合的制剂选择实例为：可湿性 粉剂(WP)、水溶性的粉末(SP)、水溶性的浓缩物、浓缩乳剂(EC)、例如油在水中分散和水在油中分散的乳剂(EW)、可喷洒溶液、悬浮剂浓缩物(SC)、可分散油悬浮剂(OD)、以油或水为稀释剂的悬浮液、可混溶油的溶液、粉末(DP)、胶囊悬浮液(CS)、包核
(seeddressing)组合物、用于撒播和土壤施药的颗粒、喷射颗粒、涂覆颗粒和吸收颗粒，水中可分散的颗粒(WG)、水溶性的颗粒(SG)、ULV(超低容量)配方、微囊和蜡制品。这些单个的制剂类型为已知的，在下述文献中有描述，例如Winnacker-Küchler，“Chemische Techonologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986；Wade van Valkenburg，“Pesticide Formulations”，Marcel Dekker，N.Y.，1973；K.Martens，“Spray Drying”手册，第3版1979，G.Goodwin Ltd.London。
必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂同样为已知的，并在下述文件中描述，例如Watkins的“粉末稀释剂杀虫剂和载体手册”，第二版，Darland书Caldwell N.J.；H.v.01phen“粘土胶体化学的入门”，第二版，J.Wiley和Sons，N.Y.；C.Marsden的“溶剂指南”第二版，Interscience，N.Y.1963；McCutcheon的“洗涤剂和乳化剂年报”，MC发行公司，Ridgewood N.J.；Sisley和Wood，“表面活性剂百科全书”，化学出版公司，N.Y.1964；的[环氧乙烷加成物表面活性剂]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-Küchler的“Chemische Technologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986。
可湿性粉剂能均匀地可分散在水中，除了活性物质，还包括稀释剂或惰性物质、离子和非离子型表面活性剂(润湿剂、分散剂)，例如聚乙氧基烷基酚、聚乙氧基脂肪醇、聚氧乙基脂肪族胺、脂肪醇聚二醇醚硫酸盐、烷基磺酸盐、烷基苯基磺酸盐、木质磺酸钠、2,2’-二萘甲烷-6,6’-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为了制备可湿性粉剂，将除草剂的活性物质细磨，例如使用常用的仪器，如用锤磨机、风扇磨碎机和喷气式磨碎机，同时或顺序混入助剂。
将活性物质溶解在有机溶剂中制备浓缩乳剂，溶剂例如丁醇、环己酮、二甲基甲酰胺、二甲苯或较高沸点的芳族化合物或碳氢化合物或溶剂的混合物，并再加入一种或多种离子的和/或非离子型表面活性剂(乳化剂)。可以使用的乳化剂的例子为例如十二烷基苯磺酸钙的烷基芳基磺酸钙，或非离子乳化剂，例如脂肪酸聚二醇酯、烷基芳香基聚二醇醚、脂肪醇聚二醇醚、氧化丙烯-环氧乙烷缩合产物、烷基聚醚、例如山梨糖醇酐脂肪酸酯的山梨聚糖酯，或例如聚氧化乙烯山梨糖醇酐脂肪酯的聚氧化乙烯山梨聚糖酯。
将活性物质和细碎的固态物质研磨得到粉末，固态物质例如滑石、如高岭土、皂土和叶蜡石的天然粘土、或硅藻土。以水或油为基底的悬浮液可以通过下述方法制备，例如利用商业上通用的玻珠研磨机进行湿磨，加入或不加入上述另一个制剂类型的表面活性剂。
制备例如水包油乳化剂(EW)的乳剂，可以使用含水的有机溶剂，使用搅拌器、胶体研磨器和/或静态混合器，如果需要，加入如上所述另一个制剂类型的表面活性剂。
用下述方法制备颗粒剂，将活性物质喷到吸附物上，使用惰性物料颗粒化，或将活性物质浓缩到例如沙、高岭石载体的表面，通过粘合剂将惰性物料粒化，粘合剂例如聚乙烯醇、聚丙烯酸钠或矿物油。可以用制备肥料颗粒剂的方法将合适的活性物质粒化，如果需要可以 混有肥料。使用通常的方法制备水悬浮颗粒剂，例如喷洒-干燥，流化床造粒、磨盘造粒、使用高速混合机混合，并在无固体惰性物料的情况下挤压。
关于使用磨盘、流化床、挤压机和喷涂颗粒剂的制备方法，参见下述工艺，例如“Spray Drying手册”第三版1979，G.Goodwin有限公司，伦敦；J.E.Browning，“Agglomeration”，化学和工程1967，147ff页；“Perry’s化学的工程师手册”，第五版，McGraw-Hill，纽约1973，8-57页。如果要知道关于作物保护产品的制剂，参见例如，G.C.Klingman,“Weed Control as a Science”，John Wiley和Sons公司，纽约，1961 81-96页和J.D.Freyer，S.A.Evans“杂草防除手册”，第五版，Blackwell Scientific Rublications，牛津大学1968，101-103页。
农用化学品制剂通常包含按重量计0.1到99％，特别是0.1到95％的活性物质式I。可湿性粉剂中活性物质的浓度为，按重量计例如从大约10到99％，通常的制剂组分构成按重量计剩余量到100％。活性物质在浓缩乳剂中的浓度按重量计可以为大约1到90％，优选5到80％。粉末制剂包含按重量计1到30％的活性物质，通常优选按重量计5到20％的活性物质，然而可喷洒的溶液包含按重量计大约0.05到80％，优选2到50％的活性物质。关于水悬浮颗粒剂中活性物质的含量，主要根据活性物质为液体还是固态，和造粒时使用的助剂、填料等等。水悬浮颗粒剂中活性物质的含量例如按重量计在1到95％之间，优选按重量计在10到80％之间。
另外所述的活性物质的制剂可以包括增粘剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂和通常在所有情况下都常用的pH和粘度调节剂。
以这些制剂为基础，也可能和其他杀虫剂活性物质例如杀虫剂、杀螨剂、除草剂和杀菌剂混合，也可以和安全剂、肥料和/或植物生长调节剂混合，混合方式可以为预先混合好的或灌装混合。
在混配制剂或桶混制剂中，可以和本发明的式I化合物混合的合适的活性物质为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的除草剂活性物质可以和化合物1混合(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：
(1)HPPD(Hydroxyphenyl Pyruvate Dioxygenase)抑制剂类：包括但不限于下述类型，
1)三酮类，例如，磺草酮(Sulcotrione，CAS NO：99105-77-8)；硝磺草酮(Mesotrione，CAS NO：104206-82-8)；氟吡草酮(bicyclopyrone，CAS NO：352010-68-5)；环磺酮(tembotrione，CAS NO：335104-84-2)；呋喃磺草酮(tefuryltrione，CAS NO：473278-76-1)；双环磺草酮(Benzobicyclon，CAS NO：156963-66-5)；
2)二酮腈类，例如，2-氰基-3-环丙基-1-(2-甲基磺酰基-4-三氟甲基苯基)丙-1，3-二酮(CAS NO：143701-75-1)；2-氰基-3-环丙基-1-(2-甲基磺酰基-3,4-二氯苯基)丙-1，3-二酮(CAS NO：212829-55-5)；2-氰基-1-[4-(甲基磺酰基)-2-三氟甲基苯基]-3-(1-甲基环丙基)丙-1,3-二酮(CAS NO：143659-52-3)；
3)异噁唑类，例如，异噁氟草(isoxaflutole，CAS NO：141112-29-0)；异噁氯草酮(isoxachlortole，CAS NO：141112-06-3)；异恶草酮(clomazone，CAS NO：81777-89-1)；
4)吡唑类，例如，苯唑草酮(topramezone，CAS NO：210631-68-8)；磺酰草吡唑(pyrasulfotole，CAS NO：365400-11-9)；苄草唑(pyrazoxyfen，CAS NO：71561-11-0)；吡唑特(pyrazolate，CAS NO：58011-68-0)；吡草酮(benzofenap，CAS NO：82692-44-2)；双唑草酮(CAS NO：1622908-18-2)；Tolpyralate(CAS NO：1101132-67-5)；苯唑氟草酮(CAS NO：1992017-55-6)；环吡氟草酮(CAS NO：1855929-45-1)；三唑磺草酮(CAS NO：1911613-97-2)；
5)二苯酮类；
6)其他类：lancotrione(CAS NO：1486617-21-3)；fenquinotrione(CAS NO：1342891-70-6)；fufengcao’an(CAS NO：2421252-30-2)；
以及专利CN105264069A提及的那些。
(2)EPSPS(Enolpyruvyl Shikimate Phosphate Synthase)抑制剂类：如草硫膦(sulphosate)，草甘膦(Glyphosate)，草甘膦异丙胺盐(glyphosate-isopropylammonium)和草甘膦三甲基硫盐(glyphosate-trimesium)；
(3)PPO(Protoporphyrinogen Oxidase)抑制剂类：分为嘧啶二酮(pyrimidinediones)、二苯醚(diphenyl-ethers)、苯基吡唑(phenylpyrazoles)、N-苯基酰亚胺(N-phenylphthalimides)、噻二唑(thiadiazoles)、噁二唑(oxadiazoles)、三唑啉酮(triazolinones)、噁唑烷二酮(oxazolidinediones)和其他不同化学结构的除草剂。
在一个示例性实施例中，嘧啶二酮类除草剂包括但不限于氟丙嘧草酯(CAS NO：134605-64-4)、苯嘧磺草胺(CAS NO：372137-35-4)、双苯嘧草酮(CAS NO：158755-95-4)、氟嘧硫草酯(tiafenacil，CAS NO：1220411-29-9)、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶基氧基]乙酸乙酯(Epyrifenacil，CAS NO：353292-31-6)、1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]噁嗪-6-基)-1H-嘧啶-2,4-二酮(CAS NO：1304113-05-0)、3-[7-氯-5-氟-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)-1H-嘧啶-2,4-二酮(CAS NO：212754-02-4)、flupropacil(CAS NO：120890-70-2)、CN105753853A中公开的含异恶唑啉的尿嘧啶类(如化合物WO2017/202768中公开的尿嘧啶吡啶以及WO2018/019842中公开的尿嘧啶类；
二苯醚类除草剂包括但不限于氟磺胺草醚(fomesafen，CAS NO：72178-02-0)、乙氧氟草醚(CAS NO：42874-03-3)、苯草醚(CAS NO：74070-46-5)、氟乳醚(CAS NO：131086-42-5)、乳氟禾草灵(CAS NO：77501-63-4)、甲氧除草醚(CAS NO：32861-85-1)、草枯醚(CAS NO：1836-77-7)、乙羧氟草醚(CAS NO：77501-90-7)、三氟羧草醚或钠盐(acifluorfen，CAS NO：50594-66-6或62476-59-9)、甲羧除草醚(CAS NO：42576-02-3)、氯氟草醚(CAS NO：188634-90-4)、fluoronitrofen(CAS NO：13738-63-1)、furyloxyfen(CAS NO：80020-41-3)、nitrofluorfen(CAS NO：42874-01-1)和halosafen(CAS NO：77227-69-1)；
苯基吡唑类除草剂包括但不限于吡草醚(CAS NO：129630-19-9)和异丙吡草酯(fluazolate，CAS NO：174514-07-9)；
N-苯基酰亚胺类除草剂包括不限于丙炔氟草胺(CAS NO：103361-09-7)、吲哚酮草酯(CAS NO：142891-20-1)、Flumipropyn(CAS NO：84478-52-4)和氟烯草酸(CAS NO：87546-18-7)；
噻二唑类除草剂包括不限于嗪草酸甲酯(fluthiacet-methyl，CAS NO：117337-19-6)、嗪草酸(CAS NO：149253-65-6)和噻二唑草胺(CAS NO：123249-43-4)；
噁二唑类除草剂包括不限于丙炔噁草酮(CAS NO：39807-15-3)和噁草酮(CAS NO：19666-30-9)；
三唑啉酮类除草剂包括不限于唑草酮(carfentrazone，CAS NO：128621-72-7)、唑草酮乙酯(carfentrazone ethyl，CAS NO：128639-02-1)、甲磺草胺(sulfentrazone，CAS NO：122836-35-5)、唑啶草酮(CAS NO：68049-83-2)和酰苯草酮(bencarbazone，CAS NO：173980-17-1)；
噁唑烷二酮类除草剂包括不限于环戊噁草酮(CAS NO：110956-75-7)；
其他除草剂包括不限于双唑草腈(CAS NO：158353-15-2)、氟哒嗪草酯(CAS NO：188489-07-8)、氟唑草胺(CAS NO：190314-43-3)、三氟草嗪(trifludimoxazin，CAS NO：1258836-72-4)、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：452100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]噁嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷-2，4-二酮(CAS NO：451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]噁嗪-6-基)-4,5,6,7-四氢-异吲哚-1,3-二酮(CAS NO：1300118-96-0)、(E)-4-[2-氯-5-[4-氯-5-(二氟甲氧基)-1H-甲基-吡唑-3-基]-4-氟-苯氧基]-3-甲氧基-丁-2-烯酸甲酯(CAS NO：948893-00-3)、WO2016/120116中公开的苯吡啶类、EP09163242.2中公开的苯并噁嗪酮衍生物以及CN113105405A中公开的羧酸衍生物取代的亚氨基芳基化合物；
(4)ALS(Acetolactate Synthase)抑制剂类包括但不限于如下除草剂或其混合物：
磺酰脲类如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、苄嘧黄隆甲酯(bensulfuron-methyl)、氯嘧黄隆(chlorimuron)、氯嘧黄隆乙酯(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯磺隆(ethametsulfuron)、胺苯磺隆甲酯(ethametsulfuron-methyl)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、氟啶黄隆甲酯钠盐(flupyrsulfuron-methyl-sodium)、甲酰胺黄隆(foramsulfuron)、氯吡嘧磺隆(halosulfuron)、氯吡嘧磺隆甲酯(halosulfuron-methyl)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、碘黄隆甲酯钠盐(iodosulfuron-methyl-sodium)、iofensulfuron、iofensulfuron钠盐、甲磺胺黄隆(mesosulfuron)、嗪吡嘧磺隆(metazosulfuron)、甲磺隆(metsulfuron)、甲磺隆甲酯(metsulfuron-methyl)、烟黄隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧黄隆(oxasulfuron)、氟嘧磺隆(primisulfuron)、氟嘧磺隆甲酯(primisulfuron-methyl)、丙嗪嘧磺隆(propyrisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、吡嘧黄隆乙酯(pyrazosulfuron-ethyl)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、嘧黄隆甲酯 (sulfometuron-methyl)、乙黄黄隆(sulfosulfuron)、噻磺隆(thifensulfuron)、噻磺隆甲酯(thifensulfuron-methyl)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、苯黄隆甲酯(tribenuron-methyl)、三氟啶黄隆(trifloxysulfuron)、Trifloxysulfuron-Na(三氟啶黄隆-钠盐)、氟胺磺隆(triflusulfuron)、氟胺磺隆甲酯(triflusulfuron-methyl)和三氟甲磺隆(tritosulfuron)；
咪唑啉酮类如咪草酯(imazamethabenz)、咪草甲酯(imazamethabenz-methyl)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)和咪草烟(imazethapyr)；
三唑并嘧啶除草剂和磺酰苯胺类如氯酯磺草胺(cloransulam)、氯酯磺草胺甲酯(cloransulam-methyl)、唑嘧磺胺(diclosulam)、氟唑啶草(flumetsulam)、双氟磺草胺(florasulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、吡唑磺草胺(pyroxsulam)、pyrimisulfan和氟酮磺草胺(triafamone)；
嘧啶基苯甲酸类如双草醚(bispyribac)、双草醚钠盐(bispyribac-sodium)、嘧啶肟草醚(pyribenzoxim)、pyriftalid、pyriminobac、嘧草醚(pyriminobac-methyl)、嘧硫苯甲酸(pyrithiobac)、嘧硫苯甲酸(pyrithiobac)钠盐，4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧]苯基]甲基]氨基]-苯甲酸-1-甲基乙酯(CAS NO：420138-41-6)、4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧]苯基]甲基]氨基]-苯甲酸丙酯(CAS NO：420138-40-5)、N-(4-溴苯基)-2-[(4,6-二甲氧基-2-嘧啶基)氧]苯甲胺(CAS NO：420138-01-8)；
磺酰氨基羰基-三唑啉酮类除草剂如氟酮磺隆(flucarbazone)、氟酮磺隆钠盐(flucarbazone-sodium)、丙苯磺隆(propoxycarbazone)、丙苯磺隆钠盐(propoxycarbazone-sodium)、噻酮磺隆(thiencarbazone)和噻酮磺隆甲酯(thiencarbazone-methyl)。
(5)ACCase(Acetyl CoA Carboxylas)抑制剂类：如噻唑禾草灵(Fenthiaprop)、禾草灭(alloxydim)、禾草灭钠盐(alloxydim-sodium)、丁氧环酮(butroxydim)、烯草酮(clethodim)、炔草酸(clodinafop)、炔草酸炔丙酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop)、氰氟草丁酯(cyhalofop-butyl)、氯甲草(diclofop)、氯甲草甲酯(diclofop-methyl)、唑禾草灵(fenoxaprop)、唑禾草灵乙酯(fenoxaprop-ethyl)、精唑禾草灵(fenoxaprop-P)、精唑禾草灵乙酯(fenoxaprop-P-ethyl)、吡氟禾草灵(fluazifop)、吡氟禾草灵丁酯(fluazifop-butyl)、精吡氟禾草灵(fluazifop-P)、精吡氟禾草灵丁酯(fluazifop-P-butyl)、氟吡禾灵(haloxyfop)、氟吡甲禾灵甲酯(haloxyfop-methyl)、精氟吡甲禾灵(haloxyfop-P)、精氟吡禾灵甲酯(haloxyfop-P-methyl)、唑酰草胺(metamifop)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵乙酯(quizalofop-ethyl)、喹禾灵四氢糠酯(quizalofop-tefuryl)、精喹禾灵(quizalofop-P)、精喹禾灵乙酯(quizalofop-P-ethyl)、精喹禾灵四氢糠酯(quizalofop-P-tefuryl)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)，4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯基]-3-基)-5-羟-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS NO：1312337-72-6)；4-(2',4'-二氯-4-环丙基[1,1'-联苯基]-3-基)-5-羟-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS NO：1312337-45-3)；4-(4'-氯-4-乙基-2'-氟[1,1'-联苯基]-3-基)-5-羟-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS NO：1033757-93-5)；4-(2',4'-二氯-4-乙基[1,1'-联苯基]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS NO：1312340-84-3)；5-(乙酰氧基)-4-(4'-氯-4-环丙基-2'-氟[1,1'- 联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS NO：1312337-48-6)；5-(乙酰氧基)-4-(2',4'-二氯-4-环丙基-[1,1'-联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮；5-(乙酰氧基)-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS NO：1312340-82-1)；5-(乙酰氧基)-4-(2',4'-二氯-4-乙基[1,1'-联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS NO：1033760-55-2)；4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯(CAS NO：1312337-51-1)；4-(2',4'-二氯-4-环丙基-[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯；4-(4'-氯-4-乙基-2'-氟[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯(CAS NO：1312340-83-2)；4-(2',4'-二氯-4-乙基[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯(CAS NO：1033760-58-5)；
(6)GS(Glutamine Synthetase)抑制剂类：如双丙氨酰膦(Bialaphos/bilanafos)，双丙氨酰膦钠(Bilanaphos-natrium)，草铵膦铵盐(Glufosinate-ammonium)，草铵膦(Glufosinate)和精草铵膦(glufosinate-P)；
(7)PDS(Phytoene Desaturase)抑制剂类：如氟咯草酮(flurochloridone)，呋草酮(flurtamone)，氟丁酰草胺(beflubutamid)，达草灭(norflurazon)，氟草酮(fluridone)，吡氟草胺(Diflufenican)，氟吡酰草胺(Picolinafen)，以及4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(CAS NO：180608-33-7)；
(8)DHPS(Dihydropteroate Synthase)抑制剂类：如磺草灵(Asulam)；
(9)DXPS(Deoxy-D-Xyulose Phosphate Synthase)抑制剂类：如Bixlozone和异噁草松(Clomazone)；
(10)HST(Homogentisate Solanesyltransferase)抑制剂类：如Cyclopyrimorate；
(11)SPS(Solanesyl Diphosphate Synthase)抑制剂类：如苯草醚(Aclonifen)；
(12)纤维素合成抑制剂(Cellulose Synthesis)类：如茚嗪氟草胺(Indaziflam)，Triaziflam，氯硫酰草胺(Chlorthiamid)，敌草腈(Dichlobenil)，异恶草胺(Isoxaben)，胺草唑(Flupoxam)，1-环己基-5-五氟苯氧基-14-[1,2,4,6]噻三嗪-3-基胺(CAS NO：175899-01-1)，以及CN109688807A中公开的吖嗪类；
(13)VLCFAS(Very Long-Chain Fatty Acid Synthesis)抑制剂类：包括但不限于下述类型，
1)氯乙酰胺类如乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、精异丙甲草胺(metolachlor-S)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、毒草安(propachlor)、异丙草胺(propisochlor)和噻醚草胺(thenylchlor)；
2)α-氧乙酰胺类(α-Oxyacetamides)如氟噻草胺(flufenacet)和苯噻草胺(mefenacet)；
3)α-硫代乙酰胺类(α-Thioacetamides)如莎稗磷(anilofos)和哌草磷(piperophos)；
4)唑基甲酰胺类如唑草胺(cafenstrole)、四唑草胺(fentrazamide)和ipfencarbazone；
5)苯并呋喃类如Benfuresate和乙氧呋草黄(Ethofumesate)；
6)异恶唑啉类如fenoxasulfone和派罗克杀草砜(pyroxasulfone)；
7)环氧乙烷类如Indanofan和灭草环(Tridiphane)；
8)硫代氨基甲酸酯类如草灭特(Cycloate)，哌草丹(Dimepiperate)，S-乙基二丙基硫代氨基甲酸酯(EPTC)，戊草丹(Esprocarb)，禾草敌(Molinate)，Orbencarb，苄草丹(Prosulfocarb)，禾草丹(Thiobencarb/Benthiocarb)，野麦畏(Triallate)，Vernolate，和式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉类化合物，以及WO 2006/024820、WO 2006/037945、WO 2007/071900和WO 2007/096576等专利中提及的其他异唑啉化合物。
(14)脂肪酸硫酯酶(fatty acid thioesterase)抑制剂类：如环庚草醚Cinmethylin、Methiozolin；
(15)丝氨酸苏氨酸蛋白磷酸酶(serine threonine protein phosphatase)抑制剂类：如Endothall；
(16)番茄红素环化酶(lycopene cyclase)抑制剂类：如Amitrole。
(17)微管组装(Microtubule Assembly)抑制剂类：如氟草胺(Benefin/benfluralin)、地乐胺Butralin、氟硫草定Dithiopyr、噻唑烟酸Thiazopyr、乙丁烯氟灵Ethalfluralin、氨基丙氟灵Prodiamine、抑草磷Butamifos、氨磺乐灵Oryzalin、二甲戊灵Pendimethalin、氯钛酸甲酯Chlorthaldimethyl/DCPA、氟乐灵Trifluralin、炔苯酰草胺Propyzamide/pronamide、敌乐胺(Dinitramine，CAS NO：29091-05-2)；
(18)生长素模拟物类(Auxin Mimics)：如2,4,5三氯苯氧基乙酸(2,4,5-T)，2,4-二氯苯氧乙酸(2,4-D)，2,4-二氯苯氧丁酸(2,4-DB)，3,4-二氯苯氧丁酸(3,4-DB)，2,4-DEB(CAS NO：94-83-7)，4-氯苯氧基乙酸(4-CPA)，4-CPP(CAS NO：3307-39-9)，cloprop(CAS NO：101-10-0)，clofop(CAS NO：26129-32-8)，氯甲酰草胺Clomeprop，2,4-滴丙酸Dichlorprop，2甲4氯(MCPA)， 二甲四氯丁酸(MCPB)，2甲4氯丙酸(Mecoprop)，氯氨吡啶酸Aminopyralid，二氯吡啶酸Clopyralid，氯丙嘧啶酸Aminocyclopyrachlor，氯氟吡啶酯Florpyrauxifen，氟氯吡啶酯Halauxifen，二氯喹啉酸Quinclorac，草除灵乙酯Benazolin-ethyl，毒莠定Picloram，草灭平Chloramben，氯甲喹啉酸Quinmerac，氯氟吡氧乙酸Fluroxypyr，三氯吡氧乙酸Triclopyr，麦草畏Dicamba；
(19)D1丝氨酸264结合剂(和其他非组氨酸215结合剂)(D1Serine 264 binders(and other non-histidine 215binders))：如莠灭净Ametryne，莠去津Atrazine，草津净Cyanazine，异戊乙净Dimethametryn，扑灭通Prometon，扑草净Prometryne，扑灭津Propazine，西玛津Simazine，特丁津Terbuthylazine，特丁净Terbutryne，绿麦隆Chlorotoluron，敌草隆Diuron，伏草隆Fluometuron，异丙隆Isoproturon，利谷隆Linuron，秀谷隆Metobromuron，Methabenz thiazuron(CAS NO：18691-97-9)，灭草隆Monuron，丁噻隆Tebuthiuron，环嗪酮Hexazinone，苯嗪草酮Metamitron，嗪草酮Metribuzin，除草定Bromacil，环草定Lenacil，特草定Terbacil，杀草敏Chloridazon/pyrazon，胺唑草酮Amicarbazone，甜菜安Desmedipham，甜菜宁Phenmedipham，丁酰草胺(Chloranocryl/dicryl，CAS NO：2164-09-2)，敌稗Propanil，可乐津(chlorazine，CAS NO：580-48-3)，环草津(cyprazine，CAS NO：22936-86-3)，草达津(trietazine，CAS NO：1912-26-1)，methoprotryne(CAS NO：841-06-5)，西草净simetryn；
(20)D1组氨酸215结合剂(D1Histidine 215binders)：如溴苯腈Bromoxynil，碘苯腈Ioxynil，哒草特Pyridate，灭草松Bentazon；
(21)生长素转运(Auxin Transport)抑制剂类：如氟吡草腙(Diflufenzopyr，CAS NO：109293-97-2)，抑草生Naptalam；
(22)PS l电子转移(PS l Electron Diversion)：如敌草快Diquat，百草枯Paraquat；
(23)微管组织抑制剂类(Inhibition of Microtubule Organization)：如卡草胺(Carbetamide，CAS NO：16118-49-3)，燕麦灵(Barban，CAS NO：101-27-9)，氯苯胺灵Chlorpropham；
(24)解偶联剂(Uncouplers)：如地乐酚Dinoseb，4,6-二硝基邻甲酚(DNOC)；
(25)其他：如地散磷Bensulide，溴丁酰草胺Bromobutide，苄草隆Cumyluron，野燕枯Difenzoquat，稗草畏(Pyributicarb，CAS NO：88678-67-5)，甲基砷酸二钠DSMA，单甲基砷酸钠MSMA，杀草隆Dymron/daimuron，乙氧苯草胺Etobenzanid，麦草氟甲酯Flamprop-m，调节膦Fosamine，噁嗪草酮Oxaziclomefone，天竺葵酸Pelargonic acid，草乃敌Diphenamid，萘丙胺Naproanilide，草萘胺Napropamide，Napropamide-m，Benzofluor(CAS NO：68672-17-3)，Cambendichlor(CAS NO：56141-00-5)，dipropalin(CAS NO：1918-08-7)，etnipromid(CAS NO：76120-02-0)，bromobonil(CAS NO：25671-46-9)，monisouron(CAS NO：55807-46-0)，bromofenoxim(CAS NO：13181-17-4)，氯酰草膦(clacyfos，CAS NO：215655-76-8)，chlorazifop(CAS NO：60074-25-1)，喹草烯，brompyrazon(CAS NO：304284-0)，乙嗪草酮ethiozin，methiuron(CAS NO：21540-35-2)，甲氧隆(metoxuron，CAS NO：19937-59-8)，四氟隆(tetrafluron，27954-37-6)，噻苯隆(thidiazuron，CAS NO：51707-55-2)，丙烯醛acrolein，氟萘禾草灵。
在一个具体实施方式中，和化合物1(组分A)混合的另一种除草剂(组分B)选自以下化合物中的一种或两种以上：苄嘧磺隆(CAS号：83055-99-6)、吡嘧磺隆(CAS号：93697-74-6)、五氟磺草胺(CAS号：219714-96-2)、噻吩磺隆(CAS号：79277-27-3)、唑嘧磺草胺(CAS号：98967-40-9)、噁草酮(CAS号：19666-30-9)、丙炔噁草酮(CAS号：39807-15-3)、乙氧氟草醚(CAS号：42874-03-3)、双唑草腈(CAS号：158353-15-2)、丙炔氟草胺(CAS号：103361-09-7)、敌稗(CAS号：709-98-8)、灭草松(CAS号：25057-89-0)、异丙隆(CAS号：34123-59-6)、绿麦隆(CAS号：15545-48-9)、嗪草酮(CAS号：21087-64-9)、莠去津(CAS号：1912-24-9)、特丁津(CAS号：5915-41-3)、扑草净(CAS号：7287-19-6)、氯氟吡啶酯(CAS号：1390661-72-9)、氯氟吡氧乙酸(CAS号：69377-81-7)、2甲4氯异辛酯(CAS号：29450-45-1)、2,4-滴异辛酯(CAS号：25168-26-7)、三唑磺草酮(CAS号：1911613-97-2)、双唑草酮(CAS号：1622908-18-2)、苯唑氟草酮(CAS号：1992017-55-6)、硝磺草酮(CAS号：104206-82-8)、双环磺草酮(CAS号：156963-66-5)、呋喃磺草酮(CAS号：473278-76-1)、异噁唑草酮(CAS号：141112-29-0)、乙草胺(CAS号：34256-82-1)、丙草胺(CAS号：51218-49-6)、丁草胺(CAS号：23184-66-9)、苯噻酰草胺(CAS号：73250-68-7)、四唑酰草胺(CAS号：158237-07-1)、莎稗磷(CAS号：64249-01-0)、砜吡草唑(CAS号：447399-55-5)、野麦畏(CAS号：2303-17-5)、二甲戊灵(CAS号：40487-42-1)、仲丁灵(CAS号：33629-47-9)、吡氟酰草胺(CAS号：83164-33-4)、Beflubutamid-M(CAS号：113614-08-7)、异噁草松(CAS号：81777-89-1)、二氯异噁草酮(CAS号：81777-95-9)、噁嗪草酮(CAS号：153197-14-9)、氰氟草酯(CAS号：122008-85-9)、噁唑酰草胺(CAS号：256412-89-2)、环苯草酮(CAS号：139001-49-3)。
一般而言，如果如本文所述的可在本发明的上下文中使用的除草化合物能够形成几何异构体例如E/Z异构体，则可能在根据本发明的组合物中使用两者，纯异构体及其混合物。如果如本文所述的除草化合物具有一个或多个手性中心(通式I所示化合物至少存在3个手性中心C1*、C2*和C4*)，且因而以对映异构体或非对映异构体存在，则可能在根据本发明的组合物中使用两者，纯对映异构体和非对映异构体及其混合物。如果如本文所述的除草化合物具有可离子化官能团，则它们还可以以其农业上可接受的盐的形式使用。通常，那些阳离子的盐和那些酸的酸加成盐是适合的，它们的阳离子和阴离子分别对活性化合物的活性无副作用。优选的阳离子为碱金属的离子，优选锂、钠和钾离子，碱土金属的离子，优选钙和镁离子，以及过渡金属的离子，优选锰、铜、锌和铁的离子，进一步为铵和取代的铵，其中1个至4个氢原子被C1-C4-烷基、羟基-C1-C4-烷基、C1-C4-烷氧基-C1-C4-烷基、羟基-C1-C4-烷氧基-C1-C4-烷基、苯基或苄基取代，优选铵、甲基铵、异丙基铵、二甲基铵、二异丙基铵、三甲基铵、庚基铵、十二烷基铵、十四烷基铵、四甲基铵、四乙基铵、四丁基铵、2-羟乙基铵(olamine盐)、2-(2-羟基乙-1-氧基)乙-1-基铵(二甘醇胺盐)、二(2-羟基乙-1-基)铵(二醇胺盐)、三(2-羟乙基)铵(三硝乙醇胺盐)、三(2-羟丙基)铵、苄基三甲基铵、苄基三乙基铵、N,N,N-三甲基乙醇铵(胆碱盐)，此外鏻离子，锍离子，优选三(C1-C4-烷基)锍诸如三甲基锍，和氧化锍离子，优选三(C1-C4-烷基)氧化锍离子，以及最终多元胺诸如N,N-双-(3-氨基丙基)甲基胺和二亚乙基三胺的盐。可用酸加成盐的阴离子主要为氯离子、溴离子、氟离子、碘离子、硫酸氢根、甲基硫酸根、硫酸根、磷酸二氢根、氢磷酸根、硝酸根、碳酸氢根、碳酸根、六氟硅酸根、六氟磷酸根、苯甲酸根以及还有C1-C4-链烷酸的阴离子，优选甲酸根、乙酸根、丙酸根和丁酸根。
如本文所述的具有羧基的除草剂化合物可以以酸的形式、以上文提及的农业上适合盐或另外以农业上可接受的衍生物的形式使用，例如作为酰胺诸如单-和二-C1-C6-烷基酰胺或芳基酰胺，作为酯例如烯丙酯、炔丙酯、C1-C10-烷基酯、烷氧基烷基酯、tefuryl((四氢呋喃-2-基)甲基)酯以及还作为硫酯例如作为C1-C10-烷基硫酯。优选的单-和二-C1-C6-烷基酰胺为甲基和二甲基酰胺。优选的芳基酰胺为，例如N-酰苯胺(anilide)和2-氯苯胺(2-chloroanilide)。优选的烷基酯为例如甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、mexyl(1-甲基己基)、meptyl(1-甲基庚基)、庚基、辛基或异辛基(2-乙基己基)酯。优选的C1-C4-烷氧基-C1-C4-烷基酯为直链或支链C1-C4-烷氧基乙酯，例如2-甲氧基乙酯、2-乙氧基乙酯、2-丁氧基乙基(butotyl)酯、2-丁氧基丙酯或3-丁氧基丙酯。直链或支链C1-C10-烷基硫酯的实例为乙基硫酯。
当使用时，如果需要，将市售的制剂以常见的方式稀释，例如在可湿性粉剂、浓缩乳剂、悬浮液和在水中悬浮的颗粒时，使用水稀释。粉末、土壤施药所用的颗粒剂或撒播和喷洒的溶液，一般在使用前不需要进一步用惰性物质稀释。随着外部条件的变化，要求的式I化合物的使用量也不同，外部条件为，例如温度、湿度、使用的除草剂的性质等等。它可以有大 的变化幅度，例如在0.001到1.0kg a.i./ha之间，或更多的活性物质，但优选在0.005到750g
a.i./ha之间。
具体实施方式
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。
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。
表1化合物结构及其1HNMR




表A-H如以上表1相同构造，除了将有手性中心(通式I所示化合物中C1*、C2*和C4*处碳原子为手性中心)的消旋体化合物分别替换为(1R,2R,4R)构型、(1S,2R,4R)构型、(1R,2S,4R)构型、(1R,2R,4S)构型、(1S,2S,4R)构型、(1R,2S,4S)构型、(1S,2R,4S)构型、(1S,2S,4S)构型，且在表A中，“序号”列标题下面的条目依次叙述为“1(1R,2R,4R)-79(1R,2R,4R)”，其他表格具有相同构造。例如，“1(1R,2R,4R)”对应于表1中化合物“1”在C1*位置处为R构型、C2*位置处为R构型且C4*处位置处为R构型。
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。
以下提供的方法实施例用于促进对本发明的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。
代表性化合物的实施例如下，其他化合物的合成方法类似，此处不再详细说明。
1、化合物1的合成
将1-2(0.37g，2.2mmol，1.1eq)、NaH(96mg，2.4mmol，1.2eq)溶于20ml DMF中，室温下搅拌0.5小时后加入1-1(0.53g，2.0mmol，1eq)，升温至40℃，反应5h，监测反应直到原料反应完全。将反应液倒入20ml冰水中，再用20ml乙酸乙酯重复萃取三次。减压浓缩有机相，过硅胶柱分离纯化得到化合物1(0.4g，产率57％)。
2、化合物3的合成
将3-1(1.13g,4.4mmol，1eq)溶解在20ml DMF中，冰浴下加入氢化钠(0.21g,8.8mmol，2eq)，室温下搅拌0.5h，加入环庚草醚醇中间体1-2(0.8g，4.4mmol，1.1eq)，室温下搅拌12h，监测反应直到起始原料消失。反应液加水用乙酸乙酯萃取三次，饱和食盐水洗涤三次。无水硫酸钠干燥，拌样过柱，馏分旋干得到化合物3(0.92g，产率54.1％)。
3、化合物1(1S,2R,4R)的合成
将1-3(1eq)加入到5ml DMF中，冰浴下加入氢化钠(2eq)，保持冰浴搅拌0.5h，再向反应液中加入1-4(1eq)，室温反应过夜，中控反应完成，向反应液加水淬灭反应，加入EA萃取两次，有机相用饱和食盐水洗涤两次，无水硫酸钠干燥，拌样正相纯化得化合物1(1S,2R,4R)。
4、化合物1(1S,2S,4R)的合成
将1-5(1eq)加入到5ml DMF中，冰浴下加入氢化钠(2eq)，保持冰浴搅拌0.5h，再向反应液中加入1-4(1eq)，室温反应过夜，中控反应完成，向反应液加水淬灭反应，加入EA萃取两次，有机相用饱和食盐水洗涤两次，无水硫酸钠干燥，拌样正相纯化得化合物1(1S,2S,4R)。
生物活性评价：
(1)苗前测试实验：
植物破坏(即生长控制率)的活性级别标准如下：
9级：完全死亡；
8级：生长控制率大于等于90％且小于100％；
7级：生长控制率大于等于80％且小于90％；
6级：生长控制率大于等于70％且小于80％；
5级：生长控制率大于等于50％且小于70％；
4级：生长控制率大于等于30％且小于50％；
3级：生长控制率大于等于20％且小于30％；
2级：生长控制率大于等于10％且小于20％；
1级：生长控制率小于10％；
0级：无效果。
以上生长控制率为鲜重控制率。
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、花生、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周后观察实验结果，所用化合物剂量为3.75、7.5、15、30、60、120g a.i./ha。代表性数据列于表2。
表2苗前测试实验结果
注：N代表无数据，对照化合物A：对照化合物B：对 照化合物C：
由上可以发现，本发明化合物效果优异，除草活性明显高于对照化合物A和B，且与对照化合物C相比在维持高除草活性的同时对作物安全性提高，即具有良好的选择性，尤其是使用对照化合物C进行封闭除草对小麦有不可接受的药害。
同时，我们经过小麦田和水稻田主要杂草测试发现，本发明所述化合物普遍具有较好的杂草防效，尤其是我们注意到对于ALS抑制剂有抗性的鸭舌草、异型莎草、丁香蓼、黑麦草、看麦娘、菵草等阔叶杂草和莎草有极高的活性，具有非常好的商业价值。
(2)移栽水稻和水直播水稻安全性评价与水田杂草防效评价：
在1/1,000,000公顷罐中装入水田土壤后，播种稗草、稻稗、鸭舌草、千金子、丁香蓼的种子，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、稻稗、千金子达到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。
直播水稻模拟田间，先将容器内加5厘米水层，充分混合打泥浆，然后撒入水稻种子，等泥浆澄清后，去掉水层，保持土壤湿润，用喷雾法均匀喷施药液。施药后3-4天复水3厘米。
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2-3厘米，第二天以移栽深度2-3厘米来移植3叶期的水稻(粳稻)。移植后第3天与上述同样地处理本发明化合物。
上述实验中所用化合物剂量为3.75、7.5、15、30、60、120g a.i./ha。分别用肉眼观察药剂处理后第14天杂草生育状态，药剂处理后第7天水稻的生育状态，以上述活性标准级别评价效果，代表性数据列于表3。
表3移栽水稻和水直播水稻安全性评价与水田杂草防效评价实验结果
注：稗草、稻稗、鸭舌草采集自中国黑龙江，经过检测对常规剂量的吡嘧磺隆有抗药性。
由此而见，本发明化合物与对照化合物A、B和C相比，具有更好的除草活性和/或水稻安全性。
(3)组合物活性测试：
所需活性成分B由试剂公司购买或由已知方法合成。原药均采用丙酮作溶剂，用含量0.1％乳化剂吐温-80水溶液稀释，现用现稀释。
(A)苗后早期茎叶喷雾处理(F-EP)：
杂草采用盆栽法培养，用180х140mm塑料营养钵，摆放于搪瓷盘中，内装从农田采回经风干过筛的表层土壤(4/5处)，土壤湿度初期均控制在20％，挑选籽粒饱满均一的杂草种子，用25℃温水浸泡6小时，在28℃生化培养箱(黑暗)中催芽，将刚刚露白的杂草种子均匀摆放在土壤表面，根据种子粒径大小然后覆土0.5-1cm。
在可控日光温室内进行培养，温度20～30℃，自然光照，相对湿度57％～72％。土壤类型为壤土，有机质含量为1.63％，pH＝7.1，碱解氮84.3mg/kg，速效磷38.5mg/kg，速效钾82.1mg/kg。
每处理重复4次，每次处理4盆，每盆播种杂草种子20粒。
试验共用药1次。待杂草1-2叶期，间苗，每处理保留10株备用。
将培养好的试材均匀摆放在面积0.5m2的平台上，用3WP-2000型行走式喷雾塔茎叶喷雾，喷液量按450公斤/公顷计，喷雾压力0.3MPa。待全部药液喷完后，关闭气阀，30秒后，打开喷雾塔门，取出营养钵。然后打开气阀，喷清水50mL，清洗喷液管。试材处理后移入温室常规培养。
(B)土壤封闭处理(S)：
杂草在可控日光温室内进行培养，温度20～30℃，自然光照，相对湿度57％～72％。土壤类型为壤土，有机质含量为1.63％，pH＝7.1，碱解氮84.3mg/kg，速效磷38.5mg/kg，速效钾82.1mg/kg。试验土壤定量装至盆钵的3/4处，然后从盆钵底部浇灌，使土壤完全湿润至饱和状态。供试杂草种子催芽处理至露白，然后均匀定量撒播表面，根据种子大小覆土0.5-1cm，播种后72小时备用。
每处理重复4次，每次每处理4盆，每盆播种杂草种子20粒。
将播种好的试材均匀摆放在面积0.5m2的平台上，用3WP-2000型行走式喷雾塔进行土壤喷雾，喷液量按450公斤/公顷计，喷雾压力0.3MPa。待全部药液喷完后，关闭气阀，30秒后，打开喷雾塔门，取出营养钵。然后打开气阀，喷清水50mL，清洗喷液管。
(C)数据调查与统计分析
采用绝对数调查法，用刀片沿土壤表面切断存活杂草整株幼苗，用分析天平称量杂草鲜重。对于已经死亡的杂草，按鲜重为零计。
处理后21天调查，共调查1次。
用Gowing法计算各处理混合组合的理论鲜重抑制率(E0＝X+Y-X*Y/100)，然后与实测抑制率(E)相比较，评价二者混用对杂草的联合作用类型，当E-E0值大于10％为增效作用、小于-10％为拮抗作用、在-10％～10％之间为加成作用。并根据实际防效和除草剂特点、配方的平衡性等因素确定最佳配比。式中X为活性成分A用量为P时的鲜重抑制率；Y为活性成分B用量为Q时的鲜重抑制率。统计结果见表4。
表4化合物1混配对杂草的实际防效与联合作用评价


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甘蔗、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。

Claims (10)

  1. 一种氧杂双环烷类化合物，如通式I所示：
    其中，A、B分别独立地代表烷基；
    X、Y、Z分别独立地代表氢、硝基、卤素、氰基、甲酰基、硫氰基、巯基、OR1、COR1、COOR1、OCOR1、OCOOR1、NR3SO2R2、OSO2R2、S(O)mR2、NR3COR1、NR3COOR1、C(O)NR3OR1、SO2OR1、C(O)NR4R5、NR3C(O)NR4R5、OC(O)NR4R5、SO2NR4R5、C(S)R1、C(S)OR1、C(S)SR2、C(O)SR2、SC(O)R1、SC(S)R1、OC(S)R1、-烷基-C(S)R1、-烷基-C(S)OR1、-烷基-C(O)SR1、-烷基-C(S)SR1、-烷基-SC(O)R1、-烷基-OC(S)R1、-烷基-SC(S)R1、-O-烷基-NR4R5、-S-烷基-NR4R5、-烷基-O-烷基-NR4R5、-烷基-S-烷基-NR4R5、-烷基-(C＝S)n-NR4R5、-NH-烷基-NR4R5、-烷基-OR1、-烷基-COR1、-烷基-CO2R1、-烷基-OCOR1、-烷基-NR3COR1、-烷基-SO2OR1、-烷基-NR3SO2R2、-烷基-OSO2R2、-烷基-S(O)mR2、-烷基-CONR4R5、-烷基-SO2NR4R5、NR4R5、P(O)(OR6)2、CH2P(O)(OR6)2、-烷基-CN、烷基、烯基、炔基、环烷基、环烷基烷基、环烯基、环烯基烷基、杂环基、杂环基烷基、芳基或芳基烷基，其中，所述“烷基”、“烯基”或“炔基”分别独立地是未取代的或被卤素所取代的，所述“环烷基”、“环烷基烷基”、“环烯基”、“环烯基烷基”、“杂环基”、“杂环基烷基”、“芳基”或“芳基烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-烷基-(CO)OR10中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    R1、R3、R4、R5分别独立地代表氢、芳基、芳基烷基、杂环基、杂环基烷基、烷基、卤代烷基、烯基、卤代烯基、炔基、卤代炔基、环烷基、卤代环烷基、烷氧基烷基、环烷基烷基，其中后10个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和烷氧基烷氧基羰基的取代基取代；
    R2为芳基、芳基烷基、杂环基、杂环基烷基、烷基、烯基、炔基、环烷基、环烷基烷基，其中后5个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和烷氧基烷氧基羰基的基团 取代；
    R6为甲基或乙基；
    R7、R8分别独立地代表为氢、烷基、烯基或炔基；
    R9为烷基、烯基或炔基；
    R10分别独立地代表氢，烷基，卤代烷基，苯基或被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基；
    m代表0、1或2，n代表0或1，s代表0、1、2、3、4或5。
  2. 根据权利要求1所述的氧杂双环烷类化合物，其特征在于，
    A、B分别独立地代表C1-C8烷基；
    X、Y、Z分别独立地代表氢、硝基、卤素、氰基、甲酰基、硫氰基、巯基、OR1、COR1、COOR1、OCOR1、OCOOR1、NR3SO2R2、OSO2R2、S(O)mR2、NR3COR1、NR3COOR1、C(O)NR3OR1、SO2OR1、C(O)NR4R5、NR3C(O)NR4R5、OC(O)NR4R5、SO2NR4R5、C(S)R1、C(S)OR1、C(S)SR2、C(O)SR2、SC(O)R1、SC(S)R1、OC(S)R1、-(C1-C8烷基)-C(S)R1、-(C1-C8烷基)-C(S)OR1、-(C1-C8烷基)-C(O)SR1、-(C1-C8烷基)-C(S)SR1、-(C1-C8烷基)-SC(O)R1、-(C1-C8烷基)-OC(S)R1、-(C1-C8烷基)-SC(S)R1、-O-(C1-C8烷基)-NR4R5、-S-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-O-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-S-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-(C＝S)n-NR4R5、-NH-(C1-C8烷基)-NR4R5、-(C1-C8烷基)-OR1、-(C1-C8烷基)-COR1、-(C1-C8烷基)-CO2R1、-(C1-C8烷基)-OCOR1、-(C1-C8烷基)-NR3COR1、-(C1-C8烷基)-SO2OR1、-(C1-C8烷基)-NR3SO2R2、-(C1-C8烷基)-OSO2R2、-(C1-C8烷基)-S(O)mR2、-(C1-C8烷基)-CONR4R5、-(C1-C8烷基)-SO2NR4R5、NR4R5、P(O)(OR6)2、CH2P(O)(OR6)2、-(C1-C8烷基)-CN、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、C3-C8环烯基、C3-C8环烯基C1-C8烷基、杂环基、杂环基C1-C8烷基、芳基或芳基C1-C8烷基，其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”分别独立地是未取代的或被卤素所取代的，所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“C3-C8环烯基”、“C3-C8环烯基C1-C8烷基”、“杂环基”、“杂环基C1-C8烷基”、“芳基”或“芳基C1-C8烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8烷基)-(CO)OR10中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素所 取代的-OCH2CH2-或-OCH2O-形成稠环；
    R1、R3、R4、R5分别独立地代表氢、芳基、芳基C1-C8烷基、杂环基、杂环基C1-C8烷基、C1-C8烷基、卤代C1-C8烷基、C2-C8烯基、卤代C2-C8烯基、C2-C8炔基、卤代C2-C8炔基、C3-C8环烷基、卤代C3-C8环烷基、C1-C8烷氧基C1-C8烷基、C3-C8环烷基C1-C8烷基，其中后10个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C8烷氧基C1-C8烷氧基羰基的取代基取代；
    R2为芳基、芳基C1-C8烷基、杂环基、杂环基C1-C8烷基、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，其中后5个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C8烷氧基C1-C8烷氧基羰基的基团取代；
    R6为甲基或乙基；
    R7、R8分别独立地代表为氢、C1-C8烷基、C2-C8烯基或C2-C8炔基；
    R9为C1-C8烷基、C2-C8烯基或C2-C8炔基；
    R10分别独立地代表氢，C1-C8烷基，卤代C1-C8烷基，苯基或被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基；
    m代表0、1或2，n代表0或1，s代表0、1、2、3、4或5。
  3. 根据权利要求1所述的氧杂双环烷类化合物，其特征在于，
    A、B分别独立地代表C1-C6烷基；
    X、Y、Z分别独立地代表氢、硝基、卤素、氰基、甲酰基、硫氰基、巯基、OR1、COR1、COOR1、OCOR1、OCOOR1、NR3SO2R2、OSO2R2、S(O)mR2、NR3COR1、NR3COOR1、C(O)NR3OR1、SO2OR1、C(O)NR4R5、NR3C(O)NR4R5、OC(O)NR4R5、SO2NR4R5、C(S)R1、C(S)OR1、C(S)SR2、C(O)SR2、SC(O)R1、SC(S)R1、OC(S)R1、-(C1-C6烷基)-C(S)R1、-(C1-C6烷基)-C(S)OR1、-(C1-C6烷基)-C(O)SR1、-(C1-C6烷基)-C(S)SR1、-(C1-C6烷基)-SC(O)R1、-(C1-C6烷基)-OC(S)R1、-(C1-C6烷基)-SC(S)R1、-O-(C1-C6烷基)-NR4R5、-S-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-O-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-S-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-(C＝S)n-NR4R5、-NH-(C1-C6烷基)-NR4R5、-(C1-C6烷基)-OR1、-(C1-C6烷基)-COR1、-(C1-C6烷基)-CO2R1、-(C1-C6烷基)-OCOR1、-(C1-C6烷基)-NR3COR1、-(C1-C6烷基)-SO2OR1、-(C1-C6烷基)-NR3SO2R2、-(C1-C6烷基)-OSO2R2、-(C1-C6烷基)-S(O)mR2、-(C1-C6烷基)-CONR4R5、 -(C1-C6烷基)-SO2NR4R5、NR4R5、P(O)(OR6)2、CH2P(O)(OR6)2、-(C1-C6烷基)-CN、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、C3-C6环烯基、C3-C6环烯基C1-C6烷基、杂环基、杂环基C1-C6烷基、芳基或芳基C1-C6烷基，其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”分别独立地是未取代的或被卤素所取代的，所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“C3-C6环烯基”、“C3-C6环烯基C1-C6烷基”、“杂环基”、“杂环基C1-C6烷基”、“芳基”或“芳基C1-C6烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6烷基)-(CO)OR10中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    R1、R3、R4、R5分别独立地代表氢、芳基、芳基C1-C6烷基、杂环基、杂环基C1-C6烷基、C1-C6烷基、卤代C1-C6烷基、C2-C6烯基、卤代C2-C6烯基、C2-C6炔基、卤代C2-C6炔基、C3-C6环烷基、卤代C3-C6环烷基、C1-C6烷氧基C1-C6烷基、C3-C6环烷基C1-C6烷基，其中后10个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C6烷氧基C1-C6烷氧基羰基的取代基取代；
    R2为芳基、芳基C1-C6烷基、杂环基、杂环基C1-C6烷基、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，其中后5个基团被s个选自氰基、卤素、硝基、氰硫基、OR7、S(O)mR9、NR7R8、NR8OR7、COR7、OCOR7、SCOR7、NR8COR7、CO2R7、COSR7、CONR7R8和C1-C6烷氧基C1-C6烷氧基羰基的基团取代；
    R6为甲基或乙基；
    R7、R8分别独立地代表为氢、C1-C6烷基、C2-C6烯基或C2-C6炔基；
    R9为C1-C6烷基、C2-C6烯基或C2-C6炔基；
    R10分别独立地代表氢，C1-C6烷基，卤代C1-C6烷基，苯基或被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的至少一个基团所取代的苯基；
    m代表0、1或2，n代表0或1，s代表0、1、2、3、4或5。
  4. 根据权利要求1所述的氧杂双环烷类化合物，其特征在于，所述化合物选自表1及表A-H中任意一个。
  5. 一种如权利要求1-4任意一项所述的氧杂双环烷类化合物的制备方法，其特征在于，包括以下步骤：
    将通式Ⅱ所示的化合物和通式Ⅲ所示的化合物进行取代反应，制得通式Ⅰ所述的化合物；其化学反应方程式如下：
    其中，Hal代表卤素，其他取代基A、B、X、Y、Z的定义如权利要求1-4任意一项所示；
    优选地，所述反应在NaH或无水碳酸盐和溶剂的存在下进行；更优选地，所述溶剂选自DMF、二甲基乙酰胺、THF、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种。
  6. 一种除草组合物，其特征在于，其包括(i)除草有效量的权利要求1-4任意一项所述的氧杂双环烷类化合物中的至少一种。
  7. 根据权利要求6所述的组合物，其特征在于，还包括(ii)一种或多种除草有效量的另外的除草剂和/或安全剂；优选地，所述另外的除草剂选自苄嘧磺隆、吡嘧磺隆、五氟磺草胺、噻吩磺隆、唑嘧磺草胺、噁草酮、丙炔噁草酮、乙氧氟草醚、双唑草腈、丙炔氟草胺、敌稗、灭草松、异丙隆、绿麦隆、嗪草酮、莠去津、特丁津、扑草净、氯氟吡啶酯、氯氟吡氧乙酸、2甲4氯异辛酯、2,4-滴异辛酯、三唑磺草酮、双唑草酮、苯唑氟草酮、硝磺草酮、双环磺草酮、呋喃磺草酮、异噁唑草酮、乙草胺、丙草胺、丁草胺、苯噻酰草胺、四唑酰草胺、莎稗磷、砜吡草唑、野麦畏、二甲戊灵、仲丁灵、吡氟酰草胺、Beflubutamid-M、异噁草松、二氯异噁草酮、噁嗪草酮、氰氟草酯、噁唑酰草胺、环苯草酮。
  8. 根据权利要求6-7任意一项所述的组合物，其特征在于，还包括(iii)农业化学上可接受的制剂助剂。
  9. 一种防治不希望的植物的方法，其特征在于，包括将除草有效量的权利要求1-4任意一项所述的氧杂双环烷类化合物中的至少一种或权利要求6-8任意一项所述的除草组合物施用至植物或者其场所或施用至土壤或水体以防治不希望的植物出苗或生长；优选地，所述不希望的植物包括除草剂抗性或耐受性杂草物种。
  10. 如权利要求1-4任意一项所述的氧杂双环烷类化合物中的至少一种或权利要求6-8任意一项所述的除草组合物在控制不希望的植物上的用途，优选地，将所述的氧杂双环烷类化合物用于防除有用作物中的杂草；更优选地，所述有用作物包括转基因作物或者基因组编辑技术处理过的作物，所述杂草包括除草剂抗性或耐受性杂草物种。
PCT/CN2023/127411 2022-11-09 2023-10-28 一种氧杂双环烷类化合物及其制备方法、除草组合物和应用 Ceased WO2024099118A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2023379359A AU2023379359A1 (en) 2022-11-09 2023-10-28 Oxabicycloalkane compounds, preparation method therefor, and herbicidal composition and use thereof
EP23887808.6A EP4617275A1 (en) 2022-11-09 2023-10-28 Oxabicycloalkane compounds, preparation method therefor, and herbicidal composition and use thereof
JP2025526605A JP2025537252A (ja) 2022-11-09 2023-10-28 オキサビシクロアルカン化合物、その製造方法、ならびに除草剤組成物およびその用途

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202211395248 2022-11-09
CN202211395248.3 2022-11-09
CN202211597464.6 2022-12-12
CN202211597464.6A CN118005577A (zh) 2022-11-09 2022-12-12 一种氧杂双环烷类化合物及其制备方法、除草组合物和应用

Publications (1)

Publication Number Publication Date
WO2024099118A1 true WO2024099118A1 (zh) 2024-05-16

Family

ID=90941657

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/127411 Ceased WO2024099118A1 (zh) 2022-11-09 2023-10-28 一种氧杂双环烷类化合物及其制备方法、除草组合物和应用

Country Status (5)

Country Link
EP (1) EP4617275A1 (zh)
JP (1) JP2025537252A (zh)
CN (1) CN118005577A (zh)
AU (1) AU2023379359A1 (zh)
WO (1) WO2024099118A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119032950A (zh) * 2024-08-20 2024-11-29 扬州大学 一种除草组合物及其制备方法和应用

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0131624A1 (en) 1983-01-17 1985-01-23 Monsanto Co PLASMIDS FOR TRANSFORMING PLANT CELLS.
EP0142924A2 (en) 1983-09-26 1985-05-29 Mycogen Plant Science, Inc. Insect resistant plants
US4567283A (en) * 1982-09-13 1986-01-28 Shell Oil Company Intermediates for oxabicycloalkane herbicides
EP0193259A1 (en) 1985-01-18 1986-09-03 Plant Genetic Systems N.V. Modifying plants by genetic engineering to combat or control insects
EP0221044A1 (en) 1985-10-25 1987-05-06 Monsanto Company Novel plant vectors
EP0242246A1 (en) 1986-03-11 1987-10-21 Plant Genetic Systems N.V. Plant cells resistant to glutamine synthetase inhibitors, made by genetic engineering
EP0257993A2 (en) 1986-08-26 1988-03-02 E.I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
CN87106867A (zh) * 1986-10-10 1988-04-27 纳慕尔杜邦公司 氧杂二环烷烃的选择性使用方法
CN1045786A (zh) 1989-03-14 1990-10-03 纳幕尔杜邦公司 选择性的氧杂双环烷
WO1991003464A1 (en) * 1989-09-11 1991-03-21 E.I. Du Pont De Nemours And Company Herbicidal oxabicyclo ethers
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
WO1991013972A1 (en) 1990-03-16 1991-09-19 Calgene, Inc. Plant desaturases - compositions and uses
WO1991019806A1 (en) 1990-06-18 1991-12-26 Monsanto Company Increased starch content in plants
WO1992000377A1 (en) 1990-06-25 1992-01-09 Monsanto Company Glyphosate tolerant plants
WO1992010501A1 (en) * 1990-12-10 1992-06-25 E.I. Du Pont De Nemours And Company Herbicidal ethers
WO1992011376A1 (en) 1990-12-21 1992-07-09 Amylogene Hb Genetically engineered modification of potato to form amylopectin-type starch
CN1064077A (zh) * 1991-01-30 1992-09-02 纳幕尔杜邦公司 具有除草活性的双环醚
WO1992014827A1 (en) 1991-02-13 1992-09-03 Institut Für Genbiologische Forschung Berlin Gmbh Plasmids containing dna-sequences that cause changes in the carbohydrate concentration and the carbohydrate composition in plants, as well as plant cells and plants containing these plasmids
WO2006024820A1 (en) 2004-09-03 2006-03-09 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2006037945A1 (en) 2004-10-05 2006-04-13 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2007071900A1 (en) 2005-12-21 2007-06-28 Syngenta Limited Novel herbicides
CN105264069A (zh) 2013-04-30 2016-01-20 巴斯夫欧洲公司 具有增加的除草剂耐受性的植物
CN105753853A (zh) 2014-12-16 2016-07-13 沈阳中化农药化工研发有限公司 一种含异恶唑啉的脲嘧啶类化合物及其用途
WO2016120116A1 (en) 2015-01-29 2016-08-04 Basf Se Herbicidal phenylpyridines
WO2017202768A1 (en) 2016-05-24 2017-11-30 Basf Se Herbicidal uracilpyrid
WO2018019842A1 (en) 2016-07-29 2018-02-01 Basf Se Method for controlling ppo resistant weeds
CN109688807A (zh) 2016-07-15 2019-04-26 巴斯夫欧洲公司 具有增加的除草剂耐受性的植物
CN113105405A (zh) 2020-01-11 2021-07-13 青岛清原化合物有限公司 一种羧酸衍生物取代的亚氨基芳基化合物及其制备方法、除草组合物和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000128886A (ja) * 1998-10-27 2000-05-09 Nissan Chem Ind Ltd ７−オキサビシクロ［２．２．１］ヘプタン化合物および除草剤
GB0603891D0 (en) 2006-02-27 2006-04-05 Syngenta Ltd Novel herbicides

Patent Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4567283A (en) * 1982-09-13 1986-01-28 Shell Oil Company Intermediates for oxabicycloalkane herbicides
EP0131624A1 (en) 1983-01-17 1985-01-23 Monsanto Co PLASMIDS FOR TRANSFORMING PLANT CELLS.
EP0142924A2 (en) 1983-09-26 1985-05-29 Mycogen Plant Science, Inc. Insect resistant plants
EP0193259A1 (en) 1985-01-18 1986-09-03 Plant Genetic Systems N.V. Modifying plants by genetic engineering to combat or control insects
EP0221044A1 (en) 1985-10-25 1987-05-06 Monsanto Company Novel plant vectors
EP0242236A1 (en) 1986-03-11 1987-10-21 Plant Genetic Systems N.V. Plant cells resistant to glutamine synthetase inhibitors, made by genetic engineering
EP0242246A1 (en) 1986-03-11 1987-10-21 Plant Genetic Systems N.V. Plant cells resistant to glutamine synthetase inhibitors, made by genetic engineering
EP0257993A2 (en) 1986-08-26 1988-03-02 E.I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
CN87106867A (zh) * 1986-10-10 1988-04-27 纳慕尔杜邦公司 氧杂二环烷烃的选择性使用方法
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
CN1045786A (zh) 1989-03-14 1990-10-03 纳幕尔杜邦公司 选择性的氧杂双环烷
WO1991003464A1 (en) * 1989-09-11 1991-03-21 E.I. Du Pont De Nemours And Company Herbicidal oxabicyclo ethers
WO1991013972A1 (en) 1990-03-16 1991-09-19 Calgene, Inc. Plant desaturases - compositions and uses
WO1991019806A1 (en) 1990-06-18 1991-12-26 Monsanto Company Increased starch content in plants
WO1992000377A1 (en) 1990-06-25 1992-01-09 Monsanto Company Glyphosate tolerant plants
WO1992010501A1 (en) * 1990-12-10 1992-06-25 E.I. Du Pont De Nemours And Company Herbicidal ethers
WO1992011376A1 (en) 1990-12-21 1992-07-09 Amylogene Hb Genetically engineered modification of potato to form amylopectin-type starch
CN1064077A (zh) * 1991-01-30 1992-09-02 纳幕尔杜邦公司 具有除草活性的双环醚
WO1992014827A1 (en) 1991-02-13 1992-09-03 Institut Für Genbiologische Forschung Berlin Gmbh Plasmids containing dna-sequences that cause changes in the carbohydrate concentration and the carbohydrate composition in plants, as well as plant cells and plants containing these plasmids
WO2006024820A1 (en) 2004-09-03 2006-03-09 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2006037945A1 (en) 2004-10-05 2006-04-13 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2007071900A1 (en) 2005-12-21 2007-06-28 Syngenta Limited Novel herbicides
CN105264069A (zh) 2013-04-30 2016-01-20 巴斯夫欧洲公司 具有增加的除草剂耐受性的植物
CN105753853A (zh) 2014-12-16 2016-07-13 沈阳中化农药化工研发有限公司 一种含异恶唑啉的脲嘧啶类化合物及其用途
WO2016120116A1 (en) 2015-01-29 2016-08-04 Basf Se Herbicidal phenylpyridines
WO2017202768A1 (en) 2016-05-24 2017-11-30 Basf Se Herbicidal uracilpyrid
CN109688807A (zh) 2016-07-15 2019-04-26 巴斯夫欧洲公司 具有增加的除草剂耐受性的植物
WO2018019842A1 (en) 2016-07-29 2018-02-01 Basf Se Method for controlling ppo resistant weeds
CN113105405A (zh) 2020-01-11 2021-07-13 青岛清原化合物有限公司 一种羧酸衍生物取代的亚氨基芳基化合物及其制备方法、除草组合物和应用

Non-Patent Citations (20)

* Cited by examiner, † Cited by third party
Title
"Spray-Drying Handbook", 1979, G. GOODWIN LTD.
"World Herbicide New Product Technology Handbook", September 2010, CHINA AGRICULTURAL SCIENCE AND FARMING TECHNIQUES PRESS
BRAUN ET AL., EMBO J., vol. 11, 1992, pages 3219 - 3227
CALDWELL N.J.H. V. OLPHEN: "An Introduction to Clay Colloid Chemistry", 1963, INTERSCIENCE, N.Y.
CHRISTOU, TRENDS IN PLANT SCIENCE, vol. 1, 1996, pages 423 - 431
G. C. KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS INC., pages: 81 - 96
J. D. FREYERS. A. EVANS: "Weed Control Handbook", 1968, BLACKWELL SCIENTIFIC PUBLICATIONS, pages: 101 - 103
J. E. BROWNING: "Agglomeration", CHEMICAL AND ENGINEERING, 1967, pages 147
K. MARTENS: "Handbook", 1979, G. GOODWIN LTD., article "Spray Drying"
no. 1992017-55-6
SAMBROOK ET AL.: "Molecular Cloning, A Laboratory Manual", 1989, COLD SPRING HARBOR LABORATORY PRESS
SCHÖNFELDTWISS. VERLAGAGESELL.: "Grenzflüchenaktive Äthylenoxidaddkte", SURFACE-ACTIVE ETHYLENE OXIDE ADDUCTS, 1976
See also references of EP4617275A1
SISLEYWOOD: "Encyclopedia of Surface Active Agents", CHEM. PUBL. CO. INC., 1964
SONNEWALD ET AL., PLANT J., vol. 1, 1991, pages 95 - 106
WADE VAN VALKENBURG: "Perry's Chemical Engineer's Handbook", 1973, MARCEL DEKKER, pages: 8 - 57
WATKINS: "Dorland Books", J. WILEY & SONS, article "Handbook of Insecticide Dust Diluents and Carriers"
WINNACKER: "Genes and Clones", 1996, VCH WEINHEIM, article "Gene und Klone"
WINNACKER-KUCHLER: "Chemical Technology", vol. 7, 1986, C. HAUSER VERLAG MUNICH, article "Chemische Technologie"
WOLTER ET AL., PROC. NATL. ACAD. SCI. USA, vol. 85, 1988, pages 846 - 850

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119032950A (zh) * 2024-08-20 2024-11-29 扬州大学 一种除草组合物及其制备方法和应用

Also Published As

Publication number Publication date
JP2025537252A (ja) 2025-11-14
AU2023379359A1 (en) 2025-06-26
EP4617275A1 (en) 2025-09-17
CN118005577A (zh) 2024-05-10

Similar Documents

Publication Publication Date Title
CN115707690B (zh) 一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用
JP6695967B2 (ja) ピラゾール化合物またはその塩、それらの製造方法、除草組成物およびその使用
JP7673073B2 (ja) カルボン酸誘導体で置換されたイミノアリール化合物、その調製方法、除草剤組成物及び使用
CN107629035B (zh) 一种吡唑酮类化合物或其盐、除草剂组合物及用途
JP7739280B2 (ja) 置換イソキサゾリン含有芳香族化合物、その調製方法、その除草剤組成物及びその使用
KR102276572B1 (ko) 피라졸 화합물 또는 그의 염, 및 제조 방법, 제초제 조성물 및 그의 용도
JP7419372B2 (ja) Ｎ－（１，３，４－オキサジアゾール－２－イル）アリールカルボキサミドまたはその塩、調製方法、除草組成物およびその用途
CN113149975A (zh) 一种异噁唑啉甲酸肟酯类化合物及其制备方法、除草组合物和应用
CN108586357A (zh) 取代的嘧啶甲酰基肟衍生物及其制备方法、除草组合物和应用
JP2022553987A (ja) キラル硫黄酸化物を含むアリールホルムアミド化合物またはその塩、調製方法、除草剤組成物およびそれらの使用
CN113024531A (zh) 一种含异噁唑啉的化合物及其制备方法、除草组合物和应用
JP2023139056A (ja) Ｒ－ピリジルオキシカルボン酸、その塩、そのエステル誘導体、その調製方法、その除草組成物及びその用途
CN107674025B (zh) 一种4-苯甲酰吡唑类化合物及其制备方法和应用
WO2024099118A1 (zh) 一种氧杂双环烷类化合物及其制备方法、除草组合物和应用
CN107759581B (zh) 取代的苯甲酰基异恶唑类化合物或其互变异构体、盐、制备方法、除草组合物及应用
JP7576548B2 (ja) 置換１，２，４－トリアゾロ［４，３－ａ］ピリジン誘導体、その製造方法、除草剤組成および使用
CN111285863B (zh) 4-(3-杂环基-1-苯甲酰基)吡唑类化合物或其盐、制备方法、除草剂组合物及用途
CN107353238B (zh) 取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用
CN109400526B (zh) 吡啶氧基硫酯衍生物及其制备方法、除草组合物和应用
CN107629046B (zh) 吡唑酮类化合物或其盐、除草剂组合物及用途
RU2812578C1 (ru) Диоксид замещенного тиадиазинона, способ его получения, его гербицидная композиция и его применение
US12441695B2 (en) Substituted thiadiazinone dioxide and preparation method therefor, herbicidal composition, and application therefor
RU2836575C1 (ru) Замещенное изоксазолинсодержащее ароматическое соединение, способ его получения, гербицидная композиция и ее применение
RU2777594C2 (ru) Замещенное производное пиримидинилформилоксима, способ его получения, его гербицидная композиция и применение
CN107987068A (zh) 一种二噁嗪衍生物及其制备方法、除草组合物和应用

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: 23887808

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 820301

Country of ref document: NZ

ENP Entry into the national phase

Ref document number: 2025526605

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025526605

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2501003061

Country of ref document: TH

WWE Wipo information: entry into national phase

Ref document number: 202517053319

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: AU2023379359

Country of ref document: AU

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112025009185

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2023887808

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023887808

Country of ref document: EP

Effective date: 20250610

ENP Entry into the national phase

Ref document number: 2023379359

Country of ref document: AU

Date of ref document: 20231028

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 202517053319

Country of ref document: IN

WWP Wipo information: published in national office

Ref document number: 2023887808

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 112025009185

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20250508