WO2019148850A1 - 吡啶环取代的哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用 - Google Patents

吡啶环取代的哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用 Download PDF

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WO2019148850A1
WO2019148850A1 PCT/CN2018/105407 CN2018105407W WO2019148850A1 WO 2019148850 A1 WO2019148850 A1 WO 2019148850A1 CN 2018105407 W CN2018105407 W CN 2018105407W WO 2019148850 A1 WO2019148850 A1 WO 2019148850A1
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group
alkyl
cycloalkyl
substituted
alkoxy
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PCT/CN2018/105407
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English (en)
French (fr)
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连磊
征玉荣
华荣保
王建峰
彭学岗
崔琦
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青岛清原化合物有限公司
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Priority claimed from CN201811035345.5A external-priority patent/CN110878081B/zh
Application filed by 青岛清原化合物有限公司 filed Critical 青岛清原化合物有限公司
Priority to US16/966,686 priority Critical patent/US20210032229A1/en
Priority to BR112020015704-0A priority patent/BR112020015704A2/pt
Publication of WO2019148850A1 publication Critical patent/WO2019148850A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—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 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N43/72—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
    • A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the invention belongs to the technical field of pesticides, and in particular relates to a pyridine ring-substituted pyridazine alcohol compound and a derivative thereof, a preparation method, a herbicidal composition and application.
  • weeds The control of weeds is a crucial part of the process of achieving high-efficiency agriculture.
  • herbicides on the market, such as azine-based herbicides.
  • Pyridazinol Etc. which belongs to the photosystem II inhibitor herbicide, inhibits the progress of photosynthesis by blocking electron transfer and transfer of light energy.
  • the present invention provides a pyridine ring-substituted pyridazinol compound, a derivative thereof, a preparation method, a herbicidal composition and use thereof, the compound, a derivative thereof, and a composition
  • the herbicidal activity is very high and safe and selective for crops.
  • r is an integer between 0 and 4
  • m is 0 or 1
  • n, q are each selected from an integer between 0 and 8
  • p is selected from an integer between 1 and 8; wherein each of the above groups is m, n, q, p are independently taken values, and the values are such that the Y groups are different from each other;
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl with or without halogen, and unsubstituted or substituted aryl, arylalkyl, heteroaryl Base, heteroarylalkyl;
  • R 1 , R 2 and R 3 are each independently selected from the group consisting of hydrogen, nitro, hydroxy, amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl with or without halogen.
  • alkoxy alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkane Alkylcarbonyl, alkylcarbonylalkyl, alkylacyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, Dialkylphosphono group, and unsubstituted or substituted aryl, arylalkyl, aryloxy, arylalkyloxy, aryloxyalkyl, arylcarbonyl, arylsulfonyl, heteroaryl , heteroarylalkyl, heteroaryloxyalkyloxy, heteroaryloxyalkyl, heteroaryloxyalky
  • Y each independently selected from hydrogen, halo, cyano, nitro, azido, C with or without halogen-containing alkyl group having 1 to 8, C 2 - 8 alkenyl, C 2 - 8 alkynyl group, C ⁇ . 3 8 cycloalkyl, C 5 ⁇ 8 cycloalkenyl group, C 3 ⁇ 8 1 ⁇ C 8 cycloalkyl group, unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen-containing alkyl group having 1 to 8,. 3 ⁇ C 8 cycloalkyl group,.
  • r is an integer between 0 and 4
  • m is 0 or 1
  • n, q are each selected from an integer between 0 and 6
  • p is selected from an integer between 1 and 6; wherein each of the above groups is m, n, q, p are independently taken values, and the values are such that the Y groups are different from each other;
  • R is selected from hydrogen, or halogen-containing C 1 ⁇ 8 alkyl, C 2 ⁇ 8 alkenyl group, C 2 ⁇ 8 alkynyl group, C 3 ⁇ 8 cycloalkyl, C 5 ⁇ 8 cycloalkenyl, C 3 ⁇ 8 cycloalkyl C 1-8 alkyl, and unsubstituted or 1-5 selected independently from halogen, cyano, nitro, hydroxy, carboxy, thiol, amino and C 1-8 with or without halogen alkyl group, C 3 ⁇ 8 cycloalkyl, C 3 ⁇ 8 cycloalkyl C 1 ⁇ 8 alkyl, C 2 ⁇ 8 alkenyl group, C 2 ⁇ 8 alkynyl group, C 1 ⁇ 8 alkoxy, C 1 ⁇ An aryl group substituted with a group of an 8 -alkylcarbonyl group, a C 1-8 alkoxycarbonyl group, a C 1-8 alkylsulf
  • R 1, R 2, R 3 are each independently selected from hydrogen, nitro, hydroxy, amino, C with or without halogen-containing alkyl group having 1 to 8, C 2 - 8 alkenyl, C 2 - 8 alkynyl, C 3 - 8 cycloalkyl, C 5 ⁇ 8 cycloalkenyl group, C 3 ⁇ 8 cycloalkyl C 1 ⁇ 8 alkyl, C 1 ⁇ 8 alkoxy, C 2 ⁇ 8 alkenyloxy, C 2 ⁇ 8 alkynyl group, C 3 ⁇ 8 cycloalkyl group, C 1 ⁇ 8 alkoxy-C 1 ⁇ 8 alkyl, C 1 ⁇ 8 alkoxycarbonyl, C 1 ⁇ 8 alkylcarbonyl, C 1 ⁇ 8 alkoxy a group, a C 1-8 alkylthiocarbonyl group, a C 1-8 alkylsulfonyl group, a C 1-8 alkylsulfonyl C 1-8 alky
  • Y is independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, azide, C 1-6 alkyl, C 2 -6 alkenyl, C 2 with or without fluorine, chlorine, bromine. ⁇ 6 alkynyl, C 3-6 cycloalkyl, C 5-6 cycloalkenyl, C 3-6 cycloalkyl C 1-6 alkyl, unsubstituted or 1 to 3 independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and C with or without a fluorine, chlorine, bromine 1-6 alkyl, C 1-6 cycloalkyl. 3,.
  • r is 0, 1, 2, 3 or 4
  • m is 0 or 1
  • n, q are respectively selected from 0, 1, 2, 3 or 4
  • p is selected from 1, 2, 3 or 4; wherein the above group
  • Each of m, n, q, and p is independently taken, and the values are such that the Y groups are different from each other;
  • R is selected from hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 5-6 cycloalkenene containing or not containing fluorine, chlorine or bromine.
  • a C 3-6 cycloalkyl C 1-6 alkyl group and unsubstituted or 1-3 independently selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxy, thiol, amino, and or C 1 to 6 alkyl group, C 3 to 6 cycloalkyl group, C 3 to 6 cycloalkyl C 1 to 6 alkyl group, C 2 to 6 alkenyl group, C 2 to 6 alkynyl group which do not contain fluorine, chlorine or bromine , C 1-6 alkoxy, C 1-6 alkylcarbonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylsulfonyl, C 1-6 alkylamino or C 1-6 alkyl acyl
  • R 1 , R 2 and R 3 are each independently selected from the group consisting of hydrogen, nitro, hydroxy, amino, C 1 to 6 alkyl, C 2 to 6 alkenyl, C 2 to 6 with or without fluorine, chlorine and bromine.
  • the aryl group is Heteroaryl is selected from R' represents hydrogen, nitro, hydroxy, amino, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl with or without fluorine, chlorine, bromine C 5-6 cycloalkenyl, C 3-6 cycloalkyl C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyloxy, C 2-6 alkynyloxy, C 3 to 6 cycloalkyloxy group, C 1-6 alkoxy C 1-6 alkyl group, C 1-6 alkoxycarbonyl group, C 1-6 alkylthiocarbonyl group, C 1-6 alkylsulfonyl group, C 1 to 6 alkylsulfonyl C 1-6 alkyl, C 1-6 alkylcarbonyl, C 1-6 alkylcarbonyl C 1-6 alkyl, C 1-6 alkyl acyloxy, C 1 ⁇ 6 alkyla
  • X is selected from the group consisting of chlorine, cyano, methyl, ethyl, trifluoromethyl, pentafluoroethyl, difluoromethyl, monofluoromethyl, methoxy, ethoxy, trifluoromethoxy Base, pentafluoroethoxy,
  • r 0, 1, 2, 3 or 4;
  • Y is independently selected from the group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, fluoro, chloro, bromo, amino, cyano, trifluoromethyl,
  • Derivatives of the invention refers to agriculturally acceptable hydroxy derivatives at the 4-position of the pyridazine ring of formula I, including derivatives such as salts, esters, hydrazines, hydroxylamines and ethers.
  • the salt derivative is a salt used in a usual agricultural chemical, for example, an alkali metal salt, an alkaline earth metal salt or an amine salt, or, when a basic portion is present in the molecule, for example, a sulfate or a hydrochloric acid can be prepared. Salts of salts, nitrates, phosphates, and the like. When these salts are used as herbicides for agriculture and horticulture, they are also included in the present invention.
  • the "alkali metal salt” may, for example, be a sodium salt, a potassium salt or a lithium salt, preferably a sodium salt or a potassium salt.
  • the "alkaline earth metal salt” may be, for example, a calcium salt or a magnesium salt, preferably a calcium salt.
  • the "amine salt” may, for example, be an alkyl secondary amine salt, an alkyl tertiary amine salt or an alkyl quaternary ammonium salt; an alkanol primary amine salt, an alkyl alcohol secondary amine salt, an alkyl alcohol tertiary amine salt or an alkanol.
  • a quaternary ammonium salt an alkylalkanol primary amine salt, an alkylalkanol secondary amine salt, an alkylalkanol tertiary amine salt or an alkylalkanol tertiary amine salt; or an alkoxyalkanol primary amine salt, an alkoxyalkylene salt a secondary alcohol salt, an alkoxyalkanol tertiary amine salt or an alkoxyalkanol quaternary ammonium salt, preferably wherein the alkyl group, the alkanol and the alkoxy group are independently saturated and independently contain C1-C4 More preferably, it is a monoethanolamine salt, a dimethylethanolamine salt, a triethanolamine salt, a dimethylamine salt, a triethylamine salt, an isopropylamine salt, a choline salt or a diglycolamine salt.
  • Solvates of the compounds of the invention are also included in the invention.
  • the compound of the present invention also contains a compound having an asymmetric carbon atom.
  • the present invention also encompasses a mixture of an optically active body and a plurality of optically active substances in an arbitrary ratio.
  • the ester derivative is formed by bonding an acyl group (including a carbonyl group, a thiocarbonyl group, a sulfoxide group, a sulfonyl group, a phosphoryl group, a thiophosphoryl group, etc.) to an oxygen atom of a hydroxyl group at the 4-position of the pyridazine ring.
  • an acyl group including a carbonyl group, a thiocarbonyl group, a sulfoxide group, a sulfonyl group, a phosphoryl group, a thiophosphoryl group, etc.
  • the compound may, for example, be a methyl(thio)acyl group or a C1-C18 alkane (thio)carbonyl group which may be substituted [the substituent is a halogen atom, an amino group, a C3-C8 cycloalkyl group, a C1-C8 alkoxy group, a C1 group).
  • the substituent is an oxo group and a benzoyl group which may be substituted (the substituent is a halogen atom, a C1 to C8 alkyl group, a C1 to C8 halogenated alkyl group, a C1 to C8 alkoxycarbonyl group,
  • the oxycarbonyl group ⁇ The ring of the hetero ring contains one nitrogen atom, an oxygen atom or a sulfur atom, and may
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • substituents C3 to C8 cycloalkane (thio)carbonyl, adamantyl (thio)carbonyl, C2 to C8 alkenyl (thio)carbonyl which may be substituted ⁇
  • the substituent is from a halogen atom, C1 ⁇ C8 alkoxy, and can be a phenyl, phenylthio or phenoxy group (the substituent is selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 haloalkyl group, and a C1-C8 alkoxycarbonyl group)
  • substituents selected from the same or different 1-3 substituents ⁇ , a C2-C8 alkynyl (thio)carbonyl group, a substituted benzoyl (thio) acyl group or Naphthyl (thio) acyl group The substituent is from a halogen
  • the substituent is an oxo group and a benzoyl group which may be substituted (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group, and The same or different 1 to 2 substituents selected from the same or different 1 to 3 substituents selected from the C1 to C8 alkylsulfonyl groups ⁇ , a phenyl group, a nitro group, and a C1 group which may be substituted.
  • a C8 alkoxy group (the substituent is the same or different 1-3 substituents selected from a halogen atom and a phenyl group), a phenoxy group, a 5 or 6-membered heterocyclic oxycarbonyl group which may be substituted.
  • the heterocyclic ring contains one nitrogen atom, an oxygen atom or a sulfur atom, and may further contain one or two nitrogen atoms.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • the ring of the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 ⁇ 2 nitrogen atoms.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • the heterocyclic ring contains one nitrogen atom, an oxygen atom or a sulfur atom, and may further contain one or two nitrogen atoms, or may form one
  • the substituent is a C1-C8 alkyl group which may be substituted from a halogen atom (the substituent is one or more the same or different substituents selected from a halogen atom and a phenyl group), and a C1-C8 alkylcarbonyl group.
  • a C1-C8 alkoxycarbonyl group a phenyl group which may be substituted (the substituent is the same or different 1-3 halogen atoms), a nitro group, a hydroxyl group, a C1-C8 alkoxy group, a phenoxy group, a C1 ⁇ a C8 alkylthio group, a C2 to C8 alkenylthio group, and the same or different 1 to 3 substituents selected from the phenylthio group ⁇ , a 5 to 14 membered condensed bicyclic or tricyclic heterocyclic ring which may be substituted (thio)carbonyl group (the ring of the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms or oxygen atoms.
  • the substituent is a halogen atom and a C1-C8 alkyl group.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • the substituent is a C1-C8 alkyl group which may be substituted (the substituent is a halogen atom, a C1-C8 alkane)
  • substituents selected from the same or different 1 to 3 substituents selected from the C1 to C8 alkylsulfonyl groups, and the C3 to C8 cycloalkenyloxy which may be substituted Sulfonyl group ⁇
  • the substituent is an oxo group and a benzoyl group which may be substituted (the substituent is a halogen atom, a C1 to C8 alkyl group, a C1 to C8 haloalkyl group, a C1 to C8 alkoxycarbonyl group, a nitro group).
  • the sulfamoyl group contains one nitrogen atom, an oxygen atom or a sulfur atom, and may further contain 1 to 2 nitrogen atoms.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • the ring of the heterocyclic ring contains one nitrogen atom, an oxygen atom or a sulfur atom, and may further contain 1 to 2 nitrogen atom
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • it may be a C1-C10 alkane (thio)carbonyl group which may be substituted.
  • the substituent is from fluorine, chlorine, bromine, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio.
  • a C1-C6 alkoxycarbonyl group a C1-C6 alkylcarbonyl group, a C1-C6 alkylcarbonyloxy group, a phenyl group which may be substituted, a phenylthio group, a phenoxy group or a benzyloxy group (the substituent is from fluorine or chlorine)
  • substituents selected from the group consisting of bromine, C1-C6 alkyl, and the same or different 1-3 substituents selected from C1 to C6 alkoxy groups ⁇ , C3 to C6 a cycloalkane (thio)carbonyl group, a C2-C6 alkenyl (thio)carbonyl group which may be substituted.
  • the substituent is a fluorine, chlorine, bromine, C1-C6 alkoxy group, a phenyl group which may be substituted, a phenylthio group or a phenoxy group (the substituent is one or more selected from the group consisting of fluorine, chlorine, bromine, C1-C6 alkyl group, and the same or different 1-3 substituents selected from C1-C6 alkoxy groups)
  • the same or different substituents ⁇ , a benzoyl (thio) acyl group or a naphthyl (thio) acyl group which may be substituted.
  • the substituent is a C1-C6 alkyl group or a C1 group which may be substituted from fluorine, chlorine, bromine.
  • C6 alkoxy group (the substituent is the same or different from fluorine, chlorine, bromine and phenyl) 1 to 3 substituents), a cyano group, a hydroxyl group, a C1 to C6 alkylcarbonyl group, a C1 to C6 alkoxycarbonyl group, a C1 to C6 alkylcarbonyloxy group, a C1 to C6 alkylcarbonylamino group, an amino group which may be substituted (this
  • the substituent is the same or different 1-3 substituents selected from C1 to C6 alkyl, C1-C6 alkoxy, C1-C6 alkylcarbonyl, halogenated C1-C6 alkyl and phenyl), benzene
  • 1 to 3 substituents selected from the group consisting of a nitro group and a
  • the substituent is a C1-C6 alkyl group which may be substituted from fluorine, chlorine, bromine (the substituent is one or more the same or different substituents selected from fluorine, chlorine, bromine and phenyl) , C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenyl which may be substituted (the substituent is the same or different 1-3 substituents selected from fluorine, chlorine, bromine), nitro , a hydroxyl group, a C1-C6 alkoxy group, a phenoxy group, a C1-C6 alkylthio group, a C2-C6 alkenylthio group, and the same or different 1 to 3 substituents selected from the phenylthio group, may be a substituted 5 to 14 membered fused bicyclic or tricyclic heterocyclic (thio)carbonyl group (the heterocyclic ring is The substituent is the same or different 1 to 3 substituents
  • alkylthio (thio)carbonyl group (the substituent is one or more of the same or different substituents selected from the group consisting of fluorine, chlorine, bromine, C1-C6 alkoxy, and phenyl), C3 to C6 naphthenic Alkoxy (thio)carbonyl, C3-C6 cycloalkylthio(thio)carbonyl, phenoxy(thio)carbonyl which may be substituted, phenylthio(thio)carbonyl, benzene C1-C6 alkyloxy ( Sulfur)carbonyl or benzene C1-C6 alkylthio(thio)carbonyl (the substituent is from fluorine, chlorine, bromine, C1-C6 alkyl, cyano, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl , the same or different 1 to 3 substituents selected from the nitro group and the C1 to C6 alkoxy group
  • An alkylaminosulfonyl group (the substituent is one or more identical or different substituents selected from fluorine, chlorine, and bromine), (Het is R a and R b independently represent a compound in which hydrogen, a C1 to C6 alkyl group, a di(C1-C6 alkyl)phosphoryl group, or a di(C1-C6 alkyl)thiophosphoryl group are bonded.
  • the anthracene derivative refers to a sulfhydryl group formed by bonding an oxygen atom of a hydroxyl group at the 4-position of the pyridazine ring.
  • R 11 and R 22 each independently represent hydrogen, a C1 to C18 alkyl group which may be substituted or a C 2 -C 18 alkenyl group (the substituent is a halogen atom, a C1 to C8 alkoxy group, C1).
  • a C8 alkylthio group one or more identical or different substituents selected from a C1 to C8 alkylamino group, a phenyl group, a phenyl group or a 5-6 membered heterocyclic group which may be substituted (this The substituent is a halogen atom, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C1-C8 haloalkyl group, a C1-C8 alkylcarbonyl group, a C1-C8 alkoxy group.
  • R 11 and R 22 each independently represent hydrogen, a C 1 -C 10 alkyl group which may be substituted or a C 2 -C 10 alkenyl group (the substituent is a fluorine, chlorine, bromine, C 1 -C 6 alkoxy group).
  • a C1-C6 alkylthio group one or more identical or different substituents selected from a C1-C6 alkylamino group, a phenyl group, a phenyl group or a 5-6 membered heterocyclic group which may be substituted
  • the aromatic heterocyclic group is The substituent is from fluorine, chlorine, bromine, C1-C6 alkyl group, C3-C6 cycloalkyl group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxy group, C1-C6 alkoxycarbonyl group.
  • R 11 , R 22 forms a 5, 6 membered saturated carbocyclic ring or a 5 or 6 membered heterocyclic ring (containing at least one hetero atom such as oxygen, sulfur, nitrogen, etc.).
  • the hydroxylamine derivative is a hydroxyl group-containing group formed by bonding an oxygen atom of a hydroxyl group at the 4-position of the pyridazine ring.
  • R 11 ', R 22 ' may independently represent hydrogen, a C1 to C18 alkyl group which may be substituted or a C2 to C18 alkenyl group (the substituent is a halogen atom, a C1 to C8 alkoxy group).
  • a C1-C8 alkylthio group one or more identical or different substituents selected from a C1-C8 alkylamino group, a phenyl group which may be substituted (the substituent is a halogen atom, a C1-C8 alkane) a group, a C2 to C8 alkenyl group, a C2 to C8 alkynyl group, a C3 to C8 cycloalkyl group, a C1 to C8 haloalkyl group, a C1 to C8 alkylcarbonyl group, a C1 to C8 alkoxy group, a C1 to C8 alkoxycarbonyl group, a C1 ⁇ a C8 alkylamino group, a hydroxyl group, a carboxyl group, a decyl group, an amino group, a cyano group, a nitro group, and the same or different 1-3 substituents selected from the group consisting of a C1 to
  • the substituent is an oxo group and a benzoyl group which may be substituted (the substituent is a halogen atom, a C1 to C8 alkyl group, a C1 to C8 halogenated alkyl group, a C1 to C8 alkoxycarbonyl group,
  • a nitro group a C1 to C8 alkoxy group which may be substituted, a C1 to C8 alkylamino group or a C1 to C8 alkylthio group (the substituent is the same or different from the halogen atom and the phenyl group) 3 substituents), phenoxy group, 5 or 6 membered heterocyclic oxycarbonyl group which may be substituted ⁇
  • the ring of the hetero ring contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 Nitrogen atom.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • the ring of the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 ⁇ 2 nitrogen atoms.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • R 11 ', R 22 ' may independently represent hydrogen, a C1-C10 alkyl group or a C2-C10 alkenyl group which may be substituted (the substituent is selected from fluorine, chlorine, bromine) One or more of the same or different substituents), a C1-C10 alkoxycarbonyl group, a phenyl group or a benzoyl group which may be substituted (the substituent is from fluorine, chlorine, bromine, C1-C6 alkyl, C2-C6) Alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylamino, The same or different 1-3 substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a decy
  • the ether derivative refers to a compound which is bonded to an oxygen atom of a hydroxyl group at the 4-position of the pyridazine ring, and may be, for example, a C1 to C18 alkyl group or a C2 to C18 alkenyl group which may be substituted (
  • the substituent is a halogen atom, a C1-C8 alkoxy group, a C1-C8 alkylthio group, a C1-C8 alkylamino group, a di-C1-C8 alkylamino group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkoxycarbonyl group.
  • substituents selected from the oxy group a phenyl group, a benzyl group or a benzoyl group C1 to C8 alkyl group which may be substituted
  • the substituent is a halogen atom, which may be substituted a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group or a C3-C8 cycloalkyl group (the substituent is the same or different one to three substituents selected from a halogen atom and a phenyl group) , cyano, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C2-C8 alkenyloxycarbonyl which may be substituted.
  • the substituent is a C3-C8 cycloalkyl group. a cyano group and a benzoyl group which may be substituted (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group, and a C1-C8 alkylsulfonyl group).
  • Selected phase Or the same or different 1 to 3 substituents selected from 1 to 3 substituents ⁇ , a C3 to C8 cycloalkenyloxycarbonyl group which may be substituted.
  • the substituent is from oxo and can be a substituted benzoyl group (the substituent is the same selected from the group consisting of a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group, and a C1-C8 alkylsulfonyl group)
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • the ring of the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 ⁇ 2 nitrogen atoms.
  • the substituent is a phenoxy group which may be substituted from a halogen atom, a C1-C8 alkyl group (the substituent is a halogen atom, a C1-C8 alkyl group, a C1-C8 halogenated alkyl group, a C3-C8 cycloalkyl group, and C1).
  • it may be a C8-C18 alkyl group or a C8-C18 alkenyl group, a substituted C1-C10 alkyl group or a C2-C10 alkenyl group (the substituent is from a fluorine, chlorine, bromine, C1-C6 alkoxy group).
  • a C1-C6 alkylthio group, a C1-C6 alkylamino group, a C1-C6 alkoxycarbonyl group, or one or more identical or different substituents selected from a C1-C6 alkoxycarbonyloxy group may be substituted Phenyl, benzyl or benzoyl C1-C6 alkyl (the substituent is from fluorine, chlorine, bromine, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic a C1-C6 haloalkyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxy group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylamino group, a hydroxyl group, a carboxyl group, a decyl group, an amino group, a cyano group,
  • a method for preparing the pyridine ring-substituted pyridazinol compound comprising the steps of:
  • L 1 and L 2 each independently represent a halogen, preferably chlorine, bromine or iodine.
  • the reaction temperature is in the range of 20 to 150 ° C, preferably 50 to 130 ° C.
  • the step (1) is carried out in the presence of a catalyst, a base and a solvent, and the catalyst is Pd(dppf)Cl 2 CH 2 Cl 2 , Pd(dba) 2 , Pd 2 (dba) 3 , Pd(PPh 3 ) 4 , PdCl 2 , Pd(OAc) 2 , Pd(dppf)Cl 2 , Pd(PPh 3 ) 2 Cl 2 or Ni(dppf)Cl 2 , the base is selected from the group consisting of Et 3 N, NaHCO 3 , KOAc, K 2 CO 3 , K 3 or more of PO 4 , Na 2 CO 3 , CsF, Cs 2 CO 3 , t-BuONa, EtONa, KOH and NaOH, and the solvent is THF/water, toluene/water, DMF/water, 1, 4-dioxane/water, toluene/ethanol/water or acetonitrile/water, THF, to
  • Q 1 halogen, preferably chlorine or bromine
  • Q 2 halogen preferably chlorine or fluorine.
  • the reaction for preparing the ester and the ether derivative and the second step of preparing the hydrazine and the hydroxylamine derivative are carried out in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, and the like.
  • the solvent is THF, 1,4-dioxane, toluene, 1,2-di Ethyl chloride, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane or chloroform;
  • the first step in the preparation of the oxime and hydroxylamine derivatives is carried out in the presence of a halogenating agent and a solvent, the halogen
  • the reagent is Phenofluor / cesium fluoride or POCl 3
  • the solvent is selected from one or more of toluene, 1,2-dichloroethane, DMF;
  • the reaction temperature is selected from the range of 0 to 120 ° C Internally, it is preferably 20-80 °C.
  • the compounds of the present invention may exist in the form of one or more stereoisomers.
  • the various isomers include enantiomers, diastereomers, geometric isomers. It is within the scope of the invention for these isomers to include mixtures of such isomers.
  • a herbicidal composition comprising (i) a pyridine ring-substituted pyridazinol compound of the formula I and derivatives thereof.
  • it further comprises (ii) one or more additional herbicides and/or safeners.
  • an agrochemically acceptable formulation aid is also included.
  • the additional herbicide is selected from the group consisting of an HPPD inhibitor, a hormone, and a PDS inhibitor; preferably, the HPPD inhibitor is sulcotrione, mesotrione, oxazolone, sulfonone, fluoropyridin Oxalone, furanone, dicyclohexanone, lancotrione, oxazolone, ciprofloxacin, triazosulfone, oxazolone, sulfonylpyrazole, pyrazol, piracet Ketone, tolpyralate, fenquinotrione, isoxaflutole; hormones are flufenoxyacetic acid, fluorochloropyridinium, chlorofluoropyridyl ester, quinclorac, chloromethyl quinolinic acid, 2 methyl 4-chloro, 2-methyl 4-chlorophenoxypropionic acid, MCPB, 2,4-D, 2,4-D-propionic acid, 2,4-DB
  • the flupiroxyacetic acid derivative comprises, but is not limited to: isooctyl chlorofluoxetine; 2 methyl 4-chloro, 2-methyl-4-chlorophenoxypropionic acid, MCPB derivatives include but are not limited to: sodium Salt, potassium salt, dimethylammonium salt, isopropylamine salt, etc., and methyl ester, ethyl ester, isooctyl ester, ethyl thioester, etc.; 2,4-D, 2,4-D-propionic acid, 2,4-DB Derivatives include, but are not limited to, salts such as sodium salts, potassium salts, dimethylammonium salts, triethanolammonium salts, isopropylamine salts, choline, and the like, and esters such as methyl esters, ethyl esters, butyl esters, isooctyl esters, and the like.
  • a method for controlling a harmful plant comprising using at least one of the herbicidal effective amount of the pyridine ring-substituted pyridazine compound and a derivative thereof or the herbicidal composition for use on a plant or a harmful plant region.
  • At least one of the pyridine ring-substituted pyridazinol compounds and derivatives thereof or the herbicidal composition described is used to control harmful plants in useful crops.
  • the useful crop is a crop that has been treated with a genetically modified crop or genome editing technique.
  • the compounds of formula I of the present invention have outstanding herbicidal activity.
  • the active substances of the present invention are also effective for perennial weeds which grow from rhizomes, rhizomes, or other perennial organs and are difficult to control. In this regard, it is generally not important to use the substance before, before, or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the invention, without limiting the identified species.
  • weed species in which the active substance is effective include monocotyledons: annual oats, rye, grasses, maiden, ferraris, medlar, genus, foxtail, and sedge, and perennial ice. Genus, Bermudagrass, Rhizoma and sorghum, and perennial sedge.
  • dicotyledonous weed species species whose effects can be extended to, for example, the annual genus Polyporus, Amaranth, Pomna, Wild Sesame, Stellaria, Amaranthus, White Mustard, Ipomoea, and Yellow Flower Genus, Matricaria and genus, and perennial weeds, genus, genus and genus.
  • the active substance of the present invention effectively controls harmful plants under the conditions of rice sowing, such as cockroaches, genus, genus, genus, genus, cane, and sedge.
  • the compound of the present invention is applied to the surface of the soil before germination, the weeds of the weeds can be completely prevented before the weeds grow, or when the weeds grow out of the cotyledons, and finally completely die after three to four weeks.
  • the compound of the present invention is particularly resistant to the following plants, and is active in the following plants, such as Apila, Xiaoye Sesame, Rolling Stalk, Poria, Ivy, Herba, Arabian, Pansy, Pansy, Poria and Kochia. .
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no damage to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. Or the damage is trivial. In particular, it is well compatible with cereal crops such as wheat, barley and corn, especially wheat. Thus, the compounds of the invention are highly suitable for the selective control of unwanted plants in agricultural or ornamental plants.
  • Transgenic plants Due to their herbicidal nature, these active substances can be used to control harmful plants in genetically engineered plant cultivation that is known or to be present.
  • Transgenic plants generally have superior traits, such as resistance to specific insecticides, particularly specific herbicides, resistance to pathogenic microorganisms of plant diseases or plant diseases, such as specific insect or fungal, bacterial or viral microorganisms.
  • Other specific traits are related to the following conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients.
  • the obtained transgenic plant product has an increased starch content or an improved starch quality or a different fatty acid composition.
  • the compounds of the formula I according to the invention and their derivatives are preferably used for economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or for beets Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of the formula I and their derivatives are preferably used as herbicides for the cultivation of useful plants which are resistant or tolerant to the toxic effects of the herbicide by genetic engineering.
  • transgenic crop plant such as cotton which is capable of producing Bacillus thuringiensis toxin (Bt toxin) which protects against specific pests against plants (EP-0142924A, EP-0193259A);
  • Plant cells of the activity-reducing gene product can be prepared by, for example, expressing at least one appropriate antisense-RNA, sense-RNA to achieve co-suppression, or by expressing at least one appropriately constructed ribozyme, It specifically cleaves the transcription product of the above gene product.
  • DNA molecules comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and the use of DNA molecules comprising only a portion of the coding sequence, which must be sufficiently long to achieve antisense in the cell Effect. Sequences that are highly homologous but not identical to the gene product coding sequence can also be used.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • These sequences are known to those skilled in the art (see, for example, Braun et al, EMBO J. 11 (1992) 3219-3227; Wolter et al, Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).
  • Transgenic plant cells can be recombined into whole plants using known techniques.
  • the control can be improved or expanded.
  • the range of weeds, the application rate at the time of application is preferably a combination of the resistance of the transgenic crops and the performance of the herbicide, and the effects of the growth and yield of the transgenic crop plants.
  • the invention therefore also provides the use of said compounds as herbicides to control harmful plants in plants of transgenic crops.
  • the compounds of the invention can significantly modulate the growth of crop plants. By modulating the involvement of plant metabolism, these compounds are used to orient the components of the plant and promote harvesting, such as drying and dwarfing the plants. Moreover, they are also suitable for regulating and inhibiting unwanted plant growth without destroying the growth of the crop. Inhibition of plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, as this reduces or completely prevents lodging.
  • the compound of the present invention can be applied using a general formulation, and a wettable powder, a concentrated emulsion, a sprayable solution, a powder or granules can be used.
  • a herbicidal composition comprising a compound 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, concentrated emulsions (EC), emulsions such as oil dispersed in water and water dispersed in oil (EW) , sprayable solution, suspension concentrate (SC), dispersible oil suspension (OD), oil or water diluent, solution of miscible oil, powder (DP), capsule suspension (CS) ), seed dressing composition, particles for spreading and soil application, sprayed particles, coated particles and absorbent particles, water dispersible particles (WG), water soluble particles (SG), ULV (super Low volume) formula, microcapsules and wax products.
  • WP wettable powders
  • SP water soluble powders
  • EC concentrated emulsions
  • EW oil dispersed in water and water dispersed in oil
  • SC sprayable solution, suspension concentrate
  • OD dispersible oil suspension
  • DP powder
  • Wettable powders can be uniformly dispersed in water, in addition to active substances, including diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersing agents), such as polyethoxylated alkylphenols, poly Ethoxylated fatty alcohol, polyoxyethyl aliphatic amine, fatty alcohol polyglycol ether sulfate, alkyl sulfonate, alkyl phenyl sulfonate, sodium lignosulfonate, 2, 2'- dinaphthylmethane Sodium 6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate.
  • the herbicide active substance is finely ground, for example, using a conventional apparatus such as a hammer mill, a fan mill and a jet mill, and an auxiliary agent is simultaneously or sequentially mixed.
  • a concentrated emulsion such as butanol, cyclohexanone, dimethylformamide, xylene or a higher boiling aromatic compound or a mixture of hydrocarbons or solvents, and adding one more One or more ionic and/or nonionic surfactants (emulsifiers).
  • emulsifiers which can be used are, for example, calcium alkylaryl sulfonates of calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A glycan ester.
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A gly
  • the active substance and the finely divided solid matter are ground to obtain a powder, a solid substance such as talc, a natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • a water or oil based suspension can be prepared by, for example, wet milling using a commercially available bead mill with or without the addition of a surfactant of the other formulation type described above.
  • an aqueous organic solvent may be used, using a stirrer, a colloid mill and/or a static mixer, and if necessary, a surfactant of another formulation type as described above may be added.
  • the granules are prepared by spraying the active material onto the adsorbate, granulating with an inert material, or concentrating the active material onto the surface of, for example, a sand or kaolinite carrier, granulating the inert material by a binder, and adhering Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • Suitable actives can be plasmidized by the method of preparing fertilizer granules, and if necessary, fertilizer can be mixed.
  • the water-suspended granules are prepared by a usual method such as spray-drying, fluidized bed granulation, disc granulation, mixing using a high speed mixer, and extrusion without a solid inert material.
  • the agrochemical formulations usually comprise from 0.1 to 99% by weight, in particular from 0.1 to 95%, of the active substance I.
  • the concentration of the active substance in the wettable powder is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remaining amount by weight to 100%.
  • the concentration of the active substance in the concentrated emulsion may range from about 1 to 90%, preferably from 5 to 80% by weight.
  • the powder formulation comprises from 1 to 30% by weight of active substance, usually from 5 to 20% by weight of active substance, whereas the sprayable solution comprises from about 0.05 to 80%, preferably from 2 to 50% by weight of active substance. .
  • the content of the active material in the water-suspended granules mainly depending on whether the active material is liquid or solid, and auxiliaries, fillers and the like used in granulation.
  • the content of the active substance in the aqueous suspension granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the preparation of the active substance may include a tackifier, a wetting agent, a dispersing agent, an emulsifier, a penetrating agent, a preservative, an antifreezing agent, a solvent, a filler, a carrier, a coloring agent, an antifoaming agent, an evaporation inhibitor, and pH and viscosity modifiers commonly used in all cases.
  • insecticide active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and/or plant growth regulators.
  • safeners for premixed or filled mix.
  • the commercially available formulations are diluted in a conventional manner, for example, in wettable powders, concentrated emulsions, suspensions, and granules suspended in water, diluted with water.
  • Granules for granules or soil application or sprayed and sprayed solutions are generally not required to be further diluted with inert materials prior to use.
  • the amount of the compound of formula I required varies with external conditions, such as temperature, humidity, the nature of the herbicide used, and the like. It can have a large range of variation, for example between 0.001 and 1.0 kg/ha, or more active substance, but preferably between 0.005 and 750 g/ha, in particular between 0.005 and 250 g/ha.
  • Tables 1-5 In view of the economics and diversity of the compounds, we prefer to synthesize some of the compounds, and among the many compounds synthesized, the selected parts are listed in Tables 1-5 below. The specific compound structure and corresponding compound information are shown in Table 1-5. The compounds in Tables 1-5 are for the purpose of better illustrating the present invention, but are not intended to limit the invention, and it is understood by those skilled in the art that the scope of the present invention is limited to the following compounds.
  • reaction solution was cooled to 25 ° C, 1M HCl was added dropwise to the reaction solution until the pH of the solution was about 5, the process controlled temperature (not higher than 25 ° C), solid precipitation, the precipitated solid was suction filtered, with After washing with a large amount of water, the solid was purified by methyl-t-butyl ether (20mL) and a small amount of methanol (1mL), and the solid was filtered and dried to give 500 mg (2mmol, yield 54%) of compound 1-7 (gray solid).
  • the compound 1-1 was synthesized by the above-mentioned method 1, and the compound 1-1 (1 g, 4.8 mmol), potassium carbonate (2 g, 14.4 mmol), acetonitrile (20 mL) was placed in a round bottom flask, and the reaction system was carried out at 25 ° C at 25 ° C.
  • the compound I-1-a (1.08 g, 7.2 mmol) was added dropwise, and the mixture was reacted at 25 ° C for 5 hours.
  • the reaction system was filtered to remove the remaining potassium carbonate solid, and the mother liquid was concentrated and separated by column chromatography. 1 g (3.1 mmol, yield 67%) of compound 1-1 (white solid) was obtained.
  • Compound 2-1 was synthesized by the method 1 above, and Compound 2-1 (2 g, 9.6 mmol), potassium carbonate (4 g, 28.8 mmol), Compound I-2-a (2.4 g, 14.4 mmol), acetonitrile (40 mL) In a round bottom flask, the reaction was carried out at 25 ° C overnight (about 12 hours), after the end of the reaction by high performance liquid chromatography, the reaction system was filtered off the remaining potassium carbonate solid, the mother liquid was concentrated, and separated by prep-HPLC to obtain a yellow solid compound I -2 (600 mg, yield 18.5%).
  • Compound 1-1 was synthesized by referring to the above Method 1, and a compound 1-1 (1 equivalent), triethylamine (3 equivalent) and dichloromethane (5 V) were added to a 50 mL single-mouth eggplant flask under ice bath, and dropped in an ice bath. plus (1.2 equivalents), then stirred at room temperature for 30 minutes. TLC detection reaction has been completed, the reaction is added with water (5V), extracted with dichloromethane (5V*3), dichloromethane is distilled off under reduced pressure, and the residue is separated by column chromatography silica gel (100 mesh to 200 mesh) to obtain product. The rate is 76%.
  • Compound 1-1 was synthesized by referring to the above Method 1, and a compound 1-1 (1 equivalent), Phenofluor (1.5 equivalent), cesium fluoride (3 equivalent), and toluene (10 V) were added to a 50 mL single-mouth eggplant flask at room temperature. Stir to 80 ° C for 18 h. The TLC assay reaction has been completed and the post-treatment intermediate compound I-5-a. Add compound I-5-a (1 equivalent) in another 50 mL single-mouth eggplant bottle at room temperature, (1.2 equivalents), potassium carbonate (3 equivalents) and acetonitrile (10V), warmed to 80 ° C and stirred for 18 h. The TLC detection reaction was completed, and the reaction system was evaporated to remove acetonitrile under reduced pressure. Water (5V) was dissolved and extracted with ethyl acetate (5V*3), and ethyl acetate was evaporated under reduced pressure. Separation to 200 mesh) gave the product in a yield of 62%.
  • Compound 1-1 was synthesized by referring to the above Method 1, and a compound 1-1 (1 equivalent), POCl 3 (1.5 equivalent), 1,2-dichloroethane (10 V), 5 was added at room temperature in a 50 mL single-mouth eggplant bottle. % N,N-dimethylformamide, warmed to 80 ° C and stirred for 6 h. The TLC detection reaction was completed, and after adding water (5 V), it was extracted with 1,2-dichloroethane (5V*3), and 1,2-dichloroethane was distilled off under reduced pressure to obtain compound I-6-a.
  • the activity level criteria for harmful plant damage are as follows:
  • Grade 9 growth control rate is above 90%
  • Level 6 The growth control rate is above 60%
  • Level 3 growth control rate is above 30%
  • Level 1 The growth control rate is less than 20%
  • the above growth control rate is the fresh weight control rate.
  • Post-emergence test Place monocotyledonous and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, canola, millet, sorghum) in a plastic pot containing soil, then cover 0.5-2 Cm soil, so that it grows in a good greenhouse environment, after 2-3 weeks of sowing, the test plants are treated in the 4-5 leaf stage, and the tested compound of the present invention is dissolved in acetone, and then Tween 80 is added, with a certain amount. The water is diluted to a concentration of the solution and sprayed onto the plants using a spray tower. After the application, the culture was carried out for 3 weeks in the greenhouse, and the experimental effects of the weeds after 3 weeks are shown in Table 6.
  • the compounds of the present invention have significantly higher herbicidal activity than the comparative compounds A and B.
  • the compound of the present invention to be tested was dissolved in acetone, and then Tween 80 was added thereto, and diluted to a certain concentration with a certain amount of water, and sprayed immediately after sowing. After application for 4 weeks in the greenhouse, the results of the experiment were observed after 3 weeks, and it was found that most of the agents of the present invention were excellent in the measurement of 250 g/ha, especially for weeds such as valerian, horse pond, ramie, and many other compounds. Good selectivity for corn, wheat, rice, soybeans, and rapeseed.
  • the paddy soil After filling the paddy soil in a 1/1,000,000 hectare tank, seeds of valerian, flamingo, wolf grass, and wild sage were planted, and the soil was gently covered thereon. Thereafter, it was placed in a greenhouse at a depth of 0.5 to 1 cm, and the tubers of the wild sage were implanted the next day or two days later. Thereafter, the water retention depth is 3-4 cm, and the wettability of the compound of the present invention is prepared according to the usual preparation method at the time when the grass, the firefly, the wolf grass reaches 0.5 leaf, and the wild sage reaches the primary leaf stage. A water dilution of a powder or a suspension is uniformly dripped with a pipette to achieve a prescribed amount of active ingredient.
  • the transplanting depth was 3 cm to transplant the rice (japan) in the 3 leaf stage.
  • the compound of the present invention was treated in the same manner as above on the fifth day after transplantation.

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Abstract

本发明属于农药技术领域，具体涉及一种吡啶环取代的哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用。所述化合物如通式（I）所示：（I）其中，X选自卤素、氰基、烷基、卤代烷基、烷氧基、卤代烷氧基、R1R2N-(C＝O)-、R1R 2N-、羟基、未取代或取代的芳基；Y彼此独立地选自氢，卤素，氰基，硝基，R-O-(CH2) n-，R1R2R3SiO-等；r为0～4之间的整数，m为0或1，n、q分别选自0～8之间的整数，p选自1～8之间的整数；R选自氢，含有或不含有卤素的烷基、链烯基、炔基、环烷基等；R1、R2、R3分别独立地选自氢，硝基，羟基等。所述化合物及其衍生物、组合物的除草活性非常高且对作物安全、选择性好。

Description

吡啶环取代的哒嗪醇类化合物及其衍生物、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，具体涉及一种吡啶环取代的哒嗪醇类化合物及其衍生物、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，目前市场上的除草剂种类多样，如哒嗪类除草剂哒草特
Figure PCTCN2018105407-appb-000001
哒嗪醇
Figure PCTCN2018105407-appb-000002
等，其属于光系统Ⅱ抑制剂类除草剂，通过阻塞电子传递和光能的转移，从而抑制光合作用的进行。
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，本发明提供了一种吡啶环取代的哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用，所述化合物及其衍生物、组合物的除草活性非常高且对作物安全、选择性好。
本发明采用的技术方案如下：
一种如通式I所示的吡啶环取代的哒嗪醇类化合物及其衍生物：
Figure PCTCN2018105407-appb-000003
其中，X选自卤素、氰基、烷基、卤代烷基、烷氧基、卤代烷氧基、R 1R 2N-(C＝O)-、R 1R 2N-、羟基、未取代或取代的芳基；
Y彼此独立地选自氢，卤素，氰基，硝基，叠氮基，含有或不含有卤素的烷基、烯基、炔基、环烷基、环烯基、环烷基烷基，未取代或取代的芳基、芳基烷基、杂芳基、杂芳基烷基，R-O-(CH 2) n-，R-O-(CH 2) p-O-(CH 2) q-，R-O-(CH 2) p-S-(CH 2) q-，R-S-(CH 2) n-，R-S-(CH 2) p-O-(CH 2) q-，R-S-(CH 2) p-S-(CH 2) q-，R-O-(CH 2) n-(C＝O)-(CH 2) q-(O) m-，R-S-(CH 2) n-(C＝S)-(CH 2) q-(S) m-，R-O-(CH 2) n-(C＝O)-(CH 2) q-(S) m-， R-O-(CH 2) n-(C＝S)-(CH 2) q-(O) m-，R-S-(CH 2) n-(C＝O)-(CH 2) q-(O) m-，R-O-(CH 2) n-(C＝S)-(CH 2) q-(S) m-，R-S-(CH 2) n-(C＝O)-(CH 2) q-(S) m-，R-S-(CH 2) n-(C＝S)-(CH 2) q-(O) m-，R-(C＝O)-(CH 2) n-，R-(C＝S)-(CH 2) n-，R-(C＝O)-(CH 2) n-O-(CH 2) q-，R-(C＝S)-(CH 2) n-S-(CH 2) q-，R-(C＝O)-(CH 2) n-S-(CH 2) q-，R-(C＝S)-(CH 2) n-O-(CH 2) q-，R-SO-(CH 2) n-(O) m-，R-SO-(CH 2) n-(S) m-，R-SO-(CH 2) n-(NR 3) m-，R-SO 2-(CH 2) n-(O) m-，R-SO 2-(CH 2) n-(S) m-，R-SO 2-(CH 2) n-(NR 3) m-，R 1R 2N-(CH 2) n-，R 1R 2N-(CH 2) n-O-(CH 2) q-(O) m-，R 1R 2N-(CH 2) n-O-(CH 2) q-(S) m-，R 1R 2N-(CH 2) n-O-(CH 2) q-(NR 3) m-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-(O) m-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-(S) m-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-(NR 3) m-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-(O) m-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-(S) m-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-(NR 3) m-，R 1R 2PO 3-(O) m-(CH 2) q-，R 1R 2R 3SiO-(CH 2) q-，R 1R 2R 3Si-(CH＝CH) m-(CH 2) q-，R 1R 2C＝N-(O) m-(CH 2) n-，R 1R 2C＝N-NH-(CH 2) n-；或者相邻两个Y一起形成-OCH 2O-、-CH 2CH 2O-、-OCH 2CH 2O-、-OCH(CH 3)O-、-OC(CH 3) 2O-、-OCF 2O-、-CF 2CF 2O-、-OCF 2CF 2O-或-CH＝CH-CH＝CH-；
r为0～4之间的整数，m为0或1，n、q分别选自0～8之间的整数，p选自1～8之间的整数；其中，上述基团中各m、n、q、p分别独立地取值，且取值使各Y基团之间互不相同；
R选自氢，含有或不含有卤素的烷基、烯基、炔基、环烷基、环烯基、环烷基烷基，以及未取代或取代的芳基、芳基烷基、杂芳基、杂芳基烷基；
R 1、R 2、R 3分别独立地选自氢，硝基，羟基，氨基，含有或不含有卤素的烷基、烯基、炔基、环烷基、环烯基、环烷基烷基、烷氧基、烯基氧基、炔基氧基、环烷基氧基、烷氧基烷基、烷氧基羰基、烷硫基羰基、烷基磺酰基、烷基磺酰基烷基、烷基羰基、烷基羰基烷基、烷基酰氧基、烷基氨基、烷基氨基羰基、烷氧基氨基羰基、烷氧基羰基烷基、烷氨基羰基烷基、三烷基甲硅烷基、二烷基膦酰基，以及未取代或取代的芳基、芳基烷基、芳基氧基、芳基烷基氧基、芳基氧基烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基烷基、杂芳基氧基、杂芳基烷基氧基、杂芳基氧基烷基、杂芳基羰基、杂芳基磺酰基；或者R 1R 2N-选自未取代或取代的六元杂环基。
优选地，X选自卤素、氰基、C 1～8烷基、卤代C 1～8烷基、C 1～8烷氧基、卤代C 1～8烷氧基、R 1R 2N-(C＝O)-、R 1R 2N-、羟基、未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基；
Y彼此独立地选自氢，卤素，氰基，硝基，叠氮基，含有或不含有卤素的C 1～8烷基、C 2～8 烯基、C 2～8炔基、C 3～8环烷基、C 5～8环烯基、C 3～8环烷基C 1～8烷基，未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基、芳基C 1～8烷基、杂芳基、杂芳基C 1～8烷基，R-O-(CH 2) n-，R-O-(CH 2) p-O-(CH 2) q-，R-O-(CH 2) p-S-(CH 2) q-，R-S-(CH 2) n-，R-S-(CH 2) p-O-(CH 2) q-，R-S-(CH 2) p-S-(CH 2) q-，R-O-(CH 2) n-(C＝O)-(CH 2) q-，R-S-(CH 2) n-(C＝S)-(CH 2) q-，R-O-(CH 2) n-(C＝S)-(CH 2) q-，R-S-(CH 2) n-(C＝O)-(CH 2) q-，R-O-(C＝O)-(CH 2) q-(O) m-，R-S-(C＝S)-(CH 2) q-(S) m-，R-O-(C＝O)-(CH 2) q-(S) m-，R-O-(C＝S)-(CH 2) q-(O) m-，R-S-(C＝O)-(CH 2) q-(O) m-，R-O-(C＝S)-(CH 2) q-(S) m-，R-S-(C＝O)-(CH 2) q-(S) m-，R-S-(C＝S)-(CH 2) q-(O) m-，R-O-(CH 2) n-(C＝O)-(O) m-，R-S-(CH 2) n-(C＝S)-(S) m-，R-O-(CH 2) n-(C＝O)-(S) m-，R-O-(CH 2) n-(C＝S)-(O) m-，R-S-(CH 2) n-(C＝O)-(O) m-，R-O-(CH 2) n-(C＝S)-(S) m-，R-S-(CH 2) n-(C＝O)-(S) m-，R-S-(CH 2) n-(C＝S)-(O) m-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-(CH 2) n-O-，R-(C＝S)-(CH 2) n-S-，R-(C＝O)-(CH 2) n-S-，R-(C＝S)-(CH 2) n-O-，R-(C＝O)-O-(CH 2) q-，R-(C＝S)-S-(CH 2) q-，R-(C＝O)-S-(CH 2) q-，R-(C＝S)-O-(CH 2) q-，R-SO-(O) m-，R-SO-(S) m-，R-SO-(NR 3) m-，R-SO 2-(O) m-，R-SO 2-(S) m-，R-SO 2-(NR 3) m-，R-SO-(CH 2) n-，R-SO 2-(CH 2) n-，R 1R 2N-，R 1R 2N-(CH 2) n-O-(CH 2) q-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-，R 1R 2N-(CH 2) n-(C＝O)-(O) m-，R 1R 2N-(CH 2) n-(C＝O)-(S) m-，R 1R 2N-(CH 2) n-(C＝O)-(NR 3) m-，R 1R 2N-(CH 2) n-SO 2-(O) m-，R 1R 2N-(CH 2) n-SO 2-(S) m-，R 1R 2N-(CH 2) n-SO 2-(NR 3) m-，R 1R 2N-(C＝O)-(CH 2) n-(O) m-，R 1R 2N-(C＝O)-(CH 2) n-(S) m-，R 1R 2N-(C＝O)-(CH 2) n-(NR 3) m-，R 1R 2N-SO 2-(CH 2) q-(O) m-，R 1R 2N-SO 2-(CH 2) q-(S) m-，R 1R 2N-SO 2-(CH 2) q-(NR 3) m-，R 1R 2N-(CH 2) n-O-，R 1R 2N-O-(CH 2) q-，R 1R 2PO 3-(O) m-，R 1R 2R 3SiO-，R 1R 2R 3Si-(CH＝CH) m-，R 1R 2C＝N-(O) m-，R 1R 2C＝N-NH-；或者相邻两个Y一起形成-OCH 2O-、-CH 2CH 2O-、-OCH 2CH 2O-、-OCH(CH 3)O-、-OC(CH 3) 2O-、-OCF 2O-、-CF 2CF 2O-、-OCF 2CF 2O-或-CH＝CH-CH＝CH-；
r为0～4之间的整数，m为0或1，n、q分别选自0～6之间的整数，p选自1～6之间的整数；其中，上述基团中各m、n、q、p分别独立地取值，且取值使各Y基团之间互不相同；
R选自氢，含有或不含有卤素的C 1～8烷基、C 2～8烯基、C 2～8炔基、C 3～8环烷基、C 5～8环烯基、C 3～8环烷基C 1～8烷基，以及未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基、芳基C 1～8烷基、杂芳基、杂芳基C 1～8烷基；
R 1、R 2、R 3分别独立地选自氢，硝基，羟基，氨基，含有或不含有卤素的C 1～8烷基、C 2～8烯基、C 2～8炔基、C 3～8环烷基、C 5～8环烯基、C 3～8环烷基C 1～8烷基、C 1～8烷氧基、C 2～8烯基氧基、C 2～8炔基氧基、C 3～8环烷基氧基、C 1～8烷氧基C 1～8烷基、C 1～8烷氧基羰基、C 1～8烷基羰基C 1～8烷基、C 1～8烷硫基羰基、C 1～8烷基磺酰基、C 1～8烷基磺酰基C 1～8烷基、C 1～8烷基羰基、C 1～8烷基酰氧基、C 1～8烷基氨基、C 1～8烷基氨基羰基、C 1～8烷氧基氨基羰基、C 1～8烷氧基羰基C 1～8烷基、C 1～8烷氨基羰基C 1～8烷基、三C 1～8烷基甲硅烷基、二C 1～8烷基膦酰基，以及未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基、芳基C 1～8烷基、芳基氧基、芳基C 1～8烷基氧基、芳基氧基C 1～8烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基C 1～8烷基、杂芳基氧基、杂芳基C 1～8烷基氧基、杂芳基氧基C 1～8烷基、杂芳基羰基、杂芳基磺酰基；或者R 1R 2N-选自未取代或被选自C 1～8烷基、卤代C 1～8烷基、C 1～8烷氧基、卤代C 1～8烷氧基、C 1～8烷氧基羰基、卤素取代的环上含有或不含有其他杂原子的六元杂环基。
更优选地，X选自氟、氯、溴、氰基、C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基、卤代C 1～6烷氧基、R 1R 2N-(C＝O)-、R 1R 2N-、羟基、未取代或被1～3个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的苯基；
Y彼此独立地选自氢，氟，氯，溴，氰基，硝基，叠氮基，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基，未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的芳基、芳基C 1～6烷基、杂芳基、杂芳基C 1～6烷基，R-O-，R-O-(CH 2) p-O-，R-O-(CH 2) p-S-，R-S-，R-S-(CH 2) p-O-，R-S-(CH 2) p-S-，R-O-(C＝O)-(O) m-，R-S-(C＝S)-(S) m-，R-O-(C＝O)-(S) m-，R-O-(C＝S)-(O) m-，R-S-(C＝O)-(O) m-，R-O-(C＝S)-(S) m-，R-S-(C＝O)-(S) m-，R-S-(C＝S)-(O) m-，R-O-(C＝O)-(CH 2) q-，R-S-(C＝S)-(CH 2) q-，R-O-(C＝S)-(CH 2) q-，R-S-(C＝O)-(CH 2) q-，R-O-(CH 2) n-(C＝O)-，R-S-(CH 2) n-(C＝S)-，R-O-(CH 2) n-(C＝S)-，R-S-(CH 2) n-(C＝O)-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-O-，R-(C＝S)-S-，R-(C＝O)-S-，R-(C＝S)-O-，R-SO-，R-SO 2-，R 1R 2N-，R 1R 2N-O-，R 1R 2N-(C＝O)-(CH 2) p-，R 1R 2N-(C＝O)-(O) m-，R 1R 2N-(C＝O)-(S) m-， R 1R 2N-(C＝O)-(NR 3) m-，R 1R 2N-SO 2-(CH 2) p-，R 1R 2N-SO 2-，R 1R 2N-(CH 2) p-(C＝O)-，R 1R 2N-(CH 2) p-SO 2-，R 1R 2N-(CH 2) p-O-，R 1R 2N-O-(CH 2) p-，R 1R 2PO 3-，R 1R 2R 3SiO-，R 1R 2R 3Si-，R 1R 2R 3Si-CH＝CH-，R 1R 2C＝N-，R 1R 2C＝N-O-，R 1R 2C＝N-NH-；或者相邻两个Y一起形成-CH＝CH-CH＝CH-；
r为0、1、2、3或4，m为0或1，n、q分别选自0、1、2、3或4，p选自1、2、3或4；其中，上述基团中各m、n、q、p分别独立地取值，且取值使各Y基团之间互不相同；
R选自氢，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基，以及未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的芳基、芳基C 1～6烷基、杂芳基、杂芳基C 1～6烷基；
R 1、R 2、R 3分别独立地选自氢，硝基，羟基，氨基，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基、C 1～6烷氧基、C 2～6烯基氧基、C 2～6炔基氧基、C 3～6环烷基氧基、C 1～6烷氧基C 1～6烷基、C 1～6烷氧基羰基、C 1～6烷硫基羰基、C 1～6烷基磺酰基、C 1～6烷基磺酰基C 1～6烷基、C 1～6烷基羰基、C 1～6烷基羰基C 1～6烷基、C 1～6烷基酰氧基、C 1～6烷基氨基、C 1～6烷基氨基羰基、C 1～6烷氧基氨基羰基、C 1～6烷氧基羰基C 1～6烷基、C 1～6烷氨基羰基C 1～6烷基、三C 1～6烷基甲硅烷基、二C 1～6烷基膦酰基，以及未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的芳基、芳基C 1～6烷基、芳基氧基、芳基C 1～6烷基氧基、芳基氧基C 1～6烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基C 1～6烷基、杂芳基氧基、杂芳基C 1～6烷基氧基、杂芳基氧基C 1～6烷基、杂芳基羰基、杂芳基磺酰基；或者R 1R 2N-选自
Figure PCTCN2018105407-appb-000004
Figure PCTCN2018105407-appb-000005
所述芳基为
Figure PCTCN2018105407-appb-000006
Figure PCTCN2018105407-appb-000007
杂芳基选自
Figure PCTCN2018105407-appb-000008
Figure PCTCN2018105407-appb-000009
Figure PCTCN2018105407-appb-000010
R’代表氢，硝基，羟基，氨基，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基、C 1～6烷氧基、C 2～6烯基氧基、C 2～6炔基氧基、C 3～6环烷基氧基、C 1～6烷氧基C 1～6烷基、C 1～6烷氧基羰基、C 1～6烷硫基羰基、C 1～6烷基磺酰基、C 1～6烷基磺酰基C 1～6烷基、C 1～6烷基羰基、C 1～6烷基羰基C 1～6烷基、C 1～6烷基酰氧基、C 1～6烷基氨基、C 1～6烷基氨基羰基、C 1～6烷氧基氨基羰基、C 1～6烷氧基羰基C 1～6烷基、C 1～6烷氨基羰基C 1～6烷基、三C 1～6烷基甲硅烷基、二C 1～6烷基膦酰基，以及未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的
Figure PCTCN2018105407-appb-000011
芳基、芳基C 1～6烷基、芳基氧基、芳基C 1～6烷基氧基、芳基氧基C 1～6烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基C 1～6烷基、杂芳基氧基、杂芳基C 1～6烷基氧基、杂芳基氧基C 1～6烷基、杂芳基羰基、杂芳基磺酰基。
进一步优选地，X选自氯、氰基、甲基、乙基、三氟甲基、五氟乙基、二氟甲基、一氟 甲基、甲氧基、乙氧基、三氟甲氧基、五氟乙氧基、
Figure PCTCN2018105407-appb-000012
r为0、1、2、3或4；
Y彼此独立地选自氢、甲基、乙基、甲氧基、乙氧基、氟、氯、溴、氨基、氰基、三氟甲基、
Figure PCTCN2018105407-appb-000013
或者
Figure PCTCN2018105407-appb-000014
代表
Figure PCTCN2018105407-appb-000015
本发明所述衍生物
Figure PCTCN2018105407-appb-000016
是指农业上可接受的通式I中哒嗪环4位上的羟基衍生物，包括盐、酯、肟、羟胺和醚类等衍生物。
所述盐衍生物为通常的农药中使用的盐，例如，可以制成碱金属盐、碱土金属盐或胺盐，或者，当分子中存在碱性部分时，可以制成例如硫酸盐、盐酸盐、硝酸盐、磷酸盐等的盐。当这些盐只要是作为农业、园艺用的除草剂使用时，也被包含在本发明中。本发明中，“碱金属盐”例如可以为，钠盐、钾盐或锂盐，优选为钠盐或钾盐。本发明中，“碱土金属盐”例如可以为，钙盐或镁盐，优选为钙盐。本发明中，“胺盐”例如可以为，烷基仲胺盐、烷基叔胺盐或烷基季胺盐；烷醇伯胺盐、烷醇仲胺盐、烷醇叔胺盐或烷醇季胺盐；烷基烷醇伯胺盐、烷基烷醇仲胺盐、烷基烷醇叔胺盐或烷基烷醇季胺盐；或烷氧基烷醇伯胺盐、烷氧基烷醇仲胺盐、烷氧基烷醇叔胺盐或烷氧基烷醇季胺盐，优选地，其中所述烷基、烷醇和烷氧基团独立地为饱和的以及独立地含有C1-C4个碳原子，更优选为单乙醇胺盐、二甲基乙醇胺盐、三乙醇胺盐、二甲胺盐、三乙胺盐、异丙胺盐、胆碱盐或二甘醇胺盐。
本发明化合物的溶剂合物也包含在本发明中。
本发明化合物中也包含具有不对称碳原子的化合物，在该情况下，本发明中也包含一种光学活性体和多种光学活性体按任意比例的混合物。
所述酯衍生物是指在哒嗪环4位上的羟基的氧原子上键合了酰基(包括羰基、硫羰基、亚砜基、磺酰基、磷酰基、硫代磷酰基等)而形成的化合物，例如可以为，可被取代的甲(硫)酰基或C1～C18烷(硫)羰基[该取代基为从卤素原子、氨基、C3～C8环烷基、C1～C8烷氧基、C1～C8烷硫基、C1～C8烷氧基羰基、C1～C8烷羰基氧基、C1～C8烷羰基、可被取代的C2～C8烯基氧基羰基{该取代基为从C3～C8环烷基、氰基以及可被取代的苯甲酰基(该 取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、羟基甲基氧膦基、可被取代的C3～C8环烯基氧基羰基{该取代基为从氧代以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～2个取代基}、可被取代的5或6元杂环氧基羰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的苯基、苯氧基、苄氧基、苯硫基和苄硫基(该取代基为从卤素原子、C1～C8烷基、C1～C8烷氧基、C1～C8卤代烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、以及C1～C8烷硫基中选出的1个或多个相同或不同的取代基]、C3～C8环烷(硫)羰基、金刚烷基(硫)羰基、可被取代的C2～C8烯基(硫)羰基{该取代基为从卤素原子、C1～C8烷氧基、以及可被取代的苯基、苯硫基或苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8烷氧基、C1～C8卤代烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)中选出的1个或多个相同或不同的取代基}、C2～C8炔基(硫)羰基、可被取代的苯甲(硫)酰基或萘甲(硫)酰基[该取代基为从卤素原子、可被取代的C1～C8烷基(该取代基为从卤素原子和苯基中选出的1个或多个相同或不同的取代基)、氰基、羟基、C1～C8烷羰基、C1～C8烷氧基羰基、C1～C8烷羰基氧基、C1～C8烷羰基氨基、可被取代的氨基(该取代基为从C1～C8烷基、C1～C8烷氧基、C1～C8烷羰基、卤代C1～C8烷基和苯基中选出的相同或不同的1～3个取代基)、可被取代的C2～C8烯基氧基羰基{该取代基为从C3～C8环烷基、氰基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的C3～C8环烯基氧基羰基{该取代基为从氧代以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～2个取代基}、苯基、硝基、可被取代的C1～C8烷氧基(该取代基为从卤素原子以及苯基中选出的相同或不同的1～3个取代基)、苯氧基、可被取代的5或6元杂环氧基羰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以 再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}以及可被取代的5或6元杂环氧基磺酰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}中选出的相同或不同的1～3个取代基]、被卤素取代的巯基甲酰基、可被取代的3～8元杂环(硫)羰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子，也可以形成在杂环内的任意的碳原子上含有1～2个氧原子的5～6元螺环。该取代基为从卤素原子、可被取代的C1～C8烷基(该取代基为从卤素原子以及苯基中选出的1个或多个相同或不同的取代基)、C1～C8烷羰基、C1～C8烷氧基羰基、可被取代的苯基(该取代基为相同或不同的1～3个卤素原子)、硝基、羟基、C1～C8烷氧基、苯氧基、C1～C8烷硫基、C2～C8烯基硫基以及苯硫基中选出的相同或不同的1～3个取代基}、可被取代的5～14元的缩合二环或三环式杂环(硫)羰基(该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子或氧原子。该取代基为从卤素原子以及C1～C8烷基中选出的相同或不同的1～3个取代基)、5或6元杂环(硫)羰基(硫)羰基(该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子)、可被取代的C1～C18烷氧基(硫)羰基或C1～C18烷硫基(硫)羰基(该取代基为从卤素原子、C1～C8烷氧基以及苯基中选出的1个或多个相同或不同的取代基)、C2～C8烯基氧基(硫)羰基、C2～C8烯基硫基(硫)羰基、C2～C8链炔基氧基(硫)羰基、C2～C8链炔基硫基(硫)羰基、C3～C8环烷基氧基(硫)羰基、C3～C8环烷基硫基(硫)羰基、可被取代的苯氧基(硫)羰基、苯硫基(硫)羰基、苯C1～C8烷基氧基(硫)羰基或苯C1～C8烷基硫基(硫)羰基(该取代基为从卤素原子、C1～C8烷基、氰基、C1～C8烷羰基、C1～C8烷氧基羰基、硝基以及C1～C8烷氧基中选出的相同或不同的1～3个取代基)、缩合多环式烃氧基(硫)羰基、缩合多环式烃硫基(硫)羰基、可被取代的5或6元杂环氧基(硫)羰基或5或6元杂环硫基(硫)羰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～ C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的氨基甲(硫)酰基{该取代基为从可被取代的C1～C8烷基(该取代基为从卤素原子、C1～C8烷氧基羰基、氰基、苯基以及C1～C8烷氧基中选出的1个或多个相同或不同的取代基)、C2～C8烯基、苯基、C1～C8烷羰基、C1～C8烷氧基羰基以及C1～C8烷氧基中选出的相同或不同的1～3个取代基}、
Figure PCTCN2018105407-appb-000017
(Het为5-6元杂环，该环上除含有C和1-位上的N原子外，还含有0-3个以下原子或基团作为环的组成部分：O、NR b、C＝O，R a和R b独立地代表氢、C1～C8烷基)、可被取代的C1～C8烷基亚砜基、C1～C8烷基磺酰基、C2～C8烯基磺酰基或C3～C8环烷基磺酰基(该取代基为从卤素原子、C1～C8烷基磺酰基中选出的1个或多个相同或不同的取代基)、可被取代的苯基磺酰基、苄基磺酰基或萘基磺酰基[该取代基为从卤素原子、C1～C8烷基、卤代C1～C8烷基、氰基、C1～C8烷羰基、C1～C8烷氧基羰基、硝基、C1～C8烷氧基、卤代C1～C8烷氧基、C1～C8烷基磺酰基、可被取代的氨基酰基(该取代基为C1～C8烷基)、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、可被取代的C2～C8烯基氧基磺酰基{该取代基为从C3～C8环烷基、氰基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的C3～C8环烯基氧基磺酰基{该取代基为从氧代以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～2个取代基}以及可被取代的5或6元杂环氧基磺酰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}中选出的相同或不同的1～3个取代基]、可被取代的5-10元芳杂环基磺酰基或5-10元杂环氧基磺酰基{该杂环的环中含 有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、C1～C8烷氧基磺酰基、可被取代的C1～C8烷基氨基磺酰基(该取代基为从卤素原子中选出的1个或多个相同或不同的取代基)、
Figure PCTCN2018105407-appb-000018
(Het为5-6元杂环，该环上除含有C和1-位上的N原子外，还含有0-3个以下原子或基团作为环的组成部分：O、NR b、C＝O，R a和R b独立地代表氢、C1～C8烷基)、二(C1～C8烷基)磷酰基、二(C1～C8烷基)硫代磷酰基所键合的化合物。
优选地，可以为，可被取代的C1～C10烷(硫)羰基{该取代基为从氟、氯、溴、C3～C6环烷基、C1～C6烷氧基、C1～C6烷硫基、C1～C6烷氧基羰基、C1～C6烷羰基、C1～C6烷羰基氧基、可被取代的苯基、苯硫基、苯氧基或苄氧基(该取代基为从氟、氯、溴、C1～C6烷基、C1～C6烷氧基中选出的相同或不同的1～3个取代基)中选出的1个或多个相同或不同的取代基}、C3～C6环烷(硫)羰基、可被取代的C2～C6烯基(硫)羰基{该取代基为从氟、氯、溴、C1～C6烷氧基、可被取代的苯基、苯硫基或苯氧基(该取代基为从氟、氯、溴、C1～C6烷基、C1～C6烷氧基中选出的相同或不同的1～3个取代基)中选出的1个或多个相同或不同的取代基}、可被取代的苯甲(硫)酰基或萘甲(硫)酰基{该取代基为从氟、氯、溴、可被取代的C1～C6烷基或C1～C6烷氧基(该取代基为从氟、氯、溴和苯基中选出的相同或不同的1～3个取代基)、氰基、羟基、C1～C6烷羰基、C1～C6烷氧基羰基、C1～C6烷羰基氧基、C1～C6烷羰基氨基、可被取代的氨基(该取代基为从C1～C6烷基、C1～C6烷氧基、C1～C6烷羰基、卤代C1～C6烷基和苯基中选出的相同或不同的1～3个取代基)、苯基、硝基、苯氧基中选出的相同或不同的1～3个取代基}、可被取代的3～8元杂环(硫)羰基{该杂环为
Figure PCTCN2018105407-appb-000019
Figure PCTCN2018105407-appb-000020
该取代基为从氟、氯、溴、可被取代的C1～C6烷基(该取代基为从氟、氯、溴以及苯基中选出的1个或多个相同或不同的取代基)、C1～C6烷羰基、C1～C6烷氧基羰基、可被取代的苯基(该取代基为从氟、氯、溴中选出的相同或不同的1～3个取代基)、硝基、羟基、C1～C6烷氧基、苯氧基、C1～C6烷硫基、C2～C6烯基硫基以及苯硫基中选 出的相同或不同的1～3个取代基}、可被取代的5～14元的缩合二环或三环式杂环(硫)羰基(该杂环为
Figure PCTCN2018105407-appb-000021
Figure PCTCN2018105407-appb-000022
Figure PCTCN2018105407-appb-000023
该取代基为从氟、氯、溴以及C1～C6烷基中选出的相同或不同的1～3个取代基)、可被取代的C1～C10烷氧基(硫)羰基或C1～C10烷硫基(硫)羰基(该取代基为从氟、氯、溴、C1～C6烷氧基以及苯基中选出的1个或多个相同或不同的取代基)、C3～C6环烷基氧基(硫)羰基、C3～C6环烷基硫基(硫)羰基、可被取代的苯氧基(硫)羰基、苯硫基(硫)羰基、苯C1～C6烷基氧基(硫)羰基或苯C1～C6烷基硫基(硫)羰基(该取代基为从氟、氯、溴、C1～C6烷基、氰基、C1～C6烷羰基、C1～C6烷氧基羰基、硝基以及C1～C6烷氧基中选出的相同或不同的1～3个取代基)、可被取代的氨基甲(硫)酰基{该取代基为从可被取代的C1～C6烷基(该取代基为从氟、氯、溴中选出的1个或多个相同或不同的取代基)、C2～C6烯基、苯基、C1～C6烷羰基、C1～C6烷氧基羰基以及C1～C6烷氧基中选出的相同或不同的1～3个取代基}、
Figure PCTCN2018105407-appb-000024
(Het为
Figure PCTCN2018105407-appb-000025
Figure PCTCN2018105407-appb-000026
R a和R b独立地代表氢、C1～C6烷基)、可被取代的C1～C6烷基亚砜基、C1～C6烷基磺酰基、C2～C6烯基磺酰基或C3～C6环烷基磺酰基(该取代基为从氟、氯、溴、C1～C6烷基磺酰基中选出的1个或多个相同或不同的取代基)、可被取代的苯基磺酰基、苄基磺酰基或萘基磺酰基{该取代基为从氟、氯、溴、C1～C6烷基、卤代C1～C6烷基、氰基、C1～C6烷羰基、C1～C6烷氧基羰基、硝基、C1～C6烷氧基、卤代C1～C6烷氧基、C1～C6烷基磺酰基、可被取代的氨基酰基(该取代基为C1～C6烷基)、可被取代的苯氧基(该取代基为从氟、氯、溴、C1～C6烷基、C1～C8卤代烷基、C3～C6环烷基以及C1～C6烷氧基羰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的5-10元芳杂环基磺酰基{该杂环为
Figure PCTCN2018105407-appb-000027
Figure PCTCN2018105407-appb-000028
Figure PCTCN2018105407-appb-000029
该取代基为从氟、氯、溴、C1～C6烷基、可被取代的苯氧基(该取代基为从氟、氯、溴、C1～C6烷基、C1～C6卤代烷基、C3～C6环烷基以及C1～C6烷氧基羰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的C1～C6烷基氨基磺酰基(该取代基为从氟、氯、溴中选出的1个或多个相同或不同的取代基)、
Figure PCTCN2018105407-appb-000030
(Het为
Figure PCTCN2018105407-appb-000031
R a和R b独立地代表氢、C1～C6烷基)、二(C1～C6烷基)磷酰基、二(C1～C6烷基)硫代磷酰基所键合的化合物。
所述肟衍生物是指在哒嗪环4位上的羟基的氧原子上键合而形成的含有肟基
Figure PCTCN2018105407-appb-000032
的化合物，例如可以为，R 11、R 22分别独立地代表氢、可被取代的C1～C18烷基或C2～C18烯基(该取代基为从卤素原子、C1～C8烷氧基、C1～C8烷硫基、C1～C8烷基氨基中选出的1个或多个相同或不同的取代基)、可被取代的苯基、苯基酰基或5-6元芳杂环基(该取代基为从卤素原子、C1～C8烷基、C2～C8烯基、C2～C8炔基、C3～C8环烷基、C1～C8卤代烷基、C1～C8烷羰基、C1～C8烷氧基、C1～C8烷氧基羰基、C1～C8烷基氨基、羟基、羧基、巯基、氨基、氰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基，芳杂环基含至少一个氧、硫、氮等杂原子)，或者R 11、R 22形成5、6元饱和碳环或5、6元杂环(含至少一个氧、硫、氮等杂原子)。
优选地，可以为，R 11、R 22分别独立地代表氢、可被取代的C1～C10烷基或C2～C10烯基(该取代基为从氟、氯、溴、C1～C6烷氧基、C1～C6烷硫基、C1～C6烷基氨基中选出的1个或多个相同或不同的取代基)、可被取代的苯基、苯基酰基或5-6元芳杂环基(该芳杂环基为
Figure PCTCN2018105407-appb-000033
Figure PCTCN2018105407-appb-000034
该取代基为从氟、氯、溴、C1～C6烷基、C3～C6环烷基、C1～C6卤代烷基、C1～C6烷羰基、C1～C6烷氧基、C1～C6烷氧基羰基、C1～C6烷基氨基、羟基、羧基、巯基、氨基、氰基、硝基以及C1～C6烷基磺酰基中选出的相同或不同的1～3个取代基)，或者R 11、R 22形成5、6元饱和碳环或5、6元杂环(含至少一个氧、硫、氮等杂原子)。
所述羟胺衍生物是指在哒嗪环4位上的羟基的氧原子上键合而形成的含有羟胺基
Figure PCTCN2018105407-appb-000035
的化合物，例如可以为，R 11’、R 22’分别独立地代表氢、可被取代的C1～C18烷基或C2～C18烯基(该取代基为从卤素原子、C1～C8烷氧基、C1～C8烷硫基、C1～C8烷基氨基中选出的1个或多个相同或不同的取代基)、可被取代的苯基(该取代基为从卤素原子、C1～C8烷基、C2～C8烯基、C2～C8炔基、C3～C8环烷基、C1～C8卤代烷基、C1～C8烷羰基、C1～C8烷氧基、C1～C8烷氧基羰基、C1～C8烷基氨基、羟基、羧基、巯基、氨基、氰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)、C1～C18烷氧羰基、可被取代的苯甲酰基[该取代基为从卤素原子、可被取代的C1～C8烷基、C2～C8烯基、C2～C8炔基或C3～C8环烷基(该取代基为从卤素原子和苯基中选出的相同或不同的1～3个取代基)、氰基、C1～C8烷羰基、C1～C8烷氧基羰基、C1～C8烷基磺酰基、可被取代的C2～C8烯基氧基羰基{该取代基为从C3～C8环烷基、氰基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的C3～C8环烯基氧基羰基{该取代基为从氧代以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～2个取代基}、羟基、羧基、巯基、氨基、苯基、硝基、可被取代的C1～C8烷氧基、C1～C8烷基氨基或C1～C8烷硫基(该取代基为从卤素原子以及苯基中选出的相同或不同的1～3个取代基)、苯氧基、可被取代的5或6元杂环氧基羰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}以及可被取代的5或6元杂环氧基磺酰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基} 中选出的相同或不同的1～3个取代基]。
优选地，可以为，R 11’、R 22’分别独立地代表氢、可被取代的C1～C10烷基或C2～C10烯基(该取代基为从氟、氯、溴中选出的1个或多个相同或不同的取代基)、C1～C10烷氧羰基、可被取代的苯基或苯甲酰基(该取代基为从氟、氯、溴、C1～C6烷基、C2～C6烯基、C2～C6炔基、C3～C6环烷基、C1～C6卤代烷基、C1～C6烷羰基、C1～C6烷氧基、C1～C6烷氧基羰基、C1～C6烷基氨基、羟基、羧基、巯基、氨基、氰基、硝基以及C1～C6烷基磺酰基中选出的相同或不同的1～3个取代基)。
所述醚衍生物是指在哒嗪环4位上的羟基的氧原子上键合如下基团而形成的化合物，例如可以为，可被取代的C1～C18烷基或C2～C18烯基(该取代基为从卤素原子、C1～C8烷氧基、C1～C8烷硫基、C1～C8烷基氨基、二C1～C8烷基氨基、C1～C8烷氧羰基、C1～C8烷氧羰基氧基中选出的1个或多个相同或不同的取代基)、可被取代的苯基、苄基或苯甲酰基C1～C8烷基[该取代基为从卤素原子、可被取代的C1～C8烷基、C2～C8烯基、C2～C8炔基或C3～C8环烷基(该取代基为从卤素原子和苯基中选出的相同或不同的1～3个取代基)、氰基、C1～C8烷羰基、C1～C8烷氧基羰基、C1～C8烷基磺酰基、可被取代的C2～C8烯基氧基羰基{该取代基为从C3～C8环烷基、氰基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}、可被取代的C3～C8环烯基氧基羰基{该取代基为从氧代以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～2个取代基}、羟基、羧基、巯基、氨基、苯基、硝基、可被取代的C1～C8烷氧基、C1～C8烷基氨基或C1～C8烷硫基(该取代基为从卤素原子以及苯基中选出的相同或不同的1～3个取代基)、苯氧基、可被取代的5或6元杂环氧基羰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}以及可被取代的5或6元杂环氧基磺酰基{该杂环的环中含有1个氮原子、氧原子或硫原子，还可以再含有1～2个氮原子。该取代基为从卤素原子、C1～C8烷基、可被取代的苯氧基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C3～C8环烷基以及C1～C8烷氧基羰基中选出的相同或不 同的1～3个取代基)、2，3-二氢-1H-茚氧基以及可被取代的苯甲酰基(该取代基为从卤素原子、C1～C8烷基、C1～C8卤代烷基、C1～C8烷氧基羰基、硝基以及C1～C8烷基磺酰基中选出的相同或不同的1～3个取代基)中选出的相同或不同的1～3个取代基}中选出的相同或不同的1～3个取代基]。
优选地，可以为，C8～C18烷基或C8～C18烯基、被取代的C1～C10烷基或C2～C10烯基(该取代基为从氟、氯、溴、C1～C6烷氧基、C1～C6烷硫基、C1～C6烷基氨基、C1～C6烷氧羰基、C1～C6烷氧羰基氧基中选出的1个或多个相同或不同的取代基)、可被取代的苯基、苄基或苯甲酰基C1～C6烷基(该取代基为从氟、氯、溴、C1～C6烷基、C2～C6烯基、C2～C6炔基、C3～C6环烷基、C1～C6卤代烷基、C1～C6烷羰基、C1～C6烷氧基、C1～C6烷氧基羰基、C1～C6烷基氨基、羟基、羧基、巯基、氨基、氰基、硝基以及C1～C6烷基磺酰基中选出的相同或不同的1～3个取代基)。
一种所述的吡啶环取代的哒嗪醇类化合物的制备方法，包括以下步骤：
(1)采用化合物Ⅱ与化合物Ⅲ发生Suzuki反应，制备如通式Ⅳ所示的化合物；
(2)将如通式Ⅳ所示的化合物进行卤代反应，制备如通式Ⅴ所示的化合物；
(3)采用如通式Ⅴ所示的化合物水解制备如通式Ⅰ所示的化合物；
其化学反应方程式如下：
Figure PCTCN2018105407-appb-000036
L 1和L 2分别独立地代表卤素，优选氯、溴、碘。
所述反应温度均在20～150℃范围内，优选50～130℃。
所述步骤(1)在催化剂、碱和溶剂的存在下进行，催化剂为Pd(dppf)Cl 2CH 2Cl 2、Pd(dba) 2、Pd 2(dba) 3、Pd(PPh 3) 4、PdCl 2、Pd(OAc) 2、Pd(dppf)Cl 2、Pd(PPh 3) 2Cl 2或Ni(dppf)Cl 2，碱选自Et 3N、NaHCO 3、KOAc、K 2CO 3、K 3PO 4、Na 2CO 3、CsF、Cs 2CO 3、t-BuONa、EtONa、KOH和NaOH中的一种或两种以上，溶剂为THF/水、甲苯/水、DMF/水、1,4-二氧六环/水、甲苯/乙醇/水或乙腈/水、THF、甲苯、1,4-二氧六环、乙腈、DMF体系；所述步骤(2)在卤代试剂、催化剂和溶剂的存在下进行，卤代试剂为N-氯代琥珀酰亚胺、N-溴代琥珀酰亚胺或N-碘代琥珀酰亚胺，催化剂为过氧化苯甲酰，溶剂为乙腈；所述步骤(3)在碱和溶剂的存在下进行或者在三溴化硼、氢溴酸醋酸溶液、盐酸甲醇溶液、盐酸乙酸乙酯溶液的存在下进行， 所述碱优选NaOH、KOH、醋酸钾、醋酸钠，所述溶剂优选水、DMSO。
制备其酯和醚类衍生物的化学反应方程式如下：
Figure PCTCN2018105407-appb-000037
其中，Q 1代卤素，优选氯、溴；
制备其肟和羟胺类衍生物的化学反应方程式如下：
Figure PCTCN2018105407-appb-000038
其中，Q 2代卤素，优选氯、氟。
所述制备其酯和醚类衍生物的反应以及制备其肟和羟胺类衍生物的第二步反应均在碱和溶剂的存在下进行，碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸铯、三乙胺和二异丙基乙基胺中的一种或两种以上；溶剂为THF、1,4-二氧六环、甲苯、1,2-二氯乙烷、乙酸乙酯、乙腈、DMF、丙酮、二氯甲烷或氯仿；所述制备其肟和羟胺类衍生物的反应中第一步在卤代试剂和溶剂的存在下进行，所述卤代试剂为Phenofluor/氟化铯或POCl 3，所述溶剂选自甲苯、1,2-二氯乙烷、DMF中的一种或两种以上；所述反应温度均选自0～120℃范围内，优选20-80℃。
本发明涉及的化合物可以以一种或者多种立体异构体的形式存在。各种异构体包括对映异构体、非对映异构体、几何异构体。这些异构体包括这些异构体的混合物均在本发明的范围内。
一种除草剂组合物，包括(i)如通式I所示的吡啶环取代的哒嗪醇类化合物及其衍生物。
优选地，还包括(ii)一种或多种另外的除草剂和/或安全剂。
更优选地，还包括(iii)农业化学上可接受的制剂助剂。
所述另外的除草剂选自HPPD抑制剂、激素类、PDS抑制剂中的一种；优选地，HPPD抑制剂为磺草酮、硝磺草酮、苯唑草酮、环磺酮、氟吡草酮、呋喃磺草酮、双环磺草酮、lancotrione、双唑草酮、环吡氟草酮、三唑磺草酮、苯唑氟草酮、磺酰草吡唑、吡唑特、吡草酮、tolpyralate、fenquinotrione、异噁唑草酮；激素类为氯氟吡氧乙酸、氟氯吡啶酯、氯氟吡啶酯、二氯喹啉酸、氯甲喹啉酸、2甲4氯、2-甲基-4-氯苯氧丙酸、MCPB、2,4-D、2,4-滴丙酸、2,4-DB、麦草畏、氨氯吡啶酸、三氯吡氧乙酸、二氯吡啶酸、绿草定及其衍生物，PDS 抑制剂为氟咯草酮、呋草酮、吡氟酰草胺、氟吡酰草胺、氟丁酰草胺、氟草敏、氟啶草酮。
其中，氯氟吡氧乙酸衍生物包含但不限于：氯氟吡氧乙酸异辛酯；2甲4氯、2-甲基-4-氯苯氧丙酸、MCPB衍生物包含但不限于：钠盐、钾盐、二甲铵盐、异丙胺盐等，以及甲酯、乙酯、异辛酯、乙硫酯等；2,4-D、2,4-滴丙酸、2,4-DB衍生物包含但不限于：盐如钠盐、钾盐、二甲铵盐、三乙醇铵盐、异丙胺盐、胆碱等，以及酯如甲酯、乙酯、丁酯、异辛酯等。
一种控制有害植物的方法，包括将除草有效量的所述的吡啶环取代的哒嗪醇类化合物及其衍生物中的至少一种或所述的除草剂组合物使用在植物上或者有害植物区域。
所述的吡啶环取代的哒嗪醇类化合物及其衍生物中的至少一种或所述的除草剂组合物在控制有害植物上的用途。
优选地，将所述的吡啶环取代的哒嗪醇类化合物及其衍生物中的至少一种或所述的除草剂组合物用于防除有用作物中的有害植物。
更优选地，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
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化合物及其衍生物优选用于，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化合物及其衍生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-0221044A，EP-0131624A)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-0242236A，EP-0242246A)或对草甘膦类除草剂(WO 92/00377)，或对磺酰脲类除草剂(EP-0257993A，US-5013659A)；
-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-0142924A，EP-0193259A)；
-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；
Figure PCTCN2018105407-appb-000039
的
Figure PCTCN2018105407-appb-000040
[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。
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/ha之间，或更多的活性物质，但优选在0.005到750g/ha之间，特别是在0.005到250g/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1-5中。具体的化合物结构及相应的化合物信息如表1-5所示。表1-5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(1)结构及其 1HNMR数据
Figure PCTCN2018105407-appb-000041
Figure PCTCN2018105407-appb-000042
Figure PCTCN2018105407-appb-000043
Figure PCTCN2018105407-appb-000044
Figure PCTCN2018105407-appb-000045
Figure PCTCN2018105407-appb-000046
Figure PCTCN2018105407-appb-000047
Figure PCTCN2018105407-appb-000048
Figure PCTCN2018105407-appb-000049
Figure PCTCN2018105407-appb-000050
Figure PCTCN2018105407-appb-000051
表2化合物(2)结构及其 1HNMR数据
Figure PCTCN2018105407-appb-000052
Figure PCTCN2018105407-appb-000053
Figure PCTCN2018105407-appb-000054
Figure PCTCN2018105407-appb-000055
Figure PCTCN2018105407-appb-000056
Figure PCTCN2018105407-appb-000057
Figure PCTCN2018105407-appb-000058
Figure PCTCN2018105407-appb-000059
表3化合物(3)结构及其 1HNMR数据
Figure PCTCN2018105407-appb-000060
Figure PCTCN2018105407-appb-000061
Figure PCTCN2018105407-appb-000062
Figure PCTCN2018105407-appb-000063
Figure PCTCN2018105407-appb-000064
Figure PCTCN2018105407-appb-000065
Figure PCTCN2018105407-appb-000066
表4衍生化合物I’中基团M的结构
Figure PCTCN2018105407-appb-000067
Figure PCTCN2018105407-appb-000068
Figure PCTCN2018105407-appb-000069
Figure PCTCN2018105407-appb-000070
Figure PCTCN2018105407-appb-000071
Figure PCTCN2018105407-appb-000072
Figure PCTCN2018105407-appb-000073
Figure PCTCN2018105407-appb-000074
Figure PCTCN2018105407-appb-000075
Figure PCTCN2018105407-appb-000076
Figure PCTCN2018105407-appb-000077
Figure PCTCN2018105407-appb-000078
Figure PCTCN2018105407-appb-000079
表5衍生化合物I’的结构及其 1HNMR数据
Figure PCTCN2018105407-appb-000080
Figure PCTCN2018105407-appb-000081
Figure PCTCN2018105407-appb-000082
Figure PCTCN2018105407-appb-000083
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：
1、化合物1-7的合成
Figure PCTCN2018105407-appb-000084
(1)将化合物1-7-a(10g，67mmol)，化合物1-7-b(10.5g,67mmol)，碳酸钾(27.8g,201mmol)置于圆底三口烧瓶中，加入1,4-二氧六环(100mL)/水(20mL)后置换氮气三次，氮气保护下迅速加入Pd(dppf)Cl 2CH 2Cl 2(0.2g)后置换氮气三次，然后反应液再次置换氮气三次，于100℃下反应16小时，高效液相色谱检测反应结束后，将反应体系浓缩，柱层析分离，得到12g(53mmol,收率80％)化合物1-7-c(白色固体)。
(2)将化合物1-7-c(12g，53mmol)，N-氯代琥珀酰亚胺(7.1g，53mmol)，过氧化苯甲酰(0.5g，催化量)，乙腈(120mL)置于圆底三口烧瓶中，于80℃下反应16小时，高效液相色谱检测原料少量剩余，浓缩，柱层析分离，得到6g(23mmol，收率43％)化合物1-7-d(白色固体)。
(3)将化合物1-7-d(1g，3.8mmol)，醋酸钾(1.88g，19mmol)，10mL DMSO置于圆底三口烧瓶中，于120℃下反应2小时，高效液相色谱检测反应结束后，将反应液降温至25℃，向反应液中滴加1M HCl至溶液pH至5左右，此过程控制温度(不高于25℃)，有固体析出，将析出的固体抽滤，用大量水洗涤，固体用甲基叔丁基醚(20mL)和少量甲醇(1mL)打浆纯化，固体抽滤后干燥，得到500mg(2mmol，收率54％)化合物1-7(灰色固体)。
2、化合物I-1的合成
Figure PCTCN2018105407-appb-000085
参照上述方法1合成化合物1-1，将化合物1-1(1g，4.8mmol)，碳酸钾(2g，14.4mmol)，乙腈(20mL)置于圆底烧瓶中，于25℃下向反应体系中滴加化合物I-1-a(1.08g，7.2mmol)，于25℃反应5小时，高效液相色谱检测反应结束后，将反应体系过滤掉剩余碳酸钾固体，母液浓缩，柱层析分离，得到1g(3.1mmol，收率67％)化合物I-1(白色固体)。
3、化合物I-2的合成
Figure PCTCN2018105407-appb-000086
参照上述方法1合成化合物2-1，将化合物2-1(2g，9.6mmol)，碳酸钾(4g，28.8mmol)，化合物I-2-a(2.4g，14.4mmol)，乙腈(40mL)置于圆底烧瓶中，于25℃反应过夜(约12小时)，高效液相色谱检测反应结束后，将反应体系过滤掉剩余碳酸钾固体，母液浓缩，经prep-HPLC分离，得到黄色固体化合物I-2(600mg，收率18.5％)。
4、化合物I-3的合成
Figure PCTCN2018105407-appb-000087
参照上述方法1合成化合物1-1，在50mL的单口茄形瓶中室温下加入化合物1-1(1当量)、
Figure PCTCN2018105407-appb-000088
(1.1当量)、碳酸钾(3当量)和乙腈(10V)，升温80℃搅拌6小时。TLC检测反应已经完成，反应体系通过减压蒸馏除去乙腈，加水(5V)溶解后用乙酸乙酯萃取(5V*3)，减压蒸馏去除乙酸乙酯，残余物通过柱层析硅胶(100目到200目)分离，得到产物，收率为82％。
5、化合物I-4的合成
Figure PCTCN2018105407-appb-000089
参照上述方法1合成化合物1-1，在50mL的单口茄形瓶中冰浴下加入化合物1-1(1当量)、三乙胺(3当量)和二氯甲烷(5V)，冰浴下滴加
Figure PCTCN2018105407-appb-000090
(1.2当量)，然后室温 搅拌30分钟。TLC检测反应已经完成，反应加水(5V)用二氯甲烷萃取(5V*3)，减压蒸馏去除二氯甲烷，残余物通过柱层析硅胶(100目到200目)分离，得到产物，收率为76％。
6、化合物I-5的合成
Figure PCTCN2018105407-appb-000091
参照上述方法1合成化合物1-1，在50mL的单口茄形瓶中室温下加入化合物1-1(1当量)、Phenofluor(1.5当量)、氟化铯(3当量)、甲苯(10V)，升温至80℃，搅拌18h。TLC检测反应已经完成，后处理的中间体化合物物I-5-a。在另外一个50mL的单口茄形瓶中室温下加入化合物I-5-a(1当量)、
Figure PCTCN2018105407-appb-000092
(1.2当量)、碳酸钾(3当量)和乙腈(10V)，升温至80℃，搅拌18h。TLC检测反应已经完成，反应体系通过减压蒸馏除去乙腈，加水(5V)溶解后用乙酸乙酯萃取(5V*3)，减压蒸馏去除乙酸乙酯，残余物通过柱层析硅胶(100目到200目)分离，得到产物，收率为62％。
7、化合物I-6的合成
Figure PCTCN2018105407-appb-000093
参照上述方法1合成化合物1-1，在50mL的单口茄形瓶中室温下加入化合物1-1(1当量)、POCl 3(1.5当量)、1,2-二氯乙烷(10V)、5％N,N-二甲基甲酰胺，升温至80℃，搅拌6h。TLC检测反应已经完成，加水(5V)溶解后用1,2-二氯乙烷萃取(5V*3)，减压蒸馏去除用1，2-二氯乙烷，得化合物I-6-a。在另外一个50mL的单口茄形瓶中室温下加入化合物I-6-a(1当量)、
Figure PCTCN2018105407-appb-000094
(1.2当量)、氢氧化钾(3当量)和N,N-二甲基甲酰胺(10V)，升温至100℃，搅拌18h。TLC检测反应已经完成，加水(5V)溶解后用乙酸乙酯萃取(5V*3)，减压蒸馏去除乙酸乙酯，残余物通过柱层析硅胶(100目到200目)分离，得到产物，收率为49％。
生物活性评价：
有害植物破坏(即生长控制率)的活性级别标准如下：
10级：完全死亡；
9级：生长控制率在90％以上；
8级：生长控制率在80％以上；
7级：生长控制率在70％以上；
6级：生长控制率在60％以上；
5级：生长控制率在50％以上；
4级：生长控制率在40％以上；
3级：生长控制率在30％以上；
2级：生长控制率在20％以上；
1级：生长控制率低于20％；
0级：无效果。
以上生长控制率为鲜重控制率。
苗后测试实验：将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种2-3周后在4-5叶期处理测试植物，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，用喷雾塔喷施到植物上。施药后在温室中培养3周，3周后杂草的实验效果列于表6。
表6.化合物I及其衍生物I’苗后杂草试验
化合物序号 反枝苋 蔊菜 婆婆纳 藜 计量
1-1 10 10 10 10 2000克/公顷
1-2 10 10 10 10 2000克/公顷
1-3 10 10 10 10 2000克/公顷
1-4 10 10 10 10 2000克/公顷
1-5 10 10 10 10 2000克/公顷
1-6 10 10 7 10 2000克/公顷
1-7 10 10 10 10 2000克/公顷
1-8 10 10 10 10 2000克/公顷
1-11 10 10 10 10 2000克/公顷
1-23 10 10 10 10 2000克/公顷
1-57 10 10 10 10 2000克/公顷
1-58 10 10 10 10 2000克/公顷
1-60 10 10 7 10 2000克/公顷
1-63 10 10 10 10 2000克/公顷
1-90 10 10 7 10 2000克/公顷
1-105 10 10 10 10 2000克/公顷
1-131 10 10 10 10 3000克/公顷
2-3 10 10 10 10 1000克/公顷
2-5 10 10 10 10 1000克/公顷
2-10 10 10 10 10 1000克/公顷
2-11 10 10 10 10 1000克/公顷
2-13 10 10 10 10 1000克/公顷
2-23 10 10 10 10 1000克/公顷
3-3 10 10 10 10 2000克/公顷
3-7 10 10 10 10 2000克/公顷
3-8 10 10 10 10 2000克/公顷
3-18 10 10 10 10 2000克/公顷
3-19 10 10 10 10 2000克/公顷
3-30 10 10 10 10 2000克/公顷
I-1 10 10 10 10 2000克/公顷
I-4 10 10 10 10 2000克/公顷
I-7 10 10 10 10 2000克/公顷
对比实验：
苗后测试条件同上，实验结果如表7所示。
对照化合物A：
Figure PCTCN2018105407-appb-000095
对照化合物B：
Figure PCTCN2018105407-appb-000096
表7.对比实验结果
化合物序号 稗草 狗尾草 马唐 蔊菜 猪殃殃 婆婆纳 计量
1-1 8 10 7 10 9 9 300克/公顷
1-2 10 10 8 10 9 10 300克/公顷
1-4 8 10 8 10 10 10 300克/公顷
1-7 10 10 8 10 9 10 300克/公顷
2-3 10 10 10 10 10 10 300克/公顷
I-7 8 9 7 10 9 9 300克/公顷
对照化合物A 0 2 1 3 5 6 300克/公顷
对照化合物B 0 2 0 3 4 6 300克/公顷
由上表可知，与对照化合物A和B相比，本发明化合物明显有更高的除草活性。
苗前测试实验：
将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，播种后立即喷施。施药后在温室中培养4周，3周后观察实验结果，发现本发明的药剂多数在250克/公顷计量下效果出众，尤其对稗草、马塘、苘麻等杂草，且很多化合物对玉米、小麦、水稻、大豆、油菜有良好的选择性。
移栽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、萤蔺、狼把草、野慈姑的种子，在其上轻轻地覆盖土。其后以蓄水深0.5-1厘米的状态静置于温室内，第二天或者2天后植入野慈姑的块茎。其后保持蓄水深3-4厘米，在稗草、萤蔺、狼把草达到0.5叶，野慈姑达到初生叶期的时间点，将按照通常的制剂方法调制本发明化合物而成的可湿性粉剂或者悬浮剂的水稀释液，用吸液管进行均匀的滴下处理以达到规定的有效成分量。
另外，在1/1,000,000公顷罐中装入水田土壤后，进行平整，使蓄水深3-4厘米，第二天以移栽深度3厘米来移植3叶期的水稻(粳稻)。移植后第5天与上述同样地处理本发明化合物。
分别用肉眼观察药剂处理后第14天稗草、萤蔺、狼把草及野慈姑的生育状态，药剂处理后第21天水稻的生育状态，以1-10的活性标准级别评价除草效果，试验发现很多本发明的化合物有优秀的活性和选择性，尤其对于野慈姑和稗草。
注：稗草、萤蔺、野慈姑、狼把草种子均采集自中国黑龙江，经过检测对常规剂量的吡嘧磺隆有抗药性。
同时经过很多测试发现，本发明所述化合物及其组合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性，能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的小麦、玉米、水稻、甘蔗、大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。

Claims (10)

  1. 一种如通式I所示的吡啶环取代的哒嗪醇类化合物及其衍生物：
    Figure PCTCN2018105407-appb-100001
    其中，X选自卤素、氰基、烷基、卤代烷基、烷氧基、卤代烷氧基、R 1R 2N-(C＝O)-、R 1R 2N-、羟基、未取代或取代的芳基；
    Y彼此独立地选自氢，卤素，氰基，硝基，叠氮基，含有或不含有卤素的烷基、烯基、炔基、环烷基、环烯基、环烷基烷基，未取代或取代的芳基、芳基烷基、杂芳基、杂芳基烷基，R-O-(CH 2) n-，R-O-(CH 2) p-O-(CH 2) q-，R-O-(CH 2) p-S-(CH 2) q-，R-S-(CH 2) n-，R-S-(CH 2) p-O-(CH 2) q-，R-S-(CH 2) p-S-(CH 2) q-，R-O-(CH 2) n-(C＝O)-(CH 2) q-(O) m-，R-S-(CH 2) n-(C＝S)-(CH 2) q-(S) m-，R-O-(CH 2) n-(C＝O)-(CH 2) q-(S) m-，R-O-(CH 2) n-(C＝S)-(CH 2) q-(O) m-，R-S-(CH 2) n-(C＝O)-(CH 2) q-(O) m-，R-O-(CH 2) n-(C＝S)-(CH 2) q-(S) m-，R-S-(CH 2) n-(C＝O)-(CH 2) q-(S) m-，R-S-(CH 2) n-(C＝S)-(CH 2) q-(O) m-，R-(C＝O)-(CH 2) n-，R-(C＝S)-(CH 2) n-，R-(C＝O)-(CH 2) n-O-(CH 2) q-，R-(C＝S)-(CH 2) n-S-(CH 2) q-，R-(C＝O)-(CH 2) n-S-(CH 2) q-，R-(C＝S)-(CH 2) n-O-(CH 2) q-，R-SO-(CH 2) n-(O) m-，R-SO-(CH 2) n-(S) m-，R-SO-(CH 2) n-(NR 3) m-，R-SO 2-(CH 2) n-(O) m-，R-SO 2-(CH 2) n-(S) m-，R-SO 2-(CH 2) n-(NR 3) m-，R 1R 2N-(CH 2) n-，R 1R 2N-(CH 2) n-O-(CH 2) q-(O) m-，R 1R 2N-(CH 2) n-O-(CH 2) q-(S) m-，R 1R 2N-(CH 2) n-O-(CH 2) q-(NR 3) m-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-(O) m-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-(S) m-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-(NR 3) m-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-(O) m-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-(S) m-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-(NR 3) m-，R 1R 2PO 3-(O) m-(CH 2) q-，R 1R 2R 3SiO-(CH 2) q-，R 1R 2R 3Si-(CH＝CH) m-(CH 2) q-，R 1R 2C＝N-(O) m-(CH 2) n-，R 1R 2C＝N-NH-(CH 2) n-；或者相邻两个Y一起形成-OCH 2O-、-CH 2CH 2O-、-OCH 2CH 2O-、-OCH(CH 3)O-、-OC(CH 3) 2O-、-OCF 2O-、-CF 2CF 2O-、-OCF 2CF 2O-或-CH＝CH-CH＝CH-；
    r为0～4之间的整数，m为0或1，n、q分别选自0～8之间的整数，p选自1～8之间的整数；
    R选自氢，含有或不含有卤素的烷基、烯基、炔基、环烷基、环烯基、环烷基烷基，以及未取代或取代的芳基、芳基烷基、杂芳基、杂芳基烷基；
    R 1、R 2、R 3分别独立地选自氢，硝基，羟基，氨基，含有或不含有卤素的烷基、烯基、炔基、环烷基、环烯基、环烷基烷基、烷氧基、烯基氧基、炔基氧基、环烷基氧基、烷氧基烷基、烷氧基羰基、烷硫基羰基、烷基磺酰基、烷基磺酰基烷基、烷基羰基、烷基羰基烷基、 烷基酰氧基、烷基氨基、烷基氨基羰基、烷氧基氨基羰基、烷氧基羰基烷基、烷氨基羰基烷基、三烷基甲硅烷基、二烷基膦酰基，以及未取代或取代的芳基、芳基烷基、芳基氧基、芳基烷基氧基、芳基氧基烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基烷基、杂芳基氧基、杂芳基烷基氧基、杂芳基氧基烷基、杂芳基羰基、杂芳基磺酰基；或者R 1R 2N-选自未取代或取代的六元杂环基。
  2. 根据权利要求1所述的一种吡啶环取代的哒嗪醇类化合物及其衍生物，其特征在于，
    X选自卤素、氰基、C 1～8烷基、卤代C 1～8烷基、C 1～8烷氧基、卤代C 1～8烷氧基、R 1R 2N-(C＝O)-、R 1R 2N-、羟基、未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基；
    Y彼此独立地选自氢，卤素，氰基，硝基，叠氮基，含有或不含有卤素的C 1～8烷基、C 2～8烯基、C 2～8炔基、C 3～8环烷基、C 5～8环烯基、C 3～8环烷基C 1～8烷基，未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基、芳基C 1～8烷基、杂芳基、杂芳基C 1～8烷基，R-O-(CH 2) n-，R-O-(CH 2) p-O-(CH 2) q-，R-O-(CH 2) p-S-(CH 2) q-，R-S-(CH 2) n-，R-S-(CH 2) p-O-(CH 2) q-，R-S-(CH 2) p-S-(CH 2) q-，R-O-(CH 2) n-(C＝O)-(CH 2) q-，R-S-(CH 2) n-(C＝S)-(CH 2) q-，R-O-(CH 2) n-(C＝S)-(CH 2) q-，R-S-(CH 2) n-(C＝O)-(CH 2) q-，R-O-(C＝O)-(CH 2) q-(O) m-，R-S-(C＝S)-(CH 2) q-(S) m-，R-O-(C＝O)-(CH 2) q-(S) m-，R-O-(C＝S)-(CH 2) q-(O) m-，R-S-(C＝O)-(CH 2) q-(O) m-，R-O-(C＝S)-(CH 2) q-(S) m-，R-S-(C＝O)-(CH 2) q-(S) m-，R-S-(C＝S)-(CH 2) q-(O) m-，R-O-(CH 2) n-(C＝O)-(O) m-，R-S-(CH 2) n-(C＝S)-(S) m-，R-O-(CH 2) n-(C＝O)-(S) m-，R-O-(CH 2) n-(C＝S)-(O) m-，R-S-(CH 2) n-(C＝O)-(O) m-，R-O-(CH 2) n-(C＝S)-(S) m-，R-S-(CH 2) n-(C＝O)-(S) m-，R-S-(CH 2) n-(C＝S)-(O) m-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-(CH 2) n-O-，R-(C＝S)-(CH 2) n-S-，R-(C＝O)-(CH 2) n-S-，R-(C＝S)-(CH 2) n-O-，R-(C＝O)-O-(CH 2) q-，R-(C＝S)-S-(CH 2) q-，R-(C＝O)-S-(CH 2) q-，R-(C＝S)-O-(CH 2) q-，R-SO-(O) m-，R-SO-(S) m-，R-SO-(NR 3) m-，R-SO 2-(O) m-，R-SO 2-(S) m-，R-SO 2-(NR 3) m-，R-SO-(CH 2) n-，R-SO 2-(CH 2) n-，R 1R 2N-，R 1R 2N-(CH 2) n-O-(CH 2) q-，R 1R 2N-(CH 2) n-(C＝O)-(CH 2) q-，R 1R 2N-(CH 2) n-SO 2-(CH 2) q-，R 1R 2N-(CH 2) n-(C＝O)-(O) m-，R 1R 2N-(CH 2) n-(C＝O)-(S) m-，R 1R 2N-(CH 2) n-(C＝O)-(NR 3) m-，R 1R 2N-(CH 2) n-SO 2-(O) m-，R 1R 2N-(CH 2) n-SO 2-(S) m-，R 1R 2N-(CH 2) n-SO 2-(NR 3) m-，R 1R 2N-(C＝O)-(CH 2) n-(O) m-， R 1R 2N-(C＝O)-(CH 2) n-(S) m-，R 1R 2N-(C＝O)-(CH 2) n-(NR 3) m-，R 1R 2N-SO 2-(CH 2) q-(O) m-，R 1R 2N-SO 2-(CH 2) q-(S) m-，R 1R 2N-SO 2-(CH 2) q-(NR 3) m-，R 1R 2N-(CH 2) n-O-，R 1R 2N-O-(CH 2) q-，R 1R 2PO 3-(O) m-，R 1R 2R 3SiO-，R 1R 2R 3Si-(CH＝CH) m-，R 1R 2C＝N-(O) m-，R 1R 2C＝N-NH-；或者相邻两个Y一起形成-OCH 2O-、-CH 2CH 2O-、-OCH 2CH 2O-、-OCH(CH 3)O-、-OC(CH 3) 2O-、-OCF 2O-、-CF 2CF 2O-、-OCF 2CF 2O-或-CH＝CH-CH＝CH-；
    r为0～4之间的整数，m为0或1，n、q分别选自0～6之间的整数，p选自1～6之间的整数；
    R选自氢，含有或不含有卤素的C 1～8烷基、C 2～8烯基、C 2～8炔基、C 3～8环烷基、C 5～8环烯基、C 3～8环烷基C 1～8烷基，以及未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基、芳基C 1～8烷基、杂芳基、杂芳基C 1～8烷基；
    R 1、R 2、R 3分别独立地选自氢，硝基，羟基，氨基，含有或不含有卤素的C 1～8烷基、C 2～8烯基、C 2～8炔基、C 3～8环烷基、C 5～8环烯基、C 3～8环烷基C 1～8烷基、C 1～8烷氧基、C 2～8烯基氧基、C 2～8炔基氧基、C 3～8环烷基氧基、C 1～8烷氧基C 1～8烷基、C 1～8烷氧基羰基、C 1～8烷基羰基C 1～8烷基、C 1～8烷硫基羰基、C 1～8烷基磺酰基、C 1～8烷基磺酰基C 1～8烷基、C 1～8烷基羰基、C 1～8烷基酰氧基、C 1～8烷基氨基、C 1～8烷基氨基羰基、C 1～8烷氧基氨基羰基、C 1～8烷氧基羰基C 1～8烷基、C 1～8烷氨基羰基C 1～8烷基、三C 1～8烷基甲硅烷基、二C 1～8烷基膦酰基，以及未取代或被1～5个独立选自卤素、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有卤素的C 1～8烷基、C 3～8环烷基、C 3～8环烷基C 1～8烷基、C 2～8烯基、C 2～8炔基、C 1～8烷氧基、C 1～8烷基羰基、C 1～8烷氧基羰基、C 1～8烷基磺酰基、C 1～8烷基氨基或C 1～8烷基酰氧基中的基团所取代的芳基、芳基C 1～8烷基、芳基氧基、芳基C 1～8烷基氧基、芳基氧基C 1～8烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基C 1～8烷基、杂芳基氧基、杂芳基C 1～8烷基氧基、杂芳基氧基C 1～8烷基、杂芳基羰基、杂芳基磺酰基；或者R 1R 2N-选自未取代或被选自C 1～8烷基、卤代C 1～8烷基、C 1～8烷氧基、卤代C 1～8烷氧基、C 1～8烷氧基羰基、卤素取代的环上含有或不含有其他杂原子的六元杂环基；
    所述衍生物是指农业上可接受的通式I中哒嗪环4位上的羟基衍生物。
  3. 根据权利要求1或2所述的一种吡啶环取代的哒嗪醇类化合物及其衍生物，其特征在于，
    X选自氟、氯、溴、氰基、C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基、卤代C 1～6烷氧基、R 1R 2N-(C＝O)-、R 1R 2N-、羟基、未取代或被1～3个独立选自卤素、氰基、硝基、羟基、羧基、 巯基、氨基以及含有或不含有卤素的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的苯基；
    Y彼此独立地选自氢，氟，氯，溴，氰基，硝基，叠氮基，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基，未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的芳基、芳基C 1～6烷基、杂芳基、杂芳基C 1～6烷基，R-O-，R-O-(CH 2) p-O-，R-O-(CH 2) p-S-，R-S-，R-S-(CH 2) p-O-，R-S-(CH 2) p-S-，R-O-(C＝O)-(O) m-，R-S-(C＝S)-(S) m-，R-O-(C＝O)-(S) m-，R-O-(C＝S)-(O) m-，R-S-(C＝O)-(O) m-，R-O-(C＝S)-(S) m-，R-S-(C＝O)-(S) m-，R-S-(C＝S)-(O) m-，R-O-(C＝O)-(CH 2) q-，R-S-(C＝S)-(CH 2) q-，R-O-(C＝S)-(CH 2) q-，R-S-(C＝O)-(CH 2) q-，R-O-(CH 2) n-(C＝O)-，R-S-(CH 2) n-(C＝S)-，R-O-(CH 2) n-(C＝S)-，R-S-(CH 2) n-(C＝O)-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-O-，R-(C＝S)-S-，R-(C＝O)-S-，R-(C＝S)-O-，R-SO-，R-SO 2-，R 1R 2N-，R 1R 2N-O-，R 1R 2N-(C＝O)-(CH 2) p-，R 1R 2N-(C＝O)-(O) m-，R 1R 2N-(C＝O)-(S) m-，R 1R 2N-(C＝O)-(NR 3) m-，R 1R 2N-SO 2-(CH 2) p-，R 1R 2N-SO 2-，R 1R 2N-(CH 2) p-(C＝O)-，R 1R 2N-(CH 2) p-SO 2-，R 1R 2N-(CH 2) p-O-，R 1R 2N-O-(CH 2) p-，R 1R 2PO 3-，R 1R 2R 3SiO-，R 1R 2R 3Si-，R 1R 2R 3Si-CH＝CH-，R 1R 2C＝N-，R 1R 2C＝N-O-，R 1R 2C＝N-NH-；或者相邻两个Y一起形成-CH＝CH-CH＝CH-；
    r为0、1、2、3或4，m为0或1，n、q分别选自0、1、2、3或4，p选自1、2、3或4；
    R选自氢，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基，以及未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的芳基、芳基C 1～6烷基、杂芳基、杂芳基C 1～6烷基；
    R 1、R 2、R 3分别独立地选自氢，硝基，羟基，氨基，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基、C 1～6烷氧基、C 2～6烯基氧基、C 2～6炔基氧基、C 3～6环烷基氧基、C 1～6烷氧基C 1～6烷基、C 1～6烷氧基羰基、C 1～6烷硫基羰基、C 1～6烷基磺酰基、C 1～6烷基磺酰基C 1～6烷基、C 1～6烷基羰基、C 1～6烷基羰基C 1～6烷基、C 1～6烷基酰氧基、C 1～6烷基氨基、C 1～6烷基氨基羰基、C 1～6烷氧基氨基羰基、C 1～6烷氧 基羰基C 1～6烷基、C 1～6烷氨基羰基C 1～6烷基、三C 1～6烷基甲硅烷基、二C 1～6烷基膦酰基，以及未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的芳基、芳基C 1～6烷基、芳基氧基、芳基C 1～6烷基氧基、芳基氧基C 1～6烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基C 1～6烷基、杂芳基氧基、杂芳基C 1～6烷基氧基、杂芳基氧基C 1～6烷基、杂芳基羰基、杂芳基磺酰基；或者R 1R 2N-选自
    Figure PCTCN2018105407-appb-100002
    Figure PCTCN2018105407-appb-100003
    所述芳基为
    Figure PCTCN2018105407-appb-100004
    Figure PCTCN2018105407-appb-100005
    杂芳基选自
    Figure PCTCN2018105407-appb-100006
    Figure PCTCN2018105407-appb-100007
    Figure PCTCN2018105407-appb-100008
    R’代表氢，硝基，羟基，氨基，含有或不含有氟、氯、溴的C 1～6烷基、C 2～6烯基、C 2～6炔基、C 3～6环烷基、C 5～6环烯基、C 3～6环烷基C 1～6烷基、C 1～6烷氧基、C 2～6烯基氧基、C 2～6炔基氧基、C 3～6环烷基氧基、C 1～6烷氧基 C 1～6烷基、C 1～6烷氧基羰基、C 1～6烷硫基羰基、C 1～6烷基磺酰基、C 1～6烷基磺酰基C 1～6烷基、C 1～6烷基羰基、C 1～6烷基羰基C 1～6烷基、C 1～6烷基酰氧基、C 1～6烷基氨基、C 1～6烷基氨基羰基、C 1～6烷氧基氨基羰基、C 1～6烷氧基羰基C 1～6烷基、C 1～6烷氨基羰基C 1～6烷基、三C 1～6烷基甲硅烷基、二C 1～6烷基膦酰基，以及未取代或被1～3个独立选自氟、氯、溴、氰基、硝基、羟基、羧基、巯基、氨基以及含有或不含有氟、氯、溴的C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氧基、C 1～6烷基羰基、C 1～6烷氧基羰基、C 1～6烷基磺酰基、C 1～6烷基氨基或C 1～6烷基酰氧基中的基团所取代的
    Figure PCTCN2018105407-appb-100009
    芳基、芳基C 1～6烷基、芳基氧基、芳基C 1～6烷基氧基、芳基氧基C 1～6烷基、芳基羰基、芳基磺酰基、杂芳基、杂芳基C 1～6烷基、杂芳基氧基、杂芳基C 1～6烷基氧基、杂芳基氧基C 1～6烷基、杂芳基羰基、杂芳基磺酰基；
    所述衍生物是指农业上可接受的通式I中哒嗪环4位上的羟基衍生物，包括盐、酯、肟、羟胺和醚类衍生物。
  4. 根据权利要求1或2所述的一种吡啶环取代的哒嗪醇类化合物及其衍生物，其特征在于，
    X选自氯、氰基、甲基、乙基、三氟甲基、五氟乙基、二氟甲基、一氟甲基、甲氧基、乙氧基、三氟甲氧基、五氟乙氧基、
    Figure PCTCN2018105407-appb-100010
    r为0、1、2、3或4；
    Y彼此独立地选自氢、甲基、乙基、甲氧基、乙氧基、氟、氯、溴、氨基、氰基、三氟甲基、
    Figure PCTCN2018105407-appb-100011
    或者
    Figure PCTCN2018105407-appb-100012
    代表
    Figure PCTCN2018105407-appb-100013
    所述衍生物是指农业上可接受的通式I中哒嗪环4位上的羟基衍生物，包括盐、酯、肟、羟胺和醚类衍生物。
  5. 一种如权利要求1-4任意一项所述的吡啶环取代的哒嗪醇类化合物及其衍生物的制备方法，其特征在于，所述的吡啶环取代的哒嗪醇类化合物的制备方法包括以下步骤：
    (1)采用化合物Ⅱ与化合物Ⅲ发生Suzuki反应，制备如通式Ⅳ所示的化合物；
    (2)将如通式Ⅳ所示的化合物进行卤代反应，制备如通式Ⅴ所示的化合物；
    (3)采用如通式Ⅴ所示的化合物水解制备如通式Ⅰ所示的化合物；
    其化学反应方程式如下：
    Figure PCTCN2018105407-appb-100014
    L 1和L 2分别独立地代表卤素，优选氯、溴、碘；
    制备其酯和醚类衍生物的化学反应方程式如下：
    Figure PCTCN2018105407-appb-100015
    其中，Q 1代卤素，优选氯、溴；
    制备其肟和羟胺类衍生物的化学反应方程式如下：
    Figure PCTCN2018105407-appb-100016
    其中，Q 2代卤素，优选氯、氟。
  6. 根据权利要求5所述的一种吡啶环取代的哒嗪醇类化合物及其衍生物的制备方法，其特征在于，所述反应温度均在20～150℃范围内，优选50～130℃；所述步骤(1)在催化剂、碱和溶剂的存在下进行，催化剂为Pd(dppf)Cl 2CH 2Cl 2、Pd(dba) 2、Pd 2(dba) 3、Pd(PPh 3) 4、PdCl 2、Pd(OAc) 2、Pd(dppf)Cl 2、Pd(PPh 3) 2Cl 2或Ni(dppf)Cl 2，碱选自Et 3N、NaHCO 3、KOAc、K 2CO 3、K 3PO 4、Na 2CO 3、CsF、Cs 2CO 3、t-BuONa、EtONa、KOH和NaOH中的一种或两种以上，溶剂为THF/水、甲苯/水、DMF/水、1,4-二氧六环/水、甲苯/乙醇/水或乙腈/水、THF、甲苯、1,4-二氧六环、乙腈、DMF体系；所述步骤(2)在卤代试剂、催化剂和溶剂的存在下进行，卤代试剂为N-氯代琥珀酰亚胺、N-溴代琥珀酰亚胺或N-碘代琥珀酰亚胺，催化剂为过氧化苯甲酰，溶剂为乙腈；所述步骤(3)在碱和溶剂的存在下进行或者在三溴化硼、氢溴酸醋酸溶液、盐酸甲醇溶液、盐酸乙酸乙酯溶液的存在下进行，所述碱优选NaOH、KOH、醋酸钾、醋酸钠，所述溶剂优选水、DMSO；所述制备其酯和醚类衍生物的反应以及制备其肟和羟胺类衍生物的第二步反应均在碱和溶剂的存在下进行，碱选自氢氧化钠、氢氧化钾、碳酸钠、 碳酸钾、碳酸氢钠、碳酸铯、三乙胺和二异丙基乙基胺中的一种或两种以上；溶剂为THF、1,4-二氧六环、甲苯、1,2-二氯乙烷、乙酸乙酯、乙腈、DMF、丙酮、二氯甲烷或氯仿；所述制备其肟和羟胺类衍生物的反应中第一步在卤代试剂和溶剂的存在下进行，所述卤代试剂为Phenofluor/氟化铯或POCl 3，所述溶剂选自甲苯、1,2-二氯乙烷、DMF中的一种或两种以上；所述反应温度均选自0～120℃范围内，优选20-80℃。
  7. 一种除草剂组合物，其特征在于，包括(i)权利要求1-4任意一项如通式I所示的吡啶环取代的哒嗪醇类化合物及其衍生物；优选地，还包括(ii)一种或多种另外的除草剂和/或安全剂；更优选地，还包括(iii)农业化学上可接受的制剂助剂。
  8. 根据权利要求7所述的一种除草剂组合物，其特征在于，所述另外的除草剂选自HPPD抑制剂、激素类、PDS抑制剂中的一种；优选地，HPPD抑制剂为磺草酮、硝磺草酮、苯唑草酮、环磺酮、氟吡草酮、呋喃磺草酮、双环磺草酮、lancotrione、双唑草酮、环吡氟草酮、三唑磺草酮、苯唑氟草酮、磺酰草吡唑、吡唑特、吡草酮、tolpyralate、fenquinotrione、异噁唑草酮；激素类为氯氟吡氧乙酸、氟氯吡啶酯、氯氟吡啶酯、二氯喹啉酸、氯甲喹啉酸、2甲4氯、2-甲基-4-氯苯氧丙酸、MCPB、2,4-D、2,4-滴丙酸、2,4-DB、麦草畏、氨氯吡啶酸、三氯吡氧乙酸、二氯吡啶酸、绿草定及其衍生物，PDS抑制剂为氟咯草酮、呋草酮、吡氟酰草胺、氟吡酰草胺、氟丁酰草胺、氟草敏、氟啶草酮。
  9. 一种控制有害植物的方法，其特征在于，包括将除草有效量的权利要求1-4任意一项所述的吡啶环取代的哒嗪醇类化合物及其衍生物中的至少一种或权利要求7-8任意一项所述的除草剂组合物使用在植物上或者有害植物区域。
  10. 如权利要求1-4任意一项所述的吡啶环取代的哒嗪醇类化合物及其衍生物中的至少一种或权利要求7-8任意一项所述的除草剂组合物在控制有害植物上的用途，优选地，将所述的吡啶环取代的哒嗪醇类化合物及其衍生物用于防除有用作物中的有害植物，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
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