WO2023088426A1 - 氧代丁(-2-烯酸)酸类化合物及其制备方法、除草剂组合物及其应用和除草剂 - Google Patents

氧代丁(-2-烯酸)酸类化合物及其制备方法、除草剂组合物及其应用和除草剂 Download PDF

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WO2023088426A1
WO2023088426A1 PCT/CN2022/132867 CN2022132867W WO2023088426A1 WO 2023088426 A1 WO2023088426 A1 WO 2023088426A1 CN 2022132867 W CN2022132867 W CN 2022132867W WO 2023088426 A1 WO2023088426 A1 WO 2023088426A1
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alkyl
coo
combination
group
substituted
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French (fr)
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席真
王大伟
张瑞波
杨皇泽
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南开大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/38—Sulfur atoms
    • 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
    • C07D401/10—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 linked by a carbon chain containing aromatic rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the invention relates to the field of herbicides, in particular to an oxobut(-2-enoic acid) acid compound and a preparation method thereof, a herbicide composition containing an oxobut(-2-enoic acid) acid compound and its Application and herbicides containing oxobut(-2-enoic acid) acid compounds.
  • Protoporphyrinogen oxidase is an important target for the development of agricultural herbicides. It is the last common enzyme in the same biosynthetic step of chlorophyll and heme, widely exists in various organisms, and can catalyze the oxidation of protoporphyrinogen IX to protoporphyrin IX. In plants, protoporphyrin IX is an important substance for the synthesis of chlorophyll. If the PPO enzyme activity in plants is inhibited, it will lead to the rapid accumulation of the substrate protoporphyrinogen IX and overflow into the cytoplasm.
  • protoporphyrinogen IX can be self-oxidized to protoporphyrin IX. Under the irradiation of light, protoporphyrin IX reacts with oxygen and produces a large amount of singlet oxygen, which causes lipid peroxidation and plant albino death.
  • PPO herbicides can be traced back to around the 1960s. With the widespread use of PPO herbicides, weeds have developed resistance to more and more PPO herbicides and are showing a trend of gradual spread.
  • the object of the present invention is to overcome the aforementioned problems in the prior art, and to provide a kind of oxobut(-2-enoic acid) acid compound, which has higher herbicidal activity when used for controlling weeds.
  • the first aspect of the present invention provides an oxobut(-2-enoic acid) acid compound, which has a structure shown in formula (I),
  • R 1 and R 2 are each independently selected from halogen, H, -CN, C 1 -C 6 alkyl, -OR 11 , -SO 2 -R 11 ;
  • R 11 is selected from C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one halogen;
  • X is CH, N;
  • Y is selected from O, -N-OCH 3 , -N-OCH 2 CH 3 , -CN, C 1 -C 6 alkyl, phenyl substituted by at least one group in combination A;
  • R 3 and R 6 are each independently selected from H, halogen, -CN, C 1 -C 6 alkyl, phenyl substituted by at least one group in combination A;
  • R 4 and R 7 are each independently selected from H, -COO-CH 3 , -COO-CH 2 CH 3 , -CN, C 1 -C 6 alkyl, substituted by at least one group in combination A phenyl;
  • n is an integer of 0-6;
  • R 5 is selected from -OR 51 , -N(R 52 )(R 53 ), -CN, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one halogen, phenyl, benzyl base;
  • R 51 is selected from H, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, C 3 -C 15 cycloalkyl, C 3 -C 15 alkenyl, C 3 -C 15 alkynyl, -(CH 2 ) m -COO-R 51 , -CH(CH 3 )-COO-R 51 , -C(CH 3 ) 2 -COO- R 51 , -CHF-COO-R 51 , -CF 2 -COO-R 51 , -(CH 2 ) m -R 52 , -(CH 2 ) m -OR 51 , -(CH 2 ) m -NH-R 51 , -(CH 2 ) m -N(R 51 ) 2 ;
  • R 52 and R 53 are each independently selected from H, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, C 3 -C 15 cycloalkane C 3 -C 15 alkenyl, C 3 -C 15 alkynyl, -(CH 2 ) m -R 52 , -SOOR 53 , -SOO-N(R 51 ) 2 , -(CH 2 ) m -COO-R 51 , -OR 51 , -O-CO-R 51 , -O-(CH) m -COO-R 51 , and R 52 and R 53 are not H at the same time; or R 52 and R 53 are connected with A 4-6-membered ring formed by the N atoms of R 52 and R 53 together;
  • n is an integer selected from 1-10;
  • R 51 is selected from C 1 -C 15 alkyl, C 3 -C 15 alkenyl, C 3 -C 15 alkynyl;
  • R 52 is selected from phenyl, phenyl substituted by at least one group in combination A;
  • R 53 is selected from C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, phenyl, benzene substituted by at least one group in combination A base;
  • the combination A is composed of halogen, C 3 -C 6 cycloalkyl, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one halogen;
  • Q is selected from any one of the following groups:
  • R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are each independently selected from H, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one halogen, amino, C 1 -C 6 alkoxy substituted by at least one halogen;
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , and A 11 are each independently selected from O and S.
  • the second aspect of the present invention provides the application of the oxobut(-2-enoic acid) acid compound described in the aforementioned first aspect in controlling weeds.
  • the third aspect of the present invention provides a herbicidal composition containing a herbicidally effective amount of the oxobut(-2-enoic acid) acid compound described in the aforementioned first aspect.
  • the fourth aspect of the present invention provides the use of the herbicide composition described in the aforementioned third aspect for controlling weeds.
  • the fifth aspect of the present invention provides a herbicide, which is composed of an active ingredient and an auxiliary material, and the active ingredient is the herbicide composition described in the aforementioned third aspect.
  • the oxobut(-2-enoic acid) acid compound provided by the invention has higher herbicidal activity when used for controlling weeds.
  • C 1 -C 15 alkyl means an alkyl group with a total of 1-15 carbon atoms, including straight chain alkyl and branched chain alkyl, for example, the total number of carbon atoms can be 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14 and 15 straight chain alkyl, branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.
  • C 1 -C 10 alkyl "C 1 -C 6 alkyl", etc., except that the total number of carbon atoms is different.
  • Halogen means fluorine, chlorine, bromine or iodine.
  • a C 1 -C 15 alkyl group substituted by at least one halogen means an alkyl group with a total of 1-15 carbon atoms, including straight-chain alkyl groups and branched-chain alkyl groups, and at least one of the C 1-15 alkyl groups is One H is substituted by a halogen atom selected from halogen, for example, 1, 2, 3, 4, 5 or 6 H in the C 1-15 alkyl group are substituted by any one selected from fluorine, chlorine, bromine, iodine, or A plurality of halogen atoms can be substituted, for example, trifluoromethyl, difluoromethyl, monofluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl and the like. There is a similar interpretation for "C 1 -C 10 alkyl substituted by at least one halogen", "C 1 -C 6 alkyl substituted by at least one halogen", etc., except that the total
  • a C 1 -C 15 alkyl group substituted by at least one group in combination A means an alkyl group with a total of 1-15 carbon atoms, including straight-chain alkyl groups and branched-chain alkyl groups, and the C 1 -C At least one H in the alkyl group of 15 is substituted by at least one group in the A combination (the present invention is defined in detail later), for example, the total number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 straight chain alkyl, branched chain alkyl.
  • C 1 -C 10 alkyl substituted by at least one group in combination A "C 1 -C 6 alkyl substituted by at least one group in combination A", etc. have the same Similar explanation, except that the total number of carbon atoms is different.
  • Phhenyl substituted by at least one group in combination A has a similar definition thereto.
  • a C 1 -C 6 alkoxy group substituted by at least one halogen means an alkoxy group with a total of 1-6 carbon atoms, including straight-chain alkoxy and branched-chain alkoxy, the C 1 -C 6 alkoxy 1, 2, 3, 4, 5 or 6 H in the group are replaced by any one or more halogen atoms selected from fluorine, chlorine, bromine and iodine, such as trifluoromethoxy, difluoromethoxy group, a fluoromethoxy group, a fluoroethoxy group, a difluoroethoxy group, a trifluoroethoxy group, etc.
  • C 3 -C 15 cycloalkyl refers to a cycloalkyl group with a total of 3-15 carbon atoms and contains at least one ring. There is no special requirement for the number of carbon atoms in the ring, which can be 3, 4, 5, or 6 , 7, 8, 9, 10, etc.
  • the definitions of "C 3 -C 10 cycloalkyl", “C 3 -C 6 cycloalkyl” etc. are similar to it, except that the total number of carbon atoms is different.
  • C 3 -C 15 alkenyl means an alkenyl group with a total of 3-15 carbon atoms, and contains at least one alkenyl group, which may or may not be directly connected to the parent core structure.
  • Nuclear Structural Connections The definitions of "C 3 -C 10 alkenyl", “C 3 -C 6 alkenyl” etc. are similar to it, except that the total number of carbon atoms is different.
  • a C 3 -C 15 alkynyl group means an alkynyl group with a total of 3-15 carbon atoms, and contains at least one alkynyl group.
  • the alkynyl group may or may not be directly connected to the parent nucleus structure.
  • Nuclear Structural Connections The definition of "C 3 -C 10 alkynyl group", “C 3 -C 6 alkynyl group” etc. is similar to it, except that the total number of carbon atoms is different.
  • n is an integer of 0-6, which means that n can be an integer of 0, 1, 2, 3, 4, 5, or 6.
  • n is selected from an integer of 1-10, which means that m can be an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • R 52 and R 53 form a 4-6 membered ring together with the N atom connecting R 52 and R 53 , which means that R 52 and R 53 together with the N atom form a 4-membered heterocycle, a 5-membered heterocycle and a 6-membered ring containing N atoms heterocycle.
  • the wavy line of each group in the present invention indicates the connection position, that is, the group is connected to the mother core structure through a chemical bond at the site where the wavy line is located.
  • the first aspect of the present invention provides an oxobut(-2-enoic acid) acid compound.
  • R 1 and R 2 are each independently selected from halogen
  • X is CH
  • Y is selected from O, -N-OCH 3 , -N-OCH 2 CH 3 ;
  • R 3 and R 6 are each independently selected from H, halogen, C 1 -C 6 alkyl
  • R 4 and R 7 are each independently selected from H, -COO-CH 3 , -COO-CH 2 CH 3 , C 1 -C 6 alkyl;
  • n is an integer of 0-6;
  • R 5 is selected from -OR 51 , -N(R 52 )(R 53 ), -CN, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one halogen;
  • R 51 is selected from H, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, C 3 -C 15 cycloalkyl, C 3 -C 15 alkenyl, C 3 -C 15 alkynyl, -(CH 2 ) m -COO-R 51 , -CH(CH 3 )-COO-R 51 , -C(CH 3 ) 2 -COO- R 51 , -CHF-COO-R 51 , -CF 2 -COO-R 51 , -(CH 2 ) m -R 52 , -(CH 2 ) m -OR 51 , -(CH 2 ) m -NH-R 51 , -(CH 2 ) m -N(R 51 ) 2 ;
  • R 52 and R 53 are each independently selected from H, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, C 3 -C 15 cycloalkane C 3 -C 15 alkenyl, C 3 -C 15 alkynyl, -(CH 2 ) m -R 52 , -SOOR 53 , -SOO-N(R 51 ) 2 , -(CH 2 ) m -COO-R 51 , -OR 51 , -O-CO-R 51 , -O-(CH) m -COO-R 51 , and R 52 and R 53 are not H at the same time; or R 52 and R 53 are connected with A 4-6-membered ring formed by the N atoms of R 52 and R 53 together;
  • n is an integer selected from 1-10;
  • R 51 is selected from C 1 -C 15 alkyl, C 3 -C 15 alkenyl, C 3 -C 15 alkynyl;
  • R 52 is selected from phenyl, phenyl substituted by at least one group in combination A;
  • R 53 is selected from C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, phenyl, benzene substituted by at least one group in combination A base;
  • the combination A is composed of halogen, C 3 -C 6 cycloalkyl, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one halogen;
  • Q is selected from any one of the following groups:
  • R 1 and R 2 are each independently selected from halogen
  • X is CH
  • Y is selected from O, -N-OCH 3 , -N-OCH 2 CH 3 ;
  • R 3 and R 6 are each independently selected from H, halogen, C 1 -C 6 alkyl
  • R 4 and R 7 are each independently selected from H, -COO-CH 3 , -COO-CH 2 CH 3 , C 1 -C 6 alkyl;
  • n is an integer of 0-6;
  • R 5 is selected from -OR 51 , -N(R 52 )(R 53 ), -CN, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one halogen;
  • R 51 is selected from H, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, C 3 -C 15 cycloalkyl, C 3 -C 15 alkenyl, C 3 -C 15 alkynyl, -(CH 2 ) m -COO-R 51 , -CH(CH 3 )-COO-R 51 , -C(CH 3 ) 2 -COO- R 51 , -CHF-COO-R 51 , -CF 2 -COO-R 51 , -(CH 2 ) m -R 52 , -(CH 2 ) m -OR 51 , -(CH 2 ) m -NH-R 51 , -(CH 2 ) m -N(R 51 ) 2 ;
  • R 52 and R 53 are each independently selected from H, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, C 3 -C 15 cycloalkane C 3 -C 15 alkenyl, C 3 -C 15 alkynyl, -(CH 2 ) m -R 52 , -SOOR 53 , -SOO-N(R 51 ) 2 , -(CH 2 ) m -COO-R 51 , -OR 51 , -O-CO-R 51 , -O-(CH) m -COO-R 51 , and R 52 and R 53 are not H at the same time; or R 52 and R 53 are connected with A 4-6-membered ring formed by the N atoms of R 52 and R 53 together;
  • n is an integer selected from 1-10;
  • R 51 is selected from C 1 -C 15 alkyl, C 3 -C 15 alkenyl, C 3 -C 15 alkynyl;
  • R 52 is selected from phenyl, phenyl substituted by at least one group in combination A;
  • R 53 is selected from C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one group in combination A, phenyl, benzene substituted by at least one group in combination A base;
  • the combination A is composed of halogen, C 3 -C 6 cycloalkyl, C 1 -C 15 alkyl, C 1 -C 15 alkyl substituted by at least one halogen;
  • R1 is F
  • R2 is Cl
  • X is CH
  • Y is selected from O, -N-OCH 3 , -N-OCH 2 CH 3 ;
  • R 3 and R 6 are each independently selected from H, halogen
  • R 4 and R 7 are each independently selected from H, -COO-CH 3 , -COO-CH 2 CH 3 , -CH 3 , -CH 2 CH 3 ;
  • n is an integer of 0-4;
  • R 5 is selected from -OR 51 , -N(R 52 )(R 53 ), -CN, C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by at least one halogen;
  • R 51 is selected from H, C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by at least one group in combination A, C 3 -C 10 cycloalkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, -(CH 2 ) m -COO-R 51 , -CH(CH 3 )-COO-R 51 , -C(CH 3 ) 2 -COO- R 51 , -CHF-COO-R 51 , -CF 2 -COO-R 51 , -(CH 2 ) m -R 52 , -(CH 2 ) m -OR 51 , -(CH 2 ) m -NH-R 51 , -(CH 2 ) m -N(R 51 ) 2 ;
  • R 52 and R 53 are each independently selected from H, C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by at least one group in combination A, C 3 -C 10 cycloalkane C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, -(CH 2 ) m -R 52 , -SOOR 53 , -SOO-N(R 51 ) 2 , -(CH 2 ) m -COO-R 51 , -OR 51 , -O-CO-R 51 , -O-(CH) m -COO-R 51 , and R 52 and R 53 are not H at the same time; or R 52 and R 53 are connected with A 4-6-membered ring formed by the N atoms of R 52 and R 53 together;
  • n is an integer selected from 1-10;
  • R 51 is selected from C 1 -C 10 alkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl;
  • R 52 is selected from phenyl, phenyl substituted by at least one group in combination A;
  • R 53 is selected from C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by at least one group in combination A, phenyl, benzene substituted by at least one group in combination A base;
  • the combination A is composed of halogen, C 3 -C 6 cycloalkyl, C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by at least one halogen;
  • R1 is F
  • R2 is Cl
  • X is CH
  • Y is selected from O, N-OCH 3 , N-OCH 2 CH 3 ;
  • R 3 and R 6 are each independently selected from H, fluorine, chlorine, bromine, iodine;
  • R 4 and R 7 are each independently selected from H, -COO-CH 3 , -COO-CH 2 CH 3 , -CH 3 , -CH 2 CH 3 ;
  • n 0;
  • R 5 is selected from -OR 51 , -N(R 52 )(R 53 ), -CN, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one halogen;
  • R 51 is selected from H, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one group in combination A, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, -(CH 2 ) m -COO-R 51 , -CH(CH 3 )-COO-R 51 , -C(CH 3 ) 2 -COO- R 51 , -CHF-COO-R 51 , -CF 2 -COO-R 51 , -(CH 2 ) m -R 52 , -(CH 2 ) m -OR 51 , -(CH 2 ) m -NH-R 51 , -(CH 2 ) m -N(R 51 ) 2 ;
  • R 52 and R 53 are each independently selected from H, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one group in combination A, C 3 -C 6 cycloalkane C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, -(CH 2 ) m -R 52 , -SOOR 53 , -SOO-N(R 51 ) 2 , -(CH 2 ) m -COO-R 51 , -OR 51 , -O-CO-R 51 , -O-(CH) m -COO-R 51 , and R 52 and R 53 are not H at the same time; or R 52 and R 53 are connected with A 4-6-membered ring formed by the N atoms of R 52 and R 53 together;
  • n is an integer selected from 1-6;
  • R 51 is selected from C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl;
  • R 52 is selected from phenyl, phenyl substituted by at least one group in combination A;
  • R 53 is selected from C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one group in combination A, phenyl, benzene substituted by at least one group in combination A base;
  • the combination A is composed of fluorine, chlorine, bromine, iodine, cyclopropyl, cyclobutyl, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by at least one halogen;
  • the compound of the structure shown in the compound formula (I) of formula (I) is selected from any one in the following table 1:
  • n in the above compounds are all 0; X are all CH; R 1 are all F; R 2 are all Cl.
  • the present invention has no special limitation on the preparation method of the compound described in the aforementioned first aspect, and those skilled in the art can determine a suitable reaction route according to the structural formula combined with known methods in the field of organic synthesis.
  • the present invention preferably adopts the methods described in the following preferred embodiments to obtain the compounds described in the first aspect.
  • the present invention provides a method for preparing the oxobut(-2-enoic acid) acid compound described in the aforementioned first aspect, the method comprising:
  • n X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are correspondingly the same as those in the aforementioned first aspect.
  • the present invention will not be described in detail here, and those skilled in the art should not understand it as limiting the present invention.
  • the present invention has no particular limitation on the specific conditions of the contact reaction, those skilled in the art can select according to the known conditions in the art and the conditions recorded in the examples of the present invention later.
  • the present invention provides the synthetic method shown in the following route to obtain the compound described in the aforementioned first aspect of the present invention, and the definition of each substituent in each structural formula in the following synthetic route is correspondingly the same as the definition of the aforementioned first aspect:
  • A1: Y in the formula (I-1) is O Target synthetic route:
  • the compound of the structure shown in the formula (I-1) and glacial acetic acid, 2-dimethylamino-4-trifluoromethyl-6H-1,3-oxazin-6-one that is, the formula (I-2) Show compound
  • reflux reaction after the reaction is completed, cool to room temperature, extract and remove the solvent under reduced pressure; after dissolving the residue in DMF, add cesium carbonate and methyl iodide, react at room temperature, extract after the reaction is completed, wash, dry, Filtrate, concentrate under reduced pressure, and obtain a solid by column chromatography; then add glacial acetic acid, water and concentrated sulfuric acid to heat and react, after the reaction is completed, cool to room temperature, filter with suction, wash, and dry to obtain the compound with the structure shown in a1.
  • the first step of this synthetic route is the same as that of A1 synthetic route, and will not be repeated here.
  • A2 Y in the formula (I-1) is O Target synthetic route:
  • the compound shown in I-1 was mixed with hydrochloric acid and cooled to -9°C, sodium nitrite was slowly added dropwise and stirred for 1 h. SnCl 2 and concentrated hydrochloric acid were slowly added to the resulting reaction system, and the stirring reaction was continued for 2 h. Then trifluoropyruvate was added to the reaction system to continue stirring for 1 h, and the obtained intermediate was used for subsequent reactions after being filtered and dried.
  • the first step of the synthetic route is the same as the synthetic route A2, and will not be repeated here.
  • A3: Y in the formula (I-1) is O Target synthetic route:
  • the first step of the synthetic route is the same as the synthetic route A3, and will not be repeated here.
  • A4 Y in the formula (I-1) is O Target synthetic route:
  • the first step of the synthetic route is the same as the synthetic route A4, and will not be repeated here.
  • the method for preparing oxobut(-2-enoic acid) acid compounds provided by the invention has the advantages of high purity and high yield of the target product.
  • the second aspect of the present invention provides the use of the oxobut(-2-enoic acid) acid compound described in the first aspect in the control of weeds.
  • the third aspect of the present invention provides a herbicidal composition, which contains a herbicidally effective amount of the oxobut(-2-enoic acid) acid compound described in the first aspect.
  • the herbicide composition also contains 2,4-dibutyl ester, clodinafop-propargyl, clodinafop-propargyl, pinoxaden, penfentrazone-ethyl, flumethachlor-methyl, metaflufen-methyl, Flufenpyr-methyl, Cyhalofop-methyl, Indoxazone-methyl, Flumifenpyr, Clomazone, Propyrylclomazone, Clomazone, Sulcotrione, Mesotrione, Difemazone , pendimethalin, trifluralin, grass-killing, acifluorfen, fenben, methoxyfen, afluorifluorfen, ethoxyfluorfen, pyrizafen, fomesafen, B Carboxyfluorfen, Pyrisulfachlor, Pyrimidin, Bisfluben, Thiadiafen, Flusulam, Alachlor, Metolachlor, Pretilachlor, But
  • the inventors of the present invention have found that when the oxobut(-2-enoic acid) acid compounds provided by the present invention are used in conjunction with at least one of the above-mentioned herbicides, the activity of controlling weeds, crop safety and The range of weed types that can be controlled can achieve an effect far greater than the sum of the two alone.
  • the content of the active ingredient is 0.01-99% by weight; preferably 0.01-70% by weight; more preferably 5-60% by weight.
  • the fourth aspect of the present invention provides the use of the oxobut(-2-enoic acid) acid compound described in the first aspect in the control of weeds.
  • the weeds are selected from broadleaf weeds and/or gramineous weeds.
  • the weeds are selected from the group consisting of quinoa, cocklebur, sorrel, Hemeng, mustard, february, velvetleaf, cassia, rice bract, snakehead sausage, morning glory, alfalfa, pokeweed, At least one of false sorghum, barngrass, dogtail, barnyardgrass, barnyardgrass, sorghum, echinacea, thrush, teff, clubhead grass, kangaroo, bluegrass and goosegrass .
  • the fifth aspect of the present invention provides a herbicide, the herbicide is composed of an active ingredient and an auxiliary material, and the active ingredient is the herbicide composition described in the aforementioned third aspect.
  • the content of the active ingredient is 1-99.99% by weight; preferably 5-90% by weight.
  • the auxiliary materials are emulsifiers, dispersants, wetting agents, spreading agents, stabilizers, defoamers, synergists, penetrating agents, adhesives, safeners, carriers, surfactants and fillers at least one of .
  • the dosage form of the herbicide is at least one selected from the group consisting of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.
  • Triphosgene (1.5 mmol, 0.5 eq.) and toluene (50 mL) were added to the reaction flask and cooled to 0 °C.
  • I-1a2-5 (3mmol, 1.0eq.) was dissolved in toluene (50mL), and then triethylamine (6mmol, 2.0eq.) was added, and the solution system was slowly dropped into the above reaction flask. After dropping, the mixture was stirred and reacted for 0.5h in an ice-water bath, and the temperature was slowly raised to reflux for 10h. After the reaction was completed, the system was cooled down to room temperature, and the solvent was removed under reduced pressure, and the obtained residue was dissolved in toluene (100 mL).
  • Test Example 1 For determining the herbicidal activity of comparative compounds and target compounds
  • each target compound was dissolved with N,N-dimethylformamide and diluted with distilled water to prepare a medicinal solution with a concentration of 0.2g/L, which was passed through an automatic spray tower (model: 3WPSH-700E, Nanjing Produced by Agricultural Mechanization Research Institute) after spraying, move the weed foliage drug liquid into the greenhouse for cultivation after drying, and investigate the results after 15 days.
  • the herbicidal activity inhibition rate (%) results are shown in Table 3-Table 6.
  • the method for calculating the herbicidal activity inhibition rate is (in the formula: E: fresh weight inhibition rate; C: fresh weight of the above-ground part of the control plant; T: fresh weight of the above-ground part of the treatment plant):
  • test results are graded according to the following grading methods:
  • grade B When 80% ⁇ E ⁇ 90%, grade B;
  • Test Example 2 Used to determine the herbicidal spectrum of the target compound I.1a2
  • Test method Take a flower pot with an inner diameter of 7.5 cm, fill it with compound soil (vegetable garden soil: seedling substrate, 1:2, v/v) to the height of 3/4 of the flower pot, and directly sow the tested weed targets in Table 7 ( Bud rate ⁇ 85%), cover with soil 0.2cm, wait for the weeds to grow to about 3 leaf stage for later use.
  • the target compound I.1a25 was sprayed according to the dose by the automatic spray tower (model: 3WPSH-700E, produced by Nanjing Institute of Agricultural Mechanization), the leaves of the weeds were dried and moved to the greenhouse for cultivation, and the results were investigated after 30 days.
  • the herbicidal activity inhibition rate (%) results are shown in Table 7.
  • the herbicidal activity inhibition rate calculation method is (in the formula: E 1 : fresh weight inhibition rate; C: contrast plant aerial part fresh weight; T: process plant aerial part fresh weight):
  • test result E1 is graded according to the same grading method as Test Example 1.
  • Test Example 3 Used to determine the safety of target compounds on post-emergence crops
  • the doses used in this test case were 37.5g a.i./ha and 18.75g a.i./ha respectively.
  • Test method Take a flowerpot with an inner diameter of 9.0cm, fill it with compound soil (vegetable garden soil: seedling substrate, 1:2, v/v) to the height of 3/4 of the flowerpot, and directly sow the crop target (germination rate ⁇ 85%) covered with soil 0.2cm, and wait for the weeds to grow to about 3 leaf stage for later use. After the target compound was sprayed by the automatic spray tower according to the dose, the liquid on the weed leaves was dried and then moved into the greenhouse for cultivation, and the results were investigated after 30 days. The results of its inhibition rate (%) on crop growth are shown below.
  • the calculation method of crop growth inhibition rate is (wherein: E 2 : inhibition rate of fresh weight; C: fresh weight of aerial parts of control plants; T: fresh weight of aerial parts of treated plants):

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Abstract

本发明涉及除草剂领域，公开了一种氧代丁(-2-烯酸)酸类化合物及其制备方法、除草剂组合物及其应用和除草剂，该化合物具有式(I)所示的结构。本发明提供的氧代丁(-2-烯酸)酸类化合物用于防治杂草时具有较高的除草活性。

Description

氧代丁(-2-烯酸)酸类化合物及其制备方法、除草剂组合物及其应用和除草剂
相关申请的交叉引用
本申请要求2021年11月22日提交的中国专利申请202111388237.8的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及除草剂领域，具体涉及一种氧代丁(-2-烯酸)酸类化合物及其制备方法、含有氧代丁(-2-烯酸)酸类化合物的除草剂组合物及其应用和含有氧代丁(-2-烯酸)酸类化合物的除草剂。
背景技术
原卟啉原氧化酶(PPO，EC1.3.3.4)是一个重要的农用除草剂开发靶标。它是叶绿素和亚铁血红素相同生物合成步骤中的最后一个共同酶，广泛存在于各种生物体内，能够将原卟啉原IX催化氧化成原卟啉IX。在植物体内，原卟啉IX是合成叶绿素的重要物质。如果植物体内PPO酶活性被抑制，将会导致底物原卟啉原IX的迅速积累并溢出到细胞质中。在细胞质中原卟啉原IX能够自氧化为原卟啉IX，在光的照射下原卟啉IX与氧气反应并产生大量的单线态的氧，从而引起脂质的过氧化和植物的白化死亡。
PPO除草剂的使用历史可以追溯到20世纪60年代左右。随着PPO除草剂的广泛使用，杂草已经对越来越多PPO除草剂产生了抗性，并呈现出逐渐蔓延的趋势。
发明内容
本发明的目的是为了克服现有技术存在的前述问题，提供一种氧代丁(-2-烯酸)酸类化合物，该化合物用于防治杂草时具有较高的除草活性。
为了实现上述目的，本发明的第一方面提供一种氧代丁(-2-烯酸)酸类化合物，该化合物具有式(Ⅰ)所示的结构，
Figure PCTCN2022132867-appb-000001
其中，在式(I)中，
R 1、R 2各自独立地选自卤素、H、-CN、C 1-C 6的烷基、-O-R 11、-SO 2-R 11；
R 11选自C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基；
X为CH、N；
Y选自O、-N-OCH 3、-N-OCH 2CH 3、-CN、C 1-C 6的烷基、由组合A中的至少一种基团取代的苯基；
R 3和R 6各自独立地选自H、卤素、-CN、C 1-C 6的烷基、由组合A中的至少一种基团取代的苯基；
R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、-CN、C 1-C 6的烷基、由组合A中的至少一种基团取代的苯基；
n为0-6的整数；
R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基、苯基、苄基；
其中，R 51选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、 C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
R 52、R 53各自独立地选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
m选自1-10的整数；
R 51选自C 1-C 15的烷基、C 3-C 15的烯基、C 3-C 15的炔基；
R 52选自苯基、由组合A中的至少一种基团取代的苯基；
R 53选自C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、苯基、由组合A中的至少一种基团取代的苯基；
所述组合A由卤素、C 3-C 6的环烷基、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基组成；
Q选自以下基团中的任意一种：
Figure PCTCN2022132867-appb-000002
其中，R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27各自独立地选自H、C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基、氨基、由至少一个卤素取代的C 1-C 6的烷氧基；
A 1、A 2、A 3、A 4、A 5、A 6、A 7、A 8、A 9、A 10、A 11各自独立地选自O、S。
本发明的第二方面提供前述第一方面中所述的氧代丁(-2-烯酸)酸类化合物在防治杂草中的应用。
本发明的第三方面提供一种除草剂组合物，该组合物含有除草有效量的前述第一方面中所述的氧代丁(-2-烯酸)酸类化合物。
本发明的第四方面提供前述第三方面中所述的除草剂组合物在防治杂草中的应用。
本发明的第五方面提供一种除草剂，该除草剂由活性成分和辅料组成，所述活性成分为前述第三方面中所述的除草剂组合物。
本发明提供的氧代丁(-2-烯酸)酸类化合物用于防治杂草时具有较高的除草活性。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
在本发明中，在未作相反说明的情况下，本发明的术语解释如下：
C 1-C 15的烷基，表示碳原子总数为1-15的烷基，包括直链烷基、支链烷基，例如可以为碳原子总数为1、2、3、4、5、6、7、8、9、10、11、12、13、14和15的直链烷基、支链烷基，例如可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基等。针对“C 1-C 10的烷基”、“C 1-C 6的烷基”等具有与此相似的解释，所不同的是，碳原子总数不同。
卤素，表示氟、氯、溴或碘。
由至少一个卤素取代的C 1-C 15的烷基，表示碳原子总数为1-15的烷基，包括直链烷基、支链烷基，并且该C 1-15的烷基中的至少一个H由选自卤素的卤原子取代，例如该C 1-15的烷基中的1、2、3、4、5或6个H由选自氟、氯、溴、碘中的任意一个或者多个卤原子取代，例如可以为三氟甲基、二氟甲基、一氟甲基、一氟乙基、二氟乙基、三氟乙基等。针对“由至少一个卤素取代的C 1-C 10的烷基”、“由至少一个卤素取代的C 1-C 6的烷基”等具有与此相似的解释，所不同的是，碳原子总数不同。
由组合A中的至少一种基团取代的C 1-C 15的烷基，表示碳原子总数为1-15的烷基，包括直链烷基、支链烷基，并且该C 1-C 15的烷基中的至少一个H由A组合(本发明的后文中有详细定义)中的至少一种基团取代，例如可以为碳原子总数为1、2、3、4、5、6、7、8、9、10、11、12、13、14和15的直链烷基、支链烷基。针对“由组合A中的至少一种基团取代的C 1-C 10的烷基”、“由组合A中的至少一种基团取代的C 1-C 6的烷基”等具有与此相似的解释，所不同的是，碳原子总数不同。“由组合A中的至少一种基团取代的苯基”具有与其类似的定义。
由至少一个卤素取代的C 1-C 6的烷氧基，表示碳原子总数为1-6的烷氧基，包括直链烷氧基、支链烷氧基，该C 1-C 6的烷基中的1、2、3、4、5或6个H由选自氟、氯、溴、碘中的任意一个或者多个卤原子取代，例如可以为三氟甲氧基、二氟甲氧基、一氟甲氧基、一氟乙氧基、二氟乙氧基、三氟乙氧基等。
C 3-C 15的环烷基，表示碳原子总数为3-15的环烷基，且至少含有一个环，对成环的碳原子数没有特别的要求，可以为3、4、5、6、7、8、9、10等。“C 3-C 10的环烷基”、“C 3-C 6的环烷基”等的定义与其相似，不同的是，碳原子总数不同。
C 3-C 15的烯基，表示碳原子总数为3-15的烯基，并且其中至少含有一个烯基基团，该烯基基团可以直接与母核结构连接，也可以不直接与母核结构连接。“C 3-C 10的烯基”、“C 3-C 6的烯基”等的定义与其相似，不同的是，碳原子总数不同。
C 3-C 15的炔基，表示碳原子总数为3-15的炔基，并且其中至少含有一个炔基基团，该炔基基团可以直接与母核结构连接，也可以不直接与母核结构连接。“C 3-C 10的炔基”、“C 3-C 6的炔基”等的定义与其相似，不同的是，碳原子总数不同。
n为0-6的整数，表示n可以为0、1、2、3、4、5、6的整数。
m选自1-10的整数，表示m可以为1、2、3、4、5、6、7、8、9、10的整数。
-SOOR 53，表示具有
Figure PCTCN2022132867-appb-000003
的结构。针对“-SOO-N(R 51) 2”、“-SO 2-R 11”、“-(CH 2) m-COO-R 51”、“-O-(CH) m-COO-R 51”、“-COO-CH 3”等具有与此类似的结构。
R 52和R 53与连接R 52和R 53的N原子一起形成4-6元环，表示R 52和R 53与N原子一起形成含N原子的4元杂环、5元杂环和6元杂环。
本发明中各基团的波浪线表示连接位置，也即该基团通过该波浪线所在位点与母核结构通过化学键连接。
以下针对本发明的各方面进行展开说明。
第一方面
如前所述，本发明的第一方面提供了一种氧代丁(-2-烯酸)酸类化合物。
根据优选的具体实施方式1-1，在式(I)中，
R 1、R 2各自独立地选自卤素；
X为CH；
Y选自O、-N-OCH 3、-N-OCH 2CH 3；
R 3和R 6各自独立地选自H、卤素、C 1-C 6的烷基；
R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、C 1-C 6的烷基；
n为0-6的整数；
R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基；
其中，R 51选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
R 52、R 53各自独立地选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
m选自1-10的整数；
R 51选自C 1-C 15的烷基、C 3-C 15的烯基、C 3-C 15的炔基；
R 52选自苯基、由组合A中的至少一种基团取代的苯基；
R 53选自C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、苯基、由组合A中的至少一种基团取代的苯基；
所述组合A由卤素、C 3-C 6的环烷基、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基组成；
Q选自以下基团中的任意一种：
Figure PCTCN2022132867-appb-000004
根据优选的具体实施方式1-2，在式(I)中，
R 1、R 2各自独立地选自卤素；
X为CH；
Y选自O、-N-OCH 3、-N-OCH 2CH 3；
R 3和R 6各自独立地选自H、卤素、C 1-C 6的烷基；
R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、C 1-C 6的烷基；
n为0-6的整数；
R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基；
其中，R 51选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
R 52、R 53各自独立地选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的 环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
m选自1-10的整数；
R 51选自C 1-C 15的烷基、C 3-C 15的烯基、C 3-C 15的炔基；
R 52选自苯基、由组合A中的至少一种基团取代的苯基；
R 53选自C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、苯基、由组合A中的至少一种基团取代的苯基；
所述组合A由卤素、C 3-C 6的环烷基、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基组成；
Q选自
Figure PCTCN2022132867-appb-000005
根据优选的具体实施方式1-3，在式(I)中，
R 1为F；
R 2为Cl；
X为CH；
Y选自O、-N-OCH 3、-N-OCH 2CH 3；
R 3和R 6各自独立地选自H、卤素；
R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、-CH 3、-CH 2CH 3；
n为0-4的整数；
R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 10的烷基、由至少一个卤素取代的C 1-C 10的烷基；
其中，R 51选自H、C 1-C 10的烷基、由组合A中的至少一种基团取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 3-C 10的烯基、C 3-C 10的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
R 52、R 53各自独立地选自H、C 1-C 10的烷基、由组合A中的至少一种基团取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 3-C 10的烯基、C 3-C 10的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
m选自1-10的整数；
R 51选自C 1-C 10的烷基、C 3-C 10的烯基、C 3-C 10的炔基；
R 52选自苯基、由组合A中的至少一种基团取代的苯基；
R 53选自C 1-C 10的烷基、由组合A中的至少一种基团取代的C 1-C 10的烷基、苯基、由组合A中的至少一种基团取代的苯基；
所述组合A由卤素、C 3-C 6的环烷基、C 1-C 10的烷基、由至少一个卤素取代的C 1-C 10的烷基组成；
Q选自
Figure PCTCN2022132867-appb-000006
根据优选的具体实施方式1-4，在式(I)中，
R 1为F；
R 2为Cl；
X为CH；
Y选自O、N-OCH 3、N-OCH 2CH 3；
R 3和R 6各自独立地选自H、氟、氯、溴、碘；
R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、-CH 3、-CH 2CH 3；
n为0；
R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基；
其中，R 51选自H、C 1-C 6的烷基、由组合A中的至少一种基团取代的C 1-C 6的烷基、C 3-C 6的环烷基、C 3-C 6的烯基、C 3-C 6的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
R 52、R 53各自独立地选自H、C 1-C 6的烷基、由组合A中的至少一种基团取代的C 1-C 6的烷基、C 3-C 6的环烷基、C 3-C 6的烯基、C 3-C 6的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
m选自1-6的整数；
R 51选自C 1-C 6的烷基、C 3-C 6的烯基、C 3-C 6的炔基；
R 52选自苯基、由组合A中的至少一种基团取代的苯基；
R 53选自C 1-C 6的烷基、由组合A中的至少一种基团取代的C 1-C 6的烷基、苯基、由组合A中的至少一种基团取代的苯基；
所述组合A由氟、氯、溴、碘、环丙基、环丁基、C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基组成；
Q选自
Figure PCTCN2022132867-appb-000007
根据优选的具体实施方式1-5，式(I)所示结构的化合物式(I)所示结构的化合物选自以下表1中的任意一种：
表1
Figure PCTCN2022132867-appb-000008
Figure PCTCN2022132867-appb-000009
Figure PCTCN2022132867-appb-000010
Figure PCTCN2022132867-appb-000011
Figure PCTCN2022132867-appb-000012
Figure PCTCN2022132867-appb-000013
Figure PCTCN2022132867-appb-000014
Figure PCTCN2022132867-appb-000015
Figure PCTCN2022132867-appb-000016
Figure PCTCN2022132867-appb-000017
且上述化合物中的n均为0；X均为CH；R 1均为F；R 2均为Cl。
本发明对前述第一方面中所述的化合物的制备方法没有特别的限制，本领域技术人员可以根据结构式结合有机合成领域内的已知方法确定合适的反应路线。
但是，为了获得纯度更高且收率更高的化合物，本发明优选采用如下优选的具体实施方式所述的方法获得该第一方面中所述的化合物。
优选地，本发明提供一种制备前述第一方面中所述的氧代丁(-2-烯酸)酸类化合物的方法，该方法包括：
将式(I-1)所示结构的化合物与式(Ⅰ-2)所示的化合物、式(Ⅰ-3)所示的化合物、式(Ⅰ-4)所示的化合物和(Ⅰ-5)所示的化合物的组合中的任意一种化合物进行接触反应，
Figure PCTCN2022132867-appb-000018
其中，n、X、Y、R 1、R 2、R 3、R 4、R 5、R 6、R 7的定义与前述第一方面中的定义对应相同。本发明在此不再赘述，本领域技术人员不应理解为对本发明的限制。
本发明对所述接触反应的具体条件没有特别的限制，本领域技术人员可以根据本领域的已知条件和本发明后文的实例中记载的条件进行选择。
示例性地，本发明提供以下路线所示的合成方法获得本发明前述第一方面所述的化合物，以下合成路线中各结构式中的各取代基的定义与前述第一方面的定义对应相同：
A1：式(I-1)中Y为O目标合成路线：
Figure PCTCN2022132867-appb-000019
具体地，如下：
将式(I-1)所示结构的化合物与冰乙酸、2-二甲氨基-4-三氟甲基-6H-1,3-噁嗪-6-酮(即式(I-2)所示化合物)回流反应，待反应完毕后冷却至室温，萃取并减压除去溶剂；将残留物溶于DMF后，加入碳酸铯和碘甲烷，室 温下反应，待反应完毕后萃取，洗涤，干燥，过滤，减压浓缩后柱层析得固体；随后加入冰乙酸、水和浓硫酸加热反应，待反应完毕后，冷却至室温，抽滤，洗涤，干燥得a1所示结构的化合物。
B1：式(I-1)中Y为-NOCH 3或-NOCH 2CH 3(R 8为-CH 3或-CH 2CH 3)目标合成路线：
Figure PCTCN2022132867-appb-000020
具体地，如下：
该合成路线前1个步骤与A1合成路线相同，在此不再赘述。
(2)将a1所示结构的化合物与N-甲基羟胺盐酸盐或N-乙基羟胺盐酸盐、乙醇和吡啶加热反应，待反应完毕后，冷却至室温，减压除去溶剂，萃取，洗涤，干燥，减压浓缩后柱层析得a2所示结构的化合物。
A2：式(I-1)中Y为O目标合成路线：
Figure PCTCN2022132867-appb-000021
具体地，如下：
将I-1所示的化合物与盐酸混合并冷却到-9℃，缓慢滴入亚硝酸钠并搅拌反应1h。向所得反应体系中缓慢加入SnCl 2和浓盐酸，并继续搅拌反应2h。再向反应体系中加入三氟丙酮酸继续搅拌反应1h，所得中间体经过滤干燥后用于后续反应。
将所得中间体用甲苯溶解(加入少量三乙胺促溶)后，滴加(PhO) 2PON 3，并升温至回流反应2h。待反应完毕后，脱干溶剂。向反应体系中加入DMF，碱和甲基化试剂室温搅拌反应3h后。将反应体系倒入水中，用有机溶剂萃取，有机相经洗涤、干燥、减压浓缩后柱层析得a3所示结构的化合物。
B2：式(I-1)中Y为-NOCH 3或-NOCH 2CH 3(R 8为-CH 3或-CH 2CH 3)目标合成路线：
Figure PCTCN2022132867-appb-000022
具体地，如下：
该合成路线前1个步骤与A2合成路线相同，在此不再赘述。
(2)将a3所示结构的化合物与N-甲基羟胺盐酸盐或N-乙基羟胺盐酸盐、乙醇和吡啶加热反应，待反应完毕后，冷却至室温，减压除去溶剂，萃取，洗涤，干燥，减压浓缩后柱层析得a4所示结构的化合物。
A3：式(I-1)中Y为O目标合成路线：
Figure PCTCN2022132867-appb-000023
具体地，如下：
将式(I-1)所示结构的化合物与冰乙酸、4,5,6,7-四氢-1,3-异苯并呋喃二酮(即式(I-4)所示结构的化合物)回流反应，待反应完毕后冷却至室温，萃取，洗涤，干燥，抽滤减压浓缩得a6所示结构的化合物。
B3：式(I-1)中Y为-NOCH 3或-NOCH 2CH 3(R 8为-CH 3或-CH 2CH 3)目标合成路线：
Figure PCTCN2022132867-appb-000024
具体地，如下：
该合成路线前1个步骤与A3合成路线相同，在此不再赘述。
(2)将a5所示结构的化合物与N-甲基羟胺盐酸盐或N-乙基羟胺盐酸盐、乙醇和吡啶加热反应，待反应完毕后，冷却至室温，减压除去溶剂，萃取，洗涤，干燥，减压浓缩后柱层析得a6所示结构的化合物。
A4：式(I-1)中Y为O目标合成路线：
Figure PCTCN2022132867-appb-000025
具体地，如下：
将式(I-1)所示结构的化合物与甲苯、三光气、三乙胺在0℃下反应，待反应完毕后移至室温下反应，然后升温回流反应，待反应完毕后冷却至室温，减压除去溶剂，将混合物与N,N'-二甲基硫脲(即式(I-5)所示结构的化合物)，三乙胺、甲苯、N',N-羰基二咪唑加热反应，待反应完毕后冷却至室温，萃取，洗涤，干燥，过滤，减压浓缩后柱层析得a7所示结构的化合物。
B4：式(I-1)中Y为-NOCH 3或-NOCH 2CH 3(R 8为-CH 3或-CH 2CH 3)目标合成路线：
Figure PCTCN2022132867-appb-000026
具体地，如下：
该合成路线前1个步骤与A4合成路线相同，在此不再赘述。
(2)将a7所示结构的化合物与N-甲基羟胺盐酸盐或N-乙基羟胺盐酸盐、乙醇和吡啶加热反应，待反应完毕后，冷却至室温，减压除去溶剂，萃取，洗涤，干燥，减压浓缩后柱层析得a8所示结构的化合物。
本发明提供的制备氧代丁(-2-烯酸)酸类化合物的方法具有目标产物的纯度高和收率高的优势。
第二方面
如前所述，本发明的第二方面提供了前述第一方面中所述的氧代丁(-2-烯酸)酸类化合物在防治杂草中的应用。
第三方面
如前所述，本发明的第三方面提供了一种除草剂组合物，该组合物含有除草有效量的前述第一方面中所述的氧代丁(-2-烯酸)酸类化合物。
任选地，所述除草剂组合物还含有2,4-滴丁酯、炔草酸、炔草酯、唑啉草酯、唑酮草酯、氟丙嘧草酯、异丙吡草酯、吡氟苯草酯、氰氟草酯、吲哚酮草酯、氟胺草酯、恶草酮、丙炔恶草酮、异恶草酮、磺草酮、硝磺草酮、双苯醚草酮、二甲戊乐灵、氟乐灵、草除灵、三氟羧草醚、除草醚、甲氧除草醚、氟草醚、乙氧氟草醚、嘧草硫醚、氟磺胺草醚、乙羧氟草醚、嘧硫草醚、嘧啶肟草醚、双草醚、噻二唑草胺、双氟磺草胺、甲草胺、异丙甲草胺、丙草胺、丁草胺、苯噻酰草胺、二氯喹啉酸、乳氟禾草灵、吡氟禾草灵、精吡氟禾草灵、精恶唑禾草灵、精喹禾灵、精吡氟氯禾灵、氰草律、扑草净、莠灭净、莠去津、烯草酮、胺唑草酮、烯禾啶、异丙隆、烟嘧磺隆、砜嘧磺隆、吡嘧磺隆、苄嘧磺隆、胺苯磺隆、甲嘧磺隆、噻吩磺隆、咪唑磺隆、三氟啶磺隆钠盐、磺酰磺隆、环丙嘧磺隆、酰嘧磺隆、氟啶嘧磺隆、阔叶枯、百草枯、麦草畏、灭草松、敌草快、敌草隆、咪唑乙烟酸、2甲4氯钠、阿畏达、苯嘧磺草胺、丙炔氟草胺、草硫磷、磺草磷、草丁磷、草甘膦和草铵膦中的至少一种。
本发明的发明人发现，本发明提供的氧代丁(-2-烯酸)酸类化合物与上述除草剂中的至少一种相互配合使用时，能够提高防治杂草的活性、作物安全性和防治的杂草种类范围，实现远大于两者单独使用之和的效果。
优选地，以所述除草剂组合物的总重量为基准，所述活性成分的含量为0.01-99重量％；优选为0.01-70重量％；更优选为5-60重量％。
第四方面
如前所述，本发明的第四方面提供了前述第一方面中所述的氧代丁(-2-烯酸)酸类化合物在防治杂草中的应用。
优选情况下，所述杂草选自阔叶杂草和/或禾本科杂草。
更加优选地，所述杂草选自小藜、苍耳、酸模、合萌、芥菜、二月兰、苘麻、决明、饭苞草、鳢肠、牵牛、紫花苜宿、商陆、假高粱、虮子草、狗尾、水稗草、节节麦、碱茅、披碱草、弯叶画眉、画眉草、棒头草、看麦娘、早熟禾和牛筋草中的至少一种。
第五方面
如前所述，本发明的第五方面提供了一种除草剂，该除草剂由活性成分和辅料组成，所述活性成分为前述第 三方面所述的除草剂组合物。
优选地，以所述除草剂的总重量为基准，所述活性成分的含量为1-99.99重量％；优选为5-90重量％。示例性地为1重量％、5重量％、10重量％、20重量％、30重量％、40重量％、50重量％、60重量％、70重量％、80重量％、90重量％、95重量％。
优选情况下，所述辅料为乳化剂、分散剂、润湿剂、展着剂、稳定剂、消泡剂、增效剂、渗透剂、粘着剂、安全剂、载体、表面活性剂和填料中的至少一种。
优选地，该除草剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、母液和母粉中的至少一种。
以下将通过实例对本发明进行详细描述。
以下实例中，在没有特别说明的情况下，使用的各种原料均来自商购，纯度为化学纯。
制备例1：制备化合物I.1a2
Figure PCTCN2022132867-appb-000027
将化合物I.1a2-1(22.77mmol)置于反应瓶中，用超干二氯甲烷(50mL)溶解后再滴入两滴DMF，冰水浴降温。边搅拌边滴入草酰氯(68.32mmol，3.0eq.)，滴毕，继续冰水浴0.5h，然后室温搅拌0.5h。反应结束后，减压脱出溶剂，制得酰氯中间体。
将丙二酸二乙酯(27.33mmol，1.2eq.)、无水氯化镁(20.50mmol，0.9eq.)和超干乙酸乙酯(40mL)置于250mL两口瓶中，N 2保护和搅拌下升温至50℃。将制备的酰氯中间体用乙酸乙酯(30mL)溶解后，滴入上述反应体系。滴毕，继续控温50℃反应0.5h。将上述反应体系滴入37wt％的浓盐酸(80mL)和水(40mL)的溶液中，用乙酸乙酯萃取，旋干溶剂。
向上述反应体系中加入乙酸(50mL)、水(20mL)和98wt％的硫酸(20mL)，升温至95℃-100℃反应3h。待反应结束后，将体系降至室温后倒入冰水中，用二氯甲烷萃取，有机相依次用水和饱和NaCl溶液洗涤，无水Na 2SO 4干燥，抽滤后旋干溶剂，残留物经硅胶柱层析后，得到4.12g的中间体I.1a2-2，收率83％。
1H NMR(400MHz,CDCl 3)δ8.39(dd,J＝8.0,1.6Hz,1H),7.43(dd,J＝10.0,1.6Hz,1H),2.70(d,J＝1.6Hz,3H)
Figure PCTCN2022132867-appb-000028
将中间体I.1a2-2(58.30mmol，1.0eq.)、50wt％乙醛酸水溶液(174.89mmol，3.0eq.)、乙酸(120mL)和37wt％的浓盐酸(12mL)置于反应瓶中，N 2保护下升温至回流反应16h。反应结束后，待体系冷却至室温后倒入500g冰水混合物中，用200mL的二氯甲烷萃取。有机层依次用水和饱和NaCl溶液洗涤，无水Na 2SO 4干燥，抽滤后旋干溶剂，残留物经硅胶柱层析后，得到8.11g的中间体I.1a2-3，收率51％。
1H NMR(400MHz,DMSO-d 6)δ13.35(s,1H),8.48(d,J＝8.0Hz,1H),8.10(d,J＝11.2Hz,1H),7.29(d,J＝16.0Hz,1H),6.58(d,J＝16.0Hz,1H)
Figure PCTCN2022132867-appb-000029
将中间体1.1a2-3(3.7mmol，1.0eq.)、Pd/C(5.0mg，0.5wt％)和乙酸乙酯(50mL)加入到反应瓶中，H 2氛围下室温搅拌8h。反应完毕后，硅藻土过滤，滤液减压浓缩后得到0.91g黄色固体的中间体1.1a2-4，收率100％。
1H NMR(400MHz,DMSO-d 6)δ12.19(s,1H),7.25(d,J＝11.2Hz,1H),7.08(d,J＝9.2Hz,1H),5.57(s,2H),3.07(t,J＝6.0Hz,2H),2.55(t,J＝6.0Hz,2H)
Figure PCTCN2022132867-appb-000030
将I.1a2-4(10.0mmol，1.0eq.)、乙酸(30mL)和I-2(10.3mmol，1.03eq.)加入到反应瓶中。搅拌加热至回流反应6h，TLC监测反应进程。反应结束后，将体系却至室温后倒入300g冰水混合物中剧烈搅拌15min。乙酸乙酯(200mL)萃取，有机层依次用水和饱和NaCl溶液洗涤，无水Na 2SO 4干燥后，抽滤后脱干溶剂得中间体。
将上述中间体、碳酸钾(12.5mmol，1.25eq.)和DMF(30mL)加入到反应瓶中并搅拌15min。室温下，向体系中滴加碘甲烷(30.0mmol，3.0eq.)，滴毕，继续搅拌反应6h。反应完毕后，向体系中加入水(75mL)和乙酸乙酯(50mL)并剧烈搅拌15min。有机层依次用水和饱和NaCl溶液洗涤，减压脱除溶剂，残留物经硅胶柱层析后，得到2.5g黄色油状式(I.1)所示的化合物I.1a2，收率57％。
1H NMR(400MHz,CDCl 3)δ7.62(d,J＝7.6Hz,1H),7.36(d,J＝9.2Hz,1H),6.36(s,1H),3.69(s,3H),3.56(s,3H),3.27(t,J＝6.4Hz,2H),2.76(t,J＝6.4Hz,2H)。
制备例2：制备化合物I.1a1
Figure PCTCN2022132867-appb-000031
N 2保护下，将化合物I.1a2(5mmol)、乙酸(20mL)、98wt％的浓硫酸(20mL)和水(20mL)加入到反应瓶中，加热至90℃搅拌反应4h。反应完毕后，待体系冷却至室温后倒入500g冰水混合物中并剧烈搅拌30min。所得固体经抽滤干燥后，得到1.84g式(I.1)所示的化合物I.1a1，收率87％。
1H NMR(400MHz,CDCl 3)δ7.62(d,J＝7.6Hz,1H),7.36(d,J＝9.2Hz,1H),6.37(s,1H),3.56(s,3H),3.27(t,J＝6.4Hz,2H),2.80(t,J＝6.4Hz,2H)。
制备例3：制备化合物I.1a52
Figure PCTCN2022132867-appb-000032
N 2保护下，将化合物I-1a2(1mmol)、HATU(1.3mmol)、DIPEA(2mmol)、DMAP(0.1mmol)、乙胺(1.05mmol)和二氯甲烷(30mL)加入到反应瓶中，搅拌反应6h。反应完毕后，向体系中加入水(50mL)并剧烈搅拌30min。水层用二氯甲烷(20mL)萃取，合并有机层。有机层依次用水、饱和碳酸钠溶液和饱和NaCl溶液洗涤，脱干溶剂后硅胶柱层析，得到0.23g黄色油状式(I.1)所示的化合物I.1a52，收率52％。
1H NMR(400MHz,CDCl 3)δ7.65(d,J＝7.6Hz,1H),7.34(d,J＝9.2Hz,1H),6.36(s,1H),5.65(s,1H),3.55(s, 3H),3.34–3.21(m,4H),2.59(t,J＝5.6Hz,2H),1.13(t,J＝7.2Hz,3H)
制备例4：制备化合物I.3a1
Figure PCTCN2022132867-appb-000033
将中间体I.1a2-4(2mmol，1.0eq.)、3,4,5,6,-四氢苯酐(3mmol，1.5eq.)和冰乙酸(20mL)置于反应烧瓶中，N 2保护下加热至回流4h。反应结束后，将体系冷却到室温并加入水(200mL)和乙酸乙酯(100mL)并剧烈搅拌30min。有机层依次用水(50mL×3)和饱和NaCl溶液(50mL×3)洗涤，无水Na 2SO 4干燥后，旋干溶剂后硅胶柱层析，得到0.42g的化合物I.3a1，收率55％。
1H NMR(400MHz,DMSO-d 6)δ12.25(s,1H),7.92(d,J＝7.6Hz,1H),7.83(d,J＝9.6Hz,1H),3.15(t,J＝6.4Hz,2H),2.58(t,J＝6.4Hz,2H),2.36(s,4H),1.74(s,4H)。
制备例5：制备化合物I.4a2
Figure PCTCN2022132867-appb-000034
将化合物I.1a2-4(4mmol，1.0eq.)、碳酸钾(5mmol，1.25eq.)和DMF(20mL)加入到反应瓶中并搅拌15min。室温下，向体系中滴加碘甲烷(8mmol，2.0eq.)，滴毕，继续搅拌反应8h。反应结束后，向体系中加入水(100mL)和乙酸乙酯(100mL)并剧烈搅拌30min。有机层依次用水(50mL×3)和饱和NaCl溶液(50mL×3)洗涤，无水Na 2SO 4干燥后，抽滤，旋干溶剂后硅胶柱层析，得到0.60g的化合物I.4a2-1，收率58％。
1H NMR(400MHz,DMSO-d 6)δ7.26(d,J＝11.2Hz,1H),7.09(d,J＝9.6Hz,1H),5.59(s,2H),3.60(s,3H),3.19–3.08(m,2H),2.69–2.61(m,2H)
Figure PCTCN2022132867-appb-000035
将三光气(1.5mmol，0.5eq.)和甲苯(50mL)加入到反应瓶中，并冷却到0℃。将I-1a2-5(3mmol，1.0eq.)用甲苯(50mL)溶解后再加入三乙胺(6mmol，2.0eq.)，将该溶液体系缓慢滴入上述反应瓶中。滴毕，在冰水浴下继续搅拌反应0.5h，缓慢升温至回流反应10h。反应完毕后，将体系降至室温后减压脱除溶剂，所得残留物用甲苯(100mL)溶解。边搅拌边向溶液中加入1,3-二甲基硫脲(3.6mmol，1.2eq.)、三乙胺(3mmol，1.0eq.)和N,N'-羰基二咪唑(6mmol，2.0eq.)并升温至85℃继续反应6h。反应结束后，待体系冷却至室温后倒入水(100mL)中，用乙酸乙酯萃取，有机层用饱和NaCl溶液洗涤，脱干溶剂，残留物经硅胶柱层析后，得到0.31g白色固体，收率50％。
1H NMR(400MHz,CDCl 3)δ7.68(d,J＝8.0Hz,1H),7.37(d,J＝9.2Hz,1H),3.78(s,6H),3.70(s,3H),3.27(t,J＝6.4Hz,2H),2.77(t,J＝6.4Hz,2H)
下表2中其余化合物参考上述合成方法制备，表征数据亦见表2。
表2
Figure PCTCN2022132867-appb-000036
Figure PCTCN2022132867-appb-000037
测试例1：用于测定对比化合物、目标化合物的除草活性
本测试例中涉及的对比化合物的结构式如下：
化合物A：
Figure PCTCN2022132867-appb-000038
本测试例中所用剂量和供试杂草靶标如表3-表6中所示。
测试方法(盆栽法)：
取内径6cm的花盆，装复合土(菜园土：育苗基质＝1：2，v/v)至花盆的3/4高度处，直接播种表3-表6中供试杂草靶标(芽率≥85％)，覆土0.2cm，待杂草长至3叶期左右备用。各目标化合物按照150g ai/ha的剂量，用N,N-二甲基甲酰胺溶解并用蒸馏水稀释，配制成浓度为0.2g/L的药液，经自动喷雾塔(型号：3WPSH-700E，南京农业机械化研究所生产)施药后，待杂草叶面药液晾干后移入温室培养，15天后调查结果。其除草活性抑制 率(％)结果如表3-表6中所示。
除草活性抑制率计算方法为(式中：E：鲜重抑制率；C：对照植株地上部分鲜重；T：处理植株地上部分鲜重)：
Figure PCTCN2022132867-appb-000039
将测试结果按照如下分级方法进行分级：
当90％＜E≤100％时，评A级；
当80％＜E≤90％时，评B级；
当60％＜E≤80％时，评C级；
当0≤E≤60％时，评D级。
表3
Figure PCTCN2022132867-appb-000040
Figure PCTCN2022132867-appb-000041
Figure PCTCN2022132867-appb-000042
表4
Figure PCTCN2022132867-appb-000043
Figure PCTCN2022132867-appb-000044
Figure PCTCN2022132867-appb-000045
Figure PCTCN2022132867-appb-000046
表5
Figure PCTCN2022132867-appb-000047
Figure PCTCN2022132867-appb-000048
表6
Figure PCTCN2022132867-appb-000049
Figure PCTCN2022132867-appb-000050
Figure PCTCN2022132867-appb-000051
测试例2：用于测定目标化合物I.1a2的杀草谱
本测试例中所用剂量和供试杂草靶标如表7中所示。
测试方法：取内径7.5cm的花盆，装复合土(菜园土：育苗基质，1：2，v/v)至花盆的3/4高度处，直接播种表7中供试杂草靶标(芽率≥85％)，覆土0.2cm，待杂草长至3叶期左右备用。目标化合物I.1a25按照剂量经自动喷雾塔(型号：3WPSH-700E，南京农业机械化研究所生产)施药后，待杂草叶面药液晾干后移入温室培养，30天后调查结果。其除草活性抑制率(％)结果如表7中所示。
除草活性抑制率计算方法为(式中：E 1：鲜重抑制率；C：对照植株地上部分鲜重；T：处理植株地上部分鲜重)：
Figure PCTCN2022132867-appb-000052
将测试结果E 1按照与测试例1相同的分级方法进行分级。
表7
Figure PCTCN2022132867-appb-000053
测试例3：用于测定目标化合物对苗后作物的安全性
本测试例中所用剂量分别为37.5g a.i./ha、18.75g a.i./ha。
测试方法：取内径9.0cm花盆，装复合土(菜园土：育苗基质，1:2，v/v)至花盆的3/4高度处，直接播种作物靶标(芽率≥85％)覆土0.2cm，待杂草长至3叶期左右备用。目标化合物按照剂量经自动喷雾塔施药后，待杂草叶面药液晾干后移入温室培养，30天后调查结果。其对作物生长抑制率(％)结果如下所示。
作物生长抑制率计算方法为(式中：E 2：鲜重抑制率；C：对照植株地上部分鲜重；T：处理植株地上部分鲜重)：
Figure PCTCN2022132867-appb-000054
结果：化合物I.1a2、化合物I.1a7、化合物I.1a24、化合物I.1a37、化合物I.1a102、化合物I.1a157、化合物I.3a1、化合物I.4a6在18.75g a.i./ha和37.5g a.i./ha剂量下对玉米具有较好的安全性。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种氧代丁(-2-烯酸)酸类化合物，其特征在于，该化合物具有式(Ⅰ)所示的结构，
    Figure PCTCN2022132867-appb-100001
    其中，在式(I)中，
    R 1、R 2各自独立地选自卤素、H、-CN、C 1-C 6的烷基、-O-R 11、-SO 2-R 11；R 11选自C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基；
    X为CH、N；Y选自O、-N-OCH 3、-N-OCH 2CH 3、-CN、C 1-C 6的烷基、由组合A中的至少一种基团取代的苯基；
    R 3和R 6各自独立地选自H、卤素、-CN、C 1-C 6的烷基、由组合A中的至少一种基团取代的苯基；R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、-CN、C 1-C 6的烷基、由组合A中的至少一种基团取代的苯基；
    n为0-6的整数；
    R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基、苯基、苄基；
    其中，R 51选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
    R 52、R 53各自独立地选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
    m选自1-10的整数；
    R 51选自C 1-C 15的烷基、C 3-C 15的烯基、C 3-C 15的炔基；R 52选自苯基、由组合A中的至少一种基团取代的苯基；R 53选自C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、苯基、由组合A中的至少一种基团取代的苯基；
    所述组合A由卤素、C 3-C 6的环烷基、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基组成；
    Q选自以下基团中的任意一种：
    Figure PCTCN2022132867-appb-100002
    其中，R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27各自独立地选自H、C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基、氨基、由至少一个卤素取代的C 1-C 6的烷氧基；
    A 1、A 2、A 3、A 4、A 5、A 6、A 7、A 8、A 9、A 10、A 11各自独立地选自O、S。
  2. 根据权利要求1所述的化合物，其中，在式(I)中，
    R 1、R 2各自独立地选自卤素；
    X为CH；Y选自O、-N-OCH 3、-N-OCH 2CH 3；
    R 3和R 6各自独立地选自H、卤素、C 1-C 6的烷基；R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、C 1-C 6的烷基；
    n为0-6的整数；
    R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基；
    其中，R 51选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
    R 52、R 53各自独立地选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
    m选自1-10的整数；
    R 51选自C 1-C 15的烷基、C 3-C 15的烯基、C 3-C 15的炔基；R 52选自苯基、由组合A中的至少一种基团取代的苯基；R 53选自C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、苯基、由组合A中的至少一种基团取代的苯基；
    所述组合A由卤素、C 3-C 6的环烷基、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基组成；
    Q选自以下基团中的任意一种：
    Figure PCTCN2022132867-appb-100003
  3. 根据权利要求1或2所述的化合物，其中，在式(I)中，
    R 1、R 2各自独立地选自卤素；
    X为CH；Y选自O、-N-OCH 3、-N-OCH 2CH 3；
    R 3和R 6各自独立地选自H、卤素、C 1-C 6的烷基；R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、C 1-C 6的烷基；
    n为0-6的整数；
    R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基；
    其中，R 51选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
    R 52、R 53各自独立地选自H、C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、C 3-C 15的环烷基、C 3-C 15的烯基、C 3-C 15的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
    m选自1-10的整数；
    R 51选自C 1-C 15的烷基、C 3-C 15的烯基、C 3-C 15的炔基；R 52选自苯基、由组合A中的至少一种基团取代的苯基；R 53选自C 1-C 15的烷基、由组合A中的至少一种基团取代的C 1-C 15的烷基、苯基、由组合A中的至少一种基团取代的苯基；
    所述组合A由卤素、C 3-C 6的环烷基、C 1-C 15的烷基、由至少一个卤素取代的C 1-C 15的烷基组成；
    Q选自
    Figure PCTCN2022132867-appb-100004
  4. 根据权利要求1-3中任意一项所述的化合物，其中，在式(I)中，
    R 1为F；R 2为Cl；
    X为CH；Y选自O、-N-OCH 3、-N-OCH 2CH 3；
    R 3和R 6各自独立地选自H、卤素；R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、-CH 3、-CH 2CH 3；
    n为0-4的整数；
    R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 10的烷基、由至少一个卤素取代的C 1-C 10的烷基；
    其中，R 51选自H、C 1-C 10的烷基、由组合A中的至少一种基团取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 3-C 10的烯基、C 3-C 10的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
    R 52、R 53各自独立地选自H、C 1-C 10的烷基、由组合A中的至少一种基团取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 3-C 10的烯基、C 3-C 10的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
    m选自1-10的整数；
    R 51选自C 1-C 10的烷基、C 3-C 10的烯基、C 3-C 10的炔基；R 52选自苯基、由组合A中的至少一种基团取代的苯基；R 53选自C 1-C 10的烷基、由组合A中的至少一种基团取代的C 1-C 10的烷基、苯基、由组合A中的至少一种基团取代的苯基；
    所述组合A由卤素、C 3-C 6的环烷基、C 1-C 10的烷基、由至少一个卤素取代的C 1-C 10的烷基组成；
    Q选自
    Figure PCTCN2022132867-appb-100005
  5. 根据权利要求1-4中任意一项所述的化合物，其中，在式(I)中，
    R 1为F；R 2为Cl；
    X为CH；Y选自O、-N-OCH 3、-N-OCH 2CH 3；
    R 3和R 6各自独立地选自H、氟、氯、溴、碘；R 4和R 7各自独立地选自H、-COO-CH 3、-COO-CH 2CH 3、-CH 3、-CH 2CH 3；
    n为0；
    R 5选自-O-R 51、-N(R 52)(R 53)、-CN、C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基；
    其中，R 51选自H、C 1-C 6的烷基、由组合A中的至少一种基团取代的C 1-C 6的烷基、C 3-C 6的环烷基、C 3-C 6的烯基、C 3-C 6的炔基、-(CH 2) m-COO-R 51、-CH(CH 3)-COO-R 51、-C(CH 3) 2-COO-R 51、-CHF-COO-R 51、-CF 2-COO-R 51、-(CH 2) m-R 52、-(CH 2) m-O-R 51、-(CH 2) m-NH-R 51、-(CH 2) m-N(R 51) 2；
    R 52、R 53各自独立地选自H、C 1-C 6的烷基、由组合A中的至少一种基团取代的C 1-C 6的烷基、C 3-C 6的环烷基、C 3-C 6的烯基、C 3-C 6的炔基、-(CH 2) m-R 52、-SOOR 53、-SOO-N(R 51) 2、-(CH 2) m-COO-R 51、-O-R 51、-O-CO-R 51、-O-(CH) m-COO-R 51，且R 52和R 53不同时为H；或者R 52和R 53与连接R 52和R 53的N原子一起形成的4-6元环；
    m选自1-6的整数；
    R 51选自C 1-C 6的烷基、C 3-C 6的烯基、C 3-C 6的炔基；R 52选自苯基、由组合A中的至少一种基团取代的苯基；R 53选自C 1-C 6的烷基、由组合A中的至少一种基团取代的C 1-C 6的烷基、苯基、由组合A中的至少一种基团取代的苯基；
    所述组合A由氟、氯、溴、碘、环丙基、环丁基、C 1-C 6的烷基、由至少一个卤素取代的C 1-C 6的烷基组成；
    Q选自
    Figure PCTCN2022132867-appb-100006
  6. 根据权利要求2-5中任意一项所述的化合物，其中，式(I)所示结构的化合物选自以下中的任意一种：
    Figure PCTCN2022132867-appb-100007
    Figure PCTCN2022132867-appb-100008
    Figure PCTCN2022132867-appb-100009
    Figure PCTCN2022132867-appb-100010
    Figure PCTCN2022132867-appb-100011
    Figure PCTCN2022132867-appb-100012
    Figure PCTCN2022132867-appb-100013
    Figure PCTCN2022132867-appb-100014
    Figure PCTCN2022132867-appb-100015
    Figure PCTCN2022132867-appb-100016
    Figure PCTCN2022132867-appb-100017
    且上述化合物中的n均为0；X均为CH；R 1均为F；R 2均为Cl。
  7. 权利要求1-6中任意一项所述的氧代丁(-2-烯酸)酸类化合物在防治杂草中的应用。
  8. 一种除草剂组合物，其特征在于，该组合物含有除草有效量的权利要求1-6中任意一项所述的氧代丁(-2-烯酸)酸类化合物；
    优选地，以所述除草剂组合物的总重量为基准，所述活性成分的含量为0.01-99重量％；优选为0.01-70重量％；更优选为5-60重量％。
  9. 权利要求8所述的除草剂组合物在防治杂草中的应用。
  10. 一种除草剂，该除草剂由活性成分和辅料组成，所述活性成分为权利要求8所述的除草剂组合物；
    优选地，以所述除草剂的总重量为基准，所述活性成分的含量为1-99.99重量％；优选为5-90重量％；
    优选地，所述辅料为乳化剂、分散剂、润湿剂、展着剂、稳定剂、消泡剂、增效剂、渗透剂、粘着剂、安全剂、载体、表面活性剂和填料中的至少一种；
    优选地，该除草剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、母液和母粉中的至少一种。
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