WO2024169666A1 - 一种苯环取代的嘧啶羧酸类化合物及其制备方法、除草组合物和应用 - Google Patents

一种苯环取代的嘧啶羧酸类化合物及其制备方法、除草组合物和应用 Download PDF

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WO2024169666A1
WO2024169666A1 PCT/CN2024/075642 CN2024075642W WO2024169666A1 WO 2024169666 A1 WO2024169666 A1 WO 2024169666A1 CN 2024075642 W CN2024075642 W CN 2024075642W WO 2024169666 A1 WO2024169666 A1 WO 2024169666A1
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alkyl
cycloalkyl
substituted
halogen
alkynyl
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English (en)
French (fr)
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连磊
彭学岗
华荣保
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Qingdao Kingagroot Chemical Compound Co Ltd
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Qingdao Kingagroot Chemical Compound Co Ltd
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Priority to AU2024221195A priority Critical patent/AU2024221195A1/en
Priority to US19/135,212 priority patent/US20260198497A1/en
Priority to EP24756040.2A priority patent/EP4667459A1/en
Publication of WO2024169666A1 publication Critical patent/WO2024169666A1/zh
Priority to MX2025009586A priority patent/MX2025009586A/es
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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
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D401/12—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 chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds

Definitions

  • the invention belongs to the technical field of pesticides, and specifically relates to a benzene ring substituted pyrimidine carboxylic acid compound, a preparation method thereof, a herbicidal composition and application thereof.
  • the present invention provides a benzene ring substituted pyrimidine carboxylic acid compound and a preparation method thereof, a herbicidal composition and application thereof.
  • the compound has excellent herbicidal activity against gramineous weeds, broadleaf weeds and the like, and is safe for crops/vegetables such as corn, wheat, rice, rapeseed, cabbage, radish and the like and has high selectivity.
  • X represents an unsubstituted or halogen-substituted alkyl group
  • Z represents bromine, haloalkyl or cycloalkyl
  • R 1 and R 2 each independently represent hydrogen
  • R 3 represents halogen or amino
  • R 4 represents hydrogen or halogen
  • R 5 represents an unsubstituted or halogen-substituted alkyl group
  • W represents hydrogen or a salt thereof, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a heterocyclic group, an aryl group
  • the "alkyl”, “alkenyl” or “alkynyl” is optionally selected from halogen, cyano, nitro, cycloalkyl, trialkylsilyl, cycloalkenyl, heterocyclic, aryl
  • the “cycloalkyl”, “cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by al
  • X 11 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, heterocyclyl, heterocyclylalkyl, aryl or arylalkyl, wherein the "alkyl”, “alkenyl” or “alkynyl” is optionally substituted by at least one group selected from halogen and alkoxy, and the "cycloalkyl”, “cycloalkylalkyl”, “cycloalkenyl”, “cycloalkenylalkyl”, “heterocyclyl", “heterocyclylalkyl", “aryl” or “arylalkyl” is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, hal
  • X 13 and X 14 each independently represent hydrogen, halogen, cyano, alkoxy, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, or the group CX 13 X 14 together forms an unsubstituted or substituted cyclic structure, or the group NX 13 X 14 together forms an unsubstituted or substituted heterocyclyl with a nitrogen atom at the 1-position, wherein the "alkyl", “alkenyl” or “alkynyl” is optionally substituted with halogen, and the "cycloalkyl", “cycloalkylalkyl", “cycloalkenyl", "cyclo
  • R10 each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.
  • X represents unsubstituted or halogen-substituted C1-C8 alkyl
  • Z represents bromine, halogenated C1-C8 alkyl or C3-C8 cycloalkyl
  • R5 represents an unsubstituted or halogen-substituted C1-C8 alkyl group
  • W represents hydrogen or a metal salt thereof, an amine salt, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, a heterocyclic group, an aryl group, wherein, the "C1-C8 alkyl", “C2-C8 alkenyl” or “C2-C8 alkynyl” is optionally selected from halogen, cyano, nitro, C3-C8 cycloalkyl, tri-C1-C8 alkylsilyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, the “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo,
  • X11 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, heterocyclyl, heterocyclylC1-C8 alkyl, aryl or arylC1-C8 alkyl, wherein the “C1-C8 alkyl”, “C2-C8 alkenyl” or “C2-C8 alkynyl” is optionally substituted by at least one group selected from halogen, C1-C8 alkoxy, and the “C3-C8 cycloalkyl”, “C3-C8 cycloalkylC1-C8 alkyl”, “C3-C8 cycloalkenyl”, “C3-C8 cycl
  • X 13 and X 14 each independently represent hydrogen, halogen, cyano, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclic or heterocyclicC1-C8 alkyl, or the group CX 13 and X 14 together form a 5- to 8-membered carbocyclic ring or a heterocyclic ring containing oxygen, sulfur or nitrogen,
  • R10 each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.
  • X represents an unsubstituted or halogen-substituted C1-C6 alkyl group
  • Z represents bromine, halogenated C1-C6 alkyl or C3-C8 cycloalkyl
  • R 5 represents an unsubstituted or halogen-substituted C1-C6 alkyl group
  • W represents hydrogen or its sodium salt, potassium salt, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic group, aryl, wherein, the "C1-C6 alkyl", “C2-C6 alkenyl” or “C2-C6 alkynyl” is optionally selected from halogen, cyano, nitro, C3-C6 cycloalkyl, tri-C1-C6 alkylsilyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, wherein the “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by 1, 2 or 3 groups selected from oxo, halogen, cyano, nitro, C1-C6 alkyl,
  • X11 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, heterocyclyl, heterocyclylC1-C6 alkyl, aryl or arylC1-C6 alkyl, wherein the “C1-C6 alkyl”, “C2-C6 alkenyl” or “C2-C6 alkynyl” is optionally substituted by at least one group selected from halogen, C1-C6 alkoxy, and the “C3-C6 cycloalkyl”, “C3-C6 cycloalkylC1-C6 alkyl”, “C3-C6 cycloalkenyl”, “C3-C6 cycl
  • X13 and X14 independently represent hydrogen, halogen, cyano, C1-C6 alkoxy, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, aryl, aryl C1-C6 alkyl, heterocyclic or heterocyclic C1-C6 alkyl, or the groups CX13 and X14 together form a 5-8 membered saturated carbocyclic ring, Or the group NX 13 X 14 together forms wherein the “C1
  • R10 each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by 1, 2 or 3 groups selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.
  • X represents methyl, CHF 2 , CH 2 F or CF 3 ;
  • Z represents bromine, CF 3 or cyclopropyl
  • R 3 represents fluorine, chlorine or amino
  • R 4 represents hydrogen or fluorine
  • R 5 represents methyl, CHF 2 , CH 2 F or CF 3 .
  • the present invention also provides an intermediate compound, as shown in general formula II:
  • Alkyl groups having more than two carbon atoms may be straight-chain or branched.
  • the alkylene group may be -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, etc.
  • Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl.
  • alkenyl is, for example, vinyl, allyl, 1-methylprop-2-ene-1-yl, 2-methylprop-2-ene-1-yl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl.
  • Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be at any position of each unsaturated group.
  • Cycloalkyl is a carbocyclic saturated ring system with, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cycloalkenyl is a monocyclic alkenyl with, for example, three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein double bonds can be at any position.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • the "aryl” mentioned in the present invention includes but is not limited to phenyl, naphthyl,
  • the "heterocyclic group” includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., also including but not limited to heteroaryl, i.e. aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms among the ring atoms are selected from oxygen, nitrogen and sulfur, for example
  • a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned.
  • identical or different substitution characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude compounds that are known to the person skilled in the art to be chemically unstable under standard conditions.
  • substituted by at least one group in the present invention means substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without specific connection positions can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules.
  • a heteroaryl substituted by 1 methyl group Can represent wait.
  • the compounds of the general formula I and their derivatives may exist as stereoisomers. For example, if there are one or more asymmetric carbon atoms, enantiomers and diastereomers may occur.
  • Stereoisomers can be obtained from the mixture obtained in the preparation by conventional separation methods, for example by chromatographic separation. Stereoisomers can also be selectively prepared by using stereoselective reactions and using optically active starting materials and/or auxiliaries.
  • the present invention also relates to all stereoisomers and mixtures thereof contained in the general formula I but not specifically defined.
  • the preparation method of the benzene ring substituted pyrimidine carboxylic acid compound comprises the following steps:
  • Hal represents halogen, preferably Cl; substituents R 1 , R 2 , R 3 , R 4 , X, Y, Z, Q and W are as defined above.
  • the reaction is carried out in the presence of a catalyst, a base and a solvent.
  • the catalyst is a palladium catalyst [such as Pd(dppf)Cl 2 ⁇ CH 2 Cl 2 , Pd(dppf)Cl 2 , Pd(PPh 3 ) 4 , methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl) (2'-methylamino-1,1'-biphenyl-2-yl) palladium (II) (CAS No: 1599466-87-1) or methanesulfonic acid (tri-tert-butylphosphino) (2'-methylamino-1,1'-biphenyl-2-yl) palladium (II) (CAS No. 1621274-11-0) etc.] or nickel catalyst.
  • a palladium catalyst such as Pd(dppf)Cl 2 ⁇ CH 2 Cl 2 , Pd(dppf)Cl 2 , Pd(PPh 3 ) 4 , methane
  • the base is selected from at least one of an inorganic base (such as K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaHCO 3 , KHCO 3 , KF, CsF, K 3 PO 4 , K 2 HPO 4 , NaOH, KOH, etc.) or an organic base (such as pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa, etc.).
  • an inorganic base such as K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaHCO 3 , KHCO 3 , KF, CsF, K 3 PO 4 , K 2 HPO 4 , NaOH, KOH, etc.
  • organic base such as pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa
  • the solvent is an organic solvent/water, and the volume ratio of the two is preferably 20/1-1/1.
  • the organic solvent is preferably dioxane, toluene, DMF, DMSO, DMA, methanol, ethanol, isopropanol, n-butanol, acetonitrile, dichloroethane, dichloromethane or ethyl acetate.
  • the compound represented by the general formula I can be prepared by referring to the method shown in WO2009029735 and the like.
  • a herbicide composition comprises a herbicidally effective amount of at least one of the benzene ring substituted pyrimidine carboxylic acid compounds, and preferably further comprises a formulation adjuvant.
  • a method for controlling weeds comprises applying a herbicidally effective amount of at least one of the benzene ring substituted pyrimidine carboxylic acid compounds or the herbicide composition on plants or weedy areas.
  • the use of at least one of the benzene ring substituted pyrimidinecarboxylic acid compounds or the herbicide composition in controlling weeds is used to control weeds in useful crops, and the useful crops are transgenic crops or crops treated with genome editing technology.
  • the compounds of formula I of the present invention have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants.
  • the active substances of the present invention are also effective against perennial weeds, which grow from rhizomes, rootstocks, or other perennial organs and are difficult to control. In this regard, it is generally unimportant whether the substance is used before sowing, before germination, or after germination.
  • Representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention are particularly mentioned, without limiting to certain species.
  • weed species on which the active substances are effective include monocotyledonous plants: annual Avena, Lolium, Alopecuroides, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus, and perennial Agropyron, Cynodon, Imperata and Sorghum, and perennial Cyperus.
  • dicotyledonous weed species With regard to dicotyledonous weed species, its effect can be extended to species such as annual Galium, Viola, Veronica, Sesame, Chickweed, Amaranth, Sinapis, Ipomoea, Rhizoma Coptidis, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia.
  • the active substance of the present invention effectively controls harmful plants such as Echinochloa, Sagittaria, Alisma, Eriobotrya, Sugarcane and Cyperus under such undetermined conditions of rice sowing.
  • the seedlings of the weeds can be completely prevented before the weeds grow, or the weeds stop growing when the cotyledons grow, and finally die completely after three to four weeks.
  • the compound of the present invention is particularly good in activity against the following plants, Apila, Sesame, Polygonum, Chickweed, Veronica hedera, Veronica arabica, Pansy and Amaranth, Galium and Kochia.
  • the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they do not damage economically important crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybeans at all, or the damage is negligible. In particular, they are very compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compounds of the invention are very suitable for selectively controlling unwanted plants in agricultural crops or ornamental plants.
  • Transgenic plants often have advantageous traits, such as resistance to specific pesticides, especially specific herbicides, resistance to plant diseases or to the causative microorganisms of plant diseases, such as specific insects or fungi, bacteria or pathogens.
  • Other specific traits are related to the following conditions of the product, for example, quantity, quality, storage stability, composition and specific ingredients. Thus, it is known to obtain transgenic plant products with increased starch content or improved starch quality or different fatty acid composition.
  • the compounds of formula I of the present invention or their salts are preferably used in economically important genetically modified crops and ornamental plants, for example cereals, for example wheat, barley, rye, oats, millet, rice, cassava and corn, or in the cultivation of beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of formula I are preferably used as herbicides for the cultivation of useful plants, which are resistant or genetically engineered to the toxic effects of herbicides.
  • glufosinate e.g. EP-0242236 A, EP-0242246 A
  • glyphosate herbicides WO 92/00377
  • sulfonylurea herbicides EP-0257993 A, US-5013659 A
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins that protect plants against attack by certain pests (EP-0142924 A, EP-0193259 A);
  • Plant cells in which the activity of a gene product is reduced can be prepared by, for example, expressing at least one appropriate antisense RNA, sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme which specifically cleaves the transcript of the above gene product.
  • DNA molecule comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and to use a DNA molecule comprising only a portion of the coding sequence, which portion must be long enough to achieve an antisense effect in the cell. It is also possible to use sequences that have a high degree of homology to the gene product coding sequence, but are not identical.
  • the synthesized protein When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, for localization in a specific compartment, it is possible, for example, to link the coding region and the DNA sequence to ensure localization at a specific position. These sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992) 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).
  • the transgenic plant cells can be recombined into whole plants using known techniques.
  • the active substance of the present invention when used on genetically modified crops, in addition to the effect of inhibiting harmful plants observed on other crops, there are often special effects on the corresponding genetically modified crops, such as improving or expanding the scope of weed control, improving the application rate during application, preferably combining the resistance of genetically modified crops with the performance of herbicides well, and affecting the growth and yield of genetically modified crop plants. Therefore, the present invention also provides the use of the compound as a herbicide to control harmful plants in genetically modified crop plants.
  • the compounds according to the invention can significantly regulate the growth of crop plants.
  • these compounds can be used to control the composition of the plant and promote the harvest, for example to dry out and dwarf the growth of the plant. They are also suitable for regulating and inhibiting undesirable plant growth without destroying the growth of the crop. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, because this can reduce or completely prevent lodging.
  • the compounds of the present invention can be applied using general formulations, and wettable powders, emulsion concentrates, sprayable solutions, powders or granules can be used.
  • the present invention also provides herbicidal compositions comprising compounds of formula I.
  • compounds of formula I can be formulated in a variety of ways.
  • Suitable formulation selection examples are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, concentrated emulsions (EC), emulsions such as oil-in-water dispersions and water-in-oil dispersions (EW), sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, solutions of miscible oils, powders (DP), capsule suspensions (CS), seeddressing compositions, granules for broadcasting and soil application, spray granules, coated granules and absorbed granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra-low volume) formulations, microcapsules and wax products.
  • WP wettable powders
  • SP water-soluble powders
  • EC concentrated emulsions
  • EW emulsions
  • SC dispersible oil suspensions
  • OD dispers
  • Wettable powders are uniformly dispersible in water and, in addition to the active substance, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkyl sulfonates, alkylphenyl sulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthomethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyl taurate.
  • ionic and nonionic surfactants such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates
  • the concentrated emulsion is prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of aromatic compounds or hydrocarbons with a higher boiling point or solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers).
  • organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of aromatic compounds or hydrocarbons with a higher boiling point or solvents.
  • emulsifiers examples include calcium alkylaryl sulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters.
  • calcium alkylaryl sulfonates such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene
  • Powders are obtained by grinding the active substance with finely divided solid materials, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspensions based on water or oil can be prepared, for example, by wet grinding using a commercially available bead mill, with or without the addition of a surfactant of another formulation type as described above.
  • Emulsions such as oil-in-water emulsions (EW) can be prepared using aqueous organic solvents using stirrers, colloid mills and/or static mixers and, if necessary, adding surfactants of another formulation type as described above.
  • EW oil-in-water emulsions
  • Granules are prepared by spraying the active substance onto an adsorbent, granulating with an inert material, or concentrating the active substance on the surface of a carrier such as sand or kaolinite and granulating the inert material with a binder such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • a carrier such as sand or kaolinite
  • Suitable active substances can be granulated by the same method as for preparing fertilizer granules, and fertilizers can be mixed if necessary.
  • Water suspension granules are prepared by the usual methods, such as spray-drying, fluidized bed granulation, disc granulation, mixing with a high-speed mixer, and extrusion in the absence of solid inert material.
  • Agrochemical formulations usually contain 0.1 to 99% by weight, in particular 0.1 to 95% of active substance formula I.
  • the concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remainder to 100% by weight.
  • the concentration of active substance in concentrated emulsions can be about 1 to 90% by weight, preferably 5 to 80%.
  • Powder formulations contain 1 to 30% by weight of active substance, usually preferably 5 to 20% by weight of active substance, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% of active substance.
  • the content of active substance in water-suspended granules it mainly depends on whether the active substance is liquid or solid, and the adjuvants, fillers, etc. used during granulation.
  • the content of active substance in water-suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the formulations of the active substances may additionally include tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, generally, the pH and viscosity regulators customary in each case.
  • suitable active substances that can be mixed with the active substance of the present invention are, for example, the known substances in the World New Pesticide Variety Technology Encyclopedia, China Agricultural Science and Technology Press, 2010.9 and the literature cited herein.
  • the following herbicide active substances can be mixed with the compound of formula I, (Note: the name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with a code name when appropriate): acetochlor, butachlor, alachlor, isopropyl chlor, isopropyl chlor, isopropyl chlor, pretilachlor, cypermethrin, cypermethrin, naphthamide, R-levorotatory naphthamide, propanil, mefenacet, bisbencarb, pyrifosamide, herbicide, flubutamide, bromobutamide, Dimethoate, high-efficiency dimethoate, ethomethoxam
  • the active substance is selected from one or more of the following compounds:
  • HPPD inhibitors (CAS: 2421252-30-2), bispyribac-butyl (CAS: 1622908-18-2), fenpyrazone-butyl (CAS: 1992017-55-6), cypermethrin (CAS: 1855929-45-1), triazone-sulfuron (CAS: 1911613-97-2);
  • ALS inhibitor florasulam (CAS: 145701-23-1);
  • PSII inhibitors propanil (CAS: 709-98-8), bentazon (CAS: 25057-89-0);
  • DOXP inhibitors (CAS:2766607-82-1);
  • the weight ratio of the benzene ring substituted pyrimidinecarboxylic acid compound as shown in Formula I to the aforementioned active substance in the composition is 1:500-20:1, 1:400-10:1, 1:300-5:1, 1:200-2:1, 1:100-2:1, 1:50-2:1, 1:30-2:1, 1:20-2:1, 1:10-2:1 or 1:5-1:1.
  • the commercially available preparations are diluted, if necessary, in the usual manner, for example with water in the case of wettable powders, emulsifiable concentrates, suspensions and granules suspended in water. Powders, granules for soil application or solutions for broadcasting and spraying generally do not require further dilution with inert substances before use.
  • the required amount of a compound of formula I varies with external conditions, such as temperature, humidity, the nature of the herbicide used, etc.
  • It can vary widely, for example between 0.001 and 1.0 kg a.i./ha, or more of active substance, but preferably between 0.005 and 750 g a.i./ha, in particular between 0.005 and 250 g a.i./ha.
  • the starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be appreciated by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, which are useful for preparing the compounds of the present invention. Variations or modifications of the method and the resulting various isomers of compounds are included within the scope of the invention.
  • the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, during the reaction, appropriate groups are protected, etc.
  • reaction solution was quenched with dilute hydrochloric acid, concentrated under reduced pressure to remove THF, and then extracted with ethyl acetate, washed with saturated brine (100 ml*3), dried over anhydrous sodium sulfate, and purified by silica gel column to obtain 3-2 (white solid, 4.2 g, 54.4% yield).
  • 201-5 (2.1 g, 8.5 mmol, 1 eq), 201-4 (2.14 g, 9.35 mmol, 1.1 eq), copper thiopheneate (4.8 g, 25.5 mmol, 3 eq), trifuranphosphine (0.39 g, 1.7 mmol, 0.2 eq) were dissolved in DMF (40 ml) and added to a 250 ml single-mouth bottle. The mixture was ventilated with nitrogen once, and Pd(dba) 3 (80.8 mg, 0.085 mmol, 0.01 eq) was added. The mixture was ventilated three times and heated to reflux at 100°C for 12 h.
  • 224-1 (0.341 g, 1 mmol, 1 eq) was dissolved in 20 ml toluene and 1 ml water, cyclopropylboric acid (0.103 g, 1.2 mmol, 1.2 eq), potassium phosphate (0.742 g, 3.5 mmol, 3.5 eq), N2 was replaced, palladium acetate (8.3 mg, 0.05 mmol, 0.05 eq) and tricyclohexylphosphine (28.1 mg, 0.1 mmol, 0.1 eq) were added, N2 was replaced 3 times, the temperature was raised to 80 ° C, the reaction was reacted for 12 h, and the reaction was monitored until the starting material disappeared.
  • the activity level standards for plant damage i.e., growth control rate are as follows:
  • Level 8 Growth control rate is greater than or equal to 90% and less than 100%
  • Level 7 Growth control rate is greater than or equal to 80% and less than 90%
  • Growth control rate is greater than or equal to 70% and less than 80%;
  • Level 5 Growth control rate is greater than or equal to 50% and less than 70%
  • Level 4 Growth control rate is greater than or equal to 30% and less than 50%;
  • Level 3 Growth control rate is greater than or equal to 20% and less than 30%;
  • Level 2 Growth control rate is greater than or equal to 10% and less than 20%;
  • the above growth control rates are fresh weight control rates.
  • Monocotyledonous and dicotyledonous weed seeds (artemisia selengensis, shepherd's purse, ramie, cleaver, chickweed, wheat family, shepherd's purse, alopecuroides, Japanese alopecuroides, goosegrass, weed grass, hard grass, small fleabane, candle grass, Veronica, brome, knotweed, phalaenopsis, amaranth, quinoa, dayflower, sonchus, field bindweed, prickly lettuce, nightshade, amaranth, crabgrass, barnyard grass, green foxtail, golden foxtail, kiwi, duckweed, wild arrowhead, firefly rush, cyperus, broken rice sedge, sedge, floating grass, purslane, Xanthium, morning glory, white wine grass, etc.) and major crops Seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame,
  • test plants Two weeks after sowing, the test plants were treated at the 2-3 leaf stage.
  • the tested compounds of the present invention were dissolved in acetone, and then Tween 80 was added.
  • 1.5 liters/hectare of methyl oleate emulsifiable concentrate was used as a synergist, diluted with a certain amount of water to a certain concentration of solution, and sprayed on the plants with a spray tower.
  • the compound dosages used were 120, 60, 30, and 15 g a.i./ha, repeated three times, and the average value was taken. Representative data are listed in Table 3.
  • Monocotyledonous and dicotyledonous weed seeds and main crop seeds are placed in a plastic pot filled with soil, and then covered with 0.5-2 cm of soil.
  • the tested compounds of the present invention are dissolved in acetone, and then Tween 80 is added, and diluted with a certain concentration of water to a solution, and sprayed immediately after sowing.
  • the compounds of the present invention generally have good weed control effects.
  • the compounds of the present invention have extremely high activity against broad-leaved weeds and sedges resistant to ALS inhibitors, such as Sagittaria paniculata, Rhizoma Cyperi, Cyperus difformis, Artemisia selengensis, Shepherd's purse, Rhizoma Aesculapiae, Glechoma longituba, and Cyperus rotundus, and have very good commercial value.
  • paddy field soil was filled into 1/1,000,000 hectare pots and leveled to a water depth of 3-4 cm.
  • Three-leaf rice (japonica rice) was transplanted at a transplanting depth of 3 cm the next day.
  • the compound of the present invention was treated in the same manner as above.
  • the required active ingredient B is purchased from a reagent company or a technical manufacturer or synthesized by conventional methods.
  • the active ingredient A is compound 74 in Table 1.
  • the technical drug uses acetone as a solvent and is diluted with a 0.1% emulsifier Tween-80 aqueous solution and is diluted before use.
  • Weeds were cultivated in potted plants using 180 ⁇ 140 mm plastic nutrient pots placed in enamel trays filled with air-dried and sieved surface soil (4/5 of the soil) collected from farmland. The soil moisture was initially controlled at 20%. Weed seeds with full and uniform grains were selected, soaked in 25°C warm water for 6 hours, and germinated in a 28°C biochemical incubator (darkness). The weed seeds that had just turned white were evenly placed on the soil surface and covered with 0.5-1 cm of soil according to the seed size.
  • the culture was carried out in a controlled sunlight greenhouse at a temperature of 20-30°C, natural light, and a relative humidity of 57%-72%.
  • Each treatment was repeated 4 times, with 3 pots in each treatment and 20 weed seeds sown in each pot.
  • the test used the drug once. When the weeds reached 1.5-2 leaves, thinned out the weeds, keeping 10 weeds in each pot, and kept 30 weeds for each treatment. Then continue to cultivate the Erigeron japonicus until the plant height is 10 cm. Other weeds were treated when they had 3-4 leaves.
  • the absolute number survey method was used. The whole seedlings of surviving weeds were cut off along the soil surface with a blade and the fresh weight of the weeds was weighed with an analytical balance. For dead weeds, the fresh weight was counted as zero.
  • the survey was conducted 21 days after treatment, for a total of 1 survey.
  • E measured inhibition rate
  • E-E0 value is greater than 10%, it is a synergistic effect, less than -10% is an antagonistic effect, and between -10% and 10% is an additive effect.
  • the best ratio is determined based on factors such as the actual prevention effect, the characteristics of the herbicide, and the balance of the formula.
  • X is the fresh weight inhibition rate when the dosage of active ingredient A is P
  • Y is the fresh weight inhibition rate when the dosage of active ingredient B is Q.

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Abstract

本发明属于农药技术领域，具体涉及一种苯环取代的嘧啶羧酸类化合物及其制备方法、除草组合物和应用。所述苯环取代的嘧啶羧酸类化合物，如通式(I)所示。其中，X代表未取代或被卤素取代的烷基；Y代表OR5；Z代表溴、卤代烷基或环烷基；Q代表O或S；R1、R2分别独立地代表氢；R3代表卤素或氨基；R4代表氢或卤素；R5代表未取代或被卤素取代的烷基；W代表氢或其盐、烷基、烯基、炔基、环烷基等。所述化合物对禾本科杂草、阔叶杂草等具有优异的除草活性，并对玉米、小麦、水稻、油菜、白菜、萝卜等作物/蔬菜安全，具有高选择性。

Description

一种苯环取代的嘧啶羧酸类化合物及其制备方法、除草组合物和应用 技术领域
本发明属于农药技术领域，具体涉及一种苯环取代的嘧啶羧酸类化合物及其制备方法、除草组合物和应用。
背景技术
杂草的防治是实现高效农业过程中一个至关重要的环节，尽管市场上的除草剂种类多样，然而，这些已知化合物对有害植物的除草性能和对作物的选择性并不完全令人满意。且由于市场的不断扩大、杂草的抗性、药物的使用寿命以及药物的经济性等问题以及人们对环境的日益重视，需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。
发明内容
本发明提供了一种苯环取代的嘧啶羧酸类化合物及其制备方法、除草组合物和应用，所述化合物对禾本科杂草、阔叶杂草等具有优异的除草活性，并对玉米、小麦、水稻、油菜、白菜、萝卜等作物/蔬菜安全，具有高选择性。
本发明采用的技术方案如下：
一种苯环取代的嘧啶羧酸类化合物，如通式I所示：
其中，
X代表未取代或被卤素取代的烷基；
Y代表OR5；
Z代表溴、卤代烷基或环烷基；
Q代表O或S；
R1、R2分别独立地代表氢；
R3代表卤素或氨基；
R4代表氢或卤素；
R5代表未取代或被卤素取代的烷基；
W代表氢或其盐、烷基、烯基、炔基、环烷基、环烯基、杂环基、芳基、 其中，所述“烷基”、“烯基”或“炔基”任选地被选自卤素、氰基、硝基、环烷基、三烷基硅烷基、环烯基、杂环基、芳基、 中的至少一个基团所取代，所述“环烷基”、“环烯基”、“杂环基”或“芳基”任选地被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-亚烷基-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
X11分别独立地代表氢、烷基、烯基、炔基、环烷基、环烷基烷基、环烯基、环烯基烷基、杂环基、杂环基烷基、芳基或芳基烷基，其中，所述“烷基”、“烯基”或“炔基”任选地被选自卤素、烷氧基中的至少一个基团所取代，所述“环烷基”、“环烷基烷基”、“环烯基”、“环烯基烷基”、“杂环基”、“杂环基烷基”、“芳基”或“芳基烷基”任选地被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-亚烷基-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
X13、X14分别独立地代表氢、卤素、氰基、烷氧基、烷氧基烷基、烷基羰基、烷氧基羰基、烷基磺酰基、烷基、烯基、炔基、环烷基、环烷基烷基、环烯基、环烯基烷基、芳基、芳基烷基、杂环基或杂环基烷基，或者基团CX13X14一起形成未取代或取代的环状结构，或者基团NX13X14一起形成未取代或取代的1-位为氮原子的杂环基，其中，所述“烷基”、“烯基”或“炔基”任选地被卤素取代，所述“环烷基”、“环烷基烷基”、“环烯基”、“环烯基烷基”、“芳基”、“芳基烷基”、“杂环基”或“杂环基烷基”任选地被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-亚烷基-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
R10分别独立地代表氢，烷基，卤代烷基，苯基，或被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基。
优选地，X代表未取代或被卤素取代的C1-C8烷基；
Z代表溴、卤代C1-C8烷基或C3-C8环烷基；
R5代表未取代或被卤素取代的C1-C8烷基；
W代表氢或其金属盐、胺盐、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烯基、杂环基、芳基、其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”任选地被选自卤素、氰基、硝基、C3-C8环烷基、三C1-C8烷基硅烷基、C3-C8环烯基、杂环基、芳基、 中的至少一个基团所取代，所述“C3-C8环烷基”、“C3-C8环烯基”、“杂环基”或“芳基”任选地被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8亚烷基)-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
X11分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C3-C8环烯基、C3-C8环烯基C1-C8烷基、杂环基、杂环基C1-C8烷基、芳基或芳基C1-C8烷基，其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”任选地被选自卤素、C1-C8烷氧基中的至少一个基团所取代，所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“C3-C8环烯基”、“C3-C8环烯基C1-C8烷基”、“杂环基”、“杂环基C1-C8烷基”、“芳基”或“芳基C1-C8烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8亚烷基)-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
X13、X14分别独立地代表氢、卤素、氰基、C1-C8烷氧基、C1-C8烷氧基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基磺酰基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C3-C8环烯基、C3-C8环烯基C1-C8烷基、芳基、芳基C1-C8烷基、杂环基或杂环基C1-C8烷基，或者基团CX13X14一起形成5～8元碳环或含氧、硫或氮的杂环，或者基团NX13X14一起形成 其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”任选地被卤素取代，所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“C3-C8环烯基”、“C3-C8环烯基C1-C8烷基”、“芳基”、“芳基C1-C8烷基”、“杂环基”或“杂环基C1-C8烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环 烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8亚烷基)-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环，所述“5～8元碳环或含氧、硫或氮的杂环”任选地被选自C1-C8烷基、C1-C8烷氧羰基或苄基中的至少一个基团所取代，或者与芳基或杂环基形成稠环结构；所述任选地被选自氧代、C1-C8烷基或C1-C8烷氧羰基中的至少一个基团所取代；
R10分别独立地代表氢，C1-C8烷基，卤代C1-C8烷基，苯基，或被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基。
更优选的，X代表未取代或被卤素取代的C1-C6烷基；
Z代表溴、卤代C1-C6烷基或C3-C8环烷基；
R5代表未取代或被卤素取代的C1-C6烷基；
W代表氢或其钠盐、钾盐、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烯基、杂环基、芳基、其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”任选地被选自卤素、氰基、硝基、C3-C6环烷基、三C1-C6烷基硅烷基、C3-C6环烯基、杂环基、芳基、 中的1、2或3个基团所取代，所述“C3-C6环烷基”、“C3-C6环烯基”、“杂环基”或“芳基”任选地被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6亚烷基)-(CO)OR10中的1、2或3个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
X11分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C3-C6环烯基、C3-C6环烯基C1-C6烷基、杂环基、杂环基C1-C6烷基、芳基或芳基C1-C6烷基，其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”任选地被选自卤素、C1-C6烷氧基中的至少一个基团所取代，所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“C3-C6环烯基”、“C3-C6环烯基C1-C6烷基”、“杂环基”、“杂环基C1-C6烷基”、“芳基”或“芳基C1-C6烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6亚烷基)-(CO)OR10中的1、2或3个基团所取代，或者环 上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
X13、X14分别独立地代表氢、卤素、氰基、C1-C6烷氧基、C1-C6烷氧基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基磺酰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C3-C6环烯基、C3-C6环烯基C1-C6烷基、芳基、芳基C1-C6烷基、杂环基或杂环基C1-C6烷基，或者基团CX13X14一起形成5～8元饱和碳环、或者基团NX13X14一起形成其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”任选地被卤素取代，所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“C3-C6环烯基”、“C3-C6环烯基C1-C6烷基”、“芳基”、“芳基C1-C6烷基”、“杂环基”或“杂环基C1-C6烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6亚烷基)-(CO)OR10中的1、2或3个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环，所述“5～8元饱和碳环、”任选地被选自C1-C6烷基、C1-C6烷氧羰基或苄基中的1、2或3个基团所取代，或者与芳基或杂环基形成稠环结构，所述 任选地被选自氧代、C1-C6烷基或C1-C6烷氧羰基中的1、2或3个基团所取代；
R10分别独立地代表氢，C1-C6烷基，卤代C1-C6烷基，苯基，或被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的1、2或3个基团所取代的苯基。
进一步优选地，X代表甲基、CHF2、CH2F或CF3；
Z代表溴、CF3或环丙基；
R3代表氟、氯或氨基；
R4代表氢或氟；
R5代表甲基、CHF2、CH2F或CF3。
本发明还提供了一种中间体化合物，如通式II所示：
其中，取代基R3、R4、Y和Z的定义如前所述。
在上述通式所示化合物的定义和以下所有结构式中，所用专业术语不论单独使用或者使用在复合词中，代表如下取代基：具有多于两个碳原子的烷基基团可为直链或支链的。如复合词“-O-亚烷基-(CO)OR10”中亚烷基可为-CH2-、-CH2CH2-、-CH(CH3)-、-C(CH3)2-等。烷基基团为，例如，C1烷基-甲基；C2烷基-乙基；C3烷基-丙基如正丙基或异丙基；C4烷基-丁基如正丁基、异丁基、叔丁基或2-丁基；C5烷基-戊基如正戊基；C6烷基-己基如正己基、异己基和1,3-二甲基丁基。类似地，烯基是例如乙烯基、烯丙基、1-甲基丙-2-烯-1-基、2-甲基丙-2-烯-1-基、丁-2-烯-1-基、丁-3-烯-1-基、1-甲基丁-3-烯-1-基和1-甲基丁-2-烯-1-基。炔基是例如乙炔基、炔丙基、丁-2-炔-1-基、丁-3-炔-1-基、1-甲基丁-3-炔-1-基。多重键可以在每个不饱和基团的任何位置。环烷基是具有例如三至六个碳原子的碳环饱和环体系，例如环丙基、环丁基、环戊基或环己基。类似地，环烯基是具有例如三至六个碳环成员的单环烯基，例如环丙烯基、环丁烯基、环戊烯基和环己烯基，其中双键可以在任何位置。卤素为氟、氯、溴或碘。
除非有特别说明的，本发明所述“芳基”包括但不限于苯基、萘基、 所述“杂环基”不仅包括但不限于饱和或不饱和的非芳族环状基团 等，还包括但不限于杂芳基，即含有例如3至6个环原子且还任选地有苯并环稠合的芳族环状基团，所述环原子中的1至4个(例如1、2、3或4个)杂原子选自氧、氮和硫，例如
如果一个基团被基团所取代，则这应理解为意指该基团被一个或多个相同或不同的选自所提及的那些基团的基团取代。另外，相同或不同取代基中含有的相同或不同的取代字符均独立地选择，可相同也可不同。这同样适用于由不同原子和单元形成的环体系。同时，权利要求的范围将排除那些为本领域技术人员知晓的在标准条件下化学不稳定的化合物。
另外，除非特别限定地，本发明所述“至少一个基团所取代的”是指被如1、2、3、4或5个基团所取代；未标注具体连接位置的基团(包括杂环基、芳基等)，可在任意位置连接，包括与C或N相连接的位置；如果其是被取代的，取代基同样可在任何位置取代，只要符合化合键连接规则。如被1个甲基所取代的杂芳基可代表等。
根据取代基的性质和其被连接的方式，通式I的化合物及其衍生物可作为立体异构体存在。例如，如果存在一个或多个不对称碳原子，则可出现对映异构体和非对映异构体。立体异构体可通过常规分离方法、例如通过色谱分离法从在制备中获得的混合物中获得。同样可通过使用立体选择性反应且使用光学活性的起始原料和/或助剂来选择性地制备立体异构体。本发明还涉及包含在通式I中但没有具体定义的所有立体异构体及其混合物。
所述的苯环取代的嘧啶羧酸类化合物的制备方法，包括以下步骤：
将通式II所示的化合物与通式III所示的化合物进行反应制得如通式I所示的化合物，其反应方程式如下：
其中，Hal代表卤素，优选Cl；取代基R1、R2、R3、R4、X、Y、Z、Q和W的定义如前所述。
优选地，所述反应在催化剂、碱和溶剂的存在下进行。
在一个具体实施方式中，所述催化剂为钯催化剂[如Pd(dppf)Cl2·CH2Cl2、Pd(dppf)Cl2、Pd(PPh3)4、甲烷磺酸(2-二环己基膦-2',6'-二甲氧基联苯)(2'-甲胺基-1,1'-联苯-2-基)钯 (II)(CAS No:1599466-87-1)或甲磺酸(三叔丁基膦基)(2'-甲氨基-1,1'-联苯-2-基)钯(II)(CAS号1621274-11-0)等]或镍催化剂。
在另一个具体实施方式中，所述碱选自无机碱(如K2CO3、Na2CO3、Cs2CO3、NaHCO3、KHCO3、KF、CsF、K3PO4、K2HPO4、NaOH、KOH等)或有机碱(如吡唑、三乙胺、DIEA、三甲基硅烷醇钾、AcOK、AcONa、MeONa、EtONa、t-BuONa等)中的至少一种。
在另一个具体实施方式中，所述溶剂为有机溶剂/水，二者体积比优选为20/1-1/1，所述有机溶剂优选为二氧六环、甲苯、DMF、DMSO、DMA、甲醇、乙醇、异丙醇、正丁醇、乙腈、二氯乙烷、二氯甲烷或乙酸乙酯。
如通式I所示的化合物可参照WO2009029735等所示方法制得。
一种除草剂组合物，其包括除草有效量的所述的苯环取代的嘧啶羧酸类化合物中的至少一种，优选地，还包括制剂助剂。
一种控制杂草的方法，其包括将除草有效量的所述的苯环取代的嘧啶羧酸类化合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杂草区域。
所述的苯环取代的嘧啶羧酸类化合物中的至少一种或所述的除草剂组合物在控制杂草上的用途，优选地，将所述的苯环取代的嘧啶羧酸类化合物用于防除有用作物中的杂草，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
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，例如对特定农药特别是特定除草剂的抵抗力，对植物病害或植物病害的致病微生物的抵抗力，例如特定的昆虫或真菌、细菌或病 毒的微生物。其它的特别性状与产品的下述条件有关，例如，数量、质量、贮存稳定性、组分和特殊的成分。如此，已经知道获得的转基因植物产品具有增加的淀粉含量或改进的淀粉质量或不同的脂肪酸成份。
本发明的式I化合物或其盐优选用于，经济上重要的转基因的作物和观赏植物，例如谷类，例如小麦、大麦、黑麦、燕麦、粟、稻子、木薯和玉米、或用于甜菜、棉花、大豆、油菜籽、马铃薯、番茄、豌豆及其他蔬菜类植物的耕种。式I化合物优选用于有用植物耕种的除草剂，这些植物具有抗药性或通过遗传工程对除草剂的毒害作用具有抗药性。
传统的繁育具有比已知植物具有改进性状植物的方法包括，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-0242236 A，EP-0242246 A)或对草甘膦类除草剂(WO 92/00377)，或对磺酰脲类除草剂(EP-0257993 A，US-5013659 A)；
-例如棉花的转基因作物植物，它能够产生苏芸金杆菌毒素(Bt毒素)，这种毒素可以防御特定害虫对植物的侵害(EP-0142924 A，EP-0193259 A)；
-具有改进的脂肪酸成份的转基因作物植物(WO91/13972)。
已经知道许多能够制备具有改进性状转基因植物分子生物技术(参见，例如Sambrook等，1989，分子扩增，实验手册第二版，美国冷泉港实验室出版，冷泉港，纽约；或Winnacker“Gene und Klone”[基因和克隆]，VCH Weinheim，第二版1996或Christou，“植物科学的趋势”1(1996)423-431))。为了实现遗传工程的操作，可能将核酸分子引入质粒，通过DNA序列的重组，发生突变或序列改变。利用上述的标准方法，例如可以替换碱基、除去部分序列或增加自然的或合成的序列。为了将DNA片段互相连接，有可能在片段上附带有结合体或连接体。
可以用下述方法制备降低活性的基因产品的植物细胞，例如通过表达至少一种适当的反义-RNA、正义-RNA来达到共抑制的效果，或通过表达至少一种适当构造的核糖酶，它特定裂解上述基因产品的转录产物。
为此目的，有可能使用包含基因产物全部编码序列的DNA分子，包括有可能存在的任何旁侧序列，和使用包含仅仅一部分编码序列的DNA分子，这些部分必须足够长以达到在细胞中反义的效果。也可以使用与基因产物编码序列具有高度同源性但不完全相同的序列。
当在植物中表达核酸分子时，合成的蛋白质可以在任何期望的植物细胞室中定位。然而为了在特定的室定位，有可能例如将编码区和DNA序列连接，以确保在特定位置定位。这些序列为本领域所属技术人员已知的(参见，例如Braun等，EMBO J.11(1992)3219-3227；Wolter等，Proc.Natl.Acad.Sci.USA 85(1988)，846-850；Sonnewald等Plant J.1(1991)，95-106)。
利用已知的技术可以将转基因植物细胞重组到整个植物上。转基因植物可以为任何期望的植物品种，即单子叶和双子叶植物。用这样的方式，通过超表达、禁止或抑制同源(＝自然的)基因或基因序列，或通过异种的(＝外部的)基因或者基因序列的表达，有可能获得改进性状的转基因植物。
当在转基因的作物上使用本发明的活性物质时，除了具有在其它作物上可观察到的抑制有害植物的效果外，经常在相应的转基因作物上会有特殊的效果，例如可以改进或扩大控制杂草的范围，改进应用时的施用量，优选转基因作物的抗药性和除草剂的性能很好的结合，并且转基因的作物植物的生长和产率的影响。因此本发明也提供了所述化合物的用途，作为除草剂控制转基因作物植物中的有害植物。
另外本发明化合物可以明显调节作物植物的生长。通过调节参与植物代谢，使用这些化合物定向控制植物的组分和促进收获，例如使植物干化和矮化生长。而且它们也适于调节和抑制不希望的植物生长，而不破坏作物的生长。抑制植物的生长在许多单子叶植物和双子叶植物作物中起着非常重要的作用，因为这样可以减少或完全预防倒伏。
可以使用一般的制剂来应用本发明的化合物，可使用可湿性粉剂、浓缩乳剂、可喷洒的溶液、粉末或颗粒。这样本发明也提供了包括式I化合物的除草剂组合物。根据通常的生物学和/或化学的物理参数，可以用多种方式配制式I化合物。适合的制剂选择实例为：可湿性粉剂(WP)、水溶性的粉末(SP)、水溶性的浓缩物、浓缩乳剂(EC)、例如油在水中分散和水在油中分散的乳剂(EW)、可喷洒溶液、悬浮剂浓缩物(SC)、可分散油悬浮剂(OD)、以油或水为稀释剂的悬浮液、可混溶油的溶液、粉末(DP)、胶囊悬浮液(CS)、包核(seeddressing)组合物、用于撒播和土壤施药的颗粒、喷射颗粒、涂覆颗粒和吸收颗粒，水中可分散的颗粒(WG)、水溶性的颗粒(SG)、ULV(超低容量)配方、微囊和蜡制品。这些单个的制剂类型为已知的，在下述文献中有描述，例如Winnacker-Küchler，“Chemische Techonologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986；Wade van Valkenburg，“Pesticide Formulations”，Marcel Dekker，N.Y.，1973；K.Martens，“Spray Drying”手册，第3版1979，G.Goodwin Ltd.London。
必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂同样为已知的，并在下述文件中描述，例如Watkins的“粉末稀释剂杀虫剂和载体手册”，第二版，Darland书Caldwell N.J.；H.v.01phen“粘土胶体化学的入门”，第二版，J.Wiley和Sons，N.Y.；C.Marsden的“溶剂指南”第二版，Interscience，N.Y.1963；McCutcheon的“洗涤剂和乳化剂年报”，MC发行公司，Ridgewood N.J.；Sisley和Wood，“表面活性剂百科全书”，化学出版公司，N.Y.1964；的[环氧乙烷加成物表面活性剂]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-Küchler的“Chemische Technologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986。
可湿性粉剂能均匀地可分散在水中，除了活性物质，还包括稀释剂或惰性物质、离子和非离子型表面活性剂(润湿剂、分散剂)，例如聚乙氧基烷基酚、聚乙氧基脂肪醇、聚氧乙基脂肪族胺、脂肪醇聚二醇醚硫酸盐、烷基磺酸盐、烷基苯基磺酸盐、木质磺酸钠、2,2’-二萘甲烷-6,6’-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为了制备可湿性粉剂，将除草剂 的活性物质细磨，例如使用常用的仪器，如用锤磨机、风扇磨碎机和喷气式磨碎机，同时或顺序混入助剂。
将活性物质溶解在有机溶剂中制备浓缩乳剂，溶剂例如丁醇、环己酮、二甲基甲酰胺、二甲苯或较高沸点的芳族化合物或碳氢化合物或溶剂的混合物，并再加入一种或多种离子的和/或非离子型表面活性剂(乳化剂)。可以使用的乳化剂的例子为例如十二烷基苯磺酸钙的烷基芳基磺酸钙，或非离子乳化剂，例如脂肪酸聚二醇酯、烷基芳香基聚二醇醚、脂肪醇聚二醇醚、氧化丙烯-环氧乙烷缩合产物、烷基聚醚、例如山梨糖醇酐脂肪酸酯的山梨聚糖酯，或例如聚氧化乙烯山梨糖醇酐脂肪酯的聚氧化乙烯山梨聚糖酯。
将活性物质和细碎的固态物质研磨得到粉末，固态物质例如滑石、如高岭土、皂土和叶蜡石的天然粘土、或硅藻土。以水或油为基底的悬浮液可以通过下述方法制备，例如利用商业上通用的玻珠研磨机进行湿磨，加入或不加入上述另一个制剂类型的表面活性剂。
制备例如水包油乳化剂(EW)的乳剂，可以使用含水的有机溶剂，使用搅拌器、胶体研磨器和/或静态混合器，如果需要，加入如上所述另一个制剂类型的表面活性剂。
用下述方法制备颗粒剂，将活性物质喷到吸附物上，使用惰性物料颗粒化，或将活性物质浓缩到例如沙、高岭石载体的表面，通过粘合剂将惰性物料粒化，粘合剂例如聚乙烯醇、聚丙烯酸钠或矿物油。可以用制备肥料颗粒剂的方法将合适的活性物质粒化，如果需要可以混有肥料。使用通常的方法制备水悬浮颗粒剂，例如喷洒-干燥，流化床造粒、磨盘造粒、使用高速混合机混合，并在无固体惰性物料的情况下挤压。
关于使用磨盘、流化床、挤压机和喷涂颗粒剂的制备方法，参见下述工艺，例如“Spray Drying手册”第三版1979，G.Goodwin有限公司，伦敦；J.E.Browning，“Agglomeration”，化学和工程1967，147ff页；“Perry’s化学的工程师手册”，第五版，McGraw-Hill，纽约1973，8-57页。如果要知道关于作物保护产品的制剂，参见例如，G.C.Klingman,“Weed Control as a Science”，John Wiley和Sons公司，纽约，1961 81-96页和J.D.Freyer，S.A.Evans“杂草防除手册”，第五版，Blackwell Scientific Rublications，牛津大学1968，101-103页。
农用化学品制剂通常包含按重量计0.1到99％，特别是0.1到95％的活性物质式I。可湿性粉剂中活性物质的浓度为，按重量计例如从大约10到99％，通常的制剂组分构成按重量计剩余量到100％。活性物质在浓缩乳剂中的浓度按重量计可以为大约1到90％，优选5到80％。粉末制剂包含按重量计1到30％的活性物质，通常优选按重量计5到20％的活性物质，然而可喷洒的溶液包含按重量计大约0.05到80％，优选2到50％的活性物质。关于水悬浮颗粒剂中活性物质的含量，主要根据活性物质为液体还是固态，和造粒时使用的助剂、填料等等。水悬浮颗粒剂中活性物质的含量例如按重量计在1到95％之间，优选按重量计在10到80％之间。
另外所述的活性物质的制剂可以包括增粘剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂和通常在所有情况下都常用的pH和粘度调节剂。
以这些制剂为基础，也可能和其他杀虫剂活性物质例如杀虫剂、杀螨剂、除草剂和杀菌剂混合，也可以和安全剂、肥料和/或植物生长调节剂混合，混合方式可以为预先混合好的或灌装混合。
在混配制剂或桶混制剂中，可以和本发明的活性物质混合的合适的活性物质为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的除草剂活性物质可以和式I化合物混合，(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：乙草胺、丁草胺、甲草胺、异丙草胺、异丙甲草胺、精异丙甲草胺、丙草胺、毒草胺、克草胺、萘丙酰草胺、R-左旋萘丙酰草胺、敌稗、苯噻酰草胺、双苯酰草胺、吡氟酰草胺、杀草胺、氟丁酰草胺、溴丁酰草胺、二甲噻草胺、高效二甲噻草胺、乙氧苯草胺、氟噻草胺、甲氧噻草胺、吡草胺、异恶草胺、高效麦草伏甲酯、高效麦草伏丙酯、二丙烯草胺、烯草胺、丁酰草胺、环丙草胺、氟磺酰草胺、庚酰草胺、异丁草胺、丙炔草胺、特丁草胺、二甲苯草胺、二甲草胺、落草胺、三甲环草胺、氯甲酰草胺、炔苯酰草胺、戊酰苯草胺、卡草胺、新燕灵、三环赛草胺、丁烯草胺、牧草胺、苄草胺、醌萍胺、苯氟磺胺、萘丙胺、乙酰甲草胺、萘草胺、噻草胺、吡氰草胺、苯草多克死、草克乐、氯酞亚胺、丁脒胺、氟吡草胺、莠去津、西玛津、扑草净、氰草净、西草净、莠灭净、扑灭津、异丙净、氟草净、特丁净、特丁津、三嗪氟草胺、环丙津、甘扑津、草达津、扑灭通、西玛通、叠氮净、敌草净、异戊乙净、环丙青津、灭莠津、另丁津、仲丁通、特丁通、甲氧丙净、氰草净、抑草津、可乐津、莠去通、灭草通、甘草津、三聚氰酸、Indaziflam、绿磺隆、甲磺隆、苄嘧磺隆、氯嘧黄隆、苯磺隆、噻磺隆、吡嘧黄隆、甲基二磺隆、甲基碘磺隆钠盐、甲酰氨基嘧磺隆、醚磺隆、醚苯磺隆、甲嘧磺隆、烟嘧磺隆、胺苯磺隆、酰嘧磺隆、乙氧嘧磺隆、环丙嘧磺隆、砜嘧磺隆、四唑嘧磺隆、啶嘧黄隆、单嘧磺隆、单嘧磺酯、氟唑磺隆、氟啶嘧磺隆、氟吡嘧磺隆、环氧嘧磺隆、唑吡嘧磺隆、氟嘧磺隆、丙苯磺隆、三氟丙磺隆、磺酰磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、甲磺隆钠盐、氟吡磺隆、甲硫嘧磺隆、嘧苯胺磺隆、Propyrisulfuron(丙嗪嘧磺隆)、嗪吡嘧磺隆、三氟羧草醚、氟磺胺草醚、乳氟禾草灵、乙羧氟草醚、乙氧氟草醚、草枯醚、苯草醚、氯氟草醚乙酯、甲羧除草醚、三氟甲草醚、甲氧除草醚、三氟硝草醚、氟化除草醚、氟呋草醚、除草醚、甲草醚、二甲草醚、氟酯肟草醚、氟草醚酯、Halosafen、绿麦隆、异丙隆、利谷隆、敌草隆、莎扑隆、氟草隆、苯噻隆、甲基苯噻隆、苄草隆、磺噻隆、异恶隆、特丁噻草隆、炔草隆、氯溴隆、甲基杀草隆、酰草隆、甲氧杀草隆、溴谷隆、甲氧隆、绿谷隆、灭草隆、环草隆、非草隆、氟硫隆、草不隆、枯草隆、草完隆、异草完隆、环莠隆、噻氟隆、丁噻隆、枯莠隆、对氟隆、甲胺噻唑隆、隆草特、三甲异脲、恶唑隆、Monisouron、Anisuron、Methiuron、Chloreturon、四氟隆、甜菜宁、甜菜宁-乙酯、甜菜安、磺草灵、特草灵、燕麦灵、苯胺灵、氯苯胺灵、二氯苄草酯、灭草灵、氯炔灵、Carboxazole、Chlorprocarb、Fenasulam、BCPC、CPPC、Carbasulam、丁草特、禾草丹、灭草猛、禾草特、野麦畏、哌草丹、禾草畏、稗草丹、环草敌、燕麦敌、菌达灭、乙硫草特、坪草丹、克草猛、苄草丹、仲草丹、硫烯草丹、草灭散、Isopolinate、Methiobencarb、2,4-滴丁酯、2甲4氯钠、2,4-滴异辛酯、2甲4氯异辛酯、2,4-滴钠盐、2,4-滴二甲胺盐、2甲4氯乙硫酯、2甲4氯、2,4-滴丙酸、高 2,4-滴丙酸盐、2,4-滴丁酸、2甲4氯丙酸、2甲4氯丙酸盐、2甲4氯丁酸、2,4,5-涕、2,4,5-涕丙酸、2,4,5-涕丁酸、2甲4氯胺盐、麦草畏、抑草蓬、伐草克、赛松、三氯苯酸、氨二氯苯酸、甲氧三氯苯酸、禾草灵、吡氟禾草灵、精吡氟禾草灵、氟吡甲禾灵、高效吡氟氯禾灵、喹禾灵、精喹禾灵、恶唑禾草灵、精恶唑禾草灵、喔草酯、氰氟草酯、恶唑酰草胺、炔草酯、噻唑禾草灵、炔禾灵、羟戊禾灵、三氟禾草肟、异恶草醚、百草枯、敌草快、安磺灵、乙丁烯氟灵、异丙乐灵、甲磺乐灵、环丙氟灵、氨基丙氟灵、乙丁氟灵、氯乙氟灵、氨基乙氟灵、地乐灵、氯乙地乐灵、Methalpropalin、丙硝酚、草甘膦、莎稗膦、草铵膦、甲基胺草磷、草硫膦、哌草膦、双丙氨膦、地散磷、抑草磷、蔓草磷、伐垅磷、双甲胺草磷、草特磷、咪唑烟酸、咪唑乙烟酸、咪唑喹啉酸、甲氧咪草烟、甲氧咪草烟铵盐、甲咪唑烟酸、咪草酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、二氯吡啶酸、氨氯吡啶酸、三氯吡氧乙酸、氟硫草定、卤草定、三氯吡啶酚、噻草啶、氟啶草酮、氯氨吡啶酸、氟吡草腙、三氯吡氧乙酸丁氧基乙酯、Cliodinate、稀禾啶、烯草酮、噻草酮、禾草灭、环苯草酮、丁苯草酮、肟草酮、吡喃草酮、Buthidazole、嗪草酮、环嗪酮、苯嗪草酮、乙嗪草酮、Ametridione、Amibuzin、溴苯腈、辛酰溴苯腈、辛酰碘苯腈、碘苯腈、敌草腈、二苯乙腈、双唑草腈、羟敌草腈、Iodobonil、唑嘧磺草胺、双氟磺草胺、五氟磺草胺、磺草唑胺、氯酯磺草胺、双氯磺草胺、啶磺草胺、氟草黄、双草醚、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚、双环磺草酮、硝磺草酮、磺草酮、Tembotrione、Tefuryltrione、Bicyclopyrone、Ketodpiradox、异恶唑草酮、异恶氯草酮、Fenoxasulfone、Methiozolin、异丙吡草酯、吡草醚、吡唑特、野燕枯、苄草唑、吡草酮、吡氯草胺、Pyrasulfotole、苯唑草酮、Pyroxasulfone、唑草胺、氟胺草唑、杀草强、胺唑草酮、唑啶草酮、氟唑草酮、甲磺草胺、Bencarbazone、双苯嘧草酮、氟丙嘧草酯、除草定、异草定、环草啶、特草定、Flupropacil、吲哚酮草酯、氟烯草酸、丙炔氟草胺、炔草胺、酞苄醚、Flumezin、五氯酚(钠)、地乐酚、特乐酚、特乐酯、戊硝酚、二硝酚、氯硝酚、地乐施、地乐特、丙炔恶草酮、恶草酮、环戊恶草酮、氟唑草胺、嗪草酸甲酯、四唑酰草胺、氟哒嗪草酯、杀草敏、溴莠敏、二甲达草伏、哒草醚、草哒酮、草哒松、哒草伏、Pyridafol、二氯喹啉酸、氯甲喹啉酸、苯达松、哒草特、恶嗪草酮、草除灵、异恶草酮、环庚草醚、异丙酯草醚、丙酯草醚、茚草酮、氯酸钠、茅草枯、三氯醋酸、一氯醋酸、六氯丙酮、四氟丙酸、牧草快、溴酚肟、三唑磺、灭杀唑、呋草酮、呋草磺、乙呋草磺、嘧草胺、氯酞酸、氟咯草酮、稗草稀、丙烯醛、苯草灭、灭草环、燕麦酯、噻二唑草胺、棉胺宁、羟草酮、甲氧苯酮、苯嘧磺草胺、氯酰草膦、三氯丙酸、Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、甲硫磺乐灵、Cambendichlor、环丙嘧啶酸、硫氰苯胺、解草酮、解草啶、解草安、解草唑、解草喹、解草腈、解草烷、解草胺腈、解草烯、吡唑解草酯、呋喃解草唑、肟草安、双苯噁唑酸、二氯丙烯胺、氟氯吡啶酯、DOW氯氟吡啶酯、UBH-509、D489，LS82-556、KPP-300、NC-324、NC-330、KH-218、DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、KIH-6127和KIH-2023。
在一个具体实施方式中，所述活性物质选自以下化合物中的一种或两种以上：
(1)HPPD抑制剂：(CAS:2421252-30-2)、双唑草酮(CAS:1622908-18-2)、苯唑氟草酮(CAS:1992017-55-6)、环吡氟草酮(CAS:1855929-45-1)、三唑磺草酮(CAS:1911613-97-2)；
(2)ALS抑制剂：双氟磺草胺(CAS:145701-23-1)；
(3)合成激素类：氟氯吡啶酯(CAS:CAS:943831-98-9)、氯氟吡啶酯(CAS:1390661-72-9)、氯氟吡氧乙酸异辛酯(CAS:81406-37-3)、草除灵(CAS:25059-80-7)、二氯吡啶酸(CAS:1702-17-6)、氯氨吡啶酸(CAS:150114-71-9)、氨氯吡啶酸(CAS:1918-02-1)、2甲4氯异辛酯(CAS:26544-20-7)；
(4)PSII抑制剂：敌稗(CAS:709-98-8)、灭草松(CAS:25057-89-0)；
(5)DOXP抑制剂：(CAS:2766607-82-1)；
(6)FAT抑制剂：
在另一个具体实施方式中，所述组合物中如式I所示的苯环取代的嘧啶羧酸类化合物与前述活性物质的重量比为1:500～20:1、1:400～10:1、1:300～5:1、1:200～2:1、1:100～2:1、1:50～2:1、1:30～2:1、1:20～2:1、1:10～2:1或1:5～1:1。
当使用时，如果需要，将市售的制剂以常见的方式稀释，例如在可湿性粉剂、浓缩乳剂、悬浮液和在水中悬浮的颗粒时，使用水稀释。粉末、土壤施药所用的颗粒剂或撒播和喷洒的溶液，一般在使用前不需要进一步用惰性物质稀释。随着外部条件的变化，要求的式I化合物的使用量也不同，外部条件为，例如温度、湿度、使用的除草剂的性质等等。它可以有大的变化幅度，例如在0.001到1.0kg a.i./ha之间，或更多的活性物质，但优选在0.005到750g a.i./ha之间，特别是在0.005到250g a.i./ha之间。
具体实施方式
以下实施例用于举例说明本发明，不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。
鉴于化合物的经济性与多样性，我们优选合成了一些化合物，在合成的诸多化合物中，选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1-2所示。表1中的化合物只是为了更好的说明本发明，但并不限定本发明，对于本领域的技术人员而言，不应将此理解为本发明上述主题的范围仅限于以下化合物。
表1化合物结构









表2化合物1H NMR


制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备 方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。
以下提供的方法实施例用于促进对本发明的制备方法的进一步了解，使用的具体物质、种类和条件确定为是对本发明的进一步说明，并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到，或者可以由本领域普通技术人员轻易制备得到。
代表性化合物的实施例如下，其他化合物的合成方法类似，此处不再详细说明。
1、化合物3的合成
(1)在200毫升的THF中加入3-1，在氮气保护条件下，-78℃下逐滴向反应液中加入n-BuLi(28ml，2.5mol/L，2.5eq)，滴加完毕后在此温度下搅拌1小时，继续在-78℃下滴加硼酸三甲酯(5.8g，2eq)，滴完室温搅拌过夜，LCMS检测显示原料几乎消耗完毕，有一个主要的新峰生成，MS信号正确，将反应液用稀盐酸淬灭，减压浓缩除去THF后，将反应液用乙酸乙酯萃取，饱和食盐水洗涤(100ml*3)，无水硫酸钠干燥后经硅胶柱分离纯化，得到3-2(白色固体，4.2g，54.4％收率)。
(2)25℃下，将化合物3-2(240mg，1mmol，1.5eq)溶于10mL 1,4-Dioxane：H2O＝10:1的混合溶剂中，加入氟化铯(315mg，3.0eq)，6-氨基-2-氯-5-甲氧基嘧啶-4-羧酸甲酯(3-3，150mg，0.69mmol，1.0eq)，Pd(dppf)Cl2(28mg，0.05eq)，氮气条件下升温至100℃搅拌12小时，LCMS监测至反应完全。浓缩除掉溶剂，拌硅胶正相纯化得到化合物3(白色固体，60mg，25.5％产率)。
2、化合物24的合成
25℃，向化合物24-1(100mg，0.28mol，1.0eq)的DCM溶液中加入三乙胺(3.0eq)，在缓慢滴加乙醇(20mg，1.5eq)，最后加入pybop(215mg，1.5eq)，反应1h。反应完全，将反应液倒入水中淬灭反应，使用DCM萃取三次，合并有机相，饱和食盐水洗涤一次，无水硫酸钠干燥，浓缩后拌样过硅胶柱分离纯化，得到化合物24(52mg，白色固体)。
3、化合物62的合成
25℃，向化合物24-1(100mg，0.28mol，1.0eq)的DCM溶液中加入三乙胺(3.0eq)，在缓慢滴加三氟乙醇(42mg，1.5eq)，最后加入pybop(215mg，1.5eq)，反应1h。反应完全，将反应液倒入水中淬灭反应，使用DCM萃取三次，合并有机相，饱和食盐水洗涤一次，无水硫酸钠干燥，浓缩后拌样过硅胶柱分离纯化，得到化合物62(30mg，白色固体)。
4、化合物74的合成
(1)将化合物3(50g,1.0eq)溶于500ml的THF/H2O(v/v＝4:1)中，0℃下加入LiOH·H2O(14g，2.5eq)，反应液在0℃下反应2小时，LCMS检测原料消失，产物主峰，浓缩除去THF之后，用4N盐酸调pH＝2-3，冷却有固体析出，过滤，干燥之后得到白色固体24-1(43g，89％收率)。
(2)将24-1(23g,1.0eq)溶解于250ml DCM中，溶液中加入三乙胺(12.9g,2.0eq)和乙二醇甲醚(9.7g,2.0eq)，0℃下分批加入PyBOP(39.7g,1.2eq)后升到室温反应1小时。LCMS检测产品主峰，将反应液倒入水中淬灭反应，DCM萃取三次，合并有机相，饱和食盐水洗涤一次，浓缩后柱层析分离纯化得到白色固体74(22g,82％收率)。
或者，常温下将3(5g，13.3mmol)加入到盛有乙二醇甲醚(20.0g)的三口瓶中，加入钛酸四异丙酯(0.1g，0.35mmol)，升温至120～125℃，反应1.5～2h，液相检测反应完毕，减压浓缩除去乙二醇单甲醚，经硅胶柱分离纯化，得白色的化合物74固体5.0g(11.9mmol，89.5％产率)。
5、化合物106的合成
25℃，向化合物24-1(100mg，0.28mol，1.0eq)的DCM溶液中加入三乙胺(3.0eq)，在缓慢滴加三氟乙醇(30mg，1.5eq)，最后加入pybop(215mg，1.5eq)，反应1h。反应完全，将反应液倒入水中淬灭反应，使用DCM萃取三次，合并有机相，饱和食盐水洗涤一次，无水硫酸钠干燥，浓缩后拌样过硅胶柱分离纯化，得到化合物106(50mg，白色固体)。
6、化合物116的合成
25℃，向化合物24-1(100mg，0.2mol，1.0eq)的DCM溶液中加入三乙胺(3.0eq)，在缓慢滴加环丙醇(25mg，1.5eq)，最后加入pybop(215mg，1.5eq)，反应1h。反应完全，将反应液倒入水中淬灭反应，使用DCM萃取三次，合并有机相，饱和食盐水洗涤一次，无水硫酸钠干燥，浓缩后拌样过柱得到化合物116(31mg，白色固体)。
7、化合物201和221的合成
将201-1(19g，0.1mol，1eq)、Et3N(30.6g,0.3mol,3eq)和S-甲基异硫脲硫酸盐(18.8g，0.1mol，1eq)溶解在甲醇(200ml)中加入到500ml单口瓶，80℃加热回流反应12h。监测反应完成，旋干反应液，加水和乙酸乙酯萃取分液，有机相用饱和食盐水洗涤两次、再用无水硫酸钠干燥，拌样，过正相分离得到201-2(17g，收率：73.9％)。
将上述得到的201-2粗品(17g，73mmol，1eq)和N,N-二乙基苯胺(5.5g，36.9mmol，0.5eq)溶解在三氯氧磷(200ml)中加入到500ml单口瓶，80℃加热回流反应12h。监测反应完成，旋干反应液，加水和乙酸乙酯萃取分液，有机相用饱和食盐水洗涤两次、再用无水硫酸钠干燥，拌样，过正相分离得到201-3(14g，收率：77.8％)。
将上述得到的201-3粗品(14g，5.6mmol，1eq)和碳酸铵(27g，282mmol，5eq)溶解在DMSO(200ml)中加入到500ml单口瓶，50℃加热回流反应12h。监测反应完成，加水和乙酸乙酯萃取分液，有机相用饱和食盐水洗涤两次、再用无水硫酸钠干燥，拌样，过正相分离得到201-4(9.6g，收率：74.4％)。
将201-5(2.1g，8.5mmol，1eq)、201-4(2.14g，9.35mmol，1.1eq)、噻吩酸铜(4.8g，25.5mmol，3eq)、三呋喃膦(0.39g，1.7mmol，0.2eq)溶解在DMF(40ml)中加入到250ml单口瓶，氮气抽换气一次，加入Pd(dba)3(80.8mg，0.085mmol，0.01eq)，再抽换气三次，100℃加热回流反应12h。监测反应完成，加水和乙酸乙酯萃取分液，有机相用饱和食盐水洗涤两次，再用无水硫酸钠干燥，拌样，过正相分离(EA/PE＝1/8)，得到201(691mg，收率：21.6％)。
将201(691mg，1.8mmol，1eq)溶解在四氢呋喃(16ml)和水(4ml)的混合液中加入到100ml单口瓶中，室温搅拌加入氢氧化锂(0.22g，8.9mmol，5eq)，室温反应4h。监测反应完成，旋干四氢呋喃，加稀盐酸调成酸性，产物酸析出，抽滤得221-1(589mg，收率：88.7％)。
将221-1(0.1g，0.27mmol，1eq)、甲硫醇(25.9mg，0.54mmol，2eq)、三乙胺(81.8mg，0.81mmol，3eq)溶解在20ml二氯甲烷加入到50ml单口瓶中，室温搅拌下加入Pybop(168.8mg，0.32mmol，1.2eq)，反应1h。监测反应完成，直接加硅胶拌样，过正相分离(EA/PE＝1/10)，得到化合物221(79mg，收率:73.2％)。
8、化合物224的合成
将224-1(0.341g，1mmol，1eq)溶解在20ml甲苯和1ml水中，加入环丙基硼酸(0.103g，1.2mmol，1.2eq)、磷酸钾(0.742g，3.5mmol，3.5eq)，N2置换，加入醋酸钯(8.3mg，0.05mmol，0.05eq)和三环己基磷(28.1mg，0.1mmol，0.1eq)，N2置换3次，升温至80℃，反应12h，监测反应直到起始原料消失。旋干后，加水用乙酸乙酯萃取三次，饱和食盐水洗涤三次。无水硫酸钠干燥后过柱纯化，馏分旋干得到224(139mg，产率40.1％)。
生物活性评价：
植物破坏(即生长控制率)的活性级别标准如下：
9级：完全死亡；
8级：生长控制率大于等于90％且小于100％；
7级：生长控制率大于等于80％且小于90％；
6级：生长控制率大于等于70％且小于80％；
5级：生长控制率大于等于50％且小于70％；
4级：生长控制率大于等于30％且小于50％；
3级：生长控制率大于等于20％且小于30％；
2级：生长控制率大于等于10％且小于20％；
1级：生长控制率小于10％；
0级：无效果。
以上生长控制率为鲜重控制率。
苗后测试实验：
将单子叶和双子叶杂草种子(播娘蒿、荠菜、苘麻、猪殃殃、繁缕、麦家公、蔊菜、看麦娘、日本看麦娘、牛筋草、菵草、硬草、小飞蓬、蜡烛草、婆婆纳、雀麦、节节麦、虉草、反枝苋、藜、鸭跖草、苣荬菜、田旋花、刺儿菜、龙葵、铁苋菜、马唐、稗草、绿狗尾草、金狗尾草、千金子、鸭舌草、野慈姑、萤蔺、香附子、碎米莎草、异型莎草、飘拂草、马齿苋、苍耳、牵牛、白酒草等)以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱、马铃薯、芝麻、蓖麻、白菜、萝卜等)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周后在2-3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，以1.5升/公顷油酸甲酯的乳油作为增效剂，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周后统计杂草的实验效果，所用化合物计量为120,60,30,15g a.i./ha，重复三次，取平均值。代表性数据列于表3。
表3苗后杂草试验结果

注：N代表未测试，对照化合物A：
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周后观察实验结果，发现本发明的药剂多数在250g a.i./ha计量下效果出众，尤其对稗草、马唐、苘麻等杂草，且很多化合物对玉米、小麦、水稻、大豆、有良好的选择性。
同时，我们经过小麦田和水稻田主要杂草测试发现，本发明所述化合物普遍具有较好的杂草防效，尤其是我们注意到对于ALS抑制剂有抗性的野慈姑、萤蔺、异型莎草、播娘蒿、荠菜、麦家公、猪殃殃、香附子等阔叶杂草和莎草有极高的活性，具有非常好的商业价值。
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，播种鸭舌草、雨久花、狼把草的种子，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，在鸭舌草、雨久花、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天鸭舌草、雨久花、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，以上述活性标准级别评价效果，很多化合物表现出了优异的活性和选择性，代表性数据如表4所示。
表4移栽水稻安全性评价与水田杂草防效评价结果


注：鸭舌草、雨久花、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。
组合物活性测试：
所需活性成分B由试剂公司或原药生产企业购买或通过常规方法合成，活性成分A为表1中化合物74，原药均采用丙酮作溶剂，用含量0.1％乳化剂吐温-80水溶液稀释，现用现稀释。
(A)苗后茎叶喷雾处理：
杂草采用盆栽法培养，用180×140mm塑料营养钵，摆放于搪瓷盘中，内装从农田采回经风干过筛的表层土壤(4/5处)，土壤湿度初期均控制在20％，挑选籽粒饱满均一的杂草种子，用25℃温水浸泡6小时，在28℃生化培养箱(黑暗)中催芽，将刚刚露白的杂草种子均匀摆放在土壤表面，根据种子粒径大小然后覆土0.5-1cm。
在可控日光温室内进行培养，温度20～30℃，自然光照，相对湿度57％～72％。土壤类型为壤土，有机质含量为1.63％，pH＝7.1，碱解氮84.3mg/kg，速效磷38.5mg/kg，速效钾82.1mg/kg。
每处理重复4次，每次处理3盆，每盆播种杂草种子20粒。
试验共用药1次。待杂草1.5-2叶期，间苗，保持每盆内杂草10株，每处理保留30株，然后继续培养至小飞蓬株高10厘米，其他杂草3-4叶进行处理。
将培养好的试材均匀摆放在面积0.5m2的平台上，用3WP-2000型行走式喷雾塔茎叶喷雾，喷液量按450公斤/公顷计，喷雾压力0.3MPa。待全部药液喷完后，关闭气阀，30秒后，打开喷雾塔门，取出营养钵。然后打开气阀，喷清水50mL，清洗喷液管。试材处理后移入温室常规培养。
(B)数据调查与统计分析
采用绝对数调查法，用刀片沿土壤表面切断存活杂草整株幼苗，用分析天平称量杂草鲜重。对于已经死亡的杂草，按鲜重为零计。
处理后21天调查，共调查1次。
用Gowing法计算各处理混合组合的理论鲜重抑制率(E0＝X+Y-X*Y/100)，然后与实测抑制率(E)相比较，评价二者混用对杂草的联合作用类型，当E-E0值大于10％为增效作用、小于-10％为拮抗作用、在-10％～10％之间为加成作用。并根据实际防效和除草剂特点、配方的平衡性等因素确定最佳配比。式中X为活性成分A用量为P时的鲜重抑制率；Y为活性成分B用量为Q时的鲜重抑制率。统计结果见下表5。
表5 A混配B对杂草的实际防效与联合作用评价

同时经过很多测试发现，本发明所述化合物及其组合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性，能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的甘蔗、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. 一种苯环取代的嘧啶羧酸类化合物，如通式I所示：
    其中，
    X代表未取代或被卤素取代的烷基；
    Y代表OR5；
    Z代表溴、卤代烷基或环烷基；
    Q代表O或S；
    R1、R2分别独立地代表氢；
    R3代表卤素或氨基；
    R4代表氢或卤素；
    R5代表未取代或被卤素取代的烷基；
    W代表氢或其盐、烷基、烯基、炔基、环烷基、环烯基、杂环基、芳基、 其中，所述“烷基”、“烯基”或“炔基”任选地被选自卤素、氰基、硝基、环烷基、三烷基硅烷基、环烯基、杂环基、芳基、 中的至少一个基团所取代，所述“环烷基”、“环烯基”、“杂环基”或“芳基”任选地被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-亚烷基-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    X11分别独立地代表氢、烷基、烯基、炔基、环烷基、环烷基烷基、环烯基、环烯基烷基、杂环基、杂环基烷基、芳基或芳基烷基，其中，所述“烷基”、“烯基”或“炔基”任选地被选自卤素、烷氧基中的至少一个基团所取代，所述“环烷基”、“环烷基烷基”、“环烯基”、“环烯基烷基”、“杂环基”、“杂环基烷基”、“芳基”或“芳基烷基”任选地被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-亚烷基-(CO)OR10中的至少一个基团 所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    X13、X14分别独立地代表氢、卤素、氰基、烷氧基、烷氧基烷基、烷基羰基、烷氧基羰基、烷基磺酰基、烷基、烯基、炔基、环烷基、环烷基烷基、环烯基、环烯基烷基、芳基、芳基烷基、杂环基或杂环基烷基，或者基团CX13X14一起形成未取代或取代的环状结构，或者基团NX13X14一起形成未取代或取代的1-位为氮原子的杂环基，其中，所述“烷基”、“烯基”或“炔基”任选地被卤素取代，所述“环烷基”、“环烷基烷基”、“环烯基”、“环烯基烷基”、“芳基”、“芳基烷基”、“杂环基”或“杂环基烷基”任选地被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-亚烷基-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    R10分别独立地代表氢，烷基，卤代烷基，苯基，或被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基。
  2. 根据权利要求1所述的一种苯环取代的嘧啶羧酸类化合物，其特征在于，
    X代表未取代或被卤素取代的C1-C8烷基；
    Z代表溴、卤代C1-C8烷基或C3-C8环烷基；
    R5代表未取代或被卤素取代的C1-C8烷基；
    W代表氢或其金属盐、胺盐、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烯基、杂环基、芳基、其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”任选地被选自卤素、氰基、硝基、C3-C8环烷基、三C1-C8烷基硅烷基、C3-C8环烯基、杂环基、芳基、 中的至少一个基团所取代，所述“C3-C8环烷基”、“C3-C8环烯基”、“杂环基”或“芳基”任选地被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8亚烷基)-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    X11分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C3-C8环烯基、C3-C8环烯基C1-C8烷基、杂环基、杂环基C1-C8烷基、芳基或芳基C1-C8烷基，其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”任选地被选自卤素、C1-C8烷氧基中的至少一个基团所取代，所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“C3-C8环烯基”、“C3-C8环烯基C1-C8烷基”、“杂环基”、“杂环基C1-C8 烷基”、“芳基”或“芳基C1-C8烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8亚烷基)-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    X13、X14分别独立地代表氢、卤素、氰基、C1-C8烷氧基、C1-C8烷氧基C1-C8烷基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷基磺酰基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、C3-C8环烯基、C3-C8环烯基C1-C8烷基、芳基、芳基C1-C8烷基、杂环基或杂环基C1-C8烷基，或者基团CX13X14一起形成5～8元碳环或含氧、硫或氮的杂环，或者基团NX13X14一起形成 其中，所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”任选地被卤素取代，所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“C3-C8环烯基”、“C3-C8环烯基C1-C8烷基”、“芳基”、“芳基C1-C8烷基”、“杂环基”或“杂环基C1-C8烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C8亚烷基)-(CO)OR10中的至少一个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环，所述“5～8元碳环或含氧、硫或氮的杂环”任选地被选自C1-C8烷基、C1-C8烷氧羰基或苄基中的至少一个基团所取代，或者与芳基或杂环基形成稠环结构；所述任选地被选自氧代、C1-C8烷基或C1-C8烷氧羰基中的至少一个基团所取代；
    R10分别独立地代表氢，C1-C8烷基，卤代C1-C8烷基，苯基，或被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基。
  3. 根据权利要求1或2所述的一种苯环取代的嘧啶羧酸类化合物，其特征在于，
    X代表未取代或被卤素取代的C1-C6烷基；
    Z代表溴、卤代C1-C6烷基或C3-C8环烷基；
    R5代表未取代或被卤素取代的C1-C6烷基；
    W代表氢或其钠盐、钾盐、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烯基、杂环基、芳基、其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”任选地被选自卤素、氰基、硝基、C3-C6环烷 基、三C1-C6烷基硅烷基、C3-C6环烯基、杂环基、芳基、 中的1、2或3个基团所取代，所述“C3-C6环烷基”、“C3-C6环烯基”、“杂环基”或“芳基”任选地被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6亚烷基)-(CO)OR10中的1、2或3个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    X11分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C3-C6环烯基、C3-C6环烯基C1-C6烷基、杂环基、杂环基C1-C6烷基、芳基或芳基C1-C6烷基，其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”任选地被选自卤素、C1-C6烷氧基中的至少一个基团所取代，所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“C3-C6环烯基”、“C3-C6环烯基C1-C6烷基”、“杂环基”、“杂环基C1-C6烷基”、“芳基”或“芳基C1-C6烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6亚烷基)-(CO)OR10中的1、2或3个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环；
    X13、X14分别独立地代表氢、卤素、氰基、C1-C6烷氧基、C1-C6烷氧基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基磺酰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、C3-C6环烯基、C3-C6环烯基C1-C6烷基、芳基、芳基C1-C6烷基、杂环基或杂环基C1-C6烷基，或者基团CX13X14一起形成5～8元饱和碳环、或者基团NX13X14一起形成其中，所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”任选地被卤素取代，所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“C3-C6环烯基”、“C3-C6环烯基C1-C6烷基”、“芳基”、“芳基C1-C6烷基”、“杂环基”或“杂环基C1-C6烷基”任选地被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR10、-SR10、-(CO)OR10、-(SO2)R10、-N(R10)2或-O-(C1-C6亚烷基)-(CO)OR10中的1、2或3个基团所取代，或者环上相邻两个碳原子与未取代的或被卤素所取代的-OCH2CH2-或-OCH2O-形成稠环，所述“5～8元饱和碳环、”任选地被选自C1-C6烷基、C1-C6烷氧羰 基或苄基中的1、2或3个基团所取代，或者与芳基或杂环基形成稠环结构，所述 任选地被选自氧代、C1-C6烷基或C1-C6烷氧羰基中的1、2或3个基团所取代；
    R10分别独立地代表氢，C1-C6烷基，卤代C1-C6烷基，苯基，或被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的1、2或3个基团所取代的苯基。
  4. 根据权利要求1-3任意一项所述的一种苯环取代的嘧啶羧酸类化合物，其特征在于，
    X代表甲基、CHF2、CH2F或CF3；
    Z代表溴、CF3或环丙基；
    R3代表氟、氯或氨基；
    R4代表氢或氟；
    R5代表甲基、CHF2、CH2F或CF3；
    优选地，所述化合物选自说明书表1中的任意一个。
  5. 一种中间体化合物，如通式II所示：
    其中，取代基R3、R4、Y和Z的定义如权利要求1-4任意一项所述。
  6. 一种如权利要求1-5任意一项所述的苯环取代的嘧啶羧酸类化合物的制备方法，其特征在于，包括以下步骤：
    将通式II所示的化合物与通式III所示的化合物进行反应制得如通式I所示的化合物，其反应方程式如下：
    其中，Hal代表卤素，优选Cl；取代基R1、R2、R3、R4、X、Y、Z、Q和W的定义如权利要求1-4任意一项所述。
  7. 根据权利要求6所述的方法，其特征在于，所述反应在催化剂、碱和溶剂的存在下进行；优选地，所述催化剂为钯催化剂[如Pd(dppf)Cl2·CH2Cl2、Pd(dppf)Cl2、Pd(PPh3)4、甲烷磺酸(2-二环己基膦-2',6'-二甲氧基联苯)(2'-甲胺基-1,1'-联苯-2-基)钯(II)或甲磺酸(三叔丁基膦基)(2'-甲氨基-1,1'-联苯-2-基)钯(II)等]或镍催化剂；优选地，所述碱选自无机碱(如K2CO3、Na2CO3、Cs2CO3、NaHCO3、KHCO3、KF、CsF、K3PO4、K2HPO4、NaOH、KOH等)或有机碱(如吡唑、三乙胺、DIEA、三甲基硅烷醇钾、AcOK、AcONa、MeONa、EtONa、t-BuONa等)中的至少一种；优选地，所述溶剂为有机溶剂/水，二者体积比优选为20/1-1/1，所述有机溶剂优选为二氧六环、甲苯、DMF、DMSO、DMA、甲醇、乙醇、异丙醇、正丁醇、乙腈、二氯乙烷、二氯甲烷或乙酸乙酯。
  8. 一种除草剂组合物，其特征在于，包括除草有效量的权利要求1-4任意一项所述的苯环取代的嘧啶羧酸类化合物中的至少一种，优选地，还包括制剂助剂，更优选地，还包括其他活性物质，所述活性物质优选以下化合物中的一种或两种以上：
    (1)HPPD抑制剂：双唑草酮、苯唑氟草酮、环吡氟草酮、三唑磺草酮；
    (2)ALS抑制剂：双氟磺草胺；
    (3)合成激素类：氟氯吡啶酯、氯氟吡啶酯、氯氟吡氧乙酸异辛酯、草除灵、二氯吡啶酸、氯氨吡啶酸、氨氯吡啶酸、2甲4氯异辛酯；
    (4)PSII抑制剂：敌稗、灭草松；
    (5)DOXP抑制剂：
    (6)FAT抑制剂：
    进一步优选地，所述组合物中权利要求1-4任意一项所述的苯环取代的嘧啶羧酸类化合物与其他前述活性物质的重量比为1:500～20:1、1:400～10:1、1:300～5:1、1:200～2:1、1:100～2:1、1:50～2:1、1:30～2:1、1:20～2:1、1:10～2:1或1:5～1:1。
  9. 一种控制杂草的方法，其特征在于，包括将除草有效量的权利要求1-4任意一项所述的苯环取代的嘧啶羧酸类化合物中的至少一种或权利要求8所述的除草剂组合物使用在植物上或者杂草区域。
  10. 如权利要求1-4任意一项所述的苯环取代的嘧啶羧酸类化合物中的至少一种或权利要求8所述的除草剂组合物在控制杂草上的用途，优选地，将所述的苯环取代的嘧啶羧酸类化合物用于防除有用作物中的杂草，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
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