WO2021018135A1 - 杂环基烷基取代的二氯苯甲酰类化合物及其应用 - Google Patents

杂环基烷基取代的二氯苯甲酰类化合物及其应用 Download PDF

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WO2021018135A1
WO2021018135A1 PCT/CN2020/105150 CN2020105150W WO2021018135A1 WO 2021018135 A1 WO2021018135 A1 WO 2021018135A1 CN 2020105150 W CN2020105150 W CN 2020105150W WO 2021018135 A1 WO2021018135 A1 WO 2021018135A1
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compound
alkyl
formula
independently hydrogen
present
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French (fr)
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李义涛
林健
吴庆国
张虎
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东莞市东阳光农药研发有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C07D295/116—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings with the doubly bound oxygen or sulfur atoms directly attached to a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • the present invention relates to the field of agriculture. Specifically, the present invention provides a new heterocyclyl alkyl-substituted dichlorobenzoyl compound and a preparation method thereof; a composition containing these compounds and their application in agriculture.
  • Substituted benzoyl compounds are a class of compounds with excellent biological activity, and their herbicidal activity is described in, for example, CN105766944, CN102464630, WO2004024687, and CN103025718.
  • the active ingredients known from the documents cited above have disadvantages in use, such as (a) no or only insufficient herbicidal effect on weed plants, (b) weed plants to be controlled The spectrum is too narrow or (c) the selectivity in useful plant crops is too low.
  • benzoyl compounds still need to be further developed and improved to obtain a series of benzoyl compounds with better herbicidal activity and/or selectivity.
  • the present invention provides a new heterocyclyl alkyl substituted dichlorobenzoyl compound, which has excellent herbicidal effect, broad weed control spectrum and excellent selectivity between crops and weeds.
  • the present invention provides a compound represented by formula (I) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (I):
  • R 1 is hydroxy, cyano, amino, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, halogenated C 1-6 alkyl , Halogenated C 2-6 alkenyl, halogenated C 2-6 alkynyl, halogenated C 1-6 alkoxy or C 3-8 cycloalkyl;
  • n 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
  • n 0, 1 or 2;
  • R 2 and R 2a are each independently hydrogen or C 1-6 alkyl
  • R 3 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl or C 3-8 cycloalkyl;
  • R 4 is hydrogen or -CH 2 -CO-C 6-10 aryl; wherein the -CH 2 -CO-C 6-10 aryl is optionally selected from halogen or C 1- 6 substituted by the substituent of the alkyl group.
  • R 1 is hydroxy, cyano, amino, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, halo C 1-4 alkyl, halogenated C 2-4 alkenyl, halogenated C 2-4 alkynyl, halogenated C 1-4 alkoxy or C 3-6 cycloalkyl.
  • R 1 is hydroxy, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 , cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • R 2 and R 2a are each independently hydrogen or C 1-4 alkyl.
  • R 2 and R 2a are each independently hydrogen or C 1-3 alkyl.
  • R 2 and R 2a are each independently hydrogen or methyl.
  • R 3 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, or C 3-6 cycloalkyl.
  • R 3 is hydrogen, C 1-3 alkyl, C 2-3 alkenyl, C 2-3 alkynyl, or C 3-6 cycloalkyl.
  • R 3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
  • R 4 is hydrogen or -CH 2 -CO-phenyl; wherein the -CH 2 -CO-phenyl is optionally substituted by 1, 2 or 3 selected from halogen or C 1-4 alkane The substituents of the group are substituted.
  • R 4 is hydrogen or -CH 2 -CO-phenyl; wherein said -CH 2 -CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from chlorine or methyl Replaced.
  • the present invention provides a compound, which is a compound represented by formula (Ia) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ia):
  • R 1a and R 1b are each independently hydrogen or C 1-3 alkyl.
  • the present invention provides a compound, which is a compound represented by formula (Ib) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ib):
  • Q is the following sub-structure:
  • R 1a and R 1b are each independently hydrogen or methyl.
  • n 0, 1, or 2.
  • the present invention provides a compound that is a compound represented by formula (Ia-1) or a stereoisomer, tautomer, nitroxide compound represented by formula (Ia-1) Material or salt:
  • R 1a and R 1b are each independently hydrogen or C 1-6 alkyl
  • R 2 and R 2a are each independently hydrogen or C 1-6 alkyl.
  • R 1a and R 1b are each independently hydrogen or C 1-3 alkyl; R 2 and R 2a are each independently hydrogen or C 1-3 alkyl.
  • R 1a and R 1b are each independently hydrogen or methyl; R 2 and R 2a are each independently hydrogen or methyl.
  • the present invention provides a compound which is a compound represented by formula (Ia-2) or a stereoisomer, tautomer, nitroxide compound represented by formula (Ia-2) Material or salt:
  • R 1a and R 1b are each independently hydrogen or C 1-6 alkyl.
  • R 1a and R 1b are each independently hydrogen or C 1-3 alkyl.
  • R 1a and R 1b are each independently hydrogen or methyl.
  • the present invention provides a compound which is a compound having one of the following structures or a stereoisomer, tautomer, nitrogen oxide or salt thereof of a compound having one of the following structures:
  • the present invention provides a compound, and most preferably the specific structure of the compound is:
  • the biological activity test shows that the compound represented by the formula (I) of the present invention has very good herbicidal activity, and is superior to the compound whose benzene ring 4-position substituent is methylsulfonyl.
  • spraying treatment was carried out on the post-emergence weeds.
  • Example 1 Compound I-1-1) was effective on purslane at 60g/ha and 90g/ha.
  • the control effect is 0 (Table 9); and the control effect of the compound of the present invention on Portulaca oleracea at 37.5g/ha and 75g/ha is at least 82%.
  • the compound of the present invention can effectively control weeds such as Abutilon, Portulaca, Barnyardgrass or Zinnia, and can obtain good effects at a low dosage.
  • the compound of the present invention has good safety to peanuts, corn, rice and wheat, and is preferably used to control weeds in peanut fields, corn fields, rice fields and wheat fields.
  • the present invention provides a composition comprising the compound of the present invention.
  • composition of the present invention further optionally includes at least one additional component.
  • the additional components are surfactants, solid diluents, liquid diluents, buffers, defoamers, thickeners, antifreeze agents, antimicrobial agents and/or film formers.
  • the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention in agriculture.
  • the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention as a herbicide to control weeds in useful plants.
  • the present invention provides the use of the compound of the present invention or a composition containing the compound of the present invention in controlling gramineous weeds.
  • the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention in controlling broadleaf weeds.
  • the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention in the control of Abutilon, Portulaca, Barnyardgrass and/or Zinnia.
  • the present invention provides the use of the compound of the present invention or a composition containing the compound of the present invention for controlling unwanted plants.
  • the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention as a herbicide.
  • the present invention provides the use of the compound of the present invention or a composition containing the compound of the present invention as a pre-emergence herbicide.
  • the present invention provides the use of the compound of the present invention or a composition containing the compound of the present invention as a post-emergence herbicide.
  • the present invention provides a method for controlling unwanted plants, which is characterized by applying an effective amount of the compound of the present invention to plants, plant seeds, soil in or on which plants grow, or cultivation areas.
  • the present invention provides a method for controlling the growth of weeds in useful plants, which comprises applying an effective amount of the compound of the present invention or a composition containing the compound of the present invention to the locus of the weeds.
  • the weed is one or more of Abutilon, Portulaca, Barnyard Grass or Zinnia.
  • the useful plant is at least one of peanut, corn, rice or wheat.
  • the compound provided by the present invention is a new type compound that is more effective to weeds, lower in cost, less toxic, and safe to crops.
  • the present invention includes R-isomers, S-isomers and mixtures in any ratio; due to keto/enol interconversion, there may be multiple tautomers, and the present invention includes all Tautomers and mixtures in any ratio.
  • the isotope-enriched compound has the structure described by the general formula given in the present invention, except that one or more atoms are replaced by atoms having the selected atomic weight or mass number.
  • Exemplary isotopes that can be introduced into the compounds of the present invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 17 O , 18 O, 18 F, 31 P, 32 P, 35 S, 36 Cl and 125 I.
  • Stereoisomers refer to compounds that have the same chemical structure but differ in the arrangement of the atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans) isomers, atropisomers, etc. .
  • Enantiomers refer to two isomers of a compound that cannot be superimposed but are mirror images of each other.
  • Diastereoisomers refer to stereoisomers that have two or more chiral neutralities and whose molecules are not mirror images of each other. Diastereoisomers have different physical properties, such as melting point, boiling point, spectral properties and reactivity. Mixtures of diastereomers can be separated by high-resolution analytical operations such as electrophoresis and chromatography, such as HPLC.
  • optically active compounds that is, they have the ability to rotate the plane of plane-polarized light.
  • the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule with respect to one or more chiral centers.
  • the prefixes d and l or (+) and (-) are symbols used to specify the rotation of plane-polarized light caused by the compound, where (-) or l indicates that the compound is levorotatory.
  • Compounds prefixed with (+) or d are dextrorotatory.
  • a specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture.
  • a 50:50 mixture of enantiomers is called a racemic mixture or a racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
  • tautomer or "tautomeric form” refers to structural isomers with different energies that can be converted into each other through a low energy barrier. If tautomerism is possible (as in solution), the chemical equilibrium of tautomers can be reached.
  • proton tautomers also called prototropic tautomers
  • Valence tautomers include interconversion through the recombination of some bond-forming electrons.
  • keto-enol tautomerism are those of pentane-2,4-dione, hexane-1,3-dione and 4-hydroxypent-3-en-2-one tautomers Mutual change.
  • Another example of tautomerism is phenol-ketone tautomerism.
  • a specific example of phenol-ketone tautomerism is the interconversion of pyridine-4-ol and pyridine-4(1H)-one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the present invention are within the scope of the present invention.
  • the "nitrogen oxide” in the present invention means that when the compound contains several amine functional groups, one or more nitrogen atoms can be oxidized to form an N-oxide.
  • N-oxides are N-oxides of tertiary amines or N-oxides of nitrogen-containing heterocyclic nitrogen atoms.
  • the corresponding amine can be treated with an oxidizing agent such as hydrogen peroxide or peracid (such as peroxycarboxylic acid) to form N-oxide (see Advanced Organic Chemistry, Wiley Interscience, 4th edition, Jerry March, pages).
  • N-oxides can be prepared by the method of LWDeady (Syn.Comm.1977, 7,509-514), in which, for example, in an inert solvent such as methylene chloride, the amine compound is combined with m-chloroperoxybenzoic acid (MCPBA) reaction.
  • LWDeady Syn.Comm.1977, 7,509-514
  • MCPBA m-chloroperoxybenzoic acid
  • the compounds of the present invention can be optionally substituted by one or more substituents, such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
  • substituents such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
  • substituents such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
  • substituents such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
  • a class of compounds can be used interchangeably.
  • substituted means that one or more hydrogen atoms in a given structure are replaced by a specific substituent.
  • an optional substituent group can be substituted at each substitutable position of the group.
  • substituents mentioned herein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxy, alkyl, alkoxy, alkoxyalkyl, alkane Oxyoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, alkoxy, alkoxyalkyl, alkane Oxyoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyl
  • C 1 -C 6 alkyl or “C 1-6 alkyl” specifically refers to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl. base.
  • alkyl or “alkyl group” used in the present invention refers to a saturated linear or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally One or more substituents described in this invention are substituted. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-10 carbon atoms; in one embodiment, the alkyl group contains 1-8 In another embodiment, the alkyl group contains 1-6 carbon atoms; in another embodiment, the alkyl group contains 1-4 carbon atoms; in another embodiment, the alkane The radical group contains 1-3 carbon atoms.
  • alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), isopropyl (i-Pr, -CH(CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH(CH 3 )CH 2 CH 3 ), tert-butyl (t-Bu, -C(CH 3 ) 3 ), n-pentyl (-CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH(CH 3 )CH 2 CH 2 CH 3 ), 3-pentyl (-CH(CH 2 CH 3 ) 2 ), 2-methyl -2-Butyl (-C(CH 3 ) 2
  • alkenyl means a linear or branched monovalent hydrocarbon group containing 2-12 carbon atoms, in which there is at least one unsaturation site, that is, a carbon-carbon sp 2 double bond, wherein the alkenyl group
  • the group may be optionally substituted with one or more substituents described in the present invention, which includes the positioning of "cis” and “tans", or the positioning of "E” and "Z”.
  • the alkenyl group contains 2-10 carbon atoms; in one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2-4 carbon atoms.
  • alkynyl means a linear or branched monovalent hydrocarbon group containing 2-12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may optionally be substituted by one or more One of the substituents described in this invention is substituted.
  • the alkynyl group contains 2-10 carbon atoms; in one embodiment, the alkynyl group contains 2-8 carbon atoms; in another embodiment, the alkynyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2-4 carbon atoms.
  • alkynyl groups include, but are not limited to, -C ⁇ CH, -C ⁇ CCH 3 , -CH 2 -C ⁇ CH, -CH 2 -C ⁇ CCH 3 , -CH 2 CH 2 -C ⁇ CH , -CH 2 -C ⁇ CCH 2 CH 3 , -CH 2 CH 2 -C ⁇ CCH 3 and so on.
  • alkoxy means that the alkyl group is connected to the rest of the molecule through an oxygen atom, where the alkyl group has the meaning as described in the present invention. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1-10 carbon atoms; in one embodiment, the alkoxy group contains 1-8 carbon atoms; in one embodiment, the alkoxy group contains 1-6 carbon atoms; in another embodiment, the alkoxy group contains 1-4 carbon atoms; in yet another embodiment, the alkoxy group contains 1-3 carbon atoms.
  • the alkoxy group may be optionally substituted with one or more substituents described herein.
  • alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH 3 ) 2 ), 1-butoxy (n-BuO, n- Butoxy, -OCH 2 CH 2 CH 2 CH 3 ), 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH 2 CH(CH 3 ) 2 ), 2-but Oxygen (s-BuO, s-butoxy, -OCH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH 3 ) 3 ), 1-pentyloxy (n-pentyloxy, -OCH 2 CH 2 CH 2 CH 2 CH 3 ), 2-(
  • halogen refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
  • haloalkyl means that an alkyl group is substituted with one or more halogen atoms.
  • haloalkyl groups include, but are not limited to, -CH 2 F, -CHF 2 , -CH 2 Cl, -CH 2 Br, -CF 3 , -CH 2 CF 3 , -CH 2 CH 2 F, -CH 2 CH 2 Cl, -CH 2 CH 2 Br, -CH 2 CHF 2 , -CH 2 CH 2 CF 3 , -CH 2 CH 2 CH 2 F, -CH 2 CH 2 CH 2 Cl, -CH 2 CH 2 CH 2 Br, -CHFCH 2 CH 3 , -CHClCH 2 CH 3 , etc.
  • haloalkoxy means that the alkoxy group is substituted with one or more halogen atoms.
  • halogenated alkoxy groups include, but are not limited to, -OCH 2 F, -OCHF 2 , -OCH 2 Cl, -OCH 2 Br, -OCF 3 , -OCH 2 CF 3 , -OCH 2 CH 2 F, -OCH 2 CH 2 Cl, -OCH 2 CH 2 Br, -OCH 2 CHF 2 , -OCH 2 CH 2 CF 3 , -OCH 2 CH 2 CH 2 F, -OCH 2 CH 2 CH 2 Cl, -OCH 2 CH 2 CH 2 Br, -OCHFCH 2 CH 3 , -OCHClCH 2 CH 3 , etc.
  • haloalkenyl means that an alkenyl group is substituted with one or more halogen atoms.
  • haloalkynyl means that an alkynyl group is substituted with one or more halogen atoms.
  • cycloalkyl refers to a monovalent or multivalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms.
  • the cycloalkyl group contains 3-12 carbon atoms; in one embodiment, the cycloalkyl group contains 3-10 carbon atoms; in another embodiment, the cycloalkyl group contains 3-8 carbon atoms. Atom; In yet another embodiment, the cycloalkyl group contains 3-6 carbon atoms.
  • the cycloalkyl group is optionally substituted with one or more substituents described in this invention.
  • Examples of this include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl Alkyl, adamantyl, etc.
  • unsaturated means that the group contains one or more degrees of unsaturation.
  • heteroatom refers to O, S, N, P, and Si, including any oxidation state of N, S, and P; primary, secondary, and tertiary amines and quaternary ammonium salt forms; or on the nitrogen atom in the heterocycle
  • the form in which hydrogen is substituted for example, N (like N in 3,4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like N-substituted pyrrolidinyl) NR).
  • aryl means a monocyclic, bicyclic and tricyclic carbocyclic ring system containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic Family, where each ring system contains a ring composed of 3-7 atoms, and has one or more attachment points connected to the rest of the molecule.
  • aryl can be used interchangeably with the term “aromatic ring”. Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthracenyl. The aryl group is optionally substituted with one or more substituents described in the present invention.
  • the salts of the compound of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium and ammonium cations having the formula N + (R 19 R 20 R 21 R 22 ), wherein R 19 , R 20 , R 21 and R 22 are independently selected from hydrogen, C 1 -C 6 alkyl and C 1 -C 6 hydroxyalkyl.
  • the salt of the compound represented by formula (I), formula (Ia) or formula (Ib) can be obtained by using metal hydroxides (e.g. sodium hydroxide) or amines (e.g.
  • acceptable salts can be formed from organic and inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, and malonic acid. Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid and similarly known Accepted acid.
  • organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, and malonic acid. Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methane
  • compositions and formulations of the compounds of the invention are provided.
  • the compound of the present invention can generally be used as a herbicide active ingredient in a composition or preparation, the composition or preparation has at least one additional component selected from surfactants, solid diluents, liquid diluents Agents, buffers, defoamers, thickeners, antifreeze agents, antimicrobial agents, film-forming agents, etc., components that meet the requirements of pesticide use are all within the scope of the present invention.
  • the ingredients of the formulation or composition are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors (such as soil type, humidity, and temperature).
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), etc., which may optionally be thickened into gels.
  • aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions.
  • non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.
  • the general types of solid compositions are powders, powders, granules, pellets, pellets, lozenges, tablets, filled films (including seed coatings), etc. They can be water-dispersible ("wettable") Or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are especially useful for seed treatment.
  • the active ingredient can be (micro)encapsulated and further formed into a suspension or solid preparation; or the entire active ingredient preparation can be encapsulated (or "coated”). Encapsulation can control or delay the release of active ingredients.
  • Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular formulations. High-concentration compositions are mainly used as intermediates for other formulations.
  • Sprayable formulations are usually dispersed in a suitable medium before spraying. Such liquid preparations and solid preparations are formulated into preparations that are easy to dilute in a spray medium (usually water).
  • the spray volume can be in the range of about one liter to several thousand liters per hectare, but is more typically in the range of about ten liters to several hundred liters per hectare.
  • the sprayable formulation can be mixed with water or another suitable medium in a tank, used to treat leaves by air or ground application, or applied to the growing medium of plants. Liquid and dry formulations can be metered directly into the drip irrigation system, or metered into the furrow during planting.
  • the formulation will generally contain effective amounts of active ingredients, diluents and surfactants, the sum of which is 100% by weight.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g. lactose, sucrose), silica, talc, mica, diatoms Soil, urea, calcium carbonate, sodium carbonate and sodium bicarbonate and sodium sulfate.
  • Typical solid diluents are described in Watkins et al. Handbook of Insecticide Dust Diluents and Carriers, 2nd edition, Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g. N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g. N-methylpyrrolidone) , Ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffin (e.g.
  • Liquid diluents also include glycerides of saturated and unsaturated fatty acids (usually C 6 -C 22 ), such as plant seed and fruit oils (such as olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil) , Sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil), fats of animal origin (such as beef tallow, lard, lard, cod liver oil, fish oil), and Their mixture.
  • plant seed and fruit oils such as olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil
  • fats of animal origin such as beef tallow, lard, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated (eg, methylated, ethylated, butylated) fatty acids, where fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals and can be purified by distillation.
  • alkylated (eg, methylated, ethylated, butylated) fatty acids where fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals and can be purified by distillation.
  • Typical liquid diluents are described in Marsden's Solvents Guide, 2nd edition, Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention generally contain one or more surfactants.
  • surfactants also called “surface-active agents”
  • surface-active agents usually change, most commonly reducing the surface tension of the liquid.
  • the surfactant can be used as a wetting agent, dispersant, emulsifier or defoamer.
  • Nonionic surfactants that can be used in the composition of the present invention include, but are not limited to: alcohol alkoxylates, such as based on natural alcohols and synthetic alcohols (which are branched or linear) and are composed of alcohols and ethylene oxide, Alcohol alkoxylates prepared from propylene oxide, butylene oxide or their mixtures; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, Such as ethoxylated soybean, castor and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylation, nonylphenol ethoxylation, dinonylphenol ethoxylate and ten Dialkylphenol ethoxylates (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide or their mixture
  • Usable anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and their salts; carboxylated alcohol or alkyl phenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives Compounds, such as lignosulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and benzene Phosphate esters of vinyl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfates; sulfates and sulfonates of oils and fatty acids; ethoxylated alkylphenols Sulfates and sulfonates of alcohols; Sulfates
  • Usable cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkylpropylene diamine, tripropylene triamine and dipropylene tetraamine, and ethoxylated amines, Ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or their mixtures); amine salts, such as amine acetate and diamine salts; quaternary Ammonium salts, such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides, such as alkyldimethylamine oxide and di-(2-hydroxyethyl)-alkylamine oxide.
  • amines such as N-alkylpropylene diamine, tripropylene triamine and dipropylene tetraamine, and ethoxylated amines,
  • Nonionic surfactants and anionic surfactants are also useful in the composition of the present invention.
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in multiple published references, including McCutcheon's Emulsifiers and Detergents published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co., North American and International Yearbooks Edition; Sisely and Wood's Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and AS Davidson and B. Milwidsky's Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987 .
  • composition of the present invention may also contain formulation auxiliaries and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered to function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives can control: pH (buffering agent), foaming during processing (defoaming agent such as polyorganosiloxane), sedimentation of active ingredients (suspending agent), viscosity (thixotropic thickener) ), microbial growth in the container (antimicrobial agent), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or adhesive), evaporation (anti-evaporation agent), and others Formulation attributes.
  • the film forming agent includes, for example, polyvinyl acetate, polyvinyl acetate copolymer, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer, and wax.
  • formulation auxiliaries and additives include McCutcheon's Volume 2: Functional Materials, North American and International Yearbook Edition published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and those listed in PCT Publication WO03/024222.
  • the compound of the present invention and any other active ingredients are usually incorporated into the composition of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid or dry diluent.
  • Solutions can be prepared by simply mixing the ingredients, including emulsifiable concentrates. If the solvent of the liquid composition used as emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient when diluted with water.
  • a media mill can be used to wet mill active ingredient slurries with a particle size of up to 2,000 ⁇ m to obtain particles with an average diameter of less than 3 ⁇ m.
  • the aqueous slurry can be prepared as a finished suspension concentrate (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible particles. Dry formulations generally require a dry milling step, which produces an average particle size in the range of 2 ⁇ m to 10 ⁇ m. Dusts and powders can be prepared by mixing, and usually by grinding (for example, with a hammer mill or a fluid energy mill). Granules and pellets can be prepared by spraying the active substance on a preformed granular carrier or by agglomeration techniques.
  • Granules can be prepared as described in US 4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as described in US 4,144,050, US 3,920,442 and DE.3,246,493.
  • Tablets can be prepared as described in US 5,180,587, US5,232,701 and US5,208,030.
  • the film can be prepared as proposed in GB2,095,558 and US3,299,566.
  • the herbicide of the present invention can be used by spraying plants, applying to soil, or applying to water surfaces.
  • the amount of the active ingredient is appropriately determined to meet the application purpose.
  • the content of the active ingredient is appropriately determined according to the purpose.
  • the amount of the compound of the present invention depends on the type of compound used, the target weed, the tendency of weed appearance, environmental conditions, and the type of herbicide.
  • the amount of the active ingredient is appropriately selected to be 1 g-50 kg, preferably 10 g-10 kg/ha.
  • the herbicide of the present invention is used in a liquid form, such as an emulsifiable concentrate, a wettable powder, or a flowable formulation, its amount is appropriately selected to be 0.1-50,000 ppm, preferably 10-10,000 ppm.
  • the present invention provides a method for controlling weeds in crops of useful plants, the method comprising applying to the weeds or to the locus of the weeds or to the useful plants or the locus of the useful plants.
  • the compound or composition of the invention is administered.
  • the present invention also provides a method for selectively controlling grasses and/or weeds in crops of useful plants, the method comprising applying to useful plants or their locus or cultivation areas a herbicidal effective amount of plants having the formula (I), Compounds represented by formula (Ia), formula (Ia-1), formula (Ia-2) or formula (Ib).
  • herbicide means a compound that controls or modifies the growth of plants.
  • effective amount means the amount of such a compound or a combination of such compounds capable of producing the effect of controlling or modifying plant growth.
  • the effects of control or modification include all deviations from natural development, such as killing, delaying, leaf burn, albinism, stunting, etc.
  • plant refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves and fruits.
  • location is intended to include soil, seeds, and seedlings, together with established vegetation and includes not only areas where weeds may have grown, but also areas where weeds have not yet appeared, and also includes information about useful plant crops Planting area.
  • the "planted area” includes land on which crop plants have grown, as well as land intended to grow such crop plants.
  • weed as used herein means any undesirable plant, and therefore includes not only important agronomic weeds as described below, but also volunteer crop plants.
  • the useful plant crops that may use the composition according to the present invention include but are not limited to perennial crops, such as citrus fruits, grape vines, nuts, oil palm, olives, pome fruits, stone fruits and rubber, and annual arable crops,
  • perennial crops such as citrus fruits, grape vines, nuts, oil palm, olives, pome fruits, stone fruits and rubber
  • annual arable crops For example, cereals (such as barley and wheat), cotton, rapeseed, corn, rice, soybeans, sugar beets, sugarcane, sunflowers, ornamental plants, switchgrass, turf and vegetables, especially cereals, corn and soybeans.
  • the grasses and weeds to be controlled can be monocot species, such as Bentgrass, Oats, Brachiaria, Brome, Tribulus, Cyperus, Digitaria, Barnyardgrass, Wild millet, Ryegrass, Amuletia, Panicum, Poa, Trichosanthes, Sagittaria, Scirpus, Setaria, Ceratophyllum, and Sorghum, or dicotyledon Species of the genus Amaranthus, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Laravine, Ipomoea, Kochia, Nasturtium, Polygonum, Lime, White mustard, Solanum Genus, Stellaria, Grannya, Viola and Xanthium.
  • the compounds of the present invention can show tolerance to important crops, including but not limited to alfalfa, barley, cotton, wheat, rape, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanut, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea and forests such as press trees and conifers (e.g. Loblolly pine), and turf species (such as Kentucky bluegrass, St. Augustine grass, Kentucky cow hair grass and bermudagrass).
  • important crops including but not limited to alfalfa, barley, cotton, wheat, rape, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanut, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas,
  • the compound represented by formula (I), formula (Ia), formula (Ia-1), formula (Ia-2) or formula (Ib) can also be combined with other active ingredients, such as Other herbicides and/or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators are used in combination. These mixtures, and the use of these mixtures to control the growth of weeds and/or undesirable plants form further aspects of the invention.
  • the mixture of the present invention also includes two or more different types such as those represented by formula (I), formula (Ia), formula (Ia-1), formula (Ia-2) or formula (Ib) Mixture of compounds.
  • the present invention also relates to a composition of the present invention, except for the composition shown in formula (I), formula (Ia), formula (Ia-1), formula (Ia-2) or formula (Ib)
  • the compound contains at least one additional herbicide.
  • the compounds of the present invention can be prepared by the methods described in the present invention, unless otherwise specified.
  • Proton NMR of the present invention the test conditions: at room temperature, Bruker (Bruker) 400MHz or a 600MHz NMR instrument, to CDC1 3, d 6 -DMSO, CD 3 OD or d 6 - acetone solutions (reported in ppm Unit), using TMS (0ppm) or chloroform (7.26ppm) as the reference standard.
  • s singlet
  • d doublet, doublet
  • t triplet, triplet
  • q quartet, quartet
  • m multiplet, Multiplet
  • br broadened, broad peak
  • dd doublet of doublets, doublet of doublets
  • dt doublet of triplets, doublet of triplets.
  • the coupling constant is expressed in Hertz (Hz).
  • the mass spectrometry analysis method used in the present invention is: Agilent 1260 HPLC; Agilent 6120 ESI.
  • Phase A Water (containing 0.1% formic acid); Phase B: Acetonitrile (containing 0.1% formic acid).
  • MS parameters ESI positive scan, collision induced ionization: 70V.
  • NBS N-bromosuccinimide
  • Compound (E) can be prepared by synthetic scheme 1, wherein R 1 , m and X have the meanings as described in the present invention.
  • 2,4-Dichloro-3-(bromomethyl)benzoic acid methyl ester and nitrogen-containing heterocyclic compound (M1) are reacted under alkaline conditions (such as sodium carbonate, potassium carbonate) at 0°C-35°C
  • alkaline conditions such as sodium carbonate, potassium carbonate
  • alkaline conditions such as sodium carbonate, potassium carbonate
  • alkaline conditions such as sodium carbonate, potassium carbonate
  • compound (A) is hydrolyzed under alkaline conditions (such as lithium hydroxide) to obtain compound (B);
  • compound (B) and acid chloride (such as oxalyl chloride) are halogenated at 0°C-100°C Reaction to obtain compound (C); compound (C) and cyclohexanedione undergo an esterification reaction at 0°C-35°C to obtain compound (D);
  • Compound (G) can be prepared by synthetic scheme two, wherein R 1 , m, X and R 3 have the meanings as described in the present invention.
  • Compound (C) and substituted pyrazole (F1) undergo esterification reaction at 0°C-35°C to obtain compound (F);
  • compound (F) is under the action of catalyst (such as trimethylsilyl cyanide, acetone cyanohydrin), The Fries rearrangement reaction occurs at 10°C-40°C to obtain the target compound (G).
  • catalyst such as trimethylsilyl cyanide, acetone cyanohydrin
  • Compound (H) can be prepared by synthesis scheme three, wherein R 1 , m, X and R 3 have the meanings as described in the present invention; wherein R 5 is hydrogen, C 1-6 alkyl or halogen; Y is halogen.
  • Compound (G) and compound (H1) undergo a nucleophilic substitution reaction at 25°C-50°C under alkaline conditions (such as Cs 2 CO 3 , K 2 CO 3, etc.) to obtain the target compound (H).
  • Compound (K) can be prepared by synthesis scheme four, wherein R 1 , m and X have the meanings as described in the present invention.
  • Compound (C) and bicyclo[3.2.1]octane-2,4-dione undergo an esterification reaction at 0°C-35°C to obtain compound (J);
  • compound (J) is in a catalyst (such as trimethylsilyl cyanide) Under the action of acetone cyanohydrin), Fries rearrangement reaction occurs at 10°C-40°C to obtain the target compound (K).
  • a catalyst such as trimethylsilyl cyanide
  • Step 8 Preparation of 3-oxocyclohex-1-en-1-yl 2,4-dichloro-3-(morpholinomethyl)benzoate
  • Step 3 2-((3-Cyclopropyl-4-(2,4-Dichloro-3-(morpholinomethyl)benzoyl)-1-methyl-1H-pyrazol-5-yl )Oxy)-1-phenylethanone preparation
  • Table 2 The activity of the compounds of the present invention on weeds at 300g/ha
  • Table 3 The activity of the compounds of the present invention at 150g/ha, 75g/ha, 37.5g/ha and 18.75g/ha on Abutilon and Portulaca
  • Table 5 The activity of the compounds of the present invention on Zinnia at 150g/ha, 75g/ha and 37.5g/ha
  • Table 7 show that the compound of the present invention is safe to corn at 75-300 g/ha, and still shows excellent safety to corn at high doses.
  • the compound of the present invention also shows certain safety to rice and wheat.
  • the phytotoxicity of Example 1 on wheat at 75-300g/ha is less than 15%; the phytotoxicity of Example 20 on wheat at 75-300g/ha
  • the damage to rice is below 10%, and the damage to rice is below 5%.
  • the compounds of the present invention have great effects on broad-leaved weeds (such as velvetleaf, amaranthus, zinnia, snakehead and purslane) and gramineous weeds (such as crabgrass, barnyard grass, ryegrass and setaria). Good control effect. It is safe for peanuts, corn, rice and wheat, and has a fast effect on weeds. The control effect on weeds is better than that of commercially available herbicides and benzoyl compounds with similar structures. It has good application prospects.
  • broad-leaved weeds such as velvetleaf, amaranthus, zinnia, snakehead and purslane
  • gramineous weeds such as crabgrass, barnyard grass, ryegrass and setaria.
  • Good control effect It is safe for peanuts, corn, rice and wheat, and has a fast effect on weeds.
  • the control effect on weeds is better than that of commercially available herbicides and benzoyl compounds with similar structures. It

Abstract

提供一种杂环基烷基取代的二氯苯甲酰类化合物及其应用。具体地，提供式(I)所示的化合物及其制备方法，含有这些化合物的组合物及其作为除草剂的用途。式(I)中Q为任选取代的氧代环己烯基或取代的吡唑基等；R 1为羟基、C 1-6烷基等；m为0、1、2等；X为-O-、-S(＝O) n-等；n为0、1或2。

Description

杂环基烷基取代的二氯苯甲酰类化合物及其应用 技术领域
本发明涉及农业领域，具体地，本发明提供一种新的杂环基烷基取代的二氯苯甲酰类化合物及其制备方法；含有这些化合物的组合物及其在农业中的应用。
背景技术
取代的苯甲酰类化合物是一类具有优良生物活性的化合物，其除草活性在例如CN105766944、CN102464630、WO2004024687、CN103025718中均有描述。然而，从以上引用的文献中所知的活性成分在使用中具有的不利之处在于，例如(a)对杂草植物没有或者仅具有不足够的除草作用、(b)待防治的杂草植物谱过窄或者(c)在有用植物作物中的选择性过低。
因此，苯甲酰类化合物仍需要进一步开发和改进，以获得一系列具有更优除草活性和/或选择性的苯甲酰类化合物。
发明内容
本发明提供一种新的杂环基烷基取代的二氯苯甲酰类化合物，具有优良的除草作用，宽的杂草防治谱以及在农作物与杂草之间的优良选择性。
一方面，本发明提供式(I)所示的化合物或式(I)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
Figure PCTCN2020105150-appb-000001
其中：
R 1为羟基、氰基、氨基、硝基、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、卤代C 1-6烷氧基或C 3-8环烷基；
m为0、1、2、3、4、5、6、7、8、9或10；
X为-CH 2-、-O-、-S(＝O) n-或-NH-；
n为0、1或2；
Q为以下子结构式：
Figure PCTCN2020105150-appb-000002
R 2和R 2a各自独立地为氢或C 1-6烷基；
R 3为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基或C 3-8环烷基；
R 4为氢或-CH 2-CO-C 6-10芳基；其中所述-CH 2-CO-C 6-10芳基任选地被1、2或3个选自卤素或C 1-6烷基的取代基所取代。
其中一些实施方案中，R 1为羟基、氰基、氨基、硝基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、卤代C 1-4烷氧基或C 3-6环烷基。
另外一些实施方案中，R 1为羟基、氰基、氨基、硝基、甲基、乙基、正丙基、异丙基、-CHF 2、-CF 3、-CH 2CHF 2、-CH 2CF 3、环丙基、环丁基、环戊基或环己基。
其中一些实施方案中，R 2和R 2a各自独立地为氢或C 1-4烷基。
另外一些实施方案中，R 2和R 2a各自独立地为氢或C 1-3烷基。
另外一些实施方案中，R 2和R 2a各自独立地为氢或甲基。
其中一些实施方案中，R 3为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基或C 3-6环烷基。
另外一些实施方案中，R 3为氢、C 1-3烷基、C 2-3烯基、C 2-3炔基或C 3-6环烷基。
另外一些实施方案中，R 3为氢、甲基、乙基、正丙基、异丙基、环丙基、环丁基、环戊基或环己基。
其中一些实施方案中，R 4为氢或-CH 2-CO-苯基；其中所述-CH 2-CO-苯基任选地被1、2或3个选自卤素或C 1-4烷基的取代基所取代。
另外一些实施方案中，R 4为氢或-CH 2-CO-苯基；其中所述-CH 2-CO-苯基任选地被1、2或3个选自氯或甲基的取代基所取代。
其中一些实施方案中，本发明提供一种化合物，其为如式(Ia)所示的化合物或式(Ia)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
Figure PCTCN2020105150-appb-000003
其中：
Q具有如本发明所述的含义；
R 1a和R 1b各自独立地为氢或C 1-3烷基。
其中一些实施方案中，本发明提供一种化合物，其为如式(Ib)所示的化合物或式(Ib)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
Figure PCTCN2020105150-appb-000004
其中：Q和n具有如本发明所述的含义。
另外一些实施方案中，Q为以下子结构式：
Figure PCTCN2020105150-appb-000005
另外一些实施方案中，R 1a和R 1b各自独立地为氢或甲基。
另外一些实施方案中，n为0、1或2。
其中一些实施方案中，本发明提供一种化合物，其为如式(Ia-1)所示的化合物或式(Ia-1)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
Figure PCTCN2020105150-appb-000006
其中：
R 1a和R 1b各自独立地为氢或C 1-6烷基；
R 2和R 2a各自独立地为氢或C 1-6烷基。
另外一些实施方案中，R 1a和R 1b各自独立地为氢或C 1-3烷基；R 2和R 2a各自独立地为氢或C 1-3烷基。
另外一些实施方案中，R 1a和R 1b各自独立地为氢或甲基；R 2和R 2a各自独立地为氢或甲基。
其中一些实施方案中，本发明提供一种化合物，其为如式(Ia-2)所示的化合物或式(Ia-2)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
Figure PCTCN2020105150-appb-000007
其中：
R 1a和R 1b各自独立地为氢或C 1-6烷基。
另外一些实施方案中，R 1a和R 1b各自独立地为氢或C 1-3烷基。
另外一些实施方案中，R 1a和R 1b各自独立地为氢或甲基。
其中一些实施方案中，本发明提供一种化合物，其为具有下列之一结构的化合物或具有下列之一结构化合物的立体异构体、互变异构体、氮氧化物或其盐：
Figure PCTCN2020105150-appb-000008
Figure PCTCN2020105150-appb-000009
Figure PCTCN2020105150-appb-000010
Figure PCTCN2020105150-appb-000011
其中一些实施方案中，本发明提供一种化合物，最优选地化合物的具体结构为：
Figure PCTCN2020105150-appb-000012
Figure PCTCN2020105150-appb-000013
或所述结构的立体异构体、互变异构体、氮氧化物或其盐。
生物活性测试表明本发明式(I)所示化合物具有很好的除草活性，与苯环4-位取代基为甲基磺酰基的化合物相比，除草活性更优异。以防治马齿苋为例，根据CN103025718A中的室内除草活性记载，对苗后杂草进行喷雾处理，实施例1(化合物I-1-1)在60g/ha和90g/ha对马齿苋的防效均为0(表9)；而本发明化合物在37.5g/ha和75g/ha对马齿苋的防效至少在82％以上。
CN103025718A中的实施例1(化合物I-1-1)，其化合物结构如下：
Figure PCTCN2020105150-appb-000014
本发明化合物可以有效地控制苘麻、马齿苋、稗草或百日草等杂草，在低剂量下就可以获得很好的效果。本发明化合物对花生、玉米、水稻和小麦具有很好的安全性，优选用于控制花生田、玉米田、水稻田和小麦田的杂草。
另一方面，本发明提供一种组合物，包含本发明所述的化合物。
其中一些实施方案中，本发明所述的组合物进一步任选地包含至少一种附加组分。
具体地，所述附加组分为表面活性剂、固体稀释剂、液体稀释剂、缓冲剂、消泡剂、增稠剂、防冻剂、抗微生物剂和/或成膜剂。
另一方面，本发明提供本发明所述化合物或包含本发明所述化合物的组合物在农业中的应用。
其中一些实施方案中，本发明提供本发明所述化合物或包含本发明所述化合物的组合物作为除草剂在有用植物中防治杂草的应用。
另外一些实施方案中，本发明提供本发明所述化合物或包含本发明所述化合物的组合物在防治禾本科杂草中的应用。
另外一些实施方案中，本发明提供本发明所述化合物或包含本发明所述化合物的组合物在防治阔叶科杂草中的应用。
另外一些实施方案中，本发明提供本发明所述化合物或包含本发明所述化合物的组合物 在防治苘麻、马齿苋、稗草和/或百日草中的应用。
另一方面，本发明提供本发明所述化合物或包含本发明所述化合物的组合物用于防治不想要的植物的用途。
另一方面，本发明提供本发明所述化合物或包含本发明所述化合物的组合物作为除草剂的用途。
另一方面，本发明提供本发明所述化合物或包含本发明所述化合物的组合物作为苗前除草剂的用途。
另一方面，本发明提供本发明所述化合物或包含本发明所述化合物的组合物作为苗后除草剂的用途。
另一方面，本发明提供防治不想要的植物的方法，其特征在于将有效量的本发明所述化合物施用于植物、植物种子、其中或其上生长植物的土壤，或栽培区域。
还一方面，本发明提供一种控制有用植物中杂草生长的方法，其包含向杂草所在地施用有效量的本发明所述的化合物或包含本发明所述化合物的组合物。
具体地，所述杂草为苘麻、马齿苋、稗草或百日草的一种或多种。
具体地，所述有用植物为花生、玉米、水稻或小麦中的至少一种。
本发明提供的化合物，是一种对杂草更有效、成本更低、毒性更小、对作物安全的新型化合物。
式(I)、式(Ia)、式(Ia-1)、式(Ia-2)或式(Ib)所示的化合物中，由于构型不同可以形成立体异构体(分别以R和S来表示不同的构型)，本发明包括R型异构体和S型异构体及其任何比例的混合物；由于酮/烯醇互变可以存在多种互变异构体，本发明包括所有互变异构体及其任何比例的混合物。
同位素富集的化合物具有本发明给出的通式描绘的结构，除了一个或多个原子被具有所选择原子量或质量数的原子替换。可引入本发明化合物中的示例性同位素包括氢、碳、氮、氧、磷、硫、氟和氯的同位素，如 2H， 3H， 11C， 13C， 14C， 15N， 17O， 18O， 18F， 31P， 32P， 35S， 36Cl和 125I。
前面所述内容只概述了本发明的某些方面，但并不限于这些方面及其他方面的内容将在下面作更加具体完整的描述。
本发明的详细说明
定义和一般术语
现在详细描述本发明的某些实施方案，其实例由随附的结构式和化学式说明。本发明意图涵盖所有的替代、修改和等同技术方案，它们均包括在如权利要求定义的本发明范围内。 本领域技术人员应认识到，许多与本发明所述类似或等同的方法和材料能够用于实践本发明。本发明绝不限于本发明所述的方法和材料。在所结合的文献、专利和类似材料的一篇或多篇与本申请不同或相矛盾的情况下(包括但不限于所定义的术语、术语应用、所描述的技术，等等)，以本申请为准。
应进一步认识到，本发明的某些特征，为清楚可见，在多个独立的实施方案中进行了描述，但也可以在单个实施例中以组合形式提供。反之，本发明的各种特征，为简洁起见，在单个实施方案中进行了描述，但也可以单独或以任意适合的子组合提供。
除非另外说明，本发明所使用的所有科技术语具有与本发明所属领域技术人员的通常理解相同的含义。本发明涉及的所有专利和公开出版物通过引用方式整体并入本发明。
除非另外说明，应当应用本发明所使用的下列定义。出于本发明的目的，化学元素与元素周期表CAS版，和《化学和物理手册》，第75版，1994一致。此外，有机化学一般原理可参考"Organic Chemistry",Thomas Sorrell,University Science Books,Sausalito:1999,和"March's Advanced Organic Chemistry"by Michael B.Smith and Jerry March,John Wiley&Sons,New York:2007中的描述，其全部内容通过引用并入本发明。
除非另有说明或者上下文中有明显的冲突，本文所使用的冠词“一”、“一个(种)”和“所述”旨在包括“至少一个”或“一个或多个”。因此，本文所使用的这些冠词是指一个或多于一个(即至少一个)宾语的冠词。例如，“一组分”指一个或多个组分，即可能有多于一个的组分被考虑在所述实施方案的实施方式中采用或使用。
术语“包含”为开放式表达，即包括本发明所指明的内容，但并不排除其他方面的内容。
“立体异构体”是指具有相同化学构造，但原子或基团在空间上排列方式不同的化合物。立体异构体包括对映异构体、非对映异构体、构象异构体(旋转异构体)、几何异构体(顺/反)异构体、阻转异构体，等等。
“对映异构体”是指一个化合物的两个不能重叠但互成镜像关系的异构体。
“非对映异构体”是指有两个或多个手性中性并且其分子不互为镜像的立体异构体。非对映异构体具有不同的物理性质，如熔点、沸点、光谱性质和反应性。非对映异构体混合物可通过高分辨分析操作如电泳和色谱，例如HPLC来分离。
本发明所使用的立体化学定义和规则一般遵循S.P.Parker,Ed.,McGraw-Hill Dictionary of Chemical Terms(1984)McGraw-Hill Book Company,New York；and Eliel,E.and Wilen,S.,“Stereochemistry of Organic Compounds”,John Wiley&Sons,Inc.,New York,1994中所描述的立体化学定义和规则。
许多有机化合物以光学活性形式存在，即它们具有使平面偏振光的平面发生旋转的能力。 在描述光学活性化合物时，使用前缀D和L或R和S来表示分子关于其一个或多个手性中心的绝对构型。前缀d和l或(+)和(-)是用于指定化合物所致平面偏振光旋转的符号，其中(-)或l表示化合物是左旋的。前缀为(+)或d的化合物是右旋的。一种具体的立体异构体是对映异构体，这种异构体的混合物称作对映异构体混合物。对映异构体的50:50混合物称为外消旋混合物或外消旋体，当在化学反应或过程中没有立体选择性或立体特异性时，可出现这种情况。
术语“互变异构体”或“互变异构形式”是指具有不同能量的可通过低能垒(low energy barrier)互相转化的结构异构体。若互变异构是可能的(如在溶液中)，则可以达到互变异构体的化学平衡。例如，质子互变异构体(protontautomer)(也称为质子转移互变异构体(prototropic tautomer))包括通过质子迁移来进行的互相转化，如酮-烯醇异构化和亚胺-烯胺异构化。价键互变异构体(valence tautomer)包括通过一些成键电子的重组来进行的互相转化。酮-烯醇互变异构的具体实例是戊烷-2,4-二酮、己烷-1,3-二酮和4-羟基戊-3-烯-2-酮互变异构体的互变。互变异构的另一个实例是酚-酮互变异构。酚-酮互变异构的一个具体实例是吡啶-4-醇和吡啶-4(1H)-酮互变异构体的互变。除非另外指出，本发明化合物的所有互变异构体形式都在本发明的范围之内。
本发明中，取决于外在条件(诸如溶剂、pH等)，存在酮-烯醇的互变：
Figure PCTCN2020105150-appb-000015
本发明的“氮氧化物”是指当化合物含几个胺官能团时，可将1个或大于1个的氮原子氧化形成N-氧化物。N-氧化物的特殊实例是叔胺的N-氧化物或含氮杂环氮原子的N-氧化物。可用氧化剂例如过氧化氢或过酸(例如过氧羧酸)处理相应的胺形成N-氧化物(参见Advanced Organic Chemistry,Wiley Interscience,第4版,Jerry March,pages)。尤其是，N-氧化物可用L.W.Deady的方法制备(Syn.Comm.1977,7,509-514)，其中例如在惰性溶剂例如二氯甲烷中，使胺化合物与间-氯过氧苯甲酸(MCPBA)反应。
像本发明所描述的，本发明的化合物可以任选地被一个或多个取代基所取代，如上面的通式化合物，或者像实施例里面特殊的例子，子类，和本发明所包含的一类化合物。应了解“任选取代的”这个术语与“取代或非取代的”这个术语可以交换使用。一般而言，术语“取代的”表示所给结构中的一个或多个氢原子被具体取代基所取代。除非其他方面表明，一个任选的取代基团可以在基团各个可取代的位置进行取代。当所给出的结构式中不只一个位置 能被选自具体基团的一个或多个取代基所取代，那么取代基可以相同或不同地在各个位置取代。其中所述的取代基可以是，但并不限于，氘，氟，氯，溴，碘，氰基，羟基，硝基，氨基，羧基，烷基，烷氧基，烷氧基烷基，烷氧基烷氧基，烷氧基烷氨基，芳氧基，杂芳基氧基，杂环基氧基，芳基烷氧基，杂芳基烷氧基，杂环基烷氧基，环烷基烷氧基，烷氨基，烷氨基烷基，烷氨基烷氨基，环烷基氨基，环烷基烷氨基，烷硫基，卤代烷基，卤代烷氧基，羟基取代的烷基，羟基取代的烷氨基，氰基取代的烷基，氰基取代的烷氧基，氰基取代的烷氨基，氨基取代的烷基，烷基酰基，杂烷基，环烷基，环烯基，环烷基烷基，杂环基，杂环基烷基，杂环基酰基，芳基，芳基烷基，芳氨基，杂芳基，杂芳基烷基，杂芳基氨基，酰胺基，磺酰基，氨基磺酰基等等。
另外，需要说明的是，除非以其他方式明确指出，在本发明中所采用的描述方式“各…独立地为”与“…各自独立地为”和“…独立地为”可以互换，均应做广义理解，其既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。
在本说明书的各部分，本发明公开化合物的取代基按照基团种类或范围公开。特别指出，本发明包括这些基团种类和范围的各个成员的每一个独立的次级组合。例如，术语“C 1-C 6烷基”或“C 1-6烷基”特别指独立公开的甲基、乙基、C 3烷基、C 4烷基、C 5烷基和C 6烷基。
本发明使用的术语“烷基”或“烷基基团”，表示含有1至20个碳原子，饱和的直链或支链一价烃基基团；其中所述烷基基团任选地被一个或多个本发明描述的取代基所取代。除非另外详细说明，烷基基团含有1-20个碳原子。在一实施方案中，烷基基团含有1-12个碳原子；在一实施方案中，烷基基团含有1-10个碳原子；在一实施方案中，烷基基团含有1-8个碳原子；在另一实施方案中，烷基基团含有1-6个碳原子；在又一实施方案中，烷基基团含有1-4个碳原子；还在一实施方案中，烷基基团含有1-3个碳原子。
烷基基团的实例包含，但并不限于，甲基(Me、-CH 3)，乙基(Et、-CH 2CH 3)，正丙基(n-Pr、-CH 2CH 2CH 3)，异丙基(i-Pr、-CH(CH 3) 2)，正丁基(n-Bu、-CH 2CH 2CH 2CH 3)，异丁基(i-Bu、-CH 2CH(CH 3) 2)，仲丁基(s-Bu、-CH(CH 3)CH 2CH 3)，叔丁基(t-Bu、-C(CH 3) 3)，正戊基(-CH 2CH 2CH 2CH 2CH 3)，2-戊基(-CH(CH 3)CH 2CH 2CH 3)，3-戊基(-CH(CH 2CH 3) 2)，2-甲基-2-丁基(-C(CH 3) 2CH 2CH 3)，3-甲基-2-丁基(-CH(CH 3)CH(CH 3) 2)，3-甲基-1-丁基(-CH 2CH 2CH(CH 3) 2)，2-甲基-1-丁基(-CH 2CH(CH 3)CH 2CH 3)，正己基(-CH 2CH 2CH 2CH 2CH 2CH 3)，2-己基(-CH(CH 3)CH 2CH 2CH 2CH 3)，3-己基(-CH(CH 2CH 3)(CH 2CH 2CH 3))，2-甲基-2-戊基(-C(CH 3) 2CH 2CH 2CH 3)，3-甲基-2-戊基(-CH(CH 3)CH(CH 3)CH 2CH 3)，4-甲基-2-戊基(-CH(CH 3)CH 2CH(CH 3) 2)，3-甲基-3-戊基 (-C(CH 3)(CH 2CH 3) 2)，2-甲基-3-戊基(-CH(CH 2CH 3)CH(CH 3) 2)，2,3-二甲基-2-丁基(-C(CH 3) 2CH(CH 3) 2)，3,3-二甲基-2-丁基(-CH(CH 3)C(CH 3) 3)，正庚基，正辛基，等等。
术语“烯基”表示含有2-12个碳原子的直链或支链一价烃基，其中至少有一个不饱和位点，即有一个碳-碳sp 2双键，其中，所述烯基基团可以任选地被一个或多个本发明所描述的取代基所取代，其包括“cis”和“tans”的定位，或者“E”和“Z”的定位。在一实施方案中，烯基基团包含2-10个碳原子；在一实施方案中，烯基基团包含2-8个碳原子；在另一实施方案中，烯基基团包含2-6个碳原子；在又一实施方案中，烯基基团包含2-4个碳原子。烯基基团的实例包括，但并不限于，乙烯基(-CH＝CH 2)，烯丙基(-CH 2CH＝CH 2)，丙烯基(CH 3-CH＝CH-)，-CH 2CH 2CH＝CH 2、-CH 2CH＝CHCH 3、-CH 2CH 2CH 2CH＝CH 2、-CH 2CH 2CH＝CHCH 3、-CH 2CH 2CH 2CH＝CHCH 3等等。
术语“炔基”表示含有2-12个碳原子的直链或支链一价烃基，其中至少有一个碳-碳sp三键，其中，所述炔基基团可以任选地被一个或多个本发明所描述的取代基所取代。在一实施方案中，炔基基团包含2-10个碳原子；在一实施方案中，炔基基团包含2-8个碳原子；在另一实施方案中，炔基基团包含2-6个碳原子；在又一实施方案中，炔基基团包含2-4个碳原子。炔基基团的实例包括，但并不限于，-C≡CH、-C≡CCH 3、-CH 2-C≡CH、-CH 2-C≡CCH 3、-CH 2CH 2-C≡CH、-CH 2-C≡CCH 2CH 3、-CH 2CH 2-C≡CCH 3等等。
术语“烷氧基”表示烷基基团通过氧原子与分子其余部分相连，其中烷基基团具有如本发明所述的含义。除非另外详细说明，所述烷氧基基团含有1-12个碳原子。在一实施方案中，烷氧基基团含有1-10个碳原子；在一实施方案中，烷氧基基团含有1-8个碳原子；在一实施方案中，烷氧基基团含有1-6个碳原子；在另一实施方案中，烷氧基基团含有1-4个碳原子；在又一实施方案中，烷氧基基团含有1-3个碳原子。所述烷氧基基团可以任选地被一个或多个本发明描述的取代基所取代。
烷氧基基团的实例包括，但并不限于，甲氧基(MeO、-OCH 3)，乙氧基(EtO、-OCH 2CH 3)，1-丙氧基(n-PrO、n-丙氧基、-OCH 2CH 2CH 3)，2-丙氧基(i-PrO、i-丙氧基、-OCH(CH 3) 2)，1-丁氧基(n-BuO、n-丁氧基、-OCH 2CH 2CH 2CH 3)，2-甲基-l-丙氧基(i-BuO、i-丁氧基、-OCH 2CH(CH 3) 2)，2-丁氧基(s-BuO、s-丁氧基、-OCH(CH 3)CH 2CH 3)，2-甲基-2-丙氧基(t-BuO、t-丁氧基、-OC(CH 3) 3)，1-戊氧基(n-戊氧基、-OCH 2CH 2CH 2CH 2CH 3)，2-戊氧基(-OCH(CH 3)CH 2CH 2CH 3)，3-戊氧基(-OCH(CH 2CH 3) 2)，2-甲基-2-丁氧基(-OC(CH 3) 2CH 2CH 3)，3-甲基-2-丁氧基(-OCH(CH 3)CH(CH 3) 2)，3-甲基-l-丁氧基(-OCH 2CH 2CH(CH 3) 2)，2-甲基-l-丁氧基(-OCH 2CH(CH 3)CH 2CH 3)，等等。
术语“卤素”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。
术语“卤代烷基”表示烷基基团被一个或多个卤素原子所取代。卤代烷基的实例包括，但并不限于，-CH 2F，-CHF 2，-CH 2Cl，-CH 2Br，-CF 3，-CH 2CF 3，-CH 2CH 2F，-CH 2CH 2Cl，-CH 2CH 2Br，-CH 2CHF 2，-CH 2CH 2CF 3，-CH 2CH 2CH 2F，-CH 2CH 2CH 2Cl，-CH 2CH 2CH 2Br，-CHFCH 2CH 3，-CHClCH 2CH 3，等等。
术语“卤代烷氧基”表示烷氧基基团被一个或多个卤素原子所取代。卤代烷氧基的实例包括，但并不限于，-OCH 2F，-OCHF 2，-OCH 2Cl，-OCH 2Br，-OCF 3，-OCH 2CF 3，-OCH 2CH 2F，-OCH 2CH 2Cl，-OCH 2CH 2Br，-OCH 2CHF 2，-OCH 2CH 2CF 3，-OCH 2CH 2CH 2F，-OCH 2CH 2CH 2Cl，-OCH 2CH 2CH 2Br，-OCHFCH 2CH 3，-OCHClCH 2CH 3，等等。
术语“卤代烯基”表示烯基基团被一个或多个卤素原子所取代。
术语“卤代炔基”表示炔基基团被一个或多个卤素原子所取代。
术语“环烷基”表示含有3-12个碳原子的，单价或多价的饱和单环、双环或三环体系。在一实施方案中，环烷基包含3-12个碳原子；在一实施方案中，环烷基包含3-10个碳原子；在另一实施方案中，环烷基包含3-8个碳原子；在又一实施方案中，环烷基包含3-6个碳原子。所述环烷基基团任选地被一个或多个本发明所描述的取代基所取代。这样的实例包括，但并不限于，环丙基，环丁基，环戊基，环己基，环庚基，环辛基，环壬基，环癸基，环十一烷基，环十二烷基，金刚烷基，等等。
在本发明中所使用的术语“不饱和的”表示基团中含有一个或多个不饱和度。
术语“杂原子”是指O、S、N、P和Si，包括N、S和P任何氧化态的形式；伯、仲、叔胺和季铵盐的形式；或者杂环中氮原子上的氢被取代的形式，例如，N(像3,4-二氢-2H-吡咯基中的N)，NH(像吡咯烷基中的NH)或NR(像N-取代的吡咯烷基中的NR)。
术语“芳基”表示含有6-14个环原子，或6-12个环原子，或6-10个环原子的单环、双环和三环的碳环体系，其中，至少一个环体系是芳香族的，其中每一个环体系包含3-7个原子组成的环，且有一个或多个附着点与分子的其余部分相连。术语“芳基”可以和术语“芳香环”交换使用。芳基基团的实例可以包括苯基，茚基，萘基和蒽基。所述芳基基团任选地被一个或多个本发明所描述的取代基所取代。
当本发明的化合物包含一个酸部分时，本发明所述化合物的盐，包括衍生自碱金属或碱土金属的那些以及衍生自氨和胺的那些。优选的阳离子包括钠、钾、镁以及具有化学式N +(R 19R 20R 21R 22)的铵阳离子，其中R 19、R 20、R 21和R 22独立地选自氢、C 1-C 6烷基和C 1-C 6羟基烷基。具有式(I)、式(Ia)或式(Ib)所示的化合物的盐可以通过用金属氢氧化物(例如氢氧化钠)或胺(例如氨、三甲胺、二乙醇胺、2-甲硫基丙胺、双烯丙基胺、2-丁氧基乙胺、吗啉、环十二胺或苄胺)对具有式(I)、式(Ia)或式(Ib)所示的化合物进行处理来制备。
当本发明的化合物包含一个碱部分时，可接受的盐可以由有机酸和无机酸形成，例如乙酸、丙酸、乳酸、柠檬酸、酒石酸、琥珀酸、富马酸、马来酸、丙二酸、扁桃酸、苹果酸、邻苯二甲酸、盐酸、氢溴酸、磷酸、硝酸、硫酸、甲磺酸、萘磺酸、苯磺酸、甲苯磺酸、樟脑磺酸以及类似地已知可接受的酸。
本发明化合物的组合物和制剂
本发明的化合物一般可用作组合物或制剂中的除草剂活性成分，所述组合物或制剂具有至少一种附加组分，所述附加组分选自表面活性剂、固体稀释剂、液体稀释剂、缓冲剂、消泡剂、增稠剂、防冻剂、抗微生物剂、成膜剂等等，满足农药使用要求的组分都属于本发明的范围。选择所述制剂或组合物成分，以与所述活性成分的物理特性、施用方式和环境因素(如土壤类型、湿度和温度)相一致。
有用的制剂包括液体组合物和固体组合物。液体组合物包括溶液(包括乳油)、悬浮液、乳液(包括微乳液和/或悬乳液)等，它们可以任选地被稠化成凝胶。水性液体组合物的一般类型为可溶性浓缩物、悬浮液浓缩物、胶囊悬浮液、浓缩乳液、微乳液和悬乳液。非水性液体组合物的一般类型为乳油、可微乳化的浓缩物、可分散浓缩物和油分散体。
固体组合物的一般类型为粉剂、粉末、颗粒、粒料、球粒、锭剂、片剂、填充薄膜(包括种子包衣)等，它们可以是水分散性的(“可润湿的”)或水溶性的。由成膜溶液或可流动的悬浮液形成的膜和包衣尤其可用于种子处理。活性成分可被(微)胶囊包封，并且进一步形成悬浮液或固体制剂；或者可将整个活性成分制剂胶囊包封(或“包覆”)。胶囊包封可以控制或延迟活性成分的释放。可乳化的颗粒结合了乳油制剂和干颗粒制剂两者的优点。高浓度组合物主要用作其它制剂的中间体。
可喷雾的制剂通常在喷雾之前分散在合适的介质中。将此类液体制剂和固体制剂配制成易于在喷雾介质(通常是水)中稀释的制剂。喷雾体积可以在每公顷约一升至几千升的范围内，但更典型地在每公顷约十升至几百升的范围内。可喷雾的制剂可在水槽中与水或另一种合适的介质混合，用于通过空气或地面施用来处理叶子，或者施用到植物的生长介质中。液体和干制剂可以直接定量加入到滴灌***中，或者在种植期间定量加入到垄沟中。
所述制剂通常将包含有效量的活性成分、稀释剂和表面活性剂，总和为按重量计100％。
固体稀释剂包括例如粘土例如膨润土、蒙脱石、绿坡缕石和高岭土、石膏、纤维素、二氧化钛、氧化锌、淀粉、糊精、糖(例如乳糖、蔗糖)、硅石、滑石、云母、硅藻土、尿素、碳酸钙、碳酸钠和碳酸氢钠以及硫酸钠。典型的固体稀释剂描述于Watkins等人的Handbook of Insecticide Dust Diluents and Carriers，第2版，Dorland Books，Caldwell，New Jersey中。
液体稀释剂包括例如水、N,N-二甲基烷酰胺(例如N,N-二甲基甲酰胺)、柠檬烯、二甲基亚砜、N-烷基吡咯烷酮(例如N-甲基吡咯烷酮)、乙二醇、三甘醇、丙二醇、双丙二醇、聚丙二醇、碳酸亚丙酯、碳酸亚丁酯、石蜡(例如白矿物油、正链烷烃、异链烷烃)、烷基苯、烷基萘、甘油、三乙酸甘油酯、山梨醇、芳烃、脱芳构化脂族化合物、烷基苯、烷基萘、酮(如环己酮、2-庚酮、异佛尔酮和4-羟基-4-甲基-2-戊酮)、乙酸酯(如乙酸异戊酯、乙酸己酯、乙酸庚酯、乙酸辛酯、乙酸壬酯、乙酸十三烷基酯和乙酸异冰片酯)、其它酯(如烷基化乳酸酯、二元酯和γ-丁内酯)、并且可以是直链的、支链的、饱和的或不饱和的醇(如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己醇、2-乙基己醇、正辛醇、癸醇、异癸醇、异十八醇、鲸蜡醇、月桂醇、十三烷醇、油醇、环己醇、四氢糠醇、双丙酮醇和苄醇)。液体稀释剂还包括饱和的和不饱和的脂肪酸(通常为C 6-C 22)的甘油酯，如植物种子和果实的油(例如橄榄油、蓖麻油、亚麻籽油、芝麻油、玉米油、花生油、葵花籽油、葡萄籽油、红花油、棉籽油、豆油、油菜籽油、椰子油和棕榈仁油)、动物源脂肪(例如牛脂、猪脂、猪油、鳕鱼肝油、鱼油)，以及它们的混合物。液体稀释剂还包括烷基化(例如甲基化、乙基化、丁基化)的脂肪酸，其中脂肪酸可以通过源自植物和动物的甘油酯的水解获得，并且可通过蒸馏进行纯化。典型的液体稀释剂描述于Marsden的Solvents Guide，第2版，Interscience，New York，1950中。
本发明的固体组合物和液体组合物通常包含一种或多种表面活性剂。当加进液体中时，表面活性剂(也称为“具有表面活性的试剂”)通常改变，最通常降低液体的表面张力。根据表面活性剂分子中的亲水基团和亲脂基团的性质，表面活性剂可用作润湿剂、分散剂、乳化剂或消泡剂。
表面活性剂可分为非离子表面活性剂、阴离子表面活性剂或阳离子表面活性剂。可用作本发明的组合物的非离子表面活性剂包括但不限于：醇烷氧基化物，如基于天然醇和合成醇(其为支链的或直链的)并且由醇和环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备的醇烷氧基化物；胺乙氧基化、链烷醇酰胺和乙氧基化的链烷醇酰胺；烷氧基化的甘油三酯，如乙氧基化的大豆、蓖麻和油菜籽油；烷基苯酚烷氧基化物，如辛基苯酚乙氧基化、壬基苯酚乙氧基化、二壬基苯酚乙氧基化物和十二烷基苯酚乙氧基化物(由苯酚和环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备)；由环氧乙烷或环氧丙烷和反向嵌段聚合物制备的嵌段聚合物，其中所述末端嵌段由环氧丙烷制备；乙氧基化的脂肪酸；乙氧基化的脂肪族酯和油；乙氧基化的甲基酯；乙氧基化的三苯乙烯基苯酚(包括由环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备的那些)；脂肪酸酯、甘油酯、羊毛脂基的衍生物、多乙氧基化的酯，如多乙氧基化的脱水山梨糖醇脂肪酸酯、多乙氧基化的山梨醇脂肪酸酯和多乙氧基化甘油脂肪酸 酯；其它脱水山梨糖醇衍生物，如脱水山梨糖醇酯；聚合表面活性剂如无规共聚物、嵌段共聚物、醇酸PEG(聚乙二醇)树脂、接枝或梳妆聚合物和星型聚合物；聚乙二醇(PEG)；聚乙二醇脂肪酸酯；硅酮基的表面活性剂；以及糖衍生物，如蔗糖酯、烷基聚葡萄糖苷和烷基多糖。
可用的阴离子表面活性剂包括但不限于：烷基芳基磺酸和它们的盐；羧化的醇或烷基苯酚乙氧基化物；二苯基磺酸酯衍生物；木质素和木质素衍生物，如木质素磺酸盐；马来酸或琥珀酸或它们的酸酐；烯烃磺酸酯；磷酸酯，诸如醇烷氧基化物的磷酸酯、烷基酚烷氧基化物的磷酸酯和苯乙烯基苯酚乙氧基化物的磷酸酯；蛋白质基的表面活性剂；肌氨酸衍生物；苯乙烯基苯酚醚硫酸盐；油和脂肪酸的硫酸盐和磺酸盐；乙氧基化烷基酚的硫酸盐和磺酸盐；醇的硫酸盐；乙氧基化醇的硫酸盐；胺和酰胺的磺酸盐，如N,N-烷基牛磺酸盐；苯、异丙基苯、甲苯、二甲苯以及十二烷基苯和十三烷基苯的磺酸盐；缩聚萘的磺酸盐；萘和烷基萘的磺酸盐；石油馏分的磺酸盐；磺基琥珀酰胺酸盐；以及磺基琥珀酸盐和它们的衍生物，如二烷基磺基琥珀酸盐。
可用的阳离子表面活性剂包括但不限于：酰胺和乙氧基化酰胺；胺，如N-烷基丙二胺、三亚丙基三胺和二亚丙基四胺，以及乙氧基化胺、乙氧基化二胺和丙氧基化胺(由胺和环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备)；胺盐，如胺乙酸盐和二胺盐；季铵盐，如季盐、乙氧基化季盐和二季盐；以及胺氧化物，如烷基二甲基胺氧化物和二-(2-羟基乙基)-烷基胺氧化物。
还可用于本发明的组合物的是非离子表面活性剂和阴离子表面活性剂的混合物，或非离子表面活性剂和阳离子表面活性剂的混合物。非离子、阴离子和阳离子表面活性剂以及它们被推荐的用途公开于多个已公布的参考文献中，包括由McCutcheon’s Division，The Manufacturing Confectioner Publishing Co.出版的McCutcheon′s Emulsifiers and Detergents，北美和国际年鉴版；Sisely和Wood的Encyclopedia of Surface Active Agents，Chemical Publ.Co.，Inc.，New York，1964；以及A.S.Davidson和B.Milwidsky的Synthetic Detergents，第七版，John Wiley and Sons，New York，1987。
本发明的组合物还可包含本领域技术人员已知为辅助制剂的制剂助剂和添加剂(其中一些也可被认为是起到固体稀释剂、液体稀释剂或表面活性剂作用的)。此类制剂助剂和添加剂可控制：pH(缓冲剂)、加工过程中的起泡(消泡剂如聚有机硅氧烷)、活性成分的沉降(悬浮剂)、粘度(触变增稠剂)、容器内的微生物生长(抗微生物剂)、产品冷冻(防冻剂)、颜色(染料/颜料分散体)、洗脱(成膜剂或粘合剂)、蒸发(防蒸发剂)、以及其它制剂属性。成膜剂包括例如聚乙酸乙烯酯、聚乙酸乙烯酯共聚物、聚乙烯吡咯烷酮-乙酸乙烯酯共聚物、 聚乙烯醇、聚乙烯醇共聚物和蜡。制剂助剂和添加剂的实例包括由McCutcheon’s Division，The Manufacturing Confectioner Publishing Co.出版的McCutcheon’s Volume 2：Functional Materials，北美和国际年鉴版；以及PCT公布WO03/024222中列出的那些。
通常通过将活性成分溶于溶剂中或通过在液体稀释剂或干稀释剂中研磨活性成分将本发明的化合物和任何其它的活性成分掺入到本发明的组合物中。可通过简单地混合所述成分来制备溶液，包括乳油。如果用作乳油的液体组合物的溶剂是与水不混溶的，则通常加入乳化剂使含有活性成分的溶剂在用水稀释时发生乳化。可使用介质磨来湿研磨粒径为至多2,000μm的活性成分浆液，以获得平均直径低于3μm的颗粒。水性浆液可以制备为成品悬浮液浓缩物(参见例如U.S.3,060,084)或通过喷雾干燥而进一步加工形成水分散性的颗粒。干制剂通常需要干研磨步骤，其产生在2μm至10μm范围内的平均粒径。粉剂和粉末可以通过混合，并且通常通过研磨(例如用锤磨机或流能磨)来制备。可通过将活性物质喷雾在预成形颗粒载体上或通过附聚技术来制备颗粒和粒料。参见Browning的“Agglomeration”(Chemical Engineering，1967年12月4日，第147-48页；Perry的Chemical Engineer’s Handbook，第4版，McGraw-Hill，New York，1963，第8-57页及其后页和WO91/13546。粒料可以如U.S.4,172,714中所述来制备。水分散性的和水溶性的颗粒可以如U.S.4,144,050、U.S.3,920,442和DE.3,246,493中所提出的来制备。片剂可以如U.S.5,180,587、U.S.5,232,701和U.S.5,208,030中所提出的来制备。膜可以如GB2,095,558和U.S.3,299,566中所提出的来制备。
与制剂领域相关的其他信息，参见T.S.Woods的“The Formulator’s Toolbox-Product Forms for Modern Agriculture”，Pesticide Chemistry and Bioscience，The Food-Environment Challenge，T.Brooks和T.R.Roberts编辑，Proceedings of the 9th International Congress on Pesticide Chemistry，The Royal Society of Chemistry，Cambridge，1999，第120-133页。还可参见U.S.3,235,361第6栏，第16行至第7栏，第19行和实施例10-41；U.S3,309,192第5栏，第43行至第7栏，第62行和实施例8、12、15、39、41、52、53、58、132、138-140、162-164、166、167和169-182；U.S.2,891,855第3栏，第66行至第5栏，第17行和实施例1-4；Klingman的Weed Control as a Science，John Wiley and Sons，Inc.，New York，1961，第81-96页；Hance等人的Weed Control Handbook，第8版，Blackwell Scientific Publications，Oxford，1989；以及Developments in formulation technology，PJB Publications，Richmond，UK，2000。
本发明化合物的应用
本发明除草剂可通过给植物喷雾、施加到土壤中、施加到水表面上来使用。适当地确定活性组分的用量以满足应用目的。根据该目的来适当地确定活性组分的含量。
本发明化合物的用量根据所用化合物的种类、目标杂草、杂草出现的趋势、环境条件和除草剂的种类等。当本发明除草剂自身的形式例如以粉末或颗粒的形式使用时，其用量适当地选取为1g-50kg、优选10g-10kg/公顷的活性组分。当本发明的除草剂以液体形式例如以可乳化的浓缩物、可湿性粉剂或可流动制剂的形式使用时，其用量适当地选取为0.1-50,000ppm、优选10-10,000ppm。
本发明提供了一种用于控制有用植物的作物中的杂草的方法，该方法包括向所述杂草或向所述杂草的场所或向所述有用植物或向所述有用植物的场所施用本发明的化合物或组合物。
本发明还提供了一种选择性控制有用植物的作物中的草和/或杂草的方法，该方法包括向有用植物或其场所或向栽培区域施用除草有效量的具有如式(I)、式(Ia)、式(Ia-1)、式(Ia-2)或式(Ib)所示的化合物。
术语“除草剂”意指一种控制或改变植物生长的化合物。术语“有效量”意指能够产生控制或改变植物生长效果的这样一种化合物或此类化合物的组合物的量。控制或者改变的效果包括所有自然发展的偏离，例如，杀害、延迟、叶灼伤、白化病、矮化病等。术语“植物”指的是植物的所有有形部分，包括种子、幼苗、幼株、根、块茎、茎、秆、叶和果实。术语“所在地”旨在包括土壤、种子以及幼苗，连同已经建立的植物(established vegetation)并且不仅包括杂草可能已经生长的区域，而且还包括杂草尚未出现的区域，并且还包括关于有用植物作物的种植的区域。“种植的区域”包括作物植物已经在其上生长的土地，以及打算用来种植此类作物植物的土地。如在此使用的术语“杂草”意指任何不希望的植物，并且因此不仅包括如下所述的重要的农艺杂草，而且还包括自生作物植物。
可能使用了根据本发明的组合物的有用植物作物包括但不限于多年生作物，例如柑橘类水果、葡萄树、坚果、油棕榈、橄榄、梨果类水果、核果及橡胶，以及一年生可耕作物，例如谷类(如大麦和小麦)、棉花、油菜、玉米、水稻、大豆、甜菜、甘蔗、向日葵、观赏植物、柳枝稷、草皮以及蔬菜，尤其是谷类、玉米以及大豆。
要控制的草和杂草既可以是单子叶的物种，例如剪股颖属、看麦娘属、燕麦属、臂形草属、雀麦属、蒺藜草属、莎草属、马唐属、稗属、野黍属、黑麦草属、雨久花属、黍属、早熟禾属、筒轴茅属、慈姑属、藨草属、狗尾草属、黄花稔属和高粱属，也可以是双子叶的物种，例如白麻属、苋属、藜属、菊属、大戟属、拉拉藤属、番薯属、地肤属、旱金莲属、蓼属植物、黄花稔属、白芥属、茄属、繁缕属、婆婆纳属、堇菜属和苍耳属。
本发明化合物可示出对重要农作物的耐受性，所述农作物包括但不限于苜蓿、大麦、棉花、小麦、油菜、糖用甜菜、玉米(玉蜀黍)、高粱、大豆、稻、燕麦、花生、蔬菜、番茄、 马铃薯、多年生种植作物包括咖啡、可可、油棕、橡胶、甘蔗、柑橘、葡萄、果树、坚果树、香蕉、车前草、菠萝、啤酒花、茶和森林诸如按树和针叶树(例如火炬松)、以及草皮物类(例如草地早熟禾、圣奥古斯丁草(St.Augustine grass)、Kentucky牛毛草和狗牙根草)。
如果需要的话，根据本发明的具有如式(I)、式(Ia)、式(Ia-1)、式(Ia-2)或式(Ib)所示的化合物也可以与其他活性成分，例如其他除草剂和/或杀昆虫剂和/或杀螨剂和/或杀线虫剂和/或杀软体动物剂和/或杀真菌剂和/或植物生长调节剂组合使用。这些混合物、以及这些混合物的用以控制杂草和/或不希望的植物的生长的用途又形成了本发明的另一些方面。为避免疑问，本发明的混合物也包括两种或更多种不同的具有如式(I)、式(Ia)、式(Ia-1)、式(Ia-2)或式(Ib)所示的化合物的混合物。具体地，本发明还涉及一种本发明的组合物，该组合物除如式(I)、式(Ia)、式(Ia-1)、式(Ia-2)或式(Ib)所示的化合物之外包含至少一种另外的除草剂。
一般合成过程
在本说明书中，如果在化学名称和化学结构间存在任何差异，结构是占优的。一般地，本发明的化合物可以通过本发明所描述的方法制备得到，除非有进一步的说明。
本发明核磁共振氢谱的测试条件是：室温条件下，布鲁克(Bruker)400MHz或600MHz的核磁仪，以CDC1 3，d 6-DMSO，CD 3OD或d 6-丙酮为溶剂(报导以ppm为单位)，用TMS(0ppm)或氯仿(7.26ppm)作为参照标准。当出现多重峰的时候，将使用下面的缩写：s(singlet，单峰)，d(doublet，双峰)，t(triplet，三重峰)，q(quartet，四重峰)，m(multiplet，多重峰)，br(broadened，宽峰)，dd(doublet of doublets，双二重峰)，dt(doublet of triplets，双三重峰)。偶合常数，用赫兹(Hz)表示。
本发明所用质谱分析方法为：使用Agilent 1260 HPLC；Agilent 6120 ESI。
A相：水(含0.1％甲酸)；B相：乙腈(含0.1％甲酸)。
梯度洗脱：0-3min，5-100％B；3-6min，100％B。
流速：0.6mL/min。
检测波长：254nm。
MS参数：ESI正扫描，碰撞诱导电离：70V。
干燥氮气：12L/min，雾化气压力：40psi，气体温度：350℃。
取适量样品，溶于0.5mL甲醇，进样，在正ESI模式下进行一级MS全扫描得到准分子离子峰[M+H] +读数。
下面的简写词释义贯穿本发明：
AIBN：偶氮二异丁腈
DCM：二氯甲烷
DMF：N,N-二甲基甲酰胺，二甲基甲酰胺
MeOH：甲醇
NBS：N-溴代琥珀酰亚胺
EtOH：乙醇
EtOAc：乙酸乙酯
PE或Petroleum ether：石油醚
THF：四氢呋喃
TLC：薄层色谱
SOCl 2：氯化亚砜
Na 2SO 4：硫酸钠
K 2CO 3：碳酸钾
DMSO：二甲基亚砜
下面的合成方案和实施例1-38用于进一步举例说明本发明的内容。
合成方案
合成方案一
Figure PCTCN2020105150-appb-000016
Figure PCTCN2020105150-appb-000017
化合物(E)可以通过合成方案一制备得到，其中R 1、m和X具有如本发明所述的含义。将2,4-二氯-3-(溴甲基)苯甲酸甲酯与含氮杂环化合物(M1)在碱性条件下(如碳酸钠、碳酸钾)，在0℃-35℃发生反应，得到化合物(A)；化合物(A)在碱性条件下(如氢氧化锂)水解，得到化合物(B)；化合物(B)与酰氯(如草酰氯)在0℃-100℃发生卤代反应，得到化合物(C)；化合物(C)与环己二酮在0℃-35℃发生酯化反应，得到化合物(D)；化合物(D)在催化剂(如三甲基氰硅烷、丙酮氰醇)作用下，在10℃-40℃发生Fries重排反应，得到目标化合物(E)。
合成方案二
Figure PCTCN2020105150-appb-000018
化合物(G)可以通过合成方案二制备得到，其中R 1、m、X和R 3具有如本发明所述的含义。化合物(C)与取代的吡唑(F1)在0℃-35℃发生酯化反应，得到化合物(F)；化合物(F)在催化剂(如三甲基氰硅烷、丙酮氰醇)作用下，在10℃-40℃发生Fries重排反应，得到目标化合物(G)。
合成方案三
Figure PCTCN2020105150-appb-000019
化合物(H)可以通过合成方案三制备得到，其中R 1、m、X和R 3具有如本发明所述的含义；其中R 5为氢、C 1-6烷基或卤素；Y为卤素。化合物(G)与化合物(H1)在碱性条件下(如Cs 2CO 3、K 2CO 3等)在25℃-50℃下发生亲核取代反应，得到目标化合物(H)。
合成方案四
Figure PCTCN2020105150-appb-000020
化合物(K)可以通过合成方案四制备得到，其中R 1、m和X具有如本发明所述的含义。化合物(C)与双环[3.2.1]辛烷-2,4-二酮在0℃-35℃发生酯化反应，得到化合物(J)；化合物(J)在催化剂(如三甲基氰硅烷、丙酮氰醇)作用下，在10℃-40℃发生Fries重排反应，得到目标化合物(K)。
实施例
实施例1：2-(2,4-二氯-3-(吗啉代甲基)苯甲酰基)-3-羟基环己-2-烯酮的制备
Figure PCTCN2020105150-appb-000021
步骤1：2,4-二氯-3-甲基苯乙酮的制备
Figure PCTCN2020105150-appb-000022
向单口瓶中加入氯化铝(49.68g，372.6mmol)和2,6-二氯甲苯(50g，310.5mmol)，室温搅拌，然后缓慢滴加乙酰氯(26.81g，341.6mmol)，加热至40℃反应2h，TLC监测原料反应完全。将体系缓慢倒入冰水(500mL)中，稀盐酸溶液(1M，30mL)酸化，二氯甲烷萃取(150mL x 3)，无水硫酸钠干燥，浓缩得60g无色油状物，产率95％。
步骤2：2,4-二氯-3-甲基苯甲酸的制备
Figure PCTCN2020105150-appb-000023
向单口瓶中加入2,4-二氯-3-甲基苯乙酮(30g，147.7mmol)和1,4-二氧六环(100mL)，升温至80℃，滴加次氯酸钠溶液(5％有效氯300mL)，保持该温度搅拌5h，TLC监测原料反应完全。恢复室温后分成两相，分出下层溶液，浓盐酸酸化至pH＝2，抽滤，滤饼水洗(100mL x 3)，50℃干燥，得22g白色固体，产率74％。
步骤3：2,4-二氯-3-甲基苯甲酸甲酯的制备
Figure PCTCN2020105150-appb-000024
向单口瓶中加入2,4-二氯-3-甲基苯甲酸(20g，97.54mmol)和甲醇(80mL)，降温至0℃，缓慢滴加SOCl 2(13.85mL，195.0mmol)，滴加完后升温至60℃反应10h。减压蒸馏除去绝大部分甲醇，将剩余物质缓慢加入冰水(200mL)中并用饱和碳酸氢钠溶液调节pH＝8，二氯甲烷萃取(50mL x 3)，无水硫酸钠干燥，浓缩有机相，重结晶得白色固体16.3g，产率76％。
步骤4：2,4-二氯-3-(溴甲基)苯甲酸甲酯的制备
Figure PCTCN2020105150-appb-000025
向单口瓶中加入2,4-二氯-3-甲基苯甲酸甲酯(12g，54.78mmol)，NBS(13.65g，76.69mmol)，四氯化碳(60mL)和AIBN(1.8g，10.92mmol)，氮气保护，78℃搅拌反应3.5h，TLC监测反应完全。冷却，抽滤，四氯化碳(20mL x 3)洗涤滤饼，减压蒸馏除去四氯化碳，重结晶(石油醚/乙酸乙酯(V/V)＝5/1)得15g白色固体，产率92％。
步骤5：2,4-二氯-3-(吗啉代甲基)苯甲酸甲酯的制备
Figure PCTCN2020105150-appb-000026
将吗啉(2.66g，30.54mmol)和碳酸钾(4.22g，30.54mmol)溶于乙腈(50mL)，室温搅拌30min，后缓慢滴加2,4-二氯-3-(溴甲基)苯甲酸甲酯(7g，23.49mmol)的乙腈溶液(30mL)，室温反应，TLC监测反应完全。将反应体系过滤，滤饼用乙腈洗涤(10mL x 3)，回收滤液，浓缩得粗产物为浅黄色油状物6.55g，直接用于下一步反应。
步骤6：2,4-二氯-3-(吗啉代甲基)苯甲酸的制备
Figure PCTCN2020105150-appb-000027
将2,4-二氯-3-(吗啉代甲基)苯甲酸甲酯(6.4g，21.04mmol)，一水合氢氧化锂(1.77g，42.08mmol)溶于THF(30mL)，EtOH(30mL)和H 2O(30mL)的混合溶剂中，室温反应2h，TLC监测反应完全。减压蒸馏除去有机溶剂，加水(50mL)稀释，乙酸乙酯(30mL x 2)萃取，回收水相，搅拌下滴加稀盐酸(1M)酸化至调节pH＝5，二氯甲烷(30mL x 3)萃取水相，浓缩有机相得黄色固体5.2g，产率86％。
步骤7：2,4-二氯-3-(吗啉代甲基)苯甲酰氯的制备
Figure PCTCN2020105150-appb-000028
将化合物2,4-二氯-3-(吗啉代甲基)苯甲酸(1.0g，3.45mmol)溶于超干二氯甲烷(30mL)，冷却至0℃，向该反应液中加入草酰氯(874.9mg，6.89mmol)，最后加入N,N-二甲基甲酰胺(7.24mg，0.34mmol)，室温反应3h，然后减压蒸馏除去溶剂，得到淡黄色粘稠液体848mg，产率80％。
步骤8：3-氧代环己-1-烯-1-基2,4-二氯-3-(吗啉代甲基)苯甲酸酯的制备
Figure PCTCN2020105150-appb-000029
将化合物1,3-环己二酮(338.94mg，3.02mmol)溶于超干二氯甲烷(20mL)，然后向反应液中加入三乙胺(556.14mg，5.50mmol)，冷却0℃以下，向该反应液中加入2,4-二氯-3-(吗啉代甲基)苯甲酰氯(848mg，2.75mmol)的二氯甲烷(20mL)溶液，室温反应4h。加入二氯甲烷(50mL)稀释反应体系，并用饱和碳酸氢钠溶液洗涤(50mL x 2)，回收有机相，无水Na 2SO 4干燥，过滤，二氯甲烷洗涤(10mL x 2)，柱层析分离(洗脱剂：PE/EtOAc(V/V)＝20/3)，得到黄色油状液体900mg，产率85％。
步骤9：2-(2,4-二氯-3-(吗啉代甲基)苯甲酰基)-3-羟基环己-2-烯酮的制备
Figure PCTCN2020105150-appb-000030
将化合物3-氧代环己-1-烯-1-基2,4-二氯-3-(吗啉代甲基)苯甲酸酯(900mg，2.34mmol)溶于超干乙腈(30mL)，然后向反应液中加入三乙胺(474mg，4.68mmol)，最后向该反应液中加入三甲基氰硅烷(34.85mg，0.35mmol)，室温反应6h，TLC监测原料反应完全。减压蒸馏除去有机溶剂，加水(50mL)溶解体系，稀盐酸溶液(1M)酸化至pH＝5，用二氯甲烷萃取(40mL x 3)，合并有机相，无水Na 2SO 4干燥，过滤，浓缩，柱层析分离(洗脱剂：DCM/MeOH(V/V)＝100/1)，得到白色固体400mg，产率46％。
MS(ES-API,pos.ion)m/z:384.1[M+H] +；
1H NMR(400MHz,CDCl 3)δ7.37(d,J＝8.2Hz,1H),7.02(d,J＝8.2Hz,1H),3.76(s,2H),3.68–3.63(m,4H),2.79(t,J＝6.2Hz,2H),2.59–2.52(m,4H),2.43(t,J＝6.4Hz,2H),2.08–2.01(m,2H).
实施例2：2-((3-环丙基-4-(2,4-二氯-3-(吗啉代甲基)苯甲酰基)-1-甲基-1H-吡唑-5-基)氧基)-1-苯基乙酮的制备
Figure PCTCN2020105150-appb-000031
步骤1：3-环丙基-1-甲基-1H-吡唑-5-基2,4-二氯-3-(吗啉代甲基)苯甲酸酯的制备
Figure PCTCN2020105150-appb-000032
将3-环丙基-1-甲基-5-羟基吡唑(290mg，2.10mmol)溶于超干二氯甲烷(20mL)，然后向反应液中加入三乙胺(360mg，3.57mmol)，冷却至0℃，向该反应液中加入2,4-二氯-3-(吗啉代甲基)苯甲酰氯(549mg，1.78mmol)的二氯甲烷(10mL)溶液，室温反应3h，TLC监测原料反应完全。向反应液中加入饱和碳酸氢钠溶液(100mL)，二氯甲烷萃取(50mL x 3)，合并有机相，无水Na 2SO 4干燥，过滤，二氯甲烷洗涤，柱层析分离(洗脱剂：PE/EtOAc(V/V)＝100/30)，得到642mg黄色固体，收率88％。
MS-ESI:m/z 411.10[M+H] +.
步骤2：(3-环丙基-5-羟基-1-甲基-1H-吡唑-4-基)(2,4-二氯-3-(吗啉代甲基)苯基)甲酮的制备
Figure PCTCN2020105150-appb-000033
3-环丙基-1-甲基-1H-吡唑-5-基2,4-二氯-3-(吗啉代甲基)苯甲酸酯(642mg，1.56mmol)溶于超干乙腈(20mL)，然后向反应液中加入三乙胺(314mg，3.10mmol)，最后向该反应液中加入三甲基氰硅烷(25mg，0.25mmol)，室温反应5h，TLC监测原料反应完全。将反应液用醋酸酸化到pH＝5，搅拌30min，减压蒸馏除去溶剂，加水(50mL)，再用二氯甲烷萃取(50mL x 3)，合并有机相，无水Na 2SO 4干燥，过滤，浓缩，柱层析分离(洗脱剂：DCM/MeOH(V/V)＝100/1)，得到320mg黄色固体，收率50％。
MS(ES-API,pos.ion)m/z:410.1[M+H] +.
1H NMR(400MHz,CDCl 3)δ7.37(d,J＝8.2Hz,1H),7.19(d,J＝8.2Hz,1H),3.78(s,2H),3.65–3.61(m,4H),3.50(s,3H),2.59–2.53(m,4H),0.94(d,J＝4.8Hz,1H),0.71(s,2H),0.36(d,J＝7.6Hz,2H).
步骤3：2-((3-环丙基-4-(2,4-二氯-3-(吗啉代甲基)苯甲酰基)-1-甲基-1H-吡唑-5-基)氧基)-1-苯基乙酮的制备
Figure PCTCN2020105150-appb-000034
将化合物(3-环丙基-5-羟基-1-甲基-1H-吡唑-4-基)(2,4-二氯-3-(吗啉代甲基)苯基)甲酮(150mg，0.366mmol)和K 2CO 3(75.8mg，0.548mmol)溶于DMF(10mL)，室温搅拌10min，然后向反应液中加入溴代苯乙酮(80.0mg，0.402mmol)，室温反应4h，TLC监测原料反应完全。加水(50mL)稀释体系，乙酸乙酯(50mL x 3)萃取，合并有机相，饱和食盐水溶液(50mL)洗涤有机相一次，无水Na 2SO 4干燥，过滤，浓缩，柱层析分离(洗脱剂：PE/EtOAc(V/V)＝20/4)，得到米白色固体86mg，产率45％。
MS(ES-API,pos.ion)m/z:528.1[M+H] +；
1H NMR(400MHz,CDCl 3)δ7.89(d,J＝7.4Hz,2H),7.61(t,J＝7.4Hz,1H),7.49(t,J＝7.7Hz,2H),7.36(d,J＝8.2Hz,1H),7.19(d,J＝8.2Hz,1H),5.87(s,2H),3.82(s,3H),3.74(s,2H),3.61(s,4H),2.53(s,4H),1.10–1.04(m,1H),0.78–0.73(m,2H),0.42–0.36(m,2H).
参考本发明合成方案一至四，结合具体实施例1-2的合成方法，采用相应的原料及条件， 可得到表1的目标化合物。
表1
Figure PCTCN2020105150-appb-000035
Figure PCTCN2020105150-appb-000036
Figure PCTCN2020105150-appb-000037
Figure PCTCN2020105150-appb-000038
Figure PCTCN2020105150-appb-000039
Figure PCTCN2020105150-appb-000040
Figure PCTCN2020105150-appb-000041
Figure PCTCN2020105150-appb-000042
Figure PCTCN2020105150-appb-000043
Figure PCTCN2020105150-appb-000044
Figure PCTCN2020105150-appb-000045
Figure PCTCN2020105150-appb-000046
Figure PCTCN2020105150-appb-000047
生物实施例
用分析天平(0.0001g)称取一定质量的原药，用适量DMF溶解，然后用一定体积的含1‰吐温-80乳化剂蒸馏水稀释备用。
取长宽均7.0cm花盆，装土至3/4处，直接播种预处理的杂草靶标种子，覆土0.5cm左右，待幼苗长至适龄阶段进行喷雾处理，施药后待药液自然风干后移入温室常规培养，21天后调查对杂草的活性(％)；其中0表示无伤害或生长过程正常，100表示至少地上部分完全死亡。
表2本发明化合物在300g/ha对杂草的活性
Figure PCTCN2020105150-appb-000048
Figure PCTCN2020105150-appb-000049
表3本发明化合物在150g/ha、75g/ha、37.5g/ha和18.75g/ha对苘麻和马齿苋的活性
Figure PCTCN2020105150-appb-000050
Figure PCTCN2020105150-appb-000051
表4本发明化合物在150g/ha对稗草的活性
实施例 稗草 实施例 稗草
实施例2 90 实施例3 85
实施例4 90 实施例6 90
实施例7 80 实施例8 85
实施例14 85 实施例25 87
实施例26 80 实施例32 93
表5本发明化合物在150g/ha、75g/ha和37.5g/ha对百日草的活性
Figure PCTCN2020105150-appb-000052
其中ND表示未测试。
表2至表5结果显示，本发明化合物在300g/ha、150g/ha、75g/ha、37.5g/ha和18.75g/ha对苘麻、马齿苋、百日草、稗草均具有优异的防治效果。
花生安全性测试
用分析天平(0.0001g)称取一定质量的化合物，用适量DMF溶解，然后用一定体积的含1‰吐温-80乳化剂蒸馏水稀释备用。
取长宽均7.0cm花盆，装土至3/4处，直接播种预处理的作物种子，覆土0.5cm左右，待幼苗长至适龄阶段进行喷雾处理，施药后待药液自然风干后移入温室常规培养，21天后调 查对花生的药害(％)；其中0表示无伤害或生长过程正常，100表示至少地上部分完全死亡。
表6本发明化合物对花生的安全性试验
Figure PCTCN2020105150-appb-000053
表6结果显示，本发明化合物在75-600g/ha对花生安全，与现有技术相比，相同剂量下安全性更高。本发明化合物在高剂量下仍然显示出对花生优异的安全性。
表7本发明化合物对玉米的安全性试验
Figure PCTCN2020105150-appb-000054
表7结果显示，本发明化合物在75-300g/ha对玉米安全，高剂量下仍然显示出对玉米优异的安全性。
另外，本发明化合物对水稻、小麦也显示出一定的安全性，例如实施例1在75-300g/ha对小麦的药害在15％以下；实施例20在75-300g/ha对小麦的药害在10％以下，对水稻的药害在5％以下。
本发明化合物对阔叶科杂草(如苘麻、反枝苋、百日草、鱧肠和马齿苋)和禾本科杂草(如马唐、稗草、黑麦草和狗尾草)均具有很好的防治效果。对花生、玉米、水稻和小麦安全，药效发挥快，而且对杂草的防治效果优于市售除草剂和结构近似的苯甲酰类化合物，具有很好的应用前景。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (21)

  1. 一种化合物，其为如式(I)所示的化合物或式(I)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
    Figure PCTCN2020105150-appb-100001
    其中：
    R 1为羟基、氰基、氨基、硝基、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、卤代C 1-6烷氧基或C 3-8环烷基；
    m为0、1、2、3、4、5、6、7、8、9或10；
    X为-CH 2-、-O-、-S(＝O) n-或-NH-；
    n为0、1或2；
    Q为以下子结构式：
    Figure PCTCN2020105150-appb-100002
    R 2和R 2a各自独立地为氢或C 1-6烷基；
    R 3为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基或C 3-8环烷基；
    R 4为氢或-CH 2-CO-C 6-10芳基；其中所述-CH 2-CO-C 6-10芳基任选地被1、2或3个选自卤素或C 1-6烷基的取代基所取代。
  2. 根据权利要求1所述的化合物，其中，
    R 1为羟基、氰基、氨基、硝基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、卤代C 1-4烷氧基或C 3-6环烷基；
    R 2和R 2a各自独立地为氢或C 1-4烷基。
  3. 根据权利要求1或2所述的化合物，其中，
    R 1为羟基、氰基、氨基、硝基、甲基、乙基、正丙基、异丙基、-CHF 2、-CF 3、-CH 2CHF 2、-CH 2CF 3、环丙基、环丁基、环戊基或环己基；
    R 2和R 2a各自独立地为氢或甲基。
  4. 根据权利要求1-3任意一项所述的化合物，其中，
    R 3为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基或C 3-6环烷基；
    R 4为氢或-CH 2-CO-苯基；其中所述-CH 2-CO-苯基任选地被1、2或3个选自卤素或C 1-4烷基的取代基所取代。
  5. 根据权利要求1-4任意一项所述的化合物，其中，
    R 3为氢、甲基、乙基、正丙基、异丙基、环丙基、环丁基、环戊基或环己基；
    R 4为氢或-CH 2-CO-苯基；其中所述-CH 2-CO-苯基任选地被1、2或3个选自氯或甲基的取代基所取代。
  6. 根据权利要求1-5任意一项所述的化合物，其为如式(Ia)所示的化合物或式(Ia)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
    Figure PCTCN2020105150-appb-100003
    其中：
    R 1a和R 1b各自独立地为氢或C 1-3烷基。
  7. 根据权利要求1-5任意一项所述的化合物，其为如式(Ib)所示的化合物或式(Ib)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
    Figure PCTCN2020105150-appb-100004
  8. 根据权利要求1-7任意一项所述的化合物，其中，
    Q为以下子结构式：
    Figure PCTCN2020105150-appb-100005
    Figure PCTCN2020105150-appb-100006
    R 1a和R 1b各自独立地为氢或甲基；
    n为0、1或2。
  9. 根据权利要求1-8任意一项所述的化合物，其为如式(Ia-1)所示的化合物或式(Ia-1)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
    Figure PCTCN2020105150-appb-100007
    其中：
    R 1a和R 1b各自独立地为氢或C 1-6烷基；
    R 2和R 2a各自独立地为氢或C 1-6烷基。
  10. 根据权利要求9所述的化合物，其中，
    R 1a和R 1b各自独立地为氢或C 1-3烷基；
    R 2和R 2a各自独立地为氢或C 1-3烷基。
  11. 根据权利要求9或10所述的化合物，其中，
    R 1a和R 1b各自独立地为氢或甲基；
    R 2和R 2a各自独立地为氢或甲基。
  12. 根据权利要求1-8任意一项所述的化合物，其为如式(Ia-2)所示的化合物或式(Ia-2)所示化合物的立体异构体、互变异构体、氮氧化物或盐：
    Figure PCTCN2020105150-appb-100008
    其中：
    R 1a和R 1b各自独立地为氢或C 1-6烷基。
  13. 根据权利要求12所述的化合物，其中，
    R 1a和R 1b各自独立地为氢或C 1-3烷基。
  14. 根据权利要求12或13所述的化合物，其中，
    R 1a和R 1b各自独立地为氢或甲基。
  15. 根据权利要求1-14任意一项所述的化合物，其为具有下列之一结构的化合物或具有下列之一结构化合物的立体异构体、互变异构体、氮氧化物或其盐：
    Figure PCTCN2020105150-appb-100009
    Figure PCTCN2020105150-appb-100010
    Figure PCTCN2020105150-appb-100011
  16. 一种组合物，包含权利要求1-15任意一项所述的化合物。
  17. 根据权利要求16所述的组合物，其中所述组合物进一步包括至少一种附加组分，所述附加组分为表面活性剂、固体稀释剂、液体稀释剂、缓冲剂、消泡剂、增稠剂、防冻剂、抗微生物剂、成膜剂。
  18. 权利要求1-15任意一项所述的化合物或权利要求16或17所述的组合物作为除草剂在有用植物中防治杂草的应用。
  19. 根据权利要求18所述的应用，其中所述有用植物为花生、玉米、水稻或小麦中的至少一 种；所述杂草为苘麻、马齿苋、稗草或百日草的一种或多种。
  20. 一种控制有用植物中杂草生长的方法，其包含向杂草所在地施用有效量的权利要求1-15任意一项所述的化合物或权利要求16或17所述的组合物。
  21. 根据权利要求20所述的方法，其中所述有用植物为花生、玉米、水稻或小麦中的至少一种；所述杂草为苘麻、马齿苋、稗草或百日草中的一种或多种。
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