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WO2021018135A1 - Composés de dichlorobenzoyle à substitution alkyle hétérocyclyle et leurs applications - Google Patents

Composés de dichlorobenzoyle à substitution alkyle hétérocyclyle et leurs applications Download PDF

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Publication number
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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Prior art keywords
compound
alkyl
formula
independently hydrogen
present
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PCT/CN2020/105150
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English (en)
Chinese (zh)
Inventor
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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Publication of WO2021018135A1 publication Critical patent/WO2021018135A1/fr

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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

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Abstract

L'invention concerne des composés de dichlorobenzoyle à substitution alkyle hétérocyclyle et leurs applications. L'invention concerne spécifiquement des composés représentés par la formule (I) et leurs procédés de préparation, des compositions contenant ces composés et leur utilisation en tant qu'herbicides. Dans la formule (I), Q est un oxocyclohexényle facultativement substitué ou un pyrazolyle substitué, etc ; R 1 représente hydroxyle, alkyle en C 1-6, etc. ; m vaut 0, 1, 2, etc. ; X représente -O-, -S(=O)n-, etc. ; et n vaut 0, 1 ou 2.
PCT/CN2020/105150 2019-07-31 2020-07-28 Composés de dichlorobenzoyle à substitution alkyle hétérocyclyle et leurs applications WO2021018135A1 (fr)

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CN88101455A (zh) * 1987-03-17 1988-09-28 日产化学工业株式会社 吡唑衍生物和含有该衍生物的除草剂
CN1310714A (zh) * 1998-07-24 2001-08-29 拜尔公司 取代的苯甲酰基环已二酮类化合物
CN1323292A (zh) * 1998-10-10 2001-11-21 阿温提斯作物科学有限公司 苯甲酰基环己烷二酮,其制法,及其作为除草剂与植物生长调节剂的用途
CN101573035A (zh) * 2006-12-27 2009-11-04 石原产业株式会社 含有苯甲酰吡唑系化合物的除草剂
WO2012065573A1 (fr) * 2010-11-19 2012-05-24 中国中化股份有限公司 Composé de benzoyle substitué hétérocyclique azoté et utilisation de celui-ci

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AR027575A1 (es) * 2000-03-06 2003-04-02 Bayer Ag Benzoilciclohexenonas substituidas
DE10106420A1 (de) * 2001-02-12 2002-08-14 Bayer Ag Selektive Herbizide auf Basis von substituierten Arylketonen und Safenern
DE10112104A1 (de) * 2001-03-14 2002-09-26 Bayer Ag Herbizide auf Basis von substituierten Arylketonen
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CN88101455A (zh) * 1987-03-17 1988-09-28 日产化学工业株式会社 吡唑衍生物和含有该衍生物的除草剂
CN1310714A (zh) * 1998-07-24 2001-08-29 拜尔公司 取代的苯甲酰基环已二酮类化合物
CN1323292A (zh) * 1998-10-10 2001-11-21 阿温提斯作物科学有限公司 苯甲酰基环己烷二酮,其制法,及其作为除草剂与植物生长调节剂的用途
CN101573035A (zh) * 2006-12-27 2009-11-04 石原产业株式会社 含有苯甲酰吡唑系化合物的除草剂
WO2012065573A1 (fr) * 2010-11-19 2012-05-24 中国中化股份有限公司 Composé de benzoyle substitué hétérocyclique azoté et utilisation de celui-ci

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