WO2024061348A1 - Composé 1,3-cyclohexanedione d'éther d'oxime, son procédé de synthèse et son utilisation - Google Patents

Composé 1,3-cyclohexanedione d'éther d'oxime, son procédé de synthèse et son utilisation Download PDF

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WO2024061348A1
WO2024061348A1 PCT/CN2023/120720 CN2023120720W WO2024061348A1 WO 2024061348 A1 WO2024061348 A1 WO 2024061348A1 CN 2023120720 W CN2023120720 W CN 2023120720W WO 2024061348 A1 WO2024061348 A1 WO 2024061348A1
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compound
formula
optionally substituted
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add
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邓照西
郭少雄
胡合伟
岑金
谭宾
贾云飞
杜兵兵
李志军
李君沛
杨莉娜
吴世凡
黄帅
曹展
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郑州手性药物研究院有限公司
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • 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
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    • A—HUMAN NECESSITIES
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    • 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
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
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    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
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    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/62—Oxygen or sulfur atoms
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    • C07D213/64—One oxygen atom attached in position 2 or 6
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    • C07D303/02—Compounds containing oxirane rings
    • C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to an oxime ether 1,3-cyclohexanedione compound and its synthesis method and application. Specifically, it relates to oxime ether 1,3-cyclohexanedione compounds, their use for controlling unwanted weeds in plants, and preparation methods of such compounds.
  • Cyclohexanedione compounds are a large class of substances with a wide range of biological activities such as herbicidal, bactericidal, and insecticidal activities, among which the herbicidal activity attracts the most attention. Cyclohexanedione herbicides are mainly divided into two categories. One is 2-acyl-1,3-cyclohexanedione compounds, which are HPPD inhibitors and have broad-spectrum herbicidal activity; the other is oxime ethers1 , 3-cyclohexanedione compound, an ACCase inhibitor, used to control annual or perennial grass weeds.
  • the object of the present invention is to provide an oxime ether 1,3-cyclohexanedione compound having improved herbicidal activity.
  • an oxime ether 1,3-cyclohexanedione compound having high herbicidal activity, especially high herbicidal activity at a low application rate, excellent herbicidal effect on resistant weeds, and high safety to crops is provided.
  • the purpose of the present invention is to provide a new class of oxime ether 1,3-cyclohexanedione compounds, which have higher herbicidal activity when applied in small doses compared to the existing known research and development compounds, and at the same time, have good effects on plants. It has a high degree of selectivity and compatibility for crops, showing good safety. It is effective against existing oxime ether 1,3-cyclohexanedione compound herbicides, such as phenylpropiodone, clethodim and other products. Resistant weeds have better control effects. It can be widely used in weed control in agriculture, forestry and orchards.
  • the invention provides an oxime ether 1,3-cyclohexanedione compound represented by formula I,
  • R 1 is H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 1 -C 6 alkoxy, optionally substituted C 1 -C 6 thio, optionally substituted C 1 -C 6Alkoxy -C 1 -C 6 alkyl, optionally substituted C 1 -C 6 alkylthio-C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkyl, optionally substituted C 3 -C 6 cycloalkyloxy-C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkylthio-C 1 -C 6 alkyl, optionally substituted heterocyclyl ;
  • R 2 is optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkyl;
  • R 3 is optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 3 -C 6 cycloalkyl;
  • R 4 is H, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted C 2 -C 6 alkenyl;
  • the invention also provides a method for preparing the compound of formula I.
  • the present invention also provides a herbicidal composition comprising a compound of formula I.
  • the present invention also provides the use of compounds of formula I as herbicides for controlling undesirable plants.
  • the present invention provides a method for controlling undesirable plant growth, in which a herbicidally effective amount of at least one compound of the formula I is acted upon the plant, its seeds and/or the place on which it grows. Application can be carried out before, during and/or after emergence of undesirable plants.
  • the present invention relates to processes and intermediates for the preparation of formula I.
  • the compound of the invention has more efficient herbicidal activity and is safer for crops, and at the same time shows excellent herbicidal effect on resistant weeds, and has broad application prospects.
  • control and "control” used in the present invention are synonymous.
  • the compounds of the formula I described herein have one or more chiral centers and therefore exist as enantiomers or diastereomers, the pure enantiomers, racemates or diastereomers can be used in the compositions of the invention.
  • the compounds of the formula I according to the invention have functional groups which can be ionized, they can also be used in the form of their agriculturally acceptable salts or mixtures thereof.
  • Suitable are generally salts of cations whose cations do not adversely affect the action of the active compounds ("agriculturally acceptable").
  • Preferred cations are ions of alkali metals, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium and magnesium, and ions of transition metals, preferably manganese, copper, zinc and iron.
  • the anions that are useful acid addition salts are mainly chloride ions, bromide ions, fluoride ions, iodide ions, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, and carbonate.
  • the organic moieties mentioned in particular with respect to R 1 to R 4 are, like the term halogen, a collective term for individually enumerated members of each group.
  • halogen means in each case fluorine, chlorine, bromine and iodine.
  • the integer from 0 to 3 is preferably 0, 1, 2 and 3.
  • all hydrocarbon chains ie all alkyl groups, may be straight or branched, and the subscripts Cn to Cm in each case indicate the number of carbon atoms in the group.
  • alkyl is used herein (as well as in other groups containing alkyl groups, such as the alkyl moiety of alkoxy).
  • C 1 to C 6 alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isopropyl) Butyl), 1,1-dimethylethyl (tert-butyl), n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl Propyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- Dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-
  • the substituent may include hydroxyl, cyano, nitro, halogen and alkyl.
  • a haloalkyl group is formed.
  • ring or "cycloalkyl” means in each case a monocyclic or bicyclic alicyclic radical generally having 3 to 6 carbon atoms ("C 3 to C 6 cycloalkyl").
  • monocyclic groups having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C 2 -C 6 alkenyl for example, vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- Methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl- 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-
  • C 3 -C 6 haloalkenyl C 3 -C 6 alkenyl as described above partially or completely substituted by fluorine, chlorine, bromine and/or iodine, such as 2-chloroprop-2-en-1 -yl, 3-chloroprop-2-en-1-yl, 3-chloroprop-1-enyl, 2,3-dichloropropyl -2-en-1-yl, 3,3-dichloroprop-2-en-1-yl, 2,3,3-trichloroprop-2-en-1-yl, 2,3-dichlorobutan -2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2,3-dibromoprop-2-en-1-yl , 3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromoprop-2-en-1-yl or 2,3-dibromobut-2-en-1-yl
  • Heterocyclyl a monocyclic or bicyclic saturated, partially unsaturated or aromatic heterocyclic ring having 3 or more, for example 3 to 10 ring atoms, for example, containing 1 to 4 of the same ring atoms selected from oxygen, sulfur and nitrogen. Or 3, 4, 5, 6, or 7-membered heterocycles with different heteroatoms, such as:
  • P is selected from H, -CH 3 , -C 2 H 5 , -C 3 H 7 , -Cl, -F, -Br, -I, -CN, -NO 2 or -CF 3
  • X is oxygen, sulfur and nitrogen
  • Y is C 1 -C 3 alkyl
  • n is an integer from 0 to 3.
  • the general aspect of the present invention provides an oxime ether 1,3-cyclohexanedione compound represented by formula I,
  • R 1 is H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 1 -C 6 alkoxy, optionally substituted C 1 -C 6 thio, optionally substituted C 1 -C 6Alkoxy -C 1 -C 6 alkyl, optionally substituted C 1 -C 6 alkylthio-C 1 -C 6 alkyl base, optionally substituted C 3 -C 6 cycloalkyl, optionally substituted C 3 -C 6 cycloalkyloxy-C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkyl Thio-C 1 -C 6 alkyl, optionally substituted heterocyclyl;
  • R 2 is optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkyl;
  • R 3 is optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally C 3 -C 6 cycloalkyl;
  • R 4 is H, optionally substituted C 2 -C 6 alkenyl, optionally substituted phenyl, optionally substituted heterocyclyl;
  • R 1 in the compound of formula I is -H, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 , -Q-CH 3 , -QC 2 H 5 , -CH 2 -Q-CH 3 , -QC 3 H 7 , -C 2 H 4 -Q-CH 3 , -CH 2 -QC 2 H 5 , -QC 4 H 9 , -CH 2 -QC 3 H 7 , -C 2 H 4 -QC 2 H 5 , -C 3 H 6 -Q-CH 3 , -QC 5 H 11 , -CH 2 -QC 4 H 9 , -CH 2 -QC 4 H 9 , -C 2 H 4 -QC 3 H 7 , -C 3 H 6 -QC 2 H 5 , -C 4 H 8 -Q-CH 3 , -QC
  • R 1 in the compound of formula I is -CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 -O-CH 2 CH 3 , - CH 2 CH 2 -S-CH 3 , -CH 2 -O-CH(CH 3 ) 2 , -CH 2 CH(CH 3 )SCH 2 CH 3 ,
  • R 2 in the compound of formula I is -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 , Where n is selected from an integer of 0-3, and Y is a C 1 -C 3 alkyl group.
  • R 2 in the compound of formula I is -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 )CH 2 CH 3 , -CH(CH 3 ) 2 , -CH(CH 3 )CH(CH 3 )CH 3 , -CH 2 CH 2 CH(CH 3 ) 2 .
  • Z is F, Cl, Br, I.
  • Particularly preferred compounds of the present invention are as follows:
  • the present invention also provides a method for preparing the compound of formula I, which includes the following steps: preparing the compound of formula II and formula III under acidic conditions to obtain the compound of formula I, Where R 2 , R 3 and R 4 are as defined above;
  • the above reaction is carried out in an organic solvent.
  • the organic solvent is selected from one of dichloromethane, dichloroethane, acetone, toluene, DMF, petroleum ether and methanol.
  • the acid is selected from organic acids, preferably Formic acid and acetic acid.
  • the reaction temperature of the above reaction is in the range of 0-100°C, and the reaction time is in the range of 1-10h, preferably 1-3h;
  • the above-mentioned compound of formula III is obtained by reacting the compound of formula IV and hydrazine hydrate.
  • the reaction is carried out in an organic solvent.
  • the organic solvent is selected from dichloromethane and dichloroethane.
  • the reaction is carried out at 0 to 80°C. React for 1 to 3 hours. After the reaction is completed, water is added for extraction, and the organic layer is concentrated to obtain compound III;
  • Step 1 Prepare the compound of formula VI to obtain the compound of formula V;
  • Step 2 Prepare the compound of formula IV from the compound of formula V.
  • the reaction route is as follows:
  • Step 1 includes adding compound VI and a base into an organic solvent, and adding methylsulfonyl chloride dropwise at -20-40°C to prepare compound V.
  • the organic solvent is selected from the group consisting of dichloromethane, dichloroethane, petroleum ether, ethyl acetate, acetone, and toluene
  • the base is selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. , triethylamine, sodium hydroxide, potassium hydroxide.
  • Step 2 includes adding compound V and N-hydroxyphthalimide into an organic solvent, adding a base after dissolving, and reacting at 40-100°C to prepare compound IV.
  • the organic solvent is selected from DMF, acetonitrile, 1,4-dioxane, N-methylpyrrolidone, N, N-dimethylacetamide, and the base is selected from sodium carbonate and potassium carbonate. , sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide.
  • the compound of formula I of the present invention Since the compound of formula I of the present invention has excellent herbicidal activity and crop safety, the compound of formula I of the present invention is suitable for plant protection in agriculture, forestry, and horticulture and the control of unwanted plants. Pests against which the compounds of the present invention are effective include, for example, harmful mites and nematodes. Specific examples of harmful organisms include the following pests (the listed objects are only used to illustrate the present invention, but do not limit the scope of the present invention).
  • the compound of formula I of the present invention can control weeds by using an effective amount of active compounds to control weeds.
  • the herbicidal composition of the present invention usually contains 0.1 to 95 wt%, preferably 0.5 to 90 wt% of the compound of formula (I).
  • the application rate based on the compound of formula I of the present invention is usually 0.01 to 1000g per hectare, and the preferred effective dose is 0.01 to 500g per hectare.
  • Preferred compounds of formula I of the present invention for example, compounds 1-13 can have a good weed killing effect at a dose of 0.5g/mu, and particularly preferred compounds have better weed killing effects at a dose of 0.01g/mu. Effective in killing weeds.
  • the preparation containing the compound of formula I of the present invention is usually diluted with water to a concentration of active ingredient of 0.01 Apply within the range of 5000ppm. Granules, powders, etc. can be applied without dilution.
  • the compound of formula (I) of the present invention has at least 90% killing effect on certain weeds and resistant weeds in the concentration range of 0.01 to 100 ppm (0.01 mg/L to 100 mg/L). preferred The compound has at least 90% killing effect on certain weeds and resistance in the range of 0.1ppm to 100ppm.
  • the compound of formula (I) can be prepared into conventional preparations through conventional preparation methods, such as emulsifiable concentrates, oil solutions, powders, granules, wettable powders, flowable agents, microcapsules, aerosols, smoke-generating agents, and poisonous baits. etc.
  • the form of use depends on the specific purpose of use.
  • the formulated preparations are prepared in a conventionally known manner, for example by mixing the active compounds with solvents and/or carriers, if necessary adding suitable emulsifiers and dispersants or other customary auxiliaries.
  • the agent for controlling harmful plants of the present invention contains a compound of the present invention and an inert carrier.
  • inert carrier means extenders, diluents and formulations used in the agricultural field.
  • the agent for controlling harmful plants of the present invention is usually prepared by mixing the compound of the present invention with an inert carrier such as a solid carrier, a liquid carrier or a gas carrier, and if necessary, adding surfactants and other formulation auxiliaries to prepare the agent.
  • an inert carrier such as a solid carrier, a liquid carrier or a gas carrier
  • solid carriers used in pesticide composition support formulations include: fine powders or particles of clay (e.g. kaolin clay, diatomaceous earth, bentonite), synthetic hydrous silica, talc, ceramics, other inorganic materials (e.g.
  • polyester resins such as polypropylene, polyacrylonitrile, polymethyl Methyl acrylate and polyethylene terephthalate, nylon resin, polyamide resin, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer), etc.
  • liquid carrier examples include: water, alcohol (such as methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol or phenoxyethanol), ketone (such as acetone, methyl ethyl ketone or cyclohexanone), aromatic hydrocarbons (such as toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylyylethane or methylnaphthalene); aliphatic hydrocarbons (such as hexane, cyclohexane , kerosene or light oil), esters (such as ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate or propylene glycol mono
  • alcohol such as m
  • Surfactants used in the present invention include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyethylene glycol fatty acid esters, and anionic surfactants such as alkyl sulfonic acids. Salt/benzenesulfonate/sulfate, also includes commercial surfactants such as Nongru 500, Nongru 100, Nongru 300, Nongru 400, Nongru 600, Nongru 700, Nongru 0204, Nongru 1600 , Ningru32, Ningru36.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyethylene glycol fatty acid esters
  • anionic surfactants such as alkyl sulfonic acids.
  • Salt/benzenesulfonate/sulfate also includes commercial surfactants such as Nongru 500, Nongru 100, Nongru 300, Nongru 400, Nongru 600, Nongru 700, Nongru 0204, Nongru 1600
  • binders examples include starch, gum arabic, cellulose derivatives and alginic acid, lignin derivatives, bentonite, polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid, 2,6-di-tert-butyl-4-cresol , a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol.
  • the prepared preparations usually contain 0.01 to 95% by weight, preferably 0.1 to 90% by weight of active compound.
  • the pesticide agent for controlling undesirable plants of the present invention can be used in agricultural fields with the following crops.
  • the crops include: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rape, sunflower, sugar cane, tobacco, eggplant, tomato, bell pepper, pepper, potato, Cucumber, pumpkin, zucchini, watermelon, melon, Japanese radish, daikon, horseradish, kohlrabi, bok choy, cabbage, mustard greens, broccoli, cauliflower, chrysanthemum, artichokes, lettuce, scallions, onions, garlic or asparagus, carrots, Parsley, celery, parsnips, spinach, Swiss chard, apples, pears, papayas, peaches, plums, nectarines, plums, cherries, apricots, prunes, satsumas, oranges, lemons, limes, grapefruits, chestnuts, Walnuts, hazel
  • the undesirable plants include annual or perennial weeds and resistant weeds, preferably annual grass weeds and resistant annual grass weeds, particularly preferably barnyardgrass, crabgrass, goosegrass, Stephanotis, resistant barnyardgrass.
  • the resistant weeds of the present invention are opposite to the sensitive weeds.
  • the sensitive weeds can have better control effect with a lower dosage of pesticides, while the resistant weeds require a larger dosage of pesticides, which may cause It is ten times or even a hundred times the amount of pesticide applied to sensitive weeds.
  • the test data of the present invention shows that the compound of the present invention has a good effect on preventing and controlling the resistant weed target when the dosage of the corresponding sensitive target and the resistant target is the same.
  • the compound of the present invention has better safety to farmland crops than the compounds disclosed in the prior art, especially to corn, wheat, rice, soybean and rapeseed.
  • the preparation and use of the active ingredients of formula (I) of the present invention are illustrated by, but not limited to, the following examples.
  • the raw materials in the preparation examples of the present invention can be purchased in the market, or synthesized by referring to methods disclosed in the prior art.
  • Example 5 Compound 5 2- ⁇ [1-(4-chloro-pyridin-2-oxymethyl)-butoxyimino]-cyclopropylmethyl ⁇ -3-hydroxy-5-(2-methyl (Sulfonamidoethyl)-cyclohex-2-enone
  • Example 6 Compound 6 2-[(1-allyloxymethyl-2-methylpropoxyimino)-(2-methylcyclopropyl)-methyl]-3-hydroxy-5- Isopropoxymethyl-cyclohex-2-enone
  • Example 7 Compound 7 2- ⁇ 1-[2-(4-Chloro-phenoxy)-1-methyl-ethoxyimino]-propyl ⁇ -5-(2-ethylthio-propyl)-3-hydroxy-cyclohex-2-enone
  • Example 8 Compound 8 2- ⁇ 1-[2-(4-chloro-phenoxy)-1-methyl-ethoxyimino]-butyl ⁇ -5-(2-ethylthio-propyl hydroxy)-3-hydroxy-cyclohex-2-enone
  • Example 10 Compound 10 2- ⁇ 1-[4-chloro-1-(4-nitro-phenoxymethyl)-but-2-enoxyimino]-2-methylpropyl ⁇ -3- Hydroxy-5-(2-methyl-cyclopropylsulfonamidemethyl)-cyclohex-2-enone
  • Example 11 Compound 11 2- ⁇ 1-[1-(furan-2-oxymethyl)-pentoxyimino]-2,3-dimethylbutyl ⁇ -3-hydroxy-5-(tetrahydro Thiopyran-3-yl)-cyclohex-2-enone
  • Example 12 Compound 12 5-(2-ethylthiopropyl)-3-hydroxy-2- ⁇ 4-methyl-1-[1-(4-methyl-1H-pyrrole-2-oxymethyl methyl)-propoxyimine]-pentyl ⁇ -cyclohex-2-enone
  • Example 13 Compound 13 2- ⁇ 1-[2-(2,4-dichloro-phenoxy)-1-methyl-ethoxyimino]-butyl ⁇ -5-(2-ethylsulfide hydroxy-propyl)-3-hydroxy-cyclohex-2-enone
  • Weed seeds are sown in the greenhouse.
  • the growth conditions are: soil pH ⁇ 6.8, soil organic matter content ⁇ 30%, temperature 22 to 25°C, and a 14-hour photoperiod of light. Water and nutrients are added in a timely manner, and the weeds grow to 3 to 4 leaves. During the period, dilute it with water at 450L/ha and spray it on the weeds. Observe and calculate the plant control effect after 10 days.
  • plant control effect (number of plants before treatment - number of trees after treatment)/trees before treatment * 100.
  • Medication 13 kinds of oxime ether 1,3-cyclohexanedione compounds provided in Examples 1 to 13 are prepared into 5% by weight emulsifiable concentrate for use.
  • the specific ingredients are: 5% compounds (1 to 13) + 6% agricultural milk 0204+ 4% ethanol + 85% naphtha.
  • Control sample 1 5% by weight compound e1 (CN11205208A) + 6% agricultural milk 0204 + 4% ethanol + 85% naphtha
  • Control sample 2 5% by weight compound 5 (patent CN114105842A) + 6% agricultural milk 0204 + 4% ethanol + 85% naphtha
  • Control sample 3 30% quinclorac suspension, purchased from Dezhou Luba Fine Chemical Co., Ltd., dosage 45-85ml/mu.
  • Control sample 4 25 g/L penoxsulam dispersible oil suspension, purchased from Corteva Agricultural Technology Co., Ltd., dosage 40-80 ml/mu.
  • Control sample 5 15% diclofenac suspension, purchased from Anhui Shanghe Woda Biotechnology Co., Ltd., dosage 10-18 ml/mu.
  • Control sample 6 5% by weight of benzotrione + 6% agricultural milk 0204 + 4% ethanol + 85% naphtha, self-synthesized benzotrione, the synthesis method refers to CN11205208A.
  • Control sample 7 24% clethodim EC, purchased from Jinan Kehai Co., Ltd., Shandong province, dosage 15-20 ml/mu.
  • Crop seeds were sown and cultured in a greenhouse (soil pH ⁇ 6.8, soil organic matter content ⁇ 30%, temperature 22-25°C, light intensity 14h photoperiod; timely water and nutrition supplementation), and 5% emulsifiable concentrate of the above active ingredient was applied when the seeds grew to the 2-3 leaf stage, and the plant damage was evaluated after 5-7 days.
  • the evaluation criteria for plant damage are as follows:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un composé 1,3-cyclohexanedione représenté par la formule I, ainsi qu'un stéréoisomère et un sel agrochimiquement acceptable de celui-ci, où R1, R2, R3 et R4 sont tels que définis dans la description. L'invention concerne également un procédé de préparation du composé de formule I et une utilisation de celui-ci en tant qu'herbicide. Le composé de formule I a la structure suivante : formule I.
PCT/CN2023/120720 2022-09-23 2023-09-22 Composé 1,3-cyclohexanedione d'éther d'oxime, son procédé de synthèse et son utilisation WO2024061348A1 (fr)

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