WO2023020274A1 - 一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用 - Google Patents

一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用 Download PDF

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WO2023020274A1
WO2023020274A1 PCT/CN2022/109677 CN2022109677W WO2023020274A1 WO 2023020274 A1 WO2023020274 A1 WO 2023020274A1 CN 2022109677 W CN2022109677 W CN 2022109677W WO 2023020274 A1 WO2023020274 A1 WO 2023020274A1
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cas
methyl
compound
compounds
isoxazolidinone
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PCT/CN2022/109677
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English (en)
French (fr)
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连磊
华荣保
彭学岗
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青岛清原化合物有限公司
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Priority to AU2022331659A priority Critical patent/AU2022331659A1/en
Publication of WO2023020274A1 publication Critical patent/WO2023020274A1/zh

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    • 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
    • A01N43/80—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member

Definitions

  • the invention belongs to the technical field of pesticides, and in particular relates to a 3-isoxazolidinone compound, a preparation method thereof, a herbicidal composition and application thereof.
  • the present invention provides a kind of 3-isoxazolidinone compound and its preparation method, herbicidal composition and application, said compound maintains comparable or even better herbicidal activity Basically, it has better crop safety and can establish better selectivity on crops; moreover, the compound of the present invention has better anti-volatility and is not easy to drift.
  • Q 1 and Q 2 independently represent O or S;
  • R 1 and R 2 each independently represent an alkyl group, preferably a C1-C8 alkyl group, more preferably a C1-C6 alkyl group.
  • Q 1 and Q 2 independently represent O; R 1 and R 2 independently represent methyl (ie compound 1).
  • the alkyl group with more than two carbon atoms can be straight chain or branched chain.
  • Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • the present invention also provides a preparation method of the 3-isoxazolidinone compound, comprising the following steps:
  • Hal represents halogen, preferably bromine.
  • said step is carried out in the presence of a base and a solvent.
  • the base is selected from inorganic bases (such as K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaHCO 3 , KF, CsF, KOAc, AcONa, K 3 PO 4 , t-BuONa, EtONa, NaOH, KOH, NaOMe, etc.) or at least one of organic bases (such as pyrazole, triethylamine, DIEA, etc.).
  • inorganic bases such as K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaHCO 3 , KF, CsF, KOAc, AcONa, K 3 PO 4 , t-BuONa, EtONa, NaOH, KOH, NaOMe, etc.
  • organic bases such as pyrazole, triethylamine, DIEA, etc.
  • the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, toluene or ethyl acetate.
  • the present invention also provides a herbicidal composition, which comprises (i) a herbicidally effective amount of at least one of the above-mentioned 3-isoxazolidinone compounds.
  • the herbicidal composition further comprises (ii) one or more herbicidally effective amounts of additional herbicides and/or safeners.
  • the herbicidal composition further includes (iii) an agrochemically acceptable formulation adjuvant.
  • the present invention also provides a method for controlling undesired plants, comprising applying a herbicidally effective amount of at least one of said 3-isoxazolidinone compounds or said herbicidal composition to plants or their locus or applied to soil or water bodies to control unwanted plant emergence or growth.
  • said unwanted vegetation comprises herbicide resistant or tolerant weed species.
  • the present invention also provides the use of at least one of said 3-isoxazolidinone compounds or said herbicidal composition for controlling undesired plants.
  • said 3-isoxazolidinones are used for controlling weeds in useful crops.
  • the useful crops include transgenic crops or crops treated with genome editing technology, and the weeds include herbicide-resistant or tolerant weed species.
  • the compounds of the formula I according to the invention have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants.
  • the active substances according to the invention are also effective against perennial weeds which grow from rhizomes, rhizomes or other perennial organs and are difficult to control. In this context, it is generally immaterial whether the substance is applied before sowing, before germination or after germination.
  • Representative examples of groups of monocotyledonous and dicotyledonous weeds that can be controlled by the compounds of the present invention are specifically mentioned, without limitation to a defined species.
  • weed species on which the active substances are effective include monocots: annuals Avena, rye, Grass, Aleuria, Fararis, barnyardgrass, crabgrass, Setaria and Cyperus, and perennial icegrass Grass, Bermudagrass, Imperata and Sorghum, and perennial Cyperus.
  • dicotyledonous weed species With regard to dicotyledonous weed species, its effect can be extended to species such as annual pleura, Viola, Possina, Sesame, Chickweed, Amaranthus, S. Genus, Matricaria, and Abutilus, and the perennial weeds Convolvuum, Thistle, Rumex, and Artemisia.
  • the active substance of the present invention is effective in controlling harmful plants such as Barnyardgrass, Sagittarius, Alisma, Eleocharis, Canegrass and Cyperus under undetermined conditions of rice sowing.
  • the compounds of the present invention have particularly good activity against the following plants: Apira weed, Sesame ono, Polygonum curcuma, Chickweed, Ivy leaf pombe, Arabian pansy, pansy and amaranth, chrysoprase and Kochia .
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not effective against economically important crop plants such as peanut, wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. No damage, or the damage is negligible. In particular it is well compatible with cereal crops such as wheat, barley and corn, especially wheat.
  • the compounds according to the invention are therefore very suitable for the selective control of unwanted plants in agricultural crops or ornamental plants.
  • Transgenic plants Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetically engineered plant cultivation.
  • Transgenic plants often have superior traits, such as resistance to specific insecticides, especially herbicides, resistance to plant diseases or plant disease-causing microorganisms, such as specific insects or fungal, bacterial or viral microorganisms.
  • Other specific properties are related to the following conditions of the product, for example, quantity, quality, storage stability, composition and special ingredients. Thus, it is known to obtain transgenic plant products with increased starch content or improved starch quality or different fatty acid composition.
  • the compounds of formula I according to the invention or their salts are preferably used in economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or in sugar beets, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of the formula I are preferably used as herbicides in the cultivation of useful plants which are resistant or which have been genetically engineered to be resistant to the toxic action of the herbicides.
  • glufosinate herbicides e.g. EP-0242236 A, EP-0242246 A
  • glyphosate herbicides WO 92/00377
  • sulphur Urea herbicides EP-0257993 A, US-5013659 A
  • Plant cells with reduced activity gene products can be prepared, for example, by expressing at least one appropriate antisense-RNA, sense-RNA to achieve co-suppression, or by expressing at least one appropriately constructed ribozyme, It specifically cleaves the transcripts of the above mentioned gene products.
  • DNA molecules that contain the entire coding sequence of the gene product including any flanking sequences that may be present, and to use DNA molecules that contain only a portion of the coding sequence, which must be long enough to achieve antisense in cells. Effect. Sequences with a high degree of homology, but not complete identity, to gene product coding sequences may also be used.
  • the synthesized protein When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, for localization in a specific compartment, it is possible, for example, to link the coding region and the DNA sequence to ensure localization at a specific position. These sequences are known to those skilled in the art (see, e.g., Braun et al., EMBO J. 11 (1992) 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).
  • Transgenic plant cells can be recombined into whole plants using known techniques.
  • the active substances according to the invention are used on transgenic crops, in addition to the effect of inhibiting harmful plants that can be observed on other crops, there will often be special effects on the corresponding transgenic crops, for example, the control can be improved or expanded.
  • the present invention therefore also provides the use of said compounds as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds according to the invention can significantly regulate the growth of crop plants. These compounds are used for targeted control of plant components and to facilitate harvesting, such as desiccation and dwarf growth of plants, by modulating the metabolism involved in the plant. Moreover, they are also suitable for regulating and suppressing undesired vegetative growth without destroying the growth of the crop. Inhibition of plant growth plays a very important role in many monocot and dicot crops, as lodging can be reduced or completely prevented.
  • the compounds of the invention can be applied using conventional formulations, wettable powders, concentrated emulsions, sprayable solutions, powders or granules.
  • the present invention also provides herbicidal compositions comprising a compound of formula I.
  • the compounds of formula I can be formulated in various ways. Examples of suitable formulation options are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, concentrated emulsions (EC), e.g.
  • oil-in-water and water-in-oil emulsions sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions in oil or water as diluents, oil-miscible solutions, powders (DP), capsule suspensions (CS ), seeddressing compositions, granules for broadcasting and soil application, spray granules, coated granules and absorbent granules, water dispersible granules (WG), water soluble granules (SG), ULV (ultra low volume) formulations, microcapsules and wax products.
  • Necessary formulation auxiliaries such as inert substances, surfactants, solvents and other additives are likewise known and described in, for example, Watkins' Handbook of Powder Diluent Insecticides and Carriers, 2nd Edition, Darland Books, Caldwell NJ; Hv01phen "An Introduction to the Chemistry of Clay Colloids", 2nd ed., J. Wiley and Sons, NY; C.
  • Wettable powders are uniformly dispersible in water and, in addition to active substances, also include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated Ethoxylated fatty alcohol, polyoxyethylated fatty amine, fatty alcohol polyglycol ether sulfate, alkylsulfonate, alkylphenylsulfonate, sodium lignosulfonate, 2,2'-dinaphthyl methane - Sodium 6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyl taurate.
  • the herbicide active substances are ground finely, for example using customary apparatus, for example with hammer mills, fan mills and jet mills, and the adjuvants are mixed simultaneously or sequentially.
  • Concentrated emulsions are prepared by dissolving the active substance in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of higher boiling aromatic compounds or hydrocarbons or solvents, and adding a One or more ionic and/or nonionic surfactants (emulsifiers).
  • organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of higher boiling aromatic compounds or hydrocarbons or solvents.
  • emulsifiers examples include calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohols Polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters polysaccharide ester.
  • calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohols Polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid
  • Powders are obtained by grinding the active substance with finely divided solid substances such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Water- or oil-based suspensions may be prepared, for example, by wet grinding using a commercially available bead mill, with or without the addition of surfactants of the other formulation type described above.
  • Emulsions such as oil-in-water emulsifiers (EW) can be prepared using aqueous organic solvents using stirrers, colloid mills and/or static mixers, adding, if desired, surfactants of another formulation type as described above.
  • EW oil-in-water emulsifiers
  • Granules are prepared by spraying the active substance onto the adsorbate, granulating with an inert material, or concentrating the active substance on the surface of a carrier such as sand, kaolinite, granulating the inert material through a binder, sticking Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated, if desired mixed with fertilizers, in the same way as fertilizer granules. Aqueous suspension granules are prepared using the usual methods, such as spray-drying, fluidized bed granulation, pan granulation, mixing with a high-speed mixer, and extrusion without solid inert materials.
  • the agrochemical formulations generally comprise from 0.1 to 99%, in particular from 0.1 to 95%, by weight of active substances of the formula I.
  • the active substance concentration in the wettable powders is, for example, from about 10 to 99% by weight, the usual formulation components constituting the remainder to 100% by weight.
  • the concentration of active substance in the concentrated emulsions may be from about 1 to 90%, preferably from 5 to 80%, by weight.
  • Powder formulations contain 1 to 30% by weight active substance, usually preferably 5 to 20% by weight active substance, whereas sprayable solutions contain approximately 0.05 to 80% by weight, preferably 2 to 50% active substance .
  • the content of the active substance in the water-suspended granule mainly depends on whether the active substance is liquid or solid, and the additives, fillers, etc. used in granulation.
  • the active substance content of the aqueous granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the formulation of active substances may include tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors and Commonly used pH and viscosity modifiers in all cases.
  • the mixing method can be For pre-mixed or bottled mixes.
  • suitable active substances that can be mixed with the compound of formula I of the present invention are, for example, "World Pesticide New Variety Technical Encyclopedia", China Agricultural Science and Technology Press, 2010.9 and in the literature cited here known substances.
  • the herbicide active substances mentioned below can be mixed with compound 1 (note: the name of the compound is either the common name according to the International Organization for Standardization (ISO), or the chemical name, with a code when appropriate):
  • HPPD Hydrophenyl Pyruvate Dioxygenase inhibitors: including but not limited to the following types,
  • Triketones for example, Sulcotrione (CAS NO: 99105-77-8); Mesotrione (Mesotrione, CAS NO: 104206-82-8); Bicyclopyrone (CAS NO : 352010-68-5); tembotrione (CAS NO: 335104-84-2); tefuryltrione (CAS NO: 473278-76-1); bicyclic sulcotrione (Benzobicyclon, CAS NO :156963-66-5);
  • Diketonitriles for example, 2-cyano-3-cyclopropyl-1-(2-methylsulfonyl-4-trifluoromethylphenyl) propane-1,3-dione (CAS NO : 143701-75-1); 2-cyano-3-cyclopropyl-1-(2-methylsulfonyl-3,4-dichlorophenyl)propane-1,3-dione (CAS NO: 212829-55-5); 2-cyano-1-[4-(methylsulfonyl)-2-trifluoromethylphenyl]-3-(1-methylcyclopropyl)propane-1,3 - diketone (CAS NO: 143659-52-3);
  • Isoxazoles for example, isoxaflutole (CAS NO: 141112-29-0); isoxachlortole (CAS NO: 141112-06-3); , CAS NO: 81777-89-1);
  • Pyrazoles for example, topramezone (CAS NO: 210631-68-8); pyrasulfotole (CAS NO: 365400-11-9); pyrazoxazole (pyrazoxyfen, CAS NO: 71561-11-0); pyrazolate (CAS NO: 58011-68-0); benzofenap (CAS NO: 82692-44-2); -18-2); Tolpyralate (CAS NO: 1101132-67-5); Fenflurzone (CAS NO: 1992017-55-6); Cyclofluxazone (CAS NO: 1855929-45-1); Triazole sulfotrione (CAS NO: 1911613-97-2);
  • EPSPS Enduvyl Shikimate Phosphate Synthase inhibitors: such as sulphosate, Glyphosate, glyphosate-isopropylammonium and glyphosate trimethylsulfonate ( glyphosate-trimesium);
  • PPO Protoporphyrinogen Oxidase inhibitors: divided into pyrimidinediones, diphenyl-ethers, phenylpyrazoles, N-phenylimides , thiadiazoles, oxadiazoles, triazolones, oxazolidinediones and other herbicides with different chemical structures.
  • pyrimidinedione herbicides include, but are not limited to, flumethazine (CAS NO: 134605-64-4), saflufenacil (CAS NO: 372137-35-4), Dimifluzalone (CAS NO: 158755-95-4), flumethiobacil (tiafenacil, CAS NO: 1220411-29-9), [3-[2-chloro-4-fluoro-5-(1 -Methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]ethyl acetate (Epyrifenacil, CAS NO: 353292-31-6), 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl -3,4-dihydro-2H-benzo[1,4]oxazin-6-y
  • Diphenyl ether herbicides include but are not limited to fomesafen (CAS NO: 72178-02-0), oxyfluorfen (CAS NO: 42874-03-3), aclofenfen (CAS NO: 74070-46-5), fluorinated milk ether (CAS NO: 131086-42-5), lactofen (CAS NO: 77501-63-4), methoxyben (CAS NO: 32861-85-1 ), acifluorfen (CAS NO: 1836-77-7), acifluorfen (CAS NO: 77501-90-7), acifluorfen or sodium salt (acifluorfen, CAS NO: 50594-66- 6 or 62476-59-9), carboxyfen (CAS NO: 42576-02-3), chlorofluorfen (CAS NO: 188634-90-4), fluoronitrofen (CAS NO: 13738-63-1) , furyloxyfen (CAS NO: 80020-41-3), nitrofluorfen (CAS NO: 4
  • Phenylpyrazole herbicides include but not limited to metazachlor (CAS NO: 129630-19-9) and fluazolate (CAS NO: 174514-07-9);
  • N-Phenyl imide herbicides include but not limited to Flumipropyn (CAS NO: 103361-09-7), Indoxafen (CAS NO: 142891-20-1), Flumipropyn (CAS NO: 84478-52-4) and fluoxalic acid (CAS NO: 87546-18-7);
  • Thiadiazole herbicides include but are not limited to fluthiacet-methyl (fluthiacet-methyl, CAS NO: 117337-19-6), thiadiazole acid (CAS NO: 149253-65-6) and thiadiafen (CAS NO: 123249-43-4);
  • Oxadiazole herbicides include but not limited to propargyl oxadiazone (CAS NO: 39807-15-3) and oxadiazon (CAS NO: 19666-30-9);
  • Triazolinone herbicides include but not limited to carfentrazone (CAS NO: 128621-72-7), carfentrazone ethyl (CAS NO: 128639-02-1), sulfentrazone ( sulfentrazone, CAS NO: 122836-35-5), fentrazone (CAS NO: 68049-83-2) and bencarbazone (CAS NO: 173980-17-1);
  • Oxazolidinedione herbicides include but not limited to cyclopentazone (CAS NO: 110956-75-7);
  • herbicides include, but are not limited to, fenfenpyr (CAS NO: 158353-15-2), fluridazenzap (CAS NO: 188489-07-8), flufenacet (CAS NO: 190314-43-3 ), trifludimoxazin (CAS NO: 1258836-72-4), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl- 1H-pyrazole-1-carboxamide (CAS NO: 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5- Methyl-1H-pyrazole-1-carboxamide (CAS NO: 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)- 5-Methyl-1H-pyrazole-1-carboxamide (CAS NO: 452099-05-7), N-tetrahydrofur
  • ALS (Acetolactate Synthase) inhibitors include but not limited to the following herbicides or their mixtures:
  • Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl Chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethyl Ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, formamide (foramsulfuron), halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl sodium salt -sodium), iofensulfuron, iofensulfuron sodium salt, mesosulfuron, metazosulfuron, met
  • Imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin ( imazaquin) and imazethapyr;
  • Triazolopyrimidine herbicides and sulfonanilides such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, diclosulam florasulam, metosulam, penoxsulam, pyroxsulam, pyrimisulfan, and triafamone;
  • Pyrimidinyl benzoic acids such as bispyribac (bispyribac), bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobenzoic acid ( pyrithiobac), pyrithiobac (pyrithiobac) sodium salt, 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid- 1-Methyl ethyl ester (CAS NO: 420138-41-6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino] -Propyl benzoate (CAS NO: 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzylamine ( CAS NO: 420138
  • Sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone- sodium), thiencarbazone and thiencarbazone-methyl.
  • ACCase (Acetyl CoA Carboxylas) inhibitors such as Fenthiaprop, alloxydim, alloxydim-sodium, butroxydim, methoxydim clethodim, clodinafop, clodinafop-propargyl, cyclooxydim, cyhalofop, cyhalofop-butyl, chloroform diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P Fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P Fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-methyl
  • GS (Glutamine Synthetase) inhibitors such as Bialaphos/bilanafos, Bialaphos-natrium, Glufosinate-ammonium, Glufosinate-ammonium (Glufosinate) and refined glufosinate-ammonium (glufosinate-P);
  • PDS Phytoene Desaturase inhibitors: such as flurochloridone, flurtamone, beflubutamid, norflurazon, fluridone , Diflufenican (Diflufenican), Picolinafen (Picolinafen), and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS NO: 180608-33-7);
  • DHPS Dihydropteroate Synthase inhibitors: such as Asulam;
  • DXPS Deoxy-D-Xyulose Phosphate Synthase inhibitors: such as Bixlozone and Clomazone;
  • HST Homogentisate Solanesyltransferase inhibitors: such as Cyclopyrimorate
  • SPS Solanesyl Diphosphate Synthase inhibitors: such as Aclonifen;
  • Cellulose Synthesis inhibitors such as Indaziflam, Triaziflam, Chlorthiamid, Dichlobenil, Isoxaben, Flupoxam, 1-cyclohexyl-5-pentafluorophenoxy- 1 4 -[1,2,4,6]thiatriazin-3-ylamine (CAS NO: 175899-01-1) , and the azines disclosed in CN109688807A;
  • VLCFAS Very Long-Chain Fatty Acid Synthesis inhibitors: including but not limited to the following types,
  • Chloroacetamides such as acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, and dimethenamid-P ), metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, Propisochlor and thenylchlor;
  • ⁇ -Oxyacetamides such as flufenacet (flufenacet) and mefenacet (mefenacet);
  • ⁇ -Thioacetamides such as anilofos and piperophos
  • Azolylcarboxamides such as cafenstrole, fentrazamide and ipfencarbazone;
  • Benzofurans such as Benfuresate and Ethofumesate
  • Isoxazolines such as fenoxasulfone and pyroxasulfone
  • Thiocarbamate such as Cycloate, Dimepiperate, S-ethyldipropylthiocarbamate (EPTC), Esprocarb, molinate (Molinate), Orbencarb, Prosulfocarb, Thiobencarb/Benthiocarb, Triallate, Vernolate, and Formula II.1, II.2, II.3, II.4, II. 5.
  • Isozoline compounds of II.6, II.7, II.8 and II.9, and those mentioned in patents such as WO 2006/024820, WO 2006/037945, WO 2007/071900 and WO 2007/096576 Other isoxazoline compounds.
  • Fatty acid thioesterase inhibitors such as cycloheptafen Cinmethylin, Methiozolin;
  • Serine threonine protein phosphatase (serine threonine protein phosphatase) inhibitors such as Endothall;
  • Lycopene cyclase inhibitors such as Amitrole.
  • Microtubule Assembly (Microtubule Assembly) inhibitors such as Benefin/benfluralin, Butralin, Dithiopyr, Thiazopyr, Ethalfluralin, Amprofur Prodiamine, Butamifos, Oryzalin, Pendimethalin, Chlorthaldimethyl/DCPA, DMPA Trifluralin, Propyzamide/pronamide, Dinitramine (CAS NO: 29091-05-2);
  • Auxin Mimics such as 2,4,5 trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenoxyacetic acid (2,4-D ), 2,4-dichlorophenoxybutyric acid (2,4-DB), 3,4-dichlorophenoxybutyric acid (3,4-DB), 2,4-DEB (CAS NO: 94-83 -7), 4-chlorophenoxyacetic acid (4-CPA), 4-CPP (CAS NO: 3307-39-9), cloprop (CAS NO: 101-10-0), clofop (CAS NO: 26129- 32-8), Clomeprop, Dichlorprop, 2,4-Dichlorprop, 2-methyl-4-chlorobutyric acid (MCPB), 2-methyl-4-chloropropionic acid (Mecoprop), Chloroprop Aminopyralid, Clopyralid, Aminocyclopyrachlor, Florpyraxifen, Halauxifen, Quinclorac, Benazolin-ethyl, Piclor
  • D1 Serine 264 binders (and other non-histidine 215 binders) (D1 Serine 264 binders (and other non-histidine 215 binders)): such as Ametryne, Atrazine, Cyanazine, Dimethametryn, Prometon, Prometryne, Propazine, Simazine, Terbutylazine, Terbutryne, Chlorotoluron, Diuron, Fluometuron, Iso Isoproturon, Linuron, Metobromuron, Methabenz thiazuron (CAS NO: 18691-97-9), Monuron, Tebuthiuron, Hexazinone, Metamitron, Metribuzin , Bromacil, Lenacil, Terbacil, Chloridazon/pyrazon, Amicarbazone, Desmedipham, Phenmedipham, Chloranocryl/dicryl, CAS NO: 2164- 09-2), propanil, chlorazine (CAS NO:
  • D1 Histidine 215 binders such as Bromoxynil, Ioxynil, Pyridate, Bentazon;
  • Auxin Transport inhibitors such as Diflufenzopyr (CAS NO: 109293-97-2), Naptalam;
  • PS l Electron Diversion such as Diquat, Paraquat
  • Uncouplers such as Dinoseb, 4,6-dinitro-o-cresol (DNOC);
  • another herbicide (component B) mixed with compound 1 (component A) is selected from one or more than two of the following compounds: mesotrione (CAS number: 104206 -82-8), Furosulcotrione (CAS No.: 473278-76-1), Bicyclic Sulfotrione (CAS No.: 156963-66-5), Bifentrazone (CAS No.: 1622908-18-2) , Cycloflumetrione (CAS No.: 1855929-45-1), Triazole Sulfotrione (CAS No.: 1911613-97-2), Fenzaflurone (CAS No.: 1992017-55-6), fenquinotrione (CAS number: 1342891-70-6), (CAS No.: 2421252-30-2), Isoxaflutole (CAS No.: 141112-29-0), Fluoxazone (CAS No.: 61213-25-0), Diflufenamide (CAS No.
  • Epyrifenacil (CAS No.: 353292-31-6), (CAS number: 2669821-71-8), (CAS No.: 2669111-66-2), bemiconazole (CAS No.: 1949837-17-5), atrazine (CAS No.: 1912-24-9), promezazin (CAS No.: 7287-19 -6), sigrazine (CAS No.: 1014-70-6), terbuthylazine (CAS No.: 5915-41-3), terbufen (CAS No.: 886-50-0), ametrazine ( CAS No.: 834-12-8), mecitrione (CAS No.: 21087-64-9), amfentrazone (CAS No.: 129909-90-6), chlorotoluron (CAS No.: 15545-48- 9), isoproturon (CAS number: 34123-59-6), diuron (CAS number: 330-54-1), propanil (CAS number: 709-98-8), bentazone (CAS
  • the weight ratio of active ingredients A and B in the herbicidal composition is 1:1000 ⁇ 1000:1, 1:800 ⁇ 800:1, 1:600 ⁇ 600:1, 1:500 ⁇ 500:1, 1:500 ⁇ 500:1, 1 :400 ⁇ 400:1, 1:300 ⁇ 300:1, 1:200 ⁇ 200:1, 1:180 ⁇ 180:1, 1:150 ⁇ 150:1, 1:120 ⁇ 120:1, 1:100 ⁇ 100:1, 1:80 ⁇ 80:1, 1:50 ⁇ 50:1, 1:30 ⁇ 30:1, 1:20 ⁇ 20:1, 1:10 ⁇ 10:1, 1:5 ⁇ 1 :1 or 1:1 ⁇ 5:1.
  • the mass percent content of A and B in the herbicidal composition accounts for 1-95% of the total, preferably 10-80%.
  • a herbicidal compound as described herein that can be used in the context of the present invention is capable of forming geometric isomers such as E/Z isomers, it is possible to use both, pure Isomers and mixtures thereof. If a herbicidal compound as described herein has one or more chiral centers and thus exists as enantiomers or diastereomers, it is possible to use both, the pure enantiomers, in the compositions according to the invention Enantiomers and diastereomers and mixtures thereof. If the herbicidal compounds as described herein have ionizable functional groups, they can also be used in the form of their agriculturally acceptable salts.
  • the salts of those cations and the acid addition salts of those acids are suitable, the cations and anions of which, respectively, have no adverse effect on the activity of the active compounds.
  • Preferred cations are ions of alkali metals, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium and magnesium, and transition metals, preferably manganese, copper, zinc and iron, further ammonium and substituted Ammonium of which 1 to 4 hydrogen atoms are replaced by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl , hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl substituted, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium Ammonium, trimethyl
  • the anions of available acid addition salts are mainly chloride ion, bromide ion, fluoride ion, iodide ion, hydrogen sulfate, methyl sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonic acid , hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • the herbicidal compounds having a carboxyl group as described herein may be used in acid form, in the agriculturally suitable salts mentioned above or otherwise in the form of agriculturally acceptable derivatives, for example as amides such as mono- and di-C 1 -C 6 -Alkyl amides or aryl amides, as esters such as allyl esters, propargyl esters, C 1 -C 10 -alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl) Methyl) esters and also as thioesters, for example as C 1 -C 10 -alkylthioesters.
  • amides such as mono- and di-C 1 -C 6 -Alkyl amides or aryl amides
  • esters such as allyl esters, propargyl esters, C 1 -C 10 -alkyl esters, alkoxyalkyl esters,
  • Preferred mono- and di-C 1 -C 6 -alkylamides are methyl and dimethylamide.
  • Preferred arylamides are, for example, anilide and 2-chloroanilide.
  • Preferred alkyl esters are for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl 2-ethylhexyl, octyl or isooctyl (2-ethylhexyl) ester.
  • C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl esters are linear or branched C 1 -C 4 -alkoxyethyl esters, such as 2-methoxyethyl ester, 2- Ethoxyethyl ester, 2-butoxyethyl (butotyl) ester, 2-butoxypropyl ester or 3-butoxypropyl ester.
  • An example of a straight-chain or branched C 1 -C 10 -alkylthioester is ethylthioester.
  • the commercially available formulations are, if necessary, diluted in the usual manner, for example with water in the case of wettable powders, concentrated emulsions, suspensions and granules suspended in water. Powders, granules for soil application or solutions for broadcasting and spraying generally do not require further dilution with inert substances before use.
  • the amount of the compound of formula I required to be used varies with external conditions such as temperature, humidity, the nature of the herbicide used, and the like. It can vary widely, for example between 0.001 and 1.0 kg a.i./ha, or more active material, but preferably between 0.005 and 750 ga.i./ha.
  • compound 1-1 (284mg, 1.0mmol, 1.0eq.) was dissolved in 10mL acetonitrile, then compound 1-2 (115mg, 1.0mmol, 1.0eq.), K 2 CO 3 (207mg, 1.5mmol, 1.5eq.), the reaction solution was heated to 50°C and reacted at this temperature for 1h. After the reaction was completed, it was quenched with water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, filtered, concentrated, and column chromatographed to obtain the target product 1 (232.5 mg, white solid, 73% yield).
  • the activity level criteria for plant destruction i.e. growth control rate are as follows:
  • Level 5 The growth control rate is above 85%;
  • Level 4 The growth control rate is greater than or equal to 60% and less than 85%;
  • Level 3 The growth control rate is greater than or equal to 40% and less than 60%;
  • Level 2 The growth control rate is greater than or equal to 20% and less than 40%;
  • Level 1 The growth control rate is greater than or equal to 5% and less than 20%;
  • Grade 0 The growth control rate is less than 5%.
  • the above growth control rate is the fresh weight control rate.
  • the monocotyledonous and dicotyledonous weed seeds (Artemisia sativa, shepherd's purse, velvet hemp, pig scorpion, chickweed, Maijiagong, sage, kannada, Japanese kannada, goosegrass, sage, hard Grass, candlegrass, mother-in-law, brome, knotweed, amaranthus, amaranthus, quinoa, commelina, endive, field bindweed, spiny cabbage, nightshade, iron amaranth, crabgrass, barnyardgrass Grass, green foxtail, golden foxtail, daughter of a daughter, bermudagrass, sagittarius, firefly, Cyperus cyperus, broken rice sedge, special-shaped sedge, fluttering grass, purslane, cocklebur, morning glory, liquor grass, etc.) And the main crop seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum,
  • Control compound A (clomazone dichloride); control compound B: clomazone.
  • the compound of the present invention has better crop safety than commercialized clomazone and diclomazone, especially safer for wheat and rice, and is more effective in crabgrass It has comparable or even better herbicidal activity on key weeds such as , Stephania chinensis, Abutilus velvet, and Japanese kangaroo, and can establish better selectivity on crops.
  • the activity level criteria for plant destruction i.e. growth control rate are as follows:
  • Level 8 The growth control rate is greater than or equal to 80% and less than 100%
  • Level 7 The growth control rate is greater than or equal to 70% and less than 80%;
  • Level 6 The growth control rate is greater than or equal to 60% and less than 70%
  • Level 5 The growth control rate is greater than or equal to 50% and less than 60%;
  • Level 4 The growth control rate is greater than or equal to 40% and less than 50%;
  • Level 3 The growth control rate is greater than or equal to 30% and less than 40%;
  • Level 2 The growth control rate is greater than or equal to 15% and less than 30%;
  • Level 1 The growth control rate is greater than 0% and less than 15%;
  • the above growth control rate is the fresh weight control rate.
  • the monocotyledonous and dicotyledonous weed seeds (Artemisia sativa, shepherd's purse, velvet hemp, pig scorpion, chickweed, Maijiagong, sage, kannada, Japanese kannada, goosegrass, sage, hard Grass, candlegrass, mother-in-law, brome, knotweed, amaranthus, amaranthus, quinoa, commelina, endive, field bindweed, spiny cabbage, nightshade, iron amaranth, crabgrass, barnyardgrass Grass, green foxtail, golden foxtail, daughter of a daughter, bermudagrass, sagittarius, firefly, Cyperus cyperus, broken rice sedge, special-shaped sedge, fluttering grass, purslane, cocklebur, morning glory, liquor grass, etc.) And the main crop seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum,
  • the compound of the present invention has better soil sealing safety compared with commercial clomazone and diclomazone, and can maintain comparable or even better herbicidal activity, especially for ryegrass
  • Chickweed is very sensitive to clomazone-like compounds and is a good indicator of the volatility of bleaching compounds.
  • Untreated control plates, clomazone emulsifiable concentrate, and clomazone diclomazone emulsifiable concentrate formulations were included in each test. These formulations are the reference standards for the experimental formulations for comparison.
  • the 4 inch plastic canisters were fitted with a paper basket coffee filter cut to size that was placed in the bottom of each canister to cover the drain hole and prevent soil from draining from the bottom of the canister.
  • Each pot was filled with sandy loam soil sifted through a #10 mesh screen (to remove large soil particles and debris). Fill soil pots and water lightly before applying the treatment.
  • the test solutions were applied to the soil surface with a sprayer, and each test solution was repeated 2 times at a rate of 0.25 kg a.i./ha.
  • Each replicate test was assembled by placing an empty 4 inch plastic jar on top of the greenhouse.
  • the cans contained mature chickweed, approximately 2 inches in height, placed around each empty can in an 8-spoke pattern.
  • 4 cans of mature chickweed were placed at the 3, 6, 9 and 12 o'clock directions of the spokes, while the other 3 cans were placed at the 1:30, 4:30, 7:30 and 10:30 directions of the spokes.
  • the empty 4 inch pots were removed from each assembly and a treated 4 inch soil pot was placed in its place.
  • Untreated chickweed plants were evaluated for phytotoxic injury 14 days after treatment. Volatility was assessed by measuring the distance from the center of the treated soil pot to the endpoint at which the bleaching effect was observed on each spoke.
  • Sow main crops and weeds after sowing and pre-emergence in the field After testing, spinach, radish, cabbage, sesame, rapeseed, cucumber, watermelon, melon, pumpkin, cassava, soybean, kidney bean, cowpea, kidney bean, lentil, loofah, sorghum, Garlic, rice, corn, cauliflower, cabbage, and coriander were all safe to compound 1 at a dose of 300g a.i./ha, and it was also effective against barnyard grass, stephenia, crabgrass, wormwood, shepherd's purse, pig's weed, chickweed, and ryegrass The main weeds control effect is excellent, such as , brome, and big-sui Kan Mai Niang.
  • the required active ingredient B is purchased from a reagent company or synthesized by a known method.
  • the original medicines all use acetone as a solvent, and are diluted with an aqueous solution of 0.1% emulsifier Tween-80, and are diluted immediately after use.
  • Weeds are cultivated in pots, using 180 ⁇ 140mm plastic nutrient pots, placed in enamel trays, and filled with surface soil (4/5 places) collected from the farmland and air-dried and sieved.
  • the initial soil humidity is controlled at 20%, and the seeds are selected.
  • For plump and uniform weed seeds soak them in warm water at 25°C for 6 hours, and germinate them in a biochemical incubator (dark) at 28°C. Place the newly white weed seeds evenly on the soil surface, and then cover with soil 0.5- 1cm.
  • Cultivation is carried out in a controlled sunlight greenhouse at a temperature of 20-30°C, natural light, and a relative humidity of 57%-72%.
  • Each treatment was repeated 4 times, each treatment was 4 pots, and 20 weed seeds were sown in each pot.
  • the test shared the medicine 1 time. When the weeds are at the 1.5-2 leaf stage, thin the seedlings, keep 10 weeds in each pot, and keep 10 plants for each treatment, and then continue to cultivate until 2-3 leaves of barnyardgrass, 5-6 leaves of spinach, and 3 - 4 round leaves, 3-5 leaves of Amaranthus retroflexus, barnyardgrass, ryegrass multiflora and 3 leaves of crabgrass for treatment.
  • test materials Place the cultured test materials evenly on a platform with an area of 0.5m 2 , spray the stems and leaves with a 3WP-2000 walking spray tower, the spray volume is 450 kg/ha, and the spray pressure is 0.3MPa. After all the liquid medicine is sprayed, close the air valve, and after 30 seconds, open the door of the spray tower and take out the nutrition bowl. Then open the air valve, spray 50mL of water, and clean the spray pipe. After treatment, the test materials were transferred to the greenhouse for routine cultivation.
  • the weeds are cultivated in a controlled solar greenhouse with a temperature of 20-30°C, natural light, and a relative humidity of 57%-72%.
  • the test soil is quantitatively filled to 3/4 of the pot, and then watered from the bottom of the pot to make the soil completely wet to saturated. Weed seeds of the tested weeds were accelerated to dew white, and then evenly and quantitatively sowed on the surface, covered with soil 0.5-1cm according to the size of the seeds, and set aside 72 hours after sowing.
  • Each treatment was repeated 4 times, each treatment had 4 pots, and 20 weed seeds were sown in each pot.

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Abstract

本发明属于农药技术领域，具体涉及一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用。所述3-异恶唑烷酮类化合物，如通式I所示：其中，Q1、Q2分别独立地代表O或S；R1、R2分别独立地代表烷基。所述化合物在维持相当甚至更好的除草活性的基础上具有更优异的作物安全性，能够在作物上建立更好的选择性；而且本发明的化合物拥有更好的抗挥发性，不易飘移。

Description

一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用 技术领域
本发明属于农药技术领域，具体涉及一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用。
背景技术
杂草的防治是实现高效农业过程中一个至关重要的环节，尽管市场上的除草剂种类多样，比如专利US1105357等公开了通式化合物
Figure PCTCN2022109677-appb-000001
作为除草剂的用途。然而，这些已知化合物对有害植物的除草性能和对作物的选择性并不完全令人满意。且近几年除草剂飘移药害日趋严重，必须引起重视，比如异噁草松也是常见的飘移药害，其挥发性较强，雾滴或蒸气飘移可能导致附近某些植物叶片变白或变黄。这就需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。
发明内容
为解决现有技术中存在的上述问题，本发明提供了一种3-异恶唑烷酮类化合物及其制备方法、除草组合物和应用，所述化合物在维持相当甚至更好的除草活性的基础上具有更优异的作物安全性，能够在作物上建立更好的选择性；而且本发明的化合物拥有更好的抗挥发性，不易飘移。
本发明采用的技术方案如下：
一种3-异恶唑烷酮类化合物，如通式I所示：
Figure PCTCN2022109677-appb-000002
其中，Q 1、Q 2分别独立地代表O或S；
R 1、R 2分别独立地代表烷基，优选C1-C8烷基，更优选C1-C6烷基。
在一个具体实施方案中，Q 1、Q 2分别独立地代表O；R 1、R 2分别独立地代表甲基(即化合物1)。
在上述通式所示化合物的定义和以下所有结构式中，所用专业术语不论单独使用或者使用在复合词中，代表如下取代基：具有多于两个碳原子的烷基基团可为直链或支链的。烷基基团为，例如，C1烷基-甲基；C2烷基-乙基；C3烷基-丙基如正丙基或异丙基；C4烷基-丁基如正丁基、异丁基、叔丁基或2-丁基；C5烷基-戊基如正戊基；C6烷基-己基如正己基、异己基和1,3-二甲基丁基。卤素为氟、氯、溴或碘。
本发明还提供所述3-异恶唑烷酮类化合物的制备方法，包括以下步骤：
将通式Ⅱ所示的化合物和通式Ⅲ所示的化合物进行取代反应，制得通式Ⅰ所述的化合物；其化学反应方程式如下：
Figure PCTCN2022109677-appb-000003
其中，Hal代表卤素，优选溴。
优选地，所述步骤在碱和溶剂的存在下进行。
所述碱选自无机碱(如K 2CO 3、Na 2CO 3、Cs 2CO 3、NaHCO 3、KF、CsF、KOAc、AcONa、K 3PO 4、t-BuONa、EtONa、NaOH、KOH、NaOMe等)或有机碱(如吡唑、三乙胺、DIEA等)中的至少一种。
所述溶剂选自DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷、甲苯或乙酸乙酯中的至少一种。
本发明还提供一种除草剂组合物，其包括(i)除草有效量的所述的3-异恶唑烷酮类化合物中的至少一种。
任选地，所述除草剂组合物还包括(ii)一种或多种除草有效量的另外的除草剂和/或安全剂。
优选地，所述除草剂组合物还包括(iii)农业化学上可接受的制剂助剂。
本发明还提供一种防治不希望的植物的方法，包括将除草有效量的所述的3-异恶唑烷酮类化合物中的至少一种或所述的除草剂组合物施用至植物或者其场所或施用至土壤或水体以防治不希望的植物出苗或生长。
优选地，所述不希望的植物包括除草剂抗性或耐受性杂草物种。
本发明还提供所述的3-异恶唑烷酮类化合物中的至少一种或所述的除草剂组合物在控制不希望的植物上的用途。
优选地，将所述的3-异恶唑烷酮类化合物用于防除有用作物中的杂草。
更优选地，所述有用作物包括转基因作物或者基因组编辑技术处理过的作物，所述杂草包括除草剂抗性或耐受性杂草物种。
对于许多经济上重要的单子叶和双子叶有害植物，本发明的式I化合物具有突出的除莠活性。本发明的活性物质也对于多年生杂草有效，这些杂草从根茎、根状茎、或其它的多年生的器官上生长出来，很难控制。关于这点，是否在播种前、萌发前或萌发后使用该物质一般不重要。特别提及本发明化合物可以控制的单子叶和双子叶杂草群的代表例子，没有限制到的确定的物种。活性物质有效作用的杂草物种的例子包括单子叶植物：一年生燕麦属、黑麦、草属、看麦娘属、法拉里斯、稗、马唐属、狗尾草属和莎草属，和多年生的冰草属、狗牙根属、白茅属和高粱属、以及多年生的莎草属。
关于双子叶杂草物种，其作用可以扩展到的物种例如一年生的猪殃殃属、堇菜属、婆婆纳属、野芝麻属、繁缕属、苋属、白芥属、番薯属、黄花稔属、母菊属和苘麻属，和多年生 杂草旋花属、蓟属、酸模属和艾属。本发明活性物质在水稻播种这种待定条件下有效控制有害植物，例如稗、慈姑属、泽泻属、荸荠属、蔗草和莎草属。如果将本发明化合物在萌芽前施用于土壤表面，可以在杂草长出前完全预防杂草的秧苗，或在杂草长出子叶时就停止生长，最后在三到四星期之后完全死亡。本发明化合物特别抗下述植物的活性优良，阿皮拉草、小野芝麻、卷茎蓼、繁缕、长春藤叶婆婆纳、阿拉伯婆婆纳、三色堇和苋、猪殃殃属和地肤。
虽然本发明化合物对于单子叶和双子叶的杂草具有优良的除莠活性，但对于重要的经济类作物植物，例如花生、小麦、大麦、黑麦、稻子、玉米、甜菜、棉花和大豆却根本没有损害，或者是损害是微不足道的。特别是和谷类作物相容得很好，例如小麦、大麦和玉米，特别是小麦。因此，本发明化合物非常适于有选择地控制在农用作物或观赏植物中的无用植物。
由于它们的除莠性质，在已知或将要出现的遗传工程的植物耕种中，这些活性物质可以用于控制有害植物。转基因植物通常具有优越的性状，例如对特定杀虫剂特别是特定除草剂的抵抗力，对植物病害或植物病害的致病微生物的抵抗力，例如特定的昆虫或真菌、细菌或病毒的微生物。其它的特别性状与产品的下述条件有关，例如，数量、质量、贮存稳定性、组分和特殊的成分。如此，已经知道获得的转基因植物产品具有增加的淀粉含量或改进的淀粉质量或不同的脂肪酸成份。
本发明的式I化合物或其盐优选用于，经济上重要的转基因的作物和观赏植物，例如谷类，例如小麦、大麦、黑麦、燕麦、粟、稻子、木薯和玉米、或用于甜菜、棉花、大豆、油菜籽、马铃薯、番茄、豌豆及其他蔬菜类植物的耕种。式I化合物优选用于有用植物耕种的除草剂，这些植物具有抗药性或通过遗传工程对除草剂的毒害作用具有抗药性。
传统的繁育具有比已知植物具有改进形状植物的方法包括，例如传统的交配方法和突变株繁育。换句话说，可以借助于遗传工程的方法(参见，例如EP-0221044 A，EP-0131624 A)来得到具有改进性状的新植物。例如，已经描述了几个方法：
-为了改进植物中的淀粉合成，利用遗传工程改变作物植物(例如WO 92/11376，WO 92/14827，WO 91/19806)；
-对特定的除草剂具有抗性的转基因作物植物，对草丁膦除草剂(例如EP-0242236 A，EP-0242246 A)或对草甘膦类除草剂(WO 92/00377)，或对磺酰脲类除草剂(EP-0257993 A，US-5013659 A)；
-例如棉花的转基因作物植物，它能够产生苏芸金杆菌毒素(Bt毒素)，这种毒素可以防御特定害虫对植物的侵害(EP-0142924 A，EP-0193259 A)；
-具有改进的脂肪酸成份的转基因作物植物(WO91/13972)。
已经知道许多能够制备具有改进性状转基因植物分子生物技术(参见，例如Sambrook等，1989，分子扩增，实验手册第二版，美国冷泉港实验室出版，冷泉港，纽约；或Winnacker“Gene und Klone”[基因和克隆]，VCH Weinheim，第二版1996或Christou，“植物科学的趋势”1(1996)423-431))。为了实现遗传工程的操作，可能将核酸分子引入质粒，通过DNA序列的重组，发生突变或序列改变。利用上述的标准方法，例如可以交换底物、除去部分序 列或增加自然的或合成的序列。为了将DNA片段互相连接，有可能在片段上附带有结合体或连接体。
可以用下述方法制备降低活性的基因产品的植物细胞，例如通过表达至少一种适当的反义-RNA、正义-RNA来达到共抑制的效果，或通过表达至少一种适当构造的核糖酶，它特定裂解上述基因产品的转录产物。
为此目的，有可能使用包含基因产物全部编码序列的DNA分子，包括有可能存在的任何旁侧序列，和使用包含仅仅一部分编码序列的DNA分子，这些部分必须足够长以达到在细胞中反义的效果。也可以使用与基因产物编码序列具有高度同源性但不完全相同的序列。
当在植物中表达核酸分子时，合成的蛋白质可以在任何期望的植物细胞室中定位。然而为了在特定的室定位，有可能例如将编码区和DNA序列连接，以确保在特定位置定位。这些序列为本领域所属技术人员已知的(参见，例如Braun等，EMBO J.11(1992)3219-3227；Wolter等，Proc.Natl.Acad.Sci.USA 85(1988)，846-850；Sonnewald等Plant J.1(1991)，95-106)。
利用已知的技术可以将转基因植物细胞重组到整个植物上。转基因植物可以为任何期望的植物品种，即单子叶和双子叶植物。用这样的方式，通过超表达、禁止或抑制同源(＝自然的)基因或基因序列，或通过异种的(＝外部的)基因或者基因序列的表达，有可能获得改进性状的转基因植物。
当在转基因的作物上使用本发明的活性物质时，除了具有在其它作物上可观察到的抑制有害植物的效果外，经常在相应的转基因作物上会有特殊的效果，例如可以改进或扩大控制杂草的范围，改进应用时的施用量，优选转基因作物的抗药性和除草剂的性能很好的结合，并且转基因的作物植物的生长和产率的影响。因此本发明也提供了所述化合物的用途，作为除草剂控制转基因作物植物中的有害植物。
另外本发明化合物可以明显调节作物植物的生长。通过调节参与植物代谢，使用这些化合物定向控制植物的组分和促进收获，例如使植物干化和矮化生长。而且它们也适于调节和抑制不希望的植物生长，而不破坏作物的生长。抑制植物的生长在许多单子叶植物和双子叶植物作物中起着非常重要的作用，因为这样可以减少或完全预防倒伏。
可以使用一般的制剂来应用本发明的化合物，可使用可湿性粉剂、浓缩乳剂、可喷洒的溶液、粉末或颗粒。这样本发明也提供了包括式I化合物的除草剂组合物。根据通常的生物学和/或化学的物理参数，可以用多种方式配制式I化合物。适合的制剂选择实例为：可湿性粉剂(WP)、水溶性的粉末(SP)、水溶性的浓缩物、浓缩乳剂(EC)、例如油在水中分散和水在油中分散的乳剂(EW)、可喷洒溶液、悬浮剂浓缩物(SC)、可分散油悬浮剂(OD)、以油或水为稀释剂的悬浮液、可混溶油的溶液、粉末(DP)、胶囊悬浮液(CS)、包核(seeddressing)组合物、用于撒播和土壤施药的颗粒、喷射颗粒、涂覆颗粒和吸收颗粒，水中可分散的颗粒(WG)、水溶性的颗粒(SG)、ULV(超低容量)配方、微囊和蜡制品。这些单个的制剂类型为已知的，在下述文献中有描述，例如Winnacker-Küchler，“Chemische Techonologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986；Wade van Valkenburg， “Pesticide Formulations”，Marcel Dekker，N.Y.，1973；K.Martens，“Spray Drying”手册，第3版1979，G.Goodwin Ltd.London。
必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂同样为已知的，并在下述文件中描述，例如Watkins的“粉末稀释剂杀虫剂和载体手册”，第二版，Darland书Caldwell N.J.；H.v.01phen“粘土胶体化学的入门”，第二版，J.Wiley和Sons，N.Y.；C.Marsden的“溶剂指南”第二版，Interscience，N.Y.1963；McCutcheon的“洗涤剂和乳化剂年报”，MC发行公司，Ridgewood N.J.；Sisley和Wood，“表面活性剂百科全书”，化学出版公司，N.Y.1964；
Figure PCTCN2022109677-appb-000004
的
Figure PCTCN2022109677-appb-000005
[环氧乙烷加成物表面活性剂]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-Küchler的“Chemische Technologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986。
可湿性粉剂能均匀地可分散在水中，除了活性物质，还包括稀释剂或惰性物质、离子和非离子型表面活性剂(润湿剂、分散剂)，例如聚乙氧基烷基酚、聚乙氧基脂肪醇、聚氧乙基脂肪族胺、脂肪醇聚二醇醚硫酸盐、烷基磺酸盐、烷基苯基磺酸盐、木质磺酸钠、2,2’-二萘甲烷-6,6’-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为了制备可湿性粉剂，将除草剂的活性物质细磨，例如使用常用的仪器，如用锤磨机、风扇磨碎机和喷气式磨碎机，同时或顺序混入助剂。
将活性物质溶解在有机溶剂中制备浓缩乳剂，溶剂例如丁醇、环己酮、二甲基甲酰胺、二甲苯或较高沸点的芳族化合物或碳氢化合物或溶剂的混合物，并再加入一种或多种离子的和/或非离子型表面活性剂(乳化剂)。可以使用的乳化剂的例子为例如十二烷基苯磺酸钙的烷基芳基磺酸钙，或非离子乳化剂，例如脂肪酸聚二醇酯、烷基芳香基聚二醇醚、脂肪醇聚二醇醚、氧化丙烯-环氧乙烷缩合产物、烷基聚醚、例如山梨糖醇酐脂肪酸酯的山梨聚糖酯，或例如聚氧化乙烯山梨糖醇酐脂肪酯的聚氧化乙烯山梨聚糖酯。
将活性物质和细碎的固态物质研磨得到粉末，固态物质例如滑石、如高岭土、皂土和叶蜡石的天然粘土、或硅藻土。以水或油为基底的悬浮液可以通过下述方法制备，例如利用商业上通用的玻珠研磨机进行湿磨，加入或不加入上述另一个制剂类型的表面活性剂。
制备例如水包油乳化剂(EW)的乳剂，可以使用含水的有机溶剂，使用搅拌器、胶体研磨器和/或静态混合器，如果需要，加入如上所述另一个制剂类型的表面活性剂。
用下述方法制备颗粒剂，将活性物质喷到吸附物上，使用惰性物料颗粒化，或将活性物质浓缩到例如沙、高岭石载体的表面，通过粘合剂将惰性物料粒化，粘合剂例如聚乙烯醇、聚丙烯酸钠或矿物油。可以用制备肥料颗粒剂的方法将合适的活性物质粒化，如果需要可以混有肥料。使用通常的方法制备水悬浮颗粒剂，例如喷洒-干燥，流化床造粒、磨盘造粒、使用高速混合机混合，并在无固体惰性物料的情况下挤压。
关于使用磨盘、流化床、挤压机和喷涂颗粒剂的制备方法，参见下述工艺，例如“Spray Drying手册”第三版1979，G.Goodwin有限公司，伦敦；J.E.Browning，“Agglomeration”，化学和工程1967，147ff页；“Perry’s化学的工程师手册”，第五版，McGraw-Hill，纽约1973，8-57页。如果要知道关于作物保护产品的制剂，参见例如，G.C.Klingman,“Weed Control as  a Science”，John Wiley和Sons公司，纽约，1961 81-96页和J.D.Freyer，S.A.Evans“杂草防除手册”，第五版，Blackwell Scientific Rublications，牛津大学1968，101-103页。
农用化学品制剂通常包含按重量计0.1到99％，特别是0.1到95％的活性物质式I。可湿性粉剂中活性物质的浓度为，按重量计例如从大约10到99％，通常的制剂组分构成按重量计剩余量到100％。活性物质在浓缩乳剂中的浓度按重量计可以为大约1到90％，优选5到80％。粉末制剂包含按重量计1到30％的活性物质，通常优选按重量计5到20％的活性物质，然而可喷洒的溶液包含按重量计大约0.05到80％，优选2到50％的活性物质。关于水悬浮颗粒剂中活性物质的含量，主要根据活性物质为液体还是固态，和造粒时使用的助剂、填料等等。水悬浮颗粒剂中活性物质的含量例如按重量计在1到95％之间，优选按重量计在10到80％之间。
另外所述的活性物质的制剂可以包括增粘剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂和通常在所有情况下都常用的pH和粘度调节剂。
以这些制剂为基础，也可能和其他杀虫剂活性物质例如杀虫剂、杀螨剂、除草剂和杀菌剂混合，也可以和安全剂、肥料和/或植物生长调节剂混合，混合方式可以为预先混合好的或灌装混合。
在混配制剂或桶混制剂中，可以和本发明的式I化合物混合的合适的活性物质为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的除草剂活性物质可以和化合物1混合(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：
(1)HPPD(Hydroxyphenyl Pyruvate Dioxygenase)抑制剂类：包括但不限于下述类型，
1)三酮类，例如，磺草酮(Sulcotrione，CAS NO：99105-77-8)；硝磺草酮(Mesotrione，CAS NO：104206-82-8)；氟吡草酮(bicyclopyrone，CAS NO：352010-68-5)；环磺酮(tembotrione，CAS NO：335104-84-2)；呋喃磺草酮(tefuryltrione，CAS NO：473278-76-1)；双环磺草酮(Benzobicyclon，CAS NO：156963-66-5)；
2)二酮腈类，例如，2-氰基-3-环丙基-1-(2-甲基磺酰基-4-三氟甲基苯基)丙-1，3-二酮(CAS NO：143701-75-1)；2-氰基-3-环丙基-1-(2-甲基磺酰基-3,4-二氯苯基)丙-1，3-二酮(CAS NO：212829-55-5)；2-氰基-1-[4-(甲基磺酰基)-2-三氟甲基苯基]-3-(1-甲基环丙基)丙-1,3-二酮(CAS NO：143659-52-3)；
3)异噁唑类，例如，异噁氟草(isoxaflutole，CAS NO：141112-29-0)；异噁氯草酮(isoxachlortole，CAS NO：141112-06-3)；异恶草酮(clomazone，CAS NO：81777-89-1)；
4)吡唑类，例如，苯唑草酮(topramezone，CAS NO：210631-68-8)；磺酰草吡唑(pyrasulfotole，CAS NO：365400-11-9)；苄草唑(pyrazoxyfen，CAS NO：71561-11-0)；吡唑特(pyrazolate，CAS NO：58011-68-0)；吡草酮(benzofenap，CAS NO：82692-44-2)；双唑草酮(CAS NO：1622908-18-2)；Tolpyralate(CAS NO：1101132-67-5)；苯唑氟草酮(CAS NO：1992017-55-6)；环吡氟草酮(CAS NO：1855929-45-1)；三唑磺草酮(CAS NO： 1911613-97-2)；
5)二苯酮类；
6)其他类：lancotrione(CAS NO：1486617-21-3)；fenquinotrione(CAS NO：1342891-70-6)；fufengcao’an(CAS NO：2421252-30-2)；
以及专利CN105264069A提及的那些。
(2)EPSPS(Enolpyruvyl Shikimate Phosphate Synthase)抑制剂类：如草硫膦(sulphosate)，草甘膦(Glyphosate)，草甘膦异丙胺盐(glyphosate-isopropylammonium)和草甘膦三甲基硫盐(glyphosate-trimesium)；
(3)PPO(Protoporphyrinogen Oxidase)抑制剂类：分为嘧啶二酮(pyrimidinediones)、二苯醚(diphenyl-ethers)、苯基吡唑(phenylpyrazoles)、N-苯基酰亚胺(N-phenylphthalimides)、噻二唑(thiadiazoles)、噁二唑(oxadiazoles)、三唑啉酮(triazolinones)、噁唑烷二酮(oxazolidinediones)和其他不同化学结构的除草剂。
在一个示例性实施例中，嘧啶二酮类除草剂包括但不限于氟丙嘧草酯(CAS NO：134605-64-4)、苯嘧磺草胺(CAS NO：372137-35-4)、双苯嘧草酮(CAS NO：158755-95-4)、氟嘧硫草酯(tiafenacil，CAS NO：1220411-29-9)、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶基氧基]乙酸乙酯(Epyrifenacil，CAS NO：353292-31-6)、1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]噁嗪-6-基)-1H-嘧啶-2,4-二酮(CAS NO：1304113-05-0)、3-[7-氯-5-氟-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)-1H-嘧啶-2,4-二酮(CAS NO：212754-02-4)、flupropacil(CAS NO：120890-70-2)、CN105753853A中公开的含异恶唑啉的尿嘧啶类(如化合物
Figure PCTCN2022109677-appb-000006
)、WO2017/202768中公开的尿嘧啶吡啶以及WO2018/019842中公开的尿嘧啶类；
二苯醚类除草剂包括但不限于氟磺胺草醚(fomesafen，CAS NO：72178-02-0)、乙氧氟草醚(CAS NO：42874-03-3)、苯草醚(CAS NO：74070-46-5)、氟乳醚(CAS NO：131086-42-5)、乳氟禾草灵(CAS NO：77501-63-4)、甲氧除草醚(CAS NO：32861-85-1)、草枯醚(CAS NO：1836-77-7)、乙羧氟草醚(CAS NO：77501-90-7)、三氟羧草醚或钠盐(acifluorfen，CAS NO：50594-66-6或62476-59-9)、甲羧除草醚(CAS NO：42576-02-3)、氯氟草醚(CAS NO：188634-90-4)、fluoronitrofen(CAS NO：13738-63-1)、furyloxyfen(CAS NO：80020-41-3)、nitrofluorfen(CAS NO：42874-01-1)和halosafen(CAS NO：77227-69-1)；
苯基吡唑类除草剂包括但不限于吡草醚(CAS NO：129630-19-9)和异丙吡草酯(fluazolate，CAS NO：174514-07-9)；
N-苯基酰亚胺类除草剂包括不限于丙炔氟草胺(CAS NO：103361-09-7)、吲哚酮草酯(CAS NO：142891-20-1)、Flumipropyn(CAS NO：84478-52-4)和氟烯草酸(CAS NO：87546-18-7)；
噻二唑类除草剂包括不限于嗪草酸甲酯(fluthiacet-methyl，CAS NO：117337-19-6)、嗪草酸(CAS NO：149253-65-6)和噻二唑草胺(CAS NO：123249-43-4)；
噁二唑类除草剂包括不限于丙炔噁草酮(CAS NO：39807-15-3)和噁草酮(CAS NO：19666-30-9)；
三唑啉酮类除草剂包括不限于唑草酮(carfentrazone，CAS NO：128621-72-7)、唑草酮乙酯(carfentrazone ethyl，CAS NO：128639-02-1)、甲磺草胺(sulfentrazone，CAS NO：122836-35-5)、唑啶草酮(CAS NO：68049-83-2)和酰苯草酮(bencarbazone，CAS NO：173980-17-1)；
噁唑烷二酮类除草剂包括不限于环戊噁草酮(CAS NO：110956-75-7)；
其他除草剂包括不限于双唑草腈(CAS NO：158353-15-2)、氟哒嗪草酯(CAS NO：188489-07-8)、氟唑草胺(CAS NO：190314-43-3)、三氟草嗪(trifludimoxazin，CAS NO：1258836-72-4)、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS NO：452100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]噁嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷-2，4-二酮(CAS NO：451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]噁嗪-6-基)-4,5,6,7-四氢-异吲哚-1,3-二酮(CAS NO：1300118-96-0)、(E)-4-[2-氯-5-[4-氯-5-(二氟甲氧基)-1H-甲基-吡唑-3-基]-4-氟-苯氧基]-3-甲氧基-丁-2-烯酸甲酯(CAS NO：948893-00-3)、WO2016/120116中公开的苯吡啶类、EP09163242.2中公开的苯并噁嗪酮衍生物以及CN113105405A中公开的羧酸衍生物取代的亚氨基芳基化合物；
(4)ALS(Acetolactate Synthase)抑制剂类包括但不限于如下除草剂或其混合物：
磺酰脲类如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、苄嘧黄隆甲酯(bensulfuron-methyl)、氯嘧黄隆(chlorimuron)、氯嘧黄隆乙酯(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯磺隆(ethametsulfuron)、胺苯磺隆甲酯(ethametsulfuron-methyl)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、氟啶黄隆甲酯钠盐(flupyrsulfuron-methyl-sodium)、甲酰胺黄隆(foramsulfuron)、氯吡嘧磺隆(halosulfuron)、氯吡嘧磺隆甲酯(halosulfuron-methyl)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、碘黄隆甲酯钠盐(iodosulfuron-methyl-sodium)、iofensulfuron、iofensulfuron钠盐、甲磺胺黄隆(mesosulfuron)、嗪吡嘧磺隆(metazosulfuron)、甲磺隆(metsulfuron)、甲磺隆甲酯(metsulfuron-methyl)、烟黄隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧黄隆(oxasulfuron)、氟嘧磺隆(primisulfuron)、氟嘧磺隆甲酯(primisulfuron-methyl)、丙嗪嘧磺隆(propyrisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、吡嘧黄隆乙酯(pyrazosulfuron-ethyl)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、嘧黄隆甲酯(sulfometuron-methyl)、乙黄黄隆(sulfosulfuron)、噻磺隆(thifensulfuron)、噻磺隆甲酯 (thifensulfuron-methyl)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、苯黄隆甲酯(tribenuron-methyl)、三氟啶黄隆(trifloxysulfuron)、Trifloxysulfuron-Na(三氟啶黄隆-钠盐)、氟胺磺隆(triflusulfuron)、氟胺磺隆甲酯(triflusulfuron-methyl)和三氟甲磺隆(tritosulfuron)；
咪唑啉酮类如咪草酯(imazamethabenz)、咪草甲酯(imazamethabenz-methyl)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)和咪草烟(imazethapyr)；
三唑并嘧啶除草剂和磺酰苯胺类如氯酯磺草胺(cloransulam)、氯酯磺草胺甲酯(cloransulam-methyl)、唑嘧磺胺(diclosulam)、氟唑啶草(flumetsulam)、双氟磺草胺(florasulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、吡唑磺草胺(pyroxsulam)、pyrimisulfan和氟酮磺草胺(triafamone)；
嘧啶基苯甲酸类如双草醚(bispyribac)、双草醚钠盐(bispyribac-sodium)、嘧啶肟草醚(pyribenzoxim)、pyriftalid、pyriminobac、嘧草醚(pyriminobac-methyl)、嘧硫苯甲酸(pyrithiobac)、嘧硫苯甲酸(pyrithiobac)钠盐，4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧]苯基]甲基]氨基]-苯甲酸-1-甲基乙酯(CAS NO：420138-41-6)、4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧]苯基]甲基]氨基]-苯甲酸丙酯(CAS NO：420138-40-5)、N-(4-溴苯基)-2-[(4,6-二甲氧基-2-嘧啶基)氧]苯甲胺(CAS NO：420138-01-8)；
磺酰氨基羰基-三唑啉酮类除草剂如氟酮磺隆(flucarbazone)、氟酮磺隆钠盐(flucarbazone-sodium)、丙苯磺隆(propoxycarbazone)、丙苯磺隆钠盐(propoxycarbazone-sodium)、噻酮磺隆(thiencarbazone)和噻酮磺隆甲酯(thiencarbazone-methyl)。
(5)ACCase(Acetyl CoA Carboxylas)抑制剂类：如噻唑禾草灵(Fenthiaprop)、禾草灭(alloxydim)、禾草灭钠盐(alloxydim-sodium)、丁氧环酮(butroxydim)、烯草酮(clethodim)、炔草酸(clodinafop)、炔草酸炔丙酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop)、氰氟草丁酯(cyhalofop-butyl)、氯甲草(diclofop)、氯甲草甲酯(diclofop-methyl)、唑禾草灵(fenoxaprop)、唑禾草灵乙酯(fenoxaprop-ethyl)、精唑禾草灵(fenoxaprop-P)、精唑禾草灵乙酯(fenoxaprop-P-ethyl)、吡氟禾草灵(fluazifop)、吡氟禾草灵丁酯(fluazifop-butyl)、精吡氟禾草灵(fluazifop-P)、精吡氟禾草灵丁酯(fluazifop-P-butyl)、氟吡禾灵(haloxyfop)、氟吡甲禾灵甲酯(haloxyfop-methyl)、精氟吡甲禾灵(haloxyfop-P)、精氟吡禾灵甲酯(haloxyfop-P-methyl)、唑酰草胺(metamifop)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵乙酯(quizalofop-ethyl)、喹禾灵四氢糠酯(quizalofop-tefuryl)、精喹禾灵(quizalofop-P)、精喹禾灵乙酯(quizalofop-P-ethyl)、精喹禾灵四氢糠酯(quizalofop-P-tefuryl)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)，4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯基]-3-基)-5-羟-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS NO：1312337-72-6)；4-(2',4'-二氯-4-环丙基[1,1'-联苯基]-3-基)-5-羟-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS NO：1312337-45-3)；4-(4'-氯-4-乙基-2'-氟[1,1'-联苯基]-3-基)-5-羟-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS NO：1033757-93-5)；4-(2',4'-二氯-4-乙基[1,1'-联苯基]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS NO：1312340-84-3)；5-(乙酰氧基)-4-(4'-氯-4-环丙基-2'-氟[1,1'- 联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS NO：1312337-48-6)；5-(乙酰氧基)-4-(2',4'-二氯-4-环丙基-[1,1'-联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮；5-(乙酰氧基)-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS NO：1312340-82-1)；5-(乙酰氧基)-4-(2',4'-二氯-4-乙基[1,1'-联苯基]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS NO：1033760-55-2)；4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯(CAS NO：1312337-51-1)；4-(2',4'-二氯-4-环丙基-[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯；4-(4'-氯-4-乙基-2'-氟[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯(CAS NO：1312340-83-2)；4-(2',4'-二氯-4-乙基[1,1'-联苯基]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基碳酸甲酯(CAS NO：1033760-58-5)；
(6)GS(Glutamine Synthetase)抑制剂类：如双丙氨酰膦(Bialaphos/bilanafos)，双丙氨酰膦钠(Bilanaphos-natrium)，草铵膦铵盐(Glufosinate-ammonium)，草铵膦(Glufosinate)和精草铵膦(glufosinate-P)；
(7)PDS(Phytoene Desaturase)抑制剂类：如氟咯草酮(flurochloridone)，呋草酮(flurtamone)，氟丁酰草胺(beflubutamid)，达草灭(norflurazon)，氟草酮(fluridone)，吡氟草胺(Diflufenican)，氟吡酰草胺(Picolinafen)，以及4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(CAS NO：180608-33-7)；
(8)DHPS(Dihydropteroate Synthase)抑制剂类：如磺草灵(Asulam)；
(9)DXPS(Deoxy-D-Xyulose Phosphate Synthase)抑制剂类：如Bixlozone和异噁草松(Clomazone)；
(10)HST(Homogentisate Solanesyltransferase)抑制剂类：如Cyclopyrimorate；
(11)SPS(Solanesyl Diphosphate Synthase)抑制剂类：如苯草醚(Aclonifen)；
(12)纤维素合成抑制剂(Cellulose Synthesis)类：如茚嗪氟草胺(Indaziflam)，Triaziflam，氯硫酰草胺(Chlorthiamid)，敌草腈(Dichlobenil)，异恶草胺(Isoxaben)，胺草唑(Flupoxam)，1-环己基-5-五氟苯氧基-1 4-[1,2,4,6]噻三嗪-3-基胺(CAS NO：175899-01-1)，以及CN109688807A中公开的吖嗪类；
(13)VLCFAS(Very Long-Chain Fatty Acid Synthesis)抑制剂类：包括但不限于下述类型，
1)氯乙酰胺类如乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、精异丙甲草胺(metolachlor-S)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、毒草安(propachlor)、异丙草胺(propisochlor)和噻醚草胺(thenylchlor)；
2)α-氧乙酰胺类(α-Oxyacetamides)如氟噻草胺(flufenacet)和苯噻草胺(mefenacet)；
3)α-硫代乙酰胺类(α-Thioacetamides)如莎稗磷(anilofos)和哌草磷(piperophos)；
4)唑基甲酰胺类如唑草胺(cafenstrole)、四唑草胺(fentrazamide)和ipfencarbazone；
5)苯并呋喃类如Benfuresate和乙氧呋草黄(Ethofumesate)；
6)异恶唑啉类如fenoxasulfone和派罗克杀草砜(pyroxasulfone)；
7)环氧乙烷类如Indanofan和灭草环(Tridiphane)；
8)硫代氨基甲酸酯类如草灭特(Cycloate)，哌草丹(Dimepiperate)，S-乙基二丙基硫代氨基甲酸酯(EPTC)，戊草丹(Esprocarb)，禾草敌(Molinate)，Orbencarb，苄草丹(Prosulfocarb)，禾草丹(Thiobencarb/Benthiocarb)，野麦畏(Triallate)，Vernolate，和式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉类化合物，以及WO 2006/024820、WO 2006/037945、WO 2007/071900和WO 2007/096576等专利中提及的其他异唑啉化合物。
Figure PCTCN2022109677-appb-000007
(14)脂肪酸硫酯酶(fatty acid thioesterase)抑制剂类：如环庚草醚Cinmethylin、Methiozolin；
(15)丝氨酸苏氨酸蛋白磷酸酶(serine threonine protein phosphatase)抑制剂类：如Endothall；
(16)番茄红素环化酶(lycopene cyclase)抑制剂类：如Amitrole。
(17)微管组装(Microtubule Assembly)抑制剂类：如氟草胺(Benefin/benfluralin)、地乐胺Butralin、氟硫草定Dithiopyr、噻唑烟酸Thiazopyr、乙丁烯氟灵Ethalfluralin、氨基丙氟灵Prodiamine、抑草磷Butamifos、氨磺乐灵Oryzalin、二甲戊灵Pendimethalin、氯钛酸甲酯Chlorthaldimethyl/DCPA、DMPA
Figure PCTCN2022109677-appb-000008
氟乐灵Trifluralin、炔苯酰草胺Propyzamide/pronamide、敌乐胺(Dinitramine，CAS NO：29091-05-2)；
(18)生长素模拟物类(Auxin Mimics)：如2,4,5三氯苯氧基乙酸(2,4,5-T)，2,4-二氯苯氧乙酸(2,4-D)，2,4-二氯苯氧丁酸(2,4-DB)，3,4-二氯苯氧丁酸(3,4-DB)，2,4-DEB(CAS NO： 94-83-7)，4-氯苯氧基乙酸(4-CPA)，4-CPP(CAS NO：3307-39-9)，cloprop(CAS NO：101-10-0)，clofop(CAS NO：26129-32-8)，氯甲酰草胺Clomeprop，2,4-滴丙酸Dichlorprop，2甲4氯(MCPA)，二甲四氯丁酸(MCPB)，2甲4氯丙酸(Mecoprop)，氯氨吡啶酸Aminopyralid，二氯吡啶酸Clopyralid，氯丙嘧啶酸Aminocyclopyrachlor，氯氟吡啶酯Florpyrauxifen，氟氯吡啶酯Halauxifen，二氯喹啉酸Quinclorac，草除灵乙酯Benazolin-ethyl，毒莠定Picloram，草灭平Chloramben，氯甲喹啉酸Quinmerac，氯氟吡氧乙酸Fluroxypyr，三氯吡氧乙酸Triclopyr，麦草畏Dicamba；
(19)D1丝氨酸264结合剂(和其他非组氨酸215结合剂)(D1 Serine 264 binders(and other non-histidine 215 binders))：如莠灭净Ametryne，莠去津Atrazine，草津净Cyanazine，异戊乙净Dimethametryn，扑灭通Prometon，扑草净Prometryne，扑灭津Propazine，西玛津Simazine，特丁津Terbuthylazine，特丁净Terbutryne，绿麦隆Chlorotoluron，敌草隆Diuron，伏草隆Fluometuron，异丙隆Isoproturon，利谷隆Linuron，秀谷隆Metobromuron，Methabenz thiazuron(CAS NO：18691-97-9)，灭草隆Monuron，丁噻隆Tebuthiuron，环嗪酮Hexazinone，苯嗪草酮Metamitron，嗪草酮Metribuzin，除草定Bromacil，环草定Lenacil，特草定Terbacil，杀草敏Chloridazon/pyrazon，胺唑草酮Amicarbazone，甜菜安Desmedipham，甜菜宁Phenmedipham，丁酰草胺(Chloranocryl/dicryl，CAS NO：2164-09-2)，敌稗Propanil，可乐津(chlorazine，CAS NO：580-48-3)，环草津(cyprazine，CAS NO：22936-86-3)，草达津(trietazine，CAS NO：1912-26-1)，methoprotryne(CAS NO：841-06-5)，西草净simetryn；
(20)D1组氨酸215结合剂(D1 Histidine 215 binders)：如溴苯腈Bromoxynil，碘苯腈Ioxynil，哒草特Pyridate，灭草松Bentazon；
(21)生长素转运(Auxin Transport)抑制剂类：如氟吡草腙(Diflufenzopyr，CAS NO：109293-97-2)，抑草生Naptalam；
(22)PS l电子转移(PS l Electron Diversion)：如敌草快Diquat，百草枯Paraquat；
(23)微管组织抑制剂类(Inhibition of Microtubule Organization)：如卡草胺(Carbetamide，CAS NO：16118-49-3)，燕麦灵(Barban，CAS NO：101-27-9)，氯苯胺灵Chlorpropham；
(24)解偶联剂(Uncouplers)：如地乐酚Dinoseb，4,6-二硝基邻甲酚(DNOC)；
(25)其他：如地散磷Bensulide，溴丁酰草胺Bromobutide，苄草隆Cumyluron，野燕枯Difenzoquat，稗草畏(Pyributicarb，CAS NO：88678-67-5)，甲基砷酸二钠DSMA，单甲基砷酸钠MSMA，杀草隆Dymron/daimuron，乙氧苯草胺Etobenzanid，麦草氟甲酯Flamprop-m，调节膦Fosamine，噁嗪草酮Oxaziclomefone，天竺葵酸Pelargonic acid，草乃敌Diphenamid，萘丙胺Naproanilide，草萘胺Napropamide，Napropamide-m，Benzofluor(CAS NO：68672-17-3)，Cambendichlor(CAS NO：56141-00-5)，dipropalin(CAS NO：1918-08-7)，etnipromid(CAS NO：76120-02-0)，bromobonil(CAS NO：25671-46-9)，monisouron(CAS NO：55807-46-0)，bromofenoxim(CAS NO：13181-17-4)，氯酰草膦(clacyfos，CAS NO：215655-76-8)，chlorazifop(CAS NO：60074-25-1)，喹草烯，brompyrazon(CAS NO：304284-0)，乙嗪草酮ethiozin，methiuron(CAS NO：21540-35-2)，甲氧隆(metoxuron，CAS NO：19937-59-8)，四 氟隆(tetrafluron，27954-37-6)，噻苯隆(thidiazuron，CAS NO：51707-55-2)，丙烯醛acrolein，氟萘禾草灵。
在一种具体实施方式中，和化合物1(组分A)混合的另一种除草剂(组分B)选自以下化合物中的一种或两种以上：硝磺草酮(CAS号:104206-82-8)、呋喃磺草酮(CAS号:473278-76-1)、双环磺草酮(CAS号:156963-66-5)、双唑草酮(CAS号:1622908-18-2)、环吡氟草酮(CAS号:1855929-45-1)、三唑磺草酮(CAS号:1911613-97-2)、苯唑氟草酮(CAS号:1992017-55-6)、fenquinotrione(CAS号:1342891-70-6)、
Figure PCTCN2022109677-appb-000009
(CAS号:2421252-30-2)、异噁唑草酮(CAS号:141112-29-0)、氟咯草酮(CAS号:61213-25-0)、吡氟酰草胺(CAS号:83164-33-4)、氟吡酰草胺(CAS号:137641-05-5)、氟丁酰草胺(CAS号:113614-08-7)、氟啶草酮(CAS号:59756-60-4)、异噁草松(CAS号:81777-89-1)、bixlozone(CAS号:81777-95-9)、苄嘧磺隆(CAS号:83055-99-6)、吡嘧磺隆(CAS号:93697-74-6)、氯吡嘧磺隆(CAS号:100784-20-1)、丙嗪嘧磺隆(CAS号:570415-88-2)、嗪吡嘧磺隆(CAS号:868680-84-6)、乙氧磺隆(CAS号:126801-58-9)、甲基二磺隆(CAS号:208465-21-8)、烟嘧磺隆(CAS号:111991-09-4)、氟酮磺草胺(CAS号:874195-61-6)、五氟磺草胺(CAS号:219714-96-2)、甲氧咪草烟(CAS号:114311-32-9)、咪唑乙烟酸(CAS号:81385-77-5)、双氟磺草胺(CAS号:145701-23-1)、双草醚(CAS号:125401-92-5)、乙氧氟草醚(CAS号:42874-03-3)、氟磺胺草醚(CAS号:72178-02-0)、噁草酮(CAS号:19666-30-9)、丙炔噁草酮(CAS号:39807-15-3)、甲磺草胺(CAS号:122836-35-5)、双唑草腈(CAS号:158353-15-2)、丙炔氟草胺(CAS号:103361-09-7)、环戊噁草酮(CAS号:110956-75-7)、tiafenacil(CAS号:1220411-29-9)、苯嘧磺草胺(CAS号:372137-35-4)、trifludimoxazin(CAS号:1258836-72-4)、Epyrifenacil(CAS号:353292-31-6)、
Figure PCTCN2022109677-appb-000010
(CAS号:2669821-71-8)、
Figure PCTCN2022109677-appb-000011
(CAS号:2669111-66-2)、苯嘧草唑(CAS号:1949837-17-5)、莠去津(CAS号:1912-24-9)、扑草净(CAS号:7287-19-6)、西草净(CAS号:1014-70-6)、特丁津(CAS号:5915-41-3)、特丁净(CAS号:886-50-0)、莠灭净(CAS号:834-12-8)、嗪草酮(CAS号:21087-64-9)、氨唑草酮(CAS号:129909-90-6)、绿麦隆(CAS号:15545-48-9)、异丙隆(CAS号:34123-59-6)、敌草隆(CAS号:330-54-1)、敌稗(CAS号:709-98-8)、灭草松(CAS号:25057-89-0)、辛酰溴苯腈(CAS 号:1689-99-2)、仲丁灵(CAS号:33629-47-9)、二甲戊灵(CAS号:40487-42-1)、氟硫草定(CAS号:97886-45-8)、乙草胺(CAS号:34256-82-1)、丁草胺(CAS号:23184-66-9)、丙草胺(CAS号:51218-49-6)、异丙甲草胺(CAS号:87392-12-9)、苯噻酰草胺(CAS号:73250-68-7)、精异丙甲草胺(CAS号:178961-20-1)、氟噻草胺(CAS号:142459-58-3)、敌草胺(CAS号:15299-99-7)、砜吡草唑(CAS号:447399-55-5)、莎稗磷(CAS号:64249-01-0)、二甲酚草胺(CAS号:87674-68-8)、四唑酰草胺(CAS号:158237-07-1)、三唑酰草胺(CAS号:212201-70-2)、精二甲吩草胺(CAS号:163515-14-8)、溴丁酰草胺(CAS号:74712-19-9)、苄草丹(CAS号:52888-80-9)、禾草敌(CAS号:2212-67-1)、二氯喹啉酸(CAS号:84087-01-4)、氯氟吡氧乙酸(CAS号:69377-81-7)、氯氟吡氧乙酸异辛酯(CAS号:81406-37-3)、氟氯吡啶酯(CAS号:943831-98-9)、麦草畏(CAS号:1918-00-9)、氯氟吡啶酯(CAS号:1390661-72-9)、2-甲基-4-氯苯氧乙酸(CAS号:94-74-6)、2-甲基-4-氯-苯酚乙硫酯(CAS号:25319-90-8)、2-甲基-4-氯苯氧乙酸钠(CAS号:3653-48-3)、2-甲基-4-氯苯氧乙酸异辛酯(CAS号:29450-45-1)、2,4-二氯苯氧乙酸丁酯(CAS号:94-80-4)、2,4-二氯苯氧乙酸异辛酯(CAS号:25168-26-7)、
Figure PCTCN2022109677-appb-000012
(CAS号:2445983-82-2)、2,4-二氯苯氧基乙酸(CAS号:94-75-7)、2甲4氯二甲铵盐(CAS号:2039-46-5)、三嗪氟草胺(CAS号:131475-57-5)、茚嗪氟草胺(CAS号:950782-86-2)、苯草醚(CAS号:74070-46-5)、环庚草醚(CAS号:87818-31-3)、四氟咯草胺(Tetflupyrolimet，CAS号:2053901-33-8)、噁嗪草酮(CAS号:153197-14-9)。其中，所述除草组合物中有效成分A、B的重量比为1:1000～1000:1、1:800～800:1、1:600～600:1、1:500～500:1、1:400～400:1、1:300～300:1、1:200～200:1、1:180～180:1、1:150～150:1、1:120～120:1、1:100～100:1、1:80～80:1、1:50～50:1、1:30～30:1、1:20～20:1、1:10～10:1、1:5～1:1或1:1～5:1。所述除草组合物中A和B的质量百分含量占总量的1-95％，优选10-80％。
一般而言，如果如本文所述的可在本发明的上下文中使用的除草化合物能够形成几何异构体例如E/Z异构体，则可能在根据本发明的组合物中使用两者，纯异构体及其混合物。如果如本文所述的除草化合物具有一个或多个手性中心，且因而以对映异构体或非对映异构体存在，则可能在根据本发明的组合物中使用两者，纯对映异构体和非对映异构体及其混合物。如果如本文所述的除草化合物具有可离子化官能团，则它们还可以以其农业上可接受的盐的形式使用。通常，那些阳离子的盐和那些酸的酸加成盐是适合的，它们的阳离子和阴离子分别对活性化合物的活性无副作用。优选的阳离子为碱金属的离子，优选锂、钠和钾离子，碱土金属的离子，优选钙和镁离子，以及过渡金属的离子，优选锰、铜、锌和铁的离子，进一步为铵和取代的铵，其中1个至4个氢原子被C 1-C 4-烷基、羟基-C 1-C 4-烷基、C 1-C 4-烷氧基-C 1-C 4-烷基、羟基-C 1-C 4-烷氧基-C 1-C 4-烷基、苯基或苄基取代，优选铵、甲基铵、异丙基铵、 二甲基铵、二异丙基铵、三甲基铵、庚基铵、十二烷基铵、十四烷基铵、四甲基铵、四乙基铵、四丁基铵、2-羟乙基铵(olamine盐)、2-(2-羟基乙-1-氧基)乙-1-基铵(二甘醇胺盐)、二(2-羟基乙-1-基)铵(二醇胺盐)、三(2-羟乙基)铵(三硝乙醇胺盐)、三(2-羟丙基)铵、苄基三甲基铵、苄基三乙基铵、N,N,N-三甲基乙醇铵(胆碱盐)，此外鏻离子，锍离子，优选三(C 1-C 4-烷基)锍诸如三甲基锍，和氧化锍离子，优选三(C 1-C 4-烷基)氧化锍离子，以及最终多元胺诸如N,N-双-(3-氨基丙基)甲基胺和二亚乙基三胺的盐。可用酸加成盐的阴离子主要为氯离子、溴离子、氟离子、碘离子、硫酸氢根、甲基硫酸根、硫酸根、磷酸二氢根、氢磷酸根、硝酸根、碳酸氢根、碳酸根、六氟硅酸根、六氟磷酸根、苯甲酸根以及还有C 1-C 4-链烷酸的阴离子，优选甲酸根、乙酸根、丙酸根和丁酸根。
如本文所述的具有羧基的除草剂化合物可以以酸的形式、以上文提及的农业上适合盐或另外以农业上可接受的衍生物的形式使用，例如作为酰胺诸如单-和二-C 1-C 6-烷基酰胺或芳基酰胺，作为酯例如烯丙酯、炔丙酯、C 1-C 10-烷基酯、烷氧基烷基酯、tefuryl((四氢呋喃-2-基)甲基)酯以及还作为硫酯例如作为C 1-C 10-烷基硫酯。优选的单-和二-C 1-C 6-烷基酰胺为甲基和二甲基酰胺。优选的芳基酰胺为，例如N-酰苯胺(anilide)和2-氯苯胺(2-chloroanilide)。优选的烷基酯为例如甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、mexyl(1-甲基己基)、meptyl(1-甲基庚基)、庚基、辛基或异辛基(2-乙基己基)酯。优选的C 1-C 4-烷氧基-C 1-C 4-烷基酯为直链或支链C 1-C 4-烷氧基乙酯，例如2-甲氧基乙酯、2-乙氧基乙酯、2-丁氧基乙基(butotyl)酯、2-丁氧基丙酯或3-丁氧基丙酯。直链或支链C 1-C 10-烷基硫酯的实例为乙基硫酯。
当使用时，如果需要，将市售的制剂以常见的方式稀释，例如在可湿性粉剂、浓缩乳剂、悬浮液和在水中悬浮的颗粒时，使用水稀释。粉末、土壤施药所用的颗粒剂或撒播和喷洒的溶液，一般在使用前不需要进一步用惰性物质稀释。随着外部条件的变化，要求的式I化合物的使用量也不同，外部条件为，例如温度、湿度、使用的除草剂的性质等等。它可以有大的变化幅度，例如在0.001到1.0kg a.i./ha之间，或更多的活性物质，但优选在0.005到750ga.i./ha之间。
具体实施方式
以下实施例用于举例说明本发明，不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。
鉴于化合物的经济性与多样性，我们优选合成了一些化合物，在合成的诸多化合物中，选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1所示。表1中的化合物只是为了更好的说明本发明，但并不限定本发明，对于本领域的技术人员而言，不应将此理解为本发明上述主题的范围仅限于以下化合物。
表1 化合物结构及其 1HNMR
Figure PCTCN2022109677-appb-000013
Figure PCTCN2022109677-appb-000014
制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。
以下提供的方法实施例用于促进对本发明的制备方法的进一步了解，使用的具体物质、种类和条件确定为是对本发明的进一步说明，并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到，或者可以由本领域普通技术人员轻易制备得到。
代表性化合物的实施例如下，其他化合物的合成方法类似，此处不再详细说明。
1、化合物1的合成
25℃，将化合物1-1(284mg,1.0mmol,1.0eq.)溶于10mL乙腈，然后加入化合物1-2(115mg,1.0mmol,1.0eq.)、K 2CO 3(207mg,1.5mmol,1.5eq.)，将反应液加热到50℃并且在该温度下反应1h。反应完成后，加水淬灭，乙酸乙酯萃取，无水硫酸钠干燥，过滤，浓缩，柱层析得到目标产物1(232.5mg,白色固体，73％产率)。
Figure PCTCN2022109677-appb-000015
生物活性评价：
(1)苗后测试实验：
植物破坏(即生长控制率)的活性级别标准如下：
5级：生长控制率在85％以上；
4级：生长控制率大于等于60％且小于85％；
3级：生长控制率大于等于40％且小于60％；
2级：生长控制率大于等于20％且小于40％；
1级：生长控制率大于等于5％且小于20％；
0级：生长控制率小于5％。
以上生长控制率为鲜重控制率。
将单子叶和双子叶杂草种子(播娘蒿、荠菜、苘麻、猪殃殃、繁缕、麦家公、蔊菜、看麦娘、日本看麦娘、牛筋草、菵草、硬草、蜡烛草、婆婆纳、雀麦、节节麦、虉草、反枝苋、藜、鸭跖草、苣荬菜、田旋花、刺儿菜、龙葵、铁苋菜、马唐、稗草、绿狗尾草、金狗尾草、千金子、鸭舌草、野慈姑、萤蔺、香附子、碎米莎草、异型莎草、飘拂草、马齿苋、苍耳、牵牛、白酒草等)以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱、马铃薯、芝麻、蓖麻等)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种2周后在2-3叶期处理测试植物，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，以1.5升/公顷油酸甲酯的乳油作为增效剂，用一定的水稀释成一定浓度的溶液，用喷雾塔喷施到植物上。施药后在温室中培养3周后统计杂草的实验效果，所用化合物计量为45,90,180,360,720g a.i./ha，重复三次，取平均值。代表性数据列于表2。
表2 苗后杂草试验(720g a.i./ha)
化合物序号 马唐 千金子 苘麻 日本看麦娘 水稻 小麦
1 5 5 5 4 1 1
对照化合物A 3 2 4 3 2 3
对照化合物B 3 4 3 4 3 4
注：对照化合物A：
Figure PCTCN2022109677-appb-000016
(二氯异噁草松)；对照化合物B：异噁草松。
由上述实验结果可以看出，本发明化合物与商业化的异噁草松和二氯异噁草松相比，具有更优异的作物安全性，尤其是对小麦、水稻更安全，而且在马唐、千金子、苘麻、日本看麦娘等关键杂草上具有相当甚至更好的除草活性，能够在作物上建立更好的选择性。
(2)苗前测试实验：
植物破坏(即生长控制率)的活性级别标准如下：
9级：完全死亡；
8级：生长控制率大于等于80％且小于100％；
7级：生长控制率大于等于70％且小于80％；
6级：生长控制率大于等于60％且小于70％；
5级：生长控制率大于等于50％且小于60％；
4级：生长控制率大于等于40％且小于50％；
3级：生长控制率大于等于30％且小于40％；
2级：生长控制率大于等于15％且小于30％；
1级：生长控制率大于0％且小于15％；
0级：无效果。
以上生长控制率为鲜重控制率。
将单子叶和双子叶杂草种子(播娘蒿、荠菜、苘麻、猪殃殃、繁缕、麦家公、蔊菜、看 麦娘、日本看麦娘、牛筋草、菵草、硬草、蜡烛草、婆婆纳、雀麦、节节麦、虉草、反枝苋、藜、鸭跖草、苣荬菜、田旋花、刺儿菜、龙葵、铁苋菜、马唐、稗草、绿狗尾草、金狗尾草、千金子、鸭舌草、野慈姑、萤蔺、香附子、碎米莎草、异型莎草、飘拂草、马齿苋、苍耳、牵牛、白酒草等)以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱、马铃薯、芝麻、蓖麻等)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种当天处理测试植物，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，用喷雾塔喷施到植物上。施药后在温室中培养2周后统计杂草的实验效果，所用化合物计量为3,6,12,24,48g a.i./亩(1亩＝1/15ha)，重复三次，取平均值。代表性数据列于表3。
表3 苗前杂草试验
Figure PCTCN2022109677-appb-000017
由此可见，本发明化合物与商业化的异噁草松和二氯异噁草松相比，具有更好的土壤封闭安全性，且能维持相当甚至更好的除草活性，尤其是对于黑麦草、婆婆纳、播娘蒿等麦田 关键杂草，以及稗草、千金子等水稻田杂草，具有更大的商业价值。
(3)挥发性评价
异噁草松商业化之后，收到了大量的由于挥发飘移导致的商业投诉和赔偿，据报道48％异噁草松乳油在有风情况下施用，对下风口1.6公里内的杨树和柳树产生了白化药害，对多种蔬菜、果树、枸杞等易产生不可接受的风险，严重制约了其商业价值，而本发明的化合物拥有更好的抗挥发性，明显更高的安全性。
繁缕对异噁草松类化合物非常敏感，是漂白化合物挥发性的良好指示物。每个测试中包括未处理的对照平板、异噁草松乳油和二氯异噁草松乳油制剂。这些制剂是对于比较的实验制剂的参比标准。4英寸塑料罐装有剪切至该尺寸的篮型咖啡滤纸，滤纸置于每个罐的底部以覆盖排出孔并防止土壤从罐的底部排出。每个罐用#10目筛网筛分(以去除大土壤颗粒和碎片)的砂壤土填充。填充土壤罐在应用处理之前轻微浇水。测试溶液用喷雾器用于土壤表面，每个测试溶液重复2次，比率为0.25kg a.i./ha。
每个重复测试通过在温室顶上放置空的4英寸塑料罐进行装配。罐含有成熟的繁缕，高度约2英寸，以8辐条样式放置于每个空罐的周围。4罐成熟繁缕置于辐条的3、6、9和12点的方向，而另外3罐放在辐条的1:30、4:30、7:30和10:30的方向。一旦所有的罐放于位置上，从每个装配移去空的4英寸罐并在其位置放置经处理的4英寸土壤罐。在处理后14天评价未处理的繁缕植物的植物毒性损伤。通过测量从处理的土壤罐的中心到每个辐条上观察到漂白效果的端点的距离评价挥发性。评估每种处理的所有8个辐条。挥发的量通过计算每次处理的植物毒性损伤的总平方厘米确定。异噁草松乳油被认为挥发性对照，由于其含有100％自由异噁草松。报告的挥发性是针对异噁草松乳油的相对值，异噁草松乳油被计为100％。下面的表4总结了挥发性评价的平均值。
表4 挥发性评价
Figure PCTCN2022109677-appb-000018
与异噁草松乳油以及二氯异噁草松乳油相比，本发明化合物的挥发性明显减弱。
(4)移栽水稻安全性评价与水田杂草防效评价：
在1/1,000,000公顷罐中装入水田土壤后，播种稗草、萤蔺、狼把草的种子，在其上轻轻地覆盖土。其后以蓄水深0.5-1厘米的状态静置于温室内，第二天或者2天后植入野慈姑的块 茎。其后保持蓄水深3-4厘米，在稗草、萤蔺、狼把草达到0.5叶，野慈姑达到初生叶期的时间点，将按照通常的制剂方法调制本发明化合物而成的可湿性粉剂或者悬浮剂的水稀释液，用吸液管进行均匀的滴下处理以达到规定的有效成分量。
另外，在1/1,000,000公顷罐中装入水田土壤后，进行平整，使蓄水深3-4厘米，第二天以移栽深度3厘米来移植3叶期的水稻(粳稻)。移植后第5天与上述同样地处理本发明化合物。
分别用肉眼观察药剂处理后第14天稗草、萤蔺、狼把草及野慈姑的生育状态，药剂处理后第21天水稻的生育状态，以上述活性标准级别评价效果，化合物1表现出了优异的活性和选择性。
注：稗草、萤蔺、狼把草种子及野慈姑均采集自中国黑龙江，经过检测对常规剂量的吡嘧磺隆有抗药性。
(5)田间测试
在田间播后苗前播种主要作物和杂草，经过测试发现菠菜、萝卜、白菜、芝麻、油菜、黄瓜、西瓜、甜瓜、南瓜、木薯、大豆、芸豆、豇豆、菜豆、扁豆、丝瓜、高粱、大蒜、水稻、玉米、花椰菜、甘蓝、香菜在300g a.i./ha剂量下均对化合物1安全，且对稗草、千金子、马唐、播娘蒿、荠菜、猪殃殃、繁缕、黑麦草、雀麦、大穗看麦娘等主要杂草防治效果优秀。
(6)组合物活性测试：
所需活性成分B由试剂公司购买或由已知方法合成。原药均采用丙酮作溶剂，用含量0.1％乳化剂吐温-80水溶液稀释，现用现稀释。
(A)苗后茎叶喷雾处理：
杂草采用盆栽法培养，用180х140mm塑料营养钵，摆放于搪瓷盘中，内装从农田采回经风干过筛的表层土壤(4/5处)，土壤湿度初期均控制在20％，挑选籽粒饱满均一的杂草种子，用25℃温水浸泡6小时，在28℃生化培养箱(黑暗)中催芽，将刚刚露白的杂草种子均匀摆放在土壤表面，根据种子粒径大小然后覆土0.5-1cm。
在可控日光温室内进行培养，温度20～30℃，自然光照，相对湿度57％～72％。土壤类型为壤土，有机质含量为1.63％，pH＝7.1，碱解氮84.3mg/kg，速效磷38.5mg/kg，速效钾82.1mg/kg。
每处理重复4次，每次处理4盆，每盆播种杂草种子20粒。
试验共用药1次。待杂草1.5-2叶期，间苗，保持每盆内杂草10株，每处理保留10株，然后继续培养至西来稗2-3叶，刺儿菜5-6叶，猪殃殃3-4轮叶，反枝苋3-5叶，稗草、多花黑麦草及马唐3叶1心进行处理。
将培养好的试材均匀摆放在面积0.5m 2的平台上，用3WP-2000型行走式喷雾塔茎叶喷雾，喷液量按450公斤/公顷计，喷雾压力0.3MPa。待全部药液喷完后，关闭气阀，30秒后，打开喷雾塔门，取出营养钵。然后打开气阀，喷清水50mL，清洗喷液管。试材处理后移入温室常规培养。
(B)土壤封闭处理：
杂草在可控日光温室内进行培养，温度20～30℃，自然光照，相对湿度57％～72％。土壤类型为壤土，有机质含量为1.63％，pH＝7.1，碱解氮84.3mg/kg，速效磷38.5mg/kg，速效钾82.1mg/kg。试验土壤定量装至盆钵的3/4处，然后从盆钵底部浇灌，使土壤完全湿润至饱和状态。供试杂草种子催芽处理至露白，然后均匀定量撒播表面，根据种子大小覆土0.5-1cm，播种后72小时备用。
每处理重复4次，每次每处理4盆，每盆播种杂草种子20粒。
将播种好的试材均匀摆放在面积0.5m 2的平台上，用3WP-2000型行走式喷雾塔进行土壤喷雾，喷液量按450公斤/公顷计，喷雾压力0.3MPa。待全部药液喷完后，关闭气阀，30秒后，打开喷雾塔门，取出营养钵。然后打开气阀，喷清水50mL，清洗喷液管。
(C)数据调查与统计分析
采用绝对数调查法，用刀片沿土壤表面切断存活杂草整株幼苗，用分析天平称量杂草鲜重。对于已经死亡的杂草，按鲜重为零计。
处理后21天调查，共调查1次。
用Gowing法计算各处理混合组合的理论鲜重抑制率(E0＝X+Y-X*Y/100)，然后与实测抑制率(E)相比较，评价二者混用对杂草的联合作用类型，当E-E0值大于10％为增效作用、小于-10％为拮抗作用、在-10％～10％之间为加成作用。并根据实际防效和除草剂特点、配方的平衡性等因素确定最佳配比。式中X为活性成分A用量为P时的鲜重抑制率；Y为活性成分B用量为Q时的鲜重抑制率。统计结果见表5。
表5 化合物1混配对杂草的实际防效与联合作用评价
Figure PCTCN2022109677-appb-000019
Figure PCTCN2022109677-appb-000020
Figure PCTCN2022109677-appb-000021
Figure PCTCN2022109677-appb-000022
Figure PCTCN2022109677-appb-000023
同时经过很多测试发现，本发明所述化合物及其组合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性，能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的甘蔗、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。

Claims (10)

  1. 一种3-异恶唑烷酮类化合物，如通式I所示：
    Figure PCTCN2022109677-appb-100001
    其中，Q 1、Q 2分别独立地代表O或S；
    R 1、R 2分别独立地代表烷基，优选C1-C8烷基，更优选C1-C6烷基。
  2. 根据权利要求1所述的3-异恶唑烷酮类化合物，其特征在于，
    Q 1、Q 2分别独立地代表O；
    R 1、R 2分别独立地代表甲基。
  3. 一种如权利要求1或2所述的3-异恶唑烷酮类化合物的制备方法，其特征在于，包括以下步骤：
    将通式Ⅱ所示的化合物和通式Ⅲ所示的化合物进行取代反应，制得通式Ⅰ所述的化合物；其化学反应方程式如下：
    Figure PCTCN2022109677-appb-100002
    其中，Hal代表卤素，其他取代基Q 1、Q 2、R 1和R 2的定义如权利要求1或2所示；
    优选地，所述反应在碱和溶剂的存在下进行；更优选地，所述碱选自无机碱或有机碱中的至少一种；更优选地，所述溶剂选自DMF、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种。
  4. 一种除草组合物，其特征在于，其包括(i)除草有效量的权利要求1或2所述的3-异恶唑烷酮类化合物中的至少一种。
  5. 根据权利要求4所述的组合物，其特征在于，还包括(ii)一种或多种除草有效量的另外的除草剂和/或安全剂。
  6. 根据权利要求5所述的组合物，其特征在于，所述另外的除草剂选自以下化合物中的一种或两种以上：硝磺草酮、呋喃磺草酮、双环磺草酮、双唑草酮、环吡氟草酮、三唑磺草酮、苯唑氟草酮、fenquinotrione、
    Figure PCTCN2022109677-appb-100003
    异噁唑草酮、氟咯草酮、吡氟酰草胺、氟吡酰草胺、氟丁酰草胺、氟啶草酮、异噁草松、bixlozone、苄嘧磺隆、吡嘧磺隆、氯吡嘧磺隆、丙嗪嘧磺隆、嗪吡嘧磺隆、乙氧磺隆、甲基二磺隆、烟嘧磺隆、氟酮磺草胺、五氟磺草胺、甲氧咪草烟、咪唑乙烟酸、双氟磺草胺、双草醚、乙氧氟草醚、氟磺胺草醚、 噁草酮、丙炔噁草酮、甲磺草胺、双唑草腈、丙炔氟草胺、环戊噁草酮、tiafenacil、苯嘧磺草胺、trifludimoxazin、Epyrifenacil、
    Figure PCTCN2022109677-appb-100004
    苯嘧草唑、莠去津、扑草净、西草净、特丁津、特丁净、莠灭净、嗪草酮、氨唑草酮、绿麦隆、异丙隆、敌草隆、敌稗、灭草松、辛酰溴苯腈、仲丁灵、二甲戊灵、氟硫草定、乙草胺、丁草胺、丙草胺、异丙甲草胺、苯噻酰草胺、精异丙甲草胺、氟噻草胺、敌草胺、砜吡草唑、莎稗磷、二甲酚草胺、四唑酰草胺、三唑酰草胺、精二甲吩草胺、溴丁酰草胺、苄草丹、禾草敌、二氯喹啉酸、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、氟氯吡啶酯、麦草畏、氯氟吡啶酯、2-甲基-4-氯苯氧乙酸、2-甲基-4-氯-苯酚乙硫酯、2-甲基-4-氯苯氧乙酸钠、2-甲基-4-氯苯氧乙酸异辛酯、2,4-二氯苯氧乙酸丁酯、2,4-二氯苯氧乙酸异辛酯、
    Figure PCTCN2022109677-appb-100005
    2,4-二氯苯氧基乙酸、2甲4氯二甲铵盐、三嗪氟草胺、茚嗪氟草胺、苯草醚、环庚草醚、四氟咯草胺、噁嗪草酮。
  7. 根据权利要求6所述的组合物，其特征在于，所述除草组合物中有效成分(i)和(ii)中另外的除草剂的重量比为1:1000～1000:1、1:800～800:1、1:600～600:1、1:500～500:1、1:400～400:1、1:300～300:1、1:200～200:1、1:180～180:1、1:150～150:1、1:120～120:1、1:100～100:1、1:80～80:1、1:50～50:1、1:30～30:1、1:20～20:1、1:10～10:1、1:5～1:1或1:1～5:1。
  8. 根据权利要求4-7任意一项所述的组合物，其特征在于，还包括(iii)农业化学上可接受的制剂助剂。
  9. 一种防治不希望的植物的方法，其特征在于，包括将除草有效量的权利要求1或2所述的3-异恶唑烷酮类化合物中的至少一种或权利要求4-8任意一项所述的除草组合物施用至植物或者其场所或施用至土壤或水体以防治不希望的植物出苗或生长；优选地，所述不希望的植物包括除草剂抗性或耐受性杂草物种。
  10. 如权利要求1或2所述的3-异恶唑烷酮类化合物中的至少一种或权利要求4-8任意一项所述的除草组合物在控制不希望的植物上的用途，优选地，将所述的3-异恶唑烷酮类化合物用于防除有用作物中的杂草；更优选地，所述有用作物包括转基因作物或者基因组编辑技术处理过的作物，所述杂草包括除草剂抗性或耐受性杂草物种。
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