WO2019109401A1 - 取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用 - Google Patents

取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用 Download PDF

Info

Publication number
WO2019109401A1
WO2019109401A1 PCT/CN2017/117865 CN2017117865W WO2019109401A1 WO 2019109401 A1 WO2019109401 A1 WO 2019109401A1 CN 2017117865 W CN2017117865 W CN 2017117865W WO 2019109401 A1 WO2019109401 A1 WO 2019109401A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl
halogen
alkoxy
substituted
Prior art date
Application number
PCT/CN2017/117865
Other languages
English (en)
French (fr)
Inventor
连磊
征玉荣
刘娜
刘鹏
崔琦
彭学岗
Original Assignee
青岛清原化合物有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 青岛清原化合物有限公司 filed Critical 青岛清原化合物有限公司
Publication of WO2019109401A1 publication Critical patent/WO2019109401A1/zh

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom

Definitions

  • the invention belongs to the technical field of pesticides, and in particular relates to a substituted nitrogen-containing heteroaryl cyclic formic acid ester derivative, a preparation method thereof, a herbicidal composition and application.
  • the present invention provides a substituted nitrogen-containing heteroaryl cyclic formic acid ester derivative, a preparation method thereof, a herbicidal composition and use thereof, which have excellent herbicidal activity and higher crop safety, especially for Key crops such as wheat, corn, and rice have established good selectivity.
  • R 1 and R 2 independently represent H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, substituted or unsubstituted aryl a group, a benzyl group, a heteroaryl group, an aryloxy group, an arylthio group, a heteroaryloxy group, and a heteroarylthio group; and a group represented by the formula -COR 5 , wherein R 5 represents an alkyl group, an alkyl halide Alkenyl, alkenyl, cycloalkyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, substituted or unsubstituted benzyl, aryl, Heteroaryl, aryloxy, heteroaryloxy, arylmethoxy, heteroary
  • Y represents H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, NR 3 R 4 , wherein R 3 and R 4 are independently Represents H, alkyl, alkenyl, alkynyl, hydroxy, haloalkyl, alkoxy, amino, acyl, alkoxycarbonyl, alkylcarbamoyl, alkylsulfonyl, trialkylsilyl or di
  • An alkylphosphono group, or NR 3 R 4 represents a 5- or 6-membered saturated or 5-membered unsaturated ring;
  • W represents H, halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl;
  • X represents halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl or cyano;
  • Q is selected from halogen, an alkyl group having or not containing a halogen, a cycloalkyl group, an alkoxy group, a phenyl group, a 2,3-dihydroindenyl group or a naphthyl group, or a selected from Heteroaryl, aryl or heteroaryl is unsubstituted or substituted wherein one or more substituents are selected from the group consisting of halogen, cyano, aryloxy, alkyl, alkoxy, haloalkyl Alkyl, haloalkoxy, acyl, alkylthio, phenyl, -OCH 2 CH 2 -, -OCH 2 O- or -OCH 2 CH 2 O-.
  • R 1 and R 2 independently represent H, cyano, C1-C8 alkyl, halo C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy , C1-C8 acyloxy, C1-C8 alkylthio, substituted or unsubstituted aryl, benzyl, heteroaryl, aryloxy, arylthio, heteroaryloxy and heteroaryl sulphide And a group represented by the formula -COR 5 , wherein R 5 represents a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C2-C8 alkenyl group, a C3-C8 cycloalkyl group, a C1-C8 alkoxy group.
  • Y represents H, halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 Acyloxy, C1-C8 alkylthio, NR 3 R 4 , wherein R 3 and R 4 independently represent H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, hydroxy, halo C1-C8 alkyl, C1-C8 alkoxy, amino, C1-C8 acyl, C1-C8 alkoxycarbonyl, C1-C8 alkylcarbamoyl, C1-C8 alkylsulfonyl, tri-C1-C8 alkyl a silyl group or a di-C1-C8 alkylphosphono group, or R 3 R 4 N represents
  • W represents H, halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl;
  • X represents halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl or cyano;
  • Q is selected from the group consisting of halogen, a C1-C6 alkyl group having a halogen atom, a C3-C6 cycloalkyl group, a C1-C6 alkoxy group, a phenyl group, a 2,3-indanyl group or a naphthyl group, or Selected from Heteroaryl, aryl or heteroaryl is unsubstituted or substituted wherein one or more substituents are selected from the group consisting of halogen, cyano, aryloxy, C1-C8 alkyl, C1- C8 alkoxy, halo C1-C8 alkyl, halo C1-C8 alkoxy, C1-C8 acyl, C1-C8 alkylthio, phenyl, -OCH 2 CH 2 -, -OCH 2 O- Or -OCH 2 CH 2 O-.
  • R 1 and R 2 independently represent hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, cyano, C1-C6 alkoxycarbonyl, and unsubstituted or selected a phenyl group substituted with one or more of halogen, halogenated C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy, and C2-C6 alkenyl;
  • Y represents H, NR 3 R 4 , wherein R 3 and R 4 independently represent H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 acyl;
  • W stands for H, halogen
  • X represents halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano
  • Q is selected from halogen, C1-C6 alkyl group with or without halogen, C3-C6 cycloalkyl, unsubstituted or selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 A phenyl group substituted with one or more groups in the alkyl group.
  • R 1 and R 2 independently represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, methylthio, ethylthio, cyano, Methoxycarbonyl, ethoxycarbonyl, and unsubstituted or selected from halogen, CF 3 , methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methoxy, and a phenyl group substituted with one or more groups in the oxy group;
  • X represents chlorine, bromine, methoxy, ethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyano;
  • Y stands for H, NH 2 ,
  • W stands for H, chlorine, fluorine
  • Q represents cyclopropyl, trifluoromethyl, chloro, fluoro,
  • the aryl group in the R 1 and R 2 groups preferably includes a phenyl group, a 2,3-indanyl group or a naphthyl group; and the heteroaryl group includes 1-3 O, S, N hetero atoms. 5-10 membered heteroaryl, such as pyridyl, pyrimidinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazole Base, oxadiazolyl, thiadiazolyl, pyridazinyl, triazinyl, quinolyl, quinoxalinyl, fluorenyl, benzotriazolyl, benzothienyl, benzofuranyl, iso Quinoline, tetrahydroquinolyl and the like.
  • the preparation method of the substituted nitrogen-containing heteroaryl cyclic formic acid ester derivative comprises the following steps:
  • a compound of the formula III is prepared by reacting a compound of the formula II with a compound of the formula III, and the reaction equation is as follows:
  • the reaction is carried out in an aprotic solvent, a base and a condensing agent.
  • the reaction temperature is from 0 ° C to 90 ° C, preferably from 10 ° C to 30 ° C.
  • the solvent is selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene, xylene One or more mixed solvents.
  • the base is selected from one or more of the organic bases such as triethylamine, trimethylamine, DIPEA, and DBU.
  • the condensing agent is PyBop, HATU or HOBt-EDCI.
  • a herbicidal composition comprising at least one of a herbicidally effective amount of said substituted nitrogen-containing heteroaryl cyclic formic acid ester derivative.
  • the herbicidal composition also includes a formulation aid.
  • a method of controlling a harmful plant comprising using at least one of the herbicidally effective amount of the substituted nitrogen-containing heteroaryl cyclic formic acid ester derivative or the herbicidal composition described above on a plant or a harmful plant region.
  • the substituted nitrogen-containing heteroaryl cyclic formic acid ester derivative is used to control harmful plants in useful crops.
  • the useful crop is a crop that has been treated with a genetically modified crop or genome editing technique.
  • the compounds of formula I of the present invention have outstanding herbicidal activity.
  • the active substances of the present invention are also effective for perennial weeds which grow from rhizomes, rhizomes, or other perennial organs and are difficult to control. In this regard, it is generally not important to use the substance before, before, or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the invention, without limiting the identified species.
  • weed species in which the active substance is effective include monocotyledons: annual oats, rye, grasses, maiden, ferraris, medlar, genus, foxtail, and sedge, and perennial ice. Genus, Bermudagrass, Rhizoma and sorghum, and perennial sedge.
  • dicotyledonous weed species species whose effects can be extended to, for example, the annual genus Polyporus, Amaranth, Pomna, Wild Sesame, Stellaria, Amaranthus, White Mustard, Ipomoea, and Yellow Flower Genus, Matricaria and genus, and perennial weeds, genus, genus and genus.
  • the active substance of the present invention effectively controls harmful plants under the conditions of rice sowing, such as cockroaches, genus, genus, genus, genus, cane, and sedge.
  • the compound of the present invention is applied to the surface of the soil before germination, the weeds of the weeds can be completely prevented before the weeds grow, or when the weeds grow out of the cotyledons, and finally completely die after three to four weeks.
  • the compound of the present invention is particularly resistant to the following plants, and is active in the following plants, such as Apila, Xiaoye Sesame, Rolling Stalk, Poria, Ivy, Herba, Arabian, Pansy, Pansy, Poria and Kochia. .
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no damage to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. Or the damage is trivial. In particular, it is well compatible with cereal crops such as wheat, barley and corn, especially wheat. Thus, the compounds of the invention are highly suitable for the selective control of unwanted plants in agricultural or ornamental plants.
  • Transgenic plants Due to their herbicidal nature, these active substances can be used to control harmful plants in genetically engineered plant cultivation that is known or to be present.
  • Transgenic plants generally have superior traits, such as resistance to specific insecticides, particularly specific herbicides, resistance to pathogenic microorganisms of plant diseases or plant diseases, such as specific insect or fungal, bacterial or viral microorganisms.
  • Other specific traits are related to the following conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients.
  • the obtained transgenic plant product has an increased starch content or an improved starch quality or a different fatty acid composition.
  • the compounds of the 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 for beets, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of the formula I are preferably used as herbicides for the cultivation of useful plants which are resistant or resistant to the toxic effects of the herbicide by genetic engineering.
  • glufosinate herbicides eg EP-0242236 A, EP-0242246 A
  • glyphosate herbicides WO 92/00377
  • sulfonate An ureide herbicide EP-0257993 A, US-5013659 A
  • transgenic crop plant such as cotton which is capable of producing a Bacillus thuringiensis toxin (Bt toxin) which protects against damage by a particular pest (EP-0142924 A, EP-0193259 A);
  • Plant cells of the activity-reducing gene product can be prepared by, for example, 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 transcription product of the above gene product.
  • DNA molecules comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and the use of DNA molecules comprising only a portion of the coding sequence, which must be sufficiently long to achieve antisense in the cell Effect. Sequences that are highly homologous but not identical to the gene product coding sequence can also be used.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • These sequences are known to those skilled in the art (see, for example, Braun et al, EMBO J. 11 (1992) 3219-3227; Wolter et al, Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).
  • Transgenic plant cells can be recombined into whole plants using known techniques.
  • the control can be improved or expanded.
  • the range of weeds, the application rate at the time of application is preferably a combination of the resistance of the transgenic crops and the performance of the herbicide, and the effects of the growth and yield of the transgenic crop plants.
  • the invention therefore also provides the use of said compounds as herbicides to control harmful plants in plants of transgenic crops.
  • the compounds of the invention can significantly modulate the growth of crop plants. By modulating the involvement of plant metabolism, these compounds are used to orient the components of the plant and promote harvesting, such as drying and dwarfing the plants. Moreover, they are also suitable for regulating and inhibiting unwanted plant growth without destroying the growth of the crop. Inhibition of plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, as this reduces or completely prevents lodging.
  • the compound of the present invention can be applied using a general formulation, and a wettable powder, a concentrated emulsion, a sprayable solution, a powder or granules can be used.
  • a herbicidal composition comprising a compound of formula I.
  • the compounds of formula I can be formulated in a variety of ways, depending on the usual biological and/or chemical physical parameters.
  • suitable formulations are: wettable powders (WP), water soluble powders (SP), water soluble concentrates, concentrated emulsions (EC), emulsions such as oil dispersed in water and water dispersed in oil (EW) , sprayable solution, suspension concentrate (SC), dispersible oil suspension (OD), oil or water diluent, solution of miscible oil, powder (DP), capsule suspension (CS) ), seed dressing composition, particles for spreading and soil application, sprayed particles, coated particles and absorbent particles, water dispersible particles (WG), water soluble particles (SG), ULV (super Low volume) formula, microcapsules and wax products.
  • WP wettable powders
  • SP water soluble powders
  • EC concentrated emulsions
  • EW oil dispersed in water and water dispersed in oil
  • SC sprayable solution, suspension concentrate
  • OD dispersible oil suspension
  • DP powder
  • Wettable powders can be uniformly dispersed in water, in addition to active substances, including diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersing agents), such as polyethoxylated alkylphenols, poly Ethoxylated fatty alcohol, polyoxyethyl aliphatic amine, fatty alcohol polyglycol ether sulfate, alkyl sulfonate, alkyl phenyl sulfonate, sodium lignosulfonate, 2, 2'- dinaphthylmethane Sodium 6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate.
  • the herbicide active substance is finely ground, for example, using a conventional apparatus such as a hammer mill, a fan mill and a jet mill, and an auxiliary agent is simultaneously or sequentially mixed.
  • a concentrated emulsion such as butanol, cyclohexanone, dimethylformamide, xylene or a higher boiling aromatic compound or a mixture of hydrocarbons or solvents, and adding one more One or more ionic and/or nonionic surfactants (emulsifiers).
  • emulsifiers which can be used are, for example, calcium alkylaryl sulfonates of calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A glycan ester.
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A gly
  • the active substance and the finely divided solid matter are ground to obtain a powder, a solid substance such as talc, a natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • a water or oil based suspension can be prepared by, for example, wet milling using a commercially available bead mill with or without the addition of a surfactant of the other formulation type described above.
  • an aqueous organic solvent may be used, using a stirrer, a colloid mill and/or a static mixer, and if necessary, a surfactant of another formulation type as described above may be added.
  • the granules are prepared by spraying the active material onto the adsorbate, granulating with an inert material, or concentrating the active material onto the surface of, for example, a sand or kaolinite carrier, granulating the inert material by a binder, and adhering Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • Suitable actives can be plasmidized by the method of preparing fertilizer granules, and if necessary, fertilizer can be mixed.
  • the water-suspended granules are prepared by a usual method such as spray-drying, fluidized bed granulation, disc granulation, mixing using a high speed mixer, and extrusion without a solid inert material.
  • the agrochemical formulations usually comprise from 0.1 to 99% by weight, in particular from 0.1 to 95%, of the active substance I.
  • the concentration of the active substance in the wettable powder is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remaining amount by weight to 100%.
  • the concentration of the active substance in the concentrated emulsion may range from about 1 to 90%, preferably from 5 to 80% by weight.
  • the powder formulation comprises from 1 to 30% by weight of active substance, usually from 5 to 20% by weight of active substance, whereas the sprayable solution comprises from about 0.05 to 80%, preferably from 2 to 50% by weight of active substance. .
  • the content of the active material in the water-suspended granules mainly depending on whether the active material is liquid or solid, and auxiliaries, fillers and the like used in granulation.
  • the content of the active substance in the aqueous suspension granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the preparation of the active substance may include a tackifier, a wetting agent, a dispersing agent, an emulsifier, a penetrating agent, a preservative, an antifreezing agent, a solvent, a filler, a carrier, a coloring agent, an antifoaming agent, an evaporation inhibitor, and pH and viscosity modifiers commonly used in all cases.
  • insecticide active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and/or plant growth regulators.
  • safeners for premixed or filled mix.
  • Suitable active substances which can be mixed with the active substance of the present invention in a mixed preparation or a tank mix are, for example, "World Pesticide New Variety Technology Encyclopedia", China Agricultural Science and Technology Press, 2010.9 and the literature cited herein.
  • the herbicide active substance mentioned below may be mixed with the mixture of the formula I (note: the name of the compound, or a common name according to the International Organization for Standardization (ISO), or a chemical name, if appropriate, a code): Amine, butachlor, alachlor, propisochlor, metolachlor, stilben, acetochlor, chlorfenapyr, acetochlor, naproxen, R-levoperin Acetochlor, dipivoxil, thiaceuramide, dibenzoylamine, piracetamide, herbicide, flufenic acid, bromobutyramide, dimethoprim, high-efficiency dimethyl Thiamethoxazole, acetophene, flufenacet,
  • the commercially available formulations are diluted in a conventional manner, for example, in wettable powders, concentrated emulsions, suspensions, and granules suspended in water, diluted with water.
  • Granules for granules or soil application or sprayed and sprayed solutions are generally not required to be further diluted with inert materials prior to use.
  • the amount of the compound of formula I required varies with external conditions, such as temperature, humidity, the nature of the herbicide used, and the like. It can have a large range of variation, for example between 0.001 and 1.0 kg/ha, or more active substance, but preferably between 0.005 and 750 g/ha, in particular between 0.005 and 250 g/ha.
  • the activity level criteria for harmful plant damage are as follows:
  • Grade 9 growth control rate is above 95%
  • Level 7 growth control rate is above 80%
  • Level 5 The growth control rate is above 60%
  • Level 2 growth control rate is 5-20%
  • Level 1 The growth control rate is below 5%
  • the above growth control rate is the fresh weight control rate.
  • Post-emergence test Place monocotyledonous and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, canola, millet, sorghum) in a plastic pot containing soil, then cover 0.5-2 Cm soil, so that it grows in a good greenhouse environment, after 2-3 weeks of sowing, the test plants are treated in the 4-5 leaf stage, and the tested compound of the present invention is dissolved in acetone, and then Tween 80 is added, with a certain amount. The water is diluted to a concentration of the solution and sprayed onto the plants using a spray tower. After the application, the cells were cultured for 3 weeks in the greenhouse, and the experimental effects of the weeds after 3 weeks are shown in Table 3.
  • the application dose is 250 g/ha of active ingredient and the water exchange rate is 450 kg/ha.
  • the compound of the present invention to be tested was dissolved in acetone, and then Tween 80 was added thereto, and diluted to a certain concentration with a certain amount of water, and sprayed immediately after sowing. After application for 4 weeks in the greenhouse, the results of the experiment were observed after 3 weeks, and it was found that most of the agents of the present invention were excellent in the measurement of 250 g/ha, especially for weeds such as valerian, horse pond, ramie, and many other compounds. Good selectivity for corn, wheat, rice, soybeans, and rapeseed.
  • the compounds of the present invention generally have better weed control effects, especially for major grasses such as weeds, crabgrass, and foxtail, which are widely occurring in corn fields, paddy fields, and wheat fields, and nettles.
  • the main broadleaf weeds such as amaranth and sinensis have good effects and have good commercial value.
  • the broad-leaved weeds such as amaranth, sage, amaranth, maijiagong, piglet, and sorghum, which are resistant to ALS inhibitors, have extremely high activity.
  • the paddy soil After filling the paddy soil in a 1/1,000,000 hectare tank, seeds of valerian, flamingo, wolf grass, and wild sage were planted, and the soil was gently covered thereon. Thereafter, it was placed in a greenhouse at a depth of 0.5 to 1 cm, and the tubers of the wild sage were implanted the next day or two days later. Thereafter, the water retention depth is 3-4 cm, and the wettability of the compound of the present invention is prepared according to the usual preparation method at the time when the grass, the firefly, the wolf grass reaches 0.5 leaf, and the wild sage reaches the primary leaf stage. A water dilution of a powder or a suspension is uniformly dripped with a pipette to achieve a prescribed amount of active ingredient.
  • the transplanting depth was 3 cm to transplant the rice (japan) in the 3 leaf stage.
  • the compound of the present invention was treated in the same manner as above on the fifth day after transplantation.
  • the fertility status of Valerian, Firefly, Wolfgrass and Wild Sage was observed by naked eye on the 14th day after treatment.
  • the growth status of rice on the 21st day after the treatment, the herbicidal effect was evaluated at the activity standard level of 1-10, many The compounds exhibit excellent activity and selectivity.
  • Control Compound A (from patent WO2003/011853)
  • Control Compound B (from patent CN105503712A)
  • Control compound C (Dow's Yi Nong Commercialized Variety)
  • the post-emergence test conditions are the same as above.
  • the compounds of the present invention have higher crop safety than the control compounds A and C, especially for key crops such as wheat, corn, rice, etc., while the control compound pairs The main crops are poorly selective, and it can be seen that the present invention achieves unexpected effects.
  • the herbicidal activity of the compound of the present invention is much higher than that of the control compound B, especially for weeds such as small canopy, yellow leeks, thorny vegetables, and large nests.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

本发明属于农药技术领域，具体涉及一种取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用。所述取代的含氮杂芳环甲酸亚胺酯衍生物，如通式(I)所示：其中，R1和R2独立地代表H，卤素等；Y代表H，卤素，NR3R4等；W代表H，卤素，烷氧基，烷基，卤代烷基，链烯基，炔基；X代表卤素、烷氧基等；Q选自卤素，含有或不含有卤素的烷基、环烷基、烷氧基，苯基、2,3-二氢化茚基或萘基的芳基等。所述化合物的除草活性优异，且具有更高的作物安全性，尤其是对于小麦、玉米、水稻等关键农作物建立了良好的选择性。

Description

取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用 技术领域
本发明属于农药技术领域，具体涉及一种取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、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，例如，专利WO 2003/011853公开了采用如下通式Ⅰ所示的6-芳基-4-氨基吡啶甲酸酯及其衍生物作为除草剂：
Figure PCTCN2017117865-appb-000001
但由于市场的不断扩大、杂草的抗性、药物的使用寿命以及药物的经济性等问题以及人们对环境的日益重视，需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。
发明内容
本发明提供了一种取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用，所述化合物的除草活性优异，且具有更高的作物安全性，尤其是对于小麦、玉米、水稻等关键农作物建立了良好的选择性。
本发明采用的技术方案如下：
一种取代的含氮杂芳环甲酸亚胺酯衍生物，如通式I所示：
Figure PCTCN2017117865-appb-000002
其中，
R 1和R 2独立地代表H，卤素，氰基，硝基，烷基，卤代烷基，链烯基，环烷基，烷氧基，酰氧基，烷硫基，取代或未取代的芳基、苄基、杂芳基、芳基氧基、芳基硫基、杂芳基氧基和杂芳基硫基；以及式-COR 5所示的基团，其中R 5代表烷基，卤代烷基，链烯基，环烷基，烷氧基，链烯氧基，环烷氧基，烷硫基，链烯基硫基，环烷硫基，取代或未取代的苄基、芳基、杂芳基、芳基氧基、杂芳基氧基、芳基甲氧基、杂芳基甲氧基、苄硫基、芳基硫基、杂芳基硫基和可用烷基，酰基，酰氧基，取代或未取代的芳基、杂芳基、芳基烷基、杂芳基烷 基取代的氨基；或R 1和R 2连接形成5-或6-元饱和或不饱和环；
Y代表H，卤素，氰基，硝基，烷基，卤代烷基，链烯基，环烷基，烷氧基，酰氧基，烷硫基，NR 3R 4，其中R 3和R 4独立地代表H、烷基、链烯基、炔基、羟基、卤代烷基、烷氧基、氨基、酰基、烷氧羰基、烷基氨基甲酰基、烷基磺酰基、三烷基甲硅烷基或二烷基膦酰基，或NR 3R 4代表5-或6-元的饱和环或5-元的不饱和环；
W代表H，卤素，烷氧基，烷基，卤代烷基，链烯基，炔基；
X代表卤素、烷氧基、烷基、卤代烷基、链烯基、炔基或氰基；
Q选自卤素，含有或不含有卤素的烷基、环烷基、烷氧基，苯基、2,3-二氢化茚基或萘基的芳基，或选自
Figure PCTCN2017117865-appb-000003
的杂芳基，芳基或杂芳基是未取代的或取代的，其中一个或多个取代基选自如下基团：卤素、氰基、芳基氧基、烷基、烷氧基、卤代烷基、卤代烷氧基、酰基、烷基硫代、苯基、-OCH 2CH 2-、-OCH 2O-或-OCH 2CH 2O-。
优选地，R 1和R 2独立地代表H，氰基，C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C3-C8环烷基，C1-C8烷氧基，C1-C8酰氧基，C1-C8烷硫基，取代或未取代的芳基、苄基、杂芳基、芳基氧基、芳基硫基、杂芳基氧基和杂芳基硫基；以及式-COR 5所示的基团，其中R 5代表C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C3-C8环烷基，C1-C8烷氧基，C2-C8链烯氧基，C3-C8环烷氧基，C1-C8烷硫基，C2-C8链烯基硫基，C3-C8环烷硫基，取代或未取代的苄基、芳基、杂芳基、芳基氧基、杂芳基氧基、芳基甲氧基、杂芳基甲氧基、苄硫基、芳基硫基、杂芳基硫基和可用C1-C8烷基，C1-C8酰基，C1-C8酰氧基，取代或未取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基取代的氨基；其中，所述“取代的”是指被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C3-C8环烷基、C1-C8烷氧基、C2-C8链烯氧基、C1-C8烷硫基、芳基、芳基氧基、苄基、苄氧基、C1-C8酰基、C1-C8酰氧基、C2-C8链烯基以及可用C1-C8烷基、芳基、芳基氧基、C1-C8酰基、C1-C8酰氧基和C2-C8链烯基取代的氨基中的一个或多个基团所取代；
Y代表H，卤素，氰基，硝基，C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C3-C8环烷基，C1-C8烷氧基，C1-C8酰氧基，C1-C8烷硫基，NR 3R 4，其中R 3和R 4独立地代表H、C1-C8烷基、C2-C8链烯基、C2-C8炔基、羟基、卤代C1-C8烷基、C1-C8烷氧基、氨基、C1-C8酰基、C1-C8烷氧羰基、C1-C8烷基氨基甲酰基、C1-C8烷基磺酰基、三C1-C8烷基甲硅烷基或二C1-C8烷基膦酰基，或R 3R 4N代表5-或6-元的饱和环或5-元的不饱和环；
W代表H，卤素，C1-C8烷氧基，C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C2-C8炔基；
X代表卤素、C1-C8烷氧基、C1-C8烷基、卤代C1-C8烷基、C2-C8链烯基、C2-C8炔基或氰基；
Q选自卤素，含有或不含有卤素的C1-C6烷基、C3-C6环烷基、C1-C6烷氧基，苯基、2,3-二氢化茚基或萘基的芳基，或选自
Figure PCTCN2017117865-appb-000004
的杂芳基，芳基或杂芳基是未取代的或取代的，其中一个或多个取代基选自如下基团：卤素、氰基、芳基氧基、C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷基、卤代C1-C8烷氧基、C1-C8酰基、C1-C8烷基硫代、苯基、-OCH 2CH 2-、-OCH 2O-或-OCH 2CH 2O-。
更优选地，R 1和R 2独立地代表氢，C1-C6烷基，C1-C6烷氧基，C1-C6烷硫基，氰基，C1-C6烷氧羰基，以及未取代或被选自卤素、卤代C1-C6烷基、C1-C6烷基、C1-C6烷氧基和C2-C6链烯基中的一个或多个基团所取代的苯基；
Y代表H、NR 3R 4，其中R 3和R 4独立地代表H、C1-C6烷基、C1-C6烷氧基、C1-C6酰基；
W代表H，卤素；
X代表卤素、C1-C6烷基、C1-C6烷氧基、氰基；
Q选自卤素，含有或不含有卤素的C1-C6烷基，C3-C6环烷基，未取代或被选自卤素、C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷基中的一个或多个基团所取代的苯基。
进一步优选地，R 1和R 2独立地代表氢、甲基、乙基、丙基、异丙基、正丁基、叔丁基、环丙基、甲硫基、乙硫基、氰基、甲氧羰基、乙氧羰基，以及未取代或被选自卤素、CF 3、甲基、乙基、丙基、异丙基、正丁基、叔丁基、环丙基、甲氧基和乙氧基中的一个或多个基团所取代的苯基；
X代表氯、溴、甲氧基、乙氧基、甲基、乙基、丙基、异丙基、正丁基、叔丁基、环丙基、氰基；
Y代表H、NH 2、
Figure PCTCN2017117865-appb-000005
W代表H、氯、氟；
Q代表环丙基、三氟甲基、氯、氟、
Figure PCTCN2017117865-appb-000006
上面给出的通式化合物的定义中，汇集所用术语定义如下：
所述R 1和R 2基团中的芳基优选包括苯基、2,3-二氢化茚基或萘基等；所述的杂芳基包括含有1-3个O、S、N杂原子的5-10元杂芳基，例如吡啶基、嘧啶基、吡嗪基、呋喃基、噻 吩基、吡咯基、吡唑基、噻唑基、噁唑基、异噁唑基、咪唑基、三唑基、恶二唑基、噻二唑基、哒嗪基、三嗪基、喹啉基、喹喔啉基、吲哚基、苯并三唑基、苯并噻吩基、苯并呋喃基、异喹啉基、四氢喹啉基等。
所述的取代的含氮杂芳环甲酸亚胺酯衍生物的制备方法，包括以下步骤：
使用如通式II所示的化合物与通式III所示的化合物进行反应，制备如通式I所示的化合物，反应方程式如下：
Figure PCTCN2017117865-appb-000007
所述反应在非质子型溶剂中、碱和缩合剂的作用下进行。
所述反应温度为0℃-90℃，优选10℃-30℃。
所述溶剂选自二氯甲烷、二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、四氢呋喃、甲苯、二甲苯中的一种或多种混合溶剂。
所述碱选自三乙胺、三甲胺、DIPEA和DBU等有机碱中的一种或多种。
所述缩合剂为PyBop、HATU或HOBt-EDCI。
一种除草剂组合物，包括除草有效量的所述的取代的含氮杂芳环甲酸亚胺酯衍生物中的至少一种。
所述的除草剂组合物还包括制剂助剂。
一种控制有害植物的方法，包括将除草有效量的所述的取代的含氮杂芳环甲酸亚胺酯衍生物中的至少一种或所述的除草剂组合物使用在植物上或者有害植物区域。
所述的取代的含氮杂芳环甲酸亚胺酯衍生物中的至少一种或所述的除草剂组合物在控制有害植物上的用途。
优选地，将所述的取代的含氮杂芳环甲酸亚胺酯衍生物用于防除有用作物中的有害植物。
更优选地，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
对于许多经济上重要的单子叶和双子叶有害植物，本发明的式I化合物具有突出的除莠活性。本发明的活性物质也对于多年生杂草有效，这些杂草从根茎、根状茎、或其它的多年生的器官上生长出来，很难控制。关于这点，是否在播种前、萌发前或萌发后使用该物质一般不重要。特别提及本发明化合物可以控制的单子叶和双子叶杂草群的代表例子，没有限制到的确定的物种。活性物质有效作用的杂草物种的例子包括单子叶植物：一年生燕麦属、黑麦、草属、看麦娘属、法拉里斯、稗、马唐属、狗尾草属和莎草属，和多年生的冰草属、狗 牙根属、白茅属和高粱属、以及多年生的莎草属。
关于双子叶杂草物种，其作用可以扩展到的物种例如一年生的猪殃殃属、堇菜属、婆婆纳属、野芝麻属、繁缕属、苋属、白芥属、番薯属、黄花稔属、母菊属和苘麻属，和多年生杂草旋花属、蓟属、酸模属和艾属。本发明活性物质在水稻播种这种待定条件下有效控制有害植物，例如稗、慈姑属、泽泻属、荸荠属、蔗草和莎草属。如果将本发明化合物在萌芽前施用于土壤表面，可以在杂草长出前完全预防杂草的秧苗，或在杂草长出子叶时就停止生长，最后在三到四星期之后完全死亡。本发明化合物特别抗下述植物的活性优良，阿皮拉草、小野芝麻、卷茎蓼、繁缕、长春藤叶婆婆纳、阿拉伯婆婆纳、三色堇和苋、猪殃殃属和地肤。
虽然本发明化合物对于单子叶和双子叶的杂草具有优良的除莠活性，但对于重要的经济类作物植物，例如小麦、大麦、黑麦、稻子、玉米、甜菜、棉花和大豆却根本没有损害，或者是损害是微不足道的。特别是和谷类作物相容得很好，例如小麦、大麦和玉米，特别是小麦。因此，本发明化合物非常适于有选择地控制在农用作物或观赏植物中的无用植物。
由于它们的除莠性质，在已知或将要出现的遗传工程的植物耕种中，这些活性物质可以用于控制有害植物。转基因植物通常具有优越的性状，例如对特定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 PCTCN2017117865-appb-000008
的
Figure PCTCN2017117865-appb-000009
[环氧乙烷加成物表面活性剂]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-Küchler的“Chemische Technologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986。
可湿性粉剂能均匀地可分散在水中，除了活性物质，还包括稀释剂或惰性物质、离子和非离子型表面活性剂(润湿剂、分散剂)，例如聚乙氧基烷基酚、聚乙氧基脂肪醇、聚氧乙基脂肪族胺、脂肪醇聚二醇醚硫酸盐、烷基磺酸盐、烷基苯基磺酸盐、木质磺酸钠、2,2’-二萘甲烷-6,6’-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为了制备可湿性粉剂，将除草剂的活性物质细磨，例如使用常用的仪器，如用锤磨机、风扇磨碎机和喷气式磨碎机，同时或顺序混入助剂。
将活性物质溶解在有机溶剂中制备浓缩乳剂，溶剂例如丁醇、环己酮、二甲基甲酰胺、二甲苯或较高沸点的芳族化合物或碳氢化合物或溶剂的混合物，并再加入一种或多种离子的和/或非离子型表面活性剂(乳化剂)。可以使用的乳化剂的例子为例如十二烷基苯磺酸钙的烷基芳基磺酸钙，或非离子乳化剂，例如脂肪酸聚二醇酯、烷基芳香基聚二醇醚、脂肪醇聚二醇醚、氧化丙烯-环氧乙烷缩合产物、烷基聚醚、例如山梨糖醇酐脂肪酸酯的山梨聚糖酯，或例如聚氧化乙烯山梨糖醇酐脂肪酯的聚氧化乙烯山梨聚糖酯。
将活性物质和细碎的固态物质研磨得到粉末，固态物质例如滑石、如高岭土、皂土和叶蜡石的天然粘土、或硅藻土。以水或油为基底的悬浮液可以通过下述方法制备，例如利用商业上通用的玻珠研磨机进行湿磨，加入或不加入上述另一个制剂类型的表面活性剂。
制备例如水包油乳化剂(EW)的乳剂，可以使用含水的有机溶剂，使用搅拌器、胶体研磨器和/或静态混合器，如果需要，加入如上所述另一个制剂类型的表面活性剂。
用下述方法制备颗粒剂，将活性物质喷到吸附物上，使用惰性物料颗粒化，或将活性物质浓缩到例如沙、高岭石载体的表面，通过粘合剂将惰性物料粒化，粘合剂例如聚乙烯醇、聚丙烯酸钠或矿物油。可以用制备肥料颗粒剂的方法将合适的活性物质粒化，如果需要可以混有肥料。使用通常的方法制备水悬浮颗粒剂，例如喷洒-干燥，流化床造粒、磨盘造粒、使用高速混合机混合，并在无固体惰性物料的情况下挤压。
关于使用磨盘、流化床、挤压机和喷涂颗粒剂的制备方法，参见下述工艺，例如“Spray Drying手册”第三版1979，G.Goodwin有限公司，伦敦；J.E.Browning，“Agglomeration”，化学和工程1967，147ff页；“Perry’s化学的工程师手册”，第五版，McGraw-Hill，纽约1973，8-57页。如果要知道关于作物保护产品的制剂，参见例如，G.C.Klingman,“Weed Control as a Science”，John Wiley和Sons公司，纽约，1961 81-96页和J.D.Freyer，S.A.Evans“杂草防除手册”，第五版，Blackwell Scientific Rublications，牛津大学1968，101-103页。
农用化学品制剂通常包含按重量计0.1到99％，特别是0.1到95％的活性物质式I。可湿性粉剂中活性物质的浓度为，按重量计例如从大约10到99％，通常的制剂组分构成按重量计剩余量到100％。活性物质在浓缩乳剂中的浓度按重量计可以为大约1到90％，优选5到80％。粉末制剂包含按重量计1到30％的活性物质，通常优选按重量计5到20％的活性物质，然而可喷洒的溶液包含按重量计大约0.05到80％，优选2到50％的活性物质。关于水悬浮颗粒剂中活性物质的含量，主要根据活性物质为液体还是固态，和造粒时使用的助剂、填料等等。水悬浮颗粒剂中活性物质的含量例如按重量计在1到95％之间，优选按重量计在10到80％之间。
另外所述的活性物质的制剂可以包括增粘剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂和通常在所有情况下都常用的pH和粘度调节剂。
以这些制剂为基础，也可能和其他杀虫剂活性物质例如杀虫剂、杀螨剂、除草剂和杀菌剂混合，也可以和安全剂、肥料和/或植物生长调节剂混合，混合方式可以为预先混合好的或灌装混合。
在混配制剂或桶混制剂中，可以和本发明的活性物质混合的合适的活性物质为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的除草剂活性物质可以和式I混合物混合，(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：乙草胺、丁草胺、甲草胺、异丙草胺、异丙甲草胺、精异丙甲草胺、丙草胺、毒草胺、克草胺、萘丙酰草胺、R-左旋萘丙酰草胺、敌稗、苯噻酰草胺、双苯酰草胺、吡氟酰草胺、杀草胺、氟丁酰草胺、溴丁酰草胺、二甲噻草胺、高效二甲噻草胺、乙氧苯草胺、氟噻草胺、甲氧噻草胺、吡草胺、异恶草胺、高效麦草伏甲酯、高效麦草伏丙酯、二丙烯草胺、烯草胺、丁酰草胺、环丙草胺、氟磺酰草胺、庚酰草胺、异丁草胺、丙炔草胺、特丁草胺、二甲苯草胺、二甲草胺、落草胺、三甲环草胺、氯甲酰草胺、炔苯酰草胺、戊酰苯草胺、卡草胺、新燕灵、三环赛草胺、丁烯草胺、牧草胺、苄草胺、醌萍胺、苯氟磺胺、萘丙胺、乙酰甲草胺、萘草胺、噻草胺、吡氰草胺、苯草多克死、草克乐、氯酞亚胺、丁脒胺、氟吡草胺、莠去津、西玛津、扑草净、氰草净、西草净、莠灭净、扑灭津、异丙净、氟草净、特丁净、特丁津、三嗪氟草胺、环丙津、甘扑津、草达津、扑灭通、西玛通、叠氮净、敌草净、异戊乙净、环丙青津、灭莠津、另丁津、仲丁通、特丁通、甲氧丙净、氰草净、抑草津、可乐津、莠去通、灭草通、甘草津、三聚氰酸、Indaziflam、绿磺隆、甲磺隆、苄嘧磺隆、氯嘧黄隆、苯磺隆、噻磺隆、吡嘧黄隆、甲基二磺隆、甲基碘磺隆钠盐、甲酰氨基嘧磺隆、醚磺隆、醚苯磺隆、甲嘧磺隆、烟嘧磺隆、胺苯磺隆、酰嘧磺隆、乙氧嘧磺隆、环丙嘧磺隆、砜嘧磺隆、四唑嘧磺隆、啶嘧黄隆、单嘧磺隆、单嘧磺酯、氟唑磺隆、氟啶嘧磺隆、氟吡嘧磺隆、环氧嘧磺隆、唑吡嘧磺隆、氟嘧磺隆、丙苯磺隆、三氟丙磺隆、磺酰磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、甲磺隆钠盐、氟吡磺隆、甲硫嘧磺隆、嘧苯胺磺隆、Propyrisulfuron(丙嗪嘧磺隆)、嗪吡嘧磺隆、三氟羧草醚、氟磺胺草醚、乳氟禾草灵、乙羧氟草醚、乙氧氟草醚、草枯醚、苯草醚、氯氟草醚乙酯、甲羧除草醚、三氟甲草醚、甲氧除草醚、三氟硝草醚、氟化除草醚、氟呋草醚、除草醚、甲草醚、二甲草醚、氟酯肟草醚、氟草醚酯、Halosafen、绿麦隆、异丙隆、利谷隆、敌草隆、莎扑隆、氟草隆、苯噻隆、甲基苯噻隆、苄草隆、磺噻隆、异恶隆、特丁噻 草隆、炔草隆、氯溴隆、甲基杀草隆、酰草隆、甲氧杀草隆、溴谷隆、甲氧隆、绿谷隆、灭草隆、环草隆、非草隆、氟硫隆、草不隆、枯草隆、草完隆、异草完隆、环莠隆、噻氟隆、丁噻隆、枯莠隆、对氟隆、甲胺噻唑隆、隆草特、三甲异脲、恶唑隆、Monisouron、Anisuron、Methiuron、Chloreturon、四氟隆、甜菜宁、甜菜宁-乙酯、甜菜安、磺草灵、特草灵、燕麦灵、苯胺灵、氯苯胺灵、二氯苄草酯、灭草灵、氯炔灵、Carboxazole、Chlorprocarb、Fenasulam、BCPC、CPPC、Carbasulam、丁草特、禾草丹、灭草猛、禾草特、野麦畏、哌草丹、禾草畏、稗草丹、环草敌、燕麦敌、菌达灭、乙硫草特、坪草丹、克草猛、苄草丹、仲草丹、硫烯草丹、草灭散、Isopolinate、Methiobencarb、2,4-滴丁酯、2甲4氯钠、2,4-滴异辛酯、2甲4氯异辛酯、2,4-滴钠盐、2,4-滴二甲胺盐、2甲4氯乙硫酯、2甲4氯、2,4-滴丙酸、高2,4-滴丙酸盐、2,4-滴丁酸、2甲4氯丙酸、2甲4氯丙酸盐、2甲4氯丁酸、2,4,5-涕、2,4,5-涕丙酸、2,4,5-涕丁酸、2甲4氯胺盐、麦草畏、抑草蓬、伐草克、赛松、三氯苯酸、氨二氯苯酸、甲氧三氯苯酸、禾草灵、吡氟禾草灵、精吡氟禾草灵、氟吡甲禾灵、高效吡氟氯禾灵、喹禾灵、精喹禾灵、恶唑禾草灵、精恶唑禾草灵、喔草酯、氰氟草酯、恶唑酰草胺、炔草酯、噻唑禾草灵、炔禾灵、羟戊禾灵、三氟禾草肟、异恶草醚、百草枯、敌草快、安磺灵、乙丁烯氟灵、异丙乐灵、甲磺乐灵、环丙氟灵、氨基丙氟灵、乙丁氟灵、氯乙氟灵、氨基乙氟灵、地乐灵、氯乙地乐灵、Methalpropalin、丙硝酚、草甘膦、莎稗膦、草铵膦、甲基胺草磷、草硫膦、哌草膦、双丙氨膦、地散磷、抑草磷、蔓草磷、伐垅磷、双甲胺草磷、草特磷、咪唑烟酸、咪唑乙烟酸、咪唑喹啉酸、甲氧咪草烟、甲氧咪草烟铵盐、甲咪唑烟酸、咪草酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、二氯吡啶酸、氨氯吡啶酸、三氯吡氧乙酸、氟硫草定、卤草定、三氯吡啶酚、噻草啶、氟啶草酮、氯氨吡啶酸、氟吡草腙、三氯吡氧乙酸丁氧基乙酯、Cliodinate、稀禾啶、烯草酮、噻草酮、禾草灭、环苯草酮、丁苯草酮、肟草酮、吡喃草酮、Buthidazole、嗪草酮、环嗪酮、苯嗪草酮、乙嗪草酮、Ametridione、Amibuzin、溴苯腈、辛酰溴苯腈、辛酰碘苯腈、碘苯腈、敌草腈、二苯乙腈、双唑草腈、羟敌草腈、Iodobonil、唑嘧磺草胺、双氟磺草胺、五氟磺草胺、磺草唑胺、氯酯磺草胺、双氯磺草胺、啶磺草胺、氟草黄、双草醚、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚、双环磺草酮、硝磺草酮、磺草酮、Tembotrione、Tefuryltrione、Bicyclopyrone、Ketodpiradox、异恶唑草酮、异恶氯草酮、Fenoxasulfone、Methiozolin、异丙吡草酯、吡草醚、吡唑特、野燕枯、苄草唑、吡草酮、吡氯草胺、Pyrasulfotole、苯唑草酮、Pyroxasulfone、唑草胺、氟胺草唑、杀草强、胺唑草酮、唑啶草酮、氟唑草酮、甲磺草胺、Bencarbazone、双苯嘧草酮、氟丙嘧草酯、除草定、异草定、环草啶、特草定、Flupropacil、吲哚酮草酯、氟烯草酸、丙炔氟草胺、炔草胺、酞苄醚、Flumezin、五氯酚(钠)、地乐酚、特乐酚、特乐酯、戊硝酚、二硝酚、氯硝酚、地乐施、地乐特、丙炔恶草酮、恶草 酮、环戊恶草酮、氟唑草胺、嗪草酸甲酯、四唑酰草胺、氟哒嗪草酯、杀草敏、溴莠敏、二甲达草伏、哒草醚、草哒酮、草哒松、哒草伏、Pyridafol、二氯喹啉酸、氯甲喹啉酸、苯达松、哒草特、恶嗪草酮、草除灵、异恶草酮、环庚草醚、异丙酯草醚、丙酯草醚、茚草酮、氯酸钠、茅草枯、三氯醋酸、一氯醋酸、六氯丙酮、四氟丙酸、牧草快、溴酚肟、三唑磺、灭杀唑、呋草酮、呋草磺、乙呋草磺、嘧草胺、氯酞酸、氟咯草酮、稗草稀、丙烯醛、苯草灭、灭草环、燕麦酯、噻二唑草胺、棉胺宁、羟草酮、甲氧苯酮、苯嘧磺草胺、氯酰草膦、三氯丙酸、Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、甲硫磺乐灵、Cambendichlor、环丙嘧啶酸、硫氰苯胺、解草酮、解草啶、解草安、解草唑、解草喹、解草腈、解草烷、解草胺腈、解草烯、吡唑解草酯、呋喃解草唑、肟草安、双苯噁唑酸、二氯丙烯胺、氟氯吡啶酯、DOW氯氟吡啶酯、UBH-509、D489，LS82-556、KPP-300、NC-324、NC-330、KH-218、DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、KIH-6127和KIH-2023。
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/ha之间，或更多的活性物质，但优选在0.005到750g/ha之间，特别是在0.005到250g/ha之间。
具体实施方式
以下实施例用于举例说明本发明，不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。
鉴于化合物的经济性与多样性，我们优选合成了一些化合物，在合成的诸多化合物中，选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1-2所示。表1中的化合物只是为了更好的说明本发明，但并不限定本发明，对于本领域的技术人员而言，不应将此理解为本发明上述主题的范围仅限于以下化合物。
表1 化合物结构
Figure PCTCN2017117865-appb-000010
Figure PCTCN2017117865-appb-000011
Figure PCTCN2017117865-appb-000012
Figure PCTCN2017117865-appb-000013
表2 化合物 1HNMR数据
Figure PCTCN2017117865-appb-000014
Figure PCTCN2017117865-appb-000015
Figure PCTCN2017117865-appb-000016
Figure PCTCN2017117865-appb-000017
代表性化合物的实施例如下：
化合物3的制备：
Figure PCTCN2017117865-appb-000018
在室温下，将化合物A(1.0g,3.0mmol)溶解在10mL的二氯甲烷中，依次加入TEA(0.61g,6.0mmol)和PyBop(1.7g,3.3mmol)并在室温下搅拌30min，加入化合物B(0.5g,3.6mmol)，室温搅拌过夜，TLC检测反应完全，在反应体系中加入10mL的水，分液后，水相再用10mL二氯甲烷萃取两次，合并有机相，干燥旋干，柱层析分离(石油醚:乙酸乙酯＝10:1～4:1)得到白色的固体的3(0.9g,收率67％)。
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：
生物活性评价：
有害植物破坏(即生长控制率)的活性级别标准如下：
10级：完全死亡；
9级：生长控制率在95％以上；
8级：生长控制率在90％以上；
7级：生长控制率在80％以上；
6级：生长控制率在70％以上；
5级：生长控制率在60％以上；
4级：生长控制率在50％以上；
3级：生长控制率在20％以上；
2级：生长控制率在5-20％；
1级：生长控制率在5％以下；
0级：无效果。
以上生长控制率为鲜重控制率。
苗后测试实验：将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种2-3周后在4-5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，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，3周后杂草的实验效果列于表3。
表3.苗后杂草试验
化合物序号 播娘蒿 荠菜 苘麻 野慈姑 鸭舌草
1 10 10 10 10 10
2 10 10 10 10 10
3 10 10 10 10 10
4 10 10 10 10 10
5 10 10 10 10 10
6 10 10 10 10 10
7 10 10 10 10 10
8 10 10 10 10 10
9 10 10 10 10 10
10 10 10 10 10 10
11 10 10 10 10 10
12 10 10 10 10 10
13 10 10 10 10 10
14 10 10 10 10 10
15 10 10 10 10 10
16 10 10 10 10 10
17 10 10 10 10 10
18 10 10 10 10 10
19 10 10 10 10 10
20 10 10 10 10 10
21 10 10 10 10 10
22 10 10 10 10 10
23 10 10 10 10 10
24 10 10 10 10 10
25 10 10 10 10 10
26 10 10 10 10 10
27 10 10 10 10 10
28 10 10 10 10 10
29 10 10 10 10 10
30 10 10 10 10 10
31 10 10 10 10 10
32 10 10 10 10 10
33 10 10 10 10 10
34 10 10 10 10 10
35 10 10 10 10 10
36 10 10 10 10 10
37 10 10 10 10 10
38 10 10 10 10 10
39 10 10 10 10 10
40 10 10 10 10 10
41 10 10 10 10 10
42 10 10 10 10 10
43 10 10 10 10 10
44 10 10 10 10 10
45 10 10 10 10 10
46 10 10 10 10 10
47 10 10 10 10 10
48 10 10 10 10 10
49 10 10 10 10 10
50 10 10 10 10 10
51 10 10 10 10 10
52 10 10 10 10 10
53 10 10 10 10 10
54 10 10 10 10 10
55 10 10 10 10 10
56 10 10 10 10 10
57 10 10 10 10 10
58 10 10 10 10 10
注：施用剂量为有效成分250克/公顷，兑水量为450公斤/公顷。
苗前测试实验：
将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，播种后立即喷施。 施药后在温室中培养4周，3周后观察实验结果，发现本发明的药剂多数在250克/公顷计量下效果出众，尤其对稗草、马塘、苘麻等杂草，且很多化合物对玉米、小麦、水稻、大豆、油菜有良好的选择性。
通过实验我们发现本发明所述化合物普遍具有较好的杂草防效，尤其对于玉米田、水稻田、小麦田广泛发生的杂草稗草、马唐、狗尾草等主要禾本科杂草以及苘麻、蔊菜、鬼针草等主要的阔叶杂草有良好的效果，具备良好的商业价值。尤其是我们注意到对于ALS抑制剂有抗性的蔊菜、播娘蒿、荠菜、麦家公、猪殃殃、繁缕等阔叶杂草有极高的活性。
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、野慈姑的种子，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1-10的活性标准级别评价除草效果，很多化合物表现出了优异的活性和选择性。
注：稗草、萤蔺、野慈姑、狼把草种子均采集自中国黑龙江，经过检测对常规剂量的吡嘧磺隆有抗药性。
对比实验：
对照化合物A：
Figure PCTCN2017117865-appb-000019
(来自专利WO2003/011853)
对照化合物B：
Figure PCTCN2017117865-appb-000020
(来自专利CN105503712A)
对照化合物C：
Figure PCTCN2017117865-appb-000021
(陶氏益农商业化品种)
苗后测试条件同上。
表4.对比实验结果(50克/公顷)
化合物序号 水稻 小麦 苘麻 猪殃殃 玉米 荠菜
1 0 0 10 10 0 10
3 0 0 10 10 0 10
4 0 0 10 10 1 10
5 0 0 10 10 0 10
7 0 0 10 10 0 10
9 0 0 10 10 0 10
11 0 0 10 10 0 10
12 0 0 10 10 0 10
57 0 0 10 10 0 10
58 0 0 10 10 0 10
对照化合物A 7 4 10 10 8 10
对照化合物C 4 3 10 10 7 10
由表4可以看出，本发明的化合物与对照化合物A和C相比，具有更高的作物安全性，尤其是对于小麦、玉米、水稻等关键农作物建立了良好的选择性，而对照化合物对主要作物选择性差，可见本发明取得了意料之外的效果。
表5.对比实验结果(100克/公顷)
化合物序号 小飞蓬 黄鹌菜 刺儿菜 大巢菜
17 10 10 9 10
对照化合物B 2 1 0 2
由表5可以看出，本发明化合物的除草活性远高于对照化合物B，尤其是对于小飞蓬、黄鹌菜、刺儿菜、大巢菜等杂草。
同时经过很多测试发现，本发明所述化合物很多对结缕草、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大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。

Claims (10)

  1. 一种取代的含氮杂芳环甲酸亚胺酯衍生物，如通式I所示：
    Figure PCTCN2017117865-appb-100001
    其中，
    R 1和R 2独立地代表H，卤素，氰基，硝基，烷基，卤代烷基，链烯基，环烷基，烷氧基，酰氧基，烷硫基，未取代或取代的芳基、苄基、杂芳基、芳基氧基、芳基硫基、杂芳基氧基和杂芳基硫基；以及式-COR 5所示的基团，其中R 5代表烷基，卤代烷基，链烯基，环烷基，烷氧基，链烯氧基，环烷氧基，烷硫基，链烯基硫基，环烷硫基，未取代或取代的苄基、芳基、杂芳基、芳基氧基、杂芳基氧基、芳基甲氧基、杂芳基甲氧基、苄硫基、芳基硫基、杂芳基硫基和可用烷基，酰基，酰氧基，未取代或取代的芳基、杂芳基、芳基烷基、杂芳基烷基取代的氨基；或R 1和R 2连接形成5-或6-元饱和或不饱和环；
    Y代表H，卤素，氰基，硝基，烷基，卤代烷基，链烯基，环烷基，烷氧基，酰氧基，烷硫基，NR 3R 4，其中R 3和R 4独立地代表H、烷基、链烯基、炔基、羟基、卤代烷基、烷氧基、氨基、酰基、烷氧羰基、烷基氨基甲酰基、烷基磺酰基、三烷基甲硅烷基或二烷基膦酰基，或NR 3R 4代表5-或6-元的饱和环或5-元的不饱和环；
    W代表H，卤素，烷氧基，烷基，卤代烷基，链烯基，炔基；
    X代表卤素、烷氧基、烷基、卤代烷基、链烯基、炔基或氰基；
    Q选自卤素，含有或不含有卤素的烷基、环烷基、烷氧基，苯基、2,3-二氢化茚基或萘基的芳基，或选自
    Figure PCTCN2017117865-appb-100002
    的杂芳基，芳基或杂芳基是未取代的或取代的，其中一个或多个取代基选自如下基团：卤素、氰基、芳基氧基、烷基、烷氧基、卤代烷基、卤代烷氧基、酰基、烷基硫代、苯基、-OCH 2CH 2-、-OCH 2O-或-OCH 2CH 2O-。
  2. 根据权利要求1所述的一种取代的含氮杂芳环甲酸亚胺酯衍生物，其特征在于，
    R 1和R 2独立地代表H，氰基，C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C3-C8环烷基，C1-C8烷氧基，C1-C8酰氧基，C1-C8烷硫基，未取代或取代的芳基、苄基、杂芳基、芳基氧基、芳基硫基、杂芳基氧基和杂芳基硫基；以及式-COR 5所示的基团，其中R 5代表C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C3-C8环烷基，C1-C8烷氧基，C2-C8链烯氧基，C3-C8环烷氧基，C1-C8烷硫基，C2-C8链烯基硫基，C3-C8环烷硫基，未取代或取 代的苄基、芳基、杂芳基、芳基氧基、杂芳基氧基、芳基甲氧基、杂芳基甲氧基、苄硫基、芳基硫基、杂芳基硫基和可用C1-C8烷基，C1-C8酰基，C1-C8酰氧基，未取代或取代的芳基、杂芳基、芳基C1-C8烷基、杂芳基C1-C8烷基取代的氨基；其中，所述“取代的”是指被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C3-C8环烷基、C1-C8烷氧基、C2-C8链烯氧基、C1-C8烷硫基、芳基、芳基氧基、苄基、苄氧基、C1-C8酰基、C1-C8酰氧基、C2-C8链烯基以及可用C1-C8烷基、芳基、芳基氧基、C1-C8酰基、C1-C8酰氧基和C2-C8链烯基取代的氨基中的一个或多个基团所取代；
    Y代表H，卤素，氰基，硝基，C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C3-C8环烷基，C1-C8烷氧基，C1-C8酰氧基，C1-C8烷硫基，NR 3R 4，其中R 3和R 4独立地代表H、C1-C8烷基、C2-C8链烯基、C2-C8炔基、羟基、卤代C1-C8烷基、C1-C8烷氧基、氨基、C1-C8酰基、C1-C8烷氧羰基、C1-C8烷基氨基甲酰基、C1-C8烷基磺酰基、三C1-C8烷基甲硅烷基或二C1-C8烷基膦酰基，或R 3R 4N代表5-或6-元的饱和环或5-元的不饱和环；
    W代表H，卤素，C1-C8烷氧基，C1-C8烷基，卤代C1-C8烷基，C2-C8链烯基，C2-C8炔基；
    X代表卤素、C1-C8烷氧基、C1-C8烷基、卤代C1-C8烷基、C2-C8链烯基、C2-C8炔基或氰基；
    Q选自卤素，含有或不含有卤素的C1-C6烷基、C3-C6环烷基、C1-C6烷氧基，苯基、2,3-二氢化茚基或萘基的芳基，或选自
    Figure PCTCN2017117865-appb-100003
    的杂芳基，芳基或杂芳基是未取代的或取代的，其中一个或多个取代基选自如下基团：卤素、氰基、芳基氧基、C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷基、卤代C1-C8烷氧基、C1-C8酰基、C1-C8烷基硫代、苯基、-OCH 2CH 2-、-OCH 2O-或-OCH 2CH 2O-。
  3. 根据权利要求1所述的一种取代的含氮杂芳环甲酸亚胺酯衍生物，其特征在于，
    R 1和R 2独立地代表氢，C1-C6烷基，C1-C6烷氧基，C1-C6烷硫基，氰基，C1-C6烷氧羰基，以及未取代或被选自卤素、卤代C1-C6烷基、C1-C6烷基、C1-C6烷氧基和C2-C6链烯基中的一个或多个基团所取代的苯基；
    Y代表H、NR 3R 4，其中R 3和R 4独立地代表H、C1-C6烷基、C1-C6烷氧基、C1-C6酰基；
    W代表H，卤素；
    X代表卤素、C1-C6烷基、C1-C6烷氧基、氰基；
    Q选自卤素，含有或不含有卤素的C1-C6烷基，C3-C6环烷基，未取代或被选自卤素、 C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷基中的一个或多个基团所取代的苯基。
  4. 根据权利要求1所述的一种取代的含氮杂芳环甲酸亚胺酯衍生物，其特征在于，
    R 1和R 2独立地代表氢、甲基、乙基、丙基、异丙基、正丁基、叔丁基、环丙基、甲硫基、乙硫基、氰基、甲氧羰基、乙氧羰基，以及未取代或被选自卤素、CF 3、甲基、乙基、丙基、异丙基、正丁基、叔丁基、环丙基、甲氧基和乙氧基中的一个或多个基团所取代的苯基；
    X代表氯、溴、甲氧基、乙氧基、甲基、乙基、丙基、异丙基、正丁基、叔丁基、环丙基、氰基；
    Y代表H、NH 2、
    Figure PCTCN2017117865-appb-100004
    NO 2；
    W代表H、氯、氟；
    Q代表环丙基、三氟甲基、氯、氟、
    Figure PCTCN2017117865-appb-100005
  5. 一种如权利要求1-4任意一项所述的取代的含氮杂芳环甲酸亚胺酯衍生物的制备方法，其特征在于，包括以下步骤：使用如通式II所示的化合物与通式III所示的化合物进行反应，制备如通式I所示的化合物，反应方程式如下：
    Figure PCTCN2017117865-appb-100006
  6. 根据权利要求5所述的一种取代的含氮杂芳环甲酸亚胺酯衍生物的制备方法，其特征在于，所述反应在非质子型溶剂中、碱和缩合剂的作用下进行；优选地，所述反应温度为0℃-90℃，优选10℃-30℃；所述溶剂选自二氯甲烷、二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、四氢呋喃、甲苯、二甲苯中的一种或多种混合溶剂；所述碱选自三乙胺、三甲胺、DIPEA和DBU中的一种或多种；所述缩合剂为PyBop、HATU或HOBt-EDCI。
  7. 一种除草剂组合物，其特征在于，包括除草有效量的权利要求1-5任意一项所述的取代的含氮杂芳环甲酸亚胺酯衍生物中的至少一种。
  8. 根据权利要求7所述的除草剂组合物，其特征在于，还包括制剂助剂。
  9. 一种控制有害植物的方法，其特征在于，包括将除草有效量的权利要求1-5任意一项所述的取代的含氮杂芳环甲酸亚胺酯衍生物中的至少一种或权利要求7-8任意一项所述的除草剂组合物使用在植物上或者有害植物区域。
  10. 如权利要求1-5任意一项所述的取代的含氮杂芳环甲酸亚胺酯衍生物中的至少一种或权利要求7-8任意一项所述的除草剂组合物在控制有害植物上的用途，优选地，将所述的取代的含氮杂芳环甲酸亚胺酯衍生物用于防除有用作物中的有害植物，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
PCT/CN2017/117865 2017-12-04 2017-12-22 取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用 WO2019109401A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711260779.0A CN109832277B (zh) 2017-12-04 2017-12-04 取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用
CN201711260779.0 2017-12-04

Publications (1)

Publication Number Publication Date
WO2019109401A1 true WO2019109401A1 (zh) 2019-06-13

Family

ID=66750784

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/117865 WO2019109401A1 (zh) 2017-12-04 2017-12-22 取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用

Country Status (3)

Country Link
CN (1) CN109832277B (zh)
AR (1) AR122836A1 (zh)
WO (1) WO2019109401A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0335409A2 (en) * 1988-03-31 1989-10-04 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives, processes for their production and herbicidal compositions containing them
WO1996006096A1 (fr) * 1994-08-23 1996-02-29 Nissan Chemical Industries, Ltd. Derive de pyridine
CN1551876A (zh) * 2001-07-30 2004-12-01 �ݶ�ũ�����޹�˾ 6-芳基-4-氨基吡啶甲酸酯及其作为除草剂的用途
CN101977503A (zh) * 2008-03-19 2011-02-16 拜尔农科股份公司 杀真菌剂肟基-四唑衍生物
CN102007120A (zh) * 2008-04-22 2011-04-06 拜尔农科股份公司 杀真菌剂肟基-杂环衍生物
CN105503712A (zh) * 2015-12-11 2016-04-20 中国农业大学 一种吡乙苯醚肟酯化合物及其制备方法与应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109485600A (zh) * 2017-09-11 2019-03-19 山东先达农化股份有限公司 含氟氯吡啶肟酯结构的化合物及其制备方法和应用及一种除草剂

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0335409A2 (en) * 1988-03-31 1989-10-04 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives, processes for their production and herbicidal compositions containing them
WO1996006096A1 (fr) * 1994-08-23 1996-02-29 Nissan Chemical Industries, Ltd. Derive de pyridine
CN1551876A (zh) * 2001-07-30 2004-12-01 �ݶ�ũ�����޹�˾ 6-芳基-4-氨基吡啶甲酸酯及其作为除草剂的用途
CN101977503A (zh) * 2008-03-19 2011-02-16 拜尔农科股份公司 杀真菌剂肟基-四唑衍生物
CN102007120A (zh) * 2008-04-22 2011-04-06 拜尔农科股份公司 杀真菌剂肟基-杂环衍生物
CN105503712A (zh) * 2015-12-11 2016-04-20 中国农业大学 一种吡乙苯醚肟酯化合物及其制备方法与应用

Also Published As

Publication number Publication date
AR122836A1 (es) 2022-10-12
CN109832277A (zh) 2019-06-04
CN109832277B (zh) 2020-08-18

Similar Documents

Publication Publication Date Title
WO2017113509A1 (zh) 吡唑类化合物或其盐、制备方法、除草剂组合物及用途
WO2019080224A1 (zh) 一种吡唑酮类化合物或其盐、除草剂组合物及用途
WO2017075910A1 (zh) 吡唑酮类化合物或其盐、制备方法、除草剂组合物及用途
WO2020108518A1 (zh) N-(1,3,4-噁二唑-2-基)芳基甲酰胺类或其盐、制备方法、除草组合物和应用
WO2021139482A1 (zh) 一种羧酸衍生物取代的亚氨基芳基化合物及其制备方法、除草组合物和应用
WO2019080226A1 (zh) 取代的苯甲酰基二酮腈类化合物或其互变异构体、盐、制备方法、除草组合物及应用
WO2020006869A1 (zh) 取代的嘧啶甲酰基肟衍生物及其制备方法、除草组合物和应用
CN112778289B (zh) 一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用
WO2021143677A1 (zh) 一种稠环取代的芳香类化合物及其制备方法、除草组合物和应用
WO2017113508A1 (zh) 吡唑类化合物或其盐、制备方法、除草剂组合物及用途
CN108084108B (zh) 一种5-氯苯并噁唑衍生物及其制备方法、除草组合物和应用
WO2021078174A1 (zh) 一种含手性硫氧化物的芳基甲酰胺类化合物或其盐、制备方法、除草组合物和应用
WO2019090818A1 (zh) 一种4-苯甲酰吡唑类化合物及其制备方法和应用
WO2019080227A1 (zh) 取代的苯甲酰基异恶唑类化合物或其互变异构体、盐、制备方法、除草组合物及应用
CN113149975B (zh) 一种异噁唑啉甲酸肟酯类化合物及其制备方法、除草组合物和应用
WO2020114212A1 (zh) 4-(3-杂环基-1-苯甲酰基)吡唑类化合物或其盐、制备方法、除草剂组合物及用途
CN113024531B (zh) 一种含异噁唑啉的化合物及其制备方法、除草组合物和应用
WO2019148850A1 (zh) 吡啶环取代的哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用
WO2019148851A1 (zh) 五元环取代的哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用
WO2020253696A1 (zh) 取代的吡啶甲酸吡啶亚甲基酯衍生物及其制备方法、除草组合物和应用
WO2021032033A1 (zh) 一种哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用
WO2020135236A1 (zh) 吡啶氧基羧酸肟衍生物、制备方法、除草组合物和应用
WO2020156106A1 (zh) 杂环基芳基甲酰胺类或其盐、制备方法、除草组合物和应用
WO2019033590A1 (zh) 取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用
WO2019109401A1 (zh) 取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17934116

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17934116

Country of ref document: EP

Kind code of ref document: A1