WO2019128312A1 - 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 - Google Patents

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 Download PDF

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WO2019128312A1
WO2019128312A1 PCT/CN2018/105265 CN2018105265W WO2019128312A1 WO 2019128312 A1 WO2019128312 A1 WO 2019128312A1 CN 2018105265 W CN2018105265 W CN 2018105265W WO 2019128312 A1 WO2019128312 A1 WO 2019128312A1
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substituted
compound
group
chlorobenzoxazole
alkyl
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PCT/CN2018/105265
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English (en)
French (fr)
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连磊
征玉荣
何彬
何永光
彭学岗
金涛
崔琦
刘娜
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青岛清原化合物有限公司
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Publication of WO2019128312A1 publication Critical patent/WO2019128312A1/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
    • 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
    • A01N43/82—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 three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention belongs to the technical field of pesticides, and particularly relates to a 5-chlorobenzoxazole derivative, a preparation method thereof, a herbicidal composition and application.
  • patent CN1141876C discloses a series of herbicidal compounds with the general formula
  • Patent CN106172458A discloses a herbicidal composition comprising the compound oxazolamide, the English name is metamifop, and the chemical name is: (R)-2- ⁇ (4-chloro-1,3-benzoxazole-2 -yloxy)phenoxy ⁇ -2'-fluoro-N-methylpropionanilide, the structure is The English and Chinese names do not match the structural formula.
  • Patent CN104277033A discloses an N-(arylalkyl) aryloxyphenoxycarboxylic acid amide compound and its a structure whose general formula is
  • Patent CN104277033A discloses an N-(arylalkyl) aryloxyphenoxycarboxylic acid amide compound and its a structure whose general formula is
  • the present invention provides a 5-chlorobenzoxazole derivative, a preparation method thereof, a herbicidal composition and use thereof, the derivative and the herbicidal composition thereof, such as valerian Gramineous weeds are highly effective in controlling drugs and are very safe and selective for crops such as rice.
  • X represents halogen, cyano, trifluoromethyl, methyl
  • Y represents NR 1 R 2 , R 1 represents H, alkyl, alkylsulfonyl, haloalkyl, R 2 represents unsubstituted or substituted aryl, heteroaryl; or R 1 and R 2 are bonded to form an unsubstituted or substituted 5- or 6-membered unsaturated ring;
  • substituted means an alkyl, alkenyl, cycloalkyl, alkoxy, alkenyloxy group selected from the group consisting of halogen, cyano, nitro, carboxyl, hydroxy, with or without a halogen. , alkylthio, aryl, aryloxy, benzyl, benzyloxy, alkoxycarbonyl, alkyl acyl, acyloxy and available alkyl, aryl, aryloxy, alkyl acyl, acyloxy Substituted by one or more of the amino and alkenyl substituted amino groups.
  • the aryl group includes a phenyl group, a 2,3-indanyl group or a naphthyl group; and the heteroaryl group includes a 5-10 membered heteroaryl group having 1 to 3 O, S, and N hetero atoms.
  • X represents F, Cl, Br, cyano, trifluoromethyl, methyl
  • Y represents NR 1 R 2
  • R 1 represents H, C1-C8 alkyl, C1-C8 alkylsulfonyl, halogenated C1-C8 alkyl
  • R 2 represents unsubstituted or substituted phenyl, pyridyl, pyrazole Base, isoxazolyl, thienyl, thiazolyl, thiadiazolyl, Or R 1 and R 2 are joined to form an unsubstituted or substituted
  • substituted means selected from halogen, cyano, nitro, C1-C8 alkoxycarbonyl, amino, C1-C8 alkylamino, C1-C8 alkyl with or without halogen, C1 Substituted with one or more groups of -C8 alkoxy, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl.
  • X represents Cl, cyano, trifluoromethyl, methyl
  • Y represents NR 1 R 2
  • R 1 represents H, C1-C6 alkyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkyl
  • R 2 represents unsubstituted or selected from C1-C6 alkyl, cyanide
  • R 1 represents H, C1-C6 alkyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkyl
  • R 2 represents unsubstituted or selected from C1-C6 alkyl, cyanide
  • X represents Cl
  • Y represents NR 1 R 2
  • R 1 represents H, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, SO 2 Et, CH 2 CHF 2
  • R 2 represents unsubstituted or Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyano, nitro, F, Cl, Br, CF 3 , OCF 3 , methoxy, ethoxy, Substituted by one or more substituents of a phenyl group, a halogen-substituted phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, or an amino group
  • NR 1 R 2 is not
  • the preparation method of the 5-chlorobenzoxazole derivative comprises the following steps:
  • L is Cl or Br
  • a compound of the formula III can be reacted with the compound HY in the presence of a dehydrating agent to obtain a compound of the formula I, the chemical reaction equation of which is as follows:
  • the reaction temperature is in the range of -50 to 180 ° C, preferably -10 to 80 ° C.
  • the solvent is selected from one or more of acetonitrile, ethyl acetate, toluene, xylene, DMF, DMSO, NMP, and the like.
  • the base is selected from the group consisting of anhydrous sodium carbonate, anhydrous potassium carbonate, sodium t-butoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, triethylamine, N,N-diisopropylethylamine, DBU, and the like. One or more.
  • the halogenating agent used in the step (2) is oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, oxalyl bromide, thionyl bromide, phosphorus oxybromide or phosphorus tribromide.
  • the dehydrating agent includes and is not limited to DCC, HOBt, EDCI, CDI, and the like.
  • a herbicidal composition comprising at least one of a herbicidally effective amount of the 5-chlorobenzoxazole derivative.
  • the herbicidal composition of the 5-chlorobenzoxazole derivative also includes a formulation aid.
  • a method of controlling a harmful plant comprising using at least one of the herbicidally effective amount of the 5-chlorobenzoxazole derivative or the herbicidal composition described on a plant or a harmful plant area.
  • At least one of the 5-chlorobenzoxazole derivatives or the herbicidal composition 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 useful crop is a paddy field.
  • 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 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.
  • 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 compounds of the present invention have excellent herbicidal activity against monocotyledonous weeds, they are not damaged at all for important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean, or The damage is negligible. In particular, it is well compatible with cereal crops, such as wheat, barley and corn, especially rice, and therefore, 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.
  • transgenic crop plant such as cotton which is capable of producing Bacillus thuringiensis toxin (Bt toxin) which protects against specific pests against plants (EP-0142924A, EP-0193259A);
  • 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 substance in the water-suspended granules mainly depending on whether the active substance 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.
  • 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 monocotyledon seeds and main crop seeds (rice, wheat, soybean) in plastic pots filled with soil, then cover 0.5-2 cm of soil to grow in a good greenhouse environment, sow 2 -3 weeks later, in the weed 2-3 leaf stage, the crops were treated in the 3-4 leaf stage, and the tested compounds of the invention were dissolved in acetone, then Tween 80 was added, and diluted to a certain concentration with a certain amount of water. The solution was 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 2.
  • Control compound 3 (Selected from patents CN106172458A and CN1141876C)
  • Control compound 5 (Selected from patent CN104277033A)
  • the compound of the present invention is excellent in the control activity against valerian and has higher crop safety than the control compound 1-5, and in particular, has good selectivity for rice.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

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。所述5-氯苯并噁唑衍生物，其化学结构如通式I所示：其中，X代表卤素、氰基、三氟甲基、甲基；Y代表NR 1R 2，R 1代表H、烷基、烷基磺酰基、卤代烷基，R 2代表未取代或取代的芳基、杂芳基；或者R 1和R 2连接形成未取代或取代的5-或6-元不饱和环。所述衍生物及其除草组合物对稗草等禾本科杂草的防治药性高效且对水稻等作物非常安全、选择性好。

Description

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 技术领域
本发明属于农药技术领域，具体涉及一种5-氯苯并噁唑衍生物及其制备方法、除草组合物和应用。
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，目前市场上的除草剂种类多样，例如，专利CN1141876C公开了一系列除草化合物，其通式为
Figure PCTCN2018105265-appb-000001
专利CN106172458A公开了一种除草组合物，其中包含化合物噁唑酰草胺，英文名称为metamifop，化学名称为：(R)-2-{(4-氯-1,3-苯并恶唑-2-基氧)苯氧基}-2′-氟-N-甲基丙酰替苯胺，结构为
Figure PCTCN2018105265-appb-000002
而其英文和中文名称与结构式不符，噁唑酰草胺的结构式应该为
Figure PCTCN2018105265-appb-000003
即该专利公开的结构式是噁唑酰草胺的错误写法，Cl的取代位置标注有误；专利CN104277033A公开了一种N-(芳基烷基)芳氧苯氧羧酸酰胺类化合物及其异构体，其通式为
Figure PCTCN2018105265-appb-000004
然而，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
为解决现有技术中存在的上述问题，本发明提供了一种5-氯苯并噁唑衍生物及其制备方法、除草组合物和应用，所述衍生物及其除草组合物对稗草等禾本科杂草的防治药性高效且对水稻等作物非常安全、选择性好。
本发明采用的技术方案如下：
一种5-氯苯并噁唑衍生物，其化学结构如通式I所示：
Figure PCTCN2018105265-appb-000005
其中，
X代表卤素、氰基、三氟甲基、甲基；
Y代表NR 1R 2，R 1代表H、烷基、烷基磺酰基、卤代烷基，R 2代表未取代或取代的芳基、杂芳基；或者R 1和R 2连接形成未取代或取代的5-或6-元不饱和环；
其中，所述“取代的”是指被选自卤素，氰基，硝基，羧基，羟基，含有或不含有卤素的烷基、链烯基、环烷基、烷氧基、链烯氧基、烷硫基、芳基、芳基氧基、苄基、苄氧基、烷氧羰基、烷基酰基、酰氧基以及可用烷基、芳基、芳基氧基、烷基酰基、酰氧基和链烯基取代的氨基中的一个或多个基团所取代。
上面给出的通式化合物的定义中，汇集所用术语定义如下：
所述的芳基包括苯基、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、
Figure PCTCN2018105265-appb-000006
等。
优选地，X代表F、Cl、Br、氰基、三氟甲基、甲基；
Y代表NR 1R 2，R 1代表H、C1-C8烷基、C1-C8烷基磺酰基、卤代C1-C8烷基，R 2代表未取代或取代的苯基、吡啶基、吡唑基、异噁唑基、噻吩基、噻唑基、噻二唑基、
Figure PCTCN2018105265-appb-000007
Figure PCTCN2018105265-appb-000008
或者R 1和R 2连接形成未取代或取代的
Figure PCTCN2018105265-appb-000009
其中，所述“取代的”是指被选自卤素、氰基、硝基、C1-C8烷氧羰基、氨基、C1-C8烷基氨基、含有或不含有卤素的C1-C8烷基、C1-C8烷氧基、C3-C8环烷基、C2-C8烯基、C2-C8炔基、苯基中的一个或多个基团所取代。
更优选地，X代表Cl、氰基、三氟甲基、甲基；
Y代表NR 1R 2，R 1代表H、C1-C6烷基、C1-C6烷基磺酰基、卤代C1-C6烷基，R 2代表未取代或被选自C1-C6烷基、氰基、硝基、卤素、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、苯基、卤素取代苯基、C1-C6烷氧羰基、氨基中的一种或多种取代基取代的
Figure PCTCN2018105265-appb-000010
Figure PCTCN2018105265-appb-000011
进一步优选地，X代表Cl；
Y代表NR 1R 2，R 1代表H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、SO 2Et、CH 2CHF 2，R 2代表未取代或被选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、氰基、硝基、F、Cl、Br、CF 3、OCF 3、甲氧基、乙氧基、苯基、卤素取代苯基、甲氧羰基、乙氧羰基、氨基中的一种或多种取代基取代的
Figure PCTCN2018105265-appb-000012
Figure PCTCN2018105265-appb-000013
更进一步优选地，当X为Cl时，NR 1R 2不为
Figure PCTCN2018105265-appb-000014
其中，上述通式I化合物优选为R构型(如通式I-1所示)：
Figure PCTCN2018105265-appb-000015
所述的5-氯苯并噁唑衍生物的制备方法，包括以下步骤：
(1)将化合物Ⅳ与化合物Ⅴ在碱和溶剂的存在下进行反应，制备如通式Ⅲ所示的化合物；
(2)如通式Ⅲ所示的化合物经酰卤化反应制得如通式Ⅱ所示的化合物；
(3)将如通式Ⅱ所示的化合物与化合物HY在碱和溶剂的存在下反应制得如通式Ⅰ所示的化合物；
其化学反应方程式如下：
Figure PCTCN2018105265-appb-000016
其中，L为Cl或Br；
或者将如通式Ⅲ所示的化合物与化合物HY在脱水剂的存在下反应制得如通式Ⅰ所示的化合物，其化学反应方程式如下：
Figure PCTCN2018105265-appb-000017
所述反应温度均在-50～180℃范围内，优选-10～80℃。
所述溶剂选自乙腈、乙酸乙酯、甲苯、二甲苯、DMF、DMSO、NMP等中的一种或多种。
所述碱选自无水碳酸钠、无水碳酸钾、叔丁醇钠、叔丁醇钾、甲醇钠、乙醇钠、三乙胺、N,N-二异丙基乙胺、DBU等中的一种或多种。
所述步骤(2)中采用的卤化试剂为草酰氯、氯化亚砜、三氯氧磷、三氯化磷、草酰溴、亚硫酰溴、三溴氧磷或三溴化磷等。
所述脱水剂包括并不限于DCC、HOBt、EDCI和CDI等。
当通式I化合物为R构型(如通式I-1所示)时，以化合物Ⅳ-1为原料进行上述反应。
Figure PCTCN2018105265-appb-000018
一种除草剂组合物，包括除草有效量的所述的5-氯苯并噁唑衍生物中的至少一种。
所述5-氯苯并噁唑衍生物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5-氯苯并噁唑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5-氯苯并噁唑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5-氯苯并噁唑衍生物中的至少一种或所述的除草剂组合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。
进一步优选地，所述有用作物为水稻田。
对于许多经济上重要的单子叶有害植物，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。
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。
虽然本发明化合物对于单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，特别是水稻，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-0221044A，EP-0131624A)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，WO92/14827，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-0242236A，EP-0242246A)或对草甘膦类除草剂(WO 92/00377)，或对磺酰脲类除草剂(EP-0257993A，US-5013659A)；
-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-0142924A，EP-0193259A)；
-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 PCTCN2018105265-appb-000019
的
Figure PCTCN2018105265-appb-000020
[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。
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数据
Figure PCTCN2018105265-appb-000021
Figure PCTCN2018105265-appb-000022
Figure PCTCN2018105265-appb-000023
Figure PCTCN2018105265-appb-000024
Figure PCTCN2018105265-appb-000025
Figure PCTCN2018105265-appb-000026
Figure PCTCN2018105265-appb-000027
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：
化合物01的制备
Figure PCTCN2018105265-appb-000028
18.2g化合物A1溶解于100mL DMF中，搅拌下加入40g无水碳酸钾，升温至80℃，搅拌反应1小时，降至室温，然后分批加入18.8g化合物A2，反应物继续升温至80℃搅拌反应1小时，降至室温，加入500mL水稀释，盐酸调pH至3左右，析出大量白色固体，抽滤。滤饼干燥，得到30.1g白色固体，化合物A3。收率90.4％，HPLC纯度大于95％。
取10g化合物A3，与15mL氯化亚砜混合，加热回流30min，减压蒸除过量的氯化亚砜，得到11.2g无色透明糖浆状化合物A4。将其用20mL二氯乙烷稀释，用于下一步反应。
3.3g苯胺和5mL三乙胺溶解于30mL二氯乙烷中，搅拌降温至0℃，向其中慢慢滴加上 一步制备的化合物A4的二氯乙烷溶液，控制反应温度不高于10℃。滴完后升至室温搅拌过夜。向反应液中加入30mL水，分液。有机相依次用稀盐酸、饱和碳酸氢钠溶液、水和饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩。得到的粗品经硅胶柱层析纯化，得到9.9g白色固体，收率80.9％，HPLC纯度为98.5％。
化合物02的制备
Figure PCTCN2018105265-appb-000029
将10g化合物A3、3.6g 3-氨基-4-氰基吡唑(A2)加入到20mL DMF中，室温搅拌下慢慢加入7.0g N,N'-二环己基碳二亚胺(DCC)，室温搅拌过夜。向反应液中加入30mL水，分液。有机相依次用稀盐酸、饱和碳酸氢钠溶液、水和饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩。得到的粗品经硅胶柱层析纯化，得到8.6g白色固体，收率61.0％，HPLC纯度为98.0％。
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：将单子叶种子以及主要作物种子(水稻、小麦、大豆)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周后在杂草2-3叶期，作物3-4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2。
表2.苗后杂草试验(150克/公顷)
化合物序号 稗草 水稻 小麦 大豆
1 10 0 0 0
2 10 0 0 0
3 10 0 0 0
4 10 0 0 0
5 10 0 0 0
6 10 0 0 0
7 10 0 0 0
8 10 0 0 0
9 10 0 0 0
10 10 0 0 0
11 10 0 0 0
12 10 0 0 0
13 10 0 0 0
14 10 0 0 0
15 10 0 0 0
16 10 0 0 0
17 10 0 0 0
18 10 0 0 0
19 10 0 0 0
20 10 0 0 0
21 10 0 0 0
22 10 0 0 0
23 10 0 0 0
24 10 0 0 0
25 10 0 0 0
26 10 0 0 0
27 10 0 0 0
28 10 0 0 0
29 10 0 0 0
30 10 0 0 0
31 10 0 0 0
32 10 0 0 0
33 10 0 0 0
34 10 0 0 0
35 10 0 0 0
36 10 0 0 0
37 10 0 0 0
38 10 0 0 0
39 10 0 0 0
40 10 0 0 0
41 10 0 0 0
42 10 0 0 0
43 10 0 0 0
44 10 0 0 0
45 10 0 0 0
46 10 0 0 0
47 10 0 0 0
48 10 0 0 0
49 8 0 0 0
50 10 0 0 0
51 10 0 0 0
52 10 0 0 0
53 10 0 0 0
54 10 0 0 0
55 10 0 0 0
56 10 0 0 0
57 10 0 0 0
58 10 0 0 0
59 10 0 0 0
60 10 0 0 0
对比实验：苗后测试条件同上，实验结果如表3所示。
对照化合物1：
Figure PCTCN2018105265-appb-000030
对照化合物2：
Figure PCTCN2018105265-appb-000031
对照化合物3：
Figure PCTCN2018105265-appb-000032
(选自专利CN106172458A和CN1141876C)
对照化合物4：
Figure PCTCN2018105265-appb-000033
对照化合物5：
Figure PCTCN2018105265-appb-000034
(选自专利CN104277033A)
表3.对比实验结果
Figure PCTCN2018105265-appb-000035
Figure PCTCN2018105265-appb-000036
注：水稻(直播籼稻2叶期)、稗草(4叶期)；N代表无数据。
由上表可知，与对照化合物1-5相比，本发明的化合物对于稗草的防治活性优异，且具有更高的作物安全性，尤其是对水稻建立了良好的选择性。
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。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5-氯苯并噁唑衍生物，其化学结构如通式I所示：
    Figure PCTCN2018105265-appb-100001
    其中，
    X代表卤素、氰基、三氟甲基、甲基；
    Y代表NR 1R 2，R 1代表H、烷基、烷基磺酰基、卤代烷基，R 2代表未取代或取代的芳基、杂芳基；或者R 1和R 2连接形成未取代或取代的5-或6-元不饱和环；
    其中，所述“取代的”是指被选自卤素，氰基，硝基，羧基，羟基，含有或不含有卤素的烷基、链烯基、环烷基、烷氧基、链烯氧基、烷硫基、芳基、芳基氧基、苄基、苄氧基、烷氧羰基、烷基酰基、酰氧基以及可用烷基、芳基、芳基氧基、烷基酰基、酰氧基和链烯基取代的氨基中的一个或多个基团所取代。
  2. 根据权利要求1所述的一种5-氯苯并噁唑衍生物，其特征在于，
    X代表F、Cl、Br、氰基、三氟甲基、甲基；
    Y代表NR 1R 2，R 1代表H、C1-C8烷基、C1-C8烷基磺酰基、卤代C1-C8烷基，R 2代表未取代或取代的苯基、吡啶基、吡唑基、异噁唑基、噻吩基、噻唑基、噻二唑基、
    Figure PCTCN2018105265-appb-100002
    Figure PCTCN2018105265-appb-100003
    或者R 1和R 2连接形成未取代或取代的
    Figure PCTCN2018105265-appb-100004
    其中，所述“取代的”是指被选自卤素、氰基、硝基、C1-C8烷氧羰基、氨基、C1-C8烷基氨基、含有或不含有卤素的C1-C8烷基、C1-C8烷氧基、C3-C8环烷基、C2-C8烯基、C2-C8炔基、苯基中的一个或多个基团所取代。
  3. 根据权利要求1或2所述的一种5-氯苯并噁唑衍生物，其特征在于，
    X代表Cl、氰基、三氟甲基、甲基；
    Y代表NR 1R 2，R 1代表H、C1-C6烷基、C1-C6烷基磺酰基、卤代C1-C6烷基，R 2代表未取代或被选自C1-C6烷基、氰基、硝基、卤素、C1-C6卤代烷基、C1-C6烷氧基、C1-C6 卤代烷氧基、苯基、卤素取代苯基、C1-C6烷氧羰基、氨基中的一种或多种取代基取代的
    Figure PCTCN2018105265-appb-100005
    Figure PCTCN2018105265-appb-100006
  4. 根据权利要求1-3任意一项所述的一种5-氯苯并噁唑衍生物，其特征在于，化学结构如通式I-1所示：
    Figure PCTCN2018105265-appb-100007
    X代表Cl；
    Y代表NR 1R 2，R 1代表H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、SO 2Et、CH 2CHF 2，R 2代表未取代或被选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、氰基、硝基、F、Cl、Br、CF 3、OCF 3、甲氧基、乙氧基、苯基、卤素取代苯基、甲氧羰基、乙氧羰基、氨基中的一种或多种取代基取代的
    Figure PCTCN2018105265-appb-100008
    Figure PCTCN2018105265-appb-100009
  5. 根据权利要求1-4任意一项所述的一种5-氯苯并噁唑衍生物，其特征在于，
    当X为Cl时，NR 1R 2不为
    Figure PCTCN2018105265-appb-100010
  6. 一种如权利要求1-5任意一项所述的5-氯苯并噁唑衍生物的制备方法，其特征在于，包括以下步骤：
    (1)将化合物Ⅳ与化合物Ⅴ在碱和溶剂的存在下进行反应，制备如通式Ⅲ所示的化合物；
    (2)如通式Ⅲ所示的化合物经酰卤化反应制得如通式Ⅱ所示的化合物；
    (3)将如通式Ⅱ所示的化合物与化合物HY在碱和溶剂的存在下反应制得如通式Ⅰ所示的化合物；
    其化学反应方程式如下：
    Figure PCTCN2018105265-appb-100011
    其中，L为Cl或Br；
    或者将如通式Ⅲ所示的化合物与化合物HY在脱水剂的存在下反应制得如通式Ⅰ所示的化合物，其化学反应方程式如下：
    Figure PCTCN2018105265-appb-100012
    当制备如通式I-1所示化合物
    Figure PCTCN2018105265-appb-100013
    时，以化合物
    Figure PCTCN2018105265-appb-100014
    为原料进行上述反应。
  7. 根据权利要求6所述的一种5-氯苯并噁唑衍生物的制备方法，其特征在于，所述反应温度均在-50～180℃范围内，优选-10～80℃；所述溶剂选自乙腈、乙酸乙酯、甲苯、二甲苯、DMF、DMSO、NMP中的一种或多种；所述碱选自无水碳酸钠、无水碳酸钾、叔丁醇钠、叔丁醇钾、甲醇钠、乙醇钠、三乙胺、N,N-二异丙基乙胺、DBU中的一种或多种；所述步骤(2)中采用的卤化试剂为草酰氯、氯化亚砜、三氯氧磷、三氯化磷、草酰溴、亚硫酰溴、三溴氧磷或三溴化磷；所述脱水剂为DCC、HOBt、EDCI或CDI。
  8. 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5-氯苯并噁唑衍生物中的至少一种，优选地，所述的除草剂组合物还包括制剂助剂。
  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5-氯苯并噁唑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5-氯苯并噁唑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5-氯苯并噁唑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，优选为水稻田。
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