WO2019109402A1 - Dioxazine derivative, preparation method therefor, herbicidal composition containing same, and application thereof - Google Patents

Abstract

The present invention pertains to the technical field of pesticides, and particularly relates to a dioxazine derivative, a preparation method therefor, an herbicidal composition containing the same, and an application thereof. The chemical structure of the dioxazine derivative is represented by general formula (I), in which X represents N, or C attached to a halogen, an alkoxy group, an alkyl group, a haloalkyl group, an alkenyl group, or an alkynyl group; Y represents N, or C attached to H, a halogen, an alkoxy group, an alkyl group, a haloalkyl group, an alkenyl group, or an alkynyl group; R₁, R₂, R₁', and R₂' independently represent H, a cyano group, etc.; R₃ represents a halogen, an alkoxy group, etc.; R₄ represents H, a halogen, etc.; R₅ is selected from a halogen, a C1-C6 alkyl group or C3-C6 cycloalkyl or C1-C6 alkoxy group with or without a halogen, and an unsubstituted or substituted aryl group or heteroaryl group. The derivative and the herbicidal composition containing the same are highly safe and effective on crops, and have good selectivity for crops.

Description

Dioxazine derivative, preparation method thereof, herbicidal composition and application thereof Technical field

The invention belongs to the technical field of pesticides, and particularly relates to a dioxazine derivative, a preparation method thereof, a herbicidal composition and application.

Background technique

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。 The control of weeds is a crucial part of the process of achieving high-efficiency agriculture. There are various types of herbicides on the market. For example, Japanese Patent JPH02233602 discloses a series of herbicides, the general formula of which is

However, due to the continuous expansion of the market, the resistance of weeds, the service life of drugs and the economics of drugs, and the increasing emphasis on the environment, scientists need to constantly research and develop new high-efficiency, safe, economical and Herbicide varieties with different modes of action.

Summary of the invention

In order to solve the above problems in the prior art, the present invention provides a dioxazine derivative, a preparation method thereof, a herbicidal composition and use thereof, and the derivative and the herbicidal composition thereof are very safe and highly effective for crops, Good selectivity.

The technical solution adopted by the present invention is as follows:

A dioxazine derivative having a chemical structural formula as shown in Formula I:

Wherein X represents N, C attached to a halogen, alkoxy, alkyl, haloalkyl, alkenyl or alkynyl group;

Y represents N, C attached to H, halogen, alkoxy, alkyl, haloalkyl, alkenyl or alkynyl;

R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent H, cyano, nitro, halogen, carboxyl, hydroxy, alkyl, cycloalkyl, alkenyl, alkynyl, with or without halogen, Alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkylacyl, alkoxyacyl, alkylacyloxy, alkylsulfonyl, Alkyl, haloalkyl, alkenyl, alkynyl, nitro, hydroxy, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkyl acyl, alkyl acyloxy, alkylcarbamoyl, Trialkylsilyl, dialkylphosphonyl and unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, aryl, aryloxy, arylthio , arylalkyl, arylalkyl acyl, arylalkyloxy, heteroaryl, heteroaryl acyl, heteroaryloxy, heteroarylthio;

R ₃ represents halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl or cyano;

R ₄ represents H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, alkyl acyloxy, alkylthio, NR'R", wherein R' and R" independently represents H, alkyl, alkenyl, alkynyl, hydroxy, haloalkyl, alkoxy, amino, alkyl acyl, alkoxycarbonyl, alkylcarbamoyl, alkylsulfonyl, trialkyl a silyl group or a dialkylphosphonyl group;

R _{5 is} selected from halogen, C1-C6 alkyl group having or not containing halogen, C3-C6 cycloalkyl group, C1-C6 alkoxy group, unsubstituted or substituted aryl group, heteroaryl group;

Wherein, "substituted" means selected from halogen, cyano, nitro, carboxy, hydroxy, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyloxy, alkanethio Base, aryl, aryloxy, benzyl, benzyloxy, alkyl acyl, acyloxy, alkenyl and available alkyl, aryl, aryloxy, alkyl acyl, acyloxy and chain Substituting one or more groups of the alkenyl-substituted amino groups.

Preferably, X represents N, C attached to a halogen, a C1-C8 alkoxy group, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C2-C8 alkenyl group or a C2-C8 alkynyl group;

Y represents N, C attached to H, halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;

R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent H, cyano, nitro, halogen, carboxyl, hydroxy, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2 -C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C3-C8 cycloalkoxy, C1-C8 alkylthio, C2-C8 alkenyl sulfide , C3-C8 cycloalkylthio, C1-C8 alkyl acyl, C1-C8 alkoxy acyl, C1-C8 alkyl acyloxy, C1-C8 alkylsulfonyl, C1-C8 alkyl, halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, nitro, hydroxy, amino, C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1 -C8 alkyl acyl, C1-C8 alkyl acyloxy, C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphonyl and unsubstituted or substituted aryl Or a heteroaryl-substituted amino group, and an unsubstituted or substituted aryl group, an aryl acyl group, an aryloxy group, an arylthio group, an aryl C1-C8 alkyl group, an aryl C1-C8 alkyl acyl group, an aryl group a C1-C8 alkyloxy group, a heteroaryl group, a heteroaryl acyl group, a heteroaryloxy group, a heteroarylthio group;

R ₃ represents halogen, C1-C8 alkoxy, C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 ring Alkyl or cyano;

R ₄ represents H, halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1- C8 alkyl acyloxy, C1-C8 alkylthio, NR'R", wherein R' and R" independently represent H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, hydroxy Halogenated C1-C8 alkyl, C1-C8 alkoxy, amino, C1-C8 alkyl acyl, C1-C8 alkoxycarbonyl, C1-C8 alkylcarbamoyl, C1-C8 alkylsulfonyl, three a C1-C8 alkylsilyl group or a di-C1-C8 alkylphosphono group;

R _{5 is} selected from halogen, C1-C8 alkyl group having or not containing halogen, C3-C8 cycloalkyl group, C1-C8 alkoxy group, unsubstituted or substituted aryl group, heteroaryl group;

Wherein, "substituted" means selected from halogen, cyano, nitro, carboxyl, hydroxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkane Oxy, halogenated C1-C8 alkoxy, C2-C8 alkenyloxy, C1-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, C1-C8 alkyl acyl, C1 -C8 alkyl acyloxy, C2-C8 alkenyl and C1-C8 alkyl, aryl, aryloxy, C1-C8 alkyl acyl, C1-C8 alkyl acyloxy and C2-C8 chains Substituting one or more groups of the alkenyl-substituted amino groups.

More preferably, X represents N, C attached to a halogen, a C1-C6 alkoxy group, a C1-C6 alkyl group or a halogenated C1-C6 alkyl group;

Y represents N, C attached to H, halogen, C1-C6 alkoxy, C1-C6 alkyl or halogenated C1-C6 alkyl;

R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent H, cyano, nitro, halogen, carboxyl, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkyl , C3-C6 cycloalkyl, C1-C6 alkoxyacyl, C1-C6 alkyl acyl, C1-C6 alkyl acyloxy, C1-C6 alkylsulfonyl, may be substituted by C1-C6 alkyl, phenyl Amino group, as well as unsubstituted or substituted by one or more groups selected from the group consisting of halogen, halogenated C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy and C2-C6 alkenyl Phenyl group;

R ₃ represents halogen, C1-C6 alkoxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl or cyano;

R ₄ represents H, nitro, NR'R", wherein R' and R" independently represent H, C1-C6 alkyl, C1-C6 alkyl acyl;

R ₅ represents halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, with or without halogen, unsubstituted or selected from halogen, hydroxy, C1-C6 alkyl, C1-C6 A phenyl group substituted with one or more groups in the alkoxy group.

Further preferably, X represents N, C attached to Cl, methoxy or ethoxy;

Y represents N, C linked to H, Cl or F;

R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, methylthio, ethylthio, cyano, methoxycarbonyl, An ethoxycarbonyl group, and a phenyl group which is unsubstituted or substituted with one or more groups selected from the group consisting of halogen, CF ₃ , methyl, ethyl, methoxy and ethoxy;

R ₃ represents Cl;

NO ₂； R ₄ represents NH ₂ , H,

NO ₂ ;

R ₅ represents Cl, F, cyclopropyl, trifluoromethyl,

In the definitions of the compounds of the formula given above, the terms used in the collection are defined as follows:

The aryl group includes a phenyl group, a 2,3-indanyl group or a naphthyl group, and the like; the heteroaryl group includes a 5-10 membered heteroaryl group having 1 to 3 O, S, and N hetero atoms. For example, pyridyl, pyrimidinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadipine Azyl, pyrazinyl, triazinyl, quinolinyl, quinoxalinyl, fluorenyl, benzotriazolyl, benzothienyl, benzofuranyl, isoquinolinyl, tetrahydroquinolyl Wait.

The preparation method of the dioxazine derivative comprises the following steps:

The compound of the formula I is prepared by reacting a compound of the formula II with a compound of the formula III in the presence of a base and a solvent, and the reaction equation is as follows:

Wherein X is Cl, Br or OSO ₂ CH ₃ .

The reaction temperature is from 20 ° C to 120 ° C, preferably from 30 ° C to 80 ° C.

The base is selected from one or more of inorganic bases such as potassium carbonate, sodium carbonate, potassium phosphate, and sodium phosphate.

The solvent is dimethylformamide, N,N-dimethylacetamide, methanol/water, ethanol/water, propanol/water or dioxane/water.

A herbicidal composition comprising at least one of a herbicidally effective amount of said dioxazine derivative.

The herbicidal composition of the dioxazine 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 dioxazine derivative or the herbicidal composition on a plant or a harmful plant area.

Use of at least one of the dioxazine derivatives or the herbicidal composition described above for controlling harmful plants.

Preferably, at least one of said dioxazine derivatives or said herbicidal composition is used to control harmful plants in useful crops.

More preferably, the useful crop is a crop that has been treated with a genetically modified crop or genome editing technique.

For many economically important monocotyledonous and dicotyledonous harmful plants, 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. Examples of 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.

With regard to 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. If 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. .

Although 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.

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. Thus, it is known that 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.

Conventional breeding methods having plants having improved shape compared to known plants include, for example, conventional mating methods and breeding of mutants. In other words, new plants with improved traits can be obtained by means of genetic engineering methods (see, for example, EP-0221044 A, EP-0131624 A). For example, several methods have been described:

- genetic engineering to alter crop plants in order to improve starch synthesis in plants (eg WO 92/11376, WO 92/14827, WO 91/19806);

- GM crop plants resistant to specific herbicides, glufosinate herbicides (eg EP-0242236 A, EP-0242246 A) or glyphosate herbicides (WO 92/00377), or sulfonate An ureide herbicide (EP-0257993 A, US-5013659 A);

- 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);

- Transgenic crop plants with improved fatty acid composition (WO 91/13972).

A number of molecular biotechnologies capable of producing transgenic plants with improved traits are known (see, for example, Sambrook et al., 1989, Molecular Amplification, Experimental Manual Second Edition, US Cold Spring Harbor Laboratory Publishing, Cold Spring Harbor, New York; or Winnacker "Gene und Klone "[Genes and Clones], VCH Weinheim, Second Edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431)). In order to carry out the operation of genetic engineering, it is possible to introduce a nucleic acid molecule into a plasmid, and a mutation or sequence change occurs by recombination of the DNA sequence. Using the standard methods described above, for example, substrates can be exchanged, partial sequences removed, or natural or synthetic sequences added. In order to link the DNA fragments to each other, it is possible to attach a binding body or a linker to the fragment.

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.

For this purpose, it is possible to use 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.

When a nucleic acid molecule is expressed in a plant, the synthesized protein can be localized in any desired plant cell compartment. However, in order to locate in a particular chamber, it is possible, for example, to link the coding region to the DNA sequence to ensure localization at a particular location. 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 transgenic plants can be any desired plant variety, namely monocotyledonous and dicotyledonous plants. In this manner, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or inhibiting homologous (=natural) genes or gene sequences, or by expression of heterologous (=existing) genes or gene sequences.

When the active substance of the present invention is used on a transgenic crop, in addition to having an effect of inhibiting harmful plants observed on other crops, there are often special effects on the corresponding transgenic crops, for example, 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.

In addition, 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. Thus the invention also provides 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. Examples of 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. These individual formulation types are known and are described in, for example, Winnacker-Küchler, "Chemische Techonologie" [Chemical Processes], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd edition 1979, G. Goodwin Ltd. London.

的

[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。 The necessary formulation auxiliaries, such as inert materials, surfactants, solvents and other additives, are also known and described in the following documents, for example, Watkins "Handbook of Powder Thinner Pesticide and Carrier", Second Edition, Darland Book Caldwell NJ; Hv01phen "Introduction to Clay Colloid Chemistry", Second Edition, J. Wiley and Sons, NY; C. Marsden, "Solvent Guide", Second Edition, Interscience, NY 1963; McCutcheon, "Detergents and Emulsifiers Annual Report", MC Publishing Company, Ridgewood NJ; Sisley and Wood, "Surfactant Encyclopedia", Chemical Publishing Company, NY 1964;

of

[Ethylene oxide adduct surfactant], Wis. Verlagagesell. Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie" [Chemical Process], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986.

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. In order to prepare the wettable powder, 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.

Dissolving the active substance in an organic solvent to prepare 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). Examples of 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.

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.

To prepare an emulsion such as an oil-in-water emulsifier (EW), 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.

For the preparation of abrasive discs, fluidized beds, extruders and spray granules, see the following processes, such as "Spray Drying Handbook" Third Edition 1979, G. Goodwin Ltd., London; JEBrowning, "Agglomeration", Chemistry and Engineering 1967, page 147ff; "Perry's Chemistry Engineer's Handbook", Fifth Edition, McGraw-Hill, New York, 1973, pp. 8-57. If you want to know about formulations for crop protection products, see, for example, GCKlingman, "Weed Control as a Science", John Wiley and Sons, New York, 1961 81-96 and JDFreyer, SAEvans "Weed Control Manual", Fifth Edition, Blackwell Scientific Rublications, Oxford University, 1968, pp. 101-103.

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. . Regarding 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.

Further, 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.

Based on these preparations, it may also be mixed with other insecticide active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and/or plant growth regulators. 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. Known substances. For example, 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, methoxymethafen, metazachlor, isoxachlor, high-efficiency wheat straw methyl ester, high-efficiency wheat valproate, dipropenamide, acetochlor , butyrylamine, cyclopropamide, flufenacetamide, heptylacetate, ibutachlor, propargylamine, chlorfenapyr, xetylene, dimethyl chloramine, chloramine, Trimethoprim, chloroformylamine, propyzamide, valproate, acetochlor, neoxanthine, tricyclosage, butene, forage, benzylamine, Indapamide, phenylsulfonamide, naphthylamine, acetochlor, naphthylamine, thiamatine, cyanochlor, benzodiazepine, turkey, chloropurine, butylamine, fluoropyridin Oxalamine, atrazine, simazine, chlorpyrifos, cyanaceton, cilostaz, chlorhexidine, chlorpyrifos, isopropyl, flufenate, tertidine, terbutin, triazine Amine, cyprofen, gansujin, chlordazin, chlorpyrifos, ximatong, azide net, dichlorpyrifos, isoprene, Cyclopropylidene, chlorpyrifos, another Dingjin, Zhongdingtong, Tetintong, methoxypropyl, cyanaceate, oxaloplatin, colazi, 莠通通, 灭草通, licorice, cyanuric acid, Indaziflam, chlorsulfuron, metsulfuron, bensulfuron, Chlorsulfuron, tribenuron, thiasulfuron, pyrazosulfon, methyl disulfuron, methyl iodsulfuron sodium, formylaminosulfuron, ethersulfuron, ether sulfonate, methyl Sulfonamide, nicosulfuron, ethametsulfuron, sulfonamide, ethoxysulfuron, cyprosulfuron, sulfimsulfuron, tetrazincsulfuron, flazasulfuron, monosulfuron Monosulfuron, flufensulfuron, flurazine, flupirsulfuron Long,epoxysulfuron,oxazolsulfuron-methyl, flusulfuron-methyl, propylsulfuron, triflusulfuron-methyl, sulfonylsulfuron, trifluzonsulfonate, flucarbazone, trifluoromethane Rhodium, metsulfuron-methyl salt, fluroxysulfuron, thiosulfuron-methyl, pyrimethanil, propyrisulfuron, pyrazepam, acifluorfen, flufenazone, Fluoride, flufenacetate, oxyfluorfen, oxalic acid ether, dipyridamole, flufenacetate ethyl ester, carboxy herbicide ether, trifluoromethane ether, methoxy herbicide ether, three Fluramite, fluorinated herbicide, flufenic acid, herbicidal ether, alaloin, dimethyl oxalate, fluoroester valerian, flufenate, Halosafen, chloromeron, isoproturon, Ligu Long, diuron, saponin, fluroxypyr, benzothiazol, methotrexate, benzalkon, sulfothylum, isoxon, tetrandil, acetylacea, chlorbromide, Methyl herbicide, humulocyclone, methoxapril, bromogluta, methoxyuron, glutamate, chlorpyrifos, cyclosporine, non-oxalon, fluorosulfuron, chlorpyrifos, hazel , Cao Wanlong, Xicaolong, Huanlong, Teflon, Butyl Withdrawal, fluorothiamide, methazamide, triptolide, trimethylisourea, oxazolone, Monisouron, Anisuron, Methiuron, Chlureturon, Tetrafluorouron, Beet Ning, Beet Ning-Ethyl Ester, Beet, Sulfate Cao Ling, Te Cao Ling, Oatmeal, Aniline, Chloroaniline, Diclofenac, Herbicidin, Chlorhexyne, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butachlor, Hecaodan , herbicide, grass, wild wheat, chlorpyrifos, chlorpyrifos, chlorpyrifos, valerian, ring grass enemy, oats, bacteria, chlorpyrifos, pingcao, gram grass, benzyl Dan, Cao Cao Dan, thiomethasone, chlorhexidine, Isopolinate, Methiobencarb, 2,4-butyl butyl ester, sodium 2-methyltetrachloride, 2,4-diisooctyl ester, 2 methyl 4-chloroisooctyl ester, 2,4-D sodium salt, 2,4-D dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4-chloro, 2,4-D-propionic acid, high 2,4-D-propionate, 2 , 4-D Butyric Acid, 2 M 4 Chloropropionic Acid, 2 M 4 Chloropropionate, 2 M 4 Chlorobutyric Acid, 2,4,5-Indole, 2,4,5-Mercaptoic Acid, 2,4 , 5-indolebutyric acid, 2 methyl 4-chloroamine salt, dicamba, spirulina, valerian, saison, trichlorobenzoic acid, aminodichlorobenzoic acid Trimethoprim, oxacillin, pirfenoxacil, flupirtine, flupirtine, high-efficiency flupirtine, quizalofop, quinoxaline, oxazolyl Ling, oxazocilin, valerate, cyhalofoprin, oxazolamide, clodinafop, thiazolyl, acetylene, valprofloxacin, trifluoromethane, sinister Grass ether, paraquat, diquat, sulfonate, ethene bromide, isoproterol, metformin, ciprofloxacin, aminopropionin, etidrin, chlorhexidine, Ethyl difluralin, dilofen, chlorhexidine, Methalpropalin, propofol, glyphosate, samarium phosphine, glufosinate, methylammonium, sulforaphane, piperidin, dialanine Phosphine, ground phosphorus, arsenic phosphorus, vine grass phosphorus, ruthenium phosphate, dimethicin, sulphur, imidazolium, imidazolium, imidazoquinoic acid, imazamox, imazamox Salt, methimazole nicotinic acid, imazethapyr, flufenoxyacetic acid, isooctyl clofibrate, clopyralid, amlalidonic acid, trichloropyridinic acid, flurazepam, haloform , trichloropyridinol, thiabidine, Fluroxynone, chlorpyridin, flupirtine, butoxyethyl trichloropyroxyacetate, Cliodinate, dilute pyridine, ketene, thiazolone, chlorpyrifos, benzophenone, butyl Benzorone, oxadiazon, pyridone, Buthidazole, oxazinone, cycloazinone, oxazinone, oxazinone, Ametridione, Amibuzin, bromoxynil, octanoyl bromoxynil, octanoyl iodide Benzotrile, iodobenzonitrile, dimethotrile, diphenylacetonitrile, oxazolonitrile, hydroxydicarbonitrile, Iodobonil, oxasulfuron, diflufenacil, penoxsulam, sulfoxazolamide, Chlorosulfasalamine, diclofenac, acesulfame, fluoxetine, bispyribyl ether, pyrimethoxam, cyclic ester, pyrimethanil, pyrimethanil, dicyclohexanone, nitrate Sulfosone, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxaflutole, isoxafluzate, Fenoxasulfone, Methiozolin, isopropylpyrazine, pyridoxine, pyrazol, wild swallow, Benzazol, oxacillin, chlorfenapyr, Pyrasulfotole, oxazolone, Pyroxasulfone, oxazinamide, fluoxazole, chlorpyrifos, oxazolone, oxazolidine Oxalone, fluconazole, mesoxalam, Bencarbazone, diflufenazone, fluproxil, herbicide, isoxadine, cyclohexane, tetromethine, Flupropacil, indolinone, Fluoric acid, propargylamine, clodinafamine, benzyl ether, Flumezin, pentachlorophenol (sodium), dinose, tromethool, tylosyl, pentoxide, dinitrophenol, chloronitrophenol , Dixie, Dilt, Propargyl oxalofen, oxadiazon, cyclopentazone, fluoxetamine, methyl oxazate, tetrazolam, flurazazine, chlorpyrifos , bromine sensitization, metformin, valerian, oxazolone, oxalox, valerian, Pyridafol, quinclorac, chloroquinoline, bentazon, valerate, oxazine Oxalone, herbicide, clomazone, cycloheptyl ether, isopropyl oxalate, propyl oxalate, oxadiazon, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone , tetrafluoropropionic acid, forage fast, bromophenolphthalein, triazole sulfonate, chlorfenapyr, furazolidone, furosemethane, fenfuransulfonate, pyrimethamine, chloranoic acid, fluroxypyr, valerian , acrolein, benthoprin, oxacillin, oat ester , thiadiazolamide, cottonamine, oxymatone, methoxybenzophenone, saflufenacil, chloramphenicol, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan,Chlorflurazole, Tripropindan, Sulglycapin, Methionine, Cambendichlor, cyprodinil, thiocyanuramide, oxalofen, oxadiazepine, chlorpyrifos, chlorpyrifos, chlorpyrifos, sulforaphane, turfgrass Alkane, sulfacetamide, cumin, pyrazolium, furazosalazine, valerian, dibenzoxazole, dichloropropenylamine, fluorochloropyridyl ester, DOW chlorofluoropyridyl ester, UBH- 509, D489, LS 82-556, 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 and KIH-2023.

When used, if desired, 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.

Detailed ways

The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way. The claims are intended to be defined by the claims.

In view of the economics and diversity of the compounds, we prefer to synthesize some of the compounds, and among the many compounds synthesized, the selected ones are listed in Table 1 below. The specific compound structure and corresponding compound information are shown in Table 1-2. The compounds in Table 1 are only intended to better illustrate the present invention, but are not intended to limit the invention, and it should not be understood that those skilled in the art should limit the scope of the above-mentioned subject matter to the following compounds.

Table 1 Compound Structure

Table 2 Compound ¹ H NMR data

Several methods for preparing the compounds of the present invention are illustrated in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as shown in detail. Those skilled in the art will appreciate that other synthetic routes can also be utilized to synthesize the compounds of the present invention. Although specific materials and conditions in the synthetic route have been described below, they can be easily replaced with other similar materials and conditions, such as compounds produced by variations or variants of the preparation methods of the invention. Various isomeric and the like are included in the scope of the present invention. Additionally, the methods of preparation described below can be further modified in accordance with the present disclosure, using conventional chemical methods well known to those skilled in the art. For example, the appropriate groups are protected during the reaction, and the like.

The method examples are provided below to facilitate a further understanding of the present invention, and the specific materials, types, and conditions used are determined to be further illustrative of the present invention and are not intended to limit the scope thereof. The reagents used in the synthetic compounds indicated in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

The implementation of representative compounds is as follows:

Preparation of Compound 5:

In a 50 ml single-mouth bottle containing 10 ml of DMF, II-1 (1.0 g, 4.83 mmol), III-1 (1.1 g, 5.80 mmol) and K ₂ CO ₃ (2.00 g, 14.49 mmol) were sequentially added. The reaction system was reacted at 50 ° C for 16 hours. After the reaction system was cooled, it was poured into 20 mL of ice water, extracted with 20 mL of ethyl acetate three times, and the organic phase was combined, dried, filtered, and ethyl acetate was removed, and the obtained crude product was separated by column chromatography, petroleum ether: ethyl acetate = From 10:1 to 1:1, the product 5 (0.2 g, yield 17.7%) was obtained.

Preparation of Compounds 57 and 58:

In a 50 ml single-mouth bottle containing 10 ml of DMF, II-1 (1.0 g, 4.83 mmol), III-2 (1.38 g, 5.80 mmol) and K ₃ PO ₄ (3.08 g, 14.49 mmol) were sequentially added. The reaction system was reacted at 50 ° C for 16 hours. After the reaction system was cooled, it was poured into 20 mL of ice water, extracted with 20 mL of ethyl acetate three times, and the organic phase was combined, dried, filtered, and ethyl acetate was removed, and the obtained crude product was separated by column chromatography ( petroleum ether: ethyl acetate = 10:1 to 1:1), a mixed product containing 57 and 58 (70 mg, yield 4.7%) was obtained by medium pressure preparative chromatography (Elite Intermediate Pressure Preparation System, column: SinoChrom ODS-BP, 10 μm, 30.0 mm * 250 mm; mobile phase: H ₂ O (0.1% TFA): MeOH = 75:25; flow rate: 40 mL / min; detection wavelength: 254 nm) Compounds 57 and 58 were isolated.

Biological activity evaluation:

The activity level criteria for harmful plant damage (ie growth control rate) are as follows:

Level 10: Complete death;

Grade 9: growth control rate is above 95%;

Level 8: Growth control rate is above 90%;

Level 7: growth control rate is above 80%;

Level 6: growth control rate is above 70%;

Level 5: The growth control rate is above 60%;

Level 4: Growth control rate is above 50%;

Level 3: Growth control rate is above 20%;

Level 2: growth control rate is 5-20%;

Level 1: The growth control rate is below 5%;

Level 0: No effect.

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.

Table 3. Post-emergence weed test

Compound number Swine fever Wild sage corn Rice rape 1 10 10 0 0 0 2 10 10 0 0 0 3 10 10 0 0 0 4 10 10 0 0 0 5 10 10 0 0 0 6 10 10 0 0 0 7 10 10 0 0 0 8 10 7 0 0 - 9 10 6 0 0 - 10 10 10 0 0 0 11 10 10 0 0 0 12 10 10 0 0 0 13 10 10 0 0 0 14 10 10 0 0 0 15 10 10 0 0 0 16 10 10 0 0 0 17 10 10 0 0 0 18 - - 0 0 0 19 10 10 0 0 0 20 10 10 0 0 0 twenty one 10 10 0 0 0 twenty two 10 10 0 0 0 twenty three 10 10 0 0 0 twenty four 10 10 0 0 0

25 10 10 0 0 0 26 10 10 0 0 0 27 10 10 0 0 0 28 10 10 0 0 0 29 10 10 0 0 0 30 10 10 0 0 0 33 10 10 0 0 0 34 - - 0 0 0 35 10 10 0 0 0 36 10 10 0 0 0 37 - - 0 0 0 38 10 10 0 0 0 39 10 10 0 0 0 40 - - 0 0 0 41 10 10 0 0 0 42 10 10 0 0 0 43 - - 0 0 - 44 - - 0 0 - 45 8 7 0 0 - 46 8 7 0 0 - 47 10 10 0 0 0 48 10 10 0 0 0 49 10 10 0 0 0 50 10 10 0 0 0 51 10 10 0 0 0 52 - - 0 0 - 53 10 10 0 0 0 54 10 10 0 0 0 55 10 10 0 0 0 56 10 10 0 0 0 57 10 10 0 0 0

58 10 10 0 0 0 A 0 0 0 0 0 B 0 0 0 0 0 C 0 0 0 0 0 D 0 0 0 0 0 E 0 0 0 0 0

(来自CN101687804A)，对照化合物B-E分别为

(均选自JPH02233602)。 Note: 1) - indicates no data; 2) the application dose is 150 g / ha, the water content is 450 kg / ha; 3) the control compound A is

(from CN101687804A), the control compound BE is

(all selected from JPH02233602).

Pre-emergence test experiment:

Place monocotyledonous and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, canola, millet, sorghum) in plastic pots filled with soil, then cover 0.5-2 cm of soil, respectively 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.

Through experiments, we found that the compounds of the present invention generally have good weed control effects, especially for major broadleaf weeds such as weeds, stalks, and stalks, which are widely occurring in corn fields, paddy fields, and wheat fields. The effect has good business value. In particular, we have noticed that the broad-leaved weeds such as Maijiagong, Hog Cholera, and Brassica, which are resistant to ALS inhibitors, have extremely high activity.

Evaluation of the safety of transplanted rice and the evaluation of weed control in paddy fields:

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.

In addition, after filling the paddy soil in a 1/1,000,000 hectare tank, it was leveled to make the water storage depth 3-4 cm, and the next day, 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, and 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 of the compounds of the present invention have been found to have excellent activity and selectivity, especially for wild sage and valerian.

Note: Valerian, sputum, wild sage, and wolf seed were collected from Heilongjiang, China, and tested for resistance to conventional doses of pyrazosulfuron.

Comparative Experiment:

对照化合物G：

Control compound F:

Control compound G:

The post-emergence test conditions were the same as above, and the experimental results are shown in Table 4.

Table 4. Comparison of experimental results (30 g / ha, test time 10 days)

Compound Swine fever Wild sage corn Rice rape 4 8 10 0 0 0 7 8 10 0 0 0 F 8 10 6 5 10 G 8 10 7 4 10

As can be seen from the above table, the compounds of the present invention have higher crop safety than the control compounds F and G, and particularly have good selectivity for crops such as corn, rice and rape.

At the same time, after many tests, many of the compounds of the present invention have good selectivity against grasses such as Zoysia, Bermudagrass, tall fescue, bluegrass, ryegrass, seashore gar, etc., and can prevent many key grasses. Weeds and broadleaf weeds. Tests on soybean, cotton, oil sunflower, potato, fruit trees, and vegetables under different application methods also showed excellent selectivity and commercial value.

Claims (10)

A dioxazine derivative having a chemical structural formula as shown in Formula I:

among them, X represents N, C attached to a halogen, alkoxy, alkyl, haloalkyl, alkenyl or alkynyl group; Y represents N, C attached to H, halogen, alkoxy, alkyl, haloalkyl, alkenyl or alkynyl; R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent H, cyano, nitro, halogen, carboxyl, hydroxy, alkyl, cycloalkyl, alkenyl, alkynyl, with or without halogen, Alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, alkylacyl, alkoxyacyl, alkylacyloxy, alkylsulfonyl, Alkyl, haloalkyl, alkenyl, alkynyl, nitro, hydroxy, amino, alkoxy, alkoxycarbonyl, alkylsulfonyl, alkyl acyl, alkyl acyloxy, alkylcarbamoyl, Trialkylsilyl, dialkylphosphonyl and unsubstituted or substituted aryl or heteroaryl substituted amino, and unsubstituted or substituted aryl, aryl, aryloxy, arylthio , arylalkyl, arylalkyl acyl, arylalkyloxy, heteroaryl, heteroaryl acyl, heteroaryloxy, heteroarylthio; R ₃ represents halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl or cyano; R ₄ represents H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, alkyl acyloxy, alkylthio, NR'R", wherein R' and R" independently represents H, alkyl, alkenyl, alkynyl, hydroxy, haloalkyl, alkoxy, amino, alkyl acyl, alkoxycarbonyl, alkylcarbamoyl, alkylsulfonyl, trialkyl a silyl group or a dialkylphosphonyl group; R _{5 is} selected from halogen, C1-C6 alkyl group having or not containing halogen, C3-C6 cycloalkyl group, C1-C6 alkoxy group, unsubstituted or substituted aryl group, heteroaryl group; Wherein, "substituted" means selected from halogen, cyano, nitro, carboxy, hydroxy, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyloxy, alkanethio Base, aryl, aryloxy, benzyl, benzyloxy, alkyl acyl, acyloxy, alkenyl and available alkyl, aryl, aryloxy, alkyl acyl, acyloxy and chain Substituting one or more groups of the alkenyl-substituted amino groups. A dioxin derivative according to claim 1, wherein X represents N, C attached to a halogen, a C1-C8 alkoxy group, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C2-C8 alkenyl group or a C2-C8 alkynyl group; Y represents N, C attached to H, halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl; R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent H, cyano, nitro, halogen, carboxyl, hydroxy, C1-C8 alkyl with or without halogen, C3-C8 cycloalkyl, C2 -C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C3-C8 cycloalkoxy, C1-C8 alkylthio, C2-C8 alkenyl sulfide , C3-C8 cycloalkylthio, C1-C8 alkyl acyl, C1-C8 alkoxy acyl, C1-C8 alkyl acyloxy, C1-C8 alkylsulfonyl, C1-C8 alkyl, halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, nitro, hydroxy, amino, C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1 -C8 alkyl acyl, C1-C8 alkyl acyloxy, C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphonyl and unsubstituted or substituted aryl Or a heteroaryl-substituted amino group, and an unsubstituted or substituted aryl group, an aryl acyl group, an aryloxy group, an arylthio group, an aryl C1-C8 alkyl group, an aryl C1-C8 alkyl acyl group, an aryl group a C1-C8 alkyloxy group, a heteroaryl group, a heteroaryl acyl group, a heteroaryloxy group, a heteroarylthio group; R ₃ represents halogen, C1-C8 alkoxy, C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 ring Alkyl or cyano; R ₄ represents H, halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1- C8 alkyl acyloxy, C1-C8 alkylthio, NR'R", wherein R' and R" independently represent H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, hydroxy Halogenated C1-C8 alkyl, C1-C8 alkoxy, amino, C1-C8 alkyl acyl, C1-C8 alkoxycarbonyl, C1-C8 alkylcarbamoyl, C1-C8 alkylsulfonyl, three a C1-C8 alkylsilyl group or a di-C1-C8 alkylphosphono group; R _{5 is} selected from halogen, C1-C8 alkyl group having or not containing halogen, C3-C8 cycloalkyl group, C1-C8 alkoxy group, unsubstituted or substituted aryl group, heteroaryl group; Wherein, "substituted" means selected from halogen, cyano, nitro, carboxyl, hydroxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkane Oxy, halogenated C1-C8 alkoxy, C2-C8 alkenyloxy, C1-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, C1-C8 alkyl acyl, C1 -C8 alkyl acyloxy, C2-C8 alkenyl and C1-C8 alkyl, aryl, aryloxy, C1-C8 alkyl acyl, C1-C8 alkyl acyloxy and C2-C8 chains Substituting one or more groups of the alkenyl-substituted amino groups. A dioxin derivative according to claim 1, wherein X represents N, C attached to a halogen, a C1-C6 alkoxy group, a C1-C6 alkyl group or a halogenated C1-C6 alkyl group; Y represents N, C attached to H, halogen, C1-C6 alkoxy, C1-C6 alkyl or halogenated C1-C6 alkyl; R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent H, cyano, nitro, halogen, carboxyl, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkyl , C3-C6 cycloalkyl, C1-C6 alkoxyacyl, C1-C6 alkyl acyl, C1-C6 alkyl acyloxy, C1-C6 alkylsulfonyl, may be substituted by C1-C6 alkyl, phenyl Amino group, as well as unsubstituted or substituted by one or more groups selected from the group consisting of halogen, halogenated C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy and C2-C6 alkenyl Phenyl group; R ₃ represents halogen, C1-C6 alkoxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl or cyano; R ₄ represents H, nitro, NR'R", wherein R' and R" independently represent H, C1-C6 alkyl, C1-C6 alkyl acyl; R ₅ represents halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, with or without halogen, unsubstituted or selected from halogen, hydroxy, C1-C6 alkyl, C1-C6 A phenyl group substituted with one or more groups in the alkoxy group. A dioxin derivative according to claim 1, wherein X represents N, C attached to Cl, methoxy or ethoxy; Y represents N, C linked to H, Cl or F; R ₁ , R ₂ , R ₁ ' and R ₂ ' independently represent hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, methylthio, ethylthio, cyano, methoxycarbonyl, An ethoxycarbonyl group, and a phenyl group which is unsubstituted or substituted with one or more groups selected from the group consisting of halogen, CF ₃ , methyl, ethyl, methoxy and ethoxy; R ₃ represents Cl; R ₄ represents NH ₂ , H,

NO ₂ ; R ₅ represents Cl, F, cyclopropyl, trifluoromethyl,

A method for preparing a dioxazine derivative according to any one of claims 1 to 4, which comprises the steps of: The compound of the formula I is prepared by reacting a compound of the formula II with a compound of the formula III in the presence of a base and a solvent, and the reaction equation is as follows:

Wherein X is Cl, Br or OSO ₂ CH ₃ . The method for preparing a dioxazine derivative according to claim 5, wherein the reaction temperature is from 20 ° C to 120 ° C, preferably from 30 ° C to 80 ° C; and the base is selected from the group consisting of potassium carbonate and sodium carbonate. One or more of inorganic bases such as potassium phosphate or sodium phosphate; the solvent is dimethylformamide, N,N-dimethylacetamide, methanol/water, ethanol/water, propanol/water or Dioxane/water. A herbicide composition comprising at least one of the herbicidal effective amount of the dioxazine derivative according to any one of claims 1 to 5. The herbicidal composition of claim 7 further comprising a formulation aid. A method for controlling a harmful plant, comprising: a herbicidally effective amount of at least one of the substituted dioxazine derivatives according to any one of claims 1 to 5 or any one of claims 7-8 The herbicidal compositions are used on plants or in harmful plant areas. Use of at least one of the substituted dioxazine derivatives according to any one of claims 1 to 5 or the herbicidal composition according to any one of claims 7 to 8 for controlling harmful plants, preferably The substituted dioxazine derivatives are used to control harmful plants in useful crops that are processed by transgenic crops or genome editing techniques.