WO2019080224A1 - Pyrazolone compound or salt thereof, herbicide composition and use - Google Patents

Abstract

The present application relates to the field of pesticides, and in particular, to a pyrazolone compound or salt thereof, a herbicide composition and a use. The pyrazolone compound is represented by general formula I:, where R1R2N represents a butyrolactam group or a valeroalctam group which is unsubstituted or substituted on the ring with one or more groups selected from fluorine, chlorine, methyl, ethyl, methoxyl and ethoxyl; R3 represents hydrogen, C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, or C3-6 cycloalkyl which is unsubstituted or substituted by C1-4 alkyl; R4 represents methyl, ethyl, n-propyl, isopropyl, or cyclopropyl; X represents -R5, -S(O)nR6, -CH2R7, -(C＝O)R8, -PO(OR9)2, -Si(OR9)3, or the like. The provided herbicide active matter has a good herbicide effect, convenience in use, low costs, and a great commercial value.

Description

Pyrazolone compound or salt thereof, herbicide composition and use thereof Technical field

The present application belongs to the field of pesticides, and in particular relates to a pyrazolone compound or a salt thereof, a herbicide composition and use thereof.

Background technique

The control of weeds is a crucial link in the process of achieving high-efficiency agriculture. The chemical weeding method is convenient, economical and effective. It has become an indispensable part of modern agricultural technology and has also promoted the innovation of cultivation techniques. Pyrazoles are highly effective, low toxicity and structurally diverse, and are used as herbicides as their primary application.

Patent CN105218449A and the like disclose a series of herbicidal pyrazolone herbicide compounds and a synthesis method thereof. In order to design and synthesize a more efficient herbicide compound with a broader spectrum of activity, based on this research, the present invention synthesizes a novel class of pyrazolone compounds having a novel structure and herbicidal activity.

Summary of the invention

It is an object of the present invention to provide a pyrazolone compound or a salt thereof, a herbicidal composition, and a herbicidal application in the field of pesticides. The medicinal active substance provided by the invention has good pharmacological effect, convenient use and low cost.

In order to achieve the above object, the technical solution adopted by the present invention is as follows:

A pyrazolone compound or a salt thereof as shown in Formula I:

In the formula,

R ₁ R ₂ N represents a butylactam group which is unsubstituted or substituted on the ring by one or more groups selected from the group consisting of fluorine, chlorine, methyl, ethyl, methoxy and ethoxy.

Valentylamide

R ₃ represents hydrogen, C _1-4 alkyl, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, unsubstituted or C _{3 to 6} cycloalkyl substituted with C _1-4 alkyl;

R ₄ represents a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a cyclopropyl group;

X represents -R ⁵ , -S(O) _n R ⁶ , -CH ₂ R ⁷ , -(C=O)R ⁸ , -PO(OR ⁹ ) ₂ , -Si(OR ⁹ ) ₃ , wherein

R ⁵ , R ⁶ represents a substituted or unsubstituted aryl or heterocyclic group, and n represents 1, 2, 3;

R ⁷ represents a substituted or unsubstituted aryl or heterocyclic group, a C _1-6 alkyl group substituted by a halogen, a halogen, a C _1-6 alkylamino group, a C _2-4 alkynyl group, a C _2-4 alkenyl group, C _1-6 alkoxy, nitro, cyano, C _3-6 cycloalkyl, amino, C _1-6 alkylthio;

R ⁸ represents a C _1-6 alkylamino group, a C _1-6 alkylthio group, a C _1-6 alkylamino C _1-6 alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, a halogen, an amino group. , cyano, nitro, C _1-6 alkoxy C _1-6 alkyl, substituted or unsubstituted phenyl, phenyl C _1-6 alkyl, phenoxy or phenoxy C _1-6 alkane base;

R ⁹ represents hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, substituted or unsubstituted phenyl or heterocyclic.

Preferably, R ⁵ and R ⁶ represent an unsubstituted phenyl group or a 3- to 10-membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and are selected from C _1-6 alkyl groups, C. _{1 to 6} alkoxy group, C _1-6 alkylamino group, C _1-6 alkylthio group, halogen, C _{2 to 4} alkenyl group, C _{2 to 4} alkynyl group, amino group, nitro group, cyano group, carboxyl group, C _{1 to 6} alkoxycarbonyl, C _1-6 alkoxy C _1-6 alkyl, C _1-6 alkylsulfonyl C _1-6 alkyl, C _1-6 alkylthiosulfonyl C _1-6 a phenyl group substituted with one or more groups of an alkyl group, a C _3-6 cycloalkyl group or a 3 to 10 membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and n represents 1, 2, 3;

R ⁷ represents an unsubstituted phenyl group or a 3- to 10-membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and is selected from a C _1-6 alkyl group and a C _1-6 alkoxy group. , C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, amino, nitro, cyano, carboxy, C _1-6 alkoxy Carbonyl group, C _1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylsulfonyl C _1-6 alkyl group, C _1-6 alkylthiosulfonyl C _1-6 alkyl group, C _{3 ～} a phenyl group substituted with one or more groups of ₆ cycloalkyl groups or a 3 to 10 membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and C _{1 to 6} substituted by halogen Alkyl, halogen, C _1-6 alkylamino, C _2-4 alkynyl, C _{2 to 4} alkenyl, C _1-6 alkoxy, nitro, cyano, C _3-6 cycloalkyl, amino , C _1-6 alkylthio;

R ⁸ represents a C _1-6 alkylamino group, a C _1-6 alkylthio group, a C _1-6 alkylamino C _1-6 alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, a halogen, an amino group. , cyano, nitro, C _1-6 alkoxy C _1-6 alkyl, phenyl, phenyl C _1-6 alkyl, phenoxy or phenoxy C _1-6 alkyl, selected from C _1-6 alkyl, C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, amino, nitrate group, cyano, carboxy, C _{1 ~ 6} alkoxycarbonyl, C _{1 ~ 6} alkoxy-C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkylsulfonyl C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkyl a phenyl group substituted with one or more groups of a thiosulfonyl C _1-6 alkyl group or a C _{3 -6} cycloalkyl group, a phenyl C _1-6 alkyl group, a phenoxy group or a phenoxy group C _{1 ～6} alkyl;

R ⁹ represents hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, unsubstituted phenyl or a 3 to 10 membered heterocyclic group containing 1 to 4 hetero atoms selected from O, N and S, Is selected from the group consisting of C _1-6 alkyl, C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, Amino, nitro, cyano, carboxyl, C _1-6 alkoxycarbonyl, C _1-6 alkoxy C _1-6 alkyl, C _1-6 alkylsulfonyl C _1-6 alkyl, C ₁ a phenyl group substituted with one or more groups of a ₆ alkylthiosulfonyl C _1-6 alkyl group or a C _{3 -6} cycloalkyl group or a hetero atom having 1 to 4 selected from O, N and S a 3 to 10 membered heterocyclic group.

More preferably, R ₃ represents hydrogen, methyl, ethyl, cyclopropyl;

R ₄ represents a methyl group, an ethyl group, an isopropyl group;

X represents -S(O) _n R ⁶ , -CH ₂ R ⁷ , -(C=O)R ⁸ , wherein

R ⁶ represents an unsubstituted phenyl group or a 3- to 10-membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and is selected from a C _1-6 alkyl group and a C _1-6 alkoxy group. a phenyl group substituted with one or more groups in the halogen or a 3 to 10 membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and n represents 2;

R ⁷ represents an unsubstituted phenyl group or a 3- to 10-membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and is selected from a C _1-6 alkyl group and a C _1-6 alkoxy group. a phenyl group substituted with one or more groups in a halogen or a 3 to 10 membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and C _{1 to 6} substituted by halogen An alkyl group, a C _1-6 alkylamino group, a C _2-4 alkynyl group, a C _{2 to 4} alkenyl group, a C _1-6 alkoxy group, a C _1-6 alkylthio group;

R ⁸ represents a C _1-6 alkylamino group, a C _1-6 alkylthio group, a C _1-6 alkylamino C _1-6 alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, a phenyl C group. _{1 ~ 6} alkyl group or a phenoxy group, selected from C _1-6 alkyl, C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halo, C _{2 ~ 4} Alkenyl, C _2-4 alkynyl, amino, nitro, cyano, carboxy, C _1-6 alkoxycarbonyl, C _1-6 alkoxy C _1-6 alkyl, C _1-6 alkyl sulfonate acyl C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkylsulfonyl alkylthio C _{1 ~ 6} alkyl group, C _{3 ~ 6} cycloalkyl group with one or more phenyl groups substituted C _{1 ~ 6} alkyl group Or phenoxy.

The term "heterocycle" or "heterocyclyl" denotes a 3 to 10 membered aromatic or non-aromatic heterocyclic ring containing from 1 to 4 heteroatoms selected from O, N and S and having a lactone, cyclic ether, lactam structure. A 4 to 10 membered cyclic compound and includes a bicyclic group. Thus, "heterocyclyl" includes "arylheterocyclyl" as well as dihydro or tetrahydro analogs thereof. The heterocyclic substituent may be bonded via a carbon atom or a hetero atom. The term "aromatic heterocyclic group" denotes a stable monocyclic or bicyclic ring which may be up to 7 atoms in each ring, which may include one aromatic ring and contain from 1 to 4 heteroatoms selected from O, N and S. Aromatic heterocyclic groups within the scope of this definition include, but are not limited to, acridinyl, oxazolyl, porphyrin, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, thienyl, furan Benzo, benzothienyl, benzofuranyl, quinolyl, isoquinolyl, oxazolyl, isoxazolyl, indolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl , tetrahydroquinolyl, thiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, triazinyl, as defined by a heterocyclic ring, "aromatic heterocyclic" is also understood to include any An N-oxide derivative of a nitrogen-containing aromatic heterocyclic group.

The salt is an agrochemically acceptable salt, preferably an acid addition salt obtained by reacting a compound of this type with a chemically acceptable acid, or a hydroxypyrazole compound and a base having an acidic group therein A salt formed by the reaction of a compound. Wherein, the acid is preferably selected from the group consisting of inorganic acids (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid) and organic acids (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzene). The basic compound is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate. The above pharmaceutically acceptable salts are easily separated and can be purified by conventional separation methods such as solvent extraction, dilution, recrystallization, column chromatography, and preparative thin layer chromatography.

A method of preparing the pyrazolone compound or a salt thereof, comprising the steps of:

(1) using a compound of the formula II to react with an excess of the compound R ₁ R ₂ NH to prepare a compound of the formula III;

(2) reacting a compound of the formula III with a compound X-A to obtain a compound of the formula I;

Wherein A represents halogen, methylsulfonyl or p-toluenesulfonyl, and the reaction equation is as follows:

The steps (1) and (2) are carried out in an aprotic solvent under the action of a base; the reaction temperature is from -30 ° C to 180 ° C, preferably from -5 ° C to 90 ° C.

The solvent is acetonitrile, diethyl ether, tetrahydrofuran, DMF or DMSO, preferably acetonitrile, tetrahydrofuran or DMF; the base is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate , triethylamine, NaH, DIPEA or DBU, preferably NaH, triethylamine or potassium carbonate.

A herbicidal composition comprising a herbicidally effective amount of at least one of the pyrazolone compound or a salt thereof.

The herbicidal composition also includes a formulation aid.

A method of controlling a harmful plant, which comprises using a herbicidally effective amount of at least one of the pyrazolone compound or a salt thereof or the herbicidal composition described above on a plant or a harmful plant area.

Use of at least one of the pyrazolone compound or a salt thereof or the herbicidal composition described above for controlling harmful plants, preferably using the pyrazolone compound or a salt thereof for controlling There are harmful plants in the application, which are crops treated by genetically modified crops or genome editing techniques.

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-0221044A, EP-0131624A). 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);

- transgenic crop plants resistant to specific herbicides, glufosinate herbicides (eg EP-0242236A, EP-0242246A) or glyphosate herbicides (WO 92/00377), or sulfonylureas Herbicide-like (EP-0257993A, US-5013659A);

- a 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);

- 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, exchange of substrates, removal of partial sequences Or add natural or synthetic sequences. 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-based diluent, miscible oil solution, powder (DP), capsule suspension (CS), seed dressing composition, granules for spreading and soil application, sprayed granules , coated particles and absorbent particles, water dispersible granules (WG), water soluble granules (SG), ULV (ultra low volume) formulations, 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.

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, butyl Amine, alachlor, propisochlor, metolachlor, stilbenamide, pretilachlor, chlorfenapyr, acetochlor, naproxil, R-L-naproxil, Propionate, mefenacet, dibenzoylamine, flufenacetate, herbicide, flufenic acid, bromobutyramide, dimethoprim, high-performance dimethoprim, Ethyl acetophene, flufenacet, methoxymethafen, metazachlor, isoxacillin, high-efficiency wheat straw methyl ester, high-efficiency wheat valproate, dipropenamide, acetochlor, butyrylcholine Amine, cyclopropamide, flufenacetamide, heptylacetate, isobutachlor, propargylamine, terbutachlor, xantylamine, dimethylamine, chloramine, trimethoxamine , chloroformylamine, propyzamide, valproate, acetochlor, neoxanthine, tricyclosage, butachlor, forage, benzylamine, acesulfame, benzene Fluorosulfonamide, naphthylamine, acetochlor, naprosamine, thiabalachlor, cyanochlor, benzodiazet, turkey, chloramphenmine, butylamine, flufenacet, sputum Jin, Xi Majin, Fucaojing, cyanaceous, Xicaojing, Qi Net, chlorpyrifos, isopropyl, flufenacetate, tertidine, terbutin, triazine flufenazone, cyclopropazine, gansujin, chlordazin, chlorhexidine, simazine, azide, Diquat, Isoproterenol, Cyclopropanol, Shimadzu, Other Dingjin, Zhongdingtong, Tedingtong, methoxypropyl, cyanaceate, oxacin, cola, 莠通通, 灭草Tong, Gancaojin, cyanuric acid, Indaziflam, chlorsulfuron, metsulfuron, bensulfuron-methyl, chlorsulfuron, tribenuron, thiasulfuron, pyrisulfuron, methyl disulfuron, A Sodium iodsulfuron sodium, formylaminosulfuron, ethersulfuron, ether sulfonate, sulfometuron, nicosulfuron, amphetsulfuron, sulfimsulfuron, ethoxysulfuron, ring Propionusulfuron, sulfimsulfuron, tetrazincsulfuron, flazasulfuron, monosulfuron, monosulfuron, flucarbazone, flurazine, flupirsulfuron, epoxy Bisulfuron, oxazolsulfuron, flusulfuron, propofuron, triflusulfuron, sulfonylsulfonate, triflusulfuron, flucarbazone, trifluorosulfuron, methane Sodium sulphate, flurbisulfuron, thiosulfuron, pyrimethanil, Propyris Ulfuron (promazine), oxazinsulfuron, acifluorfen, flufenazone, flufenacil, acesulfame, oxyfluorfen, oxalicid, benzene Ether, flufenacetate ethyl ester, carboxy herbicide ether, trifluoromethane ether, methoxy herbicide ether, triflurane, fluorinated herbicide, flufenic acid ether, herbicide ether, alaloin, dimethyl Grass ether, fluoroester valerian, flufenate, Halosafen, chloromeron, isoproturon, ligulon, diuron, saprolon, fluroxypyr, benzothiazol, methotrexate, Benzalonone, sulforaphane, isoxolone, terbutazone, acetylacesulfon, chlorbromide, methyl herbicide, humulocyclone, methoxapril, bromogluta, methoxyuron, Lugulong, chlorpyrifos, Huacaolong, non-grass, flucarburon, chlorpyrifos, haystow, turf, sylvestre, stagnation, teflon, thiothiazide, dry scorpion, Fluorone, methotrexate, primate, trimethylisourea, oxazolone, Monisouron, Anisuron, Methiuron, Chloreturon, Tetrafluorouron, Beet Ning, Beet Ning-Ethyl Ester, Beet Ann, Sulfacin, Special Cao Ling, oatmeal, aniline Chloranilide, diclofenac, chlorpyrifos, chlorinated alkane, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butachlor, Herbicide, Herbicide, Herbicide, Wild Maid, Piper Cao Dan, Hecao Wei, Valerian Dan, Herbaceous Enemy, Oats Enemy, Bactericide, Ethylthiophene, Pingcao Dan, Kecao Meng, Bencao Dan, Cao Cao Dan, Thiene Grass, Grass Scatter, Isopolinate, Methiobencarb, 2,4-butyl butyl ester, 2 methyl 4-chloro sodium, 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-dipropionic acid, high 2,4-D-propionate, 2,4-D-butyric acid, 2 to 4 chloropropionic acid , 2, 4-chloropropionate, 2, 4-chlorobutyric acid, 2,4,5-indole, 2,4,5-nonanoic acid, 2,4,5-indolebutyric acid, 2 methyl 4-chloroamine salt, dicamba, imapenal, valerian, saison, trichlorobenzoic acid, aminodichlorobenzoic acid, methoxytrichlorobenzoic acid, Cao Ling, pirfenoxacil, flupiroxine, flupirtine, high-efficiency flupirtine, quizalofop, quizalofop, oxazolyl, oxazolamide , valeric acid ester, cyhalofoprin, oxazolamide, clodinafop, thiazolyl, acetylene, valprofloxacin, trifluoromethane, oxalate, paraquat, diquat Fast, sulfonate, butylbutafluoride, isoproterol, metformin, ciprofloxacin, aminopropionin, etidrin, chlorhexidine, aminoethionol, diloline , chlorhexidine, Methalpropalin, propofol, glyphosate, samarium phosphine, glufosinate, methylammonium, sulforaphane, piperidin, bialaphos, disperse phosphorus, grass Phosphorus, vine grass phosphorus, ruthenium phosphate, dimethicin phosphorus, turf phosphorus, imidazolium niacin, imidazolidinic acid, imidazoquinoic acid, imazamox, imazamox, ampicillin, and imidazole Herbyl ester, flupiroxine, isoflurane chlorofluoxyacetate, two Chlorpyridinic acid, amlalididic acid, triclopyridinic acid, flurazepam, halochloridine, trichloropyridinol, thiazolidin, flufenidone, clopyralid, fluroxypyr, trichloro Butoxyethyl acetoacetate, Cliodinate, dilute pyridine, clethone, thiazinone, chlorfenazone, benzophenone, butyl ketone, oxadiazon, pyridone, Buthidazole, oxazin Ketone, cycloazinone, oxazinone, oxazinone, Ametridione, Amibuzin, bromoxynil, octanoyl bromoxynil, octanoyl iodonitrile, iodobenzonitrile, dichlorfen, diphenylacetonitrile, diazole Oxalic acid, hydroxybenzonitrile, Iodobonil, flufensulfuron, diflufenacil, penoxsulam, sulfoxazolamide, chlorsulfuron, diclofenac, acesulfame, Flurazine, bispyribyl ether, pyrimethoxam, cyclic ester, pyrimethanil, pyrithione, dicyclohexanone, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, different Oxazone, Isochlorozinone, Fenoxasulfone, Methiozolin, Isoprofen, Pyrazepam, Pyrazol, Wild Yant, Benzazol, Pyroxamate, Pyridox , Pyrasulfotole, oxazolone, Pyroxasulfone, oxazolamide, fluoxazole, chlorpyrifos, oxazolone, oxacillin, flufenone, mesalin, Bencarbazone, dipyrazon , fluproxil, herbicidal, isoxadine, cyclohexane, tetrodamine, Flupropacil, oxadiazon, flumethacic acid, propifluramine, ethinylamine, benzyl ether, Flumezin, Pentachlorophenol (sodium), dinose, telecol, tromethoate, pentoxide, dinitrophenol, chloronitrophenol, diloise, dilt, propargyl oxaloin, oxadiazon, ring Valericone, fluoxetine, methyl oxazate, tetrazoyl oxalate, flurazazine, herbicide, bromine, metformin, valerian, oxazide, grass哒松, 哒草伏, Pyridafol, quinclorac, chloroquinoline, bentazon, valerate, oxazinone, herbicide, clomazone, cycloheptyl ether, isopropyl ester Grass ether, propyl oxalate, oxadiazon, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage, bromophenol, triazole, oxazole , furoserone, furosemide, Furosemethane, pyrimethanil, chloranoic acid, fluroxypyr, valerian, acrolein, benthoprin, chlorpyrifos, oat ester, thiazolidine, cotton amine, oxymatone, Oxybenzone, saflufenacil, chlorhexylphosphine, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methionine, Cambendichlor, Ring A pyrimidinic acid, thiocyanuril, oxalyl ketone, oxadiazepine, chlorpyrifos, oxacillin, chlorpyrifos, oxalic acid, oxalic acid, sulfacetonitrile, cumin, pyrazole , furazosalazine, valerian, dibenzoxazole, dichloropropenylamine, fluorochloropyridinium, 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.

Several methods of preparing the compounds of the 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 illustrated. 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.

In view of the economics and versatility of the compounds, the method examples provided below are used to facilitate further understanding of the preparation methods of the present invention, and the specific substances, types and conditions used are determined to be further explanation of the present invention, and are not intended to be a reasonable range thereof. limits. 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 nuclear magnetic resonance spectrum conditions were as follows: ¹ H NMR was measured by an AVANCE AV-500 nuclear magnetic resonance spectrometer, TMS was an internal standard, and mass spectrometry was determined by a Shimadzu-2010A mass spectrometer.

Table 1 below shows a series of compounds with the following structural formula:

Table 1 compound structure and its ¹ H NMR data

The implementation of representative compounds is as follows:

1. Preparation of Compound 005

2.0 g of compound A1, 1.5 g of triethylamine and 10 mL of acetonitrile were mixed, cooled to 0 ° C with stirring in an ice bath, and 1.0 g of p-ethylbenzenesulfonyl chloride was slowly added dropwise at 0 to 5 ° C. Reaction 2h. Then, 50 mL of water was added dropwise to the reaction mixture to precipitate a pale yellow solid. After suction filtration, the filter cake was washed well with water and dried to give a pale yellow solid (yield: 71%).

2. Preparation of Compound 011

0.8 g of dimethylaminomethanol was dissolved in 10 mL of acetonitrile, cooled to 0 ° C with stirring in an ice bath, 0.4 g of 60% NaH was slowly added at 0 to 5 ° C, stirred for 30 min, then 2.3 g of compound A2 was added, and the mixture was stirred at room temperature. overnight. 50 mL of water was added to the reaction mixture, and the pH was adjusted to 6 with dilute hydrochloric acid. The mixture was evaporated to ethyl acetate. The rate was 72% and the HPLC purity was 97%.

3. Preparation of Compound 016

2.2 g of compound A3, 1.5 g of triethylamine and 10 mL of acetonitrile were mixed, cooled to 0 ° C with stirring in an ice bath, and 0.8 g of dimethyl chlorophosphate was slowly added at 0 to 5 ° C, and stirred at room temperature overnight. 50 mL of water was added to the reaction mixture, and the pH was adjusted to 6 with dilute hydrochloric acid, and ethyl acetate was evaporated. The yield was 77% and the HPLC purity was 94%.

4. Preparation of Compound 088

2.0 g of the compound A4, 2.0 g of anhydrous potassium carbonate and 10 mL of acetonitrile were mixed, and 0.8 g of phenyl chloroformate was slowly added dropwise with vigorous stirring. The reaction was stirred at room temperature overnight. 50 mL of water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic phase was washed with water and concentrated, and then purified, m.

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 weed experiment: Place monocotyledonous and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, canola, millet, sorghum) in a plastic pot filled with 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 compound of the present invention is dissolved in acetone, and then Tween 80 is added. 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 2.

Table 2 results of post-emergence weed experiment

Serial number	Look at Mai Niang	Hard grass	Traditional
001	10	10	10
002	10	10	10
003	10	10	10
004	10	10	10
005	10	10	10
006	10	10	10
007	10	10	10
008	10	10	10
009	10	10	10
010	10	10	10
011	10	10	10
012	10	10	10
013	10	10	10
014	10	10	10
015	10	10	10
016	10	10	10
017	10	10	10
018	10	10	10
019	10	10	10
020	10	10	10
022	10	10	10
023	10	10	10
025	10	10	10
028	10	10	10
029	10	10	10

030	10	10	10
031	10	10	10
039	10	10	10
040	10	10	10
041	10	10	10
042	10	10	10
043	10	10	10
044	10	10	10
045	10	10	10
046	10	10	10
047	10	10	10
048	10	10	10
049	10	10	10
050	10	10	10
051	10	10	10
052	10	10	10
053	10	10	10
054	10	10	10
055	10	10	10
056	10	10	10
057	10	10	10
058	10	10	10
059	10	10	10
060	10	10	10
068	10	10	10
069	10	10	10
070	10	10	10
071	10	10	10
079	10	10	10
080	10	10	10
081	10	10	10
082	10	10	10
083	10	10	10
084	10	10	10
085	10	10	10
086	10	10	10
087	10	10	10
088	10	10	10
089	10	10	10
090	10	10	10
091	10	10	10
092	10	10	10
093	10	10	10
094	10	10	10
095	10	10	10
096	10	10	10
097	10	10	10
098	10	10	10
099	10	10	10
100	10	10	10
101	10	10	10

102

10

10

10

Note: The application dose is 250 g/ha of active ingredient and the water exchange rate is 450 kg/ha.

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, sorghum, and ragweed are planted, and the soil is gently covered thereon. Thereafter, it is placed in a greenhouse at a depth of 0.5-1 cm, and the water storage depth is 3-4 cm, and 1.5 leaves are obtained in the valerian, the ginseng, and the ragweed, and the present invention is prepared according to the usual preparation method. The wettable powder of the compound or the aqueous dilution of the suspension is uniformly dripped with a pipette to achieve a predetermined 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, Qianjin, and ragwort on the 14th day after the treatment was observed with the naked eye, and the growth status of rice on the 21st day after the treatment, and the herbicidal effect was evaluated at the activity standard level of 0-10, thereby obtaining the table. 3 results.

Table 3 Experimental results of transplanted paddy field (250 g / ha active ingredient)

Serial number	Valerian	Thousand gold	Papua	Rice
006	10	10	10	0
017	10	9	10	0
018	10	10	10	0
019	10	10	9	0
020	10	10	10	0
022	10	10	10	0
023	10	10	10	0
025	10	9	10	0
028	10	10	10	0
029	10	10	10	0
030	10	10	10	0

Note: The seeds of valerian, Qianjin, and ragweed were collected from Heilongjiang, China, and tested for resistance to conventional doses of pyrazosulfuron.

Comparative Test:

The test method steps were consistent with the aforementioned post-emergence weed experiment, and the results of the comparative test of each compound are shown in Table 4-10 below, wherein the comparative examples a-j are all from the patent CN105218449A.

Table 4 comparison test results

Table 5 comparison test results

Table 6 comparison test results

Table 7 comparison test results

Table 8 comparison test results

Table 9 comparison test results

Table 10 comparison test results

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 (9)

1. A pyrazolone compound or a salt thereof as shown in Formula I:

   

   In the formula,

   R ₁ R ₂ N represents a butylamido group or a valerolactam which is unsubstituted or substituted on the ring by one or more groups selected from the group consisting of fluorine, chlorine, methyl, ethyl, methoxy and ethoxy. base;

   R ₃ represents hydrogen, C _1-4 alkyl, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, unsubstituted or C _{3 to 6} cycloalkyl substituted with C _1-4 alkyl;

   R ₄ represents a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a cyclopropyl group;

   X represents -R ⁵ , -S(O) _n R ⁶ , -CH ₂ R ⁷ , -(C=O)R ⁸ , -PO(OR ⁹ ) ₂ , -Si(OR ⁹ ) ₃ , wherein

   R ⁵ , R ⁶ represents a substituted or unsubstituted aryl or heterocyclic group, and n represents 1, 2, 3;

   R ⁷ represents a substituted or unsubstituted aryl or heterocyclic group, a C _1-6 alkyl group substituted by a halogen, a halogen, a C _1-6 alkylamino group, a C _2-4 alkynyl group, a C _2-4 alkenyl group, C _1-6 alkoxy, nitro, cyano, C _3-6 cycloalkyl, amino, C _1-6 alkylthio;

   R ⁸ represents a C _1-6 alkylamino group, a C _1-6 alkylthio group, a C _1-6 alkylamino C _1-6 alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, a halogen, an amino group. , cyano, nitro, C _1-6 alkoxy C _1-6 alkyl, substituted or unsubstituted phenyl, phenyl C _1-6 alkyl, phenoxy or phenoxy C _1-6 alkane base;

   R ⁹ represents hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, substituted or unsubstituted phenyl or heterocyclic.
2. The pyrazolone compound or a salt thereof according to claim 1, wherein

   R ⁵ and R ⁶ represent an unsubstituted phenyl group or a 3- to 10-membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and are selected from C _{1 to 6} alkyl groups, C _{1 to 6} Alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, amino, nitro, cyano, carboxy, C _1-6 Alkoxycarbonyl group, C _1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylsulfonyl C _1-6 alkyl group, C _1-6 alkylthiosulfonyl C _1-6 alkyl group, a phenyl group substituted with one or more groups of C _3-6 cycloalkyl groups or a 3 to 10 membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and n represents 1, 2 , 3;

   R ⁷ represents an unsubstituted phenyl group or a 3- to 10-membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and is selected from a C _1-6 alkyl group and a C _1-6 alkoxy group. , C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, amino, nitro, cyano, carboxy, C _1-6 alkoxy Carbonyl group, C _1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylsulfonyl C _1-6 alkyl group, C _1-6 alkylthiosulfonyl C _1-6 alkyl group, C _{3 ～} a phenyl group substituted with one or more groups of ₆ cycloalkyl groups or a 3 to 10 membered heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and C _{1 to 6} substituted by halogen Alkyl, halogen, C _1-6 alkylamino, C _2-4 alkynyl, C _{2 to 4} alkenyl, C _1-6 alkoxy, nitro, cyano, C _3-6 cycloalkyl, amino , C _1-6 alkylthio;

   R ⁸ represents a C _1-6 alkylamino group, a C _1-6 alkylthio group, a C _1-6 alkylamino C _1-6 alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, a halogen, an amino group. , cyano, nitro, C _1-6 alkoxy C _1-6 alkyl, phenyl, phenyl C _1-6 alkyl, phenoxy or phenoxy C _1-6 alkyl, selected from C _1-6 alkyl, C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, amino, nitrate group, cyano, carboxy, C _{1 ~ 6} alkoxycarbonyl, C _{1 ~ 6} alkoxy-C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkylsulfonyl C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkyl a phenyl group substituted with one or more groups of a thiosulfonyl C _1-6 alkyl group or a C _{3 -6} cycloalkyl group, a phenyl C _1-6 alkyl group, a phenoxy group or a phenoxy group C _{1 ～6} alkyl;

   R ⁹ represents hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, unsubstituted phenyl or a 3 to 10 membered heterocyclic group containing 1 to 4 hetero atoms selected from O, N and S, Is selected from the group consisting of C _1-6 alkyl, C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halogen, C _{2 to 4} alkenyl, C _{2 to 4} alkynyl, Amino, nitro, cyano, carboxyl, C _1-6 alkoxycarbonyl, C _1-6 alkoxy C _1-6 alkyl, C _1-6 alkylsulfonyl C _1-6 alkyl, C ₁ a phenyl group substituted with one or more groups of a ₆ alkylthiosulfonyl C _1-6 alkyl group or a C _{3 -6} cycloalkyl group or a hetero atom having 1 to 4 selected from O, N and S a 3 to 10 membered heterocyclic group.
3. The pyrazolone compound or a salt thereof according to claim 1 or 2, wherein

   R ₃ represents hydrogen, methyl, ethyl, cyclopropyl;

   R ₄ represents a methyl group, an ethyl group, an isopropyl group;

   X represents -S(O) _n R ⁶ , -CH ₂ R ⁷ , -(C=O)R ⁸ , wherein

   R ⁶ represents an unsubstituted phenyl group or a 3- to 10-membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and is selected from a C _1-6 alkyl group and a C _1-6 alkoxy group. a phenyl group substituted with one or more groups in the halogen or a 3 to 10 membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and n represents 2;

   R ⁷ represents an unsubstituted phenyl group or a 3- to 10-membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and is selected from a C _1-6 alkyl group and a C _1-6 alkoxy group. a phenyl group substituted with one or more groups in a halogen or a 3 to 10 membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, N and S, and C _{1 to 6} substituted by halogen An alkyl group, a C _1-6 alkylamino group, a C _2-4 alkynyl group, a C _{2 to 4} alkenyl group, a C _1-6 alkoxy group, a C _1-6 alkylthio group;

   R ⁸ represents a C _1-6 alkylamino group, a C _1-6 alkylthio group, a C _1-6 alkylamino C _1-6 alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, a phenyl C group. _{1 ~ 6} alkyl group or a phenoxy group, selected from C _1-6 alkyl, C _1-6 alkoxy, C _1-6 alkylamino, C _1-6 alkylthio, halo, C _{2 ~ 4} Alkenyl, C _2-4 alkynyl, amino, nitro, cyano, carboxy, C _1-6 alkoxycarbonyl, C _1-6 alkoxy C _1-6 alkyl, C _1-6 alkyl sulfonate acyl C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkylsulfonyl alkylthio C _{1 ~ 6} alkyl group, C _{3 ~ 6} cycloalkyl group with one or more phenyl groups substituted C _{1 ~ 6} alkyl group Or phenoxy.
4. A herbicide composition comprising a herbicidally effective amount of at least one of the pyrazolone compound according to any one of claims 1 to 3 or a salt thereof.
5. The herbicidal composition according to claim 4, further comprising a formulation auxiliary.
6. A method for controlling a harmful plant, comprising: a herbicidally effective amount of at least one of the pyrazolone compound according to any one of claims 1 to 3 or a salt thereof, or any one of claims 4-5 Herbicide composition as described On plants or in harmful plant areas.
7. The use of at least one of the pyrazolone compound or a salt thereof according to any one of claims 1 to 3 or the herbicidal composition according to any one of claims 4 to 5 for controlling harmful plants.
8. The use according to claim 6, characterized in that the pyrazolone compound or a salt thereof is used for controlling harmful plants in useful crops.
9. The use according to claim 8, characterized in that the useful crop is a crop treated by a transgenic crop or a genome editing technique.