WO2024208143A1 - Triazole compound, and preparation method therefor, herbicidal composition and use thereof - Google Patents

Abstract

The present invention belongs to the technical field of pesticides, and particularly relates to a triazole compound, and a preparation method therefor, a herbicidal composition and the use thereof. The triazole compound is as shown in general formula I, wherein M represents N or CH; X represents halogen, alkyl, haloalkyl, cyano, or haloalkoxy; Y represents hydrogen or halogen; Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkylthio, alkylsulfoxy, or alkylsulfonyl; and A and B independently represent hydrogen, halogen, cyano, alkyl, cycloalkyl, alkoxy, alkylthio, alkylthioalkyl or alkoxyalkyl, and A and B are not hydrogen at the same time. The compound has a good herbicidal activity on Gramineae weeds, broad-leaved weeds, Cyperaceae weeds, etc., even at a low application rate, and has high selectivity to crops.

Description

A triazole compound and its preparation method, herbicide composition and application Technical Field

The invention belongs to the technical field of pesticides, and specifically relates to a triazole compound and a preparation method thereof, a herbicidal composition and application thereof.

Background Art

Weed control is a crucial link in achieving efficient agriculture. Although there are many types of herbicides on the market, the weed control performance of these known compounds against harmful plants and the selectivity for crops are not completely satisfactory. In addition, due to the continuous expansion of the market, weed resistance, drug life and economic efficiency, as well as people's increasing attention to the environment, scientists need to continue to research and develop new high-efficiency, safe, economical and different modes of action herbicide varieties.

Summary of the invention

The invention provides a triazole compound and a preparation method thereof, a herbicidal composition and application thereof. The compound has excellent herbicidal activity against gramineous weeds, broadleaf weeds, sedge weeds and the like even at a low application rate and has high selectivity for crops.

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

A triazole compound, as shown in general formula I:

Wherein, M represents N or CH;

X represents halogen, alkyl, haloalkyl, cyano or haloalkoxy;

Y represents hydrogen or halogen;

Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkylthio, alkylsulfoxide or alkylsulfonyl;

A and B each independently represent hydrogen, halogen, cyano, alkyl, cycloalkyl, alkoxy, alkylthio, alkylthioalkyl or alkoxyalkyl, and A and B are not hydrogen at the same time.

In a specific embodiment, X represents halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, cyano or halogenated C1-C8 alkoxy;

Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C2-C8 alkynyloxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkylthio, C1-C8 alkylsulfoxide or C1-C8 alkylsulfonyl;

A and B independently represent hydrogen, halogen, cyano, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylthioC1-C8 alkyl or C1-C8 alkoxyC1-C8 alkyl.

In another specific embodiment, X represents halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, cyano or halogenated C1-C6 alkoxy;

Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylsulfoxide or C1-C6 alkylsulfonyl;

A and B independently represent hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylthioC1-C6 alkyl or C1-C6 alkoxyC1-C6 alkyl.

In the definition of the compounds represented by the above general formula and in all the following structural formulae, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms may be straight-chain or branched. For example, in the compound word "alkoxyalkyl", the alkyl group may be -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, etc. Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-ene-1-yl, 2-methylprop-2-ene-1-yl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be at any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system with, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl with, for example, three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein double bonds can be at any position. Halogen is fluorine, chlorine, bromine or iodine.

If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned. In addition, identical or different substitution characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude compounds known to those skilled in the art that are chemically unstable under standard conditions.

In addition, unless otherwise specified, the "aryl" described in the present invention includes but is not limited to phenyl, naphthyl, The term "substituted by at least one group" means substituted by 1, 2, 3, 4 or 5 groups; groups without specific connection positions may be connected at any position, including positions connected to C or N; if it is substituted, the substituent may also be substituted at any position as long as it complies with the chemical bond connection rules.

Depending on the nature of the substituents and the way they are connected, the compounds of the general formula I and their derivatives may exist as stereoisomers. For example, if there are one or more asymmetric carbon atoms, enantiomers and diastereomers may occur. Stereoisomers can be obtained from the mixture obtained in the preparation by conventional separation methods, for example by chromatographic separation. Stereoisomers can also be selectively prepared by using stereoselective reactions and using optically active starting materials and/or auxiliaries. The present invention also relates to all stereoisomers and mixtures thereof contained in the general formula I but not specifically defined.

The preparation method of the triazole compound comprises the following steps:

The compound represented by the general formula II is subjected to a substitution reaction with the compound represented by the general formula III to obtain the compound represented by the general formula I. The chemical reaction equation is as follows:

Wherein, Hal represents halogen, preferably Cl; substituents A, B, M, X, Y and Z are as defined above.

Preferably, the reaction is carried out in the presence of a base and a solvent; more preferably, the base is selected from at least one of an inorganic base (such as _K2CO3 , _Na2CO3 , _Cs2CO3 , _NaHCO3 , KF, CsF, KOAc, AcONa, _K3PO4 , _{t -} BuONa, EtONa, NaOH _, KOH, NaOMe, etc.) or an organic base (pyrazole or C1-C6 alkylamine, such as triethylamine, trimethylamine, N-ethyldiisopropylamine, DIEA, etc.); the solvent is selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene, toluene, cresol or o-, m- and p-xylene), THF, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, toluene or ethyl acetate.

A herbicide composition comprises (i) a herbicidally effective amount of at least one of the triazole compounds, and preferably further comprises (ii) a formulation adjuvant.

In one embodiment, the herbicidal composition further comprises (iii) a herbicidally effective amount of one or more additional herbicides and/or safeners.

A method for controlling weeds comprises applying a herbicidally effective amount of at least one of the triazole compounds or the herbicide composition on plants or weedy areas.

The use of at least one of the triazole compounds or the herbicide composition in controlling weeds, preferably, the triazole compound is used to control weeds in useful crops, and the useful crops are transgenic crops or crops treated with genome editing technology.

The compounds of formula I of the present invention have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants. The active substances of the present invention are also effective against perennial weeds, which grow from rhizomes, rootstocks, or other perennial organs and are difficult to control. In this regard, it is generally unimportant whether the substance is used before sowing, before germination, or after germination. Representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention are particularly mentioned, without limiting to certain species. Examples of weed species on which the active substances are effective include monocotyledonous plants: annual Avena, Lolium, Alopecuroides, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus, and perennial Agropyron, Cynodon, Imperata and Sorghum, and perennial Cyperus.

With regard to dicotyledonous weed species, its effect can be extended to species such as annual Galium, Viola, Veronica, Sesame, Chickweed, Amaranth, Sinapis, Ipomoea, Rhizoma Coptidis, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia. The active substance of the present invention effectively controls harmful plants such as Echinochloa, Sagittaria, Alisma, Eriobotrya, Sugarcane and Cyperus under such undetermined conditions of rice sowing. If the compound of the present invention is applied to the soil surface before germination, the seedlings of the weeds can be completely prevented before the weeds grow, or the weeds stop growing when the cotyledons grow, and finally die completely after three to four weeks. The compound of the present invention is particularly good in activity against the following plants, Apila, Sesame, Polygonum, Chickweed, Veronica hedera, Veronica arabica, Pansy and Amaranth, Galium and Kochia.

Although the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they do not cause any damage to economically important crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean, or The damage is negligible. In particular, they are very compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compounds according to the invention are very suitable for selectively controlling unwanted plants in agricultural crops or ornamental plants.

Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetically engineered plant cultivation. Transgenic plants usually have superior properties, such as resistance to specific pesticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insects or fungal, bacterial or viral microorganisms. Other special properties are related to the following conditions of the product, for example, quantity, quality, storage stability, composition and special ingredients. In this way, it is known to obtain transgenic plant products with increased starch content or improved starch quality or different fatty acid compositions.

The compounds of formula I of the present invention or their salts are preferably used in economically important genetically modified crops and ornamental plants, for example cereals, for example wheat, barley, rye, oats, millet, rice, cassava and corn, or in the cultivation of beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of formula I are preferably used as herbicides for the cultivation of useful plants, which are resistant or genetically engineered to the toxic effects of herbicides.

Conventional methods for breeding plants with improved traits compared to known plants include, for example, conventional mating methods and mutant breeding. 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 of crop plants to improve starch synthesis in plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806);

- transgenic crop plants resistant to specific herbicides, such as glufosinate (e.g. EP-0242236 A, EP-0242246 A) or glyphosate herbicides (WO 92/00377), or sulfonylurea herbicides (EP-0257993 A, US-5013659 A);

- genetically modified crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) that protect plants against attack by certain pests (EP-0142924 A, EP-0193259 A);

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

Many molecular biotechniques are known that allow the preparation of transgenic plants with improved traits (see, for example, Sambrook et al., 1989, Molecular Amplification, A Laboratory Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, New York; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431)). In order to carry out genetic engineering operations, it is possible to introduce nucleic acid molecules into plasmids and to cause mutations or sequence changes by recombination of DNA sequences. Using the standard methods described above, for example, bases can be replaced, parts of sequences can be removed or natural or synthetic sequences can be added. In order to connect DNA fragments to each other, it is possible to attach binders or connectors to the fragments.

Plant cells in which the activity of a gene product is reduced can be prepared by, for example, expressing at least one appropriate antisense RNA, sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme which specifically cleaves the transcript of the gene product.

For this purpose, it is possible to use a DNA molecule comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and to use a DNA molecule comprising only a portion of the coding sequence, which portion must be long enough to achieve an antisense effect in the cell. It is also possible to use sequences that have a high degree of homology to the gene product coding sequence, but are not identical.

When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, for localization in a specific compartment, it is possible, for example, to connect the coding region and the DNA sequence to ensure localization at a specific position. These sequences are known to those skilled in the art (see, 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).

The transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plants can be any desired plant species, i.e. monocots and dicots. In this way, it is possible to obtain transgenic plants with improved traits by overexpression, inhibition or suppression of homologous (=natural) genes or gene sequences, or by expression of heterologous (=foreign) genes or gene sequences.

When the active substance of the present invention is used on genetically modified crops, in addition to the effect of inhibiting harmful plants observed on other crops, there are often special effects on the corresponding genetically modified crops, such as improving or expanding the scope of weed control, improving the application rate during application, preferably combining the resistance of genetically modified crops with the performance of herbicides well, and affecting the growth and yield of genetically modified crop plants. Therefore, the present invention also provides the use of the compound as a herbicide to control harmful plants in genetically modified crop plants.

In addition, the compounds according to the invention can significantly regulate the growth of crop plants. By regulating the plant metabolism, these compounds can be used to control the composition of the plant and promote the harvest, for example to dry out the plant and dwarf the growth. They are also suitable for regulating and inhibiting undesirable plant growth without destroying the growth of the crop. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, because this can reduce or completely prevent lodging.

The compounds of the present invention can be applied using general formulations, and wettable powders, emulsion concentrates, sprayable solutions, powders or granules can be used. Thus, the present invention also provides herbicidal compositions comprising compounds of formula I. According to the usual biological and/or chemical physical parameters, compounds of formula I can be formulated in a variety of ways. Suitable formulation selection examples are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, concentrated emulsions (EC), such as oil-in-water dispersions and water-in-oil dispersions (EW), sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, solutions of miscible oils, powders (DP), capsule suspensions (CS), seeddressing compositions, granules for broadcasting and soil application, spray granules, coated granules and absorption granules, 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 Technology], Volume 7, C. Hauser Verlag Munich, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd edition 1979, G. Goodwin Ltd. London.

Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives are likewise known and described in documents such as Watkins, "Handbook of Powder Diluents Pesticides and Carriers", 2nd edition, Darland Books Caldwell NJ; Hv01phen, "Introduction to Clay Colloid Chemistry", 2nd edition, J. Wiley and Sons, NY; C. Marsden, "Solvent Guide", 2nd edition, Interscience, NY 1963; McCutcheon, "Detergents and Emulsifiers Annual", MC Publishing Company, Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surfactants", Chemical Publishing Company, NY 1964; of [Ethylene oxide adduct surfactant], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

Wettable powders are homogeneously dispersible in water and contain, in addition to the active substance, diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthomethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substance of the herbicide is finely ground, for example using conventional apparatus such as hammer mills, fan mills and jet mills, and adjuvants are mixed in simultaneously or sequentially.

The concentrated emulsion is prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of aromatic compounds or hydrocarbons with a higher boiling point or solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used are calcium alkylaryl sulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters.

Powders are obtained by grinding the active substance with finely divided solid materials, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspensions based on water or oil can be prepared, for example, by wet grinding using a commercially available bead mill, with or without the addition of a surfactant of another formulation type as described above.

Emulsions such as oil-in-water emulsions (EW) can be prepared using aqueous organic solvents using stirrers, colloid mills and/or static mixers and, if necessary, adding surfactants of another formulation type as described above.

Granules are prepared by spraying the active substance onto an adsorbent, granulating with an inert material, or concentrating the active substance on the surface of a carrier such as sand or kaolinite and granulating the inert material with a binder such as polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the same method as for preparing fertilizer granules, and fertilizers can be mixed if necessary. Water suspension granules are prepared by the usual methods, such as spray-drying, fluidized bed granulation, disc granulation, mixing with a high-speed mixer, and extrusion in the absence of solid inert material.

For preparation methods using grinding discs, fluidized beds, extruders and spray granules, see the following processes, for example, "Spray Drying Manual", third edition 1979, G. Goodwin Co., Ltd., London; J. E. Browning, "Agglomeration", Chemistry and Engineering 1967, pages 147ff; "Perry's Chemical Engineer's Handbook", fifth edition, McGraw-Hill, New York 1973, pages 8-57. If you want to know about the formulation of crop protection products, see, for example, G. C. Klingman, "Weed Control as a Science", John Wiley and Sons Company, New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans "Handbook of Weed Control", fifth edition, Blackwell Scientific Rublications, Oxford University 1968, pages 101-103.

Agrochemical formulations usually contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the active substance of formula I. The concentration of the active substance in wettable powders is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remainder to 100% by weight. The concentration of the active substance in concentrated emulsions can be about 1 to 90% by weight, preferably 5 to 80%. Powder formulations contain 1 to 30% by weight of active substances, usually preferably 5 to 20% by weight of active substances, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% by weight of active substances. Regarding the content of active substances in water-suspended granules, it mainly depends on whether the active substance is liquid or solid, and the adjuvants used during granulation, fillers, etc. The content of the active substance in the water-suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

The formulations of the active substances may additionally contain tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, generally, the pH and viscosity regulators customary in each case.

Based on these preparations, it is also possible to mix with other active pesticide substances such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, and the mixing method can be pre-mixed or canned mixed.

In the mixed formulation or tank-mixed formulation, suitable active substances that can be mixed with the active substance of the present invention are, for example, the known substances in the World New Pesticide Variety Technology Encyclopedia, China Agricultural Science and Technology Press, 2010.9 and the literature cited herein. For example, the following herbicide active substances can be mixed with the compound of formula I, (Note: the name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with a code name when appropriate): acetochlor, butachlor, alachlor, isopropyl chlor, isopropyl chlor, isopropyl chlor, pretilachlor, cypermethrin, chlorfenapyr, naphthamide, R-levorotatory naphthamide, propanil, benzothiachlor Acylam, bisacodyl, fluazifop, herbicide, flumethacryl, bromomethacryl, dimethoate, high-efficiency dimethoate, ethomethacryl, flumethacryl, methoxymethacryl, metazachlor, isothiocarb, high-efficiency methyl ester of wheat straw, high-efficiency propyl ester of wheat straw, propenyl chloramine, pethochlor, butyral, cyproconazole, flusulfuronamide, heptyl chloramine, isobutyral, propenyl chloramine, terbutyral, dimethyl chloramine, dimethoate, Alachlor, chloranil, trimethoate, chloranil, propyzamide, valerylbenzamid, carbam, xinyanling, tricyclic chloranil, butenesulfonamide, oxadiazine, benzylmechlor, quinone, benzylmechlor, naphthamide, acetoacetamide, naphthamide, cypermethrin, cypermethrin, benzaclostrobin, chloranil, chloranil, butyrimidine, fluazifop, atrazine, simazine, promethazine, cyanamide, simesulfuron, amethoxazole, promethazine, cypermethrin, promethazine, Metazine, Isopropylamine, Fluoromethion, Terbuthion, Terbuthion, Triazine Fluamid, Cipro, Glycyrrhizin, Cyclohexanil, Cyprodinil, Cyprodinil, Metazine, Dimethoate ... , bensulfuron-methyl, thiosulfuron-methyl, pyrazosulfuron-methyl, methyl disulfuron-methyl, methyl iodosulfuron-methyl sodium salt, foramidosulfuron-methyl, ethersulfuron-methyl, ethersulfuron-methyl, sulfosulfuron-methyl, nicosulfuron, ethametsulfuron-methyl, acylosulfuron-methyl, ethoxysulfuron-methyl, cyprosulfuron-methyl, sulfosulfuron-methyl, tetrazosulfuron-methyl, fluazifop-methyl, monosulfuron-methyl, monosulfuron ester, fluazsulfuron-methyl, fluazsulfuron-methyl, flupyrazosulfuron-methyl, epoxysulfuron-methyl, pyrazosulfuron-methyl, primisulfuron-methyl, propylbenzenesulfon , trifloxysulfuron, sulfasulfuron-methyl, trifloxysulfuron, flumethosulfuron, trifloxysulfuron, metsulfuron-methyl sodium, flucetosulfuron, methylthiosulfuron, pyrimidinesulfuron, Propyrisulfuron (promazine sulfuron), pyrazosulfuron-methyl, acifluorfen, fomesulfuron-butyl, lactofen, fluazifop-butyl, oxyfluorfen, oxazolidinone, benfibrate, chlorpyrifos ethyl, methylcarboxypyridin, trifluoroacetate, methoxyfluorfen, Benzyl, fenpyroxil, fluorinated herbicide, flutolan, fenpyroxil, fenpyroxil, chlorpyrifos, isoproturon, linuron, diuron, sapuro, flutolan, benzyl, methyl benzyl, benzyl, sulfothiocarb, isoxaluron, terbuthiuron, clodinafop, chlorbromid, methyl fenpyroxil, acetyl fenpyroxil, methoxyfenpyroxil, bromothiocarb, methoxythiocarb, chlortolan, chlorpyrifos ... Diuron, monuron, cyclomethuron, fenugreek, flusulfuron, cypermethrin, cypermethrin, isothiocarb, cypermethrin, thiosulfuron, thiothiocarb, cypermethrin, parafluron, methoxythiazol, chloranil, trimethylol urea, oxazolidinone, Monisouron, Anisuron, Methiuron, Chloreturon, tetrafluron, betaine, betaine-ethyl ester, betaine, sulfamethoxazole, tert-butyl sulfamethoxazole Carboxazole, chlorprocarb, fenazolin, chloranil, chloranil, chloranil, carboxazole, chlorprocarb, fenazolin, BCPC, CPPC, carbasulam, chloranil ... 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-methyl-4-chloropropionic acid, 2-methyl-4-chloropropionic acid salt, 2-methyl-4-chlorobutyric acid, 2,4,5-T, 2,4,5-T propionic acid, 2,4,5-T butyric acid, 2-methyl-4-chloramine salt, dicamba, cypermethrin, famoxadone, cypermethrin, trichlorobenzoic acid, aminodichlorobenzoic acid, methoxytrichlorobenzoic acid, diclofenac, fluazifop-butyl, fluazifop-butyl, high-efficiency fluazifop-butyl, quizalofop-butyl, quinazolin-butyl, oxazolidinone, quinazolin-butyl, cyfluthrin, cyfluthrin, cyfluthrin, cyfluthrin, cyfluthrin, cyfluthrin Ester, thiazolin, cypermethrin, pentothiazolin, trifloxystrobin, isothiocarb, paraquat, diquat, oryzalin, ethylbutylfluralin, isoprofen, mesosulfuron, cyprofluorin, aminopropylfluralin, ethylbutylfluralin, chloroethylfluralin, aminoethylfluralin, dichlorvos, dichlorvos, methalpropalin, propanol, glyphosate, safflower, glufosinate, methylamine glufosinate, glufosinate sulfide, piperphosinate, bialaphos, dimethoate, chlorpyrifos, chlorpyrifos, cypermethrin, chlorpyrifos, cypermethrin, chlorpyrifos, cypermethrin, imazapic, imazapic, imazapic, chlorpyrifos ammonium, imazapic, imazapic, chlorpyrifos, clofosinate, Isooctyl clofopyralid, Clopyralid, Aminopyralid, Triclopyralid, Dithiopyralid, Halofopyl, Triclopyralid, Cyclopyralid, Flupyralid, Cyclopyralid, Dipyralid, Butoxyethyl Triclopyralid, Cliodinate, Sethoxydim, Clethodim, Cyclopyralid, Cyclopyralid, Butoxydim, Cyclopyralid, Buthidazole, Methiazole, Cyclopyralid, Metamidone, Ethiazole, Ametridione, Amibuzin, Bromoxynil, Octanoyl Bromoxynil, Octanoyl Iodobenzonil, Iodobenzonil, Dichlobenil, Diphenylacetonitrile, Dimethoate, Hydroxydichlobenil, Iodobo nil, fluazifop, bispyribac, penoxsulam, sulfamethoxam, chloranil, bispyribac, pyrasulfuron, fluazifop, bispyribac-butyl, pyrimidine oxime, cyclamate, pyrimidine oxime ... otole, benzathine, Pyroxasulfone, mesotrione, fluazifop, chlorfenapyr, amine oxadiazine, oxadiazine, fluazifop, sulfentrazone, Bencarbazone, bispyribac, fluazifop-butyl, bromocriptine, isothiocarb, cypermethrin, tercloram, Flupropacil, indolone, flufenac, fluazifop-butyl, chlorfenapyr, phthalic acid, Flumezin, pentachlorophenol (sodium), dinitrophenol, terolofen, terolate, pentachlorophenol, dinitrophenol, dinitrophenol, dioxadiazine, dioxadiazine, terolate, oxadiazine, cyclopentadiazine, flumethoxam, flumethoxam, methyl tetrazoline, Flupyridazine, herbicide, bromomycin, dimethoate, pyridafol, pyridafol, quinclorac, quinclorac, bentazon, pyridafol, oxazithromycin, chloranil, isoclomazone, cyproconazole, isopropyl ester ester, propyl ester ester, indole, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, grass fast, bromophenol oxime, triazole sulfone, chloranil, furochlor, furochlor, ethyl furochlor, chloranil, chloranil, chloranil, fluchloridone, barnyard grass, acrolein, benzylpyridin, chloranil, avena citrate, thiamethoxam, cotton amine, hydroxychloride, methoxybenzone, benzylpyridin, chloranil Glufosinate, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methylsulfuron, Cambendichlor, Cyprodinil, Thiocyanamide, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Fenpyrimidine, Oxamethasone, isoxadiazine, dichloropropene, fluazifop-butyl, DOW fluazifop-butyl, UBH-509, D489, LS82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

In one embodiment, the active substance (the additional herbicide in (iii) above) is selected from one or more of the following compounds:

(1) VLCFA inhibitors: acetochlor (CAS No.: 34256-82-1), S-isopropylamine (CAS No.: 87392-12-9), pretilachlor (CAS No.: 51218-49-6), butachlor (CAS No.: 23184-66-9), mefenacet (CAS No.: 73250-68-7), cypermethrin (CAS No.: 64249-01-0), pyraclostrobin (CAS No.: 447399-55-5), flufenacet (CAS No.: 142459-58-3), tetrazomethanil (CAS No.: 158237-07-1), and propamide (CAS: 15299-99-7);

(2) Microtubule assembly inhibitors: pendimethalin (CAS No.: 40487-42-1), butalin (CAS No.: 33629-47-9), trifluralin (CAS: 1582-09-8);

(3) PSII inhibitors: metribuzin (CAS No.: 21087-64-9), promethazine (CAS No.: 7287-19-6), atrazine (CAS No.: 1912-24-9), terbuthylazine (CAS No.: 5915-41-3), isoproturon (CAS No.: 34123-59-6), chlorotoluron (CAS No.: 15545-48-9);

(4) PPO inhibitors: fluazifop-butyl (CAS No.: 103361-09-7), (CAS No.: 2759011-88-4), oxadiazon (CAS No.: 19666-30-9), oxadiazon propargyl (CAS No.: 39807-15-3), sulfentrazone (CAS No.: 122836-35-5), bispyribac (CAS No.: 158353-15-2), cyclopentadione (CAS No.: 110956-75-7), saflufenacil (CAS No.: 372137-35-4), trifluoxetine (CAS No.: 1258836-72-4), saflufenacil (CAS No.: 1949837-17-5), epyrifenacil (CAS No.: 353292-31-6), fluazifop-butyl (CAS No.: 1220411-29-9);

(5) HPPD inhibitors: isoxathiapiprolin (CAS No.: 141112-29-0), fenpyraclostrobin (CAS No.: 1992017-55-6), (CAS No.: 2421252-30-2), furansulfuron (CAS No.: 473278-76-1), bicyclonimide (CAS No.: 156963-66-5), bispyribac-imide (CAS: 1622908-18-2);

(6) DOXP inhibitors: (CAS No.: 2766607-82-1), clomazone (CAS No.: 81777-95-9);

(7) Synthetic hormones: (CAS No.: 2445983-82-2), clopyralid (CAS: 1702-17-6), dicamba (CAS: 1918-00-9), haloxicam-butyl (CAS: 943831-98-9), (CAS No.: 2445980-81-2), 2,4-D choline (CAS No.: 1048373-72-3),

(8) ALS inhibitors: benzylsulfuron-methyl (CAS No. 83055-99-6), pyrazosulfuron-methyl (CAS No. 93697-74-6), thifensulfuron-methyl (CAS No. 79277-27-3), pyrazosulfuron-methyl (CAS No. 868680-84-6), promethazinesulfuron-methyl (CAS No. 570415-88-2), thiocarbazone-sulfuron-methyl (CAS No. 317815-83-1), fluazifop-sodium (CAS No. 874195-61-6), fluazifop-sodium (CAS No. 221205-90-9);

(9) FAT inhibitors: Cyclohexanil (CAS No.: 87818-31-3), oxazithromycin (CAS No.: 153197-14-9);

(10) Lipid synthesis inhibitors: benzylcarb (CAS No.: 52888-80-9);

(11) DHODH inhibitor: tetrafluthrin (CAS No.: 2053901-33-8);

(12) EPSPS inhibitor: glyphosate (CAS: 1071-83-6);

(13) GS inhibitor: glufosinate (CAS: 77182-82-2);

(14) PSI inhibitors: paraquat (CAS: 1910-42-5), diquat (CAS: 6385-62-2).

In another specific embodiment, the weight ratio of the active ingredient (i) to the additional herbicide in (iii) in the composition is 1:100-100:1, 1:80-80:1, 1:50-50:1, 1:30-30:1, 1:20-20:1, 1:10-10:1, 1:5-1:1 or 1:1-5:1.

When used, the commercially available preparations are diluted, if necessary, in the usual manner, for example with water in the case of wettable powders, emulsifiable concentrates, suspensions and granules suspended in water. Powders, granules for soil application or solutions for broadcasting and spraying generally do not require further dilution with inert substances before use. The required amount of the compound of formula I varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It can vary widely, for example between 0.001 and 1.0 kg a.i./ha, or more of active substance, but preferably between 0.005 and 750 g a.i./ha, in particular between 0.005 and 250 g a.i./ha.

DETAILED DESCRIPTION

The following examples are used to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights required to be protected by the present invention is described by the claims.

In view of the economic efficiency and diversity of the compounds, we preferably synthesized some compounds, and among the many synthesized compounds, some are selected and listed in the following Table 1. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustrating the present invention, but not for limiting the present invention. For those skilled in the art, this should not be understood as the scope of the above subject matter of the present invention is limited to the following compounds.

Table 1 Compound structures and ¹ H NMR

Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be purchased from the market or can be prepared by methods known in the literature or as shown in the detailed description. It will be appreciated by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described below, it can be easily replaced with other similar raw materials and conditions, and these modifications or variations of the preparation method of the present invention such as various isomers of the compound are included within the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, etc.

The method examples provided below are used to promote further understanding of the preparation method of the present invention. The specific substances, types and conditions used are determined to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds shown in the following table can be purchased commercially or can be easily prepared by a person of ordinary skill in the art.

Examples of representative compounds are as follows. The synthesis methods of other compounds are similar and will not be described in detail here.

1. Synthesis of Compound 2

(1) In a 100 ml single-mouth bottle, compound 2-1 (0.5 g, 2.73 mmol, 1 eq) was dissolved in 20 ml DMF, cesium carbonate (1.42 g, 4.37 mmol, 1.6 eq) and compound 2-2 (0.56 g, 4.10 mmol, 1.5 eq) were added, _N2 was replaced, cuprous iodide (52.03 mg, 0.27 mmol, 0.1 eq) was added, the temperature was slowly raised to 120°C, the reaction was allowed to proceed for 12 h, the reaction was monitored until the starting material disappeared, the reaction solution was naturally cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate three times, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, separated and purified by silica gel column, and the fraction was spin-dried to obtain 0.42 g of 2-3 (yield 64%).

(2) 2-3 (0.42 g, 1.76 mmol, 1 eq) was dissolved in 20 ml of trifluoroacetic acid and 30% hydrogen peroxide (0.59 g, 5.27mmol, 3eq), heated to 100°C, reacted for 12h, and monitored the reaction until the starting material disappeared. The reaction solution was concentrated, the residue was extracted with ethyl acetate three times with water, and washed with saturated brine three times. Drying with anhydrous sodium sulfate, mixing the sample and separating and purifying with a silica gel column, the fraction was spin-dried to obtain 0.31g of 2-4 (yield 68%).

(3) Dissolve 2-4 (0.31 g, 1.21 mmol, 1 eq) in 10 ml of phosphorus oxychloride, heat to 80°C, react for 12 h, and monitor the reaction until the starting material disappears. Concentrate the reaction solution, add water to the residue, extract it three times with ethyl acetate, and wash it three times with saturated brine. Dry it with anhydrous sodium sulfate, purify it with a silica gel column, and spin dry the fraction to obtain 0.2 g of 2-5 (yield 60%).

(4) 2-5 (0.1 g, 0.36 mmol, 1 eq) was dissolved in 5 ml of DMF, potassium carbonate (0.1 g, 0.72 mmol, 2 eq) was added, and m-trifluoromethylphenol (0.065 g, 0.40 mmol, 1.1 eq) was added, and the temperature was raised to 120°C. The reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was cooled to room temperature naturally, and water was added to extract with ethyl acetate three times, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, and the mixture was separated and purified by a silica gel column. The fraction was dried by spin drying to obtain 0.053 g of compound 2 (yield 36%).

2. Synthesis of Compound 3

(1) In a 100 ml single-mouth bottle, compound 3-1 (0.5 g, 2.66 mmol, 1 eq) was dissolved in 20 ml DMF, cesium carbonate (1.39 g, 4.25 mmol, 1.6 eq) and compound 2-2 (0.55 g, 3.99 mmol, 1.5 eq) were added, _N2 was replaced, cuprous iodide (50.65 mg, 0.27 mmol, 0.1 eq) was added, the temperature was slowly raised to 120°C, the reaction was allowed to proceed for 12 h, the reaction was monitored until the starting material disappeared, the reaction solution was naturally cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate three times, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, separated and purified by silica gel column, and the fraction was spin-dried to obtain 0.31 g of compound 3-2 (yield 47%).

(2) Compound 3-2 (0.31 g, 1.27 mmol, 1 eq) was dissolved in 20 ml of trifluoroacetic acid and 30% dichloromethane was added. Hydrogenated water (0.43 g, 3.81 mmol, 3 eq), heated to 100 ° C, reacted for 12 h, and monitored the reaction until the starting material disappeared. The reaction solution was concentrated, and the residue was extracted with ethyl acetate three times with water, and washed with saturated brine three times. Drying with anhydrous sodium sulfate, mixing the sample and separating and purifying with a silica gel column, the fraction was spin-dried to obtain 0.2 g of 3-3 (yield 60%).

(3) 3-3 (0.2 g, 0.77 mmol, 1 eq) was dissolved in 10 ml of phosphorus oxychloride, heated to 80°C, reacted for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, and the residue was extracted with ethyl acetate three times with water and washed with saturated brine three times. Drying was performed over anhydrous sodium sulfate, and the sample was purified by silica gel column. The fraction was dried by spin drying to obtain 0.15 g of 3-4 (yield 71%).

(4) 3-4 (0.1 g, 0.36 mmol, 1 eq) was dissolved in 5 ml of DMF, potassium carbonate (0.1 g, 0.72 mmol, 2 eq) was added, and m-trifluoromethylphenol (0.064 g, 0.39 mmol, 1.1 eq) was added, and the temperature was raised to 120°C. The reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was cooled to room temperature naturally, and water was added to extract with ethyl acetate three times, and washed with saturated brine three times. The product was dried over anhydrous sodium sulfate, and the sample was purified by silica gel column. The fraction was dried by spin drying to obtain 0.045 g of compound 3 (yield 31%).

3. Synthesis of Compound 8

(1) In a 50 ml single-mouth bottle, 8-1 (1.11 g, 10 mmol, 1 eq) was dissolved in 20 ml DMF, potassium carbonate (2.76 g, 20 mmol, 2 eq) and 2-2 (1.38 g, 10 mmol, 1 eq) were added, the temperature was slowly raised to 100°C, the reaction was allowed to proceed for 12 h, the reaction was monitored until the starting material disappeared, the reaction solution was naturally cooled to room temperature, water was added, the solution was extracted with ethyl acetate three times, and the solution was washed with saturated brine three times. The solution was dried over anhydrous sodium sulfate, purified by silica gel column, and the fraction was dried by spin drying to obtain 1.869 g of 8-2 (yield 82.1%).

(2) 8-2 (0.6 g, 2.6 mmol, 1 eq) was dissolved in 10 ml of trifluoroacetic acid, 30% hydrogen peroxide (0.9 g, 7.8 mmol, 3 eq) was added, the temperature was raised to 100°C, the reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, and the residue The product was added with water and extracted with ethyl acetate three times, washed with saturated brine three times, dried over anhydrous sodium sulfate, separated and purified by silica gel column, and the fraction was dried by spin drying to obtain 0.45 g of 8-3 (yield 70.1%).

(3) 8-3 (0.45 g, 1.84 mmol, 1 eq) was dissolved in 10 ml of phosphorus oxychloride, heated to 100°C, reacted for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, and the residue was extracted with ethyl acetate three times with water and washed with saturated brine three times. Drying was performed over anhydrous sodium sulfate, and the sample was purified by silica gel column. The fraction was dried by spin drying to obtain 0.32 g of 8-4 (yield 67%).

(4) 8-4 (0.2 g, 0.76 mmol, 1 eq) was dissolved in 10 ml of DMF, potassium carbonate (0.21 g, 1.52 mmol, 2 eq) was added, and m-trifluoromethylphenol (0.13 g, 0.76 mmol, 1 eq) was added, the temperature was raised to 100°C, the reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was cooled to room temperature naturally, water was added, and the mixture was extracted with ethyl acetate three times, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, the mixture was separated and purified by a silica gel column, and the fraction was dried by spin drying to obtain 0.14 g of compound 8 (yield 47.5%).

4. Synthesis of Compound 15

(1) Compound 15-1 (1.0 g, 5.35 mmol, 1 eq), 2-bromo-5-methylpyridine (0.46 g, 2.67 mmol, 0.5 eq) and cesium carbonate (3.23 g, 22.54 mmol, 2 eq) were added to a 100 ml flask, 20 ml DMF was added to dissolve, _N2 was replaced, cuprous iodide (101.81 mg, 0.53 mmol, 0.1 eq) was added, the temperature was raised to 120 degrees Celsius, stirred for 12 hours, and after monitoring the reaction completion, water was added and extracted with ethyl acetate three times, and washed with saturated brine three times. Drying with anhydrous sodium sulfate, the sample was separated and purified by silica gel column, and the fraction was spin-dried to obtain 0.4 g of 15-2 (yield 27%).

(2) 15-2 (0.4 g, 1.44 mmol, 1 eq) was dissolved in 20 ml of trifluoroacetic acid, 30% hydrogen peroxide (0.49 g, 4.31 mmol, 3 eq) was added, the temperature was raised to 100°C, the reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, the residue was extracted with ethyl acetate three times with water, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, the sample was separated and purified by silica gel column, and the fraction was dried by spin drying to obtain 0.33 g of 15-3 (yield 78%).

(3) 15-3 (0.1 g, 0.34 mmol, 1 eq) was dissolved in 10 ml of phosphorus oxychloride, heated to 80°C, reacted for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, and the residue was extracted with ethyl acetate three times with water and washed with saturated brine three times. Drying was performed over anhydrous sodium sulfate, and the sample was separated and purified by silica gel column. The fraction was dried by spin drying to obtain 0.08 g of 15-4 (yield 75%).

(4) 15-4 (0.08 g, 0.26 mmol, 1 eq) was dissolved in 5 ml of DMF, potassium carbonate (0.07 g, 0.51 mmol, 2 eq) was added, 15-5 (0.05 g, 0.28 mmol, 1.1 eq) was added, the temperature was raised to 120°C, the reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was cooled to room temperature naturally, water was added, and the mixture was extracted with ethyl acetate three times, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, the mixture was purified by silica gel column, and the fraction was dried by spin drying to obtain 0.051 g of compound 15 (yield 45%).

5. Synthesis of Compound 16

(1) Take a 250 ml single-mouth bottle, dissolve 16-1 (3.0 g, 13.45 mmol, 1 eq) in 50 ml DMF, add potassium carbonate (3.72 g, 26.91 mmol, 2 eq), 2-2 (1.84 g, 13.45 mmol, 1 eq), slowly raise the temperature to 100 ° C, react for 12 h, monitor the reaction until the starting material disappears, cool the reaction solution to room temperature naturally, add water and extract with ethyl acetate three times, wash three times with saturated brine. Dry with anhydrous sodium sulfate, purify with silica gel column, and spin dry the fraction to obtain 16-2 of 3.8 g (yield 83%).

(2) 16-2 (1 g, 2.94 mmol, 1 eq) was dissolved in 20 ml of 1,4-dioxane and 2 ml of water, and potassium ethylene trifluoroborate (0.39 g, 2.94 mmol, 1 eq) was added, and cesium fluoride (0.89 g, 5.88 mmol, 2 eq) was added, and _N2 was replaced. 1,1'-bis(diphenylphosphino)ferrocene dichloropalladium(II) dichloromethane complex (21 mg, 0.029 mmol, 0.01 eq) was added, and _N2 was replaced 3 times. The temperature was raised to 100°C, and the reaction was reacted for 12 h. The reaction was monitored until the starting material disappeared. After concentration, water was added, and the product was extracted with ethyl acetate three times, and washed with saturated brine three times. Drying was performed over anhydrous sodium sulfate, and purification was performed over a silica gel column. The fraction was spin-dried to obtain 0.6 g of 16-3 (yield 86%).

(3) 16-3 (0.6 g, 2.5 mmol, 1 eq) was dissolved in 20 ml of methanol, palladium carbon (catalytic amount) was added, _H2 was replaced 3 times, and stirred at room temperature for 12 h. The reaction was monitored until the starting material disappeared. The reaction solution was passed through celite and concentrated to obtain 0.57 g of crude product 16-4.

(4) 16-4 (0.57 g, 2.35 mmol, 1 eq) was dissolved in 10 ml of trifluoroacetic acid, 30% hydrogen peroxide (0.8 g, 7.06 mmol, 3 eq) was added, the temperature was raised to 100°C, the reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, the residue was extracted with ethyl acetate three times with water, and washed with saturated brine three times. Drying was performed over anhydrous sodium sulfate, the sample was mixed and purified by silica gel column, and the fraction was dried by spin drying to obtain 0.45 g of 16-5 (yield 74%).

(5) 16-5 (0.45 g, 1.74 mmol, 1 eq) was dissolved in 10 ml of phosphorus oxychloride, heated to 100°C, reacted for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was concentrated, and the residue was extracted with ethyl acetate three times with water and washed with saturated brine three times. Drying was performed over anhydrous sodium sulfate, and the sample was purified by silica gel column. The fraction was dried by spin drying to obtain 0.32 g of 16-6 (yield 66%).

(6) 16-6 (0.1 g, 0.36 mmol, 1 eq) was dissolved in 5 ml of DMF, potassium carbonate (0.1 g, 0.72 mmol, 2 eq) was added, and m-trifluoromethylphenol (0.06 g, 0.36 mmol, 1 eq) was added, the temperature was raised to 100°C, the reaction was allowed to proceed for 12 h, and the reaction was monitored until the starting material disappeared. The reaction solution was cooled to room temperature naturally, water was added, and the mixture was extracted with ethyl acetate three times, and washed with saturated brine three times. The mixture was dried over anhydrous sodium sulfate, the mixture was purified by silica gel column, and the fraction was dried by spin drying to obtain 0.062 g of compound 16 (yield 42%).

6. Synthesis of Compound 18

(1) 18-1 (1.0 g, 7.51 mmol), 2-fluoro-5-bromopyridine (1.32 g, 7.51 mmol) and potassium carbonate (3.23 g, 22.54 mmol) were added to a 100 ml flask, 20 ml of DMF was added to dissolve, and stirred at 120 degrees Celsius for 10 hours. After the intermediate control reaction was completed, water was added for washing and EA was added for extraction (3 times with appropriate amount of EA). The EA phase was then washed with an appropriate amount of saturated salt. The product was washed with water twice and dried by spin drying to obtain a white solid 18-2 (800 mg, 2.77 mmol).

(2) 18-2 (800 mg, 2.77 mmol), potassium vinyl fluoroborate (0.44 g, 3.32 mmol) and potassium carbonate (1.19 g, 8.3 mmol) were added to a clean flask, and then 1,4-dioxane 20 ml and water 2 ml were added. The flask was evacuated 2-3 times under nitrogen protection. After the evacuation was completed, Pd(dppf)Cl ₂ dichloromethane complex (113.0 mg, 138.37 umol) was added, and the flask was evacuated again. The temperature was raised to 85°C overnight. After the intermediate control reaction was completed, the solvent was distilled under reduced pressure to dryness, washed with water, extracted with EA 3 times, and then the EA phase was washed with saturated brine twice. Anhydrous sodium sulfate was added to the EA phase for drying, and silica gel was added to mix the sample. 18-3 (530 mg, 2.24 mmol) was obtained by column normal phase purification.

(3) 18-3 (530 mg, 2.24 mmol) was dissolved in 20 ml of methanol, followed by the addition of 10% palladium carbon (100 mg), and the mixture was replaced with a nitrogen balloon three times. The mixture was stirred at room temperature overnight. After the intermediate control reaction was completed, the palladium carbon was filtered off with celite and the mixture was dried to obtain a light yellow solid 18-4 (500 mg, 2.10 mmol).

(4) 18-4 (500 mg, 2.10 mmol) was added to a clean flask, and 8 ml of trifluoroacetic acid was added to dissolve it. Hydrogen peroxide (713.85 mg, 20.99 mmol) was added dropwise at room temperature. The mixture was stirred at 100 °C for 10 hours. After the intermediate control reaction was completed, water was added for washing and EA was added for extraction (3 times with appropriate amount of EA). The EA phase was then washed twice with appropriate amount of saturated brine, and purified by normal phase column to obtain a white solid 18-5 (380 mg, 1.49 mmol).

(5) 18-5 (380 mg, 1.49 mmol) was added to a 50 ml flask, and 8 ml of POCl ₃ was added to dissolve it. The mixture was stirred at 80 °C for 10 h. After the intermediate control reaction was completed, water was slowly added to quench the mixture, and then EA was added for extraction (3 times with an appropriate amount of EA). The EA phase was then washed twice with an appropriate amount of saturated brine and dried to obtain a white solid 18-6 (120.0 mg, 440.7 umol).

(6) 18-6 (120.0 mg, 440.7 umol), m-trifluoromethylphenol (85.61 mg, 528.1 umol) and potassium carbonate (189.11 mg, 1.32 mmol) were added to a clean flask, and 8 ml of DMF was added to dissolve. The mixture was stirred at 100 °C for 10 hours. After the intermediate control reaction was completed, water was added to wash the mixture and EA was added to extract the mixture three times. The EA phase was then washed twice with saturated brine, concentrated, and purified on a silica gel column to obtain a white solid compound 18 (50.0 mg, 125.5 umol).

7. Synthesis of Compound 20

16-6 (150 mg, 0.543 mmol) was dissolved in 5 ml of DMF, and 20-1 (170 mg, 1.2 eq, 0.651 mmol) and potassium carbonate (225 mg, 3.0 eq, 1.63 mmol) were added in sequence. The mixture was stirred at 120°C overnight. After the intermediate control reaction was completed, water and EA were added to the system for extraction. The organic phases were combined, washed three times with semi-saturated brine, dried and concentrated, and purified by normal phase to obtain compound 20 (67 mg, 0.133 mmol).

8. Synthesis of Compound 22

(1) 16-2 (5.3 g, 15.59 mmol, 1 eq) was dissolved in 20 ml toluene and 1 ml water, cyclopropylboric acid (1.61 g, 18.7 mmol, 1.2 eq) was added, potassium phosphate (11.58 g, 54.55 mmol, 3.5 eq) was added, _N2 was replaced, palladium acetate (129.73 mg, 0.779 mmol, 0.05 eq) and tricyclohexylphosphine (437.09 mg, 1.56 mmol, 0.1 eq) were added, _N2 was replaced 3 times, the temperature was raised to 80°C, the reaction was reacted for 12 h, and the reaction was monitored until the starting material disappeared. After being spin-dried, water was added and extracted with ethyl acetate three times, and washed with saturated brine three times. After drying with anhydrous sodium sulfate, it was purified by silica gel column, and the fraction was spin-dried to obtain 22-1 of 2.5 g (yield 64%).

(2) Dissolve 22-1 (1 g, 3.93 mmol, 1 eq) in 20 ml of trifluoroacetic acid, add 30% hydrogen peroxide (1.34 g, 11.8 mmol, 3 eq), heat to 100°C, react for 12 h, and monitor the reaction until the starting material disappears. The reaction solution is concentrated, the residue is extracted with ethyl acetate three times with water, and washed with saturated brine three times. After drying over anhydrous sodium sulfate, the sample is purified by silica gel column, and the fraction is dried by spin drying to obtain 0.6 g of 22-2 (yield 56%).

(3) Dissolve 22-2 (0.6 g, 2.22 mmol, 1 eq) in 10 ml of 1,2-dichloroethane, add phosphorus oxychloride (1.02 g, 6.66 mmol, 3 eq), heat to 60°C, react for 12 h, and monitor the reaction until the starting material disappears. The reaction solution is concentrated, the residue is extracted with ethyl acetate three times with water, and washed with saturated brine three times. After drying over anhydrous sodium sulfate, the sample is purified by silica gel column, and the fraction is dried by spin drying to obtain 0.5 g of 22-3 (yield 78%).

(4) 22-3 (0.1 g, 0.34 mmol, 1 eq) was dissolved in 5 ml of DMF, potassium carbonate (0.095 g, 0.72 mmol, 2 eq) was added, and m-trifluoromethylphenol (0.062 g, 0.38 mmol, 1.1 eq) was added, and the temperature was raised to 120°C, and the reaction was carried out for 12 h. The reaction was monitored until the starting material disappeared. The reaction solution was cooled to room temperature naturally, and water was added to extract with ethyl acetate three times, and washed with saturated brine three times. After drying with anhydrous sodium sulfate, the sample was purified by silica gel column, and the fraction was spin-dried to obtain 0.03 g of compound 22 (yield 21%).

Biological activity evaluation:

(1) Post-emergence test experiment:

The activity level standards for plant damage (i.e., growth control rate) are as follows:

Level 9: Complete death;

Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

Level 4: Growth control rate is greater than or equal to 30% and less than 50%;

Level 3: Growth control rate is greater than or equal to 20% and less than 30%;

Level 2: Growth control rate is greater than or equal to 10% and less than 20%;

Level 1: Growth control rate is less than 10%;

Level 0: No effect.

The above growth control rates are fresh weight control rates.

The monocotyledonous and dicotyledonous weed seeds (artemisia selengensis, shepherd's purse, ramie, cleaver, chickweed, wheat family, shepherd's purse, alopecuroides, Japanese alopecuroides, goosegrass, weed grass, hard grass, small fleabane, candle grass, Veronica, brome, knotweed, phalaenopsis, amaranth, quinoa, dayflower, sonchus, field bindweed, prickly lettuce, nightshade, amaranth, crabgrass, barnyard grass, foxtail grass, lycopodii, duckweed, wild arrowhead, firefly rush, cyperus, broken rice sedge, sedge, floating grass, purslane, Xanthium, morning glory, white wine grass, etc.) and the main crop seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame, castor, etc.) are placed in a plastic pot filled with soil, and then covered with 0.5-2 cm of soil to make it in a good soil. The test plants were grown in a good greenhouse environment, and the test plants were treated at the 2-4 leaf stage 2 weeks after sowing. The tested compounds of the present invention were dissolved in acetone, and then Tween 80 was added. 1.5 liters/hectare of methyl oleate emulsifiable concentrate was used as a synergist, and a certain concentration of solution was diluted with a certain amount of water and sprayed on the plants with a spray tower. After culturing in a greenhouse for 3 weeks after application, the experimental effects of weeds were counted. The dosage of the compound used was 250g ai/ha, and the results were repeated three times to take the average value. After testing, some compounds had outstanding effects on broadleaf weeds and grass weeds at this dosage.

(2) Pre-emergence test experiment:

Monocotyledonous and dicotyledonous weed seeds (artemisia selengensis, shepherd's purse, ramie, cleaver, chickweed, wheatgrass, shepherd's purse, alopecuroides, Japanese alopecuroides, goosegrass, weed grass, hard grass, small eiderdown, candle grass, Veronica, brome, knotweed, phalaenopsis, amaranth, quinoa, dayflower, sonchus, field bindweed, prickly lettuce, nightshade, amaranth, crabgrass, barnyard grass, setaria, chinensis, duckweed, wild arrowhead, firefly rush, cyperus, broken rice sedge, sedge dimorphotype, floating grass, purslane, Xanthium sibiricum, morning glory, white wine grass, etc.) and main crop seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame, castor, etc.) are placed in plastic pots filled with soil and then covered with 0.5-2 cm of soil. The tested compounds of the present invention were dissolved in acetone, Tween 80 was added, diluted with a certain amount of water to a solution of a certain concentration, and sprayed on the plants using a spray tower. After culturing in a greenhouse for 3 weeks after application, the experimental effects on weeds were counted. The dosage of the compound used was 60, 30, 15, and 7.5 g a.i./ha, repeated three times, and the average value was taken. The effects were evaluated at the above-mentioned activity standard level, and representative data are listed in Table 2.

Table 2 Pre-emergence test results

Note: N means no data, reference compound A:

At the same time, we found through testing the main weeds in wheat fields and rice fields that the compounds of the present invention generally have good weed control effects. In particular, we noticed that the compounds of the present invention have extremely high activity against broad-leaved weeds and sedges resistant to ALS inhibitors, such as firefly rush, sedge, sophia japonica, shepherd's purse, wheatgrass, cleaver, and cyperus rotundus, and have very good commercial value.

(3) Safety evaluation of transplanted rice and evaluation of paddy field weed control effectiveness:

After filling a 1/1,000,000 hectare tank with paddy field soil, sow seeds of barnyard grass, firefly rush, and wolf grass, and cover them lightly with soil. Then, keep the water storage depth at 3-4 cm, and when barnyard grass, firefly rush, and wolf grass reach 0.5 leaves, the water dilution of the wettable powder or suspension prepared by the usual formulation method of the compound of the present invention is evenly dripped with a pipette to achieve the prescribed amount of active ingredient.

In addition, paddy field soil was filled into 1/1,000,000 hectare pots and leveled to a water depth of 3-4 cm. Three-leaf rice (japonica rice) was transplanted at a transplanting depth of 3 cm the next day. Five days after transplantation, the compound of the present invention was treated in the same manner as above.

The growth status of barnyard grass, firefly rush and wolf grass on the 14th day after treatment with the agent was observed with the naked eye, and the growth status of rice on the 21st day after treatment with the agent. The effects were evaluated based on the above-mentioned activity standard levels. Many compounds showed excellent activity and selectivity.

Note: Seeds of barnyard grass, firefly rush and wolf grass were collected from Heilongjiang, China, and were tested to be resistant to conventional doses of pyrazosulfuron-methyl.

(4) Water seeding pre-seedling closure experiment:

Seeds of Leptochloa chinensis, Digitaria tangutica, Dalbergia vaginalis (sulfonylurea resistant strain, collected from Hunan, China), Cyperus rotundus (sulfonylurea resistant strain, collected from Jiangsu, China) and Huai rice were sown on the surface of the nutrient pots filled with soil, and the soil was covered until the seeds were completely covered. Then the prepared nutrient pots were placed in a cultivation box, and water was poured into the box to a suitable height to keep the soil in the nutrient pots moist. The tested compounds of the present invention were dissolved in a mixture of acetone and Tween-80, and then diluted with a certain amount of water to a solution of a certain concentration. The spray tower was used for application, and the experimental effects were statistically analyzed after being placed in a greenhouse seedbed for 15 days. The compound dosages used were 120, 60, 30, and 15 g a.i./ha, and the results were repeated three times to take the average value. The effects were evaluated at the above-mentioned activity standard level, and representative data are listed in Table 3.

Table 3 Results of closed experiment at seedling stage of direct seeding

(5) Activity test of the composition:

The required active ingredient B is purchased from a reagent company or a technical drug manufacturer or synthesized by conventional methods. The technical drugs all use acetone as a solvent and are diluted with a 0.1% emulsifier Tween-80 aqueous solution, and are diluted before use.

(A) Soil sealing treatment (S):

Weeds were cultivated in a controlled sunlight greenhouse at 20-30℃, natural light, and relative humidity of 57%-72%. The soil type was loam, with an organic matter content of 1.63%, pH=7.1, 84.3mg/kg of alkaline nitrogen, 38.5mg/kg of available phosphorus, and 82.1mg/kg of available potassium. The test soil was quantitatively filled to 3/4 of the pot, and then watered from the bottom of the pot to make the soil completely wet to saturation. The weed seeds for the test were germinated until white, and then evenly and quantitatively sown on the surface, covered with 0.5-1cm of soil according to the seed size, and kept ready for use 72 hours after sowing.

Each treatment was repeated 4 times, with 4 pots per treatment and 20 weed seeds sown in each pot.

Place the sown test materials evenly on a platform with an area of ^0.5m2 , and use a 3WP-2000 walking spray tower to spray the soil. The spray volume is 450 kg/hectare and the spray pressure is 0.3MPa. After all the liquid is sprayed, close the air valve. After 30 seconds, open the spray tower door and take out the nutrient pot. Then open the air valve, spray 50mL of clean water, and clean the spray pipe.

(B) Post-emergence stem and leaf spray treatment (F):

The weed Artemisia sophora was cultivated in potted plants, using 180×140 mm plastic nutrient pots placed in enamel trays filled with air-dried and sieved surface soil (4/5 of the 4/5 locations) collected from farmland. The soil moisture was initially controlled at 20%, and the seeds were selected to be full and uniform. Treat the weed seeds with 30% hydrogen peroxide for 10 minutes, germinate them in a 15-20℃ biochemical incubator (dark), evenly place the weed seeds that have just turned white on the soil surface, and then cover them with 0.5-1cm of soil according to the size of the seeds.

The culture was carried out in a controlled sunlight greenhouse at a temperature of 20-30°C, natural light, and a relative humidity of 57%-72%. The soil type was loam, with an organic matter content of 1.63%, pH = 7.1, alkaline nitrogen 84.3 mg/kg, available phosphorus 38.5 mg/kg, and available potassium 82.1 mg/kg.

Each treatment was repeated 4 times, with 3 pots in each treatment and 20 weed seeds sown in each pot.

The drug was used once in the experiment. When the weeds reached 1.5-2 leaves, thinning was performed to keep 10 weeds in each pot, 30 weeds were kept for each treatment, and then continued to be cultivated until they reached 10 leaves for treatment.

Place the cultivated test materials evenly on a platform with an area of ^0.5m2 , and use a 3WP-2000 walking spray tower to spray the stems and leaves. The spray volume is 450 kg/hectare and the spray pressure is 0.3MPa. After all the liquid is sprayed, close the air valve. After 30 seconds, open the spray tower door and take out the nutrient pot. Then open the air valve, spray 50mL of clean water, and clean the spray pipe. After the test materials are treated, move them into the greenhouse for routine cultivation.

(C) Data investigation and statistical analysis

The absolute number survey method was used. The whole seedlings of surviving weeds were cut off along the soil surface with a blade and the fresh weight of the weeds was weighed with an analytical balance. For dead weeds, the fresh weight was counted as zero.

The survey was conducted 21 days after treatment, for a total of 1 survey.

The theoretical fresh weight inhibition rate of each treatment combination was calculated by Gowing method (E0 = X + Y - X * Y / 100), and then compared with the measured inhibition rate (E) to evaluate the type of combined action of the two on weeds. When the E-E0 value is greater than 10%, it is a synergistic effect, less than -10% is an antagonistic effect, and between -10% and 10% is an additive effect. The best ratio is determined based on factors such as the actual prevention effect, the characteristics of the herbicide, and the balance of the formula. In the formula, X is the fresh weight inhibition rate when the dosage of active ingredient A is P; Y is the fresh weight inhibition rate when the dosage of active ingredient B is Q. The statistical results are shown in Table 4.

Table 4 Actual control effect and combined action evaluation of compound 16 mixed with weeds

At the same time, after many tests, it was found that many of the compounds and compositions of the present invention have good selectivity for gramineous lawns such as zoysia, bermudagrass, tall fescue, bluegrass, ryegrass, and seashore paspalum, and can control many key gramineous weeds as well as Broadleaf weeds. Tests on sugarcane, soybean, cotton, oil sunflower, potato, fruit trees, vegetables, etc. under different application methods also showed excellent selectivity and commercial value.

Claims (10)

A triazole compound, as shown in general formula I:
Wherein, M represents N or CH; X represents halogen, alkyl, haloalkyl, cyano or haloalkoxy; Y represents hydrogen or halogen; Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkylthio, alkylsulfoxide or alkylsulfonyl; A and B each independently represent hydrogen, halogen, cyano, alkyl, cycloalkyl, alkoxy, alkylthio, alkylthioalkyl or alkoxyalkyl, and A and B are not hydrogen at the same time. A triazole compound according to claim 1, characterized in that X represents halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, cyano or halogenated C1-C8 alkoxy; Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C2-C8 alkynyloxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkylthio, C1-C8 alkylsulfoxide or C1-C8 alkylsulfonyl; A and B independently represent hydrogen, halogen, cyano, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylthioC1-C8 alkyl or C1-C8 alkoxyC1-C8 alkyl. A triazole compound according to claim 1 or 2, characterized in that: X represents halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, cyano or halogenated C1-C6 alkoxy; Z represents hydrogen, halogen, cyano, or unsubstituted or halogen-substituted C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylsulfoxide or C1-C6 alkylsulfonyl; A and B independently represent hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylthioC1-C6 alkyl or C1-C6 alkoxyC1-C6 alkyl. A triazole compound according to any one of claims 1 to 3, characterized in that the compound is selected from any one in Table 1. A method for preparing a triazole compound according to any one of claims 1 to 4, characterized in that it comprises the following steps: The compound represented by the general formula II is subjected to a substitution reaction with the compound represented by the general formula III to obtain the compound represented by the general formula I. The chemical reaction equation is as follows:
wherein Hal represents halogen; the definitions of substituents A, B, M, X, Y and Z are as shown in any one of claims 1 to 4; preferably, the reaction is carried out in the presence of a base and a solvent. A herbicide composition, characterized in that it comprises (i) a herbicidally effective amount of at least one of the triazole compounds according to any one of claims 1 to 4, preferably, further comprises (ii) a formulation adjuvant, and more preferably, further comprises (iii) one or more herbicidally effective amounts of other herbicides and/or safeners. The herbicide composition according to claim 6, characterized in that the additional herbicide is selected from one or more of the following compounds: (1) VLCFA inhibitors: acetochlor, S-isopropylamine, pretilachlor, butachlor, mefenacet, thiamethoxam, sulfamethoxam, pyraclostrobin, flufenacet, tetrazomethoate, and propachlor; (2) Microtubule assembly inhibitors: pendimethalin, butalin, trifluralin; (3) PSII inhibitors: metribuzin, promethazine, atrazine, terbuthion, isoproturon, and chlorotoluron; (4) PPO inhibitors: fluazifop-butyl, Oxadiazine, oxadiazine-propargyl, sulfentrazone, bispyribac-butyl, cypermethrin, saflufenacil, trifluoxetine, saflufenacil, epyrifenacil, fluazifop-butyl; (5) HPPD inhibitors: isoxathiapiprolin, fenpyraclostrobin, Furansulfuron, bicyclon, and bispyribac; (6) DOXP inhibitors: Clomazone; (7) Synthetic hormones: Clopyralid, dicamba, halopyralid, 2,4-D Choline, (8) ALS inhibitors: benzylsulfuron-methyl, pyrazosulfuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, promethazinesulfuron-methyl, thiocarbamide, fluazifop-sodium, and fluazifop-sodium; (9) FAT inhibitors: Cyproconazole, oxazithromycin; (10) Lipid synthesis inhibitors: benzylcarb; (11) DHODH inhibitor: tetrafluthrin; (12) EPSPS inhibitors: glyphosate; (13) GS inhibitors: glufosinate; (14) PSI inhibitors: paraquat, diquat. The herbicide composition according to claim 6 or 7, characterized in that the weight ratio of the active ingredient (i) and the other herbicide in (iii) in the composition is 1:100-100:1, 1:80-80:1, 1:50-50:1, 1:30-30:1, 1:20-20:1, 1:10-10:1, 1:5-1:1 or 1:1-5:1. A method for controlling weeds, characterized in that it comprises applying a herbicidally effective amount of at least one of the triazole compounds according to any one of claims 1 to 4 or the herbicide composition according to any one of claims 6 to 8 on plants or weedy areas. Use of at least one of the triazole compounds according to any one of claims 1 to 4 or the herbicide composition according to any one of claims 6 to 8 for controlling weeds, preferably, the triazole compound is used to control weeds in useful crops, wherein the useful crops are genetically modified crops or crops treated with genome editing technology.