Oxadiazole phenylcarboxamide compound and preparation method therefor, herbicidal composition and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to an oxadiazole phenylcarboxamide compound and a preparation method therefor, a herbicidal composition and the use thereof. The oxadiazole phenylcarboxamide compound is represented by general formula I: Formula I wherein R represents hydrogen, halogen, etc.; X represents halogen, cyano, etc.; Y represents alkyl, haloalkyl, etc.; and Z represents cyano, alkyl, etc. The compound possesses good herbicidal activity and crop safety, and can exhibit better selectivity for crops.

Description

An oxadiazole phenylformamide compound, its preparation method, herbicidal composition and application Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to an oxadiazole phenylformamide compound, its preparation method, herbicidal composition, and application. Background Technology

[0002] Weed control is a crucial aspect of achieving efficient agriculture. Although there are various herbicides on the market, such as those disclosed in patent WO2017144402A1, which discloses a general formula compound… Used as a herbicide; patent WO2018202535 A and others disclose a general formula compound. As herbicides, these known compounds are used for herbicides. However, their weed-control performance on harmful plants and their selectivity for crops are not entirely satisfactory, necessitating continuous research and development by scientists to create new, efficient, safe, economical herbicides with different modes of action. Summary of the Invention

[0003] To address the aforementioned problems in the prior art, this invention provides an oxadiazole phenylformamide compound, its preparation method, herbicidal composition, and application. The compound exhibits excellent herbicidal activity and crop safety, and can establish better selectivity on crops.

[0004] The technical solution adopted in this invention is as follows:

[0005] An oxadiazole phenylformamide compound, as shown in general formula I:

[0006] Wherein, R represents hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, or alkoxy;

[0007] X represents halogen, cyano, alkyl, haloalkyl, cycloalkyl, hydroxy, alkoxy, mercapto, alkylthio, alkoxyalkyl, alkylthioalkyl, haloalkoxy, or haloalkylthio;

[0008] Y represents alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, or alkylthioalkyl;

[0009] Z represents cyano, alkyl, cycloalkyl, or alkoxy.

[0010] Preferably, R represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, or C1-C8 alkoxy.

[0011] X represents halogen, cyano, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, hydroxyl, C1-C8 alkoxy, mercapto, C1-C8 alkylthio, C1-C8 alkoxy-C1-C8 alkyl, C1-C8 alkylthio-C1-C8 alkyl, halogenated C1-C8 alkoxy, or halogenated C1-C8 alkylthio.

[0012] Y represents C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C1-C8 alkoxy-C1-C8 alkyl, or C1-C8 alkylthio-C1-C8 alkyl.

[0013] Z represents cyano, C1-C8 alkyl, C3-C8 cycloalkyl, or C1-C8 alkoxy.

[0014] More preferably, R represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, or C1-C6 alkoxy.

[0015] X represents halogen, cyano, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, hydroxyl, C1-C6 alkoxy, mercapto, C1-C6 alkylthio, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, halo-C1-C6 alkoxy, or halo-C1-C6 alkylthio.

[0016] Y represents C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C1-C6 alkoxy-C1-C6 alkyl, or C1-C6 alkylthio-C1-C6 alkyl.

[0017] Z represents cyano, C1-C6 alkyl, C3-C6 cycloalkyl, or C1-C6 alkoxy.

[0018] In the definitions of compounds shown in the above general formulas and in all the following structural formulas, the technical terms used, whether alone or in compound terms, represent the following substituents: alkyl groups having more than two carbon atoms can be straight-chain or branched. 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. Halogens are fluorine, chlorine, bromine, or iodine.

[0019] It should be noted that the sulfur atom (S*) bonded to Y in the general formula is a chiral center, which is either R or S configuration, with R configuration being preferred. Based on the content of stereoisomers having R and S configurations at this position, it has a stereochemical purity of 60-100%(R), preferably 70-100%(R), more preferably 80-100%(R), further preferably 90-100%(R), and even more preferably 95-100%(R). Herein, "stereochemical purity" refers to the percentage of the amount of the stereoisomer relative to the total amount of stereoisomers having a chiral center.

[0020] In this invention, the stereochemical configuration at the position of the sulfur atom (S*) bonded to Y in Formula I is determined to be predominant (R) according to the Cahn-Ingold-Prelog system. However, the subject matter of this invention also relates to all stereoisomers at other positions included in Formula I, and mixtures thereof. Such Formula I compounds contain, for example, one or more additional asymmetric carbon atoms or other double bonds not specifically described in Formula I. It should be understood that this invention includes pure isomers and mixtures thereof enriched to varying degrees with pure isomers, wherein the asymmetric carbon atom at the position marked * is in the R-configuration, or in the mixture, the compound or a compound with the same chemical structure has the R-configuration at the position marked *, or is present in a proportion predominantly of the compound having the R-configuration (at least 60% R-configuration), while other asymmetric carbon atoms may be present in a racemic form or may be resolved to varying degrees. Possible stereoisomers defined by a specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers, are included in Formula I, provided that the stereochemical configuration conditions at the position marked as * are met. They can be obtained from mixtures of stereoisomers by conventional methods or prepared by stereoselective reactions in conjunction with stereochemically pure initial substances.

[0021] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0022] Stereoisomers can be obtained from mixtures prepared by optical resolution. Similarly, stereoisomers can be selectively prepared using stereoselective reactions and optically active starting materials and / or auxiliaries. For optical resolution, conventional methods (see Textbooks of Stereochemistry) can generally be used, such as physical methods for resolving mixtures into diastereomers, including crystallization, chromatography, especially column chromatography and high-performance liquid chromatography, distillation under reduced pressure as needed, extraction, and other methods, typically employing chromatographic separation on a chiral solid phase, which can separate the residual mixture of enantiomers. Suitable for preparative or industrial scales are methods such as crystallizing diastereomers, which can be obtained from the compound using optically active acids, and, if acidic groups are present, using optically active bases as needed.

[0023] The present invention also provides a method for preparing the oxadiazole phenylformamide compound, comprising the following steps:

[0024] (1) Reacting the compound shown in general formula III with the compound shown in formula IV yields the compound shown in general formula II;

[0025] (2) React the compound shown in general formula II with a peroxide to prepare the compound shown in general formula I;

[0026] The reaction equation is as follows:

[0027] Preferably, the reaction (1) is carried out in the presence of a halogenating agent, a catalyst and a solvent; more preferably, the halogenating agent is SOCl2, the catalyst is 4-dimethylaminopyridine, the solvent is pyridine, and / or the reaction temperature is 0 to 50°C.

[0028] Alternatively, preferably, the reaction (1) is carried out in the presence of a solvent; more preferably, a condensing agent and / or a base are added during the reaction; even more preferably, the base is selected from at least one of inorganic or organic bases, such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KHCO3, KF, CsF, KI, NaI, K3PO4, K2HPO4, NaOH, KOH, NaH, KH, DMAP, pyrazole, triethylamine, DIEA, potassium trimethylsilane, AcOK, AcONa, MeONa, EtONa, or t-BuONa, etc.; the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane (DCM), or ethyl acetate; and / or the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT (1-hydroxybenzotriazole), DCC, HBTU, or HATU.

[0029] Preferably, the reaction (2) is carried out in the presence of a solvent; more preferably, the peroxide is... The solvent is selected from one or a combination of two of DCM and DCE, and / or the reaction temperature is 0 to 50°C.

[0030] The present invention also provides a herbicide composition comprising (i) a herbicidally effective amount of at least one of the oxadiazole phenylformamide compounds.

[0031] Optionally, the herbicide composition further includes (ii) one or more additional herbicides and / or safeners in herbicidal amounts.

[0032] Optionally, the herbicide composition further includes (iii) an agriculturally chemically acceptable formulation adjuvant.

[0033] The present invention also provides a method for controlling unwanted plants, comprising applying an effective amount of at least one of the oxadiazole phenylformamide compounds or the herbicide composition thereof to the plant or its location or to the soil or water body to control the emergence or growth of unwanted plants.

[0034] Preferably, the unwanted plants include herbicide-resistant or tolerant weed species.

[0035] The present invention also provides the use of at least one of the oxadiazole phenylformamide compounds or the herbicide composition thereof in controlling unwanted plants.

[0036] Preferably, the oxadiazole phenylformamide compound is used to control weeds in useful crops.

[0037] More preferably, the useful crop includes genetically modified crops or crops treated with genome editing technology, and the weeds include herbicide-resistant or tolerant weed species.

[0038] For many economically important monocotyledonous and dicotyledonous pests, the compounds of Formula I of this invention exhibit outstanding herbicidal activity. The active substances of this invention are also effective against perennial weeds that grow from rhizomes, stems, or other perennial organs and are difficult to control. In this regard, it is generally not important whether the substance is used before sowing, before germination, or after germination. Representative examples of monocotyledonous and dicotyledonous weed populations that can be controlled by the compounds of this invention are specifically mentioned, without limiting the specific species. Examples of weed species to which the active substances are effective include monocotyledons: annuals of *Oat*, *Rye*, *Grass*, *Alopecurus*, *Fararis*, *Barnyardgrass*, *Digitaria*, *Setaria*, and *Sedge*, and perennials of *Agrostis*, *Bermudagrass*, *Imperata*, and *Sorghum*, as well as perennials of *Sedge*.

[0039] Regarding dicotyledonous weed species, its effects can be extended to annual species such as *Galium aparine*, *Viola*, *Veronica*, *Sesamum indicum*, *Stellaria*, *Amaranthus*, *Sinapis*, *Ipomoea*, *Heliotropium*, *Chaenomeles*, and *Abutilon*, and perennial weeds such as *Convolvulus*, *Thistle*, *Rumex*, and *Artemisia*. The active substances of this invention effectively control harmful plants such as barnyard grass, *Sagittaria*, *Alisma*, *Eupatorium*, *Sedum*, and *Sedge* under the undetermined condition of rice sowing. If the compounds of this invention are applied to the soil surface before germination, weed seedlings can be completely prevented before they emerge, or growth can be stopped when the weeds develop cotyledons, eventually leading to their complete death after three to four weeks. The compounds of this invention exhibit particularly excellent activity against the following plants: *Apira*, *Sesamum indicum*, *Polygonum cuspidatum*, *Stellaria*, *Veronica ivy*, *Veronica arabiculata*, *Viola tricolor* and *Amaranthus*, *Galium aparine*, and *Kochia scoparia*.

[0040] While the compounds of this invention exhibit excellent herbicidal activity against both monocot and dicot weeds, they cause little to no damage to important economic crops such as peanuts, wheat, barley, rye, rice, corn, sugar beets, cotton, and soybeans. They are particularly compatible with cereal crops, such as wheat, barley, and corn, especially wheat. Therefore, the compounds of this invention are highly suitable for the selective control of unwanted plants in agricultural or ornamental crops.

[0041] Due to their herbicidal properties, these active substances can be used to control harmful plants in known or future genetically engineered plant cultivation. Transgenic plants typically possess superior traits, such as resistance to specific insecticides, particularly specific herbicides, and resistance to plant diseases or pathogenic microorganisms, such as specific insects or fungi, bacteria, or viruses. Other specific traits relate to conditions such as quantity, quality, storage stability, composition, and special components of the product. Thus, it is known that transgenic plant products have increased starch content or improved starch quality or different fatty acid compositions.

[0042] The compounds of Formula I of the present invention, or salts thereof, are preferably used in the cultivation of economically important genetically modified crops and ornamental plants, such as cereals, including wheat, barley, rye, oats, millet, rice, cassava, and corn, or in the cultivation of sugar 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 that are resistant or have been genetically engineered to be resistant to the toxic effects of the herbicides.

[0043] Traditional methods for breeding plants with improved morphology compared to known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits can be obtained using genetic engineering methods (see, for example, EP-0221044 A, EP-0131624 A). Several methods have been described, for example:

[0044] - To improve starch synthesis in plants, genetic engineering is used to modify crop plants (e.g., WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0045] - Transgenic crop plants resistant to specific herbicides, such as glufosinate-methyl (e.g., EP-0242236 A, EP-0242246 A), glyphosate-based herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993 A, US-5013659 A);

[0046] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924 A, EP-0193259 A).

[0047] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0048] Many molecular biotechnologies for preparing transgenic plants with improved traits are known (see, for example, Sambrook et al., 1989, Molecular Amplification, Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory, Cold Spring Harbor, New York; or Winnacker, “Gene and Cloning,” VCH Weinheim, 2nd ed., 1996; or Christou, “Trends in Plant Science,” 1 (1996) 423-431). To perform genetic engineering operations, nucleic acid molecules may be introduced into plasmids, resulting in mutations or sequence alterations through DNA sequence recombination. Using standard methods, such as exchanging substrates, removing portions of the sequence, or adding natural or synthetic sequences, can be employed. To link DNA fragments together, it is possible to attach conjugates or linkers to the fragments.

[0049] Plant cells containing reduced-activity gene products can be prepared by methods such as expressing at least one appropriate antisense RNA or sense RNA to achieve co-inhibition, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of the aforementioned gene product.

[0050] For this purpose, it is possible to use a DNA molecule containing the entire coding sequence of the gene product, including any possible flanking sequences, or a DNA molecule containing only a portion of the coding sequence, which must be long enough to achieve an antisense effect in the cell. Alternatively, a sequence that is highly homologous to but not identical to the coding sequence of the gene product can also be used.

[0051] When nucleic acid molecules are expressed in plants, the synthesized proteins can be localized in any desired plant cell compartment. However, to localize in a specific compartment, it is possible, for example, to link the coding region to a DNA sequence to ensure localization at a specific 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).

[0052] Using known techniques, transgenic plant cells can be recombined into the entire plant. Transgenic plants can be any desired plant variety, i.e., monocots and dicots. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (=natural) genes or gene sequences, or by expressing heterologous (=external) genes or gene sequences.

[0053] When the active substances of this invention are used on genetically modified crops, in addition to the inhibitory effect on harmful plants observed in other crops, they often exhibit specific effects on the corresponding genetically modified crops. For example, they can improve or expand the range of weed control, improve the application rate, preferably combine the herbicide resistance of the genetically modified crop with the performance of the herbicide, and affect the growth and yield of the genetically modified crop. Therefore, this invention also provides the use of the compounds as herbicides to control harmful plants in genetically modified crop plants.

[0054] Furthermore, the compounds of this invention can significantly regulate crop growth. By modulating plant metabolism, these compounds can be used to directionally control plant components and promote harvesting, for example, by causing plant drying and dwarfing. They are also suitable for regulating and inhibiting unwanted plant growth without disrupting crop growth. Inhibiting plant growth plays a crucial role in many monocot and dicot crops because it can reduce or completely prevent lodging.

[0055] The compounds of the present invention can be applied using common formulations, including wettable powders, concentrated emulsions, sprayable solutions, powders, or granules. Thus, the present invention also provides herbicide compositions comprising compounds of formula I. Compounds of formula I can be formulated in various ways depending on typical biological and / or chemical physical parameters. Examples of suitable formulation choices include: 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 solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions diluted with oil or water, solutions miscible with oil, powders (DP), capsule suspensions (CS), seeddressing compositions, granules for broadcasting and soil application, spray granules, coating granules and absorbent 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 described in the following literature, for example, Winnacker-Küchler, “Chemische Techonologie” [Chemical Processes], Vol. 7, C. Hauser Verlag Munich, 4th ed. 1986; Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, NY, 1973; K. Martens, “Spray Drying” Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

[0056] Necessary formulation adjuvants, such as inert substances, surfactants, solvents, and other additives, are also known and described in the following documents, for example, Watkins's "Handbook of Powder Diluents, Insecticides, and Carriers," 2nd ed., Darland, Caldwell, NJ; Hv01phen's "Introduction to Clay Colloid Chemistry," 2nd ed., J. Wiley and Sons, NY; C. Marsden's "Solvent Guide," 2nd ed., Interscience, NY 1963; McCutcheon's "Annual Report on Detergents and Emulsifiers," MC Publishing, Ridgewood, NJ; Sisley and Wood, "Encyclopedia of Surfactants," Chemical Publishing, NY 1964; of [Ethylene oxide adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie” [Chemical Processes], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986.

[0057] Wettable powders are uniformly dispersible in water and, in addition to the active ingredient, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxyalkylphenols, polyethoxy fatty alcohols, polyoxyethyl aliphatic amines, fatty alcohol polyethylene glycol ether sulfates, alkyl sulfonates, alkyl phenyl sulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyl taurate. To prepare wettable powders, the active ingredient of the herbicide is finely ground, for example using common equipment such as hammer mills, fan mills, and jet mills, while adjuvants are mixed in simultaneously or sequentially.

[0058] Concentrated emulsions are prepared by dissolving active ingredients in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene, or a mixture of higher-boiling aromatic compounds or hydrocarbons, and then adding one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used include, for example, calcium alkylaryl sulfonate of calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyethylene glycol esters, alkyl aromatic polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyethylene oxide sorbitan esters such as polyethylene oxide sorbitan fatty acid esters.

[0059] The active substance and finely ground solid material are ground to obtain a powder. The solid material may be talc, natural clay such as kaolin, bentonite, and pyrophyllite, or diatomaceous earth. A water- or oil-based suspension may be prepared, for example, by wet grinding using a commercially available glass bead mill, with or without the addition of a surfactant of the other formulation type mentioned above.

[0060] Emulsions, such as oil-in-water (EW) emulsions, can be prepared using an aqueous organic solvent, a stirrer, a colloid mill, and / or a static mixer, and if necessary, by adding a surfactant of another formulation type as described above.

[0061] Granules can be prepared by spraying the active material onto an adsorbent and granulating it using an inert material, or by concentrating the active material onto the surface of a carrier such as sand or kaolinite and granulating it using a binder such as polyvinyl alcohol, sodium polyacrylate, or mineral oil. Suitable active materials can be granulated using methods for preparing fertilizer granules, and fertilizers can be mixed in if necessary. Aqueous suspension granules can be prepared using conventional methods such as spray-drying, fluidized bed granulation, disc granulation, mixing using a high-speed mixer, and extrusion without solid inert material.

[0062] For methods of preparing granules using grinding discs, fluidized beds, extruders, and spraying, see the following processes, for example, “Spray Drying Handbook,” 3rd edition, 1979, G. Goodwin Ltd., London; J.E. Browning, “Agglomeration,” Chemicals and Engineering, 1967, 147ff; “Perry’s Chemical Engineer’s Handbook,” 5th edition, McGraw-Hill, New York, 1973, 8–57. For information on formulations of crop protection products, see, for example, G.K. C. Lingman, “Weed Control as a Science,” John Wiley and Sons, New York, 1961, 181–96; and JD. F. Greyer, SAEvans, “Weed Control Handbook,” 5th edition, Blackwell Scientific Rublications, Oxford University Press, 1968, 101–103.

[0063] Agricultural chemical formulations typically contain 0.1% to 99%, particularly 0.1% to 95%, of active ingredient Formula I by weight. The concentration of active ingredient in wettable powders is, for example, from about 10% to 99% by weight, with the usual formulation components constituting the remainder to 100% by weight. The concentration of active ingredient in concentrated emulsions can be from about 1% to 90% by weight, preferably 5% to 80%. Powder formulations contain 1% to 30% active ingredient by weight, typically preferably 5% to 20% by weight; however, sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight. The content of active ingredient in aqueous suspension granules depends primarily on whether the active ingredient is liquid or solid, and on the adjuvants, fillers, etc., used during granulation. The content of active ingredient in aqueous suspension granules is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.

[0064] The formulation of the active substance may also include thickeners, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors, and pH and viscosity adjusters that are commonly used in all cases.

[0065] Based on these formulations, they may also be mixed with other insecticidal active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and / or plant growth regulators. The mixing method may be pre-mixed or bottled.

[0066] In compound formulations or tank-mix formulations, suitable active substances that can be mixed with the compounds of Formula I of the present invention are, for example, known substances in the *World Encyclopedia of New Pesticide Varieties*, China Agricultural Science and Technology Press, September 2010, and the literature cited herein. For example, the herbicidal active substances mentioned below can be mixed with Compound I (Note: the name of the compound is either its common name according to the International Organization for Standardization (ISO) or its chemical name, with a code where appropriate):

[0067] (1) HPPD (Hydroxyphenyl Pyruvate Dioxygenase) inhibitors: including but not limited to the following types

[0068] 1) Triketones, such as Sulcotrione (CAS NO: 99105-77-8); Mesotrione (CAS NO: 104206-82-8); Bicyclopyrone (CAS NO: 352010-68-5); Tembotrione (CAS NO: 335104-84-2); Tefuryltrione (CAS NO: 473278-76-1); Benzobicyclon (CAS NO: 156963-66-5);

[0069] 2) Diketonitriles, for example, 2-cyano-3-cyclopropyl-1-(2-methylsulfonyl-4-trifluoromethylphenyl)prop-1,3-dione (CAS NO: 143701-75-1); 2-cyano-3-cyclopropyl-1-(2-methylsulfonyl-3,4-dichlorophenyl)prop-1,3-dione (CAS NO: 212829-55-5); 2-cyano-1-[4-(methylsulfonyl)-2-trifluoromethylphenyl]-3-(1-methylcyclopropyl)prop-1,3-dione (CAS NO: 143659-52-3);

[0070] 3) Isoxazoles, such as isoxaflutole (CAS NO: 141112-29-0); isoxachlortole (CAS NO: 141112-06-3); and clomazone (CAS NO: 81777-89-1).

[0071] 4) Pyrazole compounds, such as toramezone (CAS NO: 210631-68-8); pyrasulfotole (CAS NO: 365400-11-9); pyrazoxyfen (CAS NO: 71561-11-0); pyrazolate (CAS NO: 58011-68-0); benzofenap (CAS NO: 82692-44-2); bispyrazolone (CAS NO: 1622908-18-2); tolpyralate (CAS NO: 1101132-67-5); flufenoxuron (CAS NO: 1992017-55-6); cycloflufenoxuron (CAS NO: 1855929-45-1); triazolesulfuron (CAS NO: 210631-68-8); pyrasulfotole (CAS NO: 365400-11-9); pyrazoxyfen (CAS NO: 71561-11-0); pyrazolate (CAS NO: 58011-68-0); benzofenap (CAS NO: 82692-44-2); pyrazolone (CAS NO: 1622908-18-2); tolpyralate (CAS NO: 1101132-67-5); flufenoxuron (CAS NO: 1992017-55-6); cycloflufenoxuron (CAS NO: 1855929-45-1); triazolesulfuron (CAS NO: 210631-68-8); pyrazolone ... NO: 1911613-97-2);

[0072] 5) Benzophenones;

[0073] 6) Other classes: lancotrione (CAS NO: 1486617-21-3); fenquinotrione (CAS NO: 1342891-70-6); fufengcao'an (CAS NO: 2421252-30-2);

[0074] And those mentioned in patent CN105264069A.

[0075] (2) EPSPS (Enolpyruvyl Shikimate Phosphate Synthase) inhibitors: such as sulphosate, glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium;

[0076] (3) PPO (Protoporphyrinogen Oxidase) inhibitors: These are divided into pyrimidinediones, diphenyl-ethers, phenylpyrazoles, N-phenylphthalimides, thiadiazoles, oxadiazoles, triazolinones, oxazolidinediones, and other herbicides with different chemical structures.

[0077] In one exemplary embodiment, pyrimidine dione herbicides include, but are not limited to, flufenoxuron (CAS NO: 134605-64-4), fenproxuron (CAS NO: 372137-35-4), bispyribac-methyl (CAS NO: 158755-95-4), tiafenacil (CAS NO: 1220411-29-9), and ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]ethyl acetate (CAS NO: 1220411-29-9). NO: 353292-31-6), 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidin-2,4-dione (CAS NO: 1304113-05-0), 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidin-2,4-dione (CAS NO: 212754-02-4), flupropacil (CAS NO: 120890-70-2), and isoxazoline-containing uracil derivatives (such as compounds) disclosed in CN105753853A. Uracil-pyridine disclosed in WO2017 / 202768 and uracil derivatives disclosed in WO2018 / 019842;

[0078] Diphenyl ether herbicides include, but are not limited to, flufenoxuron (CAS NO: 72178-02-0), ethoxyflufenoxuron (CAS NO: 42874-03-3), bensulfuron-methyl (CAS NO: 74070-46-5), flufenoxuron (CAS NO: 131086-42-5), quizalofop-p-ethyl (CAS NO: 77501-63-4), methoxyflufenoxuron (CAS NO: 32861-85-1), glufosinate (CAS NO: 1836-77-7), ethoxyflufenoxuron (CAS NO: 77501-90-7), acifluorfen or its sodium salt (CAS NO: 50594-66-6 or 62476-59-9), methoxyflufenoxuron (CAS NO: 42576-02-3), and chlorfluazuron (CAS NO: 72178-02-0). NO: 188634-90-4), fluoronitrofen (CAS NO: 13738-63-1), furyloxyfen (CAS NO: 80020-41-3), nitrofluorfen (CAS NO: 42874-01-1) and halosafen (CAS NO: 77227-69-1);

[0079] Phenylepiazole herbicides include, but are not limited to, imidacloprid (CAS NO: 129630-19-9) and fluazolate (CAS NO: 174514-07-9);

[0080] N-phenylimide herbicides include, but are not limited to, propyzamide (CAS NO: 103361-09-7), indole-3-propylate (CAS NO: 142891-20-1), flumipropyn (CAS NO: 84478-52-4), and flufenoxuron (CAS NO: 87546-18-7);

[0081] Thiadiazole herbicides include, but are not limited to, fluthiacet-methyl (CAS NO: 117337-19-6), fluthiacet-methyl (CAS NO: 149253-65-6), and thiadiazole-methyl (CAS NO: 123249-43-4);

[0082] Oxadiazole herbicides include, but are not limited to, propyzinoxadiazon (CAS NO: 39807-15-3) and oxadiazon (CAS NO: 19666-30-9);

[0083] Triazoline herbicides include, but are not limited to, carfentrazone (CAS NO: 128621-72-7), carfentrazone ethyl (CAS NO: 128639-02-1), sulfurtrazone (CAS NO: 122836-35-5), acetamiprid (CAS NO: 68049-83-2), and bencarbazone (CAS NO: 173980-17-1);

[0084] Oxazolidinone herbicides include, but are not limited to, cyclooxadiazon (CAS NO: 110956-75-7);

[0085] Other herbicides include, but are not limited to, bispyribac-sodium (CAS NO: 158353-15-2), flupyridaben (CAS NO: 188489-07-8), flupyrazosulfuron (CAS NO: 190314-43-3), trifludimoxazin (CAS NO: 1258836-72-4), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 915396-43-9), and N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide. H-pyrazole-1-carboxamide (CAS NO: 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thio-[1,3,5]triazinane-2,4-dione (CAS NO: 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thio-[1,3,5]triazinane-2,4-dione (CAS NO: 452099-05-7) NO: 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (CAS NO: 1300118-96-0), (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoic acid methyl ester (CAS NO: 948893-00-3), phenylpyridines disclosed in WO2016 / 120116, benzoxazinone derivatives disclosed in EP09163242.2, and carboxylic acid derivatives substituted imino aryl compounds disclosed in CN113105405A;

[0086] (4) ALS (Acetolactate Synthase) inhibitors include, but are not limited to, the following herbicides or mixtures thereof:

[0087] Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, and ethoxysulfuron. Ethoxysulfuron, Flazasulfuron, Flucetosulfuron, Flupyrsulfuron, Flupyrsulfuron-methyl-sodium, Foramsulfuron, Halosulfuron, Halosulfuron-methyl, Imazosulfuron, Iodosulfuron, Iodosulfuron-methyl-sodium methyl-sodium), iofensulfuron, iofensulfuron sodium salt, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primeisulfuron, primeisulfuron-methyl, promethazine sulfuron pyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfurosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuronTribenuron-methyl, trifloxysulfuron, Trifloxysulfuron-Na (trifloxysulfuron-sodium salt), triflusulfuron, triflusulfuron-methyl, and tritosulfuron;

[0088] Imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, and imazethapyr;

[0089] Triazolopyrimidine herbicides and sulfonyl anilines such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, floraulam, metosulam, penoxsulam, pyroxsulam, pyrimisulfan, and triafamone;

[0090] Pyrimidinylbenzoic acids such as bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac sodium salt, 1-methylethyl benzoate of 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoate (CAS NO: 420138-41-6), propyl benzoate of 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoate (CAS NO: 420138-40-5), and N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzylamine (CAS NO: 420138-40-5). NO: 420138-01-8);

[0091] Sulfonylaminocarbonyl-triazolinone herbicides include flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone, and thiencarbazone-methyl.

[0092] (5) ACCase (Acetyl CoA Carboxylas) inhibitors: such as fenthiaprop, alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, chlorpyrifos. diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl ), haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop-ethyl, quizalofop-tetrahydrofurfural (quizalofop-ethyl), quizalofop-tetrahydrofurfural (quizalofop-tetrahydrofurfural) quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, 4-(4'-chloro-4-cyclopropyl-2'-fluoro[1,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS) NO: 1312337-72-6); 4-(2',4'-dichloro-4-cyclopropyl[1,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS NO: 1312337-45-3);4-(4'-chloro-4-ethyl-2'-fluoro[1,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS NO: 1033757-93-5); 4-(2',4'-dichloro-4-ethyl[1,1'-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (CAS NO: 1312340-84-3); 5-(acetoxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS NO: 1033757-93-5); 5-(acetoxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS NO: 1033757-93-5); 5-(acetoxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one) NO: 1312337-48-6); 5-(acetoxy)-4-(2',4'-dichloro-4-cyclopropyl-[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5-(acetoxy)-4-(4'-chloro-4-ethyl-2'-fluoro[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS NO: 1312340-82-1); 5-(acetoxy)-4-(2',4'-dichloro-4-ethyl- ... NO: 1033760-55-2); 4-(4'-chloro-4-cyclopropyl-2'-fluoro[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl methyl carbonate (CAS NO: 1312337-51-1); 4-(2',4'-dichloro-4-cyclopropyl-[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl methyl carbonate; 4-(4'-chloro-4-ethyl-2'-fluoro[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl methyl carbonate (CAS NO: 1312337-51-1); 4-(2',4'-dichloro-4-cyclopropyl-[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl methyl carbonate (CAS NO: 1312337-51-1); 4-(2',4'-dichloro-4-cyclopropyl-[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl methyl carbonate) NO: 1312340-83-2); 4-(2',4'-dichloro-4-ethyl[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl methyl carbonate (CAS NO: 1033760-58-5);

[0093] (6) GS (Glutamine Synthetase) inhibitors: such as bialaphos / bilanafos, bialaphos-natrium, glufosinate-ammonium, glufosinate and glufosinate-P;

[0094] (7) PDS (Phytoene Desaturase) inhibitors: such as flurochloridone, flurtamone, beflubutamid, norflurazon, fluridone, diflufenican, Picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS NO: 180608-33-7);

[0095] (8) DHPS (Dihydropteroate Synthase) inhibitors: such as sulfadiazine (Asulam);

[0096] (9) DXPS (Deoxy-D-Xyulose Phosphate Synthase) inhibitors: such as Bixlozone and Clomazone;

[0097] (10) HST (Homogentisate Solanesyltransferase) inhibitors: such as Cyclopyrimorate;

[0098] (11) SPS (Solanesyl Diphosphate Synthase) inhibitors: such as aclonifen;

[0099] (12) Cellulose Synthesis Inhibitors: such as indaziflam, triaziflam, chlorthiamid, dichlobenil, isoxaben, flupoxam, 1-cyclohexyl-5-pentafluorophenoxy-1 4 -[1,2,4,6]thiatriazine-3-ylamine (CAS NO: 175899-01-1), and azazines disclosed in CN109688807A;

[0100] (13) VLCFAS (Very Long-Chain Fatty Acid Synthesis) inhibitors: including but not limited to the following types,

[0101] 1) Chloracetamides such as acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor, and thenylchlor;

[0102] 2) α-Oxyacetamides, such as flufenacet and mefenacet;

[0103] 3) α-Thioacetamides, such as anilofos and piperophos;

[0104] 4) Azoxystrom derivatives such as cafenstrole, fentrazamide, and ipfencarbazone;

[0105] 5) Benzofurans such as Benfuresate and Ethofumesate;

[0106] 6) Isooxazoline derivatives such as fenoxasulfone and pyroxasulfone;

[0107] 7) Ethylene oxides such as Indanofan and Tridiphane;

[0108] 8) Thiocarbamates such as Cycloate, Dimepiperate, S-ethyldipropylthiocarbamate (EPTC), Esprocarb, Molinate, Orbencarb, Prosulfocarb, Thiobencarb / Benthiocarb, Triallate, Vernolate, and isozoline compounds of formulas II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9, as well as other isozoline compounds mentioned in patents such as WO 2006 / 024820, WO 2006 / 037945, WO 2007 / 071900 and WO 2007 / 096576.

[0109] (14) Fatty acid thioesterase inhibitors: such as cyproheptadine, methiozolin;

[0110] (15) Inhibitors of serine threonine protein phosphatase: such as Endothall;

[0111] (16) Lycopene cyclase inhibitors: such as Amitrole.

[0112] (17) Microtubule assembly inhibitors: such as benefin / benfluralin, butralin, dithiopyr, thiazopyr, ethalfluralin, prodiamine, butamifos, oryzalin, pendimethalin, methyl chlorotitanate / DCPA, DMPA Trifluralin, Propyzamide / pronamide, Dinitramine (CAS NO: 29091-05-2);

[0113] (18) Auxin Mimics: such as 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-dichlorophenoxybutyric acid (2,4-DB), 3,4-dichlorophenoxybutyric acid (3,4-DB), 2,4-DEB (CAS NO: 94-83-7), 4-chlorophenoxyacetic acid (4-CPA), 4-CPP (CAS NO: 3307-39-9), cloprop (CAS NO: 101-10-0), clofop (CAS NO: 101-10-0), clofop (CAS NO: 101-10-0). NO: 26129-32-8), Clomeprop, Dichlorprop, MCPA, MCPB, Mecoprop, Aminopyralid, Clopyralid, Aminocyclopyrachlor, Florpyrauxifen, Halauxifen, Quinclorac, Benazolin-ethyl, Picloram, Chloramben, Quinmerac, Fluroxypyr, Triclopyr, Dicamba;

[0114] (19) D1 Serine 264 binders (and other non-histidine 215 binders): such as Ametryne, Atrazine, Cyanazine, Dimethametryn, Prometon, Prometryne, Propazine, Simazine, Terbuthylazine, Terbutryne, Chlorotoluron, Diuron, Fluometuron, Isoproturon, Linuron, Metobromuron, Methabenz thiazuron (CAS) NO: 18691-97-9), Monuron, Tebuthiuron, Hexazinone, Metamitron, Metribuzin, Bromacil, Lenacil, Terbacil, Chloridazon / pyrazon, Amicarbazone, Desmedipham, Phenmedipham, Chloranocryl / dicryl (CAS NO: 2164-09-2), Propanil, Chlorazine (CAS NO: 580-48-3), Cyprazine (CAS NO: 22936-86-3), Trietazine (CAS NO: 1912-26-1), Methoprotryne (CAS NO: 18691-97-9), NO: 841-06-5), Simetryn (a type of herbal medicine);

[0115] (20) D1 Histidine 215 binders: such as bromooxynil, iodobenzonitrile, pyridate, and bentazon.

[0116] (21) Auxin transport inhibitors: such as diflufenzopyr (CAS NO: 109293-97-2) and Naptalam;

[0117] (22) PS l Electron Diversion: such as Diquat, Paraquat;

[0118] (23) Inhibition of Microtubule Organization: such as Carbetamide (CAS NO: 16118-49-3), Barban (CAS NO: 101-27-9), Chlorpropham;

[0119] (24) Uncouplers: such as Dinoseb, 4,6-dinitro-o-cresol (DNOC);

[0120] (25) Others: such as Bensulide, Bromobutide, Cumyluron, Difenzoquat, Pyributicarb (CAS NO: 88678-67-5), Disodium methylarsenate (DSMA), Sodium monomethylarsenate (MSMA), Dymron / daimuron, Etobenzanid, Flamprop-m, Fosamine, Oxaziclomefone, Pelargonic acid, Diphenamid, Naproanilide, Napropamide, Napropamide-m, Benzofluor (CAS NO: 68672-17-3), Cambendichlor (CAS NO: 56141-00-5), Dipropalin (CAS NO: 1918-08-7), etnipromid (CAS NO: 1918-08-7), etc. NO: 76120-02-0), bromobonil (CAS NO: 25671-46-9), monisouron (CAS NO: 55807-46-0), bromofenoxim (CAS NO: 13181-17-4), clacyfos (CAS NO: 215655-76-8), chlorazifop (CAS NO: 60074-25-1), subalpen, brompyrazon (CAS NO: 304284-0), ethiozin, methiuron (CAS NO: 21540-35-2), metoxuron (CAS) NO: 19937-59-8), tetrafluron (27954-37-6), thidiazuron (CAS) NO: 51707-55-2), acrolein, flunaphthalene quizalofop-p-ethyl.

[0121] Generally, if a herbicidal compound, as described herein and usable in the context of this invention, is capable of forming geometric isomers, such as E / Z isomers, then both, pure isomers, and mixtures thereof may be used in compositions according to the invention. If a herbicidal compound, as described herein, has one or more chiral centers and is thus present as an enantiomer or diastereomer, then both, pure enantiomers, diastereomers, and mixtures thereof may be used in compositions according to the invention. If a herbicidal compound, as described herein, has ionizable functional groups, then it may also be used in the form of its agriculturally acceptable salts. Typically, salts of those cations and acid addition salts of those acids are suitable, whose cations and anions do not have adverse effects on the activity of the active compound, respectively. The preferred cations are alkali metal ions, preferably lithium, sodium, and potassium ions; alkaline earth metal ions, preferably calcium and magnesium ions; and transition metal ions, preferably manganese, copper, zinc, and iron ions, further preferably ammonium and substituted ammonium ions, wherein one to four hydrogen atoms are substituted by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl, or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2 - Hydroxyethylammonium (olamine salt), 2-(2-hydroxyethyl-1-oxy)ethyl-1-ylammonium (diethylene glycolamine salt), di(2-hydroxyethyl-1-yl)ammonium (diethylene glycolamine salt), tri(2-hydroxyethyl)ammonium (trinitroethanolamine salt), tri(2-hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N-trimethylethanolammonium (choline salt), in addition to phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium such as trimethylsulfonium, and sulfonium oxide ions, preferably tri(C1-C4-alkyl)sulfonium oxide ions, and finally, salts of polyamines such as N,N-bis-(3-aminopropyl)methylamine and diethylenetriamine. The main anions that can be used for acid addition salts are chloride, bromide, fluoride, iodide, hydrogen sulfate, methyl sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and anions of C1-C4-alkanoic acids, with formate, acetate, propionate, and butyrate being preferred.

[0122] Herbicidal compounds with carboxyl groups as described herein can be used in the form of acids, agriculturally suitable salts as mentioned above, or otherwise agriculturally acceptable derivatives, such as amides such as mono- and di-C1-C6-alkylamides or arylamides, and as esters such as allyl esters, propargyl esters, C1-C6-alkyl esters, etc. 10 -Alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters, and also as thioesters, for example as C1-C10 -Alkyl thioesters. Preferred mono- and di-C1-C6-alkylamides are methyl and dimethylamides. Preferred arylamides are, for example, N-anilide and 2-chloroanilide. Preferred alkyl esters are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl, or isooctyl (2-ethylhexyl) esters. Preferred C1-C4-alkoxy-C1-C4-alkyl esters are straight-chain or branched C1-C4-alkoxyethyl esters, such as 2-methoxyethyl ester, 2-ethoxyethyl ester, 2-butoxyethyl ester, 2-butoxypropyl ester, or 3-butoxypropyl ester. Straight-chain or branched C1-C 10 An example of an alkyl thioester is an ethyl thioester.

[0123] When used, commercially available formulations should be diluted in a common manner if necessary, such as with water for wettable powders, concentrated emulsions, suspensions, and granules suspended in water. Powders, granules for soil application, or solutions for broadcasting and spraying generally do not require further dilution with an inert substance before use. The required dosage of Formula I compound varies with external conditions, such as temperature, humidity, and the nature of the herbicide used. It can vary considerably, for example, from 0.001 to 1.0 kg ai / ha, or more active ingredient, but is preferably between 0.005 and 750 g ai / ha. Detailed Implementation

[0124] The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way. The scope of protection of this invention is defined by the claims.

[0125] Given the economic efficiency and diversity of the compounds, we preferentially synthesized a number of compounds, some of which are listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustration of the present invention and do not limit the invention. Those skilled in the art should not interpret this as limiting the scope of the above-mentioned subject matter of the invention to the following compounds.

[0126] Table 1. Compound structures and their properties 1 HNMR

[0127] Table A has the same structure as Table 1 above, except that the general formula I is replaced with the general formula I' which has a chiral center. Furthermore, in Table A, the entries under the "Serial Number" column heading are described sequentially as 1(R)-36(R). For example, 1(R) corresponds to the compound in Table 1 where the S position is in the R configuration.

[0128] 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 commercially available or prepared by methods known in the literature or as detailed in the description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific raw materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar raw materials and conditions. Such variations or modifications to the preparation methods of the present invention, such as various isomers of the compounds, are all included within the scope of the present invention. Furthermore, the preparation methods 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, protecting appropriate groups during the reaction process, etc.

[0129] The following examples are provided to further illustrate the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further explain the invention and are not intended to limit its reasonable scope. Examples of representative compounds are given below; the synthesis methods for other compounds are similar and will not be described in detail here.

[0130] 1. Synthesis of Compound 3

[0131] 3-1 (4 g, 25.6 mmol) was added to 1-octyl-3-methylimidazolium hexafluorophosphate (2 mL) and stirred at -78 °C. Under nitrogen protection, diethylaminosulfonium trifluoride (12.4 g, 76.9 mmol) was slowly added to the reaction system. The temperature was raised to 50 °C and the reaction was allowed to proceed for 12 h. After the reaction was completed under controlled conditions, the reaction solution was quenched with saturated sodium bicarbonate aqueous solution at 0 °C, extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 3-2 (600 mg, colorless liquid, yield 13.2%).

[0132] Dissolve 3-2 (630 mg, 3.5 mmol) and sodium hydroxide (148 mg, 3.7 mmol) in DMF (5 mL), and slowly add propanethiol (280 mg, 3.7 mmol) under ice bath conditions. React for 2 h. After the reaction is complete, wash with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, concentrate the filtrate under reduced pressure, and purify by silica gel column chromatography to obtain 3-3 (520 mg, colorless liquid, yield 62.8%).

[0133] At -78°C, 3-3 (500 mg, 2.1 mmol) was dissolved in tetrahydrofuran (10 mL). Under nitrogen protection, 2.5 M n-butyllithium (1 mL, 2.5 mmol) was added dropwise to the reaction solution, and the mixture was stirred for 30 min. After the starting material disappeared, dry ice was added to the reaction solution, and the mixture was allowed to rise to room temperature for 30 min. The reaction was then quenched with water. The organic phase was concentrated under reduced pressure, and the pH of the aqueous phase was adjusted to 1-2 with hydrochloric acid. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to give 3-4 (250 mg, light green oil, yield 42.1%).

[0134] 3-4 (250 mg, 0.9 mmol), 5-methyl-1,3,4-oxadiazol-2-amino (200 mg, 2.0 mmol), and 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphonate (HATU) (750 mg, 2.0 mmol) were dissolved in dichloromethane (5 mL), and 1-ethyl-3-(3-dimethylpropylamine)carbodiimide (EDCI) (380 mg, 2.0 mmol) was added. The reaction was carried out at room temperature for 12 h. After the reaction was completed, the mixture was washed with water, extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to give 3-5 (170 mg, white viscous compound, yield 52.3%).

[0135] Compound 3-5 (170 mg, 0.47 mmol) was dissolved in dichloromethane (5 mL), and m-chloroperoxybenzoic acid (60 mg, 0.35 mmol) was added. The reaction was carried out at room temperature for 30 min. After the reaction was completed, the reaction was quenched with sodium bisulfite aqueous solution, washed with water, extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to give compound 3 (80 mg, white viscous compound, yield 45.1%).

[0136] Bioactivity evaluation:

[0137] Post-emergence testing experiment:

[0138] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0139] Level 5: Growth control rate is above 85%;

[0140] Level 4: Growth control rate is greater than or equal to 60% and less than 85%;

[0141] Level 3: Growth control rate greater than or equal to 40% and less than 60%;

[0142] Level 2: Growth control rate greater than or equal to 20% and less than 40%;

[0143] Level 1: Growth control rate greater than or equal to 5% and less than 20%;

[0144] Grade 0: Growth control rate is less than 5%.

[0145] The above growth control rates are fresh weight control rates.

[0146] Seeds of monocotyledonous and dicotyledonous weeds (such as shepherd's purse, shepherd's purse, velvetleaf, cleavers, chickweed, wild oats, watercress, wild oats, Japanese wild oats, goosegrass, purslane, hard grass, candle grass, speedwell, wild oats, jointed goatgrass, wild oats, amaranth, lambsquarters, dayflower, sow thistle, field bindweed, sow thistle, black nightshade, iron amaranth, crabgrass, barnyard grass, green foxtail grass, golden foxtail grass, goosegrass, duckweed, arrowhead, firefly rush, nutgrass, sedge, sedge, purslane, burdock, purslane, cocklebur, morning glory, white wine grass, etc.) and the main crops Seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame, castor bean, etc.) were placed in plastic pots filled with soil, then covered with 0.5-2 cm of soil and allowed to grow in a good greenhouse environment. Two weeks after sowing, test plants were treated at the 2-4 leaf stage. The tested compound of this invention was dissolved in acetone, then Tween 80 was added, and methyl oleate emulsifiable concentrate at 1.5 L / ha was used as a synergist. The solution was diluted with water to a certain concentration and sprayed onto the plants using a spray tower. After three weeks of cultivation in the greenhouse following application, the experimental effect on weeds was statistically analyzed. The compound dosage used was 30, 60, and 240 g ai / ha, with three replicates, and the average value was taken. Representative data are listed in Table 2.

[0147] Table 2 Post-emergence weed test (60g ai / ha)

[0148] Note: N represents no data; reference compound A:

[0149] Pre-seeding test experiment:

[0150] Seeds of monocotyledonous and dicotyledonous weeds, as well as seeds of major crops (wheat, corn, rice, soybean, cotton, rapeseed, millet, and sorghum), were placed in plastic basins filled with soil and covered with 0.5-2 cm of soil. The tested compounds of this invention were dissolved in acetone, then Tween 80 was added, and the solution was diluted with water to a specific concentration. The solutions were sprayed immediately after sowing. After 4 weeks of cultivation in a greenhouse following application, the experimental results were observed. It was found that most of the herbicides of this invention were highly effective at a dosage of 250 g / ha, especially against barnyard grass, crabgrass, and velvetleaf, and many compounds showed good selectivity for corn, wheat, rice, soybeans, and rapeseed.

[0151] Through experiments, we found that the compounds described in this invention generally exhibit good weed control efficacy, especially against major grass weeds such as barnyard grass, crabgrass, and foxtail grass, which are prevalent in corn, rice, and wheat fields, as well as major broadleaf weeds such as velvetleaf, watercress, and beggar-ticks, demonstrating good commercial value. In particular, we noted extremely high activity against broadleaf weeds resistant to ALS inhibitors, such as watercress, shepherd's purse, shepherd's purse, cleavers, valerian, and chickweed.

[0152] Safety evaluation of transplanted rice and weed control efficacy evaluation in paddy fields:

[0153] After filling 1 / 1,000,000-hectare tanks with paddy field soil, sow seeds of barnyard grass, bulrush, wolfberry, duckweed, and goosegrass, and gently cover them with soil. Then, place the tanks in a greenhouse with water at a depth of 0.5-1 cm. The tubers of arrowhead are then planted the next day or two later. Maintain a water depth of 3-4 cm. When the barnyard grass, bulrush, wolfberry, duckweed, and goosegrass reach 0.5 leaves, and the arrowhead reaches the initial leaf stage, a water-diluted solution of the wettable powder or suspension of the compound of this invention, prepared according to conventional formulation methods, is evenly dripped using a pipette to achieve the specified effective ingredient dosage.

[0154] In addition, after filling the 1 / 1,000,000-hectare tank with paddy field soil, the soil is leveled to a water depth of 3-4 cm. The next day, 3-leaf stage rice (japonica / indica) is transplanted at a depth of 3 cm. The compound of the present invention is treated in the same way as described above on the 5th day after transplanting.

[0155] The growth status of barnyard grass, fireweed, wolfberry, goosegrass, arrowhead, and duckweed was observed with the naked eye on day 14 after treatment, and the growth status of rice was observed on day 21 after treatment. The herbicidal effect was evaluated using the above-mentioned activity standard level of 0-5. Many compounds showed excellent activity and selectivity.

[0156] Furthermore, numerous tests have revealed that the compounds and their compositions described in this invention exhibit excellent selectivity against many grassy lawns, including Zoysia japonica, Bermuda grass, tall fescue, Kentucky bluegrass, ryegrass, and seashore paspalum, effectively controlling many key grassy weeds as well as broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybeans, cotton, sunflowers, potatoes, fruit trees, and vegetables under different application methods also demonstrated excellent selectivity and commercial value.

Claims

1. An oxadiazole phenylformamide compound, as shown in general formula I: in, R represents hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, or alkoxy; X represents halogen, cyano, alkyl, haloalkyl, cycloalkyl, hydroxyl, alkoxy, mercapto, alkylthio, alkoxyalkyl, alkylthioalkyl, haloalkoxy, or haloalkylthio; Y represents alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, or alkylthioalkyl; Z represents cyano, alkyl, cycloalkyl, or alkoxy.

2. The oxadiazole phenylformamide compound according to claim 1, characterized in that, R represents hydrogen, halogen, C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, or C1-C8 alkoxy; X represents halogen, cyano, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, hydroxyl, C1-C8 alkoxy, mercapto, C1-C8 alkylthio, C1-C8 alkoxy-C1-C8 alkyl, C1-C8 alkylthio-C1-C8 alkyl, halogenated C1-C8 alkoxy, or halogenated C1-C8 alkylthio. Y represents C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C1-C8 alkoxy-C1-C8 alkyl, or C1-C8 alkylthio-C1-C8 alkyl. Z represents cyano, C1-C8 alkyl, C3-C8 cycloalkyl, or C1-C8 alkoxy.

3. The oxadiazole phenylformamide compound according to claim 1, characterized in that, R represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, or C1-C6 alkoxy. X represents halogen, cyano, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, hydroxyl, C1-C6 alkoxy, mercapto, C1-C6 alkylthio, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, halo-C1-C6 alkoxy, or halo-C1-C6 alkylthio. Y represents C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C1-C6 alkoxy-C1-C6 alkyl, or C1-C6 alkylthio-C1-C6 alkyl. Z represents cyano, C1-C6 alkyl, C3-C6 cycloalkyl, or C1-C6 alkoxy.

4. The oxadiazole phenylformamide compound according to any one of claims 1-3, characterized in that, The structure of the compound is The groups R, X, Y, and Z are defined as described in any one of claims 1-3.

5. The oxadiazole phenylformamide compound according to claim 1, characterized in that, The compounds are selected from any one of Table 1 and Table A.

6. A method for preparing an oxadiazole phenylformamide compound as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) Reacting the compound shown in general formula III with the compound shown in formula IV yields the compound shown in general formula II; (2) React the compound shown in general formula II with a peroxide to prepare the compound shown in general formula I; The reaction equation is as follows: Preferably, the reaction (1) is carried out in the presence of a halogenating agent, a catalyst and a solvent; more preferably, the halogenating agent is SOCl2, the catalyst is 4-dimethylaminopyridine, the solvent is pyridine, and / or the reaction temperature is 0 to 50°C. Alternatively, preferably, the reaction (1) is carried out in the presence of a solvent; more preferably, a condensing agent and / or a base is added during the reaction; even more preferably, the base is selected from at least one of inorganic or organic bases, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane or ethyl acetate, and / or the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU; Preferably, the reaction (2) is carried out in the presence of a solvent; more preferably, the peroxide is... The solvent is selected from one or a combination of two of DCM and DCE, and / or the reaction temperature is 0 to 50°C.

7. A herbicidal composition, characterized in that, It includes (i) at least one of the oxadiazole phenylformamide compounds according to any one of claims 1-5; optionally, it also includes (ii) one or more additional herbicides and / or safeners that are herbicidal in effective amounts.

8. The composition according to claim 7, characterized in that, It also includes (iii) agriculturally chemically acceptable formulation adjuvants.

9. A method for controlling unwanted plants, characterized in that, The method includes applying an effective amount of at least one of the oxadiazole phenylformamide compounds of any one of claims 1-5 or the herbicidal composition of any one of claims 7-8 to plants or their sites or to soil or water to prevent unwanted plant emergence or growth; preferably, the unwanted plants include herbicide-resistant or tolerant weed species.

10. Use of at least one of the oxadiazole phenylformamide compounds according to any one of claims 1-5 or the herbicidal composition according to any one of claims 7-8 in controlling unwanted plants, preferably, the oxadiazole phenylformamide compounds are used to control weeds in useful crops; more preferably, the useful crops include transgenic crops or crops treated with genome editing technology, and the weeds include herbicide-resistant or tolerant weed species.

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