Oxopyrazinone compound, preparation method therefor, herbicidal composition thereof, and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and particularly relates to an oxopyrazinone compound, a preparation method therefor, a herbicidal composition thereof, and use thereof. The compound is represented by general formula I, wherein X1, X2, X3, X4, X5, and X6 each independently represent hydrogen, halogen, alkyl, or the like; M4 represents CR; R1, R2, R3, R, R6, R7, and R8 each independently represent hydrogen, halogen, cyano, or the like; R4 represents halogen; R5 represents haloalkyl. The compound has excellent herbicidal activity and crop safety.

Description

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

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

[0002] Weed control is a crucial aspect of achieving efficient agriculture. Although a variety of herbicides are available on the market—for example, patent WO2009016841A1 discloses an oxopyrazine derivative and herbicide—the weeding performance and crop selectivity of these known compounds are not entirely satisfactory. Furthermore, due to the expanding market, weed resistance, herbicide lifespan, economic considerations, and increasing environmental awareness, scientists need to continuously research and develop 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 oxopyrazinone compound, its preparation method, a herbicidal composition, and its application. The compound exhibits excellent herbicidal activity and crop safety.

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

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

[0006] Wherein, X1, X2, X3, X4, X5, and X6 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, or cycloalkylalkyl, or two substituents on the same carbon atom connected to form unsubstituted or halogen-substituted -(CH2)2-, -(CH2)3-, -(CH2)4-, or -(CH2)5-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogen-substituted -CH2-, -(CH2)2-, -(CH2)3-, or -(CH2)4-;

[0007] M4 stands for CR;

[0008] R1, R2, R3, R, R6, R7, and R8 independently represent hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, and -OR, respectively. 21 -(CO)R 21 -O(CO)R 21 -(CO)OR 21 -(CO)N(R)21 )2、N(R 21 )2、-SR 21 -(SO)R 21 -(SO2)R 21 , cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic or heterocyclic alkyl;

[0009] R4 represents halogen;

[0010] R5 represents a haloalkyl group;

[0011] R 21 Each of these can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclic or heterocyclic alkyl.

[0012] The aforementioned cycloalkyl, cycloalkenyl, heterocyclic, or aryl groups are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, alkyl-substituted cycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 It is substituted by at least one group in )2;

[0013] R 10 Each can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, or haloalkynyl.

[0014] In one specific embodiment, X1, X2, X3, X4, X5, and X6 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl, or two substituents on the same carbon atom connected to form unsubstituted or halogenated -(CH2)2-, -(CH2)3-, -(CH2)4- or -(CH2)5-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3- or -(CH2)4-;

[0015] R1, R2, R3, R, R6, R7, and R8 independently represent hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, and -OR, respectively. 21-(CO)R 21 -O(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、N(R 21 )2、-SR 21 -(SO)R 21 -(SO2)R 21 C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, aryl, aryl C1-C8 alkyl, heterocyclic or heterocyclic C1-C8 alkyl;

[0016] R5 represents a halogenated C1-C8 alkyl group;

[0017] R 21 Each of these can independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl-C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, heterocyclic or heterocyclic-C1-C8 alkyl;

[0018] The aforementioned C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic, or aryl groups are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, halo-C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 ) 20 At least one group in it is replaced;

[0019] R 10 Each of these can independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, or halo-C2-C8 alkynyl.

[0020] In one specific embodiment, X1, X2, X3, X4, X5, and X6 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl-C1-C6 alkyl, or two substituents on the same carbon atom connected to form unsubstituted or halogenated -(CH2)2-, -(CH2)3-, -(CH2)4-, or -(CH2)5-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3-, or -(CH2)4-;

[0021] R1, R2, R3, R, R6, R7, and R8 independently represent hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, and -OR, respectively. 21 -(CO)R 21 -O(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-N(R 21 )2、-SR 21 -(SO)R 21 -(SO2)R 21 C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, heterocyclic or heterocyclic-C1-C6 alkyl;

[0022] R5 represents a halogenated C1-C6 alkyl group;

[0023] R 21 Each of these can independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, heterocyclic or heterocyclic-C1-C6 alkyl;

[0024] The aforementioned C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic, or aryl groups are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 ynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 ) 20 At least one group in it is replaced;

[0025] R 10 Each of these can independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, or halo-C2-C6 alkynyl.

[0026] 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. For example, in the compound term "cycloalkylalkyl," the alkyl group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, 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 groups are, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl groups are, for example, ethynyl, propynyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. Multiple bonds can be in any position in each unsaturated group. Cycloalkyl groups are carbocyclic saturated ring systems having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl groups are monocyclic alkenyl groups having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein double bonds can be in any position. Halogens are fluorine, chlorine, bromine, or iodine.

[0027] Unless otherwise specified, the term "aryl" in this invention includes, but is not limited to, phenyl, naphthyl, and... The "heterocyclic group" includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups. And, including but not limited to, heteroaryl groups, i.e., aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused with benzo[a] rings, wherein 1 to 4 (e.g., 1, 2, 3, or 4) heteroatoms are selected from oxygen, nitrogen, and sulfur, for example

[0028] The terms "optional" or "optionally" mean that the event or situation described below may or may not occur, and the description includes instances where said event or situation occurs and instances where said event or situation does not occur. For example, the term "optionally...substituted" means that the specified atom or group is unsubstituted or substituted by one or more substituents. If a group is substituted by a group, this should be understood to mean that the group is substituted by one or more groups, either the same or different, selected from those groups mentioned. Furthermore, the same or different substitution characters contained in the same or different substituents are chosen independently and may be the same or different. This also applies to ring systems formed from different atoms and units. Meanwhile, the scope of the claims excludes compounds that are chemically unstable under standard conditions, as known to those skilled in the art.

[0029] Furthermore, unless otherwise specified, the phrase "replaced by at least one group" in this invention refers to being replaced by, for example, 1, 2, 3, 4, or 5 groups; groups without specific attachment positions (including heterocyclic groups, aryl groups, etc.) can be attached at any position, including positions attached to C or N; if it is substituted, the substituent can also be substituted at any position, as long as it conforms to the rules of chemical bond attachment. For example, a heteroaryl group substituted by one methyl group. Can represent wait.

[0030] Depending on the nature of the substituents and the manner in which they are attached, compounds of general formula I and their derivatives can exist as stereoisomers. Stereoisomers can be obtained from mixtures obtained during preparation by conventional separation methods, such as chromatographic separation. Similarly, stereoisomers can be selectively prepared using stereoselective reactions and optically active starting materials and / or auxiliaries. This invention also relates to all stereoisomers contained in general formula I but not specifically defined, and mixtures thereof.

[0031] The present invention also provides a method for preparing the oxopyrazinone compounds, comprising the following steps:

[0032] Compounds II and III undergo a condensation reaction to give compound IV, and compound IV undergoes a rearrangement reaction to give compound I. The reaction formulas are as follows:

[0033] Where L represents a leaving group (such as OH, halogen, p-nitrophenoxy or cyano, etc.), and the substituents X1, X2, X3, X4, X5, X6, R1, R2, R3, R4, R5, R6, R7, R8 and M4 are defined as described above.

[0034] In one specific embodiment, the condensation reaction is carried out in the presence of a base and a solvent.

[0035] In one specific embodiment, the rearrangement reaction is carried out in the presence of a catalyst (such as acetone cyanohydrin), a base, and a solvent.

[0036] In another specific embodiment, the solvent is selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene or toluene), N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dichloroethane, dimethyl sulfoxide, 1,4-dioxane, dichloromethane or ethyl acetate.

[0037] In another specific embodiment, the base is selected from at least one of inorganic or organic bases, such as NaH, KH, NaOH, KOH, K2CO3, Na2CO3, NaHCO3, Cs2CO3, KF, CsF, pyrazole, triethylamine, N,N-diisopropylethylamine, pyridine, potassium trimethylsilanol, AcOK, AcONa, MeONa, EtONa, t-BuONa, t-BuOK, etc.

[0038] The compounds described in this invention can be prepared by referring to the relevant methods recorded in patent WO2009016841A1, etc.

[0039] The present invention also provides a herbicide composition comprising an effective amount of at least one of the oxopyrazinone compounds.

[0040] In one embodiment, the herbicide composition further includes an agriculturally chemically acceptable formulation adjuvant.

[0041] In another embodiment, the herbicide composition further includes one or more additional herbicides and / or safeners in herbicidal amounts.

[0042] The present invention also provides a method for controlling unwanted plants, comprising applying an effective amount of at least one of the oxopyrazinone 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.

[0043] Preferably, the unwanted plants include herbicide-resistant or tolerant weed species.

[0044] The present invention also provides the use of at least one of the oxopyrazinone compounds or the herbicide composition thereof in controlling unwanted plants.

[0045] Preferably, the oxopyrazinone compounds are used to control weeds in useful crops.

[0046] 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.

[0047] 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, rootstocks, 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*, *Lolium*, *Alopecurus*, *Eleocharis*, *Barnyardgrass*, *Digitaria*, *Setaria*, and *Sedge*, and perennials of *Agrostis*, *Cynodon*, *Imperata*, and *Sorghum*, as well as perennials of *Sedge*.

[0048] 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*.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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:

[0053] - 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);

[0054] - 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);

[0055] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924 A, EP-0193259 A).

[0056] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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).

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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 are alkylaryl sulfonates 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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, 81–96; and JD. F. Greyer, SAEvans, “Weed Control Handbook,” 5th edition, Blackwell Scientific Rublications, Oxford University Press, 1968, 101–103.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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):

[0076] (1) HPPD (Hydroxyphenyl Pyruvate Dioxygenase) inhibitors: including but not limited to the following types

[0077] 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);

[0078] 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);

[0079] 3) Isoxazoles, such as isoxaflutole (CAS NO: 141112-29-0); isoxachlortole (CAS NO: 141112-06-3); and clomazone (CAS NO: 81777-89-1).

[0080] 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);

[0081] 5) Benzophenones;

[0082] 6) Other classes: lancotrione (CAS NO: 1486617-21-3); fenquinotrione (CAS NO: 1342891-70-6); fufengcao'an (CAS NO: 2421252-30-2);

[0083] And those mentioned in patent CN105264069A.

[0084] (2) EPSPS (Enolpyruvyl Shikimate Phosphate Synthase) inhibitors: such as sulphosate, glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium;

[0085] (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.

[0086] 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;

[0087] 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);

[0088] Phenylepiazole herbicides include, but are not limited to, imidacloprid (CAS NO: 129630-19-9) and fluazolate (CAS NO: 174514-07-9);

[0089] 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);

[0090] 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);

[0091] Oxadiazole herbicides include, but are not limited to, propyzinoxadiazon (CAS NO: 39807-15-3) and oxadiazon (CAS NO: 19666-30-9);

[0092] 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);

[0093] Oxazolidinone herbicides include, but are not limited to, cyclooxadiazon (CAS NO: 110956-75-7);

[0094] 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 (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), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 1258836-72-4), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS NO: 125 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: 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: 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-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: 452100-03-7), 3-[7-fluoro-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: 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-prop-2-ynyl)-5-methyl-1H-oxazin-6-yl)-4,5,6,7-tetrahydro 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 derivative-substituted imino aryl compounds disclosed in CN113105405A;

[0095] (4) ALS (Acetolactate Synthase) inhibitors include, but are not limited to, the following herbicides or mixtures thereof:

[0096] 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;

[0097] Imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, and imazethapyr;

[0098] Triazolopyrimidine herbicides and sulfonyl anilines such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, floraulam, metosulam, penoxsulam, pyroxsulam, pyrimisulfan, and triafamone;

[0099] 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);

[0100] Sulfonylaminocarbonyl-triazolinone herbicides include flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone, and thiencarbazone-methyl.

[0101] (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-ylmethyl carbonate (CAS NO: 1033760-58-5);

[0102] (6) GS (Glutamine Synthetase) inhibitors: such as bialaphos / bilanafos, bialaphos-natrium, glufosinate-ammonium, glufosinate and glufosinate-P;

[0103] (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);

[0104] (8) DHPS (Dihydropteroate Synthase) inhibitors: such as sulfadiazine (Asulam);

[0105] (9) DXPS (Deoxy-D-Xyulose Phosphate Synthase) inhibitors: such as Bixlozone and Clomazone;

[0106] (10) HST (Homogentisate Solanesyltransferase) inhibitors: such as Cyclopyrimorate;

[0107] (11) SPS (Solanesyl Diphosphate Synthase) inhibitors: such as aclonifen;

[0108] (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;

[0109] (13) VLCFAS (Very Long-Chain Fatty Acid Synthesis) inhibitors: including but not limited to the following types

[0110] 1) Chloracetamides such as acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor, and thenylchlor;

[0111] 2) α-Oxyacetamides, such as flufenacet and mefenacet;

[0112] 3) α-Thioacetamides, such as anilofos and piperophos;

[0113] 4) Azoxystrom derivatives such as cafenstrole, fentrazamide, and ipfencarbazone;

[0114] 5) Benzofurans such as Benfuresate and Ethofumesate;

[0115] 6) Isooxazoline derivatives such as fenoxasulfone and pyroxasulfone;

[0116] 7) Ethylene oxides such as Indanofan and Tridiphane;

[0117] 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.

[0118] (14) Fatty acid thioesterase inhibitors: such as cyproheptadine, methiozolin;

[0119] (15) Inhibitors of serine threonine protein phosphatase: such as Endothall;

[0120] (16) Lycopene cyclase inhibitors: such as Amitrole.

[0121] (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);

[0122] (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;

[0123] (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);

[0124] (20) D1 Histidine 215 binders: such as bromooxynil, iodobenzonitrile, pyridate, and bentazon.

[0125] (21) Auxin transport inhibitors: such as diflufenzopyr (CAS NO: 109293-97-2) and Naptalam;

[0126] (22) PSI Electron Diversion: such as Diquat and Paraquat;

[0127] (23) Inhibition of Microtubule Organization: such as Carbetamide (CAS NO: 16118-49-3), Barban (CAS NO: 101-27-9), Chlorpropham;

[0128] (24) Uncouplers: such as Dinoseb, 4,6-dinitro-o-cresol (DNOC);

[0129] (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.

[0130] 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.

[0131] 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.

[0132] 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

[0133] 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.

[0134] 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.

[0135] Table 1. Compound structures and their properties 1 HNMR

[0136] 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.

[0137] The following method 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. The reagents used in the synthetic compounds shown below are either commercially available or can be easily prepared by those skilled in the art.

[0138] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0139] 1. Synthesis of Compound 1

[0140] (1) In a 100 mL single-necked flask, 1-1 (2.0 g, 1.0 eq, 14.2 mmol) was added to 20 mL of N,N-dimethylformamide, followed by o-fluoronitrobenzene (2.2 g, 1.1 eq, 15.6 mmol) and cesium carbonate (13.85 g, 3.0 eq, 42.6 mmol). The mixture was then heated to 100 °C and reacted overnight. After the reaction was completed under controlled conditions, the mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the organic phase was collected. The organic phase was then separated by normal-phase chromatography with silica gel powder. Product 1-2 was obtained, weighing 2.0 g (yield 46%).

[0141] (2) In a 250 mL single-necked flask, 1-2 (2 g, 1.0 eq, 6.7 mmol) was added to 60 mL of ethanol, followed by 20 mL of water, then ammonium chloride (1.08 g, 3.0 eq, 20.1 mmol) and iron powder (2.06 g, 5.5 eq, 36.8 mmol). The mixture was heated to 60 °C and reacted for 3 h. After the reaction was completed and no raw material remained, the mixture was filtered while hot. The filtrate was collected, and the ethanol, ethyl acetate, and water were removed by rotary evaporation. The mixture was dried over anhydrous sodium sulfate, and the organic phase was collected and evaporated to dryness. Crude product 1-3 was obtained, weighing 1.6 g (yield 88%).

[0142] (3) In a 100 mL single-necked flask, 1-3 (1.6 g, 1.0 eq, 5.9 mmol) was added to 25 mL of toluene, followed by diethyl ketomalonate (1.23 g, 1.2 eq, 7.1 mmol). The mixture was heated to 110 °C and reacted overnight. After the reaction was completed, no raw material remained. The product 1-4 (1.7 g, crude product) was obtained by rotary evaporation.

[0143] (4) In a 250 mL single-necked flask, the crude products 1-4 were added to 40 mL of 1,4-dioxane, 10 mL of water, and potassium carbonate (2.4 g, 3.0 eq, 17.7 mmol). The mixture was heated to 100 °C and reacted for 4 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation. The system was then adjusted to acidity with dilute hydrochloric acid, extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, and the organic phase was collected and evaporated to dryness to obtain product 1-5, weighing 1.1 g (crude product).

[0144] (5) In a 100 mL single-necked flask, crude product 1-5 (0.4 g, 1.0 eq, 1.1 mmol) was added to 10 mL of dichloromethane, followed by 2 drops of N,N-dimethylformamide. Oxaloyl chloride (0.21 g, 1.5 eq, 1.7 mmol) was slowly added. After reacting at room temperature for 30 min, methyl ester was detected by monitoring (methanol sample). The system was then evaporated to dryness and redissolved in dichloromethane. This solution was then slowly added dropwise at 0 °C to a dichloromethane solution of cyclohexanedione (0.15 g, 1.2 eq, 1.3 mmol) and triethylamine (0.33 g, 3.0 eq, 3.3 mmol). The mixture was stirred at room temperature for 1 h until intermediate state 1-6 was reached. After the reaction was complete, no further processing was performed, and the reaction solution was used for the next step.

[0145] (6) Add triethylamine (0.33 g, 3.0 eq, 3.3 mmol) to the reaction solution from the previous step, then add 2 drops of acetone cyanohydrin and replace with nitrogen gas. React at room temperature overnight and control the reaction until the product is obtained. After the reaction is complete, wash twice with dichloromethane / dilute hydrochloric acid, evaporate to dryness, and send to reverse phase purification to obtain product 1, weighing 70 mg (two-step yield 14%).

[0146] 2. Synthesis of Compound 3

[0147] (1) Dissolve raw material 3-1 (3.0 g, 16.7 mmol, 1.0 eq) in 60 mL of N,N-dimethylformamide and cool to 0 °C in an ice bath. Slowly add sodium hydrogen (0.67 g, 27.9 mmol, 2.0 eq), and stir at room temperature for 30 min after the addition is complete. Dissolve 2-chloro-6-fluoronitrobenzene (2.9 g, 16.7 mmol, 1.5 eq) in 10 mL of N,N-dimethylformamide and add it dropwise to the reaction system. Stir at room temperature overnight, and the reaction is completed under LCMS control. Slowly pour the reaction solution into ice water and extract three times with ethyl acetate. Combine the organic phases and wash three times with saturated sodium chloride solution. Dry and concentrate with anhydrous sodium sulfate. Purify by normal phase separation with silica gel (P / E = 3:1) to obtain 3.0 g of yellow oily product 3-2 (yield 53%).

[0148] (2) Compound 3-2 (3.0 g, 8.9 mmol, 1.0 eq) was added to a single-necked flask and dissolved in 50 ml of ethanol and 5 ml of water. Iron powder (2.7 g, 49.4 mmol, 5.5 eq) and ammonium chloride (0.8 g, 14.8 mmol, 1.5 eq) were added, and the mixture was heated to 60 °C and reacted for 2 h. The reaction was completed under LC-MS control. The reaction solution was filtered through diatomaceous earth while hot, and the filtrate was evaporated to dryness. The solution was extracted three times with ethyl acetate, and the organic phase was dried and concentrated with anhydrous sodium sulfate to obtain crude product 3-3, a yellow oily substance (yield 49%).

[0149] (3) Compound 3-3 (1.35 g, 4.4 mmol, 1.0 eq) was added to a single-necked flask and dissolved in 60 ml of toluene. Another starting material (0.8 g, 4.4 mmol, 1.0 eq) was added, and the mixture was heated to 100 °C and reacted overnight. The reaction was completed under LCMS control. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed three times with saturated sodium chloride solution. The mixture was dried over anhydrous sodium sulfate and concentrated. The mixture was then purified by normal phase separation with silica gel (P / E = 4:1) to obtain 0.28 g of a yellow oily product of 3-4 (yield 15%).

[0150] (4) Compound 3-4 (0.28 g, 0.67 mmol, 1.0 eq) was added to a single-necked flask and dissolved in 20 ml of 1,4-dioxane and 5 ml of water. Potassium carbonate (0.28 g, 2.1 mmol, 3.0 eq) was added, and the mixture was heated to 80 °C and reacted for 30 min. The reaction was completed under LCMS control. After adjusting the acidity of the reaction solution, the mixture was extracted three times with ethyl acetate. The combined organic phases were washed three times with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to give 0.17 g of the yellow solid product 3-5 (yield 65%).

[0151] (5) Take a single-necked flask and add compound 3-5 (0.17 g, 0.44 mmol, 1.0 eq), dissolve it in 20 ml of dichloromethane, add oxaloyl chloride (0.07 g, 0.53 mmol, 1.2 eq) with stirring in an ice bath, react at room temperature for 30 min, monitor the presence of methyl ester in the intermediate control (methanol sample), evaporate the system to dryness, redissolve it in dichloromethane, and slowly add it dropwise to a dichloromethane solution of cyclohexanedione (0.06 g, 0.53 mmol, 1.2 eq) and triethylamine (0.13 g, 1.3 mmol, 3.0 eq), stir the reaction at room temperature for 0.5 h, monitor the reaction to intermediate state 3-6, the reaction is complete, no post-processing is required, the reaction solution is used for the next step.

[0152] (6) After adding triethylamine (0.13 g, 1.3 mmol, 3.0 eq) to the reaction solution from the previous step, add 2 drops of acetone cyanohydrin and replace with nitrogen gas. React overnight at room temperature. Wash twice with dichloromethane / dilute hydrochloric acid, combine the organic phases and wash three times with saturated sodium chloride solution. Dry and concentrate with anhydrous sodium sulfate, and purify by normal phase separation with silica gel. Dichloromethane / methanol = 10:1 is used to give yellow solid product 3 (0.08 g, two-step yield 37%).

[0153] 3. Synthesis of Compound 59

[0154] (1) Compound 59-1 (synthetic reference 3-4, 1.2 g, 2.61 mmol) was placed in a reaction flask containing 20 mL of 1,4-dioxane. Compound 59-2 (1.33 g, 5.22 mmol), potassium acetate (1.47 g, 5.22 mmol), and catalytic amount of 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride were added at room temperature. After purging with nitrogen three times, the reaction was carried out at 100 °C for 16 h. The reaction was completed under central control, and 59-3 (1.0 g, yield = 75.59%) was obtained after purification.

[0155] (2) Compound 59-3 (1.0 g, 1.98 mmol) was weighed in a single-necked flask and dissolved in 10 mL of tetrahydrofuran. Hydrogen peroxide (0.67 g, 5.93 mmol, 30% wt) was added under ice bath conditions. The reaction was carried out at room temperature for 1 h. The reaction was completed under liquid chromatography-mass spectrometry. Ethyl acetate and water were added for extraction. The organic phase was collected, dried, filtered, and concentrated to obtain crude compound 59-4 (0.7 g, Yield = 89.42%).

[0156] (3) Compound 59-4 (0.7 g, 1.77 mmol) was dissolved in 15 mL of N,N-dimethylformamide, and compound 59-5 (0.26 g, 1.77 mmol) and potassium carbonate (0.37 g, 2.65 mmol) were added. The mixture was reacted at 80 °C for 16 hours. The reaction was monitored by LCMS until it was complete. The reaction solution was quenched with water, and extracted with ethyl acetate and water. The organic phase was collected, dried, filtered, and concentrated to obtain the crude product. The crude product was purified by normal phase to obtain the light yellow solid product compound 59-6 (0.8 g, Yield = 89.01%).

[0157] (4) Compound 59-6 (0.8 g, 1.57 mmol) was dissolved in a mixed solvent of 10 mL of 1,4-dioxane and 5 mL of water. Potassium carbonate (0.26 g, 2.36 mmol) was added, and the reaction was carried out at 80 °C for 2 hours. The reaction was monitored by LCMS until completion. The reaction solution was concentrated to remove the solvent, and water and ethyl acetate were added for extraction. The aqueous phase was collected, and the pH of the aqueous phase was adjusted to 4-6 with dilute hydrochloric acid. It was extracted with ethyl acetate, washed with saturated brine, dried with anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain the crude product, a yellow solid product 59-7 (0.6 g, Yield = 79.38%).

[0158] (5) Compound 59-7 (0.6 g, 1.25 mmol) was dissolved in 15 mL of dichloromethane, and oxalyl chloride (0.61 g, 3.75 mmol) and N,N-dimethylformamide (0.01 mmol) were added. The reaction was carried out at room temperature for 30 minutes. The solution was transferred to LCMS with methanol. After the reaction was completed, the solvent was evaporated and the solution was dried using an oil pump to prepare the acyl chloride for later use. The prepared acyl chloride was dissolved in 8 mL of dichloromethane and added dropwise at 0 °C to a 15 mL solution of dichloromethane containing cyclohexanedione (0.17 g, 1.50 mmol) and triethylamine (0.38 g, 3.75 mmol). The reaction was carried out for 1 h. LCMS showed that the reaction was complete. The reaction was not treated and the solution was directly added to the next step.

[0159] (6) Add triethylamine (0.38 g, 3.75 mmol) and acetone cyanohydrin (20 mg, 0.2 mmol) to the reaction solution from the previous step, and react at room temperature for 3 hours. Monitor the reaction using LCMS. Dilute the reaction solution with water, extract with dichloromethane, wash the organic phase with 2 M hydrochloric acid, and dry with anhydrous sodium sulfate to obtain the crude product. Purify with normal phase to obtain product 59 (0.15 g, Yield = 37.26%), a pale yellow solid.

[0160] Bioactivity evaluation:

[0161] Post-emergence testing:

[0162] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0163] Level 9: Complete death;

[0164] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0165] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0166] Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

[0167] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0168] Level 4: Growth control rate is greater than or equal to 30% and less than 50%;

[0169] Level 3: Growth control rate greater than or equal to 20% and less than 30%;

[0170] Level 2: Growth control rate greater than or equal to 10% and less than 20%;

[0171] Level 1: Growth control rate less than 10%;

[0172] Level 0: No effect.

[0173] The above growth control rates are fresh weight control rates.

[0174] Seeds of monocot and dicot weeds, as well as seeds of major crops, were placed in plastic pots filled with soil and covered with 0.5-2 cm of soil. The plants were then allowed to grow in a suitable 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, and then Tween 80 was added. Methyl oleate emulsifiable concentrate at a concentration of 900 L / ha was used as a synergist. The solution was diluted with water to a specific concentration and sprayed onto the plants using a spray tower. The plants were then incubated in the greenhouse for two weeks after application. The results were then analyzed, and the experiment was repeated three times, with the average value taken. Representative data are listed in Tables 2-3.

[0175] Table 2 Results of post-emergence testing

[0176] Table 3 Comparison of Post-emergence Weed Trial Results

[0177] Note: N represents no data; control compound A: Reference compound B: Reference compound C:

[0178] In summary, compared with the control compound, the compound described in this application maintains or even improves herbicidal activity while exhibiting higher crop safety and superior selectivity.

[0179] Furthermore, numerous tests have revealed that the compounds and compositions described in this invention can control many key grass weeds as well as broadleaf weeds. Tests on wheat, peanuts, rice, sunflowers, potatoes, fruit trees, and vegetables under different application methods have also demonstrated excellent selectivity and commercial value.

Claims

1. An oxopyrazinone compound, as shown in general formula I: in, X1, X2, X3, X4, X5, and X6 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, or cycloalkylalkyl, or two substituents on the same carbon atom connected to form unsubstituted or halogen-substituted -(CH2)2-, -(CH2)3-, -(CH2)4-, or -(CH2)5-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogen-substituted -CH2-, -(CH2)2-, -(CH2)3-, or -(CH2)4-; M4 stands for CR; R1, R2, R3, R, R6, R7, and R8 independently represent hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, and -OR, respectively. 21 -(CO)R 21 -O(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、N(R 21 )2、-SR 21 -(SO)R 21 -(SO2)R 21 , cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic or heterocyclic alkyl; R4 represents halogen; R5 represents a haloalkyl group; R 21 Each of these can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclic or heterocyclic alkyl. The aforementioned cycloalkyl, cycloalkenyl, heterocyclic, or aryl groups are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, alkyl-substituted cycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 At least one group in )2 is substituted; R 10 Each can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, or haloalkynyl.

2. The oxopyrazinone compound according to claim 1, characterized in that, X1, X2, X3, X4, X5, and X6 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl, or two substituents on the same carbon atom connected to form unsubstituted or halogen-substituted -(CH2)2-, -(CH2)3-, -(CH2)4- or -(CH2)5-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogen-substituted -CH2-, -(CH2)2-, -(CH2)3- or -(CH2)4-; R1, R2, R3, R, R6, R7, and R8 independently represent hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, and -OR, respectively. 21 -(CO)R 21 -O(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、N(R 21 )2、-SR 21 -(SO)R 21 -(SO2)R 21 C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, heterocyclic or heterocyclic-C1-C8 alkyl; R5 represents a halogenated C1-C8 alkyl group; R 21 Each of these can independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl-C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, heterocyclic or heterocyclic-C1-C8 alkyl; The aforementioned C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic, or aryl groups are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, halo-C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 ) 20 At least one group in it is replaced; R 10 Each of these can independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, or halo-C2-C8 alkynyl.

3. An oxopyrazinone compound according to claim 1 or 2, characterized in that, X1, X2, X3, X4, X5, and X6 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl, or two substituents on the same carbon atom connected to form unsubstituted or halogenated -(CH2)2-, -(CH2)3-, -(CH2)4- or -(CH2)5-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3- or -(CH2)4-; R1, R2, R3, R, R6, R7, and R8 independently represent hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, and -OR, respectively. 21 -(CO)R 21 -O(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-N(R 21 )2、-SR 21 -(SO)R 21 -(SO2)R 21 C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, heterocyclic or heterocyclic-C1-C6 alkyl; R5 represents a halogenated C1-C6 alkyl group; R 21 Each of these can independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, heterocyclic or heterocyclic-C1-C6 alkyl; The aforementioned C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic, or aryl groups are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 ynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 ) 20 At least one group in it is replaced; R 10 Each of these can independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, or halo-C2-C6 alkynyl.

4. An oxopyrazinone compound according to any one of claims 1-3, characterized in that, It is selected from any one of the options in Table 1.

5. A method for preparing an oxopyrazinone compound as described in any one of claims 1-4, characterized in that, Includes the following steps: Compound II and compound III react to give compound IV, and compound IV undergoes a rearrangement reaction to give compound I. The reaction formula is as follows: Wherein L represents a leaving group (such as OH, halogen, p-nitrophenoxy or cyano, etc.), and the substituents X1, X2, X3, X4, X5, X6, R1, R2, R3, R4, R5, R6, R7, R8 and M4 are defined as described in any one of claims 1-4; Preferably, the condensation reaction is carried out in the presence of a base and a solvent; more preferably, the rearrangement reaction is carried out in the presence of a catalyst, a base, and a solvent; even more preferably, the solvent is selected from at least one of aromatic hydrocarbons, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dichloroethane, dimethyl sulfoxide, 1,4-dioxane, dichloromethane, or ethyl acetate, the base is selected from at least one of inorganic or organic bases, and / or the catalyst is acetone cyanohydrin.

6. A herbicide composition, characterized in that, It includes at least one of the oxopyrazinone compounds according to any one of claims 1-4 in a herbicidal effective amount; preferably, it also includes an agriculturally chemically acceptable formulation adjuvant; more preferably, it also includes one or more additional herbicides and / or safeners in a herbicidal effective amount.

7. A method for controlling unwanted plants, characterized in that, This includes applying an effective amount of at least one of the oxopyrazinone compounds of any one of claims 1-4 or the herbicide composition of claim 6 to plants or their sites or to soil or water to prevent unwanted plant emergence or growth.

8. Use of at least one of the oxopyrazinone compounds according to any one of claims 1-4 or the herbicide composition according to claim 6 for controlling unwanted plants; preferably, the oxopyrazinone compounds are used to control weeds in useful crops; more preferably, the useful crops include transgenic crops or crops treated with genome editing technology.

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