Substituted heterocyclic compound and preparation method therefor, herbicidal composition, and use

Abstract

The present invention relates to the technical field of pesticides, and specifically to a substituted heterocyclic compound or a salt thereof, a preparation method therefor, an herbicidal composition thereof, and a use. The compound is as represented by general formula I: [formula I], wherein X1 and X2 each independently represent CR9 or N, and at least one of X1 and X2 is N; X3 and X4 each independently represent CR10 or N; X5 represents NR11; each R2 independently represents hydrogen, alkyl, alkenyl, alkynyl, etc.; and R1, R3, R4, R5, R6, R7, R8, R9, R10, and R11 each independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, etc. The compound has excellent herbicidal activity against grassy weeds, broadleaf weeds, sedge weeds, etc. and has high selectivity for crops.

Description

Substituted heterocyclic compounds, methods for their preparation, herbicidal compositions and uses TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticides, and particularly relates to a substituted heterocyclic compound, a method for preparing the same, a herbicidal composition and uses thereof. BACKGROUND

[0002] The control of weeds is a crucial step in the process of achieving efficient agriculture, although there are a wide variety of herbicides on the market. However, the herbicidal performance of these known compounds on harmful plants and the selectivity on crops are not entirely satisfactory. And due to the continuous expansion of the market, the resistance of weeds, the service life of drugs and the economy of drugs and other issues, as well as the increasing attention to the environment, scientists need to continuously research and develop new herbicides with high efficiency, safety, economy and different modes of action. SUMMARY

[0003] The present application provides a substituted heterocyclic compound, a method for preparing the same, a herbicidal composition and uses thereof, which has excellent herbicidal activity on gramineous weeds, broadleaf weeds, sedge weeds and the like, and high selectivity on crops.

[0004] The technical solutions adopted by the present application are as follows:

[0005] A substituted heterocyclic compound as shown in general formula I, stereoisomers and agriculturally acceptable salts thereof:

[0006] X1, X2 independently represent CR9 or N, and at least one of X1, X2 is N;

[0007] X3, X4 independently represent CR 10 or N;

[0008] X5 represents NR 11 ;

[0009] R2 independently represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, aryl, heterocyclyl, -OR, -(CO)R, -(CO)OR or -(CO)N(R)2;

[0010] R1, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11each independently represents hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, -(CO)OR, -(CO)N(R)2, or -CR=N-OR; said alkyl, alkenyl or alkynyl being optionally substituted by at least one group selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -N(R)(COR)-, -N(R)(SO2R)-, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2;

[0011] said cycloalkyl, cycloalkenyl, heterocyclyl or aryl being optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(SO)R, or -(SO2)R;

[0012] R each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkyl, alkenyl or alkynyl substituted by at least one group selected from halogen, hydroxy, alkoxy, cyano or alkoxycarbonyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0013] In a particular embodiment, R2each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl, haloC2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclyl, -OR, -(CO)R, -(CO)OR, or -(CO)N(R)2;

[0014] R1, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11Each of these groups independently represents hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, -(CO)OR, -(CO)N(R)2 or -CR=N-OR; the C1 The -C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl groups are optionally substituted by at least one group selected from halogen, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -N(R)(COR)-, -N(R)(SO2R)-, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2;

[0015] The aforementioned C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic or aryl groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 ynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(SO)R or -(SO2)R;

[0016] R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, phenyl, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, cyano or C1-C8 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy.

[0017] In another specific embodiment, R2 independently represents 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, aryl, heterocyclic, -OR, -(CO)R, -(CO)OR or -(CO)N(R)2.

[0018] In another specific embodiment, R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Each of these groups independently represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, -(CO)OR, -(CO)N(R)2 or -CR=N-OR; the C1 The -C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl groups are optionally substituted by at least one group selected from halogen, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -N(R)(COR)-, -N(R)(SO2R)-, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2;

[0019] In another specific embodiment, the aforementioned C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(SO)R or -(SO2)R.

[0020] In another specific embodiment, R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl, C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkoxycarbonyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano, or C1-C6 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy, or halo-C1-C6 alkoxy.

[0021] 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.

[0022] 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

[0023] 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.

[0024] 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.

[0025] This invention provides a compound having a chiral center as shown in Formula I', its stereoisomers, and an agriculturally usable salt:

[0026] The substituents X1, X2, X3, X4, X5, R1, R2, R3, R4, R5, R6, R7, and R8 are defined as described above, and the carbon atoms at positions 1 and 2 are chiral centers. The stereochemical purity of the carbon atom at position 1, which has R and S configurations, is 60-100%, preferably 70-100%, more preferably 80-100%, further preferably 90-100%, and even more preferably 95-100%. The stereochemical purity of the carbon atom at position 2, which has R and S configurations, is 60-100%, preferably 70-100%, more preferably 80-100%, further preferably 90-100%, and even more preferably 95-100%.

[0027] In this invention, the stereochemical configuration is determined according to the Cahn-Ingold-Prelog system as predominant (R) or (S). 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 aforementioned position is in R-configuration or S-configuration, or in the mixture, the compound or a compound with the same chemical structure has R-configuration or S-configuration at the asymmetric carbon atom at the aforementioned position, or is present in a proportion predominantly having R-configuration or S-configuration (at least 60% R-configuration or S-configuration), while other asymmetric carbon atoms may be present in racemic form or may be resolved to varying degrees. As long as the stereochemical configuration conditions at the asymmetric carbon atom in the aforementioned position are met, possible stereoisomers defined by a specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers, are all included in Formula I and can be obtained from mixtures of stereoisomers by conventional methods, or can also be prepared by stereoselective reactions in combination with stereochemically pure initial substances.

[0028] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0029] 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.

[0030] The method for preparing the substituted heterocyclic compound includes the following steps:

[0031] Compound I is prepared by a condensation reaction of compound II and compound III, and the chemical reaction equation is as follows:

[0032] Where Z represents halogen; the definitions of X1, X2, X3, X4, X5, R1, R2, R3, R4, R5, R6, R7, and R8 are as described above.

[0033] In one specific embodiment, the reaction is carried out in the presence of a solvent.

[0034] In another specific embodiment, a base is added during the reaction process.

[0035] In one specific embodiment, the solvent for the reaction is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate.

[0036] In one specific embodiment, the base used in the reaction is selected from at least one of inorganic or organic bases, such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuOK, EtONa, NaOH, KOH, NaOMe, pyrazole, triethylamine, pyridine, DMEN, DIEA, etc.

[0037] A herbicide composition comprising at least one of the substituted heterocyclic compounds in an herbicidal effective amount; preferably, it further comprises a formulation adjuvant; more preferably, it further comprises other active ingredients.

[0038] A method for controlling weeds, comprising applying a herbicide-effective amount of at least one of the substituted heterocyclic compounds or the herbicide composition to plants or weedy areas.

[0039] The use of at least one of the substituted heterocyclic compounds or the herbicide composition in controlling weeds, preferably, the use of the heterocyclic substituted aromatic compounds in controlling weeds in useful crops, said useful crops being transgenic crops or crops treated with genome editing technology.

[0040] 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*, *Fararis*, *Barnyardgrass*, *Digitaria*, *Setaria*, and *Sedge*, and perennials of *Agropyron*, *Cynodon*, *Imperata*, and *Sorghum*, as well as perennials of *Sedge*.

[0041] 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*.

[0042] 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 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.

[0043] 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 pesticides, particularly 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.

[0044] 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.

[0045] Traditional methods for breeding plants with improved traits than 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:

[0046] - 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);

[0047] - 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);

[0048] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924 A, EP-0193259 A).

[0049] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0050] 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 base substitution, removal of portions of the sequence, or addition of natural or synthetic sequences, can be employed. To link DNA fragments together, it is possible to attach conjugates or linkers to the fragments.

[0051] 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.

[0052] 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.

[0053] 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).

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] On the basis of these formulations, it is also possible to mix with other pesticidally active substances, such as insecticides, acaricides, herbicides and fungicides, but also with safeners, fertilizers and / or plant growth regulators, either in the form of ready-to-use mixtures or by tank mix.

[0068] Suitable active substances that can be mixed with the active substances of the present invention in compound formulations or tank-mixed formulations include, for example, known substances in the "World Encyclopedia of New Pesticide Varieties Technology", China Agricultural Science and Technology Press, 2010.9 and the literature cited herein. For example, the following herbicidal active substances can be mixed with compounds of Formula I (Note: the name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with a code where appropriate): acetochlor, butachlor, metolachlor, isopropachlor, isopropachlor, succinyl-metolachlor, propachlor, chlorpyrifos, chlorpyrifos, naphthalenepropanoyl-methyl, R-L-naphthalenepropanoyl-methyl, propargyl, benzylthiamethoxam, bisbenzyl-methyl, pyrifluquinazon, chlorpyrifos, flubutyroxychlor, brobutyroxychlor, dimethoate, high-efficiency dimethoate, ethoxybenzyl-methyl, flubutyroxychlor, methoxythiamethoxam, pyrifluquinazon, isoxachlor, high-efficiency methylparaben, high-efficiency methylparaben. Acetaminophen, clethodim, butyrazosulfuron, cyprochloraz, flusulfuron, heptanosulfuron, isobutyrazosulfuron, propyzamide, terbutyrazosulfuron, methylparaben, metolachlor, methylcyclohexane, chlorpyrifos, propyzamide, pendimethalin, carbaryl, succinylmethrin, tricyclomethrin, butyrazosulfuron, succinylmethrin, bensulfuron-methyl, naphthylmethrin, acetochlor, naphthylmethrin, thiamethoxam, pyrimethanil, bensulfuron-methyl, chlorpyrifos, butyrazosulfuron, flupyrazole, atrazine, simazine, promethazine, cypermethrin, cypermethrin, atrazine, pyrazosulfuron, isopropazine, flumethrin, terbutyraz, terbutyraz, triazine flumethrin, cyprochlorazine, glyphosate, chlorpyrifos Phosphatidylcholine, Simazine, Ziziphus jujuba, Dichlorvos, Isoamyl acetate, Cyprodinil, Atrazine, Butyraz, Butyraz, Terbutaline, Methoxypropazine, Cypermethrin, Herbicides, Clonazine, Atrazine, Methoxypropazine, Glycyrrhizin, Cyanobacterium trioxide, Indaziflam, Greensulfuron, Methsulfuron-methyl, Benzylsulfuron, Chlorpyrifos, Bensulfuron-methyl, Thisulfuron-methyl, Pyrimisulfuron-methyl, Methiosulfuron-methyl, Sodium formamide sulfuron, Ethersulfuron-methyl, Etherbensulfuron-methyl, Methsulfuron-methyl, Nicosulfuron-methyl, Aminosulfuron-methyl, Acylsulfuron-methyl, Ethoxysulfuron-methyl, Cyprosulfuron-methyl, Sulfadiazine, Tetraazolidinylsulfuron, Pyrimisulfuron, Monosulfuron-methyl, Fluazolidinylsulfuron, Flupyrimisulfuron, Flupyrimisulfuron, Epimethrin Sulfuric acid, pyrazosulfuron, flusulfuron, propanil, trifluprosulfuron, sulfonylsulfuron, trifluralin, flusulfanil, trifluralin, mesosulfuron sodium salt, flupyrsulfuron, thiosulfuron, pyrimethanil, propyrisulfuron, pyrazosulfuron, trifluralin, flusulfanilamide, quizalofop-p-ethyl, ethoxysulfuron, glufosinate, bensulfuron, chlorfluazuron ethyl, methylfluzoxystrobin, trifluralin, methoxysulfuron, trifluralin, flufenoxuron, flufenoxuron, oxysulfuron, metolachlor, sulfadiazine, flufenoxuron, oxysulfuron, metolachlor, flufenoxuron, flufenoxuron, halosafen, chlormequat chloride, isoproturon, linuron, diuronSaprolegnia, fluroxypyr, bensulfuron, methyl bensulfuron, bensulfuron, sulfothiamethoxam, isoxaflutole, terbutaline, clodinafop-methyl, chlorobromosulfuron, methyl methoxysulfuron, methyl methoxysulfuron, bromosulfuron, methoxysulfuron, chlorpyrifos, metribuzin, cycloroxysulfuron, felsulfuron, flusulfuron, glufosinate, fensulfuron, cyproconazole, thiamethoxam, fensulfuron, chlorpyrifos, methamidophos, thiamethoxam, trimethourea, oxazolium, Monisouron, Anisuron, Methiuron, Chloreturon, tetraflufenozide, betaine, betaine-ethyl, betaine, sulfonamide, terbutaline, fensulfuron-methyl, fensulfuron-methyl, fensulfuron-methyl, fensulfuron-methyl, chlorpyrifos, carboxazo le, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butyrazosulfan, Clethodim, Metrazine, Clethodim, Wild Grass, Permethrin, Clethodim, Barnyardgrass, Cypermethrin, Oat Grass, Dimethoate, Ethylmethazine, Methiobencarb, Clethodim, Benzoate, Methiobencarb, Thionylmethazine, Methiobencarb, 2,4-D Butyl Acetate, 2,4-D Sodium Chloride, 2,4-D Isooctyl Acetate, 2,4-D Sodium Salt, 2,4-D Dimethylamine Salt, 2,4-D Chlorethyl Thiate, 2,4-D Chloride, 2,4-D Propionic Acid, High 2,4-D Propionate, 2,4-D Butyric Acid, 2,4-D Chlorpropionic Acid, 2,4-D Propionate 2,4,5-chlorobutyric acid, 2,4,5-propylpropionic acid, 2,4,5-propylbutyric acid, 2,4,5-chloromethacin, MCPA, dicamba, quizalofop-p-ethyl, cyhalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, cyhalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl In, proponitrophenol, glyphosate, barnyardphos, glufosinate, methyl parathion, glyphosate, piperazine, diammonium phosphate, dimethoate, phosmet, fenpropathrin, fenpropathrin, fenpropathrin, dimethoate, fenpropathrin, imidacloprid, imidacloprid acetic acid, imidacloprid quinolinic acid, methoxymethylene, methoxymethylene ammonium salt, imidacloprid acetic acid, imidacloprid, clopyralid, clopyralid isooctyl ester, dichloropyridine acid, aminopyridine acid, trichloropyridine acid, fluthion, haloxypyridine, trichloropyridine phenol, thiamethoxam, flupyridine, clopyralid, flupyridine hydrazone, trichloropyridine butoxyethyl ester, cliodinate, clethodim, thiamethoxam, quizalofop-p-ethyl, cyclobenzanone, butenazine, oxadiazine, pyranazine, buthidazole, cyproconazoleAmetridione, Amibuzin, bromobenzonitrile, octanoyl bromobenzonitrile, octanoyl iodobenzonitrile, iodobenzonitrile, diphenylacetonitrile, bispyribac-sodium, hydroxybispyribac-sodium, Iodobonil, pyrimisulfuron-methyl, diflubenzuron, penoxsulam, sulfadiazine, chlorpyrifos-sulfuron-methyl, dichlorvos-sulfuron-methyl, fluroxypyr, bispyribac-sodium, pyrimisulfuron-methyl, pyrimisulfuron-methyl, pyrimisulfuron-methyl, bispyribac-sodium, nicosulfuron-methyl, sulfadiazine, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketospiradox, isoxazolidinone, isoxazolidinone, Fenoxasulfone, M ethiozolin, isopropalazine, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, bensulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, flumetsulam, pyrazosulfuron, pyrazosulfuron, flumethrin, pyrazosulfuron, flupropacil, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, flupropacil ... Herbicides, fluazinam, methyl methacrylate, tetrazolium chlorpyrifos, flupyridamole, chlorpyrifos, bromochlor, dimethomorph, pyrazosulfuron, cyprodinil, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, cyprodinil, pyrazosulfuron, bentazon, pyrazosulfuron, oxadiazon, cyprodinil, isoxadiazon, cyprodinil, isopropyl methoxysulfuron, cyprodinil, indicarb, sodium chlorate Herbicides, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage grass, bromophenol oxime, triazole sulfonate, methomyl, furazolidone, furazolidone, ethoxysulfuron, pyrimethanil, chlorpyrifos, flurfluthrin, barnyardgrass, acrolein, bensulfuron-methyl, metribuzin, oat ester, thiamethoxam, styracil, hydroxylone, methoxybenzone, pyrimethanil, chlorpyrifos, trichloropropionic acid, Al orac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, methylsulfuron, Cambendichlor, Cyproterinic acid, Thiamethoxam, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, pyrazole cypermethrin, furazolidone, oxadiazon, bis(oxazolyl)acrylic acid, dichloropropenylamine, fluorochloropyridinium, DOW fluorochloropyridinium, UBH-509D489,LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, D K-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023. ,

[0069] When used, commercially available formulations are 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 from 0.005 to 750 g ai / ha, particularly from 0.005 to 250 g ai / ha. Detailed Implementation

[0070] 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.

[0071] Given the economic efficiency and diversity of the compounds, we have synthesized a number of preferred compounds, some of which are listed in the table below. Specific compound structures and corresponding compound information are shown in Tables 1-2. The compounds listed in the table are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art should not interpret this as limiting the scope of the invention to the following compounds.

[0072] Table 1. Compound Structures and 1 H NMR

[0073] Table 2 Compound Structures and 1 H NMR

[0074] 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. Both positions 1 and 2 are chiral centers having the aforementioned configurations; in Table A, the entries under the “Serial Number” column heading are described sequentially as 1'-115'. For example, 1' corresponds to compound 1 in Table 1, which has the R configuration at position 1 and the S configuration at position 2.

[0075] Table B has the same structure as Table 1 above, except that general formula I is replaced with general formula IV' which has a chiral center. Position 1 is the chiral center having the aforementioned configuration; wherein, in Table B, the entries under the “Serial Number” column heading are described as 2-1', 2-2', etc. For example, 2-1' corresponds to the compound 1 in Table 2 that has the R configuration at position 1.

[0076] 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.

[0077] 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.

[0078] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0079] 1. Synthesis of compound 1'

[0080] (1) Compound 1-1 (3 g, 19.4 mmol) was dissolved in 30 mL of dichloromethane solution, followed by the addition of cesium fluoride (5.9 g, 38.8 mmol) and compound 1-2 (7.7 g, 29.1 mmol). The mixture was stirred overnight at 30 °C, and the reaction was monitored by LCMS to indicate completion. The mixture was extracted with dichloromethane and water, and the organic phases were combined, washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated, and purified under normal phase (PE / EA = 4 / 1) to give compound 1-3 (1.2 g, white solid, yield 30%).

[0081] (2) Compounds 1-3 (0.15 g, 0.7 mmol) were dissolved in 5 mL of dry DMF solution, followed by the addition of potassium carbonate (0.3 g, 2.2 mmol) and compounds 1-4 (0.12 g, 0.7 mmol). The mixture was stirred overnight at 90 °C, and the reaction was monitored by LCMS. The mixture was extracted several times with ethyl acetate and water, and the organic phases were combined, washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase (PE / EA = 3 / 1) to give compound 1' (90 mg, white solid, yield 37%).

[0082] 2. Synthesis of compound 62'

[0083] (1) At room temperature, compound 1-1 (0.40 g, 2.6 mmol, 1.0 eq.) was dissolved in 10 mL of DMF, and potassium carbonate (1.08 g, 7.8 mmol, 3.0 eq.) and methyl iodide (0.55 g, 3.9 mmol, 1.5 eq.) were added. The mixture was stirred overnight at room temperature. The reaction was monitored by LCMS until complete. The reaction solution was poured into water, extracted with ethyl acetate, and the organic phase was washed with saturated brine. The solution was dried, concentrated, and purified by mixing to obtain compound 62-1 (0.13 g, 30%).

[0084] (2) At room temperature, compound 62-1 (0.13 g, 0.8 mmol, 1.0 eq.) was dissolved in 10 mL of DMF, and potassium carbonate (0.33 g, 2.4 mmol, 3.0 eq.) and compound 1-4 (0.17 g, 1.0 mmol, 1.2 eq.) were added. The mixture was heated to 80 °C and stirred overnight. The reaction was monitored by LCMS until complete. The reaction solution was poured into water, extracted with ethyl acetate, and the organic phase was washed with saturated brine, dried, concentrated, and purified to obtain compound 62' (0.10 g, 44%).

[0085] Bioactivity evaluation:

[0086] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0087] Level 9: Complete death;

[0088] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0089] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0090] Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

[0091] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0092] Level 4: Growth control rate is greater than or equal to 30% and less than 50%;

[0093] Level 3: Growth control rate greater than or equal to 20% and less than 30%;

[0094] Level 2: Growth control rate greater than or equal to 10% and less than 20%;

[0095] Level 1: Growth control rate less than 10%;

[0096] Level 0: No effect.

[0097] The above growth control rates are fresh weight control rates.

[0098] Pre-seeding test experiment:

[0099] Seeds of monocotyledonous and dicotyledonous weeds, as well as seeds of major crops, were placed in plastic basins filled with soil and covered with 0.5-2 cm of soil. The tested compound of this invention was dissolved in acetone, then Tween 80 was added, and the solution was diluted with water to a certain concentration. The solution was sprayed immediately after sowing. The experimental results were observed after 12 days of cultivation in a greenhouse following application.

[0100] Table 3 Pre-seeded test data Note: N represents no data.

[0101] 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 (such as barnyard grass and Echinochloa crus-galli) as well as broadleaf weeds (such as Polygonum hydropiper) and sedges (such as Cyperus rotundus). Tests on soybeans, cotton, sunflowers, potatoes, fruit trees, and vegetables under different application methods also demonstrated excellent selectivity and commercial value.

Claims

1. A substituted heterocyclic compound as shown in general formula I, its stereoisomers, and an agriculturally usable salt: in, X1 and X2 independently represent CR9 or N, and at least one of X1 and X2 is N; X3 and X4 independently represent CR 10 Or N; X5 represents NR 11 ; R2 can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, aryl, heterocyclic, -OR, -(CO)R, -(CO)OR or -(CO)N(R)2; R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Each of the following groups independently represents hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, cycloalkenyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, -(CO)OR, -(CO)N(R)2 or -CR=N-OR; wherein the alkyl, alkenyl or alkynyl group is optionally substituted by at least one group selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -N(R)(COR)-, -N(R)(SO2R)-, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2; The aforementioned cycloalkyl, cycloalkenyl, heterocyclic or aryl groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, alkyl-substituted cycloalkyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(SO)R or -(SO2)R; R can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkyl, alkenyl, or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano, or alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

2. The substituted heterocyclic compound, its stereoisomer, and agriculturally usable salt according to claim 1, characterized in that, R2 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, aryl, heterocyclic, -OR, -(CO)R, -(CO)OR or -(CO)N(R)2; R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Each of these groups independently represents hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, -(CO)OR, -(CO)N(R)2 or -CR=N-OR; the C1 The -C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl groups are optionally substituted by at least one group selected from halogen, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -N(R)(COR)-, -N(R)(SO2R)-, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2; The aforementioned C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic or aryl groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 ynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(SO)R or -(SO2)R; R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, phenyl, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, cyano or C1-C8 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy.

3. The substituted heterocyclic compound, its stereoisomer, and agriculturally usable salt according to claim 1 or 2, characterized in that, R2 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, aryl, heterocyclic, -OR, -(CO)R, -(CO)OR or -(CO)N(R)2; R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Each of these groups independently represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, -(CO)OR, -(CO)N(R)2 or -CR=N-OR; the C1 The -C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl groups are optionally substituted by at least one group selected from halogen, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -N(R)(COR)-, -N(R)(SO2R)-, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2; The aforementioned C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic or aryl groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(SO)R or -(SO2)R; R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano or C1-C6 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1, Table 2, Table A and Table B.

4. A substituted heterocyclic compound having a chiral center as shown in Formula I', its stereoisomers, and an agriculturally usable salt: in, The substituents X1, X2, X3, X4, X5, R1, R2, R3, R4, R5, R6, R7, and R8 are defined as described in any one of claims 1-3, wherein the carbon atoms at positions 1 and 2 are chiral centers; wherein, based on the content of stereoisomers with R and S configurations on the carbon atom at position 1, they have a stereochemical purity of 60-100%, preferably 70-100%, more preferably 80-100%, further preferably 90-100%, and even more preferably 95-100%; and based on the content of stereoisomers with R and S configurations on the carbon atom at position 2, they have a stereochemical purity of 60-100%, preferably 70-100%, more preferably 80-100%, further preferably 90-100%, and even more preferably 95-100%.

5. A method for preparing the substituted heterocyclic compound, its stereoisomer, and agriculturally usable salt as described in any one of claims 1-4, comprising the following steps: Compound I is prepared by a condensation reaction of compound II and compound III, and the chemical reaction equation is as follows: Where Z represents halogen; the definitions of X1, X2, X3, X4, X5, R1, R2, R3, R4, R5, R6, R7, and R8 are as described above. Preferably, the reaction is carried out in the presence of a solvent; more preferably, a base is added during the reaction; even more preferably, the solvent of the reaction is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate, and the base of the reaction is selected from at least one of inorganic or organic bases.

6. A herbicide composition, characterized in that, The herbicide includes at least one of the substituted heterocyclic compound, its stereoisomer, and agriculturally usable salt as described in any one of claims 1-4, preferably, it also includes a formulation adjuvant, and more preferably, it also includes other active ingredients.

7. A method for controlling weeds, characterized in that, This includes applying an effective amount of at least one of the substituted heterocyclic compounds, their stereoisomers, and agriculturally usable salts as described in any one of claims 1-4, or the herbicide composition as described in claim 6, to plants or weedy areas.

8. Use of at least one of the substituted heterocyclic compound, its stereoisomer, and agricultural salt as described in any one of claims 1-4, or the herbicide composition as described in claim 6, in controlling weeds, preferably, the substituted heterocyclic compound, its stereoisomer, and agricultural salt 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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