Fused heterocyclic compound and preparation method therefor, herbicidal composition thereof and use thereof

Abstract

The present invention relates to a fused heterocyclic compound, a preparation method therefor, a herbicidal composition thereof and the use thereof. The compound is as shown in general formula I, wherein X represents O or S; Y represents a direct bond or CR 7R 8; R 1 represents haloalkyl; R 4 represents halogen; R 6 represents cycloalkylalkyl; and R 2, R 3, R 5, R 7 and R 8 each independently represent hydrogen, halogen, alkyl, alkenyl, etc. The compound has a herbicidal activity and is safe for crops.

Description

A fused heterocyclic compound, its preparation method, herbicidal composition and application Technical Field

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

[0002] Weed control is a crucial aspect of achieving efficient agriculture. Although a wide variety of herbicides are available on the market, the weed-control 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] This invention provides a fused heterocyclic compound, its preparation method, herbicidal composition, and application. The compound exhibits excellent herbicidal activity and crop safety.

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

[0005] A fused heterocyclic compound or a salt thereof, as shown in general formula I:

[0006] Where X represents O or S;

[0007] Y represents a direct bond or CR7R8;

[0008] R1 represents haloalkyl; R4 represents halogen; R6 represents cycloalkyl.

[0009] R2, R3, R5, R7, and R8 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; or R7 and R8 together form an alkylene group; 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, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2;

[0010] The aforementioned "cycloalkyl", "heterocyclic" or "aryl" may optionally be replaced by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R;

[0011] R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano or alkoxycarbonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0012] In one specific embodiment, R1 represents a halo-C1-C8 alkyl group; R6 represents a C3-C8 cycloalkyl group or a C1-C8 alkyl group.

[0013] R2, R3, R5, R7, and R8 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; or R7 and R8. Together they form a C1-C8 alkylene group; wherein the C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group is 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, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2;

[0014] The aforementioned “C3-C8 cycloalkyl”, “heterocyclic” or “aryl” may optionally be replaced by at least one group 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, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R;

[0015] R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, 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, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, phenyl 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.

[0016] In another specific embodiment, R1 represents a halo-C1-C6 alkyl group; R6 represents a C3-C6 cycloalkyl group or a C1-C6 alkyl group.

[0017] R2, R3, R5, R7, and R8 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; or R7 and R8. Together they form a C1-C6 alkylene group; wherein the C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl group is 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, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2;

[0018] The aforementioned “C3-C6 cycloalkyl”, “heterocyclic” or “aryl” may optionally be replaced 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, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R;

[0019] R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, 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, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl 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.

[0020] In another specific implementation, X represents O; Y represents CR7R8.

[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 one or more, and 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 The invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts, provided that various functional groups are present.

[0025] 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.

[0026] The method for preparing a fused heterocyclic compound includes the following steps:

[0027] The compound represented by general formula II reacts with the compound represented by general formula III to give the compound represented by general formula I. The reaction equation is as follows:

[0028] The definitions of substituents R1, R2, R3, R4, R5, R6, X, and Y are as described above.

[0029] In one specific embodiment, the reaction is carried out in the presence of a base and a solvent.

[0030] In another specific embodiment, the base is selected from at least one of inorganic bases (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KI, NaI, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, NaH, KH, etc.) or organic bases (such as DMAP, pyrazole, triethylamine, DIEA, etc.).

[0031] In another specific embodiment, the solvent is selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene or toluene), DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, toluene or ethyl acetate.

[0032] In one specific embodiment, (1) the compound represented by general formula II is prepared by reacting the compound represented by general formula IV and the compound represented by general formula V, and the reaction equation is as follows:

[0033] Or (2) The compound represented by general formula II is prepared by reacting the compound represented by general formula VI and the compound represented by general formula VII, and the reaction equation is as follows:

[0034] Wherein, W independently represents C1-C6 alkyl, aryl or aryl C1-C6 alkyl that is unsubstituted or substituted by any group selected from alkyl, halogen, alkoxy, haloalkyl or cyano.

[0035] In one specific embodiment, the reaction (1) is carried out under acidic conditions.

[0036] In one specific embodiment, the reaction (2) is carried out in the presence of a solvent and a base.

[0037] In another specific embodiment, the acid is selected from at least one of inorganic acids (such as HCl, HBr, HI, H2SO4, H2SO3, H2CO3, HNO3, H3PO4, H3PO3, H2S, etc.) or organic acids (such as formic acid, acetic acid, propionic acid, benzoic acid, p-toluenesulfonic acid, etc.).

[0038] In another specific embodiment, the base is selected from at least one of inorganic bases (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KI, NaI, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, NaH, KH, etc.) or organic bases (such as DMAP, pyrazole, triethylamine, DIEA, etc.).

[0039] In another specific embodiment, the solvent is selected from at least one of aromatic hydrocarbons (such as toluene, xylene), DMF, DMA, THF, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, or ethyl acetate.

[0040] In addition, the compounds described in this invention can be prepared by referring to the methods shown in CN102762552B, etc.

[0041] The present invention also provides an intermediate, as shown in Formula II above.

[0042] A herbicide composition comprising at least one of the fused heterocyclic compounds in an effective amount for weed control; preferably, it further comprises a formulation adjuvant; more preferably, it further comprises other active ingredients.

[0043] A method for controlling weeds, comprising applying a herbicidal effective amount of at least one of the said fused heterocyclic compounds or the said herbicide composition to plants or weedy areas.

[0044] The use of at least one of the fused heterocyclic compounds or the herbicide composition in weed control, preferably, the use of the fused heterocyclic compounds in controlling weeds in useful crops, said useful crops being transgenic crops or crops treated with genome editing technology.

[0045] 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*.

[0046] 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*.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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-0221044A, EP-0131624A). Several methods have been described, for example:

[0051] - 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);

[0052] - Transgenic crop plants resistant to specific herbicides, such as glufosinate-methyl (e.g., EP-0242236A, EP-0242246A), glyphosate-based herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993A, US-5013659A);

[0053] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924A, EP-0193259A).

[0054] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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).

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] Based on these formulations, they may also be mixed with other pesticide active substances such as insecticides, acaricides, herbicides and fungicides, as well as with safeners, fertilizers and / or plant growth regulators. The mixing method may be pre-mixed or bottled.

[0073] 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. ,

[0074] 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 between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha. Detailed Implementation

[0075] 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. Given the economy and diversity of the compounds, we have preferably synthesized several compounds, some of which are listed in Table 1 below. Specific compound structures and corresponding compound information are shown in Tables 1-2. The compounds in Table 1 are only for better illustration of the invention and do not limit it. Those skilled in the art should not interpret this as limiting the scope of the invention to the following compounds.

[0076] Table 1. Compound Structures

[0077] Table 2 Compounds 1 H NMR

[0078] 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.

[0079] 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.

[0080] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0081] 1. Synthesis of Compound 1

[0082] (1) Take a single-necked flask, dissolve 1-1 (3.6 g, 14.5 mmol) in NMP, add potassium carbonate (6.0 g, 43.5 mmol) and bromomethylcyclopropane (3.90 g, 29.0 mmol) while stirring, and stir overnight at room temperature. After the reaction is complete, add water and ethyl acetate to the reaction solution, extract three times by separation, combine the organic phases, wash three times with saturated brine, dry with anhydrous sodium sulfate, concentrate the organic phase, stir and pass through a column to obtain 1-2 (3.5 g, yield 80%).

[0083] (2) Take a single-necked flask and dissolve 1-2 (3.5 g, 11.6 mmol) in a mixed solvent of EtOH / H2O = 10 / 1. While stirring, add ammonium chloride (1.25 g, 23.2 mmol) and iron powder (1.95 g, 34.8 mmol), heat to 80 °C, and react for 2 hours. After the reaction is complete, filter the reaction solution with diatomaceous earth, wash with ethanol, evaporate the filtrate to dryness, add water and ethyl acetate, extract three times by separation, combine the organic phases, wash once with saturated brine, dry with anhydrous sodium sulfate, concentrate the organic phase, mix and pass through a column to obtain 1-3 (2.3 g, yield 73%).

[0084] (3) Take a single-necked flask, dissolve 1-3 (2.3 g, 8.45 mmol) in acetic acid, add 1-4 (1.93 g, 9.29 mmol) while stirring, heat to 120 °C, and react for 1 hour under central control. After the reaction is complete, evaporate the reaction solution to dryness, add water and ethyl acetate, extract three times by separation, combine the organic phases, wash twice with sodium bicarbonate solution, wash once with saturated brine, dry with anhydrous sodium sulfate, concentrate the organic phase, mix and pass through a column to obtain 1-5 (3.0 g, yield 81%).

[0085] (4) Take a single-necked flask, dissolve 1-5 (3.0 g, 6.89 mmol) in DMF, add potassium carbonate (2.85 g, 20.7 mmol) and 1-6 (2.74 g, 13.7 mmol) while stirring, heat to 40 °C and react overnight under central control. Add 1-6 until the starting material is almost completely reacted. After the reaction is complete, cool the reaction solution to room temperature, add water and ethyl acetate, extract three times by separation, combine the organic phases, wash three times with saturated brine, dry with anhydrous sodium sulfate, concentrate the organic phase, stir and pass through a column to obtain compound 1 (0.70 g, yield 23%).

[0086] 2. Synthesis of Compound 7

[0087] (1) Dissolve 7-1 (300 mg, 1.00 eq) in AcOH (10.0 mL), add 7-2 (262 mg, 1.10 eq), heat to 110 °C, and react for 1.5 h. Take the reaction solution, dilute with acetonitrile, and monitor by LCMS. The starting material disappears, and the product becomes the main peak. Return the reaction solution to room temperature, evaporate the residual solvent, add ethyl acetate and water for extraction, wash the aqueous phase once with saturated brine, dry with anhydrous sodium sulfate, concentrate, and use directly for the next step without purification.

[0088] (2) Dissolve the crude product 7-3 from the previous step in DMF (10.0 mL), then add K2CO3 (341 mg, 3.0 eq) and 1-6 (410 mg, 2.50 eq) sequentially. Heat to 50 °C and react overnight. Take the reaction solution, dilute with acetonitrile, and monitor by LCMS. The reaction proceeds are complete. Return the reaction solution to room temperature, pour into water, extract with ethyl acetate, concentrate the organic phase, dissolve in a small amount of acetonitrile, and purify by reverse phase to obtain compound 7 (pale yellow solid, 50 mg, yield 14%).

[0089] 3. Synthesis of Compound 67

[0090] (1) At room temperature, compound 67-1 (2.5 g, 11.6 mmol) was dissolved in DMF (10 mL). Cyclopropyl bromide (4.2 g, 35.1 mmol) and potassium carbonate (4.8 g, 35.1 mmol) were slowly added while stirring. After the addition was complete, the mixture was stirred overnight at 40 °C. LCMS analysis showed that the reaction of the starting material was basically complete, and the main peak was the product peak. Water (10 mL) was added to the reaction solution and the mixture was extracted with EA. The organic phase was washed with saturated brine (20 mL * 3). The organic phase was concentrated, and the crude product was separated by column chromatography to obtain a yellow solid compound 67-2 (1.8 g, yield 58%).

[0091] (2) At room temperature, compound 67-2 (1.8 g, 6.7 mmol) was dissolved in a mixed solvent of ethanol:water = 3:1 (20 mL). While stirring, iron powder (0.75 g, 13.4 mmol) and ammonium chloride (0.72 g, 13.4 mmol) were slowly added. After the addition was complete, the temperature was raised to 80 °C and stirred for 2 h. LCMS showed that the reaction of the starting material was basically complete, and the main peak was the product peak. The reaction solution was filtered with diatomaceous earth, the filtrate was concentrated, and the crude product was separated by column chromatography to obtain a yellow solid compound 67-3 (1.2 g, yield 75%).

[0092] (3) At room temperature, compound 67-3 (1.2 g, 5.1 mmol) was dissolved in glacial acetic acid (10 mL), and compound 1-4 (1.3 g, 6.1 mmol) was added while stirring. After the addition was complete, the temperature was raised to 120 °C and stirred for 2 h. LCMS showed that the reaction of the starting material was basically complete, and the main peak was the product peak. The reaction solution was concentrated, and the crude product was separated by column chromatography to obtain a yellow solid compound 67-4 (0.8 g, yield 40%).

[0093] (4) At room temperature, compound 67-4 (0.8 g, 2.0 mmol) was dissolved in DMF (5 mL). 1-6 (1.2 g, 6.0 mmol) and potassium carbonate (0.8 g, 6.0 mmol) were slowly added while stirring. After addition, the mixture was stirred overnight at 40 °C. LC-MS analysis showed that the reaction was essentially complete, with the main peak being the product peak. Water (10 mL) was added to the reaction solution, followed by extraction with EA. The organic phase was washed with saturated brine (20 mL * 3), and the organic phase was concentrated. The crude product was separated by column chromatography to obtain a yellow solid compound 67 (100 mg, yield 12%).

[0094] 4. Synthesis of Compound 114

[0095] (1) Compound 1-3 (0.5 g, 1.0 eq) was dissolved in 10 mL of dichloromethane, and pyridine (0.4 g, 3.0 eq) and 114-1 (0.3 g, 1.2 eq) were added under ice bath conditions. The reaction mixture was reacted at room temperature for 2 h. The reaction solution was directly evaporated to dryness, and the mixture was purified in normal phase to obtain a yellow oily compound 114-2 (0.6 g, yield 91%).

[0096] (2) Compound 114-2 (0.6 g, 1.0 eq), compound 114-3 (0.5 g, 1.2 eq), and potassium carbonate (0.7 g, 3.0 eq) were dissolved in 10 mL of N,N-dimethylformamide, heated to 120 °C, and reacted for 12 h. The system was cooled to room temperature, water was added, and ethyl acetate was added for extraction. The organic phase was washed three times with saturated brine, dried, and purified by normal phase to obtain a yellow solid compound 114-4 (0.6 g, yield 83%).

[0097] (3) Compound 114-4 (0.3 g, 1.0 eq), compound 1-6 (0.4 g, 3.0 eq), and potassium carbonate (0.5 g, 5.0 eq) were dissolved in 10 mL of N,N-dimethylformamide, heated to 45 °C, and reacted for 12 h. After the reaction was completed, water was added, and the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried, and purified by normal phase to obtain a yellow solid compound 114 (0.09 g, yield 28%).

[0098] Bioactivity evaluation:

[0099] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0100] Level 9: Complete death;

[0101] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0102] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0103] Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

[0104] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0105] Level 4: Growth control rate is greater than or equal to 30% and less than 50%;

[0106] Level 3: Growth control rate greater than or equal to 20% and less than 30%;

[0107] Level 2: Growth control rate greater than or equal to 10% and less than 20%;

[0108] Level 1: Growth control rate less than 10%;

[0109] Level 0: No effect.

[0110] The above growth control rates are fresh weight control rates.

[0111] Pre-seeding test:

[0112] 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 compounds of this invention were dissolved in acetone, then Tween 80 was added, and the solutions were diluted with water to a specific concentration. The solutions were sprayed immediately after sowing. The plants were then incubated in a greenhouse for 2-3 weeks after application, and the experimental results were observed. Representative data are listed in Tables 3-4.

[0113] Table 3. Pre-emergence test results (24g ai / ha)

[0114] Note: N represents no data.

[0115] Table 4 Results of Pre-seeding Test Comparison Experiment

[0116] Note: Reference compound A:

[0117] Post-emergence testing:

[0118] 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 2-3 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. After three weeks of cultivation in the greenhouse following application, the experimental effects on weeds were statistically analyzed. Representative data are listed in Table 5.

[0119] Table 5. Post-emergence test results (40.5 g ai / ha)

[0120] Note: N represents no data.

[0121] Furthermore, numerous tests have revealed that the compounds and compositions described in this invention can control many key grass weeds, broadleaf weeds, and sedge weeds, demonstrating excellent commercial value.

[0122] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention.

Claims

1. A fused heterocyclic compound as shown in general formula I, or a salt thereof: in, X represents O or S; Y represents a direct bond or CR7R8; R1 represents haloalkyl; R4 represents halogen; R6 represents cycloalkyl. R2, R3, R5, R7, and R8 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; or R7 and R8 together form an alkylene group; 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, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; The aforementioned "cycloalkyl", "heterocyclic" or "aryl" may optionally be replaced by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R; R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano or alkoxycarbonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

2. The fused heterocyclic compound according to claim 1, characterized in that, R1 represents a halogenated C1-C8 alkyl group; R6 represents a C3-C8 cycloalkyl group or a C1-C8 alkyl group. R2, R3, R5, R7, and R8 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; or R7 and R8. Together they form a C1-C8 alkylene group; wherein the C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group is 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, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2; The aforementioned "C3-C8 cycloalkyl", "heterocyclic" or "aryl" may optionally be replaced by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 ynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R; R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, 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, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, phenyl 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 fused heterocyclic compound according to claim 1, characterized in that, R1 represents a halogenated C1-C6 alkyl group; R6 represents a C3-C6 cycloalkyl group or a C1-C6 alkyl group. R2, R3, R5, R7, and R8 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -O(CO)R, -O(CO)OR, -(CO)R, or -(CO)N(R)2; or R7 and R8. Together they form a C1-C6 alkylene group; wherein the C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl group is 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, -O(CO)R, -O(CO)OR, -(CO)R or -(CO)N(R)2; The aforementioned "C3-C6 cycloalkyl", "heterocyclic" or "aryl" may optionally be replaced by at least one group 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, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R; R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, 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, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, phenyl 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 the compounds in Table 1 of the specification.

4. A method for preparing the fused heterocyclic compound according to any one of claims 1-3, comprising the following steps: The compound represented by general formula II reacts with the compound represented by general formula III to give the compound represented by general formula I. The reaction equation is as follows: The substituents R1, R2, R3, R4, R5, R6, X, and Y are defined as described in any one of claims 1-3. Preferably, the reaction is carried out in the presence of a base and a solvent; more preferably, the base is selected from at least one of inorganic or organic bases; and the solvent is selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene or toluene), DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, toluene or ethyl acetate.

5. The preparation method according to claim 4, characterized in that, (1) The compound represented by general formula II is prepared by reacting the compound represented by general formula IV and the compound represented by general formula V, and the reaction equation is as follows: Or (2) The compound represented by general formula II is prepared by reacting the compound represented by general formula VI and the compound represented by general formula VII, and the reaction equation is as follows: Wherein, W independently represents C1-C6 alkyl, aryl or aryl C1-C6 alkyl that is unsubstituted or substituted by any group selected from alkyl, halogen, alkoxy, haloalkyl or cyano; Preferably, the reaction (1) is carried out under acidic conditions, or the reaction (2) is carried out in the presence of a solvent and a base; more preferably, the acid is selected from at least one of inorganic acids or organic acids, or the base is selected from at least one of inorganic bases or organic bases, or the solvent is selected from at least one of aromatic hydrocarbons (such as toluene, xylene), DMF, DMA, THF, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, or ethyl acetate.

6. A herbicidal composition, characterized in that, The herbicide contains at least one of the fused heterocyclic compounds of any one of claims 1-3; preferably, it further includes a formulation adjuvant; more preferably, it further includes other active ingredients.

7. A method for controlling weeds, comprising applying a herbicidal effective amount of at least one of the fused heterocyclic compounds of any one of claims 1-3 or the herbicide composition of claim 6 to plants or weedy areas.

8. Use of the fused heterocyclic compound of any one of claims 1-3 or the composition of claim 6 in weed control, preferably, the fused heterocyclic compound is used to control weeds in a useful crop, said useful crop being a transgenic crop or a crop treated with genome editing technology.

9. An intermediate as described in Formula II of claim 4.

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