A 1,3-cyclo-diketone compound, a preparation method thereof, a weeding composition and application thereof

Abstract

The application belongs to the technical field of pesticides, and particularly relates to a 1,3-cyclic dione compound, a preparation method, a weeding composition and application thereof. 21 etc.; R2 represents hydrogen, halogen, alkyl, cycloalkyl, etc.; X1, X2, X3 independently represent N or CR3; and R3 independently represents hydrogen, halogen, alkyl, etc. The compound has excellent weeding activity and crop safety.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a 1,3-cyclic dione compound, its preparation method, herbicidal composition, and application. Background Technology

[0002] Weed control is a crucial aspect of achieving efficient agriculture, despite the wide variety of herbicides available on the market. However, 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 1,3-cyclic dione compound, its preparation method, herbicidal composition, and application. The compound exhibits excellent herbicidal activity against grass weeds, broadleaf weeds, and other weeds, and is highly selective for crops.

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

[0005] A 1,3-cyclic dione compound or a salt thereof, as shown in general formula I:

[0006]

[0007] Wherein, R1 represents hydrogen, alkyl, -alkylene, -OR 21 ,-alkylene-SR 21 ,-alkylene-O(CO)OR 21 -(CO)R 21 -(CS)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-(CO)N(R 21 (OR) 21 -(CS)OR 21 -(CS)N(R) 21 (OR) 21 ) or -(CS)N(R 21 )2;

[0008] R2 represents hydrogen, halogen, alkyl, cycloalkyl, aryl, or heterocyclic; the alkyl group is optionally selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR 21 -SR 21 -SOR 21 -(SO2)R 21-N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced;

[0009] X1, X2, and X3 each independently represent N or CR3;

[0010] R3 can independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, and -OR. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2 or -CR 21 =N-OR 21 The alkyl, alkenyl, or alkynyl group is optionally selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced;

[0011] R 21 Each of these groups independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic, or heterocyclic alkyl, wherein the alkyl, alkenyl, or alkynyl group is optionally substituted with at least one group selected from halogen, cyano, alkoxy, or haloalkoxy; or the group N(R) 21 )2 together form an unsubstituted or substituted heterocyclic group with a nitrogen atom at the 1-position;

[0012] The aforementioned cycloalkyl, heterocyclic, or aryl groups are optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, -OR 10 -SR 10 -(CO)OR10 -(SO2)R 10 or -N(R) 10 At least one group in )2 is replaced;

[0013] R 10 Each can be independently represented by hydrogen, alkyl, or haloalkyl.

[0014] In one specific embodiment, R1 represents hydrogen, C1-C8 alkyl, -(C1-C8 alkylene)-OR 21 -(C1-C8 alkylene)-SR 21 -(C1-C8 alkylene)-O(CO)OR 21 -(CO)R 21 -(CS)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-(CO)N(R 21 (OR) 21 -(CS)OR 21 -(CS)N(R) 21 (OR) 21 ) or -(CS)N(R 21 )2;

[0015] R2 represents hydrogen, halogen, C1-C8 alkyl, C3-C8 cycloalkyl, aryl, or heterocyclic group; the C1-C8 alkyl group is optionally selected from halogen, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic group, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced;

[0016] R3 can independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, and -OR. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21-(CO)OR 21 -(CO)N(R) 21 )2 or -CR 21 =N-OR 21 The C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl groups are optionally selected from halogens, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, and -OR groups. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced;

[0017] R 21 Each of these groups independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclic, or heterocyclicC1-C8 alkyl, wherein the C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl is optionally substituted by at least one group selected from halogen, cyano, C1-C8 alkoxy, or haloC1-C8 alkoxy; or the group N(R) 21 )2 together form an unsubstituted group or a group substituted by at least one group selected from oxo, C1-C8 alkyl, or C1-C8 alkoxycarbonyl. , , , or ;

[0018] The aforementioned C3-C8 cycloalkyl, heterocyclic, or aryl groups are optionally selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 At least one group in )2 is replaced;

[0019] R 10 Each can be independently represented as hydrogen, C1-C8 alkyl, or halogenated C1-C8 alkyl.

[0020] In another specific embodiment, R1 represents hydrogen, C1-C6 alkyl, -(C1-C6 alkylene)-OR 21 -(C1-C6 alkylene)-SR 21 -(C1-C6 alkylene)-O(CO)OR 21 -(CO)R 21 -(CS)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-(CO)N(R 21 (OR) 21 -(CS)OR 21 -(CS)N(R) 21 (OR) 21 ) or -(CS)N(R 21 )2.

[0021] In another specific embodiment, R2 represents hydrogen, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, aryl, or heterocyclic; the C1-C6 alkyl group is optionally selected from halogen, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced;

[0022] In another specific embodiment, R3 independently represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2 or -CR 21 =N-OR 21The C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl groups are optionally selected from halogens, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, and -OR groups. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 It is replaced by at least one group in )2.

[0023] In another specific implementation, R 21 Each of these groups independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclic, or heterocyclicC1-C6 alkyl, wherein the C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl is optionally substituted by at least one group selected from halogen, cyano, C1-C6 alkoxy, or haloC1-C6 alkoxy; or the group N(R) 21 )2 together form an unsubstituted group or a group substituted by at least one group selected from oxo, C1-C6 alkyl, or C1-C6 alkoxycarbonyl. , , , or .

[0024] In another specific embodiment, the aforementioned C3-C6 cycloalkyl, heterocyclic, or aryl group is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 It is replaced by at least one group in )2.

[0025] In another specific implementation, R 10 Each can independently represent hydrogen, C1-C6 alkyl, or halogenated C1-C6 alkyl.

[0026] In the definitions of compounds shown in the above general formulas and in all the following structural formulas, the technical terms used, whether alone or in compound terms, represent the following substituents: alkyl groups having more than two carbon atoms can be straight-chain or branched. For example, the compound term "-alkylene-OR". 21 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, the alkenyl group is, 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. Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl group having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein the double bond can be in any position. Halogens are fluorine, chlorine, bromine, or iodine.

[0027] Unless otherwise specified, the term "aryl" in this invention includes, but is not limited to, phenyl, naphthyl, and... , The "heterocyclic group" mentioned includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups. , , , , , , , , , , , , , , , , , , , , , , , , , , , , or 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 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

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

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

[0030] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0031] 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.

[0032] The method for preparing the 1,3-cyclodione compound or its salt includes the following steps:

[0033] (1) When R1 represents H, the compound represented by general formula II is reacted to prepare the compound represented by general formula I-1, and the reaction equation is as follows:

[0034]

[0035] (2) When R1 is not H, the compound represented by general formula I-1 reacts with the compound represented by general formula III to prepare the compound represented by general formula I. The reaction equation is as follows:

[0036]

[0037] Wherein, R4 represents C1-C6 alkyl or phenyl, Hal represents halogen, and the definitions of X1, X2, X3, R1 and R2 are as described above.

[0038] In one specific embodiment, the reaction (1) is carried out in the presence of a solvent and an acid.

[0039] In another specific embodiment, the solvent is selected from at least one of DMF, DMA, acetonitrile, acetone, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate.

[0040] In another specific embodiment, the acid is selected from at least one of inorganic or organic acids, such as HCl, HBr, HI, H2SO4, H2SO3, H2CO3, HNO3, H3PO4, H3PO3, H2S, formic acid, acetic acid, propionic acid, benzoic acid, p-toluenesulfonic acid, etc.

[0041] In one specific embodiment, the reaction (2) is carried out in the presence of a base and a solvent.

[0042] In another specific embodiment, the base is selected from at least one of inorganic or organic bases, such as NaH, KH, NaOH, KOH, K2CO3, Na2CO3, Cs2CO3, KF, CsF, pyrazole, triethylamine, N,N-diisopropylethylamine, pyridine, potassium trimethylsilanol, AcOK, AcONa, MeONa, EtONa, t-BuONa, t-BuOK, etc.

[0043] In another specific embodiment, the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate.

[0044] In one specific embodiment, 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, as shown in the following reaction equation:

[0045]

[0046] Here, Hal' represents halogen.

[0047] In one specific embodiment, the reaction is carried out in the presence of a solvent, a phase transfer catalyst, an organophosphorus ligand, and a palladium catalyst.

[0048] In another specific embodiment, the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate.

[0049] In another specific embodiment, the phase transfer catalyst is selected from at least one of TBAF (tetrabutylammonium fluoride), TEBA (benzyltriethylammonium chloride), tetrabutylammonium bromide, tetrabutylammonium chloride, or TBAB (tetrabutylammonium bisulfate).

[0050] In another specific embodiment, the organophosphorus ligand is selected from at least one of 1,4-bis(diphenylphosphine)butane, 2-biscyclohexylphosphine biphenyl, bis(2-diphenylphosphine) ether, or 2-(di-tert-butylphosphine)biphenyl.

[0051] In another specific embodiment, the palladium catalyst is selected from at least one of bis(triphenylphosphine)palladium dichloride, Pd(OAc)2, PdCl2, or Pd(PPh3)4.

[0052] A herbicide composition comprising a herbicidally effective amount of at least one of the 1,3-cyclodione compounds or their salts, preferably further comprising a formulation adjuvant, more preferably further comprising other active ingredients.

[0053] A method for controlling weeds, comprising applying a herbicidal effective amount of at least one of the 1,3-cyclodione compounds or their salts, or the herbicide composition thereof, to plants or weedy areas.

[0054] The use of at least one of the 1,3-cyclic dione compounds or their salts, or the herbicide composition thereof, in controlling weeds, preferably, the use of the 1,3-cyclic dione compounds or their salts in controlling weeds in useful crops, said useful crops being transgenic crops or crops treated with genome editing technology.

[0055] This application also discloses an intermediate, as shown in Formula II above.

[0056] This application also discloses an intermediate, as shown in Formula IV above.

[0057] 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*.

[0058] 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*.

[0059] 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.

[0060] 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.

[0061] 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 resist the toxic effects of the herbicides.

[0062] 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:

[0063] - To improve starch synthesis in plants, genetic engineering is used to modify crop plants (e.g., WO 92 / 11376, WO92 / 14827, WO 91 / 19806);

[0064] - Transgenic crop plants resistant to specific herbicides, such as glufosinate-methyl (e.g., EP-0242236A, EP-0242246 A), glyphosate-based herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993A, US-5013659 A);

[0065] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924 A, EP-0193259 A).

[0066] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0067] 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 und Klone”, VCH Weinheim, 2nd ed., 1996; or Christou, “Trends in Plant Science” 1 (1996) 423-431). To achieve the manipulation of genetic engineering, nucleic acid molecules may be introduced into plasmids, resulting in mutations or sequence alterations through recombination of DNA sequences. 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.

[0068] 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.

[0069] 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.

[0070] 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).

[0071] 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 the expression of homologous (=natural) genes or gene sequences, or by expressing heterologous (=external) genes or gene sequences.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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 "Guide to Solvents," 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; Schönfeldt's "Grenzflächenaktive Äthylenoxidaddkte" [Ethylene oxide adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler's "Chemische "Technologie" [Chemical Processes], Vol. 7, C. Hauser Verlag Munich, 4th edition, 1986.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] For methods of preparing granules using milling 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; and “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, GC. Klingman, “Weed Control as a Science,” John Wiley and Sons, New York, 1961, 81–96; and JD. Freyer and SA. Evans, “Weed Control Handbook,” 5th edition, Blackwell Scientific Rublications, Oxford University Press, 1968, 101–103.

[0082] 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 comprising 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 additives, 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.

[0083] 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.

[0084] 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.

[0085] 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. ,

[0086] 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

[0087] 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.

[0088] Given the economic efficiency and diversity of the compounds, we preferentially synthesized a number of compounds, some of which are listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustration of the present invention and do not limit the invention. Those skilled in the art should not interpret this as limiting the scope of the above-mentioned subject matter of the invention to the following compounds.

[0089]

[0090] Table 1. Compound Structures and Their Properties 1 H NMR

[0091]

[0092] Note: The fourth column in Table 1 ( (Column) The right side of the broken bond and group Connected.

[0093] 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.

[0094] 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.

[0095] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0096] 1. Synthesis of Compound 19

[0097] (1) Compound 19-1 (2.83 g, 1.0 eq) was dissolved in 20 mL of DMSO, and compound 19-2 (1.1 eq) and potassium tert-butoxide (1.5 eq) were added. The reaction was carried out at 110 °C for 1 hour, and the reaction was monitored by LCMS until complete. The reaction was quenched with water (20 mL), extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to obtain the crude product of compound 19-3 (yellow oil, 3.4 g, 100% yield).

[0098]

[0099] (2) Compound 19-3 (3.4 g, 1 eq) was dissolved in 30 ml of acetonitrile, and an ion exchange resin (polymer of vinylbenzenesulfonic acid and divinylbenzene, 3.4 g) was added. The reaction was carried out at 75 °C for 12 hours, and monitored by LCMS until the reaction was complete. The mixture was filtered, and the solid was washed with methanol. The organic phase was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give compound 19-4 (brownish-yellow oil, 2.83 g, yield 28.2%).

[0100]

[0101] (3) Compound 19-4 (1.2 g, 1 eq) was dissolved in 15 ml of acetone, and iodomethane (1.5 eq) and potassium carbonate (2 eq) were added. The mixture was stirred at room temperature for 2 hours, and the reaction was monitored by LCMS until complete. The mixture was filtered, and the organic phase was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give compound 19-5 (brownish-yellow oil, 1 g, yield 79.8%).

[0102]

[0103] (4) Compound 19-5 (1 g, 1 eq) was dissolved in 10 mL DMSO, and compound 19-6 (1.5 eq), TBAF (3 eq), 1,4-bis(diphenylphosphine)butane (0.2 eq), and bis(triphenylphosphine)palladium dichloride (0.1 eq) were added. The mixture was purged with nitrogen and reacted at 110 °C for 1 h. The reaction was monitored by LCMS until complete. Water was added to the reaction system, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give compound 19-7 (brown oil, 420 mg, yield 47.6%).

[0104]

[0105] (5) Compound 19-7 (420 mg, 1 eq) was dissolved in 5 ml of acetone, and 5 ml of dilute hydrochloric acid (2 M) was added. The mixture was stirred at 60 °C for 2 h. The reaction was monitored by LCMS until complete. The solvent was evaporated, 20 ml of ethyl acetate was added, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated directly to dryness to give 140 mg of compound 19-8 (yellow oil, 140 mg, yield 34.9%).

[0106]

[0107] (6) Compound 19-8 (140 mg, 1 eq) was dissolved in 10 ml DCM, and triethylamine (3 eq) was added. Compound 19-9 (1.5 eq) was added with stirring. The reaction was carried out at room temperature for 1 h. The reaction was monitored by LCMS until it was complete. The mixture was directly mixed and purified by silica gel column chromatography to obtain compound 19 (yellow oil, 124 mg, yield 67.9%).

[0108]

[0109] Bioactivity evaluation:

[0110] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0111] Level 9: Complete death;

[0112] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0113] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0114] Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

[0115] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0116] Level 4: Growth control rate greater than or equal to 30% and less than 50%;

[0117] Level 3: Growth control rate greater than or equal to 20% and less than 30%;

[0118] Level 2: Growth control rate greater than or equal to 10% and less than 20%;

[0119] Level 1: Growth control rate less than 10%;

[0120] Level 0: No effect.

[0121] The above growth control rates are fresh weight control rates.

[0122] Post-emergence testing experiment:

[0123] 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 1.5 L / ha was used as a synergist, and the solution was diluted with water to a specific concentration. The solution was then sprayed onto the plants using a spray tower. The plants were cultured in the greenhouse for two weeks after application, and the weed control was assessed. The experiment was repeated three times, and the average value was taken. Representative data are listed in Table 2.

[0124] Table 2 Results of post-emergence weed test (30g ai / ha)

[0125]

[0126] Note: N represents no data; control compound A: .

[0127] Furthermore, numerous tests have revealed that the compounds and their compositions described in this invention exhibit excellent selectivity against many grassy lawns, including Zoysia japonica, Bermuda grass, tall fescue, Kentucky bluegrass, ryegrass, and seashore paspalum, effectively controlling many key grassy weeds as well as broadleaf weeds. Tests on sugarcane, soybeans, cotton, sunflowers, potatoes, fruit trees, and vegetables under different application methods also demonstrated excellent selectivity and commercial value.

Claims

1. A 1,3-cyclic dione compound as shown in general formula I, or a salt thereof: , in, R1 represents hydrogen, alkyl, -alkylene-OR 21 ,-alkylene-SR 21 ,-alkylene-O(CO)OR 21 -(CO)R 21 -(CS)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-(CO)N(R 21 (OR) 21 -(CS)OR 21 -(CS)N(R) 21 (OR) 21 ) or -(CS)N(R 21 )2; R2 represents hydrogen, halogen, alkyl, cycloalkyl, aryl, or heterocyclic; the alkyl group is optionally selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced; X1, X2, and X3 each independently represent N or CR3; R3 can independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, and -OR. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2 or -CR 21 =N-OR 21 The alkyl, alkenyl, or alkynyl group is optionally selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced; R 21 Each of these groups independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic, or heterocyclic alkyl, wherein the alkyl, alkenyl, or alkynyl group is optionally substituted with at least one group selected from halogen, cyano, alkoxy, or haloalkoxy; or the group N(R) 21 )2 together form an unsubstituted or substituted heterocyclic group with a nitrogen atom at the 1-position; The aforementioned cycloalkyl, heterocyclic, or aryl groups are optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 At least one group in )2 is replaced; R 10 Each can be independently represented by hydrogen, alkyl, or haloalkyl.

2. A 1,3-cyclodione compound or a salt thereof according to claim 1, characterized in that, R1 represents hydrogen, C1-C8 alkyl, -(C1-C8 alkylene)-OR 21 -(C1-C8 alkylene)-SR 21 -(C1-C8 alkylene)-O(CO)OR 21 -(CO)R 21 -(CS)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-(CO)N(R 21 (OR) 21 -(CS)OR 21 -(CS)N(R) 21 (OR) 21 ) or -(CS)N(R 21 )2; R2 represents hydrogen, halogen, C1-C8 alkyl, C3-C8 cycloalkyl, aryl, or heterocyclic group; the C1-C8 alkyl group is optionally selected from halogen, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic group, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced; R3 can independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, and -OR. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2 or -CR 21 =N-OR 21 The C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl groups are optionally selected from halogens, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, and -OR groups. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced; R 21 Each of these groups independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclic, or heterocyclicC1-C8 alkyl, wherein the C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl is optionally substituted by at least one group selected from halogen, cyano, C1-C8 alkoxy, or haloC1-C8 alkoxy; or the group N(R) 21 )2 together form an unsubstituted group or a group substituted by at least one group selected from oxo, C1-C8 alkyl, or C1-C8 alkoxycarbonyl. , , , or ; The aforementioned C3-C8 cycloalkyl, heterocyclic, or aryl groups are optionally selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 At least one group in )2 is replaced; R 10 Each can be independently represented as hydrogen, C1-C8 alkyl, or halogenated C1-C8 alkyl.

3. A 1,3-cyclodione compound or a salt thereof according to claim 1 or 2, characterized in that, R1 represents hydrogen, C1-C6 alkyl, -(C1-C6 alkylene)-OR 21 -(C1-C6 alkylene)-SR 21 -(C1-C6 alkylene)-O(CO)OR 21 -(CO)R 21 -(CS)R 21 -(CO)OR 21 -(CO)N(R) 21 )2、-(CO)N(R 21 (OR) 21 -(CS)OR 21 -(CS)N(R) 21 (OR) 21 ) or -(CS)N(R 21 )2; R2 represents hydrogen, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, aryl, or heterocyclic group; the C1-C6 alkyl group is optionally selected from halogen, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic group, -OR 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced; R3 can independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, and -OR. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 -(CO)OR 21 -(CO)N(R) 21 )2 or -CR 21 =N-OR 21 The C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl groups are optionally selected from halogens, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, and -OR groups. 21 -SR 21 -SOR 21 -(SO2)R 21 -N(R) 21 )2、-O(CO)R 21 -O(CO)OR 21 -(CO)R 21 or -(CO)N(R) 21 At least one group in )2 is replaced; R 21 Each of these groups independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclic, or heterocyclicC1-C6 alkyl, wherein the C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl is optionally substituted by at least one group selected from halogen, cyano, C1-C6 alkoxy, or haloC1-C6 alkoxy; or the group N(R) 21 )2 together form an unsubstituted group or a group substituted by at least one group selected from oxo, C1-C6 alkyl, or C1-C6 alkoxycarbonyl. , , , or ; The aforementioned C3-C6 cycloalkyl, heterocyclic, or aryl groups are optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, -OR 10 -SR 10 -(CO)OR 10 -(SO2)R 10 or -N(R) 10 At least one group in )2 is replaced; R 10 Each can independently represent hydrogen, C1-C6 alkyl, or halogenated C1-C6 alkyl.

4. A 1,3-cyclodione compound or a salt thereof according to any one of claims 1-3, characterized in that, It is selected from any one of the options in Table 1.

5. A method for preparing a 1,3-cyclodione compound or a salt thereof as described in any one of claims 1-4, characterized in that, Includes the following steps: (1) When R1 represents H, the compound represented by general formula II is reacted to prepare the compound represented by general formula I-1, and the reaction equation is as follows: , (2) When R1 is not H, the compound represented by general formula I-1 reacts with the compound represented by general formula III to prepare the compound represented by general formula I. The reaction equation is as follows: , Wherein, R4 represents C1-C6 alkyl or phenyl, Hal represents halogen, and the definitions of X1, X2, X3, R1 and R2 are as described in any one of claims 1-3; Preferably, the reaction (1) is carried out in the presence of a solvent and an acid; more preferably, the solvent is selected from at least one of DMF, DMA, acetonitrile, acetone, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate; and the acid is selected from at least one of inorganic or organic acids. Preferably, the reaction (2) is carried out in the presence of a base and a solvent; the base is selected from at least one of inorganic or organic bases; the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate.

6. The method for preparing a 1,3-cyclodione compound or its salt according to claim 5, characterized in that, Includes the following steps: 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: , Hal' represents halogen; Preferably, the reaction is carried out in the presence of a solvent, a phase transfer catalyst, an organophosphorus ligand, and a palladium catalyst; more preferably, the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate; the phase transfer catalyst is selected from at least one of TBAF (tetrabutylammonium fluoride), TEBA (benzyltriethylammonium chloride), tetrabutylammonium bromide, tetrabutylammonium chloride, or TBAB (tetrabutylammonium bisulfate); the organophosphorus ligand is selected from at least one of 1,4-bis(diphenylphosphine)butane, 2-biscyclohexylphosphine biphenyl, bis(2-diphenylphosphine phenyl) ether, or 2-(di-tert-butylphosphine)biphenyl; and the palladium catalyst is selected from at least one of bis(triphenylphosphine dichloride), Pd(OAc)2, PdCl2, or Pd(PPh3)4.

7. A herbicide composition, characterized in that, The herbicide includes at least one of the 1,3-cyclodione compounds or their salts as described in any one of claims 1-4, preferably further comprising formulation adjuvants, and more preferably further comprising other active ingredients.

8. A method for controlling weeds, characterized in that, This includes applying an effective amount of at least one of the 1,3-cyclodione compounds of any one of claims 1-4 or a salt thereof, or the herbicide composition of claim 7, to plants or weedy areas.

9. Use of at least one of the 1,3-cyclic dione compounds or their salts as described in any one of claims 1-4, or the herbicide composition as described in claim 7, in controlling weeds, preferably, the 1,3-cyclic dione compounds or their salts are used to control weeds in useful crops, more preferably, the useful crops include transgenic crops or crops treated with genome editing technology.

10. An intermediate as described in Formula II of claim 5 or Formula IV of claim 6.

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