A quinazolinone 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 quinazolinone compound or a salt thereof, a preparation method thereof, a herbicidal composition and application. The compound is shown in the general formula I: wherein Q represents, or ; A represents aryl or heterocyclic group; Y1, Y2, Y3, Y4, Y5, Y6 respectively and independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl and the like; R1 represents halogen, alkyl, alkenyl, alkynyl and the like; R2, R3, R4, R5, R7, R8, R9, R 10 respectively and independently represent hydrogen, halogen, cyano, nitro, alkyl and the like; R6 represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl and the like. The compound has excellent herbicidal activity and is safe to crops, and has high selectivity.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a quinazolinone 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 quinazolinone compound, its preparation method, herbicidal composition, and application. The compound exhibits excellent herbicidal activity, is safe for crops, and has high selectivity.

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

[0005] A quinazolinone compound as shown in general formula I, its stereoisomers, and an agriculturally usable salt:

[0006]

[0007] Where Q represents , or ;

[0008] A represents aryl or heterocyclic group;

[0009] Y1, Y2, Y3, Y4, Y5, and Y6 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, or cycloalkylalkyl, or two substituents on the same carbon atom connected to form =O, or unsubstituted or halogen-substituted -(CH2)2-, -(CH2)3-, or -(CH2)4-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogen-substituted -CH2-, -(CH2)2-, -(CH2)3-, or -(CH2)4-;

[0010] R1 represents halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, nitro, cyano, alkoxyalkyl, or aryl.

[0011] R2, R3, R4, R5, R7, R8, R9, R 10Each of the following groups independently represents hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, aryl, -OR, -N(R)2, -O(CO)N(R)2, -O(CS)N(R)2, -O-alkylene-(CO)R, -(CO)OR, -SR, -(SO)R or -(SO2)R, or an alkyl, alkenyl or alkynyl group substituted with at least one group selected from halogen, cycloalkyl, -OR, -O-alkylene-OR, -SR, -(SO)R or -(SO2)R;

[0012] R6 represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic, or an alkyl, alkenyl, or alkynyl group substituted with at least one group selected from cyano, nitro, halogen, cycloalkyl, heterocyclic, aryl, -OR, -SR, -(SO)R, or -(SO2)R.

[0013] The aforementioned cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, alkyl-substituted cycloalkyl, -OR, -SR, -(CO)OR, -(SO2)R, or -N(R)2.

[0014] R can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkyl, alkenyl, or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano, or alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

[0015] In one specific embodiment, Y1, Y2, Y3, Y4, Y5, and Y6 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl, or two substituents on the same carbon atom connected to form =O, or unsubstituted or halogenated -(CH2)2-, -(CH2)3- or -(CH2)4-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3- or -(CH2)4-;

[0016] R1 represents C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy-C1-C8 alkyl, C2-C8 alkenyl, halo-C2-C8 alkenyl, C2-C8 alkynyl, halo-C2-C8 alkynyl, halogen, C3-C8 cycloalkyl, nitro, cyano or aryl.

[0017] R2, R3, R4, R5, R7, R8, R9, R 10 Each of these groups independently represents hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, heterocyclic, aryl, -OR, -N(R)2, -O(CO)N(R)2, -O(CS)N(R)2, -O-(C1-C8 alkylene)-(CO)R, -(CO)OR, -SR, -(SO)R or -(SO2)R, or a C1-C8 alkyl, C2-C8 alkenyl or C2-C8 ynyl group substituted with at least one group selected from halogen, C3-C8 cycloalkyl, -OR, -O-(C1-C8 alkylene)-OR, -SR, -(SO)R or -(SO2)R;

[0018] R6 represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclic, or a C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl substituted with at least one group selected from cyano, nitro, halogen, C3-C8 cycloalkyl, heterocyclic, aryl, -OR, -SR, -(SO)R, or -(SO2)R;

[0019] The aforementioned C3-C8 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 ynyl, halo-C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR, -SR, -(CO)OR, -(SO2)R, or -N(R)2;

[0020] R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, phenyl, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, cyano or C1-C8 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy.

[0021] In another embodiment, Y1, Y2, Y3, Y4, Y5, and Y6 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl-C1-C6 alkyl, or two substituents on the same carbon atom connected to form =O, or unsubstituted or halogenated -(CH2)2-, -(CH2)3-, or -(CH2)4-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3-, or -(CH2)4-;

[0022] R1 represents C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, halogen, C3-C6 cycloalkyl, nitro, cyano or aryl.

[0023] R2, R3, R4, R5, R7, R8, R9, R 10 Each of these groups independently represents hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, heterocyclic, aryl, -OR, -N(R)2, -O(CO)N(R)2, -O(CS)N(R)2, -O-(C1-C6 alkylene)-(CO)R, -(CO)OR, -SR, -(SO)R or -(SO2)R, or a C1-C6 alkyl, C2-C6 alkenyl or C2-C6 ynyl group substituted with at least one group selected from halogen, C3-C6 cycloalkyl, -OR, -O-(C1-C6 alkylene)-OR, -SR, -(SO)R or -(SO2)R;

[0024] R6 represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, aryl, heterocyclic, or a C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl substituted with at least one group selected from cyano, nitro, halogen, C3-C6 cycloalkyl, heterocyclic, aryl, -OR, -SR, -(SO)R, or -(SO2)R;

[0025] The aforementioned C3-C6 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 ynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR, -SR, -(CO)OR, -(SO2)R, or -N(R)2;

[0026] R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl, C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkoxycarbonyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano, or C1-C6 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy, or halo-C1-C6 alkoxy.

[0027] 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 "-O-alkylene-OR", the alkylene group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl, or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl, and 1,3-dimethylbutyl. Similarly, alkenyl groups are, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl groups are, for example, ethynyl, propynyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. Multiple bonds can be in any position in each unsaturated group. Cycloalkyl groups are carbocyclic saturated ring systems having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl groups are monocyclic alkenyl groups having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein double bonds can be in any position. Halogens are fluorine, chlorine, bromine, or iodine.

[0028] 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 .

[0029] 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.

[0030] 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.

[0031] This invention provides a quinazolinone compound having a chiral center as shown in Formula I', its stereoisomers, and an agriculturally usable salt:

[0032]

[0033] The substituents Q, A, R1, R2, R3, R4, and R5 are defined as described above; the carbon atom at position 2 is a chiral center, and based on the content of stereoisomers with R and S configurations at this position, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S); or it has a stereochemical purity of 60-100% (R), preferably 70-100% (R), more preferably 80-100% (R), further preferably 90-100% (R), and even more preferably 95-100% (R).

[0034] "Stereochemical purity" refers to the percentage of the amount of the stereoisomer relative to the total amount of stereoisomers that generate chiral centers.

[0035] In this invention, the stereochemical configuration at position 2 in Formula I' is determined to be predominantly (2S) and (2R) according to the Cahn-Ingold-Prelog system, respectively. However, the subject matter of this invention also relates to all stereoisomers at other positions included in Formulas I and I', and mixtures thereof. Such Formula I and I' compounds contain, for example, one or more additional asymmetric carbon atoms or other double bonds not specifically described in Formulas I and I'. It should be understood that this invention includes pure isomers and mixtures thereof enriched to varying degrees with pure isomers, wherein the asymmetric carbon atom at position 2 is in the S-configuration or the asymmetric carbon atom at position 2 is in the R-configuration, or in the mixture, the compound or a compound with the same chemical structure has said configuration at the marked position, or is present in a proportion predominantly containing the compound having said configuration (at least 60% of said configuration), while other asymmetric carbon atoms may be present in a racemic form or may be resolved to varying degrees. Possible stereoisomers defined by specific spatial forms, such as enantiomers, diastereomers, Z- and E-isomers, are included in Formula I and Formula I', provided that the stereochemical configuration conditions at the marked positions are met. They can be obtained from mixtures of stereoisomers by conventional methods or prepared by stereoselective reactions in conjunction with stereochemically pure initial substances.

[0036] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0037] 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.

[0038] The method for preparing the quinazolinone compound includes the following steps: using the compound... The reaction proceeds as an intermediate, where L represents a leaving group (such as OH, halogen, p-nitrophenoxy, or cyano), and the substituents A, R1, R2, R3, R4, and R5 are defined as described above.

[0039] In one specific implementation, when the target product is Q, it represents... When preparing a compound of formula I, the preparation method includes the following steps:

[0040]

[0041] In another specific implementation, when the target product is Q, it represents... When preparing a compound of formula I, the preparation method includes the following steps:

[0042]

[0043] The definitions of L, Y1, Y2, Y3, Y4, Y5, Y6, A, R1, R2, R3, R4, R5, R6 and R7 are as described above.

[0044] In one specific embodiment, the condensation reaction in step 1 is carried out in the presence of a base and a solvent.

[0045] In one specific embodiment, the rearrangement reaction in step 2 is carried out in the presence of a catalyst (such as acetone cyanohydrin), a base, and a solvent.

[0046] In another specific embodiment, the solvents for both step 1 and step 2 are selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene or toluene), N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dichloroethane, dimethyl sulfoxide, 1,4-dioxane, dichloromethane or ethyl acetate.

[0047] In another specific embodiment, the bases in steps 1 and 2 are both selected from at least one of inorganic or organic bases, such as NaH, KH, NaOH, KOH, K2CO3, Na2CO3, NaHCO3, Cs2CO3, KF, CsF, pyrazole, triethylamine, N,N-diisopropylethylamine, pyridine, potassium trimethylsilanol, AcOK, AcONa, MeONa, EtONa, t-BuONa, t-BuOK, etc.

[0048] A herbicide composition comprising at least one of the quinazolinone compounds in an herbicidal effective amount, preferably further comprising a formulation adjuvant, more preferably further comprising other active ingredients.

[0049] A method for controlling weeds, comprising applying a herbicidally effective amount of at least one of the quinazolinone compounds or the herbicide composition thereon to plants or weedy areas.

[0050] The use of at least one of the quinazoline ketone compounds or the herbicide composition in controlling weeds, preferably, the use of the quinazoline ketone compounds in controlling weeds in useful crops, more preferably, the useful crops include genetically modified crops or crops treated with genome editing technology.

[0051] 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*.

[0052] 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*.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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:

[0057] - To improve starch synthesis in plants, genetic engineering is used to modify crop plants (e.g., WO 92 / 11376, WO92 / 14827, WO 91 / 19806);

[0058] - 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);

[0059] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924 A, EP-0193259 A).

[0060] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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).

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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. ,

[0080] 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

[0081] 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.

[0082] 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.

[0083] Table 1. Compound Structures and Their Properties 1 H NMR

[0084]

[0085]

[0086] Tables AB are constructed similarly to Table 1 above, except that the general formula I is replaced with the general formula I' having a chiral center. Furthermore, in Table A, the entries under the "Serial Number" column heading are described as 1(2S)-115(2S). For example, 1(2S) corresponds to the compound in Table 1 where position 2 is the S configuration; and in Table B, the entries under the "Serial Number" column heading are described as 1(2R)-115(2R). For example, 1(2R) corresponds to the compound in Table 1 where position 2 is the R configuration.

[0087] 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.

[0088] 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.

[0089] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0090] 1. Synthesis of Compound 1

[0091] (1) Compound 1-1 (2.76 g, 9.96 mmol), α-methylbenzylamine (1.21 g, 9.99 mmol), HATU (4.55 g, 11.97 mmol), and DIEA (3.86 g, 29.87 mmol) were dissolved in 20 mL of DMF and stirred at room temperature for 1 hour. The reaction solution was poured into water and extracted with ethyl acetate. The organic phases were combined and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 4:1) to give a white solid 1-2 (3.7 g, yield 97.68%).

[0092]

[0093] (2) Dissolve 1-2 (3.7 g, 9.73 mmol) in THF, add trifluoroacetic anhydride (2.45 g, 11.68 mmol), and stir at room temperature for 1 hour. Pour the reaction solution into a saturated sodium bicarbonate aqueous solution, extract with ethyl acetate, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, and concentrate under reduced pressure to give a yellow solid 1-3 (4 g, yield 86.31%).

[0094]

[0095] (3) Dissolve 1-3 (4 g, 8.4 mmol), trifluoroacetic anhydride (2.65 g, 12.6 mmol), and triethylamine (1.27 g, 12.6 mmol) in DCM and stir at room temperature for 1 hour. Pour the reaction solution into water, extract with ethyl acetate, concentrate the organic phase under reduced pressure, and purify by silica gel column chromatography (petroleum ether / tetrahydrofuran = 4:1) to give a yellow solid 1-4 (3.5 g, yield 90.94%).

[0096]

[0097] (4) Dissolve 1-4 (2 g, 4.36 mmol) in THF, and slowly add isopropyl magnesium chloride / lithium chloride complex (4.5 mL, 2 mol / L) dropwise at -78 °C. After stirring at room temperature for 0.5 hours, introduce carbon dioxide gas into the system until the reaction is complete. Pour the reaction solution into a saturated ammonium chloride aqueous solution, extract with ethyl acetate, concentrate the organic phase under reduced pressure, and purify by silica gel column chromatography (petroleum ether / tetrahydrofuran = 2:1) to obtain a light yellow solid 1-5 (1.4 g, yield 85.23%).

[0098]

[0099] (5) Dissolve 1-5 (700 mg, 1.86 mmol) and oxalyl chloride (472 mg, 3.72 mmol) in 10 mL of DCM, add 1 drop of DMF, react for 0.5 hours, and concentrate under reduced pressure. Add a DCM solution of cyclohexanedione (250 mg, 2.23 mmol) and triethylamine (565 mg, 5.58 mmol) to the residue, stir at room temperature for 1 hour, and the resulting crude product 1-6 can be used directly in the next step without further treatment.

[0100]

[0101] (6) Add 1 drop of acetone cyanohydrin to the reaction solution from the previous step and stir at room temperature for 16 hours. Adjust the pH to 2 with 4 mol / L HCl, extract with DCM, concentrate the organic phase under reduced pressure, and purify by reversed-phase column chromatography to obtain yellow solid 1 (55 mg, yield 14.33%).

[0102]

[0103] 2. Synthesis of Compound 60

[0104] (1) Compound 60-1 (11 g, 66.6 mmol) was dissolved in DMF, and NIS (15 g, 66.6 mmol) was added. After reacting for 2 hours, the reaction was monitored by LCMS until it was complete. The system was then poured into ice water, and the precipitated yellow solid was filtered through a Buchner funnel. The solid obtained by filtration was washed three times with water and dried to obtain yellow solid 60-2 (13 g, yield 67%).

[0105]

[0106] (2) Dissolve 60-2 (3g, 10.31mmol) in DCM, add HATU (5.9g, 15.5mmol), DIEA (2.5g, 20.6mmol) and α-methylbenzylamine (2g, 15.5mmol) and react at room temperature overnight. After the reaction is completed by LCMS monitoring, pour the system into water, add DCM for extraction, combine the organic phases and dry with anhydrous sodium sulfate, concentrate the organic phase, and purify by column chromatography with EA / PE (10-50%) to obtain yellow solid 60-3 (2.3g, yield 56.6%, purity 97%).

[0107]

[0108] (3) Dissolve 60-3 (2.3 g, 5.8 mmol) in DMF, cool the reaction system in an ice bath, slowly add TFAA (1.2 g, 5.8 mmol), remove the ice bath and restore the reaction to room temperature. After 1 h of reaction, monitor the reaction to ensure it is complete with LCMS, pour the system into ice water, filter the precipitated yellow solid using a Buchner funnel, wash the filtered solid three times with water, and dry to obtain yellow solid 60-4 (2 g, yield 69.9%, purity 94%).

[0109]

[0110] (4) Compound 60-4 (2g, 4.1mmol) was dissolved in toluene, p-toluenesulfonic acid (0.72g, 4.1mmol) and dry molecular sieve were added, and the mixture was heated to reflux for 4h. After the reaction was complete as monitored by LCMS, toluene was removed, water and EA were added for extraction, the organic phase was dried with anhydrous sodium sulfate, the organic phase was concentrated, and the residue was purified by column chromatography using an EA / PE (0-10%) system to obtain yellow solid 60-5 (1.5g, yield 77.9%, purity 96%).

[0111]

[0112] (5) Dissolve 60-5 (0.8 g, 1.7 mmol) in DMF, add lithium formate (264 mg, 5.1 mmol), lithium chloride (215 mg, 5.1 mmol), acetic anhydride (345 mg, 3.4 mmol), DIEA (437 mg, 3.4 mmol) and X-PhOS-Pd-G2 (CAS No.: 1310584-14-5, 0.1 mmol), under nitrogen protection, heat to 70 °C, and after the reaction is complete as monitored by LCMS, add water and EA for extraction, combine the organic phases and dry with anhydrous sodium sulfate, remove the organic phase, and purify the residue by normal phase column chromatography to obtain yellow solid 60-6 (213 mg, yield 32.2%, purity 92%).

[0113]

[0114] (6) Dissolve 60-6 (213 mg, 0.55 mmol) in DCM, add oxalyl chloride (138 mg, 1.1 mmol), add 2-3 drops of DMF as a catalyst, react for 30 min, remove the solvent from the system by rotary evaporation, and dissolve the obtained solid in an appropriate amount of DCM for later use; take a dry eggplant-shaped flask, put in 1,3-cyclohexanedione (91.77 mg, 0.82 mmol), add DCM to dissolve, add triethylamine (513 mg, 5.1 mmol), cool the reaction system in an ice bath, slowly add the above acyl chloride to the system, remove the ice bath and restore the reaction to room temperature, monitor the reaction to complete by LCMS, and obtain crude 60-7, which can be used directly for the next step without processing.

[0115]

[0116] (7) Add acetone cyanohydrin (11.62 mg, 0.14 mmol) to the system from the previous step, react overnight at room temperature, monitor the reaction completion by LCMS, add water and DCM for extraction, combine the organic phases and dry with anhydrous sodium sulfate, and purify by reversed-phase column chromatography with ACN / H2O (10-30%) to obtain yellow solid compound 60 (77 mg, yield 29.1%, purity 99%).

[0117]

[0118] Bioactivity evaluation:

[0119] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0120] Level 9: Complete death;

[0121] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0122] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0123] Level 6: Growth control rate greater than or equal to 70% and less than 80%;

[0124] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0125] Level 4: Growth control rate greater than or equal to 30% and less than 50%;

[0126] Level 3: Growth control rate greater than or equal to 20% and less than 30%;

[0127] Level 2: Growth control rate greater than or equal to 10% and less than 20%;

[0128] Level 1: Growth control rate less than 10%;

[0129] Level 0: No effect.

[0130] The above growth control rates are fresh weight control rates.

[0131] (1) Post-emergence testing experiment:

[0132] 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 2-6 leaf stage. The tested compound of this invention was dissolved in acetone, and then Tween 80 was added. Methyl oleate emulsifiable concentrate at 900 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.

[0133] Table 2 Results of post-emergence weed test

[0134]

[0135] Note: N represents no data.

[0136] (2) Water-based closed-loop test:

[0137] Weed seeds were evenly sown into muddy soil. After standing in the greenhouse for 1-3 days, the herbicide was applied using a mobile sprayer. The application was repeated three times. After application, the soil was kept in muddy state for about 14 days to observe the weed emergence. The efficacy was evaluated and statistically analyzed. Representative data are listed in Table 3.

[0138] Table 3 Results of the water-based live-streaming closed test

[0139]

[0140] Furthermore, numerous tests have revealed that the compounds and compositions described in this invention can control many key grass weeds, as well as broadleaf and sedge weeds. Tests on crops such as peanuts, corn, and rice under different application methods have also demonstrated excellent selectivity and commercial value.

[0141] 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 quinazolinone compound as shown in general formula I, its stereoisomers, and its agriculturally usable salt: , in, Q represents , or ; A represents aryl or heterocyclic group; Y1, Y2, Y3, Y4, Y5, and Y6 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, or cycloalkylalkyl, or two substituents on the same carbon atom connected to form =O, or unsubstituted or halogen-substituted -(CH2)2-, -(CH2)3-, or -(CH2)4-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogen-substituted -CH2-, -(CH2)2-, -(CH2)3-, or -(CH2)4-; R1 represents alkyl, haloalkyl, alkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, halogen, cycloalkyl, nitro, cyano, or aryl; R2, R3, R4, R5, R7, R8, R9, R 10 Each of the following groups independently represents hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, aryl, -OR, -N(R)2, -O(CO)N(R)2, -O(CS)N(R)2, -O-alkylene-(CO)R, -(CO)OR, -SR, -(SO)R or -(SO2)R, or an alkyl, alkenyl or alkynyl group substituted with at least one group selected from halogen, cycloalkyl, -OR, -O-alkylene-OR, -SR, -(SO)R or -(SO2)R; R6 represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic, or an alkyl, alkenyl, or alkynyl group substituted with at least one group selected from cyano, nitro, halogen, cycloalkyl, heterocyclic, aryl, -OR, -SR, -(SO)R, or -(SO2)R. The aforementioned cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, halocycloalkyl, alkyl-substituted cycloalkyl, -OR, -SR, -(CO)OR, -(SO2)R, or -N(R)2. R can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkyl, alkenyl, or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano, or alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

2. The quinazolinone compound, its stereoisomer, and agriculturally usable salt according to claim 1, characterized in that, Y1, Y2, Y3, Y4, Y5, and Y6 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl, or two substituents on the same carbon atom connected to form =O, or unsubstituted or halogenated -(CH2)2-, -(CH2)3- or -(CH2)4-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3- or -(CH2)4-; R1 represents C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy-C1-C8 alkyl, C2-C8 alkenyl, halo-C2-C8 alkenyl, C2-C8 alkynyl, halo-C2-C8 alkynyl, halogen, C3-C8 cycloalkyl, nitro, cyano or aryl. R2, R3, R4, R5, R7, R8, R9, R 10 Each of these groups independently represents hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, heterocyclic, aryl, -OR, -N(R)2, -O(CS)N(R)2, -O(CO)N(R)2, -O-(C1-C8 alkylene)-(CO)R, -(CO)OR, -SR, -(SO)R or -(SO2)R, or a C1-C8 alkyl, C2-C8 alkenyl or C2-C8 ynyl group substituted with at least one group selected from halogen, C3-C8 cycloalkyl, -OR, -O-(C1-C8 alkylene)-OR, -SR, -(SO)R or -(SO2)R; R6 represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclic, or a C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl substituted with at least one group selected from cyano, nitro, halogen, C3-C8 cycloalkyl, heterocyclic, aryl, -OR, -SR, -(SO)R, or -(SO2)R; The aforementioned C3-C8 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 ynyl, halo-C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR, -SR, -(CO)OR, -(SO2)R, or -N(R)2; R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, phenyl, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, cyano or C1-C8 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy.

3. A quinazolinone compound, its stereoisomer, and an agriculturally usable salt according to claim 1 or 2, characterized in that, Y1, Y2, Y3, Y4, Y5, and Y6 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl, or two substituents on the same carbon atom connected to form =O, or unsubstituted or halogenated -(CH2)2-, -(CH2)3- or -(CH2)4-, or two substituents on different carbon atoms connected to form -O-, or unsubstituted or halogenated -CH2-, -(CH2)2-, -(CH2)3- or -(CH2)4-; R1 represents C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, halogen, C3-C6 cycloalkyl, nitro, cyano or aryl. R2, R3, R4, R5, R7, R8, R9, R 10 Each of these groups independently represents hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, heterocyclic, aryl, -OR, -N(R)2, -O(CO)N(R)2, -O(CS)N(R)2, -O-(C1-C6 alkylene)-(CO)R, -(CO)OR, -SR, -(SO)R or -(SO2)R, or a C1-C6 alkyl, C2-C6 alkenyl or C2-C6 ynyl group substituted with at least one group selected from halogen, C3-C6 cycloalkyl, -OR, -O-(C1-C6 alkylene)-OR, -SR, -(SO)R or -(SO2)R; R6 represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, aryl, heterocyclic, or a C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl substituted with at least one group selected from cyano, nitro, halogen, C3-C6 cycloalkyl, heterocyclic, aryl, -OR, -SR, -(SO)R, or -(SO2)R; The aforementioned C3-C6 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 ynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR, -SR, -(CO)OR, -(SO2)R, or -N(R)2; R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano or C1-C6 alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1, Table A and Table B.

4. A quinazolinone compound having a chiral center as shown in Formula I', its stereoisomers, and its agriculturally usable salt: , in, The substituents Q, A, R1, R2, R3, R4, and R5 are defined as described in any one of claims 1-3; the carbon atom at position 2 is a chiral center, and based on the content of stereoisomers having R and S configurations at that position, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S); or it has a stereochemical purity of 60-100% (R), preferably 70-100% (R), more preferably 80-100% (R), further preferably 90-100% (R), and even more preferably 95-100% (R).

5. A method for preparing a quinazolinone compound, its stereoisomer, and an agriculturally usable salt as described in any one of claims 1-4, comprising the following steps: With compounds The reaction is carried out as an intermediate, wherein L represents a leaving group (such as OH, halogen, p-nitrophenoxy or cyano, etc.), and the substituents A, R1, R2, R3, R4 and R5 are defined as described in any one of claims 1-4.

6. A herbicide composition, characterized in that, The herbicide includes at least one of the quinazolinone compounds, their stereoisomers, and agriculturally usable salts as described in any one of claims 1-4, preferably, it also includes formulation adjuvants, and more preferably, it also includes other active ingredients.

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

8. Use of at least one of the quinazolinone compounds, their stereoisomers, and agriculturally usable salts as described in any one of claims 1-4, or the herbicide composition as described in claim 6, in controlling weeds, preferably, the quinazolinone compounds, their stereoisomers, and agriculturally usable salts are used to control weeds in useful crops, more preferably, the useful crops include transgenic crops or crops treated with genome editing technology.

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