Phenyl isoxazoline compound, and preparation method therefor, herbicidal composition thereof and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a phenyl isoxazoline compound, and a preparation method therefor, a herbicidal composition thereof and the use thereof. The compound is as represented by general formula (I), wherein R1, R2, R3, R4 and R5 each independently represent hydrogen, halogen, cyano, nitro, alkyl, etc.; X1 represents halogen, cyano, alkyl, etc.; X2 represents hydrogen, halogen, alkyl or haloalkyl; Y represents -OR, -SR, -O-N=C(R)2, -N(R)2, etc.; Z represents halogen; and Q represents O or S. The compound has a good herbicidal activity and is safe for crops.

Description

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

[0001] This invention belongs to the field of pesticide technology, specifically relating to a phenylisoxazoline 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 phenylisoxazoline compound, its preparation method, herbicidal composition, and application. The compound exhibits excellent herbicidal activity and crop safety.

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

[0005] A phenylisoxazoline compound or a salt thereof, as shown in Formula I:

[0006] Wherein, R1, R2, R3, R4, and R5 independently represent at least one group selected from hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -SR, -alkylene-OR, -alkylene-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SOR, -SO2R, -OSO2R, -N(R)2, or -NR(OR);

[0007] X1 represents halogen, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, -OR, -SR, -alkylene-OR, -alkylene-O(CO)R, -alkylene-SR, -(CO)OR or -(CO)R;

[0008] X2 represents hydrogen, halogen, alkyl, or haloalkyl;

[0009] Alternatively, X1 and X2 may be connected together to form unsubstituted or halogenated -CH2CH2CH2- or -CH2CH2CH2CH2-;

[0010] Y represents -OR, -SR, -ON=C(R)2, -N(R)2, -NR(OR), -NR(COR), -NR(SO2R) or -NR-N(R)2;

[0011] Z represents halogen;

[0012] Q represents O or S;

[0013] The aforementioned cycloalkyl, cycloalkenyl, aryl, or heterocyclic groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, cycloalkylalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -alkylene-OR, -alkylene-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SO2R, -OSO2R, -N(R)2, or -NR(OR);

[0014] R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl group, alkyl, alkenyl or alkynyl group substituted with at least one group selected from halogen, hydroxyl, alkoxy, alkylthio, alkyl sulfoxide, alkyl sulfonyl, cyano, trialkylsilyl, cycloalkyl, heterocyclic, cycloalkenyl, phenyl, alkoxyaminocarbonyl or alkoxycarbonyl, cycloalkyl, cycloalkenyl, phenyl, heterocyclic, or cycloalkyl, cycloalkenyl, phenyl or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkyl sulfonyl, alkoxy, haloalkoxy, phenyl or halophenyl, or -C(R)2 together to form a saturated carbide ring, or -N(R)2 together to form a heterocyclic group with a nitrogen atom at the 1-position.

[0015] In one specific embodiment, R1, R2, R3, R4, and R5 each independently represent at least one group selected from hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR, -SR, -(C1-C8 alkylene)-OR, -(C1-C8 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SOR, -SO2R, -OSO2R, -N(R)2, or -NR(OR).

[0016] X1 represents halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, cyano-C1-C8 alkyl, -OR, -SR, -(C1-C8 alkylene)-OR, -(C1-C8 alkylene)-O(CO)R, -(C1-C8 alkylene)-SR, -(CO)OR or -(CO)R;

[0017] X2 represents hydrogen, halogen, C1-C8 alkyl, or halo-C1-C8 alkyl;

[0018] Alternatively, X1 and X2 may be connected together to form unsubstituted or halogenated -CH2CH2CH2- or -CH2CH2CH2CH2-;

[0019] The aforementioned C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, or heterocyclic groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 ynyl, -OR, -SR, -(C1-C8 alkylene)-OR, -(C1-C8 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SO2R, -OSO2R, -N(R)2, or -NR(OR);

[0020] R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, and a C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl group substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkylsulfonyl, cyano, triC1-C8 alkylsilyl, C3-C8 cycloalkyl, heterocyclic, C3-C8 cycloalkenyl, phenyl, C1-C8 alkoxyaminocarbonyl, or C1-C8 alkoxycarbonyl. C3-C8 cycloalkenyl, phenyl, heterocyclic, or C3-C8 cycloalkyl, C3-C8 cycloalkenyl, phenyl, or heterocyclic group 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, halo-C1-C8 alkoxy, phenyl, or halophenyl, or -C(R)2 together to form a 3- to 8-membered saturated carbon ring, or -N(R)2 together to form a 3- to 8-membered heterocyclic group with a nitrogen atom at the 1-position.

[0021] In another specific embodiment, R1, R2, R3, R4, and R5 each independently represent at least one group selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, -OR, -SR, -(C1-C6 alkylene)-OR, -(C1-C6 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SOR, -SO2R, -OSO2R, -N(R)2, or -NR(OR).

[0022] X1 represents halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, cyano-C1-C6 alkyl, -OR, -SR, -(C1-C6 alkylene)-OR, -(C1-C6 alkylene)-O(CO)R, -(C1-C6 alkylene)-SR, -(CO)OR or -(CO)R;

[0023] X2 represents hydrogen, halogen, C1-C6 alkyl, or halo-C1-C6 alkyl;

[0024] Alternatively, X1 and X2 may be connected together to form unsubstituted or halogenated -CH2CH2CH2- or -CH2CH2CH2CH2-;

[0025] The aforementioned C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, or heterocyclic groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, -OR, -SR, -(C1-C6 alkylene)-OR, -(C1-C6 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SO2R, -OSO2R, -N(R)2, or -NR(OR);

[0026] R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and a C1-C6 alkyl or C2-C6 alkenyl group substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyl, cyano, triC1-C6 alkylsilyl, C3-C6 cycloalkyl, heterocyclic, C3-C6 cycloalkenyl, phenyl, C1-C6 alkoxyaminocarbonyl, or C1-C6 alkoxycarbonyl. Alternatively, it can be formed with a C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, heterocyclic group, or a C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, phenyl, or halo-phenyl groups, or -C(R)2. Or -N(R)2 together form

[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 "-alkylene-OR", alkylene can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. Alkyl groups are, 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" includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups. And, including but not limited to, heteroaryl groups, i.e., aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused with benzo[a] rings, wherein 1 to 4 (e.g., 1, 2, 3, or 4) heteroatoms are selected from oxygen, nitrogen, and sulfur, for example

[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 phenylisoxazoline compound or a salt thereof having a chiral center as shown in Formula I':

[0032] Among them, carbon atoms at positions 3, 4 and / or 5 are chiral centers, and the substituents R1, R2, R3, R4, R5, Q, X1, X2, Y and Z are defined as described above;

[0033] Based on the content of stereoisomers having R and S configurations at the 3 positions, 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] Based on the content of stereoisomers having R and S configurations at the 4 positions, 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); and / or

[0035] Based on the content of stereoisomers having R and S configurations at the 5 positions, 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).

[0036] "Stereochemical purity" refers to the percentage of the amount of the stereoisomer relative to the total amount of stereoisomers that generate chiral centers.

[0037] In this invention, the stereochemical configurations at positions 3, 4, and 5 in Formula I are determined to be predominantly (R) or (S) according to the Cahn-Ingold-Prelog system. However, the subject matter of this invention also relates to all stereoisomers at other positions included in Formula I, and mixtures thereof. Such Formula I compounds contain, for example, one or more additional asymmetric carbon atoms or other double bonds not specifically described in Formula I. It should be understood that this invention includes pure isomers and mixtures thereof enriched to varying degrees with pure isomers, wherein the asymmetric carbon atoms at positions 3, 4, and / or 5 are respectively R-configured or S-configured, or in the mixture, the compound or a compound with the same chemical structure has an R-configuration or S-configuration at any one or more of said positions, or is present in a proportion predominantly having a compound with an R-configuration or S-configuration (at least 60% R-configuration or S-configuration), while other asymmetric carbon atoms may be present in racemic form or may be split to varying degrees. Possible stereoisomers defined by a specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers, are included in Formula I, provided that the stereochemical configuration conditions at the stated position are met. These stereoisomers can be obtained from mixtures of stereoisomers using conventional methods, or they can be prepared by stereoselective reactions in conjunction with stereochemically pure initial substances.

[0038] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0039] 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.

[0040] The method for preparing the phenylisoxazoline compound or its salt includes the following steps:

[0041] (1) The compound of general formula II is reacted with YH to prepare the compound of general formula I. The reaction equation is as follows:

[0042] Alternatively, (2) the compound represented by general formula III and the compound represented by general formula IV or their salts (such as hydrochloride) are reacted to prepare the compound represented by general formula I, and the reaction equation is as follows:

[0043] Where W represents halogen or OH, M represents halogen or OH, and the substituents R1, R2, R3, R4, R5, Q, X1, X2, Y and Z are defined as described above.

[0044] In one specific embodiment, the reaction (1) is carried out in the presence of a solvent and an acid.

[0045] In another specific embodiment, the acid is selected from at least one of sulfuric acid, hydrochloric acid, phosphoric acid, or nitric acid.

[0046] In one specific embodiment, the reaction (2) is carried out in the presence of a solvent.

[0047] In another specific embodiment, an alkali and / or a condensing agent are added during reaction (2).

[0048] In another specific embodiment, the base is selected from at least one of inorganic or organic bases, such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KI, NaI, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, NaH, KH, DMAP, pyrazole, triethylamine, or DIEA.

[0049] In another specific embodiment, the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU, or HATU.

[0050] In another specific embodiment, the solvent is selected from at least one of methanol, ethanol, diethyl ether, chloroform, acetonitrile, dichloroethane, dioxane, dichloromethane, tetrahydrofuran, or water.

[0051] In addition, the compounds described in this invention can be prepared by referring to the method shown in WO2019145245A1, etc.

[0052] An intermediate, as described in Formula II.

[0053] A herbicide composition comprising a herbicidal effective amount of at least one of the phenylisoxazoline compounds or their salts; preferably, further comprising a formulation adjuvant; more preferably, further comprising other active ingredients.

[0054] A method for controlling weeds, comprising applying a herbicidal effective amount of at least one of the phenylisoxazoline compounds or their salts, or the herbicide composition thereof, to plants or weedy areas.

[0055] The use of at least one of the phenyl isoxazoline compounds or their salts, or the herbicide composition thereof, in controlling weeds, preferably, the use of the phenyl isoxazoline compounds or their salts in controlling weeds in useful crops, said useful crops being transgenic crops or crops treated with genome editing technology.

[0056] For many economically important monocotyledonous and dicotyledonous pests, the compounds of formulas I and 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*.

[0057] 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*.

[0058] 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.

[0059] 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.

[0060] The compounds of formula I, I', or their salts thereof of the present invention 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, 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.

[0061] 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:

[0062] - To improve starch synthesis in plants, genetic engineering is used to modify crop plants (e.g., WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0063] - Transgenic crop plants resistant to specific herbicides, such as glufosinate-methyl (e.g., EP-0242236 A, EP-0242246 A), glyphosate-based herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993 A, US-5013659 A);

[0064] - For example, genetically modified cotton plants can produce Bt toxins, which can defend against certain pests (EP-0142924 A, EP-0193259 A).

[0065] - A genetically modified crop plant with improved fatty acid composition (WO91 / 13972).

[0066] Many molecular biotechnologies for preparing transgenic plants with improved traits are known (see, for example, Sambrook et al., 1989, Molecular Amplification, Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory, Cold Spring Harbor, New York; or Winnacker, “Gene and Cloning,” VCH Weinheim, 2nd ed., 1996; or Christou, “Trends in Plant Science,” 1 (1996) 423-431). To perform genetic engineering operations, nucleic acid molecules may be introduced into plasmids, resulting in mutations or sequence alterations through DNA sequence recombination. Using standard methods, such as exchanging substrates, removing portions of the sequence, or adding natural or synthetic sequences, can be employed. To link DNA fragments together, it is possible to attach conjugates or linkers to the fragments.

[0067] 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.

[0068] 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.

[0069] 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 65 (1988), 846-850; Sonnewald et al. Plant J.1 (1991), 95-106).

[0070] Using known techniques, transgenic plant cells can be recombined into the entire plant. Transgenic plants can be any desired plant variety, i.e., monocots and dicots. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (=natural) genes or gene sequences, or by expressing heterologous (=external) genes or gene sequences.

[0071] 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.

[0072] 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.

[0073] 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 formulas I and I'. Compounds of formulas I and 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.

[0074] Necessary formulation adjuvants, such as inert substances, surfactants, solvents, and other additives, are also known and described in the following documents, for example, Watkins's "Handbook of Powder Diluents, Insecticides, and Carriers," 2nd ed., Darland, Caldwell, NJ; Hv01phen's "Introduction to Clay Colloid Chemistry," 2nd ed., J. Wiley and Sons, NY; C. Marsden's "Solvent Guide," 2nd ed., Interscience, NY 1963; McCutcheon's "Annual Report on Detergents and Emulsifiers," MC Publishing, Ridgewood, NJ; Sisley and Wood, "Encyclopedia of Surfactants," Chemical Publishing, NY 1964; of [Ethylene oxide adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie” [Chemical Processes], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] For methods of preparing granules using grinding discs, fluidized beds, extruders, and spraying, see the following processes, for example, “Spray Drying Handbook,” 3rd edition, 1979, G. Goodwin Ltd., London; J.E. Browning, “Agglomeration,” Chemicals and Engineering, 1967, 147ff; “Perry’s Chemical Engineer’s Handbook,” 5th edition, McGraw-Hill, New York, 1973, 8–57. For information on formulations of crop protection products, see, for example, G.K. C. Lingman, “Weed Control as a Science,” John Wiley and Sons, New York, 1961, 181–96; and JD. F. Greyer, SAEvans, “Weed Control Handbook,” 5th edition, Blackwell Scientific Rublications, Oxford University Press, 1968, 101–103.

[0081] Agricultural chemical formulations typically contain 0.1% to 99%, particularly 0.1% to 95%, of active ingredient formula I, 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 about 1% to 90% by weight, preferably 5% to 80%. Powder formulations contain 1% to 30% by weight of active ingredient, typically preferably 5% to 20% by weight; however, sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight of active ingredient. The content of active ingredient in aqueous suspension granules depends primarily on whether the active ingredient is liquid or solid, and on the adjuvants, fillers, etc., used during granulation. The content of active ingredient in aqueous suspension granules is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.

[0082] 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.

[0083] 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.

[0084] 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 mixtures of formulas I and I' (Note: the name of the compound, 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, succinate, chlorpyrifos, chlorpyrifos, naphthylpropachlor, R-L-naphthylpropachlor, propargite, benzylthiamethoxam, bisbenzylthiamethoxam, pyrifluquinazon, chlorpyrifos, flubutyroxyfen, brobutyroxyfen, dimethomorph, methoxyfenazon, ethoxybenzylthiamethoxam, flubutyroxyfen, methoxyfenazon, pyrifluquinazon, isoxachlor, methyl parathion, methyl parathion Ester, dipropionylamine, clethodim, butyroxychloride, cyclopropionylamine, flusulfanilamide, heptanochlor, isobutanilamide, propyzoxychlor, terbutanilamide, xylazine, metolachlor, methylcyclopyr, chlorpyrifos, propyzoxychlor, pendimethalin, carbaryl, succinylamine, tricyclomethoate, butyroxychlor, succinylamine, bensulfuron-methyl, naphthylamine, acetochlor, naphthylamine, thiamethoxam, pyrimethanil, bensulfuron-methyl, chlorpyrifos, chlorpyrifos, butyroxychlor, flupyrazole, atrazine, simazine, promethazine, cyanazine, cypermethrin, atrazine, chlorpyrifos, isopropionylamine, flumethrin, terbutanil, terbutanil, triazine flumethrin, cyclopropionylamine, glyphosate, herbicides Dazine, chlorpyrifos, simazine, azidophos, dichlorvos, isoamyl acetate, cyprodinil, atrazine, terbufos, methoxypropazine, cyanazine, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, glycyrrhizin, cyanuric acid, Indaziflam, chlorsulfuron, mesosulfuron, bensulfuron, chlorpyrifos, bensulfuron, thiasulfuron, pyrimisulfuron, mesosulfuron, sodium methyl iodosulfuron, formamidosulfuron, ethersulfuron, etherbensulfuron, mesosulfuron, nicosulfuron, aminebensulfuron, acylsulfuron, ethoxysulfuron, cyprosulfuron, sulfadiazine, tetrazolium sulfadiazine, pyrimisulfuron, monosulfuron, monosulfuron, fluazolidone, flupyrimisulfuron, flupyrimisulfuron, epoxy Pyrisulfuron, azoxystrobin, flupyrsulfuron, propanilsulfuron, trifluprosulfuron, sulfonylsulfuron, trifluralinsulfuron, flusulfanilamide, trifluralin, sodium mesosulfuron, flupyrsulfuron, thiosulfuron, pyrisulfuron, propyrisulfuron, triflupyrsulfuron, flusulfanilamide, quizalofop-p-ethyl, ethoxyflufenoxam, oxyflufenoxam, bensulfuron, chlorfluazuron ethyl, methylflufenoxam, trifluralin, methoxyflufenoxam, trifluralin, flufenoxam, flufenoxam, oxyflufenoxam, metolachlor, sulfadiazine, flufenoxam, oxyflufenoxam, metolachlor, flufenoxam, 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, flumethrin, bispyribac-sodium, pyrimisulfuron-methyl, pyrimisulfuron-methyl, pyrimisulfuron-methyl, bispyribac-sodium, nicosulfuron-methyl, sulfadiazine, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxasulfuron-methyl, isoxasulfuron-methyl, 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. ,

[0085] When used, commercially available formulations should be diluted in a common manner if necessary, such as with water for wettable powders, concentrated emulsions, suspensions, and granules suspended in water. Powders, granules for soil application, or solutions for broadcasting and spraying generally do not require further dilution with an inert substance before use. The required dosage of compounds of formula I and I' 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 material, but is preferably between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha. Detailed Implementation

[0086] 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.

[0087] 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.

[0088] Table 1. Compound structures and their properties 1 H NMR

[0089] Table AF is constructed in the same way as Table 1 above, except that the general formula I is replaced with the general formula I' which has a chiral center. In Table A, the entries under the "Serial Number" column heading are listed sequentially as 1(5S)-1277(5S). For example, 1(5S) corresponds to the compound in Table 1 where position 5 is the S configuration. In Table B, the entries under the "Serial Number" column heading are listed sequentially as 1(5R)-1277(5R). For example, 1(5R) corresponds to the compound in Table 1 where position 5 is the R configuration. In Table C, the entries under the "Serial Number" column heading are listed sequentially as 1(3S,4S,5S)-1277(3S,4S,5S). For example, 1(3S,4S,5S) corresponds to the compound in Table 1 where positions 3, 4, and 5 are all S configurations. In Table D, the entries under the "Serial Number" column heading are listed sequentially as 1(3R,4R,5S)-1277(3R,4R,5S). For example, 1(3R,4R,5S) corresponds to the compound in Table 1 where positions 3 and 4 are both R configuration and position 5 is S configuration. In Table E, the entries under the "Serial Number" column heading are listed sequentially as 1(3S,4R,5S)-1277(3S,4R,5S). For example, 1(3S,4R,5S) corresponds to the compound in Table 1 where positions 3 and 5 are both S configuration and position 4 is R configuration. In Table F, the entries under the "Serial Number" column heading are listed sequentially as 1(3R,4S,5S)-1277(3R,4S,5S). For example, 1(3R,4S,5S) corresponds to the compound in Table 1 where positions 4 and 5 are both S configuration and position 3 is R configuration. In Table G, the entries under the "Serial Number" column heading are listed sequentially as 1(3S,4S,5R)-1277(3S,4S,5R). For example, 1(3S,4S,5R) corresponds to the compound in Table 1 where positions 3 and 4 are S-configured and position 5 is R-configured. In Table H, the entries under the "Serial Number" column heading are listed sequentially as 1(3R,4R,5R)-1277(3R,4R,5R). For example, 1(3R,4R,5R) corresponds to the compound in Table 1 where positions 3, 4, and 5 are R-configured. In Table I, the entries under the "Serial Number" column heading are listed sequentially as 1(3S,4R,5R)-1277(3S,4R,5R). For example, 1(3S,4R,5R) corresponds to the compound in Table 1 where positions 4 and 5 are R-configured and position 3 is S-configured. In Table J, the entries under the "Serial Number" column heading are listed sequentially as 1(3R,4S,5R)-1277(3R,4S,5R). For example, 1(3R,4S,5R) corresponds to the compound in Table 1 in which positions 3 and 5 are R configurations and position 4 is an S configuration.

[0090] 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. 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.

[0091] 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.

[0092] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0093] 1. Synthesis of compound 13 (3S, 4S, 5S)

[0094] (1) In a 50 mL single-necked flask, compound 13-1 (100 mg, 0.69 mmol) was dissolved in 5 mL of dichloromethane, followed by the addition of triethylamine (212 mg, 2.10 mmol) and 13-2 (280 mg, 1.03 mmol). The reaction was allowed to proceed at room temperature for 0.5 h. The reaction was monitored by LCMS until complete. The reaction solution was concentrated, and the residue was purified by column chromatography (MeOH / DCM = 1 / 10) to obtain crude compound 13-3 (300 mg), a brown solid.

[0095] (2) In a 50 mL single-necked flask, compound 13-3 (300 mg, crude) was dissolved in 5 mL of methanol, and 0.5 mL of sulfuric acid was added. The reaction was carried out at 60 °C for 0.5 h. The reaction was monitored by LCMS until complete. After the reaction solution was concentrated, ethyl acetate and water were added for extraction, followed by washing with saturated sodium bicarbonate. The organic phase was dried and concentrated, and the residue was purified by column chromatography (EA / PE = 1 / 1) to give compound 13 (3S, 4S, 5S) (55 mg, 20.2%), a white solid.

[0096] Bioactivity evaluation:

[0097] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0098] Level 9: Complete death;

[0099] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0100] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0101] Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

[0102] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0103] Level 4: Growth control rate is greater than or equal to 30% and less than 50%;

[0104] Level 3: Growth control rate greater than or equal to 20% and less than 30%;

[0105] Level 2: Growth control rate greater than or equal to 10% and less than 20%;

[0106] Level 1: Growth control rate less than 10%;

[0107] Level 0: No effect.

[0108] The above growth control rates are fresh weight control rates.

[0109] Pre-seeding test:

[0110] Seeds of monocotyledonous and dicotyledonous weeds, as well as seeds of major crops, were placed in plastic basins filled with soil and covered with 0.5-2 cm of soil. The tested compounds of this invention were dissolved in acetone, then Tween 80 was added, and the solutions were diluted with water to a certain concentration. The solutions were sprayed immediately after sowing. The results were observed after 15 days of cultivation in a greenhouse following application. Representative data are listed in Table 2.

[0111] Table 2 Results of the pre-emergence weed test

[0112] Post-emergence testing:

[0113] 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 1-6 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 experimental effects on weeds were statistically analyzed after two weeks of cultivation in the greenhouse following application. Representative data are listed in Table 3.

[0114] Table 3 Results of post-emergence weed control experiment Note: N represents no data.

[0115] Furthermore, numerous tests have revealed that the compounds and compositions described in this invention can control many key grass weeds as well as broadleaf weeds. Tests on cotton, peanuts, corn, and wheat under different application methods have also demonstrated excellent selectivity and commercial value.

[0116] 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 phenylisoxazoline compound of the formula I: ###00001### or a salt thereof. wherein R1, R2, R3, R4, and R5 each independently represent a group substituted by at least one of the following: hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -SR, -alkylene-OR, -alkylene-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SOR, -SO2R, -OSO2R, -N(R)2, or -NR(OR); X1 represents halogen, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, -OR, -SR, -alkylene-OR, -alkylene-O(CO)R, -alkylene-SR, -(CO)OR or -(CO)R; X2 represents hydrogen, halogen, alkyl, or haloalkyl; Alternatively, X1 and X2 may be connected together to form unsubstituted or halogenated -CH2CH2CH2- or -CH2CH2CH2CH2-; Y represents -OR, -SR, -ON=C(R)2, -N(R)2, -NR(OR), -NR(COR), -NR(SO2R) or -NR-N(R)2; Z represents halogen; Q represents O or S; The aforementioned cycloalkyl, cycloalkenyl, aryl, or heterocyclic groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, cycloalkylalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -alkylene-OR, -alkylene-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SO2R, -OSO2R, -N(R)2, or -NR(OR); R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl group, alkyl, alkenyl or alkynyl group substituted with at least one group selected from halogen, hydroxyl, alkoxy, alkylthio, alkyl sulfoxide, alkyl sulfonyl, cyano, trialkylsilyl, cycloalkyl, heterocyclic, cycloalkenyl, phenyl, alkoxyaminocarbonyl or alkoxycarbonyl, cycloalkyl, cycloalkenyl, phenyl, heterocyclic, or cycloalkyl, cycloalkenyl, phenyl or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkyl sulfonyl, alkoxy, haloalkoxy, phenyl or halophenyl, or -C(R)2 together to form a saturated carbide ring, or -N(R)2 together to form a heterocyclic group with a nitrogen atom at the 1-position.

2. The phenylisoxazoline compound or its salt according to claim 1, characterized in that: R1, R2, R3, R4, and R5 independently represent at least one group substituted from hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR, -SR, -(C1-C8 alkylene)-OR, -(C1-C8 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SOR, -SO2R, -OSO2R, -N(R)2, or -NR(OR); X1 represents halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, cyano-C1-C8 alkyl, -OR, -SR, -(C1-C8 alkylene)-OR, -(C1-C8 alkylene)-O(CO)R, -(C1-C8 alkylene)-SR, -(CO)OR or -(CO)R; X2 represents hydrogen, halogen, C1-C8 alkyl, or halo-C1-C8 alkyl; Alternatively, X1 and X2 may be connected together to form unsubstituted or halogenated -CH2CH2CH2- or -CH2CH2CH2CH2-; The aforementioned C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, or heterocyclic groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 ynyl, -OR, -SR, -(C1-C8 alkylene)-OR, -(C1-C8 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SO2R, -OSO2R, -N(R)2, or -NR(OR); R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, and a C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl group substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkylsulfonyl, cyano, triC1-C8 alkylsilyl, C3-C8 cycloalkyl, heterocyclic, C3-C8 cycloalkenyl, phenyl, C1-C8 alkoxyaminocarbonyl, or C1-C8 alkoxycarbonyl. C3-C8 cycloalkenyl, phenyl, heterocyclic, or C3-C8 cycloalkyl, C3-C8 cycloalkenyl, phenyl, or heterocyclic group 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, halo-C1-C8 alkoxy, phenyl, or halophenyl, or -C(R)2 together to form a 3- to 8-membered saturated carbon ring, or -N(R)2 together to form a 3- to 8-membered heterocyclic group with a nitrogen atom at the 1-position.

3. A phenylisoxazoline compound or a salt thereof according to claim 1 or 2, characterized in that: R1, R2, R3, R4, and R5 independently represent at least one group substituted from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 ynyl, -OR, -SR, -(C1-C6 alkylene)-OR, -(C1-C6 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SOR, -SO2R, -OSO2R, -N(R)2, or -NR(OR); X1 represents halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, cyano-C1-C6 alkyl, -OR, -SR, -(C1-C6 alkylene)-OR, -(C1-C6 alkylene)-O(CO)R, -(C1-C6 alkylene)-SR, -(CO)OR or -(CO)R; X2 represents hydrogen, halogen, C1-C6 alkyl, or halo-C1-C6 alkyl; Alternatively, X1 and X2 may be connected together to form unsubstituted or halogenated -CH2CH2CH2- or -CH2CH2CH2CH2-; The aforementioned C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, or heterocyclic groups are optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, -OR, -SR, -(C1-C6 alkylene)-OR, -(C1-C6 alkylene)-SR, -O(CO)R, -(CO)R, -(CO)OR, -(CO)N(R)2, -SO2R, -OSO2R, -N(R)2, or -NR(OR); R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and a C1-C6 alkyl or C2-C6 alkenyl group substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyl, cyano, triC1-C6 alkylsilyl, C3-C6 cycloalkyl, heterocyclic, C3-C6 cycloalkenyl, phenyl, C1-C6 alkoxyaminocarbonyl, or C1-C6 alkoxycarbonyl. Alternatively, it can be formed with a C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, heterocyclic group, or a C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, phenyl, or halo-phenyl groups, or -C(R)2. or -N(R)2 together form Preferably, the compound is selected from any one of Table 1 and Table AJ in the specification.

4. A phenylisoxazoline compound having a chiral center as shown in Formula I' or a salt thereof: ###00002### I' wherein The carbon atoms at positions 3, 4, and / or 5 are chiral centers, and the substituents R1, R2, R3, R4, R5, Q, X1, X2, Y, and Z are defined as described in any one of claims 1-3; Based on the content of stereoisomers having R and S configurations at the 3 positions, 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); Based on the content of stereoisomers having R and S configurations at the 4 positions, 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); and / or Based on the content of stereoisomers having R and S configurations at the 5 positions, 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 process for producing a phenylisoxazoline compound or a salt thereof according to any one of claims 1 to 4, characterized by, Includes the following steps: (1) when Y is not OH, a compound of the formula II is reacted with Y-H to give a compound of the formula I, as shown in the following reaction equation: Alternatively, (2) a compound represented by General Formula III and a compound represented by General Formula IV or a salt thereof are reacted to produce a compound represented by General Formula I, and the reaction equation is as follows: Wherein, W represents a halogen or OH, M represents a halogen or OH, and the substituents R1, R2, R3, R4, R5, Q, X1, X2, Y and Z are defined as described in any one of claims 1-4; Preferably, the reaction (1) is carried out in the presence of a solvent and an acid, and the reaction (2) is carried out in the presence of a solvent; more preferably, a base and / or a condensing agent are added during the reaction (2); even more preferably, the base is selected from at least one of inorganic bases or organic bases, the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU, the solvent is selected from at least one of methanol, ethanol, diethyl ether, chloroform, acetonitrile, dichloroethane, dioxane, dichloromethane, tetrahydrofuran or water, and / or the acid is selected from at least one of sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid.

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

7. A herbicidal composition, characterized by comprising: It includes at least one of the phenylisoxazoline compounds or their salts as described in any one of claims 1-4, which is effective in controlling weed growth; preferably, it also includes formulation adjuvants; more preferably, it also includes other active ingredients.

8. A method of controlling weeds, characterized by, This includes applying an effective amount of at least one of the phenylisoxazoline compounds or their salts as described in any one of claims 1-4, or the herbicide composition as described in claim 7, to plants or weedy areas.

9. Use of at least one of the phenylisoxazoline 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 phenylisoxazoline compounds or their salts are used to control weeds in useful crops, said useful crops including transgenic crops or crops treated with genome editing technology.

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