Substituted isoxazoline-containing aromatic compounds, their preparation process, herbicidal compositions and their use

Abstract

The present invention is in the field of pesticides, and specifically relates to certain substituted isoxazoline-containing aromatic compounds, their preparation, herbicidal compositions and uses. The compounds have the general formula I: [Formula 1] It is expressed as JPEG2023500353000101.jpg35153, where Q is [Case 2] JPEG2023500353000102.jpg30153; Y represents a halogen, an alkyl halide, or a cyano; Z represents a halogen; X1 and X2 each independently represent a hydrogen, a halogen, an alkyl, or the like; X3 represents a halogen, a cyano, or the like; X4 each independently represent -COOR5 or -alkyl-COOR5; and R5 each independently represent a hydrogen, an alkyl, or the like. This compound has excellent herbicidal activity against grass weeds, broadleaf weeds, and the like, even at low application rates, and is highly selectivity to crops.

Description

[Technical Field]

[0001] The present invention relates to the technical field of agrochemicals, and in particular to certain substituted isoxazoline-containing aromatic compounds, their preparation process, herbicidal compositions and their use. [Background technology]

[0002] Weed control is one of the most important links in the process of achieving high-efficiency agriculture. Various herbicides are available on the market. For example, Patent WO00 / 50409 describes the use of compounds of the general formula 1-aryl-4-thiotriazine as herbicides, and Patent CN105753853A describes the use of isoxazoline-containing uracil compounds and their herbicidal use. However, the herbicidal properties of these known compounds against harmful plants and their selectivity against crops are not entirely satisfactory. Due to challenges such as market expansion, weed resistance, the service life and economic efficiency of pesticides, and growing public concern about the environment, scientists still need to continue research and development into new herbicides with high efficacy, safety, economic efficiency, and different mechanisms of action. Summary of the Invention

[0003] The present invention provides certain substituted isoxazoline-containing aromatic compounds, a method for preparing the same, a herbicidal composition, and uses thereof. The compounds have excellent herbicidal activity against gramineous weeds, broadleaf weeds, etc., even at low application rates, and are highly selectivity for crops. DETAILED DESCRIPTION OF THE INVENTION

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

[0005] General formula I: [ka] [In the formula, Q is [ka] represents Y represents halogen, alkyl halide or cyano; Z represents a halogen; Q1, Q2, Q3, Q4, and Q5 each independently represent O or S; R1, R2, and R6 each independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkylalkyl; R7 and R8 each independently represent hydrogen, alkyl, halogen, halogenated alkyl, or amino; X1 and X2 each independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -OR3, -(CO)OR3, or phenyl, wherein "alkyl", "alkenyl", "alkynyl", "cycloalkyl", or "cycloalkylalkyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen; X3 represents halogen, cyano, formyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -OR3, -(CO)OR3, -SR3, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, or amino, and X3 does not represent methyl, wherein "alkyl," "alkenyl," or "alkynyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, cyano, -OR3, -(CO)R3, -SR3, -(SO2)R3, -O(CO)R3, -O-(SO2)R3, -(CO)OR3, -O(CO)OR3, -O-alkyl-(CO)OR3, and -O(CO)(CO)OR3. "cycloalkyl", "cycloalkylalkyl", "heterocyclyl", "heterocyclylalkyl", "aryl" or "arylalkyl" are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, alkyl halide, alkenyl halide, alkynyl halide, cycloalkyl halide, cycloalkyl substituted with alkyl, -OR, -SR, -(CO)OR, -(SO)R and -N(R); "amino" is unsubstituted or substituted with one or two substituents selected from the group consisting of -R; X4 each independently represents -COOR5 or -alkyl-COOR5; R3 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkylalkyl; R4 independently represents hydrogen, alkyl, or halogenated alkyl; Each R5 independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkylalkyl, where each "alkyl," "alkenyl," "alkynyl," "cycloalkyl," or "cycloalkylalkyl" is independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen. A substituted isoxazoline-containing aromatic compound represented by the formula:

[0006] Preferably, Y represents halogen, halogenated C1-C8 alkyl, or cyano; R1, R2, and R6 each independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, or C3-C8 cycloalkylC1-C8 alkyl; R7 and R8 each independently represent hydrogen, C1-C8 alkyl, halogen, halogenated C1-C8 alkyl, or amino; X1 and X2 each independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, -OR3, -(CO)OR3, or phenyl, wherein "C1-C8 alkyl", "C2-C8 alkenyl", "C2-C8 alkynyl", "C3-C8 cycloalkyl", or "C3-C8 cycloalkylC1-C8 alkyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen; X3 represents halogen, cyano, formyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, -OR3, -(CO)OR3, -SR3, heterocyclyl, heterocyclylC1-C8 alkyl, aryl, arylC1-C8 alkyl or amino, where "C1-C8 alkyl", "C2-C8 alkenyl" or "C Each "C1-C8 alkynyl" is independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, cyano, —OR, —(CO)R, —SR, —(SO)R, —O(CO)R, —O—(SO)R, —(CO)OR, —O(CO)OR, —O—(C1-C8 alkyl)-(CO)OR, and —O(CO)(CO)OR; and "C3-C8 cycloalkyl" is independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, cyano, —OR, —(CO)R, —SR, —(SO)R, —O(CO)R, —O—(SO)R, —(CO)OR, —O(CO)OR, —O—(C1-C8 alkyl)-(CO)OR, and —O(CO)(CO)OR. "C3-C8 cycloalkylC1-C8 alkyl", "heterocyclyl", "heterocyclylC1-C8 alkyl", "aryl" or "arylC1-C8 alkyl" are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, -OR4, -SR4, -(CO)OR4, -(SO2)R4 and -N(R4)2; "amino" is unsubstituted or substituted with at least one or two substituents selected from the group consisting of -R3; X4 each independently represents -COOR5 or -(C1-C8 alkyl)-COOR5; R3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, or C3-C8 cycloalkylC1-C8 alkyl; R4 independently represents hydrogen, C1-C8 alkyl, or halogenated C1-C8 alkyl; Each R5 independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, or C3-C8 cycloalkylC1-C8 alkyl, wherein "C1-C8 alkyl," "C2-C8 alkenyl," "C2-C8 alkynyl," "C3-C8 cycloalkyl," or "C3-C8 cycloalkylC1-C8 alkyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen.

[0007] Preferably, Y represents halogen, halogenated C1-C6 alkyl, or cyano; R1, R2, and R6 each independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkylC1-C6 alkyl; R7 and R8 each independently represent hydrogen, C1-C6 alkyl, halogen, halogenated C1-C6 alkyl, or amino; X1 and X2 each independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, -OR3, -(CO)OR3, or phenyl, wherein "C1-C6 alkyl", "C2-C6 alkenyl", "C2-C6 alkynyl", "C3-C6 cycloalkyl", or "C3-C6 cycloalkylC1-C6 alkyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen; X3 represents halogen, cyano, formyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, -OR3, -(CO)OR3, -SR3, heterocyclyl, heterocyclylC1-C6 alkyl, aryl, arylC1-C6 alkyl or amino, where "C1-C6 alkyl", "C2-C6 alkenyl" or "C Each "C1-C6 alkynyl" is independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, cyano, —OR, —(CO)R, —SR, —(SO)R, —O(CO)R, —O—(SO)R, —(CO)OR, —O(CO)OR, —O—(C1-C6 alkyl)-(CO)OR, and —O(CO)(CO)OR; and "C3-C6 cycloalkyl" "C3-C6 cycloalkylC1-C6 alkyl", "heterocyclyl", "heterocyclylC1-C6 alkyl", "aryl" or "arylC1-C6 alkyl" are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR4, -SR4, -(CO)OR4, -(SO2)R4 and -N(R4)2; "amino" is unsubstituted or substituted with at least one or two substituents selected from the group consisting of -R3; Each X4 independently represents -COOR5 or -(C1-C6 alkyl)-COOR5; R3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkylC1-C6 alkyl; R4 independently represents hydrogen, C1-C6 alkyl, or halogenated C1-C6 alkyl; Each R5 independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkylC1-C6 alkyl, wherein "C1-C6 alkyl," "C2-C6 alkenyl," "C2-C6 alkynyl," "C3-C6 cycloalkyl," or "C3-C6 cycloalkylC1-C6 alkyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen.

[0008] More preferably, Y represents a halogen; R1, R2, and R6 each independently represent C1-C6 alkyl; R7 and R8 each independently represent hydrogen or halogenated C1-C6 alkyl; X1 and X2 each independently represent hydrogen; X3 represents halogen, formyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, -OR3, phenyl, or benzyl, wherein "C1-C6 alkyl," "C2-C6 alkenyl," or "C2-C6 alkynyl" is each independently unsubstituted or substituted with one, two, or three substituents selected from the group consisting of halogen, -OR3, -(CO)R3, -O(CO)R3, -O-(C1-C3 alkyl)-(CO)OR3, and -O(CO)(CO)OR3. "C3-C6 cycloalkyl", "C3-C6 cycloalkylC1-C3 alkyl", "phenyl" or "benzyl" are each independently unsubstituted or substituted with 1, 2 or 3 substituents selected from halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, -OR4 and -(CO)OR4; X4 each independently represents -COOR5; R3 independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkylC1-C3 alkyl; R4 independently represents hydrogen, C1-C6 alkyl, or halogenated C1-C6 alkyl; Each R5 independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C3-C6 cycloalkyl.

[0009] More preferably, Y represents chlorine, Z represents fluorine; R7 represents C1-C6 alkyl; R8 represents hydrogen; X3 represents halogen, formyl, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, -OR3, -(C1-C3 alkyl)-OR3, -(C1-C3 alkyl)-O(CO)R3, -(C1-C3 alkyl)-(CO)OR3, -(C1-C3 alkyl-O-(C1-C3 alkyl)-(CO)OR3, -(C1-C3 alkyl)-O(CO)(CO)OR3, phenyl or benzyl, wherein each "C1-C6 alkyl" is independently unsubstituted or substituted with 1, 2 or 3 substituents selected from the group consisting of halogen; R3 each independently represents hydrogen or C1-C6 alkyl; Each R5 independently represents hydrogen or C1-C6 alkyl.

[0010] More preferably, Q is [ka] Represents.

[0011] In defining the compounds represented by the formula above and all structural formulas below, the terminology used, whether used alone or in compound words, represents the following substituents: An alkyl having three or more carbon atoms may be linear or branched. For example, the compound word "-alkyl-(CO)OR" may be used. 11 " may be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. Alkyl is, for example, C1 alkyl: methyl; C2 alkyl: ethyl; C3 alkyl: propyl, for example, n-propyl or isopropyl; C4 alkyl: butyl, for example, n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl: pentyl, for example, n-pentyl; C6 alkyl: hexyl, for example, n-hexyl, isohexyl or 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, butyl-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Examples of alkynyl include ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. The multiple bond may be located at any position in each unsaturated group. Examples of cycloalkyl include carbocyclic saturated ring systems having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Similarly, examples of cycloalkenyl include monocyclic alkenyl systems having 3 to 6 carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, and the double bond may be located at any position. Examples of halogen include fluorine, chlorine, bromine, and iodine.

[0012] Unless otherwise specified, "aryl" in the present invention includes the following groups: phenyl, naphthyl, [ka] "Heterocyclyl" not only includes saturated or unsaturated non-aromatic cyclic groups, but also includes "heteroaryl", which includes saturated or unsaturated non-aromatic cyclic groups such as: [ka] "Heteroaryl" includes, but is not limited to, aromatic cyclic groups having 3 to 6 ring atoms, optionally fused to a benzo ring, in which 1 to 4 (e.g., 1, 2, 3, or 4) heteroatoms in the ring are selected from the group consisting of oxygen, nitrogen, and sulfur. For example, [ka] is.

[0013] When a group is substituted with a group, it should be understood that the group is substituted with one or more of the same or different groups selected from the above groups. Furthermore, the same or different substitution characters contained in the same or different substituents are each independently selected and may be the same or different. This also applies to ring systems formed by different atoms and units. On the other hand, the claims exclude compounds that are chemically unstable under standard conditions known to those skilled in the art.

[0014] Furthermore, unless otherwise specified, "substituted with at least one group" in the present invention means, for example, substituted with 1, 2, 3, 4, or 5 groups; groups without a specified bonding site (including heterocyclyl, aryl, etc.) can be bonded to any site (including C or N site); when substituted, the substituent can be substituted at any site as long as it complies with the valence bond theory. For example, heteroaryl: [ka] is substituted with one methyl, it is [ka] etc.

[0015] General formula I: [ka] In the formula, the carbon atom (C * ) is a chiral center (i.e., X3 and X4 are not identical), it has the R or S configuration, preferably the S configuration, and the stereochemical purity is 60 to 100% (S), preferably 70 to 100% (S), more preferably 80 to 100% (S), even more preferably 90 to 100% (S), and even more preferably 95 to 100% (S), based on the content of stereoisomers having the R and S configurations at this position. Here, it should be noted that "stereochemical purity" means the amount of the described stereoisomer expressed as a percentage of the total amount of stereoisomers having a given chiral center.

[0016] Furthermore, the present invention also provides compounds of general formula I': [ka] [In the formula, X3' represents hydrogen, methyl or X3; The substituents X1, X2, X3, X4, Q, Y and Z are defined as above, and X3 and X4 are different. The present invention provides a substituted isoxazoline-containing aromatic compound having an S configuration represented by the formula:

[0017] In the present invention, the stereochemical configuration at the marked * position in Formulae I and I' is determined to be predominantly (S) according to the Cahn-Ingold-Prelog system. However, the subject matter of the present invention also relates to all stereoisomers at other positions encompassed by Formulae I and I' and mixtures thereof. Such compounds of Formulae I and I' may contain, for example, one or more additional asymmetric carbon atoms or other double bonds not specifically described in Formulae I and I'. It is understood that the present invention encompasses both pure isomers and more or less enriched mixtures thereof. Here, the asymmetric carbon atom at the marked * position is either in the S-configuration, or in a mixture, one or more compounds of the same chemical constitution have the S-configuration at the marked * position, or compounds with the S-configuration are predominantly present (at least 60% S-configuration), but other asymmetric carbon atoms may also be present in racemic form or more or less separately. All possible stereoisomers defined by their specific spatial configuration, e.g., enantiomers, diastereomers, Z- and E-isomers, are included in formulas I and I', provided that the requirement for stereochemical configuration at the marked * position is met. They can be obtained by conventional methods from mixtures of stereoisomers or can be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.

[0018] The present invention also encompasses any keto and enol tautomeric forms and mixtures and salts thereof, when the respective functional groups are present.

[0019] Stereoisomers can be obtained by optical resolution from the mixture obtained in the preparation. Stereoisomers can also be selectively prepared by using stereoselective reactions and optically active starting materials and / or auxiliaries. Conventional methods for optical resolution (see Textbooks of Stereochemistry), such as methods for separating a mixture into diastereomers, can usually be used, such as physical methods, such as crystallization, chromatography (especially column chromatography and high-pressure liquid chromatography), distillation (if necessary under reduced pressure), extraction, and other methods. It is generally possible to separate the remaining mixture of enantiomers by chromatographic separation on a chiral solid phase. A method suitable for use on a preparative or industrial scale is, for example, the crystallization of diastereomeric salts, which can be obtained from the compound, if appropriate, using an optically active acid, or, if an acidic group is present, from the compound using an optically active base.

[0020] The method for preparing a substituted isoxazoline-containing aromatic compound comprises the following steps: (1) Q is, [ka] In the case where the compound represented by general formula II-1 and the compound represented by general formula III-1 are subjected to a cyclization reaction to obtain a compound represented by general formula I-1, the chemical reaction formula of which is [ka] A process in which: (2) Q is, [ka] In the case where the compound represented by general formula II-2 and the compound represented by general formula III-2 are subjected to a cyclization reaction to obtain a compound represented by general formula I-2, the chemical reaction formula of which is [ka] A process in which: (3) A step of reacting a compound represented by general formula II-3 and a compound represented by general formula III-3 to obtain a compound represented by general formula I-3, the chemical reaction formula of which is: [ka] A process in which: (4) A process for obtaining a compound represented by general formula I-4 by reacting a compound represented by general formula II-4 with a compound represented by general formula III-4, the chemical reaction formula of which is: [ka] or (5) A step of subjecting a compound represented by general formula I-5 and R6'-Hal to a substitution reaction to obtain a compound represented by general formula I-6, the chemical reaction formula of which is: [ka] A process that is wherein L1, L2, L3, L4, L5, L6 and L7 each independently represent C1-C6 alkyl or aryl, preferably methyl, ethyl or phenyl; Hal represents halogen, preferably iodine; R6' represents an R6 group other than hydrogen; and the other substituents R1, R2, R6, R7, R8, X1, X2, X3, X4, Q1, Q2, Q3, Q4, Q5, Y and Z are defined as above.

[0021] Preferably, steps (1), (2), (4) and (5) are all carried out in the presence of a base and a solvent.

[0022] The base is at least one selected from inorganic bases (e.g., K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, etc.) and organic bases (e.g., pyrazole, triethylamine, DIEA, etc.).

[0023] The solvent is at least one selected from the group consisting of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, and ethyl acetate.

[0024] Preferably, step (3) is carried out in the presence of an acid.

[0025] The acid is selected from acetic acid, hydrochloric acid and sulfuric acid.

[0026] Additionally, Q: [ka] In the formula (I), when at least one of the substituents Q1, Q2 and Q3 is S, or at least one of the substituents Q4 and Q5 is S, such a compound can also be obtained by using Q as a raw material. [ka] Represent the corresponding compound using Lawesson's reagent: [ka] Alternatively, it can be prepared by conventional sulfur substitution reactions in the presence of phosphorus pentasulfide.

[0027] The compounds of the present invention can also be prepared by referring to the related methods described in patents WO00 / 50409, CN105753853A, etc.

[0028] A herbicidal composition comprising a herbicidally effective amount of at least one substituted isoxazoline-containing aromatic compound, and preferably further comprising a formulation adjuvant.

[0029] 1. A method for controlling weeds, comprising applying a herbicidally effective amount of at least one substituted isoxazoline-containing aromatic compound or herbicide composition to a plant or weed locus.

[0030] 1. Use of at least one substituted isoxazoline-containing aromatic compound or herbicidal composition for controlling weeds, preferably wherein the substituted isoxazoline-containing aromatic compound is used to control weeds in a useful crop, and the useful crop is a transgenic crop or a crop treated with gene editing technology.

[0031] The compounds of formula I and I' according to the present invention have significant herbicidal activity against a wide range of economically important monocotyledonous and dicotyledonous harmful plants.The active compounds also act effectively against perennial weeds that sprout from rhizomes, rhizomes, or other perennial organs and are difficult to control.In this context, it is generally unimportant whether the substance is applied before sowing, before emergence, or after emergence.Specifically, there can be mentioned several representative examples of monocotyledonous and dicotyledonous weeds that can be controlled by the compounds according to the present invention, but these are not limited to specific species. Examples of weed species on which the active compounds are effective include monocotyledonous plants such as Avena species, Lolium species, Alopecurus species, Phalaris species, Echinochloa species, Digitaria species, Setaria species, and annual Cyperus species, as well as perennial plants such as Agropyron species, Cynodon species, Imperata species, Sorghum species, and perennial Cyperus species.

[0032] In the case of dicotyledonous weed species, the range of effectiveness extends, for example, from annual weeds to Galium spp., Viola spp., Veronica spp., Lamium spp., Stellaria spp., Amaranthus spp., Sinapis spp., Ipomoea spp., Sida spp., Matricaria spp. and Abutilon spp., and in the case of perennial weeds to Convolvulus spp., Cirsium spp., Rumex spp. and Artemisia spp. The active compounds according to the invention also achieve significant control of harmful plants that occur under the specific conditions of rice cultivation, such as Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus. When the compounds according to the invention are applied to the soil surface before emergence, the emergence of weed seedlings is completely prevented, or the weeds grow to the cotyledon stage, after which they cease growth and gradually die completely after 3 to 4 weeks. In particular, the compounds according to the invention exhibit excellent activity against Apera spica venti, Chenopodium album, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica, Viola tricolor, as well as against Amaranthus spp., Cleaver spp. and Kochia spp.

[0033] The compound of the present invention has excellent herbicidal effect on monocotyledonous and dicotyledonous weeds, but does not damage economically important crops such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean at all, or the damage is negligible.In particular, they have excellent compatibility with cereals such as wheat, barley, corn, especially wheat.For these reasons, the compound is very suitable for selectively controlling undesirable plant growth in agricultural plantings or ornamental plantings.

[0034] Due to their herbicidal properties, these active compounds may be used to control harmful plants in crops of known or yet to be developed transgenic plants. Generally, transgenic plants have particularly significant properties, such as resistance to certain insecticides, especially to certain herbicides, or resistance to plant diseases or causative organisms of plant diseases (e.g., certain insects or microorganisms (e.g., fungi, bacteria, or viruses)). Other special properties relate, for example, to the quantity, quality, storage stability, composition, and specific components of the harvested product. Thus, transgenic plants with increased starch content, transgenic plants with altered starch quality, or transgenic plants with different fatty acid compositions in the harvested product are known.

[0035] The use of compounds of formula I and I' according to the invention or their salts in economically important transgenic crops of useful plants and ornamental plants is preferred, for example in crops of cereals such as wheat, barley, rye, oats, millet, rice, cassava, maize, etc., or in crops of sugar beet, cotton, soybean, rapeseed, potato, tomato, bean and other vegetable species. The compounds of formula I and I' can preferably be used as herbicides in crops of useful plants that are resistant to the phytotoxicity of herbicides or have been made resistant by genetic engineering.

[0036] Conventional methods for producing novel plants with modified properties compared to known plants include, for example, traditional breeding methods and the generation of mutants. Alternatively, novel plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A0221044, EP-A0131624). For example, in some cases: · genetic engineering changes in crop plants to modify the starch synthesized in the plants (e.g. WO92 / 11376, WO92 / 14827, WO91 / 19806); transgenic crops that are resistant to certain herbicides of the glufosinate type (see, for example, EP-A 0242236, EP-A 0242246), glyphosate type (WO 92 / 00377) or sulfonylurea type (EP-A 0257993, U.S. Pat. No. 5,013,659 A); Transgenic crops capable of producing Bacillus thuringiensis toxins (Bt toxins) that confer resistance to certain pests on plants, such as cotton (EP-A0142924, EP-A0193259); Transgenic crops with altered fatty acid composition have been described (WO91 / 13972).

[0037] Numerous molecular biology techniques that allow the creation of novel transgenic plants with modified properties are basically known; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition 1996, or Christou, "Trends in Plant Science" 1 (1996) 423-431). To perform such genetic engineering procedures, nucleic acid molecules can be introduced into plasmids, which allow DNA sequence recombination to induce mutations or changes in the sequence. Using the standard methods mentioned above, it is possible, for example, to replace bases to remove partial sequences or to add natural or synthetic sequences. To connect DNA fragments to each other, adapters or linkers can be attached to the fragments.

[0038] Plant cells with reduced gene product activity can be produced, for example, by expressing at least one suitable antisense RNA, sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of the above-mentioned gene product.

[0039] For this purpose, it is possible to use both DNA molecules containing the entire coding sequence of the gene product, including any flanking sequences that may be present, and DNA molecules containing only portions of the coding sequence (these portions must be long enough to cause an antisense effect in cells).It is also possible to use DNA sequences that are highly homologous to the coding sequence of the gene product, but not completely identical.

[0040] When expressing nucleic acid molecules in plants, synthesized proteins can be localized in any desired compartment of plant cells.However, to achieve localization in a specific compartment, for example, coding region can be linked with a DNA sequence that ensures localization to a specific compartment.Such 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).

[0041] Transgenic plant cells can be regenerated into whole plants using known techniques. In principle, the transgenic plants can be of any desired plant species, i.e., both monocotyledonous and dicotyledonous plants. In this way, transgenic plants can be obtained whose properties are modified by overexpression, suppression or inhibition of a homologous (=natural) gene or gene sequence or by expression of a heterologous (=foreign) gene or gene sequence.

[0042] When the active compound according to the present invention is used in transgenic crops, in addition to the effect on harmful plants that can be observed in other crops, there are many effects specific to the application to each transgenic crop.For example, the range of weeds that can be controlled is changed or clearly expanded, the application rate that can be used for application is improved, the favorable good combination performance with the herbicide that transgenic crops are resistant to, and the growth and yield of transgenic crops.Therefore, the present invention also provides the use of the compound according to the present invention as herbicide for controlling harmful plants in transgenic crops.

[0043] Furthermore, the substances according to the present invention have significant growth-regulating properties in crops.They are involved in the regulation of plant metabolism, which can be used for the targeted control of plant constituents and the promotion of harvest, for example, by causing drought and stunted growth.Furthermore, they are suitable for generally regulating and suppressing undesirable plant growth without destroying the plant in the process.The suppression of plant growth plays an important role in monocotyledonous and dicotyledonous crops, because it can reduce or completely prevent lodging.

[0044] The compounds according to the present invention can be applied in conventional formulations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. Thus, the present invention also provides herbicidal compositions comprising compounds of formulas I and I'. The compounds of formulas I and I' can be formulated by various methods depending on the prevailing biological and / or physicochemical parameters. Examples of suitable formulation options are wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsifiable concentrates (EW) (e.g. oil-in-water emulsions and water-in-oil emulsions), sprayable solutions, suspension concentrates (SC), oil dispersants (OD), oil-based or aqueous dispersions, oil-miscible solutions, dusts (DP), capsule suspensions (CS), seed dressing compositions, granules for dusting and soil application, granules for disintegration of fine granules (GR), spray granules, dressing granules and adsorbent granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known and are described, for example, in Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; and K. Martens, "Spray Drying" Handbook, 3rd Edition 1979, G. Goodwin Ltd. London.

[0045] Necessary formulation aids, such as inert materials, surfactants, solvents and other additives, are likewise known and can be found, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; H. v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schonfeldt, "Grenzflchenaktive thylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.

[0046] Wettable powders are formulations that are uniformly dispersible in water and contain, in addition to the active compound and a diluent or inert substance, ionic and / or nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyl taurate. To prepare wettable powders, the herbicidal active compound is finely milled using conventional equipment, such as a hammer mill, a fan mill, or an air jet mill, and mixed simultaneously or subsequently with formulation adjuvants.

[0047] Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent (e.g., butanol, cyclohexanone, dimethylformamide, xylene, or a relatively high-boiling aromatic compound or hydrocarbon, or a mixture of solvents) with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used include calcium alkylarylsulfonates (e.g., calcium dodecylbenzenesulfonate) or nonionic emulsifiers (e.g., fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensates, alkyl polyethers, sorbitan esters (e.g., sorbitan fatty acid esters), or polyoxyethylene sorbitan esters (e.g., polyoxyethylene sorbitan fatty acid esters)).

[0048] Powders are obtained by grinding the active compound with finely divided solid substances, such as talc, natural clays (e.g., kaolin, bentonite, and pyrophyllite) or diatomaceous earth. Suspensions may be aqueous or oily. They can be prepared, for example, by wet milling using conventional commercially available bead mills, with or without the addition of surfactants, as in the case of other formulation types, for example, as already mentioned above.

[0049] Emulsions, e.g., oil-in-water emulsions (EW), can be prepared, for example, by means of agitators, colloid mills and / or static mixers using, for example, aqueous organic solvents and, if desired, surfactants as already mentioned above in the case of other formulation types.

[0050] Granules can be prepared by spraying the active compound onto an absorbent granulated inert material, or by applying the active compound to the surface of a carrier, such as sand, kaolinite, or a granulated inert material, using an adhesive binder, such as polyvinyl alcohol, sodium polyacrylate, or mineral oil.Similarly, suitable active compounds can be mixed with fertilizers as needed and granulated by conventional methods for preparing fertilizer granules.Generally, water-dispersible granules are prepared by conventional methods, such as spray drying, fluidized bed granulation, disk granulation, mixing using a high-speed mixer, and extrusion without solid inert materials.

[0051] For the preparation of granules by disk, fluidized bed, extrusion and spraying, see, for example, the methods described in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff.; "Perry's Chemical Engineer's Handbook", 5th ed., McGraw-Hill, New York 1973, pp. 8-57. For further details on the formulation of crop protection products, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons Inc., New York, 1961, pages 81-96, and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

[0052] Typically, agricultural chemical formulations contain 0.1 to 99% by weight, specifically 0.1 to 95% by weight, of the active compound of formula I or I'. In wettable powders, the active compound concentration is, for example, about 10 to 99% by weight, with the remainder consisting of customary formulation constituents being up to 100% by weight. In emulsifiable concentrates, the active compound concentration can be, for example, about 1 to 90% by weight, preferably 5 to 80% by weight. Powder-form formulations contain 1 to 30% by weight, most commonly 5 to 20% by weight, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% by weight, of the active compound. In the case of water-dispersible granules, the active compound content depends in part on whether the active compound is in liquid or solid form and on the granulation aids and fillers used. In water-dispersible granules, the active compound content is, for example, 1 to 95% by weight, preferably 10 to 80% by weight.

[0053] Furthermore, the formulation of the active compound may contain tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoaming agents, evaporation retardants, pH adjusters and viscosity adjusters, each of which is conventional.

[0054] Based on these formulations, it is also possible to produce combinations with other pesticidal active ingredients, such as insecticides, acaricides, herbicides and fungicides, as well as combinations with safeners, fertilizers and / or growth regulators, for example in ready-to-use or tank-mix form.

[0055] Suitable active compounds that can be combined with the active compounds according to the present invention in mixed formulations or tank mixes are known active compounds, for example, as described in World Herbicide New Product Technology Handbook, China Agricultural Science and Farming Techniques Press, 2010.9 and the documents cited therein.For example, as herbicides that can be combined with the compounds of formula I and I', the following active compounds can be mentioned (note: compounds are named by their "trivial names" according to the International Organization for Standardization (ISO) or, where appropriate, by their chemical names, together with their conventional code numbers): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propachlor, ethachlor, napropamide and R-left-handed napropamide (R-left-handed naproxenic acid, propanil, mefenacet, diphenamide, diflufenican, ethaprochlor, beflubutamide, bromobutide, dimethenamid, dimethenamid-P, etobenzanide, flufenacet, thenylchlor, metazachlor, isoxaben, flamprop-M-methyl, flamprop-M-propyl, allidochlor, petoxamide, chloranocryl, ciprazine, mefluidide, monalid, delaclor, prinachlor, terbuchlor, xylachlor, dimethachlor, cisanilide, trimexachlor, Clomeprop, propyzamide, pentanochlor, carbetamide, benzoylpropethyl, ciprazole, butenachlor, tebutam, benzipram, mogrton, dichlofluanid, naproanilide, diethathylethyl, naptalam, flufenacet, EL-177, benzadox, chlorthiamide, chlorophthalimide, isocarbamide, picolinafen, atrazine, simazine, prometryn, cyanatrine, simetryn, ametryn, propazine, dipropetrine, SSH-108, terbutryn, terbuthylazine, triaziflam, ciprazine, proglinadin, trietazine, prometon,Simeton, adiprothrin, desmetrin, dimethamethrin, procyazine, mesoprazine, sebutylazine, secbumeton, terbumeton, metoprothrin, cyanatrin, ipazine, chlorazine, atraton, pendimethalin, eglinazine, cyanuric acid, indaziflam, chlorsulfuron, metsulfuron-methyl, bensulfuron-methyl, chlorimuron-ethyl, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, mesosulfuron, iodosulfuron-methyl sodium, foramsulfuron, cinosulfuron , triasulfuron, sulfometuron methyl, nicosulfuron, ethametsulfuron methyl, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, flazasulfuron, monosulfuron, monosulfuron ester, flucarbazone sodium, flupyrsulfuron methyl, halosulfuron methyl, oxasulfuron, imazosulfuron, primisulfuron, propoxycarbazone, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron methyl, tritosulfuron , metsulfuron methyl sodium, flucetosulfuron, HNPC-C, orthosulfamuron, propyrisulfuron, metazosulfuron, acifluorfen, fomesafen, lactofen, fluoroglycofen, oxyfluorfen, chlornitrofen, aclonifen, ethoxyfen ethyl, bifenox, nitrofluorfen, chlormethoxyfen, fluorodoifen, fluoronitrofen, freeroxifene, nitrofen, TOPE, DMNP, PPG1013, AKH-7088, halosafen, clo Lutoruron, isoproturon, linuron, diuron, daimuron, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, etidimuron, isouron, tebuthiuron, buturon, chlorbromuron, methyldaimuron, fenobenzuron, SK-85, metobromuron, metoxuron, afesin, monuron, siduron, fenuron, fluothiuron, nebron, chloroxuron, noruron, isonoruron, 3-cyclooctyl-1, thiazafluron, tebuthiuron, difenoxuron, parafluron,Methylamine tribunil, carbutilate, trimeturon, dimefuron, monisouron, anisuron, methyluron, chloreturon, tetrafluron, phenmedipham, phenmedipham-ethyl, desmedipham, asulam, terbucarb, barban, propham, chlorpropham, rowmate, swep, chlorbufam, carboxazole, chlorprocarb, fenashlam, BCPC, CPPC, carbasulam, butyrate, benthiocarb, vernolate, Molinate, Triallate, Dimepiperate, Esprocarb, Piributicarb, Cycloate, Avadex, EPTC, Ethiolate, Orbencarb, Pebulate, Prosulfocarb, Thiocarbazyl, CDEC, Dimexano, Isoporinate, Methiobencarb, 2,4-D Butyl Ester, MCPA-Na, 2,4-D Isooctyl Ester, MCPA Isooctyl Ester, 2,4-D Sodium Salt, 2,4-D Dimethylamine Salt, MCPA-Thioethyl, MCPA, 2,4-D Propionic Acid, High 2,4-D Prop Propionate, 2,4-D butyric acid, MCPA propionate, MCPA propionate, MCPA butyric acid, 2,4,5-D, 2,4,5-D propionic acid, 2,4,5-D butyric acid, MCPA amine salt, dicamba, elvon, chlorfenac, saison, TBA, chloramben, methoxy-TBA, diclofop-methyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-p, quizalofop-ethyl, quizalofop-ethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl Chil, propaquizafop, cyhalofop butyl, metamifop, clodinafop propargyl, fentiaprop ethyl, chloroazifop-propynyl, poppenate-methyl, trifopsim, isoxapyrifop, paraquat, diquat, oryzalin, ethalfluralin, isoproparin, nitralin, profluralin, prodiamine, benfluralin, fluchloralin, dinitramine,Dipropalin, chlornidine, methapropalin, dinoprop, glyphosate, anilofos, glufosinate ammonium, amiprophos methyl, sulfosate, piperophos, bialaphos sodium, bensulide, butamiphos, focarb, 2,4-DEP, H-9201, zytron, imazapyr, imazethapyr, imazaquin, imazamox, imazamox ammonium salt, imazapic, imazamethabenzmethyl, fluroxypyr, fluroxypyr isooctyl ester, clopyralid, pi Chloram, triclopyr, dithiopyr, haloxydine, 3,5,6-trichloro-2-pyridinol, thiazopyr, fluridone, aminopyralid, diflufenzopyr, triclopyr-butotyl, cliodinate, sethoxydim, clethodim, cycloxydim, alloxydim, clefoxydim, butroxydim, tralkoxydim, tepraloxydim, butidazole, metribuzin, hexazinone, metamitron, etiodin, ametridione, amivudine, bromoxynil, bromoxynil octanoate, ioxynil octanoate, ioxynil, Dichlobenil, diphenatryl, pyraclonil, chloroxynil, iodobonyl, flumetsulam, florasulam, penoxsulam, metsullam, cloransulam-methyl, diclosulam, piroxsulam, benfuresate, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, benzobisilone, mesotrione, sulcotrione, tembotrione, tefluriltrione, bicyclopyrone, ketodpiradox, isoxaflutole, clomazone, fenoxasulfo methiozolin, fluazolate, pyraflufen-ethyl, pyrazolinate, difenzoquat, pyrazoxyfen, benzofenap, nipiraclofen, pyrasulfotole, topramezone, pyroxasulfone, cafenstrole, flupoxam, aminotriazole, amicarbazone, azafenidin, carfentrazone-ethyl, sulfentrazone, bencarbazone, benzfendizone, butafenacil, bromacil, isocyl, lenacil, terbacil, flupropacil, cinidon-ethyl, flumiclorac-pentyl, flumioxazin,Propyzamide, MK-129, flumezin, pentachlorophenol, dinoseb, dinoterb, dinoterb acetate, dinosam, DNOC, chloronitrophene, medinoterb acetate, dinofenate, oxadiargyl, oxadiazon, pentoxazone, flufenacet, fluthiacet-methyl, fentrazamide, flufenpyr-ethyl, pyrazone, brompyrazone, metoflurane, kusakira, dimidazon , oxapyrazon, norflurazon, pyridafol, quinclorac, quinmerac, bentazone, pyridate, oxaziclomefone, benazolin, clomazone, cinmethylin, ZJ0702, pyribambenz-propyl, indanofan, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, flupropanate, cypercort, bromofenoxime, epronaz, methazole, flurtamone, benfuresate, esofumesate, thiochlorim, chlorthal , fluorochloridone, tabron, acrolein, bentlanil, tridiphane, chlorfenpropmethyl, thidiarizonaimin, phenisofam, busoxinone, methoxyphenone, saflufenacil, clasifos, chloropon, arorac, diethamcort, etonipromide, iprimidam, ipfencarbazone, thiencarbazone methyl, pyrisulfan, chlorflurazole, tripropindan, s Luglicapine, prosulfarin, cambendichlor, aminocyclopyrachlor, rodetanil, benoxacor, fenclorim, flurazole, fenchlorazole ethyl, cloquintocet-mexyl, oxabetrinil (MG / 91, cyometrinil, DKA-24, mefenpyr-diethyl, furilazole, fluxofenim, isoxadifen-ethyl, dichlormid, halauxifen-methyl, DOW florpyrauxifen, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201,ET-751, KIH-6127 and KIH-2023.

[0056] The formulations used, present in commercial form, are diluted, if appropriate, by customary methods, for example, with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Products in the form of dusts, granules for soil application or scattering and sprayable solutions are usually not further diluted with other inert substances prior to use. The application rate of the compounds of formulae I and I' required varies depending on external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary over a wide range, for example, from 0.001 to 1.0 kg ai / ha or more, preferably from 0.005 to 750 g ai / ha, in particular from 0.005 to 250 g ai / ha of reactive substance. [Example]

[0057] Specific Modes for Carrying Out the Invention The following embodiments are used to describe the present invention in detail, and are not intended to limit the present invention in any way. The scope of the present invention is described through the claims.

[0058] In view of the economy and diversity of compounds, preferably, multiple compounds are synthesized, some of which are shown in Table 1 below. The structures and information of specific compounds are shown in Table 1. The compounds in Table 1 are described to further illustrate the present invention, but are not intended to be limiting. Those skilled in the art should not interpret the subject matter of the present invention as being limited to the following compounds.

[0059] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4]

Table 1-5

Table 1-6

Table 1-7

Table 1-8

Table 1-9

Table 1-10

Table 1-11

Table 1-12

Table 1-13

Table 1-14

Table 1-15

Table 1-16

Table 1-17

Table 1-18

Table 1-19

[0060] Table A has a chiral center (General formula I:

Chemical formula

[0061] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4] [Table 2-5] [Table 2-6] [Table 2-7] [Table 2-8] [Table 2-9] [Table 2-10]

[0062] The methods for preparing the compounds of the present invention are described in detail in the following programs and embodiments. Materials are commercially available or prepared through known methods reported in the literature, or are shown in the routes. Those skilled in the art should understand that the compounds of the present invention can also be synthesized by other synthetic routes. Although the detailed materials and reaction conditions in the synthetic routes are described in the following text, they can also be easily replaced with other similar materials and conditions. For example, isomers of the compounds prepared by modifying the preparation methods of the present invention are also within the scope of the present invention. Furthermore, the following preparation methods can be further modified according to the disclosure of the present invention by general chemical methods known to those skilled in the art, for example, by protecting appropriate groups during the reaction process.

[0063] The following application methods can be used to further understand the preparation method of the present invention. The specific materials, classes and conditions are determined to further explain the present invention, and do not limit its reasonable scope. The reagents for the following synthetic compounds shown in the table can be purchased from the market or can be easily prepared by those skilled in the art.

[0064] Representative examples of compounds are as follows, and the synthesis methods of other compounds are similar and will not be described in detail here.

[0065] 1. Synthesis of Compound 55 (1) Compound 55-1 (1.18 g, 1.0 equiv., 10 mmol) was dissolved in THF (30 mL), and NaH (500 mg, 1.25 equiv., 12.5 mmol, 60% purity) was added under ice-water bath. The mixture was stirred under ice-water bath for 30 minutes, and then compound 55-2 (1.93 g, 1.0 equiv., 10 mmol) was added. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The reaction was monitored by TLC until completion. The reaction solution was then slowly added to water (200 mL) to quench the reaction, and extracted three times with ethyl acetate (20 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and finally concentrated to give crude compound 55-3 (1.88 g, 82% yield, 8.2 mmol, yellow oily liquid), which was used directly in the next step.

[0066] [ka]

[0067] (2) Compound a (20 g, 91.5 mmol, 1.0 equiv) was added to 150 mL of DMF. NCS (13.4 g, 100.7 mmol, 1.1 equiv) was slowly added to the reaction solution at 35 °C. After the addition, the solution was stirred at 35 °C for 1.5 h. LCMS showed that the raw material was almost consumed. The reaction solution was poured into 100 mL of HCl (1 M) and then extracted by adding dichloromethane. The organic phase was washed with saturated brine (100 mL × 3) and then concentrated to give crude product 55-4 (26 g, crude product, yellow oily liquid), which was used directly in the next step.

[0068] [ka]

[0069] (3) Compound 55-4 (1.6 g, 6.7 mmol, 1.0 eq) and EtN (1.01 g, 10.05 mmol, 1.5 eq) were added to 20 mL of DCM. Compound 55-3 (1.84 g, 8 mmol, 1.2 eq) was added to the reaction solution at 0 °C and reacted at 0 °C for 1 h. The product was then detected by LCMS. 100 mL of water was added to the reaction solution, followed by extraction with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography to give compound 55-5 (1.94 g, 65% yield, 4.35 mmol, yellow solid).

[0070] [ka]

[0071] (4) Compound 55-5 (1.80 g, 4.0 mmol, 1.0 equiv.), Fe powder (672 mg, 12.0 mmol, 3 equiv.), NHCl (530 mg, 10.0 mmol, 2.0 equiv.), and water (5 mL) were added successively to 20 mL of EtOH. The reaction solution was then reacted at 80 °C for 2 h. LCMS showed that the raw materials had been consumed and the main peak was the product peak. The reaction solution was filtered through diatomaceous earth and concentrated to remove ethanol. Water (100 mL) was then added, and the mixture was extracted with ethyl acetate and concentrated to obtain a black crude product. The crude product was separated and purified by column chromatography to obtain compound 55-6 (1.41 g, 85% yield, 3.4 mmol, yellow solid).

[0072] [ka]

[0073] (5) Compound 55-6 (1.2 g, 2.89 mmol, 1.0 equiv.) and compound 55-7 (0.50 g, 3.18 mmol, 1.1 equiv.) were added to 10 mL of toluene, and the reaction solution was heated at 110 °C for 1 h. LCMS showed that the raw materials were almost consumed, and the main peak belonged to the product. After concentrating the solvent, the crude product was separated by column chromatography to give compound 55-8 (1.29 g, 83.4% yield, 2.41 mmol, yellow solid).

[0074] [ka]

[0075] (6) Compound 55-9 (0.48 g, 2.1 mmol, 1.5 eq) and AcONa (58 mg, 0.7 mmol, 0.5 eq) were added to 10 mL of DMF. Compound 55-8 (0.75 g, 1.4 mmol, 1.0 eq) was added to the reaction solution at 60 °C, and the mixture was then reacted at 60 °C for 1 hour. The product was detected by LCMS. Water (10 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine (20 mL × 1), concentrated, and the crude product was separated by column chromatography to give compound 55 (0.58 g, 72% yield, 1.0 mmol, yellow solid).

[0076] [ka]

[0077] 2. Synthesis of Compound 119 (1) Diethyl oxalate (5.0 g, 34.2 mmol, 1.0 equiv) was dissolved in anhydrous THF (80 mL). The mixture was cooled to -60 °C in a dry ice ethanol bath under nitrogen protection, and cyclopropylmagnesium bromide (1 M THF solution, 37.6 mL, 37.6 mmol, 1.1 equiv) was slowly added dropwise. The mixture was then allowed to react at low temperature for 1 hour. LCMS showed that the raw material had almost completely consumed, and a new peak appeared. The reaction solution was heated to room temperature, and saturated aqueous ammonium chloride solution was slowly added dropwise to quench the reaction. The mixture was diluted with 100 mL of water. The aqueous phase was extracted with ethyl acetate (EA, 3 × 100 mL). The combined organic phases were dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent, affording crude product 119-1 (4.9 g, quantitative). This was used directly in the next step without further purification.

[0078] [ka]

[0079] (2) Methyltriphenylphosphonium bromide (12.2 g, 34.2 mmol, 1.0 equiv.) was dissolved in anhydrous THF (100 mL). The mixture was cooled to -60 °C in a dry ice ethanol bath under nitrogen protection, and LiHMDS (1 M THF solution, 34.2 mL, 34.2 mmol, 1.0 equiv.) was slowly added. The reaction mixture was then allowed to react at low temperature for 1 hour. A THF solution of the product 119-1 (4.9 g, 34.2 mmol, 1.0 equiv.) obtained from the last step was slowly added to the reaction mixture, and the reaction mixture was then allowed to react at low temperature for 2 hours. LCMS showed that the raw material had been consumed and a new peak had appeared. The reaction mixture was heated to room temperature. The reaction was quenched by slowly adding saturated aqueous ammonium chloride solution dropwise. Most of the solvent was removed by concentration under reduced pressure. The residue was diluted with 100 mL of water. The aqueous phase was extracted with ether (2×100 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent to give product 119-2 (3.2 g, crude yield 67%), which was used directly in the next step without purification.

[0080] [ka]

[0081] (3) Raw material 55-4 (2.8 g, 11.4 mmol, 0.5 eq) and EtN (1.7 g, 17.1 mmol, 1.5 eq) were added to 60 mL of DCM. The product 119-2 (3.2 g, 22.8 mmol, 1.0 eq) obtained from the last step was added to the reaction solution at 0 °C and reacted at 0 °C for 1 h, and then the product was detected by LCMS. 50 mL of water was added to the reaction solution, and then extracted with dichloromethane (50 mL × 3). The organic phase was dried over anhydrous sodium sulfate and concentrated, and the crude product was purified by column chromatography to obtain compound 119-3 (320 mg, 8% yield, yellow oil).

[0082] [ka]

[0083] (4) The product 119-3 (320 mg, 0.9 mmol, 1.0 equiv.) obtained from the last step, Fe powder (151 mg, 2.7 mmol, 3 equiv.), NHCl (95 mg, 1.8 mmol, 2 equiv.), and water (5 mL) were added successively to 20 mL of EtOH. After the reaction solution was reacted at 80 °C for 0.5 h, LCMS showed that the raw material had been consumed and the main peak was the product peak. The reaction solution was filtered through diatomaceous earth and concentrated to remove ethanol. Water (100 mL) was then added, extracted with ethyl acetate, and concentrated to obtain a black crude product. The crude product was separated and purified by column chromatography to obtain compound 119-4 (190 mg, 65% yield, yellow oil).

[0084] [ka]

[0085] (5) The product 119-4 (190 mg, 0.6 mmol, 1.0 equiv.) obtained from the last step, 10 mL of acetic acid, and raw material 119-5 (125 mg, 0.6 mmol, 1.0 equiv.) were added to a 50 mL round-neck flask. The mixture was heated to 125 °C and reacted for 20 min. LCMS showed that the product was formed. The reaction solution was cooled to room temperature and concentrated under reduced pressure to remove acetic acid. The residue was purified by silica gel column chromatography and then concentrated to give compound 119-6 (160 mg, 56% yield, pale yellow oil).

[0086] [ka]

[0087] (6) The product 119-6 (160 mg, 0.33 mmol, 1.0 equiv.) obtained from the last step, potassium carbonate (228 mg, 1.65 mmol, 5.0 equiv.), and methyl iodide (140 mg, 0.99 mmol, 3.0 equiv.) were added to 10 mL of anhydrous DMF. The mixture was reacted at room temperature for 3 hours. LCMS showed that the raw materials had been consumed and the product had formed. The reaction solution was diluted with ethyl acetate (EA, 60 mL), and the organic phase was washed with water (2 × 30 mL), then with saturated brine (30 mL), dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated and purified by column chromatography to give compound 119 (100 mg, 60% yield, yellow oil).

[0088] [ka]

[0089] (7) Compound 119 was subjected to chiral HPLC separation (chromatography column type: AD-5H 5 μm 21.2 × 250 mm; mobile phase: n-hexane:ethanol = 7:3; flow rate: 20 mL / min; wavelength: 220 nm) to obtain compound 119(S) (liquid purity: 98%, 93% ee).

[0090] [ka]

[0091] 3. Synthesis of Compound 206 (1) Compound 206-1 was prepared by following the preparation method of compound 119-4 described above. Compound 206-1 (0.6 g, 2.0 mmol, 1.0 equivalent) and compound 206-2 (0.38 g, 2.2 mmol, 1.1 equivalent) were added to 10 mL of 1,4-dioxane. The reaction solution was heated at 110 °C for 1 hour. LCMS showed that the raw material was almost consumed, and the main peak belonged to the product. The solvent was concentrated, and the crude product was separated by column chromatography to obtain compound 206-3 (0.7 g, 83.4% yield, white solid).

[0092] [ka]

[0093] (2) Compound 206-4 (0.47 g, 2.1 mmol, 1.5 eq) and AcONa (58 mg, 0.7 mmol, 0.5 eq) were added to 10 mL of DMF. Compound 206-3 (0.6 g, 1.4 mmol, 1.0 eq) was added to the reaction solution at 60 °C, and the mixture was then reacted at 60 °C for 1 hour. The product was detected by LCMS. Water (10 mL) was added to the reaction solution, and the mixture was then extracted with ethyl acetate. The organic phase was washed with saturated brine (20 mL × 1) and then concentrated. The crude product was separated by column chromatography to obtain compound 206 (0.4 g, yield 61.4%, white solid).

[0094] [ka]

[0095] 4. Synthesis of Compound 229 (1) Compound 55-4 (2 g, 7.94 mmol, 1.0 equiv.) and EtN (1.2 g, 11.88 mmol, 1.5 equiv.) were added to 200 mL of DCM. Compound 229-1 (1.02 g, 7.97 mmol, 1.0 equiv.) was then added to the reaction solution at 0 °C, slowly heated to 20 °C, and reacted for 2 to 4 h. The product was detected by LCMS. 100 mL of water was added to the reaction solution, and the mixture was extracted with dichloromethane (50 mL × 3). The organic phase was dried over anhydrous sodium sulfate and then concentrated. The crude product was purified by column chromatography to give compound 229-2 (860 mg, 32% yield).

[0096] [ka]

[0097] (2) Compound 229-2 (860 mg, 2.5 mmol, 1.0 equiv.), Fe powder (420 mg, 7.5 mmol, 3.0 equiv.), NHCl (265 mg, 5.0 mmol, 2 equiv.), and water (12.5 mL) were added successively to 50 mL of EtOH. The reaction solution was reacted at 80 °C for 2 h, after which LCMS showed that the raw materials had been consumed and the main peak belonged to the product. The reaction solution was cooled, filtered through diatomaceous earth, and concentrated to remove EtOH. Water was then added, and the mixture was extracted with ethyl acetate and concentrated to give black crude product 229-3 (720 mg, 90% yield), which was used directly in the next step.

[0098] [ka]

[0099] (3) Compound 229-3 (450 mg, 1.43 mmol, 1.0 equiv.), DMAP (17 mg, 0.14 mmol, 0.01 equiv.), triethylamine (217 mg, 2.15 mmol, 1.5 equiv.), and thiocarbonyldiimidazole CDI-S (306 mg, 1.72 mmol, 1.2 equiv.) were added to 20 mL of toluene. The reaction solution was reacted at room temperature for 1 hour. After removing the toluene by rotary evaporation, water was added and the mixture was extracted with ethyl acetate. The organic phase was mixed with silica gel, and the crude product was purified by column chromatography to give compound 229-4 (270 mg, 53% yield).

[0100] [ka]

[0101] (4) Compound 229-4 (270 mg, 0.76 mmol, 1.0 equiv.), cesium carbonate (739 mg, 2.27 mmol, 3.0 equiv.), and compound 229-5 (153 mg, 0.84 mmol, 1.1 equiv.) were added to 10 mL of DMF. After stirring the reaction solution at 0 °C for 2-3 h, LCMS showed that the raw materials had been consumed and the main peak belonged to the product. Water was added to the reaction solution, which was then extracted with ethyl acetate and washed with saturated brine. The organic phase was mixed with silica gel, and the crude product was purified by column chromatography to give compound 229-6 (102 mg, 27% yield).

[0102] [ka]

[0103] (5) Compound 229-6 (102 mg, 0.21 mmol, 1.0 equiv.), methyl iodide (118 mg, 0.83 mmol, 4.0 equiv.), and potassium carbonate (57 mg, 0.41 mmol, 2.0 equiv.) were added sequentially to 10 mL of DMF. The reaction solution was reacted at 25-30 °C for 4-6 h until the reaction was complete as detected by LCMS. Water was added to the reaction solution, which was then extracted with ethyl acetate and washed with saturated brine. The organic phase was mixed with silica gel, and the crude product was purified by column chromatography to give compound 229 (70 mg, 77% yield).

[0104] [ka]

[0105] 5. Synthesis of Compounds 1-62 (1) Compound 1-62-1 was prepared by referring to the synthesis method of compound 229-3 described above. Compound 1-62-1 (0.6 g, 2.0 mmol, 1.0 equivalent) and phenyl chloroformate (0.34 g, 2.2 mmol, 1.1 equivalent) were then added to 10 mL of toluene. The reaction solution was heated at 110 °C for 1 hour. LCMS showed that the raw materials had almost been consumed, and the main peak belonged to the product. The solvent was concentrated, and the crude product was separated by column chromatography to obtain compound 1-62-2 (0.7 g, 83.4% yield, white solid).

[0106] [ka]

[0107] (2) Compound 206-4 (0.48 g, 2.1 mmol, 1.5 equivalents) and AcONa (58 mg, 0.7 mmol, 0.5 equivalents) were added to 10 mL of DMF. Compound 1-62-2 (0.6 g, 1.4 mmol, 1.0 equivalents) was added to the reaction solution at 60 °C, and the mixture was reacted at 60 °C for 1 hour. The product was detected by LCMS. Water (10 mL) was added to the reaction solution, and then the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine (20 mL × 1) and then concentrated. The crude product was separated by column chromatography to obtain compound 1-62-racemate (0.4 g, yield 61.4%, white solid).

[0108] [ka]

[0109] (3) Compound 1-62-racemate (0.5 g, purity 98%) was subjected to chiral HPLC separation (column: AD-5H; column size: 3 cm × 25 cm, 5 μm; injection volume: 2.0 mL; mobile phase: Hex:i-PrOH (20% EtOH) = 6:4; flow rate: 20 mL / min; wavelength: UV 254 nm; temperature: 25 °C; sample solution: 50 mg / 2 mL EtOH solution; run time = 60 min) and then concentrated to give compound 1-62 (0.16 g, Rt = 10.51 min, 100% ee, white solid) and compound 1-62-R configuration (0.13 g, Rt = 30.81 min, 99.8% ee, white solid).

[0110] [ka]

[0111] Bioactivity evaluation The activity level criteria for plant injury (i.e., growth inhibition rate) are as follows: Level 5: Growth suppression rate is 85% or more Level 4: Growth suppression rate is 60% or more but less than 85% Level 3: Growth suppression rate is between 40% and 60% Level 2: Growth suppression rate is between 20% and 40% Level 1: Growth suppression rate is between 5% and 20% Level 0: Growth suppression rate is less than 5%

[0112] The growth inhibition rate mentioned above is the inhibition rate of fresh weight.

[0113] Experiments on herbicidal efficacy at the post-emergence stage Monocotyledonous and dicotyledonous weed seeds (Descurainia sophia, Shepherd's purse (Capsella bursa-pastoris), Abutilon theophrasti, Spotted pea (Galium aparine), Chickweed (Stellaria media), Purple laurel (Lithospermum arvense), Dogwood (Rorippa indica), Alopecurus aequalis, Alopecurus japonicus, Japanese laurel (Beckmannia syzigachne), Sclerochloa dura, Artemisia canadensis (Conyza canadensis), Timothy grass (Phleum paniculatum), and Persian laurel (Veronica didyma) Tenore, Bromaceous brome (Bromus japonicus), Cornstarch (Aegilops tauschii), Reed canary grass (Phalaris arundinacea), Redroot pigweed (Amaranthus retroflexus), Common lamb's quarter (Chenopodium album), Dayflower (Commelina communis), Taiwanese sedge (Sonchus arvensis), Common bindweed (Convolvulus arvensis), Setosum thistle (Cirsium setosum), Nightshade (Solanum nigrum), Chinese hackberry (Acalypha australis), Crabgrass (Digitaria sanguinalis), Barnyard grass (Echinochloa crusgalli), Green foxtail (Setaria viridis), Golden foxtail (Setaria glauca), Leptochloa chinensis), Monochoria vaginalis, Sagittaria trifolia, Scirpus juncoides, Cyperus rotundus, Cyperus iria, CyperusSeeds of major crops (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame, castor, etc.) were placed in plastic pots filled with soil, covered with 0.5-2 cm of soil, and grown in a greenhouse under favorable conditions. Two weeks after sowing, test plants were treated at the 2-3 leaf stage. Each test compound of the present invention was dissolved in acetone, to which Tween 80 and an emulsifiable concentrate of methyl oleate (1.5 L / ha) as a synergist were added. The solution was diluted with a certain amount of water to obtain a solution of a certain concentration, which was then sprayed on the plants using a sprayer. After application, the plants were incubated in a greenhouse for three weeks, and then the herbicidal results were compiled. The compound doses used were 500 g ai / ha, 250 g ai / ha, 125 g ai / ha, 60 g ai / ha, 15 g ai / ha, and 7.5 g ai / ha. Mean values ​​were obtained by repeating three times. Representative data are shown in Tables 2-6.

[0114] [Table 3]

[0115] [Table 4]

[0116] [Table 5]

[0117] [Table 6]

[0118] [Table 7]

[0119] Notes: N indicates no data. Control Compound A: [ka] Control Compound B: [ka]

[0120] Experiments on herbicidal effectiveness at the pre-emergence stage Seeds of monocotyledonous and dicotyledonous weeds and major crops (wheat, corn, rice, soybean, cotton, rapeseed, millet, and sorghum) were placed in plastic pots filled with soil and covered with 0.5 to 2 cm of soil. The test compounds of the present invention were dissolved in acetone, Tween 80 was added, and the solution was diluted with a certain amount of water to a certain concentration. The solution was sprayed immediately after sowing. After spraying, the resulting seeds were cultivated in a greenhouse for 4 weeks, and the test results were observed. At a spray rate of 250 g ai / ha, most herbicides were confirmed to be highly effective, particularly against weeds such as barnyardgrass (Echinochloa crusgalli), crabgrass (Digitaria sanguinalis), and velvetleaf (Abutilon theophrasti). Furthermore, many compounds showed good selectivity against corn, wheat, rice, and soybean.

[0121] Tests on major weeds in wheat and rice fields have shown that the compounds of the present invention have generally good weed control effects. In particular, it is noteworthy that the compounds of the present invention have extremely high activity against broadleaf weeds and cyperaceae weeds that are resistant to ALS inhibitors, such as arrowhead (Sagittaria trifolia), bulrush (Scirpus juncoides), cyperus difformis, whale grass (Descurainia sophia), shepherd's purse (Capsella bursa-pastoris), purple grass (Lithospermum arvense), spotted bush clover (Galium aparine L.), and nutsedge (Cyperus rotundus L.), and have excellent commercial value.

[0122] Safety evaluation of transplanted rice in paddy fields and evaluation of weed control effects Rice paddy soil was placed in 1 / 1,000,000 hectare pots. Seeds of barnyard grass (Echinochloa crusgalli), bulrush (Scirpus juncoides), and tallow grass (Bidens tripartita L.) were sown and gently covered with soil. The pots were then placed in a greenhouse with 0.5-1 cm of water. The next day or two days later, arrowhead (Sagittaria trifolia) tubers were planted. The pots were then kept with 3-4 cm of water. When barnyardgrass (Echinochloa crusgalli), bulrush (Scirpus juncoides) and tallow grass (Bidens tripartita L.) reached the 0.5-leaf stage and arrowhead (Sagittaria trifolia) reached the primary leaf stage, a water-diluted solution of WP or SC prepared according to a general method for preparing the compound of the present invention was uniformly dropped with a pipette onto the weeds to give a predetermined effective amount for treatment.

[0123] The rice paddy soil in the 1 / 1,000,000 ha pot was then leveled and water was retained at a depth of 3-4 cm. The following day, three-leaf stage rice (Japonica rice) was transplanted at a transplanting depth of 3 cm. Five days after transplanting, the compound of the present invention was similarly applied.

[0124] The fertility conditions of barnyardgrass (Echinochloa crusgalli), bulrush (Scirpus juncoides), Bidens tripartita L., and arrowhead (Sagittaria trifolia) were visually confirmed 14 days after application of the compounds of the present invention, and the fertility conditions of rice plants 21 days after application of the compounds of the present invention. The weed control effects were evaluated based on the above-mentioned activity standard levels. Many of the compounds exhibit excellent activity and selectivity.

[0125] Note: Seeds of barnyardgrass (Echinochloa crusgalli), barnyard grass (Scirpus juncoides), and Bidens tripartita L. were collected from Heilongjiang Province, China. Tests have shown that these weeds are resistant to common doses of pyrazosulfuron-ethyl.

[0126] At the same time, through several tests, it has been found that the compounds and compositions of the present invention have good selectivity against many grass plants, such as zoysia japonica, bermuda grass, tall fescue, bluegrass, ryegrass, seashore paspalum, etc., and can control many important grass weeds and broadleaf weeds. The compounds also show excellent selectivity and commercial value in tests on sugarcane, soybeans, cotton, oil sunflowers, potatoes, fruit trees and vegetables using different herbicide application methods.

Claims

1. General formula I: 【Chemical 1】 [In the formula, Q is, 【Chemistry 2】 represents Y represents halogen, halogenated C1-C4 alkyl, or cyano; Z represents a halogen; Q １ , Q ２ , Q ３ , Q ４ , Q ５ each independently represents O or S, R １ , R ２ , R ６ each independently represents C1-C4 alkyl or C3-C4 cycloalkyl; R ７ , R ８ each independently represents hydrogen or halogenated C1-C4 alkyl; X １ , X ２ are each independently hydrogen, C1-C4 alkyl, or —COOR ３ wherein each "C1-C4 alkyl" is independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen; X ３ is halogen, formyl, C1-C4 alkyl, C3-C4 cycloalkyl, C3-C4 cycloalkyl, C1-C4 alkyl, -OR ３ , -COOR ３ , phenyl or phenyl C1-C4 alkyl, but X ３ does not represent methyl, and each "C1-C4 alkyl" is independently unsubstituted or substituted with halogen, -OR ３ , -OCOR ３ , -COOR ３ , —O—C1-C4 alkyl-COOR ３ and -OCOCOOR ３ and is substituted with at least one substituent selected from the group consisting of X ４ are each independently -COOR ５ or -C1-C4 alkyl-COOR ５ represents R ３ each independently represents hydrogen, C1-C4 alkyl, C3-C4 cycloalkyl, or C3-C4 cycloalkylC1-C4 alkyl; R ５ each independently represent hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C4 cycloalkyl, or C3-C4 cycloalkylC1-C4 alkyl, wherein "C1-C4 alkyl," "C2-C4 alkenyl," "C2-C4 alkynyl," "C3-C4 cycloalkyl," or "C3-C4 cycloalkylC1-C4 alkyl" is each independently unsubstituted or substituted with at least one substituent selected from the group consisting of halogen.] A substituted isoxazoline-containing aromatic compound represented by the formula:

2. Y represents a halogen; R １ , R ２ , R ６ each independently represents C1-C4 alkyl; R ７ , R ８ each independently represents hydrogen or halogenated C1-C4 alkyl; X １ , X ２ each independently represents hydrogen; X ３ is halogen, formyl, C1-C4 alkyl, C3-C4 cycloalkyl, C3-C4 cycloalkyl, C1-C3 alkyl, -OR ３ , phenyl, or benzyl, wherein each "C1-C4 alkyl" is independently unsubstituted or substituted with a halogen, -OR ３ , -OCOR ３ , -COOR ３ , —O—C1-C3 alkyl-COOR ３ and -OCOCOOR ３ and is substituted with one, two or three substituents selected from the group consisting of: X ４ are each independently -COOR ５ represents R ３ each independently represent hydrogen, C1-C4 alkyl, C3-C4 cycloalkyl, or C3-C4 cycloalkylC1-C3 alkyl; R ５ each independently represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C4 cycloalkyl The substituted isoxazoline-containing aromatic compound according to claim 1 .

3. Y represents chlorine; Z represents fluorine; R ７ represents a halogenated C1-C4 alkyl; R ８ represents hydrogen, X ３ is halogen, formyl, C1-C4 alkyl, C3-C4 cycloalkyl, C3-C4 cycloalkyl, C1-C3 alkyl, -OR ３ , —C1-C3 alkyl-OR ３ , —C1-C3 alkyl-OCOR ３ , —C1-C3 alkyl-COOR ３ , —C1-C3 alkyl-O—C1-C3 alkyl-COOR ３ , —C1-C3 alkyl-OCOCOOR ３ , phenyl, or benzyl, wherein each "C1-C4 alkyl" is independently unsubstituted or substituted with 1, 2, or 3 substituents selected from the group consisting of halogen; R ３ each independently represents hydrogen or C1-C4 alkyl; R ５ each independently represents hydrogen or C1-C4 alkyl The substituted isoxazoline-containing aromatic compound according to claim 1 or 2.

4. Q is, 【Chemistry 3】 The substituted isoxazoline-containing aromatic compound according to any one of claims 1 to 3, characterized in that it represents:

5. General formula I': 【Chemistry 4】 [In the formula, X ３ ' is hydrogen, methyl or X ３ represents Substituent X １ , X ２ , X ３ , X ４ , Q, Y and Z are defined as in any one of claims 1 to 4, and X ３ and X ４ is different.] A substituted isoxazoline-containing aromatic compound having an S configuration represented by a stereochemical purity of 60 to 100% (S) based on the content of stereoisomers having the R and S configurations at this position; The substituted isoxazoline-containing aromatic compound is selected from the group consisting of the following compounds: 【Chemistry 5】 The substituted isoxazoline-containing aromatic compound is not

6. The substituted isoxazoline-containing aromatic compound according to claim 5, characterized in that the stereochemical purity is 70 to 100% (S) based on the content of stereoisomers having R and S configurations at this position.

7. The substituted isoxazoline-containing aromatic compound according to claim 5 or 6, characterized in that the stereochemical purity is 80 to 100% (S) based on the content of stereoisomers having R and S configurations at this position.

8. The substituted isoxazoline-containing aromatic compound according to any one of claims 5 to 7, characterized in that the stereochemical purity is 90 to 100% (S) based on the content of stereoisomers having R and S configurations at this position.

9. The substituted isoxazoline-containing aromatic compound according to any one of claims 5 to 8, characterized in that the stereochemical purity is 95 to 100% (S) based on the content of stereoisomers having R and S configurations at this position.

10. The following compounds: 【Table 1-1】 【Table 1-2】 【Table 1-3】 【Table 1-4】 or any of their S-configuration compounds, or the following compounds: 【Table 2-1】 【Table 2-2】 【Table 2-3】 【Table 2-4】 A substituted isoxazoline-containing aromatic compound selected from any one of

11. 11. A process for preparing the substituted isoxazoline-containing aromatic compound of any one of claims 1 to 10, said process comprising the steps of: (1) Q is, 【Chemistry 6】 In the case where the compound represented by general formula II-1 and the compound represented by general formula III-1 are subjected to a cyclization reaction to obtain a compound represented by general formula I-1, the chemical reaction formula of which is 【Chemistry 7】 a step of: (2) Q is, 【Chemistry 8】 In the case where the compound represented by general formula II-2 and the compound represented by general formula III-2 are subjected to a cyclization reaction to obtain a compound represented by general formula I-2, the chemical reaction formula of which is 【Chemistry 9】 or (3) Compounds represented by general formula I-5 and R ６ '-Hal to undergo a substitution reaction to obtain a compound represented by general formula I-6, the chemical reaction scheme of which is 【Chemistry 10】 A process that is where L １ , L ２ , L ３ , L ４ , L ５ , L ６ and L ７ each independently represents methyl, ethyl, or phenyl; Hal represents iodine; R ６ ' is R ６ represents a group, and other substituents R １ , R ２ , R ６ , R ７ , R ８ , X １ , X ２ , X ３ , X ４ , Q １ , Q ２ , Q ３ , Q ４ , Q ５ , Y and Z are defined as in any one of claims 1 to 4.

12. 12. The method of claim 11, wherein steps (1), (2) and (3) are all carried out in the presence of a base and a solvent.

13. 13. The method according to claim 12, wherein the base is at least one selected from an inorganic base and an organic base, and / or the solvent is at least one selected from the group consisting of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, and ethyl acetate.

14. 11. A herbicidal composition comprising a herbicidally effective amount of at least one substituted isoxazoline-containing aromatic compound according to any one of claims 1 to 10, and further comprising a formulation adjuvant.

15. 19. A method for controlling weeds, comprising applying to plants or weed locus a herbicidally effective amount of at least one substituted isoxazoline-containing aromatic compound of any one of claims 1 to 10 or the herbicide composition of claim 14.

16. Use of at least one substituted isoxazoline-containing aromatic compound according to any one of claims 1 to 10 or the herbicidal composition according to claim 14 for controlling weeds.

17. 17. The use according to claim 16, wherein the substituted isoxazoline-containing aromatic compound is used to control weeds in useful crops, and the useful crop is a transgenic crop or a crop treated with gene editing technology.

Images