Synthesis and application of cycloheptanone compound

Abstract

The invention relates to the field of pesticides and herbicides, and discloses synthesis and application of a cycloheptanone compound, and the cycloheptanone compound has a structure as shown in a formula I. The cycloheptanone compound disclosed by the invention has the advantages of novel action mode, low toxicity and high herbicidal activity. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of pesticide herbicides, and in particular to a class of cycloheptanone compounds containing an alpha-hydroxy ester structure and having herbicidal activity and application thereof in the field of pesticide herbicides. Background Art

[0002] Branched-chain amino acids (leucine, isoleucine, and valine) are important substances for protein synthesis in plants and are also essential amino acids for plant growth. The biosynthetic pathway of these amino acids requires three key enzymes: acetolactate synthase (ALS), acetohydroxyacid isomerase (KARI), and dihydroxyacid dehydratase (DHAD). DHAD mainly catalyzes the dehydration of α,β-dihydroxyacids to form α-ketoacids. When the DHAD enzyme is inhibited, the synthesis of leucine, isoleucine, and valine in the organism is blocked, resulting in a large amount of protein being unable to be synthesized normally, which seriously harms the growth of plants and even causes death. In recent years, the design and development of new herbicides with the goal of inhibiting the biosynthetic pathway of branched-chain amino acids has become an important research field. The characteristics of this type of herbicide are: high activity, wide spectrum of weed control, high safety for humans and animals, and environmentally friendly. Therefore, DHAD herbicides are a class of herbicides with great research value and development prospects. In recent years, only one natural product, aspterric acid (AA), has been reported to have a good inhibitory effect on DHAD. According to the systematic study on DHAD targets, the present invention designs and synthesizes a new type of cycloheptanone-type DHAD herbicides containing an α-hydroxy ester structure. Summary of the invention

[0003] The purpose of the present invention is to provide a class of cycloheptanone compounds containing an α-hydroxy ester structure and applications thereof. The compounds of the present invention have high herbicidal activity against broadleaf weeds and grass weeds.

[0004] In order to achieve the above object, the first aspect of the present invention provides a class of cycloheptanone compounds containing an α-hydroxy ester structure, wherein the structure thereof has the structure shown in Formula I:

[0005]

[0006] Wherein, in Formula I,

[0007] R 1 Selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 substituted by halogen 12 Alkyl, substituted or unsubstituted phenyl, benzyl, naphthyl, pyrrolyl, furanyl, tetrahydrofuranyl, thienyl, thiazolyl, imidazolyl, pyrazolyl, oxazolyl, valerolactamyl, pyridyl, pyranyl, piperidinyl, piperazinyl, pyridazinyl, pyrimidinyl, caprolactamyl, C3-C8 heterocycle;

[0008] R 2 Any group selected from the following X1-X6;

[0009]

[0010] Among them, in X1-X6, A 1 , A 2 , A 3a , A 3b , A 4 , A 5 , A 6a , A 6b Each is independently selected from H, C1-C8 alkyl, C1-C8 alkyl substituted by halogen, phenyl substituted or unsubstituted by C1-C8 alkyl and / or halogen, benzyl, naphthyl, pyridyl, furyl, thienyl, pyrazolyl, imidazolyl, phenyl substituted by C1-C8 alkoxy, benzyl, naphthyl, pyridyl, furyl, thienyl, pyrazolyl, imidazolyl, C3-C8 heterocycle substituted or unsubstituted by C1-C8 alkyl and / or halogen;

[0011] R 3 Selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 substituted by halogen 12 Alkyl, substituted or unsubstituted phenyl, benzyl, naphthyl, pyrrolyl, furanyl, tetrahydrofuranyl, thienyl, thiazolyl, imidazolyl, pyrazolyl, oxazolyl, valerolactamyl, pyridyl, pyranyl, piperidinyl, piperazinyl, pyridazinyl, pyrimidinyl, caprolactamyl, C3-C8 heterocycle;

[0012] And R 1 , R 3 The optional substituents in are each independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl substituted by halogen, C1-C6 alkoxy substituted by halogen, phenoxy, nitro, cyano, and amino;

[0013] n=1, 2, 3, 4, 5, 6.

[0014] Preferably, in the compound,

[0015] R 1 Selected from H, or CH2R 4 , where R 4Selected from H, C1-C3 alkyl, C5-C6 cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C6 alkyl substituted by halogen, or C1-C3 alkyl substituted by one or more halogens, cyano, C1-C3 alkoxy, C1-C6 alkoxy substituted by halogen, phenyl substituted or unsubstituted by nitro, naphthyl;

[0016] R 2 Any group selected from X1-X6, wherein in X1-X6, A 1 , A 2 , A 3a , A 3b , A 4 , A 5 , A 6a , A 6b Each is independently selected from H, C1-C4 alkyl, C1-C4 alkyl substituted by one or more halogens, phenyl substituted or unsubstituted by C1-C3 alkyl and / or amino and / or halogen, benzyl;

[0017] R 3 is selected from H, C1-C8 alkyl, C2-C4 alkenyl, C2-C6 alkynyl, C1-C8 substituted by halogen 12 Alkyl, phenyl, benzyl, naphthyl which are substituted or unsubstituted by C1-C3 alkyl and / or halogen and / or cyano and / or C1-C3 alkoxy and / or C1-C3 alkyl substituted by halogen and / or amino;

[0018] n=1,2,3,4.

[0019] More preferably, in the compound,

[0020] R1 is selected from -CH2-C6H5, -CH3, -CH2CH=C(CH3)2, -CH2-3,5-2F-C6H3, -CH2-4-CF3-C6H4, -CH2-2-C≡N-C6H4,

[0021] -CH2-C6H 11 , -CH2CH=CH2, -CH2-3,5-2OCH3-C6H3, -CH2CH2CH3, -CH2-2-CF3-C6H4, -CH2-2,6-2F-C6H3, -CH2-2-F-3-CF2OCH3-C6H3, -CH2-2 -Br-C6H4, -CH2-2-F-C6H4, -CH2-2-Cl-C6H4, -CH2-2,6-2Cl-C6H3, -CH2-3,4,5-3F-C6H2, -CH2-C5H9, -CH2-4-NO2-C6H4, -CH2-C 10 Any of H7;

[0022] R 2 Selected from -COOCH3, -COOC(CH3)3, -COOCH2C6H5, -COO(CH2)3C6H5, -COOCH2CHF2, -COOCH2CF3, -COONHNH- 4-CH3-C6H5, -COONHNH-4-F-C6H5, -COOSO2C6H5, -COOSO2-4-CH3-C6H5, -COOSO2-4-F-C6H5, -CON Any one of HSO2-4-CH3-C6H5, -CONHSO2-4-F-C6H5, -CONC3H6, -CON-3-OCH3-C3H5, -CON-3-F-C3H5, -CONC4H8, -CONHCH2C6H5, -CONHC6H5, -CONHCH2CH3, -CONHCH2-4-F-C6H4, -CONHCH2-4-CH3-C6H4;

[0023] R 3 Selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2-C6H5, -CH2CH=C(CH3)2, -CH2-3,5-2CH3-C6H3, -CH2-

[0024] 3,5-2F-C6H3, -CH2-4-CF3-C6H4, -CH2-2-C≡N-C6H4, -CH2-C6H 11 , -CH2CH=CH2, -CH2-4-F-C6H4, -CH2-3,5-2OCH3-C6H3, -CH2-2-CF3-C6H4, -CH2-2,6-2 F-C6H3, -CH2-2-Br-C6H4, -CH2-2-F-C6H4, -CH2-2-Cl-C6H4, -CH2-4-CH(CH3)2-C6H4, R 3 -CH2-3,4,5-3F-C6H2, -CH2-C5H9, -CH2-4-NO2-C6H4, -CH2-C 10 H7.

[0025] More preferably, in the compound,

[0026] R1 is selected from any one of -CH2-C6H5, -CH2-3,5-2F-C6H3, -CH2-4-CF3-C6H4, -CH2-2-C≡N-C6H4, -CH2-3,5-2OCH3-C6H3, -CH2CH2CH3, -CH2-2-CF3-C6H4, -CH2-2,6-2F-C6H3, -CH2-2-F-3-CF2OCH3-C6H3, -CH2-2-Br-C6H4, -CH2-2-F-C6H4, -CH2-2-Cl-C6H4, -CH2-2,6-2Cl-C6H3;

[0027] R 2 Any one selected from -COOCH3, -COOCH2C6H5, -COONHNH-4-CH3-C6H5, -COOSO2C6H5, -CONC4H8, -CONHCH2CH3;

[0028] R 3 Any one selected from -H, -CH3, -CH2CH=C(CH3)2.

[0029] More preferably, the cycloheptanone compound of the α-hydroxy ester structure of the present invention is specifically:

[0030] Compound H24119: R 1 -CH2-C6H5, R 2 For -COOCH3, R 3 is -H;

[0031] Compound H24120: R 1 -CH3, R 2 For -COOCH3, R 3 is -H;

[0032] Compound H24121: R 1 -CH2CH=C(CH3)2, R 2 For -COOCH3, R 3 is -H;

[0033] Compound H24122: R 1 -CH2-3,5-2CH3-C6H3, R 2 For -COOCH3, R 3 is -H;

[0034] Compound H24123: R 1 -CH2-3,5-2F-C6H3, R 2 For -COOCH3, R 3 is -H;

[0035] Compound H24124: R 1 -CH2-4-CF3-C6H4, R 2 For -COOCH3, R 3 is -H;

[0036] Compound H24125: R 1 -CH2-2-C≡N-C6H4, R 2 For -COOCH3, R 3 is -H;

[0037] Compound H24126: R 1 -CH2-C6H 11 , R 2 For -COOCH3, R 3 is -H;

[0038] Compound H24127: R 1 -CH2CH=CH2, R 2 For -COOCH3, R 3 is -H;

[0039] Compound H24128: R 1 -CH2-4-F-C6H4, R 2 For -COOCH3, R 3 is -H;

[0040] Compound H24129: R 1 -CH2-3,5-2OCH3-C6H3, R 2 For -COOCH3, R 3 is -H;

[0041] Compound H24130: R 1 -CH2CH2CH3, R 2 For -COOCH3, R 3 is -H;

[0042] Compound H24131: R 1 -CH2-2-CF3-C6H4, R 2 For -COOCH3, R 3 is -H;

[0043] Compound H24132: R 1 -CH2-2,6-2F-C6H3, R 2 For -COOCH3, R 3 is -H;

[0044] Compound H24133: R1 -CH2-2-F-3-CF2OCH3-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24134: R 1 -CH2-2-Br-C6H4, R 2 For -COOCH3, R 3 is -H;

[0045] Compound H24135: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -H;

[0046] Compound H24136: R 1 is -CH2-2-Cl-C6H4, R 2 For -COOCH3, R 3 is -H;

[0047] Compound H24137: R 1 -CH2-2,6-2Cl-C6H3, R 2 For -COOCH3, R 3 is -H;

[0048] Compound H24138: R 1 -CH2-4-CH(CH3)2-C6H4, R 2 For -COOCH3, R 3 is -H;

[0049] Compound H24139: R 1 -CH2-3,4,5-3F-C6H2, R 2 For -COOCH3, R 3 is -H;

[0050] Compound H24140: R 1 -CH2-C5H9, R 2 For -COOCH3, R 3 is -H;

[0051] Compound H24141: R 1 -CH2-4-NO2-C6H4, R 2 For -COOCH3, R 3 is -H;

[0052] Compound H24142: R 1 -CH2-C 10 H7, R 2For -COOCH3, R 3 is -H;

[0053] Compound H24143: R 1 -CH2-2-F-C6H4, R 2 -COOCH2C6H5, R 3 is -H;

[0054] Compound H24144: R 1 -CH2-2-F-C6H4, R 2 -COOC(CH3)3, R 3 is -H;

[0055] Compound H24145: R 1 -CH2-2-F-C6H4, R 2 -COO(CH2)3C6H5, R 3 is -H;

[0056] Compound H24146: R 1 -CH2-2-F-C6H4, R 2 For -COOCH2CHF2, R 3 is -H;

[0057] Compound H24147: R 1 -CH2-2-F-C6H4, R 2 -COOCH2CF3, R 3 is -H;

[0058] Compound H24148: R 1 -CH2-2-F-C6H4, R 2 -COONHNH-4-CH3-C6H5, R 3 is -H; Compound H24149: R 1 -CH2-2-F-C6H4, R 2 -COONHNH-4-F-C6H5, R 3 is -H; Compound H24150: R 1 -CH2-2-F-C6H4, R 2 -COOSO2C6H5, R 3 is -H;

[0059] Compound H24151: R 1 -CH2-2-F-C6H4, R 2 -COOSO2-4-CH3-C6H5, R 3 is -H; Compound H24152: R1 -CH2-2-F-C6H4, R 2 -COOSO2-4-F-C6H5, R 3 is -H;

[0060] Compound H24153: R 1 -CH2-2-F-C6H4, R 2 -CONHSO2C6H5, R 3 is -H;

[0061] Compound H24154: R 1 -CH2-2-F-C6H4, R 2 -CONHSO2-4-CH3-C6H5, R 3 is -H; Compound H24155: R 1 -CH2-2-F-C6H4, R 2 -CONHSO2-4-F-C6H5, R 3 is -H;

[0062] Compound H24156: R 1 -CH2-2-F-C6H4, R 2 For-CONC3H6, R 3 is -H;

[0063] Compound H24157: R 1 -CH2-2-F-C6H4, R 2 -CON-3-OCH3-C3H5, R 3 is -H;

[0064] Compound H24158: R 1 -CH2-2-F-C6H4, R 2 For-CON-3-F-C3H5, R 3 is -H;

[0065] Compound H24159: R 1 -CH2-2-F-C6H4, R 2 For-CONC4H8, R 3 is -H;

[0066] Compound H24160: R 1 -CH2-2-F-C6H4, R 2 For -CONHCH2C6H5, R 3 is -H;

[0067] Compound H24161: R 1-CH2-2-F-C6H4, R 2 For -CONHC6H5, R 3 is -H;

[0068] Compound H24162: R 1 -CH2-2-F-C6H4, R 2 For -CONHCH2CH3, R 3 is -H;

[0069] Compound H24163: R 1 -CH2-2-F-C6H4, R 2 -CONHCH2-4-F-C6H4, R 3 is -H;

[0070] Compound H24164: R 1 -CH2-2-F-C6H4, R 2 -CONHCH2-4-CH3-C6H4, R 3 is -H;

[0071] Compound H24165: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH3;

[0072] Compound H24166: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH3;

[0073] Compound H24167: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-C6H5;

[0074] Compound H24168: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH=C(CH3)2;

[0075] Compound H24169: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 -CH2-3,5-2CH3-C6H3; Compound H24170: R 1-CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-3,5-2F-C6H3;

[0076] Compound H24171: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-CF3-C6H4;

[0077] Compound H24172: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-C≡N-C6H4;

[0078] Compound H24173: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 -CH2-C6H 11 ;

[0079] Compound H24174: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH=CH2;

[0080] Compound H24175: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-F-C6H4;

[0081] Compound H24176: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 -CH2-3,5-2OCH3-C6H3; Compound H24177: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH2CH3;

[0082] Compound H24178: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-CF3-C6H4;

[0083] Compound H24179: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2,6-2F-C6H3;

[0084] Compound H24180: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-Br-C6H4;

[0085] Compound H24181: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-F-C6H4;

[0086] Compound H24182: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-Cl-C6H4;

[0087] Compound H24183: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 -CH2-4-CH(CH3)2-C6H4; Compound H24184: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-3,4,5-3F-C6H2;

[0088] Compound H24185: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-C5H9;

[0089] Compound H24186: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-NO2-C6H4;

[0090] Compound H24187: R 1 -CH2-2-F-C6H4, R 2For -COOCH3, R 3 -CH2-C 10 H7.

[0091] The present invention adopts the following route to synthesize the cycloheptanone compounds containing an α-hydroxy ester structure of the present invention:

[0092] Series 1:

[0093]

[0094] Series 2:

[0095]

[0096] Series Three:

[0097]

[0098] In the above-mentioned synthetic route, the substituents in Formula I-1, Formula I-2, Formula I-3, Formula I-4, Formula I-5 and Formula I-6 have the same definitions as the corresponding groups in Formula (I) of the present invention.

[0099] In the above synthetic route, in step A, the synthetic method of formula I-2 can be, for example, as follows: dissolving the raw material of formula I-1 and NH2OH·HCl in a solvent of methanol, adding sodium acetate, stirring at room temperature, and after the reaction is completed, removing the solvent of methanol by distillation under reduced pressure, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain an intermediate of formula I-2;

[0100] In step B, the synthesis method of formula I-3 can be, for example, as follows: dissolving the intermediate of formula I-2 in glacial acetic acid, slowly adding zinc powder under stirring at room temperature, after the reaction is complete, extracting, washing with saturated sodium chloride solution, combining the organic layers, drying and concentrating, and column chromatography to obtain the intermediate of formula I-3;

[0101] In step C, the synthesis method of formula I-4 can be, for example, as follows: dissolving the intermediate of formula I-3 and NaH in anhydrous tetrahydrofuran solvent, adding a halogenated compound, stirring at room temperature, and after the reaction is complete, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain the intermediate of formula I-4;

[0102] In step D, the synthesis method of formula I-5 can be, for example, as follows: dissolving the intermediate of formula I-4 and NaH in anhydrous tetrahydrofuran solvent, protecting with nitrogen, stirring at room temperature, adding DMC after a period of time, and after the reaction is complete, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain the intermediate of formula I-5;

[0103] In step E, the synthesis method of formula Ⅰ-6 can be, for example: dissolving the intermediate of formula Ⅰ-5 in solvent DMF, adding Cs2CO3, stirring at room temperature, and after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain formula Ⅰ-6.

[0104] In step F, the synthesis method of formula II-1 is: dissolve the intermediate of formula I-5 in a solvent, drop into sodium hydroxide solution, stir at room temperature, wait for the reaction to be completed, remove the organic solvent, acidify with 2N hydrochloric acid to pH = 1.5-2.5, precipitate solid, filter and dry to obtain the intermediate of formula II-1.

[0105] In step G, the synthesis method of formula II-2 is: dissolving raw material II-1 in a solvent, adding oxalyl chloride dropwise, stirring and reacting at -5°C to 5°C, and after the reaction is completed, removing the solvent and the remaining solid is the intermediate of formula II-2;

[0106] In step H, an alcohol raw material or an amine raw material or a sulfonic acid or sulfonamide or cyclic amine intermediate is dissolved in a solvent at 0-5°C, and triethylamine is added. After stirring, the intermediate solution of formula II-2 dissolved in the solvent is added dropwise to the above reaction system; after the reaction is completed, a saturated sodium bicarbonate solution is added to the reaction system, the organic layers are extracted and combined, dried, concentrated, and subjected to column chromatography to obtain intermediate II-3.

[0107] In step I, the synthesis method of formula II-4 is: dissolving intermediate II-3 and Cs2CO3 in a solvent, stirring at room temperature under aerobic conditions, and after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain formula II-4;

[0108] In step J, the synthesis method of formula III can be, for example: dissolving formula I-6 and K2CO3 in a solvent, adding a halide, stirring at room temperature, and after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain formula III.

[0109] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials used are commercially available.

[0110] The terms of the present invention are explained below.

[0111] “C1-C 12The term "alkyl" refers to an alkyl group having 1 to 12 carbon atoms, including a straight-chain alkyl group, a branched alkyl group or a cycloalkyl group, for example, a straight-chain alkyl group, a branched alkyl group or a cycloalkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, an ethylcyclopropyl group, a cyclobutyl group, a methylcyclobutyl group, an ethylcyclobutyl group, a cyclopentyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group and the like.

[0112] In the present invention, "C1-C 12 The term "alkoxy" refers to an alkoxy group having 1 to 12 carbon atoms, for example, methyloxy, ethyloxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, n-hexyloxy, cyclopropyloxy, methylcyclopropyloxy, ethylcyclopropyloxy, cyclopentyloxy, methylcyclopentyloxy and cyclohexyloxy.

[0113] In the present invention, "C1-C 12 The term "alkylamino" refers to an amino group substituted by an alkyl group having 1 to 12 carbon atoms, which may be substituted by a single or double alkyl group, wherein when substituted by a double alkyl group, the alkyl groups may be the same and / or different.

[0114] In the present invention, "C1-C 12 The term "alkylmercapto" refers to an alkylmercapto group having 1 to 12 carbon atoms, for example, methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, n-butylmercapto, isobutylmercapto, tert-butylmercapto, n-pentylmercapto, isopentylmercapto, n-hexylmercapto, cyclopropylmercapto, methylcyclopropylmercapto, ethylcyclopropylmercapto, cyclopentylmercapto, methylcyclopentylmercapto, cyclohexylmercapto, and the like.

[0115] In the present invention, "C2-C6 alkenyl" means a monoalkenyl, diene or polyalkenyl group having 1 to 6 carbon atoms, for example, vinyl, n-propenyl, isopropenyl, n-butenyl, n-dibutenyl, isobutenyl, tert-butenyl, n-pentenyl, 1,3-pentadienyl, isopentenyl, n-hexenyl, 1,3-hexadienyl, cyclopropenyl, methylcyclopropenyl, ethylcyclopropenyl, cyclopentenyl, methylcyclopentenyl and cyclohexenyl.

[0116] In the present invention, "C2-C6 alkynyl" means a monoalkynyl, dialkynyl or polyalkynyl group having 1 to 6 carbon atoms, for example, ethynyl, n-propynyl, isopropynyl, n-butynyl, n-dibutynyl, isobutynyl, tert-butynyl, n-pentynyl, 1,3-pentadiynyl, isopentynyl, n-hexynyl, 1,3-hexadiynyl, cyclopropynyl, methylcyclopropynyl, ethylcyclopropynyl, cyclopentynyl, methylcyclopentynyl and cyclohexynyl.

[0117] In the present invention, the “substituted or unsubstituted C3-C8 heterocycle” refers to a heterocycle containing at least one element of N, O and S.

[0118] In the present invention, "halogen" means at least one element selected from the group consisting of fluorine, chlorine, bromine and iodine.

[0119] The present invention has no particular limitation on the method for synthesizing the cycloheptanone compounds containing an α-hydroxy ester structure represented by formula (I). A person skilled in the art can obtain a suitable method for preparing the derivatives represented by formula (I) based on the compound structure provided by the present invention in combination with a synthesis method in the field of chemistry, and the present invention will not elaborate on them one by one.

[0120] The second aspect of the present invention provides the use of the cycloheptanone compound containing an α-hydroxy ester structure described in the first aspect in inhibiting the target dihydroxyacid dehydratase (DHAD) in weeds.

[0121] The third aspect of the present invention provides the use of the cycloheptanone compounds containing an α-hydroxy ester structure described in the first aspect in the prevention and control of weeds. The weeds include foxtail, barnyard grass, lycopodii, crabgrass, aestivum, brome, wild oats, foxtail, Japanese foxtail, ryegrass, rice bag grass, cassia, morning glory, cocklebur, sedge, vetch, Amaranthus retroflexus, Physalis alkekengi, channa oleraceus, Amaranthus spinulosa, Bidens pilosa, Paspalum distachyon, Lishi grass, water bamboo leaves, wild arrowhead, oriental water plantain, rain long flower, Commelina, Duck tongue grass, Firefly rush, Cyperus dimorphus, etc., more specifically foxtail, barnyard grass, channa oleraceus and Amaranthus retroflexus, etc.

[0122] Preferably, the present invention provides use of the cycloheptanone compounds containing an α-hydroxy ester structure as described in the first aspect above in controlling broadleaf weeds, grass weeds, and / or sedge weeds.

[0123] More preferably, in the present invention, the broadleaf weeds include Amaranth, Gray Vegetable, Abutilon, Rice Bag Grass, Cassia, Morning Glory, Xanthium, Amaranthus retroflexus, Physalis, Channa intestine, Portulaca oleracea, Amaranthus spinulosa, Water Bamboo Leaf, Sagittaria, Alisma, Yujiuhua, Commelina, Dalbergia tongue and the like.

[0124] More preferably, in the present invention, the weeds of the Cyperaceae family are Cyperus rotundus, Cyperus difformis and the like.

[0125] More preferably, in the present invention, the grass weeds include Setaria viridis, Echinochloa crusgalli, Leptochloa chinensis, Digitaria sanguinalis, Aegilops tauschii, Bromus, Avena sativa, Alopecurus japonica, Amaranthus chinensis, Chenopodium album, Amaranthus retroflexus and the like.

[0126] The fourth aspect of the present invention provides the use of the cycloheptanone compounds containing an α-hydroxy ester structure as described in the first aspect as an active ingredient in the preparation of pesticide herbicides.

[0127] The weeds targeted by the pesticide herbicide are as described in the third aspect.

[0128] The fifth aspect of the present invention provides a pesticide herbicide, wherein the active ingredient in the pesticide herbicide includes at least one of the cycloheptanone compounds containing an α-hydroxy ester structure described in the first aspect.

[0129] Preferably, the pesticide herbicide is composed of an active ingredient and an auxiliary material, and the content of the active ingredient is 1 to 99.9999% by weight;

[0130] More preferably, the content of the active ingredient is 1 to 50% by weight.

[0131] More preferably, the formulation of the pesticide herbicide can be emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous solution, poison bait, mother solution or mother powder, etc., which can be selected according to the reagent requirements.

[0132] The present invention has the following advantages:

[0133] First, the compound herbicide of the present invention has a novel mode of action. Cycloheptanone compounds containing an α-hydroxy ester structure act on dihydroxyacid dehydratase (DHAD). Currently, there are no independently designed and synthesized compounds that act on this target and no marketed herbicides. The present invention has high herbicidal activity, and the cycloheptanone compounds with an α-hydroxy ester structure have a strong inhibitory effect on weeds. Compared with penoxsulam and bispyribac-sodium, the inhibitory effect of some compounds is comparable to them, and has very good application value.

[0134] Secondly, the compound of the present invention has a simple structure and is easy to prepare. The cycloheptanone compound containing an α-hydroxy ester structure of the present invention has a simple chemical formula and is easy to prepare. At the same time, the compound of the present invention is safe for mammals as a herbicide. The cycloheptanone compound with an α-hydroxy ester structure is a herbicide designed for the branched-chain amino acid biosynthesis pathway, and the branched-chain amino acid biosynthesis pathway only exists in plants and some microorganisms, so it is safe for mammals. DETAILED DESCRIPTION

[0135] Below in conjunction with embodiment, the present invention is described in further detail. Reagents used or instruments and equipment that do not indicate the manufacturer are all considered as conventional products that can be purchased on the market. The endpoints and any value of the scope disclosed in this article are not limited to this accurate scope or value, and these scopes or values ​​should be understood as comprising values ​​close to these scopes or values. For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between the separate point value, can be combined with each other and obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed in this article.

[0136] Example 1: Synthesis of Compound I-3

[0137]

[0138] The initial raw material I-1 (10 mmol), NH2OH·HCl (10 mmol), and sodium acetate (20 mmol) were dissolved in methanol and stirred at room temperature for about 3 h. The reaction was monitored by TLC. After the reaction was completed, the solvent methanol was removed by distillation under reduced pressure, ethyl acetate (50 mL) was added for extraction, and the organic phase was washed three times with saturated brine (200 ml). The organic layers were combined, and the organic phase was dried, concentrated, and subjected to column chromatography to obtain compound I-2 (white solid).

[0139] The intermediate I-2 (1 mmol) was dissolved in acetic acid, zinc powder (6 mmol) was added, and the reaction was stirred at room temperature for 15 min. Then 1,3-cycloheptanedione was slowly added to the reaction system, and the stirring was continued at room temperature for 4 h. The reaction was monitored by TLC until the end. The reaction system was then poured into 150 g of ice water, extracted three times with ethyl acetate (15 ml), the organic layers were combined, and the organic layers were washed three times with saturated sodium chloride solution (100 ml). The organic phase was dried and concentrated, and column chromatography (ethyl acetate: petroleum ether = 1:4) was performed to obtain compound I-3 (yellow solid).

[0140] Example 2: Synthesis of Compound H24120

[0141]

[0142] The intermediate I-3 (1mmol) was dissolved in anhydrous tetrahydrofuran (15ml), and NaH (4mmol) was added under ice bath conditions. After the reaction system was stable, methyl iodide (2mmol) was added and stirred at room temperature until the reaction was completed as monitored by TLC. Ice water was added to the reaction system to quench NaH, and tetrahydrofuran was removed by distillation under reduced pressure. Ethyl acetate (15ml) was added and extracted three times, the organic layers were combined, and the organic phase was washed three times with saturated sodium chloride solution (100ml), dried, concentrated, and column chromatography was performed to obtain the intermediate I-4a (yellow solid).

[0143] The intermediate I-4a (1mmol) was dissolved in anhydrous tetrahydrofuran (5ml), and slowly added to a 10ml Schlenk bottle containing NaH (5mmol) with a 10ml syringe under ice bath conditions. The entire reaction system was carried out under nitrogen protection. After the reaction system was stable, the temperature of the reaction system was increased to 70°C, and DMC (10mmol) was slowly added to the reaction system with a 10ml syringe. Stir at 70°C until the reaction was completed by TLC monitoring. Ice water was added to the reaction system to quench NaH, and tetrahydrofuran was removed by vacuum distillation. Ethyl acetate (15mml) was added and extracted three times. The organic layers were combined, and the organic phases were washed three times with saturated sodium chloride solution (100ml), dried, concentrated, and column chromatography was performed to obtain the intermediate I-5a (yellow-brown oily liquid).

[0144] Intermediate I-5a (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was used to monitor the reaction until it was completed. Water was added to the reaction system to terminate the reaction, and the mixture was extracted three times with ethyl acetate (15 mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24120 (yellow solid). Example 3: Synthesis of compound H24119

[0145]

[0146] The intermediate I-3 (1mmol) was dissolved in anhydrous tetrahydrofuran (15ml), and NaH (4mmol) was added under ice bath conditions. After the reaction system was stable, benzyl bromide (2mmol) was added and stirred at room temperature until the reaction was completed as monitored by TLC. Ice water was added to the reaction system to quench the NaH, and tetrahydrofuran was removed by distillation under reduced pressure. Ethyl acetate (15ml) was added and extracted three times, the organic layers were combined, and the organic phase was washed three times with saturated sodium chloride solution (100ml), dried, concentrated, and column chromatography was performed to obtain the intermediate I-4b (white solid).

[0147] The intermediate I-4b (1mmol) was dissolved in anhydrous tetrahydrofuran (5ml), and slowly added to a 10ml Schlenk bottle containing NaH (5mmol) with a 10ml syringe under ice bath conditions. The entire reaction system was carried out under nitrogen protection. After the reaction system was stable, the temperature of the reaction system was increased to 70°C, and DMC (10mmol) was slowly added to the reaction system with a 10ml syringe. Stir at 70°C until the reaction was completed by TLC monitoring. Ice water was added to the reaction system to quench NaH, and tetrahydrofuran was removed by vacuum distillation. Ethyl acetate (15mml) was added and extracted three times. The organic layers were combined, and the organic phases were washed three times with saturated sodium chloride solution (100ml), dried, concentrated, and column chromatography was performed to obtain the intermediate I-5b (white solid).

[0148] Intermediate I-5b (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was monitored until the reaction was completed. Water was added to the reaction system to terminate the reaction, and ethyl acetate (15 mml) was used for extraction three times. The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24119 (white solid).

[0149] Example 4: Synthesis of Compound H24121

[0150]

[0151] The preparation of other reference compound H24119 is different in that 4-bromo-2-methyl-2-butene is used to replace the NH position of intermediate I-3.

[0152] Example 5: Synthesis of Compound H24122

[0153]

[0154] The preparation of other reference compound H24119 differs in that 3,5-dimethylbenzyl bromide is used to replace the NH position of intermediate I-3.

[0155] Example 6: Synthesis of Compound H24123

[0156]

[0157] The preparation of other reference compound H24119 is different in that 3,5-difluorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0158] Example 7: Synthesis of Compound H24124

[0159]

[0160] The preparation of other reference compound H24119 is different in that 4-trifluoromethylbenzyl bromide is used to replace the NH position of intermediate I-3.

[0161] Example 8: Synthesis of Compound H24125

[0162]

[0163] The preparation of other reference compound H24119 differs in that 2-cyanobenzyl bromide is used to replace the NH position of intermediate I-3.

[0164] Example 9: Synthesis of Compound H24126

[0165]

[0166] The preparation of other reference compound H24119 differs in that 2-cyanobenzyl bromide is used to replace the NH position of intermediate I-3.

[0167] Example 10: Synthesis of Compound H24127

[0168]

[0169] The other reference compound H24119 was prepared by using 3-bromo-1-propene to replace the NH position of the intermediate I-3.

[0170] Example 11: Synthesis of Compound H24128

[0171]

[0172] The preparation of other reference compound H24119 is different in that 4-fluorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0173] Example 12: Synthesis of Compound H24129

[0174]

[0175] The preparation of other reference compound H24119 is different in that 3,5-dimethoxybenzyl bromide is used to replace the NH position of intermediate I-3.

[0176] Example 13: Synthesis of Compound H24130

[0177]

[0178] The preparation of other reference compound H24119 differs in that iodopropane is used to replace the NH position of intermediate I-3.

[0179] Example 14: Synthesis of Compound H24131

[0180]

[0181] The preparation of other reference compound H24119 is different in that 2-trifluoromethylbenzyl bromide is used to replace the NH position of intermediate I-3.

[0182] Example 15: Synthesis of Compound H24132

[0183]

[0184] The preparation of other reference compound H24119 is different in that 2,6-difluorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0185] Example 16: Synthesis of Compound H24134

[0186]

[0187] The other reference compound H24119 was prepared by using 2-bromobenzyl bromide to replace the NH position of the intermediate I-3.

[0188] Example 17: Synthesis of Compound H24135

[0189]

[0190] The preparation of other reference compound H24119 is different in that 2-fluorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0191] Example 18: Synthesis of Compound H24136

[0192]

[0193] The preparation of other reference compound H24119 differs in that 2-chlorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0194] Example 19: Synthesis of Compound H24137

[0195]

[0196] The preparation of other reference compound H24119 is different in that 2,6-dichlorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0197] Example 20: Synthesis of Compound H24138

[0198]

[0199] The preparation of other reference compound H24119 differs in that 4-isopropylbenzyl bromide is used to replace the NH position of intermediate I-3.

[0200] Example 21: Synthesis of Compound H24139

[0201]

[0202] The preparation of other reference compound H24119 is different in that 3,4,5-trifluorobenzyl bromide is used to replace the NH position of intermediate I-3.

[0203] Example 22: Synthesis of Compound H24140

[0204]

[0205] The preparation of other reference compound H24119 differs in that bromomethylcyclopentane is used to replace the NH position of intermediate I-3.

[0206] Example 23: Synthesis of Compound H24141

[0207]

[0208] The preparation of other reference compound H24119 differs in that 4-nitrobenzyl bromide is used to replace the NH position of intermediate I-3.

[0209] Example 24: Synthesis of Compound H24142

[0210]

[0211] The preparation of other reference compound H24119 differs in that 1-bromomethylnaphthalene is used to replace the NH position of intermediate I-3.

[0212] Example 25: Synthesis of Compound II-2a

[0213]

[0214] Dissolve compound I-5a (1 mmol) in 10 ml of solvent (methanol: water = 1: 1), then weigh sodium hydroxide (1.5 mmol) and dissolve it in water (2 ml), and slowly add it drop by drop into the reaction system. Monitor the reaction by TLC until compound I-5a disappears. After the reaction is completed, remove the methanol and acidify with 2N hydrochloric acid to pH = 2. At this time, a large amount of white solid precipitates, which is filtered and dried to obtain product II-1a (white solid).

[0215] Dissolve compound II-1a (15 mmol) in DCM, slowly add oxalyl chloride (22.5 mmol) dropwise, stir the reaction at -5°C to 5°C, monitor the reaction by TLC, and after the reaction is completed, remove DCM and the remaining solid (white solid) is intermediate II-2a.

[0216] Example 26: Synthesis of Compound H24164

[0217]

[0218] At low temperature (0-5°C), 4-methylbenzylamine (2mmol) was dissolved in DCM, and triethylamine (3mmol) was added. After stirring for 15min, the solution of intermediate II-2a (2.4mmol) dissolved in DCM was slowly added dropwise to the reaction system; TLC monitoring was performed until the reaction was completed, saturated sodium bicarbonate solution (50ml) was added to the reaction system, and ethyl acetate (15mml) was used for extraction three times. The organic layers were combined, and the organic phases were washed three times with saturated brine (100ml). The organic layers were extracted and combined, dried, concentrated, and subjected to column chromatography to obtain compound II-3a (white solid).

[0219] Intermediate II-3a (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was used to monitor the reaction until it was complete. Water was added to the reaction system to terminate the reaction, and the mixture was extracted three times with ethyl acetate (15 mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24162 (white solid).

[0220] Example 27: Synthesis of Compound H24156

[0221]

[0222] The preparation of other reference compound H24164 differs in that cyclobutylamine is used to replace the acyl chloride position of intermediate II-2a.

[0223] Example 28: Synthesis of Compound H24157

[0224]

[0225] The preparation of other reference compound H24164 differs in that 3-methoxycyclobutylamine is used to replace the acyl chloride position of intermediate II-2a.

[0226] Example 29: Synthesis of Compound H24158

[0227]

[0228] The preparation of other reference compound H24164 is different in that 3-fluorocyclobutylamine is used to replace the acyl chloride position of intermediate II-2a.

[0229] Example 30: Synthesis of Compound H24159

[0230]

[0231] The preparation of other reference compound H24164 differs in that cyclopentylamine is used to replace the acyl chloride position of intermediate II-2a.

[0232] Example 31: Synthesis of Compound H24160

[0233]

[0234] The preparation of other reference compound H24164 differs in that benzylamine is used to replace the acyl chloride position of intermediate II-2a.

[0235] Example 32: Synthesis of Compound H24161

[0236]

[0237] The preparation of other reference compound H24164 differs in that aniline is used to replace the acyl chloride position of intermediate II-2a.

[0238] Example 33: Synthesis of Compound H24162

[0239]

[0240] The preparation of other reference compound H24164 differs in that ethylamine is used to replace the acyl chloride position of intermediate II-2a.

[0241] Example 34: Synthesis of Compound H24163

[0242]

[0243] The other reference compound H24164 was prepared by using 4-fluorobenzylamine to replace the acyl chloride position of intermediate II-2a.

[0244] Example 35: Synthesis of Compound H24143

[0245]

[0246] Benzyl alcohol (2mmol) was dissolved in DCM at low temperature (0-5°C), and triethylamine (3mmol) was added. After stirring for 15min, the solution of intermediate II-2a (2.4mmol) dissolved in DCM was slowly added dropwise to the reaction system. After TLC monitoring, saturated sodium bicarbonate solution (50ml) was added to the reaction system, and the mixture was extracted three times with ethyl acetate (15mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100ml), dried, concentrated, and subjected to column chromatography to obtain compound II-3c (light yellow oily liquid).

[0247] Intermediate II-3c (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was used to monitor the reaction until it was complete. Water was added to the reaction system to terminate the reaction, and the mixture was extracted three times with ethyl acetate (15 mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24143 (light yellow solid).

[0248] Example 36: Synthesis of Compound H24144

[0249]

[0250] The preparation of other reference compound H24143 is different in that tert-butyl alcohol is used to replace the acyl chloride position of intermediate II-2a.

[0251] Example 37: Synthesis of Compound H24145

[0252]

[0253] The preparation of other reference compound H24143 is different in that phenylpropanol is used to replace the acyl chloride position of intermediate II-2a.

[0254] Example 38: Synthesis of Compound H24146

[0255]

[0256] The preparation of other reference compound H24143 is different in that 2-difluoro-1-ol is used to replace the acyl chloride position of intermediate II-2a.

[0257] Example 39: Synthesis of Compound H24147

[0258]

[0259] The other reference compound H24143 was prepared by using 2-trifluoro-1-ol to replace the acyl chloride position of intermediate II-2a.

[0260] Example 40: Synthesis of Compound H24148

[0261]

[0262] At room temperature, the intermediate II-1a (2mmol) was dissolved in DCM, p-methylphenylhydrazine (2mmol) was added, and triethylamine (3mmol) was added after stirring for 5min, and stirring was continued for 15min, and HATU (3mmol) was added, and stirred at room temperature for 2h. The reaction was monitored by TLC until completion. After removing the solvent, saturated sodium bicarbonate solution (50ml) was added, and the mixture was extracted three times with ethyl acetate (15mml), washed with saturated brine (100ml), and the organic layers were combined, dried, concentrated, and subjected to column chromatography to obtain compound II-3d (yellow solid).

[0263] Intermediate II-3d (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was used to monitor the reaction until it was completed. Water was added to the reaction system to terminate the reaction, and the mixture was extracted three times with ethyl acetate (15 mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24148 (yellow solid).

[0264] Example 41: Synthesis of Compound H24149

[0265]

[0266] The preparation of other reference compound H24148 differs in that p-fluorophenylhydrazine is used to condense the carboxyl group of intermediate II-1a.

[0267] Example 42: Synthesis of Compound H24150

[0268]

[0269] Dissolve benzenesulfonic anhydride (3mmol) in DCM at low temperature (0-5°C), add DMAP (2mmol), stir for 5min, then add intermediate II-2a (2mmol) dissolved in DCM dropwise, add triethylamine (3mmol) after the addition is complete, stir from low temperature to room temperature, and monitor the reaction by TLC until completion. Remove the solvent, add saturated sodium bicarbonate (50ml) solution, extract three times with ethyl acetate (15mml), wash with saturated brine (100ml), combine the organic layers, dry and concentrate, and perform column chromatography to obtain compound II-3e (light yellow oily liquid).

[0270] Intermediate II-3e (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was used to monitor the reaction until it was completed. Water was added to the reaction system to terminate the reaction, and the mixture was extracted three times with ethyl acetate (15 mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24150 (yellow solid).

[0271] Example 43: Synthesis of Compound H24151

[0272]

[0273] The preparation of other reference compound H24150 is different in that p-toluenesulfonic anhydride is used to replace the acyl chloride position of intermediate II-2a.

[0274] Example 44: Synthesis of Compound H24152

[0275]

[0276] The preparation of other reference compound H24150 is different in that p-fluorobenzenesulfonic anhydride is used to replace the acyl chloride position of intermediate II-2a.

[0277] Example 45: Synthesis of Compound H24153

[0278]

[0279] Dissolve benzenesulfonamide (3mmol) in DCM at low temperature (0-5°C), add HATU (2mmol), stir for 5 minutes, then add intermediate II-2a (2mmol) dissolved in DCM dropwise, add triethylamine (3mmol) after the addition is complete, stir from low temperature to room temperature, and monitor the reaction by TLC until completion. Remove the solvent, add saturated sodium bicarbonate (50ml) solution, extract three times with ethyl acetate (15mml), wash with saturated brine (100ml), combine the organic layers, dry and concentrate, and perform column chromatography to obtain compound II-3f (light yellow solid).

[0280] Intermediate II-3f (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was used to monitor the reaction until it was completed. Water was added to the reaction system to terminate the reaction, and the mixture was extracted three times with ethyl acetate (15 mml). The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24153 (yellow solid).

[0281] Example 46: Synthesis of Compound H24154

[0282]

[0283] The preparation of other reference compound H24153 differs in that p-toluenesulfonamide is used to replace the acyl chloride position of intermediate II-2a.

[0284] Example 47: Synthesis of Compound H24155

[0285]

[0286] The preparation of other reference compound H24143 is different in that p-fluorobenzenesulfonamide is used to replace the acyl chloride position of intermediate II-2a.

[0287] Example 48: Synthesis of Compound H24165

[0288]

[0289] Compound H24135 (1 mmol) was dissolved in tetrahydrofuran (15 ml), K2CO3 (4 mmol) was added under ice bath conditions, and after the reaction system was stable, iodomethane (2 mmol) was added, and the mixture was stirred at room temperature until the reaction was completed as monitored by TLC. The tetrahydrofuran was removed by distillation under reduced pressure, and ethyl acetate (15 ml) was added and extracted three times, the organic layers were combined, and the organic phase was washed three times with saturated sodium chloride solution (100 ml), dried, concentrated, and column chromatographed to obtain compound H24165 (yellow solid).

[0290] Example 49: Synthesis of Compound H24166

[0291]

[0292] The preparation of the other reference compound H24165 is different in that ethyl bromide is used to replace the hydroxyl position of compound H24135.

[0293] Example 50: Synthesis of Compound H24167

[0294]

[0295] The preparation of the other reference compound H24165 is different in that ethyl bromide is used to replace the hydroxyl position of compound H24135.

[0296] Example 51: Synthesis of Compound H24168

[0297]

[0298] The preparation of the other reference compound H24165 is different in that 4-bromo-2-methyl-dibutene is used to replace the hydroxyl position of compound H24135.

[0299] Example 52: Synthesis of Compound H24169

[0300]

[0301] The preparation of the other reference compound H24165 was different in that 2,4-dimethylbenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0302] Example 53: Synthesis of Compound H24170

[0303]

[0304] The preparation of the other reference compound H24165 was different in that 2,4-difluorobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0305] Example 54: Synthesis of Compound H24171

[0306]

[0307] The preparation of the other reference compound H24165 was different in that 4-trifluoromethylbenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0308] Example 55: Synthesis of Compound H24172

[0309]

[0310] The preparation of the other reference compound H24165 was different in that 2-cyanobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0311] Example 56: Synthesis of Compound H24173

[0312]

[0313] The preparation of the other reference compound H24165 differs in that bromomethylcyclohexane is used to replace the hydroxyl position of compound H24135.

[0314] Example 57: Synthesis of Compound H24174

[0315]

[0316] The other reference compound H24165 was prepared, except that 3-bromopropylene was used to replace the hydroxyl position of compound H24135.

[0317] Example 58: Synthesis of Compound H24175

[0318]

[0319] The preparation of the other reference compound H24165 was different in that 4-fluorobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0320] Example 59: Synthesis of Compound H24176

[0321]

[0322] The preparation of the other reference compound H24165 is different in that 3,5-dimethoxybenzyl bromide is used to replace the hydroxyl position of compound H24135.

[0323] Example 60: Synthesis of Compound H24177

[0324]

[0325] The other reference compound H24165 was prepared, except that iodopropane was used to replace the hydroxyl position of compound H24135.

[0326] Example 61: Synthesis of Compound H24178

[0327]

[0328] The preparation of the other reference compound H24165 was different in that 2-trifluoromethylbenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0329] Example 62: Synthesis of Compound H24179

[0330]

[0331] The preparation of the other reference compound H24165 was different in that 2,4-difluorobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0332] Example 63: Synthesis of Compound H24180

[0333]

[0334] The other reference compound H24165 was prepared, except that 2-bromobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0335] Example 64: Synthesis of Compound H24181

[0336]

[0337] The preparation of the other reference compound H24165 was different in that 2-fluorobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0338] Example 65: Synthesis of Compound H24182

[0339]

[0340] The preparation of the other reference compound H24165 was different in that 2-chlorobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0341] Example 66: Synthesis of Compound H24183

[0342]

[0343] The preparation of the other reference compound H24165 is different in that 4-isopropylbenzyl bromide is used to replace the hydroxyl position of compound H24135.

[0344] Example 67: Synthesis of Compound H24184

[0345]

[0346] The preparation of the other reference compound H24165 was different in that 3,4,5-trifluorobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0347] Example 68: Synthesis of Compound H24185

[0348]

[0349] The preparation of the other reference compound H24165 differs in that bromomethylcyclopentane is used to replace the hydroxyl position of compound H24135.

[0350] Example 69: Synthesis of Compound H24186

[0351]

[0352] The preparation of the other reference compound H24165 was different in that 4-nitrobenzyl bromide was used to replace the hydroxyl position of compound H24135.

[0353] Example 70: Synthesis of Compound H24187

[0354]

[0355] The other reference compound H24165 was prepared, except that 1-bromomethylnaphthalene was used to replace the hydroxyl position of compound H24135.

[0356] Example 71: Synthesis of Compound H24133

[0357]

[0358] The intermediate I-3 (1mmol) was dissolved in anhydrous tetrahydrofuran (15ml), and NaH (4mmol) was added under ice bath conditions. After the reaction system was stable, 2-fluoro-3-trifluoromethylbenzyl bromide (2mmol) was added, and the mixture was stirred at room temperature until the reaction was completed by TLC monitoring. Methanol was added to the reaction system to quench the NaH, and tetrahydrofuran was removed by distillation under reduced pressure. Ethyl acetate (15ml) was added and extracted three times, the organic layers were combined, and the organic phase was washed three times with a saturated sodium chloride solution (100ml), dried, concentrated, and subjected to column chromatography to obtain the intermediate I-4c (white solid).

[0359] The intermediate I-4c (1mmol) was dissolved in anhydrous tetrahydrofuran (5ml), and slowly added to a 10ml Schlenk bottle containing NaH (5mmol) with a 10ml syringe under ice bath conditions. The entire reaction system was carried out under nitrogen protection. After the reaction system was stable, the temperature of the reaction system was increased to 70°C, and DMC (10mmol) was slowly added to the reaction system with a 10ml syringe. Stir at 70°C until the reaction was completed by TLC monitoring. Ice water was added to the reaction system to quench NaH, and tetrahydrofuran was removed by vacuum distillation. Ethyl acetate (15mml) was added and extracted three times. The organic layers were combined, and the organic phases were washed three times with saturated sodium chloride solution (100ml), dried, concentrated, and column chromatography was performed to obtain the intermediate I-5c (white solid).

[0360] Intermediate I-5c (1 mmol) was dissolved in DMF (10 ml), and then Cs2CO3 (1.5 mmol) was added. TLC was monitored until the reaction was completed. Water was added to the reaction system to terminate the reaction, and ethyl acetate (15 mml) was used for extraction three times. The organic layers were combined, and the organic phases were washed three times with saturated brine (100 ml), dried, concentrated, and subjected to column chromatography to obtain compound H24133 (white solid).

[0361] The cycloheptanone derivatives containing an α-hydroxy ester structure of the present invention were synthesized according to the above method. The structural characterization data of some compounds of the present invention are listed in Table 1 below.

[0362] Table 1 Physical properties and spectral characterization of specific compounds of formula I

[0363]

[0364]

[0365]

[0366]

[0367]

[0368] Example 13: Herbicidal activity test (greenhouse pot method)

[0369] Preliminary screening test (pot method): The test targets are Setaria, Echinochloa crus-galli, Channa chus and Amaranthus retroflexus. Take a flower pot with an inner diameter of 7 cm, fill it with composite soil (vermiculite: seedling medium = 1:2, v / v) to 3 / 4, directly sow the above four weed targets (germination rate ≥ 85%), cover with 0.2 cm of soil, and wait for the weeds to grow to the 3-leaf stage for use. After each compound is applied at a dose of 150 g ai / ha in an automatic spray tower, the crop leaves are dried and then moved into a greenhouse for cultivation (28℃-32℃, humidity 70%). The results are investigated after 21 days. The results are shown in Table 2.

[0370] Investigation method: 30 days after the test treatment, visually observe the target damage symptoms and growth inhibition, weigh the fresh weight of the above-ground part, calculate the fresh weight inhibition rate (%), and use the fresh weight inhibition rate to express the prevention effect (%).

[0371] Fresh weight inhibition rate (%) = (control fresh weight - treatment fresh weight) / control fresh weight × 100

[0372] Weed suppression is divided into the following five levels based on fresh weight suppression rate and visual observation of weed damage symptoms:

[0373] A: Complete death. The fresh weight inhibition rate is greater than 80% and less than or equal to 100%, and the weed leaves are dried up and dead;

[0374] B: Basically dead. The fresh weight inhibition rate is greater than 60% and less than or equal to 80%. Most of the weed leaves have dried up or the plants are deformed, with white leaf tips, and cannot grow normally.

[0375] C: A small number of weeds died. The fresh weight inhibition rate was greater than 40% and less than or equal to 60%. A small number of weed leaves had dried up or the plants had slight deformities and the leaf tips were partially bleached.

[0376] D: Slightly inhibited, but not killing. Fresh weight inhibition rate is greater than 20% and less than or equal to 40%, weed leaves have not dried up, and the height or thickness of the plants show slight inhibition;

[0377] E: Basically no inhibitory effect. The plants basically grew normally, with no obvious inhibitory effect.

[0378] Table 2 Herbicidal activity inhibition rate (%) of some compounds of formula I (dosage 150 g.i. / ha)

[0379]

[0380]

[0381] From the above weed control preliminary screening data, it can be seen that the inhibitory effect of some compounds on weed growth is comparable to that of the control agents penoxsulam and bispyribac-sodium. The inhibition of Amaranthus retroflexus to Amaranthus retroflexus reached a death effect, which is comparable to the control agent. Among them, H24124, H24125, H24128, H24129, H24130, H24131, H24132, H24133, H24136, and H24137 also showed high activity in the inhibitory effect on the growth of Amaranthus retroflexus. H24135 showed high activity against both grass weeds, and H24123, H24124, H24130, H24131, H24134, H24136, and H24168 showed high activity against both broadleaf weeds. From the perspective of the inhibitory effect on four weeds, H24135 showed good inhibitory effect, and its herbicidal activity was comparable to that of commercial drugs penoxsulam and bispyribac-sodium, which provided a clear direction for the future optimization of this series of compounds. Therefore, this type of compound has a good application prospect.

[0382] In summary, the cycloheptanone compounds containing an α-hydroxy ester structure described in the present invention have the characteristics of simple structure, convenient preparation, novel mode of action, low toxicity, high activity, etc., and show good inhibitory effect on various weeds, and are worthy of further research and development.

[0383] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A cycloheptanone derivative compound containing an α-hydroxy ester structure, the compound having a structure shown in Formula I, in, In Formula I, R 1 is selected from H, substituted or substituted C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, substituted or unsubstituted phenyl, benzyl, naphthyl, pyrrolyl, furanyl, tetrahydrofuranyl, thienyl, thiazolyl, imidazolyl, pyrazolyl, oxazolyl, valerolactamyl, pyridyl, pyranyl, piperidinyl, piperazinyl, pyridazinyl, pyrimidinyl, caprolactamyl, C3-C8 heterocycle; R 2 Any group selected from the following X1-X6; Among them, in X1-X6, A 1 , A 2 , A 3a , A 3b , A 4 , A 5 , A 6a , A 6b Each is independently selected from H, C1-C8 alkyl, C1-C8 alkyl substituted by halogen, phenyl substituted or unsubstituted by C1-C8 alkyl and / or halogen, benzyl, naphthyl, pyridyl, furyl, thienyl, pyrazolyl, imidazolyl, phenyl substituted by C1-C8 alkoxy, benzyl, naphthyl, pyridyl, furyl, thienyl, pyrazolyl, imidazolyl, C3-C8 heterocycle substituted or unsubstituted by C1-C8 alkyl and / or halogen; R 3 is selected from H, substituted or unsubstituted C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, substituted or unsubstituted phenyl, benzyl, naphthyl, pyrrolyl, furanyl, tetrahydrofuranyl, thienyl, thiazolyl, imidazolyl, pyrazolyl, oxazolyl, valerolactamyl, pyridyl, pyranyl, piperidinyl, piperazinyl, pyridazinyl, pyrimidinyl, caprolactamyl, C3-C8 heterocycle; And R 1 , R 3 The optional substituents in are each independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl substituted by halogen, C1-C6 alkoxy substituted by halogen, phenoxy, nitro, cyano and amino; n＝1，2，3，4，5，6。 2. The compound according to claim 1, characterized in that Among the compounds, R 1 Selected from H, or CH2R 4 , where R 4 Selected from H, C1-C3 alkyl, C5-C6 cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C6 alkyl substituted by halogen, or C1-C3 alkyl substituted by one or more halogens, cyano, C1-C3 alkoxy, C1-C6 alkoxy substituted by halogen, phenyl substituted or unsubstituted by nitro, naphthyl; R 2 Any group selected from X1-X6, wherein in X1-X6, A 1 , A 2 , A 3a , A 3b , A 4 , A 5 , A 6a , A 6b Each is independently selected from H, C1-C4 alkyl, C1-C4 alkyl substituted by one or more halogens, phenyl substituted or unsubstituted by C1-C3 alkyl and / or amino and / or halogen, benzyl; R 3 is selected from H, C1-C8 alkyl, C2-C4 alkenyl, C2-C6 alkynyl, C1-C8 substituted by halogen 12 Alkyl, phenyl, benzyl, naphthyl which are substituted or unsubstituted by C1-C3 alkyl and / or halogen and / or cyano and / or C1-C3 alkoxy and / or C1-C3 alkyl substituted by halogen and / or amino; n＝1，2，3，4。 3. The compound according to claim 1, characterized in that Among the compounds, R1 is selected from -CH2-C6H5, -CH3, -CH2CH=C(CH3)2, -CH2-3,5-2F-C6H3, -CH2-4-CF3-C6H4, -CH2-2-C≡N-C6H4, -CH2-C6H 11 , -CH2CH=CH2, -CH2-3,5-2OCH3-C6H3, -CH2CH2CH3, -CH2-2-CF3-C6H4, -CH2-2,6-2F-C6H3, -CH2-2-F-3-CF2OCH3-C6H3, -CH2-2 -Br-C6H4, -CH2-2-F-C6H4, -CH2-2-Cl-C6H4, -CH2-2,6-2Cl-C6H3, -CH2-3,4,5-3F-C6H2, -CH2-C5H9, -CH2-4-NO2-C6H4, -CH2-C 10 Any of H7; R 2 Selected from -COOCH3, -COOC(CH3)3, -COOCH2C6H5, -COO(CH2)3C6H5, -COOCH2CHF2, -COOCH2CF3, -COONHNH- 4-CH3-C6H5, -COONHNH-4-F-C6H5, -COOSO2C6H5, -COOSO2-4-CH3-C6H5, -COOSO2-4-F-C6H5, -CON Any one of HSO2-4-CH3-C6H5, -CONHSO2-4-F-C6H5, -CONC3H6, -CON-3-OCH3-C3H5, -CON-3-F-C3H5, -CONC4H8, -CONHCH2C6H5, -CONHC6H5, -CONHCH2CH3, -CONHCH2-4-F-C6H4, -CONHCH2-4-CH3-C6H4; R 3 Selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2-C6H5, -CH2CH=C(CH3)2, -CH2-3,5-2CH3-C6H3, -CH2-3,5-2F-C6H3, -CH2-4-CF3-C6H4, -CH2-2-C≡N-C6H4, -CH2-C6H 11 , -CH2CH=CH2, -CH2-4-F-C6H4, -CH2-3,5-2OCH3-C6H3, -CH2-2-CF3-C6H4, -CH2-2,6-2 F-C6H3, -CH2-2-Br-C6H4, -CH2-2-F-C6H4, -CH2-2-Cl-C6H4, -CH2-4-CH(CH3)2-C6H4, R 3 -CH2-3,4,5-3F-C6H2, -CH2-C5H9, -CH2-4-NO2-C6H4, -CH2-C 10 H7; Preferably, in the compound, R1 is selected from any one of -CH2-C6H5, -CH2-3,5-2F-C6H3, -CH2-4-CF3-C6H4, -CH2-2-C≡N-C6H4, -CH2-3,5-2OCH3-C6H3, -CH2CH2CH3, -CH2-2-CF3-C6H4, -CH2-2,6-2F-C6H3, -CH2-2-F-3-CF2OCH3-C6H3, -CH2-2-Br-C6H4, -CH2-2-F-C6H4, -CH2-2-Cl-C6H4, -CH2-2,6-2Cl-C6H3; R 2 Any one selected from -COOCH3, -COOCH2C6H5, -COONHNH-4-CH3-C6H5, -COOSO2C6H5, -CONC4H8, -CONHCH2CH3; R 3 Any one selected from -H, -CH3, -CH2CH=C(CH3)2.

4. The compound according to any one of claims 1 to 3, characterized in that The compound is selected from any one of the following: Compound H24119: R 1 -CH2-C6H5, R 2 For -COOCH3, R 3 is -H; Compound H24120: R 1 -CH3, R 2 For -COOCH3, R 3 is -H; Compound H24121: R 1 -CH2CH=C(CH3)2, R 2 For -COOCH3, R 3 is -H; Compound H24122: R 1 -CH2-3,5-2CH3-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24123: R 1 -CH2-3,5-2F-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24124: R 1 -CH2-4-CF3-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24125: R 1 -CH2-2-C≡N-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24126: R 1 -CH2-C6H 11 , R 2 For -COOCH3, R 3 is -H; Compound H24127: R 1 -CH2CH=CH2, R 2 For -COOCH3, R 3 is -H; Compound H24128: R 1 -CH2-4-F-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24129: R 1 -CH2-3,5-2OCH3-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24130: R 1 -CH2CH2CH3, R 2 For -COOCH3, R 3 is -H; Compound H24131: R 1 -CH2-2-CF3-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24132: R 1 -CH2-2,6-2F-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24133: R 1 -CH2-2-F-3-CF2OCH3-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24134: R 1 -CH2-2-Br-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24135: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24136: R 1 is -CH2-2-Cl-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24137: R 1 -CH2-2,6-2Cl-C6H3, R 2 For -COOCH3, R 3 is -H; Compound H24138: R 1 -CH2-4-CH(CH3)2-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24139: R 1 -CH2-3,4,5-3F-C6H2, R 2 For -COOCH3, R 3 is -H; Compound H24140: R 1 -CH2-C5H9, R 2 For -COOCH3, R 3 is -H; Compound H24141: R 1 -CH2-4-NO2-C6H4, R 2 For -COOCH3, R 3 is -H; Compound H24142: R 1 -CH2-C 10 H7, R 2 For -COOCH3, R 3 is -H; Compound H24143: R 1 -CH2-2-F-C6H4, R 2 -COOCH2C6H5, R 3 is -H; Compound H24144: R 1 -CH2-2-F-C6H4, R 2 -COOC(CH3)3, R 3 is -H; Compound H24145: R 1 -CH2-2-F-C6H4, R 2 -COO(CH2)3C6H5, R 3 is -H; Compound H24146: R 1 -CH2-2-F-C6H4, R 2 For -COOCH2CHF2, R 3 is -H; Compound H24147: R 1 -CH2-2-F-C6H4, R 2 -COOCH2CF3, R 3 is -H; Compound H24148: R 1 -CH2-2-F-C6H4, R 2 -COONHNH-4-CH3-C6H5, R 3 is -H; Compound H24149: R 1 -CH2-2-F-C6H4, R 2 -COONHNH-4-F-C6H5, R 3 is -H; Compound H24150: R 1 -CH2-2-F-C6H4, R 2 -COOSO2C6H5, R 3 is -H; Compound H24151: R 1 -CH2-2-F-C6H4, R 2 -COOSO2-4-CH3-C6H5, R 3 is -H; Compound H24152: R 1 -CH2-2-F-C6H4, R 2 -COOSO2-4-F-C6H5, R 3 is -H; Compound H24153: R 1 -CH2-2-F-C6H4, R 2 -CONHSO2C6H5, R 3 is -H; Compound H24154: R 1 -CH2-2-F-C6H4, R 2 -CONHSO2-4-CH3-C6H5, R 3 is -H; Compound H24155: R 1 -CH2-2-F-C6H4, R 2 -CONHSO2-4-F-C6H5, R 3 is -H; Compound H24156: R 1 -CH2-2-F-C6H4, R 2 For-CONC3H6, R 3 is -H; Compound H24157: R 1 -CH2-2-F-C6H4, R 2 -CON-3-OCH3-C3H5, R 3 is -H; Compound H24158: R 1 -CH2-2-F-C6H4, R 2 For-CON-3-F-C3H5, R 3 is -H; Compound H24159: R 1 -CH2-2-F-C6H4, R 2 For-CONC4H8, R 3 is -H; Compound H24160: R 1 -CH2-2-F-C6H4, R 2 For -CONHCH2C6H5, R 3 is -H; Compound H24161: R 1 -CH2-2-F-C6H4, R 2 For -CONHC6H5, R 3 is -H; Compound H24162: R 1 -CH2-2-F-C6H4, R 2 -CONHCH2CH3, R 3 is -H; Compound H24163: R 1 -CH2-2-F-C6H4, R 2 -CONHCH2-4-F-C6H4, R 3 is -H; Compound H24164: R 1 -CH2-2-F-C6H4, R 2 -CONHCH2-4-CH3-C6H4, R 3 is -H; Compound H24165: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH3; Compound H24166: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH3; Compound H24167: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-C6H5; Compound H24168: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH=C(CH3)2; Compound H24169: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-3,5-2CH3-C6H3; Compound H24170: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-3,5-2F-C6H3; Compound H24171: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-CF3-C6H4; Compound H24172: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-C≡N-C6H4; Compound H24173: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 -CH2-C6H 11 ; Compound H24174: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH=CH2; Compound H24175: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-F-C6H4; Compound H24176: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-3,5-2OCH3-C6H3; Compound H24177: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2CH2CH3; Compound H24178: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-CF3-C6H4; Compound H24179: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2,6-2F-C6H3; Compound H24180: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-Br-C6H4; Compound H24181: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-F-C6H4; Compound H24182: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-2-Cl-C6H4; Compound H24183: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-CH(CH3)2-C6H4; Compound H24184: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-3,4,5-3F-C6H2; Compound H24185: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-C5H9; Compound H24186: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 is -CH2-4-NO2-C6H4; Compound H24187: R 1 -CH2-2-F-C6H4, R 2 For -COOCH3, R 3 -CH2-C 10 H7.

5. The method for preparing a compound according to any one of claims 1 to 4, characterized in that: The synthetic route of the compound is selected from any one of the following series 1 to series 3: Series 1: Series 2: Series Three: Wherein, the substituents in the synthetic route have the same definitions as the corresponding groups in formula (I) of the present invention; In step A, the synthesis method of formula I-2 is: dissolving the raw material of formula I-1 and NH2OH·HCl in a solvent of methanol, adding sodium acetate, stirring at room temperature, and after the reaction is completed, removing the solvent of methanol by distillation under reduced pressure, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain an intermediate of formula I-2; In step B, the synthesis method of formula Ⅰ-3 is as follows: dissolving the intermediate of formula Ⅰ-2 in glacial acetic acid solvent, slowly adding zinc powder under stirring at room temperature, after the reaction is completed, extracting, washing with saturated sodium chloride solution, combining the organic layers, drying and concentrating, and column chromatography to obtain the intermediate of formula Ⅰ-3; In step C, the synthesis method of formula I-4 is: dissolving the intermediate of formula I-3 and NaH in anhydrous tetrahydrofuran solvent, adding a halogenated compound, stirring at room temperature, and after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain the intermediate of formula I-4; In step D, the synthesis method of formula Ⅰ-5 is: dissolving the intermediate of formula Ⅰ-4 and NaH in anhydrous tetrahydrofuran solvent, protecting with nitrogen, stirring at room temperature, and then adding DMC, after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain the intermediate of formula Ⅰ-5; In step E, the synthesis method of formula I-6 is: dissolving the intermediate of formula I-5 in solvent DMF, adding Cs2CO3, stirring at room temperature, after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain formula I-6; In step F, the synthesis method of formula II-1 is: dissolving the intermediate of formula I-5 in a solvent, dropping a sodium hydroxide solution, stirring at room temperature, and after the reaction is completed, removing the organic solvent, acidifying with 2N hydrochloric acid to pH = 1.5-2.5, precipitating a solid, and filtering and drying to obtain the intermediate of formula II-1; In step G, the synthesis method of formula II-2 is: dissolving raw material II-1 in a solvent, adding oxalyl chloride dropwise, stirring and reacting at -5°C to 5°C, and after the reaction is completed, removing the solvent and the remaining solid is the intermediate of formula II-2; In step H, an alcohol raw material or an amine raw material or a sulfonic acid or sulfonamide or cyclic amine intermediate is dissolved in a solvent at 0-5°C, and triethylamine is added. After stirring, the intermediate solution of formula II-2 dissolved in the solvent is added dropwise to the above reaction system; after the reaction is completed, a saturated sodium bicarbonate solution is added to the reaction system, the organic layers are extracted and combined, dried, concentrated, and subjected to column chromatography to obtain intermediate II-3; In step I, the synthesis method of formula II-4 is: dissolving intermediate II-3 and Cs2CO3 in a solvent, stirring at room temperature under aerobic conditions, and after the reaction is completed, extracting, washing with saturated brine, combining the organic layers, drying and concentrating, and column chromatography to obtain formula II-4; In step J, the synthesis method of formula III is as follows: dissolve formula I-6 and K2CO3 in a solvent, add a halide, stir at room temperature, wait for the reaction to be completed, extract, wash with saturated brine, combine the organic layers, dry and concentrate, and perform column chromatography to obtain formula III.

6. The preparation method according to claim 5, characterized in that: The solvent in steps AJ is selected from any one of water, N,N-dimethylformamide, acetonitrile, N,N-diethylacetamide, dichloromethane, 1,4-dioxane, toluene, dimethyl sulfoxide, tetrahydrofuran, acetic acid, methanol and ethanol.

7. Use of the compound according to any one of claims 1 to 4 in the preparation of pesticide herbicides.

8. The use according to claim 7, characterized in that: The pesticide herbicide controls at least one weed of grass weeds, broadleaf weeds and sedge weeds; Preferably, the broadleaf weeds are any one of Amaranth, Grey Vegetable, Abutilon, Rice Bag Grass, Cassia, Morning Glory, Xanthium, Amaranthus retroflexus, Physalis, Channa, Purslane, Amaranthus spinulosa, Water Bamboo Leaf, Sagittaria, Alisma, Rain Long Flower, Commelina, and Duck Tongue; Preferably, the Cyperaceae weeds are selected from at least one of Cyperus rotundus and Cyperus difformis; Preferably, the grass weeds are at least one of Setaria viridis, Echinochloa crusgalli, Leptochloa chinensis, Digitaria sanguinalis, Aegilops tauschii, Bromus striata, Avena sativa, Avena arvense, Alopecuroides australis, and Alopecurus japonicus.

9. A pesticide herbicide, wherein the active ingredient of the pesticide herbicide comprises at least one of the compounds according to any one of claims 1 to 4; Preferably, the pesticide herbicide is composed of an active ingredient and an auxiliary material, and the content of the active ingredient is 1 to 99.9999% by weight; More preferably, the content of the active ingredient is 1 to 50% by weight.

10. The pesticide herbicide according to claim 9, wherein: The formulation of the pesticide herbicide is selected from any one of emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous solution, poison bait, mother liquor or mother powder.

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