Substituted phenoxypropionic acid diester compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of pesticides, and provides a substituted phenoxypropionic acid diester compound as well as a preparation method and application thereof, the diester compound can be connected with different substituent groups through two ester bonds, and rich and diversified bridge chain structures are also formed between the two ester bonds. Therefore, the substituted phenoxypropionic acid diester compound is synthesized by adopting substituted phenoxypropionic acid as a leading structure and applying a heterologous oligomerization technology, so that the structural diversity of the compound can be greatly enriched, the defects that the herbicide controlling spectrum is narrow, the drug resistance is easy to generate and the like are overcome, and a novel herbicide which is wider in herbicide controlling spectrum, higher in activity and lower in resistance risk is obtained through screening. The substituted phenoxypropionic acid diester compound synthesized by the invention shows excellent herbicidal activity, and compared with a parent compound, the herbicidal effect is equivalent or better, and the herbicide controlling spectrum is wider.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and in particular to a substituted phenoxypropionic acid diester compound and a preparation method and application thereof. Background Art

[0002] The selective pressure caused by the application of pesticides can cause weeds and other harmful organisms to develop resistance. Once weeds develop resistance, they will become less sensitive to a certain type of pesticide, or even multiple types of pesticides, which will further reduce or even completely lose the control effect, causing significant losses in agricultural production. Therefore, it is necessary to continuously develop new agricultural biological active compounds with high-efficiency herbicidal activity and low resistance risk to meet the needs of weed resistance management and agricultural production. In addition, as people pay more and more attention to their health and environmental protection, higher standards are also being put forward for pesticides that directly affect the safety of agricultural products and the environment. It is urgent to develop new varieties of pesticides such as high-efficiency, low-toxic, and environmentally friendly herbicides, insecticides, and fungicides. Summary of the invention

[0003] The purpose of the present invention is to overcome the defects in the prior art and provide a substituted phenoxypropionic acid diester compound and a preparation method and application thereof.

[0004] The present invention provides a substituted phenoxypropionic acid diester compound and a preparation method and application thereof. The diester compound can connect different substituent groups through two ester bonds, and the two ester bonds also have a rich and diverse bridge chain structure. Therefore, using substituted phenoxypropionic acid as a leading structure and using hetero-oligomerization technology to synthesize substituted phenoxypropionic acid diester compounds can greatly enrich the structural diversity of such compounds, overcome the drawbacks of narrow herbicidal spectrum and easy to produce drug resistance, thereby screening out a new herbicide with a wider herbicidal spectrum, higher activity and lower resistance risk.

[0005] The present invention connects herbicides such as fluazifop-butyl, quizalofop-butyl, clodinafop-butyl and the like, which act on acetyl-CoA carboxylase ACCase, and growth hormone analogs 2-methyl-4-chloro-4-pyraclostrobin, quinclorac, acetolactate synthase ALS inhibitors imazethapyr and bispyribac-butyl, and protoporphyrinogen oxidase PPO inhibitors acifluorfen and the like through an O-group-containing connecting arm, thereby constructing a substituted phenoxypropionic acid diester compound. The herbicidal activity assay results show that compared with the parent compound used alone or in combination, the synthesized substituted phenoxypropionic acid diester compound has higher herbicidal activity. In addition, the compound of the present invention has a simple preparation process, is environmentally friendly, and has a short reaction history. DETAILED DESCRIPTION

[0006] The present invention provides a substituted phenoxypropionic acid diester compound, the structure of the substituted phenoxypropionic acid diester compound is as follows:

[0007]

[0008] Wherein, R1 is selected from one of the following groups:

[0009]

[0010] X is selected from one of the following groups:

[0011] C2-C12 alkyl, C2-C12 alkyl substituted by one or more of the following: halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl; C2-C12 alkenyl, C2-C12 alkenyl substituted by one or more of the following: halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl; C2-C12 alkynyl, C2-C12 alkynyl substituted by halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl; C1-C8 alkyl, C1-C8 one or more of haloalkyl, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, C0-C8 nitro, C0-C8 cyano, C0-C8 hydroxy, C0-C8 carbonyl, C0-C8 acyl, C0-C8 trifluoromethanesulfonyl, substituted or unsubstituted phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyrrolyl, thienyl, furanyl, pyrazolyl, oxazolyl, isoxazolyl, quinolyl, isoquinolyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, piperidinyl, tetrahydropyrimidinyl, tetrahydrothienyl, cyclobutanyl, cyclopropanyl;

[0012] R2 is selected from one of the following groups:

[0013]

[0014] In the present invention, in the structural formula of the substituted phenoxypropionic acid diester compound, R1 is selected from one of the following groups:

[0015]

[0016] X is selected from one of the following groups:

[0017] C2-C6 alkyl, C2-C6 alkyl substituted by one or more of halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl, C2-C6 alkenyl, C2-C6 alkynyl substituted by one or more of halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl, C2-C6 alkynyl substituted with fluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl or alkynyl, phenyl substituted or unsubstituted with one or more of halogen, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, C0-C8 nitro, C0-C8 cyano, C0-C8 hydroxy, C0-C8 carbonyl, C0-C8 acyl or C0-C8 trifluoromethanesulfonyl;

[0018] R2 is selected from one of the following groups:

[0019]

[0020] In the present invention, in the structural formula of the substituted phenoxypropionic acid diester compound, R1 is

[0021]

[0022] X is selected from one of the following groups: C2-C6 alkyl, phenyl;

[0023] R2 is selected from one of the following groups:

[0024]

[0025] The present invention also provides a method for preparing the substituted phenoxypropionic acid diester compound, which is selected from one of method 1, method 2, and method 3:

[0026] The method 1 comprises the following steps:

[0027] (1) mixing a carboxylic acid compound containing R1, a catalyst, a chloride and a solvent to react to obtain an acyl chloride compound containing R1;

[0028] A carboxylic acid compound containing R2, a catalyst, a chloride and a solvent are mixed and reacted to obtain an acyl chloride compound containing R2;

[0029] (2) mixing one of the acyl chloride compounds, a linker arm, a base and a solvent to react to obtain a monoester intermediate;

[0030] (3) mixing the monoester intermediate, a base, a solvent and another acyl chloride compound to react, thereby obtaining the substituted phenoxypropionic acid diester compound;

[0031] The second method comprises the following steps:

[0032] (I) mixing a carboxylic acid compound containing R1, a condensing agent, a linker arm, a base and a solvent to react to obtain a monoester intermediate;

[0033] (II) mixing a carboxylic acid compound containing R2, a condensing agent, a monoester intermediate, a base and a solvent for reaction to obtain the substituted phenoxypropionic acid diester compound;

[0034] or;

[0035] (III) mixing a carboxylic acid compound containing R2, a condensing agent, a linker arm, a base and a solvent to react to obtain a monoester intermediate;

[0036] (IV) mixing a carboxylic acid compound containing R1, a condensing agent, a monoester intermediate, a base and a solvent for reaction to obtain the substituted phenoxypropionic acid diester compound;

[0037] The method three comprises the following steps:

[0038] (a) mixing a carboxylic acid compound containing R1, a catalyst, a chloride and a solvent to react to obtain an acyl chloride compound containing R1; or;

[0039] A carboxylic acid compound containing R2, a catalyst, a chloride and a solvent are mixed and reacted to obtain an acyl chloride compound containing R2;

[0040] (b) mixing an acyl chloride compound, a linker arm, a base and a solvent to react to obtain a monoester intermediate;

[0041] (c) mixing a carboxylic acid compound, a condensing agent, a monoester intermediate, a base and a solvent to react, thereby obtaining the substituted phenoxypropionic acid diester compound;

[0042] When the carboxylic acid compound containing R1 is reacted to obtain an acyl chloride compound containing R1, the acyl chloride compound in step (b) refers to the acyl chloride compound containing R1, and the carboxylic acid compound in step (c) refers to the carboxylic acid compound containing R2;

[0043] When the carboxylic acid compound containing R2 is reacted to obtain an acyl chloride compound containing R2, the acyl chloride compound in step (b) refers to the acyl chloride compound containing R2, and the carboxylic acid compound in step (c) refers to the carboxylic acid compound containing R1;

[0044] or;

[0045] (d) mixing a carboxylic acid compound containing R1, a condensing agent, a linker arm, a base and a solvent to react to obtain a monoester intermediate;

[0046] (e) mixing a carboxylic acid compound containing R2, a catalyst, a chloride and a solvent to react to obtain an acyl chloride compound containing R2;

[0047] (f) mixing an acyl chloride compound containing R2, a condensing agent, a monoester intermediate, a base and a solvent to react to obtain the substituted phenoxypropionic acid diester compound.

[0048] In the present invention, in method 1, method 2 and method 3, the structure of the carboxylic acid compound containing R1 is:

[0049]

[0050] The structure of the carboxylic acid compound containing R2 is:

[0051]

[0052] The structure of the connecting arm is HO-X-OH.

[0053] In the present invention, the role of the solvent in method 1, method 2 and method 3 is to provide a reaction environment and is used in excess.

[0054] The catalyst in step (1) is N,N-dimethylformamide.

[0055] The chloride in step (1) is independently thionyl chloride, oxalyl chloride or triphosgene.

[0056] The solvent in step (1) is independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0057] The amount ratio of the carboxylic acid compound containing R1, the catalyst and the chloride in step (1) is preferably 1mmol:0.2-5mL:1-2mmol, more preferably 1mmol:2.5-4.5mL:1.2-1.8mmol, and more preferably 1mmol:3-4mL:1.4-1.6mmol.

[0058] The amount ratio of the carboxylic acid compound containing R2, the catalyst and the chloride in step (1) is preferably 1mmol:0.2-5mL:1-2mmol, more preferably 1mmol:2.5-4.5mL:1.2-1.8mmol, and more preferably 1mmol:3-4mL:1.4-1.6mmol.

[0059] The temperature during the reaction of the carboxylic acid compound containing R1 in step (1) is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the reaction time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0060] The temperature during the reaction of the carboxylic acid compound containing R2 in step (1) is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the reaction time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0061] The base in step (2) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine.

[0062] The solvent in step (2) is one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0063] In step (2), the molar ratio of one of the acyl chloride compounds, the linker arm and the base is preferably 1:1.1-4:1-8, more preferably 1:1.1-1.3:2-7, and more preferably 1:1.15-1.2:4-5.

[0064] The reaction temperature in step (2) is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the reaction time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0065] The base in step (3) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine.

[0066] The solvent in step (3) is one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0067] The molar ratio of the monoester intermediate, the base and the other acyl chloride compound in step (3) is preferably 1:3-8:1.1-4, more preferably 1:4-7:1.5-3, and more preferably 1:5-6:2-2.5.

[0068] The reaction temperature in step (3) is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the reaction time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0069] In the present invention, the condensing agent in step (I) and step (II) is independently dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.

[0070] The base in step (I) and step (II) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine.

[0071] The solvents in step (I) and step (II) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0072] The molar ratio of the carboxylic acid compound containing R1, the condensing agent, the linker and the base in step (I) is preferably 1:1.1-5:1.1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0073] The molar ratio of the carboxylic acid compound containing R2, the condensation agent, the monoester intermediate and the base in step (II) is preferably 1:1.1-5:1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0074] The temperature of the reaction in step (I) and step (II) is independently preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0075] In the present invention, the condensing agent in step (III) and step (IV) is independently dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.

[0076] The base in step (III) and step (IV) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine.

[0077] The solvents in step (III) and step (IV) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0078] The molar ratio of the carboxylic acid compound containing R2, the condensing agent, the linker and the base in step (III) is preferably 1:1.1-5:1.1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0079] The molar ratio of the carboxylic acid compound containing R1, the condensation agent, the monoester intermediate and the base in step (IV) is preferably 1:1.1-5:1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0080] The temperature of the reaction in step (III) and step (IV) is independently preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0081] In the present invention, the catalyst in step (a) is N,N-dimethylformamide.

[0082] In step (a), the chloride is independently thionyl chloride, oxalyl chloride or triphosgene.

[0083] The solvent in step (a) is independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0084] The amount ratio of the carboxylic acid compound containing R1, the catalyst and the chloride in step (a) is preferably 1mmol:0.2-5mL:1-2mmol, more preferably 1mmol:2.5-4.5mL:1.2-1.8mmol, and more preferably 1mmol:3-4mL:1.4-1.6mmol.

[0085] The amount ratio of the carboxylic acid compound containing R2, the catalyst and the chloride in step (a) is preferably 1mmol:0.2-5mL:1-2mmol, more preferably 1mmol:2.5-4.5mL:1.2-1.8mmol, and more preferably 1mmol:3-4mL:1.4-1.6mmol.

[0086] The temperature during the reaction of the carboxylic acid compound containing R1 in step (a) is preferably 20 to 30°C, more preferably 22 to 28°C, more preferably 24 to 26°C; or preferably 40 to 160°C, more preferably 60 to 140°C, more preferably 80 to 120°C, and the reaction time is preferably 2 to 12h, more preferably 4 to 10h, more preferably 6 to 8h.

[0087] The temperature during the reaction of the carboxylic acid compound containing R2 in step (a) is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the reaction time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0088] The base in step (b) and step (c) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine.

[0089] The solvents in step (b) and step (c) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0090] The condensing agent in step (c) is dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.

[0091] The molar ratio of the acyl chloride compound, the linker arm and the base in step (b) is preferably 1:1.1-4:1-8, more preferably 1:1.5-3.5:2-7, and more preferably 1:2-3:4-5.

[0092] The molar ratio of the carboxylic acid compound, the condensing agent, the monoester intermediate and the base in step (c) is preferably 1:1.1-5:1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0093] The temperature of the reaction in step (b) and step (c) is independently preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0094] In the present invention, the condensing agent in step (d) and step (f) is independently dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.

[0095] The base in step (d) and step (f) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine.

[0096] The solvents in step (d), step (e) and step (f) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.

[0097] The catalyst in step (e) is N,N-dimethylformamide.

[0098] The chloride in step (e) is thionyl chloride, oxalyl chloride or triphosgene.

[0099] The molar ratio of the carboxylic acid compound containing R1, the condensing agent, the linker and the base in step (d) is preferably 1:1.1-5:1.1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0100] The amount ratio of the carboxylic acid compound containing R2, the catalyst and the chloride in step (e) is preferably 1mmol:0.2-5mL:1-2mmol, more preferably 1mmol:2.5-4.5mL:1.2-1.8mmol, and more preferably 1mmol:3-4mL:1.4-1.6mmol.

[0101] The molar ratio of the acyl chloride compound containing R2, the condensation agent, the monoester intermediate and the base in step (f) is preferably 1:1.1-5:1.1-4:1.1-5, more preferably 1:1.5-4.5:1.5-3.5:1.5-4.5, and more preferably 1:2-3:2-3:2-3.

[0102] The reaction temperature in step (d), step (e) and step (f) is independently preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; or preferably 40-160°C, more preferably 60-140°C, more preferably 80-120°C, and the reaction time is preferably 2-12h, more preferably 4-10h, more preferably 6-8h.

[0103] The present invention also provides application of the substituted phenoxypropionic acid diester compound in weed control.

[0104] In the present invention, the weeds are weeds in orchards, non-cultivated land, dry fields and paddy fields.

[0105] The weeds are broad-leaved weeds, such as ramie, Amaranthus retroflexus, Chenopodium album, Commelina, Kochia scoparia, Echinochloa ciliata, Polygonum aviculare, etc.; Gramineae weeds, such as Echinochloa crusgalli, Digitaria sanguinea, Setaria viridis, etc.; Cyperus weeds, such as Firefly rush, Scirpus flat-stalked, Cyperus rotundus, and Feltrum sinense.

[0106] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0107] The substituted phenoxypropionic acid diester compounds of the present invention include but are not limited to one of the following structures, as shown in Table 1.

[0108] Table 1 Structures of substituted phenoxypropionic acid diesters

[0109]

[0110]

[0111] Example 1

[0112] Take 4mmol of 2-methyl-4-chloro-4, 4.8mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 4.8mmol of 4-dimethylaminopyridine in a dry round-bottom flask, and then add 20mL of ultra-dry dichloromethane. After the reactants are completely dissolved, use a syringe to extract 9mmol of dried ethylene glycol and add it to the reaction solution. Stir well and react at 25°C for 3h. Monitor by TLC [V (petroleum ether): V (ethyl acetate) = 3:1] until the raw material point disappears, and stop the reaction. Wash the reaction solution with clean water, adjust the pH to neutral with dilute hydrochloric acid solution, transfer all the reaction solution to a 250mL separatory funnel, extract the organic phase with ethyl acetate, extract 3 times, combine all the organic phases into a 250mL conical flask, dry the organic phase with anhydrous sodium sulfate for 4h, and then filter, rotary evaporate, and concentrate to obtain a crude product. The crude product was dissolved in a small amount of ethyl acetate, and then separated by column chromatography [V (petroleum ether): V (ethyl acetate) = 3:1] to obtain the target product intermediate 2-methyl-4-chloro-ethylene glycol monoester.

[0113] Take 2mmol of fluazifop-butyl, 2mmol of 4-chloro-2-methyl-ethylene glycol monoester, 2.4mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 2.4mmol of 4-dimethylaminopyridine to a dry 100mL round-bottom flask, then add 20mL of ultra-dry dichloromethane, stir well and react at 25°C for 3h. Detect by thin layer chromatography (TLC) [V(petroleum ether): V(ethyl acetate) = 1:1] until the raw material point disappears, stop the reaction, wash with clean water, and adjust the pH to neutral with dilute hydrochloric acid solution. Transfer all the reaction liquid to a 250mL separatory funnel, extract the organic phase with ethyl acetate, extract 3 times, combine all the organic phases into a 250mL conical flask, dry the organic phase with anhydrous sodium sulfate for 4h, and then filter, rotary evaporate and concentrate to obtain a crude product. The crude product was dissolved in a small amount of ethyl acetate, and separated by column chromatography in a petroleum ether and ethyl acetate system [V (petroleum ether): V (ethyl acetate) = 1:1] to obtain the target compound A1.

[0114] NMR data: 1H NMR (600MHz, DMSO-d6) δppm=8.22(s,1H),7.96(d,J=2.0Hz,1H),7.12(d,J=2.2Hz,1H),7.09-7.05(m,3H),6.93(d,J=9.0Hz ,2H),6.57(d,J=8.7Hz,1H),4.76(q,J=6.8Hz,1H),4.60-4.52(m,2H),4.47-4.36(m,4H),2.24(s,3H),1.63(d,J=6.8Hz,3H)

[0115] Example 2

[0116] Preparation of Compounds A2-A6

[0117] The target compounds A2-A6 can be obtained by replacing the ethylene glycol in Example 1 with propylene glycol, butylene glycol, pentanediol, hexanediol and hydroquinone, while keeping other reactants and operating conditions unchanged.

[0118] NMR data (A2): 1 H NMR (600MHz, DMSO-d6) δppm=8.25(s,1H),7.96(d,J=2.0Hz,1H),7.13(d,J=2.3Hz,1H),7.09-7.07(m,2H),7.07-7.05(m,1H),6.94-6.91(m,2H ),6.60(dd,J=8.7,3.6Hz,1H),4.76(q,J=6.8Hz,1H),4.62(s,2H),4.26-4.17(m,4H),2.25(s,3H),2.02-1.96(m,2H),1.64(d,J=6.4Hz,3H)..

[0119] NMR data (A3): 1 H NMR (600MHz, DMSO-d6) δppm=8.25(dd,J=2.1,1.0Hz,1H),7.95(d,J=2.0Hz,1H),7.13(dd,J=2.6,0.5Hz,1H),7.09-7.05(m,3H), 6.94-6.90(m,2H),6.60(d,J=8.7Hz,1H),4.76(q,J=6.8Hz,1H),4.61(s,2H),4.21-4.14(m,4H),2.25(s,3H),1.67-1.62(m,7H).

[0120] NMR data (A4): 1H NMR (600MHz, DMSO-d6) δppm=8.25(s,1H),7.96(s,1H),7.13(s,1H),7.08(d,J=8.9Hz,3H),6.93(d,J=9.0Hz,2H),6.61(dd,J=8.6 ,4.0Hz,1H),4.75(q,J=6.6Hz,1H),4.61(s,2H),4.22-4.14(m,4H),2.25(s,3H),1.70-1.62(m,8H),1.31(dt,J=15.4,7.8Hz,2H).

[0121] NMR data (A5): 1 H NMR (600MHz, DMSO-d6) δppm=8.25(s,1H),7.96(s,1H),7.13(s,1H),7.07(d,J=8.8Hz,3H),6.93(d,J=8.8Hz,2H),6.61(d ,J=8.6Hz,1H),4.75(q,J=6.7Hz,1H),4.62(s,2H),4.20-4.14(m,4H),2.25(s,3H),1.67-1.61(m,7H),1.32-1.26(m,4H).

[0122] NMR data (A6): 1 H NMR (600MHz, DMSO-d6) δppm=8.25(s,1H),7.96(d,J=1.8Hz,1H),7.24-7.18(m,4H),7.13(d,J=1.8Hz,1H),7.09-7.05(m ,3H),6.93(d,J=8.8Hz,2H),6.61(d,J=8.8Hz,1H),4.75(q,J=6.8Hz,1H),4.6(s,2H),2.25(s,3H),1.64(d,J=6.8Hz,3H)

[0123] Example 3

[0124] Preparation of compound B2

[0125] Take 2mmol of dichloroquinoline acid into a dry round-bottom flask, then add 20mL of ultra-dry dichloromethane. After the reactants are completely dissolved, use a syringe to extract 3mmol of oxalyl chloride, slowly add it dropwise to the reaction bottle under ice-water bath conditions, stir and react for 30min, then use a syringe to extract 2mL of ultra-dry N,N-dimethylformamide and drop it into the reaction solution to catalyze the reaction. React at 25℃ for 5h, monitor TLC [V(petroleum ether):V(ethyl acetate)=3:1] until the raw material point disappears, and set aside.

[0126] The above reaction solution was poured into a reaction bottle containing 3 mmol of dried propylene glycol, 3 mmol of triethylamine was pipetted with a pipette and added to the reaction solution, and the reaction was carried out at 25°C for 4 hours. The reaction was stopped when the raw material point disappeared after TLC monitoring [V (petroleum ether): V (ethyl acetate) = 3:1], and the reaction was washed with clean water, and the pH was adjusted to neutral with a saturated sodium bicarbonate solution. The reaction solution was transferred to a 250 mL separatory funnel, and the organic phase was extracted with ethyl acetate. After extraction 3 times, all the organic phases were combined into a 250 mL conical flask, and the organic phase was dried with anhydrous sodium sulfate for 4 hours, and then filtered, rotary evaporated, and concentrated to obtain a crude product. The crude product was dissolved with a small amount of ethyl acetate, and column chromatography was performed in a petroleum ether and ethyl acetate system [V (petroleum ether): V (ethyl acetate) = 3:1] to obtain the intermediate dichloroquinoline acid propylene glycol monoester.

[0127] Take 2mmol of fluazifop-butyl, 2mmol of dichloroquinoline-propylene glycol monoester, 2.4mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 2.4mmol of 4-dimethylaminopyridine to a dry 100mL round-bottom flask, and then add 20mL of ultra-dry dichloromethane, stir well and react for 3h at room temperature. Detect by thin layer chromatography (TLC) [V(petroleum ether): V(ethyl acetate) = 1:1] until the raw material point disappears, stop the reaction, wash with clean water, and then adjust the pH to neutral with dilute hydrochloric acid solution. Transfer all the reaction liquid to a 250mL separatory funnel, extract the organic phase with ethyl acetate, extract 3 times, combine all the organic phases into a 250mL conical flask, dry the organic phase with anhydrous sodium sulfate for 4h, and then filter, rotary evaporate and concentrate to obtain a crude product. The crude product was dissolved in a small amount of ethyl acetate and separated by column chromatography in a petroleum ether and ethyl acetate system [V (petroleum ether): V (ethyl acetate) = 1:1] to obtain the target compound B2.

[0128] NMR data: 1 H NMR (600MHz, DMSO-d6) δppm=8.81(d,J=2.3Hz,1H),8.24(s,1H),8.13(d,J=2.3Hz,1H),7.95(d,J=1.9Hz,1H),7.75(d,J=8.8Hz,1H),7.57(d,J=8.8Hz,1 H),7.05(d,J=9.0Hz,2H),6.94(d,J=9.0Hz,2H),4.78(q,J=6.7Hz,1H),4.6 2-4.55(m,2H),4.43-4.36(m,2H),2.22-2.14(m,2H),1.65(d,J=6.8Hz,3H).

[0129] Example 4

[0130] Preparation of compound C1

[0131] Take 4mmol of fluazifop-butyl, 4.8mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 4.8mmol of 4-dimethylaminopyridine in a dry round-bottom flask, and then add 20mL of ultra-dry dichloromethane. After the reactants are completely dissolved, 9mmol of dried ethylene glycol is drawn with a syringe and added to the reaction solution. Stir well and react for 3h at 25°C. TLC monitors [V(petroleum ether): V(ethyl acetate) = 3:1] until the raw material point disappears and the reaction is stopped. The reaction solution is washed with clean water, and then the pH is adjusted to neutral with a dilute hydrochloric acid solution. The reaction solution is transferred to a 250mL separatory funnel, and the organic phase is extracted with ethyl acetate. After extraction 3 times, all the organic phases are combined into a 250mL conical flask, and the organic phase is dried with anhydrous sodium sulfate for 4h, and then filtered, rotary evaporated, and concentrated to obtain a crude product. The crude product was dissolved in a small amount of ethyl acetate, and then separated by column chromatography [V (petroleum ether): V (ethyl acetate) = 3:1] to obtain the target product intermediate fluazifop-ethylene glycol monoester.

[0132] Weigh 2mmol of imidazolyl nicotinic acid, 2mmol of fluazifop-ethylene glycol monoester, 2.4mmol of EDCI, and 2.4mmol of DMAP into a dry 100mL round-bottom flask, then add 20mL of ultra-dry dichloromethane, stir well and react at 25°C for 3h, detect by thin layer chromatography (TLC) [V (petroleum ether): V (ethyl acetate) = 1:1] until the raw material point disappears, stop the reaction, wash with clean water, and adjust the pH to neutral with dilute hydrochloric acid solution, transfer all the reaction liquid into a 250mL separatory funnel, extract the organic phase with ethyl acetate, extract 3 times, combine all the organic phases into a 250mL conical flask, dry the organic phase with anhydrous sodium sulfate for 4h, and then filter, rotary evaporate, and concentrate to obtain a crude product. Dissolve the crude product with a small amount of ethyl acetate, and separate by column chromatography in a petroleum ether and ethyl acetate system [V (petroleum ether): V (ethyl acetate) = 1:1] to obtain the target compound C1.

[0133] NMR data: 1H NMR (600MHz, DMSO-d6) δppm=8.85(d,J=9.3Hz,1H),8.51(d,J=4.7Hz,1H),8.25(s,1H) ,7.98(s,1H),7.61(s,1H),6.92(dt,J=14.0,8.4Hz,4H),4.74(dd,J=6.4,3.5Hz,1H),4 .61-4.44(m,4H),2.73(dd,J=15.1,7.5Hz,2H),2.05(s,1H),1.61(d,J=6.7Hz,3H),1. 35(d,J=6.4Hz,3H),1.28(t,J=7.8Hz,3H),1.03(d,J=6.4Hz,3H),0.85(d,J=5.7Hz,3H)

[0134] Example 5

[0135] Preparation of compound D1

[0136] Take 4mmol of trifluorfen, 4.8mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 4.8mmol of 4-dimethylaminopyridine in a dry round-bottom flask, and then add 20mL of ultra-dry dichloromethane. After the reactants are completely dissolved, use a syringe to extract 9mmol of dried ethylene glycol and add it to the reaction solution. Stir well and react at 25°C for 3h. TLC monitors [V (petroleum ether): V (ethyl acetate) = 3:1] until the raw material point disappears, and the reaction is stopped. The reaction solution is washed with clean water, and then the pH is adjusted to neutral with dilute hydrochloric acid solution. The reaction solution is transferred to a 250mL separatory funnel, and the organic phase is extracted with ethyl acetate. After extraction 3 times, all the organic phases are combined into a 250mL conical flask, and the organic phase is dried with anhydrous sodium sulfate for 4h, and then filtered, rotary evaporated, and concentrated to obtain a crude product. The crude product was dissolved in a small amount of ethyl acetate, and then separated by column chromatography [V (petroleum ether): V (ethyl acetate) = 3:1] to obtain the target product intermediate trifluorfen-ethylene glycol monoester.

[0137] Weigh 2mmol of fluazifop-butyl, 2mmol of trifluorfen-ethylene glycol monoester, 2.4mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 2.4mmol of 4-dimethylaminopyridine into a dry round-bottom flask, add 20mL of ultra-dry dichloromethane, stir well and react at 25°C for 3h, detect by thin layer chromatography (TLC) [V(petroleum ether): V(ethyl acetate)=1:1] until the raw material point disappears, stop the reaction, wash with clean water, and adjust the pH to neutral with dilute hydrochloric acid solution. Transfer all the reaction liquid into a 250mL separatory funnel, extract the organic phase with ethyl acetate, extract 3 times, combine all the organic phases into a 250mL conical flask, dry the organic phase with anhydrous sodium sulfate for 4h, and then filter, rotary evaporate and concentrate to obtain a crude product. The crude product was dissolved in a small amount of ethyl acetate and separated by column chromatography in a petroleum ether and ethyl acetate system [V (petroleum ether): V (ethyl acetate) = 1:1] to obtain the target compound D1.

[0138] NMR data: 1 H NMR (600MHz, DMSO-d6) δppm=8.50(d,J=2.0Hz,1H),8.45-8.41(m,1H),8.16(d,J=9.0Hz,1 H),8.12(d,J=1.9Hz,1H),7.81(dd,J=8.8,2.0Hz,1H),7.53(d,J=8.5Hz,1H),7.42(d,J=2 .8Hz,1H),7.32(dd,J=9.0,2.8Hz,1H),7.10-7.04(m,2H),6.95-6.88(m,2H),4.95(q,J=6 .8Hz, 1H), 4.49 (dd, J = 6.1, 2.3Hz, 2H), 4.40 (dd, J = 6.0, 2.3Hz, 2H), 1.49 (d, J = 6.8Hz, 3H).

[0139] Common weeds such as Abutilon, Amaranthus retroflexus, Echinochloa crusgalli, and Digitaria were selected for weed control tests to evaluate the herbicidal activity of substituted phenoxypropionic acid diester compounds. Two concentrations were set for each agent, and three replicates were set for each concentration. Each replicate had one pot, and each pot had 10 weeds. The weed control effect was visually investigated 14 days after application. The results are shown in Tables 2 to 6.

[0140] Table 2 The control effect of series A compounds on grass weeds

[0141]

[0142] Note: “-” represents the protection efficiency is less than 20%, the same below.

[0143] Table 3 Control effect of series A compounds on broadleaf weeds

[0144]

[0145]

[0146] Table 4 Control effect of compound B2 on grass weeds

[0147]

[0148] Table 5 Control effect of C1 compound on weeds

[0149]

[0150]

[0151] Table 6 Control effect of D1 compound on weeds

[0152]

[0153] It can be seen from the above examples that the substituted phenoxypropionic acid diester compounds synthesized in the present invention all exhibit excellent herbicidal activity, and compared with the parent compound, the herbicidal effect is equivalent to or better, and the herbicidal spectrum is wider.

[0154] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A substituted phenoxypropionic acid diester compound, characterized in that: The structure of the substituted phenoxypropionic acid diester compound is as follows: Wherein, R1 is selected from one of the following groups: X is selected from one of the following groups: C2-C12 alkyl, C2-C12 alkyl substituted by one or more of the following: halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl; C2-C12 alkenyl, C2-C12 alkenyl substituted by one or more of the following: halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl; C2-C12 alkynyl, C2-C12 alkynyl substituted by halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl; C1-C8 alkyl, C1-C8 one or more of haloalkyl, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, C0-C8 nitro, C0-C8 cyano, C0-C8 hydroxy, C0-C8 carbonyl, C0-C8 acyl, C0-C8 trifluoromethanesulfonyl, substituted or unsubstituted phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyrrolyl, thienyl, furanyl, pyrazolyl, oxazolyl, isoxazolyl, quinolyl, isoquinolyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, piperidinyl, tetrahydropyrimidinyl, tetrahydrothienyl, cyclobutanyl, cyclopropanyl; R2 is selected from one of the following groups:

2. The substituted phenoxypropionic acid diester compound according to claim 1, characterized in that: In the structural formula of the substituted phenoxypropionic acid diester compound, R1 is selected from one of the following groups: X is selected from one of the following groups: C2-C6 alkyl, C2-C6 alkyl substituted by one or more of halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl, C2-C6 alkenyl, C2-C6 alkynyl substituted by one or more of halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl, alkynyl, C2-C6 alkynyl substituted with fluoromethyl, nitro, cyano, aryl, alkoxy, alkenyl or alkynyl, phenyl substituted or unsubstituted with one or more of halogen, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, C0-C8 nitro, C0-C8 cyano, C0-C8 hydroxy, C0-C8 carbonyl, C0-C8 acyl or C0-C8 trifluoromethanesulfonyl; R2 is selected from one of the following groups:

3. The substituted phenoxypropionic acid diester compound according to claim 1 or 2, characterized in that: In the structural formula of the substituted phenoxypropionic acid diester compound, R1 is X is selected from one of the following groups: C2-C6 alkyl, phenyl; R2 is selected from one of the following groups:

4. The method for preparing the substituted phenoxypropionic acid diester compound according to any one of claims 1 to 3, characterized in that: Select one of Method 1, Method 2, and Method 3: The method 1 comprises the following steps: (1) mixing a carboxylic acid compound containing R1, a catalyst, a chloride and a solvent to react to obtain an acyl chloride compound containing R1; A carboxylic acid compound containing R2, a catalyst, a chloride and a solvent are mixed and reacted to obtain an acyl chloride compound containing R2; (2) mixing one of the acyl chloride compounds, a linker arm, a base and a solvent to react to obtain a monoester intermediate; (3) mixing the monoester intermediate, a base, a solvent and another acyl chloride compound to react, thereby obtaining the substituted phenoxypropionic acid diester compound; The second method comprises the following steps: (I) mixing a carboxylic acid compound containing R1, a condensing agent, a linker arm, a base and a solvent to react to obtain a monoester intermediate; (II) mixing a carboxylic acid compound containing R2, a condensing agent, a monoester intermediate, a base and a solvent for reaction to obtain the substituted phenoxypropionic acid diester compound; or; (III) mixing a carboxylic acid compound containing R2, a condensing agent, a linker arm, a base and a solvent to react to obtain a monoester intermediate; (IV) mixing a carboxylic acid compound containing R1, a condensing agent, a monoester intermediate, a base and a solvent for reaction to obtain the substituted phenoxypropionic acid diester compound; The method three comprises the following steps: (a) mixing a carboxylic acid compound containing R1, a catalyst, a chloride and a solvent to react to obtain an acyl chloride compound containing R1; or; A carboxylic acid compound containing R2, a catalyst, a chloride and a solvent are mixed and reacted to obtain an acyl chloride compound containing R2; (b) mixing an acyl chloride compound, a linker arm, a base and a solvent to react to obtain a monoester intermediate; (c) mixing a carboxylic acid compound, a condensing agent, a monoester intermediate, a base and a solvent to react, thereby obtaining the substituted phenoxypropionic acid diester compound; When the carboxylic acid compound containing R1 is reacted to obtain an acyl chloride compound containing R1, the acyl chloride compound in step (b) refers to the acyl chloride compound containing R1, and the carboxylic acid compound in step (c) refers to the carboxylic acid compound containing R2; When the carboxylic acid compound containing R2 is reacted to obtain an acyl chloride compound containing R2, the acyl chloride compound in step (b) refers to the acyl chloride compound containing R2, and the carboxylic acid compound in step (c) refers to the carboxylic acid compound containing R1; or; (d) mixing a carboxylic acid compound containing R1, a condensing agent, a linker arm, a base and a solvent to react to obtain a monoester intermediate; (e) mixing a carboxylic acid compound containing R2, a catalyst, a chloride and a solvent to react to obtain an acyl chloride compound containing R2; (f) mixing an acyl chloride compound containing R2, a condensing agent, a monoester intermediate, a base and a solvent to react to obtain the substituted phenoxypropionic acid diester compound.

5. The method for preparing the substituted phenoxypropionic acid diester compound according to claim 4, characterized in that: In method 1, method 2 and method 3, the structure of the carboxylic acid compound containing R1 is: The structure of the carboxylic acid compound containing R2 is: The structure of the connecting arm is HO-X-OH; The catalyst in step (1) is N,N-dimethylformamide; The chloride in step (1) is independently thionyl chloride, oxalyl chloride or triphosgene; The solvent in step (1) is independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; The ratio of the carboxylic acid compound containing R1, the catalyst and the chloride used in step (1) is 1 mmol: 0.2-5 mL: 1-2 mmol; The ratio of the carboxylic acid compound containing R2, the catalyst and the chloride used in step (1) is 1 mmol: 0.2-5 mL: 1-2 mmol; The temperature during the reaction of the carboxylic acid compound containing R1 in step (1) is 20 to 30° C. or 40 to 160° C. and the reaction time is 2 to 12 hours; The temperature during the reaction of the carboxylic acid compound containing R2 in step (1) is 20 to 30°C or 40 to 160°C and the reaction time is 2 to 12 hours; The base in step (2) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine; The solvent in step (2) is one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; In step (2), the molar ratio of one of the acyl chloride compounds, the linker arm and the base is 1:1.1-4:1-8; The reaction temperature in step (2) is 20-30°C or 40-160°C; the reaction time is 2-12h; The base in step (3) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine; The solvent in step (3) is one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; In step (3), the molar ratio of the monoester intermediate, the base and the other acyl chloride compound is 1:3-8:1.1-4; The reaction temperature in step (3) is 20-30°C or 40-160°C; and the reaction time is 2-12h.

6. The method for preparing the substituted phenoxypropionic acid diester compound according to claim 4, characterized in that: The condensing agent in step (I) and step (II) is independently dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride; The base in step (I) and step (II) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine; The solvents in step (I) and step (II) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; In step (I), the molar ratio of the carboxylic acid compound containing R1, the condensing agent, the linker and the base is 1:1.1-5:1.1-4:1.1-5; The molar ratio of the carboxylic acid compound containing R2, the condensing agent, the monoester intermediate and the base in step (II) is 1:1.1-5:1-4:1.1-5; The reaction temperature in step (I) and step (II) is independently 20-30°C or 40-160°C; the reaction time is independently 2-12h.

7. The method for preparing the substituted phenoxypropionic acid diester compound according to claim 4, characterized in that: The condensing agent in step (III) and step (IV) is independently dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride; The base in step (III) and step (IV) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine; The solvents in step (III) and step (IV) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; In step (III), the molar ratio of the carboxylic acid compound containing R2, the condensing agent, the linker and the base is 1:1.1-5:1.1-4:1.1-5; In step (IV), the molar ratio of the carboxylic acid compound containing R1, the condensing agent, the monoester intermediate and the base is 1:1.1-5:1-4:1.1-5; The reaction temperature in step (III) and step (IV) is independently 20-30°C or 40-160°C; the reaction time is independently 2-12h.

8. The method for preparing the substituted phenoxypropionic acid diester compound according to claim 4, characterized in that: The catalyst in step (a) is N,N-dimethylformamide; The chloride in step (a) is independently thionyl chloride, oxalyl chloride or triphosgene; The solvent in step (a) is independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; The ratio of the carboxylic acid compound containing R1, the catalyst and the chloride used in step (a) is 1 mmol: 0.2-5 mL: 1-2 mmol; The ratio of the carboxylic acid compound containing R2, the catalyst and the chloride used in step (a) is 1 mmol: 0.2-5 mL: 1-2 mmol; The temperature during the reaction of the carboxylic acid compound containing R1 in step (a) is 20 to 30° C. or 40 to 160° C. and the reaction time is 2 to 12 hours; The temperature during the reaction of the carboxylic acid compound containing R2 in step (a) is 20 to 30° C. or 40 to 160° C. and the reaction time is 2 to 12 hours; The base in step (b) and step (c) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine; The solvents in step (b) and step (c) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; The condensing agent in step (c) is dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride; In step (b), the molar ratio of the acyl chloride compound, the linker arm and the base is 1:1.1-4:1-8; In step (c), the molar ratio of the carboxylic acid compound, the condensation agent, the monoester intermediate and the base is 1:1.1-5:1-4:1.1-5; The reaction temperature in step (b) and step (c) is independently 20-30°C or 40-160°C; the reaction time is independently 2-12h.

9. The method for preparing the substituted phenoxypropionic acid diester compound according to claim 4, characterized in that: The condensing agent in step (d) and step (f) is independently dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride; The base in step (d) and step (f) is independently one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, pyridine and 4-dimethylaminopyridine; The solvents in step (d), step (e) and step (f) are independently one or more of tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, chloroform, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine; The catalyst in step (e) is N,N-dimethylformamide; The chloride in step (e) is thionyl chloride, oxalyl chloride or triphosgene; In step (d), the molar ratio of the carboxylic acid compound containing R1, the condensing agent, the linker arm and the base is 1:1.1-5:1.1-4:1.1-5; In step (e), the ratio of the carboxylic acid compound containing R2, the catalyst and the chloride is 1 mmol: 0.2-5 mL: 1-2 mmol; In step (f), the molar ratio of the acyl chloride compound containing R2, the condensation agent, the monoester intermediate and the base is 1:1.1-5:1.1-4:1.1-5; The reaction temperatures in step (d), step (e) and step (f) are independently 20 to 30° C. or 40 to 160° C.; and the reaction times are independently 2 to 12 hours.

10. Use of the substituted phenoxypropionic acid diester compound according to any one of claims 1 to 3 in controlling weeds.

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