Herbicidal compositions comprising r-type pyridyloxy carboxylic acid derivatives and use thereof

Abstract

The present application belongs to the field of pesticides, and particularly relates to a herbicidal composition containing R-type pyridyloxy carboxylic acid derivatives and application thereof. The herbicidal composition comprises a herbicidal effective amount of active ingredient A and active ingredient B, wherein the active ingredient A is selected from one or more of R-type pyridyloxy carboxylic acids and salt, ester derivatives thereof as shown in formula I: wherein R1 and R2 independently represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl; R3 represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl; Q represents C1-C6 alkyl, etc.; Y represents amino, etc. The active ingredient B is selected from one or more of glyphosate, glufosinate-ammonium, endothall, paraquat or acid / salt thereof. The composition can effectively prevent various weed problems in crop fields, has the characteristics of expanding the herbicidal spectrum, reducing the application amount, being able to produce a synergistic effect and solving the problem of resistant weeds, etc.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of pesticides, and particularly relates to a herbicidal composition containing R-type pyridyloxy carboxylic acid derivatives and application thereof. BACKGROUND

[0002] Chemical weeding is the most economical and effective means in the prevention and control of weeds in farmland, but long-term continuous high-dose use of single variety or single action mode of chemical herbicides is prone to cause weed tolerance and resistance evolution and other problems. Rational compounding or mixing of herbicide compounds has the advantages of expanding weed spectrum, improving prevention and control effect, delaying the occurrence and development of weed tolerance and resistance, etc., and is one of the most effective methods to solve the above problems. Therefore, it is still necessary to develop herbicidal composition varieties with high safety, wide weed spectrum, synergistic effect and resistance to resistant weeds in production. SUMMARY

[0003] To solve the above problems in the prior art, the present application provides a herbicidal composition containing R-type pyridyloxy carboxylic acid derivatives and application thereof. The composition can effectively prevent and control various weed problems in crop fields, has the characteristics of expanding weed spectrum, reducing application amount, producing synergistic effect and solving resistant weeds, etc.

[0004] A herbicidal composition containing R-type pyridyloxy carboxylic acid derivatives, comprising a herbicidally effective amount of active ingredient A and active ingredient B, wherein,

[0005] The active ingredient A is selected from one or more of R-type pyridyloxy carboxylic acids and salt, ester derivatives thereof as shown in formula I:

[0006]

[0007] wherein R1 and R2 independently represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl;

[0008] R3 represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl;

[0009] Q represents CrC6alkyl, halogenated CrC6alkyl, C3-C6cycloalkyl, C2-C6alkenyl, C2-C6alkinyl, halogen, cyano, amino, nitro, formyl, CrC6alkoxy, CrC6alkylthio, CrC6alkoxycarbonyl, hydroxyCrC6alkyl, CrC6alkoxyCrC6alkyl, cyanoCrC6alkyl, CrC6alkylaminoCrC6alkyl, and phenyl, benzyl, naphthyl, furanyl, thienyl, thiazolyl, pyrazolyl, pyridyl or pyrimidinyl unsubstituted or substituted by at least one radical selected from the group consisting of CrC6alkyl, cyano, halogenated CrC6alkyl, CrC6alkylamino, halogen and CrC6alkoxy;

[0010] Y represents amino, CrC6alkylamino, CrC6alkylcarbonylamino, and phenylcarbonylamino, benzylamino or furanylmethylamino unsubstituted or substituted by at least one radical selected from the group consisting of CrC6alkyl, halogen, cyano, CrC6alkylamino, CrC6alkoxy and halogenated CrC6alkyl;

[0011] said salt is a metal salt, an ammonium salt NH4 + , a primary amine salt R"NH2, a secondary amine salt (R")2NH, a tertiary amine salt (R")3N, a quaternary amine salt (R")4N + , a polyamine salt, a morpholine salt, an N-methylmorpholine salt, a piperidine salt, a pyridine salt, an aminopropylmorpholine salt, a Jeffamine D-230 salt, a salt of 2,4,6-tris(dimethylaminomethyl)phenol and sodium hydroxide, a C1-C16alkylsulfonium salt (preferably a C1-C6alkylsulfonium salt), a C1-C16alkyloxosulfonium salt (preferably a C1-C6alkyloxosulfonium salt), a C1-C16alkylphosphonium salt (preferably a C1-C6alkylphosphonium salt) or a C1-C16alkylphosphinidene salt (preferably a C1-C6alkylphosphinidene salt);

[0012] wherein R" independently represents C1-C16alkyl, C1-C16alkyl (preferably C1-C6alkyl) substituted by one or more radicals selected from the group consisting of halogen, hydroxy, CrC6alkoxy, CrC6alkylthio, hydroxyCrC6alkoxy, C2-C12alkenyl (preferably C2-C6alkenyl), C2-C12alkinyl (preferably C2-C6alkinyl), C3-C12cycloalkyl, phenyl or benzyl unsubstituted or substituted by CrC6alkyl;

[0013] said ester is wherein X represents O or S;

[0014] M represents CrC18alkyl, halogenated CrC8alkyl, non-substituted or substituted with CrC6alkyl, C3-C6cycloalkyl, C2-C6alkenyl, halogenated C2-C6alkenyl, C2-C6alkinyl, CrC6alkyloxy, CrC6alkyloxycarbonyl, CrC6alkylsulfonyl, cyano CrC6alkyl, nitro CrC6alkyl, CrC6alkyloxy CrC6alkyl, -(CrC6alkyl)-Z, and non-substituted or substituted with at least one group selected from CrC6alkyl, halogenated CrC6alkyl, cyano, CrC6alkylamino, halogen and CrC6alkyloxy, tetrahydrofuranyl, pyridyl, naphthyl, furanyl, thienyl, pyrrolyl, pyrazolyl or imidazolyl;

[0015] Z represents and non-substituted or substituted with at least one group selected from CrC6alkyl, CrC6alkyloxy, CrC6alkylamino, halogenated CrC6alkyl, cyano and halogen, phenyl, tetrahydrofuranyl, pyridyl, pyrazolyl, thienyl, furanyl or naphthyl;

[0016] R4, R5, R6 independently represent hydrogen, CrC6alkyl, CrC6alkyloxycarbonyl, and non-substituted or substituted with at least one group selected from CrC6alkyl, CrC6alkyloxy, CrC6alkylamino, halogenated CrC6alkyl, cyano and halogen, phenyl;

[0017] R7 represents CrC6alkyl, C2-C6alkenyl,

[0018] The active ingredient B is selected from one or more of glyphosate, glufosinate, paraquat, or its acid / salts.

[0019] Preferably, R1, R2 independently represent fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl;

[0020] R3 represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl;

[0021] Q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, ethenyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, hydroxymethyl, benzyl, naphthyl furanyl pyridyl pyrimidinyl and thiazolyl which is unsubstituted or substituted by chlorine thienyl which is unsubstituted or substituted by fluorine unsubstituted or substituted by methyl or fluorine phenyl which is unsubstituted or substituted by at least one of the groups methyl, trifluoromethyl, chlorine and methoxy;

[0022] Y represents NH2,

[0023] The salts are alkali metal (e.g. sodium, lithium, potassium, cesium and rubidium) salts, alkaline earth metal (e.g. calcium, magnesium, barium and strontium) salts, and salts of metals such as antimony, bismuth, cadmium, cerium, chromium, cobalt, scandium, titanium, manganese, copper, iron, silver, gold, zinc, aluminum, amine salts such as ammonium salts, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, N-hexadecyltrimethylammonium salts, N-benzyltrimethylammonium salts, benzyltriethylammonium salts, choline salts, monomethylamine salts, dimethylamine salts, trimethylamine salts, monoethylamine salts, diethylamine salts, triethylamine salts, n-propylamine salts, dipropylamine salts, tripropylamine salts, isopropylamine salts, diisopropylamine salts, triisopropylamine salts, n-butylamine salts, dibutylamine salts, tributylamine salts, isobutylamine salts, tert-butylamine salts, amylamine salts, hexylamine salts, heptylamine salts, octylamine salts, dodecylamine salts, tetradecylamine salts, diallylamine salts, cyclohexylamine salts, cyclododecylamine salts, aniline salts, o-toluidine salts, m-toluidine salts, p-toluidine salts, diphenylamine salts, benzylamine salts, monoethanolamine salts, N-methylmonoethanolamine salts, N,N-dimethylethanolamine salts, N-ethylmonoethanolamine salts, N,N-diethylethanolamine salts, N-propylmonoethanolamine salts, N,N-di-n-propylethanolamine salts, N-butylmonoethanolamine salts, diethanolamine salts, N-methyldiethanolamine salts, N-ethyldiethanolamine salts, N-propyldiethanolamine salts, N-butyldiethanolamine salts, N,N-dibutylethanolamine salts, triethanolamine salts, tripropanolamine salts, triisopropanolamine salts, tris(2-hydroxypropyl)amine salts, diglycolamine salts, polyamine salts (e.g. hexamethylenetetramine salts, ethylenediamine salts, diethylenetriamine salts, dimethylaminopropylamine salts, 1,2-propanediamine salts, triethylenediamine salts, triethylenetetramine salts, diphenylamine salts, N,N-bis[aminopropyl]methylamine salts), 2-methylthiopropylamine salts, 2-butoxyethylamine salts, AEPD salts, tris(hydroxymethyl)aminomethane salts, morpholine salts, N-methylmorpholine salts, piperidine salts, pyridine salts, aminopropylmorpholine salts, Jeffamine D-230 (®) n is 2 or 3) salts, 2,4,6-tris(dimethylaminomethyl)phenol and sodium hydroxide, sulfonium salts such as alkylsulfonium salts (e.g. trimethylsulfonium salts, triethylsulfonium salts), alkylsulfoxonium salts, phosphonium salts such as alkylphosphonium salts or alkyloxyphosphonium salts;

[0024] X in said I-1 represents O or S;

[0025] M represents methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, trifluoromethyl, pentafluoroethyl, 3-chlorobutyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, allyl, 2-propynyl, methoxy, ethoxycarbonyl, methylsulfonyl, tetrahydrofuranyl tetrahydrofuranylmethylene pyridinyl pyridinylmethylene naphthyl naphthylmethylene furanyl furanylmethylene thienyl thienylmethylene and unsubstituted or methyl-substituted unsubstituted or methyl-, dimethylamino-, chloro-, methoxy-, trifluoromethyl- or i-propyl-substituted phenyl, unsubstituted or trifluoromethyl-, bromo-, chloro-, fluoro-, methoxy-, cyano- or methyl-substituted benzyl;

[0026] R' represents hydrogen, methyl, ethyl, difluoromethyl.

[0027] More preferably, the active ingredient A is selected from one or more of the following compounds:

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] The preparation method of the active ingredient A comprises the following steps:

[0045] The compound represented by general formula III is reacted with the compound represented by general formula II to obtain the compound represented by general formula I-1-1; the reaction equation is as follows:

[0046]

[0047] wherein, W represents hydrogen or alkali metal, preferably K, Na; Hal represents halogen, preferably Br, Cl; the reaction is carried out in the presence of a catalyst and a solvent, preferably the catalyst is TBAB, and the solvent is one or a combination of DCM, DCE, ACN, THF, DMF.

[0048] The compound represented by general formula I-1-1 is reacted in the presence of aqueous lithium hydroxide and a solvent to obtain the compound represented by general formula I; the reaction equation is as follows:

[0049]

[0050] Preferably, the solvent is selected from one or a combination of methanol, ethanol, isopropanol.

[0051] The compound represented by general formula I is reacted with M-SH to obtain the compound represented by general formula I-1-2; the reaction equation is as follows:

[0052]

[0053] wherein, the reaction is carried out in the presence of a dehydrating agent and a solvent, preferably the dehydrating agent is DCC, and the solvent is selected from one or a combination of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene, xylene.

[0054] or when Y represents NR1R2 (R1, R2 are not hydrogen), a compound of general formula I-2 or a compound of general formula I-1-3 is reacted with the corresponding halide;

[0055] wherein the halide is preferably chloro or bromo; the reaction is carried out in the presence of a base selected from one or more than one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate; and a solvent selected from one or more of THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane and chloroform; and a catalyst, preferably DMAP, can also be added during the reaction.

[0056] The salt is a pharmaceutically acceptable salt, preferably formed by reacting the R-type pyridyloxy carboxylic acid compound of the present application with a chemically acceptable basic compound. The pharmaceutically acceptable salt is easily isolated and can be purified by conventional separation methods such as solvent extraction, dilution, recrystallization, column chromatography and preparative thin layer chromatography.

[0057] wherein the weight ratio of A to B is 1:100-100:1 or 1:50-50:1; preferably 1:30-30:1 or 1:20-20:1; more preferably 1:10-10:1 or 1:8-8:1; further preferably 1:5-5:1 or 1:1-2:1.

[0058] The mass percentage of A and B in the herbicidal composition is 1-95%, preferably 10-80% of the total amount.

[0059] The herbicidal composition further comprises conventional adjuvants, which include carriers and surfactants.

[0060] The term "carrier" herein denotes an organic or inorganic, natural or synthetic substance. They facilitate the application of the active ingredients, the carrier is generally inert and must be agriculturally acceptable, particularly by the treated plants. The carrier can be solid, such as clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum distillates, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.

[0061] The surfactants can include emulsifiers, dispersants or wetting agents, which can be ionic or non-ionic. Examples that can be mentioned are salts of polyacrylic acid, lignosulphonic acid, phenolsulphonic acid or naphthalenesulphonic acid, polymers of ethylene oxide with aliphatic or with aromatic alcohols or with fatty acids or with fatty acid amines or with substituted phenols (in particular alkylphenols or arylphenols), sulphosuccinic acid salts, taurine derivatives (in particular taurine alkyls) and phosphoric esters of polyols or of fatty alcohols or of fatty acid amines, alkylsulphates, alkyl- arylsulphonates, alkyl sulphates, lauryl ether sulphates, fatty alcohol sulphates, and sulphated hexa-, hepta- and octadecanol, and sulphated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulphonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkyl- aryl polyether alcohols, alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulphite waste liquors, and proteins, denatured proteins, polysaccharides (for example methylcellulose), hydrophobically modified starches, polyvinyl alcohol, polycarboxylic acid salts, polyalkoxylates, polyvinyl amines, polyvinylpyrrolidone and copolymers thereof. At least one surfactant is required to be present in order to facilitate the dispersion of the active ingredients in water and to enable them to be applied correctly to the plants.

[0062] The above-mentioned compositions can also contain various other components, such as protective colloids, binders, thickeners, thixotropic agents, penetrants, stabilizers, sequestering agents, dyes, colorings and polymers.

[0063] In addition, the compositions of the present invention can be mixed with the following active substances, such as those in *World Encyclopedia of New Pesticide Varieties*, China Agricultural Science and Technology Press, September 2010, and known substances cited herein. Examples of herbicidal active substances mentioned below (Note: the name of the compound, either according to the common name of the International Organization for Standardization (ISO) or the chemical name, with a code where appropriate): acetochlor, butachlor, metolachlor, isopropachlor, isopropachlor, S-metolachlor, propachlor, chlorpyrifos, chlorpyrifos, chlorpyrifos, naphthalenepropionylchlor, R-L-naphthalenepropionylchlor, propargite, benzylthiamethoxam, bisbenzylchlor, pyrifluquinazon, chlorpyrifos, flubutyroxychlor, brobutyroxychlor, dimethoate, high-efficiency dimethoate, ethoxybenzylchlor, flumethiamethoxam, methoxythiamethoxam, pyrifluquinazon, isoxachlor, high-efficiency methyl parathion, high-efficiency methyl parathion, dipropionylchlor, clethodim, butyroxychlor Cyclopropamide, flusulfanilamide, heptamethrin, isobutanilamide, propyzamide, terbutanilamide, methylparaben, metolachlor, styraclostrobin, chlorpyrifos, acetochlor, valproic acid, pendimethalin, carbaryl, styraclostrobin, tricyclomethoate, butenazolamide, styraclostrobin, bensulfuron-methyl, naphthylpropamide, acetochlor, naphthylparaben, thiamethoxam, pyrimethanil, bensulfuron-methyl, chlorpyrifos, chlorpyrifos, butachlor, flupyrazole, atrazine, simazine, cypermethrin, cypermethrin, cypermethrin, pyrazosulfuron, chlorpyrifos ... Atrazine, cyprofen, cyprofen, cyprofen, cyprofen, methoxypropazine, cypermethrin, cyprofen, cyprofen, cyprofen, cyprofen, cyprofen, cyprofen, cyprofen, cyprofen, cyanuric acid, Indaziflam, chlorsulfuron, mesosulfuron, bensulfuron, chlorpyrifos, bensulfuron, thiasulfuron, pyrimisulfuron, mesosulfuron, sodium iodosulfuron, formamidosulfuron, ethersulfuron, etherbensulfuron, methylsulfuron, nicosulfuron, aminebensulfuron, acylsulfuron, ethoxysulfuron, cyprofensulfuron, sulfadiazine, sulfadiazine, tetrazoliumsulfuron, pyrimisulfuron, monosulfuron, monosulfuron, fluazolidone, flupyrimisulfuron, flupyrimisulfuron, cyclopyrimisulfuron, pyrimisulfuron, flupyrimisulfuron, flupyrimisulfuron, pyrimisulfuron, flupyrimisulfuron, pyrimisulfuron, flupyrimisulfuron, pyrimisulfuron, flupyrimisulfuron, pyrimisulfuron, pyrimisulfuron, trifluoromethyl Sulfuron, sulfonylsulfuron, trifluralin, flusulfanilamide, trifluralin, sodium sulfonylsulfuron, flupyrsulfuron, methoxysulfuron, pyrimethanil, propyrisulfuron, pyrimethanil, trifluralin, flusulfanilamide, quizalofop-p-ethyl, ethoxysulfuron, glyphosate, bensulfuron, chlorfluazuron, methylfluazuron, trifluralin, methoxysulfuron, trifluralin, flufenoxuron, flufenoxuron, chlorfluazuron, metolachlor, methylfluazuron, flufenoxuron, chlorfluazuron, methylfluazuron, methylfluazuron, halosafen, chlorfluazuron, isoproturon, linuron, diuron, sapura, fluroxypyr, bensulfuron, methylbensulfuron, bensulfuron, sulfothiamethoxamIsoxuron, terbuthoxynil, clodinafop-methyl, chlorobromopropylate, methyl methoxynil, methoxynil, bromonazine, methoxynil, chlorpyrifos, metribuzin, cyclorhizobium, fenitrothion, flusulfuron, glufosinate, fenfluramide, isosulfuron, cyclorhizobium, thiamethoxam, thiamethoxam, fenfluramide, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam Oat-based herbicides, chlorfenapyr, dichlorvos, metribuzin, chlorpyrifos, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, butadiene, quizalofop-p-ethyl ... Isooctyl ester butyl ester, 2,4-methylchlorosodium ester, 2,4-D isooctyl ester isooctyl ester, 2,4-methylchloroisooctyl ester, 2,4-D isooctyl ester sodium salt, 2,4-D isooctyl ester dimethylamine salt, 2,4-methylchloroethyl thioester, 2,4-methylchloro, 2,4-D isooctyl ester propionate, high-2,4-D isooctyl ester propionate, 2,4-D isooctyl ester butyrate, 2,4-methylchloropropionate, 2,4-methylchloropropionate, 2,4,5-chlorobutyrate, 2,4,5-tetrate, 2,4,5-tetrate propionate 2,4,5-Thymolbutyric acid, 2,4-methyl chloramine salt, dicamba, sedge, chlorpyrifos, trichlorobenzoic acid, aminodichlorobenzoic acid, methoxytrichlorobenzoic acid, quizalofop-P-ethyl, pyrfluthrin, quizalofop-P-ethyl, flupyrfluthrin, quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, cyhalofop-P-ethyl, oxazolidinone, cyhalofop-P-ethyl, oxazolidinone, clodinafop-P-ethyl, thiamethoxam, quizalofop-P-ethyl, haloxyfop-P-ethyl, trifluralin, isoxaflutole, paraquat, diquat, azoxystrobin, ethylbutadiene, isopropoxynone, mesosulfuron-methyl, cyprofen, aminopropoxynone, ethylbutadiene, chlorfluazol, diflubenzuron, chlorfluazol, mesopropoxynone, cyprofen Glufosinate, glufosinate, methyl parathion, glufosinate, piperazine, diammonium phosphate, dimethoate, phosmet, fenpropathrin, fenpropathrin, fenpropathrin, dimethoate, fenpropathrin, imazalil, imazalil ethion, imazalil quinolinic acid, methoxymethylene, methoxymethylene ammonium salt, imazalil, imazalil, clopyralid, clopyralid isooctyl ester, dichloropyridine acid, aminopyridine acid, trichloropyridine acid, fluthion, haloxypyridine, trichloropyridine phenol, thiamethoxam, flupyridine, clopyralid, flupyridine hydrazone, trichloropyridine butoxyethyl ester, cliodinate, clethodim, thiamethoxam, quizalofop-p-ethyl, cyclobenzanone, butenazol, oxadiazon, pyranazol, buthidazole, cyproconazoleAmetridione, Amibuzin, bromobenzonitrile, octanoyl bromobenzonitrile, octanoyl iodobenzonitrile, iodobenzonitrile, diphenylacetonitrile, bispyribac-sodium, hydroxybispyribac-sodium, Iodobonil, pyrimisulfuron-methyl, diflubenzuron, penoxsulam, sulfadiazine, chlorpyrifos-sulfuron-methyl, dichlorvos-sulfuron-methyl, fluroxypyr, bispyribac-sodium, pyrimisulfuron-methyl, pyrimisulfuron-methyl, pyrimisulfuron-methyl, dicyclosulfuron-methyl, mesosulfuron-methyl, sulfadiazine, Tembotrione Tefuryltrione, Bicyclopyrone, Ketodpiradox, Isoxazolidinone, Isoxazolidinone, Fenoxasulfone, Methiozolin, Isopropalazine, Pyrazosulfuron, Pyrazosulfuron, Pyrasulfotole, Benzosulfuron, Pyroxasulfone, Fluroxypyr, Herbicides, Ampicillin, Pyrazosulfuron, Fluroxypyr, Mesosulfuron, Bencarbazone, Bicyclopyr, Fluroxypyr, Herbicides, Isopropalazine, Cyclopyralid, Tebuconazole Flupropacil, indole-methyl, flupropargyl, propyzoxystrobin, clodinafop-methyl, phthalimide, flumezin, pentachlorophenol (sodium), dichlorophen, terbuphen, terbuphen, pentonitrophenol, dinitrophenol, chlorophen, dichlorophen, propyzoxystrobin, cyclopentadiazon, fluazinam, methyl methazine, tetrazolium, flupyridaben, bromochlor, dimethomorph, pyrazosulfuron, herbicides Pyridafol, quinclorac, chloroquinoline, bentazon, pyrazoline, oxadiazon, cyprodinil, isoxadiazon, cyclohexane, isopropyltriazon, propargite, indicarbone, sodium chlorate, coumarin, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage grass, bromophenol oxime, triazolesulfonium, methomyl, furazolidone, furazolidone, ethoxysulfonium, pyrimethanil, chlorpyrifos, fluroxypyr The following are listed as examples of herbicides: barnyardgrass, acrolein, bensulfuron, metribuzin, oat ester, thiamethoxam, styraxanil, hydroxylamine, methoxybenzone, pyrimisulfuron, chlorpyrifos, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, methylsulfuron, Cambendichlor, cypropyridine, thiamethoxam, pyrazosulfuron ...D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO 535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

[0064] The herbicidal composition further comprises at least one safener selected from the group consisting of:

[0065] a) the class of the dichlorophenylpyrazoline-3-carboxylic acids (S1), preferred compounds being, for example, 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3- carboxylic acid ethyl ester (S1-1, mefenpyr-diethyl, PM, pages 594-595), and related compounds as described in, for example, WO 91 / 07874 and PM (pages 594-595).

[0066] b) the class of the dichlorophenylpyrazole carboxylic acid derivatives, preferred compounds being, for example, 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylic acid ethyl ester (S1-2), 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylic acid ethyl ester (S1-3), 1-(2,4-dichlorophenyl)-5-(1,1-dimethyl-ethyl)pyrazole-3-carboxylic acid ethyl ester (S1-4), 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylic acid ethyl ester (S1-5), and related compounds as described in EP-A-333131 and EP-A-269806.

[0067] c) the class of the triazole carboxylic acids (S1), preferred compounds being, for example, fenchlorazole, i.e. 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1 H)-1,2,4-triazole-3-carboxylic acid ethyl ester (S1-6) and related compounds (cf. EP-A-174562 and EP-A-346620).

[0068] d) 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2- isoxazoline-3-carboxylic acid compounds, preferred compounds are, for example, 5-(2,4- dichlorobenzyl)-2-isoxazoline-3-carboxylic acid ethyl ester (S1-7) or 5-phenyl-2- isoxazoline-3-carboxylic acid ethyl ester (S1-8) and related compounds described in WO 91 / 08202, or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-9, isoxadifen- ethyl) or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid n-propyl ester (S1-10) or 5-(4- fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-11) described in patent application WO-A-95 / 07897.

[0069] e) 8-quinolinyloxyacetic acid (S2) compounds, preferably 1-methylhex-1-yl (5-chloro-8- quinolinyloxy)acetate (S2-1, cloquintocet-mexyl, as in PM (pages 195-196), (1,3- dimethylbut-1-yl)(5-chloro-8-quinolinyloxy)acetate (S2-2), 4-allyloxybutyl(5-chloro-8- quinolinyloxy)acetate (S2-3), 1-allyloxypropan-2-yl(5-chloro-8-quinolinyloxy)acetate (S2-4), (5-chloro-8-quinolinyloxy)acetic acid ethyl ester (S2-5), (5-chloro-8- quinolinyloxy)acetic acid methyl ester (S2-6), (5-chloro-8-quinolinyloxy)acetic acid allyl ester (S2-7), 2-(2-propylideneiminooxy)-1-ethyl(5-chloro-8-quinolinyloxy)acetate (S2-8), 2- oxopropan-1-yl(5-chloro-8-quinolinyloxy)acetate (S2-9), and related compounds described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366.

[0070] f) (5-chloro-8-quinolinyloxy)malonic acid compounds, preferred compounds are, for example, (5-chloro-8-quinolinyloxy)malonic acid diethyl ester, (5-chloro-8- quinolinyloxy)malonic acid diallyl ester, (5-chloro-8-quinolinyloxy)malonic acid methyl ethyl ester and related compounds described in EP-A-0582198.

[0071] g) phenoxyacetic acid, phenoxypropionic acid or aromatic carboxylic acid active compounds, for example 2,4-dichlorophenoxyacetic acid (and esters) (2,4-D), 4-chloro-2- methylphenoxypropionic acid ester (mecoprop), MCPA or 3,6-dichloro-2-methoxybenzoic acid (and esters) (dicamba).

[0072] h) pyrimidines, for example "fenclorim" (PM, pages 386-387) (= 4,6-dichloro-2- phenylpyrimidine),

[0073] i) dichloroacetamides, which are used as pre-planting safeners (safeners for the soil), for example "dichloromid" (PM, pages 270-271) (= N,N-diallyl-2,2- dichloroacetamide), "AR-29148" (= 3-dichloroacetyl-2,2,5-trimethyl-1,3- oxazolidinone, from Stauffer), "benoxacor" (PM, pages 74-75) (= 4- dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazin), "APPG-1292" (= N- allyl-N-[(1,3-dioxolan-2-yl)-methyl]dichloroacetamide, from PPG Industries), "ADK-24" (= N-allyl-N-[(allylaminocarbonyl)-methyl]-dichloroacetamide, from Sagro-Chem), "AAD-67" or "AMON 4660" (= 3-dichloroacetyl-1 -oxa-3-aza- spiro[4,5]decane, from Nitrokemia or Monsanto), "diclonon" or "ABAS 145138" or "ALAB 145138" (= (= 3-dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo[4.3.0]nonane, from BASF), and "furilazol" or "AMON 13900" (see PM, pages 482-483) (= (RS)-3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidinone),

[0074] j) dichloroacetone derivatives, for example "AMG 191 " (CAS Reg. No. 96420-72-3) (= 2-dichloromethyl-2-methyl-1,3-dioxolane, from Nitrokemia),

[0075] k) the class of active compounds of the oxylimino compounds, which are known as seed dressing materials, for example "oxabetrinil" (PM, page 689) (= (Z)-1,3-dioxolan-2-ylmethyloximino(phenyl)acetonitrile), which is known as a safener in seed dressing to prevent damage by metolachlor, "fluxofenim" (PM, pages 467-468) (= 1-(4-chlorophenyl)-2,2,2-trifluoro-1- ethanone O-(1,3-dioxolan-2-ylmethyl)-oxime, which is known as a safener in seed dressing to prevent damage by metolachlor, and "cyometrinil" or "A-CGA-43089" (PM, page 983) (= (Z)-cyanomethyloximino(phenyl)acetonitrile), which is known as a safener in seed dressing to prevent damage by metolachlor,

[0076] l) the class of active compounds of the thiazole carboxylates, which are known as seed dressing materials, for example "flurazol" (PM, pages 450-451 ) (= 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylic acid benzyl ester), which is known as a safener in seed dressing to prevent damage by alachlor and metolachlor,

[0077] m) the class of active compounds of the naphthalene dicarboxylic acid derivatives, which are known as seed dressing agents, for example "naphthalic anhydride" (PM, pages 1009-1010) (= 1,8-naphthalic anhydride), which is known as a safener in seed dressing of corn to prevent damage by thiocarbamate herbicides,

[0078] n) the class of active compounds of the chromane acetic acid derivatives, for example "ACL 304415" (CAS Registry Number 31541-57-8) (= 2-84-carboxychroman-4-yl)acetic acid, available from American Cyanamid),

[0079] o) Active compounds that, in addition to their herbicidal effect on harmful plants, also act as plant safety agents, such as "dimepiperate" or "AMY-93" (PM, pp. 302-303) (=S-1-methyl-1-phenylethylpiperidine-1-thiocarboxylate), "daimuron" or "ASK23" (PM, p. 247) (=1-(1-methyl-1-phenylethyl)-3-p-tolylurea), "benzuron" (c “umyluron” = “AJC-940” (=3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl-ethyl)urea, see JP-A-60087254), “methoxyphenon” or “ANK049” (=3,3'-dimethyl-4-methoxy-benzophenone), “CSB” (=1-bromo-4-(chloromethylsulfonyl)benzene) (CAS Registry No. 54091-06-4, purchased from Kumiai).

[0080] The safener is preferably one or more of the following: bis(benzyloxazol) (CAS: 163520-33-0), cyprosulfamide (CAS: 221667-31-8), pyrazole-methyl (CAS: 135590-91-9), quinoline (CAS: 99607-70-2), gibberellic acid (CAS: 7-06-5), furilazole (CAS: 121776-33-8), and metcamifen (CAS: 129531-12-0).

[0081] In the context of this specification, if the abbreviation of the common name of the active compound is used, it includes, in each case, all conventional derivatives, such as esters and salts, and isomers, particularly optical isomers, especially one or more commercially available forms. If the common name indicates an ester or salt, it also includes, in each case, all other conventional derivatives, such as other esters and salts, free acids and neutral compounds, and isomers, particularly optical isomers, especially one or more commercially available forms. The chemical name of the compound given indicates at least one compound covered by the common name, which is generally preferred. In the case of sulfonamides such as sulfonylureas, the salt also includes salts formed by the exchange of hydrogen atoms in the sulfonamide group with a cation. For example, 2,4-chloro derivatives include, but are not limited to: sodium salt, potassium salt, dimethylammonium salt, isopropylamine salt, etc., as well as methyl 2,4-chloro, ethyl 2,4-chloro, isooctyl 2,4-chloro, ethyl 2,4-chloro, etc.; 2,4-D derivatives include, but are not limited to: 2,4-D salts such as sodium salt, potassium salt, dimethylammonium salt, triethanolamine salt, isopropylamine salt, choline, etc., as well as 2,4-D esters such as methyl 2,4-chloro, ethyl 2,4-chloro, butyl 2,4-chloro, isooctyl 2,4-chloro, etc.

[0082] In the context of the present application, the salts of the compounds are preferably in the form of the respective alkali metal salts, alkaline earth metal salts or ammonium salts, preferably in the form of the respective alkali metal salts, more preferably in the form of the respective sodium or potassium salts, most preferably in the form of the respective sodium salts.

[0083] The compositions of the present application can be used directly or diluted by the user prior to use. They are prepared by the customary methods of processing, i.e. by mixing the active substance with liquid solvents or solid carriers and, if desired, one or more surfactants, such as emulsifiers, stabilizers, wetters, adhesives, and the like.

[0084] Specific formulations of the herbicidal compositions are dispersible oil concentrates, aqueous suspensions, suspoemulsions, wettable powders, emulsifiable concentrates, water-dispersible granules (dry flowables), emulsions, and microemulsions.

[0085] In short, the compositions of the present application can be mixed with the solid and liquid additives conventionally used in the formulations of the prior art.

[0086] In addition, the compositions of the present application can be applied to the foliage of the plants to be treated, i.e. to the weeds, in particular to the surfaces affected by weed infestation or susceptible to infestation, by the method of spraying.

[0087] Further, the present application also provides the use of the herbicidal compositions for controlling weeds; and a method for controlling the growth of unwanted plants, which comprises applying the herbicidal compositions to the plants, plant parts, plant seeds, or areas where the plants grow. Preferably, the herbicidal compositions are used for selectively controlling weeds in useful crops, more preferably the useful crops are genetically modified crops or crops treated by genome editing technology.

[0088] The compounds of the present application can be used for the treatment of all plants and plant parts. The plants varieties and cultivars can be obtained by traditional breeding methods or by biotechnological methods or by combinations of both, i.e. by genetic engineering methods. Genetically modified plants (GM

[0089] Genetically modified plant cultivars that can be treated according to the application include those that are resistant to one or more biotic stresses (pests such as nematode animals, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil

[0090] The following abbreviations T1 to T37 are used for the traits in Table 1'. "-" means the entry is not available.

[0091]

[0092] Table 1' Genetically modified plants

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100] * Argentinean oilseed rape (Brassica napus), ** Polish white cabbage (B. rapa), # eggplant.

[0101] When applying the herbicidal compositions of the present application, unexpected synergistic effects are obtained and the herbicidal activity is more pronounced than the expected sum of the activities of the individual herbicides used, as well as more pronounced than the activity of the individual herbicides. The synergistic effects are manifested in reduced application rates, a broader spectrum of weed control, faster and more persistent herbicidal action, properties that are desired in weed control practice. In terms of the properties described, the new compositions are clearly superior to existing herbicides, allowing for reduced use, and being more environmentally friendly.

[0102] The synergistic herbicidal compositions of the present application also have the following advantages:

[0103] (1) The compositions of the present application are environmentally friendly and readily degradable in the environment.

[0104] (2) The herbicidal composition of the present application is low in cost and convenient to use, and has great economic and social benefits in popularization and application. DETAILED DESCRIPTION

[0105] The following examples are not intended to limit the present application, but merely serve to illustrate how the present application can be implemented. These examples show particularly significant effectiveness for certain weeds. Examples are as follows:

[0106] wherein the structural formula of active ingredient A is shown in the above table, and active ingredient B is as follows: glyphosate (CAS No.: 1071-83-6), glufosinate ammonium (CAS No.: 77182-82-2), diquat dibromide monohydrate (CAS No.: 6385-62-2), and paraquat dichloride (CAS No.: 1910-42-5).

[0107] A) Examples

[0108] 1. A172 + glyphosate (20 + 30) dispersible oil suspending agent

[0109] 20% A172 + 30% glyphosate + 6% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% ricin oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate

[0110] 2. A66 + glyphosate (10 + 30) dispersible oil suspending agent

[0111] 10% A66 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 5% ricin oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate

[0112] 3. A1 + glyphosate (9 + 30) dispersible oil suspending agent

[0113] 9% A1 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 5% ricin oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate

[0114] 4. A3 + glyphosate (12 + 30) dispersible oil suspending agent

[0115] 12% A3 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 5% ricin oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate

[0116] 5. A171 + glyphosate (20 + 30) dispersible oil suspension

[0117] 20% A171 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate supplement

[0118] 6. A211 + glyphosate (10 + 30) dispersible oil suspension

[0119] 10% A211 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate supplement

[0120] 7. A93 + glyphosate (20 + 30) dispersible oil suspension

[0121] 20% A93 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate supplement

[0122] 8. A173 + glyphosate (10 + 30) dispersible oil suspension

[0123] 10% A173 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate supplement

[0124] 9. A212 + glyphosate (20 + 30) dispersible oil suspension

[0125] 20% A212 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate supplement

[0126] 10. A140 + glyphosate (10 + 30) dispersible oil suspension

[0127] 10% A140 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 6% fatty alcohol polyoxyethylene ether + 6% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate supplement

[0128] 11. A162 + glyphosate (10 + 30) dispersible oil suspension

[0129] 10% A162 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 8% fatty alcohol polyoxyethylene ether + 5% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate to 100%

[0130] 12. A129 + glyphosate (10 + 30) dispersible oil suspensions

[0131] 10% A129 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 7% fatty alcohol polyoxyethylene ether + 5% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate to 100%

[0132] 13. A213 + glyphosate (10 + 30) dispersible oil suspensions

[0133] 10% A213 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 7% fatty alcohol polyoxyethylene ether + 5% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate to 100%

[0134] 14. A214 + glyphosate (10 + 30) dispersible oil suspensions

[0135] 10% A214 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 7% fatty alcohol polyoxyethylene ether + 5% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate to 100%

[0136] 15. A168 + glyphosate (10 + 30) dispersible oil suspensions

[0137] 10% A168 + 30% glyphosate + 5% calcium dodecylbenzenesulfonate + 7% fatty alcohol polyoxyethylene ether + 5% castor oil oxyethylene ether + 0.5% organic bentonite + 15% 100# solvent oil + methyl oleate to 100%

[0138] The dispersible oil suspensions described above are processed by mixing kettle, colloid mill, sand mill, shear machine, storage tank, etc.

[0139] The dispersible oil suspensions described above are processed by mixing kettle, colloid mill, sand mill, shear machine, storage tank, etc.

[0140] B) Efficacy test

[0141] Post-emergence stem and leaf spray treatment:

[0142] 1) Test conditions

[0143] 1.1), Test target

[0144] The weeds were collected from Huangdao, Shandong province, such as Digitaria sanguinalis, Amaranthus retroflexus, Conyza canadensis, Brassica rapa, Eragrostis japonica; from Si county, Anhui province, such as Raphanus raphanistrum; from Tianchang, Anhui province, such as Alopecurus japonicus; from Siyang, Jiangsu province, such as Veronica longifolia. The weeds were cultivated in pots with 180x140mm plastic pots, placed in enamel trays, and filled with surface soil (4 / 5) collected from farmland, dried and sieved. The soil moisture was controlled at 20% at the initial stage. The seeds with full and uniform grains were soaked in 25℃ water for 6 hours, and then germinated in a 28℃ biochemical incubator (darkness). The just-germinated weed seeds were evenly placed on the soil surface, and then covered with 0.5-1cm soil according to the size of the seed.

[0145] 1.2) Cultivation conditions

[0146] The experiment was carried out in a controlled sunlight greenhouse with a temperature of 20-30℃, natural light, and a relative humidity of 57%-72%. The soil type was loam with an organic matter content of 1.63%, a pH of 7.1, an alkaline hydrolysis nitrogen of 84.3mg / kg, an available phosphorus of 38.5mg / kg, and an available potassium of 82.1mg / kg.

[0147] 1.3) Instruments and equipment

[0148] 3WP-2000 type walking spray tower, Nanjing Agricultural Machinery Institute of the Ministry of Agriculture; GA10 type one-thousandth electronic balance (Germany); ZDR2000 intelligent data recorder (Hangzhou Zeda Instrument Co., Ltd.); SPX type intelligent biochemical incubator (Ningbo Jiangnan Instrument Factory).

[0149] 2) Experimental design

[0150] 2.1) Reagents

[0151] The required active ingredient A was obtained from patent CN201911321469.4, and the preparation of representative compounds was as follows. The synthesis methods of other compounds were similar, and therefore will not be described again.

[0152] (1) Synthesis of compound A66

[0153] Compound a (0.5g, 2.13mmol), compound b (313mg, 2.55mmol), a catalytic amount of TBAB (10mg), and DMF (10mL) were placed in a round-bottom flask, stirred at room temperature 15℃ for 24 hours. Liquid mass detection showed that a small amount of raw material remained, which could be treated. The reaction liquid was poured into 50mL water, extracted twice with methyl tert-butyl ether (50mL x 2), the organic phase was dried and concentrated, and then separated and purified by column chromatography to obtain compound A66 (300mg, yield 50%). Compound A66 was a white solid.

[0154]

[0155] (2) Synthesis of compound A1

[0156] Compound A66 (0.3 g, 1.06 mmol), methanol (20 mL) were placed in a 100 mL single-neck flask, lithium hydroxide (44.5 mg, 1.06 mmol) was dissolved in 2 mL water, and was slowly added dropwise into the single-neck flask at room temperature, and was stirred at room temperature for 12 hours. After the raw material was completely reacted by liquid chromatography-mass spectrometry detection, the pH was adjusted to 5-6 with 0.5 M dilute hydrochloric acid, and was concentrated, and was extracted with water and ethyl acetate. The organic phase was dried and concentrated to obtain compound A1 (200 mg, yield 70%), which was a white solid.

[0157]

[0158] (3) Synthesis of compound A211

[0159] Compound A1 (200 mg, 0.74 mmol), compound c (85 mg, 0.74 mmol), DCC (152 mg, 0.74 mmol), anhydrous DCM (20 mL) were placed in a 100 mL round-bottom flask, and were reacted at room temperature for 12 hours. After the raw material was completely reacted by liquid chromatography-mass spectrometry detection, the reaction liquid was concentrated, and was separated by column chromatography to obtain compound A211 (200 mg, yield 73%), which was a white solid.

[0160]

[0161] (4) Synthesis of compound A173

[0162] Compound d (2 g, 18.16 mmol), compound b (3.64 g, 21.80 mmol), a catalytic amount of TBAB (10 mg), DMF (20 mL) were placed in a round-bottom flask, and were stirred at room temperature at 15°C for 24 hours. After a small amount of raw material remained by liquid chromatography-mass spectrometry detection, the reaction liquid was poured into 50 mL of water, extracted twice with methyl tert-butyl ether (100 mL x 2), the organic phase was dried and concentrated, and was purified by column chromatography to obtain compound e (1.5 mg, yield 42%). Compound e was a white solid.

[0163]

[0164] Compound e (0.5 g, 2.55 mmol) was dissolved in acetonitrile (20 mL) and placed in a 100 mL single-neck flask, NCS (850.7 mg, 6.37 mmol) and a catalytic amount of BPO (10 mg) were added at room temperature, the temperature was raised to 70°C, and the reaction was carried out for 2 hours. After the raw material was completely reacted by liquid chromatography-mass spectrometry detection, it was concentrated, and was purified by column chromatography to obtain compound A173 (300 mg, yield 44%), which was a white solid.

[0165]

[0166] (5) Synthesis of compound A174 and A212

[0167] Compound e (0.5 g, 2.55 mmol) was dissolved in acetonitrile (20 mL) and placed in a 100 mL single-neck flask, NBS (1.13 mg, 6.37 mmol) and a catalytic amount of BPO (10 mg) were added at room temperature, and the temperature was raised to 70 °C, and the reaction was carried out for 2 hours. The liquid phase was detected by LC-MS, and the raw material was completely reacted. After concentration, column chromatography was used for separation and purification to obtain compound A174 (500 mg, yield 54%), which was a white solid.

[0168]

[0169] Compound A174 (0.5 g, 1.41 mmol), methanol (20 mL) were placed in a 100 mL single-neck flask, lithium hydroxide (59.3 mg, 1.41 mmol) was dissolved in 2 mL of water, and slowly added to the single-neck flask at room temperature. Stirring at room temperature for 12 hours. The liquid phase was detected by LC-MS, and the raw material was completely reacted. The pH was adjusted to 5-6 with 0.5M dilute hydrochloric acid, concentrated, and extracted with water and ethyl acetate. The organic phase was dried and concentrated to obtain compound A212 (350 mg, yield 73%), which was a white solid.

[0170]

[0171] (6) Synthesis of compound A168

[0172] Compound A1 (200 mg, 0.74 mmol), compound f (75 mg, 0.74 mmol), DCC (152 mg, 0.74 mmol), anhydrous DCM (20 mL) were placed in a 100 mL round-bottom flask and reacted at room temperature for 12 hours. The liquid phase was detected by LC-MS, and the raw material was completely reacted. The reaction liquid was concentrated and separated by column chromatography to obtain compound A168 (200 mg, yield 77%), which was a white solid.

[0173]

[0174] The required active ingredient B was purchased from a reagent company. The original drug used acetone as the solvent, and was diluted with a 0.1% emulsifier Tween-80 aqueous solution. It was diluted on demand.

[0175] 2.2), test treatment

[0176] 2.2.1), dose setting

[0177] In determining the ratio or content of A and active ingredient B, the action characteristics and toxicity of the two agents should be considered, as well as the main purpose of the formulation. Based on the preliminary test, the active ingredient A and B were used alone and mixed in different amounts as shown in the table. Water containing no agent, the same solvent and emulsifier were used as blank controls.

[0178] 2.2.2) Test repetition

[0179] Each treatment was repeated 4 times, with 3 pots per treatment, 20 seeds of weed per pot, and a total of 60 plants per treatment.

[0180] 2.3) Treatment method

[0181] 2.3.1) Treatment time and frequency

[0182] The test was conducted once with the agent. After 3-4 leaf stage of the weeds, the seedlings were thinned to maintain 15 plants per pot, and 45 plants per treatment were reserved, and then the culture was continued until the grass weeds reached 4-5 leaf stage and the broadleaf weeds reached 5-6 leaf stage for treatment.

[0183] 2.3.2) Use of equipment and method of application

[0184] The well-cultivated test materials were evenly placed on a platform with an area of 0.5 m 2 The stem and leaf were sprayed with a 3WP-2000 type walking spray tower, and the amount of spray was 450 kg / ha. The spray pressure was 0.3 MPa. After all the liquid was sprayed, the valve was closed, and after 30 seconds, the spray tower door was opened and the nutrient pots were removed. Then the valve was opened and 50 mL of water was sprayed to clean the spray pipe.

[0185] 3) Test method

[0186] Pot culture method was used. The weed culture was as described in 1.1), and the test was conducted according to the "Guidelines for Indoor Biological Determination of Pesticides - Herbicides". The method of application was as described in 2.3.2), and the stem and leaf treatment method was used. After treatment, the culture was moved to the greenhouse for normal culture.

[0187] 4) Data investigation and statistical analysis

[0188] 4.1) Investigation method

[0189] The absolute number investigation method was used, and the surviving weed seedlings were cut off along the soil surface with a blade, and the fresh weight of the weeds was weighed with an analytical balance. For the dead weeds, the fresh weight was taken as zero.

[0190] 4.2) Investigation time and frequency

[0191] Investigation was conducted 20 days after treatment, and a total of 1 time.

[0192] 4.3) Data statistical analysis

[0193] The theoretical fresh weight inhibition rate (E0=X+Y-X*Y / 100) of each treatment mixture combination was calculated by Gowing method, and then compared with the measured inhibition rate (E) to evaluate the joint action type of the two mixtures on weeds. When the value of E-E0 is greater than 10%, it is a synergistic effect; when it is less than -10%, it is an antagonistic effect; when it is between -10% and 10%, it is an additive effect. The best ratio is determined according to the actual control effect, the characteristics of herbicides, the balance of formula, and other factors. In the formula, X is the fresh weight inhibition rate when the amount of active ingredient A is P; Y is the fresh weight inhibition rate when the amount of active ingredient B is Q. The statistical results are shown in Tables 1-56 below.

[0194] Table 1 Actual control effect and joint action evaluation of A172 mixed with glyphosate on Digitaria sanguinalis

[0195]

[0196] Table 2 Actual control effect and joint action evaluation of A172 mixed with glufosinate-ammonium on Galium aparine

[0197]

[0198] Table 3 Actual control effect and joint action evaluation of A66 mixed with glyphosate on Digitaria sanguinalis

[0199]

[0200]

[0201] Table 4 Actual control effect and joint action evaluation of A66 mixed with glyphosate on Eleusine indica

[0202]

[0203] Table 5 Actual control effect and joint action evaluation of A66 mixed with glyphosate on Brassica campestris

[0204]

[0205] Table 6 Actual control effect and joint action evaluation of A66 mixed with glyphosate on Alopecurus japonicus

[0206]

[0207] Table 7 Actual control effect and joint action evaluation of A66 mixed with glufosinate-ammonium on Galium aparine

[0208]

[0209] Table 8 Actual control effect and joint action evaluation of A66 mixed with glufosinate-ammonium on Amaranthus retroflexus

[0210]

[0211] Table 9 Actual control effect and joint action evaluation of A66 mixed paraquat on creeping Jenny

[0212]

[0213] Table 10 Actual control effect and joint action evaluation of A66 mixed diquat on speedwell

[0214]

[0215]

[0216] Table 11 Actual control effect and joint action evaluation of A1 mixed glyphosate on crabgrass

[0217]

[0218] Table 12 Actual control effect and joint action evaluation of A1 mixed glyphosate on Chinese creeper

[0219]

[0220] Table 13 Actual control effect and joint action evaluation of A1 mixed glyphosate on wild mustard

[0221]

[0222] Table 14 Actual control effect and joint action evaluation of A1 mixed glyphosate on Japanese brome

[0223]

[0224] Table 15 Actual control effect and joint action evaluation of A1 mixed glufosinate-ammonium on shepherd's purse

[0225]

[0226] Table 16 Actual control effect and joint action evaluation of A1 mixed glufosinate-ammonium on pigweed

[0227]

[0228] Table 17 Actual control effect and joint action evaluation of A3 mixed glyphosate on crabgrass

[0229]

[0230] Table 18 Actual control effect and joint action evaluation of A3 mixed glyphosate on Chinese creeper

[0231]

[0232] Table 19 Actual control effect and joint action evaluation of A3 mixed glyphosate on wild mustard

[0233]

[0234] Table 20 Actual efficacy and joint action evaluation of A3 mixed glyphosate on Japanese brome

[0235]

[0236] Table 21 Actual efficacy and joint action evaluation of A3 mixed glufosinate-ammonium on Galium aparine

[0237]

[0238] Table 22 Actual efficacy and joint action evaluation of A3 mixed glufosinate-ammonium on Amaranthus retroflexus

[0239]

[0240] Table 23 Actual efficacy and joint action evaluation of A171 mixed glyphosate on Digitaria sanguinalis

[0241]

[0242] Table 24 Actual efficacy and joint action evaluation of A171 mixed glufosinate-ammonium on Galium aparine

[0243]

[0244] Table 25 Actual efficacy and joint action evaluation of A211 mixed glyphosate on Digitaria sanguinalis

[0245]

[0246]

[0247] Table 26 Actual efficacy and joint action evaluation of A211 mixed glufosinate-ammonium on Galium aparine

[0248]

[0249] Table 27 Actual efficacy and joint action evaluation of A93 mixed glyphosate on Digitaria sanguinalis

[0250]

[0251] Table 28 Actual efficacy and joint action evaluation of A93 mixed glufosinate-ammonium on Galium aparine

[0252]

[0253] Table 29 Actual efficacy and joint action evaluation of A173 mixed glyphosate on Digitaria sanguinalis

[0254]

[0255] Table 30 Actual control effect and joint action evaluation of A173 mixed glufosinate-ammonium on Galium aparine

[0256]

[0257] Table 31 Actual control effect and joint action evaluation of A212 mixed glyphosate on Digitaria sanguinalis

[0258]

[0259] Table 32 Actual control effect and joint action evaluation of A212 mixed glufosinate-ammonium on Galium aparine

[0260]

[0261]

[0262] Table 33 Actual control effect and joint action evaluation of A140 mixed glyphosate on Digitaria sanguinalis

[0263]

[0264] Table 34 Actual control effect and joint action evaluation of A140 mixed glufosinate-ammonium on Galium aparine

[0265]

[0266] Table 35 Actual control effect and joint action evaluation of A162 mixed glyphosate on Digitaria sanguinalis

[0267]

[0268] Table 36 Actual control effect and joint action evaluation of A162 mixed glyphosate on Eleusine indica

[0269]

[0270] Table 37 Actual control effect and joint action evaluation of A162 mixed glyphosate on Brassica campestris

[0271]

[0272] Table 38 Actual control effect and joint action evaluation of A162 mixed glyphosate on Alopecurus japonicus

[0273]

[0274] Table 39 Actual control effect and joint action evaluation of A162 mixed glufosinate-ammonium on Galium aparine

[0275]

[0276] Table 40 Actual control and joint action evaluation of A162 mixed glufosinate-ammonium on amaranthus retroflexus

[0277]

[0278] Table 41 Actual control and joint action evaluation of A162 mixed paraquat on penny cress

[0279]

[0280] Table 42 Actual control and joint action evaluation of A162 mixed diquat on veronica longifolia

[0281]

[0282] Table 43 Actual control and joint action evaluation of A129 mixed glyphosate on crabgrass

[0283]

[0284] Table 44 Actual control and joint action evaluation of A129 mixed glufosinate-ammonium on shepherd's purse

[0285]

[0286] Table 45 Actual control and joint action evaluation of A213 mixed glyphosate on crabgrass

[0287]

[0288] Table 46 Actual control and joint action evaluation of A213 mixed glufosinate-ammonium on shepherd's purse

[0289]

[0290] Table 47 Actual control and joint action evaluation of A214 mixed glyphosate on crabgrass

[0291]

[0292]

[0293] Table 48 Actual control and joint action evaluation of A214 mixed glufosinate-ammonium on shepherd's purse

[0294]

[0295] Table 49 Actual control and joint action evaluation of A168 mixed glyphosate on crabgrass

[0296]

[0297] Table 50 Actual control and joint action evaluation of A168 mixed glyphosate on elephant grass

[0298]

[0299] Table 51 Actual control and joint action evaluation of A168 mixed with glyphosate against wild mustard

[0300]

[0301] Table 52 Actual control and joint action evaluation of A168 mixed with glyphosate against Japanese bromegrass

[0302]

[0303] Table 53 Actual control and joint action evaluation of A168 mixed with glufosinate against shepherd's-purse

[0304]

[0305] Table 54 Actual control and joint action evaluation of A168 mixed with glufosinate against pigweed

[0306]

[0307] Table 55 Actual control and joint action evaluation of A168 mixed with paraquat against baby's breath

[0308]

[0309] Table 56 Actual control and joint action evaluation of A168 mixed with glyphosate against speedwell

[0310]

[0311] C) Indoor evaluation test

[0312] The herbicide compositions prepared in A) Examples 1-15 were used for indoor evaluation tests, and the test methods were the same as the corresponding parts of B) efficacy test.

[0313] Test weeds: barnyardgrass, crabgrass, goosegrass, green foxtail, green foxtail, pigweed, Palmer amaranth, ironweed.

[0314] Test crops (containing glyphosate, 2,4-D resistance traits): corn SmartStax TM Pro x Enlist TM (Event Name MON87427 x MON89034 x TC1507 x MON87411 x 59122x DAS40278), soybean Conkesta Enlist E3 TM (Event Name DAS81419 x DAS44406).

[0315] Stem leaf treatment leaf age: weed 3-5 leaf stage, corn 3-5 leaf 1 heart stage, soybean 2nd to 3rd trifoliate stage.

[0316] The specific test agent, dosage and the control effect after 20 days of application are shown in Table 57.

[0317] Weed fresh weight control effect (%) = (blank control weed fresh weight-agent treated weed fresh weight) / blank control weed fresh weight x 100

[0318] Application of the compound composition described in Table 57 on transgenic herbicide-resistant crops

[0319] Formulation Rate (g a.i. / ha) Fresh weight control effect on weeds (%) Safety to crops - corn Safety to crops - soybean 1 1125 93.1 Safe Safe 2 900 96.4 Safe Safe 3 877.5 97.2 Safe Safe 4 945 95.2 Safe Safe 5 1125 94.9 Safe Safe 6 900 92.3 Safe Safe 7 1125 91.7 Safe Safe 8 900 93.9 Safe Safe 9 1125 94.6 Safe Safe 10 900 92.0 Safe Safe 11 900 95.5 Safe Safe 12 900 94.2 Safe Safe 13 900 91.6 Safe Safe 14 900 93.2 Safe Safe 15 900 96.0 Safe Safe

[0320] After a large number of experiments and explorations, the present application unexpectedly found that the composition is used for preventing and treating acropteron repens, amaranthus retroflexus, commelina communis, spinifex littoreus, convolvulus arvensis, conyza canadensis, sonchus oleraceus, solanum nigrum and the like broadleaf weeds, euphorbia heterophylla, digitaria sanguinalis, eleusine indica, setaria viridis, setaria pumila, panicum dichotomiflorum, and the like gramineous weeds, and equisetum arvense and the like equisetaceae weeds, has a surprising and unexpected synergistic effect, which is more significant at a low dosage, can reduce the dosage, reduce environmental pollution, and reasonable compounding reduces agricultural costs, is efficient for ALS and ACCase inhibitor-resistant weeds, has a good application prospect. At the same time, after testing, it shows good selectivity and excellent synergistic effect in wheat fields, corn fields, rice fields, peanuts, sugarcane, sorghum, millet, potatoes, rapeseed, soybeans, cotton, vegetables, poa annua, festuca ovina, zoysia japonica and the like fields, and can be developed into a herbicide mixture with wide market value.

Claims

1. A herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative, characterized in that, It includes active ingredients A and B, which are effective in controlling weed growth. Active ingredient A is selected from one of the following compounds: When active ingredient A is A1, A3, A93, A129, A140, A171, A172, A173, A211, A212, A213 or A214, active ingredient B is glyphosate or glufosinate. When active ingredient A is A66, A162 or A168, active ingredient B is glyphosate, glufosinate, diquat or paraquat. The weight ratio of active ingredients A to B is 1:8 to 2:

1.

2. The herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to claim 1, characterized in that, The weight ratio of A to B is 1:5 to 1:

1.

3. A herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to any one of claims 1-2, characterized in that, The herbicidal composition contains A and B in a mass percentage of 1-95% of the total.

4. The herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to claim 3, characterized in that, The herbicidal composition contains A and B in a mass percentage of 10-80% of the total.

5. A herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to any one of claims 1-2, characterized in that, The herbicidal composition also includes conventional adjuvants.

6. The herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to claim 5, characterized in that, The conventional additives include carriers or surfactants.

7. A herbicidal composition comprising an R-type pyridinoxycarboxylic acid derivative according to any one of claims 1-2, characterized in that, The herbicidal composition further includes at least one safener.

8. The herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to claim 7, characterized in that, The safener is selected from one or more of the following: bis(oxazolyl) acid, cyprosulfamide, pyrazole herbicide, quinoline, gibberellic acid, furilazole, and metcamifen.

9. A herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative according to any one of claims 1-2, characterized in that, The specific formulation of the herbicidal composition is a dispersible oil suspension, an aqueous suspension, a suspension emulsion, a wettable powder, an emulsifiable concentrate, a water-dispersible granule, an emulsion, or a microemulsion.

10. The use of a herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative as described in any one of claims 1-9 for weed control.

11. The application according to claim 10, characterized in that, The herbicidal composition is used to selectively control weeds in useful crops.

12. The application according to claim 11, characterized in that, The useful crops are genetically modified crops or crops treated with genome editing technology.

13. A method for controlling unwanted plant growth, comprising applying a herbicidal composition comprising an R-type pyridineoxycarboxylic acid derivative as described in any one of claims 1-2 to a plant, plant part, plant seed or area where the plant is growing.

14. The method according to claim 13, characterized in that, The herbicidal composition is used to selectively control weeds in useful crops.

15. The method according to claim 14, characterized in that, The useful crops are genetically modified crops or crops treated with genome editing technology.

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