CN112273395A - Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives and use thereof - Google Patents

Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives and use thereof Download PDF

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CN112273395A
CN112273395A CN202010228317.6A CN202010228317A CN112273395A CN 112273395 A CN112273395 A CN 112273395A CN 202010228317 A CN202010228317 A CN 202010228317A CN 112273395 A CN112273395 A CN 112273395A
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salt
alkyl
salts
methyl
unsubstituted
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彭学岗
赵德
崔琦
金涛
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Qingdao Kingagroot Chemical Compound Co Ltd
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Qingdao Kingagroot Chemical Compound Co Ltd
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Priority to AU2020322972A priority Critical patent/AU2020322972A1/en
Priority to US17/627,221 priority patent/US20220264878A1/en
Priority to JP2022504220A priority patent/JP7494285B2/en
Priority to BR112022001311A priority patent/BR112022001311A2/en
Priority to PCT/CN2020/101901 priority patent/WO2021017817A1/en
Priority to CA3147473A priority patent/CA3147473A1/en
Priority to MX2022000846A priority patent/MX2022000846A/en
Priority to EP20846511.2A priority patent/EP4005384A4/en
Priority to PE2022000089A priority patent/PE20220703A1/en
Publication of CN112273395A publication Critical patent/CN112273395A/en
Priority to CONC2022/0000361A priority patent/CO2022000361A2/en
Priority to ZA2022/00908A priority patent/ZA202200908B/en
Priority to CL2022000133A priority patent/CL2022000133A1/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the field of pesticides, and particularly relates to a weeding composition containing an R-type pyridyloxy carboxylic acid derivative and application thereof. The weeding composition comprises an active ingredient A and an active ingredient B which are used for weeding effective dose, wherein the active ingredient A is selected from one or more of R-type pyridyloxy carboxylic acid shown as a formula I and salts and ester derivatives thereof:
Figure DDA0002428464750000011
wherein R is1、R2Each independently represents halogen, C1-C6 alkyl, haloC1-C6 alkyl, C3-C6 cycloalkyl; r3Represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl; q represents a C1-C6 alkyl group, etc.; y represents an amino group or the like. The active ingredient B is selected from one or more of glyphosate, glufosinate, diquat and paraquat or acid/salt thereof. The composition can effectively prevent and kill various weeds in crop fields, and has the characteristics of expanding a weed control spectrum, reducing application amount, generating a synergistic effect, solving resistant weeds and the like.

Description

Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives and use thereof
Technical Field
The invention belongs to the field of pesticides, and particularly relates to a weeding composition containing an R-type pyridyloxy carboxylic acid derivative and application thereof.
Background
Chemical weeding is the most economic and effective means in preventing and removing weeds in farmlands, but the problems of drug resistance and resistance evolution of weeds and the like are easily caused by using a single variety or a single action mode of chemical herbicide continuously at a high dose for a long time. The reasonable compounding or mixing of the herbicide compound has the advantages of expanding the weed spectrum, improving the control effect, delaying the occurrence and development of drug resistance and drug resistance of weeds and the like, and is one of the most effective methods for solving the problems. Therefore, the development of a weeding composition variety which has high safety and wide weed control spectrum, can produce synergistic effect and solve the problem of resistant weeds is still needed in production.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and use thereof. The composition can effectively prevent and kill various weeds in crop fields, and has the characteristics of expanding a weed control spectrum, reducing application amount, generating a synergistic effect, solving resistant weeds and the like.
A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative comprising a herbicidally effective amount of an active ingredient A and an active ingredient B, wherein,
the active ingredient A is selected from one or more of R-type pyridyloxy carboxylic acid shown as a formula I and salt and ester derivatives thereof:
Figure BDA0002428464740000011
wherein R is1、R2Independently represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl;
R3represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl;
q represents C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, amino, nitro, formyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxycarbonyl, hydroxyC 1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, cyano C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, and phenyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyrazolyl, pyridyl or pyrimidinyl, unsubstituted or substituted by at least one group selected from C1-C6 alkyl, cyano, halogenated C1-C6 alkyl, C1-C6 alkylamino, halogen and C1-C6 alkoxy;
y represents amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, and phenylcarbonylamino, benzylamino or furanylmethyleneamino unsubstituted or substituted by at least one group selected from C1-C6 alkyl, halogen, cyano, C1-C6 alkylamino, C1-C6 alkoxy and halogeno C1-C6 alkyl;
the salt is metal salt or ammonium salt NH4 +Primary amine salt R' NH2Salts of secondary amines (R')2NH, tertiary amine salt (R')3N, quaternary ammonium salt (R')4N+Polyamine salts, morpholine salts, N-methylmorpholine salts, piperidine salts, pyridine salts, aminopropylmorpholine salts, Jeff amine D-230 salts, salts of 2,4, 6-tris (dimethylaminomethyl) phenol and sodium hydroxide, C1-C16 alkyl sulfonium salts (preferably C1-C6 alkyl sulfonium salts), C1-C16 alkyl sulfoxonium salts (preferably C1-C6 alkyl sulfoxonium salts), C1-C16 alkyl phosphonium salts (preferably C1-C6 alkyl phosphonium salts) or C1-C16 alkanol phosphonium salts (preferably C1-C6 alkanol phosphonium salts);
wherein, R' respectively and independently represents C1-C16 alkyl, C1-C16 alkyl (preferably C1-C6 alkyl) substituted by one or more groups selected from halogen, hydroxy, C1-C6 alkoxy, C1-C6 alkylthio and hydroxy C1-C6 alkoxy, C2-C12 alkenyl (preferably C2-C6 alkenyl), C2-C12 alkynyl (preferably C2-C6 alkynyl), C3-C12 cycloalkyl, phenyl or benzyl unsubstituted or substituted by C1-C6 alkyl;
the ester is
Figure BDA0002428464740000021
Wherein X represents O or S;
m represents C1-C18 alkyl, halogenated C1-C8 alkyl, C3-C6 cycloalkyl which is unsubstituted or substituted by C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, cyano C1-C6 alkyl, nitro C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, - (C1-C6 alkyl) -Z,
Figure BDA0002428464740000022
and phenyl which is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, halogenated C1-C6 alkyl, cyano, C1-C6 alkylamino, halogen and C1-C6 alkoxy,
Figure BDA0002428464740000023
Tetrahydrofuranyl, pyridinyl, naphthyl, furanyl, thienyl, pyrrolyl, pyrazolyl or imidazolyl;
z represents
Figure BDA0002428464740000024
And unsubstituted or substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, halogeno C1-C6 alkyl, cyano and halogen
Figure BDA0002428464740000025
Phenyl, tetrahydrofuryl, pyridyl, pyrazolyl, thienyl, furyl or naphthyl;
R4、R5、R6each independently represents hydrogen, C1-C6 alkyl, C1-C6 alkoxycarbonyl, and phenyl unsubstituted or substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, haloC 1-C6 alkyl, cyano and halogen;
R7represents C1-C6 alkyl, C2-C6 alkenyl,
Figure BDA0002428464740000031
The active ingredient B is selected from one or more of glyphosate, glufosinate, diquat and paraquat or acid/salt thereof.
Preferably, R1、R2Each independently represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl;
R3represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl;
q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, chloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2, 2-trifluoroethyl, hydroxymethyl,
Figure BDA0002428464740000032
benzyl, naphthyl
Figure BDA0002428464740000033
Furyl radical
Figure BDA0002428464740000034
Pyridyl radical
Figure BDA0002428464740000035
Pyrimidinyl radicals
Figure BDA0002428464740000036
And thiazolyl which is unsubstituted or substituted by chlorine
Figure BDA0002428464740000037
Thienyl unsubstituted or substituted by fluorine
Figure BDA0002428464740000038
Unsubstituted or substituted by methyl or fluorine
Figure BDA0002428464740000039
Figure BDA00024284647400000310
Phenyl unsubstituted or substituted with at least one group selected from methyl, trifluoromethyl, chlorine and methoxy;
y represents NH2、
Figure BDA00024284647400000311
The salts are alkali metal salts (such as sodium, lithium, potassium, cesium and rubidium), alkaline earth metal salts (such as calcium, magnesium, barium and strontium) and salts of metals such as antimony, bismuth, cadmium, cerium, chromium, cobalt, scandium, titanium, manganese, copper, iron, silver, gold, zinc, aluminum, etc., amine salts such as ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, N-hexadecyltrimethylammonium salt, N-benzyltrimethylammonium salt, benzyltriethylammonium salt, choline salt, monomethylamine salt, dimethylamine salt, trimethylamine salt, monoethylamine salt, diethylamine salt, triethylamine salt, N-propylamine salt, dipropylamine salt, tripropylamine salt, monoisopropylamine salt, diisopropylamine salt, triisopropylamine salt, N-butylamine salt, dibutylamine salt, isobutylamine salt, tert-butylamine salt, pentylamine salt, hexylamine salt, heptylamine salt, octylamine salt, dodecylamine salt, tetradecylamine salt, diisopropylamine salt, triethylamine salt, and the like, Diallylamine salt, cyclohexylamine salt, cyclododecylamine salt, aniline salt, o-toluidine salt, m-toluidine salt, p-toluidine salt, diphenylamine salt, benzylamine salt, monoethanolamine salt, N-methylmonoethanolamine salt, N-dimethylethanolamine salt, N-ethylmonoethanolamine salt, N-diethylethanolamine salt, N-propylmonoethanolamine salt, N-di-N-propylethanolamine salt, N-butylmonoethanolamine salt, diethanolamine salt, N-methyldiethanolamine salt, N-ethyldiethanolamine salt, N-propyldiethanolamine salt, N-butyldiethanolamine salt, N-dibutylethanolamine salt, triethanolamine salt, triperopanolamine salt, triisopropanolamine salt, tris (2-hydroxypropyl) amine salt, diglycolamine salt, polyamine salt (such as hexamethylenetetramine salt, p-toluidine salt, diphenylamine salt, benzylamine salt, N-methylmonoethanolamine salt, N-butylethanolamine salt, triethanolamine, Ethylenediamine salt, diethylenetriamine salt, dimethylaminopropylamine salt, 1, 2-propylenediamine salt, triethylenediamine salt, triethylenetetramine salt, benzidine salt, triethylamine salt, and the like,N, N-bis [ aminopropyl ] s]Methylamine salt), 2-methylthiopropylamine salt, 2-butoxyethylamine salt, AEPD
Figure BDA0002428464740000041
Salt, tris (hydroxymethyl) aminomethane
Figure BDA0002428464740000042
Salts, morpholine salts, N-methylmorpholine salts, piperidine salts, pyridine salts, aminopropylmorpholine
Figure BDA0002428464740000043
Salt, Jeff amine D-230(
Figure BDA0002428464740000044
n is 2 or 3) salts, salts of 2,4, 6-tris (dimethylaminomethyl) phenol and sodium hydroxide, sulfonium salts such as alkylsulfonium salts (e.g., trimethylsulfonium salt, triethylsulfonium salt), alkylsulfonium oxide salts, phosphonium salts such as alkylphosphonium salts or alkylol phosphonium salts;
x in the I-1 represents O or S;
m represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-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,
Figure BDA0002428464740000045
Figure BDA0002428464740000046
tetrahydrofuranyl group
Figure BDA0002428464740000051
Tetrahydrofuryl methylene radical
Figure BDA0002428464740000052
Pyridyl radical
Figure BDA0002428464740000053
Figure BDA0002428464740000054
Pyridylmethylene
Figure BDA0002428464740000055
Naphthyl radical
Figure BDA0002428464740000056
Naphthyl methylene
Figure BDA0002428464740000057
Furyl radical
Figure BDA0002428464740000058
Furyl methylene group
Figure BDA0002428464740000059
Thienyl radical
Figure BDA00024284647400000510
Thienyl methylene group
Figure BDA00024284647400000511
Figure BDA00024284647400000512
And unsubstituted or methyl-substituted
Figure BDA00024284647400000513
Figure BDA00024284647400000514
Phenyl which is unsubstituted or substituted by methyl, dimethylamino, chloro, methoxy, trifluoromethyl or isopropyl, benzyl which is unsubstituted or substituted by trifluoromethyl, bromo, chloro, fluoro, methoxy, cyano or methyl;
r' represents hydrogen, methyl, ethyl, difluoromethyl.
More preferably, the active ingredient a is selected from one or more of the following compounds:
Figure BDA00024284647400000515
Figure BDA0002428464740000061
Figure BDA0002428464740000071
Figure BDA0002428464740000081
Figure BDA0002428464740000091
Figure BDA0002428464740000101
Figure BDA0002428464740000111
Figure BDA0002428464740000121
Figure BDA0002428464740000131
Figure BDA0002428464740000141
Figure BDA0002428464740000151
Figure BDA0002428464740000161
Figure BDA0002428464740000171
Figure BDA0002428464740000181
Figure BDA0002428464740000191
Figure BDA0002428464740000201
the preparation method of the active ingredient A comprises the following steps:
reacting a compound shown in a general formula III with a compound shown in a general formula II to obtain a compound shown in a general formula I-1-1; the reaction equation is as follows:
Figure BDA0002428464740000202
wherein W represents hydrogen or an 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 more combination of DCM, DCE, ACN, THF and DMF.
Reacting a compound shown as a general formula I-1-1 in the presence of a lithium hydroxide aqueous solution and a solvent to prepare a compound shown as a general formula I; the reaction equation is as follows:
Figure BDA0002428464740000203
preferably, the solvent is selected from one or more of methanol, ethanol and isopropanol.
Reacting the compound shown in the general formula I with M-SH to obtain a compound shown in the general formula I-1-2; the reaction equation is as follows:
Figure BDA0002428464740000211
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 one or more of dichloromethane, dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, toluene and xylene.
Or when Y represents NR1R2(R1、R2Not simultaneously hydrogen), the compound shown in the general formula I-2 is added
Figure BDA0002428464740000212
Or a compound of the formula I-1-3
Figure BDA0002428464740000213
Reacting with corresponding halide to obtain the product;
among them, the halide is preferably chloride or bromide; the reaction is carried out in the presence of a base and a solvent, wherein the base is one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate; the solvent is one or more of THF, 1, 4-dioxane, toluene, 1, 2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane and chloroform; a catalyst, preferably DMAP, may also be added during the reaction.
The salt is an agriculturally pharmaceutically acceptable salt, and preferably the R-type pyridyloxy carboxylic acid compound is generated by reacting with a chemically acceptable alkaline compound. The pharmaceutically acceptable salts are easily separated and can be purified by conventional separation methods, such as solvent extraction, dilution, recrystallization, column chromatography, preparative thin layer chromatography, and the like.
Wherein the A, B weight ratio 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; more preferably 1:5 to 5:1 or 1:1 to 2: 1.
The weight percentage of A and B in the weeding composition accounts for 1-95% of the total weight, and preferably 10-80%.
The weeding composition also comprises conventional auxiliaries which comprise a carrier and a surfactant.
The term "carrier" herein denotes an organic or inorganic, natural or synthetic substance. They facilitate the application of the active ingredient, the carrier being generally inert and must be agriculturally acceptable, in particular for the treated plant. The carrier may be a solid, such as a clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer, or the like; or liquids such as water, alcohols, ketones, petroleum distillates, aromatic or waxy hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.
Surfactants may include emulsifying, dispersing or wetting agents, which may be ionic or non-ionic. Examples which may be mentioned are salts of polyacrylic acids, lignosulphonates, salts of phenolsulphonic or naphthalenesulphonic acids, polymers of ethylene oxide with aliphatic alcohols or with aliphatic acids or with aliphatic amines and substituted phenols, in particular alkylphenols or arylphenols, sulphosuccinates, taurine derivatives, in particular taurine alkyl esters, and phosphoric esters of alcohols or polyhydroxyethylated phenols, alkylsulfonates, alkylarylsulphonates, alkylsulfates, lauryl ether sulphates, fatty alcohol sulphates, and sulphated hexadec, heptadeca-and octadecanols and sulphated fatty alcohol glycol ethers, and furthermore condensates of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, polystearylphenyl polyglycol ether, Alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors, and also proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols, polycarboxylates, polyalkoxylates, polyvinylamines, polyvinylpyrrolidone and copolymers thereof. At least one surfactant is required to be present to facilitate dispersion of the active ingredients in water and to facilitate their proper application to the plant.
The compositions may also contain various other components such as protective colloids, binders, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents, dyes, colorants, and polymers.
In addition, the composition of the present invention can be mixed with the following active substances, for example, known substances in "the world Wide Specification of New agricultural chemical products", the Chinese agricultural science and technology Press, 2010.9 and the references cited therein. For example, herbicidal active substances mentioned below (remarks: the name of the compound, or the generic name according to the International organization for standardization (ISO), or the chemical name, when appropriate with a code), acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propachlor, butachlor, napropamide, R-laevo-napropamide, propanil, mefenacet, diphenoyl-oxamide, diflufenican, flumetsulam, bebutamid, dimethenamid, ethoxybenclamide, flufenacet, methoxyfenacet, metazachlor, isooxachlor, lofluvalinate, dimethenamid, butachlor, propisochlor, mefenamid, flucetochlor, propyzamide, dimethenamid, Terbutamid, dimethenamid, dimethachlor, norfluramine, trifoliamine, chlorantraniliprole, propyzamide, penflufen, napropamide, acetometazachlor, naproxen, fenacet, pyraflufen, metolachlor, clofenamide, butachlor, butamidin, fluazinam, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipretryn, fluroxypyr, terbutryn, terbutazine, triazineon, cyhalofop, ganciclovir, prometryn, simazine, triazazine, dimethametrazine, isopentetryn, cycloprozine, terbutryn, sec-butyn, terbutaline, terbutryn, metolachlor, cyhalofop, metolachlor, prometryn, simazine, atrazine, dimethametryn, dimethametin, terbutryn, metolachlor, dimethachlor, dimethozin, atrazine, metolachloraz, metolachlor, metolac, Cyanuric acid, Indaziflam, chlorsulfuron, metsulfuron, bensulfuron-methyl, chlorimuron-ethyl, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, mesosulfuron-methyl, iodosulfuron-methyl sodium, formamidosulfuron, cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron-methyl, amidosulfuron, ethoxysulfuron, cyclosulfamuron-methyl, rimsulfuron, azimsulfuron-methyl, monosulfuron-methyl, primisulfuron-methyl, flusulfuron-methyl, flazasulfuron-methyl, propsulfuron-methyl, prosulfuron-methyl, trifloxysulfuron, triflusulfuron-methyl, metsulfuron-methyl, primisulfuron-methyl, propulsulfuron-methyl, propaferon-methyl, triflusulfuron-methyl, sulfometuron-methyl, pyrisulfuron-methyl, propalis-ethyl, thiuron-methyl, sulfometuron-methyl, sulfometuron-ethyl, sulfometuron-ethyl, sulfofluridone, sulfometuron-ethyl, sulfofluridone, sulfometuron, sulfo, Dicumyl ether, aclonifen, ethoxyfen-ethyl, bifenox, trifluoromethoxyfen, metoxyfen, trifluornitrofen, fluoroglycofen, fluridone, bifenox, dimethofen, fluazifop-butyl, Halosafen, chlortoluron, isoproturon, linuron, diuron, fenpropuron, fluometuron, methabenzthiazuron, benzuron, sulfosulfuron, clofenuron, tebuthiuron, clodinuron, meturon, metoxuron, bromuron, metoxuron, meturon, metoxuron, metoron, Betalain, asulam, tefurazol, avenacalin, anilazine, chlorpropham, dichlofenamate, imazalil, cloropham, Carboxazole, chlorerprocarb, Fenasulam, BCPC, CPPC, Carbasulam, buticarb, thiobencarb, dimethenate, triallate, dichloropetalum, ethiofen, prosulfocarb, cloquintocet, prosulfocarb, dichloropetalum, dichloropetalate, dichloropetal, 2-methyl-4-chloropropionate, 2-methyl-4-chlorobutyric acid, 2,4, 5-nasal discharge propionic acid, 2,4, 5-nasal discharge butyric acid, 2-methyl-4-chloroamine salt, dicamba, woollen boom, varparvax, cypress, triclosan, dichlorfenamic acid, metoclopramide, diclofop-p-ethyl, haloxyfop-methyl, haloxyfop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, cyhalofop-butyl, fenoxaprop-p-ethyl, cloroph-ethyl, haloxyfop-ethyl, trifoliate-ethyl, clomazone, paraquat, dixyl, asulam, flutolon, isoproturon, chlorothalofop-ethyl, cyhalofop-p-ethyl, propafen-ethyl, butyfen-ethyl, fluroxypyr, metalaxyl, propafen, propaferin, propafen, glyphosate, anilofos, glufosinate, sulfosate, piperaphos, bialaphos, bensulide, imazapyr, mepyrazine, varroa, amifostine, glufosinate, imazethapyr ammonium salt, imazethapyr, imazamethabenz ester, fluroxypyr, isooctyl fluroxypyr, clopyralid, picloram, triclopyr, dithiopyr, haloxyfen, triclopyr, thiazopyr, flurazinone, aminopyralid, flurazone, diflufenzopyr, butoxyethyl triclopyr, ciodinate, sethoxydim, clethodim, thiacet, sethoxydim, clethodim, carfenflurazone, buthiazole, metribuzin, carfenflurazone, metamitron, fenflurazone, fenpyr, benzone, iodoxynil, bromoxynil, isoflurazone, isofluroxypyr, bensulam, isofluroxypyr, clomazone, ioxynil, dichlobenil, tolfenacet, pyraclonil, Iodobonil, flumetsulam, florasulam, penoxsulam, sulfentrazone, cloransulam, diclosulam, pyroxsulam, fluralin, bispyribac, pyribenzoxim, pyriminobac-methyl, pyrithiobac-methyl, bicyclosulfuron, mesotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketoxydipradox, isoxaflutole, fenoxasulfolane, Methiozolin, isopyrafen, pyraflufen, pyraflutole, pyrazotocide, pyraclonil, pyraclofenacetone, flumetsulcotrione, flumetsulam, fenflurazole, fentrazachlor, amicarbazone, fentrazachlor, pyrazachlor, pyraclonil, flumicloram, flumioxazone, fenflurazole, flumicloram, bexapyroxadim, flumicloram, bexadim, flumicloram, benfluroram, flumicl, Phthalidyl ether, Flumezin, pentachlorophenol (sodium), dinol, terbenol, terbutal, pendimethalin, dinitrophenol, chloronitrophenol, dimethomorph, oxadiargyl, oxadiazon, pentoxazone, flumetsulam, mefenoxaprop-p-ethyl, tetrazolyl amine, fluridazin, oxamyl, bromamine, dimethenamid, pyridaben, pyridate, pyrirfalol, quinclorac, bentazone, pyridate, oxaziclorac, benazolin, clomazone, clomeptyl, isoprox, iprodione, propamocarb, cumylfen, indoxacarb, sodium chlorate, dalton, dalapon, trichloroacetic acid, monochloroacetone, hexachloroacetone, tetrafluoropropionic acid, pasture, bromophenol oxime, triazoxide, fentrazol, furamethon, fursulam, ethon, benfurazolin, pyrimethanil, clorac, clodinafop, clorac, cumquat, cumarone, clorac, Thidiazuron, alantin, hydroxybenone, metophenone, saflufenacil, dichlorophosphoric, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iphridam, Ipfancarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurflurazone, Tripropindan, Sulglycapin, Sumbelanoline, Campandichlor, Cytopyrimidic acid, thiocyananilide, clethodim, fenclorim, cloquintocet, mequintocet, oxaziclomex, oxabetrinil, pyroxaglim, furazolidone, imazaquin, isoxadifen, dichlormid, halauxin, halauxifen, DOWF, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.
The herbicidal composition further comprises at least one safener selected from the group consisting of:
a) dichlorophenyl pyrazoline-3-carboxylic acid (S1) compounds, preferred compounds are, for example, ethyl 1- (2, 4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylate (S1-1 mefenpyr-diethyl, PM, p. 594-595), and related compounds described, for example, in WO91/07874 and PM (p. 594-595).
b) Dichlorophenyl pyrazole carboxylic acid derivatives, preferred compounds are, for example, ethyl 1- (2, 4-dichlorophenyl) -5-methylpyrazole-3-carboxylate (S1-2), ethyl 1- (2, 4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1- (2, 4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylate (S1-4), ethyl 1- (2, 4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate (S1-5), and related compounds as described in EP-A-333131 and EP-A-269806.
c) Triazole carboxylic acids (S1) and preferred compounds are, for example, fenchlorazole (fenchlorazole), i.e. ethyl 1- (2, 4-dichlorophenyl) -5-trichloromethyl- (1H) -1,2, 4-triazole-3-carboxylate (S1-6) and related compounds (see EP-A-174562 and EP-A-346620).
d) 5-benzyl-or 5-phenyl-2-isoxazoline-3-carboxylic acids or 5, 5-diphenyl-2-isoxazoline-3-carboxylic acids, preferred compounds being, for example, ethyl 5- (2, 4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (S1-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-8) and related compounds described in WO91/08202, or ethyl 5, 5-diphenyl-2-isoxazoline-3-carboxylate (S1-9, isoxadifen-ethyl)) or 5 described in the patent application (WO-A-95/07897), n-propyl 5-diphenyl-2-isoxazoline-3-carboxylate (S1-10) or ethyl 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylate (S1-11).
e) 8-Quinolinyloxyacetic acids (S2) of the class of compounds, preferably 1-methylhexan-1-yl (5-chloro-8-quinolinyloxy) acetate (S2-1, cloquintocet-mexyl), such as PM (p. 195-), (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), (ethyl 5-chloro-8-quinolinyloxy) acetate (S2-5), (methyl 5-chloro-8-quinolinyloxy) acetate (S2-6), allyl (5-chloro-8-quinolinyloxy) acetate (S2-7), 2- (2-propyleneiminoyloxy) -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.
f) (5-chloro-8-quinolinoxy) propanedioic acid-based compounds, preferred compounds are, for example, diethyl (5-chloro-8-quinolinoxy) malonate, (diallyl (5-chloro-8-quinolinoxy) malonate, (methylethyl (5-chloro-8-quinolinoxy) -malonate and related compounds described in EP-A-0582198.
g) Phenoxyacetic acid, phenoxypropionic acid or aromatic carboxylic acids, such as 2, 4-dichlorophenoxyacetic acid (and esters) (2,4-D), 4-chloro-2-methylphenoxypropionate (2-methyl-4-chloropropionic acid (mecoprop)), MCPA or 3, 6-dichloro-2-methoxybenzoic acid (and esters) (dicamba).
h) Pyrimidines, such as fenclorim (PM, page 386-387) (═ 4, 6-dichloro-2-phenylpyrimidine),
i) dichloroacetamide-based active compounds, which are frequently used as pre-emergence safeners (soil-working safeners), for example "dichloroallylamine (dichlormid)" (PM, page 270-271) (═ N, N-diallyl-2, 2-dichloroacetamide), "AR-29148" (-3-dichloroacetyl-2, 2, 5-trimethyl-1, 3-oxazolidinone from Stauffer), "benoxacor" (PM, page 74-75) (-4-dichloroacetyl-3, 4-dihydro-3-methyl-2H-1, 4-benzoxazine), "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 nitrkemia or Monsanto), "diclonon" or "ABAS 145138" or "ala b 145138" (═ 3-dichloroacetyl-2, 5, 5-trimethyl-1, 3-diazabicyclo [4.3.0] nonane, from BASF), and "furilazol" or "AMON 13900" (see PM, 482-483) ((RS) -3-dichloroacetyl-5- (2-furyl) -2, 2-dimethyloxazolidinone),
j) dichloroacetone derivative-based active compounds, for example, "AMG 191" (CAS registry No. 96420-72-3) (═ 2-dichloromethyl-2-methyl-1, 3-dioxolane, available from Nitrokemia),
k) oxyimino compounds as active compounds, which are referred to as seed dressing materials, for example "oxabetrinil" (PM, page 689) (═ Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile), which in seed dressing is referred to as safener in order to prevent damage to metolachlor (metallachlor), "fluoroxyfen" (PM, page 467 468) (═ 1- (4-chlorophenyl) -2,2, 2-trifluoro-1-ethanone O- (1, 3-dioxolan-2-ylmethyl) -oxime, which in seed dressing is referred to as safener in order to prevent damage to metolachlor (metallachlor), and "cyanohydrin" or "a-CGA-43089" (PM, page 983) ((Z) -cyanomethoxyimino (phenyl) acetonitrile), which is called safener in seed dressing, to prevent the damage of metolachlor (metolachlor),
l) Thiazolecarboxylic acid ester active compounds, which are known as seed dressing materials, for example "flurazon" (PM, p. 450. 451), (-2-chloro-4-trifluoromethyl-1, 3-thiazole-5-carboxylic acid benzyl ester), which are known as safeners in seed dressing to prevent damage to alachlor (alachlor) and metolachlor,
m) active compounds of the naphthalenedicarboxylic acid derivative class, which are known as seed dressings, for example "naphthalic anhydride" (PM, pp 1009-1010) (═ 1, 8-naphthalic anhydride), which are known as safeners in corn seed dressings to prevent damage to thiocarbamate herbicides,
n) chromanoic acid derivatives such as "ACL 304415" (CAS registry No. 31541-57-8) (═ 2-84-carboxychroman-4-yl) acetic acid available from american cyanamid),
o) active compounds which, in addition to herbicidal action on harmful plants, also have safener action on plants, for example "penetryn (dimerate)" or "AMY-93" (PM, p.302-303) (═ S-1-methyl-1-phenylethylpiperidine-1-thiocarboxylate), "diuron (daimuron)" or "ASK 23" (PM, p.247) (═ 1- (1-methyl-1-phenylethyl) -3-p-tolylureｃA), "cumyluron (cumyluron)", "jc-940" ((3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenyl-ethyl) ureｃA, see JP- ｃA-60087254), "benzophenone (methoxyphenon)" or "ANK 049" (═ 3,3' -dimethyl-4-methoxy-benzophenone), "CSB" (═ 1-bromo-4- (chloromethylsulfonyl) benzene) (CAS registry No. 54091-06-4, available from Kumiai).
The safener is preferably one or more of isoxadifen (CAS: 163520-33-0), cyprosulfamide (CAS: 221667-31-8), mefenpyr (CAS: 135590-91-9), cloquintocet (CAS: 99607-70-2), gibberellic acid (CAS: 7-06-5), furilazole (CAS: 121776-33-8) and metacamifen (CAS: 129531-12-0).
In the context of the present specification, if the abbreviated forms of the common name of the active compounds are used, all customary derivatives, such as esters and salts, and also isomers, in particular optical isomers, in particular one or more commercially available forms, are included in each case. If the generic name denotes esters or salts, all other customary derivatives, such as other esters and salts, free acids and neutral compounds, and also isomers, in particular optical isomers, in particular one or more commercially available forms, are also included in each case. The chemical name given for a compound means at least one compound covered by the generic name, with compounds generally being preferred. In the case of sulfonamides, such as sulfonylureas, salts also include those formed by exchange of cations with hydrogen atoms in the sulfonamide group. For example, 2-methyl-4-chloro derivatives include, but are not limited to: 2 methyl 4 chloro sodium salt, potassium salt, dimethyl ammonium salt, isopropyl amine salt, etc., and 2 methyl 4 chloromethyl ester, ethyl ester, isooctyl ester, ethyl thioester, 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 and the like, and 2,4-D esters such as methyl ester, ethyl ester, butyl ester, isooctyl ester and the like.
In the context of the present invention, the salts of the compounds are preferably in the form of the respective alkali metal, alkaline earth metal 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.
The compositions of the present invention may be diluted or used directly by the user prior to use. The formulation can be prepared by conventional processing methods, i.e., mixing the active substance with a liquid solvent or solid carrier, and adding one or more surfactants such as dispersants, stabilizers, wetting agents, binders, defoamers, etc.
The specific preparation of the weeding composition is dispersible oil suspending agent, water suspending agent, suspending emulsion, wettable powder, missible oil, water dispersible granule (dry suspending agent), emulsion in water and microemulsion.
In short, the compositions of the present invention may be mixed with solid and liquid additives conventionally used in prior art formulations.
In addition, the compositions according to the invention can be applied by spraying to the foliage of the plants to be treated, i.e. to the weeds, in particular to surfaces infested or susceptible to infestation by weeds.
Further, the invention also provides an application of the weeding composition in weed control; and to provide a method of controlling unwanted plant growth comprising applying the herbicidal composition to a plant, part of a plant, plant seed, or area where a plant is growing. Preferably, the herbicidal compositions are used to selectively control weeds in crops of useful plants, more preferably, the useful plants are transgenic plants or plants treated with genome editing techniques.
The compounds of the invention can be used for the treatment of all plants and plant parts. Plant varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the genome of the plant. A transgene defined by its specific location in the plant genome is referred to as a transformation event or transgenic event.
Plant cultivars that have been genetically modified to be treated according to the invention include those resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or which comprise other desirable characteristics. Plants can be genetically modified to exhibit traits such as herbicide tolerance, insect tolerance, modified oil characteristics, or drought tolerance. Useful genetically modified plants comprising a single genetic transformation event or a combination of transformation events are listed in table 1'. Additional information regarding the genetic modifications listed in table 1' may be obtained from publicly available databases maintained, for example, by the U.S. department of agriculture.
The following abbreviations T1 to T37 are used for the traits of table 1'. "-" indicates that the entry is not available.
Figure BDA0002428464740000281
TABLE 1' genetically modified plants
Figure BDA0002428464740000282
Figure BDA0002428464740000291
Figure BDA0002428464740000301
Figure BDA0002428464740000311
Figure BDA0002428464740000321
Figure BDA0002428464740000331
Figure BDA0002428464740000341
Argentina brassicae napus (Brassica napus)), pakchoi brassicae (turnip (b.rapa)), and eggplant.
When the herbicidal composition of the present invention is applied, an unexpected synergistic effect is obtained, and the herbicidal activity is more remarkable than the expected sum of the activities using individual herbicides, and the activities of the individual herbicides. The synergistic effect is manifested by reduced application rates, a broader spectrum of weed control, and a faster and longer lasting herbicidal action, which are desirable in the practice of weed control. These new compositions are clearly superior to existing herbicides in terms of the properties described, achieving reduced use and being more environmentally friendly.
The synergistic herbicidal composition of the invention also has the following advantages:
(1) the composition of the invention is environment-friendly and is easy to degrade in the environment.
(2) The weeding composition has low cost and convenient use, and has great economic and social benefits when being popularized and applied.
Detailed Description
The following examples are not intended to limit the invention, but merely to illustrate how the invention may be carried out. These examples show particularly significant effectiveness against certain weeds. Examples are as follows:
wherein the structural formula of the active ingredient A is shown in the table, and the active ingredient B is as follows: glyphosate (Glyphosate, CAS number: 1071-83-6), Glufosinate-ammonium (Glufosinate ammonium, CAS number: 77182-82-2), Diquat monobromide monohydrate (CAS number: 6385-62-2), Paraquat dichloride (CAS number: 1910-42-5).
A) Examples of the embodiments
Dispersible oil suspension agent of A172+ glyphosate (20+30)
20% of A172, 30% of glyphosate, 6% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 6% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A66+ Glyphosate (10+30)
10% of A66, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A1+ Glyphosate (9+30)
9% of A1, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A3+ Glyphosate (12+30)
12% of A3, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A171+ glyphosate (20+30)
20% of A171, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 6% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A211+ Glyphosate (10+30)
10% of A211, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 6% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A93+ Glyphosate (20+30)
20% of A93, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 6% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
A173+ glyphosate (10+30) dispersible oil suspending agent
10% of A173+ 30% of glyphosate + 5% of calcium dodecyl benzene sulfonate + 6% of fatty alcohol-polyoxyethylene ether + 6% of castor oil-polyoxyethylene ether + 0.5% of organic bentonite + 15% of 100# solvent oil + methyl oleate
Dispersible oil suspension of A212+ Glyphosate (20+30)
20% of A212, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 6% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A140+ glyphosate (10+30)
10% of A140, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 6% of fatty alcohol-polyoxyethylene ether, 6% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A162+ glyphosate (10+30)
10% of A162, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 8% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A129+ glyphosate (10+30)
10% of A129, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 7% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
A213+ Glyphosate (10+30) dispersible oil suspension
10% of A213, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 7% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
A214+ glyphosate (10+30) dispersible oil suspension
10% of A214, 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 7% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
Dispersible oil suspension of A168+ Glyphosate (10+30)
10% of A168+ 30% of glyphosate, 5% of calcium dodecyl benzene sulfonate, 7% of fatty alcohol-polyoxyethylene ether, 5% of castor oil-polyoxyethylene ether, 0.5% of organic bentonite, 15% of 100# solvent oil and methyl oleate
The processing equipment of the dispersible oil suspending agent comprises the following steps: mixing kettle, colloid mill, sand mill, shearing machine, storage tank, etc.
The processing process of the dispersible oil suspending agent comprises the following steps: putting all materials into a mixing kettle, stirring and mixing, passing through a colloid mill, then entering a sand mill for three-stage sand milling, finally uniformly shearing in a shearing machine, and transferring to a storage tank for filling after the test is qualified.
B) Test of drug efficacy
Spraying treatment of stems and leaves after seedling:
1) test conditions
1.1) test target
The crab grass, the amaranthus retroflexus, the horseweed herb, the shepherd's purse and the eleusine indica are collected from Shandong Huangdao, the wild rape is collected from Anhui Sixian county, the Japanese mother-witness is collected from Anhui Tian, and the grand mother is collected from the Jiangsu Siyang. The weeds are cultured by a pot culture method, plastic nutrition bowls with the size of 180 х 140mm are placed in an enamel tray, surface soil (4/5) which is collected from a farmland and is dried and sieved is filled in the enamel tray, the soil humidity is controlled to be 20% at the initial stage, weed seeds with full and uniform seeds are selected, the weed seeds are soaked in warm water with the temperature of 25 ℃ for 6 hours, germination is accelerated in a biochemical incubator (dark) with the temperature of 28 ℃, the weed seeds which are just exposed to the white are uniformly placed on the surface of the soil, and then the enamel tray is covered with 0.5-1cm of soil according to the particle size of the seeds.
1.2) culture conditions
The method is carried out in a controllable sunlight greenhouse, the temperature is 20-30 ℃, the natural illumination is carried out, and the relative humidity is 57-72%. The soil type is loam, the organic matter content is 1.63%, the pH value is 7.1, the alkaline hydrolysis nitrogen is 84.3mg/kg, the quick-acting phosphorus is 38.5mg/kg, and the quick-acting potassium is 82.1 mg/kg.
1.3), instrumentation
3WP-2000 model walking spray tower, Minn Jing agricultural machinery research institute of agricultural department. Ten thousandth electronic balance type GA10 (germany); ZDR2000 intelligent data recorder (hangzhou ze large instruments ltd); SPX type intelligent biochemical incubator (Ningbo Jiangnan Instrument factory).
2) Design of experiments
2.1), reagents
The desired active ingredient a is obtained from patent CN201911321469.4, and the preparation examples of representative compounds are as follows, and the synthesis methods of other compounds are similar, so the details are not repeated.
(1) Synthesis of Compound A66
Compound a (0.5g, 2.13mmol), compound b (313mg, 2.55mmol), a catalytic amount of TBAB (10mg), DMF (10mL) was placed in a round bottom flask and stirred at room temperature 15 ℃ for 24 h. And (5) detecting a small amount of residual raw materials by liquid quality, and then treating. The reaction solution was poured into 50mL of water, extracted 2 times with methyl t-butyl ether (50mL × 2), organic phase dried, concentrated, and purified by column chromatography to give compound a66(300mg, yield 50%). Compound a66 was a white solid.
Figure BDA0002428464740000371
(2) Synthesis of Compound A1
Compound A66(0.3g, 1.06mmol) and methanol (20mL) were placed in a 100mL single-neck flask, lithium hydroxide (44.5mg, 1.06mmol) was dissolved in 2mL water, and the solution was slowly added dropwise to the single-neck flask at room temperature, followed by stirring at room temperature for 12 hours. After the reaction of the raw materials is finished, adjusting the pH to 5-6 with 0.5M dilute hydrochloric acid, concentrating, and extracting with water and ethyl acetate. The organic phase was dried and concentrated to give compound a1(200mg, yield 70%) compound a1 as a white solid.
Figure BDA0002428464740000381
(3) Synthesis of Compound A211
Compound A1(200mg, 0.74mmol), compound c (85mg, 0.74mmol), DCC (152mg, 0.74mmol), and anhydrous DCM (20mL) were placed in a 100mL round-bottomed flask and reacted at room temperature for 12 hours. After the reaction of the starting materials was completed, the reaction mixture was concentrated and separated by column chromatography to obtain compound a211(200mg, yield 73%) as a white solid.
Figure BDA0002428464740000382
(4) Synthesis of Compound A173
Compound d (2g, 18.16mmol), compound b (3.64g, 21.80mmol), a catalytic amount of TBAB (10mg), DMF (20mL) was placed in a round bottom flask and stirred at room temperature 15 ℃ for 24 h. And (5) detecting a small amount of residual raw materials by liquid quality, and then treating. The reaction was poured into 50mL of water, extracted 2 times with methyl tert-butyl ether (100mL × 2), the organic phase was dried, concentrated, and purified by column chromatography to give compound e (1.5mg, yield 42%). Compound e was a white solid.
Figure BDA0002428464740000383
Compound e (0.5g,2.55mmol) was dissolved in acetonitrile (20mL) and placed in a 100mL single-neck flask, NCS (850.7mg, 6.37mmol) and catalytic amount of BPO (10mg) were added at room temperature, the temperature was raised to 70 ℃ and reaction was carried out for 2 hours, the liquid chromatography starting material was reacted completely, concentrated, and purified by column chromatography to give compound a173(300mg, yield 44%) as a white solid.
Figure BDA0002428464740000384
(5) Synthesis of Compounds A174 and A212
Dissolving the compound e (0.5g,2.55mmol) in acetonitrile (20mL), placing in a 100mL single-neck bottle, adding NBS (1.13mg, 6.37mmol) and a catalytic amount of BPO (10mg) at room temperature, heating to 70 ℃, reacting for 2 hours, completely reacting the liquid chromatography raw materials, concentrating, and separating and purifying by column chromatography to obtain the compound A174(500mg, yield 54%) which is a white solid.
Figure BDA0002428464740000391
Compound A174(0.5g, 1.41mmol) and methanol (20mL) were placed in a 100mL single-neck flask, and lithium hydroxide (59.3mg, 1.41mmol) was dissolved in 2mL of water, and the solution was slowly added dropwise to the single-neck flask at room temperature, followed by stirring at room temperature for 12 hours. After the reaction of the raw materials is finished, adjusting the pH to 5-6 with 0.5M dilute hydrochloric acid, concentrating, and extracting with water and ethyl acetate. The organic phase was dried and concentrated to give compound a212(350mg, yield 73%) as a white solid.
Figure BDA0002428464740000392
(6) Synthesis of Compound A168
Compound A1(200mg, 0.74mmol), compound f (75mg, 0.74mmol), DCC (152mg, 0.74mmol), and anhydrous DCM (20mL) were placed in a 100mL round-bottomed flask and reacted at room temperature for 12 hours. After the reaction of the raw materials was completed, the reaction solution was concentrated and separated by column chromatography to obtain compound a168(200mg, yield 77%) as a white solid.
Figure BDA0002428464740000393
The desired active ingredient B was purchased from the reagent company. The raw medicines are all diluted by using an emulsifier Tween-80 aqueous solution with the content of 0.1 percent and taking acetone as a solvent.
2.2) test treatment
2.2.1), dose setting
When determining the ratio or content of the component A and the component B, the main use purpose of the formula is also considered according to the action characteristics of the two medicaments and the measurement of toxicity and the like. On the basis of preliminary experiments, A, B active ingredients are respectively used singly and mixed in different amounts. Water without drug, containing the same solvent and emulsifier was used as a blank.
2.2.2), test repetition
Each treatment was repeated 4 times, 3 pots each time, 20 weed seeds were sown per pot, 60 plants each time.
2.3) treatment method
2.3.1), treatment time and number of times
The test was performed 1 time in total. And (3) thinning when the weeds are in a 3-4 leaf period, keeping 15 weeds in each pot, keeping 45 weeds in each treatment, and then continuously culturing until 4-5 leaves of gramineous weeds and 5-6 leaves of broadleaf weeds are treated.
2.3.2), instruments and methods of use
Uniformly placing the cultured test material on a 0.5m area2Spraying stem and leaf by using a 3WP-2000 model walking spray tower on the platform, wherein the liquid spraying amount is 450 kg/hectare. The spraying pressure is 0.3 MPa. And after all the liquid medicine is sprayed, closing the air valve, opening the spraying tower door after 30 seconds, and taking out the nutrition pot. Then the air valve is opened, 50mL of clean water is sprayed, and the liquid spraying pipe is cleaned.
3) Test method
The potting method is adopted. The weed cultivation is shown in 1.1), and the method is carried out according to 'herbicide in pesticide indoor bioassay test guidelines'. The application method is shown in 2.3.2), and stem and leaf treatment method is adopted. After treatment, the cells were transferred to a greenhouse for conventional culture.
4) Data investigation and statistical analysis
4.1) investigation method
The complete survival weed seedlings are cut off along the soil surface by a blade by adopting an absolute number survey method, and the fresh weight of the weeds is weighed by an analytical balance. For the weeds that have died, the fresh weight is zero.
4.2), investigation time and number of surveys
The investigation was carried out 20 days after the treatment, and the total number of the investigations was 1.
4.3), statistical analysis of data
The theoretical fresh weight inhibition rate (E0 ═ X + Y-X Y/100) of each treatment mixed combination is calculated by a Gowing method, and then compared with the actually measured inhibition rate (E), the combined action type of the two mixed combinations on the weeds is evaluated, and when the E-E0 value is more than 10 percent, the effect is synergistic, when the E-E0 value is less than-10 percent, the effect is antagonistic, and when the E-E0 value is between-10 percent and 10 percent, the effect is additive. And the optimal proportion is determined according to factors such as actual control effect, characteristics of the herbicide, balance of the formula and the like. Wherein X is the fresh weight inhibition rate when the dosage of the active component A is P; y is the fresh weight inhibition rate of the active component B when the dosage is Q. The statistical results are shown in tables 1-56 below.
TABLE 1 evaluation of actual control and combination of glyphosate mixed with crab grass
Figure BDA0002428464740000401
TABLE 2 evaluation of actual control and combination of glufosinate-ammonium mixed with Capsella bursa-pastoris
Figure BDA0002428464740000402
Table 3A 66 evaluation of actual control and combination of Glyphosate blends on crab grass
Figure BDA0002428464740000403
Figure BDA0002428464740000411
TABLE 4A 66 evaluation of the actual control and combination of goosegrass with glyphosate
Figure BDA0002428464740000412
TABLE 5A 66 evaluation of the actual control and combination of Glyphosate blends on Brassica napus
Figure BDA0002428464740000413
TABLE 6A 66 evaluation of the actual control and combination of Glyphosate blends for Nissan-Beech
Figure BDA0002428464740000414
TABLE 7 evaluation of actual control and combination of glufosinate-ammonium compounded with Capsella bursa-pastoris A66
Figure BDA0002428464740000415
TABLE 8A 66 evaluation of the actual control and Combined action of the compounded glufosinate-ammonium on Amaranthus retroflexus
Figure BDA0002428464740000416
TABLE 9A 66 evaluation of the actual control and combination of paraquat on erigeron breviscapus
Figure BDA0002428464740000417
TABLE 10A 66 evaluation of the actual control and combination of the compounded diquat against the effect of Veronica
Figure BDA0002428464740000418
Figure BDA0002428464740000421
TABLE 11A 1 evaluation of the actual control and Combined action of Glyphosate blends on crab grass
Figure BDA0002428464740000422
TABLE 12 evaluation of actual control and combination of goosegrass with glyphosate mixed in 1
Figure BDA0002428464740000423
TABLE 13A 1 evaluation of the actual control and Combined action of Glyphosate blends on Brassica napus
Figure BDA0002428464740000424
TABLE 14A 1 evaluation of the actual control and Combined action of Glyphosate blends on the Japanese bride
Figure BDA0002428464740000425
TABLE 15A 1 evaluation of the actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000426
TABLE 16A 1 evaluation of the actual control and Combined action of glufosinate-ammonium on Amaranthus retroflexus
Figure BDA0002428464740000427
TABLE 17 evaluation of actual control and Combined action of glyphosate compounded with A3 on crab grass
Figure BDA0002428464740000428
TABLE 18A 3 evaluation of the actual control and Combined action of Glyphosate blends on Eleusine indica
Figure BDA0002428464740000431
TABLE 19 evaluation of actual control and Combined action of Glyphosate blend 19A 3 on Brassica napus
Figure BDA0002428464740000432
TABLE 20A 3 evaluation of the actual control and Combined action of Glyphosate blends on Nissan-Beech
Figure BDA0002428464740000433
TABLE 21A 3 evaluation of actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000434
TABLE 22A 3 evaluation of the actual control and Combined action of the compounded glufosinate-ammonium on Amaranthus retroflexus
Figure BDA0002428464740000435
TABLE 23A 171 evaluation of the actual control and Combined action of glyphosate mixed on crab grass
Figure BDA0002428464740000436
TABLE 24A 171 evaluation of actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000437
TABLE 25 evaluation of actual control and Combined action of Glyphosate blend to crab and Tang
Figure BDA0002428464740000438
Figure BDA0002428464740000441
TABLE 26A 211 evaluation of the actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000442
TABLE 27A 93 evaluation of actual control and Combined action of Glyphosate blends on crab grass
Figure BDA0002428464740000443
TABLE 28A 93 evaluation of actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000444
TABLE 29 evaluation of actual control and Combined action of Glyphosate blend 29A 173 on crab and Tang
Figure BDA0002428464740000445
TABLE 30A 173 evaluation of actual control and Combined action of glufosinate-ammonium mixed with Capsella bursa-pastoris
Figure BDA0002428464740000446
TABLE 31A 212 evaluation of actual control and Combined action of Glyphosate blends on crab grass
Figure BDA0002428464740000447
TABLE 32A 212 evaluation of the actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000448
Figure BDA0002428464740000451
TABLE 33A 140 evaluation of actual control and Combined action of Glyphosate blends on crab and Tang
Figure BDA0002428464740000452
TABLE 34 evaluation of actual control and combination of glufosinate-ammonium compounded with Capsella bursa-pastoris
Figure BDA0002428464740000453
TABLE 35 evaluation of actual control and Combined action of glyphosate compounded with A162 on crab and Tang
Figure BDA0002428464740000454
TABLE 36A 162 evaluation of the actual control and Combined action of Glyphosate blends on Eleusine indica
Figure BDA0002428464740000455
TABLE 37A 162 evaluation of the actual control and Combined action of Glyphosate blends on oilseed rape
Figure BDA0002428464740000456
TABLE 38 evaluation of actual control and Combined action of Glyphosate mixture of A162 on Nissan Dairy
Figure BDA0002428464740000457
TABLE 39A 162 evaluation of actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000458
TABLE 40A 162 evaluation of actual control and Combined action of Glufosinate-ammonium compounded on Amaranthus retroflexus
Figure BDA0002428464740000461
TABLE 41A 162 evaluation of the actual control and combination of paraquat on erigeron breviscapus
Figure BDA0002428464740000462
TABLE 42A 162 evaluation of the actual control and combination of the compounded diquat to Veronica
Figure BDA0002428464740000463
TABLE 43 evaluation of actual control and Combined action of Glyphosate combinations with 129A and B on crab and Tang
Figure BDA0002428464740000464
TABLE 44 evaluation of actual control and combination of glufosinate-ammonium mixed with Capsella bursa-pastoris
Figure BDA0002428464740000465
TABLE 45 evaluation of actual control and Combined action of 213 Glyphosate blends on crab and Tang
Figure BDA0002428464740000466
TABLE 46 evaluation of actual control and combination of glufosinate-ammonium mixed with Capsella bursa-pastoris
Figure BDA0002428464740000467
TABLE 47A 214 evaluation of actual control and Combined action of Glyphosate blends on crab and Tang
Figure BDA0002428464740000468
Figure BDA0002428464740000471
TABLE 48A 214 evaluation of actual control and combination of glufosinate-ammonium for Capsella bursa-pastoris
Figure BDA0002428464740000472
TABLE 49 evaluation of actual control and Combined action of A168 Glyphosate blends on crab grass
Figure BDA0002428464740000473
TABLE 50 evaluation of the actual control and combination of goosegrass with glyphosate mixture
Figure BDA0002428464740000474
TABLE 51 evaluation of the actual control and Combined action of glyphosate mixed with canola
Figure BDA0002428464740000475
TABLE 52 evaluation of the actual control and combination of Glyphosate blends for Nissan-Beech
Figure BDA0002428464740000476
TABLE 53 evaluation of actual control and combination of glufosinate-ammonium compounded with Capsella bursa-pastoris A168
Figure BDA0002428464740000477
TABLE 54 evaluation of actual control and Combined action of Glufosinate-ammonium mixture on Amaranthus retroflexus
Figure BDA0002428464740000478
TABLE 55A 168 evaluation of the actual control and combination of paraquat for erigeron breviscapus
Figure BDA0002428464740000481
TABLE 56A 168 evaluation of the actual control and Combined action of the compounded diquat on Veronica
Figure BDA0002428464740000482
C) Indoor evaluation test
The herbicide compositions prepared in A) examples 1 to 15 were used for indoor evaluation tests, and the concrete test methods were the same as those in the corresponding portions of the efficacy test of B).
The tested weeds: cockspur grass, crab grass, goosegrass herb, green bristlegrass herb, wild millet, redroot amaranth, piemarker and acalypha australis.
Test crops (containing glyphosate, 2,4-D resistance trait): corn (corn)SmartStaxTMPro x EnlistTM(Event Name MON87427 x MON89034 x TC1507 x MON87411 x 59122x DAS40278), Soybean Conkesta Enlist E3TM(Event Name DAS81419 x DAS44406)。
Leaf treatment and leaf age: 3-5 leaf stage of weeds, 3-5 leaf stage of corn, 1 heart stage of corn and 2 nd to 3 rd third leaflet stage of soybean.
The concrete test agents, the amounts of the test agents and the control effects 20 days after the application are shown in Table 57.
Weed fresh weight control effect (%) - (blank control weed fresh weight-medicament treatment weed fresh weight)/blank control weed fresh weight x 100
Application of compound composition in table 57 to transgenic herbicide-resistant trait crops
Medicament Dosage (g a.i./ha) Fresh weight control of weeds (%) Crop safety-corn Crop safety-soybean
1 1125 93.1 Secure Secure
2 900 96.4 Secure Secure
3 877.5 97.2 Secure Secure
4 945 95.2 Secure Secure
5 1125 94.9 Secure Secure
6 900 92.3 Secure Secure
7 1125 91.7 Secure Secure
8 900 93.9 Secure Secure
9 1125 94.6 Secure Secure
10 900 92.0 Secure Secure
11 900 95.5 Secure Secure
12 900 94.2 Secure Secure
13 900 91.6 Secure Secure
14 900 93.2 Secure Secure
15 900 96.0 Secure Secure
Through a large number of tests and explorations, the invention unexpectedly discovers that the composition is used for preventing and killing broad-leaf weeds such as copperleaf herb, amaranthus retroflexus, dayflower, cephalanoplos chinensis, endive, black nightshade and the like, gramineous weeds such as barnyard grass, crab grass, goosegrass herb, green bristlegrass, golden green bristlegrass, broomcorn millet, broom corn millet and the like, and equisetum weeds such as field horsetail and the like, has a surprising and unexpected synergistic effect, has more remarkable performance under low dosage, can reduce the dosage, reduces the pollution to the environment, reasonably compounds and reduces the agricultural cost, is efficient on ALS and ACCase inhibitor resistant weeds, and has good application prospect. Meanwhile, the herbicide composition shows good selectivity and excellent synergism in wheat fields, corn fields, paddy fields, peanuts, sugarcane, sorghum, millet, potatoes, rape, soybeans, cotton, vegetables, bluegrass, tall fescue, zoysia japonica and other fields through tests, and can be developed into herbicide mixtures with wide market value.

Claims (10)

1.A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative comprising a herbicidally effective amount of an active ingredient A and an active ingredient B, wherein,
the active ingredient A is selected from one or more of R-type pyridyloxy carboxylic acid shown as a formula I and salt and ester derivatives thereof:
Figure FDA0002428464730000011
wherein R is1、R2Each independently represents halogen, C1-C6 alkyl,Halogenated C1-C6 alkyl, C3-C6 cycloalkyl;
R3represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl;
q represents C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, amino, nitro, formyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxycarbonyl, hydroxyC 1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, cyano C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, and phenyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyrazolyl, pyridyl or pyrimidinyl, unsubstituted or substituted by at least one group selected from C1-C6 alkyl, cyano, halogenated C1-C6 alkyl, C1-C6 alkylamino, halogen and C1-C6 alkoxy;
y represents amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, and phenylcarbonylamino, benzylamino or furanylmethyleneamino unsubstituted or substituted by at least one group selected from C1-C6 alkyl, halogen, cyano, C1-C6 alkylamino, C1-C6 alkoxy and halogeno C1-C6 alkyl;
the salt is metal salt or ammonium salt NH4 +Primary amine salt R' NH2Salts of secondary amines (R')2NH, tertiary amine salt (R')3N, quaternary ammonium salt (R')4N+Polyamine salts, morpholine salts, N-methylmorpholine salts, piperidine salts, pyridine salts, aminopropylmorpholine salts, Jeff amine D-230 salts, salts of 2,4, 6-tris (dimethylaminomethyl) phenol and sodium hydroxide, C1-C16 alkyl sulfonium salts, C1-C16 alkyl sulfonium oxide salts, C1-C16 alkyl phosphonium salts or C1-C16 alkanol phosphonium salts;
wherein, R' respectively and independently represents C1-C16 alkyl which is unsubstituted or substituted by one or more groups selected from halogen, hydroxyl, C1-C6 alkoxy, C1-C6 alkylthio and hydroxyl C1-C6 alkoxy, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, phenyl or benzyl which is unsubstituted or substituted by C1-C6 alkyl;
the ester is
Figure FDA0002428464730000012
Wherein X represents O or S;
m represents C1-C18 alkyl, halogenated C1-C8 alkyl, C3-C6 cycloalkyl which is unsubstituted or substituted by C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, cyano C1-C6 alkyl, nitro C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, - (C1-C6 alkyl) -Z,
Figure FDA0002428464730000021
and phenyl which is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, halogenated C1-C6 alkyl, cyano, C1-C6 alkylamino, halogen and C1-C6 alkoxy,
Figure FDA0002428464730000022
Tetrahydrofuranyl, pyridinyl, naphthyl, furanyl, thienyl, pyrrolyl, pyrazolyl or imidazolyl;
z represents
Figure FDA0002428464730000023
And unsubstituted or substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, halogeno C1-C6 alkyl, cyano and halogen
Figure FDA0002428464730000024
Phenyl, tetrahydrofuryl, pyridyl, pyrazolyl, thienyl, furyl or naphthyl;
R4、R5、R6each independently represents hydrogen, C1-C6 alkyl, C1-C6 alkoxycarbonyl, and phenyl unsubstituted or substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, haloC 1-C6 alkyl, cyano and halogen;
R7represents C1-C6 alkyl, C2-C6 alkenyl,
Figure FDA0002428464730000025
The active ingredient B is selected from one or more of glyphosate, glufosinate, diquat and paraquat or acid/salt thereof.
2.A herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives according to claim 1,
R1、R2each independently represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl;
R3represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl;
q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, chloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2, 2-trifluoroethyl, hydroxymethyl,
Figure FDA0002428464730000026
benzyl, naphthyl, furyl, pyridyl, pyrimidyl, and thiazolyl which is unsubstituted or substituted by chlorine, thienyl which is unsubstituted or substituted by fluorine, or thienyl which is unsubstituted or substituted by methyl or fluorine
Figure FDA0002428464730000027
Phenyl unsubstituted or substituted with at least one group selected from methyl, trifluoromethyl, chlorine and methoxy;
y represents NH2、
Figure FDA0002428464730000028
The salt is sodium salt, lithium salt, potassium salt, cesium salt, rubidium salt, calcium salt, magnesium salt, barium salt, strontium salt, antimony salt, bismuth salt, cadmium salt, cerium salt, chromium salt, cobalt salt, scandium salt, titanium salt, manganese salt, copper salt, iron salt, silver salt, gold salt, zinc salt, aluminum salt, ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, N-hexadecyltrimethylammonium salt, N-benzyltrimethylammonium salt, benzyltriethylammonium salt, choline salt, monomethylamine salt, dimethylamine salt, trimethylamine salt, monoethylamine salt, diethylamine salt, triethylamine salt, N-propylamine salt, dipropylamine salt, tripropylamine salt, monoisopropylamine salt, diisopropylamine salt, triisopropylamine salt, dibutylamine salt, tributylamine salt, isobutylamine salt, tert-butylamine salt, pentylamine salt, hexylamine salt, heptylamine salt, octylamine salt, dodecylamine salt, tetradecylamine salt, Diallylamine salt, cyclohexylamine salt, cyclododecylamine salt, aniline salt, o-toluidine salt, m-toluidine salt, p-toluidine salt, diphenylamine salt, benzylamine salt, monoethanolamine salt, N-methylmonoethanolamine salt, N-dimethylethanolamine salt, N-ethylmonoethanolamine salt, N-diethylethanolamine salt, N-propylmonoethanolamine salt, N-di-N-propylethanolamine salt, N-butylmonoethanolamine salt, diethanolamine salt, N-methyldiethanolamine salt, N-ethyldiethanolamine salt, N-propyldiethanolamine salt, N-butyldiethanolamine salt, N-dibutylethanolamine salt, triethanolamine salt, triperopanolamine salt, triisopropanolamine salt, tris (2-hydroxypropyl) amine salt, diglycolamine salt, hexamethylenetetramine salt, triethanolamine salt, p-toluidine salt, diphenylamine salt, aniline salt of N, N-diethylethanolamine salt, N-N-butylethanolamine salt, N, Ethylenediamine salt, diethylenetriamine salt, dimethylaminopropylamine salt, 1, 2-propylenediamine salt, triethylenediamine salt, triethylenetetramine salt, benzidine salt, N-bis [ aminopropyl ] methylamine salt, 2-methylthiopropylamine salt, 2-butoxyethylamine salt, AEPD salt, tris (hydroxymethyl) aminomethane salt, morpholine salt, N-methylmorpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, Jeff amine D-230 salt, 2,4, 6-tris (dimethylaminomethyl) phenol and sodium hydroxide salt, trimethylsulfonium salt, triethylsulfonium salt;
x in the I-1 represents O or S;
m represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-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,
Figure FDA0002428464730000031
Figure FDA0002428464730000032
Figure FDA0002428464730000041
tetrahydrofuryl, tetrahydrofurylmethylene, pyridyl, pyridylmethylene, naphthyl, naphthylmethylene, furyl, furanylmethylene, thienyl, thienylmethylene,
Figure FDA0002428464730000042
and unsubstituted or methyl-substituted
Figure FDA0002428464730000043
Phenyl which is unsubstituted or substituted by methyl, dimethylamino, chloro, methoxy, trifluoromethyl or isopropyl, benzyl which is unsubstituted or substituted by trifluoromethyl, bromo, chloro, fluoro, methoxy, cyano or methyl;
r' represents hydrogen, methyl, ethyl, difluoromethyl.
3.A herbicidal composition according to claim 1 or 2, comprising R-type pyridyloxycarboxylic acid derivatives, characterized in that the active ingredient a is selected from one or more of the following compounds:
Figure FDA0002428464730000044
Figure FDA0002428464730000051
Figure FDA0002428464730000061
Figure FDA0002428464730000071
Figure FDA0002428464730000081
Figure FDA0002428464730000091
Figure FDA0002428464730000101
Figure FDA0002428464730000111
Figure FDA0002428464730000121
Figure FDA0002428464730000131
Figure FDA0002428464730000141
Figure FDA0002428464730000151
Figure FDA0002428464730000161
Figure FDA0002428464730000171
Figure FDA0002428464730000181
Figure FDA0002428464730000191
4.a herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives according to any one of claims 1 to 3 wherein A, B is present in a weight ratio of 1:100 to 100:1 or 1:50 to 50: 1; preferably 1: 30-30: 1 or 1: 20-20: 1; more preferably 1: 10-10: 1 or 1: 8-8: 1; more preferably 1:5 to 5:1 or 1:1 to 2: 1.
5.A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative according to any one of claims 1 to 4 wherein the weight percentages of A and B in the herbicidal composition are from 1 to 95%, preferably from 10 to 80% of the total weight.
6.A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative according to any one of claims 1 to 4 wherein the composition further comprises conventional adjuvants, preferably wherein the conventional adjuvants comprise carriers or surfactants.
7.A herbicidal composition comprising pyridyloxycarboxylic acid derivatives of the R type according to any one of claims 1 to 4, characterized in that the herbicidal composition further comprises at least one safener, preferably the safener is selected from one or more of isoxadifen, cyprosulfamide, mefenpyr, cloquintocet-mexyl, gibberellic acid, furilazole, metacamifen.
8.A herbicidal composition containing R-type pyridyloxycarboxylic acid derivatives according to any one of claims 1 to 7, wherein the herbicidal composition is formulated as dispersible oil suspension, aqueous suspension, suspoemulsion, wettable powder, emulsifiable concentrate, water dispersible granule, aqueous emulsion or microemulsion.
9. Use of a herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative according to any one of claims 1 to 7 for the control of weeds, preferably for the selective control of weeds in crops of useful plants, more preferably in transgenic or genome editing technology treated crops.
10.A method for controlling unwanted plant growth, which comprises applying a herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative according to any one of claims 1 to 7 to a plant, a part of a plant, a plant seed or an area where a plant is growing, preferably for use in the selective control of weeds in a useful crop, more preferably the useful crop is a transgenic crop or a crop treated by genome editing techniques.
CN202010228317.6A 2019-07-27 2020-03-27 Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives and use thereof Pending CN112273395A (en)

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CA3147473A CA3147473A1 (en) 2019-07-27 2020-07-14 Herbicidal composition comprising r-pyridyloxycarboxylic acid and derivative and an application thereof
EP20846511.2A EP4005384A4 (en) 2019-07-27 2020-07-14 Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof
JP2022504220A JP7494285B2 (en) 2019-07-27 2020-07-14 Herbicidal compositions comprising R-pyridyloxycarboxylic acids and derivatives and methods of application thereof
BR112022001311A BR112022001311A2 (en) 2019-07-27 2020-07-14 A herbicidal composition comprising r-pyridyloxycarboxylic acid and derivatives and an application thereof
PCT/CN2020/101901 WO2021017817A1 (en) 2019-07-27 2020-07-14 Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof
AU2020322972A AU2020322972A1 (en) 2019-07-27 2020-07-14 Herbicidal composition containing R-type pyridyloxy carboxylic acid derivative and use thereof
MX2022000846A MX2022000846A (en) 2019-07-27 2020-07-14 Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof.
US17/627,221 US20220264878A1 (en) 2019-07-27 2020-07-14 Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof
PE2022000089A PE20220703A1 (en) 2019-07-27 2020-07-14 HERBICIDE COMPOSITION COMPRISING R-PYRIDILOXYCARBOXYLIC ACID AND DERIVATIVE AND AN APPLICATION THEREOF
CONC2022/0000361A CO2022000361A2 (en) 2019-07-27 2022-01-18 Herbicide composition comprising r-pyridyloxycarboxylic acid and derivative and an application thereof
ZA2022/00908A ZA202200908B (en) 2019-07-27 2022-01-19 Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof
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CN104957171A (en) * 2015-06-22 2015-10-07 广东中迅农科股份有限公司 Weeding composition containing glyphosate and trichlopyr and application thereof
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