阅读说明：本技术 包含r型吡啶氧基羧酸衍生物和合成激素类抑制剂的除草组合物及其应用 (Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivative and synthetic hormone inhibitor and application thereof ) 是由 彭学岗 赵德 金涛 张景远 刘娜 于 2020-05-14 设计创作，主要内容包括：本发明属于农药领域,具体涉及一种包含R型吡啶氧基羧酸衍生物和合成激素类抑制剂的除草组合物及其应用。所述组合物包括除草有效量的活性成分A和B,A选自如式Ⅰ所示的R型吡啶氧基羧酸及其盐、酯衍生物中的一种或多种：其中,R-(1)、R-(2)分别独立地代表卤素等；R-(3)代表卤素等；Q代表C1-C6烷基等；Y代表氨基等；B选自以下合成激素类抑制剂除草化合物或其酸/盐中的一种或多种：三氯吡氧乙酸、2甲4氯、麦草畏、氨氯吡啶酸、氯氨吡啶酸、氯氟吡氧乙酸、氯氟吡啶酯、氟氯吡啶酯、二氯喹啉酸、二氯吡啶酸。该组合物能有效防除禾本科或阔叶类等各种杂草问题,具有扩大杀草谱、减少施用量、能够产生增效作用并解决抗性杂草等特点。(The invention belongs to the field of pesticides, and particularly relates to a weeding composition containing an R-type pyridyloxy carboxylic acid derivative and a synthetic hormone inhibitor and application thereof. The composition comprises active ingredients A and B with effective weeding amount, wherein A is selected from one or more of R-type pyridyloxy carboxylic acid shown as a formula I and salt and ester derivatives thereof: wherein R is 1 、R 2 Each independently represents halogen or the like; r 3 Represents halogen, etc.; q represents a C1-C6 alkyl group, etc.; y represents amino, etc.; b is selected from one or more of the following synthetic hormone inhibitor herbicidal compounds or acid/salt thereof: triclopyr, 2-methyl-4-chloro, dicamba, picloram, aminopyralid, fluroxypyr, quinclorac, and clopyralid. The composition can effectively prevent and kill various weeds of gramineae or broadleaf and the like, and has the characteristics of expanding a weed control spectrum, reducing application amount, generating a synergistic effect, solving resistant weeds and the like.)

1. A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor, 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:

wherein R is₁、R₂Independently represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl;

R₃represents hydrogen, halogen, C1-C6 alkaneA halo C1-C6 alkyl group;

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 isWherein X represents O or S;

m represents C1-C18 alkyl, halogenated C1-C8 alkyl, C3-C6 cycloalkane unsubstituted or substituted by C1-C6 alkylC2-C6 alkenyl, halogeno 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,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,Tetrahydrofuranyl, pyridinyl, naphthyl, furanyl, thienyl, pyrrolyl, pyrazolyl or imidazolyl;

z representsAnd 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 halogenPhenyl, 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,

The active ingredient B is selected from one or more of the following synthetic hormone inhibitor weeding compounds or acid/salt thereof:

triclopyr, 2-methyl-4-chloro, dicamba, picloram, aminopyralid, fluroxypyr, quinclorac, and clopyralid.

2. A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor 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,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 fluorinePhenyl unsubstituted or substituted with at least one group selected from methyl, trifluoromethyl, chlorine and methoxy;

y represents NH₂、

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-dibutylethanolamine salt, triethanolamine salt of N-butyldiethanolamine salt, triethanolamine salt of N-methylethanolamine salt, triethanolamine salt of a mixture of a compound, a mixture of a compound, a compound, 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, cyclopropylCyclobutyl, cyclopentyl, cyclohexyl, allyl, 2-propynyl, methoxy, ethoxycarbonyl, methylsulfonyl,

tetrahydrofuryl, tetrahydrofurylmethylene, pyridyl, pyridylmethylene, naphthyl, naphthylmethylene, furyl, furanylmethylene, thienyl, thienylmethylene,and unsubstituted or methyl-substitutedPhenyl 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 and synthetic hormone inhibitors, characterized in that the active ingredient a is selected from one or more of the following compounds:

4. the herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor according to any one of claims 1 to 3, wherein the weight ratio of A, B is 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 1: 2.

5. A herbicidal composition according to any one of claims 1 to 4, comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor, wherein the amount of A and B is 1 to 95% by mass, preferably 10 to 80% by mass, based on the total amount of the composition.

6. A herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor 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 an R-type pyridyloxycarboxylic acid derivative and a synthetic hormonal suppressor 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 the group consisting of isoxadifen, cyprosulfamide, mefenpyr, cloquintocet, gibberellic acid, furilazole and mecamifen.

8. The herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor according to any one of claims 1 to 7, wherein the formulation of the herbicidal composition is dispersible oil suspension, water suspension, suspoemulsion, wettable powder, emulsifiable concentrate, water dispersible granule, water emulsion or microemulsion.

9. Use of a herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor according to any one of claims 1 to 7 for the control of weeds, preferably for the selective control of weeds in a useful crop, more preferably a transgenic or genome editing technology treated crop.

10. A method of controlling unwanted plant growth, which comprises applying a herbicidal composition comprising an R-type pyridyloxycarboxylic acid derivative and a synthetic hormone inhibitor according to any one of claims 1 to 7 to a plant, 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 with genome editing techniques.

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 a synthetic hormone inhibitor 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 a synthetic hormone inhibitor, and use thereof. The composition can effectively prevent and kill various weeds of gramineae or broadleaf and the like, 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 and a synthetic hormone inhibitor, 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:

wherein R is₁、R₂Independently represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl;

R₃represents hydrogen, halogenElement, 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 isWherein 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,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,Tetrahydrofuranyl, pyridinyl, naphthyl, furanyl, thienyl, pyrrolyl, pyrazolyl or imidazolyl;

z representsAnd 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 halogenPhenyl, 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,

The active ingredient B is selected from one or more of the following synthetic hormone inhibitor weeding compounds or acid/salt thereof:

triclopyr (CAS number: 55335-06-3), 2-methyl-4-chloro (MCPA, CAS number: 94-74-6), dicamba (dicamba, CAS number: 1918-00-9), picloram (CAS number: 1918-02-1), aminopyralid (CAS number: 150114-71-9), fluroxypyr (CAS number: 69377-81-7), fluroxypyr (fluroxypyr, CAS number: 69377-81-7), fluroxypyr (fluroxyafenacin benzyl, CAS number: 1390661-72-9), fluroxypyr (halauxifen-methyl, CAS number: 943831-98-9), quinclorac (CAS number: 84087-01-4), clopyralid (CAS number: 1702-17-6).

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,benzyl, naphthylFuryl radicalPyridyl radicalPyrimidinyl radicalsAnd thiazolyl which is unsubstituted or substituted by chlorineThienyl unsubstituted or substituted by fluorineUnsubstituted or substituted by methyl or fluorine Phenyl unsubstituted or substituted with at least one group selected from methyl, trifluoromethyl, chlorine and methoxy;

y represents

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, cyclohexylamine, cyclododecylamine, aniline, o-toluidine, m-toluidine, p-toluidine, diphenylamine, benzylamine, monoethanolamine, N-methylmonoethanolamine, N-dimethylethanolamine, N-ethylmonoethanolamine, N-diethylethanolamine, N-propylmonoethanolamine, N-di-N-propylethanolamine, N-butylmonoethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-dodecylamine, N-ethyldiethanolamine, N-methylethanolamine, a salt,N-propyldiethanolamine salt, N-butyldiethanolamine salt, N-dibutylethanolamine salt, triethanolamine salt, tripropanolamine salt, triisopropanolamine salt, tris (2-hydroxypropyl) amine salt, diglycolamine salt, polyamine salt (such as hexamethylenetetramine salt, ethylenediamine salt, diethylenetriamine salt, dimethylaminopropylamine salt, 1, 2-propylenediamine salt, triethylenediamine salt, triethylenetetramine salt, benzidine salt, N-bis [ aminopropyl ] amine salt]Methylamine salt), 2-methylthiopropylamine salt, 2-butoxyethylamine salt, AEPDSalt, tris (hydroxymethyl) aminomethaneSalts, morpholine salts, N-methylmorpholine salts, piperidine salts, pyridine salts, aminopropylmorpholineSalt, Jeff amine D-230Salts 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 alkylolphosphonium 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, tetrahydrofuranyl groupTetrahydrofuryl methylene radicalPyridyl radical PyridylmethyleneNaphthyl radicalNaphthyl methyleneFuryl radicalFuryl methylene groupThienyl radicalThienyl methylene group And unsubstituted or methyl-substituted 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:

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:

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:

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:

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 addedOr a compound of the formula I-1-3Reacting 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 1: 2.

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.

The herbicidal composition further comprises at least one safener, which may in particular be selected from any of the safeners mentioned in CN 101194623A. Preferably, the safener is selected from 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 mecamifen (CAS: 129531-12-0).

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.

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. The amount of the effective ingredient to be used varies depending on external conditions such as temperature, humidity, the nature of the herbicide to be used, and the like. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 500 g/ha.

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 can be found in CN 106659159A. Additional information for the genetic modifications listed therein may be obtained from publicly available databases maintained, for example, by the U.S. department of agriculture.

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:

efficacy test (post-emergence spray treatment of stems and leaves):

1) test conditions

1.1) test target

The weeds are cultivated by a pot culture method, plastic nutrition bowls with the grain 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 soil is covered by 0.5-1cm according to the grain 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. 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.

(1) Synthesis of Compound A1

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 a67(300mg, yield 50%). Compound a67 was a white solid.

Compound A67(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.

(2) Synthesis of Compound A2

Compound A1(200mg, 0.74mmol), compound c (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 for liquid chromatography was completed, the reaction solution was concentrated and separated by column chromatography to obtain compound a2(200mg, yield 77%) which was a white solid as compound a 2.

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

Repeating the treatment for 4 times, wherein 10 pots of weed seeds are sowed in each pot, and 3 plants are sowed in each pot.

2.3) treatment method

2.3.1), treatment time and number of times

The test was performed 1 time in total. And thinning when the weeds are in the 6-8 leaf period, keeping 3 weeds in each pot, keeping 30 weeds in each treatment, and then continuously culturing until the height of the erigeron breviscapus is 10 cm for treatment.

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 24 days after the treatment, and was carried out 1 time.

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 1-10 below.

Table 1A 2 evaluation of the actual control and combined action of triclopyr on erigeron breviscapus

Table 2A 2 evaluation of actual control and combination of 2-methyl-4-chlorophenoxyacetic acid on erigeron breviscapus

Table 3A 2 evaluation of the actual control and Combined action of Dicamba compounded on erigeron breviscapus

TABLE 4A 2 evaluation of the actual control and combination of Aminopyribac sodium

TABLE 5A 2 evaluation of the actual control and combination of Aminopyribac sodium

TABLE 6A 2 evaluation of the actual control and Combined Effect of fluroxypyr on erigeron breviscapus

TABLE 7 evaluation of the actual control and Combined action of chlorofluoropyridino esters blended with cyhalofop 2 on erigeron breviscapus

TABLE 8A 2 evaluation of the actual control and combination of fluroxypyr-meptyl

TABLE 9A 2 evaluation of the actual control and combination of quinclorac on erigeron breviscapus

TABLE 10A 2 evaluation of the actual control and combination of clopyralid on erigeron breviscapus

Through a large number of tests and explorations, the composition has a surprising and unexpected synergistic effect when used for preventing and removing broadleaf weeds, gramineous weeds and the like, the synergistic effect is more obvious under a low dose, the dosage can be reduced, the pollution to the environment is reduced, the agricultural cost is reduced through reasonable compounding, the composition is efficient on ALS and ACCase inhibitor resistant weeds, and the composition has a 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.