CN113367128A - Composition containing R-type oxadiazolyl aryl formamide compound and safener and application thereof - Google Patents

Abstract

The invention belongs to the field of pesticides, and particularly relates to a composition containing an R-type oxadiazolyl aryl formamide compound and a safener and application thereof. The R-type oxadiazole aryl formamide compound serving as an active ingredient in the weeding composition is

Description

Composition containing R-type oxadiazolyl aryl formamide compound and safener and application thereof

Technical Field

The invention belongs to the field of pesticides, and particularly relates to a composition containing an R-type oxadiazolyl aryl formamide compound and a safener and application thereof.

Background

Keeping crops away from weeds and other vegetation that inhibit crop growth is an important concern in agriculture. To help address this problem, researchers in the field of synthetic chemistry have developed a variety of chemicals and chemical formulations that are effective in controlling the undesirable weeds and other vegetation. Many types of chemical herbicides have been disclosed in the literature, for example, WO2014086746a1, WO2016146561a1, WO2017144402a1, WO2012028579a1, etc. disclose certain arylcarboxamides, and many have been used for commercial use. However, in addition to the weeds and other vegetation to be controlled, these herbicides can sometimes damage the crop being protected.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a composition containing an R-type oxadiazolyl aryl formamide compound and a safener and application thereof. The composition has high herbicidal activity, obviously improved compatibility to important crops, excellent selectivity and great economic and social benefits in popularization and application.

The composition comprises an R-type oxadiazolyl aryl formamide compound and a safener, wherein the active ingredient R-type oxadiazolyl aryl formamide compound (A) is

The safener (B) is selected from at least one of the following compounds:

a) dichlorophenyl pyrazoline-3-carboxylic acids, preferred compounds are, for example, mefenpyr diethyl (CAS No.: 135590-91-9, mefenpyr-diethyl), and related compounds as described, for example, in WO 91/07874;

b) dichlorophenyl pyrazole carboxylic acid derivatives, preferred compounds being, for example, ethyl 1- (2, 4-dichlorophenyl) -5-methylpyrazole-3-carboxylate, ethyl 1- (2, 4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate, ethyl 1- (2, 4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylate, ethyl 1- (2, 4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate, and the related compounds described in EP-A-333131 and EP-A-269806;

c) triazole carboxylic acids, preferred compounds are, for example, fenchlorazole (CAS No.: 103112-35-2, fenchorazole-ethyl) 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 e.g. ethyl 5- (2, 4-dichlorobenzyl) -2-isoxazoline-3-carboxylate or ethyl 5-phenyl-2-isoxazoline-3-carboxylate and related compounds described in WO91/08202, or bisbenzoxazoic acid (CAS number: 163520-33-0, isoxadifen-ethyl), n-propyl 5, 5-diphenyl-2-isoxazoline-3-carboxylate or ethyl 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylate;

e) 8-quinolinyloxyacetic acids, preferably cloquintocet-mexyl (CAS number: 99607-70-2, cloquintocet-mexyl, (1, 3-dimethylbut-1-yl) (5-chloro-8-quinolinoxy) acetate, 4-allyloxybutyl (5-chloro-8-quinolinoxy) acetate, 1-allyloxypropan-2-yl (5-chloro-8-quinolinoxy) acetate, ethyl (5-chloro-8-quinolinoxy) acetate, methyl (5-chloro-8-quinolinoxy) acetate, allyl (5-chloro-8-quinolinoxy) acetate, 2- (2-propyleneiminoxy) -1-ethyl (5-chloro-8-quinolinoxy) acetate, 2-oxopropan-1-yl (5-chloro-8-quinolinoxy) acetate, and related compounds as described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366;

f) (5-chloro-8-quinolinoxy) malonic acid compounds, preferred compounds being, 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 (CAS No.: 3740-92-9, fenclorim);

i) dichloroacetamide compounds, such as dichloropropyleneamine (CAS No.: 37764-25-3, dichlormid), "AR-29148" (3-dichloroacetyl-2, 2, 5-trimethyl-1, 3-oxazolidinone), benoxazine (CAS No.: 98730-04-2, benoxacor), "APPG-1292" (N-allyl-N [ (1, 3-dioxolan-2-yl) -methyl ] dichloroacetamide), "ADK-24" (N-allyl-N- [ (allylaminocarbonyl) -methyl ] -dichloroacetamide), "AAD-67" or "AMON 4660" (4-dichloroacetyl-1-oxa-4-aza-spiro [4,5] decane), "dicyclonone" or "ABAS 145138" or "ALAB 145138" (3-dichloroacetyl-2, 5, 5-trimethyl-1, 3-diazabicyclo [4.3.0] nonane), oxazazole (CAS number: 121776-33-8, furilazole) or 3-dichloroacetyl-2, 2-dimethyl-1, 3-oxazolidine (CAS No.: 39089-45-7, oxazolidine, "R-28725");

j) dichloroacetone derivatives, for example, benoxane (CAS No.: 96420-72-3, "AMG 191");

k) oxyimino compounds, which are called seed dressing materials, for example, oxabetrinil (CAS number: 74782-23-3, oxabetrinil), which is known as a safener in seed dressing to prevent damage to metolachlor (metolachlor), fluxopyr oxime (CAS number: 88485-37-4, fluxofenim), which is known as a safener in seed dressing to prevent damage to metolachlor (metolachlor), and acetochlor nitrile (CAS number: 78370-21-5, cyclometrinil, "A-CGA-43089"), which is known as a safener in seed dressing to prevent damage to metolachlor (metolachlor);

l) thiazole carboxylates, which are known as seed dressing materials, for example, benoxaden (CAS No.: 72850-64-7, flurazol), which is known as a safener in seed dressing to prevent damage to alachlor (alachlor) and metolachlor;

m) naphthalene dicarboxylic acid derivatives, which are known as seed dressings, such as naphthalic anhydride (CAS number: 81-84-5, naphthalic anhydride), which is known as a safener in corn dressing to prevent damage by thiocarbamate herbicides;

n) chromanoic acid derivatives such as "ACL 304415" (CAS registry No. 31541-57-8, 2-84-carboxychroman-4-yl) acetic acid);

o) compounds which have a safener effect on plants in addition to herbicidal effects on harmful plants, for example, penflufen (S-1-methyl-1-phenylethylpiperidine-1-thiocarboxylate, dimepiperate, "AMY-93"), jiron (1- (1-methyl-1-phenylethyl) -3-p-tolylurea, daimuron, "ASK 23"), cumyluron (3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenyl-ethyl) urea, cumyluron, "AJC-940"), benzophenone (3,3' -dimethyl-4-methoxy-benzophenone, methoxyphenon, "ANK 049"), and "CSB" (CAS number: 54091-06-4, 1-bromo-4- (chloromethylsulfonyl) benzene);

p) acylsulfonamides, such as cyclopropanesulfonamide (CAS No.: 221667-31-8, cyprosulfamide), 2-methoxy-N- { [4- (3-methylureido) phenyl ] sulfonyl } benzamide (CAS number: 129531-12-0, metcamifen, "CGA 246783").

Wherein the active ingredient A is obtained from a patent CN201911014193.5, and the specific preparation method is as follows:

(1.1) sequentially adding Cpd 1(3g,16mmol,1.0eq) and NaOH (0.72g,18mmol,1.1eq) to 30ml of DMF and then adding Cpd 2(1.28g,16.8mmol,1.05eq) dropwise at 0 ℃ followed by stirring the reaction at 0 ℃ for 1 hour. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction was poured into 30ml of water, the layers separated, the aqueous phase extracted once with 50ml of ethyl acetate and the organic phase washed three times with saturated brine (50ml), dried, spin dried and isolated by column chromatography to give Cpd 3(3.6g, 91% yield) (colourless oil).

(1.2) in 30ml of THFCpd 3(3.1g,13mmol,1.0eq) was added followed by slow addition of n-BuLi (6.42ml,2.5M,16mmol,1.2eq) at-78 deg.C, then the reaction was stirred at-78 deg.C for 0.5 h and then CO was slowly passed through₂After 10min, the reaction solution was slowly warmed to room temperature. LCMS detected product. To the reaction mixture was poured 20 ml of water, the layers were separated, the aqueous phase was extracted once with 30ml of ethyl acetate, the aqueous phase was gradually adjusted to pH 4-5 with concentrated hydrochloric acid, filtered and dried to give Cpd 4(3.2g, 87% yield) (white solid).

(1.3) to 30ml of pyridine were added sequentially Cpd 4(3.1g,11mmol,1.0eq), Cpd 5(1.66g,16.8mmol,1.5eq) and DMAP (0.13g,1.1mmol,0.1 eq). Then slowly adding SOCl at the temperature of 0 DEG C₂(2.0g,16.8mmol,1.5eq), and the reaction was stirred at room temperature for 3 hours. LCMS detected product. After removal of pyridine by concentration, 30ml of water was poured into the reaction mixture, the mixture was separated, the aqueous phase was extracted three times with 30ml of ethyl acetate, the organic phase was washed three times with saturated brine (50ml), dried, spin-dried, and isolated by column chromatography to give compound Cpd 6(2.5g, 63% yield) (white solid).

(1.4) to 10 ml of dichloromethane were added sequentially Cpd 6(1g,2.8mmol,1.0eq) and m-CPBA (0.54g,3.1mmol,1.1 eq). The reaction was then stirred at room temperature for 1 hour. The LCMS detects the product and the raw materials are basically reacted completely. The reaction was poured into 10 ml of water, quenched with sodium bisulfite, separated, the aqueous phase extracted three times with 30ml of dichloromethane, the organic phase washed once with saturated brine (30ml), dried, spun-dried and isolated by column chromatography to give compound Cpd 7(0.85g, 82% yield) (off-white solid).

¹H NMR(500MHz,DMSO-d₆)12.57(s,1H),8.07(dd,J＝8.0,7.0Hz,1H),7.82(d,J＝8.0Hz,1H),3.57-3.47(m,2H),2.48(s,3H),1.70-1.52(m,2H),1.08-0.93(m,3H).

(1.5) Compound Cpd 7(0.5g, 98% write) was resolved by chiral HPLC (Column: CHIRALPAK IG; Column Size: 3 cm. times.25 cm,5 um; Injection: 3.0 ml; Mobile phase: Hex (0.2% FA): IPA ═ 50: 50; Flow rate: 28 ml/min; Wavelength: UV 254 nm; Temperature:25 ℃; Sample solution: 70mg/ml in EtOH/DCM; Run time ═ 60mins) and concentrated after resolution, single crystal diffraction determined to give A (R configuration) as a white solid (0.16g, Rt ═ 10.51min, 100% ee, 98% purity).

The weight ratio of the active ingredient to the safener can vary within wide limits, such as 1:1000 to 1000:1, and preferably 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 2:1 to 1: 1.

The mass percentage of the active ingredients in the composition accounts for 1-95% of the total amount, preferably 10-80%.

The application rate of the active ingredients can vary within wide limits depending on outdoor conditions such as temperature, humidity and the type of herbicide used, and is generally between 0.001 and 1.0kga.i./ha, preferably between 0.1 and 750, in particular between 1 and 500, more particularly between 5 and 300, and especially between 10 and 100, ga.i./ha.

The application rate of the safener is generally between 0.001 and 1.0kga.i./ha, preferably between 0.1 and 750ga.i./ha, in particular between 1 and 500ga.i./ha, more in particular between 5 and 300ga.i./ha, especially between 10 and 100 ga.i./ha.

The 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 the active substances mentioned below (remarks: name of the compound, either common name according to the international organization for standardization (ISO) or chemical name, with code numbers where appropriate): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, mefenacet, metazachlor, isoxaflutole, ryegrass methyl ester, loflutolane, diacrylamide, pethoxamide, butachlor, propisochlor, cyprosulfamide, flumetsulam, heptanoyl, isobutramine, propyzamide, terbutamid, dimethenamid, larvamide, trimethylcyclam, clofenamid, propyzamide, penoxulamide, carpronide, diflormid, trinitrol, butachlor, butafenacet, butachlor, benfluralin, bencarbzamide, pencyhalonil, metolachlor, bencarbzamide, pencyhalonil, butachlor, benfluralin-bencarbzachlor, bencarbzamide, bencarb-N-P-N-P-N-P-N-, Grazing amine, bensulfuron, quinoxalamine, benfluanid, naphazel, naproxen, metazachlor, pyraflufen, bensulfuron-methyl, prochloraz, clofenamide, butamididine, fluazinam, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, triazineon, ciprofloxacin, ganzine, pradapazine, prometryn, simatong, azidezin, diuron, isopentetryn, cycloprozine, ametryn, terbuthylazine, terbuton, metocloprid, cyanazine, bentazon, ethacryl, clonazine, atrazine, metribuzin, cyanuric acid, indagaziflam, chlorsulfuron, meturon, bensulfuron, chlorimuron, tribenuron-methyl-, Cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, primisulfuron-methyl, flusulfuron-methyl, flupyrsulfuron-methyl, epoxysulfuron, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, metsulfuron-methyl sodium, flupyrazosulfuron, methisulfuron-methyl, primisulfuron, propysilfuron (Propyrisulfuron), metribusulfuron, acifluorfen-methyl, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfen, prosulfuron, benfuresafen, trifloxysulfuron, metofen-ethyl, metofen, trifloxysulfuron, fluroxypyr, fluridone, benfop, benfluridone, benfurazolin, benfluridone, benfurbenfluridone, benfluridone, benfurin, benfluridone, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurin, benfluridone, benfurbenfurbenfurbenfurbenfurin, benfurin, benfluridone, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurin, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfur, Dimethofen, oxyfluorfen, clofenflurate, Halosafen, chlortoluron, isoproturon, linuron, diuron, sifenuron, fluometuron, benzthiauron, methabenzuron, prosulfuron, sulfosulfuron, clomauron, clodinafuron, clofensulfuron, metoxuron, bromuron, metoxuron, meturon, fensulfuron, prosulfuron, subtilon, cuarone, metolachlor, cycloaroron, cyclouron, thifluuron, buthiuron, kuron, cumuron, metoxuron, methamidothion, metominosulfuron, trifolium, isoxafluron, isoxauron, moneuronon, aniron, methicuron, chloretron, clotururon, teuron, benuron, pennison, phenmedibensulfuron, bensulfuron, benazolin, propham, buthan, thiuron, buthan, benazolin, buthan, benazolin, buthan, benazolin, thiuron, thifenbenazolin, thiuron, thifenbenazolin, thiuron, thifenbenazolin, thiuron, thifenbencarb, thiuron, thifenbencarb, thiuron, thifenbencarb, thiuron, thifenbencarb, Hexabencarb, Mexican, diclofop, Dicamba, Echinochloa, Cypridinium, Avena, Jundamen, ethiofen, prosulfocarb, Clonon, prosulfocarb, Paraben, Sulfenpyrad, Desmodin, Isochrysin, Isopomanate, Methiobencarb, 2, 4-D-isooctyl butyl ester, 2 methyl-4-sodium chloride, 2, 4-D-isooctyl ester, 2 methyl-4-chloroisooctyl ester, 2, 4-D-isooctyl ester sodium salt, 2, 4-D-isooctyl dimethylamine salt, 2 methyl-4-chloroethyl thioester, 2 methyl-4-chloro, 2, 4-D-isooctyl propionic acid, high 2, 4-D-isooctyl propionate, 2, 4-D-isooctyl butyric acid, 2 methyl-4-chloropropionic acid salt, 2 methyl-4-chloro butyric acid, 2,4, 5-dichloro-nasal, 5-n, 2, 4-chloro-n-butyric acid, 2, 5-chloro-n, 2, 4-chloro-n, 5-chloro-n, n-n, 2, 5-chloro-n, n-chloro, n-n, n-chloro, n, Dicamba, imazapyr, valacil, cypress, triclosan, dichlorfenac, metoclopramide, diclofop-methyl, fluazifop-p-ethyl, fluazifop-methyl, haloxyfop-p-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, cyhalofop-butyl, metamifop-ethyl, thiazopyr, paraquat, benfurazone, asulam, flutolon, isoproturon, metalaxyl, cyhalofop-methyl, propafop-ethyl, benfluralin, carfentrazone-ethyl, dichlofop-ethyl, methaprocopralin, propapholate, glyphosate, cyperophos, glufosinate, methamidophos, benfop-methyl, benfop-ethyl, benfop-P, benfop-P, benfop-p-methyl, benfop-p, benfop-methyl, benfop-p, ben, benfop-p, ben, benfop-p, ben, m, ben, benfop-p, Imazapic, imazethapyr, imazaquin, imazamox, imazapyr ammonium salt, imazapic, imazamethabenz, fluroxypyr isooctyl ester, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyril, thiazopyr, flurazinone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Cliodinate, sethoxydim, clethodim, cycloxydim, metamitron, bromoxynil, octanoyl ioxynil, dichlobenil, quinconazole, isoxaflufenapyr, metam-bensulam, penoxsulam, flumetsulam, clofenapyr, halosulfuron, disulfoton, dichlobenil, diclosulfuron, pyraclonil, diclosulam, bensulam, bensulbensulam, bensulam, bensulbensulbensulam, bensulbensulbensulbensulbensulam, bensulam, bensulbensulbensulbensulam, bensulbensulbensulam, bensulben, bensulbensulben, bensulam, bensulbensulbensulbensulbensulam, bensulbensulben, bensulben, bensulbensulbensulben, ben, bensulbensulben, bensulbensulbensulam, bensulbensulam, bensulbensulben, bensulbensulam, bensulbensulben, ben, bensulam, bensulbensulbensulbensulben, ben, bensulben, bensulam, ben, bensulben, bensulbensulbensulbensulben, ben, bensulbensulbensulben, ben, bensulam, bensulbensulbensulbensulbensulam, ben, bensulbensulben, ben, bensulam, bensulbensulben, ben, bensulam, ben, bensulbensulbensulbensulam, ben, bensulam, bensulbensulbensulbensulbensulbensulam, bensulben, ben, bensulbensulbensulbensulben, ben, bensulbensulben, bensulbensulbensulbensulbensulben, bensulbensulben, ben, bensulbensulbensulben, bensulben, ben, Pyribenzoxim, fluroxypyr, bispyribac-sodium, pyribenzoxim, pyrithiobac-sodium, benzobicylon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, kettoddaldox, isoxaflutole, fenoxasulfofone, Methiozolin, ipropyr ester, pyraflufen, difenoconazole, difenzoquat, pyraflutole, pyroxaflutole, pyraclonil, pyraclonitrone, pyroxasulfofone, carfentrazone, metamitron, amicarbazone, carfentrazone, flumiclone, flumicloracil-ethyl, mefenpyr, benconazole, bensulam, metamitrofen, flumiclorafen-ethyl, flumiclodin, triclopyr, flumiclorac-ethyl, carfentrazone, flumiclorax-ethyl, carfentrazone, flumiclone, flumiclorac-ethyl, carfentrazone, flumiclone, flumiclorafen, carfenfluridofen, carfenpyr-ethyl, carfenfluridofen, carfen, flumiclone, flumiclorax-p, flumiclorap-p, carfen, flumiclorap-p, carfen, flumiclorap-p, carfen, flumiclorap-p, carfen, carl, carfen, carl, carfentrazone, carl, carfenp-p, Flufenchloracet, metamifop, fentrazamide, fluoropyridazomethyl, pyridazole, bromopicloram, dimetaluron, pyridalyl, pyridaben, pyridazole, quinclorac, chloroquinate, bentazone, pyridate, oxaziclorac, isoxaflutole, cycloheptanefen, isoproyl, propyribac, indanthrone, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, benazene, bromophenol oxime, triazasum, imazazole, flurtamone, fursulam, ethofencarbazone, ethafursulam, clofenamic acid, clofenac, flutolfenflurazone, pyributicarb, acrolein, benfurazolin, imazametham, pyrazachlor, thiabendazole, linanine, hydroxybenzophenone, metoclopramide, dichlorfenamidopropyl, isofenamidopropyl, ipriflam, iprazolin, pyrazosulfuron, iprazole, pyrazosulfuron, iprazole, propiconazole, iprazole, pyraclostrobin, propiconazole, imazachlor, bensulam, Cammondichlor, aminocyclopyrachlor, thiocyananilide, clethodim, fenclorim, benoxacor, mefenpyr-diethyl, mequindox, oxabetrinil, oxadiarane, oxabetrinil, benazolate, furazolate, flufenpyr, isoxadifen, dichlormid, halauxin, DOWFAOC, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, CO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

In the context of the present specification, if the abbreviated forms of the common names of the 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 herbicide-safener compositions of the invention can be prepared by known methods, for example as mixed preparations of the individual components, optionally with further active ingredients, additives and/or customary formulation auxiliaries, which are then applied diluted with water in a customary manner, or as so-called tank mixes which are obtained by co-dilution (co-dilution) of the individually formulated or partially individually formulated individual components with water. It is likewise possible to administer the components separately or partly separately formulated at different times (separately). It is also possible to apply the individual components or herbicide-safener combination in portions (sequential application), for example pre-emergence application followed by post-emergence application, or early post-emergence application followed by mid-or late post-emergence application. It is preferred that the active ingredients in the respective compositions are co-administered or administered sequentially.

In a particular embodiment, the composition of the 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.

For application, the formulations in the form as marketed are, if appropriate, diluted in a customary manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersants and water-dispersible granules. Before application, powders, granules for soil or for broadcasting and also sprayable solutions are usually not further diluted with other inert substances.

The specific preparation of the composition is, for example, dispersible oil suspending agent, water suspending agent, suspending emulsion, wettable powder, missible oil, water dispersible granule (dry suspending agent), emulsion in water or microemulsion and the like.

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.

Depending on their nature, the safeners present in the herbicide-safener compositions of the invention can also be used for the pretreatment of the crop plant seeds (for example for dressing seeds), or introduced into the furrows before sowing, or applied together with the herbicide before or after emergence of the plants. Pre-emergence treatment includes not only treatment of the planting area before sowing (including any water present in the planting area, for example in the case of application to rice), but also treatment of the planting area where seeds have been sown but not yet covered by growing plants. Preferably with herbicides. For this purpose, tank mixes or ready-to-use preparations can be used.

In a particular embodiment, the seed (e.g. grain, seed or vegetative propagation, such as the germinating site of a tuber or bud) or seedling is pretreated with a safener, optionally in combination with other active agrochemical ingredients. For the pretreatment of the seed, the active ingredient can be applied to the seed, for example by dressing the seed, or the active ingredient and the seed can be added to water or other solvents, and the active ingredient can be absorbed, for example, by adsorption or diffusion during immersion or by swelling or pregermination. For the pretreatment of the seedlings, the young plants can be brought into contact with safeners, optionally in combination with other active agrochemical ingredients, for example by spraying, dipping or watering, and subsequently transplanted and optionally post-treated with herbicides.

The seeds or seedlings may be treated with safeners alone or together with other active agrochemical ingredients, for example fungicides, insecticides or plant enhancers, fertilizers or swelling and emergence promoters. After the pretreatment application, the safener can then be reapplied before, after or together with one or more herbicides, also in combination with other known herbicides. The pretreatment of the seeds or seedlings can result in an improved long-term effect of the safener.

Further, the present invention also provides a method for safening the phytotoxic activity of the active ingredient a against crop plants, comprising applying the herbicidally effective amount of the active ingredient a in combination with a detoxifying active amount of a safener B.

The invention also provides the use of said composition for controlling unwanted plant growth.

The present invention also provides a method of controlling unwanted plant growth comprising applying the composition to a plant, part of a plant, plant seed, or area where a plant is growing.

Preferably, the compositions are used to selectively control weeds in crops of useful plants, more preferably, the useful plants are transgenic plants, plants treated with genome editing techniques, or herbicide tolerant plants.

The term "safeners" according to the invention is to be understood as meaning compounds which are suitable for reducing the phytotoxic effect of active ingredients, for example herbicides, in crop protection compositions on crop plants (useful crops). By "herbicidally effective amount" within the meaning of the present invention is meant an amount of one or more herbicides which is suitable to have an adverse effect on plant growth. In the context of the present invention, a "detoxifically active amount" means an amount of one or more safeners which is suitable for reducing the phytotoxic effect of an active ingredient (e.g. a herbicide) of a crop protection composition on crop plants.

The "useful crops" or "crop plants" are, for example, economically important crops, for example monocotyledonous crops, such as cereals (e.g. wheat, barley, rye, oats), rice, maize, millet/sorghum; or dicotyledonous crops, such as sugar beet, oilseed rape, cotton, sunflower and leguminous plants such as Glycine (e.g. soybean (Glycine max. (soya)) such as non-transgenic soybean (e.g. conventional varieties such as STS varieties) or transgenic soybean (e.g. RR soybean or LL soybean) and hybrids thereof), Phaseolus (Phaseolus), Pisum (Pisum), faba (Vicia), Sesamum (Sesamum) and Arachis (arachi); or vegetable crops from different flora such as potatoes, leeks, cabbage, carrots, tomatoes, onions, as well as permanent crops (permanent crop) and plantation crops such as pome and stone fruits, berries, grapes, hevea (hevea), bananas, sugar cane, coffee, tea, citrus, nut-growing plants, lawns, palm crops and forestry crops.

The expression "unwanted plants" is understood to mean all plants which grow where they are not wanted. For example, these may be harmful plants (e.g. monocotyledonous or dicotyledonous weeds or unwanted crop plants), including for example those that are resistant to certain active herbicidal compounds, such as glyphosate, atrazine, glufosinate or imidazolinone herbicides.

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.

When the herbicide-safener compositions of the invention are used in transgenic crops, they not only exert an effect on the harmful plants observed in other crops, but often also find particular effects on the application of particular transgenic crops, for example, a modified or particularly broadened spectrum of preventable weeds, modified application rates available for application, better compatibility with the herbicides to which the transgenic crops are resistant, and an effect on the growth and yield of the transgenic crop plants.

The invention has the following excellent effects: the use of the herbicide-safener combination of the invention significantly reduces the damage to crop plants and maintains excellent herbicidal activity compared to the use of individual herbicides which do not contain safeners.

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:

(1) post-emergence herbicidal and safener action

Seeds or rhizome parts of monocotyledonous and dicotyledonous crop plants and weed plants are placed in a plastic nutrition pot filled with sandy loam, covered with soil, and allowed to grow under good conditions at room temperature (aquatic plants such as rice are planted in a plastic square box containing water, which is deep to 3cm above the soil surface). Ten to twenty days after sowing, the test plants in one to three-leaf stage were treated. The herbicide-safener combination of the invention, formulated as a water-soluble powder or suspension, and the respective active ingredients formulated correspondingly in parallel tests were sprayed onto the green plant parts at different doses, at a spray volume of 450l/ha (converted), and the test plants were again placed in a greenhouse for 2-3 weeks, and the effect of the formulation was evaluated visually as compared with the untreated control group, as shown in tables 1-23. The experiments show that the use of the herbicide-safener combination according to the invention significantly reduces the damage to crop plants and maintains an excellent herbicidal activity compared to the use of individual herbicides which do not contain safeners.

TABLE 1 safe Activity of mefenpyr and herbicidal Effect of mefenpyr-diethyl in crops

TABLE 2 safe Activity of antidotal in crops

TABLE 3A and Bifenamic acid safety activity in crops and weed control

TABLE 4A and safety Activity and weed control of cyclopropanesulfonamide in crops

TABLE 5A and safety Activity of naphthalic anhydride in crops and weed control

TABLE 6 safe Activity of Dichloropropenamine in crops and weed control

TABLE 7A and safe Activity of benoxacor in crop plants and controlling efficacy against weeds

TABLE 8A and safening Activity of fenclorim in crops

TABLE 9A safety Activity of Chlorfenapyr in crops

TABLE 10A safety activity and weed control efficacy of norflurazon oxime in crops

TABLE 11A and safening Activity of chlorantraniliprole in crops and controlling Effect on weeds

TABLE 12A and safening Activity of benoxanil in crops

TABLE 13 safety Activity of Diclonone in crops

TABLE 14 safety Activity of metcamifen in crops

TABLE 15 safe Activity of Oxazolidines in crops and controlling weed

TABLE 16 safe Activity of A and AAD-67 in crops

TABLE 17A and safening Activity of cloquintocet-mexyl in crops

TABLE 18 safety Activity of A and ethyl 1- (2, 4-dichlorophenyl) -5-methylpyrazole-3-carboxylate in crops and weed control

TABLE 19A and safety Activity of 1- (2, 4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester in crops

TABLE 20 safe Activity of A and Ethyl 5- (2, 4-dichlorobenzyl) -2-isoxazoline-3-carboxylate in crops and weed control

TABLE 21 safe Activity of A and (1, 3-dimethylbut-1-yl) (5-chloro-8-quinolinyloxy) acetate in crops

TABLE 22A and safety Activity of 4-allyloxybutyl (5-chloro-8-quinolinoxy) acetate in crops

TABLE 23 safety Activity of 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy) acetate in crops

(2) Post-sowing pre-emergence herbicidal action and safener action

The monocotyledonous and dicotyledonous crop weeds, seeds or rhizome parts of plants are placed in a plastic nutrition pot filled with sandy loam and covered with soil. The herbicide-safener combination according to the invention, formulated as a water-soluble powder or suspension, and the individual active ingredients, which were formulated accordingly in a parallel test, were subsequently applied to the surface of the covering soil in different doses, at a spray rate of 225-. After treatment, the pots were placed in a greenhouse and kept under good growth conditions for the crop plants. After a test period of 2-3 weeks, plant or emergence damage and herbicidal activity were visually recorded after emergence of the test plants compared to the untreated control group and excellent soil herbicidal activity was maintained, as shown in tables 24-28. The experiments show that the use of the herbicide-safener combination according to the invention significantly reduces the damage to crop plants and maintains an excellent herbicidal activity compared to the use of a single herbicide without safener.

TABLE 24A and safety Activity and weed control of cyclopropanesulfonamide in crops

TABLE 25A and safety Activity of Dichloropropenamine in crops

TABLE 26A safety Activity of Chlorfenapyr in crops

TABLE 27 safe Activity and weed control of fenoxaprop-p-ethyl in crops

TABLE 28 safety Activity of A and n-propyl 5, 5-diphenyl-2-isoxazoline-3-carboxylate in crops

Through a large number of tests and explorations, the invention unexpectedly discovers that the composition can not only effectively prevent and kill gramineae, broadleaf weeds, cyperaceae, equisetum weeds and the like, but also shows good compatibility in crop plant fields such as wheat fields, corn fields, paddy fields, sesame, peanuts, sugarcane, sorghum, millet, potatoes, rapes, soybeans, cotton, vegetables, bluegrass, festuca arundinacea, zoysia japonica and the like, and can be developed into herbicide mixtures with wide market values.

Claims (10)

1. A composition comprising an R-type oxadiazolyl aryl carboxamide compound and a safener,

the active ingredient R type oxadiazole radical aryl formamide compound is

The safener is selected from at least one of the following compounds:

a) dichlorophenyl pyrazoline-3-carboxylic acid compounds;

b) dichlorophenyl pyrazole carboxylic acid derivatives;

c) triazole carboxylic acid compounds;

d) 5-benzyl-or 5-phenyl-2-isoxazoline-3-carboxylic acids or 5, 5-diphenyl-2-isoxazoline-3-carboxylic acids;

e) 8-quinolinyloxyacetic acids;

f) (5-chloro-8-quinolinyloxy) malonic acid compounds;

g) phenoxyacetic acid, phenoxypropionic acid, or aromatic carboxylic acids;

h) a pyrimidine compound;

i) dichloroacetamide compounds;

j) dichloroacetone derivative compounds;

k) oxyimino compounds;

l) thiazole carboxylic acid ester compounds;

m) naphthalene dicarboxylic acid derivatives;

n) chromane acetic acid derivatives;

o) compounds which have a safener action on plants in addition to a herbicidal action on harmful plants;

p) acyl sulfonamides.

2. A composition comprising an R-type oxadiazolyl arylcarboxamide compound according to claim 1 and a safener selected from at least one of the following compounds:

a) mefenpyr-diethyl;

b) ethyl 1- (2, 4-dichlorophenyl) -5-methylpyrazole-3-carboxylate, ethyl 1- (2, 4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate, ethyl 1- (2, 4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylate or ethyl 1- (2, 4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate;

c) fenchlorazole-ethyl;

d) ethyl 5- (2, 4-dichlorobenzyl) -2-isoxazoline-3-carboxylate, ethyl 5-phenyl-2-isoxazoline-3-carboxylate, isoxadifen, n-propyl 5, 5-diphenyl-2-isoxazoline-3-carboxylate, or ethyl 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylate;

e) cloquintocet-mexyl, (1, 3-dimethylbut-1-yl) (5-chloro-8-quinolinoxy) acetate, 4-allyloxybutyl (5-chloro-8-quinolinoxy) acetate, 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy) acetate, ethyl (5-chloro-8-quinolinyloxy) acetate, methyl (5-chloro-8-quinolinyloxy) acetate, allyl (5-chloro-8-quinolinyloxy) acetate, 2- (2-propyleneiminoxy) -1-ethyl (5-chloro-8-quinolinyloxy) acetate or 2-oxoprop-1-yl (5-chloro-8-quinolinyloxy) acetate;

f) diethyl (5-chloro-8-quinolinoxy) malonate, diallyl (5-chloro-8-quinolinoxy) malonate, or methylethyl (5-chloro-8-quinolinoxy) -malonate;

g)2,4-D or an ester thereof, 2-methyl-4-chloropropionic acid, MCPA, dicamba or an ester thereof;

h) fenclorim;

i) dichloropropylamine, 3-dichloroacetyl-2, 2, 5-trimethyl-1, 3-oxazolidinone, benoxazine, N-allyl-N [ (1, 3-dioxolan-2-yl) -methyl ] dichloroacetamide, N-allyl-N- [ (allylaminocarbonyl) -methyl ] -dichloroacetamide, 4-dichloroacetyl-1-oxa-4-aza-spiro [4,5] decane, 3-dichloroacetyl-2, 5, 5-trimethyl-1, 3-diazabicyclo [4.3.0] nonane, oxazazole or 3-dichloroacetyl-2, 2-dimethyl-1, 3-oxazolidine;

j) decomposing the grass alkyl;

k) oxabetrinil, fluoroxyfop-butyl or oxabetrinil;

l) metoclopramide;

m) naphthalic anhydride;

n) 2-84-carboxychroman-4-yl) acetic acid;

o) penetryn, prosulfuron, benzophenone or 1-bromo-4- (chloromethylsulfonyl) benzene;

p) cyclopropanesulfonamide or 2-methoxy-N- { [4- (3-methylureido) phenyl ] sulfonyl } benzamide.

3. The composition containing the R-type oxadiazolyl aryl carboxamide compound and the safener according to claim 1 or 2, characterized in that the weight ratio of the active ingredient to the safener is 1:1000 to 1000:1, preferably 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 2:1 to 1: 1.

4. A composition comprising an R-type oxadiazolyl arylcarboxamide compound and a safener according to claim 1 or 2, characterized in that it further comprises conventional auxiliaries, and/or other active ingredients.

5. Use of a composition according to any one of claims 1 to 4 comprising an R-type oxadiazolyl arylcarboxamide compound and a safener for controlling unwanted plant growth.

6. A method for safening the active ingredient of any one of claims 1 to 4 against phytotoxic activity of crops comprising applying a herbicidally effective amount of the active ingredient of any one of claims 1 to 4 in combination with a detoxifying-active amount of a safener.

7. A method for controlling unwanted plant growth, which comprises applying a composition comprising an R-type oxadiazolyl arylcarboxamide compound according to any one of claims 1 to 4 and a safener to the plant, to parts of the plant, to the plant seed or to the area where the plant is growing.

8. The method according to claim 7, characterized in that the composition is applied before, during and/or after the emergence of the unwanted plants.

9. Use according to claim 5 or a method according to claim 6, 7 or 8, wherein the composition is used for selective weed control in a useful crop.

10. Use or method according to claim 9, wherein the useful crop is a transgenic crop, a genome editing technology treated crop or a herbicide tolerant crop.