Selective herbicides based on substituted isoxazoline carboxamide and metcamyphen

Abstract

The present invention relates to a novel selectively herbicidally active compound combination comprising a substituted isoxazoline carboxamide or an agriculturally acceptable salt thereof and metcamifen, which can be used with particularly good results for the selective control of weeds in crops of various useful plants.

Description

[Technical Field]

[0001] The present invention relates to a novel combination of selective herbicidal compounds comprising a substituted isoxazoline carboxamide or a pesticide-acceptable salt thereof and metcamifen, which can be used with particularly good results for the selective control of weeds in various useful plant crops. [Background technology]

[0002] Substituted isoxazoline carboxamides are already known as effective herbicides from International Publication No. 2018 / 228985 and International Publication No. 2019 / 145245. However, the activity of these compounds and / or their compatibility with crop plants are not entirely satisfactory under all conditions.

[0003] Metcamifen (IUPAC: 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide; CAS: 129531-12-0) is a drug-induced mitigating agent known from European Patent No. 0365484.

[0004] Surprisingly, it was found here that certain substituted isoxazoline carboxamides, when used in combination with metcamifene as described below, very effectively prevent damage to crop plants and are particularly advantageous as broad-spectrum combination preparations for the selective control of weeds (= undesirable plants) in useful crops such as cereals and maize. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2018 / 228985 Brochure [Patent Document 2] International Publication No. 2019 / 145245 brochure [Patent Document 3] European Patent No. 0365484 Specification

Summary of the Invention

Means for Solving the Problems

[0006] The present invention relates to (a) a substituted isoxazoline carboxamide of formula (I) or an agriculturally acceptable salt thereof

Chemical Formula

Chemical formula

[0007] Definition Halogen represents a group of fluorine, chlorine, bromine and iodine. Fluorine and chlorine groups are preferred.

[0008] Alkyl is a saturated straight-chain or branched hydrocarbyl group having the number of carbon atoms specified in each case, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, etc., meaning C1-C6-alkyl.

[0009] Alkyl is an unsaturated linear or branched hydrocarbyl group having a specified number of carbon atoms and one double bond at any position, for example, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl Tyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl , 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,This refers to C2-C6 alkenyls such as 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2-propenyl.

[0010] Alkynyl represents a linear or branched hydrocarbyl group having 2 to 8, preferably 2 to 6, carbon atoms and one triple bond at any position. Non-limiting examples include ethinyl, propa-1-inyl, propa-2-inyl, buta-1-inyl, buta-2-inyl, buta-3-inyl, 1-methylpropa-2-inyl, penta-1-inyl, penta-2-inyl, penta-3-inyl, penta-4-inyl, 1-methylbuta-2-inyl, 1-methylbuta-3-inyl, 2-methylbuta-3-inyl, 3-methylbuta-1-inyl, 1,1-dimethylpropa-2-inyl, 1-ethylpropa-2-inyl, hexa-1-inyl, hexa-2-inyl, hexa-3-inyl, hexa-4-inyl, hexa-5-inyl, 1-methylpenta-2-inyl, 1- Examples include methylpenta-3-inyl, 1-methylpenta-4-inyl, 2-methylpenta-3-inyl, 2-methylpenta-4-inyl, 3-methylpenta-1-inyl, 3-methylpenta-4-inyl, 4-methylpenta-1-inyl, 4-methylpenta-2-inyl, 1,1-dimethylbuta-2-inyl, 1,1-dimethylbuta-3-inyl, 1,2-dimethylbuta-3-inyl, 2,2-dimethylbuta-3-inyl, 3,3-dimethylbuta-1-inyl, 1-ethylbuta-2-inyl, 1-ethylbuta-3-inyl, 2-ethylbuta-3-inyl, and 1-ethyl-1-methylpropa-2-inyl.

[0011] Cycloalkyl refers to a carbocyclic saturated ring system preferably having 3 to 8 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. In the case of substituted cycloalkyls, this may include ring systems with substituents, including substituents having a double bond on the cycloalkyl group, such as alkylidene groups like methylidene.

[0012] Alkoxy is a saturated linear or branched alkoxy group having the number of carbon atoms specified in each case, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2- This refers to C1-C6 alkoxys such as methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, and 1-ethyl-2-methylpropoxy. Halogenated alkoxy means a C1-C2 haloalkoxy having the number of carbon atoms specified in each case, where some or all of the hydrogen atoms of these groups may be replaced by the halogen atoms specified above, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-1,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoropropa-2-oxy.

[0013] The compounds according to the present invention are generally defined by formula (I). Preferred substituents or ranges for the groups given by the above and below formulas are shown below:

[0014] The compound of formula (I) is the compound of formula (Ia) or its pesticide-acceptable salt. [ka] (In the formula, X 3 , X 5 , R 3 And G is as described above; Z is Z-1a, Z-1b, Z-2a, Z-3a, Z-4a, Z-5a, Z-6a, Z-7a, Z-8a [ka] (In the formula, Z-4a means a mixture of both structures Z-4b and Z-4c. [ka] ; Z-8a means a mixture of both structures Z-8b and Z-8c. [ka] ; (The arrow indicates the bond to the CO-G group in formula (Ia)) (Meaning) One preferred option is a combination of herbicides.

[0015] A herbicide combination is particularly preferred in which the compound of formula (Ia) is one of the compounds in Table 1 or one of the pesticide-acceptable salts thereof. [ka]

[0016] [Table 1A] [Table 1B] [Table 1C] [Table 1D] [Table 1E] [Table 1F] [Table 1G] [Table 1H]

[0017] Surprisingly, it was found here that combinations of active compounds defined above substituted isoxazoline carboxamides and / or salts of general formula (I) are very well tolerated by crop plants, possess particularly high herbicidal activity, and can be used for the selective control of weeds (=undesirable plants) in a variety of crops, especially cereals (particularly wheat and barley) and maize, as well as soybeans, potatoes and rice.

[0018] Here, it must be considered remarkable that, among the numerous known phytotoxicity reducers or antidotes that can counteract the damaging effects of herbicides on crop plants, metcamifene virtually completely neutralizes the damaging effects of substituted isoxazoline carboxamide on crop plants without adversely affecting its herbicidal activity against weeds.

[0019] Here, the particularly advantageous effect of metcamifen is highlighted, especially in that it does not harm cereal plants such as wheat, barley, and rye, as well as maize and rice.

[0020] The combination of active compounds according to the present invention can be used, for example, in relation to the following plants: Dicotyledonous weeds of the following genera: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum. Dicotyledonous crops of the following genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita, Helianthus. The following genera of monocotyledonous weeds: Echinochloa, Setaria, Panicum, Digitalia, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, and Sorghum. The genera include Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, and Apera. Monocotyledonous crops of the following genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, and Allium.

[0021] However, the use of the active compound combinations according to the present invention is by no means limited to these genera and extends similarly to other plants. According to the present invention, crop plants include all plants and plant varieties, including transgenic plants and plant varieties, and synergistic effects can occur in transgenic plants and plant varieties.

[0022] The present invention further relates to a method for reducing crop damage by treating crop seeds with a phytotoxicity reducer before sowing. This can be done in addition to using herbicide / phytotoxicity reducer combinations and compositions containing them, which are very suitable for protecting crops from herbicide damage in pre-emergence and post-emergence treatments.

[0023] The object of the present invention was to provide a method for further reducing crop damage using known combinations of herbicides and phytotoxicity reducers and compositions containing them. Surprisingly, this object is achieved by the following treatment method / scheme. Method A Step 1: Treating seeds with metcamyphen Step 2: Application of compound (I) or a composition containing it as a post-emergence treatment. Method B Step 1: Treating seeds with metcamyphen Step 2: Application of compound (I) or a composition containing it as a pre-budding treatment. The following method is preferred: Method Aa Step 1: Treating seeds with metcamyphen Step 2: Application of compound (Ia) or a composition containing it as a post-emergence treatment. Method Ba Step 1: Treating seeds with metcamyphen Step 2: Application of compound (Ia) or a composition containing it as a pre-budding treatment. seed: Crops and plants, such as various grain species (wheat, rye, barley, rye, etc.), corn, and corn seeds.

[0024] composition The compositions in the context of the present invention include, in addition to the herbicide / phytotoxicity reduction agent combination according to the present invention, one or more further components including, but not limited to, the following: formulation aids, additives commonly used in crop protection, and further pesticide-active compounds (e.g., fungicides and insecticides).

[0025] additives Additives include, for example, fertilizers and colorants.

[0026] Method from 1 day ago The present invention further relates to a method for reducing crop damage by pre-incubating crop plants and phytotoxicity reducers for 24 hours before application of herbicides or herbicide / phytotoxicity reducer combinations / compositions.

[0027] In another embodiment, the present invention relates to a selective herbicide combination comprising at least one further herbicide (c), wherein (c) is selected from a list that includes, but is not limited to, the following: Acetochlor, aciflorphen, aciflorphen-methyl, aciflorphen-sodium, acroniphen, alachlor, alidoclor, alloxidim, alloxidim-sodium, ametrine, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralide, aminopyralide-dimethylammonium Um, aminopyralide-tripromine, amitorol, ammonium sulfamate, anirophos, ashram, ashram potassium, ashram sodium, atrazine, azaphenidine, azimusulfuron, beflubutamide, (S)-(-)-beflubutamide, beflubutamide-M, benazoline, benazoline-ethyl, benazoline-dimethylammonium, benazoline potassium, benfluralin, benfresate, bensulfuron, bensulfuron-methyl, benslid, bentazon, bentazon-sodium, benzobicyclon, benzophenate P, bicyclopyrone, bifenox, viranafos, viranafos-sodium, bipirazon, bispiribac, bispiribac-sodium, bixlozone, bromacil, bromacil-lithium, bromacil-sodium, bromobutide, bromophenoxime, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate and -octanoate, busoxinone, butachlor, butaphenacil, butamiphos, butenaclor, buttraline, butroxidime, butyrate, coffeestroke, cambenjik Lol, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chloramben, Chloramben-ammonium, Chloramben-diolamine, Chloramben-methyl, Chloramben-methylammonium, Chloramben-sodium, Chlorbromulone, Chlorfenac, Chlorfenac-ammonium, Chlorfenac-sodium, Chlorfenprop, Chlorfenprop-methyl, Chlorflurenol, Chlorflurenol-methyl, Chloridazone, Chlorimurone, Chlorumurone-ethyl, Chlorophthalium, Chlorotolurone,Chlorsulfuron, Chlortal, Chlortal-dimethyl, Chlortal-monomethyl, Synidone, Synidone-ethyl, Symmethiline, Exo-(+)-Symmethiline, i.e., (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane, Exo-(-)-Symmethiline, i.e., (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane, Sinosulfuron, Clasifos, Cretodi Mu, Clodinafop, Clodinafop-ethyl, Clodinafop-propargyl, Chromazon, Clomeprop, Clopyralid, Clopyralid-methyl, Clopyralid-olamine, Clopyralid-potassium, Clopyralid-tripomine, Chloranslam, Chloranslam-methyl, Cumilon, Cyanamide, Cyanazine, Cycloate, Cyclopyranil, Cyclopyrimolate, Cyclosulfamurone, Cycloxidim, Cyhalofop, Cyhalofop-butyl, Cyprazine, 2,4-D(ammonium, butotyl, -butyl, choline, diethylammonium) (Containing 2,4-DB-dimethylammonium, 2,4-DB-butyl Darapon, Darapon-Calcium, Darapon-Magnesium, Darapon-Sodium, Dazomet, Dazomet-Sodium, n-Decanol, 7-Deoxy-D-Sedoheptulose, Desmedifam, Detosyl-Pyrazolate (DTP), Dicamba and its salts, e.g., Dicamba-Biproamine, Dicamba-N,N-Bis(3-Aminopropyl)methylamine, Dicamba-Butotyl, Dicamba-Choline, Dicamba-Diglycolamine, Dicamba-Dimethylammonium, Dicamba-Diethanolaminemonium, Dicamba-DiethylammoniumDicamba-isopropylammonium, dicamba-methyl, dicamba-monoethanolamine, dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-triethanolamine, diclobenyl, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidine-3-one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidine-3-one, dichlorprop, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop- Etexyl, dichlorprop-ethylammonium, dichlorprop-isooctyl, dichlorprop-methyl, dichlorprop-potassium, dichlorprop-sodium, dichlorprop-P, dichlorprop-P-dimethylammonium, dichlorprop-P-ethexyl, dichlorprop-P-potassium, dichlorprop-sodium, diclohop, diclohop-methyl, diclohop-P, diclohop-P-methyl, diclothram, diphenzocoat, diphenzocoat methyl sulfate, di Flufenican, diflufenzopyr, diflufenzopyr-sodium, dimeflon, dimepiperate, dimesulfazet, dimetachlor, dimethametrin, dimetenamide, dimetenamide-P, dimethrasulfuron, dinitramine, dinoterb, dinoterb-acetate, diphenamide, diquat, diquat-dibromide, diquat-dichloride, dithiopyr, diuron, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, endotal, endotal-diammonium, endotal Dipotassium ethanol, Endotal disodium, Epirifenacil (S-3100), EPTC, Esprocarb, Etalfluralin, Etamethulfuron, Etamethulfuron-methyl, Ethiodin, Etofmesate, Ethoxyphene, Ethoxyphene-ethyl, Ethoxysulfuron, Etobenzanide, F-5231, i.e., N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazole-1-yl]phenyl]ethanesulfonamide, F-7967,That is, 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazole-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, phenoxaprop, phenoxaprop-P, phenoxaprop-ethyl, phenoxaprop-P-ethyl, phenoxasulfone, fenpyrazone, fenquinotrione, phentrazamide, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, ph Lazasulfuron, Floraslam, Florpyrauxifen, Florpyrauxifen-benzyl, Fluadifop, Fluadifop-butyl, Fluadifop-methyl, Fluadifop-P, Fluadifop-P-butyl, Flucarbazone, Flucarbazone sodium, Flucetosulfuron, Fluchloralin, Flufenacet, Flufenpyr, Flufenpyr-ethyl, Flumethoslam, Flumicrolac, Flumicrolac-pentyl, Flumioxazine, Fluomethuron, Flurenol, Flurenol-butyl, -dimethylammonium and -Methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupropanate-sodium, flupyrusulfuron, flupyrusulfuron-methyl, flupyrusulfuron-methyl-sodium, flulidone, flurochloridone, fluroxypyl, fluroxypyl-butomethyl, fluroxypyl-meptyl, flurutamone, fluthiaset, fluthiaset-methyl, homesaphen, homesaphen-sodium, horamsulfuron, horamsulfuron sodium salt, fosamine, fosamine-ammonium, glufosinate, gluho cinate-ammonium, glufosinate-sodium, L-glufosinate-ammonium, L-glufosinate-sodium, glufosinate-P-sodium, glufosinate-P-ammonium, glyphosate, glyphosate-ammonium, -isopropyl-ammonium, -diammonium, -dimethylammonium, -potassium, -sodium, sesquisodium and -trimethium, H-9201, i.e., O-(2,4-dimethyl-6-nitrophenyl)-O-ethyl-isopropylphosphoramidethioate, harauxifen,Halauxiphen-methyl, Halosaphen, Halosulfuron, Halosulfuron-methyl, Haloxyhop, Haloxyhop-P, Haloxyhop-ethoxyethyl, Haloxyhop-P-ethoxyethyl, Haloxyhop-methyl, Haloxyhop-P-methyl, Haloxyhop-sodium, Hexazinone, HNPC-A8169, i.e., propa-2-in-1-yl(2S)-2-{3-[(5-tert-butylpyridine-2-yl)oxy]phenoxy}propanoate, HW-02, i.e., 1-(dimethoxyphosphoryl)-ethyl-(2, 4-Dichlorophenoxy)acetate, hydantosidine, imazametabenz, imazametabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazakine, imazakine-ammonium, imazakine-methyl, imazetapyr, imazetapyr-ammonium, imazosulfuron, indanophan, indadiflame, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium, ioxinyl, ioxinyl-lithium Mu, -octanoate, -potassium and sodium, ipfencarbazone, isoproturone, isouron, isoxaben, isoxaflutol, carbchylate, KUH-043, i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole, ketospiradox, ketospiradox-potassium, lactofen, renacyl, linuron, MCPA, MCPA-butotyl, -butyl, -dimethyl- Nmonium, -diolamine, -2-ethylhexyl, -ethyl, -isobutyl, isooctyl, -isopropyl, -isopropylammonium, -methyl, olamine, -potassium, -sodium and -trolamine, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-butotyl, mecoprop-demethylammonium, mecoprop-diolamine, mecoprop-etexyl, mecoprop-etadyl, mecoprop-isooctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium,and mecoprop-trolamine, mecoprop-P, mecoprop-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mefluidide-diolamine, mefluidide-potassium, mesosulfuron, mesosulfuron-methyl, mesosulfuron sodium salt, mesotrione, metabenzthiazuron, metam, metamihop, metamitron, metazachlor, metazosulfuron, metabenzthiazuron, methipyrsulfuron, methiozoline, methylisothiocyanate, metobromurone, metrachlor, S-methrachlor, metoslam, metoxuron, metrivudine, metosulfuron, metosulfuron-methyl, molinate, Monolinuron, monosulfuron, monosulfuron-methyl, MT-5950, i.e., N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e., 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, NC-656, i.e., 3-[(isopropylsulfonyl)methyl]-N-(5-methyl-1,3,4-oxadiazole-2-yl)-5-(trifluoromethyl)[1,2,4]triazolo[4,3-a]pyridine-8-cal Boxamide, Nebulon, Nicosulfuron, Nonanoic acid (pelargonic acid), Norflurazone, Oleic acid (fatty acid), Olbencarb, Orthosulfamurone, Oryzalin, Oxaziargyl, Oxadiazone, Oxasulfuron, Oxadiclomefone, Oxyfluorphene, Paraquat, Paraquat-Dichloride, Paraquat-Dimethylsulfate, Pevlate, Pendimethalin, Penoxuslam, Pentachlorophenol, Pentoxazone, Petoxamide, Petroleum, Fenmedifame, Fenmedifame-Ethyl, Pichloram, Pichloram-Dimethyl Pychloram-etexyl, picloram-isooctyl, picloram-methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram-tripromine, picloram-troramine, picolinafene, pinoxadene, piperofos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxidim, prometon, prometrin, propacrol, propanil, propaxazop, propazine, profam, proxochlor, propoxycarbazone, propoxycarbazo N-sodium, propyrisulfuron, propizamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfolol, pyrazolinate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxime, pyributicarb, pyridafol, pyridate, pyrifthalide, pyriminovac, pyriminovac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium,Pyroxasulfone, Pyroxulam, Quinclorac, Quinclorac-dimethylammonium, Quinclorac-methyl, Kinmelac, Quinoclamine, Quizalophop, Quizalophop-ethyl, Quizalophop-P, Quizalophop-P-ethyl, Quizalophop-P-tefuryl, QYM201, i.e., 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazole-4-yl)carbonyl]-6-(trifluoromethyl)phenyl}piperidine-2-one, Limusulfuron, Saflufenacil, Cethoxydim, Siduro n, simazine, simetrin, SL-261, sulcotrione, sulfenthrazone, sulfomethane, sulfomethane-methyl, sulfosulfuron, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobuta-3-en-2-yl-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e., 1-[7-fluoro-3-oxo-4-(propa-2-in-1-yl)-3,4-dihydro-2H-1,4-benzoxazine-6-yl]-3-propyl-2-thioxoimidazolidine-4, 5-dione, 2,3,6-TBA, TCA (trichloroacetic acid) and its salts, e.g., TCA-ammonium, TCA-calcium, TCA-ethyl, TCA-magnesium, TCA-sodium, tebuthiurone, tefuryltrione, tenbotrione, tepraloxidim, terbasil, terbucarb, terbumetone, terbutyrazine, terbutrin, tetoflupyrrolimet, taxomin, tenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, thiafenasil, Torpyralate, Topramezone, Tralcoxidium, Triafamone, Trialate, Triasulfuron, Triaziflame, Trivenuron, Trivenuron-methyl, Triclopyr, Triclopyr-butotyl, Triclopyr-choline, Triclopyr-ethyl, Triclopyr-triethylammonium, Trietadine, Trifloxysulfuron, Trifloxysulfuron-sodium, Trifludimoxazine, Trifluralin, Triflusulfuron, Triflusulfuron-methyl, Tritosulfuron, Urea sulfate, Vernolate, XDE-848, ZJ-0862,That is, 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidine-2-yl)oxy]benzyl}aniline, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidine-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate ethyl ester, 3-chloro-2-[3-(difluoromethyl)isoxazolyl-5-yl]phenyl-5-chloropyrimidine-2-yl ether, 2-(3,4-dimethoxyphenyl )-4-[(2-hydroxy-6-oxocyclohexa-1-en-1-yl)carbonyl]-6-methylpyridazine-3(2H)-one, 2-({2-[(2-methoxyethoxy)methyl]-6-methylpyridine-3-yl}carbonyl)cyclohexane-1,3-dione, (5-hydroxy-1-methyl-1H-pyrazole-4-yl)(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophene-5-yl)methanone, 1-methyl-4-[(3,3,4-trimethyl-1,1-dioxide-2,3 -Dihydro-1-benzothiophen-5-yl)carbonyl]-1H-pyrazole-5-ylpropane-1-sulfonate, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazole-1-yl)methyl]-4-(methylsulfonyl)benzoyl}-1-methyl-1H-pyrazole-5-yl1,3-dimethyl-1H-pyrazole-4-carboxylate; cyanomethyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, propane-2-in-1-yl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, methyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylic acid, benzyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate,Ethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, Methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indole-6-yl)pyridine-2-carboxylate, Methyl 6-(1-acetyl-7-fluoro-1H-indole-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate, Methyl 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indole-6-yl]-5-fluoropyridine-2-carboxylate, Methyl 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)- [1H-indole-6-yl]pyridine-2-carboxylate, potassium 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, sodium 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indole-6-yl)pyridine-2-carboxylate, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridine-2-yl]imidazolidined-2-one, 3-(5-tert-butyl-1,2-oxazol-3-yl)-4-hydroxy-1-methylimidazolidined-2-one, Abscisic acid, acibenzol, acibenzol-S-methyl, 1-aminocyclopro-1-ylcarboxylic acid and its derivatives, 5-aminolevulinic acid, ancimidol, 6-benzylaminopurine, brassinolide, brassinolide-ethyl, catechin, chito-oligosaccharide (CO; CO differs from LCO in that it lacks the characteristic pendant fatty acid chain of LCO. CO, sometimes called N-acetyl chito-oligosaccharide, is also composed of GlcNAc residues, but has side chain decoration, which allows it to form a chitin molecule [(C8-H 13 NO5) n , CAS number 1398-61-4] and chitosan molecule [(C5H 11 NO4) n(Different from CAS number 9012-76-4), chitinous compounds, chlormecoat chloride, cloprop, cyclanilide, 3-(cyclopropa-1-enyl)propionic acid, daminozide, dazomet, dazomet-sodium, n-decanol, dikeglac, dikeglac-sodium, endotal, endotal-dipotassium, -disodium, and mono(N,N-dimethylalkylammonium), etephon, flumetraline, flurenol, flurenol-butyl, flurenol-methyl, fluruprimi Dole, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-indole-3-ylbutyrate, isoprothiolane, probenazole, jasmonic acid, jasmonic acid or its derivatives (e.g., methyl jasmonate), lipochitooligosaccharide (LCO), sometimes called the symbiotic nodule formation (Nod) signal (or Nod factor) or Myc factor, β-l,4-linked N-acetyl-D-glucosamine ("GlcNAc") residue with an N-linked fatty acid acyl chain condensed at the non-reducing end. It consists of a base oligosaccharide skeleton. As understood in the art, LCOs differ in the number of GlcNAc residues in the skeleton, the length and saturation of the fatty acid acyl chain, and the substitution of reducing and non-reducing sugar residues), linoleic acid or its derivatives, linolenic acid or its derivatives, maleic acid hydrazide, mepicote chloride, mepicote pentaborate, 1-methylcyclopropene, 3'-methylabscisic acid, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixtures 4-Oxo-4[(2-phenylethyl)amino]butyric acid, paclobutrazol, 4-phenylbutyric acid, N-phenylphthalamiic acid, prohexadione, prohexadione-calcium, prohydrojasmon, salicylic acid, methyl salicylate, strigolactone, technazene, tidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P, 2-fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine.

[0028] The active compound or combination / composition of the active compound can be converted into conventional formulations such as solutions, emulsions, wettable powders, suspensions, powders, pastes, aqueous solutions, granules, suspend emulsion concentrates, natural and synthetic materials impregnated with the active compound, and very fine capsules in polymeric materials.

[0029] These formulations are produced in known ways, for example, by mixing the active compound with an extender, i.e., a liquid solvent and / or a solid carrier, using a surfactant, i.e., optionally a surfactant, i.e., an emulsifier and / or a dispersant and / or a foaming agent.

[0030] When water is used as the filler, it is also possible to use, for example, an organic solvent as an auxiliary solvent. Suitable liquid solvents are, in essence, aromatics, such as xylene, toluene, or alkylnaphthalenes; chlorinated aromatic and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene, or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffin; petroleum fractions, mineral oils, and vegetable fats; alcohols, such as butanol or glycols, as well as their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide; and also water.

[0031] The appropriate solid carriers are as follows: Suitable solid carriers for granules include, for example, ammonium salts and pulverized natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, pulverized synthetic minerals such as fine silica, alumina, and silicates; suitable solid carriers for granules include, for example, pulverized and fractionated natural rocks such as calcite, marble, pumice, sepiolite, and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic materials such as sawdust, coconut shells, corn cobs, and tobacco stalks; suitable emulsifiers and / or foaming agents include, for example, nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and protein hydrolysates; suitable dispersants include, for example, lignosulfite wastewater and methylcellulose.

[0032] Carboxymethylcellulose, as well as natural and synthetic polymers in the form of powders, granules, or latex, such as gum arabic, polyvinyl alcohol, and polyvinyl acetate, and adhesives such as natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids, can be used in the formulation. Other possible additives are mineral oil and vegetable oil.

[0033] Inorganic pigments, such as iron oxide, titanium dioxide, and Prussian blue, as well as organic dyes, such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, and colorants such as micronutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc, can be used.

[0034] The formulation generally contains an active compound with a drug-induced harm reduction agent in an amount of 0.1 to 95% by weight, preferably between 0.5 and 90% by weight.

[0035] The active compound combination according to the present invention is generally used in the form of a finished formulation. However, the active compounds contained in the active compound combination can also be used in the form of a tank mix, i.e., mixed in individual formulations.

[0036] Novel active compound combinations can be used as is or in their formulations as mixtures with other known herbicides, and finished formulations or tank mixes are also possible. Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellents, growth factors, plant nutrients, and soil structure improving agents are also possible. For certain intended uses, particularly in post-emergence methods, it may be even more advantageous to include plant-tolerant mineral or vegetable oils (e.g., the commercially available preparation "Rako Binol®") or ammonium salts such as ammonium sulfate or ammonium thiocyanate as further additives in the formulation.

[0037] Novel active compound combinations can be used as is, in their formulation form, or in forms of use prepared therefrom by further dilution, such as ready-to-use liquids, suspensions, emulsions, powders, pastes, and granules. These are used in conventional ways, for example, by washing, spraying, atomizing, powdering, or spraying.

[0038] The advantageous effect of the crop-plant compatibility of the active compound combination / composition according to the present invention is particularly pronounced with certain amounts of herbicides and phytotoxicity reducers.

[0039] The amount of the combination of active compounds according to the present invention applied can be varied within a certain range; these depend, among other things, on weather and soil factors.

[0040] Generally, the application rate of herbicides is between 0.1 and 1000 g / ha, preferably between 0.1 and 10 g / ha.

[0041] Generally, the application rate of phytotoxicity-reducing agents is between 1 and 1000 g / ha, preferably between 10 and 200 g / ha.

[0042] For seed treatment applications, the application rate of the phytotoxicity reducer is between 0.01 and 2 g per kg of seed, preferably between 0.1 and 1 g per kg of seed.

[0043] The active compound combinations / compositions according to the present invention can be applied before and after plant emergence, i.e., by pre-emergence and post-emergence methods. [Modes for carrying out the invention]

[0044] Examples of use: Tank mix; after germination A) Explanation of the method Seeds of crops (spring wheat, TRZAS; spring barley, HORVS; maize, ZEAMA) were placed in peat pots in sandy loam soil, covered with soil, and cultivated in a greenhouse under favorable growing conditions. Two to three weeks after sowing, the test plants were treated at the one-to-three-leaf stage. In parallel tests, the herbicide / phytotoxicity-reducing active compound combinations according to the present invention, formulated as wettable powders or emulsions, and the correspondingly formulated individual active compounds, were sprayed onto the green parts of the plants at various doses using 300 l / ha (equivalent) of water.

[0045] The pots were returned to the greenhouse under favorable growing conditions, and the herbicide effect was visually evaluated at intervals of 1 to 3 weeks after herbicide application (DAT = days after treatment). The evaluation was performed on a percentage basis compared to untreated control plants (0% = no damage, 100% = complete death). The effectiveness of treatment with phytotoxicity-reducing agents is, Reduction [Difference] = Herbicide damage without phytotoxicity reducer - Herbicide damage with phytotoxicity reducer Reduction [%] = (Reduction [Difference] * 100) / Herbicide damage without phytotoxicity reducer It is shown as follows.

[0046] B) Tables based on data a) Plant species and variety: ZEAMA Sileno, phytotoxicity reduction agent (SAF): Metocamyphen

[0047] [Table 2]

[0048] b) Plant species and variety: HORVS Montoya, phytotoxicity reduction agent (SAF): Metcamyphen [Table 3]

[0049] c) Plant species, variety: TRZAS Triso, phytotoxicity reduction agent (SAF): Metocamyphen

[0050] [Table 4]

[0051] Seed treatment; before germination A) Explanation of the method For seed treatment with phytotoxicity-reducing agents, sufficient seeds of each crop (spring wheat, TRZAS; spring barley, HORVS; maize, ZEAMA) were weighed into screw-top glass bottles approximately twice the volume of the seeds.

[0052] A specific phytotoxicity-reducing agent, formulated as a wettable powder (WP), was weighed to obtain a specific amount (g ai / kg of seeds), dissolved in water (1 ml of water per 10 g of seeds), and added to the seeds to produce a slurry.

[0053] The bottle was then capped and placed in an overhead shaker (set to medium speed for approximately 60 minutes) to ensure the seeds were evenly coated with the slurry. The bottle cap was removed, the seeds were placed on paper and allowed to dry for 3-4 hours before sowing, or they were sown directly. The seeds were placed in 7-8 cm diameter pots of sandy loam soil and covered with soil.

[0054] Subsequently, the specified herbicide was applied pre-emergence to two sets of plants: a) Seed treatment with phytotoxicity-reducing agents as described above b) No treatment with phytotoxicity reduction agent

[0055] The herbicide was formulated as a WP (water-based disinfectant) and sprayed onto the soil surface as an aqueous suspension at an equivalent water application rate of 300 l / ha.

[0056] After application, the test plants were kept in a greenhouse under favorable growing conditions. At intervals of up to 4 weeks after application (=28 days post-treatment; DAT), the percentage of crop damage observed in the treated plants was visually scored compared to control plants that had not received either phytotoxicity reduction agent treatment or herbicide treatment.

[0057] The values ​​in the table below are the average values ​​over at least two iterations. The effectiveness of treatment with phytotoxicity-reducing agents is, Reduction [Difference] = Herbicide damage without phytotoxicity reducer - Herbicide damage with phytotoxicity reducer Reduction [%] = (Reduction [Difference] * 100) / Herbicide damage without phytotoxicity reducer It is shown as follows.

[0058] B) Tables based on data a) Plant species and variety: TRZAS Triso, phytotoxicity reduction agent (SAF): Metocamyphen

[0059] [Table 5]

[0060] b) Plant species and variety: HORVS Montoya, phytotoxicity reduction agent (SAF): Metcamyphen

[0061] [Table 6]

[0062] c) Plant species, variety: ZEAMA Sileno, phytotoxicity reduction agent (SAF): Metocamyphen

[0063] Table 7

Claims

1. (a) Substituted isoxazoline carboxamide of formula (Ia) or a pesticide-acceptable salt thereof 【Chemistry 1】 (In the formula, The substituents are as specified in the table below: Table 1 Z is Z-1a, Z-3a, Z-4a, Z-5a: 【Chemistry 2】 (In the formula, Z-4a means a mixture of both structures Z-4b and Z-4c. 【Transformation 3】 The arrow indicates the bond to the CO-G group in formula (Ia). (represents) and (b) Metcamifen A combination that includes this item.

2. The combination according to claim 1, for application to plants, wherein the application rate of the combination is between 0.1 and 1000 g / ha.

3. Use of the combination according to claim 1 or 2 for controlling undesirable plants.

4. A method for controlling undesirable plants, characterized by applying the combination described in claim 1 or 2 to the undesirable plants and / or their habitat.

5. A herbicide composition comprising a surfactant and / or a bulking agent in addition to the combination described in claim 1 or 2.

6. A method for preparing the herbicide composition according to claim 5, characterized by mixing the combination according to claim 1 or 2 with a surfactant and / or a bulking agent.

7. A method for reducing crop damage, characterized by treating the seeds of the crop with metcamifen before sowing (Step 1), and applying a compound of formula (Ia) or a combination / composition containing the same as described in any one of claims 1, 2, and 5 as a post-emergence treatment (Step 2).

8. A method for reducing crop damage, characterized by treating the seeds of the crop with metcamifen before sowing (Step 1), and applying a compound of formula (Ia) or a combination / composition containing the same as described in any one of claims 1, 2, and 5 as a pre-emergence treatment (Step 2).

9. The method according to claim 7 or 8, wherein the crop is a genetically modified plant.

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