Herbicidal composition containing cinmethylin and ethofumesate

Abstract

The present invention relates to a herbicidal composition containing the active ingredients cinmethylin and ethofumesate, said herbicidal composition being particularly suitable for use against weeds in crops of useful plants.

Description

[Technical field]

[0001] explanation The present invention relates to an agriculturally active herbicidal composition and its use for controlling harmful plants. [Background technology]

[0002] Cinmethylin (CAS RN 87818-31-3) is the racemic mixture of (+ / -)-2-exo-(2-methylbenzyloxy)-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane. [ka]

[0003] Here, the ratio of the two enantiomers to each other is approximately equal. The preparation of enantiomerically enriched compounds is known from EP 0081893 A2.

[0004] Ethofumesate (CAS 26225-79-6) is a chemical compound from the group of benzofurans used as a selective systemic herbicide.

[0005] Various documents disclose herbicidal compositions comprising dimethylamine and further herbicides: for example, WO2017 / 009054A1, WO2017 / 009056A1, WO2017 / 009060A1, WO2017 / 009061A1, WO2017 / 009089A1, WO2017 / 009090A1, WO2017 / 009092A1, WO2017 / 009095A1, WO20170091 24A1, WO2017 / 009134A1, WO2017 / 009137A1, WO2017 / 009138A1, WO2017 / 009139A1, WO2017 / 009140A1, WO2017 / 009142A1, WO2017 / 009143A1, WO20177009144A1, WO2017 / 009145A1, WO2017 / 009146A1, WO2017 / 009147A1. These herbicidal compositions expand the weed spectrum to be controlled compared to the respective individual active ingredients, but do not open up further application possibilities, such as use in different crops of useful plants or shifting application periods. These herbicidal compositions known from the prior art do not solve the problem of increasing the resistance development in harmful plants to active herbicidal ingredients from the group of HPPD inhibitors, which also includes sinemethyline. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application Publication No. 0081893 [Patent Document 2] International Publication No. 2017 / 009054 [Patent Document 3] International Publication No. 2017 / 009056 [Patent Document 4] International Publication No. 2017 / 009060 [Patent Document 5] International Publication No. 2017 / 009061 [Patent Document 6] International Publication No. 2017 / 009089 [Patent Document 7] International Publication No. 2017 / 009090 [Patent Document 8] International Publication No. 2017 / 009092 [Patent Document 9] International Publication No. 2017 / 009095 [Patent Document 10] International Publication No. 2017009124 [Patent Document 11] International Publication No. 2017 / 009134 [Patent Document 12] International Publication No. 2017 / 009137 [Patent Document 13] International Publication No. 2017 / 009138 [Patent Document 14] International Publication No. 2017 / 009139 [Patent Document 15] International Publication No. 2017 / 009140 [Patent Document 16] International Publication No. 2017 / 009142 [Patent Document 17] International Publication No. 2017 / 009143 [Patent Document 18] International Publication No. 2017 / 009144 [Patent Document 19] International Publication No. 2017 / 009145 [Patent Document 20] International Publication No. 2017 / 009146 [Patent Document 21] International Publication No. 2017 / 009147 Summary of the Invention [Problem to be solved by the invention]

[0007] It is therefore an object of the present invention to provide further herbicidal compositions which allow good control of undesirable plants in various crops of useful plants in a convenient time frame. [Means for solving the problem]

[0008] This object has been achieved by the provision of a herbicidal composition comprising cinmethylin and ethofumesate.

[0009] Thus, the present invention provides (A) cinmethylin (ingredient A), and (B) Ethofumesate (ingredient B) The present invention provides a herbicidal composition comprising:

[0010] As the only active herbicidal ingredient, (A) Cinmethylin, and (B) Ethofumesate Preferred is a herbicidal composition comprising:

[0011] The herbicidal composition according to the invention can further comprise or be used together with other components, such as other types of active crop protection components and / or additives and / or formulation auxiliaries customary in crop protection.Preferably, the herbicidal composition comprises cinmethylin and ethofumesate as the only active pesticide components.

[0012] The herbicidal compositions according to the invention surprisingly not only exhibit a synergistic effect against undesirable harmful plants, but also exhibit further exceptional properties: for example, they can be applied within a wide time frame in crops of useful plants against undesirable harmful plants without causing significant damage to the useful plants.

[0013] The herbicidal compositions according to the invention can be applied in a manner known to those skilled in the art, for example, together (for example, as a combination or as a tank mix) or at other different times, for a short period (split), for example, to plants, plant parts, plant seeds, or areas where plants grow. For example, individual active ingredients or herbicidal compositions can be applied in two or more separate applications (sequential application), for example, by pre-emergence application followed by post-emergence application, or by early post-emergence application followed by mid- or late post-emergence application. Here, it is preferred to apply components A and B together or successively. Likewise, application by the method from pre-emergence to early post-emergence is preferred.

[0014] In the herbicidal composition according to the present invention, the application rate of cinmethylin (component A) is typically 10 to 1000 g of active ingredient (ai) per hectare, preferably 200 to 500 g ai / ha, and the application rate of ethofumesate (component B) is typically 10 to 500 g of active ingredient per hectare, preferably 100 to 250 g ai / ha.

[0015] The synergistic effect of the herbicidal composition according to the invention is particularly pronounced at certain concentration ratios. However, the weight ratio of components A and B can be varied within a relatively wide range. In general, 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight, of ethofumesate are present per 1 part by weight of the active ingredient cinmethylin.

[0016] When applying the herbicidal composition according to the present invention, a very wide spectrum of harmful plants, such as annual and perennial monocotyledonous or dicotyledonous weeds and undesirable crop plants, are controlled pre-emergence and post-emergence.The herbicidal composition according to the present invention is particularly suitable for use in crops such as cereals, corn, rice, soybeans, rapeseed, sugar beet, cotton, sugarcane, and for use in perennial crops, plantations and uncultivated land.Preferably, it is used in cereal crops.

[0017] The present invention therefore further provides a method for controlling undesirable plants in plant crops, characterized in that components A and B of the herbicidal composition according to the invention are, for example, deployed separately or together onto plants (e.g. harmful plants such as monocotyledonous or dicotyledonous weeds or undesirable crop plants) or onto the area in which the plants grow.

[0018] Unwanted plants are understood to mean all plants which grow where they are undesirable. These may be, for example, harmful plants, such as monocotyledonous or dicotyledonous weeds or unwanted crop plants.

[0019] Monocotyledonous weeds include, for example, Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyrrhizae, and others. on), Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, and Apera.Dicotyledonous weeds include, for example, Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cistallium, irsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum, and Euphorbia.

[0020] The present invention also provides the use of a herbicidal composition according to the invention for controlling undesirable plant growth, preferably in crops of useful plants.

[0021] The herbicidal compositions according to the invention can be prepared by known methods, for example as mixed formulations of the individual components, optionally with further active ingredients, additives and / or conventional formulation auxiliaries, and then applied in a conventional manner by diluting with water or as tank mixes by jointly diluting the separately formulated or partially separately formulated individual components with water. Likewise, application at different times (split application) of the separately formulated or partially separately formulated individual components is also possible. It is also possible to apply the individual components or herbicidal compositions in several parts (sequential application), for example by pre-emergence application, followed by post-emergence application a week later, or early post-emergence application, followed by mid-emergence application or late post-emergence application. It is preferred to apply the active ingredients in each combination together or immediately successively.

[0022] The present invention further comprises: (A) Cinmethylin, and (B) Ethofumesate and, (C) Safeners The present invention provides a herbicidal composition comprising:

[0023] The present invention further comprises, as the sole active herbicidal ingredient, (A) Cinmethylin, and (B) Ethofumesate and, (C) Safeners The present invention provides a herbicidal composition comprising:

[0024] In the herbicidal composition according to the present invention, the application rate of the safener (component C) is typically 10 to 500 g of active ingredient (ai) per hectare, preferably 50 to 250 g ai / ha.

[0025] Examples of useful safeners include the following classes of compounds: S1) Compounds from the group of heterocyclic carboxylic acid derivatives: S1 a) Compounds of the type dichlorophenylpyrazoline-3-carboxylic acid (S1 a ), preferably compounds such as: 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) ("mefenpyr-diethyl"), and related compounds as described in WO-A-91 / 07874; S1 b ) Derivatives of dichlorophenylpyrazole carboxylic acid (S1 b ), preferably compounds such as: ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4) and related compounds as described in EP-A-333 131 and EP-A-269 806; S1 c ) Derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1 c ), preferably compounds such as: ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related compounds as described, for example, in EP-A-268554; S1 d ) Triazole carboxylic acid type compounds (S1 d ), preferably compounds such as: fenchlorazole (ethyl ester), i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate (S1-7) and related compounds as described in EP-A-174 562 and EP-A-346 620; S1 e) Compounds of the type 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 e ), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds as described in WO-A-91 / 08202, or 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-11) ("isoxadifen-ethyl") or n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13), which are described in patent application WO-A-95 / 07897.

[0026] S2) Compounds from the group of 8-quinolinoxy derivatives (S2): S2 a ) 8-quinolinoxyacetic acid type compounds (S2 a), preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate ("cloquintocet-mexyl") (S2-1), 1,3-dimethylbut-1-yl (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (S2-4), (5-chloro-8-quinolinoxy)ethyl acetate (S2-5), (5-chloro-8-quinolinoxy)methyl acetate (S2-6), (5-chloro-8-quinolinoxy)allyl acetate (S2-7), (5-chloro-8-quinolinoxy)2-(2-propylideneiminooxy)-1-ethyl acetate (S2-8), (5-chloro-8-quinolinoxy)2-oxoprop-1-yl acetate (S2-9) and EP-A-86 750, EP-A-94 349 and related compounds as described in EP-A-191 736 or EP-A-0 492 366, as well as (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts, such as its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, which are described in WO-A-2002 / 34048; S2 b ) (5-chloro-8-quinolinoxy)malonic acid type compounds (S2 b ), preferably compounds such as diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methylethyl (5-chloro-8-quinolinoxy)malonate and related compounds, which are described in EP-A-0 582 198.

[0027] S3) Active ingredients (S3) of the dichloroacetamide type, which are often used as pre-emergence safeners (soil-acting safeners), e.g. "Dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1), "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3), "Benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5), "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (from Sagro-Chem) (S3-6), "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane) from Nitrokemia or Monsanto (S3-7), "TI-35" (1-dichloroacetylazepane) [from TRI-Chemical RT] (S3-8), "diclonon" (dicyclonon) or "BAS145138" or "LAB145138" (S3-9), ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) [from BASF], "Furilazol" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), and its (R)-isomer (S3-11).

[0028] S4) Compounds from the group of acylsulfonamides (S4): S4 a ) Equation (S4 a ) and their salts, which are described in WO-A-97 / 45016. [ka] [During the ceremony, R A 1 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, where the latter two radicals are selected from the group halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio. A and, in the case of cyclic groups, also by (C1-C4)-alkyl and (C1-C4)-haloalkyl; R A 2 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3; m A is 1 or 2; v A is 0, 1, 2 or 3;

[0029] S4 b ) The following formula (S4 b ) and their salts, which are described in WO-A-99 / 16744. [ka] [During the ceremony, R B 1 , R B 2 are independently hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, R B 3 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl or (C1-C4)-alkoxy, and m B is either 1 or 2, for example, R B 1 = cyclopropyl, RB 2 = hydrogen and (R B 3 ) = 2-OMe ("cyprosulfamide", S4-1), R B 1 = cyclopropyl, R B 2 = hydrogen and (R B 3 ) = 5-Cl-2-OMe (S4-2), R B 1 = ethyl, R B 2 = hydrogen and (R B 3 )=2-OMe(S4-3), R B 1 = isopropyl, R B 2 = hydrogen and (R B 3 ) = 5-Cl-2-OMe (S4-4) and R B 1 = isopropyl, R B 2 = hydrogen and (R B 3 )=2-OMe(S4-5)〕;

[0030] S4 c ) Equation (S4 c ) from the class of benzoylsulfamoylphenylureas, which are described in EP-A-365484, [ka] [During the ceremony, R C 1 , R C 2 are independently hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, R C 3is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3, and m C is 1 or 2; for example, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea; 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea; 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea;

[0031] S4 d ) Equation (S4 d ) and salts thereof (which are known, for example, from CN 101838227), [ka] [During the ceremony, R D 4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3; m D is 1 or 2; R D 5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl.

[0032] S5) Active ingredients (S5) selected from the class of the hydroxyaromatic compounds and aromatic-aliphatic carboxylic acid derivatives, such as, for example, ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid (these are described in WO-A-2004 / 084631, WO-A-2005 / 015994, WO-A-2005 / 016001).

[0033] S6) Active ingredients (S6) from the class of the 1,2-dihydroquinoxalin-2-ones, such as 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one (which are described in WO-A-2005 / 112630).

[0034] S7) Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), such as, for example, methyl diphenylmethoxyacetate (CAS-Reg. No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid (which are described in WO-A-98 / 38856).

[0035] S8) Compounds of formula (S8), which are described in WO-A-98 / 27049, [ka] [wherein the symbols and indices have the following meanings: R D 1is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, R D 2 is hydrogen or (C1-C4)-alkyl, R D 3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, in which each of the aforementioned carbon-containing groups is unsubstituted or substituted with one or more, preferably up to three, identical or different groups selected from the group consisting of halogen and alkoxy; or a salt thereof, n D is an integer between 0 and 2.

[0036] S9) Active ingredients (S9) from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones, such as 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.: 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 95855-00-8) (which are described in WO-A-1999 / 000020).

[0037] S10) Formula (S10 a ) or formula (S10 b ) which are described in WO-A-2007 / 023719 and WO-A-2007 / 023764, [ka] [During the ceremony, R E 1 is halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3, Y E , Z E are independently O or S; n E is an integer from 0 to 4, R E 2 is (C1-C 16 )-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl, benzyl, halobenzyl; R E 3 is hydrogen or (C1-C6)-alkyl.

[0038] S11) Active ingredients of the oxyimino compound type (S11), which are known as seed dressing compositions, such as "Oxabetrinil" ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for millet / sorghum against damage by metolachlor, "Fluxofenim" (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as a seed dressing safener for millet / sorghum against damage by metolachlor, and "Siometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is a known seed dressing safener for millet / sorghum against injury by metolachlor.

[0039] S12) Active ingredients (S12) selected from the class of isothiochromanones, for example methyl [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (S12-1) and related compounds from WO-A-1998 / 13361.

[0040] S13) One or more compounds selected from the following group (S13): "Naphthalic anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed dressing safener for corn against injury caused by thiocarbamate herbicides; "Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as a safener for pretilachlor in sown rice; "Flurazole" (2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate benzyl) (S13-3), which is known as a seed dressing safener for millet / sorghum against injury by alachlor and metolachlor; "CL 304415" (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is known as a safener for corn against injury by imidazolinones; "MG 191" (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a safener for corn; "MG 838" (CAS Reg. No. 133993-74-5) (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) [from Nitrokemia]; "Disulfoton" (O,O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7); "Dietholate" (O,O-diethyl O-phenylphosphorothioate) (S13-8); “Mephenate” (4-chlorophenyl methylcarbamate) (S13-9).

[0041] S14) Active ingredients that have a herbicidal effect against harmful plants as well as a phytotoxicity reducing effect against crop plants such as rice, e.g. "Dimepyrate" or "MY 93" (S-1-methyl-1-phenylethylpiperidine-1-carbothioate), known as a safener for rice against injury caused by the herbicide molinate; "Dymron" or "SK 23" (1-(1-methyl-1-phenylethyl)-3-p-tolyl urea), which is known as a safener for rice against injury caused by the herbicide imazosulfuron; "Cumyluron" = "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, (see JP-A-60087254), which is known as a safener for rice against injury by some herbicides; "Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone), which is known as a safener for rice against injury caused by some herbicides; "CSB" (1-Bromo-4-(chloromethylsulfonyl)benzene) from Kumiai (CAS Reg. No. 54091-06-4), which is known as a safener against injury by some herbicides in rice.

[0042] S15) Compounds of formula (S15) or tautomers thereof (these are described in WO-A-2008 / 131861 and WO-A-2008 / 131860) [ka] [During the ceremony, R H 1 is a (C1-C6)-haloalkyl group, and R H 2 is hydrogen or a halogen, and R H 3 , R H 4 are independently hydrogen, (C1-C 16 )-Alkyl, (C2-C 16 )-alkenyl or (C2-C16 )-alkynyl, in which each of the latter three radicals is unsubstituted or substituted with one or more radicals from the group halogen, hydroxyl, cyano, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heterocyclyl, or (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, (C3-C6)-cycloalkyl (wherein the ring is fused at one side of the ring to a 4-6-membered saturated or unsaturated carbocyclic ring), or (C4-C6)-cycloalkenyl (wherein the ring is fused at one side of the ring to a 4-6-membered saturated or unsaturated carbocyclic ring), wherein each of the latter four groups is unsubstituted or substituted with one or more groups from the group halogen, hydroxyl, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy, (C1-C4) alkylthio, (C1-C4) alkylamino, di[(C1-C4) alkyl] amino, [(C1-C4) alkoxy] carbonyl, [(C1-C4) haloalkoxy] carbonyl, unsubstituted or substituted (C3-C6) cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl; or R H 3 is (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C6)-alkynyloxy or (C2-C4)-haloalkoxy; and R H 4is hydrogen or (C1-C4)-alkyl; or R H 3 and R H 4 together with the directly attached nitrogen atom, is a 4-8 membered heterocyclic ring which, in addition to the nitrogen atom, can contain further ring heteroatoms, preferably up to two further ring heteroatoms from the group N, O and S, and which heterocyclic ring is unsubstituted or substituted with one or more groups from the group halogen, cyano, nitro, (C-C)-alkyl, (C-C)-haloalkyl, (C-C)-alkoxy, (C-C)-haloalkoxy and (C-C)-alkylthio.

[0043] S16) Active ingredients which are used primarily as herbicides but which also have a phytotoxicity-safening effect on crop plants, e.g. (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-chloro-o-tolyloxy)acetic acid (MCPA), 4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 3,6-dichloro-2-methoxybenzoic acid 1-(ethoxycarbonyl)ethyl (lactidichlor-ethyl).

[0044] Preferred safeners are: cloquintocet-mexyl, cyprosulfamide, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumyluron.

[0045] Particularly preferred safeners are: cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.

[0046] Very particularly preferred is mefenpyr-diethyl.

[0047] AS / ha: When the abbreviation "AS / ha" is used herein, it means "active substance per hectare" based on 100% active ingredient. All percentages herein are weight percent (abbreviation: "wt. %) and refer to the relative weight of each component based on the total weight of the herbicidal mixture / composition (e.g., as a formulation), unless otherwise defined.

[0048] The herbicidal compositions according to the invention can also be used to control harmful plants in crops of known or yet to be developed genetically modified plants.

[0049] Generally, transgenic plants are characterized by certain advantageous properties, such as resistance to certain pest control agents, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other specific properties relate, for example, to the harvested material in terms of quantity, quality, storability, composition and specific components. For example, transgenic plants with high starch content or altered starch quality, or with different fatty acid composition in the harvested material, are known. Other specific properties can be resistance or tolerance to abiotic stress factors, such as heat, low temperature, drought, salinity and UV radiation.

[0050] Conventional methods for producing new plants with modified properties compared to existing plants consist, for example, of conventional breeding methods and the generation of mutants. Alternatively, new plants with modified properties can be generated using recombinant methods (see, for example, EP-A-0221044, EP-A-0131624). For example, the following have been described in several cases: - the genetic modification of crop plants with the aim of modifying the starch synthesised in the plants (for example WO92 / 11376, WO92 / 14827, WO91 / 19806), - transgenic crop plants which are resistant to certain herbicides of the glufosinate type (see, for example, EP-A-0242236, EP-A-242246) or of the glufosate type (WO 92 / 00377) or of the sulfonylurea type (EP-A-0257993, US-A-5013659), - transgenic crop plants, such as cotton (EP-A-0142924, EP-A-0193259), which have the ability to produce Bacillus thuringiensis toxins (Bt toxins) that render the plants resistant to certain pests; - transgenic crop plants with altered fatty acid composition (WO 91 / 13972), - genetically modified crop plants with novel compounds or secondary metabolites, e.g. novel phytoalexins that enhance disease resistance (EPA309862, EPA0464461); - genetically modified plants with reduced photorespiration that have higher yields and greater stress tolerance (EPA0305398); - transgenic crop plants producing proteins of pharmaceutical or diagnostic importance ("molecular pharming"); - transgenic crop plants characterized by higher yields or better quality, - transgenic crop plants featuring, for example, combinations of said novel traits ("gene stacking").

[0051] Numerous molecular biology techniques are known in principle that can be used to produce new transgenic plants with modified properties; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431.

[0052] For such genetic manipulation, nucleic acid molecules that allow sequence modification by mutagenesis or recombination of DNA sequences can be introduced into plasmids. Standard methods can be used, for example, to perform base exchanges, to remove parts of sequences, or to add natural or synthetic sequences. To link DNA fragments together, adapters or linkers can be added onto the fragments (see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker, "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd ed., 1996).

[0053] For example, the generation of plant cells with reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of said gene product.

[0054] For this purpose, it is possible to use, firstly, DNA molecules that contain the entire coding sequence of the gene product, including any flanking sequences that may be present, and DNA molecules that contain only parts of the coding sequence, in which case these parts must be long enough to have an antisense effect in cells.It is also possible to use DNA sequences that are highly homologous to the coding sequence of the gene product, but are not completely identical to them.

[0055] When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired compartment of plant cells.However, to achieve localization in a specific compartment, it is possible to, for example, link the coding region to a DNA sequence that ensures localization in a specific compartment.Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J.11 (1992), 3219-3227; Wolter et al., Proc.Natl.Acad.Sci.USA 85 (1988), 846-850; Sonnewald et al., Plant J.1 (1991), 95-106).Nucleic acid molecules can also be expressed in organelles of plant cells.

[0056] The transgenic plant cells can be regenerated by known techniques to give whole plants. In principle, the transgenic plants can be plants of any desired plant species, i.e., monocotyledonous as well as dicotyledonous plants.

[0057] In this way it is possible to obtain transgenic plants whose properties have been modified by overexpression, suppression or inhibition of a homologous (= natural) gene or gene sequence, or by the expression of a heterologous (= foreign) gene or gene sequence.

[0058] Preferably, the compositions according to the invention can also be used in transgenic crops which are resistant to growth regulators, such as dicamba, or herbicides which inhibit essential plant enzymes, such as acetolactate synthase (ALS), EPSP synthase, glutamine synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD), or herbicides from the groups of the sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and similar active compounds.

[0059] When the compositions according to the invention are used in transgenic crops, not only do the effects against harmful plants observed in other crops occur, but also effects specific to the application in the particular transgenic crop, such as a modified or specifically expanded spectrum of weeds that can be controlled, modified application rates that can be used for application, preferably good compatibility with herbicides to which the transgenic crop is tolerant, and effects on the growth and yield of the transgenic crop plants.

[0060] The present invention therefore also provides the use of a composition according to the invention for the control of harmful plants in transgenic crop plants.

[0061] The use of the compositions of the invention in economically important transgenic crops of useful and ornamental plants, such as cereals (e.g. wheat, barley, rye, oats), millet / sorghum, rice, cassava and maize, or sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable crops, especially maize, cotton and soybean, is preferred.

[0062] The present invention therefore also provides the use of a composition according to the invention for the control of harmful plants in transgenic crop plants or crop plants which have been rendered resistant by selective breeding.

[0063] Components A and B can be converted, together or separately, into customary formulations for application by misting, irrigation and spraying, for example solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, microencapsulation in polymeric substances, etc. The formulations can contain customary auxiliaries and additives.

[0064] These formulations are prepared in a known manner, for example by mixing components A and B with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally with the aid of surfactants, i.e. emulsifiers and / or dispersing agents and / or foaming agents.

[0065] When the extender used is water, it is also possible to use, for example, organic solvent as auxiliary solvent.Useful liquid solvents are essentially the following: aromatic compounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, such as mineral oil fractions, mineral oils and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulfoxide, and water.

[0066] Useful solid carriers include, for example, ammonium salts and ground natural minerals, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic rock powders, such as finely divided silica, alumina and silicates; useful solid carriers for granules include, for example, ground and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic ground matter, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stems; useful emulsifiers and / or foam formers include, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfates and protein hydrolysates; useful dispersants include, for example, lignosulfite waste liquor and methylcellulose.

[0067] Tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latex, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin, and synthetic phospholipids, can be used in the formulation. Further additives may be mineral and vegetable oils.

[0068] It is possible to use colorants, for example inorganic pigments such as iron oxide, titanium oxide and Prussian blue, as well as organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

[0069] In general, the formulation contains components A and B in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight.

[0070] Components A and B can also be used on their own or in their formulations, as mixtures with other active pesticide ingredients for controlling undesirable vegetation, e.g. for controlling weeds or for controlling undesirable crop plants, in which case, for example, finished formulations or tank mixes are possible.

[0071] Mixtures with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, bird feeding deterrents, plant nutrients and soil conditioners, and also with additives and formulation adjuvants which are likewise customary in crop protection, are also possible.

[0072] Components A and B can be used as such, in the form of their formulations, or in use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. Application is typically achieved, for example, by irrigation, sprinkling, spraying, broadcasting.

[0073] Components A and B can be applied to plants, plant parts or areas under cultivation (soil), preferably green plants and plant parts, and soil.One possible use is the application of active ingredients together in the form of tank mix, where optimally formulated concentrated preparations of the individual active ingredients are mixed together in a tank with water, and the resulting spray is developed.

[0074] For application, the commercial formulations are diluted, if appropriate, in a customary manner, for example with water in the case of wettable powders (dusts), emulsifiable concentrates, dispersions and water dispersible granules. Preparations in dust form, granules for soil application or granules for scattering and sprayable solutions are usually not further diluted with other inert substances before application.

[0075] Biological Examples: This study was conducted to investigate possible synergy between the herbicides cinmethylin and ethofumesate.

[0076] material and method The following plant species were selected for testing: [Table 1]

[0077] Seeds of the above biotypes were sown in 8 cm pots (LSI; pH 7.4; %C org 2.2). Temperature was kept at approximately 23°C / 15°C day / night. After herbicide application (300 l water / ha), pots were under-irrigated as required. Two trials were performed. In the pre-emergence trial, the herbicide was applied immediately after sowing at the BBCH00 growth stage. In the post-emergence trial, the herbicide was deployed at the BBCH11-12 growth stage.

[0078] The active herbicidal ingredient Cinmetin was used as the commercial emulsifiable concentrate (EC) LUMIMAX. Ethofumesate was used in the form of the commercial suspension concentrate (SC) Nortron. To ensure good retention properties, methylated seed oil (Mero) was added to the spray at a rate of 1 l / ha.

[0079] evaluation The percentage of weed control (two replicates) was rated 27 days after herbicide application (DAA) on a scale of 0 to 100, with a rating of 0 meaning no control and a rating of 100 meaning complete control.

[0080] Calculation of synergy by Colby According to Colby, synergy of the active herbicidal ingredients is indicated when the measured efficacy is higher than the expected efficacy, calculated by the formula for a two-substance mixture: EC=A+B-(AxB) / 100

[0081] Results and Conclusions Post-emergence testing According to Colby, the two-substance mixture of cinmethylin and ethofumesate showed synergistic effects against the weeds tested. In the case of Alomy, Lolli, Abuth and Matin, cinmethylin and ethofumesate had synergistic effects. [Table 2]

[0082] Pre-emergence testing According to Colby, the two-substance mixture of cinmethicillin and ethofumesate showed synergistic effects against the weeds tested. In the case of AVEFA, MATIN and VERPE, cinmethicillin and ethofumesate had synergistic effects. [Table 3]

Claims

1. A method for controlling harmful plants in a crop of useful plants, wherein a herbicidal composition containing as active herbicidal ingredients (A) simetryn, and (B) ethofumesate is applied to the harmful plants, plants, plant seeds, or the area where the plants grow.

2. A method for controlling harmful plants in a crop of useful plants, wherein a herbicidal composition containing as the only active herbicidal ingredients (A) simetryn, and (B) ethofumesate is applied to the harmful plants, plants, plant seeds, or the area where the plants grow.

3. A method for controlling harmful plants in a crop of useful plants, wherein a herbicidal composition containing as the only active herbicidal ingredients (A) simetryn, and (B) ethofumesate, and further (D) a phytotoxicity reducing agent is applied to the harmful plants, plants, plant seeds, or the area where the plants grow.

4. The herbicidal composition according to any one of claims 1 to 3, wherein the phytotoxicity reducing agent is isoxadifen-ethyl, cyprosulfamide, mefenpyr-diethyl or clomazone-methyl, including salts and hydrates.

5. The herbicidal composition according to claim 1, containing simetryn and ethofumesate in a weight ratio of 0.1 to 10.

6. The method according to claim 1, wherein the plants are from the group consisting of maize, cotton and soybean.

7. The method according to claim 1, wherein the plants are genetically modified.

8. The method according to claim 1, which is carried out by a pre-emergence or early post-emergence method.

9. The method according to claim 1, which is carried out for the control of HPPD-tolerant plants.

10. Use of the herbicidal composition according to claim 1 for the control of unwanted plants in a crop of useful plants.

11. The use according to claim 10, wherein the useful plants are from the group consisting of maize, cotton and soybean.

12. The use according to any one of claims 10 and 11, wherein simetryn is used at an application rate of 200 to 500 g / ha and ethofumesate is used at an application rate of 100 to 250 g / ha.