Herbicidal compositions

Abstract

The present invention provides compositions comprising compounds (A), (B) and (C), wherein (A) represents flumioxazin, (B) represents cinmethylin, and (C) represents a safener. The application further relates to a method and to the use of the herbicidal composition of the invention for controlling harmful plants or for regulating growth.

Description

[0001] Herbicidal compositions

[0002] Description

[0003] The invention lies in the technical field of crop protection products that can be used to counter unwanted plant growth on uncultivated land, for preparation of seed or in plant crops, and comprise a combination of at least two herbicides as herbicidally active compounds, wherein the compositions comprise herbicidally active compounds (A) and (B) and a safener (C), in which (A) represents the herbicide flumioxazin, (B) is cinmethylin, and (C) represents a safener selected from (Cl) mefenpyr-diethyl, and (C2) a compound of formula (I).

[0004] Compound A, i.e. flumioxazin, belongs to the herbicide class of inhibitors of the protoporphyrinogen IX oxidase (WSSA 14 / HRAC E). The compound is effective as herbicide against a broad spectrum of harmful plants when applied by the pre-emergence method or else by the post-emergence method, with the possibility of non-selective use for control of unwanted plant growth or selective use in plant crops.

[0005] Compound B, i.e. cinmethylin, belongs to the herbicide class of inhibitors of fatty acid thioesterases (WSSA 30 / HRAC Q). The compound is effective as herbicide against a broad spectrum of harmful plants when applied by the pre-emergence method or else by the post-emergence method, with the possibility of non-selective use for control of unwanted plant growth or selective use in plant crops.

[0006] Compound Cl, i.e. mefenpyr-diethyl, is a safener, in particular for cereals.

[0007] Compound C2 is a compound of formula (I) or an agronomically acceptable salt thereof wherein

[0008] (Ra)p-phenyl is selected from any one of the groups Q-l.l to Q-1.55

[0009] and (Rb)q-phenyl is selected from any one of the groups Q-2.1 to Q-2.55

[0010]

[0011] R‘ is hydrogen, and

[0012] Rdis hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, phenyl, benzyl,

[0013] CH2(4-Cl-Ph), CH2(4-F-Ph), CH2(4-OMe-Ph), 2-methoxyethyl, tetrahydrofuran-2- yl-methyl, tetrahydrofuran-3-yl-methyl, tetrahydropyran-2-yl-methyl, tetrahydropyran-3-yl-methyl, tetrahydropyran-4-yl-methyl, methylpropionat-3-yl, ethylpropionat-3-yl, methylacetat-2-yl, ethylacetat-2-yl, methylpivalat-2-yl, ethylpivalat-3-yl, methyl-2-methylpropanoat-3-yl, methyl-2,2-dimethylpropanoat- 3-yl, ethyl-2-methylpropanoat-3-yl, methyl-2-propanoat-2-yl, ethyl-2-propanoat-2- yl, methyl-acetat-2yl, ethyl-acetat-2yl, methyl- l-methylcyclopropancarboxylat-2yl, ethyl- 1 -methylcyclopropan-carboxylat-2yl, 2-(dimethylamino)ethyl, oxetan-3-yl, (3-methyloxetan-3-yl)methyl, 2,2,2-trifluorethyl, 2,2-difluorethyl, 2-fluorethyl,

[0014] 2.2.3.3.3-pentafluorpropyl, cyclopropylmethyl, 1-cyclopropyl-ethyl, (1-methyl- cyclopropyl)-methyl, (2,2-dichlorcyclopropyl)-methyl, (2,2-dimethyl-cyclopropyl)- methyl, allyl, propargyl (prop-2-in-l-yl), 2-chlorprop-2-en-l-yl, 3-phenylprop-2-in- 1-yl, 3,3-dichlorprop-2-en-l-yl, 3,3-dichlor-2-fluor-prop-2-en-l-yl, methylprop-2- in-l-yl, 2-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-l-yl, but-2-in-l-yl, but-3- in-l-yl, 4-chlor-but-2-in-l-yl, 3-methyl-but-2-en-l-yl, 3-methyl-but-l-en-l-yl, 1- (2e)-l-methylbut-2-en-l-yl, (e)-pent-3-en-2-yl or (z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, iso-butyl,

[0015] 1.3-dioxolan-2-ylmethyl or 1 -ethyl-5 -methyl- lh-pyrazol-4-methyl.

[0016] Preferably, C2 is selected from:

[0017] Methyl- { [1 ,5-bis(4-chloro-2-fluoorphenyl)- 1H- 1 ,2,4-triazol-3-yl]oxy } acetate

[0018]

[0019] { [ 1 ,5-Bis(4-chloro-2-fluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetic acid

[0020] Methyl- { [5-(4-chloro-2-fluorophenyl)- 1 -(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetate

[0021] { [5-(4-Chloro-2-fluorophenyl)- 1 -(2,4-difluorophenyl)-lH- 1 ,2,4-triazole-3-yl]oxy } acetic acid Methyl- { [1 -(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetate

[0022] {[l-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-lH-l,2,4-triazole-3-yl]oxy}acetic acid Methyl- { [5-(4-bromo-2-fluorophenyl)- 1 -(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetate

[0023] { [5-(4-Bromo-2-fluorophenyl)- 1 -(2,4-difluorophenyl)- 1 H- 1 ,2,4-triazole-3-yl]oxy } acetic acid Methoxyethyl- { [ 1 -(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetate

[0024] { [1 -(4-Bromo-2-fhiorophenyl)-5-(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetic acid

[0025] The compounds of formula (I) are known from international application PCT / EP2020 / 083167 (W02021 / 105101) and can be synthesized according to the processes described therein.

[0026] The efficacy of the herbicides in combination against harmful plants is at a high level, but generally depends on the application rate, the form of the respective preparation, the spectrum of harmful plants, the harmful plants to be controlled in each case, climate and soil conditions, etc. A further criterion is the duration of action or the rate of degradation of the herbicide. Other considerations, as the case may be, are changes in the susceptibility of harmful plants which may occur on prolonged use of the herbicides or in a geographically restricted manner. Compensation for losses in action in the case of individual plants by higher application rates of the herbicides is only possible to a limited degree, for example because this frequently worsens the selectivity of the herbicides or because there is no improvement in action, even in the case of a higher application rate. There is generally a need for methods of achieving herbicidal action with a lower application rate of active ingredients. A lower application rate not only reduces the amount of active ingredient required for the application but generally also reduces the amount of formulation auxiliaries needed. Both reduce economic expenditure and improve the environmental compatibility of the herbicide treatment. One way of improving the application profile of a herbicide may be to combine the active ingredient with one or more other active ingredients which contribute to the desired additional properties. However, in the case of combined application of two or more active ingredients, it is not uncommon for there to be phenomena of physical and biological incompatibility, for example lack of stability in a coformulation, decomposition of an active ingredient and / or antagonism of the active ingredients. What are desired, by contrast, are combinations of active ingredients having a favourable profile of activity, high stability and ideally an unexpectedly synergistically enhanced activity which allows the application rate to be reduced compared to the individual application of the active ingredients to be combined.

[0027] It is an object of the present invention to provide alternative or advantageous herbicidal compositions that have a good profile of biological use and have as many as possible of the abovementioned desirable favourable properties.

[0028] It has now been found that, surprisingly, this object is achieved by using a composition comprising herbicidally active compounds (A) and (B) as well as a safener (C), in which (A) represents the herbicide flumioxazin and (B) represents the herbicide cinmethylin, and (C) represents a safener selected from (Cl) mefenpyr-diethyl, and (C2) a compound of formula (I).

[0029] The compositions of the invention interact in a particularly favourable manner, for example when they are used to control unwanted plant growth in crop plants such as wheat (hard and soft wheat), maize, soya, sugarbeet, sugarcane, cotton, rice, beans (for example, bush beans and broad beans), flax, barley, oats, rye, triticale, potato and millet / sorghum, uncultivated land, pastureland and areas of grass / lawn and plantation crops. In particular useful are these combinations on cereal crops.

[0030] The compositions of the invention may contain further components, for example other active ingredients to counter harmful organisms such as harmful plants, plant-damaging animals or plant-damaging fungi, especially active ingredients from the group of the herbicides, fungicides, insecticides, acaricides, nematicides and miticides, and related substances, or else other kinds of active ingredients for crop protection (e.g. resistance inductors), crop plant-protecting active ingredients (safeners, antidotes), plant growth regulators, and / or additions and / or formulation auxiliaries that are customary in crop protection. The components may be formulated together here (ready-to-use formulation) and employed as such, or they may be formulated separately and employed together, for example in a tankmix or in sequential application.

[0031] An advantageous property of the inventive combination of herbicides (A) and (B) is found to be that active ingredients (A) and (B) are compatible with one another, meaning that they can be employed together without occurrence of significant chemical incompatibility between the active ingredients (A) and / or (B) that leads to destruction of one or more active ingredients. This avoids any reduction in the active ingredient content in formulations or spray liquors. The favourable compatibility also extends to the biological properties of the active ingredients on combined use. For instance, antagonistic effects are generally not observed in the case of control of harmful plants with the active ingredient combinations of the invention. The active ingredients (A) and (B) are thus particularly suitable for employment together with or in addition to further active ingredients for crop protection or agrochemicals. The combined application enabled permits the utilization of advantageous effects, for example the broadening of the spectrum of harmful plants to be controlled on application, or the reduction of the application rate of the individual herbicides (A) or (B) compared to the respective application rate of the herbicide in question in the case of individual application. It is thus possible to influence the degradation characteristics of the active ingredients and to achieve more favourable conditions for the subsequent growing of crop plants. A further advantage is considered to be that the development of resistances of the harmful plants to the active ingredients can often be significantly reduced or avoided through the combination of active ingredients having different mechanisms of action.

[0032] More particularly, superadditive (= synergistic) effects surprisingly occur in the case of combined use of active ingredients (A) and (B) for a greater number of economically important harmful plants. The activity in the combination is higher here than the expected sum of the activities of the individual herbicides used. The synergistic effects allow the application rate to be reduced further, a broader spectrum of broadleaved weeds and weed grasses to be controlled, a more rapid onset of the herbicidal action, longer persistence, better control of the harmful plants with only one or a few applications, and extension of the application period possible. To some extent, the use of the products also reduces the amount of harmful ingredients, such as nitrogen or oleic acid, and their introduction into the soil.

[0033] Said properties and advantages are desirable in practical weed control in order to keep agricultural crops clear of unwanted competing plants and hence to ensure and / or increase the yields in terms of quality and quantity. The technical standard is clearly surpassed by the novel combinations with regard to the properties described.

[0034] The synergistic effects are observed in the case of joint deployment of active ingredients (A) and (B) but can also frequently occur in the case of offset application (splitting). It is also possible to apply the herbicides (A) or (B) or the herbicidal composition (A) and (B) in multiple portions (sequential application). For example, one or more pre-emergence applications may be followed by a postemergence application, or an early post-emergence application may be followed by a moderately late or late post-emergence application. Preference is given to the simultaneous or immediately successive application of the active ingredients of the respective combination, if appropriate in several portions. But application of the individual active ingredients of a combination at different times is also possible and may be advantageous in the individual case. It is also possible to integrate other crop protection products into the system for application, for example the other active ingredients mentioned (other herbicides, fungicides, insecticides, acaricides etc.) and / or various auxiliaries, adjuvants and / or applications of fertilizer.

[0035] The compositions according to the present invention furthermore comprise a safener. Surprisingly, it has been found that certain compositions of the herbicidal mixture exhibit improved crop compatibility, i.e. low crop injury, in particular in cereals such as wheat or barley, especially cereal crops such as winter wheat and winter barley.

[0036] Application by the pre-emergence method or by the post-emergence method, according to the context in which the terms are used, is respectively understood to mean the application of the active ingredients before and after the visible appearance of the harmful plants above the ground, or the use of the active ingredients against the harmful plants before emergence of the crop plants and after emergence of the crop plants.

[0037] According to the invention, herbicidal compositions comprising active ingredient components (A) and (B), as defined above, in a weight ratio of 100:1 to 1:100, preferably 50:1 to 1:50, further preferably 30:1 to 1:30 can be employed.

[0038] The safener (C) can be employed in a weight ratio to the mixture of herbicides (A)+(B) of 100: 1 to 1:100, preferably 50:1 to 1:50, further preferably 30:1 to 1:30.

[0039] The combination according to the invention can be used for or applied to many crop plants, preferably cereals (e.g. in wheat and barley).

[0040] The application rates (indicated as g / ha i.e. grams of active ingredient per hectare), of the herbicide combination are as defined as follows:

[0041] Flumioxazin may be applied at a ratio of between 10 and 200 g ai / ha, preferably between 20 and 100 g ai / ha, more preferably between 30 and 60 g ai / ha.

[0042] Cinmethylin may be applied at a ratio of between 100 and 1000 g ai / ha, preferably between 150 and 800 g ai / ha, more preferably between 200 and 600 g ai / ha.

[0043] The safener (compound C) may be applied at a ratio of between 25 and 4000 g ai / ha, preferably between 50 and 1800 g ai / ha, more preferably between 100 and 1200 g ai / ha. The composition according to the invention may be used in the form of a concentrated formulation or a ready-to-use diluted spray application mixture (tank-mix).

[0044] A further aspect relates to a method of controlling weed plants in crops of useful plants, characterized in that a composition according to the invention is applied to the weed plants, plants, plant seeds, or to the area on which the weed plants are growing.

[0045] The compounds of the composition may be applied jointly or separately by the pre-emergence method, the post-emergence method or by the pre- and post-emergence method to the plants, plant parts, plant seeds or the area under cultivation.

[0046] The crop plants are preferably cereal crops.

[0047] Furthermore, the combinations of the invention can be used together with other active ingredients such as the active ingredients mentioned (herbicides, fungicides, insecticides, acaricides etc.) and / or plant growth regulators or auxiliaries from the group of additives customary in crop protection, such as adjuvants and formulation aids. The combination of the active crop protection ingredients comprising the active ingredients (A), (B) and (C) and optionally further active ingredients are referred to here as “herbicide combination” for short. Their use forms such as formulations or tankmixes are herbicidal products (compositions).

[0048] The invention therefore also provides the herbicidal products comprising the active ingredient combinations of the invention with additives customary in crop protection, such as adjuvants and formulation aids, and optionally further active crop protection ingredients.

[0049] The invention also provides for the use of, or the application method using, the active ingredient combinations of the invention as herbicides and plant growth regulators, preferably as herbicides and plant growth regulators having a synergistically active content of the respective active ingredient combination present.

[0050] In the mixtures of the invention, in the context of the application rates mentioned, required application rates of the respective active ingredient are generally lower compared to individual application.

[0051] The herbicidal compositions of the invention can also be combined with further herbicides and plant growth regulators, for example to supplement the activity spectrum. Combination partners usable for the compounds according to the invention in mixed formulations or in a tankmix are, for example, known active ingredients based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p- hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as known, for example, from Weed Research 26 (1986) 441-445 or “The Pesticide Manual”, 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006, the corresponding “e -Pesticide Manual Version 4 (2006)”, and literature cited therein. Further trade names and “common names” are listed in the “Compendium of Pesticide Common Names” (available on the Internet under http: / / www.alanwood.net / pesticides).

[0052] Examples of known herbicides which can be combined with the compounds of the invention include the active ingredients which follow (N.B.: the compounds are designated either by the common name according to the International Organization for Standardization (ISO) or by the chemical name, in some cases together with a standard code number) and always encompass all use forms, such as acids, salts, esters and isomers, such as stereoisomers and optical isomers.

[0053] The list includes one, and in some cases, also more than one herbicide selected from: acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, aminopyralid- dimethylammonium, aminopyralid- tripromine, amitrole, ammoniumsulfamate, anilofos, asulam, asulam-potassium, asulam sodium, atrazine, azafenidin, azimsulfuron, beflubutamid, (S)-(-)- beflubutamid, beflubutamid-M, benazolin, benazolin-ethyl, benazolin-dimethylammonium, benazolin- potassium, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, bentazone- sodium, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bipyrazone, bispyribac, bispyribac-sodium, bixlozone, broclozone, bromacil, bromacil-lithium, bromacil-sodium, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate und -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, cambendichlor, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chloramben-ammonium, chloramben-diolamine, chlroamben-methyl, chloramben-methylammonium, chloramben-sodium, chlorbromuron, chlorfenac, chlorfenac-ammonium, chlorfenac-sodium, chlorfenprop, chlorfenpropmethyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, cinidon, cinidon-ethyl, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-ethyl, clodinafop- propargyl, clomazone, clomeprop, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid- potassium, clopyralid-tripomine, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D (including thea mmonium, butotyl, -butyl, choline, diethylammonium, - dimethylammonium, -diolamine, -doboxyl, -dodecylammonium, etexyl, ethyl, 2-ethylhexyl, heptylammonium, isobutyl, isooctyl, isopropyl, isopropylammonium, lithium, meptyl, methyl, potassium, tetradecylammonium, triethylammonium, triisopropanolammonium, tripromine and trolamine salt thereof), 2,4-DB, 2,4-DB-butyl, -dimethylammonium, isooctyl, -potassium und -sodium, daimuron (dymron), dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium, n-decanol, 7-deoxy-D-sedoheptulose, desmedipham, detosyl-pyrazolate (DTP), dicamba and its salts, e. g. dicamba-biproamine, dicamba-N,N-Bis(3-aminopropyl)methylamine, dicamba-butotyl, dicamba-choline, dicamba-digly colamine, dicamba-dimethylammonium, dicamba- diethanolamine ammonium, dicamba-diethylammonium, dicamba-isopropylammonium, dicamba- methyl, dicamba-monoethanolamine, dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba- triethanolamine, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl- 1 ,2-oxazolidin-3-one, 2-(2,5- dichlorobenzyl)-4,4-dimethyl- 1 ,2-oxazolidin-3-one, dichlorprop, dichlorprop-butotyl, dichlorpropdimethylammonium, dichhlorprop-etexyl, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-potassium, dichlorprop-sodium, dichlorprop-P, dichlorprop-P- dimethylammonium, dichlorprop-P-etexyl, dichlorprop-P-potassium, dichlorprop-sodium, diclofop, diclofop-methyl, diclofop-P, diclofop-P-methyl, diclosulam, difenzoquat, difenzoquat-metilsulfate, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, dinoterb-acetate, diphenamid, diquat, diquat-dibromid, diquat-dichloride, dithiopyr, diuron, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, endothal, endothal-diammonium, endothal- dipotassium, endothal-disodium, Epyrifenacil (S-3100), EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-5231, i.e. N-[2-Chlor-4-fhior-5-[4-(3-fluorpropyl)-4,5-dihydro-5-oxo- IH-tetrazol-l-yl] -phenyl] -ethansulfonamid, F-7967, i.e. 3-[7-Chlor-5-fhior-2-(trifhrormethyl)-lH- benzimidazol-4-yl]-l-methyl-6-(trifluormethyl)pyrimidin-2,4(lH,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flamprop, flamprop-isoproyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop, fluazifop-butyl, fluazifop- methyl, fluazifop-P, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flufenoximacil, flumetsulam, flumiclorac, flumiclorac-pentyl, fluometuron, flurenol, flurenol-butyl, -dimethylammonium und -methyl, fluoroglycofen, fluoroglycofen- ethyl, flupropanate, flupropanate-sdium, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron-methyl- sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, foramsulfuron sodium salt, fosamine, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-sodium, L-glufosinate- ammonium, L-glufosiante-sodium, glufosinate-P-sodium, glufosinate-P-ammonium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, - sodium, sesquisodium and -trimesium, H-9201, i.e. O-(2,4-Dimethyl-6-nitrophenyl)-O-ethyl- isopropylphosphoramidothioat, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron- methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, haloxifop-sodium, hexazinone, HNPC-A8169, i.e. prop-2-yn-l-yl (2S)-2-{3-[(5- tert-butylpyridin-2-yl)oxy]phenoxy}propanoate, HW-02, i.e. l-(Dimethoxyphosphoryl)-ethyl-(2,4- dichlorphenoxy)acetat, hydantocidin, icafolin, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazaquin.methyl, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium, ioxynil, ioxynil-lithium, -octanoate, -potassium und sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, i.e. 3-({[5-(Difhrormethyl)-l-methyl-3-(trifhrormethyl)- lH-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-l,2-oxazol, ketospiradox, ketospiradox- potassium, lactofen, lancotrione, lenacil, linuron, MCPA, MCPA-butotyl, -butyl, -dimethylammonium, - diolamine, -2-ethylhexyl, -ethyl, -isobutyl, isoctyl, -isopropyl, -isopropylammonium, -methyl, olamine, - potassium, -sodium and -trolamine, MCPB, MCPB -methyl, -ethyl und -sodium, mecoprop, mecoprop- butotyl, mecoprop- demethylammonium, mecoprop-diolamine, mecoprop-etexyl, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium, and mecoprop-trolamine, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mefluidide-diolamine, mefluidide-potassium, mesotrione, mesosulfuron-methyl , methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron-methyl, MT-5950, i.e. N-[3-chlor-4-(l- methylethyl)-phenyl]-2-methylpentanamid, NGGC-011, napropamide, NC-310, i.e. 4-(2,4- Dichlorbenzoyl)-l-methyl-5-benzyloxypyrazol, NC-656, i.e. 3-[(isopropylsulfonyl)methyl]-N-(5- methyl-l,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[l,2,4]triazolo[4,3-a]pyridine-8-carboxamide, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, paraquat-dichloride, paraquat-dimethylsulfate, pebulate, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils, phenmedipham-ethyl, phenmedipham, picloram, picloram- dimethylammonium, picloram-etexyl, picloram-isoctyl, picloram-methyl, picloram-olamine, picloram- potassium, picloram-triethylammonium, picloram- tripromine, picloram- trolamine, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinclorac- dimethylammonium, quinclorac-methyl, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, QYM201, i.e. l-{2-chloro-3-[(3-cyclopropyl-5- hydroxy- 1 -methyl- 1 H-pyrazol-4-yl)carbonyl] -6-(trifluoromethyl)phenyl }piperidin-2-one, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, , SYP-249, i.e. l-Ethoxy-3-methyl-l-oxobut-3-en-2-yl-5-[2-chlor- 4-(trifluormethyl)phenoxy]-2-nitrobenzoat, SYP-300, i.e. l-[7-Fluor-3-oxo-4-(prop-2-in-l-yl)-3,4- dihydro-2H-l,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidin-4,5-dion, 2,3,6-TBA, TCA (trichloro acetic acid) and its salts, e.g. TCA-ammonium, TCA-calcium, TCA-ethyl, TCA-magnesium, TCA- sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thaxtomin, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-choline, triclopyr-ethyl, triclopyr-triethylammonium, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron- methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e. 3,4-Dichlor-N-{2-[(4,6- dimethoxypyrimidin-2-yl)oxy]benzyl} anilin, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3 , 6-dihydropyrimidin- 1 (2H) -yl)phenyl) -5 -methyl-4,5 -dihydroisoxazole-5 -carboxylic acid ethyl ester, ethyl-[(3-{2-chlor-4-fluor-5-[3-methyl-2,6-dioxo-4-(trifluormethyl)-3,6- dihydropyrimidin- 1 (2H)-yl]phenoxy }pyridin-2-yl)oxy] acetate, 3-chloro-2-[3- (difluoromethyl)isoxazolyl-5-yl]phenyl-5-chloropyrimidin-2-yl ether, 2-(3,4-dimethoxyphenyl)-4-[(2- hydroxy-6-oxocyclohex- 1 -en- 1 -yl)carbonyl] -6-methylpyridazine-3(2H)-one, 2-({ 2-[(2- methoxyethoxy)methyl]-6-methylpyridin-3-yl}carbonyl)cyclohexane-l, 3-dione, (5 -hydroxy- 1-methyl- lH-pyrazol-4-yl)(3,3,4-trimethyl- 1 , 1 -dioxido-2,3-dihydro- 1 -benzothiophen-5-yl)methanone, 1 -methyl- 4- [(3 ,3 ,4-trimethyl- 1 , 1 -dioxido-2,3-dihydro- 1 -benzothiophen-5-yl)carbonyl] - 1 H-pyrazol-5-yl propane - 1 -sulfonate, 4- { 2-chloro-3- [(3 ,5-dimethyl- 1 H-pyrazol- 1 -yl)methyl] -4-(methylsulfonyl)benzoyl } - 1 - methyl-lH-pyrazol-5-yl-l,3-dimethyl-lH-pyrazole-4-carboxylate; cyanomethyl 4-amino-3-chloro-5- fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2-carboxylate, prop-2-yn-l-yl 4-amino-3-chloro-5-fluoro-6- (7-fhroro-lH-indol-6-yl)pyridine-2-carboxylate, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH- indol-6-yl)pyridine-2-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2- carboxylic acid, benzyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2-carboxylate, ethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2-carboxylate, methyl 4-amino-3- chloro-5-fluoro-6-(7 -fluoro- 1 -isobutyryl- 1 H-indol-6-yl)pyridine-2-carboxylate, methyl 6-( 1 -acetyl-7 - fluoro-lH-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate, methyl 4-amino-3-chloro-6-[l- (2,2-dimethylpropanoyl)-7-fluoro-lH-indol-6-yl]-5-fluoropyridine-2-carboxylate, methyl 4-amino-3- chloro-5-fhioro-6-[7-fhioro-l-(methoxyacetyl)-lH-indol-6-yl]pyridine-2-carboxylate, potassium 4- amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2-carboxylate, sodium 4-amino-3-chloro-5- fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2-carboxylate, butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro- lH-indol-6-yl)pyridine-2-carboxylate, 4-hydroxy-l-methyl-3-[4-(trifluoromethyl)pyridin-2- yl]imidazolidin-2-one, 3-(5-tert-butyl-l,2-oxazol-3-yl)-4-hydroxy-l-methylimidazolidin-2-one, 3-[5- chloro-4-(trifluormethyl)pyridin-2-yl] -4-hydroxy- 1 -methylimidazolidin-2-one, 4-hydroxy- 1 -methoxy-5- methyl-3- [4-(trifluormethyl)pyridin-2-yl] imidazolidin-2-one, 6- [(2-hydroxy-6-oxocyclohex- 1 -en- 1 - yl)carbonyl]-l,5-dimethyl-3-(2-methylphenyl)quinazolin-2,4(lH,3H)-dione, 3-(2,6-dimethylphenyl)-6- [(2-hydroxy-6-oxocyclohex- 1 -en- 1 -yl)carbonyl] - 1 -methylquinazolin-2,4( 1 H,3H)-dione, 2- [2-chloro-4- (methylsulfonyl)-3-(morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohex-2-en-l-one, l-(2- carboxyethyl)-4-(pyrimidin-2-yl)pyridazin-l-ium salt (with anions such as chloride, acetate or trifluoroacetate), l-(2-carboxyethyl)-4-(pyridazin-3-yl)pyridazin-l-ium salt (with anions such as chloride, acetate or trifluoroacetate), 4-(pyrimidin-2-yl)-l-(2-sulfoethyl)pyridazin-l-ium salt (with anions such as chloride, acetate or trifluoroacetate), 4-(pyridazin-3-yl)-l-(2-sulfoethyl)pyridazin-l-ium salt (with anions such as chloride, acetate or trifluoroacetate), l-(2-Carboxyethyl)-4-(l,3-thiazol-2- yl)pyridazin-l-ium salt (with anions such as chloride, acetate or trifluoroacetate), l-(2-Carboxyethyl)-4- (l,3-thiazol-2-yl)pyridazin-l-ium salt (with anions such as chloride, acetate or trifluoroacetate).

[0054] If the respective common name encompasses more than one form of the active ingredient, the name preferably defines the commercially available form.

[0055] The combinations can be applied both by the pre-emergence method and by the post-emergence method. This applies both to pre- and post-emergence with respect to the harmful plants and, in the case of selective control of the harmful plants, to pre- or post-emergence of the crop plants. Mixed forms are also possible, for example control of the harmful plants at their pre- or post-emergence stage after emergence of the crop plants.

[0056] For application, the active ingredient combinations can be deployed onto the plants (e.g. harmful plants such as mono- or dicotyledonous weeds or unwanted crop plants), the seed (e.g. grains, seeds or vegetative propagation organs such as tubers or parts of shoots having buds), or the area in which the plants grow (e.g. the growing area).

[0057] The substances can be deployed prior to sowing (if appropriate also by incorporation into the soil), prior to emergence or after emergence. Preference is given to use by the early post-seeding pre-emergence method or by the post-emergence method in plantation crops against harmful plants that have not yet emerged or have already emerged. The application can also be integrated into weed management systems with divided repeated applications (sequential). The herbicide combination(s) / composition(s) according to the present invention have an outstanding herbicidal activity against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous harmful plants.

[0058] Specifically, examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the herbicide combination / composition according to the present invention, without the enumeration being a restriction to certain species.

[0059] In the context of the present text, reference may be made to growth stages according to the BBCH monograph “Growth stages of mono-and dicotyledonous plants", 2nd edition, 2001, ed. Uwe Meier, Federal Biological Research Centre for Agriculture and Forestry (Biologische Bundesanstalt fur Land und Forstwirtschaft).

[0060] Examples of monocotyledonous harmful plants on which the herbicide combination / composition according to the present invention act efficiently are from amongst the genera Hordeum spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp., Eriochloa spp., Setaria spp., Pennisetum spp., Phalaris sp., Eleusine spp., Eragrostis spp., Panicum spp., Lolium spp., Alopecurus sp., Apera sp. Brachiaria spp., Leptochloa spp., Avena spp., Cyperus spp., Axonopris spp., Sorghum spp., and Melinus spp..

[0061] Particular examples of monocotyledonous harmful plants species on which the herbicide combination / composition according to the present invention act efficiently are selected from amongst the species Hordeum murinum, Echinochloa crus-galli, Poa annua, Bromus rubens L., Bromus rigidus, Bromus secalinus L., Digitaria insularis, Digitaria sanguinalis, Eriochloa gracilis, Setaria faberi, Setaria viridis, Pennisetum glaucum, Eleusine indica, Eragrostis pectinacea, Panicum miliaceum, Phalaris minor, Lolium multiflorum, Lolium rigidum, Lolium perenne, Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus compressus, Cyperus esculentes, Axonopris offinis, Sorghum halapense, Alopecurus myosuroides, Apera spica- venti and Melinus repens.

[0062] Examples of dicotyledonous harmful plants on which the herbicide combination / composition according to the present invention act efficiently are from amongst the genera Amaranthus spp., Polygonum spp., Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp., Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp., Erodium spp., Erigeron spp., Senecio spp., Lamium spp., Kochia spp., Chenopodium spp., Lactuca spp., Malva spp., Ipomoea spp., Brassica spp., Sinapis spp., Urtica spp., Sida spp, Portulaca spp., Richardia spp., Ambrosia spp., Calandrinia spp., Sisymbrium spp., Sesbania spp., Capsella spp., Sonchus spp., Euphorbia spp., Helianthus spp., Coronopus spp., Salsola spp., Abutilon spp., Vicia spp., Epilobium spp., Cardamine spp., Pieris spp., Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria spp., Plantago spp., Tribulus spp., Cenchrus spp. Bidens spp., Veronica spp., and Hypochaeris spp.. Particular examples of dicotyledonous harmful plants species on which the herbicide combination / composition according to the present invention act efficiently are selected from amongst the species Amaranthus spinosus, Amaranthus palmer, Amaranthis rudis, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum offi cinale, Oenothera laciniata, Amsinckia intermedia, Erodium cicutarium, Erodium moschatum, Erigeron bonariensis, Senecio vulgaris, Lamium sp., Erigeron canadensis, Polygonum aviculare, Kochia scoparia, Chenopodium album, Lactuca serriola, Malva parviflora, Malva neglecta, Ipomoea hederacea, Ipomoea lacunose, Brassica nigra, Sinapis arvensis, Urtica dioica, Amaranthus blitoides, Amaranthus retroflexus, Amaranthus hybridus, Amaranthus lividus, Sida spinosa, Portulaca oleracea, Richardia scabra, Ambrosia artemisiifolia, Calandrinia caulescens, Sisymbrium irio, Sesbania exaltata, Capsella bursa-pastoris, Sonchus oleraceus, Euphorbia maculate, Helianthus annuus, Coronopus didymus, Salsola tragus, Abutilon theophrasti, Vicia benghalensis L., Epilobium paniculatum, Cardamine spp, Pieris echioides, Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Matricaria chamomilla, Plantago spp., Tribulus terrestris, Salsola kali, Cenchrus spp., Bidens bipinnata, Veronica sp., Galium aparine L., Papaver rhoeas, Viola arvense, Geranium, sp., Centaurea cyanus and Hypochaeris radicata.

[0063] If the active ingredient combinations of the invention are applied to the soil surface before germination, either the emergence of the weed seedlings is prevented completely or the weeds grow until they have reached the cotyledon stage, but then stop growing and ultimately die completely after three to four weeks have passed.

[0064] If the active ingredients are applied post-emergence to the green parts of the plants, growth stops after the treatment, and the harmful plants remain at the growth stage at the time of application, or they die completely after a certain time, and so this eliminates competition by the weeds, which is harmful to the crop plants, very early and in a sustained manner.

[0065] The herbicidal products of the invention are notable for a rapid onset and long duration of herbicidal action. In general, the rainfastness of the active ingredients in the combinations of the invention is favourable. A particular advantage is that the effective dosages of compounds (A), (B) and (C) that are used in the combinations can be adjusted to such a low level that their soil action is optimally low. Therefore, the use thereof in sensitive crops is not just enabled, but groundwater contamination is also virtually prevented. The inventive combination of active ingredients allows the required application rate of the active ingredients to be reduced considerably. The combined use of (A), (B) and (C) achieves performance properties extending beyond what was to be expected on account of the known properties of the individual herbicides and safeners for the combination thereof. For example, the herbicidal effects for a particular harmful plant species exceed the expected value as can be estimated by standard methods, for example according to Colby or other extrapolation methods.

[0066] A synergistic effect exists whenever the effect, the herbicidal effect here, of the active ingredient combination is greater than the sum total of the effects of the active ingredients applied individually. The expected activity for a given combination of two active ingredients can be calculated according to S.R. Colby (“Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds 15 (1967), 20-22) (see below).

[0067] The synergistic effects therefore permit, for example, a reduction in the application rates of the individual active ingredients, a higher efficacy at the same application rate, the control of species of harmful plants which are as yet uncovered (gaps), elevated residual action, an extended period of efficacy, an elevated speed of action, an extension of the period of application and / or a reduction in the number of individual applications required and - as a result for the user - weed control systems which are more advantageous economically and ecologically.

[0068] The active ingredient combinations of the invention can preferably be used as herbicides in crops of useful plants that are resistant, or have been made resistant by genetic engineering, to the phytotoxic effects of the herbicides. The active ingredient combinations of the invention can preferably also be used in transgenic crops that are resistant to protoporphyrinogen oxidase (PPO) inhibitors and which are further resistant (a) to one or more growth regulators, for example dicamba, or (b) to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS), hydroxyphenyl-pyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, the glyphosates, glufosinates or benzoylisoxazoles and analogous active ingredients.

[0069] The invention therefore also provides a method of controlling unwanted plant growth, optionally in crops of useful plants, preferably on uncultivated land or in plantation crops, characterized in that herbicide (A) is applied with herbicide (B) to the harmful plants, parts of plants or plant seeds (seed) or to the growing area, combined with the safener (C).

[0070] The invention also provides for the use of novel combinations of compounds (A)+(B)+(C) for control of harmful plants, optionally in crops of useful plants, preferably on uncultivated land and plantation crops, but also for control of harmful plants before the sowing of the subsequent useful plant, such as, in particular, for preparation for seeding ("burn-down application"). The active ingredient combinations of the invention may either take the form of mixed formulations of the two components, if appropriate with further active ingredients, additives and / or customary formulation auxiliaries, which are then applied in a customary manner diluted with water or can be prepared as what are called tankmixes by joint dilution of the separately formulated or partially separately formulated components with water.

[0071] The compounds (A), (B) and (C) or their combinations can be formulated in various ways according to which biological and / or physicochemical parameters are required. Examples of general formulation options are: wettable powders (WP), water-soluble powders (SP), emulsifiable concentrates (EC), water- soluble concentrates, aqueous solutions (SL), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, dispersions based on oil or water, oil dispersions (OD), suspoemulsions, suspension concentrates (SC), oil-miscible solutions, capsule suspensions (CS), dusting products (DP), dressings, granules for soil application or scattering, granules (GR) in the form of microgranules, spray granules, absorption and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules or waxes.

[0072] The invention therefore also provides herbicidal and plant-growth-regulating compositions containing the active ingredient combinations of the invention.

[0073] The individual formulation types are known in principle and are described, for example, in: Winnacker- Kuchler, "Chemische Technologic” [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th ed. 1986; van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973, K. Martens, "Spray Drying" Handbook", 3rd ed. 1979, G. Goodwin Ltd. London.

[0074] The necessary formulation auxiliaries such as inert materials, surfactants, solvents and further additives are likewise known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964, Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte" ["Interface-active Ethylene Oxide Adducts"], Wiss. Verlagsgesellschaft, Stuttgart 1976, Winnacker-Kuchler, "Chemische Technologic", Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

[0075] On the basis of these formulations, it is also possible to produce combinations with other pesticidally active substances, such as other herbicides, fungicides, insecticides or other pesticides (for example acaricides, nematicides, molluscicides, rodenticides, aphicides, avicides, larvicides, ovicides, bactericides, viricides etc.), and also with safeners, fertilizers and / or growth regulators, for example in the form of a finished formulation or as a tank mix.

[0076] Wettable powders are preparations which can be dispersed uniformly in water and, in addition to the active ingredient, apart from a diluent or inert substance, also comprise surfactants of the ionic and / or nonionic type (wetting agents, dispersants), for example poly oxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'- disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurate. To produce the wettable powders, the active herbicidal ingredients are finely ground, for example in customary apparatuses such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.

[0077] Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are: calcium alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or for example polyoxyethylene sorbitan fatty acid esters.

[0078] Dusting products are obtained by grinding the active ingredient with finely distributed solids, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates may be water- or oil-based. They may be produced, for example, by wetgrinding by means of commercial bead mills and optional addition of surfactants as already listed above, for example, for the other formulation types.

[0079] Emulsions, for example oil-in-water emulsions (EW), can be produced, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants as already listed above, for example, for the other formulation types.

[0080] Granules can be produced either by spraying the active ingredient onto granular inert material capable of adsorption or by applying active ingredient concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium poly acrylate or else mineral oils. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers. Water-dispersible granules are produced generally by processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

[0081] The agrochemical preparations generally contain 0.1 to 99 per cent by weight, especially 0.2% to 95% by weight, of active ingredients of types (A), (B) and (C), the following concentrations being customary, depending on the type of formulation:

[0082] In wettable powders, the active ingredient concentration is, for example, about 10% to 95% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In the case of emulsifiable concentrates, the active ingredient concentration may be about 1% to 90% by weight, preferably 5 to 80 per cent by weight.

[0083] Formulations in the form of dusts usually contain 5% to 20% by weight of active ingredient; sprayable solutions contain about 0.05 to 80, preferably 2 to 50, per cent by weight (% by weight) of active ingredient.

[0084] In the case of granules such as dispersible granules, the active ingredient content depends partly on whether the active ingredient is in liquid or solid form and on which granulation auxiliaries and fillers are used. In general, the content in the water-dispersible granules is between 1% and 95% by weight, preferably between 10% and 80% by weight.

[0085] In addition, the active ingredient formulations mentioned optionally comprise the respectively customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, colorants and carriers, antifoams, evaporation inhibitors and pH- or viscosity-modifying agents.

[0086] For application, the formulations in the commercial form are diluted if appropriate in a customary manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Dust-type preparations, granules for soil application or broadcasting and sprayable solutions are not normally diluted further with other inert substances prior to application.

[0087] The active ingredients can be deployed onto the plants, plant parts, plant seeds or the area under cultivation (soil), preferably on the green plants and plant parts, and optionally additionally onto the soil.

[0088] One possible use is the joint application of the active ingredients in the form of tankmixes, where the optimally formulated concentrated formulations of the individual active ingredients together are mixed in a tank with water, and the spray liquor obtained is deployed. A joint herbicidal formulation of the inventive combination of active ingredients (A) and (B) has the advantage that it can be applied more easily since the quantities of the components are already set at the correct ratio to one another. Moreover, the auxiliaries in the formulation can be adjusted optimally to one another, whereas a tank mix of different formulations may result in unwanted combinations of auxiliaries.

[0089] A. General formulation examples a) A dusting product is obtained by mixing 10 parts by weight of an active ingredient (A) or (B) or (C) or an active ingredient mixture (A) + (B) + (C) (and optionally further active ingredient components) and / or salts thereof and 90 parts by weight of talc as inert substance, and comminuting in a beater mill. b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of an active ingredient / active ingredient mixture, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant and grinding the mixture in a pinned-disk mill. c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of an active ingredient / active ingredient mixture with 6 parts by weight of alkylphenol polyglycol ether (Triton® X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example approximately 255 to 277°C) and grinding the mixture in a friction ball mill to a fineness of below 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of an active ingredient / active ingredient mixture, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier. e) Water-dispersible granules are obtained by mixing

[0090] 75 parts by weight of an active ingredient / active ingredient mixture,

[0091] 10 parts by weight of calcium lignosulfonate,

[0092] 5 parts by weight of sodium lauryl sulfate,

[0093] 3 parts by weight of polyvinyl alcohol and

[0094] 7 parts by weight of kaolin, grinding the mixture in a pinned-disk mill, and granulating the powder in a fluidized bed by spray application of water as a granulating liquid. f) Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill,

[0095] 25 parts by weight of an active ingredient / active ingredient mixture,

[0096] 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltaurate,

[0097] 1 part by weight of polyvinyl alcohol,

[0098] 17 parts by weight of calcium carbonate and

[0099] 50 parts by weight of water, then grinding the mixture in a bead mill and atomizing and drying the resulting suspension in a spray tower by means of a one-phase nozzle.

[0100] B. Biological examples

[0101] The following data are the results of a greenhouse investigation in which the herbicide combination according to the present invention was tested against various monocoty ledonous and dicotyledonous weeds after a pre emergence application and a post emergence application (BBCH 10-12). The following weeds were selected for testing:

[0102] Table 1 For the trials seeds of the above mentioned species were sown in 7 cm pots containing standard soil (14,7% sand, 19,9% clay, 65,4% silt and 1,8% organic matter) covered with 0.5 cm depth of sandy soil, lightly irrigated from above and used for the pre emergence trial. For the post emergence trial the pots were placed in a glasshouse (with conditions of 16 hour day and 8 hour night, 21 °C day and 12°C night and 60% relative humidity) and irrigated from above to allow the seeds to germinate and grow. Once they had reached the required growth stage BBCH 10-12 the propagated plants were used for the post emergence trial. The herbicide application was done with a track sprayer at a spray volume of 300 1 water / ha using a flat fan nozzle XR 8001 at a pressure of 1.8 bar. For the preparation of the application liquids the formulations shown in the table 2 were used. The methylated rape seed oil adjuvant Mero® was added to each application liquid with 1 1 / ha. After the application and air drying the pots were placed back into the glasshouse and allowed to grow on. The pots were irrigated as required for good plant growth.

[0103] Table 2

[0104] Visual percent of weed control (2 replicates) was rated in intervals after application, indicated in the result tables as days after herbicide application (DAA) on a scale of 0-100. A rating of 0 is defined as no control and 100 as complete control.

[0105] On employment of the combinations of the invention, herbicidal effects on a harmful plant species that exceed the formal sum total of the effects of the herbicides present when applied alone were frequently observed. Alternatively, in some cases, it was possible to observe that a smaller application rate for the herbicide combination is required in order to achieve the same effect for a harmful plant species compared to the individual preparations. Such increases in action or increases in effectiveness or reductions in application rate are a strong indication of a synergistic effect. When the observed efficacies already exceed the formal sum total of the values of the tests with individual applications, they also exceed the expected value according to Colby, which is calculated using the formula below and is likewise regarded as an indication of synergism (cf. S. R. Colby; in Weeds 15 (1967) pp. 20 to 22). According to Colby synergistic effects of herbicidal active ingredients are indicated if the measured efficacy is higher than the expected one calculated according to his formula for 2- way mixtures:

[0106] Ec= A+B - (AxB / 100) and according to his formula for 3 -way mixtures:

[0107] Ec= (A + B + C) - (AxB + AxC + BxC) / 100 + (AxBxQ / 10000 where:

[0108] A = efficacy of the active ingredient (A) in % at an application rate of a [g a.i. / ha] ;

[0109] B = efficacy of the active ingredient (B) in % at an application rate of b [g a.i. / ha] ;

[0110] C = efficacy of the active ingredient (C) in % at an application rate of c [g a.i. / ha] ;

[0111] Ec= expected value of combinations of (A), (B), (C) in % at the combined application rate of a, b, c [g a.i. / ha] .

[0112] The post emergence trial as well as the pre emergence trial results show, that the combination of flumioxazin and cinmethylin often shows less than additive effects, often clearly lower than expected according to Colby for 2-way mixtures. The addition of the safener mefenpyr or the safener Methyl- { [5- (4-chloro-2-fluorophenyl)- 1 -(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetate to flumioxazin and cinmethylin at the above mentioned dose rates produces high efficacy, clearly higher than expected according to Colby for 3-way mixtures, against target weeds tested. This indicates clear synergism in 3- way mixtures between these three active ingredients.

[0113]

[0114]

[0115] Table 4: Post emergence trial: % Efficacy against various weeds

[0116] Table 5: Pre emergence trial: % Efficacy against various weeds

[0117]

[0118] Table 6: Pre emergence trial: % Efficacy against various weeds

Claims

Claims:

1. Composition comprising herbicidally active compounds (A) and (B), and a safener (C) wherein(A) represents flumioxazin,(B) represents cinmethylin,(C) represents(Cl) mefenpyr-diethyl, or(C2) a compound of formula (I) or an agronomically acceptable salt thereofwherein(Ra)p-phenyl is selected from any one of the groups Q-l.l to Q-1.55and (Rb)q-phenyl is selected from any one of the groups Q-2.1 to Q-2.55Rcis hydrogen, andRdis hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, phenyl, benzyl, CH2(4-Cl-Ph), CH2(4-F-Ph), CH2(4-OMe-Ph), 2-methoxyethyl, tetrahydrofuran-2-yl-methyl, tetrahydrofuran-3-yl-methyl, tetrahydropyran- 2-yl-methyl, tetrahydropyran-3-yl-methyl, tetrahydropyran-4-yl-methyl, methylpropionat-3-yl, ethylpropionat-3-yl, methylacetat-2-yl, ethylacetat- 2-yl, methylpivalat-2-yl, ethylpivalat-3-yl, methyl-2-methylpropanoat-3-yl, methyl-2,2-dimethylpropanoat-3-yl, ethyl-2-methylpropanoat-3-yl, methyl- 2-propanoat-2-yl, ethyl-2-propanoat-2-yl, methyl-acetat-2yl, ethyl-acetat- 2yl, methyl- 1-methy Icy clopropancarboxylat-2yl, ethyl- 1- methylcyclopropan-carboxylat-2yl, 2-(dimethylamino)ethyl, oxetan-3-yl, (3-methyloxetan-3-yl)methyl, 2,2,2-trifluorethyl, 2,2-difluorethyl, 2- fluorethyl, 2,2,3,3,3-pentafluorpropyl, cyclopropylmethyl, 1-cyclopropyl- ethyl, (l-methyl-cyclopropyl)-methyl, (2,2-dichlorcyclopropyl)-methyl, (2,2-dimethyl-cyclopropyl)-methyl, allyl, propargyl (prop-2-in-l-yl), 2- chlorprop-2-en- 1 -yl, 3-phenylprop-2-in- 1 -yl, 3,3-dichlorprop-2-en- 1 -yl, 3 ,3-dichlor-2-fluor-prop-2-en- 1 -yl, methylprop-2-in- 1 -yl, 2-methylprop-2- en-l-yl, but-2-en-l-yl, but-3-en-l-yl, but-2-in-l-yl, but-3-in-l-yl, 4-chlor- but-2-in-l-yl, 3-methyl-but-2-en-l-yl, 3-methyl-but-l-en-l-yl, 1- (2e)-l- methylbut-2-en-l-yl, (e)-pent-3-en-2-yl or (z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, l,3-dioxolan-2-ylmethyl or l-ethyl-5-methyl-lh-pyrazol-4-methyl.

2. Composition according to claim 1 , wherein (C) is selected from:Methyl- { [1 ,5-bis(4-chloro-2-fluoorphenyl)- 1H- 1 ,2,4-triazol-3-yl]oxy } acetate{ [1 ,5-Bis(4-chloro-2-fluorophenyl)- 1H- 1 ,2,4-triazole-3-yl]oxy } acetic acidMethyl- { [5-(4-chloro-2-fluorophenyl)- 1 -(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3- yl] oxy} acetateMethyl- { [ 1 -(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)- 1 H- 1 ,2,4-triazole-3- yl] oxy} acetate{[l-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-lH-l,2,4-triazole-3-yl]oxy}acetic acidMethyl- { [5-(4-bromo-2-fluorophenyl)- 1 -(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3- yl] oxy} acetateMethoxyethyl- { [ 1 -(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)- 1H- 1 ,2,4-triazole-3- yl] oxy} acetate{[l-(4-Bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-lH-l,2,4-triazole-3-yl]oxy}acetic acid3. Composition according to claim 1 or 2, wherein (A) and (B) are provided in a weight ratio 100: 1 to 1:100, preferably 50:1 to 1:50, further preferably 30:1 to 1:30, even further preferably 20:1 to 1:20.

4. Composition according to any one of the preceding claims, wherein (C) is provided in a weight ratio to the mixture of (A)+(B) of 100:1 to 1:100, preferably 50:1 to 1:50, further preferably 30:1 to 1:30, even further preferably 20:1 to 1:20.

5. Composition according to any one of the preceding claims, additionally comprising one or more further constituents selected from the group consisting of further herbicides, water, and formulation adjuvants.

6. Composition according to any one of the preceding claims, wherein the composition in the form of a concentrated formulation or a ready-to-use diluted spray application mixture (tank-mix).

7. Method of controlling weed plants in crops of useful plants, characterized in that a composition according to any one of claims 1 to 6 is applied to the weed plants, plants, plant seeds, or to the area on which the weed plants are growing.

8. Method according to claim 7, wherein the herbicidally active compounds and safener of the composition are applied jointly or separately by the pre-emergence method, the post-emergence method or by the pre- and post-emergence method to the plants, plant parts, plant seeds or the area under cultivation.

9. Method according to claim 7 or 8, wherein the crop plant is a cereal plant.

10. Method according to any one of claims 7 to 9, wherein flumioxazin is applied at a ratio of between 10 and 200 g ai / ha, preferably between 20 and 100 g ai / ha, more preferably between 30 and 60 g ai / ha.

11. Method according to any one of claims 7 to 10, wherein cinmethylin is applied at a ratio of between 100 and 1000 g ai / ha, preferably between 150 and 800 g ai / ha, more preferably between 200 and 600 g ai / ha12. Method according to any one of claims 7 to 11, where the compound (C) is applied at an application rate of between 25 and 4000 g ai / ha, preferably between 50 and 1800 g ai / ha, more preferably between 100 and 1200 g ai / ha.

13. Use of a composition of any of claims 1 to 6 for controlling weed plants in crops, in particular in cereal crops.

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