AU2011250796B2 - Synergistically acting herbicidal mixtures - Google Patents

Abstract

The present invention relates to a synergistic herbicidal mixture. 5 The invention furthermore relates to herbicidal compositions comprising a herbicidally active amount of a synergistic herbicidal mixture as defined above and at least one liquid and/or solid carrier and, if desired, at least one further additive. Moreover, the invention relates to a method of controlling undesirable vegetation by 10 using above defined synergistic herbicidal mixture.

Description

Pool Seclion 29 Regulato 3.2(2) AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: Synergistically acting herbicidal mixtures The following statement is a full description of this invention, including the best method of performing it known to us: P111AHAU/0710 1 SYNERGISTICALLY ACTING HERBICIDAL MIXTURES FIELD OF THE INVENTION 5 The present invention relates to a synergistic herbicidal mixture. The invention furthermore relates to herbicidal compositions comprising a herbicidally active amount of a synergistic herbicidal mixture as defined above and at least one liquid and/or solid carrier and, if desired, at least one further additive. 10 Moreover, the invention relates to a method of controlling undesirable vegetation by using above defined synergistic herbicidal mixture. BACKGROUND TO THE INVENTION 15 In crop protection products, it is always desirable to increase the specific activity and/or selectivity of an active ingredient and the reliability of action. However, the activity and/or the selectivity of herbicides depends on a large number of 20 factors e.g. type of the herbicide, amount of the herbicide, formulation of the herbicide, the type of weed, the combination of crop and weed, climate, soil. etc. In many cases herbicides have an effect against a broad spectrum of weeds, however do not fight a certain type of other weeds, which is also present in the crop cultures to be 25 protected. Sometimes these obstacles can be overcome by using just bigger amounts of herbicide, however this is economically disadvantageous and may also reduce the selectivity of the herbicide, in other words may lead to damage of the crop to be protected. 30 It is a general desire in the application of agrochemicals to reduce their amount on one side and to broaden their ability to fight different weeds - which grow in certain crop cultures - without damaging the crop cultures on the other side. 35 This desire may be satisfied by combination of different herbicides having a different activity profile versus undesired weeds. However, because of the huge number of herbicide active ingredients known in the art and the many factors which influence the activity and selectivity of herbicides it is virtually 40 impossible to create the appropriate mixture just by doing some mixture experiments.

2 Therefore it is always a challenge to find an appropriate herbicide or herbicide mixture which fights a certain group of weeds in a certain crop culture. WO 00/08938 Al (now EP 1 104 241 Bl, Bayer CropScience) describes the use of 5 herbicide combinations for fighting weeds in herbicide resistant oilseed rape. Certain herbicidal compositions as such are also described, Respective herbicides are to be selected from four different groups and are to be combined with herbicides to be selected from five other groups. The gist of WO 00/08938 Al is the combination of glyphosate or glufosinate with other co herbicides. 10 The herbicide combinations of the instant application as well as their use as described in the instant application are not disclosed in WO 00/08938 Al. SUMMARY OF THE INVENTION 15 The invention provides a synergistic herbicidal mixture comprising a) imazamox, its respective isomers as well as its respective environmentally compatible salts, esters, amides or other derivatives; 20 and b) quinmerac; 25 and c) if desired, at least one herbicidal compound selected from the group consisting of clomazone, atrazin, dichlormid, benoxacor, LAB-145138, MG-191, MON-13900, cyometrinil, oxabetrinil, fluxofenim, flurazole, 30 naphtalicacidanhydride, fenchlorim, fenchlorazol, mefenpyr, cloquintocet (including its hydrate(s)), 1 -ethyl-4-hydroxy-3-(l H-tetrazol-5-yl)-1 H quinolin-2-one, 4-carboxymethyl-chroman-4-carboxylic acid, N-(2 methoxy-benzoyl)-4-(3-methyl-ureido)benzenesulfonamide, (3-oxo isothiochroman-4-ylidenemethoxy)-acetic acid methyl ester including their 35 respective isomers as well as their respective environmentally compatible salt, esters, amides or other derivatives.

3 It is an object of the present invention to increase the activity and/or selectivity of herbicides against undesirable harmful plants, in particular in certain crops (e.g. oilseed rape, canola (brassica napus)), without damaging these crops. 5 We have found that this object is achieved by the mixtures defined at the outset. We have furthermore found herbicidal compositions which comprise these mixtures, and methods of controlling undesirable vegetation. DESCRIPTION OF THE PREFERRED EMBODIMENTS 10 Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. 15 The mixtures according to the invention show a synergistic effect; the compatibility of the herbicidally active compounds of components A), B) and, if desired C) for certain crop plants is generally retained. 20 The compounds which are embraced by component A) are the following. Herbicidal imidazolinones are known e.g. from C.D.S. Tomlin, "The Pesticide Manual", 13 1h Edition, BCPC (2003), Index 5, 1337-1344 and http://www.hclrss.demon.co.ukjindexcnframe.html. 25 The term "Imidazolinones" shall mean herein the compounds as mentioned above, as well as their a) salts, e.g. salts of alkaline or earth alkaline metals or ammonium or organoammonium salts, for instance, sodium, potassium, ammonium, isopropyl ammonium etc.; b) respective isomers, e.g. stereo isomers such as the respective 30 enantiomers, in particular the respective R-or S-enantiomers (including salts, ester, amides), c) respective esters, e.g. carboxylic acid C1 -C8-(branched or non-branched) alkyl esters, such as methylesters, ethylesters, iso propyl esters, d) respective amides, e.g. carboxylic acid amides or carboxylic acid C1-C8-(branched or non-branched) mono or di alkyl amides, such as dimethylamides, diethylamides, di isopropyl amides or e) any 35 other derivative which contains the above imidazolinone structures as structural moiety. Very suitable Imidazolinones are the R-isomers, e.g. R-imazamethabenz-methyl, R imazamox, R-imazapic, R-imazapyr, R-imazaquin, R-imazethapyr, in particular R imazamox. These compounds are known e.g. from US 5,973,154 B (American Cyanamid 40 Company) and US 6,339,158 1 (American Cyanamid Company).

4 Sulfonylureas are known from C.D.S. Tomlin, "The Pesticide Manual", 13 1h Edition, BCPC (2003), Index 5, 1337-1344 and http://www.hcirss.demon.co.uk/indexcnframe.html Examples of suitable Sulfonylureas are nicosulfuron, tritosulfuron, mesosulfuron, 5 cyclosulfamuron, rimsulfuron, foramsulfuron. The term "Sulfonylureas" shall mean herein the compounds as mentioned above, as well as their a) salts, e.g. salts of alkaline or earth alkaline metals or ammonium or organoammonium salts, for instance, sodium, potassium, ammonium, isopropyl 10 ammonium etc.; b) respective isomers, e.g. stereo isomers such as the respective enantiomers, c) respective esters, e.g. C1-C8-(branched or non-branched) alkyl esters, such as methylesters, ethylesters, iso propyl esters, d) respective amides, e.g. amides or C1-C8-(branched or non-branched) mono or di alkyl amides, such as dimethylamides, diethylamides, di isopropyl amides. 15 Very suitable Sulfonylureas are cross spectrum sulfonylureas for example nicosulfuron, mesosulfuron, rimsulfuron or foramsulfuron. Examples of suitable sulfonamides (also known as "triazolopyrimidines" or "sulfonanilide 20 herbicides") are known from C.D.S. Tomlin, "The Pesticide Manual", 13 h Edition, BCPC (2003), Index 5, 1337-1344, WO 02/36596 A (Dow Agrosciences LLC) and http://www.hclrss.demon.co.uk/index cn-frame.html The term "Sulfonamides" shall mean herein the compounds as mentioned above as well 25 as their a) salts, e.g. salts of alkaline or earth alkaline metals or ammonium or organoammonium salts, for instance, sodium, potassium, ammonium, isopropyl ammonium etc.; b) their respective isomers, e.g. stereo isomers such as the respective enantiomers, c) respective esters, e.g. C1-C8-(branched or non-branched) alkyl esters, such as methylesters, ethylesters, iso propyl esters, d) respective amides, e.g. amides or 30 C1-C8-(branched or non-branched) mono or di alkyl amides, such as dimethylamides, diethylamides, di isopropyl amides. Very suitable Sulfonamides are florasulam, flumetsulam, metosulam, penoxulam, cloransulam-methyl, diclosulam and N-(5,7-dimethoxy[1,2,4]triazolo[1,5-a]pyrimidin-2-yl) 35 2-methoxy-4-(trifluoromethyl)- 3-pyridinesulfonamide (the latter disclosed in Research Disclosure July 2002, 1230-1231 and WO 02/36596 A (Dow Agrosciences LLC)), in particular florasulam, penoxulam and N-(5,7-dimethoxy[1,2,4]triazolo[1,5-a]pyrimidin-2 yI)-2-methoxy-4-(trifluoromethyl)- 3-pyridinesulfonamide. 40 The compounds which are embraced by component B) are the following. Chloro acetamides, oxyacetamides and tetrazolinones as described in C.D.S. Tomlin, 5 "The Pesticide Manual", 13 th Edition, BCPC (2003), Index 5, 1337-1344 and http://www.hclrss.demon.co.uk/index cn-frame.html. The term "Chloro Acetamides" shall mean herein the compounds as such as well as a) 5 their salts, e.g. salts of alkaline or earth alkaline metals or ammonium or organoammonium salts, for instance, sodium, potassium, ammonium, isopropyl ammonium etc. or b) their respective isomers, e.g. stereo isomers such as the respective enantiomers. 10 Suitable Chloro Acetamides are metazachlor, metolachlor, "S-metolachlor", acetochlor, dimethachlor, alachlor and dimethenamid and dimethenamid-P and pethoxamid. Metazachlor herein shall mean 2-Chloro-(2',6'-dimethyl-N-pyrazol-1-yl-methyl)-acetamid in all of his crystal modifications, in particular the monoclinic Metazachlor which is 15 described in EP 0 411 408 A (BASF Aktiengesellschaft). Metolachlor herein shall mean the racemic mixture of the compound CAS RN [51218-45 2] and the compound S-metolachlor and any mixture of S-isomer of metolachlor (CAS RN [87392-12-9]) and R-isomer of metolachlor (CAS RN [178961-20-1]. 20 Dimethenamid herein shall mean the compounds listed in C.D.S. Tomlin, "The Pesticide Manual", 1 3 th Edition, BCPC (2003), Index 5, 1337-1344 and http://www.hclrss.demon.co.uk/indexcn_frame. html, in particular the S-isomer (dimethenamid-P). 25 For clarity sake the terms Metazachlor, Metolachlor, Acetochlor and Dimetenamid shall include herein the compounds as mentioned above as well as their salts, e.g. salts of alkaline or earth alkaline metals or ammonium or organoammonium salts, for instance, sodium, potassium, magnesium, ammonium, isopropyl ammonium etc. 30 Preferred component B) comprises Metazachlor, in particular monoclinic Metazachlor, Dimethenamid, Dimethenamid-P, Metolachlor and Quinmerac. A very preferred component B) is Metazachlor, in particular monoclinic Metazachlor. 35 Further componets C) may be selected from the group consisting of clomazone, , atrazine (see C.D.S. Tomlin, "The Pesticide Manual", 13 h Edition, BCPC (2003), Index 5, 1337-1344 and http://www.hclrss.demon.co.ukjindexcn__frame.html) and the following compounds which usually function as "safeners", dichlormid, benoxacor, LAB-145138, 40 MG-191, MON-13900, cyometrinil, oxabetrinil, fluxofenim, flurazole, naphtalicacidanhydride, fenchlorim, fenchlorazol, cloquintocet (including its esters and hydrate(s)), as described in "Herbizide [Herbicides]", Hock, Fedtke, Schmidt, 1st edition, 6 Theme 1995 (s. "Dichlormid" p.263, "Benoxacor" p.263, "LAB-145138" p.263, "MG-191" p.263, "MON-13900" p.263, "Cyometrinil" p.265, "Oxabetrinil" p.265, "Fluxofenim" p.265, "Flurazole" p.265, "Naphtalicacidanhydride" p.265, "Fenchlorim" p.266, "Fenchlorazol" p.266 Isoxadifen, "Cloquintocet" p.266], or C.D.S. Tomlin, "The Pesticide Manual", 1 3 'h 5 Edition, BCPC (2003), Index 5, 1337-1344 and http:/www.hclrss.demon.co.uk/index_ cn_frame.html e.g. mefenpyr-diethyl, isoxadifen, 1 ethyl-4-hydroxy-3-(1 H-tetrazol-5-yI)-1 H-quinolin-2-one, 4-carboxymethyl-chroman-4 carboxylic acid, N-(2-methoxy-benzoyl)-4-(3-methyl-ureido)-benzenesulfona mid e, (3-oxo isothiochroman-4-ylidenemethoxy)-acetic acid methyl ester, all of these including their 10 respective isomers as well as their respective environmentally compatible salts or esters or amides or other derivatives. Preferred other components C) are clomazone, atrazin and the safeners cloquintocet (including its esters and hydrate(s)). 15 Preferred herbicidal mixtures or combinations according to the invention are the following (Ml) Imazamox + Metazachlor (monoclinic or triclinic or any mixture of those) (Mi-1) R-Imazamox + Metazachlor which contains at least 90 weight-% of the monoclinic 20 form (Ml-2) R-imazamox + Metazachlor (monoclinic or triclinic or any mixture of those) (M2) Imazamox + Metolachlor (racemic, S-isomer, or any mixture of R- and S-isomer) (M2-1) R-Imazamox + Metolachlor (racemic, S-isomer, or any mixture of R- and S 25 isomer) (M3) Imazamox + Dimethenamid (racemic or S-isomer) (M3-1) R-Imazamox + Dimethenamid (in particular the S-isomer) 30 (M4) Imazamox + Metazachlor (monoclinic or triclinic or any mixture of those) + clomazone (M4-1) R-Imazamox + Metazachlor which contains at least 90 weight-% of the monoclinic form + clomazone 35 (M5) Imazamox + Metazachlor (monoclinic or triclinic or any mixture of those) + quinmerac (M5-1) R-imazamox + Metazachlor which contains at least 90 weight-% of the monoclinic form + quinmerac 40 (M6) Imazamox + Metolachlor (including S-Metolachlor) + atrazin (M7) Imazamox + Flufenacet 7 (M8) Imazamox + Fentrazamide Particular preferred herbicidal mixtures according to the invention are the following: 5 M1, M1-1, M1-2, M4 and M4-1, M5 and M5-1, M6, M7 and M8. The present invention also extends to herbicidal compositions which comprise a herbicidally active amount of a synergistic herbicidal mixture (comprising components A), B) and, if desired, C) as described above), at least one liquid and/or solid carrier and, if 10 desired, at least one further additive, for example a surfactant, adjuvant or others. The herbicidal compositions and synergistic herbicidal mixtures according to the invention can effect very good control of broad-leaved weeds and grass weeds in many crops for example maize, cereals (for example wheat), brassica napus (canola, oilseed rape), sunflower, legumes, sugar cane, and soya without damaging the crop plants, an 15 effect observed especially even at low rates of application. Taking into consideration the variety of application method in question, the herbicidal compositions and synergistic herbicidal mixtures according to the invention can additionally be employed in a further number of crop plants for eliminating undesirable 20 plants. The herbicidal compositions and synergistic herbicidal mixtures according to the invention can preferably be used in crops which tolerate and/or are resistant to the action of ALS herbicides, preferably those ALS herbicides according to the invention. The 25 resistance and or tolerance to said herbicides may be achieved by conventional breeding and/or by genetic engineering methods. Crops which are tolerant to herbicides (e.g. tolerant to imidazolinone herbicides) are known for example from EP 0 154 204 A (MGI Pharma Inc.). Such crops are for example 30 marketed by BASF under the trade name CLEARFIELD. Examples for such crops are maize, brassica napus (canola, oilseed rape), sunflower, rice, lentils and wheat. Most preferable herbicide tolerant or herbicide resistant crops according to the invention is oilseed rape, canola (brassica napus). 35 The herbicidal mixtures or compositions according to the invention, for example the mixtures containing Imidazolinones as sole component A), preferably the mixtures of Imidazolinones and Chloro Acetamides, very preferably mixtures or compositions 8 comprising Imazamox and Metazachlor or Imazamox and at least one other herbicide of the groups B) and/or C) (for example those as disclosed under M1, M1-1, M1-2, M2, M2 1, M3, M3-1, M4, M4-1, M5 and MS-1, M6, M7 and M8) and in particular mixtures of Imazamox and Chloro Acetamides (for example those as disclosed under M1, M1-1, Ml 5 2, M2, M2-1, M3, M3-1, M4, M4-1, M5 and M5-1 are very suitable for fighting or controlling a broad spectrum of grasses and broadleaf weeds which are accompanying in general the abovementioned crops, e.g. in particular brassica napus (oil seed rape, canola). 10 Very preferably the weeds in ALS-herbicide resistant or tolerant brassica napus (oilseed rape, canola) are lighted by the herbicidal mixtures or compositions according to the invention - for example the mixtures containing Imidazolinones as sole component A), preferably the mixtures of Imidazolinones and Chloro Acetamides, very preferably mixtures of Imazamox and Chloro Acetamides (for example those as disclosed under 15 M1, M1-1, M1-2, M2, M2-1, M3, M3-1, M4, M4-1, M5, M5-1 above) and in particular those mixtures or compositions comprising Imazamox and Metazachlor. Those weeds include but are not limited to the following plant species: Alopecurus myosuroides; Apera spica-venti; Avena spec.; Brassica spec.; Capsella 20 bursa-pastoris; Galium aparine; Lamium spec.; Raphanus spec.; Sinapis spec.; Sisymbrium officinale; Stellaria media; Thiaspi arvense. Veronica spec. Very suitable ALS resistant or tolerant crop / to be controlled weed / herbicide mixture 25 (composition) combinations are the following. Controlled weeds include but are not limited to the listed plant species. ALS tolerant crop Herbicide Mixture Weed (Latin name) Canola lmazamox+Metazachlor Agropyron repens 30 Geranium pussilum Sinapis alba Sisymbrium officinale Canola lmazamox+Metazachlor Agropyron repens 35 +quinmerac Galium aparine Geranium pussilum Sinapis alba Sisymbrium officinale 40 Canola Imazamox+Metazachlor Agropyron repens +clomazone Galium aparine 9 Geranium pussilum Sinapis alba Sisymbrium officinale 5 Corn, sunflower lmazamox+(Dimethenamid or Echinochloa spec. Dimethenamid-p) Setaria spec. Digitaria spec. Corn imazamox+(Dimethenamid or Echinochloa spec. 10 Dimethenamid-p)+atrazin Setaria spec. Digitaria spec Chenopodium spec. Polygonum spec. 15 Corn, sunflower Imazamox+(Metolachlor or Echinochloa spec. S-Metolachlor) Setaria spec. Digitaria spec Chenopodium spec. Polygonum spec. 20 Corn Imazamox+(Metolachlor or Echinochloa spec. S-Metolachlor)+atrazin Setaria spec. Digitaria spec Chenopodium spec. 25 Polygonum spec Wheat lmazamox+Flufenacet Alopecurus spec. Apera spec. Galium spec. 30 Rice Imazamox+Fentrazamide Oryza rupifogon Echinochloa spec. The mixtures according to the invention, or the herbicidal compositions comprising them, 35 can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.

10 The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention. Suitable inert additives (auxiliaries) are mineral oil fractions of medium to high boiling 5 point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins, tetra hydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, such as N 10 methylpyrrolidone and water. Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be 15 homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water. 20 Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylaryl sulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its 25 derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl and tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or 30 polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose. Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the synergistic herbicidal mixture or the individual active ingredients with a solid 35 carrier.

11 Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, less, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium 5 oxide, ground synthetic material, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers. 10 The concentrations of the mixtures according to the invention in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise from 0.01 to 95% by weight, preferably 0.5 to 90% by weight, of the mixture according to the invention. 15 The components A) and B) and, if desired, C) can be formulated jointly, but also separately, and/or applied to the plants, their environment and/or seeds jointly or separately. It is preferable to apply the active ingredients simultaneously. However, it is also possible to apply them separately. 20 Moreover, it may be advantageous to apply the herbicidal compositions and synergistic herbicidal mixtures according to the invention, jointly or separately, with additional other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non 25 phytotoxic oils and oil concentrates can also be added. The mixtures according to the invention and the herbicidal compositions can be applied pre- or post-emergence. It is advantageous to apply the mixtures according to the invention post emergent when the crop has in general I to 6 leaves. 30 If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which 35 grow underneath, or the bare soil (post-directed, lay-by).

12 In the case of a post-emergence treatment of the plants, the herbicidal mixtures or compositions according to the invention are preferably applied by foliar application. Application may be effected, for example, by usual spraying techniques with water as the 5 carrier, using amounts of spray mixture of approx.15 to 1000 1/ha. The mixtures or compositions may also be applied by the so-called "low-volume" and "ultra-low-volume" methods, or in the form of so-called granules. As a rule, the synergistic herbicidal mixtures comprise components A), B) and, if desired, 10 C) in such weight ratios that the synergistic effect takes place. The ratios of component A) and B) in the mixture in general range from 1:0.001 to 1:500, preferably from 1:0.01 to 1:100, particularly preferably from 1:0.1 to 1:50. The ratios of components A) and C) in the mixture in general range from 1:0.002 to 15 1:800, preferably from 1:0.003 to 1:160, particularly preferably from 1:0.02 to 1:160. The rate of application of pure synergistic herbicidal mixture, i.e. without formulation auxiliaries, amounts in general to 0.1 to 5000 g/ha, preferably 1 to 3000 gfha, in particular 5 to 2500 g/ha, of active substance (a.s.), depending on the intended aim, the season, 20 the target plants and growth stage. The cumulated rate (sum of the amounts of all active ingredients of the respective group A)) of application of the component(s) A) is usually 5 to 75 g/ha of active substance (a.s.). 25 The rate of application of the Imidazolinones is usually 0.1 to 200 g/ha, as a rule 1 to 150 g/ha, preferably 5 to 100 g/ha, of active substance (a.s.). In particular the rate of application of Imazamox is usually 0.1 to 200 g/ha, as a rule, 1 to 30 100 g/ha, preferably 2 to 100 g/ha, of active substance (a.s.). The rate of application of the Sulfonylureas or Sulfonamides is usually 0.1 to 200 g/ha, as a rule 1 to 100 g/ha, preferably 2 to 100 g/ha, of active substance (a.s.). 35 The rate of application of component B) is usually 0.1 to 5000 g/ha, as a rule 1 to 4000 g/ha, preferably 5 to 3000 g/ha, of active substance (a.s.) 13 In particular the rate of application of Chloro Acetamide - e.g. Metazachlor, Metolachlor, Dimethenamid - is usually 50 to 5000 g/ha, as a rule 75 to 3000 g/ha, preferably 100 to 2000 g/ha, of active substance (a.s.). 5 The preferred application rates of the active ingredients of the optional component C) are compiled in the following table. Active ingredient C Rate of application (g/ha) Dichlormid 100-600 Benoxacor 10-200 LAB 145138 50-500 MG-1 91 200-1000 MON-13900 (Furilazole) 10-300 Nap htalicacidanhydride 300-1000 Fenchlorim 20-500 Fenchlorazol 5-100 Mefenpyr-diethyl 5-100 Isoxadifen-ethyl 1-100 Clo uintocet-mexyl 1-50 AD 67 50-500 R 29148 50-500 10 The herbicidal compositions and synergistic herbicidal mixtures according to the invention are very useful to control a broad spectrum of grass and broadleaf weeds. This usually leads to cleaner fields and higher purity of the harvested commodity as well as to higher yields of the respective crop, in particular brassica napus (oilseed rape, canola). 15 In particular brassica napus (oilseed rape, canola) seeds coming from fields treated with the herbicidal compositions and synergistic herbicidal mixtures according to the invention 14 usually have higher seed purity. Based on current knowledge this may be due to the removal of unwanted brassica species. A further advantage of the instant invention is the general reduction of tillage in the 5 respective fields which - based on current knowledge - usually leads to less loss of soil by e.g. wind. Examples 10 The mixtures according to the invention were applied pre- or post-emergence (foliar treatment). The herbicidal compounds of component A), B) and, if desired, of component C) were applied in the formulation in which they are present as commercially available product, e.g. Beyond or PULSAR 40 which is a Trademark of BASF and which is a liquid formulation containing imazamox as active ingredient; Raptor which is a trademark of 15 BASF and which is imazamox formulated as 70 % WG or as liquid formulation; Butisan S which is a trademark of BASF and which is 500 g/Il metazachlor formulated as SC; Outlook which is a dimethenamid P containing formulation. The herbicidally active compounds of components A), B) were applied in succession or 20 jointly, in the latter case in some cases as a tank mix and in some cases as a readymix, in the form of emulsions, aqueous solutions or suspensions, the vehicle being water (200 - 400 I/ha). In the case of the field trials, application was effected with the aid of a mobile plot sprayer. 25 The test period is specified in the respective tables. Damage by the herbicidal compositions was evaluated with reference to a scale of 0% to 100% in comparison with untreated control plots. 0 means no damage and 100 means complete destruction of the plants (cf. numbers in the column "Control" in the following 30 tables). The following examples will demonstrate the action of the herbicidal compositions which can be used according to the invention, without excluding the possibility of other uses. 35 In these examples, the value E at which only an additive effect of the individual active ingredients is to be expected was calculated by the method of S. R. Colby (Calculating 15 synergistic and antagonistic responses of herbicide combinations, Weeds 15, 20 pp (1967)). This was done using the formula 5

E=X+Y-

100 where X = Percentage of the herbicidal action of component A) at an application rate of a; 10 Y = Percentage of the herbicidal action of component B) at an application rate of b; E = expected herbicidal action of component A) + B) at rates of application a + b (in 15 If the value observed exceeds the value E calculated in accordance with Colby's formula, then synergism is present. For example the values in the columns "Control" in the following tables all show 20 synergismn. The herbicidal mixtures according to the invention exert a greater herbicidal action than would have been expected according to Colby on the basis of the observed effects of the individual components when used alone. 25 Further abbrevations in the following tables and their meaning: a.i. active ingredient (e.g. imazamox) GS Growth Stage (according to "Compendium of Growth Stage 30 Identification Keys for Mono- and Dicotyledonous Plants Extended BBCH scale, 2 nd Edition 1997 (ISBN 3-9520749-3-4) eval, evaluation after specified days after treatment DAT days after treatment n number of trials 35 GC Ground Cover [% of ground] 16 n no" y "yes" digits underneath of product name means rate of a.i. applied [g of pure ai/ha].

17 OD 00) 0 mCI 00m 45 C~~ cot- w a) IL4 d a 0) 4 0 0 0 go CO W C 10 03 r m . Q C) 0 0 ~ 0 N 0 ( (a N w N 3 W4 0' + r ro N (DON C oa Ml coC NC~ ~5 - 3 o U

-

P- r: C0 Q ' 0 0 11 4 i.. C1 r.V- Lo C C C C )7 CD m0 Cl C') 0 o m C.) C CO N c P.2 to in M01 W D 0( 00 0 0 00C(0 n O co 040 0n II- c-G o c O 0 o t- C 00 v P - m f t t m, xr 0; -oo C2 I5 - 0] CL Coj L E E 0 1 o i .- m a to Comt 0C Cx U> NT < CD___ 0. . N 0) 0) 0) 0 o 0) c 03 0)0 N 0~ CLC EX 0> ( (C0) C C -- N +

-

O O V C, 0 0) C C) 0 D 0 W I 0. W). ) r 0coa CC S + C)P Ul a)C) r 170 ( 8 C + C2 Lo +o C4 M ( 00 to EO 4* CD Sf 00 C- C E) 00 m w 2 1 r0 0 (>> N CO 0 4.'T 41 U) 0 m N rV E- 0 0. 0) ( 3 IL > 0:Uc 19 0 N a co 1l* ujf p N e 6 45> C cii C O >- r-co M 0 co0 U, C4 o + N- N NV C.)L C in >U > M)~ co co m . . Ec cc :t + EL m D1 o C mW 0 N +5 0( (a- M 0 o 0 x ' C6 go Q N E C4 c. V z T. -- r - =ON * . . -M - m L >, > 00 CD 1- 0 >45V 0 o1 C1 cco ac L - 0E cc I-45 0 20 Post emergent control of Setfaria faberi (solo herbicide application) Product Al Control Rate Name (g/ha) 1 CHECK 0 2 BEYOND 10.0 50 3 BEYOND 20.0 63 4 BEYOND 40.0 85 5 BUTISAN S 188.0 0 6 BUTISAN S 375.0 0 7 BUTISAN S 750.0 0 8 OUTLOOK 630.0 0 DUALII 1070. 9 0 MAGNUM 0 21 Post emergent control of Setfaria faberi (10 g/ha imazamox plus x g/ha co herbicide) Product Al Control Rate Name (g/ha) BEYOND 10.0 94 BUTISAN S 188.0 BEYOND 10.0 95 BUTISAN S 375.0 BEYOND 10.0 93 BUTISAN S 750.0 BEYOND 10.0 78 OUTLOOK 630.0 BEYOND 10.0 82 DUAL II 1070. MAGNUM 0 22 Post emergent control of Setfaria faberi (20 g/ha imazamox plus x g/ha co herbicide) Product Al Control Rate Name (g/ha) BEYOND 20.0 92 BUTISAN S 188.0 BEYOND 20.0 98 BUTISAN S 375.0 BEYOND 20.0 99 BUTISAN S 750.0 BEYOND 20.0 98 OUTLOOK 630.0 BEYOND 20.0 98 DUAL II 1070.0

MAGNUM

23 Post emergent control of Setfaria faberi (4Q g/ha imazamox plus x g/ha co herbicide) Product Al Control Rate Name (glha) BEYOND 40.0 99 BUTISAN S 188.0 BEYOND 40.0 99 BUTISAN S 375.0 24 Post emergent control of Avena fatura (herbicide solo application) AVEFA Product Al CONTROL Rate Name (g/ha) CHECK 0 BEYOND 10.0 30 BEYOND 20.0 30 BEYOND 40.0 38 BUTISAN S 188.0 33 BUTISAN S 375.0 32 BUTISAN S 750.0 30 OUTLOOK 630.0 23 DUAL 11 1070. MAGNUM 0 27 25 Post emergent control of Avena fatura (20 g/ha imazamox plus x g/ha co herbicide) Product Al AVEFA Rate Name Control (g/ha) BEYOND 20.0 57 OUTLOOK 630.0 Post emergent control of Avena fatura (40 g/ha imazamox plus x g/ha co herbicide) Product Al AVEFA Rate Name Control BEYOND 40.0 91 BUTISAN S 188.0 BEYOND 40.0 89 BUTISAN S 375.0 BEYOND 40.0 95 BUTISAN S 750.0 BEYOND 40.0 95 OUTLOOK 630.0 BEYOND 40.0 82 DUALII 1070. MAGNUM 0 25a Test Example I The effects of the herbicidal compositions of Imazamox and Quinmerac on the growth of undesirable plants compared to the herbicidal active compounds alone was 5 demonstrated in field experiments at three different locations in France and the United Kingdom. Imazamox was used as commercial aqueous solution (SL) having an active ingredient concentration of 120g/l (Raptor @). 10 Quinmerac was used as a wetable powder (WP) having an active ingredient concentration of 500g/kg. The herbicidally active compounds of components A) and B) were applied jointly, i.e. they 15 were diluted with water containing 0.5 % v/v of a surfactant mixture to achieve the desired application rate by applying a suitable amount of the dilution (200-400 I/ha). Application was effected as a post-emergence treatment with the aid of a sprayer. Herbicidal activity of quinmerac was assessed in winter oilseed rape field trials. 20 The performance of Imazamox, applied as a solo treatment at 35g ai/ha (ai = active ingredient), and the performance of Quinmerac, applied as a solo treatment at 250g ai/ha, as well as the performance of mixtures of the both compounds have been assessed at the growth stage (GS/ BBCH 12/14) in winter oilseed rape field trials. 25 The evaluation for the damage on undesired weeds caused by the chemical compositions was carried out using a scale from 0 to 100%, compared to the untreated control plants. Here, 0 means no damage and 100 means complete destruction of the plants. 30 Expected activity was calculated from the observed activity of the solo applications by means of Colby's formula as given on page 14f of the application. Results have been evaluated for the following weeds: CAPBP Capsella bursa-pastoris FUMOF Fumaria officinalis HORVW Hordeum vulgare MATCH Matricaria chamomilla PAPRH Papaver rhoeas TRZAW Triticum aestivum 25b VERPE Veronica persicea MERAN Mercurialis annua The results both for solo application of quinmerac and imazamox as well combined application are summarized in the following tables 1 to 3: 5 Table 1: Results of field trial at location 1 (UK), 80 DAT Active Plant variety Application Observed Expected Synergism Compound rate [g ai/ha] Activity [%] Activity [%] yes/no Imazamox HORVW 35 63 -- - Quinmerac HORVW 250 0 -- - Imazamox + HORVW 35 +250 70 63 Y Quinmerac a.i.: active ingredient DAT: Days after treatment Table 2: Results of field trial at location 2 (France), 54 DAT Active Plant Application Observed Expected Synergism Compound variety rate [g ai/ha] Activity [%] Activity [%] yes/no Imazamox PAPRH 35 30 -- - Quinmerac PAPRH 250 57 -- - Imazamox + PAPRH 35 + 250 72 70 Y Quinmerac Imazamox TRZAW 35 68 -- - Quinmerac TRZAW 250 0 -- - Imazamox + TRZAW 35 +250 75 68 Y Quinmerac Imazamox VERPE 35 63 -- - Quinmerac VERPE 250 62 -- - Imazamox + VERPE 35 + 250 98 86 Y Quinmerac 10 a.i.: active ingredient DAT: Days after treatment 25c Table 3: Results of field trial at location 3 (France), 54 DAT Active Plant Application Observed Expected Synergism Compound variety rate [g ai/ha] Activity [%] Activity [%] yes/no Imazamox CAPBP 35 97 -- - Quinmerac CAPBP 250 0 -- - Imazamox + CAPBP 35 + 250 100 97 Y Quinmerac Imazamox + CAPBP 35 + 250 100 97 Y Quinmerac Imazamox FUMOF 35 53 -- - Quinmerac FUMOF 250 0 -- - Imazamox + FUMOF 35 + 250 58 53 Y Quinmerac Imazamox MATCH 35 97 -- - Quinmerac MATCH 250 0 -- - Imazamox + MATCH 35 + 250 100 97 Y Quinmerac Imazamox MERAN 35 46 -- - Quinmerac MERAN 250 0 -- - Imazamox + MERAN 35 +250 53 46 Y Quinmerac Imazamox VERPE 35 30 -- - Quinmerac VERPE 250 0 -- - Imazamox + VERPE 35 + 250 44 30 Y Quinmerac a.i.: active ingredient DAT: Days after treatment 5 As can be seen from the data summarized in tables 1 to 3, the observed activity is always higher than the expected activity, as calculated from the observed individual activities. This clearly indicates the presence of a synergism. Test Example || 10 The tests were performed as a post-emergent treatment as described on page 14 f. of the application (greenhouse trials).

25d The following commercial formulations were used: Raptor: 120 g/Il Imazamox as SL formulation Novell: 400 g/l of Metazachlor + 100 g/l Quinmerac 5 The herbicidally active compounds of components A) and B) were applied jointly, i.e. they were diluted with water containing 0.5 % v/v of a surfactant mixture to achieve the desired application rate by applying a suitable amount of the dilution (20-40 mI/m 2 ). Application was effected with the aid of a sprayer. 10 Test plants were grown in plastic pots of approximately 12.5 cm in diameter in a substrate provided with sufficient nutrients and water to a height of 3 to 15 cm, depending on the growth habit. The plants were then treated with aqueous spray containing the active ingredient mixture. The rate of application are given in the tables below. 15 Depending on the species the plants were kept at 20-35*C for the test period. During the test period, the plants were tended. The test period was 57 days or 119 days, respectively. Damage by the herbicidal 20 compositions was evaluated at the end of the test period with reference to a scale of 0% to 100% in comparison with untreated control plots. 0 means no damage and 100 means complete destruction of the plants (cf. numbers in the column "Control" in the following tables). 25 The result of the individual application as well as the results of the combined application is given in tables 3 and 4. From the results of the individual applications the expected activity for the combined application was calculated by means of Colby's formula as described on page 14f of the application. 30 ALOMY: Alpecurus myosuroides (blackgrass) a.s.: active substance DAT: Days after treatment Table 3: Results 57 DAT Active Plant Application Observed Expected Synergism Compound variety rate [g/ha a.s.] Activity [%] Activity [%] yes/no Imazamox ALOMY 35 56 -- - Metazachlor + ALOMY 1000 + 250 23 -- -- 25e Quinmerac Imazamox + ALOMY 35 + 1000 + 70 66 Y Metazachlor + 250 Quinmerac Table 4: Results 119 DAT Active Plant Application Observed Expected Synergism Compound variety rate [g/ha a.s.] Activity [%] Activity [%] yes/no Imazamox ALOMY 35 0 -- - Metazachlor + ALOMY 1000 + 250 7 -- - Quinmerac Imazamox + ALOMY 35 + 1000 + 96 7 Y Metazachlor + 250 Quinmerac As can be seen from the data summarized in tables 3 and 4, the observed activity is 5 always higher than the expected activity, as calculated from the observed individual activities. This clearly indicates the presence of a synergism. Apart from that, the long term activity surprisingly increases, as evidenced by comparison of the results summarized in tables 3 and 4. As the results observed for the individual activities decrease with time indicating an expected activity loss with time the activity of the 10 combined application surprisingly increases with time indicating a high long-term activity.

Claims (8)

1. A synergistic herbicidal mixture comprising a) imazamox, its respective isomers as well as its respective environmentally compatible salts, esters, amides or other derivatives; and b) quinmerac; and c) if desired, at least one herbicidal compound selected from the group consisting of clomazone, atrazin, dichlormid, benoxacor, LAB-145138, MG-191, MON-13900, cyometrinil, oxabetrinil, fluxofenim, flurazole, naphtalicacidanhydride, fenchlorim, fenchlorazol, mefenpyr, cloquintocet (including its hydrate(s)), 1 -ethyl-4-hydroxy-3-(1 H-tetrazol-5-yl)-1 H quinolin-2-one, 4-carboxymethyl-chroman-4-carboxylic acid, N-(2 methoxy-benzoyl)-4-(3-methyl-ureido)-benzenesulfonamide, (3-oxo isothiochroman-4-ylidenemethoxy)-acetic acid methyl ester including their respective isomers as well as their respective environmentally compatible salts, esters, amides or other derivatives.

2. A synergistic herbicidal mixture comprising a) imazamox as well as its respective environmentally compatible salts, esters, amides or other derivatives; and b) metazachlor and quinmerac including their respective isomers as well as their respective environmentally compatible salts, esters, amides or other derivatives. 27

3. A herbicidal composition comprising a herbicidally active amount of a synergistic herbicidal mixture as claimed in claim 1 or 2, at least one inert liquid and/or solid carrier and, if desired, at least one further additive.

4. A method of controlling undesired vegetation, which comprises applying a synergistic herbicidal mixture as claimed in claim 1 or 2 before, during and/or after the emergence of undesired plants simultaneously or in succession.

5. A method as claimed in claim 4, wherein the crops are tolerant or resistant against the synergistic herbicidal mixture.

6. A mixture according to claim 1 or 2 substantially as hereinbefore described.

7. A composition according to claim 3 substantially as hereinbefore described.

8. A method according to claim 4 or 5 substantially as hereinbefore described. BASF SE WATERMARK PATENT & TRADE MARK ATTORNEYS P27641AU00