EP3897139A1

EP3897139A1 - Herbicidal combinations

Info

Publication number: EP3897139A1
Application number: EP19829415.9A
Authority: EP
Inventors: Helmut Kraus; Cyrill Zagar; Tobias SEISER; Johannes BESSAI; Tatiana DIMITRIADI; Yannick Griveau; Danielle Reid; Nocha Van Thielen; JDavid PETERS; Jeffrey A Brown; Matthew BLAKEN
Original assignee: BASF Agrochemical Products BV
Current assignee: BASF Agrochemical Products BV
Priority date: 2018-12-18
Filing date: 2019-12-09
Publication date: 2021-10-27
Also published as: WO2020126582A1; EA202191654A1

Abstract

The present invention relates to herbicidally active combinations comprising herbicides A, B, and C, wherein a.the herbicide A is R-imazamox, any non-racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or an agriculturally acceptable salt or ester thereof; and b.the herbicide B is prohexadione, or prohexadione-calcium; and c.the herbicide C is mepiquat, mepiquat-chloride or mepiquat-pentaborate.

Description

Herbicidal Combinations

The present invention relates to ternary herbicidal combinations of herbicides A, B, and C, as active ingredients and their use for controlling undesirable vegetation in cultures of crop plants, especially in crops which are tolerant to imidazolinone herbicides.

Background of the invention

In crop protection, it is principally desirable to increase the specificity and the reliability of the action of active compounds. For herbicides in particular, it is desirable that the crop protection products control the harmful plants effectively and, at the same time, are tolerated by the useful plants in question.

Imazamox (lUPAC: 2-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]-5-methoxy- methylnicotinic acid), as well as its salts and esters, is a well-known broad spectrum herbicide from the group of the imidazolinone herbicides (see C.D.S Tomlin (Ed.), The Pesticide Manual, 14th ed., 2006, BCPC Alton, Hampshire, UK, p. 587 ff.). Imazamox is known to be absorbed by the foliage or roots of the plants and effectively blocks the synthesis of branched chain amino acids by inhibition of acetolactate synthase (ALS inhibitor or AHAS inhibitor). Imazamox pro vides highly effective control of several annual and perennial grass and broadleaf weed species. Imazamox is registered for several legume crops and imidazolinone tolerant crops, such as rice, wheat, corn, lentil, sunflower and oilseed rape (canola). Imidazolinone tolerant crops are also termed Clearfield® crops. The herbicidal activity and the activity spectrum, however, are some times limited. In order to achieve a reliable herbicidal action, it has been recommended to apply imazamox in combination with adjuvants, such as Dash®. Formulations of imazamox, compris ing the active ingredient as racemate, are marketed under the trade names Beyond®, Raptor® and Sweeper®, Clearfield Vantiga®, Cleranda®, Clearvis® or Cleravo®. Cleravo®, is a sus pension concentrate containing 35 g/l imazamox and 250 g/l quinmerac.

Processes for the synthesis of the R-enantiomer of imazamox are known from EP 1 050 533 and US 6,339,158.

The herbicidal effect of combinations of the R-enantiomer of an imidazolinone compound and the R-enantiomer of a second different imidazolinone compound, such as R-imazamox + R- imazapyr, R-imazamox + R-imazaquin, and R-imazamox + R-imazethapyr, was described in EP 913 089. Furthermore, the combination of R-imazethapyr + R-imazapyr demonstrated crop se- lectivity; no or slight injury, such as stunting or chlorosis, was observed in imidazolinone tolerant corn.

Control of pitted morningglory and purple nutsedge by combinations of R-imazamox + glyphosate is described in US6,214,768.

WO 2013/037735 describes the control of Orobanche Cumana in sunflower by mixtures com prising imazamox and prohexadione. WO 2015/197831 discloses a method for controlling para sitic weeds comprising seed treatment of host plants with ALS-inhibitors such as imazamox, and post emergent treatment with plant growth regulators and fungicides or insecticides.

Jing Wei et al. found that the chiral herbicide imazamox poses enantioselective phytotoxicity on maize seedlings: the order of toxicity is R-imazamox > Rac-imazamox > S-imazamox ( Bull Envi ron Contam Toxicol (2016) 96:242-247).

C. Wang et al. discuss in their review on“Enantioselective Phytotoxicity and the Relative Mech anism of Chiral Herbicides” (Current Protein and Peptide Science, 2017, 15-21) enantioselec tive phytotoxicity of chiral herbicides, i.a. of the imidazolinone Imazapyr. The authors find that the herbicidally active enantiomer, R-imazapyr, displayed more phytotoxicity to non-target plants. They conclude that the reason for the impediment to the development of enantiomer enriched herbicides could be partially attributed to the beneficial balance between/among enan tiomers on the herbicidal activity and ecological safety (i.e. phytotoxicity).

Summary of the invention

It is an object of the present invention to provide combinations of herbicides which show en hanced herbicide action against undesirable harmful plants and/or improved compatibility with crop plants, in particular improved compatibility with legumes, such as lentils, peas, soy beans, beans or crop plants which are tolerant to herbicides which inhibit acetolactate synthase (ALS tolerant crops), in particular ALS tolerant small-grain cereal crops, such as, for example, ALS tolerant wheat, ALS tolerant durum, ALS tolerant triticale, ALS tolerant rye and ALS tolerant barley, but also with ALS tolerant corn, ALS tolerant sugar beet, ALS tolerant potato, ALS toler ant rice, ALS tolerant sunflower and/or ALS tolerant oilseed rape (canola). The combination should in particular be useful for controlling undesirable harmful plants in crops which are toler ant against imidazolinone herbicides, such as the so called Clearfield® crops mentioned above. The combination should have a good pre- to post-emergence herbicidal activity against harmful plants, in particular against annual and perennial grasses and broadleaf weeds, especially against herbicide resistant harmful plants species. Furthermore, the combination should have good compatibility with the subsequent crop plants, which are planted after harvest of the imidazolinone tolerant crops (crop rotation, re-cropping).

We have found that these and further objects are achieved, surprisingly, by herbicidally active combinations consisting of herbicides A, B, and C, wherein

a. the herbicide A is R-imazamox, any non-racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or an agriculturally ac ceptable salt or ester thereof; and

b. the herbicide B is prohexadione, or a salt or ester thereof; and

c. the herbicide C is mepiquat, or a salt thereof.

The invention furthermore relates to the use of a combination as defined herein for controlling undesirable vegetation in cultures of crop plants, wherein the crop plant is selected from imid azolinone tolerant crops.

The invention furthermore relates to the use of a combination as defined herein for controlling undesirable vegetation in cultures of crop plants, wherein the crop plant is selected from imid azolinone tolerant crops, and wherein the undesirable vegetation comprises herbicide resistant harmful plants species.

The invention furthermore relates to the use of a combination as defined herein for controlling undesirable vegetation in crops which, by genetic engineering, genome editing or by breeding, are resistant or tolerant to one or more herbicides, in particular against herbicides from the group of inhibitors of acetolactate synthase (ALS inhibitor compounds), such as imidazolinone herbicides, sulfonylurea herbicides or triazolpyrimidine herbicides and/or pathogens, such as harmful fungi, and/or to attack by insects; in particular crops which, by genetic engineering or by breeding, are resistant or tolerant to imidazolinone herbicides, such as imidazolinone resistant wheat, corn, rice, sunflower, lentils, peas and oilseed rape (canola), preferably sunflower.

The invention furthermore relates to a method for controlling undesirable vegetation which com prises applying a herbicidal combination according to the present invention to the undesirable plants, or to the locus, where undesirable vegetation is expected to occur. Application can be done before, during and/or after, preferably during and/or after, in particular after the emergence of the undesirable plants. The herbicide A, the herbicide B, and the herbicide C, can be applied simultaneously or in succession to the areas, where undesirable vegetation occurs or may oc- cur. The invention, in particular, relates to a method for controlling undesirable vegetation in crops which comprises applying an herbicidal composition according to the present invention in crops, where undesirable vegetation occurs or might occur.

The invention, furthermore, relates to a method for controlling undesirable vegetation which comprises allowing a combination according to the present invention to act on plants, their habi tat or on seed.

The invention, furthermore, relates to a method for controlling undesirable vegetation in imid- azolinone tolerant crops, which comprises the step of treating the seed of the imidazolinone tolerant crops with a composition according to the present invention.

In the methods of the present invention, it is immaterial, whether the herbicide A, the herbicide B, and the herbicide C, are formulated and applied jointly or separately. In the case of separate application, it is of minor importance, in which order the application takes place. It is only neces sary, that the herbicide A, the herbicide B, and the herbicide C are applied in a time frame that allows simultaneous action of the active ingredients on the plants, preferably within a time-frame of at most 14 days, in particular of at most 7 days.

The invention also relates to an herbicide formulation which comprises a herbicidally active combination as defined herein and at least one carrier material, including liquid and/or solid car rier materials.

Detailed description of the invention

Surprisingly, the combinations according to the present invention have better herbicidal activity against harmful plants than would have been expected by the herbicidal activity of the individual compounds. In other words, the joint action of the herbicide A, the herbicide B, and the herbi cide C results in an enhanced activity against harmful plants in the sense of a synergy effect (synergism or potentiation), even at low application rates of the herbicide A, the herbicide B, and the herbicide C. For this reason, the combination of the present invention can, based on the individual components, be used at lower application rates to achieve a herbicidal effect compa rable to the individual components.

Moreover, the combinations of the present invention provide good pre- and post-emergence herbicidal activity; in particular, the combinations are useful for combating/controlling harmful plants after their emergence (post-emergence). The combinations of the present invention also show good crop compatibility, i.e. their use in crops does not result in increased damage, in particular if the combinations are applied in crops tolerant to inhibitors of acetolactate synthase, especially in crops tolerant to imidazolinone herbicides or in crops with natural tolerance to one or all of herbicides B and C, or in crops with natural tolerance to all of herbicides A, B and C when compared to the individual application of herbicide A, herbicide B or herbicide C or com pared to the application of a combination of herbicides A and B. Moreover, the combinations also show an accelerated action on harmful plants, i.e. they damage harmful plants more quick ly when compared with application of the individual herbicides A, B or C and also compared to the application of a combination of herbicides A and B.

As used herein, the terms "controlling" and "combating" are synonyms.

As used herein, the terms "undesirable vegetation" and "harmful plants" are synonyms.

The term "combination" relates both to a composition containing the herbicides A, B, and C, as active ingredients and also the combined application of the herbicides A, B, and C, which means that the herbicides A, B, and C, are used together for controlling undesirable vegetation in crops and non-crop areas.

When using the combination of the invention for this purpose, the herbicides A, B, and C, can be applied simultaneously or in succession to the areas, where undesirable vegetation occurs or may occur. The herbicides A, B, and C, are, in particular, applied in crops, where undesirable vegetation may occur.

The term "composition" is understood as a physical admixture of the herbicides A, B, and C, and, optionally, one or more formulation auxiliaries, such as one or more surfactants. The term "composition" includes both a combo-formulation, containing a physical admixture of the herbi cides A, B, and C, and a ready to use composition, such as an aqueous spray liquor, obtained by tank mixing solo- or combo-formulations of the herbicides A, B, and C.

The term "formulation" includes both formulations, containing a physical admixture of the herbi cides A, B, and C, as well as kits-of-parts formulations, where the herbicides A, B, and C, are formulated separately, i.e. as solo formulations or as a kit-of part formulation, comprising a combo-formulation of the herbicide A and the herbicide B and a solo-formulation of the herbi cide C or as a kit-of part formulation, comprising a solo-formulation of the herbicide A and a combo-formulation of the herbicide B and the herbicide C. Both solo- and combo-formulations generally contain at least one formulation auxiliary, such as one or more surfactants, and at least one liquid or solid carrier. The combinations of the invention contain the herbicide A, which is R-imazamox (A-1), any non- racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R-imazamox is at least 80% by weight (A-2), preferably at least 90%, more preferably at least 95%, or an agricul turally acceptable salt or ester thereof.

As imazamox is a carboxylic acid, the combination may comprise R-imazamox (A-1) or any non- racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R-imazamox is at least 80% by weight (A-2), as such or as a salt of R-imazamox (A-3) or any non-racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R-imazamox is at least 80% by weight (A-4), in particular an alkalimetal salt or an ammonium salt or substituted ammonium salt as defined below. The carboxyl group of imazamox may also be present in esterified form, e.g. in the form of a Ci-Cs-alkoxycarbonyl group or in the form of a Ci-C₄-alkoxy-CrC₄- alkoxycarbonyl group. Examples of esters are the methyl, ethyl, propyl, isopropyl, butyl, isobu tyl, pentyl, mexyl (1-methylhexyl) or isooctyl (2-ethylhexyl) esters. Examples of Ci-C4-alkoxy-Cr C4-alkyl esters are the straight-chain or branched CrC4-alkoxyethyl esters, for example the methoxyethyl, ethoxyethyl or butoxyethyl (butoyl) esters. Usually, the combinations of the inven tion contain R-imazamox or any non-racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R-imazamox is at least 80% by weight, as such or as a salt of R-imazamox or any non-racemic mixture of R-imazamox and S-imazamox, wherein the proportion of R- imazamox is at least 80% by weight, in particular an alkalimetal salt or an ammonium salt as defined below.

Suitable salts of A-1 and A-2 include the alkali metal salts, preferably the lithium, sodium and potassium salts, the alkaline earth metals salts, e.g. the calcium and magnesium salts, and the transition metal salts, e.g. the manganese, copper, zinc and iron salts, furthermore ammonium and substituted ammonium salts (hereinafter also termed as organoammonium salts), in which one to four hydrogen atoms of ammonium are replaced by CrCe-alkyl, CrC4-alkyl, hydroxy-Cr C4-alkyl, in particular hydroxy-C2-C4-alkyl, Ci-C4-alkoxy-CrC4-alkyl, in particular CrC4-alkoxy- C2-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, in particular hydroxy-C2-C4-alkoxy-C2-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dime- thylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, pentylammonium, hexylammonium, heptylammonium, 2- hydroxyethylammonium (olamine salt), 2-(2-hydroxyethoxy)eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (= diethanolammonium salt or diolamine salt), tri(2- hydroxyethyl)ammonium (= triethanolammonium salt or trolamine salt), mono-, di- and tri(hydroxypropyl)ammonium (= mono-, di- and tripropanolammonium), benzyltrimethylammoni- um, benzyltriethylammonium, furthermore phosphonium ion salts and sulfonium salts, e.g.

tri(Ci-C4-alkyl)sulfonium such as trimethylsulfonium, and sulfoxonium salts. The combinations of the invention contain the herbicide B, which is prohexadione (lUPAC name: 3,5-dioxo-4-propionylcyclohexanecarboxylic acid), or an agriculturally acceptable salt or ester thereof (as defined above for the herbicide A), e.g. prohexadione-calcium. Usually, the combinations of the invention contain prohexadione as such or as calcium-salt.

In the combinations of the present invention, the relative weight ratio of the herbicide A, calcu lated as free acid of imazamox, to the herbicide B, calculated as free acid of prohexadione, is in the range from 1 :60 to 1 :2, in particular from 1 :40 to 1 :3, especially from 1 :30 to 1 :4. Preferably, the relative weight ratio is in the range from 1 :20 to 1 :5. Accordingly, in the methods and uses of the invention, the herbicides A and B are preferably applied within these weight ratios. Likewise, the compositions and formulations of the invention contain the herbicides A and B within these weight ratios.

The combinations of the present invention contain a third herbicide C, which is mepiquat (lU PAC name: 1 ,1-dimethylpiperidinium), or an agriculturally acceptable salt thereof (as defined above for the herbicide A), e.g. mepiquat-chloride or mepiquat-pentaborate. Usually, the combi nations of the invention contain mepiquat as such or as chloride- or pentaborate-salt.

In the combinations of the present invention, the relative weight ratio of the herbicide A, calcu lated as free acid of imazamox, to the herbicide C, calculated mepiquat-ion, is in the range from 1 :60 to 1 :2, in particular from 1 :40 to 1 :3, especially from 1 :30 to 1 :4. Preferably, the relative weight ratio is in the range from 1 :20 to 1 :5. Accordingly, in the methods and uses of the inven tion, the herbicides A and C are preferably applied within these weight ratios. Likewise, the compositions and formulations of the invention contain the herbicides A and C within these weight ratios.

In the combinations of the present invention, the relative weight ratio of the herbicide A to the total amount of the herbicide B and the herbicide C is preferably from 1 :200 to 1 :1 , in particular from 1 :150 to 1 :2, especially 1 :100 to 1 :3, wherein the herbicides A and B are calculated as the respective free acid forms, and the herbicide C is calculated as mepiquat-ion. Accordingly, in the methods and uses of the invention, the herbicides A, B and C are preferably applied within these weight ratios. Likewise, the compositions and formulations of the invention contain the herbicides A, B and C within these weight ratios.

Particular embodiments of the combinations according to the invention are the following combi nations 1 to 6: Combination 1 : Herbicide A: R-imazamox, any non-racemic mixture of R-imazamox and S- imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or a salt thereof;

Herbicide B: prohexadione;

Herbicide C: mepiquat.

Combination 2: Herbicide A: R-imazamox, any non-racemic mixture of R-imazamox and S- imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or a salt thereof;

Herbicide B: prohexadione

Herbicide C: mepiquat-chloride.

Combination 3: Herbicide A: R-imazamox, any non-racemic mixture of R-imazamox and S- imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or a salt thereof;

Herbicide B: prohexadione;

Herbicide C: mepiquat-pentaborate.

Combination 4: Herbicide A: R-imazamox, any non-racemic mixture of R-imazamox and S- imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or a salt thereof;

Herbicide B: prohexadione-calcium;

Herbicide C: mepiquat.

Combination 5: Herbicide A: R-imazamox, any non-racemic mixture of R-imazamox and S- imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or a salt thereof;

Herbicide B: prohexadione-calcium;

Herbicide C: mepiquat-chloride.

Combination 6: Herbicide A: R-imazamox, any non-racemic mixture of R-imazamox and S- imazamox, wherein the proportion of R-imazamox is at least 80% by weight, or a salt thereof;

Herbicide B: prohexadione-calcium;

Herbicide C: mepiquat-pentaborate. In Combinations 1 to 6, the weight ratio of herbicide A to herbicide B as well as the weight ratio of herbicide A to herbicide C and the weight ratio of herbicide A to the total amount of herbicides B and C is as defined above.

The compositions and methods of the present invention are useful for controlling a large variety of harmful plants (undesired vegetation), including monocotyledonous weeds and dicotyle donous weeds, in particular, for controlling weeds, which are selected from the genera Amaran- thus, Ambrosia, Avena, Bassia, Brassica, Bromus, Capsella, Chenopodium, Datura, Echi- nochloa, Erodium, Fallopia, Galium, Hordeum, Lolium, Malva, Orobanche, Persicaria,

Raphanus, Salsola, Setaria, Sinapsis, Sorghum, Stellaria, Striga, Thlaspi, Triticum, Urtica, Vac- caria, and Xanthium, preferably, for controlling weeds from the species Amaranthus retroflexus, Ambrosia artemisiifolia, Ambrosia trifida, Avena fatua, Bassia scoparia, Brassica napus, Bromus japonicas, Bromus sp., Capsella bursa-pastoris, Chenopodium album, Datura stramonium, Echinochloa crus-galli, Erodium cicutarium, Fallopia convolvulus, Galium aparine, Hordeum vulgare, Lolium persicum, Lolium rigidum, Malva neglecta, Malva pusilla, Orobanche sp., Persi caria lapathifolia, Raphanus raphanistrum, Salsola kali, Salsola kali ssp. ruthenica, Setaria fa- beri, Setaria pumila, Setaria viridis, Sinapis alba, Sinapis arvensis, Sorghum halepense, Stellar ia media, Striga sp., Thlaspi arvense, Triticum aestivum, Triticum durum, Urtica cannabina, Vaccaria hispanica, and Xanthium strumarium.

According to one embodiment, the compositions and methods of the present invention are use ful for controlling monocotyledonous weeds and dicotyledonous weeds in sunflower, wherein the weeds are selected from the genera Amaranthus, Ambrosia, Chenopodium, Datura, Echi nochloa, Orobanche, Setaria, Sorghum, and Xanthium, in particular from the species Amaran thus retroflexus, Ambrosia artemisiifolia, Ambrosia trifida, Chenopodium album, Datura stramo nium, Echinochloa crus-galli, Orobanche sp., Setaria faberi, Setaria viridis, Sorghum halepense, and Xanthium strumarium.

According to one embodiment, the compositions and methods of the present invention are use ful for controlling monocotyledonous weeds and dicotyledonous weeds in canola, wheat and barley, wherein the weeds are selected from the genera Amaranthus, Avena, Bassia, Brassica, Bromus, Capsella, Chenopodium, Echinochloa, Erodium, Fallopia, Galium, Hordeum, Lolium, Malva, Persicaria, Raphanus, Salsola, Setaria, Sinapsis, Stellaria, Thlaspi, Triticum, Urtica, and Vaccaria, in particular from the species Amaranthus retroflexus, Avena fatua, Bassia scoparia, Brassica napus, Bromus japonicas, Bromus sp., Capsella bursa-pastoris, Chenopodium album, Echinochloa crus-galli, Erodium cicutarium, Fallopia convolvulus, Galium aparine, Hordeum vulgare, Lolium persicum, Lolium rigidum, Malva neglecta, Malva pusilla, Persicaria lapathifolia, Raphanus raphanistrum, Salsola kali, Salsola kali ssp. ruthenica, Setaria pumila, Setaria viridis, Sinapis alba, Sinapis arvensis, Stellaria media, Striga sp., Thlaspi arvense, Triticu aestivu , Triticu durum, Urtica cannabina, and Vaccaria hispanica.

According to one embodiment, the compositions and methods of the present invention are suit able for controlling monocotyledonous weeds, in particular for controlling monocotyledonous weeds, which are selected from the families Poaceae (Gramineae), commonly known as grass es.

According to a preferred embodiment, the compositions and methods of the present invention are suitable for controlling monocotyledonous weeds, which are selected from the genera Av- ena, Bromus, Echinochloa, Hordeum, Lolium, Setaria, Sorghum, and Triticum, in particular from the species Avena fatua, Bromus japonicas, Bromus sp., Echinochloa crus-galli, Hordeum vul- gare, Lolium persicum, Lolium rigidum, Setaria faberi, Setaria pumila, Setaria viridis, Triticum aestivum, and Triticum durum.

According to a more preferred embodiment, the compositions and methods of the present in vention are suitable for controlling monocotyledonous weeds, which are selected from the gene ra Echinochloa, Setaria, and Sorghum, in particular from the species Echinochloa crus-galli, Setaria faberi, Setaria viridis, and Sorghum halepense.

According to another embodiment, the compositions and methods of the present invention are suitable for controlling dicotyledonous weeds, commonly known as broadleaf weeds.

According to a further preferred embodiment, the compositions and methods of the present in vention are suitable for controlling dicotyledonous weeds from the genera

Amaranthus, Ambrosia, Bassia, Brassica, Capsella, Chenopodium, Datura, Erodium, Fallopia, Galium, Malva, Orobanche, Persicaria, Raphanus, Salsola, Sinapsis, Stellaria, Striga, Thlaspi, Urtica, Vaccaria, and Xanthium, and in particular from the species Amaranthus retroflexus, Am brosia artemisiifolia, Ambrosia trifida, Bassia scoparia, Brassica, Capsella bursa-pastoris, Che nopodium album, Datura stramonium, Erodium cicutarium, Fallopia convolvulus, Galium apari- ne, Malva neglecta, Malva pusilla, Orobanche sp., Persicaria lapathifolia, Raphanus raphan- istrum, Salsola kali, Salsola kali ssp. ruthenica, Sinapis alba, Sinapis arvensis, Stellaria media, Striga sp., Thlaspi arvense, Urtica cannabina, Vaccaria hispanica, and Xanthium strumarium.

According to a more preferred embodiment, the compositions and methods of the present in vention are suitable for controlling dicotyledonous weeds from the genera

Amaranthus, Ambrosia, Chenopodium, Datura, Orobanche, and Xanthium, and in particular from the species Amaranthus retroflexus, Ambrosia artemisiifolia, Ambrosia trifida, Chenopodi um album, Datura stramonium, Orobanche sp., and Xanthium strumarium. According to another embodiment, the compositions and methods of the present invention are suitable for controlling monocotyledonous and dicotyledonous weeds in sunflower, wherein the weeds are selected from the genera Abutilon, Alopecurus, Amaranthus, Ambrosia, Ammi, Atri- plex, Avena, Brassica, Chenopodium, Cirsium, Convolvulus, Datura, Digitaria, Echinochloa, Fumaria, Galinsoga, Helianthus, Heliotropium, Hibiscus, Lolium, Matricaria, Orobanche, Pani- cum, Poa, Polygonum, Portulaca, Setaria, Solanum, Sonchus, Stachys, Stellaria, and Xanthi- um; and in particular from the species Abutilon theophrasti (ABUTH), Amaranthus retroflexus (AMARE), Ambrosia artemisiifolia (AMBEL), Ammi majus (AMIMA), Chenopodium album (CHEAL), Cirsium arvense (CIRAR), Convolvulus arvensis (CONAR), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Lolium multiflorum (LOLMU), Orobanche sp.

(ORASS), Panicum miliaceum (PANMI), Portulaca oleracea (POROL), Setaria viridis (SETVI), Solanum nigrum (SOLNI), and Sonchus arvensis (SONAR).

According to a more preferred embodiment, the compositions and methods of the present in vention are suitable for controlling monocotyledonous weeds in sunflower, which are selected from the genera Digitaria, Echinochloa, Lolium, Panicum, and Setaria; in particular from the species Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Lolium multiflorum (LOLMU), Panicum miliaceum (PANMI), and Setaria viridis (SETVI).

According to another more preferred embodiment, the compositions and methods of the present invention are suitable for controlling dicotyledonous weeds in sunflower, which are selected from the genera Abutilon, Amaranthus, Ambrosia, Ammi, Chenopodium, Cirsium, Convolvulus, Orobanche, Portulaca, Solanum, Sonchus; and in particular from the species Abutilon the ophrasti (ABUTH), Amaranthus retroflexus (AMARE), Ambrosia artemisiifolia (AMBEL), Ammi majus (AMIMA), Chenopodium album (CHEAL), Cirsium arvense (CIRAR), Convolvulus arven sis (CONAR), Orobanche sp. (ORASS), Portulaca oleracea (POROL), Solanum nigrum

(SOLNI), and Sonchus arvensis (SONAR).

In a particular embodiment, the compositions and methods of the present invention are suitable for controlling parasitic weeds, such as weeds from the genus Orobanche, from the genus Conopholis, from the genus Striga, or from the genus Cuscuta. Non-limiting examples of weed from the genus Orobanche include Orobanche aegyptiaca pers., O. ramosa L., O. mino Sm., O. crenata Forsk, O. cumana Wallr., and O. cernua Loefl. These examplatory parasitic weeds are known to afflict plants such as Apiaceae, Asteraceae, Brassicaceae, Cannabiceae, Chenopodi- aceae, Cucurbitaceae, Fabaceae, Liliaceae, Malvaceae and Solanaceae.

Non-limiting examples of the genus Conopholis include Conopholis alpina and Conopholis Americana. Non-limiting examples of weed from the genus Striga include Striga hermonthica and Striga asiatica. Affected host plants are for example maize, millet, rice, sorghum and sugarcane.

Non-limiting examples of the genus Cuscuta include Cuscuta approximata, Cuscuta californica, Cuscuta epithymum, Cuscuta europaea, Cuscuta pentagona, and Cuscuta salina. These exam- platory parasitic weeds are known to afflict plants such as Alfalfa, clover, tomatoes and pota toes, onion (Allium cepa L.) and chilli (Capsicum annum L). and beets (Beta vulgaris).

Host plants of parasitic weeds comprise plants of the family of Asteracea, such as Helianthus annuus; Brassicaceae such as B. napus, B. rapa, B. juncea; Poaceae such as Zea mays or Oryza sativa; Leguminosae (Fabaceae) such as Trifolium spp, Glycine max, Pisa spp, Vicia spp or Medicago spp; Solanaceae such as Solanum tuberosum, Solanum lycopersicum, Solanum melongena, Nicotiana tabacum.

In one preferred embodiment, the host plants may comprise plants such as Helianthus annuus, Brassica napus, Brassica rapa, Brassical juncea, Glycine max (soybean), Sorghum, Triticum spp (wheat), Lens culinaris (lentil), Hordeum vulgare (Barley), Dry Bean (phaseolus spp), Vigna unguiculata (cowpea) or combinations thereof.

In a preferred embodiment, the host plants may be herbicide tolerant Helianthus annuus. Pref erably, the host plant provides an herbicide tolerance trait (1) having an AHASL with an A122(At)T substitution, or (2) an AHASL variant thereof that contains both the A122(At)T substi tution and a second substitution that can be one or more of P197(At)Q, P197(At)S, P197(At)L, T203(At)l, T203(At)X, A205(At)D, A205(At)V, W574(At)L, A653(At)N, A653(At)T, A653(At)F, or A653(At)V; wherein X may be selected as any natural amino acid.

In another preferred embodiment, the host plant Helianthus annuus provides two herbicide tol erance traits, both the trait with the AHASL A122(At)T substitution and a second trait, having an AHASL with an A205(At)V substitution, an AHASL with a P197(At)S substitution, an AHASL with a P197(At)L substitution or an AHASL with a W574(At)L substitution.

In another preferred embodiment, the host plant Helianthus annuus provides a herbicide toler ance trait having one A205(At)V substitution. For example, the host plant may be Helianthus annuus Imisun sunflowers that are known as tolerant towards imidazolinones.

In another particular embodiment, the host plant Helianthus annuus provides a herbicide toler ance trait with an AHASL having one W574(At)L substitution. For example, the host plant may provide the AIR trait, giving a broad range of tolerance to sulfonylurea, imidazolinones, tria- zolopyrimidine and pyrimidyloxybenzoates.

According to another embodiment, the compositions and methods of the present invention are suitable for controlling undesirable vegetation, wherein the undesirable vegetation comprises volunteer crop plants. Volunteer crop plants are crop plants that volunteer in planted crops.

They are considered weeds, which compete with the planted crop for moisture, nutrients and light. According to a further preferred embodiment, the compositions and methods of the pre sent invention are suitable for controlling undesirable vegetation, wherein the undesirable vege tation comprises volunteer crop plants selected from the genera Brassica, Hordeum, and Triti- cum, in particular from the species Brassica napus (BRSNW, BRSNS) Hordeum vulgare (HORVW, HORVS), Triticum aestivum (TRZAW, TRZAS), Triticum durum (TRZDU).

According to another embodiment, the compositions and methods of the present invention are useful for controlling monocotyledonous and dicotyledonous species, which are herbicide re sistant or tolerant.

Exemplary herbicide resistant or tolerant weed species include, but are not limited to, biotypes resistant or tolerant to herbicides selected from the group consisting of acetyl CoA carboxylase (ACCase) inhibitors (HRAC Group A), acetolactate synthase (ALS) inhibitors (HRAC Group B), photosystem II (PS II) inhibitors (HRAC Groups C1 , C2 and C3), photosystem I (PS I) inhibitors (HRAC Group D), protoporphyrinogen oxidase (PPO) inhibitors (HRAC Group E), 4- hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors (HRAC Group F1), phytoene desatu- rase (PDS) inhibitors (HRAC Group F2), carotenoid biosynthesis inhibitors (HRAC Group F3), DOXP synthase inhibitors (HRAC Group F4), 5- enolpymvylshikimate-3-phosphate (EPSP) in hibitors (HRAC Group G), glutamine synthetase inhibitors (HRAC Group H), DHP synthase in hibitors (HRAC Group I), inhibitors of microtubuli assembly (HRAC Group K1), inhibitors of mi tosis/m icrotubuli organization (HRAC Group K2), very long chain fatty acid (VLCFA) inhibitors (HRAC Group K3), Inhibitors of cell wall synthesis (HRAC Group L), uncoupler (membran dis ruption) (HRAC Group M), Inhibitors of lipid synthesis (HRAC Group N), synthetic auxins (HRAC Group O), auxin transport inhibitors (HRAC Group P) and herbicides with unknown mode of action (HRAC Group Z).

Preferably, the herbicide resistant or tolerant weed species is selected from biotypes resistant or tolerant to herbicides selected from the group consisting of acetyl CoA carboxylase (ACCase) inhibitors (HRAC Group A), acetolactate synthase (ALS) inhibitors (HRAC Group B), photosystem II (PS II) inhibitors (HRAC Groups C1 , C2 and C3), protoporphyrinogen oxidase (PPO) inhibitors (HRAC Group E), 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors (HRAC Group F1), phytoene desaturase (PDS) inhibitors (HRAC Group F2), 5- enolpymvylshikimate-3-phosphate (EPSP) inhibitors (HRAC Group G), inhibitors of microtubuli assembly (HRAC Group K1), very long chain fatty acid (VLCFA) inhibitors (HRAC Group K3), Inhibitors of cell wall synthesis (HRAC Group L) and inhibitors of lipid synthesis (HRAC Group N).

More preferably, the herbicide resistant or tolerant weed species is selected from biotypes resistant or tolerant to herbicides selected from the group consisting of acetyl CoA carboxylase (ACCase) inhibitors (HRAC Group A), acetolactate synthase (ALS) inhibitors (HRAC Group B), photosystem II (PS II) inhibitors (HRAC Groups C1 , C2 and C3), inhibitors of microtubuli assembly (HRAC Group K1), very long chain fatty acid (VLCFA) inhibitors (HRAC Group K3) and inhibitors of lipid synthesis (HRAC Group N).

In particular, the herbicide resistant or tolerant weed species is selected from biotypes with resistance or tolerance to at least one herbicide selected from the group consisting of acetyl CoA carboxylase (ACCase) inhibitors (HRAC Group A), acetolactate synthase (ALS) inhibitors (HRAC Group B) and photosystem II (PS II) inhibitors (HRAC Groups C1 , C2 and C3).

In another embodiment, the resistant or tolerant biotype is selected from the genera Agropyron, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cynodon, Digitaria, Echinochloa, Eleusine, Is- chaemum, Leptochloa, Lolium, Panicum, Phalaris, Poa, Rottboellia, Setaria, Sorghum, Abutilon, Anthemis, Amaranthus, Ambrosia, Capsella, Centaurea, Chenopodium, Conyza, Descurainia, Galium, Geranium, Kochia, Matricaria, Papaver, Polygonum, Raphanus, Sinapis, Sisymbrium, Stellaria and Thlaspi.

Preferably, the resistant or tolerant biotype is selected from the genera Agropyron, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cynodon, Digitaria, Echinochloa, Eleusine, Ischaemum, Leptochloa, Lolium, Panicum, Phalaris, Poa, Rottboellia, Setaria, Anthemis, Amaranthus, Am brosia, Capsella, Centaurea, Chenopodium, Conyza, Descurainia, Galium, Kochia, Matricaria, Papaver, Raphanus, Sinapis, Sisymbrium, Stellaria and Thlaspi.

More preferably, the resistant or tolerant biotype is selected from the genera Alopecurus, Apera, Digitaria, Echinochloa, Leptochloa, Lolium, Phalaris, Poa, Setaria, Amaranthus, Anthemis, Capsella, Centaurea, Chenopodium, Descurania, Kochia, Matricaria, Papaver, Sisymbrium, Stellaria and Thlaspi, still more preferably selected from the genera Alopecurus, Apera, Echi nochloa, Leptochloa, Lolium, Phalaris, Poa, Amaranthus, Chenopodium, Matricaria, Papaver and Stellaria, even more preferably selected from the genera Alopecurus, Echinochloa, Lolium, Phalaris, Poa, Amaranthus, Chenopodium, Matricaria, Papaver and Stellaria, yet more prefera- bly selected from the genera Alopecurus, Echinochloa, Lolium, Phalaris, Poa and Papaver and in particular selected from the genera Alopecurus, Lolium, Phalaris and Papaver.

In another embodiment, the resistant or tolerant biotype is selected from the genera Alopecurus, Apera, Digitaria, Echinochloa, Leptochloa, Phalaris, Poa, Setaria, Amaranthus, Anthemis, Capsella, Centaurea, Chenopodium, Descurania, Kochia, Matricaria, Papaver, Sisymbrium, Stellaria and Thlaspi, more preferably selected from the genera Alopecurus, Apera, Echi nochloa, Leptochloa, Phalaris, Poa, Amaranthus, Chenopodium, Matricaria, Papaver and Stel laria, even more preferably selected from the genera Alopecurus, Echinochloa, Phalaris, Poa, Amaranthus, Chenopodium, Matricaria, Papaver and Stellaria, yet more preferably selected from the genera Alopecurus, Echinochloa, Phalaris, Poa and Papaver and in particular selected from the genera Alopecurus, Phalaris and Papaver.

In another embodiment, the resistant or tolerant biotype is selected from the genera Avena, Echinochloa, Lolium, Setaria, Sorghum, Abutilon, Amaranthus, Anthemis, Chenopodium, Gali um, Geranium, Polygonum and Stellaria.

The combinations of the present invention are suitable for combating/controlling undesired veg etation in legumes, such as lentils, peas, soy beans or in ALS tolerant crops, in particular in ALS tolerant small-grain cereal crops, such as, for example, ALS tolerant wheat, ALS tolerant durum, ALS tolerant triticale, ALS tolerant rye and ALS tolerant barley, but also in ALS tolerant corn, ALS tolerant sugar beet, ALS tolerant potato, ALS tolerant rice, ALS tolerant sunflower and ALS tolerant oilseed rape (canola). The combinations of the present invention are particularly suita ble for combating/controlling undesired vegetation in ALS tolerant sunflower.

The combinations of the invention are particularly useful in crops that are tolerant against imid- azolinone herbicides, such as Clearfield® crops, e.g. Clearfield® Canola, Clearfield® Rice, Clearfield® Corn, Clearfield® Wheat, Clearfield® Sunflower, Clearfield® Lentils, Clearfield® Corn, and Cultivance® crops, in particular in Clearfield®Sunflower.

If not stated otherwise, the combinations of the invention are suitable for application in any vari ety of the aforementioned crop plants.

The combinations according to the invention can also be used in crop plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides, such as imidazolinone herbicides, such as ima- zamox, auxinic herbicides, such as dicamba or 2,4-D; bleacher herbicides, such as 4- hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibi- tors; acetolactate synthase (ALS) inhibitors, such as sulfonylureas or imidazolinones; enolpy- ruvyl shikimate 3-phosphate synthase (EPSP) inhibitors, such as glyphosate; glutamine synthe tase (GS) inhibitors, such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosyn thesis inhibitors, such as acetylCoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering; furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glypho sate and a herbicide from another class, such as ALS inhibitors, HPPD inhibitors, auxinic herbi cides, or ACCase inhibitors. These herbicide resistance technologies are, for example, de scribed in Pest Management Science 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Science 57, 2009, 108; Australian Journal of Agricultural Research 58, 2007, 708; Science 316, 2007, 1185; and references quot ed therein. Several cultivated plants have been rendered tolerant to herbicides by mutgenesis and conventional methods of breeding, e. g., Clearfield® crops, such as Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g., imazamox, or Ex- pressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g., tribenuron. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate, imidazolinones and

glufosinate, some of which are under development or commercially available under the brands or trade names RoundupReady® (glyphosate tolerant, Monsanto, USA), Cultivance® (imidazo- linone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate tolerant, Bayer CropScience, Germany).

The combinations according to the invention can also be used in genetically modified crop plants. The term "genetically modified plants" is to be understood as plants whose genetic mate rial has been modified by the use of recombinant DNA techniques to include an inserted se quence of DNA that is not native to that plant species’ genome or to exhibit a deletion of DNA that was native to that species’ genome, wherein the modification(s) cannot readily be obtained by cross breeding, mutagenesis or natural recombination alone. Often, a particular genetically modified plant will be one that has obtained its genetic modification(s) by inheritance through a natural breeding or propagation process from an ancestral plant whose genome was the one directly treated by use of a recombinant DNA technique. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve cer tain properties of the plant. Such genetic modifications also include, but are not limited to tar geted post-translational modification of protein(s), oligo- or polypeptides e. g., by inclusion therein of amino acid mutation(s) that permit, decrease, or promote glycosylation or polymer additions such as prenylation, acetylation farnesylation, or PEG moiety attachment. The combinations according to the invention can also be used in crop plants that have been modified, e.g. by the use of recombinant DNA techniques to be capable of synthesizing one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as delta-endotoxins, e. g., CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g., VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g., Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such as Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3- hydroxy- steroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone recep tors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention, these insecticidal proteins or toxins are to be understood expressly also as including pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g.,

WO 02/015701). Further examples of such toxins or genetically modified plants capable of syn thesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP- A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are de scribed, e. g., in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publi cations mentioned above, and some of which are commercially available, such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton culti vars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars produc ing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt1 1 (e. g., Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enzyme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).

The combinations according to the invention can also be used in crop plants that have been modified, e.g. by the use of recombinant DNA techniques to be capable of synthesizing one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called“pathogenesis-related proteins” (PR proteins, see, e.g., EP-A 392 225), plant disease resistance genes (e. g., potato cultivars which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato, Solanum bulbocastanum) or T4-lysozym (e.g., potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylovora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g., in the publications mentioned above.

The combinations according to the invention can also be used in crop plants that have been modified, e.g. by the use of recombinant DNA techniques to be capable of synthesizing one or more proteins to increase the productivity (e.g., bio-mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmen tal factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

The combinations according to the invention can also be used in crop plants that have been modified, e.g. by the use of recombinant DNA techniques to be capable of producing an in creased amount of ingredients or new ingredients, which are suitable to improve human or ani mal nutrition, e. g., oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g., Nexera® rape, Dow AgroSciences, Canada).

The combinations of the present invention can be applied in a conventional manner by a skilled personal familiar with the techniques of applying herbicides. Suitable techniques include spray ing, atomizing, dusting, spreading or watering. The type of application depends on the intended purpose in a well known manner; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.

The combinations can be applied pre- or post-emergence, i.e. before, during and/or after emer gence of the undesirable plants. When the combinations are used in crops, they can be applied after seeding and before or after the emergence of the crop plants. The compositions according to the invention can, however, also be applied prior to seeding of the crop plants. It is a particular benefit of the combinations according to the invention that they have a very good post-emergence herbicide activity, i.e. they show a good herbicidal activity against emerged undesirable plants. Thus, in a preferred embodiment of invention, the combinations are applied post-emergence, i.e. during and/or after, the emergence of the undesirable plants. It is particularly advantageous to apply the combinations according to the invention post emergent when the undesirable plant starts with leaf development up to flowering. Since the combinations of the present invention show good crop tolerance, even when the crop has already emerged, they can be applied after seeding of the crop plants and, in particular, during or after the emer gence of the crop plants.

In any case, the herbicide A, the herbicide B, and the herbicide C can be applied simultaneously or in succession.

In a preferred embodiment, the combinations of the invention are applied in the form of a com position containing the combination of the present invention and a formulation additive, such as one or more surfactants. Preferably, the compositions are dilute aqueous compositions. Such dilute compositions are usually obtained by tank mixing solo- or combo-formulations, containing the herbicide A, the herbicide B, and the herbicide C, which are formulated jointly or separately.

It is also possible to apply several compositions successively, where compositions contain only one or two herbicide compounds selected from the herbicide A, the herbicide B, and the herbi cide C, provided that the compositions together comprise the herbicide A, the herbicide B, and the herbicide C.

The compositions are applied to the plants mainly by spraying, in particular foliar spraying. Ap plication can be carried out by customary spraying techniques using, for example, water as car rier and spray liquor rates of 10 to 2000 l/ha or 50 to 1000 l/ha (for example from 50 to 500 l/ha). Application of the herbicidal compositions by the low-volume and the ultra-low-volume method is possible, as is their application in the form of microgranules.

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 effect ed, for example, by usual spraying techniques with water as the carrier, using amounts of spray mixture of approx. 50 to 1000 l/ha.

In the method of the invention, the application rate of the herbicide A, calculated as the free acid of imazamox, is generally from 0.1 to 200 g/ha and in particular from 0.1 to 100 g/ha or from 0.1 to 50 g/ha. In a preferred embodiment, the application rate of the herbicide A is from 0.1 to 50 g/ha and in particular from 0.1 to 20 g/ha or from 0.5 to 10 g/ha

In the method of the invention, the application rate of the herbicide B, calculated as the free acid of prohexadione, is generally from 10 to 2500 g/ha, in particular from 50 to 1500 g/ha, prefera bly from 5 to 500 g/ha. In a preferred embodiment, the application rate of the herbicide B is from 5 to 250 g/ha and in particular from 5 to 100 g/ha or from 0.5 to 50 g/ha

In the method of the invention, the application rate of the herbicide C, calculated as the mepi- quat-ion, is generally from 1 to 1000 g/ha, in particular from 1 to 500 g/ha, preferably from 1 to 300 g/ha.

The present invention also relates to compositions and formulations comprising a combination according to the present invention.

The compositions usually contain, besides the combinations of the invention, at least one formulation additive. Generally, the formulation additive comprises one or more surfactants and, optionally, one or more formulation auxiliaries commonly used in crop protection. The compositions include both liquid dilute compositions as well as concentrate formulations containing, besides the active ingredients, at least one organic or inorganic carrier material and one or more formulation additives, in particular one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.

The compositions of the invention may be used as such or in combination with adjuvants which are conventionally used with herbicides, and which include, in particular, blends of paraffinic oils with non-ionic or anionic surfactants (crop-oils and crop-oil concentrates), blends of esterified vegetable-oils, such as methylated seed oil, and non-ionic or anionic surfactants, blends of veg etable oils and non-ionic or anionic surfactants such as Dash®, Hasten®, Agrirob®, Trend® and Mero®.

Particularly suitable adjuvants comprise a polar solvent and a phosphate ester of the formula (A)

O

R— — R^b (A)

0 H in which

R³ IS R¹-0-(C_nH_2n0)_x-(C_mH_2m0)_y-, R^b is R¹-0-(C_nH_2n0)_x-(C_mH_2m0)_y- or OH,

R¹ is Ce-Cso-alkyl,

n, m independently of one another are a value of from 2 to 6,

x, y independently of one another are a value of from 0 to 100,

x+y gives a value of from 1 to 100, and

wherein the phosphate ester of the formula (A) can be present as the free acid and/or as a salt and wherein the polar solvent is dimethyl sulfoxide or tetramethylene sulfone.

The formulation may be in the form of a single package formulation containing the herbicides A,

B, and C, together with liquid and/or solid carrier materials, and one or more formulation addi tives, such as one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions. The formulation may be in the form of a two package formula tion (two kits of parts formulation), wherein one package contains a formulation of herbicide A, while the other package contains a formulation of the herbicide B and C and wherein both for mulations contain at least one liquid and/or solid carrier material and one or more formulation additives, such as one or more surfactants and, if desired, one or more further auxiliaries cus tomary for crop protection compositions. The formulation may also be in the form of a two pack age formulation (two kits of parts formulation), wherein one package contains a formulation of herbicides A and B, while the other package contains a formulation of the herbicide C, and wherein both formulations contain at least one liquid and/or solid carrier material and one or more formulation additives, such as one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions. The formulation may also be in the form of a two package formulation (two kits of parts formulation), wherein one package contains a formulation of herbicide A, while the other package contains a formulation of the herbicide B, and wherein both formulations contain at least one liquid and/or solid carrier material and one or more formulation additives, such as one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions. The formulation may also be in the form of a three package formulation (three kits of parts formulation), wherein one package contains a formulation of herbicide compound A, a second package contains the herbicide B, and a third package which contains a formulation of the herbicide C, and wherein the three formulations contain at least one liquid and/or solid carrier material and one or more formulation additives, such as one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions. In the case of two or three package formulations the two or three formulations are preferably mixed prior to application. Preferably, the mixing is performed as a tank mix, i.e. the formulations are mixed immediately prior or upon dilution with water.

In the formulations of the present invention, the active ingredients, i.e. the herbicides A, B, and

C, may be present in suspended, emulsified or dissolved form. The formulations according to the invention can be in the form of aqueous solutions, powders, suspensions, also highly- concentrated aqueous, oily or other suspensions or dispersions, aqueous emulsions, aqueous microemulsions, aqueous suspo-emulsions, oil dispersions, pastes, dusts, materials for spread ing or granules.

Depending on the formulation type and the active ingredient, they comprise one or more liquid or solid carriers, if appropriate, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), and, if appropriate, further auxiliaries which are customary for formulating crop protection products. The person skilled in the art is sufficiently familiar with the recipes for such formulations. Further auxiliaries include e.g. organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, colorants and, for seed formulations, adhesives.

Suitable carriers include liquid and solid carriers. Liquid carriers include e.g. non-aqueous sol vents, such as cyclic and aromatic hydrocarbons, e.g. paraffins, tetrahydronaphthalene, alkylat ed 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, e.g. amines, such as N-methylpyrrolidone, and water as well as mix tures thereof. Solid carriers include e.g. mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as ammoni um 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.

Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants and also emulsifiers) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids (e.g. Borrespers-types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,

polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and proteins, denaturated proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, Lupamine types), polyethyleneimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.

Suitable further formulation auxiliaries are e.g. thickeners, antifoams, bactericides, antifreeze agents, colourants and adhesives.

Examples of thickeners (i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion) are

polysaccharides, such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), and also organic and inorganic sheet minerals, such as Attaclay® (from Engelhardt).

Examples of antifoams are silicone emulsions (such as, for example, Silikon^® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.

Bactericides can be added for stabilizing the aqueous herbicidal formulations. Examples of bactericides are bactericides based on diclorophen and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas), and also isothiazolinone derivates, such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS from Thor Chemie).

Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.

Examples of colorants are both sparingly water-soluble pigments and water-soluble dyes. Examples which may be mentioned are the dyes known under the names Rhodamin B, C.l. Pigment Red 112 and C.l. Solvent Red 1 , and also pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15: 1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.

To prepare emulsions, pastes or oil dispersions, the active the components, as such or dis solved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates consisting of active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, and these concentrates are suitable for dilution with water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitant grinding of the active the components with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be pre pared by binding the active ingredients to solid carriers.

The formulations of the invention comprise a herbicidally effective amount of the composition of the present invention. The concentrations of the active ingredients in the formulations can be varied within wide ranges. In general, the formulations comprise from 1 to 98% by weight, pref erably 10 to 60% by weight, of active ingredients (sum of herbicide compound A, herbicide compound B and herbicide compound C). The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The active herbicide compounds A and B as well as the compositions according to the invention can, for example, be formulated as follows:

1. Products for dilution with water

A Water-soluble concentrates

10 parts by weight of the herbicides A, B, and C, are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other adjuvants are added. The active compound dissolves upon dilution with water. This gives a formulation with an active compound content of 10% by weight.

B Dispersible concentrates

20 parts by weight of the herbicides A, B, and C, are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example

polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.

1. C Emulsifiable concentrates

15 parts by weight of the herbicides A, B, and C, are dissolved in 75 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The formulation has an active compound content of 15% by weight.

D Emulsions

25 parts by weight of the herbicides A, B, and C, are dissolved in 35 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.

E Suspensions

In an agitated ball mill, 20 parts by weight of the herbicides A, B, and C, are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.

F Water-dispersible granules and water-soluble granules

50 parts by weight of the herbicides A, B, and C, are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.

G Water-dispersible powders and water-soluble powders

75 parts by weight of the herbicides A, B, and C, are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.

H Gel formulations

In a ball mill, 20 parts by weight of the herbicides A, B, and C, 10 parts by weight of dispersant,

1 part by weight of gelling agent and 70 parts by weight of water or of an organic solvent are mixed to give a fine suspension. Dilution with water gives a stable suspension with active compound content of 20% by weight.

2. Products to be applied undiluted 2. I Dusts

5 parts by weight of the herbicides A, B, and C, are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dusting powder with an active compound content of 5% by weight.

3. J Granules (GR, FG, GG, MG)

0.5 parts by weight of the herbicides A, B, and C, are ground finely and associated with

99.5 parts by weight of carriers. Current methods here are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted with an active compound content of 0.5% by weight.

K ULV solutions (UL)

10 parts by weight of the herbicides A, B, and C, are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted with an active compound content of 10% by weight.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wetta- ble powders or water-dispersible granules by adding water.

It may, furthermore, be beneficial to apply the compositions of the invention alone or in combination with other herbicides, or else in the form of a mixture with other crop protection agents, for example together with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Other additives, such as non-phytotoxic oils and oil concentrates, may also be added.

USE EXAMPLES:

The effect of the herbicidal combinations according to the invention on the growth of undesira ble plants compared to the herbicidal active compounds alone was demonstrated by the follow ing greenhouse experiments.

The culture containers used were plastic pots containing loamy sand with approximately 3.0% of humus as substrate. The seeds of the test plants were sown separately for each species.

For the pre-emergence and post-emergence treatments, a tank mix containing formulations of the herbicide A, the herbicide B and the herbicide C which had been suspended or emulsified in water, were applied by means of finely/evenly distributing spray nozzles. In all use examples, plants were grown in a greenhouse environment. The containers were irrigated gently to promote germination and growth. For the post emergence treatment, the test plants were grown to growth stage 10 to 22, depending on the plant variety or to a height, depending on the plant habit, and only then treated with the active compounds which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

Depending on the species, the plants were kept at 10 - 25°C and 20 - 35°C, respectively. The test period extended over 1 to 4 weeks. During this time, the plants were tended and their re sponse to the individual treatments was evaluated.

The herbicide compounds applied in the examples were used as commercially available formu lations which have been diluted with tap water to a suitable concentration.

Beyond^® herbicide: 120g/l SL formulation of imazamox as racemate (rac)

R-imazamox: tech material, 120 g/l SL formulation

Regalis^®: Prohexadione -Calcium 10% WG

Driver^®: Mepiquat chloride 50 g/l SL

DAT : days after treatment

The evaluation for the damage 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.

The plants used in the greenhouse experiments belonged to the following species:

PS22-1A-VH, BRSNW

PX111CL (rape (winter))

Colby's formulae were applied to determine whether the composition showed synergistic action: S. R. Colby (1967)“Calculating synergistic and antagonistic responses of herbicide combina tions", Weeds 15, p. 22 ff.

E = X + Y - (X Y/100) (I) where in formula I

X = effect in percent using herbicide A + B at an application rate a or a+b, respectively;

Y = effect in percent using herbicide C at application rate c, respectively

E = expected effect (in %) of A + B + C at application rates a + b + c.

The value E corresponds to the effect (plant damage or injury) which is to be expected if the activity of the individual compounds is just additive. If the observed effect is higher than the val ue E calculated according to Colby, a synergistic effect is present.

(X*): expected value according to Colby Evaluation 12 DAT (days after treatment)

Selectivity

Table 1 :

Table 2:

Claims

1. Herbicidally active combinations comprising herbicides A, B, and C, wherein

a. the herbicide A is R-lmazamox, any non-racemic mixture of R-lmazamox and S- Imazamox, wherein the proportion of R-lmazamox is at least 80% by weight, or an ag riculturally acceptable salt or ester thereof; and

b. the herbicide B is prohexadione, or a salt or ester thereof; and

c. the herbicide C is mepiquat, or a salt thereof.

2. The combination according to claim 1 , wherein

b. the herbicide B is prohexadione-calcium; and

c. the herbicide C is mepiquat chloride.

3. The combination according to claim 1 or 2, wherein the combination consists of herbicides A, B and C.

4. The combination according to any of the preceding claims, wherein the relative weight ratio of herbicide A to herbicide B is from 1 :20 to 1 :5.

5. The combination according to any of the preceding claims, wherein the relative weight ratio of herbicide A to herbicide C is from 1 :20 to 1 :5.

6. Herbicidally active compositions comprising a combination as claimed in any one of

claims 1 to 5 and one or more auxiliaries customary in crop protection.

7. The use of herbicidally active combinations or compositions as claimed in any one of claims 1 to 6 for the selective control of undesirable vegetation in cultures of crop plants, wherein the crop plant is selected from imidazolinone tolerant crops.

8. The use according to claim 7, wherein the imidazolinone tolerant crop is selected from sunflower.

9. The use according to claims 7 or 8, wherein the undesirable vegetation is selected from the genera Abutilon, Alopecurus, Amaranthus, Ambrosia, Ammi, Atriplex, Avena, Brassi- ca, Chenopodium, Cirsium, Convolvulus, Datura, Digitaria, Echinochloa, Fumaria, Ga- linsoga, Helianthus, Heliotropium, Hibiscus, Lolium, Matricaria, Orobanche, Panicum,

Poa, Polygonum, Portulaca, Setaria, Solanum, Sonchus, Stachys, Stellaria, and Xanthi- um.

10. The use according to any of claims 7 to 9, wherein the undesirable vegetation comprises parasitic weeds.

11. The use according to claim 10, wherein the parasitic weed is selected from the genus Or obanche.

12. The use according to any of claims 7 to 9, wherein the undesirable vegetation comprises volunteer crop selected from the genera Brassica, Hordeum, and Triticum.

13. The use according to any of claims 7 to 9, wherein the undesirable vegetation comprises herbicide resistant species.

14. A method for controlling undesirable vegetation which comprises allowing the combina tions or composition as claimed in any one of claims 1 to 6 to act on plants, their habitat or on seed.

15. A method for controlling undesirable vegetation in imidazolinone tolerant crops, which comprises the step of treating the seed of the imidazolinone tolerant crops with a compo sition as claimed in claims 1 to 6.