WO2020126584A1

WO2020126584A1 - Herbicidal combinations

Info

Publication number: WO2020126584A1
Application number: PCT/EP2019/084131
Authority: WO
Inventors: Helmut Kraus; Cyrill Zagar; Tobias SEISER; Johannes BESSAI; Tatjana DIMITRIADI; Matthew BLAKEN; Andreas Landes; Yannick Griveau; Danielle Reid; Nocha Van Thielen; Jeffrey Brown; JDavid PETERS
Original assignee: Basf Agrochemical Products B.V.
Priority date: 2018-12-18
Filing date: 2019-12-09
Publication date: 2020-06-25
Also published as: EA202191652A1; EP3897141A1

Abstract

The present invention relates to herbicidally active combinations comprising a herbicide A and at least one herbicide B, wherein 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 the at least one herbicide B is selected from the groups b1) to b15): b1)lipid biosynthesis inhibitors; b2)acetolactate synthase inhibitors (ALS inhibitors); b3)photosynthesis inhibitors; b4)protoporphyrinogen-IX oxidase inhibitors; b5)bleacher herbicides; b6)enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP inhibitors); b7)glutamine synthetase inhibitors; b8)7,8-dihydropteroate synthase inhibitors (DHP inhibitors); b9)mitosis inhibitors; b10)inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); b11)cellulose biosynthesis inhibitors; b12)decoupler herbicides; b13)synthetic auxins; b14)auxin transport inhibitors; and b15)other herbicides.

Description

Herbicidal Combinations

The present invention relates to herbicidal combinations of a herbicide A and at least one herbi cide B 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. Intervix® is a herbicidal product, which comprises the racemic form of imazamox and imazapyr.

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 and US 6,277,787.

WO09112454 teaches that co-application of pyroxasulfone and the imidazolinone herbicides imazamox and imazapyr may lead to enhanced herbicidal activity. A synergistic control of Poa, Polygonum and Setaria plants is described in US6,673,748 for mixtures comprising imazamox and pendimethalin.

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.

W015/104242 teaches that co-application of the imidazolinone herbicides imazethapyr and imazamox with further herbicides selected from fomesafen, sulfentrazone and bentazone herbi cides, may lead to enhanced herbicidal activity.

W02005/096814 teaches that co-application of imidazolinone herbicides, including R- imazamox, with certain other herbicides, such as chloroacetamides or quinmerac, may lead to a synergistic herbicidal activity.

Mixtures comprising aminopyralid, imazamox and quinmerac and further active herbicides are disclosed in WO09/153246. W017/009060 describes mixtures of cinmethylin with imazamox and quinmerac.

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 comprising a herbicide A and at least one herbicide B, 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 agricul turally acceptable salt or ester thereof; and

b. the at least one herbicide B is selected from the groups b1) to b15):

b1) lipid biosynthesis inhibitors;

b2) acetolactate synthase inhibitors (ALS inhibitors);

b3) photosynthesis inhibitors;

b4) protoporphyrinogen-IX oxidase inhibitors;

b5) bleacher herbicides;

b6) enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP inhibitors);

b7) glutamine synthetase inhibitors;

b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors); b9) mitosis inhibitors;

b10) inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors);

b11) cellulose biosynthesis inhibitors;

b12) decoupler herbicides;

b13) synthetic auxins;

b14) auxin transport inhibitors; and

b15) other herbicides selected from the group consisting of bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat- metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bro mide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6- methylphenoxy)-4-pyridazinol (CAS 499223-49-3) and its salts and esters;

and agriculturally acceptable salts, esters or amides thereof.

Preferably, the at least one herbicide B is selected from b1) lipid biosynthesis inhibitors:

ACC-herbicides selected from alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxa- prop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalo- fop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim and tralkoxydim, 4-(4'-Chloro-4-cyclopropyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran- 3(6H)-one (CAS 1312337-72-6); 4-(2',4'-Dichloro-4-cyclopropyl[1 ,1'-biphenyl]-3-yl)-5-hydroxy- 2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-45-3); 4-(4'-Chloro-4-ethyl-2'-fluoro[1 ,1'- biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1033757-93-5); 4-(2',4'- Dichloro-4-ethyl[1 ,T-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (CAS 1312340-84-3); 5-(Acetyloxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-3,6- dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5-(Acetyloxy)-4-(2^',4'- dichloro-4-cyclopropyl- [1 , 1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5- (Acetyloxy)-4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H- pyran-3-one (CAS 1312340-82-1); 5-(Acetyloxy)-4-(2',4'-dichloro-4-ethyl[1 ,1'-biphenyl]-3-yl)-3,6- dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4'-Chloro-4-cyclopropyl-2'- fluoro[1 ,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312337-51-1); 4-(2^',4'-Dichloro -4-cyclopropyl- [1 ,1'-biphenyl]-3-yl)-5,6- dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester; 4-(4'-Chloro-4- ethyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312340-83-2); 4-(2',4'-Dichloro-4-ethyl[1 ,1'-biphenyl]-3-yl)-5,6-dihydro- 2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1033760-58-5); and non ACC herbicides selected from benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate; b2) ALS inhibitors:

sulfonylureas selected from amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsul- furon-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosul- furon, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, mesosul- furon-methyl, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfu- ron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfu- ron, triflusulfuron-methyl and tritosulfuron;

imidazolinones selected from imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;

triazolopyrimidine herbicides and sulfonanilides selected from cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam; pyrimidinylbenzoates selected from bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, py- riminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1 -methylethyl ester (CAS 420138-41-6), 4- [[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01-8),

sulfonylaminocarbonyl-triazolinone herbicides selected from flucarbazone, flucarbazone- sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone- methyl; and triafamone; b3) photosynthesis inhibitors:

inhibitors of the photosystem II selected from triazine herbicides selected from ametryn, atrazine, cyanazine, desmetryn, dimethametryn, prometon, prometryn, propazine, simazine, simetryn, terbu eton, terbuthylazin, terbutryn and trietazin, triazinones selected from hexazinone, metamitron and metribuzin;

triazolinone: amicarbazone; pyridazinone: chloridazon; ureas selected from chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, met amitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron;

phenyl carbamates selected from desmedipham, karbutilat, phenmedipham and phen- medipham-ethyl;

nitrile herbicides selected from bromofenoxim, bromoxynil, and ioxynil;

uracils selected from bromacil, lenacil and terbacil,

bentazone, bentazone-sodium, pyridate, pyridafol, pentanochlor, propanil; and inhibitors of the photosystem I selected from diquat, diquat-dibromide, paraquat, paraquat-dichloride and para- quat-dimetilsulfate; b4) protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, ben- carbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlometh- oxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumi- oxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, ethyl [3-[2- chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3- yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6; S-3100), N-ethyl-3-(2,6-dichloro-4-trifluoro- methylphenoxy)-5-methyl-1/-/-pyrazole-1 -carboxamide (CAS 452098-92-9), N-tetrahydrofurfuryl- 3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1/-/-pyrazole-1 -carboxamide (CAS 915396- 43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1/-/-pyrazole-1- carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoro- methylphenoxy)-5-methyl-1/-/-pyrazole-1 -carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4- (prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4- dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H- benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1 ,3-dione (CAS 1300118-96-0), 1-methyl-6- trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H- pyrimidine-2, 4-dione (CAS 1304113-05-0), methyl (£)-4-[2-chloro-5-[4-chloro-5- (difluoromethoxy)-1/-/-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate (CAS 948893-00-3), and 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1 H-benzimidazol-4-yl]-1-methyl-6- (trifluoromethyl)-1 H-pyrimidine-2, 4-dione (CAS 212754-02-4); b5) bleacher herbicides: PDS inhibitors selected from beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7);

HPPD inhibitors selected from benzobicyclon, benzofenap, bicyclopyrone, fenquintrione, isoxaflutole, isoxachlortole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate and topramezone;

DOXP-synthase inhibitors selected from bixlozone and clomazone;

bleacher with unknown target selected from aclonifen, amitrole and flumeturon; b6) EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate- potassium and glyphosate-trimesium (sulfosate); b7) glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium; b8) DHP synthase inhibitors: asulam; b9) mitosis inhibitors:

compounds of HRAC group K1 : dinitroanilines selected from benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin, phosphoramidates selected from amiprophos, amiprophos-methyl, and butamiphos, benzoic acid herbicides selected from chlorthal, chlorthal-dimethyl;

pyridines selected from dithiopyr and thiazopyr;

benzamides selected from propyzamide and tebutam;

compounds of group HRAC K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham; b10) VLCFA inhibitors:

chloroacetamides selected from acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor, oxyacetamides selected from flufenacet and mefenacet;

acetamides selected from diphenamid, naproanilide, napropamide and napropamide-M, tetrazo- linones selected from fentrazamide and ipfencarbazone, other herbicides selected from anilo- fos, cafenstrole, fenoxasulfone, piperophos and pyroxasulfone, and isoxazoline compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 b11) cellulose biosynthesis inhibitors:

chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam and 1 -cyclohexyl-5- pentafluorphenyloxy-1⁴-[1 ,2,4,6]thiatriazin-3-ylamine (CAS 175899-01-1);

b12) decoupler herbicides:

dinoseb, dinoterb and DNOC; b13) synthetic auxins: 2,4-D, clacyfos, 2,4-DB, aminocyclopyrachlor, aminopyralid, aminopyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium, benazolin, benazolin-ethyl, chloramben, dome- prop, clopyralid, dicamba, dichlorprop, dichlorprop-P, fluroxypyr, fluroxypyr-butometyl, fluroxy- pyr-meptyl, halauxifen (CAS 943832-60-8); MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, picloram, quinclorac, quinmerac, TBA (2,3,6), triclopyr, 4-amino-3-chloro-6-(4- chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylic acid and benzyl 4-amino-3- chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661-72- 9); b14) auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam- sodium; b15) other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3), dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosa- mine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine and tridiphane; and agriculturally acceptable salts, esters or amides thereof.

More preferably, the at least one herbicide B is selected from b1) from the group of the lipid biosynthesis inhibitors:

clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop-P- ethyl, fluazifop-P-butyl, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, 4-(4'-Chloro-4- cyclopropyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-72-6); 4-(2',4'-Dichloro-4-cyclopropyl[1 ,1 '-biphenyl]-3-yl)-5-hydroxy-2, 2,6,6- tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-45-3); 4-(4'-Chloro-4-ethyl-2'-fluoro[1 ,1'- biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1033757-93-5); 4-(2',4'- Dichloro-4-ethyl[1 ,T-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (CAS 1312340-84-3); 5-(Acetyloxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-3,6- dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5-(Acetyloxy)-4-(2^',4'- dichloro-4-cyclopropyl- [1 , 1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5- (Acetyloxy)-4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H- pyran-3-one (CAS 1312340-82-1); 5-(Acetyloxy)-4-(2',4'-dichloro-4-ethyl[1 ,1'-biphenyl]-3-yl)-3,6- dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4'-Chloro-4-cyclopropyl-2'- fluoro[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312337-51-1); 4-(2^',4'-Dichloro -4-cyclopropyl- [1 , 1 '-biphenyl]-3-yl)-5,6- dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester; 4-(4'-Chloro-4- ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312340-83-2); 4-(2',4'-Dichloro-4-ethyl[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro- 2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1033760-58-5); ben- furesate, dimepiperate, EPTC, esprocarb, ethofumesate, molinate, orbencarb, prosulfocarb, thiobencarb and triallate; b2) from the group of the ALS inhibitors:

amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, chlorimuron-ethyl, chlor- sulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysul- furon, flazasulfuron, florasulam, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfu- ron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, mesosulfuron-methyl, metazosulfu- ron, metosulam, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazon-sodium, propyrisulfuron, prosulfuron, pyrazosulfuron- ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, pyroxsu- lam, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone-methyl, thifensulfuron- methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl, tritosulfuron and triafamone; b3) from the group of the photosynthesis inhibitors:

ametryn, amicarbazone, atrazine, bentazone, bentazone-sodium, bromoxynil and its salts and esters, chloridazone, chlorotoluron, cyanazine, desmedipham, diquat-dibromide, diuron, fluome- turon, hexazinone, ioxynil and its salts and esters, isoproturon, lenacil, linuron, metamitron, methabenzthiazuron, metribuzin, paraquat, paraquat-dichloride, phenmedipham, propanil, pyri- date, simazine, terbutryn, terbuthylazine and thidiazuron; b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:

acifluorfen-sodium, bencarbazone, benzfendizone, butafenacil, carfentrazone-ethyl, cinidon- ethyl, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fomesafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraflufen, pyraflufen-ethyl, saflufenacil, sul- fentrazone, tiafenacil, trifludimoxazin, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl- 2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6; S- 3100), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 H- pyrazole-1 -carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoro- methylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl- 3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5- dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop- 2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1 ,3-dione (CAS 1300118-96-0); 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H- benzo[1 ,4]oxazin-6-yl)-1 H-pyrimidine-2,4-dione (CAS 13041 13-05-0), and 3-[7-chloro-5-fluoro- 2-(trifluoromethyl)-1 H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1 H-pyrimidine-2,4-dione (CAS 212754-02-4); b5) from the group of the bleacher herbicides:

aclonifen, amitrole, beflubutamid, benzobicyclon, bicyclopyrone, bixlozone, clomazone, diflufenican, fenquintrione, flumeturon, flurochloridone, flurtamone, isoxaflutole, isoxachlortole, mesotrione, norflurazon, picolinafen, pyrasulfotole, pyrazolynate, sulcotrione, tefuryltrione, tem- botrione, tolpyralate, topramezone and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)- pyrimidine (CAS 180608-33-7); b6) from the group of the EPSP synthase inhibitors:

glyphosate, glyphosate-isopropylammonium, glyphosate-potassium and glyphosate-trimesium (sulfosate); b7) from the group of the glutamine synthase inhibitors: glufosinate, glufosinate-P, glufosinate- ammonium; b8) from the group of the DHP synthase inhibitors: asulam; b9) from the group of the mitosis inhibitors: benfluralin, dithiopyr, ethalfluralin, flamprop, flam- prop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, oryzalin, pendime- thalin, thiazopyr and trifluralin; b10) from the group of the VLCFA inhibitors:

acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethenamid, dimethenamid-P, fentraza- mide, flufenacet, mefenacet, metazachlor, metolachlor, S-metolachlor, naproanilide, napropa- mide, napropamide-M, pretilachlor, fenoxasulfone, ipfencarbazone, pyroxasulfone thenylchlor and isoxazoline-compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 as mentioned above; b11) from the group of the cellulose biosynthesis inhibitors: dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam and 1-cyclohexyl-5-pentafluorphenyloxy-1⁴-[1 ,2,4,6]thiatriazin-3-ylamine (CAS 175899-01-1); b13) from the group of the synthetic auxins:

2,4-D and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2- hydroxypropyl)ammonium and its esters, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr-meptyl, halauxifen and its salts and esters (CAS 943832-60-8), MCPA and its salts and esters, MCPB and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quin- merac, triclopyr and its salts and esters, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylic acid and benzyl 4-amino-3-chloro-6-(4-chloro-2- fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661-72-9); b14) from the group of the auxin transport inhibitors: diflufenzopyr and diflufenzopyr-sodium; b15) from the group of the other herbicides: bromobutide, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, difenzoquat, difenzoquat-metilsulfate, DSMA, dymron (= daimuron), indanofan, metam, methylbromide, MSMA, oxaziclomefone, pyributicarb and tridiphane.

Especially preferably, the at least one herbicide B is selected from b1) from the group of the lipid biosynthesis inhibitors: clodinafop-propargyl, cycloxydim, cyhalo- fop-butyl, fenoxaprop-P-ethyl, pinoxaden, profoxydim, quizalofop-p-ethyl, tepraloxydim, tralkoxydim, 4-(4'-Chloro-4-cyclopropyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5-hydroxy-2, 2,6,6- tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-72-6); 4-(2',4'-Dichloro-4-cyclopropyl[1 ,1'- biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-45-3); 4-(4'- Chloro-4-ethyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1033757-93-5); 4-(2',4'-Dichloro-4-ethyl[1 ,1'-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran- 3,5(4H,6H)-dione (CAS 1312340-84-3); 5-(Acetyloxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1 ,1'- biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5- (Acetyloxy)-4-(2^',4'-dichloro-4-cyclopropyl- [1 ,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl- 2H-pyran-3-one; 5-(Acetyloxy)-4-(4'-chloro-4-ethyl-2'-fluoro[1 , 1 '-biphenyl]-3-yl)-3,6-dihydro- 2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312340-82-1); 5-(Acetyloxy)-4-(2',4'-dichloro-4- ethyl[1 ,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4'-Chloro-4-cyclopropyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo- 2H-pyran-3-yl carbonic acid methyl ester (CAS 1312337-51-1); 4-(2^',4'-Dichloro -4-cyclopropyl- [1 ,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester; 4-(4'-Chloro-4-ethyl-2'-fluoro[1 ,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo- 2H-pyran-3-yl carbonic acid methyl ester (CAS 1312340-83-2); 4-(2',4'-Dichloro-4-ethyl[1 , 1 '- biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1033760-58-5); esprocarb, prosulfocarb, thiobencarb and triallate; b2) from the group of the ALS inhibitors: azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flumetsulam, flupyrsulfu- ron-methyl-sodium, foramsulfuron, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, mesosulfuron-methyl, metazosulfuron, nicosulfuron, penoxsulam,

propoxycarbazon-sodium, propyrisulfuron, pyrazosulfuron-ethyl, pyroxsulam, rimsulfuron, sul- fosulfuron, thiencarbazon-methyl, tritosulfuron and triafamone; b3) from the group of the photosynthesis inhibitors: ametryn, atrazine, chlorotoluron, diuron, fluometuron, hexazinone, isoproturon, linuron, metribuzin, paraquat, paraquat-dichloride, pro- panil, terbutryn and terbuthylazine; b4) from the group of the protoporphyrinogen-IX oxidase inhibitors: flumioxazin, oxyfluorfen, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, trifludimoxazin, ethyl [3-[2-chloro-4- fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2- pyridyloxy]acetate (CAS 353292-31-6; S-3100), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro- 2H-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro- isoindole-1 , 3-dione (CAS 1300118-96-0), and 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo- 4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H-pyrimidine-2,4-dione (CAS 1304113- 05-0); b5) from the group of the bleacher herbicides: amitrole, bicyclopyrone, bixlozone, clomazone, diflufenican, fenquintrione, flumeturon, flurtamone, flurochloridone, isoxaflutole, isoxachlortole, mesotrione, picolinafen, sulcotrione, tefuryltrione, tembotrione, tolpyralate and topramezone; b6) from the group of the EPSP synthase inhibitors: glyphosate, glyphosate- isopropylammonium and glyphosate-trimesium (sulfosate); b7) from the group of the glutamine synthase inhibitors: glufosinate, glufosinate-P and glufosinate-ammonium; b9) from the group of the mitosis inhibitors: pendimethalin and trifluralin; b10) from the group of the VLCFA inhibitors: acetochlor, cafenstrole, dimethenamid-P, fentra- zamide, flufenacet, mefenacet, metazachlor, metolachlor, S-metolachlor, fenoxasulfone, ipfen- carbazone and pyroxasulfone; likewise, preference is given to isoxazoline compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 as mentioned above; b11) from the group of the cellulose biosynthesis inhibitors: indaziflam, isoxaben and triaziflam; b13) from the group of the synthetic auxins: 2,4-D and its salts and esters such as clacyfos, and aminocyclopyrachlor and its salts and esters, aminopyralid and its salts and its esters, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl, halauxifen, halauxi- fen-methyl, quinclorac, quinmerac, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5- fluoropyridine-2-carboxylic acid and benzyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661-72-9);

b14) from the group of the auxin transport inhibitors: diflufenzopyr and diflufenzopyr-sodium, b15) from the group of the other herbicides: dymron (= daimuron), indanofan, oxaziclomefone.

In particular, the at least one herbicide B is selected from the herbicides B.1 - B.227 as listed below in table B:

Table B:

Preferred binary combinations according to the invention are Combinations 1.1 to 1.227, which consist of herbicide A and one of herbicides B.1 to B.227 respectively.

In addition to the herbicide A and the at least one herbicide B, the combination according to the invention may further comprise at least one safener C.

In one embodiment, the combination according to the invention comprises the herbicide A, at least one herbicide B and no safener C. In another embodiment, the combination according to the invention comprises the herbicide A, at least one herbicide B and at least one safener C.

In a preferred embodiment, the combination according to the invention consists of herbicide A and one herbicide B.

In another preferred embodiment, the combination according to the invention consists of herbi cide A and two differing herbicides B.

In another preferred embodiment, the combination according to the invention consists of herbi cide A and three differing herbicides B.

In another embodiment, the combination according to the invention consists of herbicide A, one herbicide B, and one safener C.

In another preferred embodiment, the combination according to the invention consists of herbi cide A, two differing herbicides B, and one safener C.

In another preferred embodiment, the combination according to the invention consists of herbi cide A, three differing herbicides B, and one safener C.

Safeners are chemical compounds which prevent or reduce damage on useful plants without having a major impact on the herbicidal action of the herbicidal active components towards un wanted plants. Safeners can be applied before sowings (e.g. seed treatments), on shoots or seedlings as well as in the pre-emergence or post-emergence treatment of useful plants and their habitat.

Suitable safeners are e.g. (quinolin-8-oxy)acetic acids, 1-phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3- carboxylic acids, 1 -phenyl-4, 5-dihydro-5-alkyl-1 H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro- 5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2- benzoic amides, 1 ,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.

Examples of preferred safeners C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthaleneacetic acid (NAA), naphthalic anhydride (NA), oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5- trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine (R-29148, CAS 52836-31-4), N-(2-Methoxybenzoyl)- 4-[(methylaminocarbonyl)amino]benzenesulfonamide (CAS 129531-12-0) and agriculturally acceptable salts, esters or amides thereof. Especially preferred safeners C are benoxacor, cloquintocet, cyprosulfamide, dichlormid, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, naphthalic anhydride (NA), oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine (R-29148, CAS 52836-31-4), N- (2-Methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide (CAS 129531-12-0) and agriculturally acceptable salts, esters or amides thereof.

In particular, the at least one safener C is selected from the safeners C.1 to C.17 as listed below in table C:

Table C

The herbicides B and safeners C are known herbicides and safeners, see, for example, The Pesticide Manual, British Crop Protection Council, 16^th edition, 2012; The Compendium of Pes- ticide Common Names (http://www.alanwood.net/pesticides/); Farm Chemicals Handbook 2000 volume 86, Meister Publishing Company, 2000; B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart 1995; W. H. Ahrens, Herbicide Handbook, 7th edi tion, Weed Science Society of America, 1994; and K. K. Hatzios, Herbicide Handbook, Supple- merit for the 7th edition, Weed Science Society of America, 1998. 2,2,5-Trimethyl-3- (dichloroacetyl)-1 ,3-oxazolidine [CAS No. 52836-31-4] is also referred to as R-29148. 4- (Dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane [CAS No. 71526-07-3] is also referred to as AD- 67 and MON 4660.

If the herbicides B and/or safeners C as described herein are capable of forming geometrical isomers, for example E/Z isomers, it is possible to use both, the pure isomers and mixtures thereof, in the methods, uses and compositions according to the invention.

If the herbicides B and/or safeners C as described herein have one or more centers of chirality and, as a consequence, are present as enantiomers or diastereomers, it is possible to use both, the pure enantiomers and diastereomers and their mixtures, in the methods, uses and composi tions according to the invention.

If the herbicides B and/or safeners C as described herein have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. The term“agriculturally acceptable salts” is used herein to mean in general, the salts of those cations and the acid addi tion salts of those acids whose cations and anions, respectively, have no adverse effect on the herbicidal activity of the active compounds.

Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by CrC4-alkyl, hydroxy-Ci-C4-alkyl, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trime- thylammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammo- nium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium (olamine salt), 2-(2- hydroxyeth-1-oxy)eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (di- olamine salt), tris(2-hydroxyethyl)ammonium (trolamine salt), tris(2-hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N-trimethylethanolammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium, and finally the salts of polybasic amines such as N,N-bis-(3-aminopropyl)methylamine and diethylenetri- amine.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensul- fate, methylsulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C₁-C₄- alkanoic acids, preferably formate, acetate, propionate and butyrate.

The herbicides B and/or safeners C as described herein having a carboxyl, hydroxy and/or an lamino group can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative, for exam ple as amides, such as mono- and di-Ci-C₆-alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, Ci-Cio-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-

2-yl)methyl) esters and also as thioesters, for example as Ci-Cio-alkylthio esters. Preferred mono- and di-Ci-C₆-alkylamides are the methyl and the dimethylamides. Preferred arylamides are, for example, the anilides and the 2-chloroanilides. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1- methylheptyl), heptyl, octyl or isooctyl (2-ethylhexyl) esters. Preferred Ci-C4-alkoxy-Ci-C4-alkyl esters are the straight-chain or branched Ci-C4-alkoxy ethyl esters, for example the 2- methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester. An example of a straight-chain or branched Ci-Cio-alkylthio ester is the ethylthio ester.

In the case of dicamba, suitable salts include those, where the counterion is an agriculturally acceptable cation. For example, suitable salts of dicamba are dicamba-sodium, dicamba- potassium, dicamba-methylammonium, dicamba-dimethylammonium, dicamba- isopropylammonium, dicamba-diglycolamine, dicamba-olamine, dicamba-diolamine, dicamba- trolamine, dicamba-N,N-bis-(3-aminopropyl)methylamine and dicamba-diethylenetriamine. Ex amples of a suitable ester are dicamba-methyl and dicamba-butotyl.

Suitable salts of 2,4-D are 2,4-D-ammonium, 2,4-D-dimethylammonium, 2,4-D- diethylammonium, 2,4-D-diethanolammonium (2,4-D-diolamine), 2,4-D-triethanolammonium, 2,4-D-isopropylammonium, 2,4-D-triisopropanolammonium, 2,4-D-heptylammonium, 2,4-D- dodecylammonium, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2- hydroxypropyl)ammonium, 2,4-D-tris(isopropyl)ammonium, 2,4-D-trolamine, 2,4-D-lithium, 2,4- D-sodium. Examples of suitable esters of 2,4-D are 2,4-D-butotyl, 2,4-D-2-butoxypropyl, 2,4-D-

3-butoxypropyl, 2,4-D-butyl, 2,4-D-ethyl, 2,4-D-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D- isopropyl, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-propyl, 2,4-D-tefuryl and clacyfos.

Suitable salts of 2,4-DB are for example 2,4-DB-sodium, 2,4-DB-potassium and 2,4-DB- dimethylammonium. Suitable esters of 2,4-DB are for example 2,4-DB-butyl and 2,4-DB-isoctyl. Suitable salts of dichlorprop are for example dichlorprop-sodium, dichlorprop-potassium and dichlorprop-dimethylammonium. Examples of suitable esters of dichlorprop are dichlorprop- butotyl and dichlorprop-isoctyl. Suitable salts and esters of MCPA include MCPA-butotyl, MCPA-butyl, MCPA-dimethyl- ammonium, MCPA-diolamine, MCPA-ethyl, MCPA-thioethyl, MCPA-2-ethylhexyl, MCPA- isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-isopropylammonium, MCPA-methyl, MCPA- olamine, MCPA-potassium, MCPA-sodium and MCPA-trolamine.

A suitable salt of MCPB is MCPB sodium. A suitable ester of MCPB is MCPB-ethyl.

Suitable salts of clopyralid are clopyralid-potassium, clopyralid-olamine and clopyralid-tris-(2- hydroxypropyl)ammonium. Example of suitable esters of clopyralid is clopyralid-methyl.

Examples of a suitable ester of fluroxypyr are fluroxypyr-meptyl and fluroxypyr-2-butoxy-1- methylethyl, wherein fluroxypyr-meptyl is preferred.

Suitable salts of picloram are picloram-dimethylammonium, picloram-potassium, picloram- triisopropanolammonium, picloram-triisopropylammonium and picloram-trolamine. A suitable ester of picloram is picloram-isoctyl.

A suitable salt of triclopyr is triclopyr-triethylammonium. Suitable esters of triclopyr are for ex ample triclopyr-ethyl and triclopyr-butotyl.

Suitable salts and esters of chloramben include chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium and chloramben-sodium. Suitable salts and esters of 2,3,6-TBA include 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA- potassium and 2,3,6-TBA-sodium.

Suitable salts and esters of aminopyralid include aminopyralid-potassium and aminopyralid- tris(2-hydroxypropyl)ammonium.

Suitable salts of glyphosate are for example glyphosate-ammonium, glyphosate-diammonium, glyphoste-dimethylammonium, glyphosate-isopropylammonium, glyphosate-potassium, glypho- sate-sodium, glyphosate-trimesium as well as the ethanolamine and diethanolamine salts, pref erably glyphosate-diammonium, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate).

A suitable salt of glufosinate is for example glufosinate-ammonium.

A suitable salt of glufosinate-P is for example glufosinate-P-ammonium.

Suitable salts and esters of bromoxynil are for example bromoxynil-butyrate, bromoxynil- heptanoate, bromoxynil-octanoate, bromoxynil-potassium and bromoxynil-sodium.

Suitable salts and esters of ioxonil are for example ioxonil-octanoate, ioxonil-potassium and ioxonil-sodium.

Suitable salts and esters of mecoprop include mecoprop-butotyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-2-ethylhexyl, mecoprop-isoctyl, mecoprop- methyl, mecoprop-potassium, mecoprop-sodium and mecoprop-trolamine.

Suitable salts of mecoprop-P are for example mecoprop-P-butotyl, mecoprop-P- dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-isobutyl, mecoprop-P-potassium and mecoprop-P-sodium.

A suitable salt of diflufenzopyr is for example diflufenzopyr-sodium. A suitable salt of naptalam is for example naptalam-sodium.

Suitable salts and esters of aminocyclopyrachlor are for example aminocyclopyrachlor- dimethylammonium, aminocyclopyrachlor-methyl, aminocyclopyrachlor- triisopropanolammonium, aminocyclopyrachlor-sodium and aminocyclopyrachlor-potassium.

A suitable salt of quinclorac is for example quinclorac-dimethylammonium.

A suitable salt of quinmerac is for example quinclorac-dimethylammonium.

A suitable salt of imazamox is for example imazamox-ammonium.

Suitable salts of imazapic are for example imazapic-ammonium and imazapic- isopropylammonium.

Suitable salts of imazapyr are for example imazapyr-ammonium and imazapyr- isopropylammonium.

A suitable salt of imazaquin is for example imazaquin-ammonium.

Suitable salts of imazethapyr are for example imazethapyr-ammonium and imazethapyr- isopropylammonium.

A suitable salt of topramezone is for example topramezone-sodium.

In a preferred embodiment of the methods or uses of this invention, a combination comprising a herbicidally effective amount of herbicide A and at least one herbicide B (as defined herein) is applied. In yet another embodiment of the methods or uses of this invention, a combination comprising a herbicidally effective amount of herbicide A and at least one herbicide B (as defined herein) is applied wherein the herbicide A and the at least one herbicide B are the only active ingredients.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from inhibitors of the lipid biosynthesis (group b1 as defined herein). These are compounds that inhibit lipid biosynthesis. Inhibition of the lipid bio synthesis can be affected either through inhibition of acetylCoA carboxylase (hereinafter termed ACC herbicides) or through a different mode of action (hereinafter termed non-ACC herbicides). The ACC herbicides belong to the group A of the HRAC classification system whereas the non- ACC herbicides belong to the group N of the HRAC classification.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from ALS inhibitors (group b2 as defined herein). The herbicidal activity of these compounds is based on the inhibition of acetolactate synthase and thus on the inhibition of the branched chain amino acid biosynthesis. These inhibitors belong to the group B of the HRAC classification system. In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from inhibitors of photosynthesis (group b3 as defined herein). The herbicidal activity of these compounds is based either on the inhibition of the pho tosystem II in plants (so-called PSII inhibitors, groups C1 , C2 and C3 of HRAC classification) or on diverting the electron transfer in photosystem I in plants (so-called PSI inhibitors, group D of HRAC classification) and thus on an inhibition of photosynthesis. Amongst these, PSII inhibitors are preferred.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from inhibitors of protoporphyrinogen-IX-oxidase (group b4 as defined herein). The herbicidal activity of these compounds is based on the inhibition of the protoporphyrinogen-IX-oxidase. These inhibitors belong to the group E of the HRAC classi fication system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from bleachers (group b5 as defined herein). The herbi cidal activity of these compounds is based on the inhibition of the carotenoid biosynthesis. These include compounds which inhibit carotenoid biosynthesis by inhibition of phytoene de- saturase (so-called PDS inhibitors, group F1 of HRAC classification), compounds that inhibit the 4-hydroxyphenylpyruvate-dioxygenase (HPPD inhibitors, group F2 of HRAC classification), compounds that inhibit DOXsynthase (group F4 of HRAC class) and compounds which inhibit carotenoid biosynthesis by an unknown mode of action (bleacher - unknown target, group F3 of HRAC classification).

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from EPSP synthase inhibitors (group b6 as defined herein). The herbicidal activity of these compounds is based on the inhibition of enolpyruvyl shi- kimate 3-phosphate synthase, and thus on the inhibition of the amino acid biosynthesis in plants. These inhibitors belong to the group G of the HRAC classification system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from glutamine synthetase inhibitors (group b7 as de fined herein). The herbicidal activity of these compounds is based on the inhibition of glutamine synthetase, and thus on the inhibition of the aminoacid biosynthesis in plants. These inhibitors belong to the group H of the HRAC classification system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from DHP synthase inhibitors (group b8 as defined herein). The herbicidal activity of these compounds is based on the inhibition of 7,8- dihydropteroate synthase. These inhibitors belong to the group I of the HRAC classification sys tem.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from mitosis inhibitors (group b9 as defined herein). The herbicidal activity of these compounds is based on the disturbance or inhibition of microtubule formation or organization, and thus on the inhibition of mitosis. These inhibitors belong to the groups K1 and K2 of the HRAC classification system. Among these, compounds of the group K1 , in particular dinitroanilines, are preferred.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from VLCFA inhibitors (group b10 as defined herein). The herbicidal activity of these compounds is based on the inhibition of the synthesis of very long chain fatty acids and thus on the disturbance or inhibition of cell division in plants. These inhibitors belong to the group K3 of the HRAC classification system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from cellulose biosynthesis inhibitors (group b11 as de fined herein). The herbicidal activity of these compounds is based on the inhibition of the bio synthesis of cellulose and thus on the inhibition of the synthesis of cell walls in plants. These inhibitors belong to the group L of the HRAC classification system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from decoupler herbicides (group b12 as defined here in). The herbicidal activity of these compounds is based on the disruption of the cell membrane. These inhibitors belong to the group M of the HRAC classification system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from synthetic auxins (group b13 as defined herein). These include compounds that mimic auxins, i.e. plant hormones, and affect the growth of the plants. These compounds belong to the group O of the HRAC classification system.

In another embodiment, the combination comprises a herbicidally effective amount of herbicide A and at least one herbicide B selected from auxin transport inhibitors (group b14 as defined herein). The herbicidal activity of these compounds is based on the inhibition of the auxin transport in plants. These compounds belong to the group P of the HRAC classification system. As to the given mechanisms of action and classification of the active substances, see e.g.

"HRAC (Herbicide Resistance Action Committee), Classification of Herbicides According to Site of Action", http://www.hracglobal.com/pages/classificationofherbicidesiteofaction.aspx.

In another aspect of the present invention, there is provided a herbicidal combination compris ing a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B selected from inhibitors of acetyl CoA carboxylase (ACCase inhibitors). Preferably, the ACCase inhibitor is selected from aryloxyphenoxypropionates, cyclohexanediones and phenylpyrazoline. More preferably, the

the ACCase inhibitor is selected from the group consisting of clodinafop, clodinafop-propargyl, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop- P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, halox- yfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, propaquizafop, quizalofop, quizalo- fop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, alloxydim, alloxydim-sodium, butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim, pinoxaden, and agriculturally acceptable salts, esters or amides thereof, more preferably selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop-P-ethyl, fluazifop-P-butyl, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim and tralkoxydim. In one embodiment, the ACCase inhibitor is selected from aryloxyphenoxypropionates, in particular selected from the group consisting of clodinafop, clodinafop-propargyl, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxa prop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P- butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, and quizalofop- P-tefuryl, more preferably selected from the group consisting of fluazifop, fluazifop-butyl, fluazi- fop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, and quizalofop-P-tefuryl. In another embodiment, the ACCase inhibitor is selected from cyclo hexanediones, in particular selected from the group consisting of alloxydim, alloxydim-sodium, butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, and tralkoxydim, more preferably selected from the group consisting of clethodim, cycloxydim, profoxydim, seth oxydim. In yet another embodiment, the ACCase inhibitor is pinoxaden.

In yet another embodiment, the ACCase inhibitor is selected from fluazifop, fluazifop-butyl, flua- zifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, and quizalofop-P-tefuryl, clethodim, cycloxydim, profoxydim, sethoxydim, and pinoxaden. In yet another embodiment, the ACCase inhibitor is clethodim. In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from sulfonylureas. Preferably, the sulfonylurea is selected from the group consisting of ami- dosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxy- sulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfu- ron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, mesosulfuron-methyl, metazosulfu- ron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsul- furon, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl, tritosulfuron and agriculturally acceptable salts, esters or amides thereof, more preferably se lected from the group consisting of amidosulfuron, azimsulfuron, foramsulfuron, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, mesosulfuron-methyl, metsulfuron, metsulfuron-methyl, nicosulfuron, rimsulfuron, sulfosulfuron, thifensulfuron, thifensulfuron- methyl, triasulfuron, tribenuron, tribenuron-methyl, triflusulfuron, triflusulfuron-methyl, tritosulfu ron and agriculturally acceptable salts, esters or amides thereof.

In yet another embodiment, the sulfonylurea is sulfosulfuron.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from imidazolinones. Preferably, the imidazolinone is selected from the group consisting of imazamethabenz, imazamethabenz-methyl, imazapic, imazaquin and imazethapyr. In particular, the imidazolinone is imazethapyr.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from triazolopyrimidines. Preferably, the triazolopyrimidine is selected from the group con sisting of cloransulam, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, pyrimisul- fan, pyroxsulam and agriculturally acceptable salts, esters or amides thereof. More preferably, the triazolopyrimidine is selected from the group consisting of cloransulam, florasulam, flumetsulam, metosulam, penoxsulam, pyroxsulam and agriculturally acceptable salts, esters or amides thereof, even more preferably selected from the group consisting of cloransulam, flumetsulam, metosulam and agriculturally acceptable salts, esters or amides thereof. In particu lar, the triazolopyrimidine is cloransulam. In another embodiment, the triazolopyrimidine is flumetsulam or metosulam. In another embodiment, the triazolopyrimidine is flumetsulam or pyroxsulam. In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from sulfonylaminocarbonyl-triazolinones. Preferably, the sulfonylaminocarbonyl-triazolinone is selected from the group consisting of flucarbazone, propoxycarbazone, thiencarbazone and agriculturally acceptable salts, esters or amides thereof, more preferably from thiencarbazone and agriculturally acceptable salts, esters or amides thereof.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from pyrimidinylbenzoates. Preferably, the pyrimidinylbenzoate is selected from the group consisting of bispyribac, pyribenzoxim, pyriftalid, pyriminobac, pyrithiobac, 4-[[[2-[(4,6- dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1 -methylethyl ester (CAS 420138-41-6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid pro pyl ester (CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01-8), and agriculturally acceptable salts, esters or amides thereof. More preferably, the pyrimidinylbenzoate is selected from the group consisting of bispyribac, pyribenzoxim, pyriftalid, pyriminobac, and agriculturally acceptable salts, esters or amides thereof. In particular, the pyrimidinylbenzoate is selected from the group consisting of bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac and pyrimino- bac-methyl.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from inhibitors of the photosystem II. Preferably, the inhibitor of the photosystem II is metribuzin, bentazone, pyridate or an agriculturally acceptable salt, ester or amide thereof. In one embodiment, the inhibitor of the photosystem II is bentazone-sodium. In another embodi ment, the inhibitor of the photosystem II is pyridate. In a further embodiment, the inhibitor of the photosystem II is metribuzin.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from inhibitors of protoporphyrinogen-IX oxidase. Preferably, the protoporphyrinogen-IX oxi dase inhibitor is selected from acifluorfen, acifluorfen-sodium, carfentrazone, carfentrazone- ethyl, chlomethoxyfen, cinidon-ethyl, flumioxazin, pyraflufen, pyraflufen-ethyl, saflufenacil, sul- fentrazone, and trifludimoxazin. In another embodiment, the protoporphyrinogen-IX oxidase inhibitor is pyraflufen, pyraflufen-ethyl or saflufenacil.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from inhibitors of microtubule assembly (HRAC group K1). Preferably, the microtubule as sembly inhibitor is selected from butralin and dithiopyr.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from mitosis inhibitors.

Preferably, the mitosis inhibitor is selected from propyzamide, pendimethalin and Trifluralin. In one embodiment, the mitosis inhibitor is propyzamide.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from inhibitors of VLCFA.

Preferably, the VLCFA inhibitor is selected from fentrazamide, ipfencarbazone, cafenstrole, fenoxasulfone, and agriculturally acceptable salts, esters or amides thereof. In another embod iment, the VLCFA inhibitor is piperophos.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from the group of the bleacher herbicides. Preferably, the bleacher herbicide is selected from flurochloridone or aclonifen. In one embodiment, the bleacher herbicide is flurochloridone. In another embodiment, the bleacher herbicide is aclonifen. In another embodiment, the bleacher herbicide is bixlozone or clomazone.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from HPPD inhibitors. Preferably, the HPPD inhibitor is selected from benzobicyclon, ben- zofenap, bicyclopyrone, fenquintrione, isoxaflutole, isoxachlortole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, and agriculturally acceptable salts, esters or amides thereof. More preferably, the HPPD inhibitor is selected from benzobicyclon, benzofenap, isoxachlortole, pyrazolynate, pyrazoxyfen, tefuryltri one, and agriculturally acceptable salts, esters or amides thereof. In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select ed from the group of cellulose biosynthesis inhibitors, preferably indaziflam.

In still yet another aspect of the present invention, there is provided a herbicidal combination comprising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B selected from synthetic auxins.

Preferably, the synthetic auxin is selected from phenoxycarboxylic acids, benzoic acids, pyri- dinecarboxylic acids and benazolin-ethyl. More preferably, the synthetic auxin is selected from the group consisting of 2,4-D, 3,4-DA, MCPA, 2,4,5-T, 2,4-DP (dichlorprop), 2,4-DP-P, 4-CPP, 3,4-DP, fenoprop, CMPP (mecoprop), CMPP-P, 4-CPB, 2,4-DB, 3,4-DB, 2,4,5-TB, MCPB, dicamba, tricamba, chloramben, 2,3,6-TBA (2,3,6-trichlorobenzoic acid), aminopyralid, clopyra- lid, fluoroxypyr, picloram, triclopyr, halauxifen, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylic acid, benzyl 4-amino-3-chloro-6-(4-chloro-2- fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661-72-9), benazolin-ethyl, and agriculturally acceptable salts, esters or amides thereof. In another embodiment, the syn thetic auxin is selected from phenoxycarboxylic acids, in particular selected from the group con sisting of 2,4-D, 3,4-DA, MCPA, 2,4,5-T, 2,4-DP (dichlorprop), 2,4-DP-P, 4-CPP, 3,4-DP, fenoprop, CMPP (mecoprop), CMPP-P, 4-CPB, 2,4-DB, 3,4-DB, 2,4,5-TB, MCPB, and agricul turally acceptable salts, esters or amides thereof. In another embodiment, the synthetic auxin is selected from benzoic acids, in particular selected from the group consisting of dicamba, tricamba, chloramben, 2,3,6-TBA (2,3,6-trichlorobenzoic acid), and agriculturally acceptable salts, esters or amides thereof. In another embodiment, the synthetic auxin is selected from pyridinecarboxylic acids, in particular selected from the group consisting of aminopyralid, clopyralid, fluoroxypyr, picloram, triclopyr, halauxifen, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylic acid, benzyl 4-amino-3-chloro-6-(4-chloro-2- fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661-72-9), and agriculturally acceptable salts, esters or amides thereof. In yet another embodiment, the synthetic auxin is benazolin-ethyl. In still another embodiment, the synthetic auxin is benzyl 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661-72-9). In still another embodiment, the synthetic auxin is aminopyralid, aminopyralid-methyl, aminopyralid- dimethylammonium, or aminopyralid-tris(2-hydroxypropyl)ammonium. In still another embodi ment, the synthetic auxin is halauxifen, halauxifen-methyl, or 4-amino-3-chloro-5-fluoro-6-(7- fluoro-1 H-indol-6-yl)-2-pyridinecarboxylic acid. In still another embodiment, the synthetic auxin is clopyralid or picloram. In still another embodiment, the synthetic auxin is 2,4-D or dicamba.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) at least one herbicide B select- ed from the group of herbicides with unknown mode of action (HRAC group Z), preferably se lected from indanofan, methiozolin (CAS 403640-27-7), oxaziclomefone, and agriculturally ac ceptable salts, esters or amides thereof and more preferably indanofan.

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) amidosulfuron, azimsulfuron, foramsulfuron, iodosulfuron, imazosulfuron, mesosulfuron, metsulfuron, nicosulfuron, rimsulfu- ron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuron, or tritosulfuron (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) aminopyralid (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) halauxifen (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) pyridate (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) imazethapyr (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) metribuzin (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) aclonifen (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) flurochloridone (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) cloransulam, florasulam, flumetsulam, metosulam, penoxsulam, or pyroxsulam (herbicide B). In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) clopyralid, or picloram (herbi cide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) propyzamide (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) clethodim, cycloxydim, profoxydim, sethoxydim, fluazifop, haloxyfop, propaquizafop, quizalofop, or pinoxaden (herbi cide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) propoxycarbazone, flucarba- zone, or thiencarbazone (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) carfentrazone, pyraflufen, flumioxazin, acifluorfen, sulfentrazone, saflufenacil, or trifludimoxazin (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) 2,4-D, or dicamba (herbicide B).

In yet another aspect of the present invention, there is provided a herbicidal combination com prising a herbicidally effective amount of (a) herbicide A and (b) bifenox (herbicide B).

In another aspect, the present invention relates to the use of the combination as defined herein (in particular any one of the aforementioned herbicidal combinations comprising herbicide A and the specific herbicides B for controlling undesirable vegetation.

In another aspect, the present invention relates to a method for controlling undesirable vegeta tion which comprises applying to the vegetation or the locus thereof or applying to the soil or water to prevent the emergence or growth of the undesirable vegetation the combination as defined herein (in particular any one of the aforementioned herbicidal combinations comprising herbicide A and the specific herbicides B).

The aforementioned herbicidal combinations comprising herbicide A and the specific herbicides B are particularly suitable for selective weed control in 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.

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, barley, corn, rice, sunflower, lentils, peas and oilseed rape (canola), preferably oilseed rape (canola) and 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 and the at least one herbicide B can be applied sim ultaneously or in succession to the areas, where undesirable vegetation occurs or may occur.

The invention, in particular, relates to a method for controlling undesirable vegetation in crops which comprises applying an herbicidal combination 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 and the at least one herbicide B are formulated and applied jointly or separately. In the case of separate appli cation, it is of minor importance, in which order the application takes place. It is only necessary, that the herbicide A and the at least one herbicide B are applied in a time frame that allows sim ultaneous 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 and the at least one herbicide B results in an enhanced activity against harmful plants in the sense of a synergy effect (syner gism or potentiation), even at low application rates of the herbicide A and the at least one herbi cide B. 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 comparable 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, or in crops with natural tolerance to all of herbicides A and B when com pared to the individual application of herbicide A and B. Moreover, the combinations also show an accelerated action on harmful plants, i.e. they damage harmful plants more quickly when compared with application of the individual 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 herbicide A and the at least one herbicide B, as active ingredients and also the combined application of the herbicide A and the at least one herbicide B, which means that the herbicide A and the at least one herbicide B are used together for controlling undesirable vegetation in crops and non-crop areas.

When using the combination of the invention for this purpose, the herbicide A and the at least one herbicide B can be applied simultaneously or in succession to the areas, where undesirable vegetation occurs or may occur. The herbicide A and the at least one herbicide B are, in particu lar, applied in crops, where undesirable vegetation may occur.

The term "composition" is understood as a physical admixture of the herbicide A and the at least one herbicide B and, optionally, one or more formulation auxiliaries, such as one or more sur factants. The term "composition" includes both a combo-formulation, containing a physical ad mixture of the herbicide A and the at least one herbicide B, and a ready to use composition, such as an aqueous spray liquor, obtained by tank mixing solo- or combo-formulations of the herbicide A and the at least one herbicide B.

The term "formulation" includes both formulations, containing a physical admixture of the herbi cide A and the at least one herbicide B as well as kits-of-parts formulations, where the herbicide A and the at least one herbicide B are formulated separately, i.e. as solo formulations or as a kit-of part formulation.

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.

In the combinations of the present invention, the relative weight ratio of the herbicide A, calcu lated as free acid of imazamox, to the at least one herbicide B, is in the range from 1 :500 to 500:1 , in particular from 1 :200 to 200:1 , especially from 1 :50 to 50: 1 , preferably from 1 :20 to 20: 1. More 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 herbicide A and the at least one herbicide B are preferably applied within these weight ratios. Likewise, the compositions and formulations of the invention contain the herbicide A and the at least one herbicide B within these weight ratios.

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 Abutilon, Alisma, Alopecurus, Amaranthus, Ambrosia, Ammania, Ammi, Aneilema, Anthemis, Apera, Atri- plex, Avena, Barbarea, Bidens, Brassica, Bromus, Bunias, Butomus, Capsella, Centaurea, Chenopodium, Cirsium, Conium, Convolvolus, Cyperus, Datura, Daucus, Descurainia, Digitaria, Echinochloa, Fumaria, Galinsoga, Galium, Geranium, Helianthus, Heliotropium, Heteranthera, Hibiscus, Hordeum, Lamium, Leptochloa, Leersia, Lolium, Lycopsis, Matricaria, Mercurialis, Orobanche, Oryza, Panicum, Papaver, Poa, Polygonum, Portulaca, Raphanus, Scirpus, Setar- ia, Sinapis, Solanum, Sonchus, Sorghum, Sisymbrium, Stachys, Stellaria, Thlaspi, Triticum, Veronica, Viola, and Xanthium.

According to one embodiment, the compositions and methods of the present invention are use ful for controlling monocotyledonous weeds and dicotyledonous weeds in oilseed rape, wherein the weeds are selected from the genera Alopecurus, Ammi, Anthemis, Apera, Barbarea, Brassi- ca, Bromus, Bunias, Capsella, Centaurea, Chenopodium, Conium, Daucus, Descurainia, Fu maria, Galium, Geranium, Hordeum, Lamium, Lolium, Lycopsis, Matricaria, Mercurialis, Oro banche, Papaver, Raphanus, Sinapis, Sisymbrium, Stellaria, Thlaspi, Triticum, Veronica, and Viola.

According to one embodiment, the compositions and methods of the present invention are use ful for controlling monocotyledonous weeds and dicotyledonous weeds in sunflower, soy and legumes, wherein the weeds are selected from the genera Abutilon, Alopecurus, Amaranthus, Ambrosia, Ammi, Atriplex, Avena, Brassica, Chenopodium, Cirsium, Convolvolus, Datura, Digi- taria, Echinochloa, Fumaria, Galinsoga, Helianthus, Heliotropium, Hibiscus, Lolium, Matricaria, Orobanche, Panicum, Poa, Polygonum, Portulaca, Setaria, Solanum, Sonchus, Stachys, Stel laria, and Xanthium.

According to one embodiment, the compositions and methods of the present invention are use ful for controlling monocotyledonous weeds and dicotyledonous weeds in rice, wherein the weeds are selected from the genera Alisma, Ammania, Aneilema, Bidens, Butomus, Cyperus, Digitaria, Echinochloa, Heteranthera, Leptochloa, Leersia, Oryza, Panicum, Polygonum, Scir pus, and Sorghum.

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 in sunflower, which are selected from the genera Alopecurus, Avena, Digitaria, Echinochloa, Lolium, Panicum, Poa, and Setaria, prefera bly selected from the genera Digitaria, Echinochloa, Lolium, Panicum, and Setaria, and in par ticular the species Digitaria sanguinalis, Echinochloa crus-galli, Lolium multiflorum, Panicum miliaceum, and Setaria viridis. 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 in sunflower from the genera Abutilon, Amaranthus, Ambrosia, Ammi, Atriplex, Brassica, Chenopodium, Cirsium, Convolvolus, Datura, Fumaria, Galinsoga, Helianthus, Heliotropium, Hibiscus, Matricaria, Orobanche, Polygonum, Portulaca, Solanum, Sonchus, Stachys, Stellaria, and Xanthium, preferably selected from the genera Abutilon, Amaranthus, Ambrosia, Ammi, Chenopodium, Cirsium, Convolvolus, Oroban che, Portulaca, Solanum, and Sonchus, in particular from species Abutilon theophrasti, Amaran thus retroflexus, Ambrosia artemisiifolia, Ammi majus, Chenopodium album, Cirsium arvense, Convolvulus arvensis, Orobanche sp., Portulaca oleracea, Solanum nigrum, and Sonchus arvensis.

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, Helianthus, Horde- urn, and Triticum, in particular from the species Brassica napus (BRSNW, BRSNS), Helianthus annus (HELAN), 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/microtubuli 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 beans, 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 particu larly suitable for combating/controlling undesired vegetation in ALS tolerant sunflower, oilseed rape (canola), wheat and barley, preferably in ALS tolerant sunflower and oilseed rape (canola). 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, Clear field® corn, Clearfield® wheat, Clearfield® Sunflower, Clearfield Lentils, and Cultivance® crops, in particular in Clearfield® Sunflower and Clearfield® canola.

The combinations of the invention are particularly useful for combating/controlling undesired vegetation in in the following crops:

a. Brassica napus containing the CLB-1 AHASL trait having two substitutions, an A122(Af)T substitution and an S653(Af)N substitution.

b. Brassica napus containing both the CLB-1 trait and one or two additional AHASL trait(s) that each have substitution(s) at at least one of the positions A122(Af), P197(Af), R199(Af), T203(Af), A205 (At), W574(Af), S653 (At), or G654 (At). c. Brassica napus containing an AHASL trait having one A122(Af)T substitution. d. Sunflower containing the CL CLHA Plus AHASL trait having an A122(Af)T substi tution or two substitutions, an A122(Af)T substitution and an A205 (Af)V substitution. e. Sunflower containing the CL ImiSun AHASL trait having an A205 (Af)V substitu tion.

f Sunflower containing both the CL CLHA Plus or CL ImiSun trait and one or two additional AHASL trait(s) that each have substitution(s) at minimum one of the posi tions A122(Af), P197(Af), R199(Af), T203(Af), A205 (At), W574(Af), S653 (At), or G654(Af).

g. Lentil containing the LcAHASL2 trait having a A205 (Af)V substitutions, h. Rice containing the OSAHASL1 trait having a substitution(s) at minimum one of the positions A122(Af), S653 (At), or G654(Af).

/. Wheat containing the TaAHASLI D trait having a substitution(s) at minimum one of the positions A122(Af) or S653 (At).

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 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 and the at least one herbicide B 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 and the at least one herbicide B 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 and the at least one herbicide B provided that the compositions together comprise the herbicide A the at least one herbicide B.

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 1 to 200 g/ha and in particular from 2 to 100 g/ha or from 5 to 50 g/ha. In the method of the invention, the application rate of the at least one herbicide B, is generally from 1 to 2000 g/ha and in particular from 2 to 500 g/ha or from 5 to 50 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 herbicide A and the at least one herbicide B, and optionally the safener C, together with liquid and/or solid carrier materials, 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 formu lation may 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 formula tion of the at least one herbicide B and the safener 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 and the at least one herbicide B, while the other package contains a formulation of the safener C, and wherein both formulations contain at least one liquid and/or solid carrier material and one or more formu lation 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 (at least one) 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 (at least one) herbicide B, and a third package which contains a formulation of the safener C, and wherein the three formu lations contain at least one liquid and/or solid carrier material 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. 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 herbicide A and the at least one herbicide B, and optionally the safener C, may be present in suspended, emulsified or dissolved form. The formulations according to the invention can be in the form of aqueous solu tions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, aqueous emulsions, aqueous microemulsions, aqueous suspo-emulsions, oil dis persions, pastes, dusts, materials for spreading 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 A and the at least one herbi cide B). 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 herbicides A and B 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 herbicides A and B 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.

2. C Emulsifiable concentrates

15 parts by weight of herbicides A and B 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 herbicides A and B 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 herbicides A and B 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 herbicides A and B 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 herbicides A and B 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 herbicides A and B, 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

3. I Dusts

5 parts by weight of herbicides A and B 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.

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

0.5 parts by weight of herbicides A and B 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 herbicides A and B 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 and the at least one herbicide B, 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

Sulfosulfuron 80% WG

Halauxifen 5% EC

Aminopyralid 30 g/l SL

Pyridate 45% WP

Dicamba 600 g/l SL

Saflufenacil 342 g/l SC

Imazethapyr 240 g/l SL

Pyroxsulam 7.5% WP

Clethodim 240 g/l EC

Propyzamid 400 g/l SC

Thiencarbazone 10 g/l EC

Pyraflufen 26 g/l EC

Metribuzin 70% WG

Aclonifen 600 g/l SC

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:

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 - (XY/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 Table 1 :

Table 2:

Table 3:

Table 4:

Table 5:

Table 6:

Table 7:

Table 8:

Table 9:

Table 10:

Table 11 :

Table 12:

Table 13:

Table 14:

Table 15:

Table 16:

Table 17:

Table 18:

Table 19:

Table 20:

Table 21:

Table 21:

Table 22:

Table 23:

Table 24:

Table 23:

Table 24:

Table 25:

Table 26:

Table 27:

Table 28:

Table 29:

Table 30:

Table 31:

Table 32:

Claims

1. The use of herbicidally active combinations comprising herbicide A and at least one herbi cide B, for the selective control of undesirable vegetation in cultures of crop plants, where in

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 at least one herbicide B is selected from the groups b1) to b15):

b1) lipid biosynthesis inhibitors;

b2) acetolactate synthase inhibitors (ALS inhibitors);

b3) photosynthesis inhibitors;

b4) protoporphyrinogen-IX oxidase inhibitors;

b5) bleacher herbicides;

b6) enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP inhibitors); b7) glutamine synthetase inhibitors;

b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors);

b9) mitosis inhibitors;

b10) inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); b11) cellulose biosynthesis inhibitors;

b12) decoupler herbicides;

b13) synthetic auxins;

b14) auxin transport inhibitors; and

b15) other herbicides selected from the group consisting of bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difen- zoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine- ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tria- ziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (CAS 499223-49-3) and its salts and esters;

and wherein the crop plant is selected from imidazolinone tolerant crops.

2. The use according to claim 1 , wherein the imidazolinone tolerant crop is selected from sunflower, canola, wheat and barley.

3. The use according to claim 1 , wherein the imidazolinone tolerant crop is selected from sunflower.

4. The use according to claim 1 , wherein the imidazolinone tolerant crop is selected from canola.

5. The use according to any one of claims 1 to 4, wherein the combination consists of herbi cide A and one herbicide B.

6. The use according to any one of claims 1 to 4, wherein the combination consists of herbi cide A and two differing herbicides B.

7. The use according to any one of claims 1 to 6, wherein the undesirable vegetation is se lected from the genera Abutilon, Alisma, Alopecurus, Amaranthus, Ambrosia, Ammania, Ammi, Aneilema, Anthemis, Apera, Atriplex, Avena, Barbarea, Bidens, Brassica, Bromus, Bunias, Butomus, Capsella, Centaurea, Chenopodium, Cirsium, Conium, Convolvolus, Cyperus, Datura, Daucus, Descurainia, Digitaria, Echinochloa, Fumaria, Galinsoga, Gali um, Geranium, Helianthus, Heliotropium, Heteranthera, Hibiscus, Hordeum, Lamium, Lep- tochloa, Leersia, Lolium, Lycopsis, Matricaria, Mercurialis, Orobanche, Oryza, Panicum, Papaver, Poa, Polygonum, Portulaca, Raphanus, Scirpus, Setaria, Sinapis, Solanum, Sonchus, Sorghum, Sisymbrium, Stachys, Stellaria, Thlaspi, Triticum, Veronica, Viola, and Xanthium.

8. The use according to any one of claims 1 to 7, wherein the undesirable vegetation com prises volunteer crop selected from the genera Brassica, Hordeum, and Triticum.

9. The use according to any one of claims 1 to 8, wherein the undesirable vegetation com prises herbicide resistant species.

10. Herbicidally active combinations comprising a herbicide A and at least one herbicide B, wherein

b. the at least one herbicide B is selected from the groups b1) to b15):

b1) lipid biosynthesis inhibitors;

b2) acetolactate synthase inhibitors (ALS inhibitors);

b3) photosynthesis inhibitors; b4) protoporphyrinogen-IX oxidase inhibitors;

b5) bleacher herbicides;

b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors);

b9) mitosis inhibitors;

b12) decoupler herbicides;

b13) synthetic auxins;

b14) auxin transport inhibitors; and

b15) other herbicides selected from the group consisting of bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difen- zoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine- ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tria- ziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (CAS 499223-49-3) and its salts and esters.

11. The combination according to claim 10, wherein the combination consists of herbicide A and one herbicide B.

12. The combination according to claim 10, wherein the combination consists of herbicide A and two differing herbicides B.

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

claims 10 to 12 and one or more auxiliaries customary in crop protection.

14. The herbicidally active composition as claimed in claim 13, comprising an adjuvant which comprises a polar solvent and a phosphate ester of the formula (A)

O

R— — R^b (A)

0 H in which R^a 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;

and optionally and one or more further formulation auxiliaries.

15. A method for controlling undesirable vegetation which comprises applying to the vegeta tion or the locus thereof or applying to the soil or water to prevent the emergence or growth of the undesirable vegetation the combinations or composition as claimed in any one of claims 10 to 14.