Herbicide combinations
The present invention primarily relates to herbicide combinations comprising (i) aclonifen (ii) diflufenican and (iii) ethofumesate and to compositions comprising said herbicide combinations. The present invention further relates to a method for producing said herbicide combinations and compositions. The present invention also relates to the use of said herbicide combinations and compositions in the field of agriculture and for controlling harmful plants.
Aclonifen is known as a selective herbicide from DE2831262 and is used both alone and in mixtures in many countries around the world.
It is already known that diflufenican is a broad-spectrum pre- and early post-emergence herbicide for use in wheat and barley. It is often used in combination with other herbicides (W O 2009/106259, US 5674809 and EP 0531116).
Ethofumesate is known as herbicide from DE1926139 and is used both alone and in mixtures in many countries around the world.
WO 2008/075065 describes compositions of ethofumesate in combination with further herbicides (at least one, but one or more is possible) selected among e.g. pendimethalin, trifluralin, iodosulfuron, mesosulfuron, diflufenican, picolinafen, pyroxsulam.
FR2611437 describes a binary mixture comprising aclonifen in combination with oxadiazon or with diflufenican.
XP001526230 discloses compositions of diflufenican and aclonifen that are selective in sunflower. The combinations can be used pre-emergence but diflufenican is also active post emergence. Digitaria, Setaria, Brassica, Ammi majus are the weeds that can be controlled.
WO 2023/126626 describes herbicidal combinations of napropamide with a further herbicide. The herbicide is selected among ethofumesate, prosulfocarb, pyroxasulfone, propisochlor, bixlozone and aclonifen. Preferred is a combination with ethofumesate. Further preferred is a combination with aclonifen. A preferred third component is always diflufenican. The ternary compositions napropamide, diflufenican and ethofumesate/aclonifen are both disclosed explicitly.
WO 2014/001248 describes mixtures of flufenacet with diflufenican , that are called Liberate or Herold. To improve the performance of flufenacet, further herbicides can be mxed to flufenacet. Quaternary mixtures are claimed comprising flufenacet, diflufenican, aclonifen and flurtamone (p.4, 1. 4 to 9).
The herbicidal crop protection agents (herbicides) and combinations/compositions thereof known to date for controlling harmful plants or unwanted vegetation have some disadvantages, above all (a) that they have no or else insufficient herbicidal activity against specific harmful plants, (b) that the spectrum of harmful plants which can be controlled with the herbicides is not broad enough, (c) that the selectivity of herbicides in and the compatibility with crops is too low, thereby causing unwanted damage and/or unwanted reduced harvest yields of the crops, (d) that the initial herbicidal activity is not acceptable or not strong enough and/or (e) that the herbicidal activity does not last long enough. For this reason there is a constant need to develop novel herbicidal combinations/compositions which have advantages over the known ones at least in some areas.
Surprisingly, it has now been found that certain herbicide combinations or compositions comprising said herbicide combinations exhibit the desired herbicidal activity and are able to control harmful plants or unwanted vegetation in a more efficacious manner.
Furthermore, it has been found, that the combination according to the invention not only bring about the additive enhancement of the spectrum of action with respect to the harmful plants which can be controlled with the herbicides which was expected but achieves a synergistic effect which extends the range of action of the single components (i), (ii) and (iii) as well as the action of the respective two-way mixtures. Firstly, rates of application of the single components are lowered whilst the action remains equally good. Secondly, the combination still achieves a high degree of control of harmful plants even where the individual compounds have become totally ineffective in such a low application rate range. This allows, on the one hand, a substantial broadening of the spectrum of harmful plants that can be controlled and, on the other hand, increased safety in use.
The present invention relates to a combination of herbicides (herbicide combination) comprising or consisting of
(i) aclonifen,
(ii) diflufenican and
(iii) ethofumesate.
Further, the present invention relates to a combination which comprises in addition to (i), (ii) and (iii) at least one additional herbicidal active ingredient, e.g: bromoxynil, bromoxynil-butyrate, -potassium, - heptanoate, and -octanoate, benzofenap, butachlor, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, - diolamin, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, triisopropanolammonium, and -trolamine, broclozone, cinmethylin, dimethenamid, clomazone, cyclopyrimorate, propoxycarbazone, ethoxysulfuron, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P -ethyl, fenquinotrione, fentrazamide, florasulam, flufenacet, fluroxypyr, fluroxypyr-meptyl, foramsulfuron, icafolin, icafolin-methyl, iodosulfuron, iodosulfuron-methyl-sodium, isoproturon, isoxaben, isoxaflutole, mefenacet, mesosulfuron, mesosulfuron-methyl, metolachlor, S-metolachlor, l-(2-chloro-3-(3- cyclopropyl-5-hydroxy-l-methyl-lH-pyrazole-4-carbonyl)-6-(trifluoromethyl)phenyl)piperidin-2-one, metosulam, metribuzin, nicosulfuron, oxadiargyl, oxadiazon, pethoxamid, prosulfocaarb, pyrasulfotole, pyroxsulam, pyroxasulfon, tefuryltrione, tembotrione, thiencarbazone, thiencarbazone-methyl, triafamone, triallate, pendimethalin halauxifen-methyl, 2-methyl-4-chlorophenoxyacetic acid (MCPA), bixlozone. Further, the present invention relates to a combination comprising as sole herbicidally active constituents
(i) aclonifen, (ii) diflufenican and (iii) ethofumesate.
Further, the present invention relates to a combination comprising as sole herbicidally active constituents
(ii) aclonifen, (ii) diflufenican and (iii) ethofumesate and in addition at least one safener.
Further, the present invention relates to a combination which comprises in addition to (i), (ii) and (iii) at least one safener.
Further, the present invention relates to a combination which comprises in addition to (i), (ii) and (iii) at least one additional herbicidal active ingredient and at least one safener.
The salts of compounds used in the context of the present invention may be used in the form of the respective agronomically acceptable salts, such as alkali metal salts, alkaline earth salts or ammonium salts.
Definitions
Safener:
SI) Compounds of the group of heterocyclic carboxylic acid derivatives:
S 1a) Compounds of the type of dichlorophenylpyrazoline-3 -carboxylic acid (S 1a), preferably compounds such as l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S 1-1) ("mefenpyr(-diethyl)"), and related compounds, as described in WO-A-91/07874;
Slb) Derivatives of dichlorophenylpyrazolecarboxylic acid (Slb), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (Sl-2), ethyl l-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S 1-3), ethyl l-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)pyrazole-3-carboxylate (Sl-4) and related compounds, as described in EP-A-333 131 and EP-A-269 806;
ST) Derivatives of l,5-diphenylpyrazole-3-carboxylic acid (Slc), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-phenylpyrazole-3 -carboxylate (S 1-5), methyl l-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (Sl-6) and related compounds, as described, for example, in EP-A-268554;
Sld) Compounds of the type of triazolecarboxylic acids (Sld), preferably compounds such as fenchlorazole(-ethyl), i.e. ethyl l-(2,4-dichlorophenyl)-5-trichloromethyl-(lH)-l,2,4-triazole-3- carboxylate (S 1-7), and related compounds, as described in EP-A-174 562 and EP-A-346 620;
Sle) Compounds of the type of 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2- isoxazoline-3-carboxylic acid (Sle), preferably compounds such as ethyl 5 -(2, 4-dichlorobenzyl)-2-isoxazoline-3 -carboxylate (Sl-8) or ethyl 5-phenyl-2-isoxazoline-3- carboxylate (S 1-9) and related compounds, as described in WO-A-91/08202, or 5,5-diphenyl-2- isoxazolinecarboxylic acid (Sl-10) or ethyl 5, 5 -diphenyl -2 -isoxazolinecarboxylate (Sl-11) ("isoxadifen-ethyl") or n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (Sl-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (Sl-13), as described in the patent application WO-A-95/07897.
S2) Compounds of the group of 8-quinolinoxy derivatives (S2):
S2a) Compounds of the type of 8-quinolinoxyacetic acid (S2a), preferably
1-methylhexyl (5-chloro-8-quinolinoxy)acetate (common name "cloquintocet-mexyl" (S2-1),
1 ,3 -dimethyl -but- 1 -yl (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3),
1 -allyloxyprop-2 -yl (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl (5-chloro-8-quinolinoxy)acetate (S2-5), methyl (5-chloro-8-quinolinoxy)acetate (S2-6), allyl (5 -chloro- 8 -quinolinoxy)acetate (S2-7),
2-(2-propylideneiminoxy)- 1 -ethyl (5-chloro-8-quinolinoxy)acetate (S2-8),
2-oxo-prop-l-yl (5-chloro-8-quinolinoxy)acetate (S2-9) and related compounds, as described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, and also (5-chloro-8- quinolinoxy)acetic acid (S2-10), its hydrates and salts, for example its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulphonium or phosphonium salts, as described in WO-A-2002/34048;
S2b) Compounds of the type of (5 -chloro-8-quinolinoxy)malonic acid (S2b), preferably compounds such as diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-quinolinoxy)malonate and related compounds, as described in EP-A-0 582 198.
S3) Active compounds of the type of dichloroacetamides (S3) which are frequently used as pre- emergence safeners (soil-acting safeners), such as, for example,
"dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1),
"R-29148" (3 -dichloroacetyl -2, 2, 5 -trimethyl- 1, 3 -oxazolidine) (S3-2),
"R-28725" (3 -dichloroacetyl -2, 2-dimethyl- 1,3 -oxazolidine) (S3-3),
"benoxacor" (4-dichloroacetyl-3 ,4-dihydro-3 -methyl -2H-l,4-benzoxazine) (S3 -4),
"PPG-1292" (N-allyl-N-[(l,3-dioxolan-2-yl)methyl]dichloroacetamide) (S3 5),
" DKA-24 " (N -allyl-N - [(allylaminocarbonyl)methyl] dichloroacetamide) ( S3 -6),
"AD-67" or "MON 4660" (3-dichloroacetyl-l-oxa-3-aza-spiro[4,5]decane) (S3-7),
"TI-35" (1-dichloroacetylazepane) (S3-8)
"diclonon" (dicyclonon) (S3-9)
((RS)-l-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[l,2-a]pyrimidin-6-one), funlazole or MON 13900 ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazohdine) (S3 -10), and also its (R)-isomer (S3-11).
S4) Compounds of the class of acylsulphonamides (S4):
S4a) N-acylsulphonamides of the formula (S4a) and salts thereof, as described in WO-A-97/45016 in which
RA1 is (Ci -Ce)-alkyl, (C3-Ce)-cycloalkyl, where the 2 last-mentioned radicals are substituted by VA substituents from the group consisting of halogen, (Ci-C4)-alkoxy, halo-(Ci-Ce)-alkoxy and (Ci-C4)-alkylthio and, in the case of cyclic radicals, also (Ci-C4)-alkyl and (C1-C4)- haloalkyl;
RA2 is halogen, (Ci-C4)-alkyl, (C1-C4) -alkoxy, CF3 mA is 1 or 2;
VD is 0, 1, 2 or 3;
S4b) Compounds of the type of 4-(benzoylsulphamoyl)benzamides of the formula (S4b) and salts thereof,
WO-A-99/16744, in which
RB1, RB2 independently of one another are hydrogen, (Ci-Ce)-alkyl, (C3-Ce)-cycloalkyl, (C3-Ce)-alkenyl, (C3-Ce)-alkynyl,
RB3 is halogen, (Ci-C4)-alkyl, (Ci-C4)-haloalkyl or (Ci-C4)-alkoxy, ms is 1 or 2; for example those in which
RB1 = cyclopropyl, RB2 = hydrogen and (RB3) = 2-OMe ("cyprosulfamide", S4-1), RB1 = cyclopropyl, RB2 = hydrogen and (RB3) = 5-Cl-2-OMe (S4-2),
RB1 = ethyl, RB2 = hydrogen and (RB3) = 2-OMe (S4-3),
RB1 = isopropyl, RB2 = hydrogen and (RB3) = 5-Cl-2-OMe (S4-4) and
RB1 = isopropyl, RB2 = hydrogen and (RB3) = 2-OMe (S4-5);
S4C) Compounds of the class of benzoylsulphamoylphenylureas of the formula (S4C) as described in EP-A-365484, in which
Rc1, Rc2 independently of one another are hydrogen, (Ci-Cs)-alkyl, (C3-Cs)-cycloalkyl, (Cs-Ce)- alkenyl, (C3-Ce)-alkynyl,
Rc3 is halogen, (Ci-C4)-alkyl, (C1-C4) -alkoxy, CF3, mc is 1 or 2; for example l-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea, l-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea, l-[4-(N-4,5-dimethylbenzoylsulphamoyl)phenyl]-3-methylurea;
S4d) Compounds of the type of N-phenylsulphonylterephthalamides of the formula (S4d) and salts thereof, which are known, for example, from CN 101838227, in which
RD4 is halogen, (Ci-C4)-alkyl, (C1-C4) -alkoxy, CF3; mD is 1 or 2; RD5 is hydrogen, (Ci-Ce)-alkyl, (C3-Ce)-cycloalkyl, (C2-Ce)-alkenyl, (C2-Ce)-alkynyl, (Cs-Ce)- cycloalkenyl.
55) Active compounds from the class of hydroxyaromatics and aromatic -aliphatic carboxylic acid derivatives (S5), for example ethyl 3, 4, 5 -triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3, 5 -dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2 -hydroxy cinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A- 2005/016001.
56) Active compounds from the class of l,2-dihydroquinoxalin-2-ones (S6), for example l-methyl-3-(2-thienyl)-l,2-dihydroquinoxalin-2-one, l-methyl-3-(2-thienyl)-l,2- dihydroquinoxaline-2-thione, l-(2-aminoethyl)-3-(2-thienyl)-l,2-dihydroquinoxalin-2-one hydrochloride, l-(2-methylsulphonylaminoethyl)-3-(2-thienyl)-l,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
57) Compounds from the class of diphenylmethoxyacetic acid derivatives (S7), for example methyl diphenylmethoxyacetate (CAS-Reg.Nr. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate, or diphenylmethoxyacetic acid, as described in WO-A-98/38856.
58) Compounds of the formula (S8), as described in WO-A-98/27049, where the symbols and indices have the following meanings:
RD1 is halogen, (Ci-C4)-alkyl, (Ci-C^-haloalkyl, (C1-C4) -alkoxy, (Ci-C4)-haloalkoxy,
RD2 is hydrogen or (CI -C4)-alkyl,
RD3 is hydrogen, (Ci-Cs)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or substituted by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof, no is an integer from 0 to 2.
S9) Active compounds from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example
1.2-dihydro-4-hydroxy-l-ethyl-3 -(5 -tetrazolylcarbonyl)-2 -quinolone (CAS Reg. No.: 219479-18-2),
1.2-dihydro-4-hydroxy-l-methyl-3 -(5 -tetrazolylcarbonyl)-2 -quinolone (CAS Reg. No.: 95855-00- 8), as described in WO-A- 1999/000020.
S10) Compounds of the formula (S10a) or (S10b) as described in WO-A-2007/023719 and WO-A- 2007/023764
RE1 is halogen, (Ci-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3
YE, ZE independently of one another are O or S, nE is an integer from 0 to 4,
RE2 is (Ci-Cie)-alkyl, (C2-Ce)-alkenyl, (C3-Ce)-cycloalkyl, aryl; benzyl, halobenzyl,
RE3 is hydrogen or (Ci-Ce)-alkyl.
511) Active compounds of the type of oxyimino compounds (Si l), which are known as seed dressings, such as, for example, "oxabetrinil" ((Z)-l,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (SI 1-1), which is known as seed dressing safener for millet against metolachlor damage,
"fluxofenim" (l-(4-chlorophenyl)-2,2,2-trifluoro-l -ethanone O-(l,3-dioxolan-2-yhnethyl)oxime) (SI 1-2), which is known as seed dressing safener for millet against metolachlor damage, and
"cyometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (SI 1-3), which is known as seed dressing safener for millet against metolachlor damage.
512) Active compounds from the class of isothiochromanones (S12), such as, for example, methyl [(3- oxo-lH-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No.: 205121-04-6) (S12-1) and related compounds from WO-A-1998/13361.
S13) One or more compounds from group (S13):
"naphthalic anhydrid" (1,8 -naphthalenedicarboxylic anhydride) (S 13-1), which is known as seed dressing safener for com against thiocarbamate herbicide damage, "fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S 13-2), which is known as safener forpretilachlor in sown rice,
"flurazole" (benzyl 2-chloro-4-trifluoromethyl-l,3-thiazole-5-carboxylate) (SI 3-3), which is known as seed dressing safener for millet against alachlor and metolachlor damage,
"CL 304415" (CAS Reg. No.: 31541-57-8) (4-carboxy-3,4-dihydro-2H-l-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is known as safener for com against imidazolinone damage,
"MG 191" (CAS Reg. No.: 96420-72-3) (2 -dichloromethyl -2 -methyl- 1,3 -dioxolane) (S13-5) which is known as safener for com,
"MG 838" (CAS Reg. No.: 133993-74-5) (2-propenyl l-oxa-4-azaspiro[4.5]decane-4- carbodithioate) (S13-6),
"disulphoton" (0,0-diethyl S-2 -ethylthioethyl phosphorodithioate) (S13-7),
"dietholate" (0,0-diethyl O-phenyl phosphorothioate) (S13-8),
"mephenate" (4-chlorophenyl methylcarbamate) (S13-9).
514) Active compounds which, besides a herbicidal effect against harmful plants, also have a safener effect on crop plants such as rice, such as, for example, "dimepiperate" or "MY 93" (.S'- 1 -methyl- 1- phenylethyl piperidine- 1 -carbothioate), which is known as safener for rice against molinate herbicide damage,
"daimuron" or "SK 23" (1-(1 -methyl- l-phenylethyl)-3-p-tolylurea), which is known as safener for rice against imazosulphuron herbicide damage,
"cumyluron" = "JC 940" (3 -(2-chlorophenylmethyl)-l-(l -methyl- l-phenylethyl)urea, see JP-A-60087254), which is known as safener for rice against some herbicide damage,
"methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone), which is known as safener for rice against some herbicide damage,
"CSB" (l-bromo-4-(chloromethylsulphonyl)benzene) from Kumiai (CAS Reg. No. 54091-06-4), which is known as safener against some herbicide damage in rice.
515) Compounds of the formula (S 15) or its tautomers, as described in WO-A-2008/131861 and WO-A-2008/131860, in which
RH1 is (Ci-Ce)-haloalkyl,
RH2 is hydrogen or halogen,
RH3, RH4 independently of one another are hydrogen, (Ci-Cie)-alkyl, (C2-Cie)-alkenyl or (C2-Ci6)-alkynyl, where each of the 3 last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxy, cyano, (Ci-C4)-alkoxy, (C1-C4)- haloalkoxy, (Ci-C4)-alkylthio, (Ci-C4)-alkylamino, di-[(Ci-C4)-alkyl]-amino, [(C1-C4)- alkoxy] -carbonyl, [(Ci-C4)-haloalkoxy] -carbonyl, unsubstituted or substituted (Cs-Ce)- cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl; or (C3-Ce)-cycloalkyl, (C4-Ce)-cycloalkenyl, (Cs-Ce)- cycloalkyl which is at one site of the ring condensed with a 4 to 6-membered saturated or unsaturated carbocyclic ring , or (C4-Ce)- cycloalkenyl which is at one site of the ring condensed with a 4 to 6-membered saturated or unsaturated carbocyclic ring, where each of the 4 last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxy, cyano, (Ci-C4)-alkyl, (C1-C4)- haloalkyl, (C1-C4) -alkoxy, (C1-C4) -haloalkoxy, (Ci-C4)-alkylthio, (Ci-C4)-alkylamino, di- (Ci-C4)-alkyl]-amino, [(Ci-C4)-alkoxy] -carbonyl, [(Ci-C4)-haloalkoxy]-carbonyl, unsubstituted or substituted (C3-Ce)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl; or
RH3 is (Ci-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-Ce)-alkynyloxy or (C2-C4) -haloalkoxy, and
RH4 is hydrogen or (CI -C4)-alkyl, or
RH3 and RH4 together with the directly bound N-atom are a 4 to 8-membered heterocyclic ring, which can contain further hetero ring atoms besides the N-atom, preferably up to two further hetero ring atoms from the group consisting of N, O and S, and which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, nitro, (Ci-C4)-alkyl, (Ci-C4)-haloalkyl, (Ci-C4)-alkoxy, (Ci-C4)-haloalkoxy, and (C1-C4) -alkylthio.
Herbicides The herbicides used in the context of the present invention are known per se, and described inter alia in "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012 and the literature cited therein.
Combination/Composition
Compositions within the context of the present invention comprise in addition to the combinations according to the invention one or more further component(s) selected from the group consisting of formulation auxiliaries, additives customary in crop protection, and further agrochemically active compounds.
Preferred is a combination according to the invention wherein fenchlorazole-ethyl (SI), mefenpyr-diethyl
(52), isoxadifen-ethyl (S3), cyprosulfamide (S4), cloquintocet-mexyl (S5), fenclorim (S6), dichlormid (S7), benoxacor (S8), furilazole (S9), oxabetrinil (S10), fluxofenim (Si l), flurazole (S12) ornaphthalic anhydride (S13) is the safener.
More preferred is a combination according to the invention wherein mefenpyr-diethyl (S2), isoxadifen-ethyl
(53), cyprosulfamide (S4) or cloquintocet-mexyl (S5) is the safener.
Most preferred is a combination according to the invention wherein mefenpyr-diethyl (S2) or cloquintocet- mexyl (S5) is the safener.
The weight ratio of the combination according to the invention can be described by the weight of the total amount of component (i) to the total amount of component (ii) and the weight of the total amount of component (i) to the total amount of component (iii), which is as follows:
(i) to (ii) in the range of from 125 : 1 to 1 : 125 and for (i) to (iii) in the range of from 60 : 1 to 1 : 60.
Preferably, the ratio by weight of the total amount of component (i) to the total amount of component (ii) in a herbicide combination according to the present invention is in the range of from 25 : 1 to 1 : 25 and for (i) to (iii) in the range of from 10 : 1 to 1: 10.
More preferably, the ratio by weight of the total amount of component (i) to the total amount of component
(ii) in a herbicide combination according to the present invention is in the range of from 10 : 1 to 1 : 10 and for (i) to (iii) in the range of from 5 : 1 to 1: 5.
Superadditive (= synergistic) effects occur when components (i), (ii) and (iii) are used jointly. The action in the combinations is in this connection stronger than the sum to be expected of the actions of the individual herbicides used. The synergistic effects allow a reduction in the amount expended the combating of a broader spectrum of weeds, a faster onset of the herbicidal action, a longer lasting action, better control of the harmful plants, with only one or a few applications, and a broadening of the possible application period. The properties and advantages mentioned are of use for controlling harmful plants or unwanted vegetation and accordingly to safeguard and/or to increase the yields in terms of quality and quantity. The technical standard is, with regard to the properties described, clearly exceeded by these new combinations.
The combination(s)/composition(s) according to the present invention can be employed for controlling harmful plants in genetically modified crops or crops obtained by mutation/selection. These crops are distinguished as a rule by particular, advantageous properties, such as resistances to herbicidal combinations/compositions or resistances to plant diseases or causative agents of plant diseases such as particular insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, for example, transgenic plants are known whose starch content is increased or whose starch quality is altered, or those where the harvested material has a different fatty acid composition.
The present invention also relates to a method for controlling harmful plants or unwanted vegetation, which comprises applying a herbicide combination/composition according to the present invention by preemergence, early post-emergence or post-emergence treatment to harmful plants or unwanted vegetation, parts of said harmful plants or unwanted vegetation, or the area where the harmful plants or unwanted vegetation grow, for example the area under cultivation.
In the context of the present invention “controlling” denotes a significant reduction of the growth of the harmful plant(s) in comparison to the untreated harmful plants. Preferably, the growth of the harmful plant(s) is essentially diminished (60-79%), more preferably the growth of the harmful plant(s) is largely or fully suppressed (80-100%), and in particular the growth of the harmful plant(s) is almost fully or fully suppressed (90-100%).
If the herbicide combination(s)/composition(s) according to the present invention is applied to the soil surface before or after germination of the crop plant but prior to emergence from the soil, the treatment is a pre-emergence treatment.
If the herbicide combination(s)/composition(s) according to the present invention is applied to the soil surface after emergence of the crop plant, the treatment is a post-emergence treatment.
Preferred is the use as pre-emergence herbicide and post-emergence herbicide.
More preferred is the use as pre-emergence and early post-emergence herbicide.
The combination according to the invention can be used for many crop plants, preferably cereals (e.g. in wheat and barley). They are also very suitable for use in transgenic crops.
Most preferred is the use as pre-emergence and early post-emergence herbicide in cereals. The application rates (indicated as g/ha i.e. grams of active ingredient per hectare), of the herbicide combination (i), (ii) and (iii)) used in the context of the present invention, are as defined as follows:
Table 1
The herbicide combination(s)/composition(s) according to the present invention have an outstanding herbicidal activity against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous harmful plants.
Specifically, examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the herbicide combination/composition according to the present invention, without the enumeration being a restriction to certain species.
In the context of the present text, reference may be made to growth stages according to the BBCH monograph “Growth stages of mono-and dicotyledonous plants“, 2nd edition, 2001, ed. Uwe Meier, Federal Biological Research Centre for Agriculture and Forestry (Biologische Bundesanstalt fur Land und Forstwirtschaft).
Examples of monocotyledonous harmful plants on which the herbicide combination/composition according to the present invention act efficiently are from amongst the genera Hordeum spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp., Eriochloa spp., Setaria spp., Pennisetum spp., Phalaris sp., Eleusine spp., Eragrostis spp., Panicum spp., Lolium spp., Alopecurus sp., Apera sp. Brachiaria spp., Leptochloa spp., Avena spp., Cyperus spp., Axonopris spp., Sorghum spp., and Melinus spp..
Particular examples of monocotyledonous harmful plants species on which the herbicide combination/composition according to the present invention act efficiently are selected from amongst the species Hordeum murinum, Echinochloa crus-galli, Poa annua, Bromus ruhensL., Bromus rigidus, Bromus secalinus L, Digitaria insularis, Digitaria sanguinalis, Eriochloa gracilis, Setaria faheri, Setaria viridis, Pennisetum glaucum, Eleusine indica, Eragrostis pectinacea, Panicum miliaceum, Phalaris minor, Lolium multiflorum, Lolium rigidum, Lolium perenne, Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus compressus, Cyperus esculentes, Axonopris offinis, Sorghum halapense, Alopecurus myosuroides, Apera spica-venti and Melinus repens. Examples of dicotyledonous harmful plants on which the herbicide combination/composition according to the present invention act efficiently are from amongst the genera Amaranthus spp., Polygonum spp., Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp., Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp., Erodium spp., Erigeron spp., Senecio spp., Lamium spp., Kochia spp., Chenopodium spp., Lactuca spp., Malva spp., Ipomoea spp., Brassica spp., Sinapis spp., Urtica spp., Sida spp, Portulaca spp., Richardia spp., Ambrosia spp., Calandrinia spp., Sisymbrium spp., Sesbania spp., Capsella spp., Sonchus spp., Euphorbia spp., Helianthus spp., Coronopus spp., Salsola spp., Abutilon spp., Vicia spp., Epilobium spp., Cardamine spp., Pieris spp., Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria spp., Plantago spp., Tribulus spp., Cenchrus spp. Bidens spp., Veronica spp., and Hypochaeris spp..
Particular examples of dicotyledonous harmful plants species on which the herbicide combination/composition according to the present invention act efficiently are selected from amongst the species Amaranthus spinosus, Amaranthus palmer, Amaranthis rudis, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum off cinale, Oenothera laciniata, Amsinckia intermedia, Erodium cicutarium, Erodium moschatum, Erigeron honariensis, Senecio vulgaris, Lamium sp., Erigeron canadensis, Polygonum aviculare, Kochia scoparia, Chenopodium album, Lactuca serriola, Malva parviflora, Malva neglecta, Ipomoea hederacea, Ipomoea lacunose, Brassica nigra, Sinapis arvensis, Urtica dioica, Amaranthus blitoides, Amaranthus retroflexus, Amaranthus hybridus, Amaranthus lividus, Sida spinosa, Portulaca oleracea, Richardia scabra, Ambrosia artemisiifolia, Calandrinia caulescens, Sisymbrium irio, Sesbania exaltata, Capsella bursa-pastoris, Sonchus oleraceus, Euphorbia maculate, Helianthus annuus, Coronopus didymus, Salsola tragus, Abutilon theophrasti, Vicia benghalensis L, Epilobium paniculatum, Cardamine spp, Pieris echioides, Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp. , Matricaria chamomilla, Plantago spp., Tribulus terrestris, Salsola kali, Cenchrus spp., Bidens bipinnata, Veronica sp., Galium aparine L, Papaver rhoeas. Viola arvense, Geranium, sp., Centaurea cyanus and Hypochaeris radicata.
The herbicide combination(s)/composition(s) according to the present invention are easily and readily obtained, by combining the components (i), (ii) and (iii) in the ratio by weight as defined in the context of the present invention, for example by mixing the appropriate amounts of components (i), (ii) and (iii).
Thus, in a further aspect, the present invention relates to a method for producing combination(s) of herbicides according to the present invention and to a method of producing the composition(s) according to the present invention comprising the steps of
(a) providing component (i),
(b) providing component (ii), (c) providing component (iii),
(c) combining component (i), component (ii) and component (iii), such that a combination of herbicides according to the present invention or a composition according to the present invention is obtained.
The herbicides (i), (ii) and (iii) used in the herbicide combination(s)/composition(s) according to the present invention are applied once, twice or three times per Gregorian calendar year, i.e. in one application, in two applications or in three applications per year according to the Gregorian calendar.
Furthermore, the herbicides (i), (ii) and (iii) as defined herein can be used together with other agrochemically active compounds, for example from the group of safener, fungicides, insecticides, other herbicides and other plant growth regulators, or with formulation auxiliaries and additives customary in crop protection. Additives are, for example, fertilizers and colorants.
The herbicide combination(s)/composition(s) according to the present invention cannot only be used as mixed formulations which are then applied in the customary manner as a dilution with water, but also as so- called tank mixes by jointly diluting the separately formulated, or partially separately formulated, components with water.
The herbicide combination(s)/composition(s) according to the present invention can be formulated in various ways, depending on the prevailing biological and/or chemical -physical parameters. The following are examples of general possibilities for formulations: wettable powders (WP), water-soluble concentrates, emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW) such as oil-in-water and water-in- oil emulsions, sprayable solutions or emulsions, suspension concentrates (SC), oil dispersions (OD), oil- or water-based dispersions, suspoemulsions, dusts (DP), seed-dressing materials, granules for soil application or for broadcasting, or water-dispersible granules (WG), ULV formulations, microcapsules (e.g. CS) or waxes.
The individual formulation types are known in principle and are described for example, in: Winnacker- Ktichler, "Chemische Technologic", Volume 7, C. Hauser Verlag Munich, 4th Edition, 1986; van Valkenburg, "Pesticide Formulations", Marcel DekkerN.Y., 1973; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries required, such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N. J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schbnfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. Verlagsgesellschaft, Stuttgart 1976, Winnacker-Ktichler, "Chemische Technologic", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.
Wettable powders (sprayable powders) are products which are uniformly dispersible in water and which, besides the active compound, also comprise ionic or nonionic surfactants (wetters, dispersants), for example polyoxethylated alkylphenols, polyethoxylated fatty alcohols or fatty amines, alkanesulfonates or alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2’-dinaphthylmethane-6,6’-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltauride, in addition to a diluent or inert material.
Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons with addition of one or more ionic or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are: calcium salts of alkylarylsulfonic acids, such as calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or poly oxethylene sorbitol esters.
Dusts are obtained by grinding the active compound with finely divided solid materials, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates (SC) can be water- or oil-based. They can be prepared, for example, by wet grinding by means of commercially available bead mills and, if appropriate, addition of further surfactants as they have already been mentioned for example above in the case of the other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be prepared for example by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if appropriate, further surfactants as have already been mentioned for example above in the case of the other formulation types.
Granules can be prepared either by spraying the active compound onto adsorptive, granulated inert material or by applying active compound concentrates to the surface of carriers such as sand, kaolinites or granulated inert material with the aid of binders, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active compounds may also be granulated in the manner conventionally used for the production of fertilizer granules, if desired in a mixture with fertilizers. As a rule, water-dispersible granules are prepared by customary processes such as spray drying, fluidized-bed granulation, disk granulation, mixing with high-speed mixers and extrusion without solid inert material. Regarding the production of disk granules, fluidized-bed granules, extruder granules and spray granules, see, for example, the methods in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, page 147 et seq; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. As regards further details on the formulation of crop protection products, see, for example, G.C. Klingmam, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
As a rule, the agrochemical formulations comprise 1 to 95% by weight, of active compounds, the following concentrations being customary, depending on the type of formulation:
The active compound concentration in wettable powders is, for example, approximately 10 to 95% by weight, the remainder to 100% by weight being composed of customary formulation constituents . In the case of emulsifiable concentrates, the active compound concentration may amount to, for example, 5 to 80% by weight. Formulations in the form of dusts comprise, in most cases, 5 to 20% by weight of active compound, sprayable solutions approximately 0.2 to 25% by weight of active compound. In the case of granules such as dispersible granules, the active compound content depends partly on whether the active compound is present in liquid or solid form and on which granulation auxiliaries and fillers are being used. As a rule, the content amounts to between 10 and 90% by weight in the case of the water-dispersible granules.
In addition, the abovementioned active compound formulations may comprise, if appropriate, the conventional adhesives, wetters, dispersants, emulsifiers, preservatives, antifreeze agents, solvents, fillers, colorants, carriers, antifoams, evaporation inhibitors, pH regulators or viscosity regulators.
The herbicidal action of the herbicide combinations according to the present invention can be improved, for example, by surfactants, preferably by wetters from the group of the fatty alcohol polyglycol ethers. The fatty alcohol polyglycol ethers preferable contain 10 - 18 carbon atoms in the fatty alcohol radical and 2 - 20 ethylene oxide units in the polyglycol ether moiety. The fatty alcohol polyglycol ethers can be nonionic or ionic, for example in the form of fatty alcohol polyglycol ethers sulfates, which can be used, for example, as alkali metal salts (e.g. sodium salts or potassium salts) or ammonium salts, but also as alkaline earth metal salts such as magnesium salts, such as sodium Cn/Cw-fatty alcohol diglycol ether sulfate (Genapol® LRO, Clariant); see, for example, EP-A-0476555, EP-A-0048436, EP-A-0336151 or US-A-4,400,196 and also Proc. EWRS Symp. "Factors Affecting Herbicidal Activity and Selectivity", 227 - 232 (1988). Nonionic fatty alcohol polyglycol ethers are, for example, (Cw-Cis)-, preferably (Cio-Ci4)-fatty alkohol polyglycol ethers containing 2 - 20, preferably 3 - 15, ethylene oxide units (e.g. isotridecyl alcohol polyglycol ether), for example from the Genapol® series, such as Genapol® X-030, Genapol® X-060, Genapol® X-080 or Genapol® X-150 (all from Clariant GmbH).
The present invention furthermore embraces the combination of herbicides (i), (ii) and (iii) as defined above with the wetting agents mentioned above from the group of the fatty alcohol polyglycolethers which preferably contain 10 - 18 carbon atoms in the fatty alcohol radical and 2 - 20 ethylene oxide units in the polyglycol ether moiety and which can be present in nonionic or ionic form (for example as fatty alcohol polyglycol ether sulfates). Preference is given to Cn/Cw-fatty alcohol diglycol ether sulfate sodium (Genapol® LRO, Clariant); and isotridecyl alcohol polyglycol ether with 3 - 15 ethylene oxide units, for example from the Genapol® X series, such as Genapol® X-030, Genapol® X-060, Genapol® X-080 or Genapol® X- 150 (all from Clariant GmbH) . It is furthermore known that fatty alcohol polyglycol ethers such as nonionic or ionic fatty alcohol polyglycol ethers (for example fatty alcohol polyglycol ether sulfates) are also suitable for use as penetrants and activity enhancers for a number of other herbicides, inter alia also for herbicides from the group of the imidazolinones (see, for example, EP-A-0502014).
Moreover, it is known that fatty alcohol polyglycol ethers such as nonionic or ionic fatty alcohol polyglycol ethers (for example fatty alcohol polyglycol ether sulfates) are also suitable as penetrants and synergists for a number of other herbicides, inter aha also herbicides from the group of the imidazolinones; (see, for example, EP-A-0502014).
The herbicidal effect of the herbicide combinations according to the present invention can also be increased using vegetable oils. The term vegetable oils is to be understood as meaning oils from oil-plant species, such as soya oil, rapeseed oil, com oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, safflower oil or castor oil, in particular rapeseed oil, and their transesterification products, for example alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester.
The vegetable oils are preferably esters of C10-C22-, preferably Ci2-C2o-fatty acids. The Cio-C22-fatty acid esters are, for example, esters of unsaturated or saturated Cio-C22-fatty acids, in particular those with an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and, in particular, Cis-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.
Preferred Ci-C2o-alkyl-Cio-C22-fatty acid esters are the methyl, ethyl, propyl, butyl, 2-ethylhexyl and dodecyl esters. Preferred glycol- and glycerol-Cio-C22-fatty acid esters are the uniform or mixed glycol esters and glycerol esters of Cio-C22-fatty acids, in particular those fatty acids which have an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and, in particular, Cis-fatty acids such as stearic acid, oleic acid, linolic acid or linolenic acid.
The vegetable oils can be present in the herbicidal compositions according to the present invention for example in the form of commercially available oil-containing formulation additives, in particular those based on rapeseed oil such as Hasten® (Victorian Chemical Company, Australia, hereinbelow termed Hasten, main constituent: rapeseed oil ethyl ester), Actirob®B (Novance, France, hereinbelow termed ActirobB, main constituent: rapeseed oil methyl ester), Rako-Binol® (Bayer AG, Germany, termed Rako- Binol hereinbelow, main constituent: rapeseed oil), Renol® (Stefes, Germany, termed Renol hereinbelow, vegetable oil constituent: rapeseed oil methyl ester), or Stefes Mero® (Stefes, Germany, hereinbelow termed Mero, main constituent: rapeseed oil methyl ester).
For use, the formulations, which are present in commercially available form, are optionally diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, soil granules, granules for broadcasting and sprayable solutions are usually not diluted further with other inert substances prior to use .
A herbicide combination according to the present invention and a composition comprising the herbicide combination as defined in the context of the present invention are preferably applied to the harmful plants or undesired plants or parts thereof, seeds of the plants or the area under cultivation (soil of a field), preferably to the green of the harmful plants or parts thereof, or to the green parts of the undesired plants or parts thereof.
A composition comprising a herbicide combination used in the context of the present invention has the advantage of being easier to apply since the quantities of the components are already presented in the correct ratio to each other. Moreover, the adjuvants in the formulation can be matched optimally to each other.
As already described in more detail above, the present invention further relates to the use of combination of herbicides according to the present invention (preferably in one of the preferred embodiments defined herein) or a composition according to the present invention (preferably in one of the preferred embodiments defined herein) in the field of agriculture, in particular as plant growth regulators and/or for controlling harmful plants or undesired plant growth.
Examples
The following data are the results of a greenhouse investigation in which the herbicide combination according to the present invention was tested against various monocotyledonous and dicotyledonous weeds after a pre emergence application and a post emergence application (BBCH 10-12). The following weeds were selected for testing:
Table 1
For the trials seeds ofthe above mentioned species were sown in 7 cm pots containing standard soil (14,7% sand, 19,9% clay, 65,4% silt and 1,8% organic matter) covered with 0,5 cm depth of sandy soil, lightly irrigated from above and used for the pre emergence trial. For the post emergence trial the pots were placed in a glasshouse (with conditions of 16 hour day and 8 hour night, 21 °C day and 12°C night and 60% relative humidity) and irrigated from above to allow the seeds to germinate and grow. Once they had reached the required growth stage BBCH 10-12 the propagated plants were used for the post emergence trial. The herbicide application was done with a track sprayer at a spray volume of 300 1 water/ha using a flat fan nozzle XR 8001 at a pressure of 1.8 bar. For the preparation of the application liquids the formulations shown in the table 2 were used. The methylated rape seed oil adjuvant Mero® was added to each application liquid with 1 1/ha. After the application and air drying the pots were placed back into the glasshouse and allowed to grow on. The pots were irrigated as required for good plant growth.
Table 2
Visual percent of weed control compared to an untreated control was rated 21 days after herbicide applications (DAA) on a scale of 0-100. A rating of 0 is defined as no control and 100 as complete control.
According to Colby synergistic effects of herbicidal active ingredients are indicated if the measured efficacy is higher than the expected one calculated according to his formula for 3 -way mixtures:
E = (A + B + C) - (AxB + AxC + BxC)/100 + (AxBxC)/10000
The post emergence trial as well as the pre emergence trial result show, that the combination of aclonifen, diflufenikan and ethofumesate produces efficacy, clearly higher than expected according to Colby, against tested weeds. This indicates clear synergism between these three active ingredients.
Table 3: Post emergence trial: % Efficacy against various weeds
Table 4: Pre emergence trial: % Efficacy against various weeds