Technical Field:

The present invention relates to combinations of herbicides for controlling harmful undesirable plants. The present invention more specifically relates to a synergistic combination of herbicides.

Background and prior art:

Weeds are undesirable plants that can severely damage yield in crops. Farmers usually control these plants at the pre-plant stage as well as after sowing. Modern herbicides are used to either control or suppress these undesirable plants so as to allow sown crops a greater share of nutrient.

Current practices include combining herbicides with varied modes of action, which allows for broader spectrum of control and resistance management. However, the combinations currently known are not sufficient to control the resistant and persistent weeds. Growers increasingly face complex weed situations that may not be controlled with just one herbicide. Herbicides acting as Acetyl-CoA carboxylase (ACCase) inhibitors are known to control undesired vegetation such as grasses (graminids). The ACCase inhibitors were first introduced in 1978 and are widely used to control grass species. There are three chemical groups of ACCase inhibitors, Aryloxyphenoxypropionates (APP), Cylcohexanediones (CHD), and Phenylpyrazolines (PPZ). APPs are an important class of herbicides due to their high efficiency, broad spectrum, low toxicity and good selectivity. Some of the known APP herbicides are clodinafop- propargyl, cyhalofop-butyl, diclofop-methyl, diclofop-P-methyl, fenoxaprop-P-ethyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop, haloxyfop-P, haloxyfop-P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl and quizalofop-P-tefuryl. The APP herbicide, such as clodinafop-propargyl, are employed as post emergence grass herbicide (graminicide). Clodinafop-propargyl is 2-Propynyl- (2R)-2-[4-[(5-chlor-3-fluor-2-pyridinyl)oxy]phenoxy]propanoa te which is an ester of 2-(4-(3-Chloro-5-fluoro-2-pyridyloxy)-phenoxy-propionic acid. It is a systemic herbicide that acts on post-emergent weeds such as wild oats, rough meadow- grass, green foxtail, barnyard grass, persian darnel and volunteer canary seed. Clodinafop-propargyl possesses herbicidal activity against grassy weeds in winter cereals especially in wheat and barley as well as pulses. Clodinafop-propargyl interacts with and inhibits the Acetyl-CoA carboxylase, which is essential for the production of lipids or fatty acids needed for plant growth. The selectivity of this herbicide is based on the difference in the speed of herbicide breakdown in the crop versus the weeds. Clodinafop-propargyl converts from the ester form to the active acid and then to biologically inactive compounds. Microtubule Inhibitors are generally applied to control annual grasses and some broadleaf weeds in several crops and turf grass. Absorbed by both roots and shoots, these herbicides cause cell damage and are an excellent tool to control pre-emergent weeds. Pendimethalin is a microtubule inhibitor herbicide, which is used both pre and post emergent for control of broadleaf and annual grasses. Pendimethalin is known to be used in combination such as those known from WO2012177860 (Mann et.al.), which is incorporated herein by reference in its entirety.

Photosynthetic Inhibitors control many broadleaf and some grass weeds by interfering in the electron transport chain and indirectly membrane leakage and cell damage. These herbicides are excellent tools for controlling pre-emergent weeds. Metribuzin is a photosynthesis inhibitor herbicide that is used for both pre and post emergent control of broadleaf and annual grasses. Metribuzin is known to be combined with other herbicides such as the combinations known from WO2011082958 (Hubert et.al), which is incorporated herein by reference in its entirety. Combinations of herbicides are used to control a broader range of weeds. However, the combination of herbicides may not always result in the desired effect. Combination of herbicides may lead to an additive effect or an antagonistic effect. It may also result in phytotoxicity to the crops making it an undesirable combination. Agronomists must therefore carefully select the herbicides that can be combined to offer a synergistic effect that would control weeds while having no phytotoxic effect on the crop, and reduce the chances of development of herbicide resistant weeds. There is therefore a need in the art for combinations that have advantageous properties such as a herbicidal combination that is synergistic, helps in resistance management, reduces dosage of herbicides used thus causing minimal damage to the environment, and a herbicidal combination that has excellent residual effects.

Embodiments of the present invention may therefore ameliorate one or more of the above mentioned problems:

Summary of the invention:

Therefore, in one aspect, the present invention may provide a herbicidal combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide. In another aspect, the present invention may provide a herbicidal combination comprising:

(a) at least one first herbicide selected from clodinafop, clodinafop- propargyl, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop-P- ethyl, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop, fluazifop, fluazifop- butyl, fluazifop- P-butyl, haloxyfop, haloxyfop-etotyl, haloxyfop-P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P- ethyl, and quizalofop-P-tefuryl, or an agriculturally acceptable salt;

(b) at least one second herbicide selected from a triazine herbicide, triazinone herbicide, triazole herbicide, triazolone herbicide, or triazolopyrimidine herbicide; and

(c) at least one third herbicide selected from dinitroaniline herbicide.

Therefore, in one aspect, the present invention may provide a method of controlling weeds at a locus, said method comprising applying to the locus a herbicidal combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

Another aspect of the present invention may provide a method of controlling weeds at a locus, said method comprising applying to the locus a combination comprising:

(a) at least one first herbicide selected from clodinafop, clodinafop- propargyl, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop-P- ethyl, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop, fluazifop, fluazifop- butyl, fluazifop-P-butyl, haloxyfop, haloxyfop-etotyl, haloxyfop-P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P- ethyl, and quizalofop-P-tefuryl, or an agriculturally acceptable salt;

(b) at least one second herbicide selected from a triazine herbicide, triazinone herbicide, triazole herbicide, triazolone herbicide, or triazolopyrimidine herbicide; and

(c) at least one third herbicide selected from dinitroaniline herbicide.

In an aspect, the present invention may provide a herbicidal composition comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

Another aspect of the present invention may provide a composition comprising:

(a) at least one first herbicide selected from clodinafop, clodinafop- propargyl, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop-P- ethyl, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop, fluazifop, fluazifop- butyl, fluazifop-P-butyl, haloxyfop, haloxyfop-etotyl, haloxyfop-P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P- ethyl, and quizalofop-P-tefuryl, or an agriculturally acceptable salt;

(b) at least one second herbicide selected from a triazine herbicide, triazinone herbicide, triazole herbicide, triazolone herbicide, or triazolopyrimidine herbicide; and

(c) at least one third herbicide selected from dinitroaniline herbicide. Yet another aspect of the present invention may provide a method of increasing yield in a crop by application of a combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

Another aspect of the present invention may provide a method of improving the plant health, said method comprising application at the locus of the plant a combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

Detailed Description of the invention:

The term herbicide, as used herein, shall mean an active ingredient that kills, controls or otherwise adversely modifies the growth of plants. As used herein, a herbicidally effective or vegetation controlling amount is an amount of active ingredient that causes a“herbicidal effect,” i.e. , an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation. The terms“plants” and“vegetation” include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, and established vegetation. The term“locus” as used herein shall denote the vicinity of a desired crop in which weed control, typically selective weed control, of weeds is desired. The locus includes the vicinity of desired crop plants wherein the weed infestation has either emerged or is yet to emerge. The term crop shall include a multitude of desired crop plants or an individual crop plant growing at a locus.

In any aspect or embodiment described hereinbelow, the phrase comprising may be replaced by the phrases “consisting of’ or “consisting essentially of” or “consisting essentially of”. In these aspects or embodiment, the combination or composition described includes or comprises or consists of or consists essentially of or consists substantially of the specific components recited therein, to the exclusion of other fungicides or insecticide or herbicides or plant growth promoting agents or adjuvants or excipients not specifically recited therein.

Surprisingly, it has been found by the present inventors that a combination of acetyl CoA carboxylase inhibitors, microtubule inhibitor and photosystem II inhibitors results in a synergistic control of undesirable plants, at the locus of the plant.

Therefore, in one aspect, the present invention may provide a herbicidal combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide; and (c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In an embodiment, the herbicidal combinations of the present invention comprise one herbicide from these three classes of herbicides.

Therefore, in one aspect, the present invention may provide a herbicidal combination comprising:

(a) an acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) a photosystem II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide; and

(c) a microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In another aspect, the present invention provides a method of controlling weeds at a locus by applying the combination of the present invention to the locus.

Thus, in this aspect, the present invention may provide a method of controlling weeds at a locus, said method comprising applying to the locus a combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In another aspect, the present invention provides a composition comprising the combinations of the present invention, and at least another agrochemically acceptable excipient.

Therefore, in this aspect, the present invention may provide a composition comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In another aspect, the present invention provides a method for increasing yield in a crop by using the combinations of the present invention.

Therefore, in this aspect, the present invention may provide a method of increasing yield in a crop by application of a combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides; (b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide; (c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In another aspect, the present invention may provide a method of improving the plant health using the combinations of the present invention.

Therefore, in this aspect, the present invention may provide a method of improving the plant health, said method comprising application at the locus of the plant a combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide;

(c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

Each of the aspect described above may have one or more embodiments.

Each of the embodiments described hereinafter may apply to one or all of the aspects described hereinabove. These embodiments are intended to be read as being preferred features of one or all of the aspects described hereinabove. Each of the embodiments described hereinafter applies to each of the aspects described hereinabove individually. In an embodiment, the acetyl CoA carboxylase inhibitor is an arylphenoxy- propionate herbicide. In an embodiment, the arylphenoxy-propionate herbicide is selected from the group consisting of clodinafop, clodinafop-propargyl, cyhalofop-butyl, diclofop, diclofop- methyl, fenoxaprop-P-ethyl, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop, fluazifop, fluazifop-butyl, fluazifop-P-butyl, haloxyfop, haloxyfop-etotyl, haloxyfop- P-methyl, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P- ethyl, and quizalofop-P-tefuryl, or an agriculturally acceptable salt thereof.

In an embodiment, the arylphenoxy-propionate herbicide is clodinafop or clodinafop-propargyl. In an embodiment, the arylphenoxy-propionate herbicide is haloxyfop, haloxyfop- etotyl, or haloxyfop-P-methyl.

In an embodiment, the arylphenoxy-propionate herbicide is quizalofop, quizalofop- ethyl, quizalofop-P, quizalofop-P-ethyl, or quizalofop-P-tefuryl.

In an embodiment, the acetyl CoA carboxylase inhibitor is a cyclohexanedione herbicide.

In an embodiment, the cyclohexadione herbicide is a benzoylcyclohexanedione herbicide selected from fenquinotrione, ketospiradox, lancotrione, mesotrione, sulcotrione, tefuryltrione or tembotrione.

In an embodiment, the cyclohexadione herbicide is mesotrione. In an embodiment, the cyclohexadione herbicide is sulcotrione.

In an embodiment, the cyclohexadione herbicide is tembotrione. In an embodiment, the acetyl CoA carboxylase inhibitor is a phenylpyrazoline herbicide. In an embodiment, the phenylpyrazoline herbicide is selected from fluazolate, nipyraclofen, pinoxaden or pyraflufen.

In an embodiment, the phenylpyrazoline herbicide is pinoxaden. In an aspect, the combination comprises a photosynthesis II inhibitor.

In an embodiment, the photosynthesis II inhibitor is selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide.

In an embodiment, the photosynthesis II inhibitor is a triazine herbicide.

In an embodiment, the triazine herbicide is selected from the group consisting of dipropetryn, fucaojing, trihydroxytriazine, atrazine, chlorazine, cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine, propazine, sebuthylazine, simazine, terbuthylazine, trietazine, indaziflam, triaziflam, atraton, methometon, prometon, secbumeton, simeton, terbumeton, ametryn, aziprotryne, cyanatryn, desmetryn, dimethametryn, methoprotryne, prometryn, simetryn, and terbutryn.

In an embodiment, the triazine herbicide is atrazine.

In an embodiment, the photosynthesis II inhibitor is a triazinone herbicide.

In an embodiment, the triazinone herbicide is selected from ametridione, amibuzin, ethiozin, hexazinone, isomethiozin, metamitron, metribuzin and trfludimoxazin. In an embodiment, the triazinone herbicide is selected from hexazinone, metamitron and metribuzin. In an embodiment, the triazinone herbicide is hexazinone.

In an embodiment, the triazinone herbicide is metamitron.

In an embodiment, the triazinone herbicide is metribuzin.

In an embodiment, the photosynthesis II inhibitor is a triazole herbicide.

In an embodiment, the triazole herbicide is selected from amitrole, cafenstrole, epronaz and flupoxam.

In an embodiment, the photosynthesis II inhibitor is a triazolone herbicide.

In an embodiment, the triazolone herbicide is selected from amicarbazone, bencarbazone, carfentrazone, flucarbazone, ipfencarbazone, propoxycarbazone, sulfentrazone and thiencarbazone.

In an embodiment, the triazolone herbicide is selected from carfentrazone, flucarbazone and sulfentrazone. In an embodiment, the triazolone herbicide is sulfentrazone.

In an embodiment, the photosynthesis II inhibitor is a triazolopyrimidine herbicide.

In an embodiment, the triazolopyrimidine herbicide is selected from cloransulam, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam and pyroxsulam.

In an embodiment, the triazolopyrimidine herbicide is penoxsulam. In an embodiment, the photosynthesis II inhibitor is an uracil herbicide.

In an embodiment, the uracil herbicide is selected from benzfendizone, bromacil, butafenacil, flupropacil, isocil, lenacil, saflufenacil, terbacil or tiafenacil.

In an embodiment, the uracil herbicide is saflufenacil.

In an embodiment, the photosynthesis II inhibitor is a pyridazinone herbicide.

In an embodiment, the pyridazinone herbicide is selected from brompyrazon, chloridazon, dimidazon, flufenpyr, metflurazon, norflurazon, oxapyrazon or pydanon. In an embodiment, the photosystem II inhibitor is a phenyl-carbamate herbicide.

In an embodiment, the phenyl-carbamate herbicide is desmedipham.

In an embodiment, the phenyl-carbamate herbicide is phenmedipham.

In an aspect, the combination of the present invention comprises at least one microtubule assembly inhibitor.

In an embodiment, the microtubule assembly inhibitor herbicide is selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In an embodiment, the microtubule assembly inhibitor is a dinitroaniline herbicide. In an embodiment, the dinitroaniline herbicide may be selected from benfluralin, butralin, chlornidine, dinitramine, dipropalin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin and trifluralin. In an embodiment, the dinitroaniline herbicide may be selected from oryzalin and pendimethalin. In an embodiment, the microtubule assembly inhibitor is a phosphoroamidate herbicide.

In an embodiment, the phosphoroamidate herbicide is selected from amiprofos- m ethyl or butamifos.

In an embodiment, the microtubule assembly inhibitor is a pyridine herbicide.

In an embodiment, the pyridine herbicide is selected from aminopyralid, cliodinate, clopyralid, diflufenican, dithiopyr, florpyrauxifen, flufenican, fluroxypyr, halauxifen, haloxydine, picloram, picolinafen, pyriclor, pyroxsulam, thiazopyr, and triclopyr.

In an embodiment, the pyridine herbicide is diflufenican.

In an embodiment, the pyridine herbicide is fluroxypyr.

In an embodiment, the pyridine herbicide is halauxifen.

In an embodiment, the pyridine herbicide is picloram. In an embodiment, the pyridine herbicide is pyroxsulam.

In an embodiment, the microtubule assembly inhibitor is a benzamide herbicide.

In an embodiment, the benzamide herbicide is selected from pronamide or isoxaben.

In an embodiment, the microtubule assembly inhibitor is a benzoic acid herbicide. In an embodiment, the benzoic acid herbicide is selected from cambendichlor, chloramben, dicamba, 2,3,6-TBA, tricamba, bispyribac, pyriminobac or pyrithiobac. In an embodiment, the benzoic acid herbicide is dicamba.

In an embodiment, the benzoic acid herbicide is bispyribac.

Therefore, in one embodiment, the present invention may provide a herbicidal combination comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from clodinafop- propargyl, clodinafop, haloxyfop, haloxyfop-etotyl, haloxyfop-P-methyl, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, or quizalofop-P-tefuryl, mesotrione, sulcotrione, tembotrione, or pinoxaden;

(b) at least one photosynthesis II inhibitor selected from atrazine, hexazinone, metamitron, metribuzin, flucarbazone, sulfentrazone, penoxsulam, saflufencil, desmedipham or phenmedipham; and

(c) at least one microtubule assembly inhibitor herbicide selected from oryzalin, pendimethalin, diflufenican, fluroxypyr, halauxifen, picloram, pyroxsulam, dicamba or bispyribac.

In a preferred embodiment, the combinations and methods of the present invention comprise clodinafop propargyl, a second herbicide and a third herbicide. In a preferred embodiment, the second herbicide is selected from triazine, hexazinone, metamitron, metribuzin, carfentrazone, flucarbazone, sulfentrazone or penoxsulam.

In an embodiment, the third herbicide is a dinitroaniline herbicide. In an embodiment, the dinitroaniline herbicide may be selected from benfluralin, butralin, chlornidine, dinitramine, dipropalin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin and trifluralin. In an embodiment, the dinitroaniline herbicide may be selected from oryzalin and pendimethalin.

In an embodiment, the present invention provides preferred combinations, compositions and methods thereof. The methods of the invention include a method of controlling weeds at a locus by applying to the locus the combination or the composition, a method of increasing yield in a crop by application of the combination or composition, or a method of improving the plant health by application at the locus of the plant the combination or the composition. The embodiments described herein describe the preferred embodiments of all these possible combinations, compositions and methods of the invention.

Therefore, an embodiment of the present invention provides a combination and method comprising clodinafop propargyl; a second herbicide selected from triazine, hexazinone, metamitron, metribuzin, carfentrazone, flucarbazone, sulfentrazone and penoxsulam; and a third herbicide selected from oryzalin and pendimethalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, triazine, and oryzalin. An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, triazine, and pendimethalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, hexazinone, and oryzalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, hexazinone, and pendimethalin. An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, metamitron, and oryzalin. An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, metamitron and pendimethalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, metribuzin and oryzalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, metribuzin, and pendimethalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, carfentrazone, and oryzalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, carfentrazone, and pendimethalin. An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, flucarbazone, and oryzalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, flucarbazone, and pendimethalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, sulfentrazone and oryzalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, sulfentrazone and pendimethalin. An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, penoxsulam, and oryzalin.

An embodiment of the present invention provides a combination and method comprising clodinafop propargyl, penoxsulam and pendimethalin.

In an embodiment, the combinations of the present invention include the following preferred combinations. In an embodiment, each individual row appearing in the table below represents the combinations in an embodiment of the present invention.

In an embodiment, the present invention may provide a combination comprising the three herbicides as listed in each individual row from row 1 to row 594 in the table above.

These combinations may be applied to the locus of the weeds, in an herbicidally effective amount.

In an embodiment, the combination of the present invention may be combined with at least one other active such as those selected from but not limited to herbicide, insecticide, fungicide, biological agent, plant growth activator, fertilizers or combinations thereof.

Thus, in an embodiment, the combination of the present invention may be combined with a herbicide. Exemplary herbicides that may be combined with the combination of the present invention may be selected from but not limited to herbicides belonging to classes such as ALS inhibitors, EPSP synthase inhibitors, synthetic auxins, auxin transport inhibitors, glutamate synthase inhibitors, HPPD inhibitors, lipid synthesis inhibitors, long chain fatty acid inhibitors, as well as herbicides with unknown modes of action.

In an embodiment, the total amount of clodinafop propargyl in the composition may typically be in the range of 0.1 to 99% by weight, preferably 0.2 to 90% by weight. In an embodiment, the total amount of pendimethalin in the composition may be in the range of 0.1 to 99% by weight.

In an embodiment, the total amount of metribuzin in the composition may be in the range of 0.1 to 99% by weight.

In an embodiment, the constituent herbicides of the combination of the present invention may be admixed in ratio of (1-80): (1-80): (1-80) of the three herbicides respectively.

In an embodiment, the constituent herbicides of the combination of the present invention may be admixed in ratio of (1-80): (1-80): (1-80) of clodinafop propargyl, metribuzin and pendimethalin respectively. The herbicidal combination of the present invention maybe used to target weeds among the crops such corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, etc.; vegetables: solanaceous vegetables such as eggplant, tomato, pimento, pepper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, Swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc, strawberry, sweet potato, Dioscorea japonica, colocasia, etc., flowers, foliage plants, turf grasses, fruits: pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, nectarine, Prunus mume, cherry fruit, apricot, prune, etc., citrus fruits such as orange, lemon, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, cashew nuts, macadamia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., grape, kaki fruit, olive, plum, banana, coffee, date palm, coconuts, etc. , trees other than fruit trees; tea, mulberry, flowering plant, trees such as ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidate, etc.

In an aspect, the present invention may provide compositions of clodinafop propargyl, pendimethalin and metribuzin.

In an embodiment, the composition of the present invention may contain agriculturally acceptable adjuvants, carriers, diluents, emulsifiers, fillers, anti foaming agents, thickening agents, anti-freezing agents, freezing agents etc. The compositions may be either solid or liquids. They can be solids, such as, for example, dusts, granules, water-dispersible granules, microcapsules or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions, ZC formulations. They can also be provided as a pre mix or tank mixed.

Suitable agricultural adjuvants and carriers may include, but are not limited to, crop oil concentrates; methylated seed oils, emulsified methylated seed oil, nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C1 1 alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C12- C16) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate, urea ammonium nitrate; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate ; PEG(400) dioleate-99, alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-Ci8 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium stearate; alkyl- naphthalene-sulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of mono and dialkyl phosphate esters; vegetable or seed oils such as soybean oil, rapeseed/canola oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; and esters of the above vegetable oils, and in certain embodiments, methyl esters. Suitable liquid carriers that may be employed in a composition of the present invention may include water or organic solvents. The organic solvents include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono, di and polycarboxylic acids and the like. Organic solvents include, but are not limited to toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide.

Solid carriers that may be employed in the compositions of the present invention may include but are not limited to attapulgite, pyrophyllite clay, silica, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, talc, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, cellulose etc. In an aspect, the present invention may provide methods of controlling weeds at a locus, said method comprising application of a combination of clodinafop propargyl, pendimethalin and metribuzin.

Thus, embodiments of the present invention may provide, method of controlling weeds at a locus, said method comprising application of combinations of clodinafop propargyl, pendimethalin, Metribuzin and optionally a fourth active. In an embodiment, the fourth active, may selected from herbicide, insecticide, fungicide, biological agent, plant growth activator, fertilizers or combinations thereof.

The target weeds may be selected from Alopecurus myosuroides Huds. (blackgrass, ALOMY), Amaranthus palmeri (Palmer amaranth, AMAPA) Amaranthus viridis (slender amaranth, AMAVI), Avena fatua (wild oat, AVEFA), Brachiaria decumbens Stapf. or Urochloa decumbens (Stapf), Brachiaria brizantha or Urochloa brizantha, Brachiaria platyphylla (Groseb.) Nash or Urochloa platyphylla (broadleaf signalgrass, BRAPP), Brachiaria plantaginea. or Urochloa plantaginea (alexandergrass, BRAPL), Cenchrus echinatus (southern sandbur, CENEC), Digitaria horizontalis Willd. (Jamaican crabgrass, DIGHO), Digitaria insularis (sourgrass, TRCIN), Digitaria sanguinalis (large crabgrass, DIGSA), Echinochloa crus-galli (barnyardgrass, ECHCG), Echinochloa colonum (junglerice, ECHCO), Eleusine indica Gaertn. (goosegrass, ELEIN), Lolium multiflorum Lam. (Italian ryegrass, LOLMU), Panicum dichotomiflorum Michx. (fall panicum, PANDI), Panicum miliaceum L. (wild-proso millet, PANMI), Sesbania exaltata (hemp sesbania, SEBEX), Setaria faberi Herrm. (giant foxtail, SETFA), Setaria viridis (green foxtail, SETVI), Sorghum halepense (Johnsongrass, SORHA), Sorghum bicolor, Moench ssp., Arundinaceum (shattercane, SORVU), Cyperus esculentus (yellow nutsedge, CYPES), Cyperus rotundus (purple nutsedge, CYPRO), Abutilon theophrasti (velvetleaf, ABUTH), Amaranthus species (pigweeds and amaranths, AMASS), Ambrosia artemisiifolia L. (common ragweed, AMBEL), Ambrosia psilostachya DC. (western ragweed, AMBPS), Ambrosia trifida (giant ragweed, AMBTR), Anoda cristata (spurred anoda, ANVCR), Asclepias syriaca (common milkweed, ASCSY), Bidens pilosa (hairy beggarticks, BIDPI), Borreria species (BOISS), Borreria alata or Spermacoce alata Aubl. or Spermacoce latifolia (broadleaf buttonweed, BOILF), Chenopodium album L. (common lambsquarters, CHEAL), Cirsium arvense (Canada thistle, CIRAR), Commelina benghalensis (tropical spiderwort, COMBE), Datura stramonium (jimsonweed, DATST), Daucus carota (wild carrot, DAUCA), Euphorbia heterophylla (wild poinsettia, EPHHL), Euphorbia hirta or Chamaesyce hirta (garden spurge, EPHHI), Euphorbia dentata Michx. (toothed spurge, EPHDE), Erigeron bonariensis or Conyza bonariensis (hairy fleabane, ERIBO), Erigeron canadensis or Conyza canadensis (horseweed, ERICA), Conyza sumatrensis (tall fleabane, ERIFL), Helianthus annuus (common sunflower, HELAN), Jacquemontia tamnifolia (smallflower morningglory, IAQTA), Ipomoea hederacea (ivyleaf morningglory, IPOHE), Ipomoea lacunosa (white morningglory, IPOLA), Lactuca serriola (prickly lettuce, LACSE), Portulaca oleracea (common purslane, POROL), Richardia species (pusley, RCHSS), Salsola tragus (Russian thistle, SASKR), Sida species (sida, SIDSS), Sida spinosa (prickly sida, SIDSP), Sinapis arvensis (wild mustard, SINAR), Solanum ptychanthum (eastern black nightshade, SOLPT), Tridax procumbens (coat buttons, TRQPR), Rumex dentatus (RUMDE)or Xanthium strumarium (common cocklebur, XANST).

In an embodiment, the combinations of the present invention may be applied to the locus either simultaneously or sequentially, such that Clodinafop, the second herbicide and third herbicide may be applied in a tank mix or as a pre-mixed composition.

Thus, in this aspect, the present invention provides a tank-mix comprising:

(a) at least one acetyl CoA carboxylase inhibitor selected from arylphenoxy- propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides; (b) at least one photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl-carbamate herbicide; (c) at least one microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In an embodiment, the present invention may be applied either pre or post emergent. The advantage of the combination is surprisingly good residual effects, when applied in pre-emergent as well as quick knockdown when applied post emergent leading to quick control of weeds. In another embodiment, the present invention may be applied for quick burndown of weeds. Another advantage is quick knockdown in the case of burndown.

The method of control of the present invention may be carried out by spraying the suggested tank mixes, or the individual herbicides may be formulated as a kit-of- parts containing various components that may be mixed as instructed prior to spraying.

In an embodiment, the present invention provides a kit-of-parts comprising a plurality of components, wherein said plurality of components comprises:

(a) at least a first component comprising an acetyl CoA carboxylase inhibitor selected from arylphenoxy-propionate herbicides, cyclohexanedione herbicides, or phenylpyrazoline herbicides;

(b) at least a second component comprising a photosynthesis II inhibitor selected from a triazine herbicide, a triazinone herbicide, triazole herbicide, triazolone herbicide, triazolinone herbicide, uracil herbicide, pyridazinone herbicide, a triazolopyrimidine herbicide, or phenyl- carbamate herbicide;

(c) at least a third component comprising a microtubule assembly inhibitor herbicide selected from a dinitroaniline herbicide, a phosphoroamidate herbicide, pyridine herbicide, benzamide herbicide, or a benzoic acid herbicide.

In an embodiment, the kit-of-parts comprises an instructions manual, said instructions manual comprising instructions directing a user to admix the components before being used.

In an embodiment, the components of the present invention may be packaged such that clodinafop propargyl, the first herbicide and the second herbicide may be packaged separately and then tank mixed before the spraying.

In another embodiment, the components of the present invention may be packaged such that clodinafop propargyl, the first herbicide and the second herbicide may be packaged separately, whereas other additives are packaged separately, such that the two maybe tank mixed at the time of spraying.

In another embodiment, the components of the present invention may be packaged as composition such that clodinafop propargyl, the first herbicide and the second herbicide are formulated into one composition and other additives are packaged separately, such that the two maybe tank mixed at the time of spraying.

Surprisingly, it has been found by the present inventors, that clodinafop propargyl, the first herbicide and the second herbicide of the present invention, when applied individually, was ineffective in the control of weeds, but demonstrated excellent synergistic control on when applied together. The combination controlled the weed both pre and post emergently. As will be demonstrated by the examples, the combination of clodinafop propargyl, the first herbicide and the second herbicide synergistically controlled broadleaf as well as grasses and sedges at a locus. The current invention therefore provides advantageous methods of controlling weeds both pre and post emergently. The present method also provides a broader spectrum of controlling weeds that helps in resistance management, thus preventing the weed from becoming resistant to either of the herbicides while providing a broader spectrum of control at lower use rates.

Examples:

Field trial were conducted to check the efficacy of the combination of clodinafop Propargyl + Metribuzin + Pendimethalin. These trials were conducted in spring wheat crop for the percentage weed control. The results are depicted in table 1 :

TABLE 1

Means followed by same letter or symbol do not differ significantly (P=.05, Student-Newman-Keuls)

Mean comparisons performed only when AOV Treatment P(F) is significant at mean comparison OSL.

Thus, in an embodiment, the present invention provides a combination comprising clodinafop-propargyl in an amount of 60 g/ha, metribuzin in an amount of 252 g/ha and pendimethalin in an amount of 812 g/ha.

The results in table 1 clearly demonstrates synergy between Clodinafop Propargyl + metribuzin and pendimethalin in controlling various weeds.

Thus, in an embodiment, it was surprisingly found that the addition of a microtubule assembly inhibitor to a combination of a photosystem II inhibitor and an acetyl CoA carboxylase inhibitor led to a surprising and unexpected synergistic enhancement in efficacy of the combination of a photosystem II inhibitor and an acetyl CoA carboxylase inhibitor. In an embodiment, it was surprisingly found that the addition of pendimethalin to a combination of clodinafop-propargyl and metribuzin led to a surprising and unexpected synergistic enhancement in efficacy of the combination of clodinafop- propargyl and metribuzin. In an embodiment, it was surprisingly found that the addition of a photosystem II inhibitor to a combination of a microtubule assembly inhibitor and an acetyl CoA carboxylase inhibitor led to a surprising and unexpected synergistic enhancement in efficacy of the combination of a microtubule assembly inhibitor and an acetyl CoA carboxylase inhibitor.

In an embodiment, it was surprisingly found that the addition of metribuzin to a combination of clodinafop-propargyl and pendimethalin led to a surprising and unexpected synergistic enhancement in efficacy of the combination of clodinafop- propargyl and pendimethalin.

In an embodiment, it was surprisingly found that the addition of a acetyl CoA carboxylase inhibitor to a combination of a microtubule assembly inhibitor and a photosystem II inhibitor led to a surprising and unexpected synergistic enhancement in efficacy of the combination of a microtubule assembly inhibitor and a photosystem II inhibitor. In this embodiment, it was surprisingly found that the addition of clodinafop- propargyl to a combination of metribuzin and pendimethalin led to a surprising and unexpected synergistic enhancement in efficacy of the combination of metribuzin and pendimethalin. In an embodiment, the present invention provides a combination comprising clodinafop-propargyl, pendimethalin, and metribuzin wherein pendimethalin and metribuzin are used in a ratio of about 6:1.

In an embodiment, the present invention provides a combination comprising clodinafop-propargyl, pendimethalin, and metribuzin wherein pendimethalin is used in an amount of about 384.4 g/ha and metribuzin is used in an amount of about 65.6 g/ha.

In an embodiment, the present invention provides a combination comprising clodinafop-propargyl, pendimethalin, and metribuzin wherein pendimethalin and metribuzin are present as a ZC formulation.

In an embodiment, the present invention provides a combination comprising clodinafop-propargyl, pendimethalin, and metribuzin wherein pendimethalin and metribuzin are present as a ZC formulation, wherein said ZC formulation comprises encapsulated pendimethalin and a suspension concentrate of metribuzin. In an embodiment, the present invention provides a combination comprising clodinafop-propargyl, pendimethalin, and metribuzin wherein pendimethalin and metribuzin are present as a ZC formulation, wherein said ZC formulation comprises capsule suspension (CS) of pendimethalin and a suspension concentrate (SC) of metribuzin.

While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention.