Patent Application
20230404078
The present invention relates to multi-component herbicide combinations
The control of undesired vegetation is extremely important in order to achieve high crop efficiency. In many cases, while herbicides have an effect against a spectrum of weeds, they do not however fight a certain type of other weeds, which is also present in the crop cultures to be protected. Therefore, there is a strong need for mixing two or more herbicides. In addition, there is a strong and on-going need to reduce herbicide use while not sacrificing weed control efficacy to a disadvantageous degree.
Compounds (I) as detailed below, and agriculturally acceptable salts and esters thereof are described in U.S. Pat. No. 7,314,849 as belonging to a family of synthetic auxin of the picolinic acid class of herbicide compounds with weed control activity notably in broadleaf weeds.
US 2009/0062121 alleges that Compound (I) is a preferred compound for the control of weeds in various crops. U.S. Pat. No. 8,598,084 states that Compound (I) is used for the control of weeds and that the methyl ester i.e. the compound of formula (I) controls various weeds.
US 2011/0287933 relates inter alia to controlling harmful plants in specific, tolerant oil seed rape crops with compounds including compound (I) and active derivative(s) thereof, in combination with a herbicide from the group of the compounds of the following formula,
in which Z represents hydroxyl, —NHCH(CH3)CONHCH(CH3)COOH or —NHCH(CH3)CONHCH[CH2CH(CH3)2]COOH, or an ester or salt thereof, and especially glufosinate and its salts (including glufosinate-ammonium), L-glufosinate and its salts (including L-glufosinate-ammonium) and bialaphos and its salts (including bialaphos-sodium). These combinations and the teachings of this document are specifically excluded from the scope of the instant invention for most if not all embodiments. US 2013/0023413 relates inter alia to controlling weeds in specific, tolerant soybean and leguminous species with compounds including compound (I) and active derivative(s) thereof, in combination with a herbicide from the group of the compounds of the following formula,
in which Z represents hydroxyl. —NHCH(CH3)CONHCH(CH3)COOH or —NHCH(CH3)CONHCH[CH2CH(CH3)2]COOH, or an ester or salt thereof, and especially glufosinate and its salts (including glufosinate-ammonium), L-glufosinate and its salts (including L-glufosinate-ammonium) and bialaphos and its salts (including bialaphos-sodium). These compounds used in combinations with compounds (I) and the teachings of this document are specifically excluded from the scope of the instant invention for most embodiments.
Thus, in defining the scope of the inventive combinations, compositions containing them and methods for using the combinations and compositions it is possible to phrase this exclusion as a proviso such that the that said combinations etc., do not contain a herbicide from the group of the compounds of the following formula A 1,
in which Z represents hydroxyl, —NHCH(CH3)CONHCH(CH3)COOH or —NHCH(CH3)CONHCH[CH2CH(CH3)2]COOH, or an ester or salt thereof. Although compounds (I) of and especially of formula (I) detailed below, are useful herbicides, combinations of selected herbicides have several advantages over the use of a single herbicide including (i) an increase in the spectrum of weeds controlled or an extension of weed control over a longer period of time, (ii) an improvement in crop safety by using reduced, and preferably, minimum doses of selected herbicides applied in combination rather than a single high doses of one herbicide, (iii) a delay in the appearance of resistant weed species to selected herbicides (Int. J. Agri. Biol., Vol. 6, No. 1, 2004, pages 209-212), and (iv) the speed at which control is achieved. However, it has often overlooked that, an advantage that is reportedly achieved by previously reported combinations of compounds (I) etc., can concomitantly aggravate a previously minimal disadvantage of using either of the two active ingredients. This has been most pronounced when a combination achieves synergy in herbicidal activity and concomitant increased phytotoxicity as mentioned below.
Inventors note the following published material which would deter investigators from combining the broadleaf herbicides of Compound (I) type and graminicides including Cyclohexanediones, e.g., Clethodim and Aryloxyphenoxypropionate herbicides which includes, Propaquizafop.
As recently as Jan. 20, 2020, expected antagonism of e.g., Clethodim and Auxin herbicides is the prevailing view.
See, “Antagonism in the Field, What Happens When Herbicides Don't Get Along” found at: https://www.dtnpf.com/agriculture/web/ag/crops/article/2020/01/16/happens-herbicides-get-along. “Another common grass herbicide, clethodim (Select), faces the same problem with auxin antagonism.”.
Inventors are aware of a very limited number of recent combinations which apparently because they are so unusual have been the subject of patent applications. There is no indication that any other such combinations would work advantageously.
WO 2014/018407 claims combinations of a different molecule similar to compound (I) with various ACCase inhibitor herbicides including Clethodim. The subject molecule was originally also protected in the same patent as compound (I), U.S. Pat. No. 7,314,849 however, it is notable that patentees of both molecules only believed that the 5-fluorine analogue was capable of combination with the graminicides after years of study of both molecules.
WO2014/116910 claims combinations of compound (I) with the specific compounds fluazifop-P, haloxyfop-P, and quizalofop-P or their agriculturally acceptable salt etc. Inventors note that the compounds fluazifop-P, haloxyfop-P, and quizalofop-P and their agriculturally acceptable salts used in combinations with compounds (I) and the teachings of this document are specifically excluded from the scope of the instant invention.
Inventors note that the breadth of the claimed inventive combination, composition, or method, as defined in the claims for most embodiments if not all, can include a proviso that none of fluazifop-P, haloxyfop-P, and quizalofop-P or salt thereof is included within the scope of definition of either component (b) co-herbicide or as an additive to the combination with Compound (I) component (a) and co-herbicide component (b).
Based on the aspects discussed above, there is a need in the art for herbicidal combinations, which provide predictable adequate weed control often comparable to the individual compounds often with significantly reduced amounts of herbicide active ingredients and or application rates, tailored to crop varieties and species of weed. Further, there is a need to provide herbicidal combinations, which provide significantly enhanced weed control and or speed of herbicidal effect with application rates comparable to or less than those of the individual compounds, without simultaneously enhancing unwanted effects, particularly phytotoxicity.
The present invention concerns multi component, typically two-component, herbicidal combinations comprising an herbicidally effective amount of a combination of component (a), an herbicidal pyridine carboxylic acid component and component (b), a co-herbicide component.
The present subject matter relates to Halauxifen based multi component, typically two-component, weed control combinations, mixtures, admixtures, kits, compositions, and the like, and methods for their herbicidal use, that comprise combinations, application-combinations, mixtures, admixtures, compositions, kits etc. hereinafter, generally referred to as combinations, of, as first component a) not less than one Compound (I)
which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable salts and esters thereof, and most particularly, the ester compound of Formula (I), Methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3methoxyphenyl)2-pyridinecarboxylate and applied with second component b) further or co-herbicides which are each chosen to be particularly useful in combination with compounds (I), especially of Formula (I) for weed control options in specific crop environments and application modalities, be they cereals, oilseed rape, sunflower, soy and perennial crops.
However, inventors have particularly noted the advantages of the inventive multi-component, typically two-component, weed control combinations of this invention in oilseed rape, sunflower, cereals, and soy crops. The inventors most especially note the advantages and improvements achievable in oilseed rape, sunflower, cereals, and soy crops. There are specifically advantageous uses in oilseed rape, sunflower, and soy crops Each of the further herbicides of component b) are usefully referred to here as co-herbicide. The co-herbicides are often usefully chosen to be particularly useful in combination with compounds (I), especially of Formula (I) for weed control options in specific unwanted vegetation or weeds and application modalities against woody plants, broadleaf and grass weeds, and sedges without reference to whether they occur in a specific crop, be they for example, Alopecurus myosuroides, Lolium multiflorum, Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica, Viola arvensis, Cyanus segetum, Capsella bursa-pastoris, Galium, Lamium, Kochia, Amaranthus, Aeschynomene, Sesbania, Monochoria, Cyperus Schoenoplectus, Chenopodium album, Conyza bonariensis, Conyza canadensis, Amsinckia intermedia, Calandrinia ciliate, Erodium cicutarium, Malva parviflora, Medicago polymorpha, Poa annua, Panicum capillare, Agropyron repens, Amarantus retroflexus, Polygonum convolvulus, Ambrosia artemisiifolia, Xanthium strumarium, Cirsium arvense, Persicaria naculosa Echinochloa crus-galli, Setaria viridis and Setaria faberi, among others.
The further herbicides of component b) most notably found to be useful in this invention comprise, Clethodim and or Propaquizafop.
Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains, unless either, the context in which it appears commands a different meaning or explicitly stated otherwise.
The term herbicide is used herein to mean an active ingredient, or combination of active ingredients or active composition or formulation or active application protocol, etc. that kills, controls or otherwise adversely modifies the growth of plants, generally understood to be either unwanted plants or in an unwanted location. An herbicidally effective or vegetation controlling amount is an amount of herbicide which causes an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation, and the like. The terms plants and vegetation include germinant seeds, emerging seedlings, plants emerging from vegetative propagules, and most appropriate to this invention, established vegetation.
Herbicidal activity is exhibited by the multi component inventive combinations when they are applied directly to the plant or to the locus of the plant at any stage of growth. The effect observed depends upon the plant species to be controlled, the stage of growth of the plant, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. These and other factors can be adjusted as is known in the art to promote nonselective or selective herbicidal action. Generally, it is typical to apply combinations of the present invention postemergence to relatively immature undesirable vegetation to achieve the maximum control of weeds.
As is clear, the application of each component of the multi component combination can occur as separate simultaneous or sequential applications as the effect of the combination is achieved by the same location of application receiving sufficient amounts of the combination of each component within a period of time wherein the beneficial effects of combining the two components are realized.
To be clear, for the sake of brevity, compounds are often referred to as the active moiety or the base or acid form, as should be clear to those skilled in the relevant arts, the reference to a compound is intended to include all useful salts and or esters of that compound, to the extent that they will be suitable for the specific embodiment, unless specifically indicated that these varieties of compound are not intended. As a non-claimed though instructive, example, a reference to Clopyralid, will include all useful salts and esters, not limited to, clopyralid-dimethylammonium, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tripromine, to the extent that they are relevant to the particular embodiment.
The scope of crops which can benefit from herbicidal use of compounds (1), and especially of formula (I) can be broadened with the judicious choice of at least one further co-herbicide or herbicides with which compound (I) herbicides can be combined or mixed etc. each selected for its intended use environment, be it crop or weeds occurring in those crops. Perhaps more significantly, the amount of herbicide active ingredients of compounds (I) applied can be reduced below their recommended herbicidally effective amounts and the amounts of the at least one further co-herbicide or herbicide in the combination applied can also be reduced to below recommended herbicidally recommended amounts.
Often a where a herbicide is already known to be useful in a particular crop, the combined use with an additional or co-herbicide can enhance the activity of the known herbicide, to either allow reduction of the amount of herbicide applied for the same effect or to increase the efficiency of weed control of the herbicide without increasing the amount applied.
In some cases, it is the speed at which weed control is achieved for the same crop or unwanted or undesirable vegetation or weed, rather than, or in addition to, the known efficacy of the herbicide.
It has been assumed that certain herbicides, most notably auxin herbicides such as Compound (I) were incompatible with aryloxyphenoxypropionate and cyclohexanedione families of graminicides including both Propaquizafop and Clethodim. It had been widely reported (see Background cited articles) that these combinations resulted in antagonism. The inventors have found a totally surprising lack of antagonism and even increased herbicidal activity without significant phytotoxic effects when the combinations of the invention were used to combat a range of unwanted vegetation.
The activity and selectivity behavior of any specific combination is difficult to predict since the behavior of each single herbicide in the combination is often affected by the other(s) and the activity of the combination may also vary considerably depending on chemical character, plant species, growth stage, and environmental conditions. Mostly, this practice of randomly combining herbicides, results in reduced activity of the herbicides in the combination. It is worth noting that even combinations that are found to enhance the herbicidal efficacy of the individual components can, in certain examples, inadvertently enhance unwanted side-effects, e.g., phytotoxicity, of the individual components against the crops that are intended to be protected. While it is often the case that synergism between two or more herbicides is desirable, where the enhancement of weed control is synergistic the harmful effects can often be unpredictably enhanced too. This can sometimes adversely affect the selectivity of each known component of a synergistic combination.
In the seemingly constant drive to increase herbicidal efficacy to the maximum, the often quoted physicians' oath to “do no harm” is too often ignored, be that harm to the crops within which weeds occur through lack of selectivity, or to the environment, for example, through the synergy of pollutants or synergistically enhanced unwanted side effects.
The present subject matter relates to multi component herbicidally effective weed control and particularly two-component herbicidal combinations, compositions containing the herbicidal combinations and methods of using them, comprising, as herbicidal active ingredients of component (a) 4amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable derivatives thereof including salts and esters thereof; and as active components (b), additional herbicidal active compound or compounds with tailored utility in various crops and against various pests.
The present invention concerns herbicidally effective combinations, compositions containing them, and methods for their use, comprising as components (a), at least one first herbicide component selected from the group of a pyridine carboxylic acid of Compound (I)
which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable salts and esters, and combinations thereof, and most particularly, the ester compound of Formula (I), methyl 4-amino-3-chloro-6-(4-chloro2fluoro-3-methoxyphenyl) pyridine-2-carboxylate, and as component (b), a second herbicide component selected from the group consisting of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations thereof.
For the sake of clarity, component (a) of the inventive multi component herbicidally effective combination, is sometimes referred to here as the first component, whereas component (b) of the inventive multi component herbicidally effective combination, is often referred to here as the second component. These terms of first and second are merely labels to avoid confusion. No inference should be attributed to these labels as regards the order in which the components are used, applied, or compounded etc. Additionally, the labels, first and second, are not intended to limit the invention to combinations that only contain two herbicidally effective compounds, in the total absence of others. Although, in a preferred embodiment of the invention the combination either contains no significant amount of additional herbicidally effective compounds, referred to as two-component herbicidal combinations, or additional herbicidally effective compounds if present, are those that do not detrimentally affect the improvement achieved by combining components (a) and (b) in compositions and in methods of herbicidal control.
The herbicide active ingredients of component (a) are often referred to as Compound (I), 4amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable derivatives thereof, as defined above including salts and esters etc. thereof. The specific Compound (I) of formula (1), methyl 4-amino-3-chloro-6-(4-chloro2fluoro-3-methoxyphenyl)pyridine-2-carboxylate namely, Halauxifen-methyl, is the most preferred herbicide active ingredient of component (a), inter alia, because of both its commercial availability and the wealth of data available to those skilled in the arts, including the herbicidally effective amount needed to be applied as a single herbicide in the absence of other herbicidal active ingredients.
Preferably, as co-herbicide component (b), the second herbicide component is Propaquizafop or Clethodim including salt or ester thereof; and any and all combinations thereof.
In noted embodiments the invention is understood as being related to a multi-component herbicide comprising an herbicidally effective amount of a combination of
In particular embodiments, the scope of the invention is limited to exclude various compounds which are to be considered as being not reasonable to be included.
These exclusions have usefully been formulated as various provisos. So that the above definition of the multi-component herbicides, and the compositions containing them, and the methods of using them, are sometimes to be read as concluding with any or all of the following provisos or combinations thereof. These exclusions would apply equally for compositions and inventive methods of this invention.
In some embodiments the multi component herbicide, composition and methods are free of, or do not contain any or all of amidosulfuron, bensulfuron, bentazone, bispyribac, carfentrazone, chlorsulfuron, florasulam, flucarbazone, flufenacet, flupyrsulfuron, halosulfuron, imazamethabenz, imazamox, imazethapyr, iodosulfuron, mesosulfuron, metribuzin, metsulfuron, norflurazon, penoxsulam, pinoxaden, propoxycarbazone, pyrasulfotole, pyrazosulfuron, pyroxsulam, sulfosulfuron, thifensulfuron, Tribenuron. In some embodiments the term “free of”, is defined as being no more than any of 10%, 5%, 1%, or preferably no more than 0.1% of the combined herbicidal active ingredient content. Inventors have duly considered provisos to exclude significant amounts as defined above of, one, more, or all of these ingredients for several embodiments of the invention, The above provisos and combinations and parts thereof do not exclude other herbicidally active ingredients from being contained in the composition in significant amounts in certain embodiments.
Most preferably, as component (b), the second herbicide component is Clethodim or salt or ester thereof.
In particularly noted embodiments, component (a), is methyl 4-amino-3-chloro-6-(4-chloro2fluoro-3-methoxyphenyl) pyridine-2-carboxylate (Halauxifen-methyl), and component (b) is selected from the group of, 2-(propan-2-ylideneamino)oxyethyl (2R)-2-[4-(6-chloroquinoxalin-2-yl)oxyphenoxy]propanoate (Propaquizafop); and Clethodim or salt or ester thereof.
A most preferred herbicidal combination embodiment of the invention comprises a combination of Halauxifen-methyl and Clethodim. This combination widens the scope of unwanted vegetation that can be controlled by either component alone while surprisingly, not significantly increasing the phytotoxicity associated with either one. As used herein, clethodim is 2-[1-[[[(2£)-3-chloro-2-propen-l-yl]oxy]imino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one and possesses the following structure:
This compound is described in Tomlin, C, ed. A World Compendium The Pesticide Manual. 15th ed. Alton: BCPC Publications, 2009 (hereafter “The Pesticide Manual, Fifteenth Edition, 2009.”). Exemplary uses of clethodim include its use as a herbicide for, e.g., post-emergence control of annual and perennial grasses in broadleaf crops, vegetables, trees, and vines.
In reviewing several embodiments of this invention as part of studies conducted in Ukraine within the last year, in Sunflower crops, Arrow®, a commercial formulation of Clethodim, significantly increased the selective herbicidal efficacy of Heliantex® a commercially available composition of Halauxifen-methyl, against broadleaf weeds including, Xanthium strumarium (XANST), Amaranthus retroflexus (AMARE), Ambrosia artemisiifolia (AMBEL), Chenopodium album (CHEAL), and Cirsium arvense (CIRAR).
This is surprising not least because Clethodim itself has no efficacy against broadleaf weeds. Thus, even an incremental increase in herbicidal efficacy of Halauxifen by addition of a compound without such activity in broadleaf weeds would be considered by some to be synergistic, and certainly not antagonistic as the prevailing belief of those in the art. See further details in example section of this disclosure.
The addition of Vivolt® (CAS 61827-42-7) adjuvant, was found to improve the efficacy of Heliantex® against several species of weeds, but surprisingly the combination of Vivolt®, and Arrow® increased the herbicidal efficacy of Heliantex® even more than the Arrow®/Heliantex® combination or even the Vivolt®/Heliantex® combination in several weed species.
In notable results in the studies, it was found that the advantageous effect of combining Halauxifen-methyl and Clethodim was found in the speed at which herbicidal control was achieved for example in Chenopodium album. In some notable examples, both the efficacy and speed of action were increased, for example with combinations including Vivolt® in Cirsium arvense.
Importantly in all trials conducted there was no evidence of any phytotoxicity associated with any of the Halauxifen combinations with Clethodim. This has not been the case with any other Halauxifen combination tested In significant embodiments, component (a), is methyl 4-amino-3-chloro-6-(4-chloro2fluoro-3-methoxyphenyl) pyridine-2-carboxylate (Halauxifen-methyl), and component (b) is 2-(propan-2-ylideneamino)oxyethyl (2R)-2-[4-(6-chloroquinoxalin-2-yl)oxyphenoxy]propanoate (Propaquizafop).
While surprisingly increased herbicidal effect coupled with a lack of phytotoxicity was found in all weeds treated with a combination of Heliantex® 0.045 kg/ha (3.0825 g/Ha) combined with Arrow®120, 0.8 L/ha (Clethodim, 96 g/Ha), the best results were obtained in most weeds with the combination, Halauxifen 0,045 kg/ha combined with both Vivolt® 0.3 L/ha (Polyoxyethylene isodecyl ether, CAS 61827-42-7), and Arrow®120, 0.8 L/ha. This represents an approximate ratio of Halauxifen-methyl to Clethodim of 1:31 or a range of 1:25 to 1:36.
The inventors contemplate the following ratios Halauxifen-methyl: Clethodim as being significant and within the inventive concept, however all intermediate ratios within these ranges are specifically contemplated.
In noted preferred combinations the strength of the herbicidal activity is increased, although the combination is advantageous even when there is no numerical synergy, this is true when such combinations have been assumed to have concomitantly increased adverse events and or antagonistic effects. Sometimes it is the speed by which control is achieved, or the breadth of weeds that can be expanded by use of the combinations.
The inventors contemplate the following ratios Halauxifen-methyl: Propaquizafop as being significant and within the inventive concept, however all intermediate ratios and narrower ranges within these broad ranges are specifically contemplated, as it will be clear to those skilled in these arts as not departing from the invention.
Some exemplary though in no way exhaustive, combination application rates include,
In some embodiments Halauxifen-methyl is applied at a rate of between about 0.5 g/ha and 10 g/Ha.
In noted preferred combinations the strength of the herbicidal activity is increased, although the combination is advantageous even when there is no numerical synergy, this is true when such combinations have been assumed to have concomitantly increased adverse events and or antagonistic effects. Sometimes it is the speed by which control is achieved, or the breadth of weeds that can be expanded by use of the combinations. Multi-component herbicidal combinations of the invention are typically either synergistically herbicidally effective thus inter alia, allowing for the reduction of the amount used of each component and or reduce the time period required to achieve the known herbicidal effect or, perhaps even more importantly they can increase the scope of unwanted vegetation that can be controlled preferably without simultaneously, significantly increasing the unwanted activity of either component on the crop.
In those embodiments where the advantage lies in the widening scope of weeds that can be addressed, the concept and calculations related to synergy are often either difficult to calculate or irrelevant, as one component might ordinarily be almost inactive for one particular weed while the other component might be similarly inactive in another class of unwanted vegetation. The advantage lies in the breadth of activity without phytotoxicity, and not always in the increase in the numerical degree of herbicidal activity.
The present invention also provides multi component herbicidal combinations comprising an herbicidally effective amount of a combination of component (a), an herbicidal pyridine carboxylic acid component and component (b), a co-herbicide component wherein the amount of component (a) and the amount of component (b) when applied together is more effective in controlling unwanted vegetation than when each herbicide at the same amount is applied alone.
The term “more effective in controlling unwanted vegetation” is not intended to be limited to only the increase in efficacy in preventing, reducing, killing, or otherwise adversely modifying the development of the undesirable vegetation but also relates to increased advantages that accompany these effects. Non-limiting examples of advantages included in the term “more effective”, are one or more of, reducing known, or expected phytotoxicity to the crop; a reduction in known, or expected antagonism of the combination of herbicide classes; reducing expected resistance to one herbicide by addition of the other; effecting the time of application i.e., one herbicide influences the time of application of the other; increasing the speed at which control of unwanted vegetation is achieved; improvements in translocation of one of the herbicides; enhancements in the yield of the crop plants; and persistence of each of the solo herbicides.
The present invention also provides multi component herbicidal combinations comprising an herbicidally effective amount of a combination of component (a), an herbicidal pyridine carboxylic acid component including salts and esters thereof, and component (b), a co-herbicide component so as to thereby control undesired vegetation wherein the amount of active ingredient of component (a) applied, is less than the herbicidally effective amount of pyridine carboxylic acid e.g. halauxifen-methyl when halauxifen-methyl is used alone, and/or wherein the amount of each of the co-herbicide active ingredients of component (b) applied is less than the herbicidally effective amount of the co-herbicide active ingredients of component (b) when the co-herbicide active ingredient of component (b) is used alone.
Herbicidal multi component combinations of the invention having particular utility as weed control agents in crops selected from oilseed rape, cereals, sunflowers, soy and orchards, and being markedly effective in controlling Alopecurus myosuroides, Lolium multiflorum, Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica, Viola arvensis, Cyanus segetum, Capsella bursa-pastoris, Galium, Lamium, Kochia, Amaranthus, Aeschynomene, Sesbania, Monochoria, Cyperus Schoenoplectus, Chenopodium album, Conyza bonariensis), Conyza canadensis, Amsinckia intermedia, Calandrinia ciliate, Erodium cicutarium, Malva parviflora, Medicago polymorpha, Poa annua, Panicum capillare, Agropyron repens, Amarantus retroflexus, Polygonum convolvulus, Ambrosia artemisiifolia, Xanthium strumarium, Cirsium arvense, Persicaria maculosa and Setaria faberi.
Multi-component herbicidal combinations of the invention are typically either synergistically herbicidally effective thus inter alia, allowing for the reduction of the amount used of each component and or reduce the time period required to achieve the known herbicidal effect or, perhaps even more importantly they can increase the scope of unwanted vegetation that can be controlled preferably without simultaneously, significantly increasing the unwanted activity of either component on the crop.
In those embodiments where the advantage lies in the widening scope of weeds that can be addressed, the concept and calculations related to synergy are often either difficult to calculate or irrelevant, as one component might ordinarily be almost inactive for one particular weed while the other component might be similarly inactive in another class of unwanted vegetation. The advantage lies in the breadth of activity without phytotoxicity, and not always in the increase in the degree of herbicidal activity.
The present invention also provides multi component herbicidal combinations comprising an herbicidally effective amount of a combination of component (a), an herbicidal pyridine carboxylic acid component and component (b), a co-herbicide component wherein the amount of component (a) and the amount of component (b) when applied together is more effective in controlling unwanted vegetation than when each herbicide at the same amount is applied alone.
The surprising conclusion reached by inventors that an herbicidally effective amount of a combination comprising Compounds (I) as component (a), a specific group of herbicidal pyridine carboxylic acid herbicides and component (b), a co-herbicide component selected from Clethodim and Propaquizafop when applied together are not only not antagonistic, as previously believed but actually more effective in controlling unwanted vegetation than when each herbicide at the same amount is applied alone. This surprising invention could not have been predicted nor could it have been expected, even in those circumstances which do not display synergism the effect is surprisingly notable.
The present invention also provides multi component herbicidal combinations comprising an herbicidally effective amount of a combination of component (a), an herbicidal pyridine carboxylic acid component including salts and esters thereof, and component (b), a coherbicide component so as to thereby control undesired vegetation wherein the amount of active ingredient of component (a) applied, is less than the herbicidally effective amount of pyridine carboxylic acid e.g. halauxifen-methyl when halauxifen-methyl is used alone, and/or wherein the amount of each of the co-herbicide active ingredients of component (b) applied is less than the herbicidally effective amount of the co-herbicide active ingredients of component (b) when the co-herbicide active ingredient of component (b) is used alone.
Herbicidal multi component combinations of the invention having particular utility as weed control agents in crops selected from oilseed rape, cereals, sunflowers, soy and orchards, and being markedly effective in controlling Alopecurus myosuroides, Lolium multiflorum, Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica, Viola arvensis, Cyanus segetum, Capsella bursa-pastoris, Galium, Lamium, Kochia, Amaranthus, Aeschynomene, Sesbania, Monochoria, Cyperus Schoenoplectus, Chenopodium album, Conyza bonariensis), Conyza canadensis, Amsinckia intermedia, Calandrinia ciliate, Erodium cicutarium, Malva parviflora, Medicago polymorpha, Poa annua, Panicum capillare, Agropyron repens, Amarantus retroflexus, Polygonum convolvulus, Ambrosia artemisiifolia, Xanthium strumarium, Cirsium arvense, Persicaria maculosa Echinochloa crus-galli. Setaria viridis and Setaria faberi.
The agriculturally acceptable derivatives of Compound I, often have significantly different molecular weights than Compound (I) itself, but their herbicidal activity is derived from the amount of the equivalent moles of Compound (I). Thus, in discussions of the amounts of Compounds (I) of component (a) in a combination or in recitation of a rate of application, or weight ratios between the herbicidal active ingredients of component (a) to the herbicidal active ingredients of component (b), The figures disclosed are to be understood as equivalents to the underivatized compound (I) unless clearly referring to the actual weight of that agriculturally acceptable derivative. Thus when e.g. a salt of compound (I) is chosen as herbicidal active ingredient of component (a) the weight of the compound (I) which is referred to is the carboxylic acid equivalent weight.
The single exception to this above general principle relates to the choice of the most preferred derivative of Compound (I), of formula (1), methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro3methoxyphenyl)pyridine-2-carboxylate namely, Halauxifen-methyl. Halauxifen-methyl has a Molecular Weight (mol wt.) of 345 g/mol, whereas Compound (I) itself has Molecular Weight (mol wt.) of 331 g/mol, thus they differ by approximately 4%.
As Halauxifen-methyl is by far the most commercially available derivative of Compound (I), when this specific derivative of compound (I) is selected as the herbicide active ingredient of component (a) in the inventive multi component herbicide combination, the term carboxylic acid equivalent weight, when referring to herbicide ingredients of component (a), it is the actual weight of Halauxifen-methyl that should be used despite the discrepancy, thus availing ourselves of the definition herein below wherein all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about of the boundaries encompassed by any number. The clarity and ease of calculation provided by availing practitioners of this 4% leeway in calculation based on the weight of Halauxifen-methyl as the Component (a) active ingredient derivative of Compound (1) rather than the mol wt. of the acid, easily outweighs any apparent disadvantage.
Thus, in the specific singular case when Formula (1) active ingredient Halauxifen-methyl comprises an herbicide active ingredient of component (a), the value of 345 g/mol will be used and is intended to be used in calculations modified by the term carboxylic acid equivalent weight. Inventors do not believe this aberration will cause any lack of clarity, but rather will simplify the calculation process required and can only result in minor numerical discrepancies within the defined breadth of numerical recitations in this disclosure.
Often in reference to the specific herbicidal active ingredient of formula (I) which is a registered approved herbicidal ingredient of compound (I), the weight amount etc. referred to is the actual weight of the methyl ester itself, as the recommended herbicidally effective amount is available for this specific derivative. In general, the context will dictate the obvious meaning.
As used here, percentages of generally recognized and recommended herbicidally effective doses, amounts or recommended herbicidally effective rates or target rates, relate to the readily available information relating to doses, rates etc. in the accompanying manufacturer's instructions or labeling for each of the commercially available herbicidal active ingredients and compositions, that comprise each component of the inventive multi component herbicidally effective combination of herbicidal active ingredients.
Each herbicidal active ingredient is available in a plurality presentations accompanied by instructions including recommended doses and rates of application based on the manufacturers intimate knowledge of those products. For persons of skill in this field of art the herbicidally effective amounts for each active ingredient will thus clearly be understood for all commercially available presentations of each herbicidal active ingredient in each component of the multi component herbicide combinations of the invention.
Numerical examples of the percentages and corresponding amounts, of generally recognized doses or recommended herbicidally effective rates or target rates of several active ingredients within the scope of this invention are provided within this disclosure. As used herein, the term herbicidally effective, in relation to dose, rate etc. relates to those of active ingredients which cause an adversely modifying effect in targeted harmful or otherwise undesirable vegetation. Such effects include deviations from natural development, killing, regulation, desiccation, retardation, and the like.
As used herein, the term herbicidally effective amount in connection to a combination refers to an amount of the combination which is sufficient for adequately controlling undesirable vegetation or weeds in the environment of crop plants and does not cause significant damage to the treated crop plants.
As used herein, the term herbicidally effective amount in reference to an active ingredient in a component of a multi component combination, refers to an amount of that active ingredient that is commercially recommended for use to control undesirable vegetation or weeds in the environment of crop plants. The commercially recommended amount for each active component, often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation. The commercially recommended application rates of the commercial formulation may vary depending on factors such as the crop plant species and the vegetation etc to be controlled.
As used herein, the terms “control” or “controlling” refers to preventing, reducing, killing, or otherwise adversely modifying the development of the undesirable vegetation or weed.
As used herein, selective control of undesirable vegetation or weed means preventing, reducing, killing, or otherwise adversely modifying the development of the undesirable vegetation in the presence of crop plants with limited adverse effect on the crop plants. For example, weed control of 80% (rated visually) with crop injury of less than or equal to 20% (rated visually) would constitute selective control. In some embodiments the adverse effect on crop plants is limited to less than 10% visually rated crop injury. Visual crop injury is a composite rating accounting for all such phytotoxic effects including chlorosis, necrosis, growth inhibition, epinasty, delays in maturity and seed or fruit deformity. Visual weed control rating is a composite rating accounting for reductions in pest plant biomass and/or stand reduction.
As used herein the term “plant” or “crop” includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds. This term also encompasses plant crops such as fruits. The term “plant” may also include the propagation material thereof, which may include all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant. It may also include spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
As used herein, the term “locus” includes a habitat, breeding ground, plant, propagation material, soil, area, material or environment in which a pest is growing or may grow. The term “contacting”, as used herein, refers to applying the compounds and compositions of the invention to plant or vegetation, to a site of unwanted growth, to a potential site of unwanted vegetation or weeds, or the environment of and around crop plants. The application may be by methods commonly used in the art not limited to spraying, dipping, etc.
As used herein, the term “mixture” or “combination” is not limited to, a combination in any physical form, e.g., blend, solution, alloy, admix, kit or the like, but also encompasses two active components each comprising at least one more herbicidally active ingredients used in concert or a combined protocol of application with each being applied separately sequentially or simultaneously while eliciting a combined beneficial effect.
As used herein, the phrase “agriculturally acceptable carrier” means carriers which are known and accepted in the art for the formation of compositions for agricultural or horticultural use.
Throughout the application, descriptions of various embodiments use the term “comprising” or “containing”; however, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language “consisting essentially of” or “consisting of.”
The term “a” or “an” as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms “a,” “an” or “at least one” can be used interchangeably in this application. As non-limiting examples there should be no inference that reference to “a” component or “an” item is meant to mean only a single component or only a single item, and it is understood that multiple components and items are included unless specifically indicated otherwise.
For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In this regard, uses of the term “about” herein specifically includes the broader of either ±10% from the indicated values in the range, or, taking into account the limits of the specific measuring technique to which the value pertains, an indicated value includes those values which the specified measurement technique is incapable of resolving, while the term “about” refers to at least one unit of measurement either side in that technique. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.
As used herein, applying a herbicide or herbicidal composition includes delivering it directly to the targeted vegetation or to the locus thereof or to the area where control of undesired vegetation is desired, but where relevant, not directly on the crops. Where crops are specifically perennial crops such as trees, orchard crops etc. sprays or granules etc. are generally directed under the trees, with foliar exposure of the crops being avoided.
Analogs of compound (I) in which the acid is derivatized to form a related substituent that can be transformed within plants or the environment to an acid group possess essentially the same herbicidal effect and are within the scope of this disclosure. Therefore, an “agriculturally acceptable derivative”, when used to describe the carboxylic acid functionality at the 2position of the pyridine of the component (a) compound (1), is defined as any salt, ester, acyl hydrazide, imidate, thioimidate, amidine, amide, orthoester, acylcyanide, acyl halide, thioester, thionoester, dithiolester, nitrile or any other acid derivative well known in the art which (i) does not substantially negatively affect the herbicidal activity of the active ingredient, and/or (ii) is or can be hydrolyzed, oxidized or metabolized in plants or soil to a picolinic acid compound (I), a pyridine carboxylic acid or derivative.
It has been surprisingly found that by combining particular herbicides with Halauxifen compounds including those having different modes of action, when chosen judiciously, can create herbicidal treatments that have particular utility in various crop settings and/or against various unwanted vegetation that is commonly found in those crop settings and that each crop setting benefits to different degree from different groups of herbicides combined with Halauxifen (compound (I)) and agriculturally acceptable derivatives thereof especially Halauxifen-methyl.
The multi component herbicidal combinations of the invention are often synergistically herbicidally effective as herbicides against unwanted vegetation in oilseed rape, cereal, sunflower, soy, and orchard crops. However, the advantages of the combinations in controlling unwanted vegetation in oilseed rape, cereal, sunflower, soy, and orchard crops are not limited to synergy of the herbicidal efficacy of component active ingredients but include unforeseen advantageous attributes of the combinations including, though not limited to, avoiding significantly increased concomitant phytotoxicity to the crops that would be assumed to accompany compositions with increased herbicidal activity.
Particularly of note are the advantages associated in controlling unwanted vegetation in oilseed rape, cereal, sunflower, and soy crops. More outstanding perhaps are the advantages associated in controlling unwanted vegetation in oilseed rape, sunflower, and soy crops. Most surprising are the lack of antagonism that was expected by applying Compound (I) with Clethodim as co-Herbicide
Those combinations which are compositions may also contain agriculturally acceptable adjuvant, carrier, formulation aids, base or acid, pH modifiers, thickeners, surfactants etc. In a particularly noted example, the increased activity of the combination of Halauxifen-methyl and Clethodim embodiment of the invention was enhanced even further with the addition of the adjuvant marketed as Vivolt® by Corteva reportedly comprising >90% non-ionic surfactants Polyethylene oxide monoisodecyl ether (CAS 61827-42-7) see:
In some embodiments, the mixtures, compositions and/or methods all included within the combination invention disclosed herein further comprise additive. Non-herbicidally active additives may include though definitely not limited to carrier, safener, adjuvant, surfactants, pH modifying ingredient or base or acid in non-aqueous systems, as required, formulation aids or combinations thereof. An example of a common class of additive includes alkylene glycols, which have many uses in formulations.
Although typically the mixtures, compositions and/or methods all included within the combination invention are absent any further herbicidally active ingredient, inventors specifically contemplated embodiments wherein the additive comprises one or more additional herbicidally active ingredients, however only those that neither detrimentally affect the improvements achieved by combining components (a) and (b) in compositions and in methods of herbicidal control, or that change the nature of those improvements.
A non-limiting example might include a combination of Halauxifen, Aminopyralid and a base and optionally any of surfactant, carrier, adjuvant etc.
Commonly available safeners which may be usefully employed, individually or in any combination found to be useful, with the inventive combinations may include but are in no way limited to Daimuron (Dymron), Cumyluron, Dimepiperate, Fenclorim, Cloquintocet
(Cloquintocet-mexyl), Fenchlorazole-ethyl, Mefenpyr (Mefenpyr-diethyl), Isoxadifen (Isoxadifenethyl), Cyprosulfamide, Dietholate, Benoxacor, BPCMS, Cyometrinil, Dichlormid, Dicyclonon, Dietholate, Fenchlorazole, Flurazole, Fluxofenim, Furilazole, Jiecaowan, Jiecaoxi, Mephenate, Metcamifen, Naphthalic anhydride, or Oxabetrinil. Those skilled in the relevant field of art will immediately be aware of further safeners that may be employed without departing from the scope of the combination invention disclosed here. Combinations of safeners can be employed in the methods, combinations and compositions (all included in the term, combinations), of the combination invention. An illustrative, non-limiting example of a combination according to the invention which comprises safeners is e.g., a combination of Halauxifen (e.g., Halauxifen-methyl), Clopyralid (salts esters etc.), in combination with any, or all of Cloquintocet (preferably, Cloquintocet mexyl) Mefenpyr (preferably, Mefenpyr-diethyl), Isoxadifen (preferably, Isoxadifen-ethyl)
Another illustrative, non-limiting example of a combination according to the invention which comprises safeners is e.g., a combination of Halauxifen, Aminopyralid, in combination with any, some or all of Cloquintocet, Isoxadifen and Mefenpyr.
A further illustrative, non-limiting example of a combination according to the invention which comprises safeners is e.g., a combination of Halauxifen, Picloram, in combination with any, some, or all of Cloquintocet, Isoxadifen and Mefenpyr.
A further illustrative, non-limiting example of a combination according to the invention which comprises safeners is e.g., a combination of Halauxifen, Quinclorac, in combination with any, some, or all of Cloquintocet, Isoxadifen and Mefenpyr.
Yet a further illustrative, non-limiting example of a combination according to the invention which comprises safeners is e.g., a combination of Halauxifen, Tribenuron, in combination with any, some, or all of Cloquintocet, Isoxadifen and Mefenpyr.
In some embodiments, the combinations of the invention may be employed in combination with cloquintocet mexyl, either alone or together with other safeners, and adjuvants, additives etc.
In some embodiments, it is a co-herbicide that comprises component b) itself that acts as a safener for, as well as enhancing the herbicidal activity of, the pyridine carboxylic acid component a), or for that matter as a safener for other co-herbicides comprising component b).
The present invention also concerns methods of utilizing a multi component herbicidal combination comprising an herbicidally effective amount of component a) at least one first herbicide selected from the group of a pyridine carboxylic acid of Compound (I) which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable salts and esters thereof individually or in combination, and most particularly, the ester compound of Formula (1), methyl 4-amino-3-chloro-6-(4-chloro2fluoro-3-methoxyphenyl) pyridine-2-carboxylate and applied with component b), second herbicide selected from the group consisting of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate and any and all combinations etc. thereof for herbicidally effective weed control, and especially for selective control.
A further surprising and counterintuitive aspect in some embodiments is found where the inventive combination provides no higher herbicidal activity than that envisaged on the basis of the sum of activities of each of the herbicides found therein, but sometimes a wider range of crop settings or vulnerable unwanted vegetation (weeds). Surprisingly these combinations have the unexpected benefit of being able to predictably adjust the relative amount of each component herbicide without fear that the unwanted effects on the desired crop has not been boosted unpredictably which is often the case with synergistic combinations.
A further surprising and counterintuitive aspect are realized in some embodiments where a multi component herbicidal combination of the invention comprising as component (a), an amount of active ingredient, compound (I) exemplified by Halauxifen-methyl, and an amount of at least one co-herbicide of component (b) selected from the group consisting of:
Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor: Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron: Glyphosate; applied so as to thereby control undesired vegetation, wherein the amount of compound (I) active ingredient e.g. Halauxifen-methyl, applied is less than the herbicidally effective amount of e.g. Halauxifen-methyl when Halauxifen-methyl is used alone, and/or wherein the amount of each co-herbicide ingredient of component (b) applied is less than the herbicidally effective amount of co-herbicide ingredient of component (b) when the coherbicide ingredient of component (b) is used alone.
In some embodiments, the inventive combination provides a higher herbicidal activity than that envisaged on the basis of the sum of activities of each of the herbicides found therein. Such a combination allows the reduced dosages of the individual herbicides which can damage agriculturally important plants. In these embodiments each enhanced component herbicide is not associated with levels of undesired activity that is dose-dependent, or that does not display the same level of synergistic enhancement of undesirable effects as the enhancement of positive herbicidal activity.
Embodiments include providing herbicidally effective multi component weed control herbicidal combinations, comprising, as active components a) 4-amino-3-chloro-6-(4-chloro2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable derivatives thereof including salts and esters thereof, particularly alkyl esters; and component b), additional active ingredient compound or compounds being co-herbicides with tailored utility in various crops and/or unwanted vegetation or weed varieties, selected from Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin: Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil: Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations etc., thereof, dependent on the specific crop environment and the weeds etc. that are to be controlled.
In particularly preferred embodiments, component b), co-herbicides are selected from Clethodim; Propaquizafop and combinations thereof, often in the total absence of any other herbicidally active ingredient.
Further embodiments include providing herbicidally effective weed control herbicidal mixtures, combinations, admixtures etc. (combinations), comprising, as active components a) 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine2carboxylic acid, and agriculturally acceptable derivatives thereof including salts and esters thereof, particularly alkyl esters; and components b) additional active compound or compounds with tailored utility in various unwanted vegetation or weed varieties, selected from Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; 2-(propan-2-ylideneamino)oxyethyl (2R)-2-[4-(6-chloroquinoxalin-2-yl)oxyphenoxy]propanoate;
Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations etc. thereof, dependent on the specific weeds etc. that are to be controlled, most notably including Alopecurus myosuroides, Lolium multiflorum, Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica, Viola arvensis, Cyanus segetum, Capsella bursa-pastoris, Galium, Lamium, Kochia, Amaranthus, Aeschynomene, Sesbania, Monochoria, Cyperus Schoenoplectus, Chenopodium album, Conyza bonariensis), Conyza canadensis, Amsinckia intermedia, Calandrinia ciliate, Erodium cicutarium, Malva parviflora, Medicago polymorpha, Poa annua, Panicum capillare, Agropyron repens, Amarantus retroflexus, Polygonum convolvulus, Ambrosia artemisiifolia, Xanthium strumarium, Cirsium arvense, Persicaria maculosa and Setaria faberi.
Some embodiments include methods of weed control or control of harmful or otherwise undesirable vegetation by applying herbicidally effective amounts of the inventive combinations etc. to the weeds or unwanted vegetation or the locus thereof. The herbicidally effective weed control herbicidal combinations etc. comprising, as active components (a) 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable derivatives thereof including salts and esters thereof; and (b) additional active compound or compounds with tailored utility in various crops, selected from Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof): Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations etc. thereof, depending on the specific crop environment.
However, much preferred embodiments include selective methods of weed control or control of harmful or otherwise undesirable vegetation by applying herbicidally effective amounts of the inventive combinations etc. to the weeds or unwanted vegetation or the locus thereof. The herbicidally effective weed control herbicidal combinations etc. comprising, as active components (a) 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable derivatives thereof including salts and esters thereof; and (b) active compound or compounds with tailored utility in various crops, selected from Propaquizafop; Clethodim; and any and all combinations etc. thereof, depending on the specific crop environment. Often in these preferred embodiments the application is in the absence of other herbicidally active ingredients.
Of special note are embodiments that include methods of weed control or control of harmful or otherwise undesirable vegetation by applying herbicidally effective amounts of the inventive combinations etc. to the weeds or unwanted vegetation or the locus thereof. The herbicidally effective weed control herbicidal combinations etc. comprising, as active components (a) methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro3methoxyphenyl)pyridine-2-carboxylate; and (b) additional active compound or compounds with tailored utility in various crops, selected from 2-(propan-2-ylideneamino)oxyethyl (2R)-2-[4-(6-chloroquinoxalin-2-yl)oxyphenoxy]propanoate; and Clethodim.
In some embodiments, the crops are cereals and component b) any of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam: Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); and any and all combinations etc. thereof. In some embodiments the cereals are any of wheat, barley, rye, oats, corn and sorghum. In some embodiments, the crops are Oilseed Rape (OSR), and component b) any of, Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; and any and all combinations etc. thereof.
In some embodiments the crop settings are perennial crops which comprises applying a herbicidally effective amount of a) a compound (I) or agriculturally acceptable ester or salt thereof in combination with, or is applied with, or in mixture with (all included within the term, in combination with, as throughout), further herbicidal components, to the unwanted vegetation or the locus thereof. In some embodiments, compound (I) may preferably be the compound of formula (1), Halauxifen-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2fluoro3-methoxyphenyl)pyridine-2-carboxylate).
In some embodiments further herbicidal components for application with compound (I) are each chosen from any of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations etc. thereof. In some embodiments, the perennial crop is tree and fruit orchards, including almond, apple, apricot, avocado, beechnut, Brazil nut, butternut, cashew, cherry, chestnut, chinquapin, citrus, crab apple, date, feijoa, fig, filbert, hickory nut, grapefruit, kiwi, lemon, lime, loquat, macadamia nut, mandarin, mayhaws, nectarine, olives, oranges (sweet and sour), peach, pear, pecan, persimmon, pistachio, plum, pome fruit, pomegranates, prune, quince, stone fruit, tangerine, tangelo, tree nuts, and walnut; and perennial plantation crops including rubber, oil palm, coffee and cacao. In some embodiments Compound (I) is comprised of 4-amino-3-chloro-6-(4-chloro-2fluoro3-methoxyphenyl)pyridine-2-carboxylic acid together with one or several and varied agriculturally acceptable derivatives thereof.
In some embodiments the agriculturally acceptable derivatives include those that relate to acid derivatives of the carboxylic acid functionality at the 2-position of the pyridine, which (i) does not substantially affect the herbicidal activity of the active ingredient, and (ii) is or can be hydrolyzed, oxidized, or metabolized in plants or soil to compound (I). In some embodiments the specific derivatives are chosen to facilitate combining a compound (I) in the same formulation as the further herbicides chosen to be useful for the particular crop, to overcome formulation issues of solubility, pH sensitivity; wettability chemical incompatibility and the like.
Without departing from the scope of the subject matter, the mixtures, combinations admixtures etc. and formulations (combinations), of the present subject matter may be applied in separate compositions applied simultaneously, that is jointly or separately, or in succession, in sequence, in the case of separate application where individual applications are separated by up to several hours. The application of the multi component individual compounds jointly or separately generally does not have any adverse effect on the result of the control measures.
In the case of the combined use of several active ingredients, it is not a rare event for phenomena of chemical, physical incompatibility to occur, for example inadequate stability of a coformulation, decomposition of an active ingredient. High stability is always desired. In preparing the inventive combinations as combined formulations, a further choice is made within the preferred group of co-herbicides based on results of their compatibility in binary mixtures preferably together with proposed adjuvants ingredients etc. to ensure stability. Persons of skill in these arts are well aware of how such an analysis might be conducted to choose the optimum compound (I) derivative and co-herbicide and amounts of each out of the group of possible choices.
A composition can be formulated comprising a compound (I) including agriculturally acceptable derivatives thereof with the co-herbicide or co-herbicides, tank mixed with the co-herbicide or co-herbicides or applied as mentioned, formulated separately.
The weight ratio between the (a) compound (I) component or components type, and the co-herbicide (b) component or components cannot always be defined generally, as it varies depending upon various conditions such as the type of the formulation, weather conditions, the type of crop and the type of unwanted vegetation. However, quite typically the weight ratio of the pyridine carboxylic acid of the one or more compound (I) component (a) to the second (b) co-herbicide component at which the herbicidal effect is synergistic lies within the range of between 10:1 and 1:500 most typically between 5:1 and 1:256.
In some embodiments the weight ratio of the pyridine carboxylic acid of the one or more compound (I) component (a) to the (b) co-herbicide component at which the herbicidal effect is synergistic lies within the range of between 3:1 and 1:320.
An embodiment includes a multi-component herbicide comprising an herbicidally effective amount of a combination of at least one first herbicidal active ingredient of a component (a) selected from the group of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable salts and esters thereof, and most particularly, the ester compound of Formula (I), Methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3methoxyphenyl)2-pyridinecarboxylate and agriculturally acceptable salts and esters thereof, and a second co-herbicidal active ingredients component (b) comprising Clethodim.
An embodiment includes a herbicide combination or composition comprising an herbicidally effective amount of a combination of at least one first herbicidal active ingredient of a component (a) selected from the group of 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable salts and esters thereof, and most particularly, the ester compound, Methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3methoxyphenyl)2-pyridinecarboxylate, and a second co-herbicidal active ingredients component (b) comprising Clethodim, wherein the ratios of herbicidal active ingredient of component (a) to clethodim, expressed in units of weight to weight (g to g), gae/ha to gai/ha, or gae/ha to gae/ha, are within the range of about 1:140 to about 9:1, from about 1:35 to about 2.2:1 and from about 1:9 to about 1:8. In certain embodiments of the compositions and methods described herein, the first herbicide component selected from the group of a pyridine carboxylic acid of Compound (I)
which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid or salt or ester thereof is used in combination with clethodim or salt or ester thereof. With respect to the compositions, in some embodiments, the weight ratio of the Compound (1) or salt or ester thereof to clethodim or salt or ester thereof is within the range of from about 1:140 to about 9:1. In certain embodiments, the weight ratio of the Compound (I) or salt or ester thereof to clethodim or salt or ester thereof is within the range of from about 1:48 to about 3:1. In certain embodiments, the compositions provided herein comprise the Compound (I) or its methyl ester and clethodim. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein.
In some embodiments, the composition is applied at an application rate of from about 20 grams active ingredient per hectare (gai/ha) to about 580 gai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 20 grams active ingredient per hectare (gai/ha) to about 260 gai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a Compound (1) or salt or ester thereof and clethodim or salt thereof, e.g., sequentially, or simultaneously.
In some embodiments, the clethodim or salt thereof is applied at a rate from about 17.5 gai/ha to about 280 gai/ha and the Compound (I) of salt or ester thereof is applied at a rate from about 2 gae/ha to about 300 gae/ha. In some embodiments, the clethodim or salt thereof is applied at a rate from about 70 gai/ha to about 280 gai/ha and the Compound (I) or salt or ester thereof is applied at a rate from about 8 gae/ha to about 32 gae/ha. Particularly noted are the clethodim or salt application rates of 80 gai/ha to about 250 gai/ha and the Compound (I) or salt or ester thereof is applied at a rate from about 2 gae/ha to about 10 gae/ha.
In particular ratios of Halauxifen-methyl: Clethodim of 1:10 and 1:320, most particularly between 1:30 and 1:40.
In certain embodiments, the methods utilize the Compound (I), or its methyl ester and clethodim for the control of BRAPP, DIGSA, CYPES and SCPJU.
In further embodiments the methods utilize the Compound (I), or its methyl ester and clethodim for the control of any of Xanthium strumarium (XANST), Amaranthus retroflexus (AMARE), Ambrosia artemisiifolia (AMBEL), Chenopodium album (CHEAL), and Cirsium arvense (CIRAR).
In some preferred embodiments, the herbicidally effective rate at which either the first, pyridine carboxylic acid of the one or more compound (I) component (a) and or the second (b) co-herbicide component are applied in the inventive methods are significantly lower than the rate at which they would each need to be applied if they were applied in the absence of the other component, to achieve the same or comparable levels of control efficacy.
The rate at which the inventive combinations, compositions mixtures admixtures etc., which are all included in the term combinations, are applied will depend upon the particular type of weed to be controlled, the degree of control required, and the timing and method of application. In general, the combinations etc. of the invention can be applied at an application rate of between 1 gram per hectare (g/ha) and 2400 g/ha more often between 8 grams per hectare (g/ha) and 1200 g/ha based on the total amount of active ingredients in the combination. Depending upon the particular co-herbicide (b) used, the co-herbicide component is applied at a rate between 0.5 g/ha and 2,240 g/ha and typically between 4 g/ha and 1120 g/ha and the pyridine carboxylic acid of compound (1) component (a) is applied at a rate between 0.5 g/ha and 160 g/ha, more typically between 4 g/ha and 80 g/ha.
The inventive compositions, mixtures, combinations, formulations, admixtures etc. (all included in the term combinations), comprising, as active components (a) 4-amino-3chloro-6-(4-chloro-2-fluoro3-methoxyphenyl)pyridine-2-carboxylic acid, and agriculturally acceptable derivatives thereof including salts and esters thereof; and (b) additional active compound or compounds with tailored utility in various crops, each chosen from any of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin: Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations etc. thereof. But those embodiments where component (b) is Clethodim and or Propaquizafop are much preferred.
Preferably in the embodiments below, component (a) is methyl 4-amino-3-chloro-6-(4-chloro2fluoro-3-methoxyphenyl)pyridine-2-carboxylate (H-m) although combinations of one or several and varied agriculturally acceptable derivatives of compound (I) are specifically contemplated.
In those embodiments where the crops are Oilseed Rape (OSR), and component b) any of, Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; and any and all combinations etc. thereof, a range contemplated combinations, mixtures etc., all referred to as combinations, can be envisioned as a matrix e.g., Table 1 below although, as mentioned H-m, is only an exemplary component (a) compound. Using the testing examples below, the most appropriate and/or compatible of these combinations can be chosen.
This matrix table form is similarly useful in the other crops by replacing the compounds (b) with the options specified for each crop, below. Simply for the sake of brevity only a single example of this simple table is presented.
In those embodiments where the crops are Sunflower Component (a) is preferably H-m, and component (b) chosen from any of, aclonifen; imazamox, Propaquizafop; clethodim; and any and all combinations etc. thereof, although Propaquizafop and clethodim are most preferred.
In those embodiments where the crops are cereals Component (a) is preferably H-m and component b) chosen from any of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Propaquizafop and clethodim any and all combinations etc. thereof, although Propaquizafop and clethodim are most preferred.
In those embodiments where the crops are perennial crops Component a) is preferably H-m and component b) chosen from any of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox; and any and all combinations etc. thereof.
In each crop or weed embodiment the possible combinations of those combined applications suited best as appropriate can be presented in a table similar to Table 1, with the changes in appropriate co-herbicides mutatis mutandis to reflect all possible combinations. Table 1 is thus simply an example of the range of all possible combinations for one particular crop and for each crop a similar table can be prepared.
While inventors note that the advantages of combining co-herbicidal component (b) applications with pyridine carboxylic acid component (a) and/or derivatives thereof has been shown in practice, there is sound plausible reason to extrapolate that two or more component (b) co-herbicides, each proven to be enhanced by and/or to enhance pyridine carboxylic acid components (a) and/or derivatives thereof should similarly have enhanced attributes. In other words, unless proven otherwise each component (b) co-herbicide will not deleteriously effect a combination application that comprises a different co-herbicide combined with one or more pyridine carboxylic acid component (a) and/or derivatives thereof.
The inventors thus also envision the specific advantages of the combination of several herbicides in enabling the reduction in the amount of each of the active ingredients comprising the multi component combination to amounts below the levels at which they would individually be herbicidally effective in absence of the other herbicidal active ingredients of the combination.
The present subject matter also relates to methods of weed control or control of undesirable vegetation by applying herbicidally effective amounts of the inventive combinations etc. to the weeds or unwanted vegetation or the locus thereof.
In some embodiments the weed control or control of undesirable vegetation is selective control.
In some embodiments one component of the mix, combination etc. is associated with herbicide resistance while the other does not show resistance, thus companion compound is selected preferably that is not cross-resistant with other herbicides, so that one component supports the effects of other supplementary herbicides that use a different mode of action.
The present subject matter also relates to methods for the selective control of undesirable vegetation in any of Oil Seed Rape, Cereals, Sunflower, Soy or Perennial crops, and particularly Oil Seed Rape, Sunflower, Soy crops which comprises applying a herbicidally effective amount of (a) a compound (1) or agriculturally acceptable ester or salt thereof in combination with, or is applied with, or in mixture with further herbicidal components, (i.e. combinations) to the unwanted vegetation or the locus thereof. In some embodiments, compound (1) may preferably be the compound of formula (I), Halauxifen-methyl (methyl 4-amino-3-chloro-6(4chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate). In some embodiments further herbicidal components for application with compound (I) are each chosen from any of Thiencarbazone-methyl (Thiencarbazone); Pyroxsulam; Bifenox; Diflufenican; Pinoxaden (including Pinoxaden acid and enolate form thereof); Pendimethalin; Quinmerac; DMA-P (Dimethenamid-P); Metazachlor; Aclonifen; Imazamox Aminopyralid; Propaquizafop; Clethodim; Triclopyr; Saflufenacil; Paraquat; Picloram; Clopyralid; Quinclorac; Tribenuron; Glyphosate; and any and all combinations etc. thereof. Most preferred co-herbicides are Propaquizafop and/or Clethodim often in the absence of any other herbicide.
The application rates of the combination, or the combined application rates may vary, depending on the desired effect and conditions. In an embodiment, depending on the desired effect, the application rates of the combination according to the invention are from 1 g/ha to 10000 g/ha, particularly from 10 to 5000 g/ha, more particularly from 50 to 2000 g/ha. Although, with particularly efficacious combination applications and favorable conditions, desired effects are achievable with even lower rates of application without departing from the inventive concept. Similarly, over-spraying at higher rates of application e.g., as an attempt to overcome challenging environmental conditions, or even mistakenly, will also not depart from the inventive concept.
Herbicidal activity is exhibited by the combinations when they are applied directly to the plant to be controlled or to the locus of the plant to be controlled. The effect observed depends upon the plant species to be controlled, the stage of growth of the plant, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. These and other factors can be adjusted to promote non-selective or selective herbicidal action. In the present methods, the combinations described herein are typically applied in application to undesirable vegetation or to relatively immature and mature undesirable vegetation to achieve the maximum control of weeds. At an application rate of 0.5 to 80 g ae/ha, Compound I as an application is highly efficacious on several commercially relevant broadleaf and grass weeds, including chickweed (Stellaria media), pigweed (Amaranthus spp.), common lambsquarters (Chenopodium album), hairy fleabane (Conyza bonariensis), horseweed (Conyza canadensis), coast fiddleneck, (Amsinckia intermedia), Shepherd's purse (Capsellabursa-pastoris), rockpurslane (Calandrinia ciliata), redstem filaree (Erodium cicutarium), smallflower malva (Malva parviflora), California burclover (Medicago polymorpha), annual bluegrass (Poa annua), witchgrass (Panicum capillare), quackgrass (Agropyron repens), and giant foxtail (Setariafaberi). The level of crop safety exhibited by crops toward Compound I is variable, but generally post-emergence application rates of less than 20 g ae/ha cause little to no crop injury.
Additional examples of application rates for Compound I include 0.25 to 100 g ae/ha, 0.25 to 80 g ae/ha, 0.25 to 70 g ae/ha, 0.25 to 50 g ae/ha, 0.25 to 45 g ae/ha, 0.25 to 40 g ae/ha, 0.25 to 35 g ae/ha, 0.25 to 30 g ae/ha, 0.25 to 25 g ae/ha, 0.25 to 20 g ae/ha, 0.25 to 15 g ae/ha, 0.25 to 10 g ae/ha, 0.25 to 5 g ae/ha, 2.5 to 50 g ae/ha, 5 to 50 g ae/ha, 10 to 50 g ae/ha, 15 to 50 g ae/ha, 20 to 50 g ae/ha, 25 to 50 g ae/ha, 30 to 50 g ae/ha, 35 to 50 g ae/ha, 40 to 50 g ae/ha, 45 to 50 g ae/ha, 5 to 40 g ae/ha, 10 to 40 g ae/ha, 15 to 40 g ae/ha, 20 to 40 g ae/ha, 25 to 40 g ae/ha, 30 to 40 g ae/ha, 35 to 40 g ae/ha, 2.5 to 35 g ae/ha, 2.5 to 30 g ae/ha, 2.5 to 25 g ae/ha, 2.5 to 20 g ae/ha, 2.5 to 15 g ae/ha, 2.5 to 10 g ae/ha, 2.5 to 5 g ae/ha, 5 to 35 g ae/ha, 10 to 30 g ae/ha, 15 to 25 g ae/ha, and 15 to 20 g ae/ha. Further examples of application rates for Compound I include 0.25 g ae/ha, 0.5 g ae/ha, 0.75 g ae/ha, 1 g ae/ha, 1.25 g ae/ha, 1.5 g ae/ha, 1.75 g ae/ha, 2 g ae/ha, 2.25 g ae/ha, 2.5 g ae/ha, 3 g ae/ha, 4 g ae/ha, 5 g ae/ha, 6 g ae/ha, 7 g ae/ha, 8 g ae/ha, 9 g ae/ha, 10 g ae/ha, 12 g ae/ha, 14 g ae/ha, 16 g ae/ha, 18 g ae/ha, 20 g ae/ha, 22 g ae/ha, 24 g ae/ha, 26 g ae/ha, 28 g ae/ha, 30 g ae/ha, 32 g ae/ha, 34 g ae/ha, 36 g ae/ha, 38 g ae/ha, 40 g ae/ha, 42 g ae/ha, 44 g ae/ha, 46 g ae/ha, 48 g ae/ha, and 50 g ae/ha.
The combination of active substances can be diluted and applied in a customary manner, for example by watering (drenching), drip irrigation, spraying, and atomizing.
In yet another embodiment, the compositions of components may be applied in various combinations of compound (I) herbicide and co-herbicide or co-herbicides, for example in a single “ready-for-use” form, or in a combined spray combination composed from separate formulations of the individual active ingredients, such as a “tank-mix” form. In further embodiments compositions of each component, active ingredient or the entire combination may be formulated as any of various known concentrated forms to be used in in-situ to prepare a ready for use form.
In yet another embodiment, compositions are applied in the form of ready-for-use formulation comprising a) a Compound (I) and b) a co-herbicide. These formulations can be obtained by combining the multi component active ingredients in herbicidal effective amount with agriculturally acceptable carrier, surfactant, pH modifying ingredient e.g. base or acid as required, or other application-promoting adjuvant customarily employed in formulation technology. A non-limiting example might include a combination of Halauxifen, Aminopyralid and a base.
For example, a composition of the present invention is preferably applied in the form of a ready-for-use formulation comprising not less than one component a) compound (I) and not less than one component b) co-herbicide chosen to be suited to the crop environment of choice, which can be obtained by combining the active ingredients with agriculturally acceptable carrier, surfactant, pH modifying ingredient or base or acid in non-aqueous systems, as required, or other application-promoting adjuvant customarily employed in formulation technology.
The compositions embodiments of the combinations may be employed or prepared in any conventional form, for example, as wettable powders (WP), emulsion concentrates (EC), microemulsion concentrates (MEC), water-soluble powders (SP), water-soluble concentrates (SL), suspoemulsion (SE), oil dispersions (OD), concentrated emulsions (BW) such as oil in water and water-in-oil emulsions, sprayable solutions or emulsions, capsule suspensions (CS), suspension concentrates (SC), suspension concentrates, dusts (DP), oil-miscible solutions (OL), seed-dressing products, granules (GR) in the form of microgranules, spray granules, coated granules and absorption granules, granules for soil application or broadcasting, water soluble granules (SG), water-dispersible granules (WDG), ULV formulations, microcapsules or waxes. These individual formulation types and their methods of compounding and manufacture are well known in the art. According to an embodiment, compositions comprise at least one additional component selected from the group of surfactants, solid diluents and liquid diluents, dispersants, pH modifying agents, additional herbicidal active ingredients, and combinations thereof. Such compositions can be formulated using agriculturally acceptable carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology and formulation techniques that are known in the art.
Examples of suitable liquid carriers potentially useful in the present compositions include but are not limited to water; aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes; alcohols such as cyclohexanol, and decanol; ethylene glycol; polypropylene glycol; dipropropylene glycol; N,N-dimethylformamide; dimethylsulfoxide; dimethylacetamide; Nalkylpyrrolidones such as N-methyl-2-pyrrolidone; paraffins; various oils such as olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed, or coconut oil; fatty acid esters; ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy4methyl-2-pentanone; and the like.
Examples of suitable solid carriers potentially useful in the present compositions include but are not limited to mineral earths such as silica gels, silicates, talc, kaolin, sericite, attaclay, limestone, bentonite, lime, chalk, bole, mirabilite, loess, clay, dolomite, zeolite, diatomaceous earth, calcium carbonate, calcium sulfate, magnesium sulfate, magnesium oxide, sodium carbonate and bicarbonate, and sodium sulfate: ground synthetic materials: fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal, and nutshell meal; cellulose powders; and other solid carriers.
Examples of suitable surfactants include, but are not limited to, non-ionic, anionic, cationic and ampholytic types such as alkoxylated fatty alcohols, ethoxylated polysorbate (e.g. tween 20), ethoxylated castor oil, lignin sulfonates, fatty acid sulfonates (e.g. lauryl sulfonate), phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrylphenol ethoxylates, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, alkylarylsulfonates, ethoxylated alkylphenols and aryl phenols, polyalkylene glycols, sorbitol esters, alkali metal, sodium salts of lignosulphonates, tristyrylphenol ethoxylate phosphate esters, aliphatic alcohol ethoxylates, alkylphenol ethoxylates, ethylene oxide/propylene oxide block copolymers, graft copolymers and polyvinyl alcohol-vinyl acetate copolymers. Other surfactants known in the art may be used as desired.
A particular advantage was appreciated when Halauxifen-methyl combined with Clethodim was applied in a composition including the adjuvant commercially available as Vivolt® comprising Polyoxyethylene isodecyl ether, CAS 61827-42-7.
Other ingredients, such as wetting agents, anti-foaming, adhesives, neutralizers, thickeners, binders, sequestrates, fertilizers, biocides, stabilizers, buffers or anti-freeze agents, may also be added to the present compositions in order to increase the stability, density, and viscosity of the described compositions.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the components of the compositions either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is also possible to prepare concentrates comprising active ingredient, wetting agent, tackifier, dispersant or emulsifier and, if desired, a solvent or oil, which are suitable for dilution with water.
In an embodiment, the amount of the combination of active ingredients in the composition is from about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% to about 90%, 93%, 94%, 95%, 97%, 98%, 99% based on the total weight of the composition.
In another embodiment, the combined amount of Component a), one or several of compounds (I) herbicidal active ingredients and component b), one or several co-herbicidal active ingredients chosen from the group of co-herbicides suitable for the specific crop environment of intended use, as detailed above together in the ready-to-use formulations is 0.01-98 wt. %, 0.1-96 wt. % 1-95 wt. %, 10-87 wt. %, particularly 75-95 wt. %, based on the total weight of the formulation.
For example, the combined amount of compound (1) and co-herbicidal component in the ready-to-use formulations according to the invention is 0.01-95 wt. %, particularly 0.1-90 wt. %, more particularly 1-90 wt. %, even more particularly is 10-90 wt. %, based on the total weight of the formulation.
The present composition may include additional crop protection agents, for example insecticides, fungicides, bactericides, nematicides, molluscicides, growth regulators, biological agents, fertilizers, or mixtures thereof. However, for the avoidance of doubt it is understood that such additional crop protection agents are unnecessary to achieve the desired control of unwanted vegetation in the specific crop environments as achieved by the present combinations. Accordingly, the present herbicidal compositions and combinations may be limited to containing Compound (I) herbicides (e.g. H-m) and co-herbicide chosen for its suitability in the crop environment, as the only crop protection agents present.
In another embodiment, the present invention provides a kit comprising a synergistic herbicidal composition as described herein, or components thereof. Such kits may comprise, in addition to the aforementioned active components, one or more additional active and/or inactive ingredients, either within the provided herbicidal composition or separately. Certain kits comprise a) not less than one Compound (I) herbicide and b) co-herbicide(s), chosen for the intended crop environment, each in a separate container, and each optionally combined with a carrier.
As noted above, the some of the combinations including without limitation, compositions, kits and methods described herein exhibit a synergistic effect. A synergistic effect exists wherever the action of a combination of active components is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount (or an effective amount of a synergistic composition or combination) is an amount that exhibits greater herbicidal activity than the sum of the herbicidal activities of the individual components.
As noted above, some of the multi component combinations and and methods described herein advantageously, exhibit an additive herbicidal effect, while exhibiting a reduced level of unwanted negative effects including damage to the crop of interest through lack of selectivity of individual components applied individually. An additive effect exists wherever the action of a combination of active components is roughly equal, or not less than the sum of the action of each of the components alone i.e. not antagonistic.
Therefore, the exact herbicidal doses of each component can be calculated for each of the proposed combinations by simply employing known equations based on the dose related positive activities of each individual component, which is inter alia available in the literature or by simple test, while simultaneously reducing the unwanted damage and pollution levels associated with each component, without the trial and error associated with applying synergistic combinations where unwanted effects e.g. damage to crops, are enhanced together with enhanced desired effects in an unpredictable fashion.
This issue is also true for the unwanted synergy of herbicidal pollutants. See, Toxicity of Herbicides: Impact on Aquatic and Soil Biota and Human Health, Maria Aparecida et. al. http://dx.doi.org/10.5772/55851 and, Moraes, D. S. L. Avaliação dos potenciais tóxicos, citotóxicos e genotóxicos de águas ambientais de Corumbá-M S em raízes de Allium cepa. 2000. 158 f. Tese (Mestrado em Genética e Melhoramento)—Universidade Estadual de Londrina, Londrina.
The efficacy (E) of each individual component in the specific crop environment is calculated as follows using Abbott's formula:
E=(1−A/B)·100
A corresponds to the herbicidal efficacy of the individual component in the treated crop environment in % and, B corresponds to the herbicidal efficacy in the untreated (control) environment achieved by applying the intended carrier composition in the absence of any active compounds (blank) in %.
An efficacy of 0 means that the level of unwanted vegetation in the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated crop environment have been maximally controlled.
As mentioned above in the embodiments where the combinations etc. display additive effects, the amount of each component can advantageously be simply calculated as follows using the so-called Colby equation as found an article entitled “Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p. 20-22. The action expected for a given combination of two active components can be calculated as follows:
in which E represents the expected percentage of herbicidal control for the combination of the two herbicides at defined doses (for example equal to x and y respectively), X is the percentage of herbicidal control observed by the a) component, compound (I) etc. at a defined dose (equal to x), Y is the percentage of herbicidal control observed by the co-herbicide or coherbicides component b) at a defined dose (equal to y).
In exemplary embodiments various commercially available compositions are applied in combination to post emergent weeds at rates and amounts which are below the generally recognized and recommended herbicidally effective rates or target rates, and amounts applied, to achieve control of unwanted, undesired or undesirable vegetation or weeds. Levels of control are comparable with individual solo applications in the absence of the other component, but at significantly higher doses.
In embodiments within the scope of this invention, the herbicidally effective amount of the multi component combination comprises from about 5% to about 95% of the herbicidally effective amount of each herbicide active ingredient of component (a) combined with from about 95% to about 5% of the herbicidal effective amount of each herbicide active ingredient of component (b) co-herbicide, when applied in the absence of any other herbicide active ingredient.
In embodiments within the scope of this invention the herbicidally effective amounts of the multi component combination comprise any of, not less than 5%; about 10%; about 15%; about 20%; about 25%: about 30% about 35% about 40%; about 45%: about 50%; about 55%; about 60% about 65%; about 70%: about 75%; about 80% about 85%; about 90% or less than 95% of each component (a) combined with any of, not less than 5%; about 10%; about 15%; about 20%; about 25%; about 30% about 35% about 40%; about 45%: about 50%; about 55%; about 60% about 65%; about 70%; about 75%; about 80% about 85%; about 90% or less than 95% of each component (b) co-herbicide. In further exemplary embodiments, the amounts in the multi component herbicide combination and the rates at which each individual active ingredient in each component in the combination application of the multi component herbicide combination as applied are each selected from, about 35%, about 50% or about 75%, of the generally recognized or recommended, herbicidally effective amounts or rates for each herbicidal active ingredient of each component of the multi component herbicide.
The present subject matter thus also relates to methods for the selective control of undesirable vegetation in crops which comprises applying a herbicidally effective amount of a two component combination of, as component a) a compound (1) or agriculturally acceptable ester or salt thereof in combination with, or is applied with, or in mixture with, (all included in the term in combination with), further herbicidal components b) to the unwanted vegetation or the locus thereof, wherein the herbicidally effective amount of each combination comprises less than the recommended application of each component individually.
Inventors have considered that useful embodiments that the herbicidally effective amount of the multi component combination is from about 5% to about 95% of each herbicide ingredient of component (a) with from about 95% to about 5% of each component (b) co-herbicide.
In typical embodiments, the herbicidally effective amount of the multi component combination comprises from about 35% to about 75% of each component (a) active ingredient, combined with from about 35% to about 75% of each component (b) co-herbicide.
In noted embodiments the undesired vegetation is any or all of Alopecurus myosuroides, Apera spica-venti, Avena fatua, Bromus sterilis, Lolium multiflorum, Tripleurospermum inodorum, Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica, Viola arvensis, Cyanus segetum, Lamium purpureum, Chenopodium album, Sinapis arvensis L.
In order to demonstrate with further clarity, if needed, embodiments include the following exemplary multi component herbicidal combination applications, using commercial preparations of each component, with reference to the recommended individual solo application rates, see Table 2 water volume rate is 200 L/ha.
In some other exemplary embodiments, various commercially available compositions are combined and applied to post emergent Matricaria camomilla with the following observations.
Combinations of individual commercial compositions of Halauxifen-methyl and Thiencarbazone-methyl give good control at all rates of use above Halauxifen-methyl 1.75 g A/ha and Thiencarbazone-methyl 1.75 g A/ha, that is, both active ingredients at greater than 35% of the recommended herbicidally effective dose (RHED), though no greater than about 75% of the same recommended dose, though perhaps not optimal at every point within that range.
Multi-component combinations of individual compositions of Halauxifen-methyl and Diflufenican give near complete control at a wide range of rates of use particularly above Halauxifen-methyl 1.75 g A/ha (35% RHED) and Diflufenican 43.8 g A/ha (35% RHED). Combinations of individual compositions of Halauxifen-methyl and Bifenox give near complete control at a wide range of rates of use, particularly above Halauxifen-methyl 1.75 g A/ha and Bifenox above 252 g A/ha (35% RHED).
Combinations of individual compositions of Halauxifen-methyl and Pyroxsulam/Cloquintocet-mexyl give near complete control at a wide range of rates of use particularly, above Halauxifen-methyl 1.75 g A/ha and Pyroxsulam, at or above 13.1 g A/ha.
It is worth noting that in a recent article, the proposed commercial rates of Pyroxsulam of 15 g A/ha and 18 g A/ha (114%-137% of the rate above), when applied to wheat to control Lolium multiflorum caused up to 10% visual injury in wheat. Pyroxsulam when applied at 21, 30, 36 and 42 g A/ha caused even greater than 10% injury in the wheat crop. See, Zobiole, L. H. S., et al. Pyroxsulam: Sulfonamide Herbicide for Weed Control in Wheat in Brazil. Planta Daninha, 36, e018155253. Epub Sep. 3, 2018. Available from http://www.scielo.br/scielo.php?script=sci_arttext&pid=S010083582018000100263&ln g=en &nrm=iso. https://dx.doi.org/10.1590/s0100-83582018360100064
Even if the crop might eventually recover, it can be clearly be seen that being able to reduce the applied dose by greater than 12% (Pyroxsulam 13.1 g A/ha), while managing to achieve adequate control of the unwanted vegetation but with less crop damage is a clear advantage.
In some exemplary embodiments, various commercially available compositions are combined and applied to post emergent Papaver rhoeas with the following observations.
Combinations of individual commercial compositions of Halauxifen-methyl and Thiencarbazone-methyl give near complete control at rates of use particularly Halauxifenmethyl 2.5 g A/ha and Thiencarbazone-methyl 2.5 g A/ha or above, and even at a lower rate of use of Halauxifen-methyl 1.75 g A/ha and Thiencarbazone-methyl 1.75 g A/ha, the multi component combinations achieve levels of control.
Combinations of individual compositions of Halauxifen-methyl and Diflufenican give near complete control at a wide range of rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Diflufenican 43.8 g A/ha. Combinations of individual compositions of Halauxifenmethyl and Bifenox give complete control at a wide range of rates of use, particularly above Halauxifen-methyl 1.75 g A/ha and Bifenox above 252 g A/ha and is one of the most rapid acting combination against this species. Combinations of individual compositions of Halauxifen-methyl and Pyroxsulam/Cloquintocet-mexyl give near complete control at a wide range of rates of use, particularly above Halauxifen-methyl 1.75 g A/ha and Pyroxsulam/Cloquintocet-mexyl, above 13.1 g A/ha.
In some other exemplary embodiments, various commercially available compositions are combined and applied to post emergent Matricaria camomilla with the following observations. Combinations of individual commercial compositions of Halauxifen-methyl and Thiencarbazone-methyl give good control at all rates of use above Halauxifen-methyl 1.75 g A/ha and Thiencarbazone-methyl 1.75 g A/ha, though perhaps not always optimal. Combinations of individual compositions of Halauxifen-methyl and Diflufenican give near complete control at a wide range of rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Diflufenican 43.8 g A/ha. Combinations of individual compositions of Halauxifenmethyl and Bifenox give near complete control at a wide range of rates of use, particularly above Halauxifen-methyl 1.75 g A/ha and Bifenox above 252 g A/ha.
Combinations of individual compositions of Halauxifen-methyl and Pyroxsulam/Cloquintocet-mexyl give near complete control at a wide range of rates of use particularly, above Halauxifen-methyl 1.75 g A/ha and Pyroxsulam/Cloquintocet-mexyl, above 13.1 g A/ha.
In further exemplary embodiments, various commercially available compositions are combined and applied to post emergent Stellaria media with the following observations. Combinations of individual commercial compositions of Halauxifen-methyl and Thiencarbazone-methyl give near complete control at all rates of use above Halauxifenmethyl
3.75 g A/ha and Thiencarbazone-methyl 3.75 g A/ha, and even at a lower rate of use of Halauxifen-methyl 1.75 g A/ha and Thiencarbazone-methyl 1.75 g A/ha, achieves levels of control though not optimal.
Combinations of individual compositions of Halauxifen-methyl and Diflufenican give near complete control at a wide range of rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Diflufenican 43.8 g A/ha.
Combinations of individual compositions of Halauxifen-methyl and Bifenox give near complete control at a wide range of rates of use, particularly above Halauxifen-methyl 1.75 g A/ha and Bifenox above 252 g A/ha.
Combinations of individual compositions of Halauxifen-methyl and Pyroxsulam/Cloquintocet-mexyl give near complete control at a wide range of rates of use particularly, above Halauxifen-methyl 1.75 g A/ha and Pyroxsulam/Cloquintocet-mexyl, above 13.1 g A/ha.
In still further exemplary embodiments, various commercially available compositions are combined and applied to post emergent Veronica persica with the following observations.
Combinations of individual commercial compositions of Halauxifen-methyl and Thiencarbazone-methyl give near complete control at all rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Thiencarbazone-methyl 1.75 g A/ha.
Combinations of individual compositions of Halauxifen-methyl and Diflufenican give near complete control at a wide range of rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Diflufenican 43.8 g A/ha.
Combinations of individual compositions of Halauxifen-methyl and Bifenox give near complete control at a wide range of rates of use, particularly above Halauxifen-methyl 1.75 g A/ha and Bifenox above 252 g A/ha. This combination is one of the most rapid acting combinations against this species.
Combinations of individual compositions of Halauxifen-methyl and Pyroxsulam/Cloquintocet-mexyl give near complete control at a wide range of rates of use particularly, above Halauxifen-methyl 1.75 g A/ha and Pyroxsulam/Cloquintocet-mexyl, above 13.1 g A/ha.
In a limited number of exemplary embodiments, various commercially available compositions are combined and applied to post emergent Cyanus segetum with the following observations.
Combinations of individual commercial compositions of Halauxifen-methyl and Thiencarbazone-methyl give good levels of control at rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Thiencarbazone-methyl 1.75 g A/ha though not always optimal.
Combinations of individual compositions of Halauxifen-methyl and Diflufenican give levels of control at a wide range of rates of use particularly above Halauxifen-methyl 1.75 g A/ha and Diflufenican 43.8 g A/ha though not always optimal.
Combinations of individual compositions of Halauxifen-methyl and Bifenox give near complete control at a wide range of rates of use, particularly above Halauxifen-methyl 3.75 g A/ha and Bifenox above 540 g A/ha although at rates of use above Halauxifen-methyl 1.75 g A/ha and Bifenox above 252 g A/ha show good levels of control though not always optimal.
Combinations of individual compositions of Halauxifen-methyl and Pyroxsulam/Cloquintocet-mexyl give good control at a wide range of rates of use particularly, above Halauxifen-methyl 1.75 g A/ha and Pyroxsulam/Cloquintocet-mexyl, above 13.1 g A/ha though not always optimal.
In some embodiments the undesired vegetation is Alopecurus myosuroides or L)iuum multiflorum and an effective multi component combination comprises Halauxifen-methyl as component a) combined with at least two different co-herbicides as component b) to give levels of control.
In certain embodiments the herbicides are provided in separate previously compounded compositions.
In certain embodiments each of the herbicides to be applied, are independently provided in separate, previously compounded compositions, each of which may be in the form of suspension concentrate which are understood to be stable suspensions of active ingredient(s) in water, intended for dilution with water before use.
In certain embodiments each of the herbicides to be applied, are independently provided in separate, previously compounded compositions, each of which may be in the form of water dispersible granules which are understood to be dry formulations comprising granules to be applied after disintegration and dispersion in water.
In certain embodiments each of the herbicidal active ingredients to be applied, are independently provided in separate, previously compounded compositions, each of which may be in the form a liquid, often in concentrated form to be diluted before application though possibly as ready to use liquids.
In certain embodiments each of the herbicidal active ingredients to be applied, are independently provided in separate, previously compounded compositions, each of which may be in the form of liquid oil dispersion which are understood to include stable suspensions of active ingredient(s) in water-immiscible fluid, which may contain other dissolved active ingredient(s), intended for dilution with water before use.
These and other forms of compounded herbicides useful to be used in combination and will become apparent to those skilled in the arts of formulating and compounding pesticide compositions.
In some embodiments, compositions provided herein further comprise at least one agriculturally acceptable adjuvant and/or carrier. Suitable adjuvants or carriers should not be phytotoxic to valuable crops, particularly at the concentrations employed in applying the compositions for selective weed control in the presence of crops and should not react chemically with herbicidal components or other composition ingredients. Such combinations can be designed for application directly to weeds or their locus or can be concentrates or formulations that are normally diluted with additional carriers and adjuvants before application. They can be solids, such as, for example, dusts, granules, water-dispersible granules, or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions. They can also be provided as a pre-mix or tank mixed.
Suitable agricultural adjuvants and carriers that are useful in preparing the herbicidal combinations of the invention are well known to those skilled in the art.
Liquid carriers that can be employed include water, 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, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers and the like. Water is typically the carrier of choice for the dilution of concentrates.
Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.
Other adjuvants commonly used in agricultural compositions include compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, sticking agents, dispersing agents, thickening agents, freezing point depressants, antimicrobial agents, and the like.
The compositions may also contain other compatible components, for example, other herbicides, plant growth regulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.
The concentration of the herbicidally active ingredients in the multi component compositions embodiments of the present invention is generally from 0.001 to 98 percent by weight when in a composition.
Suitable agricultural adjuvants and carriers include, but are not limited to, crop oil concentrate; nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C11 alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C2-C6) ethoxylate; di-seobutylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) ioleate-99; paraffinic oil, alkoxylated alcohol non-ionic surfactant; mineral oil, surfactant blend.
Liquid carriers that can be employed include water and 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. Specific 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, liquid fertilizers and the like. In certain embodiments, water is the carrier for the dilution of concentrates.
Suitable solid carriers include but are not limited to talc, pyro-phyllite clay, silica, attapulgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, cellulose, and the like.
In some embodiments, the compositions described herein further comprise one or more surface-active agents. In some embodiments, such surface-active agents are employed in both solid and liquid compositions, and in certain embodiments those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants which may also be used in the present formulations are described, inter alia, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corporation: Ridgewood, N J, 1998 and in Encyclopedia of Surfactants, Vol. I-III, Chemical Publishing Company: New York, 1980-81.
Surface-active agents include, but are not limited to salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-Cis ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene-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.
In some embodiments, these materials, such as vegetable or seed oils and their esters, can be used interchangeably as an agricultural adjuvant, as a liquid carrier or as a surface active agent.
Other exemplary additives for use in the compositions provided herein include but are not limited to compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, sticking agents, dispersing agents, thickening agents, freezing point depressants, antimicrobial agents, and the like. The compositions may also contain other compatible components, for example, other herbicides, plant growth regulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.
In some embodiments, the concentration of the active ingredients in the compositions described herein is from 0.0005 to 98 percent by weight. In some embodiments, the concentration is from 0.0006 to 90 percent by weight. In compositions designed to be employed as concentrates, the active ingredients, in certain embodiments, are present in a concentration from 0.1 to 98 weight percent, and in certain embodiments 0.5 to 90 weight percent. Such compositions are, in certain embodiments, diluted with an inert carrier, such as water, before application. The diluted compositions usually applied to weeds or the locus of weeds contain, in certain embodiments, 0.0006 to 15.0 weight percent active ingredient and in certain embodiments contain 0.01 to 7.0 weight percent.
The present combinations can be applied to weeds or their locus by the use of conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation water, and by other conventional means known to those skilled in the art. The following examples illustrate the practice of the present invention in some of its embodiments but should not be construed as limiting the scope of the invention. Other embodiments will be apparent to one skilled in the art from consideration of the specification and examples. It is intended that the specification, including the examples, is considered exemplary only, without limiting the scope and spirit of the invention. The details of each example is not meant to limit the general principle and should not be seen to limit the teaching to the specifics of that example. For example, a detail from one example can when appropriate be combined with an experimental detail from a different example and be within the contemplated scope of the invention.
The examples below are to be seen as general guidelines as to how to conduct experiments that may be carried out to determine the optimum combination of active and inactive components. Any reference to specific compounds or experimental value is for illustrative purposes including how to evaluate a characteristic and not to display actual results achieved unless specifically stated.
Evaluation of Postemergence Herbicidal Activity of Combinations—Glasshouse pot study against various Broad Leaf Weeds.
In each pot, plant 10 seeds of the specific weed (unless known low vigor, if so, then increase the number).The plants were grown in a greenhouse. The plants were employed for testing when they reached the stage as detailed in the tables below. Different combinations incorporating the herbicide halauxifen were applied post-emergence to pot sown Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica, Cyanus segetum, Alopecurus myosuroides, and Lolium multiflorum in a glasshouse screen. Details of the Crop BBCH Scale are detailed below as are the pest stages at each application.
Treatments included the following compounds and or preparations:
Target Pest Description
Papaver rhoeas
Matricaria
chamomilla
Stella ria media
Veronica persica
Viola arvensis
Cyanus segetum
Capsella
bursapastoris
Test Parameters
BBCH 37-39 (Flag Leaf Emerging) Assessment Even though Weeds were advanced at the application timing, Efficacy against Grass Leaf Weeds comparable if not better vs active reference. A noticeable benefit from combining the two actives in Alopecurus myosuroides & Apera spica-venti. A particular benefit was found against Lolium multiflorum.
In Grass Weeds application at BBCH 30-33 clear benefit in combining the two actives compared with solo applications and even better against active comparator in several cases with Lolium multiflorum and Alopecurus myosuroides. A clear dose response correlation.
Good efficacy, given the late stage of the Crop for ALOMY+LOLMU. A definite benefit can be seen from combining the two A.I.s. Dose response was seen with this combination. No phytotoxicity was observed.
Evaluation of Postemergence Herbicidal Activity of Halauxifen Combinations, postemergence Glasshouse pot study against various Grass Leaf Weeds & Broad Leaf Weeds
In each pot, plant 10 seeds of the specific weed (unless known low vigor, if so, then increase the number). The plants were grown in a greenhouse. The plants were employed for testing when they reached the stage as detailed in the tables below. Different combinations incorporating the herbicide halauxifen were applied postemergence to pot sown Alopecurus myosuroides, Lolium multifloru, Papaver rhoeas, Matricaria chamomilla, Stellaria media, Veronica persica and Cyanas segetum in a glasshouse screen. Details of the Crop BBCH Scale are detailed below.
Treatments included the following compounds and or preparations:
Target Pest Description
Alopecurus
myosuroides
Lolium
multiflorum
Papaver
rhoeas
Matricaria
chamomilla
Stellaria
media
Veronica
persica
Cyanus
segetum
Test Parameters
Test Parameters
The field experiments were conducted by tank mixing commercially available Arrow (Clethodim 120 g/1) and commercially available Heliantex (Halauxifen methyl 68.5 g/l) 5 trials were implemented on Sunflower in Ukraine in different locations (Dnipro, Kirovograd, Kiev, Mykolaiv).
Applications were made with a Knapsack sprayer fitted with flat fan nozzle for the application of herbicides.
Experiment design was in random blocks with three replications.
Species wise weed count recorded at around
8-15 DAA(Days After Application); 20-25 days: and 30-45 DAA
Weeds:
To enable examples of implementation and performance of the embodiments where component (b) comprises Propaquizafop in the inventive combinations, compositions and methods of the invention herein presented field and greenhouse trials.
Field Trials
The field experiments are conducted by tank mixing commercially available Agil™ (Propaquizafop 100 g/l) and commercially available Heliantex (Halauxifen-methyl 68.5 g/l) Around 5 trials are implemented on Sunflower crops in European countries.
Applications are made with a Knapsack sprayer fitted with flat fan nozzle for the application of herbicides. Experiment design is in random blocks with three replications.
In those trials Broad Leaf Weeds are targeted such as, Chenopodium album, Amaranthus retroflexus, Ambrosia artemisiifolia and grasses such as, Echinochloa crus-galli, Setaria viridis. Species wise weed count are recorded at around 8-15 DAA(Days After Application), 20-25 days and 30-45 DAA.
The protocols are exemplified by those shown. Rates of Agil™ and Heliantex® application could be altered without departing from the trials of embodiments but the framework of the protocols should be maintained.
Greenhouse Trials
The pot test experiments are conducted under greenhouses by tank mixing commercially available Agil™ (Propaquizafop 100 g/l) and commercially available Heliantex (Halauxifen methyl 68.5 g/1). There are 3-4 replicates of each treatment.
In those trials Broad leave weeds such as Chenopodium album, Amaranthus retroflexus, Ambrosia artemisiifolia and grasses such as Echinocloa crus-galli, Setaria viridis are targeted. Efficacy on weeds is assessed around 7, 14 and 21 days after application. In case of need, assessment are performed even later.
The protocol should be similar to this one showed in below table. Rates of Agil and Heliantex application could be altered without departing from the trials of embodiments but the framework of the protocols should be maintained.
The following numbered statements are part of the description disclosure:
| Number | Date | Country | Kind |
|---|---|---|---|
| 20203919.4 | Oct 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IL2021/051265 | 10/26/2021 | WO |
