BR112013010388B1 - Synergistic herbicide mixture and composition, and method for controlling undesirable vegetation - Google Patents

Abstract

Synergistic herbicidal composition, which contains fluroxipir and quinclorac. The present invention relates to a synergistic herbicidal mixture of defluroxipir and quinclorac which provides post-emergence weed control in rice, cereals and grains, pastures, natural pasture areas, ivm and peat.

Description

(54) Title: SYNERGIC HERBICIDES MIXTURE AND COMPOSITION, AND METHOD TO CONTROL UNDESIRABLE VEGETATION (51) lnt.CI .: A01N 43/40; A01N 43/42; A01P 13/00 (52) CPC: A01N 43/40, A01N 43/42 (73) Holder (s): DOW AGROSCIENCES LLC (72) Inventor (s): RICHARD MANN; ÁNDREA MCVEIGH-NELSON

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Descriptive Report of the Invention Patent for SYNERGIC HERBICIDES MIXTURE AND COMPOSITION, AND METHOD TO CONTROL UNDESIRABLE VEGETATION.

[001] The present invention refers to the protection of crops against weeds and other vegetation, which inhibits the growth of the crop, it is a problem constantly recurring in agriculture.

[002] To help combat this problem, researchers in the field of synthetic chemistry produce a wide variety of chemical agents and chemical formulations that are efficient in controlling this undesirable growth. Chemical herbicides of many types have been described in the literature and a large number are in commercial use.

[003] In some cases, herbicidal activity ingredients have been shown to be more efficient in combination than when applied individually and this is referred to as synergy ”. As described in the Herbicide Handbook of theWeed Science Society of America, eighth edition, 2002, p. 462 “synergy” [is] an interaction of two or more factors, so that the effect, when combined, is greater than the predicted effect based on the response to each factor applied separately ”. The present invention is based on the discovery that fluoroxypyr and quinclorac, already known individually for their herbicidal efficacy, exhibit a synergistic effect when applied in combination.

[004] The present invention relates to a synergistic herbicidal mixture, which comprises a herbicidally effective amount of (a) fluroxypyr and (b) quinclorac. The composition can also contain an agriculturally acceptable adjuvant and / or vehicle.

[005] The present invention also relates to herbicidal compositions and methods to control the growth of undesirable vegetation, particularly in monocot crops, which include rice, wheat, barley, oats, rye, sorghum, grains, corn, pastures, grasslands, areas of natural pasture, uncultivated land, peat, gesPetition 870170049479, of 7/14/2017, p. 4/25

2/13 of industrial vegetation (IVM - Industrial Vegetation Management) and aquatic areas and the use of these synergistic compositions.

[006] The spectrum of the quinclorac species is broad and highly complementary to that of fluroxypyr. For example, it has been surprisingly discovered that a combination of quinclorac and fluroxypyr has a synergistic action in the control of rice grass (Echinochloa crusgallr, ECHCG), Chinese grass (Leptochloa chinensis', LEFCH), and wetlands (Brachiaria platyphylla; BRAPP; ), application amounts equal to or less than the amounts of the individual compounds.

[007] Fluroxypyr is the common name for [(4-amino-3,5dichloro-6-fluor-2-pyridinyl) oxide] acetic acid. Its herbicidal activity is described in The Pesticide Manual, fifteenth edition, 2009. Fluroxipir controls a wide variety of economically important broadleaf weeds. It can be used as the acid itself or as an agriculturally acceptable salt or ester The use of an ester is preferred, with the meptyl ester being especially preferred.

[008] Quincolorac is the common name for 3,7-dichloro-8quinolin carboxylic acid. Its herbicidal activity is described in The Pesticide Manual, fifteenth edition, 2009. Quinclorac controls Echinochloaspp., Brachiaria spp., Digitaria spp. and many broadleaf weeds in rice and peat.

[009] The term herbicide is used at present to designate an active ingredient that kills, controls or otherwise adversely modifies the growth of plants. A herbicidally effective or vegetative-controlling amount is an amount of the active ingredient, which causes an adversely modifying effect and includes deviations from natural development, extinction, drying, delay and similar regulation. The terms plants and vegetation include germinating seeds, emerging seedlings, plants, which emerge from vegetative propagules, and established vegetation.

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3/13 [0010] Herbicidal activity is shown by the compounds of the synergistic mixture, when they are applied directly to the plant or plant site at any stage of growth or before planting or emergence. The observed effect depends on the plant species to be controlled, the plant's growth stage, the application dilution parameters and spray droplet size, the particle size of the solid components, the environmental conditions at the time of use, the compound specific used, the specific adjuvants and vehicles used, the type of soil and similar, as well as the amount of chemical agent applied. These and other factors can be adjusted, as is known in the art, to cause a non-selective or selective herbicidal action. In general, it is preferred to apply the composition of the present invention post-emergence, with the undesirable vegetation relatively immature, to obtain maximum control of weeds.

[0011] In the composition of this invention, the weight ratio of fluroxypyr, as measured in grams of acid equivalent per hectare (g ae / ha) to quinclorac, such stalk measured in grams of active ingredient per hectare (g ia / ha) , to which the herbicidal effect is synergistic, is between 1:11 and 22: 1.

[0012] The amount to which the synergistic composition is applied depends on the specific type of weed to be controlled, the degree of control required and the regulation and method of application. Quinclorac is applied between 26 g ai / ha and 560 g ai / ha, and fluroxypyr is applied between 50 g ae / ha and 560 g ae / ha.

[0013] The components of the synergistic mixture of the present invention can be applied either separately or as part of a multi-part herbicidal system, which can be obtained as a pre-mixture or tank mixture.

[0014] The synergistic mixture of the present invention can be applied

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4/13 in conjunction with one or more other herbicides, to control a wider variety of undesirable vegetation. When used in conjunction with other herbicides, the composition can be formulated with the other herbicide or herbicides, mixed in the tank with the other herbicide or herbicides, or applied sequentially with the other herbicide or herbicides. Some of the herbicides that can be used in conjunction with the synergistic composition of the present invention include 2,4-D, acetochlor, acifluorphene, aclonifen, AE0172747, alachlor, amidosulfurone, aminotriazole, ammonium thiocyanate, aniliphos, atrazine, AVH 301, azimsulfurone, benfuresate, bensulfuron-methyl, bentazone, bentiocarb, benzobicyclone, bifenox, bispyribac-sodium, bromacil, bromoxynil, butachlor, butafenacil, butralian, cafenstrol, carbetamide, carfentrazone-ethyl, chlorofluren, chlorofluoro, chlorofluoro, chlorofluoro cloransulam-methyl, cyclosulfamurone, cycloxydim, cihalofop-butyl, dicamba, diclobenil, diclorporp-P, dichlossulam, diflufenican, difufenzopyr, dimethenamide, dimethenamide-p, diquat, dietipir, diurone, EK2612, EPTC, esurf etbenzanide, F7967, fenoxaprop, phenoxapropethyl, phenoxasprolp-ethyl + isoxadifene-ethyl, fentrazamide, flazasulfurone, florassulam, fluazifop, fluazifop-P-butyl, flucedtosulfurone (LGC-42153), flufenacet, flufenpirethyl, fluemtsulam, flumichloracpentyl, flumioxazin, flujometurone, flupirsulfurone, fomesafen, foramsulfurone, fumichlorac, glufosinate, glifosoxide, halifosulfate, glifosinate-halo , imazamox, imazapic, imazapyr, imazaquin, imazetapyr, imazosulfurone, indanofan, indaziflam, iodosulfurone, ioxynil, ipfencarbonzone (HOK-201), IR 5790, isoproturone, isoxabene, isoxaflutol, is MCAP, amofur, PA, KUH071 mecolprop-P, mefenato, mesosulfurone, mesoltrione, metamifop, metazosulfurona (NC-620), metolachlor, metosulamo, metribuzina, metsulfurona, moPetição 870170049479, of 07/14/2017, p. 7/25

5/13 linate, MSMA, napropamide, nicosulfurone, norflurazone, OK-9701, orthosulfamurone, oryzine, oxadiargyl, oxadiazone, oxaziclomefone, oxifluorfen, paraquat, pendimethalin, pentoxsulfan, pentoxazone, poxamoxy, poxamoxy, poxamoxy, petoxamide, petoxamide, petoxamide , propachlor, propanyl, propyrisulfurone (TH-547), propizamide, prosulfocarb, prosulfuron, pyraclonil, pyrazogyl, pyrazosulfurone, pyribenoxime (LGC-40863), pyriftalide, pyriminobac-methyl, pyrimisulfan (KUH-021), pyroxsulfone 485), quizalofop-ethyl-D, S-3252, setoxidime, simazine, SL-0401, SL-0402, Smetolachlor, sulcotrione, sulfentrazone, sulfosate, tebutiurone, terfluryltrione (AVH-301), terbacil thiazopyr, triclin, triclin, triclin, tiobencir. and tritosulfurone.

[0015] The synergistic composition of the present invention can also be used in conjunction with glyphosate, glufosinate, dicamba, imidazolinones, sulfonylureas or 2,4-D in glyphosate-tolerant, glufonate-tolerant, dicamba-tolerant, imidazolinone-tolerant cultures sulfonylurea and 2,4-D tolerant. In general, it is preferred to use the synergistic composition of the present invention in combination with herbicides that are selective for the crop being treated and that complement the weed spectrum controlled by these compounds in the amount of application used. It is still preferred, in general, to apply the synergistic composition of the present invention and other complementary herbicides at the same time, either as a combination formulation or as a tank mixture.

[0016] The synergistic composition of the present invention can be used, in general, in combination with known herbicide antidotes, such as benoxacor, bentiocarb, brassinolid, cloquintocet (mexicano), ciometrinil, daimuron, dichlormide, dicyclone, dimepiperate, disulfotone, fenclorazol -ethyl, fenclorima, flurazole, fluxofenima, flurilazole, harpina proteins, isoxadifeno-ethyl, mefenpir-diethyl,

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MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinyl, R29148 and N-phenyl sulfonyl benzoic acid amides, to increase their selectivity. Cloquintocet (Mexican) is a particularly preferred antidote for the synergistic compositions of the present invention, specifically antagonizing any harmful effect of synergistic compositions on rice and cereals.

[0017] In practice, it is preferable to use the synergistic composition of the present invention in mixtures, which contain a herbicidally effective amount of the herbicidal components, together with an agriculturally acceptable adjuvant or vehicle. Suitable adjuvants or vehicles should not be phytotoxic to valuable crops, particularly at the concentrations used in the application of compositions for selective weed control in the presence of crops and should not react chemically with herbicidal components or other ingredients in the composition. These mixtures can be intended for application directly to weeds or their locations, or they can be concentrated or formulated, which are usually diluted with additional vehicles and adjuvants, before application. They can be solids, such as, for example, powders, granules, water-dispersible granules, or wetting powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions.

[0018] Agriculturally suitable adjuvants and vehicles, which are useful in the preparation of the herbicidal mixtures of the invention, are well known to those skilled in the art. Some of these adjuvants include, but are not limited to, oil concentrate for culture (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkylimethyl quaternary ammonium salt; mixture of petroleum hydrocarbon, alkyl esters, organic acid and anionic antidote; Cg-Cn-alkylpolyglycoside; phosphate alcohol ethoxylate; natural primary alcohol ethoxylate (Ci ₂ -Ci ₆ ); EOPetition block copolymer 870170049479, of 7/14/2017, p. 9/25

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Di-sec-butylphenol PO; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil, tridecyl alcohol ethoxylate (synthetic) (8 EO); tallow amine ethoxylate (15 EO); dioleate-99 of PEG (400).

[0019] Liquid vehicles, which may be used, include water, toluene, xylene, petroleum naphtha, culture oil, acedone, methyl ethyl ketone, cyclohexanone, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, N-methyl-2-pyrolidinone, N, N-dimethyl alkylamides, dimethylsulfoxide, liquid fertilizers and the like. Water is, in general, the vehicle selected for the dilution of concentrates.

[0020] Suitable solid vehicles include talc, pyrophilitic clay, silica, atapu guita clay, kaolin clay, fossil flour, chalk, diatomaceous earth, lime, calcium carbonate9, bentonite clay, floor tile, cotton seed husks , wheat flour, soy flour, pumice stone, wood flour, nutshell flour, similar lignin.

[0021] It is usually desirable to incorporate one or more surfactants in the compositions of the present invention. These surfactants are advantageously used in solid and liquid compositions, especially those intended to be diluted with a vehicle before application. Surfactants can be anionic, cationic or non-ionic in character and can be used as emulsifying agents, wetting agents, suspending agents or for other purposes. Surfactants used conventionally in the formulation technique and which can also be used in the present formulations are described, among others, in “McCutcheon’s Detergents and Emulsifiers Annual”, MC Publishing Corp. Ridgewood, New Jersey, 1998 and in “Encyclopedia of Surfactants”, Vol. I-III, Chemical PublisPetição 870170049479, of 7/14/2017, p. 10/25

8/13 hing Co., New York, 1980-81. Typical agent surfactants include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkyl sulfonate salts, such as calcium dodecylbenzenesulfonate, alkylphenol-alkylene oxide addition products, such as non-phenyl-C ₈ ethoxylate; addition products of alkylene oxide alcohol such as tridecyl alcohol ethoxylate _Ci-6; soaps, such as sodium stearate, sulfonate-alkylnaphthalene salts, such as sodium dibtyl-naphthalenesulfonate, 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 dialkylphosphate esters; vegetable oils, such as soybean oil; rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, flax seed oil, palm oil, peanut oil, saffron, sesame oil, tung oil and the like; and esters from the above vegetable oils.

[0022] Other additives commonly used in agricultural compositions include compatibilizing agents, antifoaming agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, diffusion agents, penetration aids, tacking agents, dispersing agents , thickening agents, freezing point depressants, antimicrobial agents and the like. The compositions can also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, insecticides and the like, and can be formulated with liquid fertilizers or solid particulate fertilizer vehicles, such as ammonium nitrate, urea and the like.

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9/13 [0023] The concentration of active ingredients in the synergistic composition of the present invention is, in general, from 0.001 to 98% by weight. Concentrations of 0.01 to 90 weight percent are used frequently. In compositions intended to be used as concentrates, the dative ingredients are generally present in a concentration of 1 to 98 weight percent, preferably 5 to 90 weight percent. Such compositions are typically diluted with an inert carrier, such as water, before application, or applied as a dry or liquid formulation, directly to flooded rice fields. The diluted compositions, usually applied to weeds or the weed site, generally contain 0.0001 to 10 weight percent of active ingredient and preferably contain 0.001 to 5.0 weight percent.

[0024] The present compositions can be applied on weeds or their places by the use of conventional soil or aerial sprinklers, sprayed and granulate applicators, by addition to irrigation water or rice paddies, and by other means known to those skilled in the art. in the technique.

[0025] The examples below illustrate the present invention.

Evaluation of Herbicidal Post-Emergence Mixtures in the Greenhouse [0026] Seeds of the desired test plant species were planted in a planting mixture of 80% mineral soil / 20% sand, which typically has a pH of 7 , 2 and a 2.9 percent organic matter content, in plastic pots, with a surface area of 128 square centimeters (128 cm ² ). The growth medium was sterilized with steam. The plants were grown for 7-19 days in a greenhouse, with a light period of approximately 14 hours (h), which was maintained at 29 ° during the day and 26 ° during the night. Nutrients and water were added on a regular basis and supplemental lighting. Petition 870170049479, of 7/14/2017, p. 12/25

10/13 tar was made available with metal halogen lamps of 1000 Watts higher, as needed. The plants were treated with post-emergence leaf applications, when they reached the stage from the third to the fourth true leaf. All treatments were applied using a randomized complete block test model, with 4 reapplications per treatment.

Evaluation of Herbicidal Post-Emergence Mixtures in the Greenhouse [0027] The treatments consisted of the compounds, as listed in Table 1, for each compound applied alone or in combination. Formulated amounts of quinclorac methyl ether and fluroxypyr were placed in 60 milliliter (ml) glass flasks and dissolved in a 60 ml volume of an aqueous solution containing Agri-dex culture oil concentrate, in a ratio of 1% volume by volume (v / v). The requirements of the compounds are based on an application volume of 12 ml, at an amount of 187 liters per hectare (L / ha). Spray solutions of the mixtures were prepared by adding the reserved solutions to the appropriate amount of dilution solution to form 12 ml of a spray solution with active ingredients in simple combinations in two ways. The formulated compounds were applied to the plant material with an upper Mandei trail sprayer, equipped with 8002E nozzles calibrated to distribute 187 l / ha, at a spray height of 43 centimeters (cm) (18 inches) above the plant cover average.

[0028] The treated plants and the control plants were placed in a greenhouse, as described above and watered by sub-irrigation, to avoid washing the test compounds. The treatments were evaluated 21 days after application (D), in comparison with untreated control plants. Visual control of daniPetição herbs 870170049479, of 7/14/2017, p. 13/25

11/13 nhas was noted on a scale of 0 to 100 percent, with 0 corresponding to no damage and 100 corresponding to complete eradication.

[0029] Table 1 demonstrates the synergistic herbicidal efficiency of mixtures in the quinclorac + fluroxypyr-meptila tank in weed control. All test results, both for the product alone and for mixtures, are an average of 4 repetitions, evaluated 21 days after application, and the interactions of the mixture in the tank are significant at the level of P> 0.05.

[0030] Colby's equation was used to determine the expected herbicidal effects of the mixtures (Colby, S.R. Calculation of the synergistic and antagonistic response of herbicide combinations. L / l / eecfe 1967. 15, 20-22).

[0031] The following equation was used to calculate the expected activity of the mixture, which contains two active ingredients, A and B:

Expected = A + B - (A x B / 100)

A = observed efficiency of active ingredient A, at the same concentration as used in the mixture.

B = observed efficiency of active ingredient B, at the same concentration as used in the mixture.

[0032] The tested compounds, application amounts used, plant species tested and results are shown in Table

1. Quantities of quinclorac are expressed in grams of active ingredient / hectare (g ia / ha) and quantities of fluxoxypyr are expressed in grams of acid equivalent per hectare (g ae / ha) in Table 1.

Table 1. Synergistic activity of quinclorac + fluroxypyr-meptila herbicidal compositions on grass weeds, rice grass (Echinochloa crusgallr, ECHCG), Chinese sprangletop (Leptochloa chinensis ·, LEFCH), and wet swamp (Brachiaria platyphylla);

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12/13 in the greenhouse, at 21 DAA.

% of control Application quantity ECHCG BRAPP LEFCH Fluroxypyr-meptila (g Quinclorac (g ia / ha) ae / ha) Ob Ex Ob Ex Ob Ex 26 0 5 - - - 5 - 0 50 0 - - - 6 - 26 50 30 5 - - 20 10 26 0 - - - - - - 0 100 - - - - - - 26 100 - - - - - - 26 0 5 - 5 - 5 - 0 200 6 - 5 - 41 - 26 200 35 11 30 9 86 44 53 0 6 - - - 10 - 0 50 0 - - - 6 - 53 50 46 6 - - 43 15 53 0 6 - - - - - 0 100 11 - - - - - 53 100 27 15 - - - - 53 0 6 - 6 - - - 0 200 6 - 5 - - - 53 200 65 11 48 10 - - 110 0 31 - 5 - 15 - 0 50 0 - 5 - 6 - 110 50 85 31 25 10 35 20 110 0 31 - 5 - 15 - 0 100 11 - 1 - 50 - 110 100 81 38 51 6 62 57 110 0 31 - 5 - 15 - 0 200 6 - 5 - 42 - 110 200 91 35 31 9 56 50 220 0 65 - - - 11 - 0 50 0 - - - 50 - 220 50 90 65 - - 60 55 220 0 65 - 26 - - - 0 100 11 - 1 - - - 220 100 86 68 41 27 - -

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% of control Application quantity ECHCG BRAPP LEFCH Quinclorac (g ia / ha) Fluroxypyr-meptila (g ae / ha) Ob Ex Ob Ex Ob Ex 220 0 65 - 26 - - - 0 200 6 - 5 - - - 220 200 75 67 49 30 - -

BRAPP = Brachiaria platyphylla; bathed papua

ECHCG = Echinochloa crus-galli; rice grass

LEFCH = Leptochloa chinensis', Chinese grass

Ob = observed value (% of control)

Ex = expected value, calculated using Colby Analysis (% of contra le)

DAA = days after application g ia / ha = grams of active ingredient per hectare g ae / ha = grams of acid equivalent per hectare

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Claims (10)

1. Synergistic herbicidal mixture, characterized by the fact that it comprises a herbicidally effective amount of: (a) fluroxypyr, or an agriculturally acceptable salt or ester thereof, and (b) quinclorac, or an agriculturally acceptable salt or ester thereof. 2. Mixture according to claim 1, characterized by the fact that fluroxypyr, or an agriculturally acceptable salt or ester thereof, is the meptyl ester. Mixture according to claim 1, characterized in that the weight ratio of fluroxypyr in g a to quinclorac in g is between 1:11 and 22: 1. 4. Herbicidal composition, characterized in that it comprises a herbicidally effective amount of a herbicidal mixture, as defined in any one of claims 1 to 3, and an agriculturally acceptable adjuvant and / or vehicle. 5. Method for controlling undesirable vegetation, characterized by the fact that it comprises contacting the vegetation or its location, or applying a herbicidally effective amount of the herbicidal mixture, as defined in any one of claims 1 to 3, to avoid the emergence or growth of vegetation. 6. Method, according to claim 5, characterized by the fact that undesirable vegetation is controlled in rice, cereals and grains, pastures, natural pasture areas, industrial vegetation management (IVM) or peat. Method according to claim 5, characterized in that the weight ratio of fluroxypyr in g a to quinclorac in g is between 1:11 and 22: 1. Petition 870170076163, of 10/06/2017, p. 4/8 2/2 8. Method, according to claim 5, characterized by the fact that: quinclorac, or an agriculturally acceptable salt or ester thereof, is applied at a rate between 26 g ai / ha and 560 g ai / ha, and fluroxypyr, or an agriculturally acceptable salt or ester thereof, is applied at a rate between 50 g ae / ha and 560 g ae / ha. 9. Method, according to claim 5, characterized by the fact that the unwanted vegetation is rice grass (Echinochloa crusgallr, ECHCG), Chinese grass (Leptochloa chinensis', LEFCH), and swamp wood (Brachiaria platyphylla ·, BRAPP) . 10. Method according to claim 5, characterized by the fact that the synergistic mixture is applied post-emergence. Petition 870170076163, of 10/06/2017, p. 5/8