OA16933A - Synergistic herbicidal composition containing fluroxypyr and glyphosate - Google Patents

Abstract

A herbicidal composition comprising a herbicidally effective amount of fluroxypyr, or salt or ester thereof, and glyphosate, or salt or ester thereof. Also included are methods of treating undesirable vegetation comprising contacting the vegetation, locus of the vegetation, soil, or water a herbicidally effective amount of the herbicidal composition.

Description

This disclosure concems a synergistic herbiddal composition containing (a) fluroxypyr and (b) glyphosate for controlling the growth of undesirable végétation, e.g., in 10 orchards, range and pasture, industrial végétation management (IVM), rights-of-way and in any glyphosate-tolerant crop, such as glyphosate-tolerant com, glyphosate-tolérant cereal crops (including but not exclusive to wheat, barley, rice, sorghum, triticale, oats and rye), glyphosate-tolerant broadleaf crops, and any fluroxypyr-tolerant crop. These compositions are disclosed as providing, among other things, improved post-emergence herbicidal weed 15 control.

Background

The protection of crops from weeds and other végétation which inhibit crop growth is a constantly recurring problem in agriculture. To help combat this problem, researchers in the field of synthetic chemistry hâve produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted growth. Chemical herbicides of many types hâve been disclosed in the literature and a large number are in commercial use.

In some cases, herbicidal active ingrédients hâve been shown to be more effective in combination than when applied individually and this is referred to as “synergism.” As 25 described in the Herbicide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429 “‘synergism’ [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based, in part, on the response to each factor applied separately.” The présent disclosure is based on the dîscovery that fluroxypyr and glyphosate, already known individually for their herbicidal efficacy, display a 30 synergistic effect when applied in combination.

Summarv

The présent disclosure concerna a synergistic herbicidal mixture comprising and methods of controlling végétation utilizing an herbicîdally effective amount of (a) fluroxypyr and (b) glyphosate. The compositions may also contain an agriculturally acceptable adjuvant and/or carrier.

The présent disclosure also concerna herbicidal compoaitiona for and méthode of controlling the growth of undesirable végétation, e.g., in orchards, range and pasture, industrial végétation management (IVM), rights-of-way and in any glyphosate-tolerant crop, such as glyphosate-tolerant corn, glyphosate-tolerant cereals (including but not exclusive to wheat, barley, rice, oats and rye), glyphosate-tolerant broadleaf crops, fluroxypyr-tolerant crops.

Detailed Description

Provided herein are compositions comprising a herbicîdally effective amount of (a) fluroxypyr or an ester or sait thereof and (b) glyphosate or an ester or sait thereof.

Provided herein are also methods for controlling undesirable végétation comprising contacting the végétation, locus of the végétation, soil, or water a herbicîdally effective amount of (a) fluroxypyr or an ester or sait thereof and (b) glyphosate or an ester or sait thereof

Fluroxypyr is the common name for 2-[(4-amino-3,5-dichloro-6-fluoro-2pyridinyl)oxy]acetic acid. Its herbicidal activity is described in The Pesticide Manual, Fifteenth Edition, 2009. Fluroxypyr controls a range of economically important broadleaf weeds in small grain crops. Exemplary forms of fluroxypyr include, e.g., fluroxypyr-meptyl. The structure of fluroxypyr is:

OH

Cl

NH₂

Glyphosate, //-(phosphonomethyl)glycine is an EPSP synthase inhibitor. Its herbicidal activity is described in The Pesticide Mamtal, Fifteenth Edition, 2009. Glyphosate provides non-selective post-emergence weed control. Exemplary forms of glyphosate include e.g., glyphosate-îsopropylammonium. The structure ofglyphosate is:

O O

The term herbicide is used herein to mean an active ingrédient that kills, controls or otherwise adversely modifies the growth of plants. A herbicidally effective or vegetationcontrolling amount is an amount of active ingrédient which causes an adversely modifying effect, including déviations from natural development, kîlling, régulation, desiccation, retardation, and the like. Methods of application include, but are not Iimited to applications to the végétation or locus thereof, i.e., application to the area adjacent to the végétation, as well as preemergence, postemergence, foliar, bumdown and in-water applications.

The terms plants and végétation include germinant seeds, emerging seedlings, plants emerging from végétative propagules, and established végétation.

Herbicidal activity is exhibited by the compounds when they are applied directly to the plant or to the locus of the plant at any stage of growth. The effect observed dépends . 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 spécifie compound employed, the spécifie 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 non-selective or sélective herbicidal action. In some embodiments, the compositions provided herein are applied postemergence to relatively immature undesirable végétation to achieve the maximum control of weeds.

The compositions and methods described herein be used to control undesirable végétation in glyphosate-tolerant-, gjufosinate-tolerant-, dicamba-tolerant-, phenoxy auxintolerant-, pyridyloxy auxin-tolerant-, aryloxyphenoxypropionate-tolerant-, acetyl CoA carboxylase (ACCase) inhibitor-tolerant-, imidazolinone-tolerant-, acetolactate synthase (ALS) inhibitor-tolerant-, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor -tolerant, protoporphyrinogen oxîdase (PPO) inhibitor -tolérant-, triazine-tolerant-, bromoxynil16933 tolérant- crops (such as, but not limited to, soybean, cotton, canola/oilseed râpe, rice, cereals, com, turf, etc), for example, in conjunction with glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil. The compositions and methods may be used in controlling undesirable végétation in crops possessing multiple or stacked traits conferring tolérance to multiple chemistries and/or inhibitors of multiple modes of action. In some embodiments, compositions and methods further employ additîonal herbicides that are sélective for the crop being treated and which complément the spectrum of weeds controlled by these compounds at the application rate employed. In some embodiments, the fluroxypyr and glyphosate and other complementary herbicides are applied at the same time, either as a combination formulation or as a tank mix.

The compositions and methods provided herein are utilized to control «indésirable végétation. Undesirable végétation includes, but is not limited to, undesirable végétation that occurs in cereals, rice, range and pasture, row crops (e.g., com, soybean, cotton, canola), turf, trees, vines, and omamental species, aquatic or non-crop settings, (e.g., rights-of-way, industrial végétation management).

In some embodiments, the compositions and methods provided herein are utilized to control undesirable végétation in cereals. In certain embodiments, the undesirable végétation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Apera spica-venti (L.) Beauv.

(windgrass, APESV), Avenafatua L. (wild oat, AVEFA), Bromus tectorum L. (downy brome, BROTE), Lolium multiflorum Lam. (Italien ryegrass, LOLMU), Phalaris minor Retz, (littleseed canarygrass, PHAMI), Poa annua L. (annual bluegrass, POANN), Setaria purnila (Poir.) Roemer & J.A. Schultes (yellow foxtail, SETLU), Setaria viridis (L.) Beauv. (green foxtail, SETVI), Cirsium arvense (L.) Scop. (Canada thistle, CI RA R/ Galium aparine L.

(catchweed bedstraw, GALAP), Kochia scoparia (L.) Schrad. (kochia, KCHSC), Lamium purpureum L. (purple deadnettle, LAMPU), Matricaria recutita L. (wild chamomile, MATCH), Matricaria matricarioides (Less.) Porter (pineappleweed, MATMT), Papaver rhoeas L. (common poppy, PAPRH), Polygonum convolvulus L. (wild buckwheat, POLCO), Salsola tragus L. (Russian thistle, SASKR), Stellaria media (L) Vill. (common chickweed,

STEME), Veronicapersica Poir. (Persian speedwell, VERPE), Viola arvensis Murr. (field violet, VIOAR), or Viola tricolor L. (wild violet, VIOTR).

In some embodiments, the compositions and methods provided herein are utilized to control undesirable végétation in range and pasture. In certain embodiments, the undesirable végétation is Ambrosia artemisiifolia L. (common ragweed, AMBEL), Cassia obtusifolia (sickle pod, CASOB), Centaurea maculosa auct. non Lam. (spotted knapweed, CENMA), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), Convolvulus arvensis L. (field bindweed, CONAR), Euphorbia esula L. (leafy spurge, EPHES), Lactuca serriola L/Tom.

(prickly lettuce, LACSE), Plantago lanceolata L. (buckhom plantain, PLALA), Rumex obtusifolius L. (broadleaf dock, RUMOB), Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild mustard, SINAR), Sonchus arvensis L. (perennial sowthistle, SONAR), Solidago species (goldenrod, SOOSS), Taraxacum officinale G.H. Weber ex Wiggers (dandelion, TAROF), Trifolium repens L. (white clover, TRFRE), or Urlica dioica L.

(common nettle, URTDI).

In some embodiments, the compositions and methods provided herein are utilized to control undesirable végétation found in row crops. In certain embodiments, the undesirable végétation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Avena fatua L. (wild oat, AVEFA), Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria 15 sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa crus-gaili (L.) P. Beauv.

(bamyardgrass, ECHCG), Echinochloa colonum (L.) Link (junglerice, ECHCO), Lolium multiftorum Lam. (Italian ryegrass, LOLMU), Panicum dichotomiflorum Michx. (fall panicum, PANDI), Panicum miliaceum L. (wild-proso millet, PANMI), Setariafaberi Henni, (giant foxtail, SETFA), Setaria viridis (L.) Beauv. (green foxtail, SETVI), Sorghum halepense (L.) Pers. (Johnsongrass, SORHA), Sorghum bicolor (L.) Moench ssp.

Arundinaceum (shattercane, SORVU), Cyperus esculentus L. (yellow nutsedge, CYPES), Cyperus rotundus L. (purple nutsedge, CYPRO), Abutilon theophrasti Medik. (velvetleaf, ABUTH), Amaranthus species (pigweeds and amaranths, AMASS), Ambrosia artemisiifolia L. (common ragweed, AMBEL), Ambrosia psilostachya DC. (western ragweed, AMBPS), 25 Ambrosia trifida L. (giant ragweed, AMBTR), Asclépios syriaca L. (common milkweed, ASCSY), Chenopodium album L. (common lambsquarters, CHEAL), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), Commelina benghalensis L. (tropical spiderwort, COMBE), Datura stramonium L. (jimsonweed, DATST), Daucus carota L. (wild canot, DAUCA), Euphorbia heterophylla L. (wild poinsettia, EPHHL), Erigeron bonariensis L. (hairy fleabane, ERIBO), Erigeron canadensis L. (Canadian fleabane, ERICA), Helianthus annuus L. (common sunflower, HELAN), Jacquemontia tamnifolia (L.) Griseb. (smallflower momingglory, IAQTA), Ipomoea hederacea (L.) Jacq. (ivyleaf momingglory, IPOHE), Ipomoea lacunosa L. (white momingglory, IPOLA), Lactuca serriola L./Tom. (prickly lettuce, LACSE), Portulaca oleracea L. (common purslane, POROL), Sida spinosa L.

(prickly sida, SIDSP), Sinapis arvensis L. (wild mustard, SINAR), Solarium ptychanthum Dunal (eastem black nightshade, SOLPT), or Xanthium strumarium L. (common cocklebur, XANST).

In some embodiments, the compositions and methods provided herein are utilized to control undesirable végétation in rice. In certain embodiments, the undesirable végétation is Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop. (large crabgrass, D1GSA), Echinochloa crus-galli (L.) P. Beauv. (bamyardgrass, ECHCG), Echinochloa colonum (L.) LINK (junglerice, ECHCO), Echinochloa oryzoides (Ard.) Fritsch (early watergrass, ECHOR), Echinochloa oryzicola (Vasinger) Vasînger (late watergrass, ECHPH), Ischaemum rugosum Salisb. (saramollagrass, ISCRU), Leptochloa chinensis (L.) Nees (Chinese sprangletop, LEFCH), Leptochloa fascicularis (Lam.) Gray (bearded sprangletop, LEFFA), Leptochloapantcoides (Presl.) Hitchc. (Amazon sprangletop, LEFPA), Panicum dichotomiflorum (L.) Michx. (fall panîcum, PANDI), Paspalum dilatatum Poir. (dallisgrass, PASD1), Cyperus difformis L. (smatlflower flatsedge, CYPDI), Cyperus esculentus L. (yellow nutsedge, CYPES), Cyperus iria L. (rice flatsedge, CYPIR), Cyperus rotundus L. (purple nutsedge, CYPRO), Eleocharis species (ELOSS), Fimbristylis miliacea (L.) Vahl (globe fringerush, FIMMI), Schoenoplectus Juncoides Roxb. (Japanese bulrush, SPCJU), Schoenoplectus maritimus L. (sea clubrush, SCPMA), Schoenoplectus mucronatus L. (ricefield bulrush, SCPMU), Aeschynomene species, (jointvetch, AESSS), Altemanthera philoxeroides (Mart.) Griseb. (alligatorweed, ALRPH), Alisma plantago-aquatica L. (common waterplantain, ALSPA), Amaranthus species, (pigweeds and amaranths, AMASS), Ammannia coccinea Rottb. (redstem, AMMCO), Eclipta alba (L.) Hassk. (American false daisy, ECLAL), Heteranthera limosa (SW.) Willd./Vahl (ducksalad, HETLI), Heteranthera reniformis R. & P. (roundleaf mudplantain, HETRE), Ipomoea hederacea (L.) Jacq. (ivyleaf momingglory, IPOHE), Lindemia dubia (L.) Pennell (low false pimpemel, LIDDU), Monochoria korsakowil Regel & Maack (monochoria, MOOKA), Monochoria vaglnalis (Burin. F.) C. Presl ex Kuhth, (monochoria, MOOVA), Murdannia nudiflora (L) Brenan (doveweed, MUDNU), Polygonum pensylvanicum L., (Pennsylvania smartweed, POLPY), Polygonum persicaria L. (ladysthumb, POLPE), Polygonum hydropiperoides Michx. (POLHP, mild smartweed), Rotala indica (Willd.) Koehne (Indian toothcup, ROTIN), Sagittaria species, (arrowhead, SAGSS), Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill (hemp sesbania, SEBEX), or Sphenoclea zeylanica Gaertn. (gooseweed, SPDZE).

In some embodiments, the compositions and methods are utilized to control végétation selected from the following généra: anagallis, axonopus, cirsium, calopogonium, commelina, convolvus, conyza, kochio, malva, mikania, ottochloa nodosa, pspalum polygonum, or urtica. In some embodiments, a the compositions and methods are utilized to control scarlet pimpemel (Anagallis arvensis L., ANGAR), tropical caipetgrass (Axonopus compressas, AXOCO), Canada thistle (Cirsium arvense (L.) Scop., CIRAR), caïopo (Calopogonium mucunoides, CLOMU), Bengal dayflower (Commelina benghalensis L., COMBE), field bindweed (Convolvus arvensis L., CONAR), horseweed (Conyza canadensis (L.) Cronq., ERICA), kochia (Kochia scoparia (L.) Schrad., KCHSC), common mallow (Malva neglecta Wallr., MALNE), African mile-a-mînute (Mikania cordata (Burm. f.) B.L., MIKCO), slender panicgrass (Ottochloa nodosa, OTTNO), paspalum (Paspalum conjugatum Bergius, PASCO), wild buckwheat (Polygonum convolvulus L., POLCO) and stinging nettle (Urtica dioica L., URTDT) at application rates equal to or lower than the rates of the individual compounds.

The compounds or agriculturally acceptable sait or ester thereof may be used to control herbicide résistant or tolérant weeds. The methods employing the combination of fluroxypyr and glyphosate, or agriculturally acceptable sait or ester thereof, and the compositions described herein may also be employed to control herbicide résistant or tolérant weeds. Exemplary résistant or tolérant weeds include, but are not limited to, biotypes résistant or tolérant to acetolactate synthase (ALS) inhibitors, photosystem II inhibitors, acetyl CoA carboxylase (ACCase) inhibitors, synthetic auxins, photosystem I inhibitors, 5enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, microtubule assembly inhibitors, lipid synthesis inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, carotenoid biosynthesis inhibitors, very long chain fatty acid (VLCFA) inhibitors, phytoene desaturase (PDS) inhibitors, glutamine synthetase inhibitors, 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple modes-of-actîon such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals. Exemplary résistant or tolérant weeds include, but are not limited to, biotypes with résistance or tolérance to multiple herbicides, multiple chemical classes, and multiple herbicide modes-of-action.

In certain embodiments of the compositions and methods described herein, the weight ratio of glyphosate to fluroxypyr at which the herbicidal effect is synergistic lies within the range from about 1:2 to about 70:1, preferably from about 1:1 to about 40:1. The rate at which the synergistic composition is applied will dépend upon the particular type of weed to be controlled, the degree of control required, and the timing and method of application. In certain embodiments, the compositions described herein can be applied at an application rate from about 330 grams of acid équivalent per hectare (gae/ha) to about 3920 gae/ha based on the total amount of active ingrédients in the composition. In certain embodiments, fluroxypyr is applied at a rate from about 50 gae/ha to about 560 gae/ha and glyphosate is applied at a rate from about 280 gae/ha to about 3360 gae/ha. In certain embodiments, fluroxypyr is applied at a rate from about 50 gae/ha to about 400 gae/ha and glyphosate is applied at a rate from about 360 gae/ha to about 2000 gae/ha. In certain embodiments, fluroxypyr is applied at a rate from about 50 gae/ha to about 200 gae/ha and glyphosate is applied at a rate from about 360 gae/ha to about 1100 gae/ha. In certain embodiments, fluroxypyr is applied at a rate from about 200 gae/ha to about 400 gae/ha and glyphosate is applied at a rate from about 710 gae/ha to about 1500 gae/ha. In certain embodiments, fluroxypyr is applied at a rate from about 300 gae/ha to about 400 gae/ha and glyphosate is applied at a rate from about lOOOgae/ha to about 2000 gae/ha.

In some embodiments of the methods described herein, the fluroxypyr or sait or ester thereof and glyphosate or sait or ester thereof are applied simultaneously, including, e.g., in the form of a composition. In some embodiments, the components are applied sequentially, e.g., within 5,10,15, or 30 minutes of each other; 1,2,3,4, 5,10,12,24,48 hour(s) or each other, or 1 week of each other.

In some embodiments of the compositions and methods described herein, the carboxylîc acid équivalent weight ratio of fluroxypyr or sait or ester thereof to glyphosate or sait or ester thereof is from 2:1 to 1:40. As used herein, carboxylic acid équivalent (or acid équivalent weight ratio) of fluroxypyr or sait or ester thereof to glyphosate or sait or ester thereof refers to the ratio of the weight of fluroxypyr, or if a sait or ester of fluroxypyr, the weight, based on molar équivalents, of the corresponding carboxylic acid of the sait or ester, to the weight of glyphosate, or if a sait or ester of glyphosate, the weight of the corresponding carboxylic acid or the sait of the ester. For example, if the number of moles for a given amount of fluroxypyr meptyl is X grams, the acid équivalent weight would be the weight of X moles of fluroxypyr (which is a carboxylic acid). In certain embodiments, the weight ratio is from 1:1 to 1:20. In certain embodiments, the weight ratio is from 1:2.5 to 1:10.

In some embodiments, the compositions comprise and the methods utilize fluroxypyr meptyl and glyphosate ammonium, wherein the acid équivalent weight ratio of fluroxypyr meptyl to glyphosate ammonium is from 2:1 to 1:40. In certain embodiments, the weight ratio is from 1:1 to 1:20. In certain embodiments, the weight ratio is from 1:2.5 to 1:10.

The components of the synergistic mixtures described herein can be applied either separately or as part of a multipart herbicidal system.

The synergistic mixtures and methods described herein, in some embodiments, can be utilized in conjunction with one or more other herbicides to control a wider variety of undesirable végétation. When used in conjunction with other herbicides, the composition can 10 be formulated with the other herbicide or herbicides, tank-mixed with the other herbicide or herbicides or applied sequentially with the other herbicide or herbicides. Some ofthe herbicides that can be employed in conjunction with the synergistic compositions described herein include: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, 15 allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amîcarbazone, amîdosulfuron, aminocyclopyrachlor, aminopyralid, amîprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, befiubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazon, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, 20 benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac-sodium, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop-butyl, cyperquat, cyprazîne, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, diallate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofbp, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, dîsul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfiiron, ethîdimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfiiron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazîfop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenîcan, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidîne, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfiiron, fluridone, flurochloridone, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, îmazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, îodomethane, îodosulfuron, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, ΜΑΜΑ, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazinc, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyl dymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfiiron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, oriAo-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycaibazone, propyrisulfiiron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quïzalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metoIachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefiiryltrione, tembotrione, tepraloxydim, terbacil, tcrbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazïl, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulftiron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac tritosulfiiron, vemolate, DE-729 (halauxifen), xylachlor and salts, esters, optically active isomers and mixtures thereof.

The synergistic compositions and methods described herein can, further, be used in conjunction with glufosinate, dicamba, imidazolinones, sulfonylureas, or 2,4-D on glyphosate-tolerant, glufosinate-tolerant, dicamba-tolerant, imidazolinone-tolerant, sulfonylurea-tolerant and 2,4-D-tolerant crops, as well as crops that are résistant to glyphosate + fluroxypyr. In some embodiments, the synergistic compositions and methods described herein in combination with herbicides that are sélective for the crop being treated and which complément the spectrum of weeds contre lied by these compounds at the application rate empioyed. In some embodiments, the synergistic compositions described herein or active ingrédients of the compositions and other complementary herbicides at the same time, either as a combination formulation or as a tank mix. The synergistic compositions and methods described herein can generally be empioyed in combination with known herbicide safeners, such as benoxacor, benthiocarb, brassinolide, cloquintocet (mexyl), cyometrinil, daimuron, dichlormid, dicyclonon, dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, harpin proteins, isoxadifen11 ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoic acid amides, to enhance their selectivity.

In some embodiments, the compositions described herein comprise at least one agriculture! 1 y acceptable adjuvant or carrier. Suitable adjuvants or carriers should not be phytotoxic to valuable crops, particularly at the concentrations employed in applying the compositions for sélective weed control in the presence of crops, and should not react chemically with herbicidal components or other composition ingrédients. Such mixtures can be designed for application directly to weeds or their locus or can be concentrâtes 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 concentrâtes, solutions, émulsions or suspensions. They can also be provided as a pre-mix or tank mixed.

Suitable agricultural adjuvants and carriers are well known to those skilled in the art. Some of these adjuvants include, but are not limited to, crop oil concentrate (minerai oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quatemary ammonium sait; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; Cç-Ch alkylpolyglycoside; phosphated alcohol ethoxylate; naturel primary alcohol (C12-C16) ethoxylate; di-sec-butyl phénol 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) dioleate99.

Liquid carriers that can be employed include water and organic solvents. The organic solvents typically used include, but are not limited to, petroleum fractions or hydrocarbons such as minerai oil, aromatic solvents, parafitnic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, com oil, cottonseed oil, lînseed 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 stéarate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, dioctyl phthalate and the like; esters of mono, di and polycarboxylic acids and the like. Spécifie organic solvents include 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, glycérine, jV-methyl-2-pyrrolidinone, A/Mdimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers and the like. Water is generally the carrier of choice for the dilution of concentrâtes.

Suitable solid carriers include talc, pyrophyllite 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, and the like.

In some embodiments, one or more surface-active agents are incorporated into the compositions described herein. Such surface-active agents are advantageously employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationîc or nonionic în character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants conventionally used in the art of formulation and which may also be used in the présent formulations are described, inter alia, in “McCutcheon’s Détergents and Emulsifiers Annual,” MC Publishing Corp., Ridgewood, New Jersey, 1998 and in “Encyclopédie of Surfactants, Vol. I-III, Chemical Publishing Co., New York, 1980-81. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenoi-Ci8 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-Cie ethoxylate; soaps, such as sodium stéarate; 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; quatemary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stéarate; 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, com oil, cottonseed oil, Iînseed oil, palm oil, peanut oil, safïlower oil, sesame oil, tung oil and the like; and esters ofthe above vegetable oils, particularly methyl esters.

Oftentimes, some of 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 additives commonîy used in agricultural compositions include compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and bufïers, corrosion inhibitors, dyes, odorants, spreading agents, pénétration 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 régulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium sulfate, ammonium nitrate, urea and the like.

The concentration of the active ingrédients in the synergistic compositions described herein is generally from 0.1 to 98 percent by weight. Concentrations from 10 to 90 percent by weight are often employed. In compositions designed to be employed as concentrâtes, the active ingrédients are generally présent in a concentration from 5 to 98 weight percent, preferably 10 to 90 weight percent. Such compositions are typically diluted with an inert carrier, such as water, before making a postemergence, foliar application to exposed weed and crop foliage. The diluted compositions usually appiied as a postemergence, foliar application to weeds or the locus of weeds generally contain 0.03 to 20 weight percent active ingrédient and preferably contain 0.1 to 10 weight percent.

The présent compositions can be appiied to weeds or their locus by the use of conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation or paddy water, and by other conventional means known to those skilled in the art.

The described embodiments and following examples are for illustrative purposes and are not intended to limit the scope of the daims. Other modifications, uses, or combinations with respect to the compositions described herein will be apparent to a person of ordinary skill in the art without departing from the spîrit and scope of the claimed subject matter.

Examples

Evaluation of Postemergence Herbicidal Activity of Mixtures under Field Conditions Methodology

Trial sites were located in various countries around the world, including Brazil, United States, Hungary, Indonesia and Malaysia, in non-crop and perennial tree crop plantations. Trials were conducted using normal small plot R&D trials using standard research methodology. Trial plots were between 2 to 4 meters (m) wide by 3 to 10 m long.

All treatments were applied using a randomized complété block or factorial trial design with 3-4 réplications per treatment. The trial sites had naturally occurring populations of weeds. The weed spectrum included, but was not limited to, scarlet pimpemel (Anagallis arvensis L., ANGAR), tropical carpetgrass (Axonopus compressas, AXOCO), Canada thistle (Cirsium arvense (L.) Scop., CIRAR), calopo (Calopogonium mucunoides, CLOMU), Bengal dayflower (Commelina benghalensis L., COMBE), field bindweed (Convoivus arvensis,

CONAR), horseweed (Conyza canadensis (L.) Cronq., ERICA), kochia (Kochia scoparia (L.) Schrad., KCHSC), common mallow (Malva neglecta Wallr., MALNE), African mîle-aminute (Mikania cordata (Burm. f.) B.L., M1KCO), slender panïcgrass (Ottochloa nodosa, OTTNO), paspalum (Paspalum conjugatum Bergius, PASCO), wild buckwheat (Polygonum convolvulus L., POLCO) and stinging nettle (Urtica dioica L., URTDI).

Treatments consisted of tank mixes of commercially available formulations of fluroxypyr-meptyl ester (Starane® 200, Starane® 250, Starane* Ultra) and glyphosate (Roundup® isopropylammonium sait, Glizmax, Gliz) applied in water. The application volume varied from location to location but was from 100 to 450 liters per hectare (L/ha).

Application was made using a précision gas backpack sprayer at pressures ranging from 150 to 300 kPA pressure using 2 to 4 m booms utilizing 4 to 8 fiat fan nozzles to broadcast the treatments to the weeds and to the soil.

The treated and control plots were rated blind at various intervals after application. Ratings were based on Percent (%) Visual weed control, where 0 corresponds to no control 25 and 100 corresponds to complété control. Results are reported in Tables 1 to 4.

Evaluation

Data were collected and analyzed using various statîstical methods.

Colby’s équation was used to détermine the herbicidal effects expected from the mixtures (Colby, S. R. Calculation of the synergistic and antagonistic response of herbicide 30 combinations. Weeds 1967 15,20-22).

The following équation was used to calculate the expected activity of mixtures containing two active ingrédients, A and B:

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

A = observed efficacy of active ingrédient A at the same concentration as used in the 5 mixture;

B = observed efficacy of active ingrédient B at the same concentration as used in the mixture.

The results are summarized in Tables 1-4.

Table 1. Synergistic weed control of AXOCO, CLOMU, OTTNO and PASCO at 70 Days After Application (DAA) following a postemergence application of Fluroxypyrmepty! + Glyphosate-isopropylammonium to cereals

Fluroxypyrmeptyl	Glyphosateisopropylammonium	AXOCO	CLOMU	OTTNO	PASCO
(rate ln gae/ha)	Obs	Exp*	Obs	Exp*	Obs	Exp*	Obs	Exp*
53	0	0	-	69	-	0	-	0	-
0	500	59	-	64	-	59	-	59	-
53	500	89	59	99	88	84	59	89	59

Table 2. Synergistic weed control of MIKCO, KCHSC and ERICA at 28 to 43 Days

After Application (DAA) following a postemergence application of Fluroxypyrmeptyl + Glyphosate-isopropylammonium to cereals

Fluroxypyrmeptyl	Glyphosateisopropyl ammonium	Days After Application	MIKCO	KCHSC	ERICA	URTDI
(rate ln grains ae/ha)		Obs	Exp*	Obs	Exp*	Obs	Exp*	Obs	Exp*
50	0	28	42		-		-	-
0	360	28	58		-
50	360	28	94	79	-
67	0	36			48
0	280	36			23
67	280	36			73	59
140	0	43					4
0	560	43					18
140	560	43					86	21
140	0	43					4
0	840	43					73
140	840	43					98	73	-
200	0	28					-		10
0	1100	28					-		24
200	1100	28					-		95	31

Table 3. Synergistic weed control of COMBE, POLCO and CONAR 14 to 59 Days

After Application (DAA) following a postemergence application of Fluroxypyrmeptyl + Glyphosate-isopropylammonium to cereals

Fluroxypyrmeptyl	Glyphos a tels opropylammonlum	Days After Application	COMBE	POLCO	CONAR	MALNE
(rate in grams ae/ha)	Obs	Exp*	Obs	Exp*	Obs	Exp*	Obs	Exp*
200	0	28	36		-	-			-
0	710	28	43		-	-			-
200	710	28	84	63	-	-			-
200	0	14			52	-			48
0	1000	14			25	-			14
200	1000	14			80	64			90	55
200	0	59			-	-	47		-
0	2000	59			-	-	55		-
200	2000	59			-	-	91	76	-
400	0	14			68	-	-		-
0	1500	14			60	-	-		-
400	1500	14		-	98	87	-		-

Table 4. Synergistic weed control of CIRAR, CONAR, POLCO and ANGAR at 14 to

Days After Application (DAA) following a postemergence application of

Fluroxypyr-meptyl + Glyphosate-isopropylammonium to cereals

Fluroxypyrmeptyl	Glyphosateisopropylammonium	Days After Appll cation	CIRAR	CONAR	POLCO	ANGAR
(rate In grams ae/ha)	Obs	Exp*	Obs	Exp*	Obs	Exp*	Obs	Exp*
300	0	59	3		-
0	1000	59	58		-
300	1000	59	72	60	-
300	0	59	-		50
0	1500	59	-		43
300	1500	59			91	72
300	0	59	-		50
0	2000	59			55
300	2000	59	-		94	77
400	0	14	7		-		60		0
0	1000	14	58		-		25		43
400	1000	14	73	61	-		87	70	63	43
400	0	59	-		48		-		-
0	2000	59	-		55		-	-	-
400	2000	59	-		96	77	-	-	-

ANGAR » Anagallis arvensis L., scarlet pimpemel

AXOCO = Axonopus compressas, tropical carpetgrass

CIRAR = Cirslum arvense (L.) Scop., Canada thistle

CLOMU = Calopogonium mucunoides, calopo

COMBE = Commettrai benghalensîs L., Bengal dayflower

CONAR = Convolvus arvensis, field bindweed

ER1CA = Conyza canadensis (L.) Cronq., horseweed

KCHSC = Kochia scoparia (L.) Schrad., kochia

MALNE = Malva neglecta Wallr., common mallow

M1KCO = Mikania cordata (Bunn. f.) B.L. Robins., African mile-a-minute OTTNO = Ottochloa nodosa, slender panicgrass

P ASCO = Paspalum conjugatum Bergius, sour paspalum

POLCO = Polygonum convolvulus L., wild buckwheat

URTDI = Urtica dioica L., stinging nettle

Obs = Observed weed control

Exp* = Expected weed control, as per Colb/s équation calculation

Claims (20)

1. A herbicidal composition comprising a herbicidally effective amount of (a) fluroxypyr or sait or ester thereof and (b) glyphosate or sait or ester thereof.

2. The composition of claim I, wherein (a) is fluroxypyr meptyl and (b) is glyphosate ammonium.

3. The composition of claim I, wherein the carboxylic acid équivalent weight ratio of fluroxypyr or sait or ester thereof to glyphosate or sait or ester thereof is from 2:1 to 1:40.

4. The composition of claim 3, wherein the carboxylic acid équivalent weight ratio is from 1:1 to 1:20.

5. The composition of claim 4, wherein the carboxylic acid équivalent weight ratio is from 1:2.5 to 1:10.

6. The composition of claim 2, wherein the carboxylic acid équivalent weight ratio of fluroxypyr meptyl to glyphosate ammonium is from 2:1 to 1:40.

7. The composition of claim 2, wherein the carboxylic acid équivalent weight ratio of fluroxypyr meptyl to glyphosate ammonium is from I:I to 1:20.

8. The composition of claim 2, wherein the carboxylic acid équivalent weight ratio of fluroxypyr meptyl to glyphosate ammonium is from 1:2.5 to 1:10.

9. The composition of claim 1, further comprising a safener.

10. The composition of claim 1, further comprising one or more additional herbicides.

11. The composition of claim 1, wherein the composition further comprises an agriculturally acceptable adjuvant or carrier.

12. A method of treating undesirable végétation comprising contactîng the végétation, locus of the végétation, soil, or water a herbicidally effective amount of the composition of claim 1.

13. A method of treating undesirable végétation comprising contacting the végétation, locus of the végétation, soil, or water a herbicidally effective amount of the composition of claim 8.

14. A method of treating undesirable végétation comprising contacting the végétation, locus of the végétation, soil, or water a herbicidally effective amount of (a) fluroxypyr or sait or ester thereof and (b) glyphosate or sait or ester thereof.

15. The method of claim 14, wherein (a) and (b) are applied post emergently.

16. The method of claim 14, wherein (a) and (b) are applied pre emergently.

17. The method of claim 14, wherein the undesirable végétation is anagallis, axonopus, cirsium, calopogonium, commelina, cortvolvus, conyza, kochio, malva, mikania, ottochloa nodosa, pspalum polygonum, or urtica.

18. The method of daim 14, wherein the undesirable végétation is ANGAR, AXOCO, CIRAR, CLOMU, COMBE, CONAR, ER1CA, KCHSC, MALNE, M1KCO, OTTNO, PASCO, POLCO, or URTDI.

19. The method of claim 14, wherein the fluroxypyr or sait or ester thereof is applied at a rate of from 50 gae/ha to 400 gae/ha and glyphosate or sait or ester thereof is applied at a rate of from 360 gae/ha to 2000 gae/ha.

20. The method of daim 14, wherein the undesirable végétation is controlled in a cereal crop setting.