NZ625776B2 - Herbicidal composition containing certain pyridine carboxylic acids and (2,4-dichlorophenoxy)acetic acid - Google Patents

Abstract

Herbicidal compositions comprising 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid (I) or a derivative thereof and 2,4-D (2,4-Dichlorophenoxyacetic acid) or a derivative thereof. Also disclosed is a method of controlling undesirable vegetation such as Melochia, Eleusine, Lolium, Panicum, MEOPA, ELEIN, LOLMU, or PANDI. eusine, Lolium, Panicum, MEOPA, ELEIN, LOLMU, or PANDI.

Description

/067937 HERBICIDAL COMPOSITION CONTAINING CERTAIN PYRIDINE CARBOXYLIC ACIDS AND (2,4-DICHLOROPHENOXY)ACETIC ACID Cross Reference to Related Applications This application claims the benefit of US. Provisional Patent Application Serial No. 61/567,419 filed December 6, 2011.

Field Provided herein are herbicidal compositions comprising (a) 4—amino—3~chloro~6—(4— chloro—Z—[luoro—3—methoxyphenpryridine—2~carboxylic acid, or an agriculturally acceptable ester, amide, or salt thereof and (b) ichlorophenoxy)acetic acid (2,4—D) or an ester, l0 amide, or salt thereof for controlling weeds in crops or other settings, e. g. in wheat, rye, barley, oats, ale, rice, turf, es, rangelands, cereals, oil seed rape, and industrial vegetation management ([VM). 'l‘hese compositions provide ed herbicidal weed control.

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

In some cases, herbicidal active ingredients have been shown to be more effective in ation than when applied individually and this is referred to as “synergism.” As described in the ide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429, rgism’ [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response of each factor l 001047763_2.docx applied separately.” The present disclosure is based in part on the discovery that 2,4-D and certain pyridine carboxylic acids, already known individually for their herbicidal efficacy, display a synergistic effect when applied in combination.

Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment, or any form of suggestion, that this prior art forms part of the common general knowledge in New Zealand or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person d in the art.

As used herein, except where the context requires otherwise, the term "comprise" and IO variations of the term, such as ising", "comprises" and "comprised”, are not intended to exclude other additives, components, integers or steps.

Summary In one aspect of the invention there is provided a idal compositions comprising a herbicidally effective amount of (a) a pyridine carboxylic acid of the formula (I), N112 /0 (I) and agriculturally acceptable salts, esters and amides of the carboxylic acid, and (b) 2,4—D and agriculturally able salts, esters, and amides of 2,4—D. In some embodiments, the compositions contain an agriculturally acceptable adjuvant or carrier. In some ments, the compositions are employed in combination with known ide safeners, including, but not limited to, cloquintocet-mexyl. 7763_2,docx In another aspect of the invention there is ed a method of controlling undesriable vegetation comprising contacting the undesirable vegeation, area adjacent to the undesirable vegeation, or soil a herbicidally effective amount of (a) a compound of the a (I) / (I) or, with respect to the carboxylic acid moiety, an agriculturally acceptable salt, ester, or amide thereof, and (b) chlorophenoxyacetic acid (2,4—D), or, with respect to the carboxylic acid moiety, an agriculturally acceptable ester, amide, or salt thereof.

The species spectra of the pyridine carboxylic acid of formula (I) and esters, amides, and salts thereof and 2,4—D and esters, amides, and salts thereof, i.e., the weed species which the respective compounds control, is broad and highly complementary. For example, it has been found that in certain embodiments, the compositions provided herein exhibit a synergistic action in the control ofescoba blanca (Me/achia parviflora L; MEOPA), goosegrass (Eleusine indica (L.) .; ELEIN), Italian ryegrass (Lalium perenne L. ssp. multiflorum (Lam.) ; LOLMU), and fall panicum (Panicum dichotomiflorum Michx.; PANDI) at ation rates equal to and lower than the rates of the individual compounds.

PCT/U52012/067937 Detailed Description A number of pyridine carboxylic acid nds are described in US. Patent 7,314,849 (B2), including 4—amino-3—chloro—6—(4—chloro—2-fluoro-3—methoxyphenyl)pyridine— 2—carboxy1ic acid (I), which has the ing structure: /0 (l) The methyl ester is described by the halauxil'en—mcthy]. The compound of formula I or esters, salts, or amides thereof control annual grass weeds including Setaria, Pennisemm, Echinochloa; eaf weeds such as Papaver, Galium, Lamium, Kochia, Amaranthus, Aeschynomene, Sesbania, and Monochoria; and sedge species such as Cyperus and Scirpus. 2,4—1) is the common name for (2,4—dich]orophenoxy)acetic acid. Its herbicidal ty is described in The Pesticide , Fifteenth Edition, 2009. 2,4—I) es post- weeds in a variety of crops. An emergence control of annual and perennial broadleal' exemplary 2,4—1) salt is the dimethylamine salt, Provided herein are compounds comprising or methods of controlling undesirable vegetation comprising utilizing (a) the compound of formula (I) or salt, ester, or amide thereof and (b) 2,4 D or a salt, ester, or amide f. In certain embodiments, the methyl ester of the compound of formula (I) is utilized. In some embodiments, the benzyl ester of the compound of formula (I) is utilized. In some embodiments, the potassium salt of the compound of formula (I) is utilized. In certain embodiments, the 2, 4-D is the dimethyl amine salt.

PCT/U52012/067937 The term herbicide is used herein to mean an active ingredient that kills, controls or otherwise adversely es the growth of plants. A herbicidally effective or tion controlling amount is an amount of active ingredient 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 established vegetation. idal activity is exhibited by the compounds of the compositions and methods when they are applied directly to the plant or to the locus of the plant, i.e., area adjacent to 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 nd ed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of al applied. These and other factors can be ed as is known in the art to promote non—selective or selective herbicidal action. In some embodiments, the compositions described herein are applied as a post-emergence application, pre—emergence application, or in—water application, e.g., to flooded paddy rice or water bodies (e.g., ponds, lakes and streams), to relatively immature undesirable vegetation to achieve the maximum l of weeds. In certain ments, the compositions and methods are applied via burn—down.

In some embodiments, the compositions and methods ed herein are utilized to control weeds in crops, including but not limited to cereals, rice, perennial plantation crops, corn, sorghum, turf, range and pasture, rial vegetation management (IVM), rights—of- way and in any auxinic—tolerant crops. in some embodiments, the compositions and methods are utilized to control weeds in cereals or oil seed rape.

The compositions and methods described herein can be used to control undesirable vegetation in glyphosate—tolerant—, glufosinate—telerant—, dicamba—tolerant—, phenoxy auxin- tolerant—, pyridyloxy auxin—tolerant—, aryloxyphenoxypropionate-tolerant-, acetyl CoA carboxylase (ACCase) tor-tolerant-, imidazolinone-tolerant—, acetolactate se (ALS) tor—tolerant—, 4—hydroxyphenyl—pyruvate dioxygenase (HPPD) inhibitor-tolerant—, protoporphyrinogen oxidase (PPO) inhibitor—tolerant—, triazine-tolerant- and bromoxynil— PCT/USZOlZ/067937 tolerant crops, for example, in conjunction with glyphosate, inate, dicamba, phenoxy auxins, pyridyloxy , yphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil. The compositions and methods may be used in controlling rable vegetation in crops possessing multiple or stacked traits ring tolerance to multiple chemistries and/or inhibitors of multiple modes of action. In some embodiments, the compound of formula I, or salt or ester thereof, and 2,4-D, or salt or ester f, and a mentary herbicide or salt or ester thereof are used in combination with herbicides that are selective for the crop being treated and which ment the um of weeds controlled by these compounds at the IO application rate employed. In some ments, the compositions described herein and other complementary herbicides are applied at the same time, either as a combination formulation or as a tank mix.

In some embodiments, the compositions and methods provided herein are utilized to control undesirable vegetation in cereals. In certain embodiments, the undesirable vegetation is Alopecarus myosuroides I’luds. (blackgrass, ALOMY), Apera spicmventi (I ..) Beauv. (windgrass, AI’IISV), Ariana/limo L. (wild oat, ’A), s lectorum L. (downy brome, , Lolium malti/lorum Lam. (Italian ryegrass, LOLM U), Phalaris minor Retz. (littleseed canarygrass, PHAMI), Poo ammo L. (annual bluegrass, POANN), Selaria [)Llifil/(l (Poir.) Roemer & IA. Schultes (yellow foxtail, SETLII), Selaria viriclis (L.) Beauv. (green I'oxtail, SE’I‘VI), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), (Ia/lam aparine L. (catchweed bedstraw, GALAP), Koo/117a ia (L.) Schrad. (kochia, KCIISC), Lamium purpureum L. (purple deadnettle ariu. la L. (wild chamomile, , LAMPU), MATCH), Matricaria marricarioides (Less) Porter (pineappleweed, MA'I‘MT), 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), Veronica persica Poir. (Persian Speedwell, VERPE), Viola arvensis Muir. (field Violet, VIOAR), or Viola tricolor L. (wild violet, VIOTR).

In some embodiments, the compositions and methods provided herein are utilized to control undesirable vegetation in range and pasture, IVM and rights of way. In certain ments, the undesirable vegetation is Ambrosia arlemisiifolia L. (common ragweed, AMBEL), Cassia obtusifolia (sickle pod, CASOB), Centaurea maculosa auct. non Lam.

WO 85988 PCT/U52012/067937 ed knapweed, CENMA), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), Convolvulus arvensis L. (field bindweed, CONAR), Euphorbia esula L. (leafy spurge, EPHES), Lactuca serriola L./Torn. ly lettuce, LACSE), Melochia parviflora (escoba blanca, MEOPA), Plantago lata L. (buckhom plantain, PLALA), Rumex obtusifolius L. (broadleaf dock, RUMOB), Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L.

(Wild mustard, SINAR), Sanchus arvensis L. (perennial sowthistle, SONAR), Solidago species (goldenrod, SOOSS), Taraxacum ofi‘icinale G.H. Weber ex Wiggers lion, TAROF), ium repens L. (white clover, TRFRE), or Urtzfca dioica L. n nettle, URTDI).

IO In some ments, the compositions and methods ed herein are utilized to control undesirable vegetation in rice. In n ments, the undesirable vegetation is Brachiaria plalyphyl/a (Groseb.) Nash (broadleaf signalgrass, BRAPP), ria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa ems-galli (L.) I). Beauv. (barnyardgrass, ECHCG), Echinochloa colonum (L.) LINK (junglerice, ECHCO), Echinochloa oryzoides (Ard) Fritseh (early watergrass, ECHOR), Echinochloa ()Ijvzicala (Vasinger) Vasinger (late watergrass, ECHPH), Ischaemum rugosum Salisb. (saramollagrass, ISCRII), Leptochloa chinensis (L.) Nees (Chinese sprangletop, LEFCI I), Leptochloa fascicularis (Lain) Gray (bearded sprangletop, LEFFA), Leptochloa panicoides (Presl) IIitehc. (Amazon sprangletop, LEFPA), Panicmn (liChOlOmi/Yorum (L.) Michx. (fall panieum, PANDI), Paspalum (lilatatum Poir. (dallisgrass, PASDI), Cyperus difformis L. flower dge, CYPDI), Cyperus esculenlus 1.. (yellow ge, CYI’ES), Cyperus iria L. (rice llatsedge, CYPIR), Cyperus rotundus L. (purple nutsedge, CYPRO), Eleocharis species (ELOSS), Fimbrisgilis miliacea (L.) Vahl (globe ush, FIMMI), Schoenoplectus juncoides Roxb. (Japanese bulrush, , Schoenoplectus maritimus L. (sea clubrush, , Schoenoplectus mucronatus L. (rieefield bulrush, SCPMU), Aeschynomene species, (jointvetch, AESSS), Alternanthem philoxeroides (Mart) Griseb. (alligatorweed, ALRPH), Alisma plantago-aquatica L. (common waterplantain, , Amaranthus s, (pigweeds and amaranths, , Ammannia coccinea Rottb. (redstem, AMMCO), Eclipta alba (L.) Hassk. (American false daisy, ECLAL), Heteranthera limosa (SW.) Willd./Vah1 (ducksalad, HETLI), Heteranthera rem’formis R. & P. (roundleaf mudplantain, HETRE), Ipomoea hederacea (L.) Jacq. (ivyleaf morningglory, IPOHE), Lindemia dubia (L) Pennell (low false pimpernel, LIDDU), Monochoria korsakowii Regel 2012/067937 & Maack (monochoria, , Monochoria vaginalis (Burm. F.) C. Pres] ex Kuhth, (monochoria, MOOVA), Murdannia nadiflora (L) Brenan (doveweed, MUDNU), Polygonam pensylvanicam L., (Pennsylvania smartweed, POLPY), Polygonum persicaria L. (ladysthumb, POLPE), Polygonam hydropiperoides Michx. , mild smartweed), Rotala indica (Willd) Koehne (Indian toothcup, ROTIN), Sagittaria species, (arrowhead, SAGSS), Sesbam‘a exaltata (Raf) Cory/Rydb. EX Hill (hemp ia, SEBEX), or Sphenoclea ica Gaertn. (gooseweed, SPDZE).

In n embodiments, the undesirable vegetation is Alopecarus myosaroides Huds. (blackgrass, ALOMY), Avenafataa L. (wild oat, AVEFA), Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L) Scop. (large crabgrass, DIGSA), Echinochloa (:ras—galli (1..) P. Beauv. ardgrass, ECllCG), li‘c/iinochloa colonum (1..) Link (junglcrice, ECllCO), Loliam multi/Yoram Lam. (Italian ryegrass, L()1.MU), Panicum dicholmniflorwn Michx. (fall panicum, PANDI), Panicmn miliacemn L. (wild—proso millet, PANMI), .S'etariafaberi Herrm. (giant foxtail, SETII'A), Setaria viridis (1..) Beauv. (green foxtail, Sli'l‘Vl), Sorghum Izalepense (1..) Pers. (Johnsongrass, SORHA), Sorghum bicolor (1..) Moench ssp. Arzmdinaceum (shattercane, SORVU), Cyperas C’SL'LI/entlLS‘ L. (yellow nutsedge, CYPES), Cyperas rolandus L. (purple nutsedge, CYPRO), Abutilon t/ieophrasti Medik. (velvetleaf, ABUTH), thas species (pigwccds and amaranths, , ia artemisii/b/ia L. (common ragweed, AMBI‘JL), ia 2O psi/ostachya DC. (western ragweed, AMBPS), Ambrosia trifida L. (giant ragweed, AMB’I‘R), Asclepias syriaca L. (common milkweed, ASCSY), Chenopodium album 1.. (common lambsquartcrs, CHEM), Cirsiam e (1...) Scop. (Canada thistle, CIRAR), e/Ma benghalensis L. (tropical spiderwort, COMBE), Datara stramonium L. (jimsonweed, DATST), Daacas carom L. (wild carrot, DAUCA), Eaphorbia heterophylla L. (wild ttia, , on bonariensis L. (hairy fleabane, ERIBO), on canadensis L. (Canadian fleabane, ERICA), Helianthus annuus L. n sunflower, HELAN), Jacquemontia tammfolia (L.) Griseb. (smallflower morningglory, IAQTA), Ipomoea hederacea (L) Jacq. (ivyleaf morningglory, IPOHE), Ipomoea lacunosa L. (white momingglory, IPOLA), Lactuca serriola L.fTorn. (prickly e, LACSE), Portulaca oleracea L. (common purslane, POROL), Sida spinosa L. (prickly sida, , Sinapis arvensis L. (wild mustard, SINAR), m ptychanthum Dunal (eastern black nightshade, SOLPT), or Xanthium strumarium L. (common cocklebur, XANST).

PCT/U82012/067937 In some ments, the compositions are used to control GALAP, LAMAM, GAETE, CHEAL, DESSO, PAPRH, GALAP, STEME, GERSS, LAMSS, VERPE, PAPRH, ERIBO, ERICA, Conyza, GLXMA, or CHEAL.

In some embodiments, the compositions and methods provided herein are utilized to control undesirable vegetation consisting of grass, broadleaf and sedge weeds. In certain embodiments, the compositions and methods provided herein are utilized to control undesirable vegetation including species in the following genera: Melochia, Eleusine, Lolium and Panicum.

In some embodiments, the combination of a pyridine carboxylic acid of formula (I), l, 0 or an agriculturally acceptable salt or ester thereof, and 2,4 D, or agriculturally acceptable salt or ester thereof, are used to control Melochia om (Escoba blanca, MEOPA), Eleusine indica (L) Gacrtn (gooscgrass, ELEIN), lolium perenne L. ssp. multiflormn (Lam) Husnot (Italian ss, LOLMU), and Panicmn omy/0rum Michx. (fall panicum, PANDI).

In some embodiments, the compositions are used to control GALAP, LAMAM, GAETE, [5 CHEAL, DESSO, PAPRH, GALAP, STEME, GERSS, LAMSS, VERPE, PAPRH, ERIBO, ERICA, Conyza, GLXMA, or CHE/\L.

The methods and compositions employing the ation of a pyridine carboxylic acid and 2,4—D, or agriculturally acceptable salts, esters, or amides ol'either component, and the compositions described herein may also be ed to control herbicide resistant or tolerant weeds. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes resistant or tolerant to acetolaetate synthase (ALS) inhibitors, photosystem II inhibitors, acetyl CoA carboxylase (ACCase) tors, synthetic auxins, photosystem I inhibitors, S-enolpyruvylshikimate-S—phosphate (EPSP) se inhibitors, ubule assembly inhibitors, lipid synthesis tors, protoporphyrinogen oxidase (PPO) inhibitors, carotenoid thesis tors, very long chain fatty acid (VLCFA) tors, phytoene desaturase (PDS) inhibitors, glutamine synthetase inhibitors, oxyphenyl-pyruvate— dioxygenase (HPPD) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple modes-of—action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals. Exemplary resistant or tolerant weeds include, but are not d to, biotypes with resistance or tolerance to multiple herbicides, le chemical classes, and le herbicide modes-of— action.

In some embodiments, the components are applied as a post—emergence foliar application to immature, undesirable vegetation to achieve the maximum control of weeds.

In some embodiments of the compositions and methods described herein, the carboxylic acid equivalent weight ratio of the compound of formula (I) or ester, amide, or salt thereof to 2,4—D or ester, amide, or salt thereof is from about 1:224 to about 1:05. In some embodiments, the carboxylic acid equivalent weight ratio is from about 1:100 to about 1:3.

In some embodiments, the carboxylic acid equivalent weight ratio is from about 1:56 to about 1:2. In some ments, the carboxylic acid equivalent weight ratio is from about 1:28 to about 1:35.

In certain embodiments, the composition and methods provided herein utilize the methyl or benzyl ester of the compound of a (I) and 2,4-l) or ester, amide, or salt thereof. In certain embodiments, the potassium salt of the compound of a (I) is utilized. In n embodiments, the dimethyl amine salt of 2,4 D is utilized.

In certain embodiments, the benzy] ester of the compound of formula (I) and the dimethyl amine salt of 2,4—D are utilized. In certain embodiments, the carboxylic acid equivalent weight ratio of the benzyl ester of nd (I) to the dimethyl amine (DMA) salt of 2,4—I) (2,4D DMA) is from about l:56 to about 1:7. In certain embodiments, the carboxylic acid equivalent weight ratio is from about 1:28 to about 1:7. In certain embodiments, the carboxylic acid equivalent weight ratio is from about 1:28 to about 1:14.

In certain ments, the methyl ester of the compound of formula (I) and 2,4-D or a 2,4—D salt, ester, or amide are utilized. In certain embodiments, the carboxylic acid equivalent weight ratio of the methyl ester of compound (I) to the 2-4 D or 2,4-D salt, ester or amide is from about 1:100 to about 1:3. In certain embodiments, the carboxylic acid equivalent weight ratio is from about 1:56 to about 1:7. In certain embodiments, the ylic acid equivalent weight ratio is from about 1:27 to about 1:14. 2012/067937 In certain embodiments, the methyl ester of the compound of formula (I) and the dimethyl amine salt of 2,4-D are utilized. In certain embodiments, the carboxylic acid equivalent weight ratio of the methyl ester of compound (I) to the dimethyl amine (DMA) salt of 2,4—D (2,4D DMA) is from about 1:56 to about 1:7. In certain embodiments, the carboxylic acid equivalent weight ratio is from about 1:27 to about 1:14.

In certain embodiments, the potassium salt (K) of the compound of formula (I) and dimethyl amine salt of 2,4—D are utilized. In certain embodiments, the carboxylic acid equivalent weight ratio of the potassium salt of the compound of formula (I) and yl amine salt of 2,4—D is about 1:28 to about 1:2. In certain embodiments, the carboxylic acid equivalent weight ratio is from about. 1: 14 to about 1:35. In certain embodiments, the ylie acid equivalent weight ratio is from about 1:56 to about 1:7.

In certain embodiments, ear‘boxylic acid equivalent weight ratio of the compound of formula (I) or salt, ester, or amide thereof and 2,4D or salt ester or amide thereof is less than 1:7, 1:10, 1:15, '1 :20, 1:25, 1:30, 135,140, 1,245,150, 1:55, or 1:60.

The rate at which the compositions are d will depend upon the particular type of weed to be controlled, the degree of control required, and the timing and method of application. In one embodiment, the composition described herein can be applied at an application rate of from about 62 grams acid lent per hectare (g ae/ha) to about 2,950 g ae/ha based on the total amount of active ingredients in the composition. 2,4-D is applied at a rate from about 60 g ae/ha to about 2880 g ae/ha and the pyridine ylie acid of formula (I) is applied at a rate from about 2 g ae/ha to about 70 g ae/ha. In r ment, the ition described herein can be applied at an application rate from about 245 g ae/ha to 1170 g ae/ha based upon the total amount of active ingredients in the composition, wherein 2,4-D is applied from about 240 to about 1120 g ae/ha and the pyridine carboxylic acid of formula (I) is applied from about 5 to about 50 g ae/ha. In some embodiments, the pyridine carboxylic acid of formula (I) or ester, amide, or salt thereof is applied at a rate from about 2 g ae/ha to about 70 g ae/ha and 2,4-D or ester, amide, or salt thereof is applied at a rate of about 26 g ae/ha to about 960 g ae/ha. In some embodiments, the pyridine carboxylic acid of formula (I) or ester, amide, or salt thereof is d at a rate from about 3.75 g ae/ha to about 35 g ae/ha and 2,4-D or ester, amide, or salt thereof is applied at a rate of about 52.5 g ae/ha W0 2013/085988 PCT/U82012/067937 to about 480 g ae/ha. In certain embodiments, the methods utilize the methyl ester, benzyl ester, or potassium salt of the pyridine carboxylic acid of formula (I) and 2,4-D or ester, amide or salt thereof. In one embodiment, the methyl ester of the pyridine carboxylic acid of formula (I) is applied at a rate from about 17.5 g ae/ha to about 35 g ae/ha and 2,4-D DMA is applied at a rate of about 480 g ae/ha. In r embodiment, the s utilize the benzyl ester of the pyiidine carboxylic acid of formula (I) and the DMA salt of 2,4-D, wherein benzyl ester of the compound of formula (I) is applied at a rate of about 3.75 g ae/ha to about 7.5 g ae/ha, and 2,4-D DMA is applied at a rate from about 52.5 g ae/ha to about 105 g ae/ha.

In another embodiment, the methods utilize the potassium salt of the pyridine carboxylic acid IO of formula (I) and the DMA salt of 2,4—D, wherein the potassium salt of the nd of formula (I) is applied at a rate of about 3.75 g ae/ha to about 7.5 g ae/ha, and 2,4 D DMA is applied at a rate from about 52.5 g ae/ha to about 210 g ae/ha. In some embodiments, the rate of the compound of formula I is less than 10 g ae/ha.

In some embodiments of the methods described herein, the compound of formula I or derivative thereof and 2,4—1) or derivative thereof are applied simultaneously, e. g., in the form of an intact 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.

The itions and methods of the present disclosure can be applied in conjunction with one or more other ides to control a wider variety of undesirable vegetation. When used in conjunction with other herbicides, the composition can be formulated with the other ide or ides, tank mixed with the other herbicide or herbicides or applied sequentially with the other herbicide or herbicides. Some of the herbicides that can be employed in conjunction with the synergistic composition of the present disclosure e, but are not limited to: 4—CPA; 4—CPB; 4-CPP; 3,4—DA; 2,4-DB; 3,4—DB; 2,4—DEB; 2,4-DEP; 3,4—DP; 2,3,6—TBA; T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos—methyl, le, ammonium sulfamate, anilofos, anisuron, asulam, n, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, tamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, 2012/067937 benzofluor, lprop, benzthiazuron, opyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium ide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, zine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlmflurenol, Chloridazon, chlorimuron, chlomitrofen, pon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon—ethyl, cinmethylin, IO cinosull’uron, cisanilidc, clcthodim, cliodinatc, afop, clofop, Clomazonc, rop, p, cloproxydim, clopyralid, cloransulam, (EMA, copper sulfate, CI’MI", CPPC, crcdazinc, cresol, cumyluron, cyanatryn, cyanazine, cycloate, ulfamuron, cycloxydim, cycluron, cyhalol’op, uat, cyprazinc, cyprazolc, cypromid, daimuron, dalapon, dazomet, delachlor, dcsmcdipham, dcsmctryn, di-allatc, dicamba, dichlobcnil, dichloralurca, dichlonnate, dichlorprop, dichlorprop—P, diclofop, diclosulam, diethamquat, dicthatyl, dil’cnopcntcn, difonoxuron, di fcnzoquat, diflufcnican, diflufenzopyr, dimcfuron, dimcpipcratc, dimcthachlor, dimethametryn, dimethenamid, dimethcnamid—P, dimcxano, dimidazon, dinitralninc, dinofenate, dinoprop, dinosam, dinoseb, dinotcrb, diphcnamid, ctryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazinc, cndothal, cpronaz, EPTC, crbon, esprocarb, ethalfluralin, cthamctsull'uron, cthidimuron, cthiolatc, clhofumcsatc, cthoxyfcn, ethoxysulfuron, etinofen, etnipromid, ctobcnzanid, EXD, l'cnasulam, l’cnoprop, ['cnoxaprop, fcnoxaprop—P, fenoxasulfone, fcntcracol, l’anhiaprop, fcntrazamidc, ['cnuron, s sulfate, llamprop, p—M, llazasulfuron, florasulam, fluazifop, fluazifop—P, fluazolatc, bazone, flucetosulfuron, fluchloralin, flufenacet, flufcnican, pyr, ulam, flumczin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidinc, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuxon, ne, xyfen, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ulfuron, ioxynil, ipazine, ipfencarbazone, dam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, yrifop, ilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA—thioethyl, MCPB, mecoprop, op—P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotn'one, metam, fop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisom'on, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, zon, oxapyrazon, furon, oxaziclomefone, orfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pcntoxazone, perlluidone, pethoxamid, phenisopham, phcnmedipham, dipham—ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisull’uron, procyazinc, prodiaminc, prolluazol, prol'luralin, prol'oxydim, proglinazine, prometon, promctryn, propachlor, propanil, propaquizal’op, propazine, m, propisochlor, propoxycarbazone, propyrisulluron, propyzamide, prosulfalin, prosulfocarb, prosull‘uron, , prynachlor, pydanon, pyraclonil, pyrallufen, pyrasuli‘otole, lynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, ticarb, pyriclor, pyridal’ol, te, pyril‘talid, pyriminobac, pyrimisull‘an, pyrithiobac, pyroxasull'one, pyroxsulam, orac, quinmerac, quinoclamine, quinonamid, quizalol‘op, quizalofop-P, i'hodethanil, rimsulfuron, sallufenaci], S—metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, yn, SMA, sodium arsenite, sodium azidc, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, ic acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, zuron, thiencarbazone—methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, late, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, hane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tn'propindan, tritac tritosulfuron, vernolate, xylachlor and salts, choline salts, esters, optically active isomers and mixtures thereof.

PCT/U52012/067937 The compositions and s described herein can, r, be used in conjunction with glyphosate, glufosinate, dicamba, imidazolinones or 2,4—D on glyphosate—tolerant, glufosinate-tolerant, dicamba—tolerant, imidazolinone-tolerant or 2,4—D-tolerant crops. In one embodiment, the compositions and methods are used in combination with herbicides that are ive for the crop being treated and which complement the spectrum of weeds controlled by these compounds at the application rate employed. In another embodiment, the compositions and methods described herein and other complementary herbicides are applied at the same time, either as a combination formulation or as a tank mix. Similarly the herbicidal nds of the present sure can be used in conjunction with acetolactate IO synthase inhibitors on acetolactate synthase inhibitor tolerant crops.

The compositions and methods of the present sure can be employed in combination with known herbicide safeners, such as benoxacor, benthiocarb, brassinolide, cloquintocet (acid or mexyl), cyometrinil, on, dichlormid, dicyclonon, dimepiperate, disulfoton, fenchlorazole—ethyl, fenclorim, llurazole, fluxofenim, furilazole, harpin proteins, isoxadifcn-ethyl, mefenpyr—diethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29l48 and ylsulfonylbenzoic acid amides, to enhance their selectivity.

In one embodiment, Cloquintocet (acid or mexyl) is used as a safener for the compositions and methods described herein, specifically antagonizing any harmful effect of the compositions.

In one embodiment, the compositions of the present disclosure is used in mixtures containing a herbicidally effective amount of the herbicidal components along with at least one agriculturally able adjuvant or carrier. Suitable adjuvants or carriers should not be phytotoxic to valuable crops, particularly at the concentrations ed in applying the compositions for selective weed control in the presence of crops, and should not react chemically with herbicidal components or other ition ingredients. Such mixtures can be designed for application directly to weeds or their locus or can be concentrates or ations that are ly diluted with additional carriers and adjuvants before application. They can be , such as, for example, dusts, granules, 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 can be tank mixed.

PCT/U82012/067937 Suitable agricultural adjuvants and carriers that are useful in preparing the herbicidal mixtures of the compositions described herein are well known to those skilled in the art.

Some of these adjuvants include, but are not limited to, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C1} alkylpolyglycoside; phosphated l ethoxylate; natural primary alcohol (Cu-C16) ethoxylate; di—sec—butylphenol EO—PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea um nitrate; fied methylated seed oil; tridecyl l (synthetic) ethoxylate (8E0); tallow amine late (15 E0); PEG(400) dioleate— 99.

Liquid carriers that can be employed include water and organic solvents. The organic solvents used 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 ning), such as 2—ethyl hexyl stearate, n—butyl olcate, pyl myristate, propylene glycol dioleate, di—octyl succinate, di—butyl adipate, yl phthalate and the like; esters of mono, di and polycarboxylic acids and the like. Specific organic ts include toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl e, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol thyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene , glycerine, N—methyl—2—pyrrolidinone, N,N—dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers and the like. In some embodiments, water is the carrier for the dilution of concentrates.

Suitable solid rs include talc, pyrophyllite clay, silica, lgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.

PCT/U82012/067937 In one embodiment, one or more surface—active agents are incorporated into the compositions of the present disclosure. Such surface-active agents are ageously employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or ic in ter and can be employed as emulsifying agents, wetting agents, suspending , or for other purposes. tants tionally used in the art of formulation and which may also be used in the present ations are described, inter alia, in “McCutcheon’s Detergents and Emulsifiers Annual,” MC Publishing Corp, Ridgewood, New Jersey, 1998 and in “Encyclopedia of Surfactants,” Vol. I—HI, Chemical Publishing Co., New York, 1980- 81, Typical surface-active agents include salts of alkyl es, such as diethanol—ammonium lauryl sulfate; alkylarylsull'onate salts, such as calcium dodecyl benzenesullbnate; alkylphenol—alkylene oxide addition products, such as nonylphenol—Clg ethoxylate; alcohol— alkylene oxide addition ts, such as tridecyl alcohol-C16 ethoxylate; soaps, such as sodium stearate; alkyl—naphthalene-sulfonate salts, such as sodium dibutyl— naphthalenesulfonate; dialkyl esters of sulfo—succinate salts, such as sodium di(2—ethylhexyl) sulfo—succinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl—ammonium 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 , including but not limited to, methyl esters of the above vegetable oils.

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 used in agricultural itions include compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, sticking agents, dispersing , thickening agents, ng point depressants, antimicrobial , 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 2012/067937 liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.

In one embodiment, the concentration of the active ingredients in the synergistic composition of the present disclosure is from 0.001 to 98 percent by weight, and in another embodiment, concentrations from 0.01 to 90 percent by weight are employed. In compositions designed to be employed as concentrates, the active ingredients are t in a concentration from 2 to 98 weight t, and in another embodiment, from 5 to 90 weight percent. In one embodiment, such compositions are diluted with an inert carrier, such as water, before application. The diluted compositions described herein that are d to weeds or the locus of weeds contain 0.004 to 10 weight percent active ingredient (ai) and, in another embodiment, contain 001 to 1.0 weight percent ai.

The present compositions can be d 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 following examples illustrate the present disclosure.

Examples Example 1: Field Evaluation of Postemergenee llerbicidal Activity of Mixtures in Range and Pasture. ology Field trials were conducted in pastures in Colombia using standard herbicide small plot research methodology. Plot size was l for small plot research, varying from 2 meters (m) wide by 6 m long. There were 4 replicates per treatment. Soil type ranged from medium to heavy soil texture. Perennial pastures were sown by hand direct dry g as per normal local cultural practices. The pastures were grown using normal al practices for fertilization and maintenance to ensure good growth of the pastures and the weeds.

Treatments were applied by backpack sprayer using either compressed air or carbon dioxide (C02), at spray pressures from 35 Bar. Spray tips were typically Flat Fan Teejet s, such as TJ8003. Spray volumes used were 400 liters per hectare (L/ha). MEOPA plant size at ation varied from 70 to 80 centimeters (cm) tall active growth at flowering stage.

For each treatment, the appropriate formulated product amount to treat the plot area, to achieve the desired application rate, based on unit area of application (hectare), was calculated, measured, and mixed in water prior to applying with the backpack sprayer.

Treatments were rated as compared to the untreated control plots. 2,4—D was used as '10 [nvesamina 480 SL®. Compound I was formulated as a 10% weight t active ingredient (wt ai% ~ 100 grams ai per L (g ai/L); 95.94 g ae/L) suspension concentrate (SC) of the corresponding methyl ester. e 2: Greenhouse Evaluation of Postemergence Herbicidal Activity of Mixtures in Various Cropping Systems.

Seeds or nutlets of the d test plant species were planted in a soil matrix prepared by mixing a sandy loam soil (28.6 percent silt, 18.8 percent clay, and 52.6 percent sand, with a pH of about 5.8 and an organic matter t of about 1.8 percent) and calcareous grit in an 80 to 20 ratio. The soil matrix was ned in plastic pots with a surface area of 84.6 cm2 and a volume of 560 cubic centimeters (em3). When required to ensure good germination and y plants, a fungicide treatment and/or other chemical or physical ent was applied. The plants were grown for 7—31 days ((1) in a greenhouse with an approximate 15 hour (h) photoperiod which was maintained at about 23w29 °C during the day and 22—28 0C during the night. Nutrients (Peters Excel® 5 5~Ca 2—Mg) and water were added on a regular basis and supplemental lighting was provided with overhead metal halide 1000—Watt lamps as necessary. The plants were employed for testing when they reached the first, second, or third true leaf stage.

Treatment requirements were calculated based upon the rates being tested, the concentration of active ingredient or acid equivalent in the formulation, and a 12 mL application volume at a rate of 187 L/ha.

PCT/U82012/067937 Treatments consisted of the potassium (K+) salt of 4-amino—3-chloro—6-(4—chloro fluoro—3—methoxy—phenyl)pyridine—2—carboxylic acid formulated as an SL or the benzyl ester of 4—amino-3—chloro-6—(4—chlorofluoro-3—methoxy—pheny1)pyridine—2-carboxylic acid as technical material, and 2,4—D dimethylamine (DMA) salt applied as Weedar® 64 EC alone and in combination. Forms of the pyridine carboxylic acid and 2,4-D were applied on an acid equivalent basis.

For treatments comprised of formulated compounds, measured amounts of compounds were placed individually in 25 mL glass vials and diluted in a volume of 1.5% (v/v) Agri—dex® crop oil concentrated to obtain 6X stock solutions. If a test compound did not dissolve readily, the mixture was warmed and/or sonicated. Application solutions were prepared by adding an appropriate amount of each stock solution (typically 2 ml.) and diluted to the appropriate final concentrations with the on of an appropriate amount of an and an appropriate amount of water so aqueous mixture of 1.5% (v/v) crop oil concentrate that. the final spray solutions contained l.25+/—O.()5% (v/v) crop oil concentrate.

For treatments comprised 01' formulated and cal compounds, d amounts of the technical materials were placed individually in 25 mL glass vials and dissolved in a volume of 97:3 v/v acetone/DMSO to obtain 6X stock solutions, and measured amounts of the formulated compounds were placed individually in 25 mL glass vials and diluted in a volume 01' 1.5% (v/v) crop oil concentrate to obtain 6X stock solutions. 11’ a test nd did not. dissolve readily, the mixture was warmed and/or sonicated. Application solutions were prepared by adding an appropriate amount of each stock solution (eg, 2 mL) and diluted to the appropriate final concentrations with the addition of an appropriate amount of an of water so aqueous mixture of 1.5% (v/v) crop oil concentrate and an appropriate amount that the final spray ons contained 1.25% (v/v) crop oil concentrate. The final acetone and DMSO concentrations of the application solutions containing technical material were 16.2% and 0.5%, respectively.

All stock solutions and ations ons were visually inspected for compound ibility prior to application. nd requirements are based upon a 12 mL ation volume at a rate of 187 liters per e (Uha). Application solutions were applied to the plant material with an overhead Mandel track sprayer equipped with 8002B PCT/U52012/067937 s calibrated to deliver 187 L/ha over an application area of 0.503 square meters (m2) at a spray height of 18 to 20 inches above the average plant canopy height. Control plants were sprayed in the same manner with the solvent blank.

The treated plants and control plants were placed in a greenhouse as bed above and watered by sub-irrigation to prevent wash—off of the test compounds. After approximately 2 weeks, the condition of the test plants as ed with that of the untreated plants was determined visually and scored on a scale of O to 100 percent where 0 corresponds to no injury and 100 ponds to complete kill. tion Data were collected and analyzed using various statistical methods.

For both Example 1 and Example 2, the Colby equation was used to determine the herbicidal effects expected from the mixtures (Colby, S. R. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967, 15, 20—22.).

The following equation was used to calculate the expected activity of mixtures containing two active ingredients, A and B: Expected = A + B — (A x B/lOO) A 2 observed efficacy of active ient A at the same concentration as used in the mixture.

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

Some of the compounds tested, application rates employed, plant species tested, and results are given in Tables 1 through 4.

Field Results Table 1. Synergistic weed control of MEOPA at 14 Days After Application (DAA) following treatment with pyridine carboxylic acid and 2,4-D idal compositions in range and pasture crops.

Pyridine (yigfitfiol)* Carboxylic Acid 2,4—D DAA 0 . l Ester) (grams ae/ha)* 175 0 14 48.5 0 480 14 3.8 17.5 480 14 7O 0 14 63.1 0 480 14 3.8 480 14 80.8 Greenhouse Results Table 2. Synergistic weed control of PANDI at 16 Days After ation (DAA) following a foliar treatment with pyridine carboxylic acid and 2,4-D herbicidal compositions to weeds common to row crops.

Carli()yxr;(li:‘lel\cid) . . 2’44) PANDP: ’ (Dimcthyl Amine)' ' , , (/0 Control)(I (Potassium Salt.) (grams ae/ha)* 3.75 0 52.5 52.5 PCT/U82012/067937 Table 3. Synergistic weed control of LOLMU at 14 Days After ation (DAA) following a foliar treatment with ne carboxylic acid and 2,4-D herbicidal compositions t0 WCGdS common to I‘OW CI'OpS.

Pyridine 2’4'D LOLMU Carboxylic Acid hyl Amine). . (% Control) (Potassium Salt) (grams ae/ha)* Obs* Exp* 3.75 O 14 1 5 7.5 0 14 35 —— O 52.5 14 0 -— O 105 14 O -— 3.75 52.5 14 25 15 7.5 52.5 14 4O 35 3.75 1 05 14 20 15 7.5 105 14 5O 35 Table 4. Synergistic weed control ol'ELEIN at 14 Days After Application (DAA) following a foliar treatment with pyridine carboxylic acid and 2,4—D herbicidal compositions to weeds COIHlllOl'l [0 row CTOPS.

Pyridine 2,4— D El .EIN Carboxylic Acid (Dimethyl Amine) (% Control) (Benzyl Ester) (grams ae/ha)* 3.75 MEOPA — escoba blanca (Melochia parviflora) ELELN— goosegrass (Eleusine indica (L) Gaertn.) LOLMU — n ryegrass (Lolium perenne L. ssp. multg'florum (Lam) Husnot) PANDI — fall panicum (Panicum dichotomiflomm Michx.) g ae/ha = grams acid equivalent per hectare Obs* = Observed percent weed l Exp* = Expected weed control per Colby analysis 7763_2.docx

Claims (25)

WHAT IS CLAIMED IS:

1. A herbicidal composition comprising a herbicidally effective amount of (a) a compound of the formula (I) /0 (I) or, with respect to the carboxylic acid moiety, an agriculturally acceptable salt, ester, or amide thereof, and (b) 2,4—dichlorophenoxyacetie acid (2,4—D), or, with respect to the carboxylic acid moiety, an agriculturally able ester, amide, or salt f.

2. The composition of claim 1, wherein the composition r comprises a herbicide safener. 10

3. The composition ofclaim 2, wherein the herbicide safener is cloquintocet mexyl or acid.

4. The composition of any one of the preceding claims, wherein (a) is the benzyl ester, methyl ester, or potassium salt of the compound of formula (I).

5. The composition ol‘claim 4, wherein (a) is the methyl ester. 15

6. The composition of claim 4, wherein (b) is the dimethyl amine salt of 2,4 D.

7. The composition of claim 5, wherein (b) is the yl amine salt of 2,4 D.

8. The composition of any one of the preceding claims, wherein the carboxylic acid equivalent weight ratio of the nd of formula (I) or salt, ester or amide thereof to 2,4-D or salt, ester, or amide thereof is from 1:100 to 123.5. 20

9. The composition of any one of claims 1 to 7, wherein the carboxylic acid lent weight ratio of the compound of formula (I) or salt, ester or amide thereof to 2,4—D or salt, ester, or amide thereof is from 1:56 to 1:7. 1001047763_2.docx

10. The composition of claim 5, wherein the carboxylic acid equivalent weight ratio of the methyl ester of the compound of formula (I) to 2,4-D or salt, ester, or amide thereof is from about 1:56 to about 1:7.

11. The composition of claim 10, wherein the ylic acid equivalent weight ratio is from about 1:27 to about 1:14.

12. The ition of claim 4, wherein (a) is the benzyl ester, and the carboxylic acid equivalent weight ratio of the benzyl ester of the compound of a (1) to 2,4—D or salt, ester, or amide thereof is from about 1:28 to about 1:7.

13. The ition ofclaim 4, wherein (a) is the potassium salt, and the carboxylic acid 10 equivalent weight ratio of the potassium salt of the compound of formula (I) to 2,4~D or salt, ester, or amide thereot‘is from about 1:56 to about 1:7.

14. The composition ofclaim 10, wherein (b) is the dimethyl amine salt of 2,4—D.

15. The composition ofclaim 1 1, wherein (b) is the dimethyl amine salt ol’2,4—D.

16. The composition of any one of the preceding claims, wherein the composition further 15 comprises an agriculturally acceptable adjuvant or carrier.

17. The composition of any one of the preceding claims, wherein the composition is synergistic under the Colby equation.

18. A method of controlling undesirable vegetation which comprises contacting the undesirable vegetation or area adjacent to the undesirable tion with a herbicidally 20 ive amount the composition of any one of the preceding claims.

19. The method of claim 18, wherein the composition is a applied post-emergently.

20. The method of claim 18, wherein the composition is applied pre-emergently.

21. The method of claim 18, wherein the undesirable vegetation is Melochz'a, Eleusz'ne, Lolium or Panicum. 25

22. The method of claim 21, wherein the rable vegetation is MEOPA, ELEIN, LOLMU, or PANDI. 1001047763_2.docx

23. A method of controlling undesriable vegetation comprising contacting the undesirable vegeation, area adjacent to the undesirable vegeation, or soil a herbicidally effective amount (a) a compound of the formula (I) 5 /O (I) or, with t to the carboxylic acid , an lturally acceptable salt, ester, or amide thereof, and (b) 2,4—dichlorophenoxyacetic acid (2,4—D), or, with respect to the carboxylic acid moiety, an agriculturally acceptable ester, amide, or salt thereof. 10

24. The method ol‘claim 23, wherein (a) is the methyl ester.

25. The method of claim 24, wherein (b) is the dimethyl amine salt of2,4—D.