# Patent

## Title
Herbicidal compositions comprising 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylic acid or a derivative thereof and a protoporphyrinogen oxidase inhibitor

## Abstract

Provided herein are synergistic herbicidal compositions containing (a) a compound of formula (I):




or an agriculturally acceptable salt or ester thereof and (b) a protoporphyrinogen oxidase inhibitor, e.g., acifluorfen, azafeniden, bifenox, carfentrazone-ethyl-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen-ethyl and saflufenacil, or a salt or ester thereof. The compositions and methods provided herein provide control of undesirable vegetation, e.g., in direct-seeded, water-seeded and transplanted rice, cereals, wheat, barley, oats, rye, sorghum, corn or maize, sugarcane, sunflower, oilseed rape, canola, sugar beet, soybean, cotton, pineapple, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, plantation crops, vegetables, industrial vegetation management (IVM) and rights-of-way (ROW).

## Background
PRIORITY CLAIM
This application claims the benefit of U.S. provisional patent application No. 61/675,067 filed on Jul. 24, 2012, this provisional application is incorporated herein by reference in its entirety.


FIELD
Provided herein are herbicidal compositions comprising (a) 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid or an agriculturally acceptable ester or salt thereof and (b) a protoporphyrinogen oxidase inhibitor. Provided herein are also methods of controlling undesirable vegetation comprising applying (a) 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid or an agriculturally acceptable ester or salt thereof and (b) a protoporphyrinogen oxidase inhibitor.
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. However, there remains a need for compositions and methods that are effective in controlling undesirable vegetation.
SUMMARY
Provided herein are herbicidal compositions comprising a herbicidally effective amount of (a) a compound of the formula (I)




or an agriculturally acceptable salt or ester of thereof, and (b) a protoporphyrinogen oxidase inhibitor. The compositions may also contain an agriculturally acceptable adjuvant or carrier. Provided herein are also methods of controlling undesirable vegetation comprising applying (a) a compound of formula (I) or an agriculturally acceptable ester or salt thereof and (b) a protoporphyrinogen oxidase inhibitor, e.g., acifluorfen, azafeniden, bifenox, carfentrazone-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen and saflufenacil, or an agriculturally acceptable salt or ester thereof.

Several embodiments are recited below. In the embodiments, the ratio of compound (a) to compound (b) can be expressed in units of weight to weight (g to g), gae/ha to gae/ha or gae/ha to gai/ha.
A first embodiment of the invention provided herein includes a synergistic herbicidal composition comprising a herbicidally effective amount of (a) a compound of the formula (I)




or an agriculturally acceptable salt or ester thereof and (b) a protoporphyrinogen oxidase inhibitor.

A second embodiment includes a method of controlling undesirable vegetation which comprises contacting the vegetation or the locus thereof with or applying to the soil or water to prevent the emergence or growth of vegetation the composition of embodiment 1.
A third embodiment includes a method of controlling undesirable vegetation which comprises contacting the vegetation or the locus thereof with or applying to the soil or water to prevent the emergence or growth of vegetation a herbicidally effective amount of (a) a compound of the formula (I)




or an agriculturally acceptable salt or ester thereof and (b) a protoporphyrinogen oxidase inhibitor.



DETAILED DESCRIPTION
Definitions
As used herein, the compound of formula (I) has the following structure:




The compound of formula (I) can be identified by the name 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylic acid and has been described in U.S. Pat. No. 7,314,849 (B2), which is incorporated herein by reference in its entirety. Exemplary uses of the compound of the formula (I) include controlling undesirable vegetation, including grass, broadleaf and sedge weeds, in multiple non-crop and cropping situations.

Without being limited to any theory, protoporphyrinogen oxidase inhibitors are believed to interfere with chlorophyll, lipid and protein production, causing plant cells to dry and disintegrate. Exemplary protoporphyrinogen oxidase inhibitors include, but are not limited to, acifluorfen, azafeniden, bifenox, carfentrazone-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen-ethyl and saflufenacil and derivatives thereof.
As used herein, acifluorfen is 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid. Acifluorfen possesses the following structure:




The herbicidal activity of acifluorfen is exemplified in Tomlin, C., ed. A World Compendium The Pesticide Manual. 15th ed. Alton: BCPC Publications, 2009 (hereafter “The Pesticide Manual, Fifteenth Edition, 2009.”). An exemplary form of acifluorfen includes its sodium salt. Exemplary uses of acifluorfen include its use for post-emergence control of broadleaf weeds in soybeans and rice.
As used herein, bifenox is methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate. Bifenox possesses the following structure:




The herbicidal activity of bifenox is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of bifenox include its use for control of barnyardgrass and sedges, e.g., in transplanted rice.
As used herein, carfentrazone-ethyl is ethyl α,2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate. Carfentrazone-ethyl possesses the following structure:




The herbicidal activity of carfentrazone-ethyl is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of carfentrazone-ethyl include its use for post-emergence control of a wide range of broadleaf weeds, e.g., in cereals.
As used herein, flumioxazin is 2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl]-4,5,6,7-tetrahydro-1H-isoindole-1,3(2H)-dione. Flumioxazin possesses the following structure:




The herbicidal activity of flumioxazin is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of flumioxazin include its use for pre-emergence control of broad-leaved weeds and grasses, e.g., in soybeans and tree and vine crops.

As used herein, oxadiargyl is 3-[2,4-dichloro-5-(2-propynyloxy)phenyl]-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one. Oxadiargyl possesses the following structure:




Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of oxadiargyl include its use for pre-emergence and early post-emergence control of broad-leaved weeds, grasses and annual sedges, e.g., in rice, sunflowers, potatoes, vegetables, sugar cane, fruit trees, and citrus.
As used herein, oxadiazon is 3-[2,4-dichloro-5-(1-methylethoxy)phenyl]-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one. Oxadiazon possesses the following structure:




Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of oxadiazon include its use for control of mono- and dicotyledonous weeds, e.g., in rice, and pre-emergence control of bindweed, annual broad-leaved weeds and grass; and post-emergence control of bindweed and annual broad-leaved weeds, e.g., in carnations, gladioli, roses, fruit trees and bushes, vines, ornamental trees and shrubs, hops, cotton, rice, soya beans, sunflower, onions and turf.
As used herein, oxyfluorfen is 2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene. It possesses the following structure:




Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of oxyfluorfen include its use for pre- and post-emergence control of annual broadleaved and grass weeds, e.g., in tropical and subtropical crops.
As used herein, pentoxazone, is 3-[4-chloro-5-(cyclopentyloxy)-2-fluorophenyl]-5-(1-methylethylidene)-2,4-oxazolidinedione and possesses the following structure:




Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of pentoxazone include its use for pre- and post-emergence control of Echinochloa spp. and Monchoria vaginalis, e.g., in paddy rice, before, during or after transplantation.
As used herein, pyraclonil is 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-(methyl-2-propynylamino)-1H-pyrazole-4-carbonitrile and possesses the following structure:




As used herein, pyraflufen-ethyl is ethyl 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl)-4-fluorophenoxy]acetate. ethyl 2-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1-methyl-1H-pyrazol-3-yl]-4-fluorophenoxy]acetate. Pyraflufen-ethyl possesses the following structure:




The herbicidal activity of pyraflufen-ethyl is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of pyraflufen-ethyl include its use for post-emergence control of broadleaf weeds, e.g., in cereals.
As used herein, saflufenacil is 2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluoro-N-[[methyl(1-methylethyl)amino]sulfonyl]benzamide and saflufenacil possesses the following structure:




Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of saflufenacil include its use for foliar and residual control of broadleaf weeds.
As used herein, herbicide means a compound, e.g., active ingredient that kills, controls or otherwise adversely modifies the growth of plants.
As used herein, a herbicidally effective or vegetation controlling amount is an amount of active ingredient which causes an adversely modifying effect to the vegetation e.g., causing deviations from natural development, killing, effecting regulation, causing desiccation, causing retardation, and the like.
As used herein, controlling undesirable vegetation means preventing, reducing, killing, or otherwise adversely modifying the development of plants and vegetation. Described herein are methods of controlling undesirable vegetation through the application of certain herbicide combinations or compositions. Methods of application include, but are not limited to applications to the vegetation or locus thereof, e.g., application to the area adjacent to the vegetation, as well as preemergence, postemergence, foliar (broadcast, directed, banded, spot, mechanical, over-the-top, or rescue), and in-water applications (emerged and submerged vegetation, broadcast, spot, mechanical, water-injected, granular broadcast, granular spot, shaker bottle, or stream spray) via hand, backpack, machine, tractor, or aerial (airplane and helicopter) application methods.
As used herein, plants and vegetation include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.
As used herein, agriculturally acceptable salts and esters refer to salts and esters that exhibit herbicidal activity, or that are or can be converted in plants, water, or soil to the referenced herbicide. Exemplary agriculturally acceptable esters are those that are or can be hydrolyzed, oxidized, metabolized, or otherwise converted, e.g., in plants, water, or soil, to the corresponding carboxylic acid which, depending on the pH, may be in the dissociated or undissociated form.
Exemplary salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Exemplary cations include sodium, potassium, magnesium, and aminium cations of the formula:

R1R2R3R4N+

wherein R1, R2, R3 and R4 each, independently represents hydrogen or C1-C12 alkyl, C3-C12 alkenyl or C3-C12 alkynyl, each of which is optionally substituted by one or more hydroxy, C1-C4 alkoxy, C1-C4 alkylthio or phenyl groups, provided that R1, R2, R3 and R4 are sterically compatible. Additionally, any two of R1, R2, R3 and R4 together may represent an aliphatic difunctional moiety containing one to twelve carbon atoms and up to two oxygen or sulfur atoms. Salts can be prepared by treatment with a metal hydroxide, such as sodium hydroxide, with an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine or with a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide or choline hydroxide.

Exemplary esters include those derived from C1-C12 alkyl, C3-C12 alkenyl, C3-C12 alkynyl or C7-C10 aryl-substituted alkyl alcohols, such as methyl alcohol, isopropyl alcohol, 1-butanol, 2-ethylhexanol, butoxyethanol, methoxypropanol, allyl alcohol, propargyl alcohol, cyclohexanol or unsubstituted or substituted benzyl alcohols. Benzyl alcohols may be substituted with from 1-3 substituents independently selected from halogen, C1-C4 alkyl or C1-C4 alkoxy. Esters can be prepared by coupling of the acids with the alcohol using any number of suitable activating agents such as those used for peptide couplings such as dicyclohexylcarbodiimide (DCC) or carbonyl diimidazole (CDI); by reacting the acids with alkylating agents such as alkylhalides or alkylsulfonates in the presence of a base such as triethylamine or lithium carbonate; by reacting the corresponding acid chloride of an acid with an appropriate alcohol; by reacting the corresponding acid with an appropriate alcohol in the presence of an acid catalyst or by transesterification.
Compositions and Methods
Provided herein are herbicidal compositions comprising a herbicidally effective amount of (a) a compound of the formula (I)




or an agriculturally acceptable salt or ester of thereof, and (b) a protoporphyrinogen oxidase inhibitor. In some embodiments, the protoporphyrinogen oxidase inhibitor is acifluorfen, azafeniden, bifenox, carfentrazone-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen-ethyl and saflufenacil, or agriculturally acceptable salts or esters thereof.

Provided herein are also methods of controlling undesirable vegetation comprising contacting the vegetation or the locus thereof, i.e., area adjacent to the plant, with or applying to the soil or water to prevent the emergence or growth of vegetation a herbicidally effective amount of (a) the compound of formula (I) and (b) a protoporphyrinogen oxidase inhibitor. In certain embodiments, the methods employ the compositions described herein.
Furthermore, in some embodiments, the combination of compound (I) or agriculturally acceptable salt or ester thereof and a protoporphyrinogen oxidase inhibitor, or an agriculturally acceptable salt or ester thereof exhibit synergism, e.g., the herbicidal active ingredients are more effective in combination than when applied individually. Synergism has been defined as “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 applied separately.” Senseman, S., ed. Herbicide Handbook. 9th ed. Lawrence: Weed Science Society of America, 2007. In certain embodiments, the compositions exhibit synergy as determined by the Colby's equation. Colby, S. R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 15:20-22.
In certain embodiments of the compositions and methods described herein, the compound of formula (I), i.e., the carboxylic acid, is employed. In certain embodiments, a carboxylate salt of the compound of formula (I) is employed. In certain embodiments, an aralkyl or alkyl ester is employed. In certain embodiments, a benzyl, substituted benzyl, or C1-4 alkyl, e.g., n-butyl ester is employed. In certain embodiments, the benzyl ester is employed.
In some embodiments, the compound of formula (I) or salt or ester thereof and acifluorfen, azafeniden, bifenox, carfentrazone-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen-ethyl and saflufenacil, or an agriculturally acceptable salt or ester thereof are formulated in one composition, tank mixed, applied simultaneously, or applied sequentially.
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 depends upon the plant species to be controlled, the stage of growth of the plant, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. These and other factors can be adjusted to promote non-selective or selective herbicidal action. In some embodiments, the compositions described herein are applied as a post-emergence application, pre-emergence application, or in-water application to flooded paddy rice or water bodies (e.g., ponds, lakes and streams), to relatively immature undesirable vegetation to achieve the maximum control of weeds.
In some embodiments, the compositions and methods provided herein are utilized to control weeds in crops, including but not limited to direct-seeded, water-seeded and transplanted rice, cereals, wheat, barley, oats, rye, sorghum, corn/maize, sugarcane, sunflower, oilseed rape, canola, sugar beet, soybean, cotton, pineapple, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, plantation crops, vegetables, industrial vegetation management (IVM) and rights-of-way (ROW). In certain embodiments, the compositions and methods provided herein are utilized to control weeds in rice. In certain embodiments, the rice is direct-seeded, water-seeded, or transplanted rice.
The compositions and methods described herein may be used to control undesirable vegetation in glyphosate-tolerant-, 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitor-tolerant-, glufosinate-tolerant-, glutamine synthetase inhibitor-tolerant-, dicamba-tolerant-, phenoxy auxin-tolerant-, pyridyloxy auxin-tolerant-, auxin-tolerant-, auxin transport inhibitor-tolerant-, aryloxyphenoxypropionate-tolerant-, acetyl CoA carboxylase (ACCase) inhibitor-tolerant-, sulfonylurea-tolerant-, pyrimidinylthiobenzoate-tolerant-, triazolopyrimidine-tolerant-, sulfonylaminocarbonyltriazolinone-tolerant-, imidazolinone-tolerant-, acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitor-tolerant-, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor-tolerant-, phytoene desaturase inhibitor-tolerant-, carotenoid biosynthesis inhibitor-tolerant-, protoporphyrinogen oxidase (PPO) inhibitor-tolerant-, cellulose biosynthesis inhibitor-tolerant-, mitosis inhibitor-tolerant-, microtubule inhibitor-tolerant-, very long chain fatty acid inhibitor-tolerant-, fatty acid and lipid biosynthesis inhibitor-tolerant-, photosystem I inhibitor-tolerant-, photosystem II inhibitor-tolerant-, triazine-tolerant-, and bromoxynil-tolerant-crops (such as, but not limited to, soybean, cotton, canola/oilseed rape, rice, cereals, corn, sorghum, sunflower, sugar beet, sugarcane, turf, etc.), for example, in conjunction with glyphosate, EPSP synthase inhibitors, glufosinate, glutamine synthase inhibitors, dicamba, phenoxy auxins, pyridyloxy auxins, synthetic auxins, auxin transport inhibitors, aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazolines, ACCase inhibitors, imidazolinones, sulfonylureas, pyrimidinylthiobenzoates, triazolopyrimidines, sulfonylaminocarbonyltriazolinones, ALS or AHAS inhibitors, HPPD inhibitors, phytoene desaturase inhibitors, carotenoid biosynthesis inhibitors, PPO inhibitors, cellulose biosynthesis inhibitors, mitosis inhibitors, microtubule inhibitors, very long chain fatty acid inhibitors, fatty acid and lipid biosynthesis inhibitors, photosystem I inhibitors, photosystem II inhibitors, triazines, and bromoxynil. The compositions and methods may be used in controlling undesirable vegetation in crops possessing multiple or stacked traits conferring 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 complementary herbicide or salt or ester thereof are used in combination with herbicides that are selective for the crop being treated and which complement the spectrum of weeds controlled by these compounds at the application rate employed. In some embodiments, the compositions described herein and other complementary herbicides are applied at the same time, either as a combination formulation, as a tank mix, or sequentially.
The compositions and methods may be used in controlling undesirable vegetation in crops possessing agronomic stress tolerance (including but not limited to drought, cold, heat, salt, water, nutrient, fertility, pH), pest tolerance (including but not limited to insects, fungi and pathogens) and crop improvement traits (including but not limited to yield; protein, carbohydrate, or oil content; protein, carbohydrate, or oil composition; plant stature and plant architecture).
The compositions and methods provided herein are utilized to control undesirable vegetation. Undesirable vegetation includes, but is not limited to, undesirable vegetation that occurs in rice, cereals, wheat, barley, oats, rye, sorghum, corn/maize, sugarcane, sunflower, oilseed rape, canola, sugar beet, soybean, cotton, pineapple, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, plantation crops, vegetables, industrial vegetation management (IVM) and rights of way (ROW).
In some embodiments, the methods provided herein are utilized to control undesirable vegetation in rice. In certain embodiments, the undesirable vegetation is Brachiaria platyphylla (Groseb.) Nash or Urochloa platyphylla (Nash) R.D. Webster (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa species (ECHSS), Echinochloa crus-galli (L.) P. Beauv. (barnyardgrass, ECHCG), Echinochloa crus-pavonis (Kunth) Schult. (gulf cockspur, ECHCV), Echinochloa colonum (L.) LINK (junglerice, ECHCO), Echinochloa oryzoides (Ard.) Fritsch (early watergrass, ECHOR), Echinochloa oryzicola (Vasinger) Vasinger (late watergrass, ECHPH), Echinochloa phyllopogon (Stapf) Koso-Pol. (rice barnyardgrass, ECHPH), Echinochloa polystachya (Kunth) Hitchc. (creeping river grass, ECHPO), Ischaemum rugosum Salisb. (saramollagrass, ISCRU), Leptochloa chinensis (L.) Nees (Chinese sprangletop, LEFCH), Leptochloa fascicularis (Lam.) Gray (bearded sprangletop, LEFFA), Leptochloa panicoides (Presl) Hitchc. (Amazon sprangletop, LEFPA), Oryza species (red and weedy rice, ORYSS), Panicum dichotomiflorum (L.) Michx. (fall panicum, PANDI), Paspalum dilatatum Poir. (dallisgrass, PASDI), Rottboellia cochinchinensis (Lour.) W. D. Clayton (itchgrass, ROOEX), Cyperus species (CYPSS), Cyperus difformis L. (smallflower flatsedge, CYPDI), Cyperus dubius Rottb. (MAPDU), Cyperus esculentus L. (yellow nutsedge, CYPES), Cyperus iria L. (rice flatsedge, CYPIR), Cyperus rotundus L. (purple nutsedge, CYPRO), Cyperus serotinus Rottb./C.B. Clarke (tidalmarsh flatsedge, CYPSE) Eleocharis species (ELOSS), Fimbristylis miliacea (L.) Vahl (globe fringerush, FIMMI), Schoenoplectus species (SCPSS), Schoenoplectus juncoides Roxb. (Japanese bulrush, SCPJU), Bolboschoenus maritimus (L.) Palla or Schoenoplectus maritimus L. Lye (sea clubrush, SCPMA), Schoenoplectus mucronatus L. (ricefield bulrush, SCPMU), Aeschynomene species, (jointvetch, AESSS), Alternanthera philoxeroides (Mart.) Griseb. (alligatorweed, ALRPH), Alisma plantago-aquatica L. (common waterplantain, ALSPA), Amaranthus species, (pigweeds and amaranths, AMASS), Ammannia coccinea Rottb. (redstem, AMMCO), Commelina benghalensis L. (Benghal dayflower, COMBE), Eclipta alba (L.) Hassk. (American false daisy, ECLAL), Heteranthera limosa (SW.) Willd./Vahl (ducksalad, HETLI), Heteranthera reniformis R. & P. (roundleaf mudplantain, HETRE), Ipomoea species (morningglories, IPOSS), Ipomoea hederacea (L.) Jacq. (ivyleaf morningglory, IPOHE), Lindernia dubia (L.) Pennell (low false pimpernel, LIDDU), Ludwigia species (LUDSS), Ludwigia linifolia Poir. (southeastern primrose-willow, LUDLI), Ludwigia octovalvis (Jacq.) Raven (longfruited primrose-willow, LUDOC), Monochoria korsakowii Regel & Maack (monochoria, MOOKA), Monochoria vaginalis (Burm. 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 methods provided herein are utilized to control undesirable vegetation in cereals. In certain embodiments, the undesirable vegetation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Apera spica-venti (L.) Beauv. (windgrass, APESV), Avena fatua L. (wild oat, AVEFA), Bromus tectorum L. (downy brome, BROTE), Lolium multiflorum Lam. (Italian ryegrass, LOLMU), Phalaris minor Retz. (littleseed canarygrass, PHAMI), Poa annua L. (annual bluegrass, POANN), Setaria pumila (Poir.) Roemer & J.A. Schultes (yellow foxtail, SETLU), Setaria viridis (L.) Beauv. (green foxtail, SETVI), Amaranthus retroflexus L. (redroot pigweed, AMARE), Brassica species (BRSSS), Chenopodium album L. (common lambsquarters, CHEAL), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), 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), Sinapis species (SINSS), Sinapis arvensis L. (wild mustard, SINAR), Stellaria media (L.) Vill. (common chickweed, STEME), Veronica persica Poir. (Persian speedwell, VERPE), Viola arvensis Murr. (field violet, VIOAR), or Viola tricolor L. (wild violet, VIOTR).
In some embodiments, the methods provided herein are utilized to control undesirable vegetation in range and pasture, fallowland, IVM and ROW. In certain embodiments, the undesirable vegetation 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), Daucus carota L. (wild carrot, DAUCA), Euphorbia esula L. (leafy spurge, EPHES), Lactuca serriola L./Torn. (prickly lettuce, LACSE), Plantago lanceolata L. (buckhorn 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 Urtica dioica L. (common nettle, URTDI).
In some embodiments, the methods provided herein are utilized to control undesirable vegetation found in row crops, tree and vine crops, and perennial crops. In certain embodiments, the undesirable vegetation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Avena fatua L. (wild oat, AVEFA), Brachiaria decumbens Stapf. or Urochloa decumbens (Stapf) R.D. Webster (Surinam grass, BRADC), Brachiaria brizantha (Hochst. ex A. Rich.) Stapf. or Urochloa brizantha (Hochst. ex A. Rich.) R.D. (beard grass, BRABR), Brachiaria platyphylla (Groseb.) Nash or Urochloa platyphylla (Nash) R.D. Webster (broadleaf signalgrass, BRAPP), Brachiaria plantaginea (Link) Hitchc. or Urochloa plantaginea (Link) R.D. Webster (alexandergrass, BRAPL), Cenchrus echinatus L. (southern sandbar, CENEC), Digitaria horizontalis Willd. (Jamaican crabgrass, DIGHO), Digitaria insularis (L.) Mez ex Ekman (sourgrass, TRCIN), Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv. (barnyardgrass, ECHCG), Echinochloa colonum (L.) Link (junglerice, ECHCO), Eleusine indica (L.) Gaertn. (goosegrass, ELEIN), Lolium multiflorum Lam. (Italian ryegrass, LOLMU), Panicum dichotomiflorum Michx. (fall panicum, PANDI), Panicum miliaceum L. (wild-proso millet, PANMI), Setaria faberi Herrm. (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), Ambrosia trifida L. (giant ragweed, AMBTR), Anoda cristata (L.) Schlecht. (spurred anoda, ANVCR), Asclepias syriaca L. (common milkweed, ASCSY), Bidens pilosa L. (hairy beggarticks, BIDPI), Borreria species (BOISS), Borreria alata (Aubl.) DC. or Spermacoce alata Aubl. (broadleaf buttonweed, BOILF), Spermacose latifolia (broadleaved button weed, BOILF), 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 carrot, DAUCA), Euphorbia heterophylla L. (wild poinsettia, EPHHL), Euphorbia hirta L. or Chamaesyce hirta (L.) Millsp. (garden spurge, EPHHI), Euphorbia dentata Michx. (toothed spurge, EPHDE), Erigeron bonariensis L. or Conyza bonariensis (L.) Cronq. (hairy fleabane, ERIBO), Erigeron canadensis L. or Conyza canadensis (L.) Cronq. (Canadian fleabane, ERICA), Conyza sumatrensis (Retz.) E. H. Walker (tall fleabane, ERIFL), Helianthus annuus L. (common sunflower, HELAN), Jacquemontia tamnifolia (L.) Griseb. (smallflower morningglory, IAQTA), Ipomoea hederacea (L.) Jacq. (ivyleaf morningglory, IPOHE), Ipomoea lacunosa L. (white morningglory, IPOLA), Lactuca serriola L./Torn. (prickly lettuce, LACSE), Portulaca oleracea L. (common purslane, POROL), Richardia species (pusley, RCHSS), Sida species (sida, SIDSS), Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild mustard, SINAR), Solanum ptychanthum Dunal (eastern black nightshade, SOLPT), Tridax procumbens L. (coat buttons, TRQPR), or Xanthium strumarium L. (common cocklebur, XANST).
In some embodiments, the methods provided herein are utilized to control undesirable vegetation in turf. In certain embodiments, the undesirable vegetation is Bellis perennis L. (English daisy, BELPE), Cyperus esculentus L. (yellow nutsedge, CYPES), Cyperus species (CYPSS), Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Diodia virginiana L. (Virginia buttonweed, DIQVI), Euphorbia species (spurge, EPHSS), Glechoma hederacea L. (ground ivy, GLEHE), Hydrocotyle umbellata L. (dollarweed, HYDUM), Kyllinga species (kylling a, KYLSS), Lamium amplexicaule L. (henbit, LAMAM), Murdannia nudiflora (L.) Brenan (doveweed, MUDNU), Oxalis species (woodsorrel, OXASS), Plantago major L. (broadleaf plantain, PLAMA), Plantago lanceolata L. (buckhorn/narrowleaf plantain, PLALA), Phyllanthus urinaria L. (chamberbitter, PYLTE), Rumex obtusifolius L. (broadleaf dock, RUMOB), Stachys floridana Shuttlew. (Florida betony, STAFL), Stellaria media (L.) Vill. (common chickweed, STEME), Taraxacum officinale G.H. Weber ex Wiggers (dandelion, TAROF), Trifolium repens L. (white clover, TRFRE), or Viola species (wild violet, VIOSS).
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 grass, broadleaf and sedge vegetation including but not limited to Brachiaria platyphylla or Urochloa, Bolboschoenus, Cyperus, Digitaria, Echinochloa, Fimbristylis, Ipomoea, Ischaemum, Leptochloa, Papaver, Setaria or Xanthium. 
In some embodiments, the combination of compound (I) or agriculturally acceptable ester or salt thereof and a protoporphyrinogen oxidase inhibitor are used to control, including but not limited to large crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crus-galli), jungle rice (Echinochloa colona), early watergrass (Echinochloa oryzoides), ivyleaf morningglory (Ipomoea hederacea), Chinese sprangletop (Leptochloa chinensis), smallflower umbrella sedge (Cyperus difformis), yellow nutsedge (Cyperus esculentus), rice flatsedge (Cyperus iria), purple nutsedge (Cyperus rotundus), globe fringerush (Fimbristylis miliacea), Japanese bulrush (Schoenoplectus juncoides), sea clubrush (Bolboschoenus maritimus or Schoenoplectus maritimus), broadleaf signalgrass (Brachiaria platyphylla or Urochloa platyphyllas), saramollagrass (Ischaemum rugosum Salis.), green foxtail (Setaria viridis), common poppy (Papaver rhoeas), or common cocklebur (Xanthium strumarium).
The compounds of formula I or agriculturally acceptable salt or ester thereof may be used to control herbicide resistant or tolerant weeds. The methods employing the combination of a compound of formula I or agriculturally acceptable salt or ester thereof and the compositions described herein may also be employed to control herbicide resistant or tolerant weeds. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes resistant or tolerant to acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors (e.g., imidazolinones, sulfonylureas, pyrimidinylthiobenzoates, triazolopyrimidines, sulfonylaminocarbonyltriazolinones), photosystem II inhibitors (e.g., phenylcarbamates, pyridazinones, triazines, triazinones, uracils, amides, ureas, benzothiadiazinones, nitriles, phenylpyridazines), acetyl CoA carboxylase (ACCase) inhibitors (e.g., aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazolines), synthetic auxins (e.g., benzoic acids, phenoxycarboxylic acids, pyridine carboxylic acids, quinoline carboxylic acids), auxin transport inhibitors (e.g., phthalamates, semicarbazones), photosystem I inhibitors (e.g., bipyridyliums), 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors (e.g., glyphosate), glutamine synthetase inhibitors (e.g., glufosinate, bialafos), microtubule assembly inhibitors (e.g., benzamides, benzoic acids, dinitroanilines, phosphoramidates, pyridines), mitosis inhibitors (e.g., carbamates), very long chain fatty acid (VLCFA) inhibitors (e.g., acetamides, chloroacetamides, oxyacetamides, tetrazolinones), fatty acid and lipid synthesis inhibitors (e.g., phosphorodithioates, thiocarbamates, benzofuranes, chlorocarbonic acids), protoporphyrinogen oxidase (PPO) inhibitors (e.g., diphenylethers, N-phenylphthalimides, oxadiazoles, oxazolidinediones, phenylpyrazoles, pyrimidindiones, thiadiazoles, triazolinones), carotenoid biosynthesis inhibitors (e.g., clomazone, amitrole, aclonifen), phytoene desaturase (PDS) inhibitors (e.g., amides, anilidex, furanones, phenoxybutan-amides, pyridiazinones, pyridines), 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors (e.g., callistemones, isoxazoles, pyrazoles, triketones), cellulose biosynthesis inhibitors (e.g., nitriles, benzamides, quinclorac, triazolocarboxamides), 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 limited to, biotypes with resistance or tolerance to multiple herbicides, biotypes with resistance or tolerance to multiple chemical classes, biotypes with resistance or tolerance to multiple herbicide modes-of-action, and biotypes with multiple resistance or tolerance mechanisms (e.g., target site resistance or metabolic resistance).
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with acifluorfen. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to acifluorfen or an agriculturally acceptable salt thereof is within the range of from about 1:210 to about 9:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to acifluorfen is within the range of from about 1:191 to about 2:1. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and acifluorfen sodium. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 37 grams active ingredient per hectare (g ai/ha) to about 720 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 38 g ai/ha to about 470 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and acifluorfen, e.g., sequentially or simultaneously. In some embodiments, the acifluorfen is applied at a rate from about 35 g ai/ha to about 420 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and acifluorfen sodium. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with acifluorfen are used to control ECHCO.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with azafeniden. In some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to azafeniden is within the range of from about 1:220 to about 10:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to azafeniden is within the range of from about 1:109 to about 2:1. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and azafeniden. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 32 grams active ingredient per hectare (g ai/ha) to about 540 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 33 g ai/ha to about 290 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and azafeniden, e.g., sequentially or simultaneously. In some embodiments, the azafeniden is applied at a rate from about 30 g ai/ha to about 240 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and azafeniden.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with bifenox. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to bifenox is within the range of from about 1:500 to about 3:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to bifenox is within the range of from about 1:455 to about 1:2.5. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and bifenox. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 127 grams active ingredient per hectare (g ai/ha) to about 1300 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 128 g ai/ha to about 1050 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and bifenox, e.g., sequentially or simultaneously. In some embodiments, the bifenox is applied at a rate from about 125 g ai/ha to about 1000 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and bifenox. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with bifenox are used to control CYPIR, ECHOR, IPOHE, PAPRH, or SCPMA.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with carfentrazone-ethyl or salt or ester thereof. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is within the range of from about 1:60 to about 86:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is within the range of from about 1:49 to about 49:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is within the range of from about 1:0.2 to about 1:10. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is within the range of from about 1:0.4 to about 1:5. In certain embodiments, the compositions provided herein comprise the compound of formula (I) or its benzyl or n-butyl ester and carfentrazone-ethyl. In one embodiment, the composition comprises the compound of formula (I) and carfentrazone-ethyl, wherein the weight ratio of the compound of formula (I) to carfentrazone-ethyl is about 1:0.4 to about 1:5. In one embodiment, the composition comprises the benzyl ester of the compound of formula (I) and carfentrazone-ethyl, wherein the weight ratio of the benzyl ester of the compound of formula (I) to carfentrazone-ethyl is about 1:0.4 to about 1:3.2. In one embodiment, the composition comprises the n-butyl ester of the compound of formula (I) and carfentrazone-ethyl, wherein the weight ratio of the n-butyl ester of the compound of formula (I) to carfentrazone-ethyl is about 1:1.75. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. The application rate will depend upon the particular type of weed to be controlled, the degree of control required, and the timing and method of application. In some embodiments, the composition is applied at an application rate of from about 5.5 grams active ingredient per hectare (g ai/ha) to about 420 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 8 g ai/ha to about 257 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester, e.g., sequentially or simultaneously. In some embodiments, the carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is applied at a rate from about 3.5 g ai/ha to about 120 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In some embodiments, the carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is applied at a rate from about 3 g ai/ha to about 430 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 g acid equivalent per hectare (g ae/ha) to about 84 g ae/ha. In some embodiments, the carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester is applied at a rate from about 7 g ai/ha to about 215 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 4.38 g acid equivalent per hectare (g ae/ha) to about 42.4 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I), or its benzyl or n-butyl ester and carfentrazone-ethyl. In one embodiment, the methods utilize the compound of formula (I) and carfentrazone-ethyl, wherein the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 42.4 g ae/ha, and carfentrazone-ethyl is applied at a rate of about 7 g ai/ha to about 215 g ai/ha. In one embodiment, the methods utilize the benzyl ester of the compound of formula (I) and carfentrazone-ethyl, wherein the benzyl ester of the compound of formula (I) is applied at a rate of from about 8.75 g acid equivalent per hectare (g ae/ha) to about 35 g ae/ha, and carfentrazone-ethyl is applied at a rate of about 3.5 g ai/ha to about 28 g ai/ha. In one embodiment, the methods utilize the n-butyl ester of the compound of formula (I) and carfentrazone-ethyl, wherein the n-butyl ester of the compound of formula (I) is applied at a rate of about 16 g acid equivalent per hectare (g ae/ha), and carfentrazone-ethyl is applied at a rate of about 28 g ai/ha. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with carfentrazone-ethyl or carboxylic acid or carboxylate salt thereof or other ester are used to control CYPES, CYPIR, DIGSA, ECHCG, ECHOR or LEFCH.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with flumioxazin. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to flumioxazin is within the range of from about 1:300 to about 17:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to flumioxazin is within the range of from about 1:272 to about 3:1. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and flumioxazin. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 19 grams active ingredient per hectare (g ai/ha) to about 900 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 20 g ai/ha to about 650 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and flumioxazin, e.g., sequentially or simultaneously. In some embodiments, the flumioxazin is applied at a rate from about 17.5 g ai/ha to about 600 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and flumioxazin.
In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with flumioxazin are used to control ECHCO, IPOHE, SETVI, or XANST.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with ipfencarbazone. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to ipfencarbazone is within the range of from about 1:250 to about 5:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to ipfencarbazone is within the range of from about 1:227 to about 1:1. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and ipfencarbazone. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 65 grams active ingredient per hectare (g ai/ha) to about 800 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 66 g ai/ha to about 550 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and ipfencarbazone, e.g., sequentially or simultaneously. In some embodiments, the ipfencarbazone is applied at a rate from about 62.5 g ai/ha to about 500 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and ipfencarbazone.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with oxadiargyl. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxadiargyl is within the range of from about 1:1100 to about 6:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxadiargyl is within the range of from about 1:509 to about 4:1. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and oxadiargyl. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 15 grams active ingredient per hectare (g ai/ha) to about 2500 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 16 g ai/ha to about 1170 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and oxadiargyl, e.g., sequentially or simultaneously. In some embodiments, the oxadiargyl is applied at a rate from about 50 g ai/ha to about 2200 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and oxadiargyl. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with oxadiargyl are used to control IPOHE.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with oxadiazon. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxadiazon is within the range of from about 1:2240 to about 10:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxadiazon is within the range of from about 1:57 to about 2:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxadiazon is within the range of from about 1:0.9 to about 1:57. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxadiazon is within the range of from about 1:1.8 to about 1:28.5. In certain embodiments, the compositions provided herein comprise the compound of formula (I) or its benzyl or n-butyl ester and oxadiazon. In one embodiment, the composition comprises the compound of formula (I) and oxadiazon, wherein the weight ratio of the compound of formula (I) to oxadiazon is about 1:1.8 to about 1:14.3. In one embodiment, the composition comprises the benzyl ester of the compound of formula (I) and oxadiazon, wherein the weight ratio of the benzyl ester of the compound of formula (I) to oxadiazon is about 1:1.8 to about 1:28.5. In one embodiment, the composition comprises the n-butyl ester of the compound of formula (I) and oxadiazon, wherein the weight ratio of the n-butyl ester of the compound of formula (I) to oxadiazon is about 1:3.6 to about 1:14.3. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 33 grams active ingredient per hectare (g ai/ha) to about 4780 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 35 g ai/ha to about 320 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and oxadiazon, e.g., sequentially or simultaneously. In some embodiments, the oxadiazon is applied at a rate from about 31 g ai/ha to about 4480 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In some embodiments, the oxadiazon is applied at a rate from about 15 g ai/ha to about 500 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 g acid equivalent per hectare (g ae/ha) to about 140 g ae/ha. In some embodiments, the oxadiazon is applied at a rate from about 31 g ai/ha to about 250 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 4.38 g acid equivalent per hectare (g ae/ha) to about 70 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I), or its benzyl or n-butyl ester and oxadiazon. In one embodiment, the methods utilize the compound of formula (I) and oxadiazon, wherein the compound of formula (I) is applied at a rate of from about 8.75 g acid equivalent per hectare (g ae/ha) to about 35 g ae/ha, and oxadiazon is applied at a rate of about 31 g ai/ha to about 250 g ai/ha. In one embodiment, the methods utilize the benzyl ester of the compound of formula (I) and oxadiazon, wherein the benzyl ester of the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha, and oxadiazon is applied at a rate of about 31 g ai/ha to about 250 g ai/ha. In one embodiment, the methods utilize the n-butyl ester of the compound of formula (I) and oxadiazon, wherein the n-butyl ester of the compound of formula (I) is applied at a rate of about 17.5 g acid equivalent per hectare (g ae/ha) to about 70 g ae/ha, and oxadiazon is applied at a rate of about 250 g ai/ha. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with oxadiazon are used to control ECHOR or IPOHE.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with oxyfluorfen. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxyfluorfen is within the range of from about 1:1120 to about 3:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxyfluorfen is within the range of from 1:82 to about 1:2. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxyfluorfen is within the range of from about 1:2 to about 1:164. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to oxyfluorfen is within the range of from about 1:4.2 to about 1:82. In certain embodiments, the compositions provided herein comprise the compound of formula (I) or its benzyl or n-butyl ester and oxyfluorfen. In one embodiment, the composition comprises the compound of formula (I) and oxyfluorfen, wherein the weight ratio of the compound of formula (I) to oxyfluorfen is about 1:4.2 to about 1:68. In one embodiment, the composition comprises the benzyl ester of the compound of formula (I) and oxyfluorfen, wherein the weight ratio of the benzyl ester of the compound of formula (I) to oxyfluorfen is about 1:5 to about 1:82. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 92 grams active ingredient per hectare (g ai/ha) to about 2540 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 94 g ai/ha to about 402 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and oxyfluorfen, e.g., sequentially or simultaneously. In some embodiments, the oxyfluorfen is applied at a rate from about 100 g ai/ha to about 2240 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In some embodiments, the oxyfluorfen is applied at a rate from about 45 g ai/ha to about 720 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 g acid equivalent per hectare (g ae/ha) to about 85 g ae/ha. In some embodiments, the oxyfluorfen is applied at a rate from about 90 g ai/ha to about 360 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 4.38 g acid equivalent per hectare (g ae/ha) to about 42.4 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I), or its benzyl or n-butyl ester and oxyfluorfen. In one embodiment, the methods utilize the compound of formula (I) and oxyfluorfen, wherein the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 42.4 g ae/ha, and oxyfluorfen is applied at a rate of about 90 g ai/ha to about 360 g ai/ha. In one embodiment, the methods utilize the benzyl ester of the compound of formula (I) and oxyfluorfen, wherein the benzyl ester of the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha, and oxyfluorfen is applied at a rate of about 90 g ai/ha to about 360 g ai/ha. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with oxyfluorfen are used to control CYPIR, CYPRO, DIGSA, ECHCG, ECHCO, IPOHE, or SCPJU.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with pentoxazone or salt thereof. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pentoxazone is within the range of from about 1: 225 to about 6:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pentoxazone is within the range of from 1:26 to about 1:2. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pentoxazone is within the range of from about 1:0.8 to about 1:52. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pentoxazone is within the range of from about 1:1.6 to about 1:26. In certain embodiments, the compositions provided herein comprise the compound of formula (I) or its benzyl ester and pentoxazone. In one embodiment, the composition comprises the compound of formula (I) and pentoxazone, wherein the weight ratio of the compound of formula (I) to pentoxazone is about 1:1.6 to about 1:13. In one embodiment, the composition comprises the benzyl ester of the compound of formula (I) and pentoxazone, wherein the weight ratio of the benzyl ester of the compound of formula (I) to pentoxazone is about 1:6 to about 1:26. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 58 grams active ingredient per hectare (g ai/ha) to about 750 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 61 g ai/ha) to about 148 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and pentoxazone, e.g., sequentially or simultaneously. In some embodiments, the pentoxazone is applied at a rate from about 56 g ai/ha to about 450 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In some embodiments, the pentoxazone is applied at a rate from about 25 g ai/ha to about 230 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 g acid equivalent per hectare (g ae/ha) to about 70 g ae/ha. In some embodiments, the pentoxazone is applied at a rate from about 56 g ai/ha to about 112 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 4.38 g acid equivalent per hectare (g ae/ha) to about 35 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I), or its benzyl ester and pentoxazone. In one embodiment, the methods utilize the compound of formula (I) and pentoxazone, wherein the compound of formula (I) is applied at a rate of from about 8.75 g acid equivalent per hectare (g ae/ha) to about 35 g ae/ha, and pentoxazone is applied at a rate of about 56 g ai/ha to about 113 g ai/ha. In one embodiment, the methods utilize the benzyl ester of the compound of formula (I) and pentoxazone, wherein the benzyl ester of the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 8.75 g ae/ha, and pentoxazone is applied at a rate of about 56 g ai/ha to about 113 g ai/ha. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with pentoxazone are used to control CYPRO, ECHCG, FIMMI or SCPJU.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with pyraclonil or salt thereof. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pyraclonil or salt thereof is within the range of from about 1:180 to about 9:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pyraclonil or salt thereof is within the range of from about 1:62 to about 1:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pyraclonil or salt thereof is within the range of from about 1:4.4 to about 2:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pyraclonil or salt thereof is within the range of from about 1:4.4 to about 2:1. In certain embodiments, the compositions provided herein comprise the compound of formula (I) or its benzyl or n-butyl ester and pyraclonil. In one embodiment, the composition comprises the compound of formula (I) and pyraclonil, wherein the weight ratio of the compound of formula (I) to pyraclonil is about 1:1 to about 2:1. In one embodiment, the composition comprises the benzyl ester of the compound of formula (I) and pyraclonil, wherein the weight ratio of the benzyl ester of the compound of formula (I) to pyraclonil is about 1:2 to about 2:1. In one embodiment, the composition comprises the n-butyl ester of the compound of formula (I) and pyraclonil, wherein the weight ratio of the n-butyl ester of the compound of formula (I) to pyraclonil is about 1:4.4 to about 2:1. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 36 grams active ingredient per hectare (g ai/ha) to about 660 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 41 g ai/ha to about 305 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and pyraclonil or salt thereof, e.g., sequentially or simultaneously. In some embodiments, the pyraclonil is applied at a rate from about 34 g ai/ha to about 360 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In some embodiments, the pyraclonil or salt thereof is applied at a rate from about 4 g ai/ha to about 140 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 g acid equivalent per hectare (g ae/ha) to about 45 g ae/ha. In some embodiments, the pyraclonil or salt thereof is applied at a rate from about 8.75 g ai/ha to about 70 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 4.38 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I), or its benzyl or n-butyl ester and pyraclonil. In one embodiment, the methods utilize the compound of formula (I) and pyraclonil, wherein the compound of formula (I) is applied at a rate of from about 8.75 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha, and pyraclonil is applied at a rate of about 8.75 g ai/ha to about 17.5 g ai/ha. In one embodiment, the methods utilize the benzyl ester of the compound of formula (I) and pyraclonil, wherein the benzyl ester of the compound of formula (I) is applied at a rate of from about 8.75 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha, and pyraclonil is applied at a rate of about 8.75 g ai/ha to about 17.5 g ai/ha. In one embodiment, the methods utilize the n-butyl ester of the compound of formula (I) and pyraclonil, wherein the n-butyl ester of the compound of formula (I) is applied at a rate of about 16 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha, and pyraclonil is applied at a rate of about 70 g ai/ha to about 17.5 g ai/ha. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with pyraclonil are used to control BRAPP, CYPRO, ECHCG, ECHCO, ECHOR IPOHE or ISCRU.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with pyraflufen-ethyl or carboxylic acid or carboxylate salt thereof or other ester. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pyraflufen-ethyl or carboxylic acid or carboxylate salt thereof or other ester is within the range of from about 1:6 to about 150:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to pyraflufen-ethyl or carboxylic acid or carboxylate salt thereof or other ester is within the range of from about 1:5.5 to about 25:1. In certain embodiments, the compositions comprise the compound of formula (I) or its benzyl or n-butyl ester and pyraflufen-ethyl. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 4 grams active ingredient per hectare (g ai/ha) to about 312 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 5 g ai/ha to about 62 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and pyraflufen-ethyl or carboxylic acid or carboxylate salt thereof or other ester, e.g., sequentially or simultaneously. In some embodiments, the pyraflufen-ethyl or carboxylic acid or carboxylate salt thereof or other ester is applied at a rate from about 2 g ai/ha to about 12 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I) or its benzyl or n-butyl ester and pyraflufen-ethyl. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with pyraflufen-ethyl are used to control CYPIR or ECHCG.
In certain embodiments of the compositions and methods described herein, the compound of formula (I) or salt or ester thereof is used in combination with saflufenacil or salt thereof. With regard to the compositions, in some embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to saflufenacil or salt or ester thereof is within the range of from about 1:100 to about 60:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to saflufenacil or salt or ester thereof is within the range of from about 1:9 to about 12:1. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to saflufenacil or salt thereof is within the range of from about 1:0.1 to about 1:10. In certain embodiments, the weight ratio of the compound of formula (I) or salt or ester thereof to saflufenacil or salt thereof is within the range of from about 1:0.3 to about 1:5. In certain embodiments, the compositions provided herein comprise the compound of formula (I) or its benzyl or n-butyl ester and saflufenacil. In one embodiment, the composition comprises the compound of formula (I) and saflufenacil, wherein the weight ratio of the compound of formula (I) to saflufenacil is about 1:0.3 to about 1:5. In one embodiment, the composition comprises the benzyl ester of the compound of formula (I) and saflufenacil, wherein the weight ratio of the benzyl ester of the compound of formula (I) to saflufenacil is about 1:0.3 to about 1:5. In one embodiment, the composition comprises the n-butyl ester of the compound of formula (I) and saflufenacil, wherein the weight ratio of the n-butyl ester of the compound of formula (I) to saflufenacil is about 1:1.1. With respect to the methods, in certain embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation a composition described herein. In some embodiments, the composition is applied at an application rate of from about 7 grams active ingredient per hectare (g ai/ha) to about 500 g ai/ha based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at an application rate of from about 9 g ai/ha to about 110 g ai/ha based on the total amount of active ingredients in the composition. In some embodiments, the methods comprise contacting the undesirable vegetation or locus thereof or applying to the soil or water to prevent the emergence or growth of vegetation with a compound of formula (I) or salt or ester thereof and saflufenacil or salt thereof, e.g., sequentially or simultaneously. In some embodiments, the saflufenacil or salt or ester thereof is applied at a rate from about 5 g ai/ha to about 200 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 grams acid equivalent per hectare (g ae/ha) to about 300 g ae/ha. In some embodiments, the saflufenacil or salt thereof is applied at a rate from about 2 g ai/ha to about 80 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 2 g acid equivalent per hectare (g ae/ha) to about 140 g ae/ha. In some embodiments, the saflufenacil or salt thereof is applied at a rate from about 5 g ai/ha to about 40 g ai/ha and the compound of formula (I) of salt or ester thereof is applied at a rate from about 4.38 g acid equivalent per hectare (g ae/ha) to about 70 g ae/ha. In certain embodiments, the methods utilize the compound of formula (I), or its benzyl or n-butyl ester and saflufenacil. In one embodiment, the methods utilize the compound of formula (I) and saflufenacil, wherein the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 70 g ae/ha, and saflufenacil is applied at a rate of about 5 g ai/ha to about 40 g ai/ha. In one embodiment, the methods utilize the benzyl ester of the compound of formula (I) and saflufenacil, wherein the benzyl ester of the compound of formula (I) is applied at a rate of from about 4.38 g acid equivalent per hectare (g ae/ha) to about 17.5 g ae/ha, and saflufenacil is applied at a rate of about 5 g ai/ha to about 20 g ai/ha. In one embodiment, the methods utilize the n-butyl ester of the compound of formula (I) and saflufenacil, wherein the n-butyl ester of the compound of formula (I) is applied at a rate of about 35 g acid equivalent per hectare (g ae/ha), and saflufenacil is applied at a rate of about 40 g ai/ha. In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with saflufenacil or salt thereof are used to control CYPIR, CYPRO, ECHCG, ECHCO, ECHOR, ISCRU, or LEFCH.
The components of the mixtures described herein can be applied either separately or as part of a multipart herbicidal system.
The mixtures described herein can be applied in conjunction with one or more other herbicides to control a wider variety of undesirable vegetation. When used in conjunction with other herbicides, the composition can be formulated with the other herbicide or herbicides, 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 compositions and methods described herein include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 2,4-D choline salt, 2,4-D esters and amines, 2,4-DB; 3,4-DA; 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, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benthiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bialaphos, bicyclopyrone, 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, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop-propargyl, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop-butyl, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop-methyl, 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, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethbenzamide, ethametsulfuron, ethidimuron, ethiolate, ethobenzamid, etobenzamid, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P-ethyl, fenoxaprop-P-ethyl+isoxadifen-ethyl, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, fluorochloridone, fluoroxypyr, fluoroxypyr-meptyl, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, fumiclorac, furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P-ammonium, glyphosate, halauxifen, halauxifen-methyl, halosafen, halosulfuron-methyl, haloxydine, haloxyfop-methyl, haloxyfop-P-methyl, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazosulfuron, imazethapyr, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron-ethyl-sodium, iofensulfuron, ioxynil, ipazine, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA esters and amines, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxapyrazon, oxasulfuron, oxaziclomefone, paraflufen-ethyl, parafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron-methyl, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prohexadione-calcium, prometon, prometryn, pronamide, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P-ethyl, rhodethanil, rimsulfuron, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin, swep, SYN-523, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thifensulfurn-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, tricamba, triclopyr choline salt, triclopyr esters and salts, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac tritosulfuron, vernolate, xylachlor and salts, esters, optically active isomers and mixtures thereof.
The compositions and methods described herein, can further be used in conjunction with glyphosate, 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, glufosinate, glutamine synthetase inhibitors, dicamba, phenoxy auxins, pyridyloxy auxins, synthetic auxins, auxin transport inhibitors, aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazolines, acetyl CoA carboxylase (ACCase) inhibitors, imidazolinones, sulfonylureas, pyrimidinylthiobenzoates, triazolopyrimidines, sulfonylaminocarbonyltriazolinones, acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, phytoene desaturase inhibitors, carotenoid biosynthesis inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, cellulose biosynthesis inhibitors, mitosis inhibitors, microtubule inhibitors, very long chain fatty acid inhibitors, fatty acid and lipid biosynthesis inhibitors, photosystem I inhibitors, photosystem II inhibitors, triazines, and bromoxynil on glyphosate-tolerant, EPSP synthase inhibitor-tolerant, glufosinate-tolerant, glutamine synthetase inhibitor-tolerant, dicamba-tolerant, phenoxy auxin-tolerant, pyridyloxy auxin-tolerant, auxin-tolerant, auxin transport inhibitor-tolerant, aryloxyphenoxypropionate-tolerant, cyclohexanedione-tolerant, phenylpyrazoline-tolerant, ACCase-tolerant, imidazolinone-tolerant, sulfonylurea-tolerant, pyrimidinylthiobenzoate-tolerant, triazolopyrimidine-tolerant, sulfonylaminocarbonyltriazolinone-tolerant, ALS- or AHAS-tolerant, HPPD-tolerant, phytoene desaturase inhibitor-tolerant, carotenoid biosynthesis inhibitor tolerant, PPO-tolerant, cellulose biosynthesis inhibitor-tolerant, mitosis inhibitor-tolerant, microtubule inhibitor-tolerant, very long chain fatty acid inhibitor-tolerant, fatty acid and lipid biosynthesis inhibitor-tolerant, photosystem I inhibitor-tolerant, photosystem II inhibitor-tolerant, triazine-tolerant, bromoxynil-tolerant, and crops possessing multiple or stacked traits conferring tolerance to multiple chemistries and/or multiple modes of action via single and/or multiple resistance mechanisms. In some embodiments, the compound of formula (I) or salt or ester thereof and complementary herbicide or salt or ester thereof are used in combination with herbicides that are selective for the crop being treated and which complement the spectrum of weeds controlled by these compounds at the application rate employed. In some embodiments, the compositions described herein and other complementary herbicides are applied at the same time, either as a combination formulation, as a tank mix, or as a sequential application.
In some embodiments, the compositions described herein are employed in combination with one or more herbicide safeners, such as AD-67 (MON 4660), benoxacor, benthiocarb, brassinolide, cloquintocet (mexyl), cyometrinil, daimuron, dichlormid, dicyclonon, dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, harpin proteins, isoxadifen-ethyl, jiecaowan, jiecaoxi, mefenpyr-diethyl, mephenate, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoic acid amides, to enhance their selectivity. In some embodiments, the safeners are employed in rice, cereal, corn, or maize settings. In some embodiments, the safener is cloquintocet or an ester or salt thereof. In certain embodiments, cloquintocet is utilized to antagonize harmful effects of the compositions on rice and cereals. In some embodiments, the safener is cloquintocet (mexyl).
In some embodiments, the compositions described herein are employed in combination with one or more plant growth regulators, such as 2,3,5-tri-iodobenzoic acid, IAA, IBA, naphthaleneacetamide, α-naphthaleneacetic acids, benzyladenine, 4-hydroxyphenethyl alcohol, kinetin, zeatin, endothal, ethephon, pentachlorophenol, thidiazuron, tribufos, aviglycine, gibberellins, gibberellic acid, abscisic acid, ancymidol, fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat, 2,3,5-tri-iodobenzoic acid, morphactins, dichlorflurenol, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, brassinolide, brassinolide-ethyl, cycloheximide, ethylene, methasulfocarb, prohexadione, triapenthenol and trinexapac.
In some embodiments, the plant growth regulators are employed in one or more crops or settings, such as rice, cereal crops, corn, maize, broadleaf crops, oilseed rape/canola, turf, pineapple, sugarcane, sunflower, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, plantation crops, vegetables, and non-crop (ornamentals) settings. In some embodiments, the plant growth regulator is mixed with the compound of formula (I), or mixed with the compound of formula (I) and a protoporphyrinogen oxidase to cause a preferentially advantageous effect on plants.
In some embodiments, compositions provided herein further comprise at least one agriculturally 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 selective weed control in the presence of crops, and should not react chemically with herbicidal components or other composition ingredients. Such mixtures can be designed for application directly to weeds or their locus or can be concentrates or formulations that are normally diluted with additional carriers and adjuvants before application. They can be solids, such as, for example, dusts, granules, water-dispersible granules, or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions. They can also be provided as a pre-mix or tank mixed.
Suitable agricultural adjuvants and carriers include, but are not limited to, crop oil concentrate; nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C11 alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C12-C16) ethoxylate; di-sec-butylphenol 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) dioleate-99.
Liquid carriers that can be employed include water and organic solvents. The organic solvents include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono, di and polycarboxylic acids and the like. Specific organic solvents include, but are not limited to toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers and the like. In certain embodiments, Water is the carrier for the dilution of concentrates.
Suitable solid carriers include but are not limited to talc, 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, cellulose, and the like.
In some embodiments, the compositions described herein further comprise one or more surface-active agents. In some embodiments, such surface-active agents are employed in both solid and liquid compositions, and in certain embodiments those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants which may also be used in the present formulations are described, inter alia, in “McCutcheon's Detergents and Emulsifiers Annual,” MC Publishing Corp., Ridgewood, N.J., 1998 and in “Encyclopedia of Surfactants,” Vol. I-III, Chemical Publishing Co., New York, 1980-81. Surface-active agents include, but are not limited to salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C16 ethoxylate; soaps, such as sodium stearate; alkyl-naphthalene-sulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of mono and dialkyl phosphate esters; vegetable or seed oils such as soybean oil, rapeseed/canola oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; and esters of the above vegetable oils, and in certain embodiments, methyl esters.
In some embodiments, these materials, such as vegetable or seed oils and their esters, can be used interchangeably as an agricultural adjuvant, as a liquid carrier or as a surface active agent.
Other exemplary additives for use in the compositions provided herein include but are not limited to compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, sticking agents, dispersing agents, thickening agents, freezing point depressants, antimicrobial agents, and the like. The compositions may also contain other compatible components, for example, other herbicides, plant growth regulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.
In some embodiments, the concentration of the active ingredients in the compositions described herein is from about 0.0005 to 98 percent by weight. In some embodiments, the concentration is from about 0.0006 to 90 percent by weight. In compositions designed to be employed as concentrates, the active ingredients, in certain embodiments, are present in a concentration from about 0.1 to 98 weight percent, and in certain embodiment's about 0.5 to 90 weight percent. Such compositions are, in certain embodiments, diluted with an inert carrier, such as water, before application. The diluted compositions usually applied to weeds or the locus of weeds contain, in certain embodiments, about 0.0006 to 3.0 weight percent active ingredient and in certain embodiments contain about 0.01 to 1.0 weight percent.
The present compositions can be applied to weeds or their locus by the use of conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation 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 claims. 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 spirit and scope of the claimed subject matter.
EXAMPLES
Results in Examples I, II, III and IV are greenhouse trial results.
Example I
Evaluation of Postemergence Foliar-Applied Herbicidal Mixtures for Weed Control in Direct Seeded Rice
Seeds or nutlets of the desired test plant species were planted in a soil matrix prepared by mixing a loam or sandy loam soil (e.g., 28.6 percent silt, 18.8 percent clay, and 52.6 percent sand, with a pH of about 5.8 and an organic matter content of about 1.8 percent) and calcareous grit in an 80 to 20 ratio. The soil matrix was contained in plastic pots with a volume of 1 quart and a surface area of 83.6 square centimeters (cm2). When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 8-22 days in a greenhouse with an approximate 14 h photoperiod which was maintained at about 29° C. during the day and 26° C. during the night. Nutrients (Peters Excel® 15-5-15 5-Ca 2-Mg and iron chelate) were applied in the irrigation solution as needed and water was added on a regular basis. Supplemental lighting was provided with overhead metal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the first through fourth true leaf stage.
Treatments consisted of the acid or esters of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (Compound A), each formulated as an SC (suspension concentrate), and various herbicidal components alone and in combination. Forms of compound A were applied on an acid equivalent basis.
Forms of compound A (compound of formula I) tested include:




Other herbicidal components were applied on an active ingredient basis and included protoporphyrinogen oxidase (PPO)-inhibiting herbicides carfentrazone-ethyl formulated as Aim® EC, oxyfluorfen formulated as GoalTender® SC or technical material, pyraclonil formulated as Pyraclon®, oxadiazon formulated as Ronstar® 50W, and saflufenacil formulated as Sharpen®, acifluorfen sodium salt formulated as Blazer, bifenox formulated as Fox or technical grade material, flumioxazin formulated as Payload, and pyraflufen-ethyl (technical grade material).

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.
For treatments comprised of formulated compounds, measured amounts of compounds were placed individually in 25 mL glass vials and diluted in a volume of 1.25% (v/v) Agri-Dex® crop oil concentrated to obtain 12× 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 (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.25% (v/v) crop oil concentrate so that the final spray solutions contained 1.25+/−0.05% (v/v) crop oil concentrate.
For treatments comprised of technical compounds, weighed amounts can be placed individually in 25 mL glass vials and dissolved in a volume of 97:3 v/v acetone/DMSO to obtain 12× stock solutions. If a test compound does not dissolve readily, the mixture can be warmed and/or sonicated. Application solutions can be prepared by adding an appropriate amount of each stock solution (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.5% (v/v) crop oil concentrate so that the final spray solutions contain 1.25% (v/v) crop oil concentrate. When technical materials are used, the concentrated stock solutions can be added to the spray solutions so that the final acetone and DMSO concentrations of the application solutions are 16.2% and 0.5%, respectively.
For treatments comprised of formulated and technical compounds, weighed 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 12× stock solutions, and measured amounts of the formulated compounds were placed individually in 25 mL glass vials and diluted in a volume of 1.5% (v/v) crop oil concentrate or water to obtain 12× 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 (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of an appropriate amount of an aqueous mixture of 1.5% (v/v) crop oil concentrate so that the final spray solutions contained 1.25% (v/v) crop oil concentrate. When required, additional water and/or 97:3 v/v acetone/DMSO was added to individual application solutions so that the final acetone and DMSO concentrations of the application solutions being compared were 8.1% and 0.25%, respectively.
All stock solutions and applications solutions were visually inspected for compound compatibility prior to application. Spray solutions were applied to the plant material with an overhead Mandel track sprayer equipped with a 8002E nozzles calibrated to deliver 187 L/ha over an application area of 0.503 m2 at a spray height of 18 to 20 inches (46 to 50 cm) above 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 described above and watered by sub-irrigation to prevent wash-off of the test compounds. After approximately 3 weeks, the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury or growth inhibition and 100 corresponds to complete kill.
Colby's equation was used to determine the herbicidal effects expected from the mixtures (Colby, S. R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 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×B/100)

A=observed efficacy of active ingredient A at the same concentration as used in the mixture.
B=observed efficacy of active ingredient B at the same concentration as used in the mixture.
The compounds tested, application rates employed, plant species tested, and results are given in Tables 1-21.







TABLE 1





Synergistic Activity of Foliar-Applied Compound A Acid and


Carfentrazone-ethyl Herbicidal Compositions on Weed Control in a


Rice Cropping System.



















Visual Weed Control (%) - 21


Compound
Carfentrazone-
DAA










A Acid
ethyl
DIGSA
ECHCG












g ae/ha
g ai/ha
Obs
Exp
Obs
Exp





 4.38
0
33
—
33
—


 8.75
0
40
—
55
—


17.5 
0
43
—
93
—


0  
14
0
—
10
—


 4.38
14
50
33
50
39


 8.75
14
35
40
70
60


17.5 
14
60
43
95
93















Compound
Carfentrazone-





A Acid
ethyl



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) -



21 DAA



CYPES












4.38
0
18
—



8.75
0
80
—



0  
7
0
—



0  
14
0
—



4.38
7
40
18



8.75
7
95
80



4.38
14
50
18



8.75
14
90
80










Visual Weed




Control (%) -



19 DAA



LEFCH












19.4 
0
5
—



0  
28
10
—



19.4 
28
38
15

















TABLE 2







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester and


Carfentrazone-ethyl Herbicidal Compositions on Weed Control in a Rice


Cropping System.











Visual Weed


Compound

Control (%) - 21


A Benzyl
Carfentrazone-
DAA










Ester
ethyl
ECHCG
CYPIR












g ae/ha
g ai/ha
Obs
Exp
Obs
Exp















8.75
0
55
—
85
—


0
3.5
0
—
0
—


0
7
0
—
0
—


0
14
10
—
0
—


8.75
3.5
75
55
100
85


8.75
7
90
55
100
85


8.75
14
80
60
85
85
















TABLE 3







Synergistic Activity of Foliar-Applied Compound A n-Butyl Ester and


Carfentrazone-ethyl Herbicidal Compositions on Weed Control in a


Rice Cropping System.














Visual Weed




Compound

Control (%) -



A n-Butyl
Carfentrazone-
19 DAA



Ester
ethyl
LEFCH












g ae/ha
g ai/ha
Obs
Exp
















16
0
10
—



0
28
10
—



16
28
35
19

















TABLE 4







Synergistic Activity of Foliar-Applied Compound A Acid and Oxyfluorfen


(technical) Herbicidal Compositions on Weed Control in a Rice Cropping


System.














Visual Weed






Control (%) - 21



Compound

DAA



A Acid
Oxyfluorfen
DIGSA












g ae/ha
g ai/ha
Obs
Exp
















5.3
0
20
—



10.6
0
30
—



21.2
0
35
—



0
90
70
—



0
180
50
—



0
360
85
—



5.3
90
60
76



10.6
90
99
79



21.2
90
99
81



5.3
180
100
60



10.6
180
95
65



21.2
180
100
68



5.3
360
100
88



10.6
360
100
90



21.2
360
100
90

















TABLE 5







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester and


Oxyfluorfen (technical) Herbicidal Compositions on Weed Control in a


Rice Cropping System.












Compound






A Benzyl





Ester
Oxyfluorfen




g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control



(%) - 21



DAA



DIGSA












4.38
0
10
—



8.75
0
45
—



17.5
0
70
—



0
180
50
—



4.38
180
100
55



8.75
180
99
73



17.5
180
95
85










Visual Weed




Control



(%) - 21



DAA



CYPIR












4.38
0
30
—



0
90
0
—



0
180
30
—



0
360
40
—



4.38
90
95
30



4.38
180
100
51



4.38
360
100
58

















TABLE 6







Synergistic Activity of Foliar-Applied Compound A Acid and


Oxyfluorfen (SC) Herbicidal Compositions on Weed Control in a Rice


Cropping System.












Compound






A Acid
Oxyfluorfen



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 23



DAA



ECHCG












4.38
0
45
—



8.75
0
55
—



17.5
0
80
—



0
180
30
—



4.38
180
80
62



8.75
180
85
69



17.5
180
80
86










Visual Weed




Control (%) - 23



DAA



ECHCO












4.38
0
15
—



8.75
0
60
—



0
90
50
—



4.38
90
95
58



8.75
90
100
80

















TABLE 7







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester and


Oxyfluorfen (SC) Herbicidal Compositions on Weed Control in a Rice


Cropping System.












Compound






A Benzyl




Ester
Oxyfluorfen



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 23



DAA



DIGSA












4.38
0
0
—



8.75
0
0
—



17.5
0
15
—



0
180
60
—



4.38
180
65
60



8.75
180
100
60



17.5
180
100
66










Visual Weed




Control (%) - 23



DAA



ECHCG












4.38
0
40
—



0
90
30
—



0
180
30
—



0
360
95
—



4.38
90
80
58



4.38
180
100
58



4.38
360
100
97










Visual Weed




Control (%) - 23



DAA



IPOHE












4.38
0
10
—



8.75
0
10
—



17.5
0
40
—



0
90
85
—



0
180
85
—



4.38
90
100
87



8.75
90
100
87



17.5
90
100
91



4.38
180
99
87



8.75
180
100
87



17.5
180
100
91

















TABLE 8





Synergistic Activity of Foliar-Applied Compound A Acid and Pyraclonil


Herbicidal Compositions on Weed Control in a Rice Cropping System.






















Visual Weed






Control (%) - 20



Compound

DAA



A Acid
Pyraclonil
BRAPP












g ae/ha
g ai/ha
Obs
Exp







4.38
0
10
—



0  
33.75
0
—



0  
67.5
0
—



0  
135
0
—



4.38
33.75
45
10



4.38
67.5
50
10



4.38
135
55
10


















Visual Weed




Compound

Control (%) - 20 DAA














A Acid
Pyraclonil
ECHCG

ECHCO















g ae/ha
g ai/ha
Obs
Exp
Obs
Exp







4.38
0
25
—
50
—



8.75
0
80
—
75
—



0  
33.75
0
—
0
—



0  
67.5
0
—
15
—



0  
135
0
—
20
—



4.38
33.75
65
25
75
50



8.75
33.75
90
80
95
75



4.38
67.5
85
25
70
58



8.75
67.5
95
80
80
79



4.38
135
90
25
70
60



8.75
135
95
80
90
80
















Compound






A Acid
Pyraclonil



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 21



DAA



ECHCG












17.5
0
88
—



35  
0
85
—



0 
270
0
—



17.5
270
90
88



35  
270
100
85










Visual Weed




Control (%) - 21



DAA



IPOHE












35  
0
45
—



0 
270
45
—



35  
270
88
70

















TABLE 9







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester and


Pyraclonil Herbicidal Compositions on Weed Control in a Rice


Cropping System.












Compound






A Benzyl



Ester
Pyraclonil



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control



(%) - 20



DAA



ECHCO












4.38
0
40
—



0
33.75
0
—



0
67.5
15
—



0
135
20
—



4.38
33.75
50
40



4.38
67.5
60
49



4.38
135
75
52










Visual Weed




Control



(%) - 21



DAA



IPOHE












17.5
0
10
—



35
0
50
—



0
270
45
—



17.5
270
70
51



35
270
93
73










Visual Weed




Control



(%) - 21



DAA



ISCRU












8
0
20
—



16
0
0
—



0
67.5
0
—



0
135
0
—



0
270
0
—



8
67.5
50
20



16
67.5
30
 0



8
135
70
20



16
135
100
 0



8
270
95
20



16
270
60
 0

















TABLE 10







Synergistic Activity of Foliar-Applied Compound A Acid and Oxadiazon


Herbicidal Compositions on Weed Control in a Rice Cropping System.












Compound






A Acid
Oxadiazon



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 20



DAA



IPOHE












8.75
0
10
—



0
31.25
15
—



0
62.5
20
—



0
125
30
—



8.75
31.25
20
24



8.75
62.5
50
28



8.75
125
50
37










Visual Weed




Control (%) - 20



DAA



IPOHE












17.5
0
30
—



35
0
45
—



0
250
5
—



17.5
250
63
34



35
250
75
48

















TABLE 11







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester and


Oxadiazon Herbicidal Compositions on Weed Control in a Rice


Cropping System.












Compound






A Benzyl




Ester
Oxadiazon



g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 20



DAA



IPOHE












4.38
0
10
—



8.75
0
10
—



17.5
0
15
—



0
31.25
15
—



0
62.5
20
—



0
125
30
—



4.38
31.25
40
24



8.75
31.25
40
24



17.5
31.25
60
28



4.38
62.5
60
28



8.75
62.5
30
28



17.5
62.5
30
32



4.38
125
50
37



8.75
125
55
37



17.5
125
50
41










Visual Weed




Control (%) - 21



DAA



IPOHE












17.5
0
10
—



0
250
5
—



17.5
250
45
15

















TABLE 12







Synergistic Activity of Foliar-Applied Compound A n-Butyl Ester and


Oxadiazon Herbicidal Compositions on Weed Control in a Rice


Cropping System.














Visual Weed




Compound

Control (%) - 21



A n-Butyl

DAA



Ester
Oxadiazon
IPOHE












g ae/ha
g ai/ha
Obs
Exp
















17.5
0
40
—



0
250
5
—



17.5
250
60
43

















TABLE 13





Synergistic Activity of Foliar-Applied Compound A Acid and Saflufenacil


Herbicidal Compositions on Weed Control in a Rice Cropping System.






















Visual Weed






Control (%) - 20



Compound

DAA



A Acid
Saflufenacil
LEFCH












g ae/ha
g ai/ha
Obs
Exp







 4.38
0
0
—



 8.75
0
30
—



17.5 
0
30
—



0  
5
0
—



 4.38
5
30
 0



 8.75
5
30
30



17.5 
5
45
30
















Visual Weed



Compound

Control (%) - 20 DAA












A Acid
Saflufenacil
ECHCO

CYPIR













g ae/ha
g ai/ha
Obs
Exp
Obs
Exp





4.38
0
40
—
30
—


0  
5
0
—
0
—


0  
10
40
—
0
—


0  
20
40
—
100
—


4.38
5
45
40
100
30


4.38
10
70
64
70
30


4.38
20
80
64
100
100 
















TABLE 14







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester


and Saflufenacil Herbicidal Compositions on Weed Control in


a Rice Cropping System.











Compound





A Benzyl



Ester
Saflufenacil












g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 20



DAA



ECHCO












4.38
0
60
—



8.75
0
80
—



0  
10
40
—



0  
20
40
—



4.38
10
40
76



8.75
10
99
88



4.38
20
90
76



8.75
20
90
88










Visual Weed




Control (%) - 20



DAA



LEFCH












8.75
0
30
—



17.5 
0
50
—



0  
5
0
—



0  
10
0
—



8.75
5
80
30



17.5 
5
40
50



8.75
10
20
30



17.5 
10
70
50










Visual Weed




Control (%) - 20



DAA



CYPIR












4.38
0
70
—



0  
5
0
—



0  
10
0
—



0  
20
100
—



4.38
5
100
70



4.38
10
100
70



4.38
20
100
100 










Visual Weed




Control (%) - 21



DAA



ISCRU












8  
0
20
—



16   
0
0
—



0  
10
0
—



0  
20
0
—



8  
10
100
20



16   
10
70
 0



8  
20
70
20



16   
20
70
 0

















TABLE 15







Synergistic Activity of Foliar-Applied Compound A Acid and Oxadiargyl


Herbicidal Compositions on Weed Control in a Rice Cropping System.














Visual Weed






Control (%) - 22



Compound

DAA



A Acid
Oxadiargyl
IPOHE












g ae/ha
g ai/ha
Obs
Exp
















4.38
0
15
—



8.75
0
35
—



17.5 
0
50
—



0  
50
25
—



4.38
50
85
36



8.75
50
70
51



17.5 
50
70
63

















TABLE 16







Synergistic Activity of Foliar-Applied Compound A Benzyl


Ester and Oxadiargyl Herbicidal Compositions on Weed


Control in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 22



A Benzyl

DAA



Ester
Oxadiargyl
IPOHE












g ae/ha
g ai/ha
Obs
Exp
















4.38
0
10
—



8.75
0
35
—



0
50
25
—



4.38
50
85
33



8.75
50
75
51

















TABLE 17







Synergistic Activity of Foliar-Applied Compound A Benzyl


Ester and Acifluorfen Sodium Herbicidal Compositions on Weed


Control in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 21



A Benzyl
Acifluorfen
DAA



Ester
sodium
ECHCO












g ae/ha
g ai/ha
Obs
Exp
















8
0
40
—



0
140
0
—



0
280
25
—



8
140
60
40



8
280
65
55

















TABLE 18







Synergistic Activity of Foliar-Applied Compound A Benzyl


Ester and Bifenox (technical) Herbicidal Compositions on Weed


Control in a Rice Cropping System.












Compound

Visual Weed




A Benzyl

Control (%) - 22



Ester
Bifenox
DAA












g ae/ha
g ai/ha
Obs
Exp














IPOHE













8
0
10
—



16
0
40
—



32
0
45
—



0
360
40
—



0
720
65
—



8
360
70
46



16
360
80
64



32
360
70
67



8
720
95
69



16
720
80
79



32
720
100
81










CYPIR













8
0
10
—



16
0
60
—



0
180
0
—



0
720
0
—



8
180
30
10



16
180
100
60



8
720
30
10



16
720
70
60

















TABLE 19







Synergistic Activity of Foliar-Applied Compound A Benzyl


Ester and Bifenox (Fox ®) Herbicidal Compositions on Weed


Control in a Rice Cropping System.












Compound

Visual Weed




A Benzyl

Control (%) - 21



Ester
Bifenox
DAA












g ae/ha
g ai/ha
Obs
Exp














IPOHE













16
0
10
—



32
0
45
—



0
180
55
—



16
180
95
60



32
180
100
75










CYPIR













8
0
30
—



0
180
0
—



0
360
0
—



0
720
0



8
180
30
30



8
360
85
30



8
720
50
30

















TABLE 20







Synergistic Activity of Foliar-Applied Compound A Benzyl


Ester and Flumioxazin Herbicidal Compositions on Weed


Control in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 20



A Benzyl

DAA



Ester
Flumioxazin
ECHCO












g ae/ha
g ai/ha
Obs
Exp
















8
0
40
—



16 
0
60
—



0
140
60
—



0
280
70
—



8
140
90
76



16 
140
90
84



8
280
90
82



16 
280
100
88

















TABLE 21







Synergistic Activity of Foliar-Applied Compound A Benzyl


Ester and Pyraflufenethyl Herbicidal Compositions on Weed


Control in a Rice Cropping System.












Compound 

Visual Weed




A Benzyl
Pyraflufen-
Control (%) - 21



Ester
ethyl
DAA












g ae/ha
g ai/ha
Obs
Exp














ECHCG













8
0
45
—



0
5.3
15
—



0
10.6
15
—



8
5.3
65
53



8
10.6
80
53










CYPIR













8
0
35
—



0
2.65
0
—



0
5.3
0
—



0
10.6
20
—



8
2.65
50
35



8
5.3
70
35



8
10.6
60
48
























BRAPP
Brachiaria platyphylla (Griseb.) Nash
signalgrass, broadleaf


CYPDI
Cyperus difformis L.
sedge, smallflower




umbrella


CYPES
Cyperus esculentus L.
nutsedge, yellow


CYPIR
Cyperus iria L.
flatsedge, rice


DIGSA
Digitaria sanguinalis (L.) Scop.
crabgrass, large


ECHCG
Echinochloa crusgalli (L.) Beauv.
barnyardgrass


ECHCO
Echinochloa colona (L.) Link
junglerice


IPOHE
Ipomoea hederacea Jacq.
morningglory, ivyleaf


ISCRU
Ischaemum rugosum Salisb.
saramollagrass


LEFCH
Leptochloa chinensis (L.) Nees
sprangletop, Chinese


SCPJU
Schoenoplectus juncoides (Roxb.) Palla
bulrush, Japanese







g ae/ha = grams acid equivalent per hectare


g ai/ha = grams active ingredient per hectare


Obs = observed value


Exp = expected value as calculated by Colby's equation


DAA = days after application









Example II
Evaluation of in-Water Applied Herbicidal Mixtures for Weed Control in Transplanted Paddy Rice
Weed seeds or nutlets of the desired test plant species were planted in puddled soil (mud) prepared by mixing a shredded, non-sterilized mineral soil (50.5 percent silt, 25.5 percent clay, and 24 percent sand, with a pH of about 7.6 and an organic matter content of about 2.9 percent) and water at a 1:1 volumetric ratio. The prepared mud was dispensed in 365 mL aliquots into 16-ounce (oz.) non-perforated plastic pots with a surface area of 86.59 square centimeters (cm2) leaving a headspace of 3 centimeters (cm) in each pot Mud was allowed to dry overnight prior to planting or transplanting. Rice seeds were planted in Sun Gro MetroMix® 306 planting mixture, which typically has a pH of 6.0 to 6.8 and an organic matter content of about 30 percent, in plastic plug trays. Seedlings at the second or third leaf stage of growth were transplanted into 840 mL of mud contained in 32-oz. non-perforated plastic pots with a surface area of 86.59 cm2 4 days prior to herbicide application. The paddy was created by filling the headspace of the pots with 2.5 to 3 cm of water. When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 4-22 days in a greenhouse with an approximate 14 h photoperiod which was maintained at about 29′C during the day and 26° C. during the night. Nutrients were added as Osmocote® (19:6:12, N:P:K+minor nutrients) at 2 g per 16-oz. pot and 4 g per 32-oz. pot. Water was added on a regular basis to maintain the paddy flood, 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 through fourth true leaf stage.
Treatments consisted of the acid or esters of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (compound A) each formulated as an SC and various herbicidal components alone and in combination. Forms of compound A were applied on an acid equivalent basis.
Forms of compound A (compound of formula I) tested include:




Other herbicidal components were applied on an active ingredient basis and included protoporphyrinogen oxidase (PPO)-inhibiting herbicides carfentrazone-ethyl formulated as Aim® EC, oxyfluorfen formulated as an SC or technical material, pyraclonil formulated as Pyraclon®, oxadiazon formulated as Ronstar® 50W, saflufenacil formulated as Sharpen®, pentoxazone (technical grade material), bifenox formulated as Fox® or technical grade material and oxadiargyl (technical grade material).

Treatment requirements for each compound or herbicidal component were calculated based upon the rates being tested, the concentration of active ingredient or acid equivalent in the formulation, an application volume of 2 mL per component per pot, and an application area of 86.59 cm2 per pot.
For formulated compounds, a measured amount was placed in an individual 100 or 200 mL glass vial and was dissolved in a volume of 1.25% (v/v) Agri-Dex® crop oil concentrate to obtain application solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated.
For technical grade compounds, a weighed amount was placed in an individual 100 to 200 mL glass vial and was dissolved in a volume of acetone to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions obtained were diluted with an equivalent volume of an aqueous mixture containing 2.5% (v/v) crop oil concentrate so that the final application solutions contained 1.25% (v/v) crop oil concentrate.
Applications were made by injecting with a pipetter appropriate amounts of the application solutions, individually and sequentially, into the aqueous layer of the paddy. Control plants were treated in the same manner with the solvent blank. Applications were made so that all treated plant material received the same concentrations of acetone and crop oil concentrate.
The treated plants and control plants were placed in a greenhouse as described above and water was added as needed to maintain a paddy flood. After approximately 3 weeks the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury or growth inhibition and 100 corresponds to complete kill.
Colby's equation was used to determine the herbicidal effects expected from the mixtures (Colby, S. R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 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×B/100)

A=observed efficacy of active ingredient A at the same concentration as used in the mixture.
B=observed efficacy 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 22-38.







TABLE 22







Synergistic Activity of In-Water Applications of Compound A Acid and


Carfentrazone-ethyl Herbicidal Compositions on Weed Control in a


Rice Cropping System.











Compound
Carfentrazone-



A Acid
ethyl












g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 21



DAA



ECHCG












8.75
0
0
—



17.5
0
0
—



35
0
40
—



0
14
0
—



0
28
20
—



8.75
14
0
 0



17.5
14
20
 0



35
14
95
40



8.75
28
30
20



17.5
28
50
20



35
28
95
52










Visual Weed




Control (%) - 19



DAA



ECHOR












42.4
0
15
—



0
215
65
—



42.4
215
100
70

















TABLE 23







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Carfentrazone-ethyl Herbicidal Compositions


on Weed Control in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 21



A Benzyl
Carfentrazone-
DAA



Ester
ethyl
LEFCH












g ae/ha
g ai/ha
Obs
Exp
















 8.75
0
20
—



17.5
0
30
—



35
0
55
—



 0
28
10
—



 8.75
28
40
28



17.5
28
40
37



35
28
65
60

















TABLE 24







Synergistic Activity of In-Water Applications of Compound A Acid and


Oxyfluorfen (technical) Herbicidal Compositions on Weed Control


in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 22



A Acid
Oxyfluorfen
DAA












g ae/ha
g ai/ha
Obs
Exp














CYPRO













10.6
0
0
—



21.2
0
25
—



42.4
0
95
—



0
180
50
—



10.6
180
90
50



21.2
180
90
63



42.4
180
100
98










SCPJU













8.75
0
60
—



17.5
0
70
—



35
0
95
—



0
180
0
—



0
360
0
—



8.75
180
55
60



17.5
180
90
70



35
180
100
95



8.75
360
75
60



17.5
360
80
70



35
360
100
95

















TABLE 25







Synergistic Activity of In-Water Applications of Compound A Acid and


Oxyfluorfen (SC) Herbicidal Compositions on Weed Control


in a Rice Cropping System.











Compound





A Acid
Oxyfluorfen












g ae/ha
g ai/ha
Obs
Exp














Visual Weed




Control (%) - 22



DAA



CYPRO












8.75
0
0
—



17.5
0
20
—



35
0
50
—



0
180
30
—



0
360
20
—



8.75
180
50
30



17.5
180
100
44



35
180
95
65



8.75
360
85
20



17.5
360
85
36



35
360
50
60










Visual Weed




Control (%) - 21



DAA



CYPRO












16
0
0
—



32
0
20
—



64
0
85
—



0
135
0
—



0
270
0
—



16
135
20
 0



32
135
20
20



64
135
95
85



16
270
40
 0



32
270
60
20



64
270
100
85

















TABLE 26







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Oxyfluorfen (SC) Herbicidal Compositions on


Weed Control in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 21



A Benzyl

DAA



Ester
Oxyfluorfen
CYPRO












g ae/ha
g ai/ha
Obs
Exp
















32
0
90
—



 0
135
0
—



 0
270
0
—



32
135
95
90



32
270
100
90

















TABLE 27







Synergistic Activity of In-Water Applications of Compound A


Acid and Pyraclonil Herbicidal Compositions on Weed Control


in a Rice Cropping System.














Visual Weed






Control (%) - 20



Compound

DAA



A Acid
Pyraclonil
ECHCG












g ae/ha
g ai/ha
Obs
Exp
















 8.75
0
40
—



17.5
0
30
—



 0
45
0
—



 8.75
45
100
40



17.5
45
100
30

















TABLE 28







Synergistic Activity of In-Water Applications of Compound A Benzyl


Ester and Pyraclonil Herbicidal Compositions on Weed Control in a


Rice Cropping System.











Compound

Visual Weed



A Benzyl

Control (%) - 20



Ester
Pyraclonil
DAA












g ae/ha
g ai/ha
Obs
Exp
















ECHOR












4.38
0
10
—



8.75
0
20
—



17.5 
0
30
—



0  
45
40
—



4.38
45
45
46



8.75
45
80
52



17.5 
45
100
58













CYPRO












4.38
0
20
—



8.75
0
20
—



0  
45
0
—



0  
90
0
—



4.38
45
20
20



8.75
45
90
20



4.38
90
85
20



8.75
90
85
20
















TABLE 29







Synergistic Activity of In-Water Applications of Compound A Acid


and Oxadiazon Herbicidal Compositions on Weed Control in a


Rice Cropping System.













Visual Weed





Control (%) - 21



Compound

DAA



A Acid
Oxadiazon
ECHOR












g ae/ha
g ai/ha
Obs
Exp















8.75
0
10
—



17.5
0
20
—



35
0
35
—



0
62.5
15
—



0
125
20
—



8.75
62.5
40
24



17.5
62.5
40
32



35
62.5
75
45



8.75
125
40
28



17.5
125
50
36



35
125
60
48



35
0
10
—



70
0
28
—



0
250
18
—



35
250
40
26



70
250
85
40
















TABLE 30







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Oxadiazon Herbicidal Compositions on


Weed Control in a Rice Cropping System.













Visual Weed



Compound

Control (%) - 21



A Benzyl

DAA



Ester
Oxadiazon
ECHOR












g ae/ha
g ai/ha
Obs
Exp















8.75
0
25
—



17.5
0
60
—



0
62.5
15
—



8.75
62.5
70
36



17.5
62.5
75
66
















TABLE 31







Synergistic Activity of In-Water Applications of Compound A


n-Butyl Ester and Oxadiazon Herbicidal Compositions on


Weed Control in a Rice Cropping System.














Visual Weed




Compound

Control (%) - 21




A n-Butyl

DAA




Ester
Oxadiazon
ECHOR













g ae/ha
g ai/ha
Obs
Exp















35
0
25
—



70
0
38
—



0
250
18
—



35
250
43
38



70
250
70
48
















TABLE 32





Synergistic Activity of In-Water Applications of Compound A


Acid and Saflufenacil Herbicidal Compositions on Weed


Control in a Rice Cropping System.




















Visual Weed



Compound

Control (%) - 20 DAA













A Acid
Saflufenacil
ECHCG

LEFCH













g ae/ha
g ai/ha
Obs
Exp
Obs
Exp





17.5
0
50
—
0
—


35  
0
95
—
30
—


0 
10
0
—
0
—


0 
20
10
—
0
—


17.5
10
85
50
30
0


35  
10
100
95
30
30


17.5
20
70
55
30
0


35  
20
100
96
70
30















Compound






A Acid
Saflufenacil














g ae/ha
g ai/ha
Obs
Exp
















Visual Weed





Control (%) - 20





DAA





CYPRO












 8.75
0
0
—



17.5
0
20
—



35  
0
80
—



0 
10
0
—



 8.75
10
20
0



17.5
10
30
20



35  
10
95
80













Visual Weed





Control (%) - 21





DAA





LEFCH












35
0
5
—



70
0
23
—



 0
40
5
—



35
40
58
33



70
40
55
38
















TABLE 33







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Saflufenacil Herbicidal Compositions on


Weed Control in a Rice Cropping System.











Compound

Visual Weed



A Benzyl

Control (%) - 20



Ester
Saflufenacil
DAA












g ae/ha
g ai/ha
Obs
Exp
















ECHOR












4.38
0
10
—



8.75
0
15
—



0  
10
0
—



0  
20
0
—



4.38
10
0
10



8.75
10
30
15



4.38
20
40
10



8.75
20
45
15













LEFCH












4.38
0
0
—



8.75
0
20
—



17.5 
0
30
—



0  
10
0
—



0  
20
0
—



4.38
10
50
0



8.75
10
40
20



17.5 
10
100
30



4.38
20
100
0



8.75
20
60
20



17.5 
20
100
30
















TABLE 34







Synergistic Activity of In-Water Applications of Compound A


n-Butyl Ester and Saflufenacil Herbicidal Compositions on


Weed Control in a Rice Cropping System.













Visual Weed



Compound

Control (%) - 21



A n-Butyl

DAA



Ester
Saflufenacil
LEFCH












g ae/ha
g ai/ha
Obs
Exp















35
0
8
—



0
40
5
—



35
40
28
12
















TABLE 35







Synergistic Activity of In-Water Applications of Compound A


Acid and Pentoxazone Herbicidal Compositions on Weed


Control in a Rice Cropping System.













Visual Weed



Compound

Control (%) - 21



A Acid
Pentoxazone
DAA












g ae/ha
g ai/ha
Obs
Exp
















ECHCG












8.75
0
15
—



17.5 
0
20
—



35   
0
95
—



0  
56.25
0
—



8.75
56.25
30
15



17.5 
56.25
40
20



35   
56.25
99
95













CYPRO












35   
0
70
—



0  
56.25
0
—



0  
112.5
0
—



35   
56.25
85
70



35   
112.5
100
70













FIMMI












8.75
0
0
—



0  
56.25
25
—



0  
112.5
20
—



8.75
56.25
50
25



8.75
112.5
99
20













SCPJU












8.75
0
40
—



17.5 
0
60
—



35   
0
95
—



0  
56.25
0
—



0  
112.5
0
—



8.75
56.25
40
40



17.5 
56.25
95
60



35   
56.25
100
95



8.75
112.5
60
40



17.5 
112.5
90
60



35   
112.5
100
95
















TABLE 36







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Pentoxazone Herbicidal Compositions on


Weed Control in a Rice Cropping System.













Visual Weed



Compound

Control (%) - 21



A Benzyl

DAA



Ester
Pentoxazone
CYPRO












g ae/ha
g ai/ha
Obs
Exp















4.38
0
30
—



8.75
0
60
—



0
56.25
0
—



0
112.5
0
—



4.38
56.25
80
30



8.75
56.25
75
60



4.38
112.5
50
30



8.75
112.5
80
60
















TABLE 37







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Bifenox (technical) Herbicidal Compositions


on Weed Control in a Rice Cropping System.













Visual Weed



Compound

Control (%) - 21



A Benzyl

DAA



Ester
Bifenox
ECHOR












g ae/ha
g ai/ha
Obs
Exp















8
0
20
—



16
0
45
—



32
0
60
—



0
720
40
—



8
720
85
52



16
720
100
67



32
720
100
76
















TABLE 38







Synergistic Activity of In-Water Applications of Compound A


Benzyl Ester and Bifenox (Fox ®) Herbicidal Compositions


on Weed Control in a Rice Cropping System.













Visual Weed



Compound

Control (%) - 21



A Benzyl

DAA



Ester
Bifenox
SCPMA












g ae/ha
g ai/ha
Obs
Exp















48
0
0
—



96
0
0
—



0
180
40
—



48
180
0
40



96
180
60
40























CYPRO
Cyperus rotundus L.
nutsedge, purple


ECHCG
Echinochloa crusgalli (L.) Beauv.
barnyardgrass


ECHOR
Echinochloa oryzoides (Ard.) Fritsch
watergrass, early


FIMMI
Fimbristylis miliacea (L.) Vahl
fringerush, globe


LEFCH
Leptochloa chinensis (L.) Nees
sprangletop, Chinese


SCPJU
Schoenoplectus juncoides (Roxb.) Palla
bulrush, Japanese


SCPMA
Schoenoplectus maritimus (L.) Lye
clubrush, sea







g ae/ha = grams acid equivalent per hectare


g ai/ha = grams active ingredient per hectare


Obs = observed value


Exp = expected value as calculated by Colby's equation


DAA = days after application









Example III
Evaluation of Postemergence Herbicidal Activity of Mixtures in Cereal Crops in the Greenhouse
Seeds of the desired test plant species were planted in Sun Gro MetroMix® 306 planting mixture, which typically has a pH of 6.0 to 6.8 and an organic matter content of about 30 percent, in plastic pots with a surface area of 103.2 square centimeters (cm2). When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 7-36 days in a greenhouse with an approximate 14 hour photoperiod which was maintained at about 18° C. during the day and about 17° C. during the night. Nutrients 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 second or third true leaf stage.
Treatments consisted of the benzyl ester of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (Compound A), formulated as an SC, a second cereal herbicide alone and then both in combination.
Forms of compound A (compound of formula I) tested include:




Other herbicidal components were applied on an active ingredient basis and included PSII-inhibiting herbicides.
Measured aliquots of benzyl ester of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (Compound A) were placed in 25 milliliter (mL) glass vials and diluted in a volume of 1.25% (v/v) Agri-Dex® crop oil concentrate to obtain stock solutions. Compound requirements are based upon a 12 mL application volume at a rate of 187 liters per hectare (L/ha). Spray solutions of the second cereal herbicide and experimental compound mixtures were prepared by adding the stock solutions to the appropriate amount of dilution solution to form 12 mL spray solution with active ingredients in two- and three-way combinations. Formulated compounds were applied to the plant material with an overhead Mandel track sprayer equipped with an 8002E nozzle calibrated to deliver 187 L/ha over an application area of 0.503 square meters (m2) at a spray height of 18 inches (46 cm) above average plant canopy. Control plants were sprayed in the same manner with the solvent blank.
The treated plants and control plants were placed in a greenhouse as described above and watered by sub-irrigation to prevent wash-off of the test compounds. After 20-22 days, the condition of the test plants as compared with that of the control plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complete kill.
Colby's equation was used to determine the herbicidal effects expected from the mixtures (Colby, S. R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 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×B/100)

A=observed efficacy of active ingredient A at the same concentration as used in the mixture.
B=observed efficacy of active ingredient B at the same concentration as used in the mixture.
The compounds tested, application rates employed, plant species tested, and results are given in Table 39.







TABLE 39







Synergistic Activity of Foliar-Applied Compound A Benzyl Ester


and Bifenox Herbicidal Compositions on Weed Control in a


Cereals Cropping System.













Visual Weed



Compound

Control (%) - 21



A Benzyl

DAA



Ester
Bifenox
PAPRH












g ai/ha
g ai/ha
Obs
Exp















5
0
28
—



10
0
35
—



0
180
5
—



0
360
8
—



0
780
8
—



5
180
33
32



5
360
35
33



5
780
70
34



10
780
68
40





PAPRH Papaver rhoeas L. poppy, common


g ae/ha = grams acid equivalent per hectare


g ai/ha = grams active ingredient per hectare


Obs = observed value


Exp = expected value as calculated by Colby's equation


DAA = days after application






Example IV
Evaluation of Pre-emergence Soil-Applied Herbicidal Mixtures for Weed Control
Seeds or nutlets of the desired test plant species were planted in a soil matrix prepared by mixing a loam soil (32 percent silt, 23 percent clay, and 45 percent sand, with a pH of about 6.5 and an organic matter content of about 1.9 percent) and calcareous grit in an 80 to 20 ratio. The soil matrix was contained in plastic pots with a volume of 1 quart and a surface area of 83.6 square centimeters (cm2).
Treatments consisted of the benzyl ester of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (compound A) formulated as an SC (suspension concentrate) and various herbicidal components alone and in combination. Forms of compound A were applied on an acid equivalent basis.
Forms of compound A (compound of formula I) tested include:




Other herbicidal components were applied on an acid equivalent or active ingredient basis and included the protoporphyrinogen oxidase (PPO)-inhibiting herbicides, flumioxazin formulated as Payload® and oxadiazon formulated as Ronstar® 50W.
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.
For treatments comprised of formulated compounds, measured amounts of compounds were placed individually in 25 mL glass vials and diluted in a volume of 1.25% (v/v) Agri-Dex® crop oil concentrate (COC) to obtain 12× 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 (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.25% (v/v) COC so that the final spray solutions contained 1.25% (v/v) COC.
For treatments comprised of technical compounds, weighed amounts can be placed individually in 25 mL glass vials and dissolved in a volume of 97:3 (v/v) acetone/DMSO to obtain 12× stock solutions. If a test compound does not dissolve readily, the mixture can be warmed and/or sonicated. Application solutions can be prepared by adding an appropriate amount of each stock solution (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.5% (v/v) COC so that the final spray solutions contain 1.25% (v/v) COC. When technical materials are used, the concentrated stock solutions can be added to the spray solutions so that the final acetone and DMSO concentrations of the application solutions are 16.2% and 0.5%, respectively.
For treatments comprised of formulated and technical compounds, weighed amounts of the technical materials can be placed individually in 25 mL glass vials and dissolved in a volume of 97:3 (v/v) acetone/DMSO to obtain 12× stock solutions, and measured amounts of the formulated compounds can be placed individually in 25 mL glass vials and diluted in a volume of 1.5% (v/v) COC or water to obtain 12× stock solutions. If a test compound does not dissolve readily, the mixture can be warmed and/or sonicated. Application solutions can be prepared by adding an appropriate amount of each stock solution (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of an appropriate amount of an aqueous mixture of 1.5% (v/v) COC so that the final spray solutions contain 1.25% (v/v) COC. As required, additional water and/or 97:3 (v/v) acetone/DMSO can be added to individual application solutions so that the final acetone and DMSO concentrations of the application solutions being compared are 8.1% and 0.25%, respectively.
All stock solutions and applications solutions were visually inspected for compound compatibility prior to application. Spray solutions were applied to the soil with an overhead Mandel track sprayer equipped with a 8002E nozzles calibrated to deliver 187 L/ha over an application area of 0.503 m2 at a spray height of 18 inches (46 cm) above average pot height. Control pots were sprayed in the same manner with the solvent blank.
The treated and control pots were placed in a greenhouse and top watered as needed. When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The pots were maintained in a greenhouse with an approximate 14 hr photoperiod which was maintained at about 29° C. during the day and 26° C. during the night. Nutrients (Peters® Excel 15-5-15 5-Ca 2-Mg) were applied in the irrigation solution as needed and water was added on a regular basis. Supplemental lighting was provided with overhead metal halide 1000-Watt lamps as necessary. After approximately 4 weeks, the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury or growth inhibition and 100 corresponds to complete kill.
Colby's equation was used to determine the herbicidal effects expected from the mixtures (Colby, S. R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 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×B/100)

A=observed efficacy of active ingredient A at the same concentration as used in the mixture.
B=observed efficacy 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 40-41.







TABLE 40







Synergistic Activity of Soil-applied, Pre-emergence Applications


of Compound A Benzyl Ester and Flumioxazin Herbicidal


Compositions on Weed Control.











Compound





A Benzyl





Ester
Fumioxazin













g ae/ha
g ai/ha
Obs
Exp
















Visual Weed





Control (%) - 28





DAA





IPOHE












16
0
13
—



32
0
23
—



 0
105
70
—



 0
210
70
—



 0
420
90
—



16
105
100
74



32
105
80
77



16
210
85
74



32
210
100
77



16
420
100
91



32
420
100
92













Visual Weed





Control (%) - 29





DAA





XANST












16
0
0
—



32
0
5
—



 0
105
18
—



 0
210
48
—



16
105
38
18



32
105
30
22



16
210
40
48



32
210
65
50













Visual Weed





Control (%) - 28





DAA





SETVI












16
0
10
—



32
0
10
—



 0
105
73
—



16
105
100
75



32
105
80
75
















TABLE 41







Synergistic Activity of Soil-applied, Pre-emergence Applications


of Compound A Benzyl Ester and Oxadiazon Herbicidal


Compositions on Weed Control.













Visual Weed



Compound

Control (%) - 32



A Benzyl

DAA



Ester
Oxadiazon
IPOHE












g ae/ha
g ai/ha
Obs
Exp















8
0
65
—



16
0
83
—



0
560
50
—



0
1120
100
—



8
560
100
83



16
560
100
91



32
560
100
100























IPOHE
Ipomoea hederacea (L.) Jacq.
morningglory, ivyleaf


SETVI
Setaria viridis (L.) Beauv.
foxtail, green


XANST
Xanthium strumarium L.
cocklebur, common







g ae/ha = grams acid equivalent per hectare


g ai/ha = grams active ingredient per hectare


Obs = observed value


Exp = expected value as calculated by Colby's equation


DAA = days after application

## Claims

1. A synergistic herbicidal composition comprising a herbicidally effective amount of (a) a compound of the formula (I)




or an alkyl or benzyl ester, or an agriculturally acceptable salt of formula (I) and (b) a herbicidal protoporphyrinogen oxidase inhibitor, wherein (a) and (b) are present in the composition in a ratio such that the composition exhibits herbicidal synergy.

2. The composition of claim 1, wherein (a) is a C1-4 alkyl or benzyl ester of the compound of formula (I).

3. The composition of claim 1, wherein (a) is a C1-4 alkyl ester of the compound of formula (I).

4. The composition of claim 2, wherein (a) is a benzyl ester of the compound of formula (I).

5. The composition of claim 1, wherein (a) is the carboxylic acid of the compound of formula (I).

6. The composition of claim 1, further comprising at least one compound selected from the group consisting of agriculturally acceptable herbicide safeners, adjuvants, and carriers.

7. The composition of claim 1, wherein (b) is selected from acifluorfen, azafeniden, bifenox, carfentrazone-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen-ethyl and saflufenacil, or an agriculturally acceptable salt or ester thereof.

8. A method of controlling undesirable vegetation, comprising a step of:
contacting a plant, wherein the plant is undesirable vegetation, or the locus thereof, or soil or water, wherein the soil or the water allows for the growth of the undesirable vegetation, with a herbicidally effective amount of (a) a compound of the formula (I)





or an alkyl or benzyl ester, or an agriculturally acceptable salt of formula (I) and (b) a herbicidal protoporphyrinogen oxidase inhibitor, wherein (a) and (b) are present in the composition in a ratio such that the composition exhibits herbicidal synergy, and wherein the undesirable vegetation is controlled in direct-seeded, water-seeded and transplanted rice, cereals, wheat, barley, oats, rye, sorghum, corn or canola crops.

9. The method of claim 8, wherein the composition comprising (a) and (b) is applied to water.

10. The method of claim 9, wherein the water is part of a flooded rice paddy.

11. The method of claim 8, wherein the composition comprising (a) and (b) is applied pre-emergently to the undesirable vegetation.

12. The method of claim 8, wherein the composition comprising (a) and (b) is applied post-emergently to the undesirable vegetation.

13. The method of claim 8, wherein the undesirable vegetation is controlled in glyphosate-, 5-enolpyruvylshikimate-3-phosphate synthase inhibitor-, glufosinate-, glutamine synthetase inhibitor-, dicamba-, phenoxy auxin-, pyridyloxy auxin-, synthetic auxin-, auxin transport inhibitor-, aryloxyphenoxypropionate-, cyclohexanedione-, phenylpyrazoline-, acetyl CoA carboxylase inhibitor-, imidazolinone-, sulfonylurea-, pyrimidinylthiobenzoate-, triazolopyrimidine-, sulfonylaminocarbonyltriazolinone-, acetolactate synthase or acetohydroxy acid synthase inhibitors-, 4-hydroxyphenyl-pyruvate dioxygenase inhibitor-, phytoene desaturase inhibitor-, carotenoid biosynthesis inhibitor-, protoporphyrinogen oxidase inhibitor-, cellulose biosynthesis inhibitor-, mitosis inhibitor-, microtubule inhibitor-, very long chain fatty acid inhibitor-, fatty acid and lipid biosynthesis inhibitor-, photosystem I inhibitor-, photosystem II inhibitor-, triazine-, or bromoxynil- tolerant crops.

14. The method of claim 13, wherein the tolerant crops possess multiple or stacked traits conferring tolerance to multiple herbicides.

15. The method of claim 8, wherein the undesirable vegetation comprises a herbicide resistant or tolerant weed.

16. The method of claim 15, wherein the weed is resistant or tolerant to multiple herbicides.

17. The method of claim 15, wherein the weed is resistant or tolerant to acetolactate synthase or acetohydroxy acid synthase inhibitors, photosystem II inhibitors, acetyl CoA carboxylase inhibitors, synthetic auxins, auxin transport inhibitors, photosystem I inhibitors, 5-enolpyruvylshikimate-3-phosphate synthase inhibitors, microtubule assembly inhibitors, fatty acid and lipid synthesis inhibitors, protoporphyrinogen oxidase inhibitors, carotenoid biosynthesis inhibitors, very long chain fatty acid inhibitors, phytoene desaturase inhibitors, glutamine synthetase inhibitors, 4-hydroxyphenyl-pyruvate-dioxygenase inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple modes-of-action, quinclorac, arylaminopropionic acids, difenzoquat, endothall, or organoarsenicals.

18. The method of claim 8, wherein (b) is selected from acifluorfen, azafeniden, bifenox, carfentrazone-ethyl, flumioxazin, ipfencarbazone, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraclonil, pyraflufen-ethyl and saflufenacil, or an agriculturally acceptable salt or ester thereof.