WO2023114652A1

WO2023114652A1 - Method of applying a composition comprising 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylic acid or a derivative thereof

Info

Publication number: WO2023114652A1
Application number: PCT/US2022/080891
Authority: WO
Inventors: Natalino DALLA VALLE; Richard K. Mann
Original assignee: Corteva Agriscience LLC
Current assignee: Corteva Agriscience LLC
Priority date: 2021-12-16
Filing date: 2022-12-05
Publication date: 2023-06-22
Anticipated expiration: 2024-06-16

Abstract

Provided herein are methods of using herbicidal compositions containing a compound of formula (I): ("4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylic acid"), or an agriculturally acceptable salt or ester thereof. The methods provide control of undesirable vegetation in rice paddies. Embodiments of the methods include, among other things, applying a herbicidal composition containing a compound of formula (I) "pre-planting."

Description

METHOD OF APPLYING A COMPOSITION COMPRISING 4-AMINO-3-CHLORO-5- FLUORO-6-(4-CHLORO-2-FLUORO-3 -METHOXYPHENYL) PYRIDINE-2- CARBOXYLIC ACID OR A DERIVATIVE THEREOF

FIELD

[0001] Provided herein are methods of using compositions comprising 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.

BACKGROUND

[0002] 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

[0003] Provided herein are methods of using a composition comprising an herbici dally effective amount of a compound of the formula (I):

or an agriculturally acceptable salt or ester of thereof. The composition additionally may contain an agriculturally acceptable adjuvant or carrier. In embodiments of the methods, the composition is applied to a rice paddy prior to planting rice.

[0004] In certain embodiments of the methods, (a) a compound of formula (I), or an agriculturally acceptable salt or ester thereof, and (b) a second herbicide are applied to a rice paddy subsequent to emergence of dry seeded rice, wet seeded rice or planting transplanted rice and/or prior to or after emergence of undesirable vegetation.

[0005] In certain embodiments of the method, the second herbicide is a tiazolopyrimidine sulfonamide. Exemplary triazolopyrimidine sulfonamides include, but are not limited to, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, and pyroxsulam or an agriculturally acceptable salt, carboxylic acid, carboxylate salt, or ester thereof. In a particular embodiment of the method, the second herbicide is penoxsulam.

DETAILED DESCRIPTION

Definitions

[0006] 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 (i.e., florpyrauxifen) and has been described in U.S. Patent Nos. 8,883,688 and 8,906,825, among others, each of which is incorporated by reference herein in its entirety. The compound of formula (I) and its benzyl ester have been found to control undesirable vegetation, including grass, broadleaf and sedge weeds, in multiple non-crop and cropping situations. For example, the methods provided herein have demonstrated control of the following typically undesirable vegetation: Heteranthera reniformis R. & P. (/.< ., “roundleaf mudplantain,” “HETRE”), Heteranthera limosa (SW.) Willd./Vahl (z.e., “duck salad,” “HETLI”), Echinocloa species (“ECHSS,” e.g., Echinocloa crus-galli (L.) P.Beauv., i.e., “barnyardgrass,” “ECHCG”), Cyperus difformis L. (z.e., “smallflower flatsedge,” “CYPDI”), Polygonum species (z.e., “POLSS,” e.g., wild buckwheat), and Ammannia coccinea Rottb. i.e., “redstem,” “AMMCO”).

[0007] As used herein, triazolopyrimidine sulfonamides are a chemical class of herbicides having a triazolopyrimidine sulfonamide core structure. Without being limited by any theory, the mode of action of triazolopyrimidine sulfonamides is believed to involve the inhibition of acetolactate synthase (“ALS”), an enzyme common to plants and microorganisms but not found in animals. Exemplary herbicidal uses of triazolopyrimidine sulfonamides include, but are not limited to, use for control of nuisance sedge, broadleaf and grass weeds.

[0008] Exemplary triazolopyrimidine sulfonamides include, but are not limited to, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, and pyroxsulam.

[0009] As used herein, cloransulam-methyl is methyl 3-chloro-2-[[(5-ethoxy-7- fhioro[l,2,4]triazolo[l,5-c]pyrimidin-2-yl)sulfonyl]amino]benzoate and possesses the following structure:

Its herbicidal activity is exemplified in Tomlin, C., ed. A World Compendium The Pesticide Manual. 15^th ed. Alton: BCPC Publications, 2009 (hereafter “The Pesticide Manual, Fifteenth Edition, 2009 ”). Exemplary uses of cloransulam-methyl include its use as a herbicide for post-emergence control of broadleaf weeds in soybeans and other broadleaf crops.

[0010] As used herein, diclosulam is 7V-(2,6-dichlorophenyl)-5-ethoxy-7- fhioro[l,2,4]triazolo[l,5-c]pyrimidine-2-sulfonamide and possesses the following structure:

Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009.

Exemplary uses of diclosulam include its use as a herbicide for broadleaf weed control in peanuts and soybeans.

[0011] As used herein, florasulam is A-(2,6-difluorophenyl)-8-fluoro-5- methoxy[l,2,4]triazolo[l,5-c]pyrimidine-2-sulfonamide and possesses the following structure:

Exemplary uses of florasulam includes its use as a herbicide in post-emergence control of broadleaf weeds in cereals and maize.

[0012] As used herein, flumetsulam is A-(2,6-difluorophenyl)-5- methyl[l,2,4]triazolo[l,5-a]pyrimidine-2-sulfonamide and possesses the following structure:

Exemplary uses of flumetsulam include its use as a herbicide for the control of broadleaf weeds and grasses in soya beans, field peas and maize.

[0013] As used herein, metosulam is A-(2,6-dichloro-3-methylphenyl)-5,7- dimethoxy[l,2,4]triazolo[l,5-a]pyrimidine-2-sulfonamide and possesses the following structure:

Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of metosulam includes its use as a herbicide for post-emergence control of broadleaf weeds in wheat, barley and rye, and pre- or post-emergence control of broadleaf weeds in maize.

[0014] As used herein, penoxsulam is 2-(2,2-difluoroethoxy)-A-(5,8- dimethoxy[l,2,4]triazolo[l,5-c]pyrimidin-2-yl)-6-(trifluoromethyl)benzenesulfonamide and possesses the following structure:

Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of penoxsulam includes its use as a herbicide for post-emergence control of Echinochloa spp., broadleaf weeds and annual sedge weeds in rice, as well as Echinochloa spp. and broadleaf weeds in sorghum, turf, cereals and tree and vine crops. In another example, penoxsulam is used to control aquatic weeds in lakes and ponds.

[0015] As used herein, pyroxsulam is A-(5,7-dimethoxy[l,2,4]triazolo[l,5-a]pyrimidin-2- yl)-2-methoxy-4-(trifluoromethyl)-3 -pyridinesulfonamide and possesses the following structure:

Its herbicidal activity is exemplified in The Pesticide Manual, Fifteenth Edition, 2009. Exemplary uses of pyroxsulam includes its use as a herbicide for broad spectrum postemergence control of annual grass and broadleaf weeds in cereals.

[0016] As used herein, herbicide means a compound, e.g., active ingredient that kills, controls or otherwise adversely modifies the growth of plants.

[0017] As used herein, a herbicidally effective amount or vegetation controlling amount each is an amount of active ingredient that 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.

[0018] 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, and in-water applications. [0019] 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.

[0020] 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 certain factor(s) including, e.g., pH, may be in the dissociated or undissociated form.

[0021] 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-methyl- thiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine or with a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide or choline hydroxide.

[0022] 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, butoxy ethanol, 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 alkyl sulfonates 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. In certain embodiments of the methods provided herein, the compound of formula (I) is a benzyl ester of the compound of formula (I).

Embodiments

[0023] Provided herein are methods of using a composition comprising an herbicidally effective amount of a compound of the formula (I):

or an agriculturally acceptable salt or ester thereof. In certain embodiments of the methods provided herein, the compound of formula (I) or agriculturally acceptable salt or ester thereof is a benzyl ester of the compound of formula (I):

The composition additionally may contain an agriculturally acceptable adjuvant or carrier. In embodiments of the methods, the composition is applied to a rice paddy prior to planting of rice (i.e., “pre-planting”).

[0024] In certain embodiments of the methods, (a) a compound of formula (I), or an agriculturally acceptable salt or ester thereof, and (b) a second herbicide are applied to a rice paddy subsequent to emergence of rice plants and/or undesirable vegetation (z.e., “postemergence”).

[0025] In certain embodiments of the method, the second herbicide is a tiazolopyrimidine sulfonamide. Exemplary triazolopyrimidine sulfonamides include, but are not limited to, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, and pyroxsulam or an agriculturally acceptable salt, carboxylic acid, carboxylate salt, or ester thereof. In a particular embodiment of the method, the second herbicide is penoxsulam.

[0026] In certain embodiments of the methods provided herein, the compound of formula (I), z.e., the carboxylic acid, is applied pre-planting to a rice paddy. In certain embodiments, a carboxylate salt of the compound of formula (I) is applied pre-planting to a rice paddy. In certain embodiments, an aralkyl or alkyl ester is applied pre-planting to a rice paddy. In certain embodiments, a benzyl, substituted benzyl, or Ci-4 alkyl, e.g., n-butyl ester is applied pre-planting to a rice paddy. In certain embodiments, the benzyl ester is applied pre-planting to a rice paddy.

[0027] In some embodiments of the methods provided herein, the compound of formula (I) or salt or ester thereof and cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, and pyroxsulam or an agriculturally acceptable salt, carboxylic acid, carboxylate salt, or ester thereof, are formulated in one composition, tank mixed, applied simultaneously, or applied sequentially post-emergence to a rice paddy.

[0028] The effect observed can depend on several factors including but not limited to 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 postemergence 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.

[0029] In certain embodiments, the methods provided herein are utilized to control undesirable vegetation (e.g., weeds) in rice. In certain embodiments, the rice is direct seeded, water seeded, or transplanted rice. [0030] The compositions and methods described herein be used to control undesirable vegetation on glyphosate-tolerant-, glufosinate-tolerant-, di camba-tol erant-, phenoxy auxin- tolerant-, pyridyloxy auxin-tolerant-, aryl oxyphenoxypropionate-tol erant-, acetyl CoA carboxylase (“ACCase”) inhibitor-tolerant-, imidazolinone-tolerant-, acetolactate synthase (“ALS”) inhibitor-tolerant-, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor - tolerant-, protoporphyrinogen oxidase (“PPO”) inhibitor -tolerant-, triazine-tolerant-, bromoxynil-tolerant-rice, for example, in conjunction with glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil. The methods may be used in controlling undesirable vegetation in rice 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 second herbicide or salt or ester thereof are used in combination with herbicides that are selective for the crop (e.g., rice) 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 secondary herbicides are applied at the same time, either as a combination formulation or as a tank mix.

[0031] In certain embodiments, the methods provided herein are utilized to control undesirable vegetation in rice. In certain embodiments, the undesirable vegetation is Urochloa platyphylla (Groseb.) Nash (/.< ., “broadleaf signalgrass,” “BRAPP”), Digitaria sanguinalis (L.) Scop, (i.e., “large crabgrass,” “DIGSA”), Echinocloa species (“ECHSS”), e.g., Echinochloa crus-galli (L.) P. Beauv. (i.e., “bamyardgrass,” “ECHCG”), Echinochloa colonum (L.) LINK (/.< ., “junglerice,” “ECHCO”), Echinochloa oryzoides (Ard.) Fritsch (/.< ., “early watergrass,” “ECHOR”), Echinochloa phyllopogon (Vasinger) Vasinger (/.< ., “late watergrass,” “ECHPH”), Ischaemum rugosum Salisb. (/.< ., “saramollagrass,” “ISCRU”), Leptochloa chinensis (L.) Nees (i.e., “Chinese sprangletop,” “LEFCH”), Leptochloa fascicularis (Lam.) Gray (i.e., “bearded sprangletop,” “LEFFA”), Leptochloa panicoides (Presl.) Hitchc. (i.e., “Amazon sprangletop,” “LEFPA”), Panicum dichotomiflorum (L.) Michx. (z.e., “fall panicum,” “PANDI”), Paspalum dilatatum Poir. (z.e., “dallisgrass,” “PASDI”), Cyperus difformis E. (i.e., “smallflower flatsedge,” “CYPDI”), Cyperus esculentus L. i.e., “yellow nutsedge,” “CYPES”), Cyperus iria L. (i.e., “rice flatsedge,” “CYPIR”), Cyperus rotundus L. (i.e., “purple nutsedge,” “CYPRO”), Eleocharis species (i.e.,

“ELOSS”), Fimbristylis miliacea (L.) Vahl (i.e., “globe fringerush,” “FIMMI”), Schoenoplectus juncoides Roxb. (i.e., “Japanese bulrush,” “SPCJU”), Schoenoplectus maritimus L. i.e., “sea clubrush,” “SCPMA”), Schoenoplectus mucronatus L. (i.e., “ricefield bulrush,” “SCPMU”), Aeschynomene species, (i.e., “jointvetch,” “AESSS”), Alternanthera philoxeroides (Mart.) Griseb. (i.e., “alligatorweed,” “ALRPH”), Alisma plantago-aquatica V. (i.e., “common waterplantain,” “ALSPA”), Amaranthus species (i.e., “AMASS,” e.g., pigweeds and amaranths), Ammannia coccinea Rottb. (i.e., “redstem,” “AMMCO”), Eclipta alba (L.) Hassk. (i.e., “American false daisy,” “ECLAL”), Heteranthera limosa (SW.) Willd./Vahl (i.e., “ducksalad,” “HETLI”), Heteranthera reniformis R. & P. (i.e., “roundleaf mudplantain,” “HETRE”), Ipomoea hederacea (L.) Jacq. (i.e., “ivyleaf morningglory,” “IPOHE”), Lindernia dubia (L.) Pennell (i.e., “low false pimpernel,” “LIDDU”), Monochoria korsakowii Regel & Maack (i.e., “monochoria,” “MOOKA”), Monochoria vaginalis (Burm. F.) C. Presl ex Kuhth, (i.e., “monochoria,” “MOOVA”), Murdannia midiflora (L.) Brenan (i.e., “doveweed,” “MUDNU”), Polygonum species (i.e., “POLSS”), e.g., Polygonum pensylvanicum L. (i.e., “Pennsylvania smartweed,” “POLPY”), Polygonum persicaria . (i.e., “ladysthumb,” “POLPE”), and Polygonum hydropiperoides Michx. (i.e., “mild smartweed,” “POLHP”), Rotala indica (Willd.) Koehne (i.e., “Indian toothcup,” “ROTIN”), Sagittaria species, (i.e., “arrowhead,” “SAGSS”), Sesbania exaltata (Raf.) Cory /Ry db. Ex Hill (i.e., “hemp sesbania,” “SEBEX”), or Sphenoclea zeylanica Gaertn. (i.e., “gooseweed,” “SPDZE”).

[0032] In some embodiments, the compositions and methods provided herein are utilized to control undesirable vegetation consisting of grass, broadleaf and sedge weeds. In certain embodiments, the compositions and methods provided herein are utilized to control undesirable vegetation including Brachiaria, Chamomilla, Cirsium, Cyperus, Digitaria, Echinochloa, Ipomoea, Lamium, Leptochloa, Salsola, Schoenoplectus, Veronica and Viola. [0033] 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 utilized 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”) inhibitors, photosystem II inhibitors, acetyl CoA carboxylase (“ACCase”) inhibitors, synthetic auxins, photosystem I inhibitors, 5- enolpyruvylshikimate-3 -phosphate (“EPSP”) synthase inhibitors, microtubule assembly inhibitors, lipid synthesis inhibitors, protoporphyrinogen oxidase (“PPG”) inhibitors, carotenoid biosynthesis inhibitors, very long chain fatty acid (“VLCFA”) inhibitors, phytoene desaturase (“PDS”) inhibitors, glutamine synthetase inhibitors, 4-hydroxyphenyl -pyruvatedioxygenase (“HPPD”) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple modes-of-action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes with resistance or tolerance to multiple herbicides, multiple chemical classes, and multiple herbicide modes-of- action.

[0034] In certain embodiments, the methods and compositions utilizing the compound of formula (I) or salt or ester thereof in combination with the second herbicide or salt, carboxylic acid, carboxylate salt, or ester thereof are used to control HETRE, HETLI, ECHGC, ECHSS, CPYDI, and/or AMMCO.

[0035] The components of the mixtures described herein can be applied either separately or as part of a multipart herbicidal system.

[0036] 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, acifluorfen, 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, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benthiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac- sodium, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone-ethyl, 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, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, 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, 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, fluazifop, fluazifop-P -butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr-ethyl, flumezin, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, fumiclorac, furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P-ammonium, glyphosate, halosafen, halosulfuron-methyl, haloxydine, haloxyfop-methyl, haloxyfop-P- methyl, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazosulfuron, cloransulam-methyl, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron-ethyl-sodium, iofensulfuron, ioxynil, ipazine, ipfencarbazone, 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, 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, or/Ao-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraflufen- ethyl, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, pentachlorophenol, pentanochlor, pentoxazone, 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, propoxy carb azone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen- ethyl, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac-sodium, pyroxasulfone, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P-ethyl, rhodethanil, rimsulfuron, saflufenacil, 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, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, 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. [0037] 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 -phenyl-sulfonylbenzoic acid amides, to enhance their selectivity. In some embodiments, the safeners are employed in rice, cereal, com, 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 isoxadifen-ethyl.

[0038] 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. [0039] 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- ec-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.

[0040] 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, //-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, 7V-methyl-2-pyrrolidinone, N,N-di methyl alkylamides, dimethyl sulfoxide, liquid fertilizers and the like. In certain embodiments, Water is the carrier for the dilution of concentrates.

[0041] 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.

[0042] 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, New Jersey, 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-Cis ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-Ci6 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.

[0043] 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.

[0044] 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.

[0045] 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 embodiments 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 0.0003 to 1.5 weight percent active ingredient and in certain embodiments contain about 0.0008 to 1.0 weight percent.

[0046] 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. [0047] 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

Evaluation of Pre-Planting and additionally Post-Emergence Foliar- Applied Herbicidal Mixtures for Weed Control in Direct Seeded Rice.

[0048] Prior to direct seeding of Oriza sativa (“ORYSA” or “common rice”), Heteranthera reniformis R. & P. (“roundleaf mudplantain,” “HETRE”) and Echinocloa species (“ECHSS”) had emerged on 3-meter-by-10-meter plots. Pre-plant application occurred about 7 days prior to direct seeding of ORYSA. If weeds were substantially present, post-emergence applications occurred at BBCH 13-21 stage. Visual control (%) was observed and recorded 7 days after the final application. When applied, the treatments were applied using a backpack sprayer equipped with a flat fan nozzle, with spray volumes as set forth in Table 1 and at a pressure range of from about 200 to about 300 kPa. Formula A contained 25 g of the benzyl ester of the compound of formula (I) per liter. Formula B contained 20 g of penoxsulam and 12.5 g of the benzyl ester of the compound of formula (I) per liter.

Table 1. Activity of pre-plant application of Formula A (comprising compound of formula (I), benzyl ester) and additionally post-emergence application of Formula B (comprising compound of formula (I), benzyl ester + penoxsulam) on Weed Control in a Rice Cropping System.

Further Evaluation of Pre-Planting and additionally Post-Emergence Foliar- Applied Herbicidal Mixtures for Weed Control in Direct Seeded Rice.

[0049] Prior to direct seeding of Oriza sativa (“ORYSA” or “common rice”), Heteranthera reniformis R. & P. (“roundleaf mudplantain,” “HETRE”) and Echinochloa crus-galli (L.) P. Beauv. (z.e., “bamyardgrass,” “ECHCG”) had emerged on 3 -meter-by- IOmeter plots, but Cyperus difformis L. (z.e., “smallflower flatsedge,” “CYPDI”) and Polygonum species (z.e., “POLSS”) had not yet emerged. Pre-plant application occurred about 7 days prior to direct seeding of ORYSA. If weeds were substantially present, postemergence applications occurred at BBCH 13-21 stage. Visual control (%) was observed and recorded 7 days after the final application. When applied, the treatments were applied using a backpack sprayer equipped with a flat fan nozzle, with spray volumes as set forth in Table 1 and at a pressure range of from about 200 to about 300 kPa. Formula A contained 25 g of the benzyl ester of the compound of formula (I) per liter. Formula B contained 20 g of penoxsulam and 12.5 g of the benzyl ester of the compound of formula (I) per liter.

Table 2. Activity of pre-plant application of Formula A (comprising compound of formula (I), benzyl ester) and additionally post-emergence application of Formula B (comprising compound of formula (I), benzyl ester + penoxsulam) on Weed Control in a Rice

Cropping System.

Even Further Evaluation of Pre-Planting and additionally Post-Emergence Foliar- Applied Herbicidal Mixtures for Weed Control in Direct Seeded Rice.

[0050] Prior to direct seeding of Oriza sativa (“ORYSA” or “common rice”), Heteranthera reniformis R. & P. (“roundleaf mudplantain,” “HETRE”) and Echinocloa species (“ECHSS”) had emerged on 3-meter-by-10-meter plots,

coccinea Rottb. (z.e., “redstem,” “AMMCO”) and Cyperus difformis L. (z.e., “smallflower flatsedge,” “CYPDI”) had not yet emerged. Pre-plant application occurred about 7 days prior to direct seeding of ORYSA. If weeds were substantially present, post-emergence applications occurred at BBCH 13-21 stage. Visual control (%) was observed and recorded 7 days after the final application. When applied, the treatments were applied using a backpack sprayer equipped with a flat fan nozzle, with spray volumes as set forth in Table 1 and at a pressure range of from about 200 to about 300 kPa. Formula A contained 25 g of the benzyl ester of the compound of formula (I) per liter. Formula B contained 20 g of penoxsulam and 12.5 g of the benzyl ester of the compound of formula (I) per liter.

Table 3. Activity of pre-plant application of Formula A (comprising compound of formula (I), benzyl ester) and additionally post-emergence application of Formula B (comprising compound of formula (I), benzyl ester + penoxsulam) on Weed Control in a Rice

Cropping System.

Claims

WHAT IS CLAIMED IS:

1. A method of controlling undesirable vegetation in rice comprising applying to a rice paddy prior to planting rice a herbicidally effective amount of a compound of the formula (I):

or an agriculturally acceptable salt or ester thereof.

2. The method of claim 1, further comprising applying (a) a compound of formula (I), or an agriculturally acceptable salt or ester thereof, and (b) a second herbicide to a rice paddy subsequent to emergence of dry seeded rice, wet seeded rice or planting transplanted rice and/or prior to or after emergence of undesirable vegetation.

3. The method of claim 1 or 2, wherein the composition is applied to water.

4. The method of claim 3, wherein the water is part of a flooded rice paddy.

5. The method of claim 1 or 2, wherein the composition is applied to soil.

6. The method of any one of claims 1-5, wherein the additional composition is applied to water.

7. The method of claim 6, wherein the water is part of a flooded rice paddy.

8. The method of any one of claims 1-7, wherein the undesirable vegetation is controlled in glyphosate-, glufosinate-, dicamba-, phenoxy auxins-, pyridyloxy auxins-, aryloxyphenoxypropionates-, acetyl CoA carboxylase (“ACCase”) inhibitors-, imidazolinones-, acetolactate synthase (“ALS”) inhibitors-, 4-hydroxyphenyl-pyruvate dioxygenase (“HPPD”) inhibitors-, protoporphyrinogen oxidase (“PPO”) inhibitors-, triazines-, or bromoxynil- tolerant rice.

9. The method of claim 8, wherein the tolerant rice possesses multiple or stacked traits conferring tolerance to multiple herbicides or inhibitors of multiple modes of action.

10. The method of any one of claims 1-9, wherein the undesirable vegetation comprises a herbicide resistant or tolerant weed.

11. The method of claim 10, wherein the herbicide resistant or tolerant weed is a biotype with resistance or tolerance to multiple herbicides, multiple chemical classes, or inhibitors of multiple herbicide modes-of-action.

12. The method of claim 10, wherein the herbicide resistant or tolerant weed is a biotype resistant or tolerant to acetolactate synthase (“ALS”) inhibitors, photosystem II inhibitors, acetyl CoA carboxylase (“ACCase”) inhibitors, synthetic auxins, photosystem I inhibitors, 5 -enolpyruvylshikimate-3 -phosphate (“EPSP”) synthase inhibitors, microtubule assembly inhibitors, lipid synthesis inhibitors, protoporphyrinogen oxidase (“PPO”) inhibitors, carotenoid biosynthesis inhibitors, very long chain fatty acid (“VLCFA”) inhibitors, phytoene desaturase (“PDS”) inhibitors, glutamine synthetase inhibitors, 4- hydroxyphenyl-pyruvate-dioxygenase (“HPPD”) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple modes-of-action, quinclorac, arylaminopropionic acids, difenzoquat, endothall, or organoarsenicals.

13. The method of any one of claims 1-12, wherein the compound of formula (I) or an agriculturally acceptable salt or ester thereof is the benzyl ester of the compound of formula (I).