WO2025212359A1 - Bixlozone mixture, composition and herbicidal method - Google Patents

Abstract

This invention is directed to a mixture comprising (a) bixlozone, and salts thereof and (b) a compound of Formula I or Formula II. Also disclosed is a composition comprising this mixture. This invention also includes a herbicidal mixture further comprising at least one additional active ingredient. Also disclosed is a method of applying the mixture or composition to undesired vegetation comprising contacting the undesired vegetation or its environment with an effective amount of the mixture of the invention.

Description

TITLE

BIXLOZONE MIXTURE, COMPOSITION AND HERBICIDAL METHOD

FIELD OF THE INVENTION

This invention relates to a mixture of bixlozone in combination with a second active ingredient, compositions containing the mixture, and methods for using the mixture for controlling undesirable vegetation.

BACKGROUND OF THE INVENTION

The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Many products are commercially available for these purposes, but the need continues for new mixtures, compositions and their method of use that are more effective, less costly, less toxic, environmentally safer or have different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to a mixture comprising (a) bixlozone, and salts thereof and (b) a compound of Formula I or Formula II

This invention also includes the herbicidal mixture further comprising (c) at least one additional active ingredient. This invention also relates to a herbicidal composition comprising a mixture of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a mixture of the invention (e.g., as a composition described herein).

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a mixture, composition or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such mixture, composition or method.

The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of’ is used to define a mixture, composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’.

Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of’ or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular. As referred to herein, the term “seedling”, used either alone or in a combination of words means a young plant developing from the embryo of a seed. As referred to herein, the term “broadleaf’ used either alone or in words such as “broadleaf weed” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.

Combinations of herbicides are typically used to broaden the spectrum of plant control or enhance the level of control of any given species through additive effect. Certain rare combinations surprisingly give a greater-than-additive effect. Such valuable mixtures, compositions and methods have now been discovered.

United States Patent 4,405,357 discloses certain 3-isoxazolidinones which exhibit desirable selective herbicidal activity. Specifically, such compounds are shown to be effective in controlling grassy and broadleaf weed species while leaving legumes, particularly soybeans, unaffected. Among the compounds specifically disclosed in this patent is 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone (CA No. 81777-95-9) which is biologically active against a number of weed species.

Bixlozone is a herbicide recently introduced by FMC with the CAS name of 2-(2,4- dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone. For convenience, bixlozone is sold commercially as (a formulated material as) “Overwatch” and has also previously been referred to as “DCPMI”, “F9600”, “2,4-DC” and “dichloroclomazone”. The term “bixlozone” as used herein means a composition comprising at least 90% by weight pure 2-(2,4-dichlorophenyl) methyl-4,4-dimethyl-3-isoxazolinone. In one embodiment bixlozone may be technical grade bixlozone with purity range of 90 to 95% by weight. In another embodiment, the bixlozone may be a composition comprising more than 95% by weight pure 2-(2,4-dichlorophenyl) methyl-4,4-dimethyl-3-isoxazolinone. The term “pure bixlozone” means 100% pure 2-(2,4- dichlorophenyl) methyl-4,4-dimethyl-3-isoxazolinone.

Bixlozone can be prepared according to the procedure described in WO 2019/209847. Alternatively, bixlozone can be purchased as a composition (formulation) as Overwatch® from the FMC corporation. The compound of Formula I is assigned the common name “rimisoxafen” and can be prepared by using general procedures described in WO 2015/108779 or WO 2021/113284. The compound of Formula II can be prepared as described in WO 2016/196606.

Bixlozone can exist as one or more rotomers, or in different crystal forms (for example WO 2019/030177 and WO 2019/243104). The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers are therefore included in this disclosure. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geo isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of Formulae I and II may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form. A compound of Formulae I and II of this invention can exist as one or more conformational isomers due to restricted rotation about a single bond. This invention comprises mixtures of conformational isomers. In addition, this invention includes a compound of Formulae I and II that is enriched in one conformer relative to others.

Rimixoafen (i.e. a compound of Formula I, CAS No. 1801862-02-1) can also exist in various rotomeric forms, depending on if the compouind is in the solid form, or if it is dissolved in a particular solvent. This discloseure encompasses all of the various forms of both bixlozone and rimisoxafen. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

This disclosure comprises racemic mixtures, for example, equal amounts of one rotamer/crystal form. In addition, this disclosure includes a mixture of either bixlozone and rimisoxafen that is enriched in one rotamer/crystal form in comparison to the opposite rotamer or other crystal structure. Also included in this disclosure is the essentially pure rotamer/crystal form of bixlozone and the compound of Formulae I or II.

Component (b) of the present invention is a compound of Formula I or Formula II. Preferred as a compound of component (b) is a compond of Formula II. More preferred as a compound of component (b) is a compond of Formula I.

Where component (a) or component (b) of the present recitatation contain a nitrogen atom with a free pair of electons capable of protonation, salt formation can occour in the presence of an acid. Under some conditions, salt formation can be brought about in th presence of a base. In the present disclosure and claims, unless indicated otherwise, the molecular weight of Formula I is 358.13 g/mole, and that of Formula II is 365.13 g/mole.

The compounds of Formulae I and II can exist in more than one form, and thus include all crystalline and non-crystalline forms of the compounds they represent. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of the compounds of component (a) or (b) can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compounds of component (a) or (b). Preparation and isolation of a particular polymorph of compounds of component (a) or (b) can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of compounds of Formulae I and II are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of compounds of Formulae I and II include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.

Embodiments of the present invention as described in the Summary of the Invention include the following:

Embodiment 1. The mixture as described in the Summary of the Invention.

Embodiment 2. The mixture of Embodiment 1 wherein component (b) is the compound of Formula I.

Embodiment 3. The mixture of Embodiment 1 wherein component (b) is the compound of Formula II.

Embodiment 4. The mixture of any one of Embodiments 1 through 3 wherein component (a) is applied from about 25 g a.i./ha to about 1000 g a.i./ha.

Embodiment 5. The mixture of Embodiment 4 wherein component (a) is applied at from about 30 g a.i./ha to about 500 g a.i./ha.

Embodiment 6. The mixture of Embodiment 5 wherein component (a) is applied from about 40 g a.i./ha to about 450 g a.i./ha.

Embodiment 7. The mixture of Embodiment 6 wherein component (a) is applied from about 50 g a.i./ha to about 400 g a.i./ha.

Embodiment 8. The mixture of Embodiment 7 wherein component (a) is applied from about 60 g a.i./ha to about 350 g a.i./ha.

Embodiment 9. The mixture of Embodiment 8 wherein component (a) ia applied from about 65 g a.i./ha to about 300 g a.i./ha. Embodiment 10. The mixture of Embodiment 9 wherein component (a) is applied from about 70 g a.i./ha to about 275 g a.i./ha.

Embodiment 11. The mixture of Embodiment 10 wherein component (a) is applied from about 75 g a.i./ha to about 250 g a.i./ha.

Embodiment 12. The mixture of Embodiment 11 wherein component (a) is applied from about 80 g a.i./ha to about 225 g a.i./ha.

Embodiment 13. The mixture of Embodiment 12 wherein component (a) is applied at least about 80 g a.i./ha.

Embodiment 14. The mixture of Embodiment 12 wherein component (a) is applied at least about 90 g a.i./ha.

Embodiment 15. The mixture of Embodiment 12 wherein component (a) is applied at least about 100 g a.i./ha.

Embodiment 16. The mixture of Embodiment 12 wherein component (a) is applied at least about 110 g a.i./ha.

Embodiment 17. The mixture of Embodiment 12 wherein component (a) is applied at least about 120 g a.i./ha.

Embodiment 18. The mixture of Embodiment 12 wherein component (a) is applied at least about 130 g a.i./ha.

Embodiment 19. The mixture of Embodiment 12 wherein component (a) is applied at least about 140 g a.i./ha.

Embodiment 19A. The mixture of any one of Embodiments 1 through 19 wherein component (b) is applied at least about 20 g a.i./ha.

Embodiment 19B. The mixture of Embodiment 19A wherein component (b) is applied at least about 30 g a.i./ha.

Embodiment 19C. The mixture of Embodiment 19B wherein component (b) is applied at least about 40 g a.i./ha.

Embodiment 19D. The mixture of Embodiment 19C wherein component (b) is applied at least about 50 g a.i./ha.

Embodiment 19E. The mixture of Embodiment 19C wherein component (b) is applied at least about 60 g a.i./ha.

Embodiment 19F. The mixture of Embodiment 19C wherein component (b) is applied at least about 70 g a.i./ha.

Embodiment 19G. The mixture of any one of Embodiments 19A through 19F wherein component (b) is applied at less than about 200 g a.i./ha.

Embodiment 19H. The mixture of any one of Embodiments 19A through 19F wherein component (b) is applied at less than about 150 g a.i./ha.

Embodiment 191. The mixture of any one of Embodiments 19A through 19F wherein component (b) is applied at less than about 125 g a.i./ha. Embodiment 19J. The mixture of any one of Embodiments 19A through 19F wherein component (b) is applied at less than about 100 g a.i./ha.

Embodiment 19K. The mixture of any one of Embodiments 19A through 19F wherein component (b) is applied at less than about 80 g a.i./ha

Embodiment 20. The mixture of any one of Embodiments 1 through 19 wherein the weight ratio of (a) to (b) is from about 100:1 to about 1: 1.

Embodiment 21. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 75:1 to about 1: 1.

Embodiment 22. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 50:1 to about 1: 1.

Embodiment 23. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 40:1 to about 1:1.

Embodiment 24. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 30:1 to about 1:1.

Embodiment 25. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 24:1 to about 1.5:1.

Embodiment 26. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 12: 1 to about 1.5:1.

Embodiment 26A. The mixture of Embodiment 20 wherein the weight ratio (a) to (b) is from about 7: 1 to about 6:1.

Embodiment 26B. The mixture of Embodiment 20 wherein the weight ratio (a) to (b) is from about 6.75: 1 to about 6.50: 1.

Embodiment 27. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 6: 1 to about 1.5: 1.

Embodiment 28. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 4: 1 to about 1.5: 1.

Embodiment 29. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 3 : 1 to about 1.5:1.

Embodiment 30. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 2: 1 to about 1.5:1.

Embodiment 31. The mixture of Embodiment 20 wherein the weight ratio of (a) to (b) is from about 1.5:1 to about 1:1.

Embodiment 32. The mixture of any one of Embodiments 1 through 31 wherein the mixture further comprises a safener.

Embodiment 33. The mixture of Embodiment 32 wherein the ratio of component (a) to (b) to the safener is about 5:1 :0.35.

Embodiment 34. The mixture of Embodiment 33 wherein the safener is selected from mefenpyr and cloquintocet. Embodiment 35. The mixture of Emodiment 34 wherein the safener is selected from mefenpyr-diethyl and cloquintocet-mexyl.

Embodiment 36. The mixture of Embodiment 35 wherein the safener is cloquintocet- mexyl.

Embodiment 37. A composition comprising the mixture as defined in any one of 1 through 36.

Embodiment 38. The composition of Embodiment 37 comprising at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

Embodiment 39. The composition of Embodiment 38 in the form of a suspension concentrate (SC).

Embodiment 40. The composition of Embodiment 38 in the form of an oil dispersion (OD).

Embodiment 41. The composition of Embodiment 38 in the form of a wettable powder (WP).

Embodiment 42. The composition of Embodiment 38 in the form of a water dispersible granules (WG or WDG).

Embodiment 43. The composition of Embodiment 38 in the form of a suspo-emulsion (SE).

Embodiment 44. The composition of Embodiment 38 in the form of a capsule suspension (CS).

Embodiment 45. The composition of Embodiments 43 and 44 in the form of a mixed formulation of a SE and CS (ZC).

Embodiment 46. A method for controlling undesired vegetation comprising appling a) the mixture defined in any of Embodiments 1 through 36, or b) the composition defined in any of Embodiments 37 through 45 to the undesired vegetation.

Embodiment 47. The method of Embodiment 46 wherein the undesired vegetation is selected from grass weeds and broad-leaf weeds.

Embodiment 48. The method of any one of Embodiments 46 through 47 wherein the applying pre-emergence (i.e. before the undesired vegetation has emerged).

Embodiment 49. The method of any one of Embodiments 46 through 47 wherein the applying is post-emergence (i.e. after the undesired vegetation has emerged).

Embodiment 50. The method of any one of Embodiments 47 through 49 whererein the undesired vegetation is selected from the genus Amaranthus, Avena and Malva.

Embodiment 51. The method of Embodiment 50 wherein the undesired vegetation is redroot pigweed {Amaranthus relmjlexiis). Embodiment 52. The method of Embodiments 46 through 47 wherein the undesired vegetation is selected from the genus Lolium and Raphanus.

Embodiment 53. The method of Embodiment 46 wherein said undesired vegetation is selected from the group consisting of annual blue grass, annual ryegrass (Lolium rigidum), ball medic (Medicago spp.), barley grass (Hordeum murinum), bedstraw (Galium tricornutum), Benghal dayflower, bifora (Bifora testiculata), black grass, black night shade, broadleaf signal grass, brome grass (Bromus spp.), Canada thistle, capeweed (Arctotheca calendula), cheat, chickweed (Stellaria media), common cocklebur (Xanthium pensylvanicum), common ragweed, corn poppies, doublegee (Emex australis), field violet, fleabane (Conyza bonariensis) giant foxtail, fumitory (Fumaria spp), goose grass, green fox tail, guinea grass, hairy beggarticks, herbicide-resistant black grass, horseweed, Indian hedge mustard (Sisymbrium orientate), Italian rye grass, Jersey cudweed (Gnaphalium luteoalbum), jimsonweed, johnsongrass (Sorghum halepense), large crabgrass, lesser loosestrife (Lythrum hyssopifolia), little seed cany grass, morning glory, Patterson’s Curse (Echium plantagineum), Pennsylvania smartweed, phalaris (Phalaris paradoxa), pitted momingglory, prickly lettuce (Lactuca serriola), prickly sida, quack grass, redflowered mallow (Modiola caroliniana), redroot pigweed, rough poppy (Papaver hybridum), serradella, shatter cane, shepherd’s purse, silky windgrass, silvergrass (Vulpia bromoides), sowthistle (Sonchus oleraceus), sub-clover (Trifolium spp.), sunflower (as weed in potato), volunteer chickpea, faba beans, field peas, lentils, lupins and vetch, wild buckwheat (Polygonum convolvulus), wild mustard (Brassica kaber), wild oat (Avena fatua), wild pointsettia, wild radish (Raphanus raphanistrum), wild turnip (Rapistrum rugosum, Brassica tournefortii), wireweed (Polygonum aviculare), yellow foxtail and yellow nutsedge (Cyperus esculentus).

Embodiment 54. The method of Embodiment 53 wherein said undesired vegetation is selected from annual ryegrass (Lolium rigidum) and wild radish (Raphanus raphanistrum).

Embodiment 55. The method of Embodiment 54 wherein said undesired vegetation is selected from wild radish (Raphanus raphanistrum).

Embodiment 56. The method of Embodiment 50 wherein the undesired vegetation is wild oat (Avena fatua).

Embodiment 56A. The method of Embodiment 56 wherein the undesired vegetation is wild oat (Avena fatua) evaluated at greater than 21-35 days after application.

Embodiment 56B. The method of Embodiment 56 wherein the undesired vegetation is wild oat (Avena fatua) evaluated at greater than 35 days after application. Embodiment 56C. The method of Embodiment 56B wherein the undesired vegetation is wild oat (Avena fatud) evaluated at greater than 40 days after application.

Embodiment 56D. The method of Embodiment 56C wherein the undesired vegetation is wild oat (Avena fatud) evaluated at greater than 42 days after application Embodiment 56E. The method of Embodiment 50 wherein the undesired vegetation is wild oat (Avena fatud evaluated at 42-56 days after application.

Embodiment 56F. The method of Embodiment 53 or 54 wherein the undesired vegetation is other than wild oat (Avena fatud).

Embodiment 57. The method of Embodiment 50 wherein the undesired species is round-leaved mallow (Malva pusilia).

Embodiment 58. The method of any one Embodiment 47 through 49 wherein the undersired vegetation is selected from the genus Avena, Alopecurus, Bromus, Ambrosia and Kochia.

Embodiment 59. The method of Embodiment 58 whererein the undesired vegetation is selected from Avena fatua, Alopecurus myosuroides, Bromus tectorum, Ambrosia artemisiifolia, Kochia scoparia.

Embodiment 60. The method of any of Embodiments 47 through 59 wherein the undesired vegetaion is growing in spring wheat (triticum aestivum).

Embodiment 61. The method of any of Embodiments 47 through 59 wherin the undesired vegetation is growing in banana, barley, bean, beet, cassava, citrus, cocoa, coconut, coffee, com, grape, hops, oil palm, oilseed rape, pea, peanut, pomes, potato, rice, sugar cane, sunflower, tea, tobacco, walnut, almond, pecan, hickory, cashew, hazelnut or wheat.

Embodiment 61 A. The method of any of Embodiments 47 through 59 wherein the undesired vegetation is growing in banana, barley, bean, beet, cassava, citrus, cocoa, coconut, coffee, com, grape, hops, oats, oil palm, oilseed rape, pea, peanut, pomes, potato, rice, sugar cane, sunflower, tea, tobacco, walnut, almond, pecan, hickory, cashew, hazelnut or wheat.

Embodiment 6 IB. The method of Embodiment 61 A wherein the undesired vegetation is growing in barley, oats and wheat.

Embodiment 61C. The method of Embodiment 6 IB wherein the undesired vegetation is growing in barley and wheat.

Embodiment 61D. The method of any of Embodiments 47 through 59 wherein the undesired vegetation is growing in pulse crops selected from soybean, mung bean, lupin, field pea, chickpea, faba bean and lentil.

Embodiment 6 IE. The method of Embodiment 61D wherein the undesired vegetation is growing in pulse crops selected from lupin, field pea, chickpea, faba bean and lentil. Embodiment 6 IF. The method of Embodiment 6 ID wherein the undesired vegetation is growing in pulse crops selected from soybean and mung bean.

The mixture of this invention further comprising (c) at least one additional active ingredient includes herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Mixtures of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Thus the present invention also pertains to a composition further comprising at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a present mixture, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula I, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.

Appropriate as the one additional active ingredient, (i.e. as component (c)) at least one additional active ingredient can be one or more of the following herbicides particularly useful for weed control: acetochlor, acifhiorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, beflubutamid-M, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, benquitrione, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bipyrazone, bispyribac and its sodium salt, broclozone, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol - methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinflubrolin, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, cypyrafluone, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, dioxopyritrione, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, epyrifenacil, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, feproxydim, fenquinotrione, fenpyrazone, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, fluchloraminopyr, flufenacet, flufenpyr, flufenoximacil, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol- butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, flusulfinam, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate), halauxifen, halauxifen-benzyl, halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop- methyl, hexazinone, hydantocidin, icafolin, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, indolauxipyr, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil- sodium, ipfencarbazone, iptriazopyrid, isoproturon, isouron, isoxaben, isoxafhitole, isoxachlortole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metproxybicyclone, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, pethoxyamid, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyraquinate, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriflubenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, tiafenacil, tiocarbazil, tolpyralate, topramezone, tralkoxydim, tri-allate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron-methyl, tripyrasulfone, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-l-methyl- 1 ,5 -naphthyridin-2( 1 //)-one, 5 -chloro-3 - [(2-hydroxy-6-oxo- 1 -cyclohexen- 1 -yl)carbony 1] - 1 - (4-methoxyphenyl)-2(l//)-quinoxalinone, 2-chloro-A-(l-methyl-l//-tetrazol-5-yl)-6- (trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)- 8-hydroxypyrido[2,3-/>]pyrazin-6(5//)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6- dimethyl-3(2//)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5- methyl-3-(3-methyl-2-thienyl)isoxazole (previously methioxolin), 4-(4-fluorophenyl)-6-[(2- hydroxy-6-oxo-l -cyclohexen- l-yl)carbonyl|-2-methyl- 1, 2, 4-triazine-3, 5(2//, 4//)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2- pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-A-(l-methyl-l//-tetrazol-5-yl)-4-

(trifluoromethyl)benzamide and 2-methyl-A-(4-methyl- 1 ,2,5-oxadiazol-3-yl)-3- (methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include bioherbicides such as Allernaria deslruens Simmons, Collelolrichum gloeosporiod.es (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.

Preferred for better control of undesired vegetation (e.g., lower use rate such as from greater-than-additive effects, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds are mixtures of a compound of this invention with a herbicide selected from the group consisting of atrazine, azimsulfuron, beflubutamid, beflubutamid-M, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, clopyralid potassium, cloransulam-methyl, ethametsulfuron-methyl, fhimetsulam, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-l- cyclohexen-l-yl)carbonyl]-2- methyl- 1, 2, 4-triazine-3,5-(2//,4//)-dione, flupyrsulfuron-methyl, fluthiacet-methyl, fomesafen, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, pethoxamid, picloram, pyroxasulfone, quinclorac, rimsulfuron, S-metolachlor, sulfentrazone, thifensulfuron-methyl, tetflupyrolimet, triflusulfuron-methyl and tribenuron-methyl.

Mixtures of this invention can also be used in combination with plant growth regulators such as aviglycine, phenyl methyl)- 1 H-purin-6-amine, epocholeone, gibberellic acid, gibberellin A₄ and A₇, harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.

General references for agricultural protectants (i.e. herbicides, herbicide safeners, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners are used, the mixing partners are typically used in the amounts similar to amounts customary when the mixture partners are used alone. More particularly in mixtures, active ingredients are often applied at an application rate between one-half and the full application rate specified on product labels for use of active ingredient alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (in total) to the present mixture is typically between about 1 :3000 and about 3000: 1. Of note are weight ratios between about 1 :300 and about 300:1 (for example ratios between about 1 :30 and about 30: 1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the present mixture alone.

In certain instances, combinations of a mixture of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients as component (c) of the invention) can result in a greater-than-additive effect on weeds and/or a less-than- additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable. When greater-than-additive effects of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. When safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition. Of note is a combination of a mixture of the invention with at least one other herbicidal active ingredient (i.e. as component (c)). Of particular note is such a combination where the other herbicidal active ingredient has different site of action from either component (a) or component (b) of the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action. For example, bixlozone can be provided as a formulated mixture with pethoxamid as described in PCT/US23/34070 or as a formulated mixture with beflubutamid (or beflubutamid-M) as described in PCT/US23/34068.

The mixtures of this invention can also be used in combination with herbicide safeners (i.e. as component (c)) selected from allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr- diethyl, mephenate, methoxyphenone naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, A-(aminocarbonyl)-2-methylbenzenesulfonamide, N- (aminocarbonyl) -

2-fluorobenzenesulfonamide, l-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4- (dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl- 1,3-dioxolane (MG 191), ethyl l,6-dihydro-l-(2-methoxyphenyl)-6-oxo-2-phenyl-5- pyrimidinecarboxylate, 2-hydroxy-AGV-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo- 1 -cyclohex en-l-yl l-(3,4-dimethylphenyl)-l,6-dihydro-6-oxo-2-phenyl-5- pyrimidinecarboxylate, 2,2-dichloro-l-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2- methoxy-A-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the mixtures of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a mixture of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a mixture of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.

This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the mixture of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the mixtures of embodiments described above. Mixtures of the invention are particularly useful for selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, oilseed rape and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops. Of note of the present invention is the selective control of weeds in a transplanted rice crop. Also of note is the selective control of weeds in a direct- seeded rice crop.

A mixture of this invention will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.

Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in -water emulsions, flowable concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from filmforming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active Ingredient as a Diluent Surfactant mixture

Water-Dispersible and Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and Powders

Oil Dispersions, Suspensions, 1-50 40-99 0-50

Emulsions, Solutions (including

Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.001-99 5-99.999 0-15

High Strength Compositions 90-99 0-10 0-2

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

Liquid diluents include, for example, water, N.A'-dimethylalkan amides (e.g., NW-dimethylformamide), limonene, dimethyl sulfoxide, -alkylpyrrolidones (e.g., A-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and y-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolinbased derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, hut are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N- alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as Aralkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquatemary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon ’s Emulsifiers and Detergents, annual American and International Editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone- vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon ’s Volume 2: Eunctional Materials, annual International and North American editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222. Bixlozone can be provided as a formulated active ingredient as a biodegradeable oil dispersion as described in PCT/US23/34067, or as a homo-ZC as described in PCT/US/23/34075, or as a wettable dispersible granule as described in PCT/US23/34071. The mixtures of a compound of Formulae I and II and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 pm can be wet milled using media mills to obtain particles with average diameters below 3 pm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 pm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, “The Formulator’ s Toolbox - Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.

Example A

High Strength Concentrate Component (a) and Component (b) 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

Example B

Wettable Powder

Component (a) and Component (b) 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0% Example C

Granule

Component (a) and Component (b) 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0%

U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet

Component (a) and Component (b) 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate

Component (a) and Component (b) 10.0% polyoxyethylene sorbitol hexoleate 20.0%

C₆-C₁₀ fatty acid methyl ester 70.0%

Example F Microemulsion

Component (a) and Component (b) 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0% Example G

Suspension Concentrate

Component (a) and Component (b) 35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0. 1 % l,2-benzisothiazolin-3-one 0.1% water 53.7%

Example H

Emulsion in Water

Component (a) and Component (b) 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% l,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0 water 58.7%

Example I

Oil Dispersion

Component (a) and Component (b) 25% polyoxyethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5%

Test results indicate that the mixtures of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. The mixtures of the present invention generally show highest activity for postemergence weed control (i.e. applied after weed seedlings emerge from the soil) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of the mixtures of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors can readily be determined by performing routine biological and/or biochemical assays. Mixtures of this invention may show tolerance to important agronomic crops including, but is not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, com (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Of note is a rice crop that is direct- seeded. Of note is a rice crop that transplanted. Mixtures of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all mixtures are equally effective against all weeds. Alternatively, the subject mixtures are useful to modify plant growth.

As the mixture of the invention have both preemergent and postemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the mixture can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a mixture of the invention, or a composition comprising said mixture and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.

A herbicidally effective amount of the mixtures of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of mixtures of this invention is about 0.001 to 20 kg/ha with a preferred range of about 0.004 to 1 kg/ha, about 0.004 to 0.5 kg/ha, about 0.004 to 0.25 kg/ha, about 0.004 to 0.1 kg/ha, 0004 to 0.075 kg/ha or 0.004 to 0.05 kg/ha. One skilled in the art can determine the herbicidally effective amount necessary for the desired level of weed control.

In one common embodiment, a mixture of the invention is applied, typically in a formulated composition, to a locus comprising desired vegetation (e.g., crops) and undesired vegetation (i.e. weeds), both of which may be seeds, seedlings and/or larger plants, in contact with a growth medium (e.g., soil). In this locus, a composition comprising a mixture of the invention can be directly applied to a plant or a part thereof, particularly of the undesired vegetation, and/or to the growth medium in contact with the plant.

Plant varieties and cultivars of the desired vegetation in the locus treated with a mixture of the invention can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.

Genetically modified plant cultivars in the locus which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are found in publicly available databases maintained, for example, by the U.S. Department of Agriculture.

The herbicidal mixture can be formulated as single, separate ingredients (i.e as a copack) and mixed together (i.e. as a tank mix). Alternatively, the herbicidal mixture can be formulated separately, then mixed together before adding to the spray tank (i.e. a homogenous blend of soluble granules). Alternatively, the herbicidal mixture can be formulated together, then formulated, (i.e. as soluble granules). The amount of each compound of the herbicidal mixture (i.e. as compounent (a) and (b) (and optionally (c)) can be adjusted according to field conditions present. Likewise, the method of applying the herbicidal mixture or composition also comprises the sequential application of component (a) followed by component (b), or in reverse order (otherwise known as a “split” application).

Of note is a composition comprising a mixture of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

The following Tests demonstrate the control efficacy of the mixture of this invention against specific weeds. The weed control afforded by the mixture is not limited, however, to these species. The abbreviation “Cmpd. No.” stands for “Compound Number”.

BIOLOGICAL EXAMPLES OF THE INVENTION

TEST A

Seeds of wild oat (AVEFA, Avena fatua), blackgrass (ALOMY, Alopecurus myosuroides), downy brome (BROTE, Bromus teciorum). common ragweed (AMBEL, Ambrosia artemisiifolia), and kochia (KCHSC, Kochia scoparia) were sown at approximately 0.5 cm depth in 6.4 cm pots filled with a silt loam soil containing 1.83% organic matter content. Plants were grown in a greenhouse using supplemental lighting to maintain a photoperiod of approximately 16 h; daytime and nighttime temperatures were approximately 26-29 °C and 24-26 °C, respectively. Two timings were targeted for herbicide application of bixlozone and rimisoxafen: one post sowing pre-emergence and one in postemergence. Preemergence applications were made to the soil surface approximately one day after sowing. Postemergence applications were targeted at the 2 to 3 (BBCH 12-13) leaf stage of the treated plants. Formulated suspension concentrate samples of the test chemicals were diluted in distilled water and applied at 281 L/ha. Treated plants and non-treated control pots were maintained in the greenhouse for 28 days following application, after that time assessments for visual weed control were made. Visual weed control was evaluated on a 0 to 100% scale, where 0% is no effect and 100% is complete plant control. Plant response ratings are summarized in Tables A and B and are the mean of either 4 (AVEFA, AMBEL, KCHSC) or 6 (ALOMY, BROTE) replications. A dash (-) response means no test result.

Colby’s Equation was used to determine the herbicidal effects expected from the mixtures and compare them with the observed efficacies. Colby’s Equation (Colby, S. R. “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations,” Weeds' 1967 75(1), pp 20-22) calculates the expected additive effect of herbicidal mixtures and for two active ingredients is of the standard form. Table A: Observed and Expected Results (28 DAA) in Grass Weed Species From Bixlozone alone and The Compound of Formula I Alone and in Tank-Mix Combination Table A: Grass Weeds (Continued)

Table B: Observed and Expected Results in Broadleaf Weed Species From Bixlozone alone, The Compound of Formula I Alone And Their Tank Mixture

As can be seen from the results listed in Tables A and B, all the observed results were greater than additive for all the weed species tested. Exception include the 75+25 g ai/ha combination for BROTE applied postemergence, 150+75 g ai/ha combination for AVEFA applied preemergence and the 150+25 g ai/ha combination for BROTE and KCHSC applied postemergence.

TEST B

Field trials were initiated near Saskatoon (Saskatchewan), Gwinne (Alberta) Hanley (Saskatchewan), Taber (Alberta) and Elm Creek (Manitoba) in field sown with spring winter wheat. Applications of bixlozone (formulated as an SC) and a compound of Formula I (formulated as an SC) or Formula II (formulated as an SC) were applied alone and in combination (i.e. as a tank-mix), along with a safener (cloquintocet-mexyl) post-emergence to the crop and the unwanted vegetaion (weeds) of wild oat (AVENA, avena fatua). Visual observations were made at 21-35 and 42-56 DAA. POS means post-application, N/A means “not available”, DAA is days after application, “Treat No.” means treatment number.

The addition of the Compound of Formula I and Formula II to bixlozone show improvements in wild oat control at 42-56 DA A.

21-35 DAA 42-56 DAA

Claims

CLAIMS What is claimed is:

1. and (b) a compound of Formula I or Formula II

2. The mixture of Claim 1 wherein (b) is a compound of Formula I.

3. The mixture of Claim 1 wherein (b) is a compound of Formula II.

4. The mixture of Claim 1 wherein the application rate of (a) is from about 25 g a.i./ha to about 1000 g a.i./ha.

5. The mixture of Claim 1 wherein the weight ratio of (a) to (b) is from about 100:1 to about 1:1.

6. The mixture of Claim 5 wherein the weight ratio of (a) to (b) is from about 30: 1 to about 1:1.

7. The mixture of Claim 6 wherein the weight ratio of (a) to (b) is from about 4:1 to about 1.5:1.

8. The mixture of Claim 1 further comprising an additional active ingredient.

9. The mixture of Claim 8 wherein the additional active ingredient comprises a safener.

10. The mixture of Claim 9 wherein the safener is selected from mefenpyr and cloquintocet.

11. The mixture of Claim 10 wherein the safener is cloquintocet- mexyl.

12. A composition comprising a mixture of any of Claims 1 through 11 further comprising a component selected from the group consisting of surfactants, solid diluents and liquid diluents.

13. The composition of Claim 12 wherein component (a) is in the form of a suspension concentrate and component (b) is in the form of a suspension concentrate.

14. The composition of Claim 13 wherein both component (a) and component (b) are combined in the form of a suspension concentrate.

15. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a mixture of Claim 1.

16. The method of Claim 15 wherein the undesired vegetation is growing in spring wheat.

17. The method of Claim 16 wherein the undesired vegetation is avenafatua.

18. The method of Claim 15 wherein the undesired vegetation is selected from annual ryegrass (Lolium rigidum) and wild radish (Raphanus raphanistrum).

19. The method of Claim 18 wherein the undesired vegetation is wild radish (Raphanus raphanistrum).