RU2773915C2 - Herbicidal mixture, composition and method - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: herbicidal mixture contains a compound of the formula I

and its salts, where A¹ is CCF₃, A² is CH, A³ is CH, B¹ is CF, B² is CH, B³ is CH; R¹ is C₁-C₄ alkyl; and (b) 4-amino-3-chlor-6-(4-chlor-2-fluor-3-methoxyphenyl)-5-fluor-phenyl methyl composite ester of 2-pyridine carboxylic acid of the formula II

and its salts. The herbicidal mixture may additionally contain auxiliary substances and additional active ingredients selected from herbicides, herbicide antidotes, fungicides, insecticides, nematicides, bactericides and acaricides. The herbicidal mixture is used in a method for control of unwanted vegetation, including bringing unwanted vegetation or medium surrounding it into contact with the effective amount of an herbicidal mixture.

EFFECT: proposed herbicidal mixture is an active pre-emergence and/or post-emergence herbicide and/or a plant growth regulator, is suitable for selective control of cereal and broad-leaved weeds in agricultural crops, shows tolerance to important agronomical crops, including rice.

11 cl, 15 tbl, 9 ex

Description

Scope of the invention

The present invention relates to a mixture of certain substituted pyrrolidinone compounds and their salts with florpyrauxifen-benzyl, compositions containing them, as well as methods of using them to control unwanted vegetation.

Prerequisites for the creation of the invention

The control of unwanted vegetation is very important to achieve high efficiency of crops. It is highly desirable to provide selective control of weed growth, especially in useful crops such as, but not limited to, rice, soybeans, sugar beet, corn, potatoes, wheat, barley, tomatoes, and plantation crops. The uncontrolled growth of weeds in such useful crops can lead to a significant reduction in productivity and thus an increase in cost to the consumer. Many products are commercially available for this purpose, but there remains a need for new mixtures, compositions, and methods of application that are more effective, less costly, less toxic, more environmentally friendly, or have different sites of action.

Herbicide combinations are typically used to broaden the range of controlled plants or to increase the degree of control of any given species through an additive effect. Certain rare combinations unexpectedly provide a reinforcing additive effect. Such valuable mixtures, compositions and methods have now been discovered.

Documents WO 2015/084796 and WO 2016/196593 describe a variety of substituted cyclic amides, methods for their use as herbicides and methods for their preparation. The herbicidal mixture, composition and method of the present invention are not described in these publications.

Statement of the Invention

The present invention relates to a mixture containing (a) a compound of formula I and its salts

,

,

where

A ¹ is CCF ₃ , A ² is CH and A ³ is CH; or

A ¹ is CH, A ² is CCF ₃ and A ³ is CH; or

A ¹ is N, A ² is CCF ₃ and A ³ is CH; or

A ¹ is CCH ₃ , A ² is N and A ³ is COCHF ₂ ;

R ¹ is C ₁ -C ₄ alkyl;

B ¹ is CF, B ² is CH and B ³ is CH; or

B ¹ is CF, B ² is CF and B ³ is CH; or

B ¹ is CF, B ² is N and B ³ is CF;

and (b) 2-pyridinecarboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-,phenylmethyl ester (i.e., florpyrauxifen-benzyl) and its salt.

The present invention also includes a herbicidal mixture further comprising (c) at least one additional active ingredient.

The present invention also relates to a herbicidal composition comprising a mixture of the invention (ie, in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

The present invention further relates to a method for controlling the growth of unwanted vegetation, comprising contacting the vegetation or its environment with a herbicidally effective amount of a mixture of the invention (eg, in the form of a composition described herein).

Detailed description of the invention

As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "accommodates", "accommodating", "different", or any other variations thereof, are intended to be non-exclusive. an inclusion that is subject to any explicit restriction. For example, a mixture, composition, or method that contains a list of elements is not necessarily limited to only those elements, but may include other elements not explicitly stated or inherent in such a mixture, composition, or method.

The transitive phrase "consisting of" excludes any unspecified element, step, or ingredient. When used in a claim, such a phrase will prevent materials other than those listed from being included in the claims, with the exception of impurities normally associated with them. When using the phrase "consisting of" in a claim of the main part of the claims, and not immediately after the introductory part, it limits only the element specified in this claim; other elements are not excluded from the claims 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 expressly described, provided that those additional materials, steps, features, components, or the elements do not significantly affect the main (s) and new (s) characteristic (s) of the claimed invention. The term "consisting essentially of" occupies a middle position between the terms "comprising" and "consisting of".

Where Applicants use an open term such as "comprising" in an invention or part thereof, it is to be understood that (unless otherwise indicated) the description is also to be interpreted as describing such an invention using the terms "consisting essentially of" or "consisting of".

Additionally, unless explicitly stated otherwise, the conjunction "or" refers to an inclusive "or" and not to an exclusive "or". For example, the condition "A or B" is true in any one of the following situations: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both elements A and B true (or present).

In addition, the use of the singular when describing an element or component of the invention is intended to be non-limiting as to the number of examples (ie, mentions) of the element or component. Therefore, a singular element or component must include "one" or "at least one", and a singular element or component also includes the plural, unless the number clearly means singular.

In this document, the term "seedling", used alone or in combination of words, means a young plant developing from a seed germ. As used herein, the term broadleaf, alone or in words such as broadleaf weed, means a dicotyledonous or dicotyledonous plant and is used to describe a group of angiosperms characterized by embryos having two cotyledons.

In the above listings, the term "alkyl" includes straight or branched chain alkyl such as methyl, ethyl, n-propyl, isopropyl, or various isomers of butyl. In the compound of formula I, the ring containing the variables A ¹ , A ² and A ³ can be represented by the following structures shown in example 1, where the link projecting to the right indicates the place of attachment of the remainder of the formula I.

Example 1

In the compound of formula I, the ring containing the variables B ¹ , B ² and B ³ can be represented by the following structures shown in example 2, where the link projecting to the left indicates the place of attachment of the remainder of the formula I.

Example 2

The total number of carbon atoms in a substituent group is indicated by the prefix "C _i -C _j ", where i and j are numbers from 1 to 4. For example, C ₁ -C ₄ alkyl means a compound from methyl to butyl, including various isomers of the alkyl group.

The compound of formula I of the present invention can be prepared using the procedures described in US Patent Applications No. 15/101,615 (WO 2015/084796) and PCT/US2016/035214 (WO 2016/196593), both of which are incorporated by reference.

The compound of formula I of the present invention may exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers, and geometric isomers. Stereoisomers are isomers of identical composition but differ in the arrangement of their atoms in space and include enantiomers, diastereomers, cis and trans isomers (also known as geometric isomers), and atropisomers. Atropisomers result from limited rotation around single bonds, where the rotating barrier is high enough to allow isomeric compounds to be isolated. The person skilled in the art will understand that one stereoisomer may be more active and/or may have beneficial effects if it is greater relative to the other(s) stereoisomer(s) or when separated from the other(s) stereoisomer(s) . In addition, the person skilled in the art knows how to separate, enrich and/or selectively obtain these stereoisomers. The compound of formula I may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. The compound of formula I of the present invention may exist as one or more conformational isomers due to limited rotation around the amide bond (eg, -C(=O)-NH-) in formula I. The present invention contains mixtures of conformational isomers. In addition, the present invention includes a compound of formula I in which one conformational isomer predominates over the others.

For example, the C=O(NH) fragment (bonded to carbon at position 3 of the pyrrolidinone ring) and the ring containing the variables A ¹ , A ² and A ³ (bonded to carbon at position 4 of the pyrrolidinone ring) are essentially in the trans configuration . Each of these two carbon atoms is in a chiral center. The two most common enantiomer pairs are shown as Formula I' and Formula I" below, where chiral centers (i.e., 3S,4S or 3R,4R) are defined. point of view is defined as Formula I' (i.e. 3S,4S configuration) and is preferably trans.For a comprehensive description of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

The images of molecules given in this document follow the standard display principles adopted in stereochemistry. To indicate the stereochemical configuration, the bonds rising above the plane of the figure towards the observer are indicated by solid wedges, with the wide end of the wedge attached to the atom rising above the plane of the figure towards the observer. Bonds falling below the plane of the figure and away from the observer are indicated by dotted wedges, with the wide end of the wedge attached to an atom further removed from the observer. Lines with constant width indicate links with a direction opposite or neutral to the links shown by solid or dashed wedges; lines of constant width also depict bonds in molecules or portions of molecules that are not intended to indicate a particular stereochemical configuration.

The present invention contains racemic mixtures, for example, equal amounts of enantiomers of formula I' and I". In addition, the present invention includes a compound of formula I that is enriched in one of the enantiomers of the compound of formula I compared to the above racemic mixture. Substantially pure enantiomers are also included compounds of formula I, for example formula I' and formula I".

When enriched by an enantiomer, one enantiomer is present in greater amounts than the other, and the degree of enrichment can be determined by the expression of enantiomeric excess (EI), which is defined as (2x - 1) 100%, where x is the mole fraction of the predominant enantiomer in the mixture (for example , EI 20% corresponds to the ratio of enantiomers 60 : 40).

Preferably the compositions of the present invention have an enantiomeric excess of at least 50%; more preferably an enantiomeric excess of at least 75%; even more preferably an enantiomeric excess of at least 90%; and most preferably an enantiomeric excess of at least 94% of the more active isomer. Of particular note are enantiomerically pure embodiments of the more active isomer.

Component (b) of the present invention is florpyrauxifen-benzyl (for example, a compound of formula II; 2-pyridinecarboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5- a fluoro, phenylmethyl ester with CAS registry number 1390661-72-9), which contains florpyrauxifen (containing an acid functional group (–CO ₂ H)), esterified with a benzyl group (i.e. –CH ₂ C ₆ H ₅ ) ;

.

.

Although embodiments of the compound of formula II are depicted with a benzyl group, they involve replacing the benzyl with hydrogen or a C ₁ -C ₄ alkyl group, resulting in an acid or C ₁ -C ₄ alkyl ester. Florpyrauxifen-benzyl is commercially available as, for example, Loyant™ herbicide with Rinskor™ active (Dow AgroSciences). For these enumerations, the compound of formula II was prepared in accordance with the methods described in WO 2010/125332 A1 and Org. Lett. 2015, 17, 2905, melting point 138–142°C. Alternatively, florpyrauxifen (ie, acid) may be prepared according to the methods described in US Pat. No. 7,314,849 (B2), which is incorporated by reference, or purchased in amounts suitable for research purposes. Florpyrauxifen-benzyl contains a nitrogen atom with a free pair of electrons that can protonate and form salts with acids. In particular, salts formed with bases can be used in the present mixture, composition and method. Florpyrauxifen-benzyl is known to mimic the plant growth hormone auxin, thereby causing uncontrolled and unorganized growth resulting in plant death in susceptible species ("auxin mimic"). In the present description and claims, the molecular weight of florpyrauxifen-benzyl is calculated to be 439.2 g/mol.

The compounds of formulas I and II may 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 that are solids such as waxes and gums, as well as embodiments that are liquids such as solutions and melts. Crystal forms include embodiments that are essentially one type of crystal and embodiments that are a mixture of polymorphs (ie, different types of crystal structure). The term "polymorph" refers to a specific crystalline form of a chemical compound, which can crystallize into different crystalline forms, and these forms have different configurations and/or conformations of molecules in the crystal lattice. Although polymorphs may have the same chemical composition, they may also differ in composition due to the presence or absence of co-crystallized water or other molecules that may be weakly or strongly bonded in the lattice. Polymorphs may differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. One skilled in the art will appreciate that a polymorph of the compounds of formulas I and II may provide beneficial effects (eg, provide useful formulations, improve biological performance) over another polymorph or mixture of polymorphs of the same compounds of formulas I and II. Preparation and isolation of a particular polymorph of the compounds of formulas I and II can be performed by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. For a comprehensive description of polymorphism, see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

One of skill in the art will appreciate that since, in the environment and under physiological conditions, the salts of chemical compounds are in equilibrium with their corresponding non-salt forms, the salts also have the biological benefits of the non-salt forms. Thus, a wide variety of salt compounds of formulas I and II can be used to control unwanted vegetation (ie they are agriculturally suitable). Salts of compounds of formulas 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 acid.

The embodiments of the present invention described in the Summary of the Invention section include the following, wherein Formula I as used in the following embodiments includes salts thereof:

Embodiment 1. The mixture described in the Summary of the Invention, wherein A ¹ is CCF ₃ , A ² is CH, and A ³ is CH.

Embodiment 2 A mixture as described in the Summary of the Invention, wherein A ¹ is CH, A ² is CCF ₃ , and A ³ is CH.

Embodiment 3 A mixture as described in the Summary of the Invention, wherein A ¹ is N, A ² is CCF ₃ , and A ³ is CH.

Embodiment 4 A mixture as described in the Summary of the Invention, wherein A ¹ is CCH ₃ , A ² is N, and A ³ is COCHF ₂ .

Embodiment 5 A mixture according to any one of Embodiments 1-4 wherein R ¹ is methyl, ethyl or propyl.

Embodiment 6 The mixture of Embodiment 5 wherein R ¹ is methyl or ethyl.

Embodiment 7 The mixture of Embodiment 6 wherein R ¹ is methyl.

Embodiment 8 A mixture according to any one of Embodiments 1-7 wherein B ¹ is CF, B ² is CH and B ³ is CH.

Embodiment 9 A mixture according to any one of Embodiments 1-7 wherein B ¹ is CF, B ² is CF and B ³ is CH.

Embodiment 10 A mixture according to any one of Embodiments 1-7 wherein B ¹ is CF, B ² is N and B ³ is CF.

Embodiment 11. The mixture of any one of Embodiments 5-7, wherein if A ¹ is CCF ₃ , A ² is CH and A ³ is CH, then B ¹ is CF, B ² is CH and B ³ is CH (compound 1).

Embodiment 12. The mixture of any one of Embodiments 5-7, wherein if A ¹ is CCF ₃ , A ² is CH and A ³ is CH, then B ¹ is CF, B ² is N, and B ³ is CF (compound 2).

Embodiment 13 A mixture according to any one of Embodiments 5-7 wherein if A ¹ is N, A ² is CCF ₃ and A ³ is CH, then B ¹ is CF, B ² is CH and B ³ is CH (compound 3).

Embodiment 14 A mixture according to any one of Embodiments 5-7 wherein if A ¹ is CCH ₃ , A ² is N and A ³ is COCHF ₂ , then B ¹ is CF, B ² is CF and B ³ is CH (compound 4).

Embodiment 15. The mixture of any one of Embodiments 5-7, wherein if A ¹ is CH, A ² is CCF ₃ and A ³ is CH, then B ¹ is CF, B ² is CF, and B ³ is CH (compound 5).

Embodiment 16 A mixture according to any one of Embodiments 5-7 wherein if A ¹ is CH, A ² is CCF ₃ and A ³ is CH, then B ¹ is CF, B ² is N, and B ³ is CF (compound 6).

Embodiment 17 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 1:20 to about 56:1.

Embodiment 18 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 1:6 to about 19:1.

Embodiment 19 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 1:2 to about 4:1.

Embodiment 20 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 100:1 to about 4:1.

Embodiment 21 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 75:1 to about 5:1.

Embodiment 22 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 50:1 to about 10:1.

Embodiment 23 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is from about 40:1 to about 10:1.

Embodiment 24 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is between 37.5:1 and 12.5:1.

Embodiment 25 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is between 25:1 and 12.5:1.

Embodiment 26 A mixture as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is between 18.75:1 and 12.5:1.

Embodiment 27 A blend as described in the Summary of the Invention or any one of Embodiments 1-16 wherein the weight ratio of (a) and (b) is between 25:1 and 18.75:1.

Embodiment 28 A mixture as described in the Summary of the Invention or any one of Embodiments 1-27 that is in admixture with solid or liquid diluents.

Embodiment 29 The mixture of Embodiment 28 formulated as solid soluble granules.

Embodiment 30 A mixture according to any one of Embodiments 1-29 that controls the growth of grass weeds.

Embodiment 31 A mixture according to any one of Embodiments 1-29 which controls the growth of broadleaf weeds.

Embodiment 32 A mixture according to any one of Embodiments 1-29 that controls the growth of sedge weeds.

Embodiment 33 A mixture according to any one of Embodiments 1-29 which controls the growth of weeds of a genus selected from the group consisting of Cyperus, Echinochloa, Heteranthera, Leptochloa and Monochoria.

Embodiment 34. The mixture of Embodiment 33 which controls the growth of weeds of the genus Cyperus.

Embodiment 35 The mixture of Embodiment 34 wherein the species is difformis.

Embodiment 36. The mixture of Embodiment 33 which controls the growth of weeds of a genus selected from the group consisting of Echinochloa and Leptochloa.

Embodiment 37 The mixture of Embodiment 36 which controls the growth of weeds of the genus Echinochloa.

Embodiment 38 The mixture of Embodiment 37 wherein the species is chinensis.

Embodiment 39 The mixture of Embodiment 37 wherein the species is a phyllopogon.

Embodiment 40. The mixture of Embodiment 33 which controls the growth of weeds of the genus Leptochloa.

Embodiment 41 The mixture of Embodiment 40 wherein the species is chinensis.

Embodiment 42. The mixture of Embodiment 33 which controls the growth of weeds of a genus selected from the group consisting of Heteranthera or Monochoria.

Embodiment 43. The mixture of Embodiment 42 which controls the growth of weeds of the genus Heteranthera.

Embodiment 44 The mixture of Embodiment 43 wherein the species is limosa.

Embodiment 45. The mixture of Embodiment 42 which controls the growth of weeds of the genus Monochoria.

Embodiment 46 The mixture of Embodiment 45 wherein the species is vaginalis.

Embodiment 47 A mixture according to any one of Embodiments 30-46 wherein weeds grow in Japanese rice (Oryza sativa).

Embodiments of the present invention, including embodiments 1-47 above, as well as any other embodiments described herein, and any combination thereof, relate to the compositions and methods of the present invention.

Embodiment combinations 1-47 are illustrated as follows:

Embodiment A A mixture as described in the Summary of the Invention, wherein R ¹ is methyl, ethyl, or propyl.

Embodiment B. The mixture described in the Summary of the Invention, wherein R ¹ is methyl.

Embodiment C. A blend as described in the Summary of the Invention wherein the weight ratio of (a) and (b) is from about 1:20 to about 56:1.

Embodiment D. A mixture as described in the Summary of the Invention that controls the growth of weeds of a genus selected from the group consisting of Cyperus, Echinochloa, Heteranthera, Leptochloa and Monochoria.

Embodiment E The mixture of Embodiment D which controls the growth of weeds of the genus Cyperus.

Embodiment F The mixture of Embodiment E wherein the species is difformis.

Embodiment G. A mixture as described in the Summary of the Invention or any one of Embodiments A through F, wherein the weeds grow in Oryza sativa.

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

As one additional active ingredient (i.e. as component (c)) at least one additional active ingredient may be one or more of the following herbicides, in particular used for weed control: acetochlor, aciflurofen and its sodium salt , aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametrine, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (eg methyl, ethyl) and salts (eg sodium, potassium), amino pyralide, amitrol, ammonium sulfamate, anilophos , asulam, atrazine, azimsulfuron, beflubutamide, benazoline, benazoline-ethyl, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclone, benzofenap, bicyclopyrone, bifenox, bilanaphos, bispyribac and its sodium salt, bromacyl, bromophenoxim, bromophenoxim , bromoxynil, bromoxynyl octanoate, butachlor, butafenacil, butamiphos, butralin, butroxydim, butylate, caffenstrol, carbetamide, carfentrazone-ethyl, catechin, chlo methoxyfen, chloramben, chlorbromuron, chloroflurenol-methyl, chloridazone, chlorimuron-ethyl, chlorotoluron, chlorprofam, chlorsulfuron, chlorthal-dimethyl, chlorthiamide, cynidone-ethyl, cinmethylin, cinosulfuron, clacifos, clefoxidim, cletodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cyclooxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters, its dimethylammonium, diolamine and trolamine salts , daimuron, dalapon, dalapon sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedifam, desmetrin, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, dichlorfop-methyl, diclosulam , diphenzoquat methyl sulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethamethrin, dimethenamide, dimethenamid-R, dimethipine, dimethylarsinic acid and its sodium salt , dinitramine, dinoterb, diphenamide, diquat dibromide, dithiopyr, diuron, dinitro-o-cresol (DNOC), endothal, ethyl-N, N-di-n-propylthiocarbamate (EPTC), esprocarb, ethalfluralin, ethametsulfuron-methyl, etiosin, etofumesate, ethoxyphene, ethoxysulfuron, etobenzanide, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrion, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazine, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl. fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, ammonium fosamine, glufosinate, ammonium glufosinate, glufosinate-P, glyphosate and its salts, such as ammonium, isopropylammonium, potassium, sodium (including sodium sesquioxide salt) and trimesium (alternatively called sulfosate) salt, galauxifen, galauxifen-benzyl, galauxifen-methyl, halosulfuron-methyl, haloxyfop-ethothyl, haloxifop-methyl, hexazinon, hydantocidin, imazamethabenz-methyl, imazamox, imazapic, imazapir, imazakhin, imazakhin-ammonium , imazethapir, imazethapyr ammonium, imazosulfuron, indanophane, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynyl octanoate, ioxynyl sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutol, isoxachlorotol, lactofen, lenacil, linuron, maleic hydrazide, 2 -methyl-4-chlorophenoxyacetic acid (MCPA) and its salts (e.g. MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g. MCPA-2-ethylhexyl, MCPA-butothy k) and thioesters (e.g. MCPA-thioethyl), 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB) and its salts (e.g. MCPB-sodium) and esters (e.g. MCPB-ethyl), mecoprop , mecoprop-R, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, methamifop, metamitron, metazachlor, metazosulfuron, metabenthiazuron, methylarsinic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, methobenzuron, metobromuron, metolachlor, S-metolachlor, methosulam, methoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxulam, pentanochlor, pentoxazone, perfluidone, petoxamide, petoxyamide, phenmedifam, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, p rhodiamin, profoxydim, promethone, promethrin, propachlor, propanil, propaquizafop, propazin, profam, propisochlor, propoxycarbazone, propyrisulfuron, propizamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazogyl, pyrazolinate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxime, pyributicarb, pyridate, pyrifthalide, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxulam, quinclorac, quinmerac, quinoclamin, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, setoxydim, siduron, simazine, simethrin, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-trichlorobenzoic acid (TBA), trichloroacetic acid (TCA), TCA sodium salt, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumetone, terbutylazine, terbutrin, tenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, thiafenacil, thiocarbazil, tolpyralate, toprameson, tralkoxydim, triallate , triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridifan, trietazine, trifloxysulfuron, trifludimoxazine, trifluralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6- difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl] -1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3 ,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one), 4-(2,6-diethyl-4 -methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3- (3-methyl-2-thienyl)isoxazole (formerly methioxoline), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl -1,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2 -pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoro pmethyl)benzamide; and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.

Mixtures of a compound of the present invention with the herbicide of choice are preferred for more effective control of unwanted vegetation (e.g., less frequency of application, e.g., through reinforcing additive effects, a wider range of weed control, or improved crop safety) or to prevent the development of resistant weeds. from the group consisting of atrazine, azimsulfuron, beflubutamide, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, potassium clopyralide, cloransulam-methyl, etametsulfuron-methyl, flumetsulam, 4-(4-fluorophenyl)-6- [(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrsulfuron-methyl, fluthiacetate -methyl, fomesafen, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, petoxamide, picloram, pyroxasulfone, quinclorac, rimsulfuron, S-metolachlor, sulfentrazone, triphensulfuron-methyl, triflusulfu ron-methyl and tribenuron-methyl.

The mixtures of the present invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purine-6-amine, epocholeon, gibberellic acid, gibberellin A ₄ and A ₇ , harpin protein, mepiquat chloride, calcium prohexadione, prohydrojasmone, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.

General references to agricultural remedies (e.g., 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.

In embodiments that use one or more of these different blending options, the blend components are typically used in amounts similar to those typically used when these blend components are used alone. More specifically, in mixtures, the active ingredients are often applied at a frequency of application ranging from half to the full frequency of application indicated on product labels in relation to the use of the active ingredient alone. These quantities are listed in reference materials such as The Pesticide Manual and The BioPesticide Manual. The weight ratios of these various components of the mixture (totally) and the present mixture typically range from about 1:3000 to about 3000:1. Weight ratios of about 1:300 to about 300:1 are noteworthy (e.g., ratios from about 1:30 to about 30:1). One skilled in the art can easily determine, through simple experimentation, the biologically effective amounts of active ingredients needed to achieve the desired spectrum of biological activity. It will be apparent that the inclusion of these additional components can broaden the spectrum of weed control compared to the spectrum of weeds controlled by the present mixture alone.

In certain instances, combinations of the mixture of the present invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) may result in a weed enhancing additive effect and/or a weed attenuating additive effect (i.e. improved safety) in relation to crops or other desirable plants. Reducing the amount of active ingredients released to the environment while still providing effective pest control is always desirable. It is also desirable to use higher amounts of active ingredients to provide more effective weed control without excessive damage to crops. If the herbicidal active ingredients produce a weed-enhancing additive effect with application frequencies that provide agronomically satisfactory levels of weed control, such combinations may be advantageous in reducing crop production costs and environmental burden. If herbicidal active ingredients have less effect on crops, such combinations may be preferred to enhance crop protection by reducing weed competition.

Noteworthy is the combination of the mixture of the invention with at least one other herbicidal active ingredient (ie component (c)). Particularly noteworthy is such a combination where another herbicidal active ingredient has a site of action different from component (a) or component (b) according to the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of inhibition but a different site of action will be particularly advantageous in preventing the development of resistance. Thus, the composition of the present invention may 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.

The mixtures of the present invention can also be used in combination with herbicide safeners (i.e. such as component (c)) selected from allidochlor, benoxacor, cloquintocet-mexil, cumiluron, cyometrinil, cyprosulfonamide, daimuron, dichlormide, dicyclonone, dietholate, dimepiperate , fenchlorazole-ethyl, fenclorim, flurazol, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mefenate, methoxyphenone naphthalene anhydride (1,8-naphthalene anhydride), oxabethrinyl, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-( aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)-sulfonyl]-benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2- (dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N ,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide and 3-oxo-1-cyclohexen-l-yl 1-(3,4-dimethylphenyl)-l,6-dihydro-6-oxo-2-phenyl -5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl -3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide, to improve the safety of certain crops. Antidote effective amounts of herbicide safeners can be applied simultaneously with the mixtures of the present invention or applied as seed treatments. Thus, an aspect of the present invention relates to a herbicide mixture comprising the mixture of the present invention and an antidote effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control because it physically limits the antidote effect to crop plants. Thus, a particularly useful embodiment of the present invention is a method for selectively inhibiting the growth of undesirable vegetation in a crop, comprising contacting a portion of the crop with a herbicidally effective amount of the mixture of the present invention, wherein the seed from which the crop is grown are treated with an antidote effective amount of an antidote. Antidote effective amounts of antidotes can be readily determined by one of ordinary skill in the art by simple experimentation.

The present invention also relates to a method of suppressing the growth of unwanted vegetation, which includes applying to the area of vegetation an effective herbicidal amount of a mixture of the invention (for example, in the form of a composition described herein). Noteworthy are the embodiments relating to the methods of use, which include mixtures of the embodiments described above. The mixtures of the invention are particularly suitable for selective weed control in agricultural crops such as wheat, barley, corn, soybean, sunflower, cotton, oilseed rape and rice, as well as in specialized crops such as sugarcane, citrus, fruit and nut crops. . It should be noted that the present invention relates to selective weed control in seedling rice crop. It should also be noted that it refers to selective weed control in seedless rice crop.

The mixture of the present invention will essentially be applied as the herbicidal active ingredient in the composition, i.e. in the composition, while at least one additional component is selected from the group consisting of surfactants, solid diluents and liquid diluents, which are used as a carrier. The ingredients of the formulation or composition are selected to suit the physical properties of the active ingredient, the method of application, and environmental factors such as soil type, humidity and temperature.

Useful formulations include both liquid and solid formulations. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and/or suspoemulsions), and the like, which may optionally be thickened to form gels. General types of aqueous liquid compositions include soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, fluid concentrate, and suspoemulsion. General types of non-aqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

Common types of solid compositions are dusts, powders, granules, pellets, prills, lozenges, tablets, filled films (including seed coating compositions), and the like, which may be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly suitable for seed treatment. The active ingredient may be (micro)encapsulated and further formulated into a suspension or solid formulation; alternatively, the entire formulation of the active ingredient may be encapsulated (or "coated"). Encapsulation may control or delay the release of the active ingredient. The emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are mainly used as intermediates for additional composition.

Spray formulations are usually diluted in a suitable medium prior to spraying. Such liquid and solid formulations are formulated so that they can be rapidly reconstituted in a spray medium, usually water, but in some cases other suitable medium such as an aromatic or paraffinic mineral or vegetable oil. Spray volumes may range from about one to several thousand liters per hectare, but are more typically in the range from about ten to several hundred liters per hectare. Spray formulations may be tank-mixed with water or other suitable medium for foliar application by air or ground application, or for application to a plant growth medium. Liquid and dry formulations can be dispensed directly into drip irrigation systems or dispensed into the furrow at planting time.

The compositions will generally contain effective amounts of the active ingredient, diluent and surfactant in the following approximate ranges, which are adjusted to 100 wt%.

Weight percentage Active
mixed ingredient Diluent Surface-active substance Water-dispersible and water-soluble granules, tablets and powders 0.001–90 0–99.999 0–15 Oil dispersions, suspensions, emulsions, solutions (including emulsifiable concentrates) 1–50 40–99 0–50 Dust 1–25 70–99 0–5 Granules and balls 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, diatomite , urea, calcium carbonate, sodium carbonate and sodium bicarbonate and 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,N-dimethylalkanamides (eg, N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (eg, N-methylpyrrolidone), alkyl phosphates (eg, 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, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic hydrocarbons, alkylbenzenes, alkylnaphthalenes, ketones, such 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 lactic acid esters , dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols, which may 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 esters of glycerol with saturated and unsaturated fatty acids (typically C ₆ -C ₂₂ ), such as plant and fruit seed oils (e.g. olive, castor, linseed, sesame, corn (maize), peanut , sunflower, grape, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel oils), animal fats (eg beef tallow, lard, lard, cod liver oil, fish oil) and mixtures thereof. Liquid diluents also include alkylated fatty acids (eg, methylated, ethylated, butylated), which fatty acids can be obtained by hydrolysis of esters of glycerol from vegetable 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 surfactants) essentially change, most often decrease, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be used as wetting agents, dispersing agents, emulsifiers or antifoam agents.

Surfactants can be classified as non-ionic, anionic or cationic. Nonionic surfactants that may be used in the present compositions include, without limitation: alcohol alkoxylates such as natural and synthetic alcohol alkoxylates (which may be branched or linear) derived from 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, dinonylphenol ethoxylates and dodecylphenol ethoxylates (derived from phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers derived from ethylene oxide or propylene oxide and reverse block polymers, the end blocks derived from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those derived from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin 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 esters of sorbitan; polymeric surfactants such as random copolymers, block copolymers, polyethylene glycol alkyd resins, graft or comb polymers, and star polymers; polyethylene glycols (PEG); esters of polyethylene glycol and fatty acids; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, without limitation: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefinsulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkyl phenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein based surfactants; sarcosine derivatives; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; alcohol sulfates; sulfates of ethoxylated alcohols; amine and amide sulfonates such as N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene and dodecyl- and tridecylbenzenes; condensed naphthalenes sulfonates; naphthalene and alkylnaphthalene sulfonates; fractionated petroleum sulfonates; sulfosuccinamates and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, without limitation: amides and ethoxylated amides; amines such as N-alkylpropanediamines, tripropylenetriamines, and dipropylenetetramines, as well as ethoxylated amines, ethoxylated diamines, and propoxylated amines (derived from amines and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as aminoacetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary 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 described in a variety of published sources, 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.

The compositions of the present invention may also contain formulation auxiliaries and additives known to those skilled in the art as formulation auxiliaries (some of which may also act as solid diluents, liquid diluents, or surfactants). Such formulation auxiliaries and additives can affect: pH (buffers), foaming during processing (antifoam agents such as polyorganosiloxanes), precipitation of active ingredients (suspending agents), viscosity (thixotropic thickeners), growth of microorganisms inside the container (antimicrobial agents) product freezing (antifreezes), coloring (dyes/pigment dispersions), leaching (film formers or adhesives), evaporation (evaporative retardants) and other formulation characteristics. 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: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication No. WO 03/024222.

Mixtures of a compound of formula I and any other active ingredients are generally incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding into a liquid or dry diluent. Solutions including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of the liquid composition to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient when diluted with water. Suspensions of active ingredients with particle diameters up to 2000 µm can be wet milled using mills to obtain particles with average diameters of less than 3 µm. Aqueous suspensions can be converted to final suspension concentrates (see, for example, U.S. Patent 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require dry grinding processes that produce particles with an average particle size in the range of 2 to 10 microns. Dusts and powders can be obtained by mixing and, as a rule, grinding (for example, using a hammer mill or jet mill). Granules and beads can be obtained by spraying the active material onto 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, pp. 8–57ff, and WO 91 /13546. The beads can be made as described in U.S. Pat. 4,172,714. Water-dispersible and water-soluble granules can be prepared as described in U.S. 4,144,050 U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as described in US Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can be prepared as described in GB 2,095,558 and U.S. 3,299,566.

For additional information related to formulation techniques, 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, from post. 6, line 16, to post. 7, line 19, and examples 10–41; U.S. 3,309,192, from post. 5, line 43, to post. 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, from post. 3, line 66, to post. 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 examples below, all percentages are by weight and all formulations are prepared by standard methods. Compound numbers refer to compounds in index table A. Without further elaboration, it is believed that one skilled in the art, by applying the foregoing description, will be able to make full use of the present invention. Thus, the following examples are to be considered as illustrative only, and in no way limit the invention. Unless otherwise indicated, percentages are by weight.

Example A

High Strength Concentrate Comm. No. 1 and Florpyrauxifen-Benzyl 98.5% silicate airgel 0.5% synthetic amorphous fine silica 1.0%

Example B

Wettable Powder Comm. No. 1 and Florpyrauxifen-Benzyl 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium lignin sulfonate 4.0% sodium silicic aluminate 6.0% montmorillonite (calcined) 23.0%

Example C

Granule Comm. No. 1 and Florpyrauxifen-Benzyl 10.0% attapulgite granules (low volatility, 0.71/0.30 mm; sieves U.S.S. No. 25-50) 90.0%

Example D

extruded balls Comm. No. 1 and Florpyrauxifen-Benzyl 25.0% anhydrous sodium sulfate 10.0% crude calcium lignin sulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

Example E

Emulsifiable concentrate Comm. No. 1 and Florpyrauxifen-Benzyl 10.0% polyoxyethylene sorbitol hexoleate 20.0% fatty acid methyl ester C ₆ -C ₁₀ 70.0%

Example F

Microemulsion Comm. No. 1 and Florpyrauxifen-Benzyl 5.0% copolymer of polyvinylpyrrolidone and vinyl acetate 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G

Suspension concentrate Comm. No. 1 and Florpyrauxifen-Benzyl 35% butylpolyoxyethylene/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 antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% water 53.7%

Example H

emulsion in water Comm. No. 1 and Florpyrauxifen-Benzyl 10.0% butylpolyoxyethylene/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 antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% petroleum-based aromatic hydrocarbon 20.0 water 58.7%

Example I

Oil dispersion Comm. No. 1 and Florpyrauxifen-Benzyl 25% polyoxyethylene sorbitol hexaoleate fifteen% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5%

The present description also includes examples A-I above, except that "Comp. No. 1" was replaced by "connect. No. 2", "connect. No. 3", "connect. No. 4", "connect. No. 5 "and" connection. No. 6".

The test results show that the mixtures of the present invention are very active pre-emergence and/or post-emergence herbicides and/or plant growth regulators. The mixtures of the present invention essentially exhibit the highest activity in post-emergence weed control (ie, applied after weeds emerge from the soil) and pre-emergence weed control (ie, applied before weeds emerge from the soil). Many of the mixtures of the present invention, by virtue of selective metabolism in crops versus weeds, or selective activity at the site of physiological inhibition in crops and weeds, or through selective placement on or within the media of crop and weed mixtures, can be used to selectively control grass and broadleaf weeds in the crop/weed mixture. One skilled in the art will appreciate that the preferred combination of these selectivity factors can be readily determined by performing standard biological and/or biochemical assays. The mixtures of the present invention can demonstrate tolerance to important agronomic crops, including, without limitation, alfalfa, barley, cotton, wheat, rapeseed, sugar beet, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomatoes, potatoes , perennial plantation crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, banana, banana vegetable, pineapple, hops, tea, and forests such as eucalyptus and conifers (e.g., frankincense pine), and various types of turf (for example, bluegrass meadow, narrow-furrow lopsided, reed fescue and pig fingered). Noteworthy is the rice crop, which is seedless. Noteworthy is the rice crop, which is a seedling. The mixtures of the present invention can be used in crops genetically modified or bred to be herbicide resistant, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other beneficial traits. Those skilled in the art will appreciate that not all mixtures are equally effective against all weeds. Alternatively, mixtures can be used to modify plant growth.

Since the mixture of the invention has both pre-emergence and post-emergence herbicidal activity, to control unwanted vegetation by killing or damaging vegetation or reducing its growth, the mixture can be used for application in a variety of ways, including contacting a herbicidally effective amount of the mixture according to the invention or a composition comprising said mixture and at least one of a surfactant, a solid diluent or a liquid diluent, with the leaves or other part of the undesirable vegetation, or with the environment of the undesirable vegetation, such as soil or water, in which the undesirable vegetation grows or which surrounds seeds or other growths of unwanted vegetation.

The herbicidal effective amount of the mixtures of the present invention is determined by a number of factors. These factors include: composition chosen, method of application, amount and type of vegetation present, growth conditions, etc. In general, the effective herbicidal amount of the mixtures of the present invention is from about 0.001 to 20 kg/ha, with the preferred range being from about 0.004 to 1 kg/ha, from about 0.004 to 0.5 kg/ha, from about 0.004 up to 0.25 kg/ha, from about 0.004 to 0.1 kg/ha, from about 0004 to 0.075 kg/ha, or from about 0.004 to 0.05 kg/ha. One skilled in the art can determine the herbicidally effective amount needed to achieve the desired level of weed control.

In one general embodiment, the mixture of the invention is applied, typically as part of a composition, to an area containing desired vegetation (eg, crops) and undesired vegetation (i.e., weeds), both of which may be seeds, seedlings, and/ or larger plants, in contact with the growing medium (eg, soil). In this area, the composition containing the mixture according to the invention can be directly applied to the plant or part thereof, in particular to unwanted vegetation and/or to the growth medium in contact with the plant.

Plant diversity and cultivars of desired vegetation in an area treated with the mixture of the invention may be obtained by conventional propagation and breeding techniques or by genetic engineering techniques. Genetically modified plants (transgenic plants) are plants in which a heterologous gene (transgene) is stably integrated into the plant genome. A transgene that is defined by its specific location in the plant genome is called a transformed or transgenic entity.

Genetically modified crop plants at the site that can be treated in accordance with the invention include plants that are resistant to one or more biotic loads (pests such as nematodes, insects, mites, fungi, etc.) or abiotic loads (drought, cold temperature, soil salinity, etc.) or which contain other desirable characteristics. Plants can be genetically modified to have traits such as, for example, herbicide tolerance, insect tolerance, modified oil profiles, or drought tolerance. Useful genetically modified plants containing single gene transformed entities or combinations of transformed entities are listed in Example C. Additional information on the genetic modifications listed in Example C can be obtained from public databases owned by, for example, the US Department of Agriculture.

The herbicidal mixture may be formulated as single individual ingredients (ie, as a kit) and may be mixed (ie, as a tank mix). Alternatively, the herbicidal mixture can be formulated separately and then mixed before being added to the spray tank (ie a homogeneous mixture of soluble granules). Alternatively, the herbicidal mixture may be formulated and then formulated (ie, as soluble granules). The amount of each herbicide mixture compound (i.e., as component (a) and (b) (and optionally (c)) can be adjusted according to field conditions. Similarly, the method of applying the herbicide mixture or composition also includes sequential applying component (a) followed by component (b) or vice versa.

Noteworthy is a composition comprising a mixture according to the invention (in an effective amount from the point of view of herbicidal action), 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 effectiveness of the mixture of the present invention against specific weeds. However, the weed control provided by the mixture is not limited to these species. Table A provides descriptions of the compounds. The abbreviation "connect. No" means "connection number".

Index table A

R ¹ is CH ₃ T.P. °C Comm. No. one A ¹ is CCF ₃ , A ² is CH, A ³ is CH, B ¹ is CF, B ² is CH, and B ³ is CH 141.2–142.3 2 A ¹ is CCF ₃ , A ² is CH, A ³ is CH, B ¹ is CF, B ² is N, and B ³ is CF 139–140 3 A ¹ is N, A ² is CCF ₃ , A ³ is CH, B ¹ is CF, B ² is CF, and B ³ is CH * four A ¹ is CCH ₃ , A ² is N, A ³ is COCHF ₂ , B ¹ is CF, B ² is CF, and B ³ is CH * 5 A ¹ is CH, A ² is CCF ₃ , A ³ is CH, B ¹ is CF, B ² is CF, and B ³ is CH 164–165.7 6 A ¹ is CH, A ² is CCF ₃ , A ³ is CH, B ¹ is CF, B ² is N, and B ³ is CF *

* ¹ H NMR data are given in index table B.

Index table B

Comm. No. ¹ H NMR data (CDCl ₃ solution unless otherwise noted) ^a 3 δ 3.04 (s, 3H), 3.53 (dd, 1H), 3.64 (d, 1H), 3.83 (dd, 1H), 4.19 (q, 1H), 6.87 –6.93 (m, 1H), 7.00–7.05 (m, 1H), 7.71 (d, 1H), 7.90 (d, 1H), 7.95 (t, 1H), 8.79 (s, 1H), 10.0 (s, 1H). four δ 2.48 (s, 3H), 3.01 (s, 3H), 3.43 (dd, 1H), 3.62 (d, 1H), 3.78 (dd, 1H), 4.06 ( dd, 1H), 6.69 (s, 1H), 6.88–6.93 (m, 1H), 6.95 (s, 1H), 7.01–7.05 (m, 1H), 7 .51 (t, 1H), 7.97–8.01 (m, 1H), 10.03 (s, 1H). 6 δ 3.02 (s, 3H), 3.48 (dd, 1H), 3.64 (d, 1H), 3.81 (dd, 1H), 4.12 (q, 1H), 6.78 (dd, 1H), 7.49 (d, 2H), 7.65 (d, 2H), 8.72 (m, 1H), 10.07 (s, 1H).

a ¹ H NMR data are given in ppm downfield from tetramethylsilane. Bonds are designated as (s) - singlet, (e) - doublet, (t) - triplet, (m) - multiplet, (q.) - quartet, (dd) - doublet of doublets.

Biological examples of the invention

Test A

Seeds of Asian cornweed (LEPCH, Leptochloa chinensis), heterogeneous succulent (CYPDI, Cyperus difformis), monochoria (MOOVA, Monochoria vaginalis) and duck lettuce (HETLI, Heteranthera limosa) were sown on the soil surface in four separate quadrants of 16 cm containers filled with pasteurized steam soil Tama. At the same time, common barnyard grass (ECHCG, Echinochloa crus-galli), Japanese rice (ORYSA, Oryza sativa), and late barnyard barnyard grass (ECHPH, Echinochloa phyllopogon) were sown in separate seedling cassettes. Plants were grown in a greenhouse using supplemental lighting to maintain a photoperiod of approximately 16 hours; day and night temperatures were approximately 27-30°C and 24-27°C, respectively. After 8 days, barnyard grass, rice and late barnyard grass were transplanted into 3 quadrants of a separate container and the water level was adjusted to a final depth of 3 cm. Application of herbicides such as Comm. No. 1 and florpyrauxifen-benzyl (CAS No. 1390661-72-9; 439.2 g/mol) were planned at the 2.0-2.5 leaf stage and the plants were treated with test chemicals prepared in a non-phytotoxic solvent. The treated plants and controls were kept in the greenhouse for 14 days, after which all species were compared with controls and visually evaluated. The plant scores are shown in Table A and are based on a scale of 0 to 100, where 0 indicates no effect and 100 represents complete control and is the average of the two scores. A result (–) means no test result.

The Colby equation was used to determine the herbicidal effects expected from mixtures. The Colby equation (Colby, S. R. “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations,” Weeds 1967 15(1), pp 20–22) calculates the expected additive effect of herbicide mixtures and for two active ingredients has the following form:

P _{a + b} \u003d P _a + P _b - (P _a P _b / 100),

where P _a+b is the percentage effect of the mixture expected in the case of an additive effect of the individual components:

_Pa is the observed effect in percent of the first active ingredient at the same dose as in the mixture, and

P _b is the observed effect in percent of the second active ingredient at the same dose as in the mixture.

The results and expected additive effects calculated by the Colby equation are shown in Table A. The doses applied are grams of active ingredient per hectare (g ai/ha). "Ob." represents the observed effect, and Exp. is the expected effect calculated using the Colby equation.

Table A. Observed and expected results for compound 1 alone and in combination with florpyrauxifen-benzyl (CAS no. 1390661-72-9; 439.2 g/mol)

Applied dose
(g a.i./ha) Agriculture cereal weeds ORYSA ECHCG ECHPH LEPCH Comm. No. 1 florpyrauxifen-benzyl Obs. Expect. Obs. Expect. Obs. Expect. Obs. Expect. fifty - 0 - 70 - 75 - 75 - 75 - 0 - 70 - 85 - 85 - - 2 0 - 0 - 0 - 0 - - four 0 - 0 - 0 - 0 - fifty 2 0 0 75 70 85 75 75 75 75 2 0 0 75 70 90 85 90 85 fifty four 0 0 75 70 80 75 75 75 75 four 0 0 75 70 90 85 85 85

Table A (continued)

Applied dose
(g a.i./ha) broadleaf weeds Sedge MOOVA HETLI CYPDI Comm. No. 1 Florpyrauxifen-benzyl Obs. Expect. Obs. Expect. Obs. Expect. fifty - 70 - 70 - 0 - 75 - 70 - 70 - 0 - - 2 90 - 90 - 80 - - four 100 - 100 - 85 - fifty 2 100 97 100 97 80 80 75 2 100 97 100 97 85 80 fifty four 100 100 100 100 100 85 75 four 100 100 100 100 100 85

As can be seen from the results listed in Table A, all of the observed results for different weed species were higher than the expected results according to the Colby equation, indicating an additive effect of compound 1 and florpyrauxifen-benzyl on ECHCG and ECHPH. The observed results for different weed species were greater than the additive effects or were equal to the expected results according to the Colby equation, indicating additive or expected results for LEPCH and CYPDI. In addition, excellent preservation of the rice culture was observed using a mixture similar to that when compound 1 and florpyrauxifen-benzyl were applied separately.

Trial B

Seeds of plant species selected from common brambles (Echinochloa crus-galli), kochia (Kochia scoparia), ragweed (ragweed ragweed, Ambrosia elatior), italian chaff (Italian chaff, Lolium multiflorum), green foxtail (green foxtail, Setaria viridis) and amaranth (Amaranthus retroflexus) were sown in a mixture of loamy soil and sand and treated until emergence with directed soil sprays using the studied chemical compounds contained in a non-phytotoxic solvent mixture that included a surfactant.

At the same time, plants selected from these weed species, as well as wheat (Triticum aestivum), corn (Zea may), mousetail foxtail (Alopecurus myosuroides) and bedstraw (Galium aparine) were sown in pots containing the same mixture of loamy soil and sand, and treated after emergence by applying test chemicals prepared in a similar manner. At post-emergence treatment, the plants were 2 to 10 cm tall and were at the one to two leaf stage. The treated plants and untreated controls were kept in the greenhouse for approximately 10 days, after which all treated plants were compared to untreated controls and visually assessed for damage. The plant evaluation results shown in Table B are based on a scale of 0 to 100, where 0 indicates no effect and 100 represents complete control. A result (–) means no test result.

Table B Comm. No. Table B Comm. No. 125 g a.i./ha four 31 g a.i./ha four After emergence After emergence Yezhovnik 90 Yezhovnik 80 Foxtail 70 Foxtail 60 Corn 80 Corn 60 Bristle green 90 Bristle green 70 Bedstraw 60 Bedstraw 0 Kochia twenty Kochia 0 Amaranth 60 Amaranth twenty Ambrosia 60 Ambrosia 0 Chaff italian 70 Chaff italian thirty Wheat 70 Wheat 40 Table B Comm. No. Table B Comm. No. 125 g a.i./ha four 31 g a.i./ha four Before the shoot Before the shoot Yezhovnik 100 Yezhovnik 100 Bristle green 100 Bristle green 100 Kochia 80 Kochia 0 Amaranth 90 Amaranth 40 Ambrosia twenty Ambrosia 0 Chaff italian 90 Chaff italian thirty

Trial C

Plants in a test with a flooded rice crop selected from rice (Oryza sativa), sedge, sativa (cyperus difformis), duck lettuce (Heteranthera limosa), and barnyard grass (Echinochloa crus-galli) were grown to the 2 leaf stage for the purpose of the test. . At the time of treatment, test pots were flooded 3 cm above the soil surface, treated by applying test compounds directly to the rice crop, and then kept at this water depth for the entire test period. The treated plants and controls were kept in the greenhouse for 13–15 days, after which all species were compared with controls and visually evaluated. The plant evaluation results shown in Table C are based on a scale of 0 to 100, where 0 indicates no effect and 100 represents complete control. A result (–) means no test result.

Table C Comm. No. 250 g a.i./ha four Flooding Yezhovnik 85 duck salad 100 Rice thirty sedge 0

Claims (18)

1. Herbicidal mixture containing (a) a compound of formula I and its salts

, where A ¹ is CCF ₃ , A ² is CH, A ³ is CH, B ¹ is CF, B ² is CH, B ³ is CH; R ¹ is C ₁ -C ₄ alkyl; and (b) 2-pyridinecarboxylic acid 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluorophenylmethyl ester of formula II and its salts

. 2. A mixture according to claim 1, in which R ¹ represents methyl, ethyl or propyl. 3. A mixture according to claim 2, wherein R ¹ is methyl. 4. A mixture according to claim 1, wherein the weight ratio of (a) and (b) is from about 1:20 to about 56:1. 5. The mixture according to claim 1 further comprising (c) at least one additional active ingredient selected from herbicides, herbicide safeners, fungicides, insecticides, nematicides, bactericides and acaricides. 6. A mixture according to claim 1, further containing at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. 7. A method for controlling the growth of unwanted vegetation, which includes bringing the vegetation or its environment into contact with an effective herbicidal amount of the mixture according to claim 1. 8. The method of claim 7 wherein the mixture controls the growth of weeds of a genus selected from the group consisting of Cyperus, Echinochloa, Heteranthera, Leptochloa and Monochoria. 9. The method of claim 8, wherein the mixture controls the growth of weeds of the genus Cyperus. 10. The method of claim 9 wherein the weed is Cyperus difformis. 11. The method of claim 10 wherein the weeds grow in Oryza sativa.