阅读说明：本技术 包含羧酸吡啶除草剂和羧酸唑安全剂的组合物 (Compositions comprising a pyridine carboxylate herbicide and an azole carboxylate safener ) 是由 N·M·萨奇维 J·基斯特 于 2019-10-30 设计创作，主要内容包括：本文公开了包含(a)羧酸吡啶除草剂或其农业上可接受的N-氧化物、盐或酯和(b)羧酸唑安全剂或其农业上可接受的盐或酯的安全组合物。本文还公开了控制不希望的植被的方法,所述方法包括向植被或与所述植被相邻的区域施用或在土壤或水中施用(a)羧酸吡啶除草剂或其农业上可接受的N-氧化物、盐或酯和(b)羧酸唑安全剂或其农业上可接受的盐或酯以控制植被的出苗或生长。(Disclosed herein are safe compositions comprising (a) a carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a carboxyazole safe, or an agriculturally acceptable salt or ester thereof. Also disclosed herein are methods of controlling undesirable vegetation comprising applying to vegetation or an area adjacent the vegetation or applying to soil or water to control the emergence or growth of vegetation (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a fentrazole safener or an agriculturally acceptable salt or ester thereof.)

1. A security composition, comprising:

(a) (a) a carboxypyridine herbicide defined by formula (I):

wherein:

R¹is cyanomethyl or propargyl;

R²and R^2′Independently of each other is hydrogen, C₁-C₆Alkyl, formyl, alkoxycarbonyl or acyl;

R³、R^3′、R^3″and R^3″′Independently of one another is hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₃Alkoxy or C₁-C₃A haloalkoxy group;

or an agriculturally acceptable N-oxide, salt, or ester thereof; and

(b) a safener of a carboxylic acid azole or an agriculturally acceptable salt or ester thereof.

2. The composition of claim 1, wherein the carboxylic acid pyridine herbicide compound is cyanomethyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate:

3. the composition of claim 1, wherein the carboxylic acid pyridine herbicide compound is propargyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate:

4. a composition according to any one of claims 1 to 3 wherein the carboxylic acid azole safener is selected from the group consisting of: cloquinconazole, cloquintocet-mexyl, mefenpyr-diethyl, isoxadifen-ethyl, pyrazoline oxalic acid, agriculturally acceptable salts or esters thereof, and mixtures thereof.

5. The composition of claim 4 wherein the agriculturally acceptable ester of the carboxylic acid azole safener is selected from the group consisting of: methyl esters, ethyl esters, diethyl esters, and combinations thereof.

6. The composition of claim 4, wherein the agriculturally acceptable salt of the carboxylic acid azole safener is selected from the group consisting of: sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropoxylammonium, triisopropanolammonium, choline, N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium and isopropylammonium salts, and combinations thereof.

7. The composition of any one of claims 1-6, wherein the weight ratio of the carboxypyridine herbicide (in g ae/ha) to the ribavirin safener (in g ai/ha) is from about 1:5 to about 5: 1.

8. The composition of any one of claims 1-7, further comprising an additional pesticide.

9. The composition of any one of claims 1-8, wherein the composition does not comprise a herbicidal active ingredient other than (a).

10. A method of controlling undesirable vegetation, the method comprising applying a security composition to vegetation or an area adjacent the vegetation, or applying a security composition to soil or water to limit the emergence or growth of vegetation, the security composition comprising:

(a) (a) a carboxypyridine herbicide defined by formula (I):

wherein

R¹Is cyanomethyl or propargyl;

R²and R^2'Independently of each other is hydrogen, C₁-C₆Alkyl, formyl, alkoxycarbonyl or acyl;

R³、R^3'、R^3″and R^3″′Independently of one another is hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₃Alkoxy or C₁-C₃A haloalkoxy group;

or an agriculturally acceptable N-oxide, salt, or ester thereof; and

(b) a carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof;

wherein the herbicide is applied in an amount of at least 1g ae/ha; and is

Wherein the carboxylic acid azole safener is applied in an amount of at least 1g ai/ha.

11. The method of claim 10, wherein the carboxylic acid pyridine herbicide compound is cyanomethyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate:

12. the method of claim 10, wherein the carboxylic acid pyridine herbicide compound is propargyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate:

13. the method of any one of claims 10-12, wherein the herbicide and the safener are applied simultaneously.

14. The method of any one of claims 10-13, wherein the carboxylic acid azole safener is selected from the group consisting of: cloquinconazole, cloquintocet-mexyl, mefenpyr-diethyl, isoxadifen-ethyl, pyrazoline oxalic acid, agriculturally acceptable salts or esters thereof, and mixtures thereof.

15. The method of claim 14, wherein the agriculturally acceptable ester of the carboxylic acid azole safener is selected from the group consisting of: methyl esters, ethyl esters, diethyl esters, and combinations thereof.

16. The method of claim 14, wherein the agriculturally acceptable salt of the carboxylic acid azole safener is selected from the group consisting of: sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropoxylammonium, triisopropanolammonium, choline, N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium and isopropylammonium salts, and combinations thereof.

17. The method of any one of claims 10-16, wherein the herbicide is provided in an amount of 1gae/ha to 300g ae/ha.

18. The method of any one of claims 10-17, wherein the picolinate herbicide is applied to the undesirable vegetation pre-or post-emergence and the fentrazole safener is applied to the crop as a seed treatment.

19. The method of any one of claims 10-18, wherein the weight ratio of the carboxypyridine herbicide (in g ae/ha) to the carboxypyridine safener (in g ai/ha) is about 1:5 to about 5: 1.

20. The method of any one of claims 10-19, further comprising applying an additional pesticide.

21. The method of any one of claims 10-20, wherein the composition does not comprise a herbicidal active ingredient other than (a).

Technical Field

The present disclosure includes safened compositions comprising a picolinate herbicide and a carboxyazole safener, and methods of using the compositions to control undesirable vegetation.

Background

Many recurring problems in agriculture relate to controlling the growth of undesirable vegetation, which may, for example, negatively affect the growth of desirable vegetation. To help control undesirable vegetation, researchers have produced a variety of chemicals and chemical formulations that are effective in controlling such undesirable growth.

In some cases, although herbicides can be effective in controlling undesirable vegetation, it can also produce phytotoxic effects on crops and cause damage or even kill crops. There is a need for new herbicides in combination with safeners in order to limit the phytotoxicity of the herbicidal active ingredients of the desired crop plants.

Disclosure of Invention

Disclosed herein are safe compositions useful as herbicides, for example, in crops. The safener composition may comprise (a) a carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a carboxyazole safener, or an agriculturally acceptable salt or ester thereof. (a) The weight ratio of (a) to (b) may be 1:5 to 5:1 (e.g., from 1:3 to 3:1, or from 1:2 to 2: 1).

In some aspects, the safe composition comprises (a) a carboxypyridine herbicide defined by formula (I):

wherein:

R¹is cyanomethyl or propargyl;

R²and R²' independently is hydrogen, C₁-C₆Alkyl, formyl, alkoxycarbonyl or acyl;

R³、R³'、R^3"and R³' is independently hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₃Alkoxy or C₁-C₃A haloalkoxy group;

or an agriculturally acceptable N-oxide, salt, or ester thereof; and

(b) a safener of a carboxylic acid azole or an agriculturally acceptable salt or ester thereof.

In some aspects, the safe composition comprises:

(a) the carboxylic acid pyridine herbicide compound cyanomethyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate, hereinafter referred to as compound a:

or an agriculturally acceptable N-oxide, salt, or ester thereof; and

(b) a safener of a carboxylic acid azole or an agriculturally acceptable salt or ester thereof.

In some aspects, the safe composition comprises:

(a) the carboxylic acid pyridine herbicide compound propargyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate, hereinafter referred to as compound B:

or an agriculturally acceptable N-oxide, salt, or ester thereof; and

(b) a safener of a carboxylic acid azole or an agriculturally acceptable salt or ester thereof.

In some aspects, the carboxylic acid azole safener can be selected from the group consisting of: cloquinconazole, cloquintocet-mexyl, mefenpyr-diethyl, isoxadifen-ethyl, pyrazoline oxalic acid, agriculturally acceptable salts or esters thereof, and combinations thereof.

In some aspects, the composition may further comprise an agriculturally acceptable adjuvant or carrier, an additional pesticide, or a combination thereof. In some aspects, the only active ingredients in the composition are (a) and (b). In some aspects, the compositions can be provided as herbicidal concentrates.

Also disclosed herein are methods of controlling undesirable vegetation, the methods comprising applying to vegetation, an area adjacent the vegetation, or to soil or water a safety composition to control the emergence or growth of vegetation, the safety composition comprising: (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt or ester thereof; and (b) a carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof. In some aspects, (a) and (b) are administered simultaneously. In some aspects, (a) and (b) are administered sequentially. In some aspects, (a) and (b) are applied prior to emergence of the undesirable vegetation. In some aspects, (a) is applied to the undesirable vegetation pre-or post-emergence, and (b) is applied to the crop as a seed treatment. In some aspects, (a) and (b) are applied after emergence of the undesirable vegetation. In some aspects, the undesirable vegetation is in cereals. In some aspects, the undesirable vegetation is in maize, wheat, barley, rice, sorghum, millet, or oats. In some aspects, the undesirable vegetation is in broadleaf crops. In some aspects, the undesirable vegetation is in canola, flax, sunflower, soybean, or cotton.

In some cases, the picolinate herbicide (a) may be applied in an amount of from 0.1 grams active ingredient per hectare (g ai/ha) to 300g ai/ha (e.g., from 30g ai/ha to 40g ai/ha). In some cases, the carboxyazole safener (b) can be applied in an amount of 1g ai/ha to 300g ai/ha (e.g., 30g ai/ha to 40g ai/ha). In some cases, (a) and (b) can be applied in a weight ratio of 1:5 to 5:1 (e.g., 1:3 to 3:1, or 1:2 to 2: 1).

The following description sets forth details of one or more aspects of the disclosure. Other features, objects, and advantages will be apparent from the description and from the claims.

Detailed Description

The present disclosure includes a secured composition comprising: (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt or ester thereof, and (b) a carboxyazole safener or an agriculturally acceptable salt or ester thereof. The present disclosure also includes methods for controlling undesirable vegetation. In some aspects, the undesirable vegetation is in cereals. In some aspects, the undesirable vegetation is in maize, wheat, barley, rice, sorghum, millet, or oats. In some aspects, the undesirable vegetation is in broadleaf crops. In some aspects, the undesirable vegetation is in canola, flax, sunflower, soybean, or cotton.

I.Definition of

Unless otherwise indicated, terms used herein shall have their customary meaning in the art. The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. To the extent that the term "or" (e.g., a or B) is employed, it is intended to mean "a or B or both". If the disclosure is intended to indicate "only A or B and not both," the term "only A or B and not both" will be used. Thus, use of the term "or" herein is the inclusive and not the exclusive use.

Chemical moieties (e.g., the term "alkyl") referred to in defining variable positions within the general formulae described herein are collective terms for the individual substituents encompassed by the chemical moiety. Prefix C preceding a group or moiety_n-C_mDenotes the number of possible carbon atoms in the group or moiety which follows in each case.

As used herein, the terms "herbicide" and "herbicidally active ingredient" can be understood to include active ingredients that kill, control, or otherwise adversely alter the growth of vegetation, particularly undesirable vegetation (e.g., weed species), when applied in appropriate amounts.

As used herein, the term "herbicidal effect" can be understood to include the adverse alteration of vegetation by the active ingredient, including, for example, deviation from natural growth or development, killing, regulation, desiccation, growth inhibition, growth reduction, and retardation. The term "herbicidal activity" generally refers to the herbicidal action of the active ingredient.

As used herein, "applying" an herbicide or herbicidal composition refers to delivering it directly to the target vegetation or locus thereof or to an area where control of undesirable vegetation is desired. Methods of application include, but are not limited to, pre-emergence contact with soil or water, post-emergence contact with the undesirable vegetation or an area adjacent to the undesirable vegetation.

As used herein, the term "vegetation" may include, for example, dormant seeds, germinating seeds, emerging seedlings, plants propagated from vegetative propagules, immature vegetation, and established vegetation.

As used herein, the term "crop" refers to desired vegetation, e.g., plants grown to provide food, shelter, pasture, erosion control, and the like. Example crops include cereals, beans, vegetables, turf, fruit and wood trees, grapevines, and the like. Preferably, the herbicide or herbicidal composition has zero or minimal herbicidal effect on the crop.

As used herein, the term "undesirable vegetation" refers to unwanted vegetation in a given area, such as weed species. Herbicides or herbicidal compositions are used to control undesirable vegetation. Preferably, the herbicide or herbicidal composition has a substantial or complete herbicidal effect on undesirable vegetation.

As used herein, "active ingredient" or "ai" can be understood to include a compound or composition having an effect on the integument; specifically, it has a herbicidal effect or a safety effect on vegetation.

As used herein, "acid equivalent" or "ae" is understood to include the amount of the acid form of the active ingredient as calculated from the amount of the salt or ester form of the active ingredient. For example, if the acid form of active ingredient "Z" has a molecular weight of 100 daltons, and the salt form of Z has a molecular weight of 130 daltons, then applying 130g of the Z salt of ai/ha would be equivalent to applying 100g of the acid form of Z of ae/ha:

130g ai/ha Z salt (100Da Z acid/130 Da Z salt) ═ 100g ae/ha Z acid.

As used herein, unless otherwise indicated, the term "acyl" is understood to include groups of the formula-C (O) R, wherein "C (O)" is the abbreviation for C ═ O. In the acyl group, R may be an alkyl group (e.g., C)₁-C₆Alkyl), haloalkyl (e.g. C)₁-C₆Haloalkyl), alkenyl (e.g. C)₂-C₆Alkenyl), haloalkenyl (e.g., C)₂-C₆Halogenated alkenyl) Alkynyl (e.g., C)₂-C₆Alkynyl), aryl or heteroaryl or arylalkyl (e.g., C)₇-C₁₀Alkynyl).

As used herein, the term "alkyl" is understood to include saturated, straight-chain, branched-chain, or cyclic saturated hydrocarbon moieties. Unless otherwise indicated, C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Alkyl groups are contemplated. Examples of alkyl groups include methyl, ethyl, propyl, cyclopropyl, 1-methyl-ethyl, butyl, cyclobutyl, 1-methyl-propyl, 2-methyl-propyl, 1-dimethyl-ethyl, pentyl, cyclopentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2-dimethyl-propyl, 1-ethyl-propyl, hexyl, cyclohexyl, 1-dimethyl-propyl, 1, 2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1-dimethyl-butyl, 1, 2-dimethyl-butyl, 1-methyl-butyl, 2-pentyl, and 2-pentyl, or 2-pentyl, or a, 1, 3-dimethyl-butyl, 2, 2-dimethyl-butyl, 2, 3-dimethyl-butyl, 3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1, 2-trimethyl-propyl, 1,2, 2-trimethyl-propyl, 1-ethyl-1-methyl-propyl, and 1-ethyl-2-methyl-propyl. The alkyl substituent may also be substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆Alkoxy radical, C₁-C₆Haloalkoxy, C₁-C₆Acyl radical, C₁-C₆Alkylthio radical, C₁-C₆Haloalkylthio, C₁-C₆Alkylsulfinyl radical, C₁-C₆Haloalkylsulfinyl radical, C₁-C₆Alkylsulfonyl radical, C₁-C₆Haloalkylsulfonyl group, C₁-C₆Alkoxycarbonyl group, C₁-C₆Halogenoalkoxycarbonyl, C₁-C₆Carbamoyl radical, C₁-C₆Halocarbamoyl, hydroxycarbonyl, C₁-C₆Alkylcarbonyl group, C₁-C₆Halogenated alkylcarbonyl group, ammoniaCarbonyl radical, C₁-C₆Alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆Dialkylaminocarbonyl, and C₁-C₆Dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and that the rules for chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆An alkoxy group.

As used herein, the term "haloalkyl" may be understood to include alkyl groups in which a hydrogen atom may be partially or fully substituted with a halogen atom. Unless otherwise indicated, C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Alkyl groups are contemplated. Examples include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2,2, 2-trichloroethyl, pentafluoroethyl, and 1,1, 1-trifluoropropan-2-yl. The haloalkyl substituent may also be substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆Alkoxy radical, C₁-C₆Haloalkoxy, C₁-C₆Acyl radical, C₁-C₆Alkylthio radical, C₁-C₆Haloalkylthio, C₁-C₆Alkylsulfinyl radical, C₁-C₆Haloalkylsulfinyl radical, C₁-C₆Alkylsulfonyl radical, C₁-C₆Haloalkylsulfonyl group, C₁-C₆Alkoxycarbonyl group, C₁-C₆Halogenoalkoxycarbonyl, C₁-C₆Carbamoyl radical, C₁-C₆Halocarbamoyl, hydroxycarbonyl, C₁-C₆Alkylcarbonyl group, C₁-C₆Halogenated alkylcarbonyl, aminocarbonyl, C₁-C₆Alkyl ammoniaAlkylcarbonyl, haloalkylaminocarbonyl, C₁-C₆Dialkylaminocarbonyl, and C₁-C₆Dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and that the rules for chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆An alkoxy group.

As used herein, the term "alkoxy" may be understood to include groups having the formula R-O-, wherein R is unsubstituted or substituted alkyl as defined above. Wherein R is C, unless otherwise indicated₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Alkoxy groups of alkyl groups are contemplated. Examples include methoxy, ethoxy, propoxy, 1-methyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1-dimethyl-ethoxy, pentyloxy, 1-methyl-butoxy, 2-methyl-butoxy, 3-methyl-butoxy, 2-dimethyl-propoxy, 1-ethyl-propoxy, hexyloxy, 1-dimethyl-propoxy, 1, 2-dimethyl-propoxy, 1-methyl-pentyloxy, 2-methyl-pentyloxy, 3-methyl-pentyloxy, 4-methyl-phenoxy, 1-dimethyl-butoxy, 1, 2-dimethyl-butoxy, 1-methyl-propoxy, 2-methyl-propoxy, n-butyl-oxy, n-butyl-1, n-methyl-propoxy, n-butoxy, n-propoxy, n-butyl-propoxy, n-butoxy, n-butyl, n-propoxy, n-2-propoxy, n-butoxy, n-butyl, n-propoxy, n-2-propoxy, n-butoxy, p-butyl, n-butyl, p-2, p-butyl, p-2-butyl, p-2, p-butyl, p-butyl, p-p, 1, 3-dimethyl-butoxy, 2, 2-dimethyl-butoxy, 2, 3-dimethyl-butoxy, 3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1, 2-trimethyl-propoxy, 1,2, 2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy.

As used herein, the term "alkoxycarbonyl" can be understood to include groups having the formula-c (o) OR, wherein R is unsubstituted OR substituted alkyl as defined above. Wherein R is C, unless otherwise indicated₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Alkoxycarbonyl groups for alkyl groups are contemplated. Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methyl-ethoxycarbonyl, butoxycarbonyl, 1-methyl-propylOxycarbonyl, 2-methyl-propoxycarbonyl, 1-dimethyl-ethoxycarbonyl, pentoxycarbonyl, 1-methyl-butyloxycarbonyl, 2-methyl-butoxycarbonyl, 3-methyl-butoxycarbonyl, 2-dimethyl-propoxycarbonyl, 1-ethyl-propoxycarbonyl, hexyloxycarbonyl, 1-dimethyl-propoxycarbonyl, 1, 2-dimethyl-propoxycarbonyl, 1-methyl-pentoxycarbonyl, 2-methyl-pentoxycarbonyl, 3-methyl-pentoxycarbonyl, 4-methyl-pentoxycarbonyl, 1-dimethyl-butoxycarbonyl, 1, 2-dimethyl-butoxycarbonyl, n-butyl-oxycarbonyl, p-2-butoxycarbonyl, n-2-methyl-propoxycarbonyl, 2-propoxy-oxycarbonyl, 2-methyl-propoxy-oxycarbonyl, 3-methyl-propoxy-carbonyl, 4-propoxy-carbonyl, 1-propoxy-1, 1-propoxy-carbonyl, 1-2-propoxy-oxycarbonyl, 2-propoxy-carbonyl, 2-carbonyl, or a, 1, 3-dimethyl-butoxycarbonyl, 2, 2-dimethyl-butoxycarbonyl, 2, 3-dimethyl-butoxycarbonyl, 3-dimethyl-butoxycarbonyl, 1-ethyl-butoxycarbonyl, 2-ethylbutoxycarbonyl, 1, 2-trimethyl-propoxycarbonyl, 1,2, 2-trimethyl-propoxycarbonyl, 1-ethyl-1-methyl-propoxycarbonyl and 1-ethyl-2-methyl-propoxycarbonyl.

As used herein, the term "haloalkoxy" may be understood to include groups having the formula R-O-, wherein R is an unsubstituted or substituted haloalkyl group as defined above. Wherein R is C, unless otherwise specified₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Haloalkoxy groups of alkyl groups are contemplated. Examples include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2, 2-difluoroethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2,2, 2-trichloroethoxy, pentafluoroethoxy and 1,1, 1-trifluoroprop-2-oxy.

As used herein, the term "aryl" and derivative terms such as aryloxy may be understood to include groups comprising monovalent aromatic carbocyclic groups of 6 to 14 carbon atoms. The aryl group may include a single ring or multiple fused rings. In some aspects, the aryl group comprises C₆-C₁₀An aryl group. Examples of aryl radicalsIncluding but not limited to phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl, and indanyl. In some aspects, the aryl group can be phenyl, indanyl, or naphthyl.

As used herein, the term "heteroaryl" as well as derivative terms such as "heteroaryloxy" may be understood to include 5-or 6-membered aromatic rings containing one or more heteroatoms (e.g., N, O or S). Heteroaryl rings may be fused with other aromatic systems. The aryl or heteroaryl substituents may be substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₁-C₆Alkoxy radical, C₁-C₆Haloalkyl, C₁-C₆Haloalkoxy, C₁-C₆Acyl radical, C₁-C₆Alkylthio radical, C₁-C₆Alkylsulfinyl radical, C₁-C₆Alkylsulfonyl radical, C₁-C₆Alkoxycarbonyl group, C₁-C₆Carbamoyl, hydroxycarbonyl, C₁-C₆Alkylcarbonyl, aminocarbonyl, C₁-C₆Alkylaminocarbonyl radical, C₁-C₆Dialkylaminocarbonyl, provided that the substituents are sterically compatible and satisfy the rules for chemical bonding and strain energy. Preferred substituents include halogen, C₁-C₄Alkyl and C₁-C₄A haloalkyl group.

As used herein, the term "halogen" includes derivative terms such as "halo," and refers to fluorine, chlorine, bromine, and iodine.

As used herein, agriculturally acceptable salts and esters are understood to include salts and esters which exhibit herbicidal activity or which are or can be converted in plants, water or soil to the herbicides mentioned. Exemplary agriculturally acceptable esters are those that are hydrolyzed, oxidized, metabolized, or otherwise converted to the corresponding carboxylic acid or that are hydrolyzable, oxidized, metabolized, or otherwise converted to the corresponding carboxylic acid, e.g., in plants, water, or soil, which depending on pH, may be in dissociated or undissociated form.

The compounds described herein may include N-oxides. Pyridine N-oxides can be obtained by oxidation of the corresponding pyridine. Suitable oxidation processes are described, for example, in Houben-Weyl, Methoden der organischen chemistry [ Methods in organic chemistry ] [ Methods of organic chemistry ], 4 th edition extension and subsequent volume, volume E7 b, page 565 f.

II.Carboxylic acid pyridine herbicides

The compositions and methods of the present disclosure include the following safe compositions comprising (a) a carboxylic pyridine herbicide defined by formula (I):

wherein:

R¹is cyanomethyl or propargyl;

R²and R²' independently is hydrogen, C₁-C₆Alkyl, formyl, alkoxycarbonyl or acyl;

R³、R³'、R^3"and R³' is independently hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₃Alkoxy or C₁-C₃A haloalkoxy group;

or an agriculturally acceptable N-oxide, salt, or ester thereof; and

(b) a safener of a carboxylic acid azole or an agriculturally acceptable salt or ester thereof.

In some aspects, the compositions and methods of the present disclosure include the following safety compositions comprising (a) the carboxylic acid pyridine herbicide cyanomethyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate, compound a:

or an agriculturally acceptable N-oxide, salt or ester thereof, and (b) a carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof.

In some aspects, the compositions and methods of the present disclosure include the following safe compositions comprising (a) the carboxylic acid pyridine herbicide propargyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate, compound B:

or an agriculturally acceptable N-oxide, salt or ester thereof, and (b) a carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof.

The carboxylate pyridine herbicides defined by formula (I) and methods of making these carboxylate pyridine herbicides are disclosed in application PCT/US 2018/031004 filed on 4.5.2018, the entire disclosure of which is expressly incorporated herein by reference.

In some aspects, the carboxypyridine herbicide can be provided as an agriculturally acceptable salt. Exemplary agriculturally acceptable salts of the pyridine carboxylate herbicides include, but are not limited to: a sodium salt; a potassium salt; ammonium or substituted ammonium salts, especially mono-C₁-C₈Alkyl ammonium salt, di-C₁-C₈Alkyl ammonium salts and tri-C₁-C₈Alkyl ammonium salts (such as methyl ammonium, dimethyl ammonium and isopropyl ammonium salts); mono-hydroxy-C₂-C₈Alkyl ammonium salt, di-hydroxy-C₂-C₈Alkyl ammonium salts and tri-hydroxy-C₂-C₈Alkyl ammonium salts (such as hydroxyethyl ammonium salt, di (hydroxyethyl) ammonium salt, tri (hydroxyethyl) ammonium salt, hydroxypropyl ammonium salt, di (hydroxypropyl) ammonium salt and tri (hydroxypropyl) ammonium salt); an ethanolamine salt; a diglycolamine salt; a choline salt; and quaternary ammonium salts (e.g., of the formula R)⁹R¹⁰R¹¹R¹²N⁺Those of the formulae and wherein R⁹、R¹⁰、R¹¹And R¹²(e.g., R)⁹-R¹²) Can each independently represent hydrogen or C₁-C₁₀Alkyl radical, C₂-C₈Alkenyl radical, C₂-C₈Alkynyl, C₁-C₈Alkoxy radical, C₁-C₈Alkylthio, or aryl radicals, with the proviso that R⁹-R¹²Spatially compatible).

In some aspects, the carboxypyridine herbicide can be provided as an agriculturally acceptable ester. Exemplary agriculturally acceptable esters of the pyridine carboxylate herbicides include, but are not limited to: methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 1-ethyl-propyl, hexyl, 1-methyl-hexyl (mexyl), 2-ethylhexyl, heptyl, 1-methyl-heptyl (meptyl), octyl, isooctyl (isooctyl, isoctyl), butoxyethyl (butotyl), and benzyl.

The carboxypyridine herbicide, or agriculturally acceptable N-oxide, salt, or ester thereof, can be applied to vegetation or an area adjacent the vegetation or to soil or water in an amount sufficient to induce herbicidal action to prevent the emergence or growth of vegetation. In some aspects, a carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, is applied to vegetation or an area adjacent to the vegetation or to soil or water in an amount to prevent the emergence or growth of vegetation by: 0.1 gram acid equivalent/hectare (g ae/ha) or more, for example, 0.2g ae/ha or more, 0.3g ae/ha or more, 0.4gae/ha or more, 0.5g ae/ha or more, 0.6g ae/ha or more, 0.7g ae/ha or more, 0.8g ae/ha or more, 0.9g ae/ha or more, 1g ae/ha or more, 1.1g ae/ha or more, 1.2g ae/ha or more, 1.3g ae/ha or more, 1.4g ae/ha or more, 1.5g ae/ha or more, 1.6g ae/ha or more, 1.7g ae/ha or more, 1.8g ha/ha or more, 1.2g ha/ha or more, 2g ae/ha or more, 2g ha/ha or more, 2.5g ae/ha or more, 2.75g ae/ha or more, 3g ae/ha or more, 4g ae/ha or more, 5g ae/ha or more, 6g ae/ha or more, 7g ae/ha or more, 8g ae/ha or more, 9g ae/ha or more, 10g ae/ha or more, 11g ae/ha or more, 12g ae/ha or more, 13g ae/ha or more, 14g ae/ha or more, 15g ae/ha or more, 16g ae/ha or more, 17g ae/ha or more, 18g ae/ha or more, 19g ae/ha or more, 20g ae/ha or more, 22g ae/ha or more, 24g ae/ha or more, 25g ae/ha or more, 26g ae/ha or more, 28g ae/ha or more, 30g ae/ha or more, 32g ae/ha or more, 34g ae/ha or more, 35g ae/ha or more, 36g ae/ha or more, 38g ae/ha or more, 40g ae/ha or more, 42.5g ae/ha or more, 45g ae/ha or more, 47.5g ae/ha or more, 50g ae/ha or more, 52.5g ae/ha or more, 55g ae/ha or more, 57.5g ae/ha or more, 60g ae/ha or more, 65g ae/ha or more, 70g ae/ha or more, 75g ae/ha or more, 80g ha/ha or more, 85g ae/ha or more, 90g ae/ha or more, 95g ae/ha or more, 100g ae/ha or more, 110g ae/ha or more, 120g ae/ha or more, 130g ae/ha or more, 140g ae/ha or more, 150g ae/ha or more, 160gae/ha or more, 170g ae/ha or more, 180g ae/ha or more, 190g ae/ha or more, 200g ae/ha or more, 210g ae/ha or more, 220g ae/ha or more, 230g ae/ha or more, 240g ae/ha or more, 250g ae/ha or more, 260g ae/ha or more, 270g ae/ha or more, 280g ae/ha or more, Or 290g ae/ha or more; in the following amounts: 300g ae/ha or less, e.g., 290g ae/ha or less, 280g ae/ha or less, 270g ae/ha or less, 260g ae/ha or less, 250g ae/ha or less, 240g ae/ha or less, 230g ae/ha or less, 220g ae/ha or less, 210g ae/ha or less, 200g ae/ha or less, 190g ae/ha or less, 180g ae/ha or less, 170g ae/ha or less, 160g ae/ha or less, 150g ae/ha or less, 140g ae/ha or less, 130g ae/ha or less, 120g ae/ha or less, 110g ae/ha or less, 100g ae/ha or less, 95g ae/ha or less, 90g ae/ha or less, 85g ae/ha or less, 80g ae/ha or less, 75g ae/ha or less, 70g ae/ha or less, 65g ae/ha or less, 60g ae/ha or less, 57.5g ae/ha or less, 55g ae/ha or less, 52.5g ae/ha or less, 50g ae/ha or less, 47.5g ae/ha or less, 45g ae/ha or less, 42.5g ae/ha or less, 40g ae/ha or less, 38g ae/ha or less, 36g ae/ha or less, 35g ae/ha or less, 34g ae/ha or less, 32g ae/ha or less, 30g ae/ha or less, 28g ha/ha or less, 28g ae/ha or less, 26g ae/ha or less, 25g ae/ha or less, 24g ae/ha or less, 22g ae/ha or less, 20g ae/ha or less, 19g ae/ha or less, 18g ae/ha or less, 17g ae/ha or less, 16g ae/ha or less, 15g ae/ha or less, 14g ae/ha or less, 13g ae/ha or less, 12g ae/ha or less, 11g ae/ha or less, 10g ae/ha or less, 9g ae/ha or less, 8g ae/ha or less, 7g ae/ha or less, 6g ae/ha or less, 5g ae/ha or less, 4g ae/ha or less, 3g ae/ha or less, 2g ae/ha or less, 18g ae/ha or less, 17g ae/ha or less, 6g ae/ha or less, or more, 2.75g ae/ha or less, 2.5g ae/ha or less, 2.25g ae/ha or less, 2g ae/ha or less, 1.9g ae/ha or less, 1.8g ae/ha or less, 1.7g ae/ha or less, 1.6g ae/ha or less, 1.5g ae/ha or less, 1.4g ae/ha or less, 1.3g ae/ha or less, 1.2g ae/ha or less, 1.1g ae/ha or less, 1g ae/ha or less, 0.9g ae/ha or less, 0.8g ae/ha or less, 0.7g ae/ha or less, 0.6g ae/ha or less, 0.5g ae/ha or less, 0.4g ae/ha or less, 0.3g ae/ha or less, or 0.2g ae/ha or less; or an amount within any range defined between any pair of the foregoing values (from 0.1g ae/ha to 300g ae/ha, from 1g ae/ha to 150g ae/ha, from 10g ae/ha to 200g ae/ha, from 25g ae/ha to 75g ae/ha, or from 40g ae/ha to 100g ae/ha).

III.Carboxylic acid azole safeners

In addition to the picolinate herbicide, the compositions and methods of the present disclosure may also include a carboxylate azole safener or an agriculturally acceptable salt or ester thereof. Herbicide safeners are molecules used in combination with herbicides that can make them "safer", i.e., reduce the herbicidal effect of the herbicide on the crop and improve the selectivity between the crop and the undesirable vegetation to which the herbicide is directed. Herbicide safeners can be used to pretreat crop seeds prior to planting. The herbicide safener can also be sprayed on the plants in a mixture with the herbicide or separately or sequentially from the herbicide.

Oxazoles are a class of five-membered nitrogen heterocyclic compounds that contain at least one additional heteroatom (e.g., nitrogen, sulfur, or oxygen) within the heterocyclic ring. Examples of oxazoles include, for example, pyrazole, imidazole, thiazole, oxazole, isoxazole and triazole.

Carboxylic acid azole safeners are a class of safeners based on carboxylate-substituted azole moieties. Examples of carboxylic acid azole safeners include carboxylic acid pyrazole safeners, carboxylic acid imidazole safeners, carboxylic acid thiazole safeners, carboxylic acid oxazole safeners, carboxylic acid isoxazole safeners, and carboxylic acid triazole safeners. In some aspects, the composition may include a carboxylic acid azole safener selected from the group consisting of: cloquinconazole, cloquintocet-mexyl, mefenpyr-diethyl, isoxadifen-ethyl, pyrazoline oxalic acid, agriculturally acceptable salts or esters thereof, or combinations thereof. In some aspects, the carboxylic acid azole safener can include mefenpyr ethyl ester, isoxadifen ethyl ester, mefenpyr ethyl ester, or a combination thereof.

In some aspects, the fenchlorazole safener may include cloquintocet as shown below, or an agriculturally acceptable salt or ester thereof. Cloquinconazole safety activity is described in The Pesticide Manual, eighteenth edition, 2016.

In some aspects, the cloquintocet-mexyl is provided in the form of an agriculturally acceptable salt or ester. An exemplary agriculturally acceptable fenchlorazole shown below is fenchlorazole ethyl.

In some aspects, the carboxylic acid azole safener can include cloquintocet-mexyl, shown below, or an agriculturally acceptable salt or ester thereof. The safening activity of benoxacor is described in The Pesticide Manual, eighteenth edition, 2016.

In some aspects, the fentrazole safener can include furilazole, as shown below, or an agriculturally acceptable salt or ester thereof. Oxazaline safety activity is described in The Pesticide Manual, eighteenth edition, 2016.

In some aspects, the carboxylic acid azole safener can include bisbenzoxazole acid, as shown below, or an agriculturally acceptable salt or ester thereof. The safty activity of isoxadifen is described in The Pesticide Manual, eighteenth edition, 2016.

In some aspects, the isoxadifen is provided in the form of an agriculturally acceptable salt or ester. An exemplary agriculturally acceptable isoxadifen acid shown below is ethyl isoxadifen acid.

In some aspects, the carboxylic acid azole safener can include pyrazoline oxalic acid, as shown below, or an agriculturally acceptable salt or ester thereof. Pyrazolidineacetic acid safety activity is described in The Pesticide Manual, eighteenth edition, 2016.

In some aspects, the pyrazolinoxidic acid is provided in the form of an agriculturally acceptable salt or ester. An exemplary agriculturally acceptable pyrazolinolytic acid shown below is diethyl pyrazolinolyticate.

In some aspects, the carboxylic acid azole safener can be provided as an agriculturally acceptable ester. Suitable esters include, but are not limited to, methyl, ethyl, isopropyl, butyl, hexyl, heptyl, isoheptyl, 1-methyl-hexyl (mexyl), isooctyl, 2-ethylhexyl, and butoxyethyl esters, and aryl esters such as benzyl. Exemplary agriculturally acceptable esters of the azole safeners described herein include methyl, ethyl, and diethyl esters.

In some aspects, the carboxylic acid azole safener can comprise an agriculturally acceptable salt of the carboxylic acid azole safener. Agriculturally acceptable salts of the azole carboxylate safeners include, for example, the sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropanolammonium, triisopropanolammonium, choline, N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium, and isopropylammonium salts of the azole carboxylate safeners.

Safeners of carboxylic acid azoles when applied in combination with herbicides can reduce phytotoxicity to crops such as wheat, barley, triticale, rye, sedge, oats, maize, sorghum, millet, rice, millet, canola/oilseed rape, flax, soybeans, sunflowers, sugar beet, cotton, sugar cane and pasture grasses.

The carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof may be used in an amount sufficient to elicit a safening effect. In some aspects, the carboxylic acid azole safener is selected from the group consisting of: mefenpyr, fenclorim, cloquintocet-mexyl, mefenpyr-diethyl, isoxadifen, mefenpyr-diethyl, or a combination thereof, and is applied to vegetation or an area adjacent the vegetation or to soil or water in an amount such that: 1g active ingredient/hectare (ai/ha) or more, for example 2g ai/ha or more, 3g ai/ha or more, 4g ai/ha or more, 5g ai/ha or more, 6g ai/ha or more, 7g ai/ha or more, 8g ai/ha or more, 9g ai/ha or more, 10g ai/ha or more, 11g ai/ha or more, 12g ai/ha or more, 13g ai/ha or more, 14g ai/ha or more, 15g ai/ha or more, 16g ai/ha or more, 17g ai/ha or more, 18g ai/ha or more, 19g ai/ha or more, 20g ai/ha or more, 22g ai/ha or more, 24g ai/ha or more, 25g ai/ha or more, 26g ai/ha or more, 28g ai/ha or more, 30g ai/ha or more, 32g ai/ha or more, 34g ai/ha or more, 35g ai/ha or more, 36g ai/ha or more, 38g ai/ha or more, 40g ai/ha or more, 42.5g ai/ha or more, 45g ai/ha or more, 47.5g ai/ha or more, 50g ai/ha or more, 52.5g ai/ha or more, 55g ai/ha or more, 57.5g ai/ha or more, 60g ai/ha or more, 65g ai/ha or more, 70g ai/ha or more, 75g ai/ha or more, 80g ai/ha or more, 85g ai/ha or more, 90g ai/ha or more, 95g ai/ha or more, 100g ai/ha or more, 110g ai/ha or more, 120g ai/ha or more, 130g ai/ha or more, 140g ai/ha or more, 150g ai/ha or more, 160g ai/ha or more, 170g ai/ha or more, 180g ai/ha or more, 190g ai/ha or more, 200g ai/ha or more, 210g ai/ha or more, 220g ai/ha or more, 230g ai/ha or more, 240g ai/ha or more, 250g ai/ha or more, 260g ai/ha or more, 270g ai/ha or more, 280g ai/ha or more, or 290g ai/ha or more; in the following amounts: 300g ai/ha or less, e.g., 290g ai/ha or less, 280g ai/ha or less, 270g ai/ha or less, 260g a/ha or less, 250g ai/ha or less, 240g ai/ha or less, 230g ai/ha or less, 220g ai/ha or less, 210g ai/ha or less, 200g ai/ha or less, 190g ai/ha or less, 180g ai/ha or less, 170g ai/ha or less, 160g ai/ha or less, 150g ai/ha or less, 140g ai/ha or less, 130g ai/ha or less, 120g ai/ha or less, 110g ai/ha or less, 100g ai/ha or less, 95g ai/ha or less, 90g ai/ha or less, 85g ai/ha or less, 80g ai/ha or less, 75g ai/ha or less, 70g ai/ha or less, 65g ai/ha or less, 60g ai/ha or less, 57.5g ai/ha or less, 55g ai/ha or less, 52.5g ai/ha or less, 50g ai/ha or less, 47.5g ai/ha or less, 45g ai/ha or less, 42.5g ai/ha or less, 40g ai/ha or less, 38g ai/ha or less, 36g ai/ha or less, 35g ai/ha or less, 34g ai/ha or less, 32g ai/ha or less, 30g ai/ha or less, 28g ai/ha or less, 26g ai/ha or less, 25g ai/ha or less, 24g ai/ha or less, 22g ai/ha or less, 20g ai/ha or less, 19g ai/ha or less, 18g ai/ha or less, 17g ai/ha or less, 16g ai/ha or less, 15g ai/ha or less, 14g ai/ha or less, 13g ai/ha or less, 12g ai/ha or less, 11g ai/ha or less, 10g ai/ha or less, 9g ai/ha or less, 8g ai/ha or less, 7g ai/ha or less, 6g ai/ha or less, 5g ai/ha or less, 4g ai/ha or less, 3g ai/ha or less, or 2g ai/ha or less; or an amount within any range defined between any pair of values recited above (e.g., from 1g ai/ha to 300gai/ha, from 5g ai/ha to 150g ai/ha, from 10g ai/ha to 200g ai/ha, from 20g ai/ha to 75g ai/ha, or from 40g ai/ha to 100g ai/ha).

IV.Safety composition

A safener composition comprising (a) a picolinate herbicide or an agriculturally acceptable N-oxide, salt or ester thereof may be mixed with or applied in combination with (b) a fentrazole safener or an agriculturally acceptable salt or ester thereof.

In some aspects, the amounts of (a) and (b) used are sufficient to cause an unexpectedly enhanced herbicidal effect (e.g., increased injury or damage to undesirable vegetation) while still exhibiting good crop compatibility (e.g., no increased injury or minimal increased injury or damage to crops) when compared to the application of the herbicidal compound (a) or (b) alone. In some aspects, the damage or injury to the undesirable vegetation caused by the safety compositions and methods disclosed herein is assessed using a scale of 0% to 100% when compared to untreated control vegetation, where 0% represents no damage to the undesirable vegetation and 100% represents complete destruction of the undesirable vegetation. Similarly, in some aspects, the injury or damage caused to a crop by the safety compositions and methods disclosed herein is assessed using a scale from 0% to 100% when compared to a control crop treated with herbicide or safety agent alone, where 0% indicates no injury to the crop and 100% indicates complete destruction of the crop.

In some aspects, the combined action of (a) a carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt or ester thereof, and (b) a carboxyazole safener, or an agriculturally acceptable salt or ester thereof, results in an unexpected enhancement of the herbicidal effect on undesirable vegetation, even at application rates that are lower than those of herbicides that typically have herbicidal action on their own. In some aspects, the compositions and methods disclosed herein can be used at lower application rates based on the individual components to achieve a herbicidal effect comparable to the effect produced by the individual components at normal application rates. In some aspects, the combined action of (a) a carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt or ester thereof, and (b) a carboxyazole safener, or an agriculturally acceptable salt or ester thereof, results in the unexpected protection of a desired crop from damage that may be caused to the crop by the individual herbicides.

In some aspects, the weight ratio of (a) the picolinic acid herbicide or agriculturally acceptable N-oxide, salt or ester thereof (in g ae/ha) to (b) the azole safener or agriculturally acceptable salt or ester thereof (in g ai/ha) can be 1:5 or more, e.g., 1:4.75 or more, 1:4.5 or more, 1:4.25 or more, 1:4 or more, 1:3.75 or more, 1:3.5 or more, 1:3 or more, 1:2.75 or more, 1:2.5 or more, 1:2.25 or more, 1:2 or more, 1:1.9 or more, 1:1.8 or more, 1:1.7 or more, 1:1.6 or more, 1:1.5 or more, 1:1.4 or more, 1:1.3 or more, 1:1.2 or more, 1: 1.1.1.1.1, 1: 1.1.1, 1:1.1, 1:1.5 or more, 1:1.4 or more, 1:1.3 or more, 1.1.1, 1: 1.1.1, 1.1, 1.1.1, 1.1, 1, 1.1.1, or more, 1.1.1, 1, 1.5 or more, 1, or 1, or 1.5 or more, 1, 1.5 or more, or less, or a mixture of the like, 1.3:1 or higher, 1.4:1 or higher, 1.5:1 or higher, 1.6:1 or higher, 1.7:1 or higher, 1.8:1 or higher, 1.9:1 or higher, 2:1 or higher, 2.25:1 or higher, 2.5:1 or higher, 2.75:1 or higher, 3:1 or higher, 3.25:1 or higher, 3.5:1 or higher, 3.75:1 or higher, 4:1 or higher, 4.25:1 or higher, 4.5:1 or higher, 4.75:1 or higher, or 5:1 or higher; (a) the weight ratio to (b) may be 5:1 or less, e.g., 4.75:1 or less, 4.5:1 or less, 4.25:1 or less, 4:1 or less, 3.75:1 or less, 3.5:1 or less, 3.25:1 or less, 3:1 or less, 2.75:1 or less, 2.5:1 or less, 2.25:1 or less, 2:1 or less, 1.9:1 or less, 1.8:1 or less, 1.7:1 or less, 1.6:1 or less, 1.5:1 or less, 1.4:1 or less, 1.3:1 or less, 1.2:1 or less, 1.1:1 or less, 1:1.1 or less, 1:1.2 or less, 1:1.3 or less, 1:1.4 or less, 1: 1.5:1 or less, 1.1:1 or less, 1.1: 1.2 or less, 1:1.1 or less, 1:1.3 or less, 1:1.1 or less, 1.1:1 or less, 1:1 or less, 1.1.1, 1:1 or less, 1:1 or less, 1.1, 1, or less, 1.1.2 or less, 1.1.1, or 1:1, or less, 1.1: 1.2 or less, or 1, or 1.1.1.1: 1, or less, or 1.2 or less, or 1.3, or 1, or 1.1.1.1.1, or less, or 1.1, or less, or 1.1.1.1, or 1.1:1, or 1.1, or 1.1.1.1.1, or 1:1, or less, or 1, or 1.1, or less, or 1, or 1.1.1, or 1:1, or 1:1, or 1.1.1.1, or 1:1, or less, or 1, or 1.2 or 1.1.1, or 1.1.1.1, or 1.1, or less, or 1, or 1.1.1, or 1, or 1.1, or 1, or 1.1, or 1, or 1.1.1, or 1, or less, or 1, or 2 or 1, or 1.8:1, or 2 or less, or 1, or, 1:2.75 or less, 1:3 or less, 1:3.25 or less, 1:3.5 or less, 1:3.75 or less, 1:4 or less, 1:4.25 or less, 1:4.5 or less, or 1:4.75 or less; or the weight ratio of (a) to (b) can range from any of the minimum to any of the maximum ratios provided above, e.g., from 1:5 to 5:1, from 1:2 to 5:1, from 1:1 to 3:1, from 1:3 to 4:1, or from 1:1.5 to 3.5: 1.

In some aspects, according to Nuclear Magnetic Resonance (NMR) spectroscopy, (a) and (b) can be used independently in a purity of 90% to 100% (e.g., 95% to 100%).

V.Preparation

The present disclosure also includes formulations and methods of the compositions disclosed herein.

A.Additive agent

The compositions and methods disclosed herein may also be mixed with or applied with additives. In some aspects, the additives are added sequentially. In some aspects, the additives are added simultaneously. In some aspects, the additive is premixed with the carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof. In some aspects, the additive is premixed with the carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof.

1.Other pesticides

Some aspects of the disclosed safety compositions include adding one or more additional pesticide active ingredients to the safety composition. These pesticide active ingredients may include one or more of herbicides, insecticides, fungicides, nematicides, acaricides, arthropodicides, bactericides, plant growth regulators, or combinations thereof that are compatible with the compositions of the present disclosure.

In some aspects, the additive is an additional herbicide. For example, the compositions described herein may be applied in combination with one or more additional herbicides to control undesirable vegetation. The composition may be formulated with the one or more additional herbicides, tank mixed with the one or more additional herbicides, or applied sequentially with the one or more additional herbicides. Exemplary additional herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2, 4-D; 2,4-D choline salt; 2,4-D salts, esters and amines; 2, 4-DB; 3, 4-DA; 3, 4-DB; 2, 4-DEB; 2, 4-DEP; 2, 4-DP; 3, 4-DP; 2,3, 6-TBA; 2,4, 5-T; 2,4, 5-TB; acetochlor (acetochlor); acifluorfen (acifluorfen); aclonifen (aclonifen); acrolein (acrolein); alachlor (alachlor); death from grass poisoning (alidochor); graminis (alloxidim); allyl alcohol (allyl alcohol); pentachlorophenonoic acid (alorac); tezine (ametridione); ametryne; tebufzin (amibuzin); amicarbazone (amicarbazone); amidosulfuron (amidosulfuron); aminocyclopyrachlor (aminocyclopyrachlor); 4-aminopyralid-based herbicides (such as halauxifen (halaxifen); halauxifen-methyl (halauxifen-methyl); fluroxypyridine (flurpyrauxin); and those described in U.S. Pat. Nos. 7,314,849 and 7,432,227 to Balko et al); aminopyralid (aminopyralid); amifos-methyl; imazapyr (amitrole); ammonium sulfamate (ammonium sulfamate); anilofos (anilofos); white-head (anisuron); asulam (asulam); atraton (atraton); atrazine (atrazine); fenclodinium (azafenidin); azimsulfuron (azimsulfuron); azinpropryne; barban (barban); BCPC; beflubutamid (beflubutiamid); benazolin (benazolin); benzcarbazone-sodium (bencrarbazone); flumioxazin (benfluralin); benfuresate (benfuresate); bensulide (bensulide); bensulfuron-methyl (bensuluron); fenoxycarb (benthiocarb); bentazone (bentazone); amine acid killer (benzadox); benfenacil (benzfendizone); benazolin (benzzipram); benzobicyclon (benzobicyclon); bicyclon (benzofenap); fomesafen (benzofluor); new yangling (benzolprop); thidiazuron (benzthiazuron); bialaphos (bialaphos); fluroxypyr (bicyclopyrone); bifenox (bifenox); bialaphos (bilinafos); bispyribac-sodium (bispyribac); borax (borax); bromacil (bromiacil); furfuryl cyanide (bromobionil); beflubutamid (bromobutide); herbicidal agents (bromofenoxim); bromoxynil (bromoxynil); herbicidally (bromopyrazon); butachlor (butachlor); butafenacil (butafenacil); phosphinyl (butamifos); butachlor (butenachlor); tebufenpyrad (buthiazole); buthiuron (buthiuron); (ii) dinolamine (butralin); butroxydim; clodinafop-propargyl (buturon); suprinate (butyl); cacodylic acid (cacodylic acid); cafenstrole (cafenstrole); calcium chlorate (calcium chloride); calcium cyanamide (calcium cyanamide); kechlor ester (camlandichlor); carbaryl (carbasulam); grass long kill (carbetamide); fenoxacarb (carboxazole); death from grass failure (chlorocarb); carfentrazone-ethyl (carfentrazone-ethyl); CDEA; CEPC; metoxyfen (chloroxyfen); chloramben (chloramben); butachlor (chlorocarpyl); ethynyl (chlorezifop); clonazine (clonazine); chlorobromouron (chlorobromouron); clodinafop (chlorobufam); ethoxyphenyl-ron (chloretron); varek (chlorefenac); avenanthrate (chlorefenprox); fluoropyrimidines (chloroflurazole); chlordane (chloroflurenol); chloramine (chlordizazon); chlorimuron-ethyl (chlorimuron); cumyl ether (chlorotrofen); trichloropropionic acid (chloropon); chlortoluron (chlorotoluron); chlorsulfuron (chloroxuron); chloroxynil (chloroxynil); chlorpropham (chlorpropham); chlorsulfuron (chlorsulfuron); chlorophthalic acid (chlorethal); chloramben (chlorethaamid); cinidon-ethyl ester; cinmethylin (cinmethylin); cinosulfuron (cinosulfuron); fluazuron (cisanilide); chloracyl phosphinyl (clacyfos); clethodim (clethodim); iodochloropyridine ester (Clodinate); clodinafop-propargyl (clodinafop-propargyl); neoprene (clofep); clomazone; barnyard grass amine (clomeprop); cloproic acid (cloprox); cyclobutenedione (cycloproxydim); clopyralid (clopyralid); cloransulam-methyl; CMA; copper sulfate (copper sulfate); CPMF; CPPC; pyriminobac (credazine); cresol (cresol); prosulfuron (cumyluron); cyanazine (cyanatryn); cyanazine (cyanazine); chlorambete (cycloate); cyclopyrinate; cyclosulfamuron (cyclosulfamuron); cycloxydim (cycloxydim); cyclouron (cyclouron); cyhalofop-butyl (cyhalofop-butyl); fast pasture (cyperquat); ciprofloxacin (cyprazine); cyprosulfamide (cyprazole); cypamide (cypromid); vanilla-methyl (daimuron); dalapon (dalapon); dazomet (dazomet); dichloflur (delachlor); desmedipham; desmetryn (desmetryn); avenanthramide (di-allate); dicamba (dicamba); dichlobenil (dichlobenil); chlorsulfuron (dichloralurea); benzylamine (dichlormate); 2,4-d propionic acid (dichlorprop); 2,4-D fine propionic acid (dichlorprop-P); chloromethyl-methyl (diclofop-methyl); diclosulam (diclosulam); diethylcarbamylquat (diethyl quat); antra (diethylhexyl); fluoropentenoic acid (difenopentene); cumarone (difenoxuron); difenzoquat (difenoquat); diflufenican (diflufenican); difluoropyrazopyr (diflufenzopyr); oxazolon (dimefuron); piprazole (dimepiperate); dimethachlor (dimethachlor); penoxsulam (dimethametryn); dimethenamid (dimethenamid); dimethenamid-P; enemy (dimetano); chlorfenapyr (dimazon); dinoamine (dinitramine); dinofenate (dinofenate); nitrophenol (dinoprop); pentoxyphenol (dinosam); dinoseb (dinoseb); dinoterb (dinoterb); molinate (diphenamid); dimethoate (dipropetryn); diquat (diquat); 2,4-d sulfuric acid (disul); dithiopyr (dithiopyr); diuron (diuron); DMPA; DNOC; DSMA; EBEP; licorice (eglinazine); endothecium (endothal); pennisetum flaccidum (epronaz); EPTC; aweto (erbon); dicamba (esprocarb); cyhalofop butyl (ethalfluralin); ethametsulfuron (ethametsulfuron); ethansulamide (ethbenzamide); ethametsulfuron (ethametsulfuron); thiadiazoluron (ethidimuron); methiocarb (ethiolate); ethoxybenzylamine (ethobenzamid); ethofumesate (ethofumesate); fluroxypyr ether (ethoxyfen); ethoxysulfuron (ethoxysulfuron); nitrophenol (etinofen); pyrimethamine (etnipromid); ethoxyphenyl grass (etobenzanid); EXD; carbosulfan (fenasulam); 2,4, 5-rhinopropionic acid (fenoprop); fenoxaprop-p (fenoxaprop); fenoxaprop-P-ethyl; fenoxaprop-P-ethyl + isoxadifen-ethyl; metamifop (fenoxsulfone); fequinolone (fenquinotrione); chlorophenoxyethanol (fenteracol); thiazopyr (fenthiaprop); fentrazamide (fentrazamide); fenuron (fenuronon); ferrous sulfate (ferrous sulfate); flulark (flamprop); prodiamine (flamprop-M); flazasulfuron (flazasulfuron); florasulam (florasulam); fluazifop-butyl (fluazifop); fluazifop-P-butyl; pyraflufen-ethyl (fluazolate); flucarbazone (flucarbazone); flotepsulfuron (flucetosulfuron); fluquinacrid (fluchloralin); flufenacet (flufenacet); flufenacet (flurfenacin); flufenpyr-ethyl (flufenpyr-ethyl); flumetsulam (flumetsulam); trifluorooxazine (flumezin); fluoroelenic-pentyl (flumiclorac-pentyl); flumioxazin (flumioxazin); propyzamide (flumipropyn); fluometuron (fluometuron); bifenthrin (fluorodifen); fluoroglycofen (fluoroglycofen); fenzopyr (fluomonidine); fluorobenazolin (fluoroonitrofen); fluothilon (fluoxon); flubenconazole (flupoxam); primisulfuron-methyl (flupropacil); tetrafluoropropionic acid (flupropanate); flapwifsulfuron (flupyrsulfuron); fluazinone (fluridone); fluorochloridone (fluorochlorodone); fluroxypyr (fluroxypyr); fluroxypyr (fluroxypyr-meptyl); flurtamone (flurtamone); daphnofluor (fluthiacet); fomesafen (fomesafen); foramsulfuron (formamsulfuron); phosphino-aminine (fosamine); fluoroelenic acid (furomicrac); flurbiprofen (furyloxyfen); glufosinate (glufosinate); glufosinate-ammonium; glufosinate-P-ammonium; glyphosate salts and esters (glyphosate salts and esters); fluorosulfamide (halosafe); halosulfuron-methyl (halosulfuron); haloxydine (haloxydine); haloxyfop (haloxyfop); hexachloroacetone (hexachloroacetone); hexafluoroarsonate (hexaflurate); hexazinone (hexazinone); imazamethabenz (imazamethabenz); imazethapyr (imazamox); imazapic (imazapic); imazapyr (imazapyr); imidazoquinolinic acid (imazaquin); imazethapyr (imazethapyr); imazosulfuron (imazosulfuron); indene silicone (indanofan); indoxazine flumioxazin (indaziflam); iodobonil (iodobonil); iodomethane (iodomethane); iodosulfuron (iodosulfuron); iodosulfuron-ethyl-sodium; iofensulfuron; ioxynil (ioxynil); metribuzin (ipazine); triazolam (ipfenbacazone); propadine (iprymidam); cimetidine (isocarbamid); isoxidin (isocil); butazinone (isomethiozin); isopulegon (isonoruron); rhizoma Dioscoreae Septemlobae (isopolinate); isoprotulin (isopopalin); isoproturon (isoproturon); isoxolone (isouron); isoxaben (isoxaben); isoxachlorotole (isoxacachlorortole); isoxaflutole (isoxaflutole); oxazapyr (isoxapyrop); terbutaline (karbutilate); kriroxol (ketospiradox); lactofen (lactofen); lenacil (lenacil); linuron (linuron); MAA; MAMA; MCPA esters and amines; thiophenate (MCPA-thioethyl); MCPB; 2-methyl-4-chloropropionic acid (mecoprop); 2-methyl-4-chloropropionic acid (mecoprop-P) hydrochloride; butanenitrophenol (medinoterb); mefenacet (mefenacet); mefluazide (meflunidide); atrazine (mesotrazine); mesosulfuron (methylsulfuron); mesotrione (mesotrione); metam (metam); metamifop (metamifop); metamitron (metamitron); metazachlor (metazachlor); pyridaben (metaflurazon); thidiazuron (methabenzyazuron); primodium flurandrum (methalpropalin); triclopyr (methazole); methiocarb (methiobencarb); methiazoline (methiozolin); metoxuron (methiuron); ethofenprophoron (methoeton); fenugreek (thiophanate); methyl bromide (methyl bromide); methyl isothiocyanate (methyl isothiocyanate); styrene-propylron (methydyron); chromanone (metobenzuron); bromogluron (metobrooron); metolachlor (metolachlor); metosulam (metosulam); metoxuron (metoxuron); metribuzin (metribuzin); metsulfuron methyl (methylsufuron); molinate (molinate); heptanoyl amide (monoalide); texalone (monisouron); monochloroacetic acid (monochloroacetic acid); chlorgluron (monolinuron); metoxuron (monuron); varroa (morfamquat); MSMA; naproxylamine (naproanilide); naproxamide (napropamide); naproxamide (napropamide-M); naphazel (naptalam); stephania (neburon); nicosulfuron (nicosulfuron); diclofop-methyl (nipyraclofen); metalaxyl (nitralin); herbicidal ethers (nitrofen); trifolium triflate (nitroflurfen); norflurazon (norflurazon); kurroa (noruron); OCH; turfgrass (orbencarb); ortho-dichlorobenzene (ortho-dichlorobenzzene); orthosulfamuron (orthosulfamuron); oryzalin; oxadiargyl (oxadiargyl); oxadiargyl (oxadiazinon); oxadiazine (oxapyrazon); rimsulfuron (oxasulfuron); chlorazinomethane (oxaziclomefone); oxyfluorfen (oxyfluorfen); pyraflufen-ethyl (paraflufen-ethyl); para-fludron (parafluron); paraquat (paraquat); kekuprey (pebulate); pelargonic acid (pelargonic acid); pendimethalin (pendimethalin); penoxsulam (penoxsulam); pentachlorophenol (pentachlorophenol); chlorantraniliprole (pentaochlor); penoxazone (pentoxazone); fomesafen (perfluidone); pethoxamid (pethoxamid); alaninin (phenosopham); phenmedipham (phenmedipham); phenmedipham-ethyl (phenmedipham-ethyl); stringy stonecrop (phenobenzuron); phenylmercury acetate (phenylmercury acetate); picloram (picloram); picolinafen (picolinafen); pinoxaden (pinoxaden); pipophos (piprophos); potassium arsenite (potassium arsenite); potassium azide (potassium azide); potassium cyanate (potassium cyanate); pretilachlor (pretilachlor); primisulfuron (primisulfuron); cyazosin (procyazine); prodiamine (prodiamine); flufenacet (profluzol); ciprofloxacin (profluralin); clethodim (profoxydim); propaquinone (proglinazine); prohexadione-calcium; prometon (prometon); prometryn (prometryne); pronamide (pronamide); propachlor; propanil (propanil); propaquizafop (propaquizafop); propazine (propazine); anilazine (propham); propisochlor (propiochlor); tribenuron-methyl (propofol) is disclosed; propyrisulfuron (propyrisulfuron); propyzamide (propylzamide); sulfoima (prosufalin); prosulfocarb (prosulfocarb); prosulfuron (prosulfuron); promethan (proxan); guanacol (prynachlor); biadenong (pydanon); pyraclonil (pyraclonil); pyraflufen-ethyl (pyraflufen); sulfonyloxalazole (pyrasulfotole); pyrazoxynil (pyrazogyl); pyriminobac (pyrazone); pyrazolate (pyrazolilynate); pyrazosulfuron-ethyl (pyrazosulfuron); benazol (pyrazoxyfen); pyribenzoxim (pyribenzoxim); barnyard grass (pyributicarb); triclopyr (pyriclor); dacao Zhi (pyridafol); pyridate (pyridate); pyriftalid (pyriftalid); pyriminobac-methyl (pyriminobac); pyriproxyfen (pyrimisulfan); pyrithiobac-sodium (pyrithiobac-sodium); pyroxasulfone (pyroxasulfone); pyroxsulam (pyroxsulam); quinclorac (quinclorac); chloroquinolinic acid (quinmerac); diafenquinone (quinoclamine); chloranilide (quinoamid); quizalofop (quizalofop); ethyl quizalofop-P-ethyl; quizalofop-P-tefuryl (quizalofop-P-tefuryl); thiocyanatophenethanolamine (rhodethanil); rimsulfuron (rimsulfuron); saflufenacil (saflufenacil); s-metolachlor (S-metallachlor); terbuthylazine (sebutylazine); spatzle bugs (secbumeton); sethoxydim (sethoxydim); siduron (siduron); simazine; cimatone (simeton); simetryn (simetryn); SMA; sodium arsenite (sodium arsenite); sodium azide (sodium azide); sodium chlorate (sodium chloride); sulcotrione (sulcotrione); lawn-death (sulfate); sulfentrazone (sulfentrazone); sulfometuron (sulfometuron); phosphinothricin (sulfosate); sulfosulfuron (sulfofuron); sulfuric acid (sulfuric acid); azelate (sulglycoacin); swep (swep); TCA; grazing amine (tebutam); tebuthiuron (tebuthiiuron); mesotrione (tefuryltrione); tembotrione (tembotrione); tepraloxydim; terfenadine (terbacil); terbufagin (terbucarb); ragweed (terbuchlor); metoclopramide (terbumeton); terbuthylazine (terbuthylazine); terbutryn (terbutryne); fluoxolone (tetrafluron); methoxyfenacet (theosylchloride); thifensulfuron methyl (thiameturon); thizafluron (thiamafluron); fenthizamide (thiazopyr); thiadiazolidines (thiazimin); thidiazuron (thidiazuron); thiencarbazone (thiencarbazone); thifensulfuron-methyl (thifensulfuron); thiobencarb (thiobencarb); tiafenan (tiafenacil); carbofuran (tiocarbazil); pyrimethanil (tioclorim); tolpyrate (tolpyrate); topramezone (topramezone); tralkoxydim (tralkoxydim); triallate (tri-allate); pyroxsulam (triafamone); triasulfuron (triasulfuron); triazinyl flumioxazin (triaziflam); tribenuron-methyl (tribenuron); tribenuron-methyl (tribenuron); dicamba (tricamba); triclopyr choline salt (triclopyr choline salt); triclopyr acetate and salts (triclopyr esters and salts); chloranthus japonicus (tridephane); madazine (trietazine); trifloxysulfuron (trifloxysulfuron); trifluoxazine (trifludimoxazin); trifluralin (trifluralin); triflusulfuron (triflusulfuron); trifluorophenoxypropionic acid (trifop); trifolium oxime (trifopsime); trihydroxytriazine (trihydroxytriazine); triton (trimeturon); indandim (tripropinidan); prankx (tritac); triflusulfuron-methyl (tritosulfuron); vernolate (vernolate); xylacolor; and salts, esters, optically active isomers and mixtures thereof.

In some aspects, the additional pesticide or agriculturally acceptable salt or ester thereof is provided in a pre-mixed formulation with (a), (b), or a combination thereof. In some aspects, the carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, is provided in a pre-mixed formulation with an additional pesticide. In some aspects, the carboxylic acid azole safener, or an agriculturally acceptable salt or ester thereof, is provided in a pre-mixed formulation with an additional pesticide.

In some aspects, the safe composition may include one or more herbicidal active ingredients in addition to (a). In some aspects, the safe composition does not include a herbicidal active ingredient other than (a). In some aspects, the safe composition may exclude one or more of the above herbicidal active ingredients. In some aspects, the safe composition may include one or more herbicidal active ingredients in addition to (a), but may exclude one or more herbicidal ingredients as described above. In some aspects, the security composition may include one or more security agents in addition to (b). In some aspects, the security composition does not include a security agent other than (b). In some aspects, the composition may include other components, such as adjuvants, but not including herbicidal active ingredients other than (a) and safeners other than (b).

2.Auxiliary agent

In some aspects, the additive comprises an agriculturally acceptable adjuvant. Exemplary agriculturally acceptable adjuvants include, but are not limited to, antifreeze agents, antifoam agents, compatibilizing agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, colorants, odorants, penetration aids, wetting agents, spreading agents, dispersants, thickeners, freeze point depressants, antimicrobial agents, crop oils, binders (e.g., for use in seed formulations), surfactants, protective colloids, emulsifiers, tackifiers, and mixtures thereof.

Examples of agriculturally acceptable adjuvants include, but are not limited to, agricultureA mineral oil concentrate (e.g., 85% mineral oil + 15% emulsifier); nonylphenol ethoxylate; benzyl coconut alkyl dimethyl quaternary ammonium salt; a mixture of petroleum hydrocarbon, alkyl ester, organic acid and anionic surfactant; c₉-C₁₁An alkyl polyglycoside; a phosphate alcohol ethoxylate; natural primary alcohol (C)₁₂-C₁₆) An ethoxylate; di-sec-butylphenol EO-PO block copolymers; a polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrate; an emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylates (e.g., 8 EO); tallow amine ethoxylates (e.g., 15 EO); and PEG (400) dioleate-99.

Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants, emulsifiers) include, but are not limited to, alkali metal, alkaline earth metal, and ammonium salts of fatty acids or aromatic sulfonic acids (e.g., lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid); alkyl sulfonates and alkylaryl sulfonates; alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates; salts of sulfated hexa-, hepta-and octadecanols; salts of fatty alcohol glycol ethers; condensates of sulfonated naphthalene and its derivatives with formaldehyde; condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde; polyoxyethylene octylphenol ether; ethoxylated isooctyl, octyl or nonyl phenols, alkylphenyl or tributylphenyl polyglycol ethers; an alkylaryl polyether alcohol; isotridecyl alcohol; fatty alcohol/ethylene oxide condensates; ethoxylated castor oil; polyoxyethylene alkyl ether or polyoxypropylene alkyl ether; lauryl alcohol polyglycol ether acetate; sorbitol esters; lignin sulfite waste liquor and proteins; denatured proteins, polysaccharides (e.g., methylcellulose); hydrophobically modified starch; and polyvinyl alcohols, polycarboxylates, polyalkoxylates, polyvinylamines, polyethyleneimines, polyvinylpyrrolidone and copolymers thereof.

Exemplary thickening agents include, but are not limited to, polysaccharides (e.g., xanthan gum), organic and inorganic plate-like minerals, and mixtures thereof.

Exemplary defoamers include, but are not limited to, silicone emulsions, long chain alcohols, fatty acids, fatty acid salts, organofluorine compounds, and mixtures thereof.

Exemplary antimicrobial agents include, but are not limited to, germicides based on dichlorophene and benzyl alcohol hemiformal; isothiazolinone derivatives such as alkylisothiazolinone and benzisothiazolinone; and mixtures thereof.

Exemplary anti-freeze agents include, but are not limited to, ethylene glycol, propylene glycol, urea, glycerol, and mixtures thereof.

Exemplary colorants include, but are not limited to, known dyes known under the name rhodamine B, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108, and mixtures thereof.

Exemplary binders include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof.

3.Carrier

In some aspects, the additive comprises a carrier. In some aspects, the additive comprises a liquid or solid carrier. In some aspects, the additive comprises an organic or inorganic carrier. Exemplary liquid carriers include, but are not limited to: water; petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oil, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc.; esters of the above vegetable oils and the like; esters of monohydric or dihydric alcohols, trihydric or other lower polyhydric alcohols (containing 4 to 6 hydroxyl groups) such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, dibutyl adipate, dioctyl phthalate, etc.; esters of mono-, di-, and polycarboxylic acids, and the like; toluene; xylene; petroleum jelly; a crop oil; acetone; methyl ethyl ketone; cyclohexanone; trichloroethylene; perchloroethylene; ethyl acetate; amyl acetate; butyl acetate; propylene glycol monomethyl ether and diethylene glycol monomethyl ether; methanol; ethanol; isopropyl alcohol; amyl alcohol; ethylene glycol; propylene glycol; glycerol; n-methyl-2-pyrrolidone; n, N-dimethyl alkyl amide; dimethyl sulfoxide; and liquid fertilizers, and mixtures thereof. Exemplary solid supports include, but are not limited to: silica, silica gel, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium oxide, ground synthetic materials, pyrophyllite clay, attapulgite clay, dunaliella, calcium carbonate, bentonite, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, cereal flour, bark flour, wood flour and nut shell flour, cellulose flour, and mixtures thereof.

B.Physical state

In some aspects, the formulations of (a) the carboxypyridine herbicide, or agriculturally acceptable N-oxide, salt or ester thereof, and (b) the carboxyazole safener, or agriculturally acceptable salt or ester thereof, can be present in suspended, emulsified, dissolved or solid form. Exemplary formulations include, but are not limited to, aqueous solutions, aqueous suspensions, aqueous dispersions, aqueous emulsions, aqueous microemulsions, aqueous suspoemulsions, oil solutions, oil suspensions, oil dispersions, oil emulsions, oil microemulsions, oil suspoemulsions, self-emulsifying formulations, pastes, powders, dusts, granules, and materials for spreading.

In some aspects, (a) the carboxypyridine herbicide, or agriculturally acceptable N-oxide, salt or ester thereof, or (b) the ribavirin safener, or agriculturally acceptable salt or ester thereof, is an aqueous solution that can be diluted prior to use. In various aspects, (a) or (b) is provided in a high strength formulation, such as a concentrate. In some aspects, the concentrate is stable and maintains efficacy during storage and transport. In various aspects, the concentrate is a clear, homogeneous liquid that is stable at a temperature of 54 ℃ or greater. In some aspects, the concentrate does not exhibit any precipitation of solids at temperatures of-10 ℃ or higher. In some aspects, the concentrate does not exhibit separation, precipitation, or crystallization of any of the components at low temperatures. For example, the concentrate maintains a clear solution at a temperature below 0 ℃ (e.g., below-5 ℃, below-10 ℃, below-15 ℃). In some aspects, the concentrate exhibits a viscosity of less than 50 centipoise (50 megapascals), even at temperatures as low as 5 ℃. In some aspects, the concentrate does not exhibit separation, precipitation, or crystallization of any component during storage for 2 weeks or more (e.g., 4 weeks, 6 weeks, 8 weeks, 3 months, 6 months, 9 months, or 12 months or more).

In some aspects, the emulsion, paste or oil dispersion may be prepared by homogenizing (a) and (b) in water using a wetting agent, tackifier, dispersant or emulsifier. In some aspects, a concentrate suitable for dilution with water may be prepared comprising (a), (b), a wetting agent, a viscosity increasing agent, and a dispersing or emulsifying agent.

In some aspects, a powder, material for dispersion, or dust may be prepared by mixing or concomitantly grinding (a) and (b), and optionally other additives, with a solid carrier.

In some aspects, particles (e.g., coated particles, impregnated particles, and homogeneous particles) can be prepared by combining (a) and (b) with a solid carrier.

In some aspects, the formulation comprises 1% to 99% of (a) and 1% to 99% of (b) (e.g., 95% of (a) and 5% of (b); 70% of (a) and 30% of (b); or 30% of (a) and 70% of (b)), by total weight of (a) and (b)). In formulations designed for use as concentrates, the total amount of (a) and (b) may be present in a concentration of about 0.1 to about 98 weight percent (wt.%) based on the total weight of the formulation. For example, the total amount of (a) and (b) can be present in a concentration of low to about 1 wt.%, about 2.5 wt.%, about 5 wt.%, about 7.5 wt.%, about 10 wt.%, about 15 wt.%, about 20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, about 40 wt.%, about 45 wt.%, high to about 50 wt.%, about 55 wt.%, about 60 wt.%, about 65 wt.%, about 70 wt.%, about 75 wt.%, about 80 wt.%, about 85 wt.%, about 90 wt.%, about 95 wt.%, about 97 wt.%, or within any range defined between two of the aforementioned values, e.g., about 1 wt.% to about 97 wt.%, about 10 wt.% to about 90 wt.%, about 20 wt.% to about 45 wt.%, and about 25 wt.% to about 50 wt.%, based on the total weight of the formulation. The concentrate may be diluted with an inert carrier, such as water, prior to application. The diluted formulation applied to the undesired vegetation or the locus of the undesired vegetation may contain 0.0006 to 8.0 wt.% (e.g., 0.001-5.0 wt.%) of the total amount of (a) and (b), based on the total weight of the diluted formulation.

C.Package (I)

In some aspects, the formulation may be in the form of a single packaged formulation, which includes both: (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt or ester thereof; and (b) a carboxylic acid azole safener or an agriculturally acceptable salt or ester thereof. In some aspects, the formulation may be in the form of a single-package formulation comprising both (a) and (b) and further comprising at least one additive. In some aspects, the formulation may be in the form of a multi-pack formulation, for example a two-pack formulation, wherein one pack contains (a) and optionally at least one additive, and the other pack contains (b) and optionally at least one additive. In some aspects of the two packaged formulations, the formulation comprising (a) and optionally at least one additive and the formulation comprising (b) and optionally at least one additive are mixed prior to administration and then administered simultaneously. In some aspects, the mixing is performed in a tank mix (e.g., mixing the formulation immediately before or after dilution with water). In some aspects, the formulation comprising (a) and the formulation comprising (b) are not mixed but are administered sequentially (continuously) with each other, e.g., immediately or within 1 hour, within 2 hours, within 4 hours, within 8 hours, within 16 hours, within 24 hours, within 2 days, or within 3 days.

VI.Application method

The compositions disclosed herein may be applied in any known technique for applying herbicides. Exemplary application techniques include, but are not limited to, spraying, atomizing, dusting, scattering, or direct application into water. The method of application may vary depending on the intended purpose. In some aspects, the method of administration may be selected to ensure the best possible distribution of the compositions disclosed herein.

In some aspects, disclosed herein is a method of controlling undesirable vegetation comprising contacting the vegetation or the locus thereof with or applying to soil or water to prevent the emergence or growth of vegetation any of the compositions disclosed herein.

The compositions disclosed herein can be applied pre-emergence (before emergence of the undesirable vegetation) or post-emergence (e.g., during and/or after emergence of the undesirable vegetation). In some aspects, the composition is applied post-emergence to undesirable vegetation. In some aspects, the picolinate herbicide and the carboxyazole safener are applied simultaneously. In some aspects, the carboxypyridine herbicide and the carboxypyridine safener are applied sequentially, e.g., immediately or with minimal delay, within about 10 minutes, within about 20 minutes, within about 30 minutes, within about 40 minutes, within about 1 hour, within about 2 hours, within about 4 hours, within about 8 hours, within about 16 hours, within about 24 hours, within about 2 days, or within about 3 days of each other.

In some aspects, the picolinate herbicide may be applied to the undesirable vegetation pre-or post-emergence, and the fentrazole safener may be applied to the crop seed as a seed treatment. When used as seed treatment, the application rate of the safener of carboxylic acid azoles is 0.01 to 10g ai safener per kg crop seed (g ai/kg), preferably 0.05 to 1g ai/kg crop seed, in particular 0.1 to 0.5g ai/kg crop seed. If the seed is treated with a solution of the safener, the concentration of the safener in the solution is, for example, 1 to 10000ppm, preferably 100 to 1000ppm, based on weight.

When these compositions are used in crops, they can be applied after sowing and before or after the emergence of the crop plants. In some aspects, the compositions disclosed herein exhibit good crop tolerance even when the crop has emerged, and can be applied during or after the crop plant emerges. In some aspects, when these compositions are used in crops, they may be applied prior to sowing of the crop plants.

In some aspects, the compositions disclosed herein are applied to the vegetation or an area near the vegetation, or to soil or water, by spraying (e.g., foliar spraying) to prevent the emergence or growth of vegetation. In some aspects, the spray technique uses, for example, water as a carrier and the ratio of spray volumes is from 2 liters per hectare (L/ha) to 2000L/ha (e.g., 10-1000L/ha or 50-500L/ha). In some aspects, the compositions disclosed herein are administered by a low volume or ultra low volume method, wherein the administration is in the form of microparticles. In some aspects, where certain crop plants are less tolerant to the compositions disclosed herein, the compositions can be applied with the aid of a spray device in such a way that they are barely in contact with the foliage of sensitive crop plants (if any) while reaching the foliage of undesirable vegetation growing on the bottom or bare soil (e.g., post-orientation or back-up). In some aspects, the compositions disclosed herein can be applied as a dry formulation (e.g., granules, powder, or dust).

In some aspects, wherein the undesirable vegetation is post-emergence treated, the compositions disclosed herein are applied by foliar application. In some aspects, the compounds of the mixture exhibit herbicidal activity when applied to plants or the locus of plants directly at any stage of growth or prior to planting or emergence. The observed effect may depend on the type of undesirable vegetation to be controlled, the stage of growth of the undesirable vegetation, the application parameters of dilution and spray droplet size, the particle size of the solid components, the environmental conditions at the time of use, the particular compound used, the particular adjuvant and carrier used, the type of soil, etc., and the amount of chemical applied. In some aspects, these and other factors can be adjusted to promote non-selective or selective herbicidal action.

The compositions and methods disclosed herein can be used to control undesirable vegetation in a variety of applications. The compositions and methods disclosed herein can be used to control undesirable vegetation in areas including, but not limited to, farmlands, turfgrass, rangelands, grasslands, rangelands, fallowland, wayside, aquatic environments, trees and vines, wildlife management areas, or rangelands. In some aspects, undesirable vegetation is controlled in cultivated crops. Exemplary crops include, but are not limited to, wheat, barley, triticale, rye, bran, oats, maize, cotton, soybean, sorghum, rice, millet, sugar cane, and grasslands (e.g., pasture grasses). In some aspects, the compositions and methods disclosed herein can be used to control undesirable vegetation in maize, wheat, barley, rice, sorghum, millet, or oats, or a combination thereof. In some aspects, the compositions and methods disclosed herein can be used to control undesirable vegetation in broadleaf crops. In some aspects, the compositions and methods disclosed herein can be used to control undesirable vegetation in canola, flax, sunflower, soybean or cotton. In some aspects, the compositions and methods disclosed herein can be used for Industrial Vegetation Management (IVM) or for utility, pipeline, wayside, and railroad wayside applications. In some aspects, the compositions and methods disclosed herein can also be used in forestry (e.g., for field preparation or for combating undesirable vegetation in an artificial forest). In some aspects, the compositions and methods disclosed herein can be used to control undesirable vegetation in nursery planning lands (CRPs), trees, vines, grasslands, and planting grasses (grasses growing for seeds). In some aspects, the compositions and methods disclosed herein can be used on lawns (e.g., residential, industrial, and institutional), golf courses, parks, cemeteries, sports fields, and turf farms.

The compositions and methods disclosed herein may also be used in crop plants that are resistant to, for example, herbicides, pathogens, and/or insects. In some aspects, the compositions and methods disclosed herein can be used in crops that are resistant to one or more herbicides due to genetic engineering or breeding. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more pathogens, such as phytopathogenic fungi, due to genetic engineering or breeding. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to insect infestation due to genetic engineering or breeding. Exemplary resistant crops include, but are not limited to, crops that are resistant to photosystem II inhibitors, or crop plants that are resistant to certain insects due to the introduction of bacillus thuringiensis (or Bt) toxin genes by genetic modification. In some aspects, the compositions and methods described herein may be used in combination with glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, acetyl-coa carboxylase (ACCase) inhibitors, imidazolinones, acetolactate synthase (ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, and bromoxynil to control vegetation in crops tolerant to glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, bromoxynil, or combinations thereof. In some aspects, undesirable vegetation is controlled in crops that are tolerant to glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil, the crops having a single trait, multiple traits, or additive traits that confer tolerance to single or multiple chemicals and/or multiple modes of action. In some aspects, undesirable vegetation may be controlled in a crop of ACCase tolerance, ALS tolerance, or a combination thereof. (a) The combination of (a) and (b) may be used in combination with one or more herbicides which are selective for the crop being treated and which complement the range of weeds controlled by these compounds at the application rates used. In some aspects, the compositions described herein and other complementary herbicides are applied simultaneously in a combined formulation or in a tank mix or in a sequential application format. The compositions and methods are useful for controlling undesirable vegetation in crops having agronomic stress tolerance (including but not limited to drought, cold, high temperature, salt, water, nutrients, fertility, pH), pest tolerance (including but not limited to insects, fungi, and pathogens), and crop improvement traits (including but not limited to yield; protein, carbohydrate or oil content; protein, carbohydrate or oil composition; plant height and plant configuration).

In some aspects, the compositions disclosed herein can be used to control undesirable vegetation, including grasses, broadleaf weeds, sedges, and combinations thereof. In some aspects, the compositions disclosed herein may be used to control undesirable vegetation, including, but not limited to, Polygonum species (Polygonum species), Amaranthus species (Amaranthus species), Chenopodium species (Chenopodium species), Sida species (Sida species), Ambrosia species (Ambrosia species), Cyperus species (Cyperus species), Setaria species (Setaria species), Sorghum species (Sorgum species), Acanthopanax species (Acanthopanax species), Anthemis species (Anthemis species), Atriplex species (Atridia species), Brassica species (Brassica species), Cirsium species (Cirsum species), Convolvulus species (Coccinum species), Eupatorium species (Costus), Eupatorium species (Gessica species), Salix species (Costus species), Periploca species (Costus species), Moraceae species (Costus species), Eupatorium species (Gessica species), Gemma species (Costus species), Gessima species (Gessima species), Echinus species (Gessima species), Gessima species (Gessima species), Echinaceae species (Gernia species), Gernia species (Gernica species), Gernica species (Gernica species), Gernia species), Gernica species (Gernica species), Gernica species, Gernia species, Gernica species, Gernia species, Gernica, Gernia, Gernica, Gernia, Gernica, Gernia, Gernica, Geranium, Gernica, Gernia, Gernica, Gernia, Geranium, Gernia, Geranium, Gernica, Geranium, ipomoea species (Ipomoea species), episesaria species (Lamium species), Lolium species (Lolium species), Malva species (Malva species), Matricaria species (Matricaria species), Mucuna species (Prosopis species), Rumex species (Rumex species), Allium species (Sisymbrium species), Solanum species (Solanum species), Trifolium species (Trifolium species), Xanthium species (Xanthium species), Veronica species (Veronica species), and Viola species (Viola species). In some aspects, undesirable vegetation includes common curly fungus (Stellaria media), velveteen (Abutilon theophrasti), pelargonium majus (Sesbania exaltata Cory), mallow coronaria (Andoa cristata), Bidens pilosa (Bidens piposa), Kaberella Brassica (Brassica kaber), Capsella bursa-pastoris (Capsella bursa-toras), cornflower (Centaurella grisea) or Centaurella blue (Cyanus segetum), yellow weasel flower (Galeopsis tequilensis), cleaver serpylis (Galium aparine), common sunflower (Helianthus annuus), Japanese rockfoil (Desmodium), Lolium peregrina (Lorantia), Lolium perennis (Lonicera), Lolium purpurea japonica (Lorentz), Lolium purpurea japonica (Lolium purpurea sinensis (L), Lolium purpurea japonica (Lolium purpurea fruticosa (Lolium (L) (Lorentz), Lolium purpurea sinensis (L.) and Lolium purpurea sinensis (L), Lolium purpurea sinensis (L), Lolium purpurea sinensis (L) Wild mustard (Raphanus raphanium), broadleaf dock (broadleaf-leaf dock) (Rumex obtusifolius), Russian thistle (Salsola kali)), wild mustard (Sinkia wild rape (Sinapis arvensis)), endive (Sonchus arvensis), Thlaspi arvense (Thlaspi arvense), Tagetes (Tagetes minuta), Royal rufa (Richardia fasciata (Richardtia brasiliensis), Plantago major (Plantago major), Plantago major (Plantago lancifera), Orthosiphon (Arabian wia), Veronica (Veronica), Swine (Amaranthus retroflexus), rape (Brassica rapa), Brassica campestris (Brassica oleracea), Brassica oleracea (Brassica) and Brassica oleracea (Brassica oleracea), Brassica oleracea (L) and (L) or Brassica oleracea (L) and (L) or L Wild chamomile (german chamomile (Matricaria chamomilla)), pseudo chamomile (chamomilla recutita), chamomile (chamomilla), common buckwheat (buckwheat), wild buckwheat (Polygonum convolvulus), oryza sativa (Setaria faraci), Setaria viridis (Setaria viridis), common Sorghum (Sorghum vulgare)), wild pansy (Viola tricolor), or a combination thereof.

The compositions described herein are useful for controlling herbicide resistant or tolerant weeds. Methods employing the compositions described herein can also be used to control herbicide resistant or tolerant weeds. Exemplary resistant or tolerant weeds include, but are not limited to, acetolactate synthase (ALS) or acetohydroxyacid synthase (AHAS) inhibitors (e.g., imidazolinones, sulfonylureas, pyrimidylthiobenzoates, triazolopyrimidines, sulfonylaminocarbonyltriazolinones), photosystem II inhibitors (e.g., phenylcarbamates, pyridazinones, triazines, triazinones, uracils, amides, ureas, benzothiadiazinones, nitriles, phenylpyridazines), acetyl-coa carboxylase (ACCase) inhibitors (e.g., aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazoline), synthetic auxins (e.g., benzoic acid, phenoxycarboxylic acid, pyridinecarboxylic acid, quinolinecarboxylic acid), auxin transport inhibitors (e.g., phthalates, hemicarbazolones), photosystem I inhibitors (e.g., bipyridinium), 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors (e.g., glyphosate), glutamine synthetase inhibitors (e.g., glufosinate, bialaphos), microtubule assembly inhibitors (e.g., benzamide, benzoic acid, dinitroaniline, phosphoramidate, pyridine), mitosis inhibitors (e.g., carbamate), Very Long Chain Fatty Acid (VLCFA) inhibitors (e.g., acetamide, chloroacetamide, oxyacetamide, tetrazolinone), fatty acid and lipid synthesis inhibitors (e.g., dithiophosphate, thiocarbamate, benzofuran, chlorocarbonate), protoporphyrinogen oxidase (PPO) inhibitors (e.g., diphenyl ether, N-phenylphthalimide, oxadiazole, oxazolidinedione, phenylpyrazole, pyrimidinedione, thiadiazole, triazolinone), carotenoid biosynthesis inhibitors (e.g., isoxaflutole, furazolidone), and the like, Phytoene Dehydrogenase (PDS) inhibitors (e.g., amides, anilines (anilidex), furanones, phenoxybutanamides, pyridazinones (pyridiazinones), pyridine), 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors (e.g., cajeput (calilstemones), isoxazoles, pyrazoles, triones), cellulose biosynthesis inhibitors (e.g., nitriles, benzamides, quinclorac, triazolocarboxamides), herbicides with multiple modes of action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothecium, and biotypes resistant or tolerant to organic arsenic. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes with or tolerant to multiple herbicides, biotypes with or tolerant to multiple chemical classes, biotypes with or tolerant to multiple herbicide modes-of-action, and biotypes with multiple resistance or tolerance mechanisms (e.g., targeted site resistance or metabolic resistance).

By way of non-limiting illustration, examples of some aspects of the disclosure are given below. Parts and percentages are by weight unless otherwise indicated.

Examples of the invention

Greenhouse test method-evaluation of post-emergence herbicidal safety in crops

At a surface area of 103.2 square centimeters (cm)²) In a plastic pot of (2), seeds of the desired test plant species are planted at 90% to 10% v/v (volume/volume)BX (Premier Tech Horticulture), Quakertown, Pa., USA) andGREENS GRADE^TM(Profil Products LLC, Buffalo Grove, Ill.) planting a mixture of mixes that typically has a pH of 5.2 to 6.2 and an organic content of at least 50%. When it is desired to ensure good germination and healthy plants, fungicide treatments and/or other chemical or physical treatments are applied. Plants were grown in the greenhouse for 7-36 days (d), with a photoperiod of about 14 hours (h), maintained at about 23 ℃ during the day and 22 ℃ at night. Nutrients and water were added periodically and supplemental lighting was provided using an overhead metal halide 1000 watt lamp if necessary. When the plant reached the second or third true leaf stage, it was used for testing.

Emulsifiable concentrates of each of the pyridine carboxylate herbicides (compound a or compound B) were prepared at 100 grams acid equivalent per liter (g ae/L). An aliquot of each emulsifiable concentrate was placed into a 25mL glass vial and mixed with 1.25% (v/v)Esterified rapeseed oil (Bayer Crop Science, Research Triangle Park, North Carolina, USA) orConcentrates andan aqueous mixture of methylated soybean oil (Loveland Products, Loveland, colorado, usa) was diluted at a rate of 187 liters per hectare (L/ha) based on 12 milliliters (mL) of application volume to obtain a concentrated stock solution at the highest application rate for each herbicide. The concentrated stock solution was used at 1.25% v/vB orConcentrates andfurther diluted to obtain a stock solution of low application rate of each herbicide. A spray solution of the herbicide combination (compound a or compound B plus safener) is prepared by adding a weighed or aliquot of the fentrazole-carboxylate safener to a stock solution of compound a or compound B to form a binary combined 12-mL spray solution.

The spray solution was applied to the plant material using an overhead Mandel track sprayer equipped with an 8002E nozzle calibrated to 0.503 square meters (m)²) Delivered 187L/ha at a spray height 18 inches (43 centimeters (cm)) above the average plant canopy. Control plants were sprayed with solvent blank in the same manner. All herbicide (component a) application rates are given in "g ae/ha" and all safener (component b) application rates are given in "g ai/ha".

The treated and control plants were placed in a greenhouse as described above and watered by sub-irrigation to prevent the test compounds from being washed away. After 20-22 days, the condition of the test plants compared to the condition of the control plants was determined visually and scored on a scale of 0 to 100%, where 0 corresponds to no damage and 100 corresponds to complete kill.

The safety compositions and crops tested are detailed in the examples below.

Example 1

Safe compositions comprising cloquintocet-mexyl and compound a were also tested on spring wheat (trza) and spring barley (HORVS) and the phytotoxicity of the safe compositions was measured for each crop. In addition, the efficacy of the safe compositions was measured on undesirable vegetation including winter rape (BRSNW, brassica napus), wild chamomile (MATCH, chamomile, germany), and russian thistle (SASKR, suaeda salsa).

The results are summarized in table 1 below.

Table 1. safety of the effect (% visual damage) of mefenpyr ethyl ester and compound a on cereals and weeds.

g/ha-g/ha

TRZAS common wheat (spring wheat)

Horvs ═ barley (spring barley)

BRSNW as rape (winter rape)

MATCH ═ German chamomile (wild chamomile)

SASKR ═ spiny awning (russian thistle)

Example 2

Safe compositions comprising diethyl pyrazolinoxate and compound a were also tested on spring barley (HORVS), spring wheat (TRZAS) and winter wheat (TRZAW) and the phytotoxicity of the safe compositions was measured for each crop.

The results are summarized in table 2 below.

Table 2 safety of the effect (% visual damage) of mefenpyr and compound a on cereal crops.

g/ha-g/ha

Horvs ═ barley (spring barley)

TRZAS common wheat (spring wheat)

TRZAW common wheat (winter wheat)

Example 3

A safe composition comprising diethyl pyrazolecarboxylate and compound a was also tested on spring wheat (TRZAS) and the phytotoxicity of the safe composition on the crop was measured. In addition, the efficacy of the safe composition was measured on undesirable vegetation including pigweed (AMARE, amaranth), Cyperus rotundus (CYPES, Cyperus esculentus), and common sunflower (HELAN, sunflower).

The results are summarized in table 3 below.

TABLE 3 safety of Effect (% visual impairment) of Pyrazolidineacetic acid diethyl ester and Compound A on cereals and weeds And (4) sex.

g/ha-g/ha

TRZAS common wheat (spring wheat)

Amare ═ Amaranthus retroflexus (pig grass)

CYPES ═ cyperus (cyperus rotundus)

Helan sunflower (common sunflower)

Example 4

Safe compositions comprising diethyl pyrazolinoxate and compound a were also tested on spring wheat (trza) and spring barley (HORVS) and the phytotoxicity of the safe compositions was measured for each crop. Furthermore, the efficacy of the safe composition was measured on undesirable vegetation including wild chamomile (MATCH, german chamomile) and russian thistle (SASKR, suaeda salsa).

The results are summarized in table 4 below.

TABLE 4 neutralization of mezlazole diethyl oxalateSafening of the Effect (% visual impairment) of Compound A on cereal crops and weeds And (4) sex.

g/ha-g/ha

TRZAS common wheat (spring wheat)

Horvs ═ barley (spring barley)

MATCH ═ German chamomile (wild chamomile)

SASKR ═ spiny awning (russian thistle)

Example 5

A safe composition comprising diethyl pyrazololate and compound a was also tested on maize (ZEAMX) and the phytotoxicity of the safe composition on this crop was measured. In addition, the efficacy of the safe composition was measured on undesirable vegetation including pigweed (AMARE, amaranth), Cyperus rotundus (CYPES, Cyperus esculentus), and common sunflower (HELAN, sunflower).

The results are summarized in table 5.

TABLE 5 Effect (% visual impairment) of Pyrazolidineacetic acid diethyl ester and Compound A on maize and weedsHarmful) in the environment.

g/ha-g/ha

ZEAMX corn (maize)

Amare ═ Amaranthus retroflexus (pig grass)

CYPES ═ cyperus (cyperus rotundus)

Helan sunflower (common sunflower)

Example 6

A safe composition comprising cloquintocet-mexyl and compound a was also tested on winter wheat (TRZAW), rice (ORYSA) and maize (ZEAMX), and the phytotoxicity of the safe composition on the crop was measured. Furthermore, the efficacy of the safety composition was measured on undesirable vegetation including chorionic villi leaves (ABUTH, abutilon), black grass (ALOMY, alopecurus, pigweed (AMARE, amaranthus retroflexus), wild oats (AVEFA, wild oats), winter rape (BRSNW, brassica napus), common grey vegetables (CHEAL, chenopodium album), canada thistle (CIRAR, field thistle), Cyperus rotundus (CYPES, Cyperus rotundus), large crab grass (DIGSA, crab grass), barnyard grass (ECHCG, cockspur grass), canada bur (ERICA, micropropagoda), soybean (GLXMA, sculpox), common sunflower (hela, sunflower), hedyotis perennialis (ipe, morning glory), schizophyllan, kochia (kchoides), kochia scoparia japonica (kchoi-R), herbicide-resistant kochia scoparia (hsc-R, broom), lewishlia (leya, lolium rosewort), wild ryegrass (lco), lolium (lco, italica (lco), polygonum convolvulus), oryza sativa (SETFA, setaria viridis), jamesona (SORHA, lemongrass), and wild pansy (VIOTR, pansy).

The results are summarized in table 6 below.

Table 6. safety of the effect (% visual impairment) of fenchlorazole and compound a on crops and weeds.

g/ha-g/ha

TRZAW common wheat (winter wheat)

ORYSA ═ rice (ordinary rice)

ZEAMX corn (maize)

ABUTH ═ abutilon (velveteen leaf)

ALOMY ═ big ear straw chopper (black grass)

Amare ═ Amaranthus retroflexus (pig grass)

AVEFA ═ wild oat (wild oat)

BRSNW as rape (winter rape)

CHEAL ═ Chen (common lima vegetable)

CIRAR ═ field thistle (jiana thistle)

CYPES ═ cyperus (cyperus rotundus)

DIGSA ═ Tang (large Tang grass)

ECHCG Betula platyphylla (barnyard grass)

ERICA ═ small grass (canadian chazu grass)

GLXMA ═ scull bean (soybean)

Helan sunflower (common sunflower)

Ipot ═ schizophyllum pharbitidis (ivy leaf pharbitidis flower)

KCHSC-broom (Kochia scoparia)

KCHSC-R ═ Kochia (herbicide resistant Kochia)

LEFCH ═ stephania root (chinese stephania root)

Lolmu-lolium multiflorum (Italy ryegrass)

POLCO (wild buckwheat)

Seta ta (millet weed)

SORHA ═ Shimao (Jansen grass)

VIOTR (pansy wild)

Example 7

A safe composition comprising diethyl pyrazololate and compound a was also tested on winter wheat (TRZAW), rice (ORYSA) and maize (ZEAMX), and the phytotoxicity of the safe composition on the crop was measured. Furthermore, the efficacy of the safety composition was measured on undesirable vegetation including chorionic villi leaves (ABUTH, abutilon), black grass (ALOMY, alopecurus, pigweed (AMARE, amaranthus retroflexus), wild oats (AVEFA, wild oats), winter rape (BRSNW, brassica napus), common grey vegetables (CHEAL, chenopodium album), canada thistle (CIRAR, field thistle), Cyperus rotundus (CYPES, Cyperus rotundus), large crab grass (DIGSA, crab grass), barnyard grass (ECHCG, cockspur grass), canada bur (ERICA, micropropagoda), soybean (GLXMA, sculpox), common sunflower (hela, sunflower), hedyotis perennialis (ipe, morning glory), schizophyllan, kochia (kchoides), kochia scoparia japonica (kchoi-R), herbicide-resistant kochia scoparia (hsc-R, broom), lewishlia (leya, lolium rosewort), wild ryegrass (lco), lolium (lco, italica (lco), polygonum convolvulus), oryza sativa (SETFA, setaria viridis), jamesona (SORHA, lemongrass), and wild pansy (VIOTR, pansy).

The results are summarized in table 7 below.

Table 7. safety of effect (% visual damage) of mezlocinolytic diethyl oxalate and compound a on crops and weeds.

g/ha-g/ha

TRZAW common wheat (winter wheat)

ORYSA ═ rice (ordinary rice)

ZEAMX corn (maize)

ABUTH ═ abutilon (velveteen leaf)

ALOMY ═ big ear straw chopper (black grass)

Amare ═ Amaranthus retroflexus (pig grass)

AVEFA ═ wild oat (wild oat)

BRSNW as rape (winter rape)

CHEAL ═ Chen (common lima vegetable)

CIRAR ═ field thistle (jiana thistle)

CYPES ═ cyperus (cyperus rotundus)

DIGSA ═ Tang (large Tang grass)

ECHCG Betula platyphylla (barnyard grass)

ERICA ═ small grass (canadian chazu grass)

GLXMA ═ scull bean (soybean)

Helan sunflower (common sunflower)

Ipot ═ schizophyllum pharbitidis (ivy leaf pharbitidis flower)

KCHSC-broom (Kochia scoparia)

KCHSC-R ═ Kochia (herbicide resistant Kochia)

LEFCH ═ stephania root (chinese stephania root)

Lolmu-lolium multiflorum (Italy ryegrass)

POLCO (wild buckwheat)

Seta ta (millet weed)

SORHA ═ Shimao (Jansen grass)

VIOTR (pansy wild)

The compositions and methods of the appended claims are not to be limited in scope by the specific compositions and methods described herein, which are intended as illustrations of several aspects of the claims, and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of the compositions and method steps are intended to fall within the scope of the appended claims even if not specifically recited. Thus, a combination of steps, elements, components, or ingredients may be specifically referred to herein; however, other combinations of steps, elements, components, and ingredients are included, even if not explicitly stated. As used herein, the term "comprising" and variations thereof is used synonymously with the term "including" and variations thereof, and is an open, non-limiting term. Although the terms "comprising" and "including" have been used herein to describe various aspects, the terms "consisting essentially of … …" and "consisting of … …" may also be used in place of "comprising" and "including" to provide more specific aspects of the invention and are also disclosed. Other than in the examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in light of the number of significant digits and ordinary rounding techniques and are not intended to limit application of the doctrine of equivalents to the scope of the claims.