阅读说明：本技术 包含羧酸吡啶除草剂和喹氧乙酸的安全组合物 (Safe compositions comprising a pyridine carboxylate herbicide and quinoxyacetic acid ) 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：本文公开了安全组合物,所述安全组合物包含(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)喹啉氧基乙酸酯安全剂或其农业上可接受的盐或酯。本文还公开了控制不希望的植被的方法,所述方法包括将(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)喹啉氧基乙酸酯安全剂或其农业上可接受的盐或酯施用至植被或与所述植被相邻的区域或施用至土壤或水中以控制植被的出苗或生长。(Disclosed herein are safe compositions comprising (a) a pyridine carboxylate herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a quinolinyloxyacetate 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 pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof.)

1. A safe composition comprising:

(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 comprising quindox or an agriculturally acceptable salt or ester thereof.

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

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

4. the composition of any one of claims 1-3, wherein the safener comprises an agriculturally acceptable ester of quinoxyacetic acid.

5. The composition of claim 4, wherein the agriculturally acceptable ester of quinoxyacetic acid is selected from the group consisting of: methyl, ethyl, and methyl hexyl esters of quinatidyl acetate, and combinations thereof.

6. The composition of any one of claims 1-3, wherein the safener comprises an agriculturally acceptable salt of quinoxyacetic acid.

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

8. The composition of any one of claims 1-7, wherein the weight ratio of the picolinate herbicide (in g ae/ha) to safener (in g ai/ha) is from about 1:5 to about 65: 1.

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

10. A composition as claimed in any one of claims 1 to 9, wherein the composition does not comprise a herbicidally active ingredient other than (a).

11. A method of controlling undesirable vegetation in crops comprising applying a security composition to vegetation or an area adjacent the vegetation or 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 safener comprising quindox 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 safener is applied in an amount of at least 1g ai/ha.

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

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

14. the method of any one of claims 11-13, wherein the herbicide and the safener are applied simultaneously.

15. The method of any one of claims 11-14, wherein the safener comprises an agriculturally acceptable ester of quinoxyacetic acid.

16. The method of claim 15, wherein the agriculturally acceptable ester of quinoxyacetic acid is selected from the group consisting of: methyl, ethyl, and methyl hexyl esters of quinatidyl acetate, and combinations thereof.

17. The method of any one of claims 11-16, wherein the safener comprises an agriculturally acceptable salt of quinoxyacetic acid.

18. The method of claim 15, wherein the agriculturally acceptable salt of quinoxyacetic acid is selected from the group consisting of: sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropoxyammonium, triisopropanolammonium, choline, N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium and isopropylammonium salts of quindox acid, and combinations thereof.

19. A method as claimed in any one of claims 11 to 18, wherein the herbicide is provided in an amount of from 1g ae/ha to 300g ae/ha.

20. The method of any one of claims 11-19, wherein the weight ratio of the pyridine carboxylate herbicide (in g ae/ha) to the safener (in g ai/ha) is from about 1:5 to about 65: 1.

21. The method of any one of claims 11-20, wherein the pyridine carboxylate herbicide is applied to the undesirable vegetation pre-or post-emergence and the safener is applied to the crop as a seed treatment.

22. The method of any one of claims 11-21, further comprising applying an additional pesticide.

23. A method as claimed in any one of claims 11 to 22, wherein the composition does not comprise a herbicidally active ingredient other than (a).

Technical Field

The present disclosure includes a secured composition comprising a pyridine carboxylate herbicide and a safener, quindox, and methods of controlling undesirable vegetation using the secured composition.

Background

Many recurring problems in agriculture relate to controlling the growth of undesirable vegetation (e.g., which may adversely 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, they can also have phytotoxic effects on and cause damage to, or even kill, crops. Thus, there is a need for new herbicides in combination with safeners, which limit the phytotoxicity of the herbicidal active ingredients to the desired crop.

Disclosure of Invention

Disclosed herein are safe compositions that can be used as herbicides, for example, in crops. The safened composition can comprise (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener, quinoxyacetic acid or an agriculturally acceptable salt or ester thereof. (a) The weight ratio of (a) to (b) can be 1:5 to 65:1 (e.g., 1:5 to 5:1, or 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 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 group、C₁-C₃Alkoxy, or C₁-C₃A haloalkoxy group;

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

(b) a safener comprising quindox, or an agriculturally acceptable salt or ester thereof.

In some aspects, the safe composition comprises:

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

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

(b) a safener comprising quindox or an agriculturally acceptable salt or ester thereof.

In some aspects, the safe composition comprises:

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

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

(b) a safener comprising quindox or an agriculturally acceptable salt or ester 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).

Also disclosed herein are methods of controlling undesirable vegetation comprising applying a security composition to vegetation, an area adjacent the vegetation, or soil or water to control the emergence or growth of vegetation, the security composition comprising: (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a safener comprising quindox 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 pre-emergence of the undesirable vegetation. In some aspects, (a) and (b) are applied post-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, undesirable vegetation is present in the grain. In some aspects, the undesirable vegetation is found in corn, wheat, barley, rice, sorghum, millet, or oats. In some aspects, undesirable vegetation is present in broadleaf crops. In some aspects, the undesirable vegetation is found 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 quinatil acid (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 65:1 (e.g., 1:5 to 5:1, 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 safe composition comprising: (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinoxy acetate safener, quinoxyacetic acid or an agriculturally acceptable salt or ester thereof. The present disclosure also includes methods for controlling undesirable vegetation. In some aspects, undesirable vegetation is present in the grain. In some aspects, the undesirable vegetation is found in corn, wheat, barley, rice, sorghum, millet, or oats. In some aspects, undesirable vegetation is present in broadleaf crops. In some aspects, the undesirable vegetation is found 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. The present disclosure also contemplates other embodiments that "comprise," "consist of," and "consist essentially of" the embodiments or elements presented herein, whether or not explicitly stated. 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 each substituent 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 undesirable vegetation, or contact with an area adjacent to 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, legumes, 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" may be understood to include having an effect on vegetation; in particular, compounds or compositions having herbicidal or safety effects on vegetation.

As used herein, "acid equivalent" or "ae" can be 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 active ingredient "Z" has a molecular weight of 100 daltons in acid form and 130 daltons in salt form, then applying 130g of ai/ha of the Z salt would be equivalent to applying 100g of ae/ha of the acid form of Z:

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" may be understood to include groups having the formula-C (O) R, wherein "C (O)) "is a shorthand notation of 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-C₆Haloalkenyl), alkynyl (e.g., C)₂-C₆Alkynyl), aryl or heteroaryl, or arylalkyl (e.g., C)₇-C₁₀An arylalkyl group.

As used herein, the term "alkyl" may be understood to include saturated, straight-chain, branched-chain, or cyclic saturated hydrocarbon moieties. Unless otherwise indicated, means C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) An alkyl group. 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-methyl-butyl, 1-methyl-butyl, 2-butyl, or 2-butyl, 2-butyl, 2-butyl, 2-butyl, 2-butyl, 2, 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-C₆Haloalkyl groupSulfonyl radical, C₁-C₆Alkoxycarbonyl group, C₁-C₆Halogenoalkoxycarbonyl, C₁-C₆Carbamoyl radical, C₁-C₆Halocarbamoyl, hydroxycarbonyl, C₁-C₆Alkylcarbonyl group, C₁-C₆Halogenated alkylcarbonyl, aminocarbonyl, C₁-C₆Alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆Dialkylaminocarbonyl, and C₁-C₆Dihaloalkylaminocarbonyl groups, provided that the substituents are sterically compatible and satisfy the rules of chemical bonding and strain energy. Preferred substituents include cyano and C₁-C₆An alkoxy group.

As used herein, the term "haloalkyl" may be understood to include alkyl groups in which hydrogen atoms may be partially or fully substituted with halogen atoms. Unless otherwise indicated, means C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) An alkyl group. 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-C₆Alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆Dialkylaminocarbonyl, and C₁-C₆Dihaloalkylaminocarbonyl groups, provided that the substituents are sterically compatible and satisfy the rules of chemical bonding and strain energy. 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. Unless otherwise indicated, means wherein R is C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Alkoxy groups of alkyl groups. 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. Unless otherwise indicated, means wherein R is C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Alkoxycarbonyl for alkyl. Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methyl-ethoxycarbonyl, butoxycarbonyl, 1-methyl-propoxycarbonyl, 2-methyl-propoxycarbonyl, 1-dimethyl-ethoxycarbonyl, pentoxycarbonyl, 1-methyl-butoxycarbonyl, 2-methyl-butoxycarbonyl, 3-methyl-butoxycarbonyl, 2-dimethyl-propoxycarbonyl, 1-ethyl-propoxycarbonyl, hexoxycarbonyl, 1-dimethyl-propoxycarbonyl, 1, 2-dimethyl-propoxycarbonyl, 1-methyl-pentoxycarbonyl, 2-methyl-pentoxycarbonyl, 3-methyl-pentoxycarbonyl, 4-methyl-pentyloxycarbonyl, 1-dimethyl-butoxycarbonyl, 1, 2-dimethyl-butoxycarbonyl, 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 unsubstituted or substituted haloalkyl as defined above. Unless otherwise indicated, means wherein R is C₁-C₂₀(e.g., C)₁-C₁₂、C₁-C₁₀、C₁-C₈、C₁-C₆Or C₁-C₄) Haloalkoxy of alkyl. 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 comprising 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 groups include, but are not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl, and indanyl. In some aspects, the aryl group can be a phenyl, indanyl, or naphthyl group.

As used herein, the term "heteroaryl" as well as derivative terms such as "heteroaryloxy" can 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. An aryl or heteroaryl substituent may also 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 groups, 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", including derivative terms such as "halo", refers to fluorine, chlorine, bromine and iodine.

As used herein, agriculturally acceptable salts and esters may be understood to include salts and esters that exhibit herbicidal activity, or 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 ], 4 th edition extension and subsequent volumes, volume E7 b, 565 nd and later pages.

II.Carboxylic acid pyridine herbicides

The compositions and methods of the present disclosure comprise a safe composition comprising: (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 comprising quindox or an agriculturally acceptable salt or ester thereof.

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

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

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

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

The carboxylate pyridine herbicides defined by formula (I) and methods of preparing these carboxylate pyridine herbicides are disclosed in application PCT/US 2018/031004 filed on 4.5.2018, the entire disclosure of which is hereby expressly incorporated 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-, di-and tri-C₁-C₈Alkyl ammonium salts, such as methyl ammonium, dimethyl ammonium and isopropyl ammonium; mono-, di-and tri-hydroxy-C₂-C₈Alkyl ammonium salts, such as hydroxyethylammonium, di (hydroxyethyl) ammonium, tri (hydroxyethyl) ammonium, hydroxypropylammonium, di (hydroxypropyl) ammonium and tri (hydroxypropyl) ammonium salts; an ethanolamine salt; a diglycolamine salt; a choline salt; and quaternary ammonium salts, e.g. of the formula R⁹R¹⁰R¹¹R¹²N⁺And wherein R is⁹、R¹⁰、R¹¹And R¹²(e.g., R)⁹-R¹²) Each independently may represent hydrogen or C₁-C₁₀Alkyl radical, C₂-C₈Alkenyl radical, C₂-C₈Alkynyl, C₁-C₈Alkoxy radical, C₁-C₈Alkylthio, or aryl, provided that R is⁹-R¹²Are spatially 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 (methylhexyl), 2-ethylhexyl, heptyl, 1-methyl-heptyl (methylheptyl), octyl, isooctyl (isooctyl), butoxyethyl (butoxyethyl), and benzyl.

A carboxypyridine herbicide, or an 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 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 amounts to prevent the emergence or growth of vegetation: 0.1 gram acid equivalent/hectare (g ae/ha) or more, such as 0.2g ae/ha or more, 0.3g ae/ha or more, 0.4g ae/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, 160g ae/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 more, Or 290g ae/ha or more; 300g ae/ha or less, such as 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, such as 0.1g ae/ha to 300g ae/ha, 1g ae/ha to 150g ae/ha, 10g ae/ha to 200g ae/ha, 25g ae/ha to 75g ae/ha, or 40g ae/ha to 100g ae/ha.

III.Quinoxyacetic acid

In addition to the carboxylate pyridine herbicides, the compositions and methods of the present disclosure may include a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof. Herbicide safeners are molecules used in combination with herbicides to make them "safer" -i.e., to reduce the herbicidal action of the herbicide on the crop plants and to 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 safeners can also be sprayed on the plants in the form of a mixture with the herbicide or separately and sequentially from the herbicide.

Quinolinyloxyacetate safeners are known in the art and are described, for example, in U.S. patent No. 4,902,340 and U.S. patent application publication No. 2014/0031224, the disclosures of which are both incorporated herein by reference. Quinolinyloxyacetate safeners include, for example, quinatoacetic acid and its derivatives. Quinatoacetic acid is a quinoline compound having the following chemical structure:

this form of quetiapine acid may also be referred to as "free quetiapine acid".

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

In some aspects, the safener can include an agriculturally acceptable ester of quinoxyacetic acid. Agriculturally acceptable esters of quindox include, for example, the methyl, ethyl, propyl, butyl, or methylhexyl (also known as methylhexyl) esters of quindox. In some aspects, the safener comprises cloquintocet-mexyl, the structure of which is shown below.

In some aspects, the safener can include free quindox, an agriculturally acceptable salt of quindox, an agriculturally acceptable ester of quindox, or a mixture thereof. Quinclorac may be a safener when applied in combination with a herbicide and may be used to reduce phytotoxicity to crops such as wheat, barley, triticale, rye, bran, oats, maize, sorghum, rice, millet, canola/rape, sunflower, sugar beet, cotton, sugar cane and pasture grasses. In some aspects, undesirable vegetation is present in broadleaf crops. In some aspects, the undesirable vegetation is found in canola, flax, sunflower, soybean, or cotton.

The quinatidyl acid or agriculturally acceptable salts or esters thereof may be used in an amount sufficient to cause a safety effect. In some aspects, the quinatil acid or agriculturally acceptable salt or ester thereof is applied to vegetation or an area adjacent the vegetation or to soil or water in the following amounts: 1g active ingredient/hectare (ai/ha) or more, such as 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, and, 280g ai/ha or more, or 290g ai/ha or more; 300g ai/ha or less, such as 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, 24g ai/ha or less, Or 2g ai/ha or less; or an amount within any range defined between any pair of the foregoing values, such as 1g ai/ha to 300g ai/ha, 5g ai/ha to 150g ai/ha, 10g ai/ha to 200g ai/ha, 20g ai/ha to 75g ai/ha, or 40g ai/ha to 100g ai/ha.

IV.Safety composition

A safened composition comprising (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof can be mixed or applied in combination with (b) a safener comprising quinoxyacetic acid or an agriculturally acceptable salt or ester thereof.

In some aspects, (a) and (b) are used in amounts sufficient to induce unexpectedly enhanced herbicidal action (e.g., increased damage or injury to undesirable vegetation) while still showing good crop compatibility (e.g., no or minimal increase in damage or injury to the crop) when compared to the application of the herbicidal compound (a) or (b) alone. In some aspects, the damage or injury to 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 damage or injury to a crop caused by the safety compositions and methods disclosed herein is assessed on a scale of 0% to 100% when compared to a control crop treated with herbicide or safener alone, where 0% indicates no damage 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 quinoxyacetic acid safener, or agriculturally acceptable salt or ester thereof, results in an unexpectedly enhanced herbicidal action against undesirable vegetation, even at application rates lower than those typically used for herbicides having herbicidal action by themselves. 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 quinoxyacetic acid safener, or an agriculturally acceptable salt or ester thereof, produces an unexpected protective effect on a desired crop to prevent damage to the crop that may be caused by the herbicide alone.

In some aspects, the weight ratio of (a) the pyridine carboxylate herbicide or agriculturally acceptable N-oxide, salt, or ester thereof (in g ae/ha) to (b) the quindox safener or agriculturally acceptable salt or ester thereof (in g ai/ha) may be 1:5 or greater, such as 1:4.75 or greater, 1:4.5 or greater, 1:4.25 or greater, 1:4 or greater, 1:3.75 or greater, 1:3.5 or greater, 1:3.25 or greater, 1:3 or greater, 1:2.75 or greater, 1:2.5 or greater, 1:2.25 or greater, 1:2 or greater, 1:1.9 or greater, 1:1.8 or greater, 1:1.7 or greater, 1:1.6 or greater, 1:1.5 or greater, 1:1.4 or greater, 1:1.1 or greater, 1: 1.1.1 or greater, 1: 1.1: 1.5 or greater, 1: 1.1.1 or greater, 1:1.1 or greater, 1:1.5 or greater, 1.1:1 or greater, 1.1: 1.1 or greater, 1.1, or greater, 1, or greater, 1, or greater, or 1, or greater, or 1, or greater, or 1, or more, or 1, or more, or 1, or 1, or, 1.2:1 or greater, 1.3:1 or greater, 1.4:1 or greater, 1.5:1 or greater, 1.6:1 or greater, 1.7:1 or greater, 1.8:1 or greater, 1.9:1 or greater, 2:1 or greater, 2.25:1 or greater, 2.5:1 or greater, 2.75:1 or greater, 3:1 or greater, 3.25:1 or greater, 3.5:1 or greater, 3.75:1 or greater, 4:1 or greater, 4.25:1 or greater, 4.5:1 or greater, 4.75:1 or greater, 5:1 or greater, 6:1 or greater, 7:1 or greater, 8:1 or greater, 9:1 or greater, 10:1 or greater, 11:1 or greater, 12:1 or greater, 1: 16:1 or greater, 1:1 or greater, 15:1 or greater, 1:1 or greater, 15:1 or greater, 1:1 or greater, 1:1, or greater, 10:1, or greater, 12:1, or greater, 1:1, or greater, 1, or greater, 1:1, or greater, 1:1, or greater, 1, or greater, 1, or greater, 1, or greater, 1, or greater, 1, or greater, 1:1, or greater, 1, or greater, 1, or greater, 30:1 or greater, 35:1 or greater, 40:1 or greater, 45:1 or greater, 50:1 or greater, 55:1 or greater, or 60:1 or greater; (a) the weight ratio to (b) may be 65:1 or less, such as 60:1 or less, 55:1 or less, 50:1 or less, 45:1 or less, 40:1 or less, 35:1 or less, 30:1 or less, 25:1 or less, 20:1 or less, 19:1 or less, 18:1 or less, 17:1 or less, 16:1 or less, 15:1 or less, 14:1 or less, 13:1 or less, 12:1 or less, 11:1 or less, 10:1 or less, 9:1 or less, 8:1 or less, 7:1 or less, 6:1 or less, 5:1 or less, 4.75:1 or less, 4.5:1 or less, 4.25:1 or less, 4:1 or less, 3.1: 1 or less, 3:1 or less, 3.75:1 or less, 3:1 or less, 2:1 or less, 3.75:1 or less, 3:1 or less, 2:1 or less, or 1 or less, or 1, or less, preferably, 1, or less, or a weight ratio of (b, preferably, or less, or a weight ratio of (B) of a compound (B) or a compound (B) a, 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 or less, 1:1.6 or less, 1:1.7 or less, 1:1.8 or less, 1:1.9 or less, 1:2 or less, 1:2.25 or less, 1:2.5 or less, 1:2.75 or less, 1: 3: 1.75 or less, 1:1.5 or less, 1:2.75 or less, 1:3.75 or less, 1: 4: 1.5 or less, 1: 4: 1.75 or less; or the weight ratio of (a) to (b) can range from any of the minimum ratios provided above to any of the maximum ratios, such as 1:5 to 65:1, 1:2 to 25:1, 1:1 to 15:1, 1:3 to 4:1, or 1:1.5 to 10: 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.Formulations

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 quinclorac safener or an agriculturally acceptable salt or ester thereof.

1.Other pesticides

Some aspects of the security compositions include adding one or more additional pesticide active ingredients to the security 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 one or more additional herbicides, tank mixed with one or more additional herbicides, or applied sequentially with 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; acifluorfen; aclonifen; acrolein; alachlor; killing the grass by poison; killing grass; allyl alcohol; pentachlorophenonoic acid (alorac); amine ketazine (ametridione); ametryn; tebufzin (amibuzin); amicarbazone; amidosulfuron; aminocyclopyrachlor; 4-aminopyralid-based herbicides such as halauxifen, and those described in U.S. Pat. Nos. 7,314,849 and 7,432,227 to Balko et al; aminopyralid; glufosinate-methyl; strong weed control; ammonium sulfamate; anilofos; white-head (anisuron); asulam; 1, atrazine; atrazine; (ii) azapridine; azimsulfuron; azidezine; herba Ainsliaeae Yunnanensis; BCPC; beflubutamid; benazolin; benzcarbazone-sodium (bencrarbazone); flumetsulam; benfuresate; d, dispersing phosphorus; bensulfuron-methyl; a herbicide controlling pill; bentazone; killing by amino acid; 1, bensulfuron-methyl; benoxanil; mesotrione; bicyclon; fomesafen (benzofluor); new Yanling; thidiazuron; bialaphos; fluroxypyr; bifenthrin; bialaphos; bispyribac-sodium; borax; weeding; furfuryl cyanide (bromobionil); bromobutylachlor; a bromophenol oxime; bromoxynil; bromoamectin; butachlor; butafenacil-ethyl; inhibiting grass phosphorus; butachlor; butylthioimidazolone; tribenuron-methyl; butralin; butylbenzone; clodinafop-propargyl; buthoxydim; dimethylarsinic acid; ketoconazole; calcium chlorate; calcium cyanamide; kechlor ester (camlandichlor); carbaryl (carbasulam); diacyl urea; fenoxacarb (carboxazole); death from grass failure (chlorocarb); carfentrazone-ethyl; CDEA; CEPC; methoxybenfuresate; 1, clomazone; butachlor; ethynyl (chlorezifop); (ii) clonidine; chlorobromouron; (ii) clodinafop-propargyl; ethoxyphenyl-ron (chloretron); 2, varek; esters of oats; killing by flufenamic; chloromethane lead; chlorphenamine; chlorimuron-ethyl; cumyl ether; trichloropropionic acid; chlortoluron; withered grass; hydroxydinitrile; chlorpropham; chlorosulfonyl; chlorthal; 2, grass Kele; cinidon-ethyl; cinmethylin; cinosulfuron; a fluazuron; oxalyl chloride phosphine; clethodim; iodochloropyridine ester (Clodinate); clodinafop-propargyl (clodinafop-propargyl); neoprene (clofep); clomazone; clomeprop; adjusting fruit acid; cyclobutenedione (cycloproxydim); clopyralid; cloransulam-methyl; CMA; copper sulfate; CPMF; CPPC; pyriminobac-sodium; cresol; a benzuron; cyanazine; cyanazine; 2, the herbicide is clomazone; cyclopyramid (cyclopyramid); cyclosulfamuron; cycloxydim; a ring, Xiulong; cyhalofop-butyl; the pasture is quick; cyhalofop-butyl; tricyclothiachlor; a aroyl-amine; killing the weed with the fensulfuron methyl; dalapon grass; a dazomet; isobutanamide; 7, desmodium betaine; diquat and diquat respectively; oat enemy; dicamba; dichlobenil; chlorodiurea; benzylamine ethyl; 2, 4-dichlorprop acid; 2, 4-D-propionic acid; diclofop-methyl; diclosulam; diethylcarbamylquat (diethyl quat); acetochlor; teff-grass (difenopentene); kularuron; delphinium chloride; diflufenican; diflufenzopyr; oxazolon; pterosamine; dimethachlor; isoamyl acetate; dimethenamid; prophenamid; killing the enemy; pyridazinone (dimrazon); 2, D-Dilleamine; a dinotefuran; propylene nitrophenol; pent-nitrophenol; dinotefuran; a terbenol; a molinate; iprovalbumin; diquat chloride; 5, loosening; dithiopyr; diuron; DMPA; DNOC; DSMA; EBEP; liquiritijin; sorrel; triazolesulfonic acid; EPTC; grass inhibition; penflufen; ethyl butene fluoro ling; ethametsulfuron-methyl; ethyl salicylamine; ethametsulfuron-methyl; sulfosulfuron; fenobucarb; ethoxybenoxamid (ethobenzamid); ethoxy benfuresate yellow; a fluorinated lacto-ether; ethoxysulfuron; nitrophenol (etinofen); pyrimethamine (etnipromid); ethoxybenoxanil; EXD; carbosulfan (fenasulam); aldicacid; fenoxaprop-p-ethyl; fenoxaprop-p-ethyl; fenoxaprop-p-ethyl and ethyl isoxadifen; metamifop; fequinolone (fenquinotrione); chlorophenoxyethanol (fenteracol); thiazole diclofop-methyl; fentrazamide; fenuron; ferrous sulfate; wheat straw fluoride; high-efficiency wheat straw fluorine; flazasulfuron-methyl; florasulam; fluazifop-butyl; fluazifop-p-butyl; iprodione ester; flucarbazone-sodium; flucetosulfuron; b, weeding; flufenacet; flufenacet (flurfenacin); fluazinaxate; flumetsulam; trifluorooxazine (flumezin); esters of oxyfluorfen; flumioxazin; propyzamide (flumipropyn); fluometuron; trinitroflurazon ether; fluoroglycofen-ethyl; fentrazamide; fluorofen-ethyl; fluosulfuron; flubenconazole; butafenacil (flupropacil); fluoropropionic acid; flazasulfuron; fluazinone; fluorochloridone; fluroxypyr; fluroxypyr-meptyl; flurtamone; oxazine oxalic acid; fomesafen; foramsulfuron; killing the wood phosphine; fluoroelenic acid (furomicrac); fluridone; glufosinate-ammonium; glufosinate-ammonium; refined glufosinate-ammonium; glyphosate salts and esters; a fluorosulfonamide; halosulfuron-methyl; fluroxypyr; haloxyfop-methyl; hexachloroacetone; a hexafluoro salt; hexazinone; imazamethabenz methyl ester; imazamox cigarette; imazapic methyl; the weed-killing tobacco; imazaquin; imazethapyr; pyrazosulfuron-ethyl; indene ketone; indazidine triazine; iodobonil (iodobonil); methyl iodide; iodosulfuron-methyl; iodosulfuron-ethyl-sodium; isoprofenesulfuron (iofensulfuron); ioxynil; oxazine; triazolam; propadine (iprymidam); cimetimide; isoxidin; butazinone; all-grass of Isocaotou Longum; rhizoma Dioscoreae Septemlobae (isopolinate); (iii) isopsoralen; isoproturon; isooxalong; isoxaben; clomazone; isoxaflutole; isoxaben; longxie (Longxie grass); ketospiro heterooxides (ketospiradox); lactofen; lenacil; linuron; MAA; MAMA; MCPA esters and amines; MCPA-thioethyl; MCPB; 2-methyl-4-chloropropionic acid; 2-methyl-4-chloropropionic acid; dilepisha; mefenacet; fluorosulfonyl oxamide; atrazine; mesosulfuron-methyl; mesotrione; metham sodium; metamifop; metamitron; metazachlor; ddy grass volts; methabenzthiazuron; primodium flurandrum (methalpropalin); imazamox; methiocarb (methiobencarb); isoxathiobac-sodium (methiozolin); killing weeds and keeping constant; ethoxydim is prepared; gecaojing; methyl bromide; methyl isothiocyanate; methyl-fensulfuron-methyl; metoxuron methyl; xiuguolong; metolachlor; sulfentrazone; metoxuron; metribuzin; metsulfuron methyl; molinate-ammonium; killing weeds and benefiting; texalone (monisouron); monochloroacetic acid; 2, green valley and long; 2, fensulfuron-methyl; fast grass cutting; MSMA; naphthylpropylamine; napropamide; napropamide (napropamide-M); suppressing grasses; nicosulfuron; diclofen; sulbactam; herbicidal ethers; trifluoromethoxyfen; daloxan; finishing the grass; OCH; turfgrass lead; ortho-dichlorobenzene; orthosulfamuron; amisulpride; oxadiargyl; oxadiazon; pyridaben; epoxy sulfometuron-methyl; oxaziclomefone; oxyfluorfen; pyraflufen-ethyl (paraflufen-ethyl); para-fluon-methyl; paraquat; kecaokang; pelargonic acid; pendimethalin; penoxsulam; pentachlorophenol; mechloranilide; pentoxazone; yellow grass photovoltaic; pethoxamid; a group of compounds selected from the group consisting of alanines; betanin; betanin-ethyl; 2, Dioluong; phenylmercuric acetate; picloram; picolinafen; pinoxaden; mepiquat chloride; potassium arsenite; potassium azide; potassium cyanate; pretilachlor; flazasulfuron; cyclopropanecarbonitrile; 2, prodiamine; flufenacet; ciprofloxacin; (ii) clethodim; ganpujin; adjusting cyclamic acid-calcium; putting out the medicine; prometryn; taking out of the grass; propachlor; propanil; propaquizafop-butyl; propazine; aniline; propisochlor; tribenuron-methyl; propyrisulfuron; propyzamide; metalaxyl-methyl; prosulfocarb; triflusulfuron-methyl; putting out the raw materials; propyzamide; biadenong (pydanon); pyraclonil; pyraflufen-ethyl (pyraflufen); sulfonylopyrazole; pyrazoxynil (pyrazogyl); killing phytocide; pyrazolate; pyrazosulfuron-ethyl; benazol; pyribenzoxim; barnyard grass; triclopyr; chloropyristin (pyridafol); pyridate; pyriftalid; pyriminobac-methyl; pyrithion (pyrimisulfan); pyrithiobac-sodium; pyraflufen-ethyl; pyroxsulam; quinclorac; chloroquinolinic acid; killing algae and quinone; chlorantraniliprole; quizalofop-ethyl; quizalofop-ethyl; quizalofop-p-ethyl-tetrahydrofuranyl; thiocyananilide; rimsulfuron; saflufenacil; s-metolachlor; additionally butylated hydroxytoluene; sec-butyl ketone; sethoxydim; all-grass of Anoplopanax; simazine; xishitong (western code for Chinese character); simetryn; SMA; sodium arsenite; sodium azide; sodium chlorate; sulcotrione; killing grass; sulfentrazone; sulfometuron-methyl; phosphinothricin; sulfosulfuron; sulfuric acid; azelate (sulglycoacin); a herbicide-benazolin; TCA; pasture amine; buthiuron; tefuretrione; a cyclic sulfonic ketone; obtaining weed control; terbacil; terbufagin; tert-butyl ammonium chloride; terbutone; terbuthylazine; terbutryn; teflon; methoxyfenacet; thifensulfuron methyl; thifluuron; thiabendazole; thiadiazoles; thidiazuron; thiencarbazone-methyl; thifensulfuron methyl; thiobencarb; primisulfuron-methyl ester; cortex Parabarium sulfate; pyroxsulam (tioclorim); topiramate (tolpyralate); topramezone; tralkoxydim; triallate; pyroxsulam; triasulfuron methyl; triazine flumioxazin; tribenuron-methyl; tribenuron-methyl; herbicidal agents; triclopyr choline salt; triclopyr ester and amine; weeding rings; madazine; trifloxysulfuron; trifluooxazine; trifluralin; triflusulfuron-methyl; trifluorophenoxypropionic acid (trifop); trifluoro grass oxime; trihydroxy triazine; trimethone; tripropylene glycol (tripropinidan); 2, pradak; triflusulfuron-methyl; b, weeding fierce; xylyl oxamide; and salts, esters, optical 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 quinatil acid 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 comprise one or more herbicidal active ingredients other than (a). In some aspects, the safe composition does not comprise a herbicidally active ingredient other than (a). In some aspects, the safe composition may not comprise one or more herbicidal active ingredients specified above. In some aspects, the safe composition may comprise one or more herbicidal active ingredients other than (a), but may not comprise one or more herbicidal ingredients specified above. In some aspects, the security composition may comprise one or more security agents other than (b). In some aspects, the security composition does not comprise a security agent other than (b). In some aspects, the compositions may comprise other components, such as adjuvants, but do not comprise a herbicidally active ingredient other than (a) or a safener 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.

Exemplary agriculturally acceptable adjuvants include, but are not limited to, crop oil concentrates (e.g., 85% mineral oil + 15% emulsifier); nonylphenol ethoxylate; benzyl cocoalkyl-dimethyl quaternary ammonium salt; petroleum hydrocarbons, alkyl esters, organic acids, anda blend of anionic surfactants; c₉-C₁₁An alkyl polyglycoside; a phosphate alcohol ethoxylate; natural primary alcohol (C)₁₂-C₁₆) An ethoxylate; di-sec-butylphenol EO-PO block copolymers; a methyl terminated polysiloxane; 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, viscosity increasing agents, dispersing agents, emulsifiers) include, but are not limited to: alkali metal salts, alkaline earth metal salts, and ammonium salts of fatty acids or aromatic sulfonic acids (e.g., lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid); alkyl-and alkylaryl sulfonates; alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates; salts of sulfated hexadecanol, heptadecanol and octadecanol; salts of fatty alcohol glycol ethers; condensates of sulfonated naphthalenes and their derivatives with formaldehyde; condensates of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde; polyoxyethylene octylphenol ether; ethoxylated isooctyl-, octyl-or nonylphenols, 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; lignosulfite 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: fungicides 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, glycerin, and mixtures thereof.

Exemplary colorants include, but are not limited to, 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 oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, and the like; esters of the above vegetable oils; esters of 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 monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids, and the like; toluene; xylene; naphtha; 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, kakko clay, calcium carbonate, bentonite, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut hull 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 formulation of (a) a carboxypyridine herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a quinoxyacetic acid safener, or an agriculturally acceptable salt or ester thereof, may 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) and (b) are aqueous solutions that can be diluted prior to use. In various aspects, (a) and (b) are provided as high concentration formulations (e.g., concentrates). 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, 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 temperatures 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 remains a clear solution at temperatures 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 of the components during storage for a period of 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 with a wetting, viscosity increasing, dispersing or emulsifying agent. 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 can be prepared by mixing or simultaneously milling (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)), based on the total weight of (a) and (b)). In formulations designed for use as concentrates, the total amount of (a) and (b) may be present at 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) may be present at a concentration of as little as 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.%, up 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 any range defined between any two of the foregoing values, such as from 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 comprise (a) and (b) in a total amount of 0.0006 to 8.0 wt.% (e.g., 0.001 to 5.0 wt.%), 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 package formulation comprising both: (a) a carboxypyridine herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a quinatil 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 plurality of packaged formulations, such as two packaged formulations, wherein one package comprises (a) and optionally at least one additive, and the other package comprises (b) and optionally at least one additive. In some aspects of the two-pack formulation, 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 application and then applied 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 applied sequentially (continuously) to 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. method of use

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 any composition to the soil or water to prevent the emergence or growth of vegetation.

The compositions disclosed herein can be applied pre-emergence (before emergence of the undesirable vegetation) or post-emergence (e.g., during 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 quinoxyacetic acid safener are applied simultaneously. In some aspects, the picolinate herbicide and the quinoxyacetic acid safener are applied sequentially to each other, 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. In some aspects, the picolinate herbicide may be applied to the undesirable vegetation pre-or post-emergence and the quinoxyacetic acid safener may be applied to the crop seed as a seed treatment. When applied as a seed treatment, the quinatil acid safener is applied at a rate of 0.01 to 10g ai safener per kg (g ai/kg) of crop seed, preferably 0.05 to 1g ai/kg crop seed, especially 0.1 to 0.5g ai/kg crop seed. If a solution of the safener is used to treat the seeds, the concentration of the safener in the solution is, for example, 1 to 10000ppm, preferably 100 to 1000ppm, on a weight basis.

When the composition is used in crops, the composition may be applied after sowing and before or after 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 the composition is used in a crop, the composition may be applied prior to seeding of the crop plant.

In some aspects, the compositions disclosed herein are applied to vegetation or an area adjacent to 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 a spray volume ratio of 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 by means of a spraying apparatus in such a way that they are hardly 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-emergence basal application or last field work). 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 treated post-emergence, 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, turf grasses, rangelands, pastures, fallowland, wayside, aquatic environments, trees and vines, wildlife management areas, or pastures. In some aspects, undesirable vegetation is controlled in cultivated crops. Exemplary crops include, but are not limited to, wheat, barley, triticale, rye, moss, oats, corn, cotton, soybean, sorghum, rice, millet, sugar cane, and pastures (e.g., pastures). In some aspects, the compositions and methods disclosed herein can be used to control undesirable vegetation in corn, wheat, barley, rice, sorghum, millet, or oats, or combinations 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, or insects. In some aspects, the compositions and methods disclosed herein can be used in crop plants 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 insect infestations 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 that are 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 single, multiple, or additive traits conferring single or multiple modes of action on one or more chemicals. 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 spectrum of weeds controlled by these compounds at the application rates employed. In some aspects, the compositions described herein and other complementary herbicides are applied simultaneously or in a sequential application as a combined formulation or tank mix. The compositions and methods are useful for controlling undesirable vegetation in crops having agronomic stress resistance (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 architecture).

In some aspects, the compositions disclosed herein can be used to control undesirable vegetation, including grasses, broadleaf weeds, sedge weeds, and combinations thereof. In some aspects, the compositions disclosed herein may be used to control undesirable vegetation, including, but not limited to, Polygonum (Polygonum) species, Amaranthus (Amaranthus) species, Chenopodium (Chenopodium) species, Sida (Sida) species, Ambrosia (Ambrosia) species, Cyperus (Cyperus) species, Setaria (Setaria) species, Sorghum (Sorghum) species, Acanthospermum (Acanthospermum) species, Anthemis (Anthemis) species, Atriplex (Atriplex) species, Brassica (Brassica) species, Cirsium (Cirsium) species, Convolvulus (Convolvulus) species, Kalopanax (Conyza) species, Cassia (Cassia) species, Commelina (Comelina) species, Datura (Datura) species, Euphorbia (Euphorbia) species, Geranium (Gelvia) species, Gelvia (Iridium) species, Gelvinoria (Iridium) species, Gelvinova species, Eupatorium (Ipomoea) species, Eupatorium species, Gelvia species, Gelvinova species, Gelvinola species, Gelvinoculum, Geranium, Gelvinoculum species, Geranium, Gelvinoculum, Geranium, and Geranium, etc, Matricaria species, mesquite (Prosopis) species, Rumex species, allium species, Solanum species, clover species, Xanthium species, Veronica species, and Viola species. In some aspects, the undesirable vegetation includes common chicory (comfred) (chickweed (Stellaria media)), velvety leaf (Abutilon theopterasi), pelargonium macrocarpium (Sesbania exaltata Cory)), malva coronaria (Andora cristata), Bidens pilosa (Bidens piposa), Brassica napobrassica (Brassica kaber), Capsella bursa (shepherd's disease) (Capsella bursa-pastoris), cornflower (cornflower) (Centaurea cytus) or cornflower (Cyanuus setosum)), yellow weat petal (Mempnetle) (weasel (Jasminum), Helicoverpa sativa (Helicornia)), Helicornia nigra (Helicoccus nigra (L.) or Helicoverum), Helicoverum japonicum (Hepialus nigra), Helicoverum (Hepialus nigrum setosum (Hepialus nigrum), Helicoverum japonicum (Hepialus nigra (Hepialus officinalis (Hepialus), Helicornia officinalis (Hepialus nigra officinalis (Hepialus setum) and Helicornia officinalis (Hepialus), Annual indigo (Mercurylis annua), forget-me-not (Myosotis arvensis), corn poppy (corn poppy) (Papaver rhoeas), radish (Raphanus rapanifolium), Rumex latifolia (Brooad-leaf dock) (Rumex obtusifolius), Russian thistle (Russian thistle) (Salsola kali)), wild mustard (Sinapis arvensis), endive (Sonchus arvensis), Thlaspi arvense (Thlaspi arvense), Adenophora microphylla (Targeted minuta), Medicago sativa (Richardtii briensis), Plantago major (Plantago), Plantago major (Brazilian) and Veronica griffii (Brazilian) or Veronica officinalis (Braziliana), Carpestalum arvensis (Braziliana), Plantago arvensis (Brassica indica), Lipora indica (Veronica) and Veronica (Brassica) or Veronica) and Veronica (Verbenaria) may be incorporated into the plants (L. canadensis (L.) and the plant (L, and the plant (Brassica) may be, the plant (Verbenaria) may be, the plant (L, the plant (Verbenne (L, the plant) may be, the plant (L) may be, the plant (L) may, the plant (L) may be, the plant (L) may, the plant (L) may be, the plant (L, the plant (L) may, the plant (L) may be, the plant (L) may, the plant (L) may be, the plant (L) may, the plant (C, the plant) may, the plant (C, the plant) may be, the plant (C, the plant) may, the plant (C, the plant) may be (C, the plant) may, the plant (C, the plant) may, the plant (C, the plant) may, the plant (C, the plant) may, the plant (C, the plant) may, Cyperus rotundus (nutsche) nutgrass (cypermus esculentus), poinsettia (poinsettia) (chimpanzee (euphorbia herpothylla)), lettuce (prinkly lette) (Lactuca sativa (Lactuca serola)), sesames excelsior (purplenetle) (Lamium sativum), Matricaria (wilfordii) (Matricaria chamomilla), chamomile (Matricaria inodora), feverfew (field chamomile) (chamomile), common buckwheat (Sorghum vulgare), wild buckwheat (buckwheat millet buckwheat), wild buckwheat (Sorghum vulgare, wild buckwheat (Sorghum), wild buckwheat (Sorghum vulgare, Sorghum), wild buckwheat (Sorghum vulgare, wild buckwheat (Sorghum), wild buckwheat (Sorghum vulgare, wild buckwheat (Sorghum), wild buckwheat (Sorghum, wild buckwheat (Sorghum), wild buckwheat (Sorghum, wild buckwheat, wild green, Large crabgrass (large crabgrass), barnyardgrass (barnyardgrass) (Echinochloa crus-galli), canna canadensis (Canada horseweeed) (Erigeron canadensis), volunteer soja (gonella soja) (giken (Glycine max)), hedera helix (gonella morningglory) (Ipomoea heimerica), Chinese stephania japonica (chincosane glory) (leptospermaceae), and Johnson grass (Johnson grass) (sora, Sorghum halepense (Sorghum haloense)), or combinations 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, sulfonylaminocarbonyl-triazolinones), 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, semicarbazones), 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-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors (e.g., caelmetone (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 acid, difenzoquat, furcellaran or organoarsenics are resistant or tolerant biotypes. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes with resistance or tolerance to multiple herbicides, biotypes with resistance or tolerance to multiple chemical classes, biotypes with resistance or tolerance to multiple herbicide modes of action, and biotypes with multiple resistance or tolerance mechanisms (e.g., targeted site resistance or metabolic resistance).

By way of non-limiting illustration, examples of certain aspects of the present disclosure are given below. Parts and percentages are on a per weight basis 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 plastic pots with seeds of the desired test plant species planted inBX (Premier Tech Horticulture, Quickton, Pa., USA) andGREENS GRADE^TM(Profile Products, Inc., Buffarogov, Ill.) planting a mixture of 90: 10% v/v (volume/volume) of the mixture, which typically has a pH of 5.2 to 6.2 and an organic matter 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.

Preparation at 100g acid equivalent/L (g ae/L)Emulsifiable concentrates of each of the respective picolinate herbicides (compound a or compound B). An aliquot of each emulsifiable concentrate was placed in a 25mL glass vial and washed with 1.25% (v/v)Esterified rapeseed oil (Bayer Crop Science, triangular research park, North Carolina, USA) orConcentrates andan aqueous mixture of methylated soybean oil (Loveland Products, lofrand, colorado, usa) was diluted to obtain concentrated stock solutions at the highest application rate for each herbicide (at a rate of 187 liters per hectare (L/ha) based on 12 milliliter (mL) application volume). The concentrated stock solution was further diluted with 1.25% v/vB orConcentrates andto obtain a stock solution with reduced application rates for each herbicide. A spray solution of the herbicide combination (compound a or compound B plus safener) was prepared by adding a weighed amount or aliquot of safener to a stock solution of compound a or compound B to form a binary combination of 12-mL spray solutions.

The spray solution was applied to the plant material using an overhead mantel track sprayer equipped with an 8002E nozzle calibrated to be at 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 treated with solvent in the same mannerThe blank was sprayed. The application rates for all herbicides (component a) are given in "g ae/ha" and for all safeners (component b) 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 injury and 100 corresponds to complete kill.

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

Example 1

A safe composition comprising free quinoxyacetic acid (CQC-a) and compound a was tested on spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), spring barley (HORVS), winter barley (HORVW), and common oats (AVESA), and phytotoxicity of the safe composition to each crop was measured. Furthermore, the efficacy of the safety composition was measured on undesirable vegetation including feverfew (ANTAR, chamomile), winter rape (BRSNW, brassica napus), chamomile (MATIN, chamomile), and wild mustard (SINAR, mustards).

The results are summarized in tables 1-4 below.

TABLE 1 safety of the action of free quetiacetic acid (CQC-a) and Compound A on cereal crops (% visual damage).

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

TRZDU wheat (hard wheat)

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

AVESA ═ oat (common oat)

TABLE 2 Effect safety (% visual damage) of free Quinoxyacetic acid (CQC-a) and Compound A on cereal crops and weeds.

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

MATIN ═ light chamomile (chamomile shape spring yellow)

SINAR ═ wild mustard (wild mustard)

TABLE 3 safety of the action of free quetiacetic acid (CQC-a) and Compound A on cereal crops (% visual damage).

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

Horvs ═ barley (spring barley)

TABLE 4 Effect safety (% visual damage) of free Quinoxyacetic acid (CQC-a) and Compound A on cereal crops and weeds.

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

ANTAR ═ Chamomile (feverfew)

BRSNW as rape (winter rape)

Example 2

Safe compositions comprising quinoxyacetic acid-dimethylammonium salt (CQC-DMA) and compound a were tested on spring barley (HORVS), winter wheat (TRZAW), winter barley (HORVW), spring wheat (TRZAS), durum wheat (TRZDU), and common oats (AVESA), and phytotoxicity of the safe compositions to each crop was measured. Furthermore, the efficacy of the security composition was measured on undesirable vegetation including feverfew (MATCH, german chamomile), russian thistle (SASKR, salsola), and winter rape (BRSNW, brassica napus).

The results are summarized in tables 5-6 below.

TABLE 5 safety of the action of the quinoxyacetic acid-dimethylammonium salt (CQC-DMA) and Compound A on cereal crops (% visual damage).

g/ha-g/ha

Horvs ═ barley (spring barley)

TRZAW ═ wheat (winter wheat)

Horvw ═ barley (winter barley)

TRZAS ═ wheat (spring wheat)

TRZDU wheat (hard wheat)

AVESA ═ oat (common oat)

TABLE 6 safety of the action of the quinatidyl acetate-dimethylammonium salt (CQC-DMA) and Compound A on cereal crops and weeds (% visual damage).

g/ha-g/ha

Horvs ═ barley (spring barley)

TRZAS ═ wheat (spring wheat)

MATCH ═ German chamomile (feverfew)

SASKR ═ salsola collina (Russian thistle)

BRSNW as rape (winter rape)

Example 3

Safe compositions comprising cloquintocet-ethyl-triethylamine salt (CQC-TEA) and compound a were tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and phytotoxicity of the safe compositions to each crop was measured. Furthermore, the efficacy of the security composition was measured on undesirable vegetation including feverfew (MATCH, german chamomile), russian thistle (SASKR, salsola), and winter rape (BRSNW, brassica napus).

The results are summarized in tables 7-8 below.

TABLE 7 safety of the effect of the quinoxyacetic acid-triethylamine salt (CQC-TEA) and Compound A on cereal crops (% visual damage).

g/ha-g/ha

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

TRZDU wheat (hard wheat)

AVESA ═ oat (common oat)

TABLE 8 Effect safety (% visual damage) of Quinoxyacetic acid-triethylamine salt (CQC-TEA) and Compound A on cereal crops and weeds.

g/ha-g/ha

Horvs ═ barley (spring barley)

TRZAS ═ wheat (spring wheat)

MATCH ═ German chamomile (feverfew)

SASKR ═ salsola collina (Russian thistle)

BRSNW as rape (winter rape)

Example 4

Safe compositions comprising cloquintocet-ethyl-triethylamine salt (CQC-TEA) and compound B were tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and phytotoxicity of the safe compositions was measured for each crop.

The results are summarized in table 9 below.

TABLE 9 safety of the effect of the quinoxyacetic acid-triethylamine salt (CQC-TEA) and Compound B on cereal crops (% visual damage).

g/ha-g/ha

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

TRZDU wheat (hard wheat)

AVESA ═ oat (common oat)

Example 5

A safe composition comprising quindox-triisopropanolamine (CQC-TIPA) and compound a was tested on spring barley (HORVS) and spring wheat (TRZAS), and the phytotoxicity of the safe composition on each crop was measured. Furthermore, the efficacy of the security composition was measured on undesirable vegetation including feverfew (MATCH, german chamomile), russian thistle (SASKR, salsola), and winter rape (BRSNW, brassica napus).

The results are summarized in table 10 below.

TABLE 10 action safety (% visual damage) of Quinoxyacetic acid-Triisopropanolamine salt (CQC-TIPA) and Compound A on cereal crops and weeds.

g/ha-g/ha

Horvs ═ barley (spring barley)

TRZAS ═ wheat (spring wheat)

MATCH ═ German chamomile (feverfew)

SASKR ═ salsola collina (Russian thistle)

BRSNW as rape (winter rape)

Example 6

A safe composition comprising quinoxyacetic acid-methyl (CQC-methyl) and compound a was tested on spring barley (HORVS) and spring wheat (TRZAS), and the phytotoxicity of the safe composition was measured for each crop. Furthermore, the efficacy of the security composition was measured on undesirable vegetation including feverfew (MATCH, german chamomile), russian thistle (SASKR, salsola), and winter rape (BRSNW, brassica napus).

The results are summarized in table 11 below.

TABLE 11 Effect safety (% visual damage) of Quinoxyacetic acid-methyl (CQC-methyl) and Compound A on cereal crops and weeds.

g/ha-g/ha

Horvs ═ barley (spring barley)

TRZAS ═ wheat (spring wheat)

MATCH ═ German chamomile (feverfew)

SASKR ═ salsola collina (Russian thistle)

BRSNW as rape (winter rape)

Example 7

A safe composition comprising cloquintocet-mexyl (CQC-methylhexyl) and compound B was tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and phytotoxicity of the safe composition to each crop was measured. Furthermore, the efficacy of the safe composition was measured on undesirable vegetation including winter rape (BRSNW, brassica napus), buckwheat common (FAGES, buckwheat), wild buckwheat (POLCO, buckwheat runner), russian thistle (SASKR, salsola), and wild mustard (SINAR, wasabi).

The results are summarized in tables 12-13 below.

TABLE 12 safety of the effect of cloquintocet-mexyl (CQC-methylhexyl) and Compound B on cereal crops (% visual damage).

g/ha-g/ha

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

TRZDU wheat (hard wheat)

AVESA ═ oat (common oat)

TABLE 13 action safety (% visual damage) of cloquintocet-mexyl (CQC-methylhexyl) and Compound B on cereal crops and weeds.

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

Horvs ═ barley (spring barley)

BRSNW as rape (winter rape)

FAGES ═ buckwheat (common buckwheat)

POLCO (wild buckwheat)

SASKR ═ salsola collina (Russian thistle)

SINAR ═ wild mustard (wild mustard)

Example 8

Safe compositions comprising cloquintocet-mexyl (CQC-methylhexyl) and compound a were tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and phytotoxicity of the safe compositions to each crop was measured. Furthermore, the efficacy of the safety composition was measured on undesirable vegetation including feverfew (ANTAR, chamomile), winter rape (BRSNW, brassica napus), chamomile (MATIN, chamomile), and wild mustard (SINAR, mustards).

The results are summarized in tables 14-16 below.

TABLE 14 safety of the effect of cloquintocet-mexyl (CQC-methylhexyl) and Compound A on cereal crops (% visual damage).

g/ha-g/ha

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

TRZDU wheat (hard wheat)

AVESA ═ oat (common oat)

TABLE 15 action safety (% visual damage) of cloquintocet-mexyl (CQC-methylhexyl) and Compound A on cereal crops and weeds.

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

ANTAR ═ Chamomile (feverfew)

BRSNW as rape (winter rape)

TABLE 16 action safety (% visual damage) of cloquintocet-mexyl (CQC-methylhexyl) and Compound A on cereal crops and weeds.

g/ha-g/ha

TRZAS ═ wheat (spring wheat)

TRZAW ═ wheat (winter wheat)

Horvs ═ barley (spring barley)

Horvw ═ barley (winter barley)

MATIN ═ light chamomile (chamomile shape spring yellow)

SINAR ═ wild mustard (wild mustard)

Example 9

A safe composition comprising cloquintocet-mexyl (CQC-methylhexyl) and compound a was tested on corn (ZEAMX) and the phytotoxicity of the safe composition on crops was measured. Furthermore, the efficacy of the safe composition was measured on undesirable vegetation including pigweed (AMARE, amaranth), cyperus rotundus (CYPES, cyperus rotundus), and common sunflower (HELAN, sunflower).

The results are summarized in table 17 below.

TABLE 17 safening of the effect of cloquintocet-mexyl (CQC-methylhexyl) and Compound A on corn and weeds (% visual damage).

g/ha-g/ha

Zea mays (corn)

Amare ═ Amaranthus retroflexus (pig grass)

CYPES ═ cyperus (cyperus rotundus)

Helan sunflower (common sunflower)

Example 10

A safe composition comprising free quindox (CQC-a) and compound a was tested on corn (ZEAMX) and phytotoxicity of the safe composition on crops was measured. Furthermore, the efficacy of the safe composition was measured on undesirable vegetation including pigweed (AMARE, amaranth), cyperus rotundus (CYPES, cyperus rotundus), and common sunflower (HELAN, sunflower).

The results are summarized in table 18 below.

TABLE 18 safety of the effect of free quetiacetic acid (CQC-a) and Compound A on corn and weeds (% visual damage).

g/ha-g/ha

Zea mays (corn)

Amare ═ Amaranthus retroflexus (pig grass)

CYPES ═ cyperus (cyperus rotundus)

Helan sunflower (common sunflower)

Example 11

A safe composition comprising cloquintocet-mexyl (CQC-methylhexyl) and compound a was tested on winter wheat (TRZAW), rice (ORYSA) and corn (ZEAMX) and its phytotoxicity to crops was measured. Furthermore, the efficacy of the safety composition was measured on undesirable vegetation including chorionic villous leaf (ABUTH, abutilon), black grass (ALOMY, alopecurus), swine grass (AMARE, amaranth), wild oats (AVEFA, wild oats), winter rape (BRSNW, brassica napus), common grey vegetable (ches, quinoa), Canada thistle (CIRAR, field thistle), cyperus rotundus (CYPES, cyperus oleander), large crab grass (DIGSA, crab grass), barnyard grass (ECHCG, barnyard grass), canadian burry (ERICA, eriap canada), soybean (GLXMA, sculellaria), common sunflower (HELAN, sunflower), ivy leaf morning glory (IPOHE, petunia), kochia (KCHSC, kochia), chinese stephania (LEFCH, stephania japonica), italian buckwheat (lou, pou), wild wheat straw (pogo), wild vines (lolium japonicum), crataegula (lecania, crataegueta), crataegueta (crataegueta, crataegula, crataegueta), crataegus canada (kola, fava (kola, fava), kola, fava (kola), kola, fava (kola), kola, fava (kola), kola, fava (kola), kola, fava (kola), kola, fava (fava), kola, fava (kola), kola, fava (kola), kola, fava (kola), kola, fava (kola), kola), kola), kola, fava (kola), ko, Johnsongrass (SORHA, sorghum halepense), and wild pansy (VIOTR, pansy).

The results are summarized in table 19 below.

TABLE 19 safety of the effect of cloquintocet-mexyl (CQC-methylhexyl) and Compound A on corn and weeds (% visual damage).

g/ha-g/ha

TRZAW ═ wheat (winter wheat)

ORYSA ═ rice (ordinary rice)

Zea mays (corn)

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 ═ barnyard grass (barnyard grass)

ERICA ═ canada erigeron (canadian chawing)

GLXMA ═ scull bean (soybean)

Helan sunflower (common sunflower)

Ipot ═ schizophyllum pharbitidis (ivy leaf pharbitidis flower)

KCHSC ═ broom cypress fruit (Kochia scoparia)

LEFCH ═ stephania root (chinese stephania root)

Lolmu-lolium multiflorum (Italy ryegrass)

POLCO (wild buckwheat)

Seta ta (millet weed)

SORHA jowar (johnsongrass)

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. The term "comprising" and variations thereof as used herein 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 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.