Safened herbicidal compositions comprising a pyridine carboxylic acid herbicide

FIELD OF THE DISCLOSURE

The disclosure relates to safened herbicidal compositions comprising a pyridine carboxylic acid herbicide, as well as methods of controlling undesirable vegetation using the same.

BACKGROUND

Many recurring problems in agriculture involve controlling the growth of undesirable vegetation that can, for instance, negatively affect the growth of desirable vegetation. To help control undesirable vegetation, researchers have produced a variety of chemicals and chemical formulations effective in controlling such unwanted growth.

In some cases, although a herbicide may be effective in controlling undesirable vegetation, it may also have a phytotoxic effect on a crop and cause injury or even kill the crop. Accordingly, safeners can be provided with the herbicide to limit the phytotoxicity of the herbicidal active ingredient.

SUMMARY OF THE DISCLOSURE

Disclosed herein are safened herbicidal compositions. The safened herbicidal compositions can comprise (a) a pyridine carboxylic acid herbicide or agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof. The weight ratio of (a) to (b) can be from 65:1 to 1:5 (e.g., from 5:1 to 1:5, or from 2:1 to 1:2).

The pyridine carboxylic acid herbicide can comprise a compound defined by Formula (I)

embedded image

wherein

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio or C₁-C₃haloalkylthio;

R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, cyano, or a group of the formula —CR¹⁷═CR¹⁸—SiR¹⁹R²⁰R²¹, wherein R¹⁷is hydrogen, F, or Cl; R¹⁸is hydrogen, F, Cl, C₁-C₄alkyl, or C₁-C₄haloalkyl; and R¹⁹, R²⁰, and R²¹are independently C₁-C₁₀alkyl, C₃-C₆cycloalkyl, phenyl, substituted phenyl, C₁-C₁₀alkoxy, or OH;

R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, C₁-C₆trialkylsilyl, C₁-C₆dialkylphosphonyl, or R³and R⁴taken together with N is a 5- or 6-membered saturated ring, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′ and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino, or, R^3′ and R^4′ taken together with ═C represent a 5- or 6-membered saturated ring;

A is one of groups A1 to A36

embedded image

R⁵, if applicable to the A group, is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, OH, or CN;

R⁶, R^6′, and R^6″, if applicable to the A group, are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino or C₂-C₄halo alkylamino, OH, CN, or NO₂;

R⁷and R^7′ are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, C₁-C₄haloalkylamino, or phenyl;

R⁸is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, C₁-C₆trialkylsilyl, or phenyl;

- or an agriculturally acceptable N-oxide or salt thereof.

In certain embodiments, the pyridine carboxylic acid herbicide can comprise a compound defined by Formula (II):

embedded image

wherein

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

R⁵is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, OH, or CN;

R⁶, R^6′, and R^6″ are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino or C₂-C₄halo alkylamino, OH, CN, or NO₂;

or an agriculturally acceptable N-oxide or salt thereof.

In some embodiments, R¹is OR^1′, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl. In certain embodiments, R²is Cl, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; A is A15; R⁵is hydrogen or F; R⁶is hydrogen or F; and R^6″ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂.

In certain embodiments, the pyridine carboxylic acid herbicide can comprise a compound defined by Formula (III):

embedded image

wherein

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio or C₁-C₃haloalkylthio;

R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, cyano, or a group of the formula —CR¹⁷═CR¹⁸—SiR¹⁹R²⁰R²¹, wherein R¹⁷is hydrogen, F, or Cl; R¹⁸is hydrogen, F, Cl, C₁-C₄alkyl, or C₁-C₄haloalkyl; and R¹⁹, R²⁰, R²¹are independently C₁-C₁₀alkyl, C₃-C₆cycloalkyl, phenyl, substituted phenyl, C₁-C₁₀alkoxy, or OH;

R⁶and R^6′ are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino or C₂-C₄halo alkylamino, OH, CN, or NO₂;

or an agriculturally acceptable N-oxide or salt thereof.

In some embodiments, X is N, CH or CF. In certain embodiments, X is CF, R¹is OR^1′, wherein R^1′is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl; R²is Cl, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; R⁶is hydrogen or F; and R^6′ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂.

In certain embodiments, the pyridine carboxylic acid herbicide can include 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) picolinic acid, or an agriculturally acceptable N-oxide, salt, or ester thereof.

In some embodiments, the quinolinyloxyacetate safener comprises cloquintocet or an agriculturally acceptable salt or ester thereof.

In some embodiments, the composition can further comprise an agriculturally acceptable adjuvant or carrier, an additional pesticide, or a combination thereof. In certain embodiments, the active ingredients in the composition consist of (a) and (b).

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 carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof. In some embodiments, (a) and (b) are applied simultaneously. In some embodiments, (a) and (b) are applied post-emergence of the undesirable vegetation. In one embodiment, the undesirable vegetation is in corn (e.g., maize). In another embodiment, the undesirable vegetation is in cereals.

In some embodiments, (a) can comprise a pyridine carboxylic acid herbicide described above. In some embodiments, the quinolinyloxyacetate safener comprises cloquintocet or an agriculturally acceptable salt or ester thereof. In some cases, (a) can be applied in an amount of from 0.1 gram acid equivalent per hectare (g ae/ha) to 300 g ae/ha (e.g., from 30 g ae/ha to 40 g ae/ha) and/or (b) can be applied in an amount of from 1 grams active ingredient per hectare (g ai/ha) to 300 g ai/ha (e.g., from 30 g ai/ha to 40 g ai/ha). In some cases, (a) and (b) can be applied in a weight ratio of from 65:1 to 1:5 (e.g., from 5:1 to 1:5, or from 2:1 to 1:2).

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

DETAILED DESCRIPTION

The present disclosure relates to safened herbicidal compositions comprising a herbicidally effective amount of (a) a pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener. The present disclosure also relates to methods for controlling undesirable vegetation. In one embodiment, the undesirable vegetation is in corn (e.g., maize). In another embodiment, the undesirable vegetation is in cereals.

I. Definitions

Terms used herein will have their customary meaning in the art unless specified otherwise. The organic moieties mentioned when defining variable positions within the general formulae described herein (e.g., the term “halogen”) are collective terms for the individual substituents encompassed by the organic moiety. The prefix C_n-C_mpreceding a group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows.

As used herein, the terms “herbicide” and “herbicidal active ingredient” refer to an active ingredient that kills, controls, or otherwise adversely modifies the growth of vegetation, particularly undesirable vegetation, such as weeds, when applied in an appropriate amount.

As used herein, a herbicidally effective amount” refers to an amount of an active ingredient that causes a “herbicidal effect,” i.e., an adversely modifying effect including, for instance, a deviation from natural growth or development, killing, regulation, desiccation, growth inhibition, growth reduction, and retardation.

As used herein, applying a herbicide or herbicidal composition refers to delivering it directly to the targeted vegetation or to the locus thereof or to the area where control of undesired vegetation is desired. Methods of application include, but are not limited to pre-emergently contacting soil or water, post-emergently contacting the undesirable vegetation or area adjacent to the undesirable vegetation.

As used herein, the terms “crops” and “vegetation” can include, for instance, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.

As used herein, immature vegetation refers to small vegetative plants prior to reproductive stage, and mature vegetation refers to vegetative plants during and after the reproductive stage.

As used herein, unless otherwise specified, the term “acyl” refers to a group of formula —C(O)R, where R is hydrogen, alkyl (e.g., C₁-C₁₀alkyl), haloalkyl (C₁-C₈haloalkyl), alkenyl (C₂-C₈alkenyl), haloalkenyl (e.g., C₂-C₈haloalkenyl), alkynyl (e.g., C₂-C₈alkynyl), alkoxy (C₁-C₈alkoxy), haloalkoxy (C₁-C₈alkoxy), aryl, or heteroaryl, arylalkyl (C₇-C₁₀arylalkyl), as defined below, where “C(O)” or “CO” is short-hand notation for C═O. In some embodiments, the acyl group can be a C₁-C₆acyl group (e.g., a formyl group, a C₁-C₅alkylcarbonyl group, or a C₁-C₅haloalkylcarbonyl group). In some embodiments, the acyl group can be a C₁-C₃acyl group (e.g., a formyl group, a C₁-C₃alkylcarbonyl group, or a C₁-C₃haloalkylcarbonyl group).

As used herein, the term “alkyl” refers to saturated, straight-chained or branched saturated hydrocarbon moieties. Unless otherwise specified, C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, C₁-C₄) alkyl groups are intended. Examples of alkyl groups include methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 1,3-dimethyl-butyl, 2,2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl, 1-ethyl-1-methyl-propyl, and 1-ethyl-2-methyl-propyl. Alkyl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆acyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆haloalkoxycarbonyl, C₁-C₆carbamoyl, C₁-C₆halocarbamoyl, hydroxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆dialkylaminocarbonyl, and C₁-C₆dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆alkoxy.

As used herein, the term “haloalkyl” refers to straight-chained or branched alkyl groups, wherein these groups the hydrogen atoms may partially or entirely be substituted with halogen atoms. Unless otherwise specified, C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, C₁-C₄) alkyl groups are intended. Examples include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-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-trifluoroprop-2-yl. Haloalkyl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆acyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆haloalkoxycarbonyl, C₁-C₆carbamoyl, C₁-C₆halocarbamoyl, hydroxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆dialkylaminocarbonyl, and C₁-C₆dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆alkoxy.

As used herein, the term “alkenyl” refers to unsaturated, straight-chained, or branched hydrocarbon moieties containing a double bond. Unless otherwise specified, C₂-C₂₀(e.g., C₂-C₁₂, C₂-C₁₀, C₂-C₈, C₂-C₆, C₂-C₄) alkenyl groups are intended. Alkenyl groups may contain more than one unsaturated bond. Examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2-propenyl. The term “vinyl” refers to a group having the structure —CH═CH₂; 1-propenyl refers to a group with the structure-CH═CH—CH₃; and 2-propenyl refers to a group with the structure —CH₂—CH═CH₂. Alkenyl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆acyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆haloalkoxycarbonyl, C₁-C₆carbamoyl, C₁-C₆halocarbamoyl, hydroxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆dialkylaminocarbonyl, and C₁-C₆dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆alkoxy. The term “haloalkenyl,” as used herein, refers to an alkenyl group, as defined above, which is substituted by one or more halogen atoms.

As used herein, the term “alkynyl” represents straight-chained or branched hydrocarbon moieties containing a triple bond. Unless otherwise specified, C₂-C₂₀(e.g., C₂-C₁₂, C₂-C₁₀, C₂-C₈, C₂-C₆, C₂-C₄) alkynyl groups are intended. Alkynyl groups may contain more than one unsaturated bond. Examples include C₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2-propynyl. Alkynyl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆acyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆haloalkoxycarbonyl, C₁-C₆carbamoyl, C₁-C₆halocarbamoyl, hydroxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆dialkylaminocarbonyl, and C₁-C₆dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆alkoxy.

As used herein, the term “alkoxy” refers to a group of the formula R—O—, where R is unsubstituted or substituted alkyl as defined above. Unless otherwise specified, alkoxy groups wherein R is a C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, C₁-C₄) alkyl group are intended. Examples include methoxy, ethoxy, propoxy, 1-methyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1-dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy, 2,2-dimethyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy.

As used herein, the term “haloalkoxy” refers to a group of the formula R—O—, where R is unsubstituted or substituted haloalkyl as defined above. Unless otherwise specified, haloalkoxy groups wherein R is a C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, C₁-C₄) haloalkyl group are intended. Examples include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-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 “alkylthio” refers to a group of the formula R—S—, where R is unsubstituted or substituted alkyl as defined above. Unless otherwise specified, alkylthio groups wherein R is a C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, C₁-C₄) alkyl group are intended. Examples include methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio, and 1-ethyl-2-methylpropylthio.

As used herein, the term “haloalkylthio” refers to an alkylthio group as defined above wherein the carbon atoms are partially or entirely substituted with halogen atoms. Unless otherwise specified, haloalkylthio groups wherein R is a C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, C₁-C₄) alkyl group are intended. Examples include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoro-methylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and 1,1,1-trifluoroprop-2-ylthio.

As used herein, the term “aryl,” as well as derivative terms such as aryloxy, refers to groups that include a monovalent aromatic carbocyclic group of from 6 to 14 carbon atoms. Aryl groups can include a single ring or multiple condensed rings. In some embodiments, aryl groups include C₆-C₁₀aryl groups. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl, and indanyl. In some embodiments, the aryl group can be a phenyl, indanyl or naphthyl group. The term “heteroaryl”, as well as derivative terms such as “heteroaryloxy”, refers to a 5- or 6-membered aromatic ring containing one or more heteroatoms, viz., N, O or S; these heteroaromatic rings may be fused to other aromatic systems. The aryl or heteroaryl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, halogen, nitro, cyano, formyl, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkyl, C₁-C₆haloalkoxy, C₁-C₆acyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆carbamoyl, hydroxycarbonyl, C₁-C₆alkylcarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, C₁-C₆dialkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include halogen, C₁-C₂alkyl and C₁-C₂haloalkyl.

As used herein, the term “alkylcarbonyl” refers to an unsubstituted or substituted alkyl group bonded to a carbonyl group. C₁-C₃alkylcarbonyl and C₁-C₃haloalkylcarbonyl refer to groups wherein a C₁-C₃unsubstituted or substituted alkyl or haloalkyl group is bonded to a carbonyl group (the group contains a total of 2 to 4 carbon atoms).

As used herein, the term “alkoxycarbonyl” refers to a group of the formula

embedded image

wherein R is unsubstituted or substituted alkyl.

As used herein, the term “arylalkyl” refers to an alkyl group substituted with an unsubstituted or substituted aryl group. C₇-C₁₀arylalkyl refers to a group wherein the total number of carbon atoms in the group is 7 to 10, not including the carbon atoms present in any substituents of the aryl group.

As used herein, the term “alkylamino” refers to an amino group substituted with one or two unsubstituted or substituted alkyl groups, which may be the same or different.

As used herein, the term “haloalkylamino” refers to an alkylamino group wherein the alkyl carbon atoms are partially or entirely substituted with halogen atoms.

As used herein, C₁-C₆alkylaminocarbonyl refers to a group of the formula RNHC(O)— wherein R is C₁-C₆unsubstituted or substituted alkyl, and C₁-C₆dialkylaminocarbonyl refers to a group of the formula R₂NC(O)— wherein each R is independently C₁-C₆unsubstituted or substituted alkyl.

As used herein, the term “alkylcarbamyl” refers to a carbamyl group substituted on the nitrogen with an unsubstituted or substituted alkyl group.

As used herein, the term “alkylsulfonyl” refers to a group of the formula

embedded image

where R is unsubstituted or substituted alkyl.

As used herein, the term “carbamyl” (also referred to as carbamoyl and aminocarbonyl) refers to a group of the formula

embedded image

As used herein, the term “dialkylphosphonyl” refers to a group of the formula

embedded image

where R is independently unsubstituted or substituted alkyl in each occurrence.

As used herein, C₁-C₆trialkylsilyl refers to a group of the formula —SiR₃wherein each R is independently a C₁-C₆unsubstituted or substituted alkyl group (the group contains a total of 3 to 18 carbon atoms).

As used herein, Me refers to a methyl group; OMe refers to a methoxy group; and i-Pr refers to an isopropyl 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 refer to salts and esters that exhibit herbicidal activity, or that are or can be converted in plants, water, or soil to the referenced herbicide. Exemplary agriculturally acceptable esters are those that are or can be hydrolyzed, oxidized, metabolized, or otherwise converted, e.g., in plants, water, or soil, to the corresponding carboxylic acid which, depending on the pH, may be in the dissociated or undissociated form.

Compounds described herein can include N-oxides. Pyridine N-oxides can be obtained by oxidation of the corresponding pyridines. Suitable oxidation methods are described, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods in organic chemistry], expanded and subsequent volumes to the 4th edition, volume E 7b, p. 565 f.

Pyridine Carboxylic Acid Herbicides

Compositions and methods of the present disclosure can include a pyridine carboxylic acid herbicide defined by Formula (I)

embedded image

wherein

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio or C₁-C₃haloalkylthio;

R¹is OR^1′ or NR^1″R^1′″ wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl, and R^1″and R^1′″ are independently hydrogen, C₁-C₁₂alkyl, C₃-C₁₂alkenyl, or C₃-C₁₂alkynyl;

A is one of groups A1 to A36

embedded image

or an agriculturally acceptable N-oxide or salt thereof.

In some embodiments, R¹is OR^1′, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl. In some embodiments, R^1′ is hydrogen or C₁-C₈alkyl. In some embodiments, R^1′ is hydrogen.

In some embodiments, R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkynyl, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, C₁-C₄-alkoxy, or C₁-C₄haloalkoxy. In some embodiments, R²is halogen, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, or C₁-C₄-alkoxy. In some embodiments, R²is halogen. In some embodiments, R²is C₂-C₄-alkenyl or C₂-C₄haloalkenyl. In some embodiments, R²is C₁-C₄alkoxy. In some embodiments, R²is Cl, OMe, vinyl, or 1-propenyl. In some embodiments, R²is Cl. In some embodiments, R²is OMe. In some embodiments, R²is vinyl or 1-propenyl.

In some embodiments, R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′ and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, or C₁-C₆alkylamino. In some embodiments, R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′ and R^4′ are independently hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy or C₁-C₆alkylamino. In some embodiments, R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, formyl, C₁-C₃alkylcarbonyl, or C₁-C₃haloalkylcarbonyl. In some embodiments, at least one of R³and R⁴are hydrogen. In some embodiments, R³and R⁴are both hydrogen.

In some embodiments, X is N, CH or CF. In some embodiments, X is N. In some embodiments, X is CH. In some embodiments, X is CF. In other embodiments, X is C—CH₃.

In some embodiments, A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, or A20. In other embodiments, A is one of A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, and A36.

In some embodiments, A is one of groups A1, A2, A3, A7, A8, A9, A10, A13, A14, and A15. In some embodiments, A is one of groups A1, A2, A3, A13, A14, and A15. In some embodiments, A is one of groups A13, A14, and A15. In some embodiments, A is A15.

In some embodiments, R⁵is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, or amino. In some embodiments, R⁵is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, or amino. In some embodiments, R⁵is hydrogen, halogen, C₁-C₄alkyl or C₁-C₄alkoxy. In some embodiments, R⁵is hydrogen or F. In some embodiments, R⁵is hydrogen.

In other embodiments, R⁵is F.

In some embodiments, R⁶is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkoxy, or C₁-C₃haloalkoxy. In some embodiments, R⁶is hydrogen or fluorine. In some embodiments, R⁶is hydrogen. In some embodiments, R⁶is fluorine.

In some embodiments, R^6′ is hydrogen or halogen. In some embodiments, R^6′ is hydrogen, F, or Cl. In some embodiments, R^6′ is hydrogen or F. In some embodiments, R^6′ is hydrogen.

In some embodiments, R^6″ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂. In some embodiments, R^6″ is hydrogen. In some embodiments, R^6″ is halogen. In some embodiments, R^6″ is C₁-C₄alkyl. In some embodiments, R^6″ is C₁-C₄haloalkyl. In some embodiments, R^6″ is cyclopropyl. In some embodiments, R^6″ is C₂-C₄alkynyl. In some embodiments, R^6″ is CN. In some embodiments, R^6″ is NO₂.

In some embodiments:

X is N, CH, CF, CCl, or CBr;

R¹is OR^1′, wherein R^1′ is hydrogen or C₁-C₄alkyl;

R²is chlorine;

R³and R⁴are hydrogen;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, or A20;

R⁵is hydrogen, halogen, OH, amino, CN, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylamino, or cyclopropyl;

R⁶, R^6′, and R^6″ are independently hydrogen, halogen, OH, NH₂, CN, C₁-C₃alkyl, C₁-C₃alkoxy, cyclopropyl, or vinyl;

R⁷and R^7′ are independently hydrogen, halogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio, cyclopropyl, C₁-C₃alkylamino, or phenyl; and

R⁸is hydrogen, C₁-C₃alkyl, phenyl, or C₁-C₃alkylcarbonyl.

In some embodiments, R²is halogen, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, or C₁-C₄-alkoxy; R³and R⁴are both hydrogen; and X is N, CH, or CF.

In some embodiments, R²is halogen; R³and R⁴are both hydrogen; and X is N, CH, or CF.

In some embodiments, R²is C₂-C₄-alkenyl or C₂-C₄haloalkenyl; R³and R⁴are both hydrogen; and X is N, CH, or CF.

In some embodiments, R²is C₁-C₄-alkoxy; R³and R⁴are both hydrogen; and X is N, CH, or CF.

In some embodiments, R²is halogen, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, or C₁-C₄-alkoxy; R³and R⁴are both hydrogen; X is N, CH, or CF; R⁵is hydrogen or F; R⁶is hydrogen or F; R^6′ is hydrogen; R^6″, if applicable to the relevant A group, is hydrogen or halogen; and R⁷and R^7′, if applicable to the relevant A group, are independently hydrogen or halogen.

In some embodiments, R²is halogen, C₁-C₄-alkoxy, or C₂-C₄-alkenyl; R³and R⁴are hydrogen; X is N, CH, or CF; and A is one of groups A1 to A20.

In some embodiments, R²is chlorine; R³and R⁴are hydrogen; X is N, CH, or CF; A is one of groups A1 to A20; R⁵is hydrogen or F; R⁶and R^6′ are independently hydrogen or F; and R⁷and R^7′, if applicable to the relevant A group, are independently hydrogen, halogen, C₁-C₄alkyl, or C₁-C₄haloalkyl.

In some embodiments, R²is chlorine, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; and X is N, CH, or CF.

In some embodiments, R²is chlorine; R³and R⁴are hydrogen; and X is N, CH, or CF.

In some embodiments, R²is vinyl or 1-propenyl; R³and R⁴are hydrogen; and X is N, CH, or CF.

In some embodiments, R²is methoxy; R³and R⁴are hydrogen; and X is N, CH, or CF.

In some embodiments, R²is chlorine; R³and R⁴are hydrogen; and X is N.

In some embodiments, R²is chlorine; R³and R⁴are hydrogen; and X is CH.

In some embodiments, R²is chlorine; R³and R⁴are hydrogen; and X is CF.

In some embodiments, R²is chlorine; R³and R⁴are hydrogen; X is CF; A is one of A1, A2, A3, A7, A8, A9, A10, A13, A14, or A15; R⁵is F; and R⁶is H.

In some embodiments, R²is chlorine, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; X is N, CH, or CF; and A is one of A21-A36.

In some embodiments, R²is chlorine, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; X is CF; and A is one of

embedded image

wherein R⁵is hydrogen or F.

In some embodiments, R²is chlorine, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; X is N, CH, or CF; and A is

embedded image

where R⁵is hydrogen or F.

In some embodiments, R²is chlorine, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; X is N, CH, or CF; and A is

embedded image

In some embodiments, R²is chlorine, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; X is CF; and A is

embedded image

In some embodiments, the pyridine carboxylic acid herbicide can comprise a compound defined by Formula (I)

embedded image

wherein

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R¹is OR^1′ or NR^1″R^1′″, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl, and R^1″ and R^1′are independently hydrogen, C₁-C₁₂alkyl, C₃-C₁₂alkenyl, or C₃-C₁₂alkynyl;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

or an agriculturally acceptable N-oxide or salt thereof,

with the proviso that the pyridine carboxylic acid herbicide is not a compound defined by Formula (I)

embedded image

wherein

X is N, CH, CF, CCl, or CBr;

R¹is OR^1′, wherein R^1′ is hydrogen or C₁-C₄alkyl;

R²is chlorine;

R³and R⁴are hydrogen;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, or A20;

R⁵is hydrogen, halogen, OH, amino, CN, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylamino, or cyclopropyl;

R⁶, R^6′, and R^6″ are independently hydrogen, halogen, OH, NH₂, CN, C₁-C₃alkyl, C₁-C₃alkoxy, cyclopropyl, or vinyl;

R⁷and R^7′ are independently hydrogen, halogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio, cyclopropyl, C₁-C₃alkylamino, or phenyl; and

R⁸is hydrogen, C₁-C₃alkyl, phenyl, or C₁-C₃alkylcarbonyl;

or an agriculturally acceptable N-oxide or salt thereof.

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is CY, wherein Y is C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

In some of these embodiments, R¹is OR¹. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R¹is OR^1′ or NR^1″R^1′″, wherein R^1′ is C₅-C₈alkyl, or C₇-C₁₀arylalkyl, and R^1″ and R^1′″are independently hydrogen, C₁-C₁₂alkyl, C₃-C₁₂alkenyl, or C₃-C₁₂alkynyl;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R²is F, Br, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, cyano, or a group of the formula —CR¹⁷═CR¹⁸—SiR¹⁹R²⁰R²¹, wherein R¹⁷is hydrogen, F, or Cl; R¹⁸is hydrogen, F, Cl, C₁-C₄alkyl, or C₁-C₄haloalkyl; and R¹⁹, R²⁰, and R²¹are independently C₁-C₁₀alkyl, C₃-C₆cycloalkyl, phenyl, substituted phenyl, C₁-C₁₀alkoxy, or OH;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R³and R⁴are independently C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, C₁-C₆trialkylsilyl, C₁-C₆dialkylphosphonyl, or R³and R⁴taken together with N is a 5- or 6-membered saturated ring, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′ and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino, or, R^3′ and R^4′ taken together with ═C represent a 5- or 6-membered saturated ring;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, cyano, or a group of the formula —CR¹²═CR¹⁸—SiR¹⁹R²⁰R²¹, wherein R¹⁷is hydrogen, F, or Cl; R¹⁸is hydrogen, F, Cl, C₁-C₄alkyl, or C₁-C₄haloalkyl; and R¹⁹, R²⁰, and R²¹are independently C₁-C₁₀alkyl, C₃-C₆cycloalkyl, phenyl, substituted phenyl, C₁-C₁₀alkoxy, or OH;

R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, C₁-C₆trialkylsilyl, C₁-C₆dialkylphosphonyl, or R³and R⁴taken together with N is a 5- or 6-membered saturated ring, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino, or, R^3′and R^4′ taken together with ═C represent a 5- or 6-membered saturated ring;

A is A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

R⁷and R^7′are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, or phenyl; and

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, C₁-C₆trialkylsilyl, C₁-C₆dialkylphosphonyl, or R³and R⁴taken together with N is a 5- or 6-membered saturated ring, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino, or, R^3′and R^4′ taken together with ═C represent a 5- or 6-membered saturated ring;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, or A20;

R⁵is C₁-C₄alkyl, C₁-C₄haloalkyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₄alkylamino, or C₂-C₄haloalkylamino;

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

R¹is OR^1′ or NR^1″R^1′″, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl, and R^1″ and R^1′″are independently hydrogen, C₁-C₁₂alkyl, C₃-C₁₂alkenyl, or C₃-C₁₂alkynyl; R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, cyano, or a group of the formula —CR¹⁷═CR¹⁸—SiR¹⁹R²⁰R²¹, wherein R¹⁷is hydrogen, F, or Cl; R¹⁸is hydrogen, F, Cl, C₁-C₄alkyl, or C₁-C₄haloalkyl; and R¹⁹, R²⁰, and R²¹are independently C₁-C₁₀alkyl, C₃-C₆cycloalkyl, phenyl, substituted phenyl, C₁-C₁₀alkoxy, or OH;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, or A20;

R⁶, R^6′, and R^6″ are independently C₁-C₄alkyl, C₁-C₄haloalkyl, halocyclopropyl, C₃-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₄alkylamino or C₂-C₄haloalkylamino, or NO₂;

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, or A18;

R⁷and R^7′ are independently C₁-C₄alkyl, C₁-C₄haloalkyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃haloalkoxy, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, or C₂-C₄haloalkylamino; and

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In some embodiments:

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, or C₁-C₃haloalkylthio;

A is A3, A6, A11, A12, A15, A18, A19, or A20;

R⁸is C₃-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, or C₁-C₆trialkylsilyl.

In some of these embodiments, R¹is OR¹. In some of these embodiments, X is CF. In some of these embodiments, A is A15. In some of these embodiments, R⁵is F.

In certain embodiments, the pyridine carboxylic acid herbicide can comprise a compound defined by Formula (II):

embedded image

wherein

R³and R⁴are independently hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbamyl, C₁-C₆alkylsulfonyl, C₁-C₆trialkylsilyl, C₁-C₆dialkylphosphonyl, or R³and R⁴taken together with N is a 5- or 6-membered saturated ring, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino, or, R^3′and R^4′ taken together with ═C represent a 5- or 6-membered saturated ring;

A is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, or A36;

R⁷and R^7′are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, halocyclopropyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, C₂-C₄haloalkylamino, or phenyl; and

or an agriculturally acceptable N-oxide or salt thereof.

In some embodiments:

R¹is OR^1′, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl;

R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄-alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, or C₁-C₄haloalkylthio;

R³and R⁴are hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino;

A is A1, A2, A3, A7, A8, A9, A10, A11, A12, A13, A14, A15, A21, A22, A23, A24, A27, A28, A29, A30, A31, or A32;

R⁵is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, amino, C₁-C₄alkylamino, or C₂-C₄haloalkylamino;

R⁷and R^7′ are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, cyclopropyl, amino or C₁-C₄alkylamino; and

R⁸is hydrogen, C₁-C₆alkyl, C₁-C₄haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxycarbonyl, or C₁-C₆alkylcarbamyl.

In some embodiments, R¹is OR^1′, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl.

In some embodiments, R²is halogen, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, or C₁-C₄-alkoxy. In certain embodiments, R²is Cl, methoxy, vinyl, or 1-propenyl. In some embodiments, R³and R⁴are hydrogen.

In some embodiments, A is A1, A2, A3, A7, A8, A9, A10, A13, A14, or A15. In certain embodiments, A is A1, A2, A3, A13, A14, or A15. In certain embodiments, A is A15.

In some embodiments, R⁵is hydrogen or F. In certain embodiments, R⁵is F. In certain embodiments, R⁵is H.

In some embodiments, R⁶is hydrogen or F. In certain embodiments, R⁶is F. In certain embodiments, R⁶is H. In some embodiments, R^6″ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂. In certain embodiments, R⁶, R^6′, and R^6″ are all hydrogen.

In certain embodiments, R²is Cl, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; A is A15; R⁵is hydrogen or F; R⁶is hydrogen or F; and R^6″ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂.

In certain embodiments, the pyridine carboxylic acid herbicide can comprise a compound defined by Formula (III):

embedded image

wherein

X is N or CY, wherein Y is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio or C₁-C₃haloalkylthio;

or an agriculturally acceptable N-oxide or salt thereof.

In some embodiments:

X is N, CH, CF, CCl, or CBr;

R¹is OR^1′, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl;

R²is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄-alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄-alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, or C₁-C₄haloalkylthio;

R³and R⁴are hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, formyl, C₁-C₃alkylcarbonyl, C₁-C₃haloalkylcarbonyl, or R³and R⁴taken together represent ═CR^3′(R^4′), wherein R^3′ and R^4′ are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy or C₁-C₆alkylamino;

R⁷and R^7′ are independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, cyclopropyl, amino or C₁-C₄alkylamino; and

In some embodiments, X is N, CH or CF. In some embodiments, X is N. In some embodiments, X is CH. In some embodiments, X is CF. In other embodiments, X is C—CH₃.

In some embodiments, R⁶is hydrogen or F. In certain embodiments, R⁶is F. In certain embodiments, R⁶is H. In some embodiments, R^6′ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂. In certain embodiments, R⁶and R^6′ are both hydrogen.

In certain embodiments, R⁷and R^7′ are both hydrogen.

In certain embodiments, R⁶, R^6′, R⁷, and R^7′ are all hydrogen.

In certain embodiments, X is CF, R¹is OR^1′, wherein R^1′ is hydrogen, C₁-C₈alkyl, or C₇-C₁₀arylalkyl; R²is Cl, methoxy, vinyl, or 1-propenyl; R³and R⁴are hydrogen; R⁶is hydrogen or F; and R^6′ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyclopropyl, C₂-C₄alkynyl, CN, or NO₂.

In certain embodiments, the pyridine carboxylic acid herbicide can comprise one of Compounds 1-24, the structures of which are shown in the table below.

Compound

No.
Structure

1

embedded image

In certain embodiments, the pyridine carboxylic acid herbicide can comprise 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) picolinic acid, or an agriculturally acceptable N-oxide, salt, or ester thereof.

In some embodiments, the pyridine carboxylic acid herbicide can be provided as an agriculturally acceptable salt. Exemplary agriculturally acceptable salts of the pyridine carboxylic acid herbicides of Formula (I) include, but are not limited to, sodium salts, potassium salts, ammonium salts or substituted ammonium salts, in particular mono-, di- and tri-C₁-C₈-alkylammonium salts such as methyl ammonium, dimethylammonium and isopropylammonium, mono-, di- and tri-hydroxy-C₂-C₈-alkylammonium salts such as hydroxyethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts, olamine salts, diglycolamine salts, choline salts, and quaternary ammonium salts such as those represented by the formula R⁹R¹⁰R¹¹R¹²N⁺ and wherein R⁹, R¹⁰, R¹¹and R¹²(e.g., R⁹-R¹²) each independently can represent hydrogen, C₁-C₁₀alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, C₁-C₈alkoxy, C₁-C₈alkylthio, or aryl groups, provided that R⁹-R¹²are sterically compatible.

In some embodiments, the pyridine carboxylic acid herbicide can be provided as an agriculturally acceptable ester. Suitable esters include, but are not limited to, C₁-C₈-alkyl esters and C₁-C₄-alkoxy-C₂-C₄-alkyl esters, such as methyl esters, ethyl esters, isopropyl, butyl, hexyl, heptyl, isoheptyl, isooctyl, 2-ethylhexyl, butoxyethyl esters, substituted or unsubstituted aryl esters, orthoesters, substituted or unsubstituted alkylaryl esters, and substituted or unsubstituted arylalkyl esters. In some embodiments, the ester can comprise a C₁-C₈alkyl ester, wherein the C₁-C₈alkyl group is optionally substituted with one or more moieties selected from the group consisting of cyano, C₂-C₈alkoxy, and C₂-C₈alkylsulfonyl. For example, the ester can comprise a methyl, —CH₂CN, —CH₂OCH₃, —CH₂OCH₂CH₂OCH₃, or —CH₂CH₂SO₂CH₃ester.

The ester can also be an acetal (e.g., a cyclic acetal) formed by protection of the carbonyl group in the pyridine carboxylic acid herbicides described above (e.g., by Formula (I)). For example, the pyridine carboxylic acid herbicides described above can be reacted with a suitable diol (e.g., a diol such as ethane-1,2-diol or butane-2,3-diol, for example, using standard protecting group chemistry, such as taught in Greene, et al., Protective Groups in Organic Synthesis, John Wiley and Sons, Fourth Edition, 2007, hereby incorporated by reference) to form a cyclic acetal. In one embodiment, the ester can be a cyclic acetal defined by the structure below, where R², R³, R⁴, X, and A are as described above.

embedded image

In some embodiments, the ester can comprise a substituted or unsubstituted benzyl ester. In some embodiments, the ester can comprise a benzyl ester optionally substituted with one or more moieties selected from the group consisting of halogen, C₁-C₂alkyl, C₁-C₂haloalkyl, and combinations thereof. In some embodiments, the ester can comprise a methyl ester.

The pyridine carboxylic acid herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, can be applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount sufficient to induce a herbicidal effect. In some embodiments, the pyridine carboxylic acid herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, is applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount of 0.1 grams acid equivalent per hectare (g ae/ha) or greater (e.g., 0.2 g ae/ha or greater, 0.3 g ae/ha or greater, 0.4 g ae/ha or greater, 0.5 g ae/ha or greater, 0.6 g ae/ha or greater, 0.7 g ae/ha or greater, 0.8 g ae/ha or greater, 0.9 g ae/ha or greater, 1 g ae/ha or greater, 1.1 g ae/ha or greater, 1.2 g ae/ha or greater, 1.3 g ae/ha or greater, 1.4 g ae/ha or greater, 1.5 g ae/ha or greater, 1.6 g ae/ha or greater, 1.7 g ae/ha or greater, 1.8 g ae/ha or greater, 1.9 g ae/ha or greater, 2 g ae/ha or greater, 2.25 g ae/ha or greater, 2.5 g ae/ha or greater, 2.75 g ae/ha or greater, 3 g ae/ha or greater, 4 g ae/ha or greater, 5 g ae/ha or greater, 6 g ae/ha or greater, 7 g ae/ha or greater, 8 g ae/ha or greater, 9 g ae/ha or greater, 10 g ae/ha or greater, 11 g ae/ha or greater, 12 g ae/ha or greater, 13 g ae/ha or greater, 14 g ae/ha or greater, 15 g ae/ha or greater, 16 g ae/ha or greater, 17 g ae/ha or greater, 18 g ae/ha or greater, 19 g ae/ha or greater, 20 g ae/ha or greater, 21 g ae/ha or greater, 22 g ae/ha or greater, 23 g ae/ha or greater, 24 g ae/ha or greater, 25 g ae/ha or greater, 26 g ae/ha or greater, 27 g ae/ha or greater, 28 g ae/ha or greater, 29 g ae/ha or greater, 30 g ae/ha or greater, 31 g ae/ha or greater, 32 g ae/ha or greater, 33 g ae/ha or greater, 34 g ae/ha or greater, 35 g ae/ha or greater, 36 g ae/ha or greater, 37 g ae/ha or greater, 38 g ae/ha or greater, 39 g ae/ha or greater, 40 g ae/ha or greater, 41 g ae/ha or greater, 42 g ae/ha or greater, 43 g ae/ha or greater, 44 g ae/ha or greater, 45 g ae/ha or greater, 46 g ae/ha or greater, 47 g ae/ha or greater, 48 g ae/ha or greater, 49 g ae/ha or greater, 50 g ae/ha or greater, 55 g ae/ha or greater, 60 g ae/ha or greater, 65 g ae/ha or greater, 70 g ae/ha or greater, 75 g ae/ha or greater, 80 g ae/ha or greater, 85 g ae/ha or greater, 90 g ae/ha or greater, 95 g ae/ha or greater, 100 g ae/ha or greater, 110 g ae/ha or greater, 120 g ae/ha or greater, 130 g ae/ha or greater, 140 g ae/ha or greater, 150 g ae/ha or greater, 160 g ae/ha or greater, 170 g ae/ha or greater, 180 g ae/ha or greater, 190 g ae/ha or greater, 200 g ae/ha or greater, 210 g ae/ha or greater, 220 g ae/ha or greater, 230 g ae/ha or greater, 240 g ae/ha or greater, 250 g ae/ha or greater, 260 g ae/ha or greater, 270 g ae/ha or greater, 280 g ae/ha or greater, or 290 g ae/ha or greater). In some embodiments, the pyridine carboxylic acid herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, is applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount of 300 g ae/ha or less (e.g., 290 g ae/ha or less, 280 g ae/ha or less, 270 g ae/ha or less, 260 g ae/ha or less, 250 g ae/ha or less, 240 g ae/ha or less, 230 g ae/ha or less, 220 g ae/ha or less, 210 g ae/ha or less, 200 g ae/ha or less, 190 g ae/ha or less, 180 g ae/ha or less, 170 g ae/ha or less, 160 g ae/ha or less, 150 g ae/ha or less, 140 g ae/ha or less, 130 g ae/ha or less, 120 g ae/ha or less, 110 g ae/ha or less, 100 g ae/ha or less, 95 g ae/ha or less, 90 g ae/ha or less, 85 g ae/ha or less, 80 g ae/ha or less, 75 g ae/ha or less, 70 g ae/ha or less, 65 g ae/ha or less, 60 g ae/ha or less, 55 g ae/ha or less, 50 g ae/ha or less, 49 g ae/ha or less, 48 g ae/ha or less, 47 g ae/ha or less, 46 g ae/ha or less, 45 g ae/ha or less, 44 g ae/ha or less, 43 g ae/ha or less, 42 g ae/ha or less, 41 g ae/ha or less, 40 g ae/ha or less, 39 g ae/ha or less, 38 g ae/ha or less, 37 g ae/ha or less, 36 g ae/ha or less, 35 g ae/ha or less, 34 g ae/ha or less, 33 g ae/ha or less, 32 g ae/ha or less, 31 g ae/ha or less, 30 g ae/ha or less, 29 g ae/ha or less, 28 g ae/ha or less, 27 g ae/ha or less, 26 g ae/ha or less, 25 g ae/ha or less, 24 g ae/ha or less, 23 g ae/ha or less, 22 g ae/ha or less, 21 g ae/ha or less, 20 g ae/ha or less, 19 g ae/ha or less, 18 g ae/ha or less, 17 g ae/ha or less, 16 g ae/ha or less, 15 g ae/ha or less, 14 g ae/ha or less, 13 g ae/ha or less, 12 g ae/ha or less, 11 g ae/ha or less, 10 g ae/ha or less, 9 g ae/ha or less, 8 g ae/ha or less, 7 g ae/ha or less, 6 g ae/ha or less, 5 g ae/ha or less, 4 g ae/ha or less, 3 g ae/ha or less, 2.75 g ae/ha or less, 2.5 g ae/ha or less, 2.25 g ae/ha or less, 2 g ae/ha or less, 1.9 g ae/ha or less, 1.8 g ae/ha or less, 1.7 g ae/ha or less, 1.6 g ae/ha or less, 1.5 g ae/ha or less, 1.4 g ae/ha or less, 1.3 g ae/ha or less, 1.2 g ae/ha or less, 1.1 g ae/ha or less, 1 g ae/ha or less, 0.9 g ae/ha or less, 0.8 g ae/ha or less, 0.7 g ae/ha or less, 0.6 g ae/ha or less, 0.5 g ae/ha or less, 0.4 g ae/ha or less, 0.3 g ae/ha or less, or 0.2 g ae/ha or less).

Quinolinyloxyacetate Safener

In addition to the pyridine carboxylic acid herbicide, the compositions and methods of the present disclosure can 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”—that is, to reduce the effect of the herbicide on crop plants and to improve selectivity between crop plants and weed species being targeted by the herbicide. Herbicide safeners can be used to pre-treat crop seeds prior to planting or they can be sprayed on plants as a mixture with the herbicide.

Quinolinyloxyacetate safeners are known in the art, and described for example in U.S. Pat. No. 4,902,340 and U.S. Patent Application Publication No. 2014/0031224. Quinolinyloxyacetate safeners include, for example, cloquintocet and the derivatives thereof.

In some embodiments, the quinolinyloxyacetate safener can comprise cloquintocet or an agriculturally acceptable salt or ester thereof. Cloquintocet is a quinoline compound having the following chemical structure.

embedded image

Cloquintocet can be a safener when applied in combination with herbicides and can be used to reduce phytotoxicity to crops such as wheat, barley, triticale, rye, teff, oats, corn/maize, sorghum, rice, sugarcane, and pasture grasses.

In some embodiments, the quinolinyloxyacetate safener can comprise an agriculturally acceptable ester of cloquintocet, such as cloquintocet-mexyl, the structure of which is shown below.

embedded image

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

The quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof can be used in an amount sufficient to induce a safening effect. In some embodiments the quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof is applied to vegetation or an area adjacent the vegetation or applied to soil or water in an amount of 1 gram active ingredient per hectare (g ai/ha) or greater (e.g., 2 g ai/ha or greater, 3 g ai/ha or greater, 4 g ai/ha or greater, 5 g ai/ha or greater, 6 g ai/ha or greater, 7 g ai/ha or greater, 8 g ai/ha or greater, 9 g ai/ha or greater, 10 g ai/ha or greater, 11 g ai/ha or greater, 12 g ai/ha or greater, 13 g ai/ha or greater, 14 g ai/ha or greater, 15 g ai/ha or greater, 16 g ai/ha or greater, 17 g ai/ha or greater, 18 g ai/ha or greater, 19 g ai/ha or greater, 20 g ai/ha or greater, 21 g ai/ha or greater, 22 g ai/ha or greater, 23 g ai/ha or greater, 24 g ai/ha or greater, 25 g ai/ha or greater, 26 g ai/ha or greater, 27 g ai/ha or greater, 28 g ai/ha or greater, 29 g ai/ha or greater, 30 g ai/ha or greater, 31 g ai/ha or greater, 32 g ai/ha or greater, 33 g ai/ha or greater, 34 g ai/ha or greater, 35 g ai/ha or greater, 36 g ai/ha or greater, 37 g ai/ha or greater, 38 g ai/ha or greater, 39 g ai/ha or greater, 40 g ai/ha or greater, 41 g ai/ha or greater, 42 g ai/ha or greater, 43 g ai/ha or greater, 44 g ai/ha or greater, 45 g ai/ha or greater, 46 g ai/ha or greater, 47 g ai/ha or greater, 48 g ai/ha or greater, 49 g ai/ha or greater, 50 g ai/ha or greater, 55 g ai/ha or greater, 60 g ai/ha or greater, 65 g ai/ha or greater, 70 g ai/ha or greater, 75 g ai/ha or greater, 80 g ai/ha or greater, 85 g ai/ha or greater, 90 g ai/ha or greater, 95 g ai/ha or greater, 100 g ai/ha or greater, 110 g ai/ha or greater, 120 g ai/ha or greater, 130 g ai/ha or greater, 140 g ai/ha or greater, 150 g ai/ha or greater, 160 g ai/ha or greater, 170 g ai/ha or greater, 180 g ai/ha or greater, 190 g ai/ha or greater, 200 g ai/ha or greater, 210 g ai/ha or greater, 220 g ai/ha or greater, 230 g ai/ha or greater, 240 g ai/ha or greater, 250 g ai/ha or greater, 260 g ai/ha or greater, 270 g ai/ha or greater, 280 g ai/ha or greater, or 290 g ai/ha or greater).

In some embodiments the quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof is applied to vegetation or an area adjacent the vegetation or applied to soil or water in an amount of 300 g ai/ha or less (e.g., 290 g ai/ha or less, 280 g ai/ha or less, 270 g ai/ha or less, 260 g a/ha or less, 250 g ai/ha or less, 240 g ai/ha or less, 230 g ai/ha or less, 220 g ai/ha or less, 210 g ai/ha or less, 200 g ai/ha or less, 190 g ai/ha or less, 180 g ai/ha or less, 170 g ai/ha or less, 160 g ai/ha or less, 150 g ai/ha or less, 140 g ai/ha or less, 130 g ai/ha or less, 120 g ai/ha or less, 110 g ai/ha or less, 100 g ai/ha or less, 95 g ai/ha or less, 90 g ai/ha or less, 85 g ai/ha or less, 80 g ai/ha or less, 75 g ai/ha or less, 70 g ai/ha or less, 65 g ai/ha or less, 60 g ai/ha or less, 55 g ai/ha or less, 50 g ai/ha or less, 49 g ai/ha or less, 48 g ai/ha or less, 47 g ai/ha or less, 46 g ai/ha or less, 45 g ai/ha or less, 44 g ai/ha or less, 43 g ai/ha or less, 42 g ai/ha or less, 41 g ai/ha or less, 40 g ai/ha or less, 39 g ai/ha or less, 38 g ai/ha or less, 37 g ai/ha or less, 36 g ai/ha or less, 35 g ai/ha or less, 34 g ai/ha or less, 33 g ai/ha or less, 32 g ai/ha or less, 31 g ai/ha or less, 30 g ai/ha or less, 29 g ai/ha or less, 28 g ai/ha or less, 27 g ai/ha or less, 26 g ai/ha or less, 25 g ai/ha or less, 24 g ai/ha or less, 23 g ai/ha or less, 22 g ai/ha or less, 21 g ai/ha or less, 20 g ai/ha or less, 19 g ai/ha or less, 18 g ai/ha or less, 17 g ai/ha or less, 16 g ai/ha or less, 15 g ai/ha or less, 14 g ai/ha or less, 13 g ai/ha or less, 12 g ai/ha or less, 11 g ai/ha or less, 10 g ai/ha or less, 9 g ai/ha or less, 8 g ai/ha or less, 7 g ai/ha or less, 6 g ai/ha or less, 5 g ai/ha or less, 4 g ai/ha or less, 3 g ai/ha or less, or 2 g ai/ha or less).

The quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof can be applied to vegetation or an area adjacent the vegetation or applied to soil or water in an amount ranging from any of the minimum values described above to any of the maximum values described above. In some embodiments, the quinolinyloxyacetate safener or agriculturally acceptable salt or ester thereof is applied to vegetation or an area adjacent the vegetation or applied to soil or water in an amount of from 1-300 g ai/ha (e.g., from 2-150 g ai/ha, from 5-75 g ai/ha, from 5-40 g ai/ha, from 30-40 g ai/ha, or from 5-15 g ai/ha). In some embodiments, the quinolinyloxyacetate safener or agriculturally acceptable salt or ester thereof is applied in an amount from 30-40 g ai/ha.

II. Compositions

A. Herbicidal Mixtures or Combinations

The (a) pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof is mixed with or applied in combination with (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof.

In some embodiments, the (a) pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof is mixed with or applied in combination with (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof in an amount sufficient to induce a synergistic effect. In some embodiments, (a) and (b) are used in an amount sufficient to induce a synergistic herbicidal effect while still showing good crop compatibility (i.e. their use in crops does not result in increased damage to crops or reduces damage to crops when compared to the individual application of the herbicidal compounds (a) or (b)).

As described in the Herbicide Handbook of the Weed Science Society of America, Tenth Edition, 2014, p. 487, “‘synergism’ [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response to each factor applied separately.” Synergistic in the herbicide context can mean that the use of (a) and (b) as defined above results in an increased weed control effect compared to the weed control effects that are possible with the use of (a) or (b) alone. In some embodiments, the damage or injury to the undesired vegetation or the crop caused by the compositions and methods disclosed herein is evaluated using a scale from 0% to 100%, when compared with the untreated control vegetation, wherein 0% indicates no damage to the undesired vegetation and 100% indicates complete destruction of the undesired vegetation. In some embodiments, Colby's formula is applied to determine whether using (a) and (b) in combination shows a synergistic effect: S. R. Colby, Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, WEEDS 15, p. 22 (1967)

$E = X + Y - \frac{X * Y}{100}$

wherein

X=effect in percent using (a) a pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof at an application rate a;

Y=effect in percent using (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof at an application rate b;

E=expected effect (in %) of (a)+(b) at application rates a and b.

In Colby's equation, the value E corresponds to the effect (plant damage or injury) that is to be expected if the activity of the individual compounds is additive. If the observed effect is higher than the value E calculated according to the Colby equation, then a synergistic effect is present according to the Colby equation. Likewise, with respect to the desired crop, if the observed effect is lower than the value E calculated according to the Colby equation, then a synergistic effect is present according to the Colby equation with respect to crop safening.

In some embodiments, the compositions and methods disclosed herein are synergistic as defined by the Colby equation. In some embodiments, the joint action of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof results in enhanced activity against undesired vegetation (via synergism), even at application rates below those typically used for the pesticide to have a herbicidal effect on its own. In some embodiments, the compositions and methods disclosed herein can, based on the individual components, be used at lower application rates to achieve a herbicidal effect comparable to the effect produced by the individual components at normal application rates. In some embodiments, the compositions and methods disclosed herein provide an accelerated action on undesired vegetation (i.e. they effect damaging of undesired vegetation more quickly compared with application of the individual herbicides). In some embodiments, the joint action of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof results in reduced activity against desired vegetation/crops (via synergism).

In some embodiments, the observed effect for undesired vegetation is at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15%, at least 20%, or at least 25% greater than the effect (E) calculated according to the Colby equation (e.g., an observed effect of 96% would be 4% greater than an calculated effect (E) of 92%). In some embodiments, for undesired vegetation, the difference (Do) between 100% and the observed effect is at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% less than the difference (DE) between 100% and the effect (E) calculated according to the Colby equation (e.g., an observed effect of 96% would produce a Do of 4%, a calculated effect (E) of 92% would produce a DE of 8%, and Do would be 50% less than or half of DE). In some embodiments, the observed effect for desired vegetation/crops is at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% less than the effect (E) calculated according to the Colby equation. In some embodiments, for desired vegetation/crops, the difference (Do) between 100% and the observed effect is at least 2%, at least 5%, at least 10%, at least 15%, at least 20%, or at least 25% greater than the difference (DE) between 100% and the effect (E) calculated according to the Colby equation.

In some embodiments, the weight ratio of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof (in g ae/ha) to (b) the quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof (in g ai/ha) is 1:5 or more (e.g., 1:4.75 or more, 1:4.5 or more, 1:4.25 or more, 1:4 or more, 1:3.75 or more, 1:3.5 or more, 1:3.25 or more, 1:3 or more, 1:2.75 or more, 1:2.5 or more, 1:2.25 or more, 1:2 or more, 1:1.9 or more, 1:1.8 or more, 1:1.7 or more, 1:1.6 or more, 1:1.5 or more, 1:1.4 or more, 1:1.3 or more, 1:1.2 or more, 1:1.1 or more, 1:1 or more, 1.1:1 or more, 1.2:1 or more, 1.3:1 or more, 1.4:1 or more, 1.5:1 or more, 1.6:1 or more, 1.7:1 or more, 1.8:1 or more, 1.9:1 or more, 2:1 or more, 2.25:1 or more, 2.5:1 or more, 2.75:1 or more, 3:1 or more, 3.25:1 or more, 3.5:1 or more, 3.75:1 or more, 4:1 or more, 4.25:1 or more, 4.5:1 or more, 4.75:1 or more, 5:1 or more, 6:1 or more, 7:1 or more, 8:1 or more, 9:1 or more, 10:1 or more, 11:1 or more, 12:1 or more, 13:1 or more, 14:1 or more, 15:1 or more, 16:1 or more, 17:1 or more, 18:1 or more, 19:1 or more, 20:1 or more, 25:1 or more, 30:1 or more, 35:1 or more, 40:1 or more, 45:1 or more, 50:1 or more, 55:1 or more, or 60:1 or more). In some embodiments, the weight ratio of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof (in g ae/ha) to (b) a quinolinyloxyacetate safener, or an agriculturally acceptable salt or ester thereof (in g ai/ha) is 65:1 or less (e.g., 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, 3.75:1 or less, 3.5:1 or less, 3.25:1 or less, 3:1 or less, 2.75:1 or less, 2.5:1 or less, 2.25:1 or less, 2:1 or less, 1.9:1 or less, 1.8:1 or less, 1.7:1 or less, 1.6:1 or less, 1.5:1 or less, 1.4:1 or less, 1.3:1 or less, 1.2:1 or less, 1.1:1 or less, 1:1 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 or less, 1:3.25 or less, 1:3.5 or less, 1:3.75 or less, 1:4 or less, 1:4.25 or less, 1:4.5 or less, or 1:4.75 or less).

The weight ratio of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof (in g ae/ha) to (b) a quinolinyloxyacetate safener, or an agriculturally acceptable salt or ester thereof (in g ai/ha) can range from any of the minimum ratios described above to any of the maximum values described above. In some embodiments, the weight ratio of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof to (b) a quinolinyloxyacetate safener, or an agriculturally acceptable salt or ester thereof is from 65:1 to 1:5 (e.g., from 60:1 to 1:5, from 55:1 to 1:5, from 50:1 to 1:5, from 45:1 to 1:5, from 40:1 to 1:5, from 35:1 to 1:5, from 30:1 to 1:5, from 25:1 to 1:5, from 20:1 to 1:5, from 15:1 to 1:5, from 10:1 to 1:5, from 1:1 to 1:4, from 5:1 to 1:5, 4.5:1 to 1:4.5, from 4:1 to 1:4, from 3.5:1 to 1:3.5, from 3:1 to 1:3, from 2.5:1 to 1:2.5, from 2:1 to 1:2, from 1.9:1 to 1:1.9, from 1.8:1 to 1:1.8, from 1.7:1 to 1:1.7, from 1.6:1 to 1:1.6, from 1.5:1 to 1:1.5, from 1.4:1 to 1:1.4, from 1.3:1 to 1:1.3, from 1.2:1 to 1:1.2, from 1.1:1 to 1:1.1). In some embodiments, the weight ratio of (a) the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof to (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof is 1:1.

In some examples, the active ingredients in the compositions disclosed herein consist of (a) a pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt or ester thereof and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof.

B. Formulations

The present disclosure also relates to formulations of the compositions and methods disclosed herein. In some embodiments, the formulation can be in the form of a single package formulation including both (a) a pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof. In some embodiments, the formulation can be in the form of a single package formulation including both (a) and (b) and further including at least one additive. In some embodiments, the formulation can be in the form of a two-package formulation, wherein one package contains (a) and optionally at least one additive while the other package contains (b) and optionally at least one additive. In some embodiments of the two-package formulation, the formulation including (a) and optionally at least one additive and the formulation including (b) and optionally at least one additive are mixed before application and then applied simultaneously. In some embodiments, the mixing is performed as a tank mix (i.e., the formulations are mixed immediately before or upon dilution with water). In some embodiments, the formulation including (a) and the formulation including (b) are not mixed but are applied sequentially (in succession), for example, 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, of each other.

In some embodiments, the formulation of (a) and (b) is present in suspended, emulsified, or dissolved form. Exemplary formulations include, but are not limited to, aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, aqueous emulsions, aqueous microemulsions, aqueous suspo-emulsions, oil dispersions, self-emulsifying formulations, pastes, dusts, and materials for spreading or granules.

In some embodiments, (a) a pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and/or (b) a quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof is an aqueous solution that can be diluted before use. In some embodiments, (a) and/or (b) is provided as a high-strength formulation such as a concentrate. In some embodiments, the concentrate is stable and retains potency during storage and shipping. In some embodiments, the concentrate is a clear, homogeneous liquid that is stable at temperatures of 54° C. or greater. In some embodiments, the concentrate does not exhibit any precipitation of solids at temperatures of −10° C. or higher. In some embodiments, the concentrate does not exhibit separation, precipitation, or crystallization of any components at low temperatures. For example, the concentrate remains a clear solution at temperatures below 0° C. (e.g., below −5° C., below −10° C., below −15° C.). In some embodiments, the concentrate exhibits a viscosity of less than 50 centipoise (50 megapascals), even at temperatures as low as 5° C.

The compositions and methods disclosed herein can also be mixed with or applied with an additive. In some embodiments, the additive can be diluted in water or can be concentrated. In some embodiments, the additive is added sequentially. In some embodiments, the additive is added simultaneously. In some embodiments, the additive is premixed with the pyridine carboxylic acid herbicide or agriculturally acceptable N-oxide, salt, or ester thereof. In some embodiments, the additive is premixed with the quinolinyloxyacetate safener or agriculturally acceptable salt or ester thereof.

C. Other Actives

In some embodiments, the additive is an additional pesticide. For example, the compositions described herein can be applied in conjunction with one or more additional herbicides to control undesirable vegetation. The composition can be formulated with the one or more additional herbicides, tank mixed with the one or more additional herbicides, or applied sequentially with the one or more additional herbicides. Exemplary additional herbicides include, but are not limited to: 4-CPA, 4-CPB, 4-CPP, 2,4-D, 2,4-D choline salt, 2,4-D esters and amines, 2,4-DB, 3,4-DA, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, 4-aminopicolinic acid based herbicides, such as halauxifen, halauxifen-methyl, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylic acis, benzyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, and those described in U.S. Pat. Nos. 7,314,849 and 7,432,227 to Balko, et al, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulide, benthiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, borax, bromacil, bromobonil, bromobutide, bromofenoxim, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cisanilide, clacyfos, clethodim, cliodinate, clodinafop-propargyl, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop-butyl, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop-methyl, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethbenzamide, ethametsulfuron, ethidimuron, ethiolate, ethobenzamid, etobenzamid, ethofumesate, ethoxyfen, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P-ethyl, fenoxaprop-P-ethyl+isoxadifen-ethyl, fenoxasulfone, fenquinotrione, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, fluazifop, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, fumiclorac, furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P-ammonium, glyphosate salts and esters, halosafen, haloxydine, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazapic, imazapyr, imazaquin, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron-ethyl-sodium, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA esters and amines, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraflufen-ethyl, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron-methyl, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prohexadione-calcium, prometon, prometryn, pronamide, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen, pyributicarb, pyriclor, pyridafol, pyridate, pyrithiobac-sodium, pyroxasulfone, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P-ethyl, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiameturon, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thifensulfurn-methyl, thiobencarb, tiafenacil, tiocarbazil, tioclorim, tolpyralate, topramezone, tralkoxydim, tri-allate, triafamone, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, tricamba, triclopyr choline salt, triclopyr esters and amines, tridiphane, trietazine, trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, xylachlor and salts, esters, optically active isomers, and mixtures thereof.

In some embodiments, the additional pesticide or an agriculturally acceptable salt or ester thereof is provided in a premixed formulation with (a), (b), or combinations thereof. In some embodiments, the pyridine carboxylic acid herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof is provided in a premixed formulation with an additional pesticide. In some embodiments, the quinolinyloxyacetate safener or an agriculturally acceptable salt or ester thereof is provided in a premixed formulation with an additional pesticide.

D. Adjuvants/Carriers/Colorants/Adhesives

In some embodiments, the additive includes 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, dispersing agents, thickening agents, freeze point depressants, antimicrobial agents, crop oil, herbicide safeners, adhesives (for instance, 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 concentrate (mineral oil (85%)+emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-C₁₁alkylpolyglycoside; phosphate alcohol ethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8 EO); tallow amine ethoxylate (15 EO); and PEG(400) dioleate-99.

In some embodiments, the additive can be an additional safener.

Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants, emulsifiers) include, but are not limited to, the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids, phenolsulfonic acids, naphthalenesulfonic acids, and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and proteins, denatured proteins, polysaccharides (e.g., methylcellulose), hydrophobically modified starches, polyvinyl alcohol, polycarboxylates, polyalkoxylates, polyvinyl amine, polyethyleneimine, polyvinylpyrrolidone and copolymers thereof.

Exemplary thickeners include, but are not limited to, polysaccharides, such as xanthan gum, and organic and inorganic sheet minerals, and mixtures thereof.

Exemplary antifoam agents include, but are not limited to, silicone emulsions, long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds, and mixtures thereof.

Exemplary antimicrobial agents include, but are not limited to, bactericides based on dichlorophen and benzyl alcohol hemiformal, and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones, and mixtures thereof.

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

Exemplary colorants include, but are not limited to, the dyes known under the names 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 adhesives include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof.

In some embodiments, the additive includes a carrier. In some embodiments, the additive includes a liquid or solid carrier. In some embodiments, the additive includes an organic or inorganic carrier. Exemplary liquid carriers include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like or less, vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like or less, esters of the above vegetable oils or less, esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like or less, esters of mono, di and polycarboxylic acids and the like, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers and the like, and water as well as mixtures thereof. Exemplary solid carriers include, but are not limited to, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, pyrophyllite clay, attapulgus clay, kieselguhr, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, and mixtures thereof.

In some embodiments, emulsions, pastes or oil dispersions, can be prepared by homogenizing (a) and (b) in water by means of wetting agent, tackifier, dispersant or emulsifier. In some embodiments, concentrates suitable for dilution with water are prepared, comprising (a), (b), a wetting agent, a tackifier, and a dispersant or emulsifier.

In some embodiments, powders or materials for spreading and dusts can be prepared by mixing or concomitant grinding of (a) and (b) and optionally an additional safener with a solid carrier.

In some embodiments, granules (e.g., coated granules, impregnated granules and homogeneous granules) can be prepared by binding the (a) and (b) to solid carriers.

The formulations disclosed herein can comprise a synergistic, herbicidally effective amount of (a) and (b). In some embodiments, the concentrations of (a) and (b) in the formulations can be varied. In some embodiments, the formulations comprise from 1% to 95% (e.g., from 5% to 95%, from 10% to 80%, from 20% to 70%, from 30% to 50%) by total weight of (a) and (b). In formulations designed to be employed as concentrates, (a) and (b) can be present in a concentration of from 0.1 to 98 weight percent (0.5 to 90 weight percent), based on the total weight of the formulation. Concentrates can be diluted with an inert carrier, such as water, prior to application. The diluted formulations applied to undesired vegetation or the locus of undesired vegetation can contain from 0.0006 to 8.0 weight percent of (a) and (b) (e.g., from 0.001 to 5.0 weight percent), based on the total weight of the diluted formulation.

In some embodiments, (a) and (b), independently, can be employed in a purity of from 90% to 100% (e.g., from 95% to 100%) according to nuclear magnetic resonance (NMR) spectrometry. In some embodiments, the concentrations of (a), (b), and additional pesticides in the formulations can be varied. In some embodiments, the formulations comprise from 1% to 95% (e.g., from 5% to 95%, from 10% to 80%, from 20% to 70%, from 30% to 50%) by total weight of (a), (b), and additional pesticides. In some embodiments, (a), (b), and additional pesticides, independently, can be employed in a purity of from 90% to 100% (e.g., from 95% to 100%) according to NMR spectrometry.

III. Methods of Use

The compositions disclosed herein can be applied in any known technique for applying herbicides. Exemplary application techniques include, but are not limited to, spraying, atomizing, dusting, spreading, or direct application into water (in-water). The method of application can vary depending on the intended purpose. In some embodiments, the method of application can be chosen to ensure the finest possible distribution of the compositions disclosed herein.

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

The compositions disclosed herein can be applied pre-emergence (before the emergence of undesirable vegetation) or post-emergence (i.e., during and/or after emergence of the undesirable vegetation). In some embodiments, the composition is applied post-emergence to the undesirable vegetation. In some embodiments, the pyridine carboxylic acid herbicide and quinolinyloxyacetate safener are applied simultaneously.

When the compositions are used in crops, the compositions can be applied after seeding and before or after the emergence of the crop plants. In some embodiments, the compositions disclosed herein show good crop tolerance even when the crop has already emerged and can be applied during or after the emergence of the crop plants. In some embodiments, when the compositions are used in crops, the compositions can be applied before seeding of the crop plants.

In some embodiments, the compositions disclosed herein are applied to vegetation or an area adjacent the vegetation or applying to soil or water to prevent the emergence or growth of vegetation by spraying (e.g., foliar spraying). In some embodiments, the spraying techniques use, for example, water as carrier and spray volume rates of from 2 liters per hectare (L/ha) to 2000 L/ha (e.g., from 10-1000 L/ha or from 50-500 L/ha). In some embodiments, the compositions disclosed herein are applied by the low-volume or the ultra-low-volume method, wherein the application is in the form of micro granules. In some embodiments, wherein the compositions disclosed herein are less well tolerated by certain crop plants, the compositions can be applied with the aid of the spray apparatus in such a way that they come into little contact, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable vegetation that grows underneath or on the bare soil (e.g., post-directed or lay-by). In some embodiments, the compositions disclosed herein can be applied as dry formulations (e.g., granules, WDGs, etc.) into water.

In some embodiments, wherein the undesirable vegetation is treated post-emergence, the compositions disclosed herein are applied by foliar application. In some embodiments, herbicidal activity is exhibited by the compounds of the mixture when they are applied directly to the plant or to the locus of the plant at any stage of growth or before planting or emergence. The effect observed can depend upon the type of undesirable vegetation to be controlled, the stage of growth of the undesirable vegetation, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. In some embodiments, 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 undesired vegetation in a variety of crop and non-crop applications. In some embodiments, the compositions and methods disclosed herein can be used for controlling undesired vegetation in crops. In some embodiments, the undesirable vegetation is controlled in a row crop. Exemplary crops include, but are not limited to, wheat, barley, triticale, rye, teff, oats, corn/maize, cotton, soy, sorghum, rice, sugarcane and range land (e.g., pasture grasses). In some embodiments, the compositions and methods disclosed herein can be used for controlling undesired vegetation in corn/maize, wheat, barley or a combination thereof.

The compositions and methods disclosed herein can be used for controlling undesired vegetation in non-crop areas. Exemplary non-crop areas include, but are not limited to, turfgrass, pastures, grasslands, rangelands, fallow land, rights-of-way, aquatic settings, tree and vine, wildlife management areas, or rangeland. In some embodiments, the compositions and methods disclosed herein can be used in industrial vegetation management (IVM) or for utility, pipeline, roadside, and railroad rights-of-way applications. In some embodiments, the compositions and methods disclosed herein can also be used in forestry (e.g., for site preparation or for combating undesirable vegetation in plantation forests). In some embodiments, the compositions and methods disclosed herein can be used to control undesirable vegetation in conservation reserve program lands (CRP), trees, vines, grasslands, and grasses grown for seeds. In some embodiments, the compositions and methods disclosed herein can be used on lawns (e.g., residential, industrial, and institutional), golf courses, parks, cemeteries, athletic fields, and sod farms.

The compositions and methods disclosed herein can also be used in crop plants that are resistant to, for instance, herbicides, pathogens, and/or insects. In some embodiments, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more herbicides because of genetic engineering or breeding. In some embodiments, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more pathogens such as plant pathogenous fungi owing to genetic engineering or breeding. In some embodiments, the compositions and methods disclosed herein can be used in crop plants that are resistant to attack by insects owing 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, owing to introduction of the gene for Bacillus thuringiensis (or Bt) toxin by genetic modification, are resistant to attack by certain insects. In some embodiments, the compositions and methods described herein can be used in conjunction with glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors, imidazolinones, acetolactate synthase (ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, and bromoxynil to control vegetation in crops tolerant to glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors, imidazolinones, acetolactate synthase (ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, bromoxynil, or combinations thereof. In some embodiments, the undesirable vegetation is controlled in glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors, imidazolinones, acetolactate synthase (ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, and bromoxynil tolerant crops possessing single, multiple or stacked traits conferring tolerance to single or multiple chemistries and/or multiple modes of action. In some embodiments, the undesirable vegetation can be controlled in a crop that is ACCase-tolerant, ALS-tolerant, or a combination thereof. The combination of (a), (b), and a complementary herbicide or salt or ester thereof can be used in combination with herbicides that are selective for the crop being treated and which complement the spectrum of weeds controlled by these compounds at the application rate employed. In some embodiments, the compositions described herein and other complementary herbicides are applied at the same time, either as a combination formulation or as a tank mix, or as sequential applications. The compositions and methods may be used in controlling undesirable vegetation in crops possessing agronomic stress tolerance (including but not limited to drought, cold, heat, salt, water, nutrient, 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 stature and plant architecture).

In some embodiments, the compositions disclosed herein can be used for controlling undesirable vegetation including grasses, broadleaf weeds, sedge weeds, and combinations thereof. In some embodiments, the compositions disclosed herein can be used for controlling undesirable vegetation including, but not limited to, Polygonum species such as wild buckwheat (Polygonum convolvulus), Amaranthus species such as pigweed (Amaranthus retroflexus), Chenopodium species such as common lambsquarters (Chenopodium album L.), Sida species such as prickly sida (Sida spinosa L.), Ambrosia species such as common ragweed (Ambrosia artemisiifolia), Cyperus species such as nutsedge (Cyperus esculentus), Setaria species such as giant foxtail (Setaria faberi), Sorghum species, Acanthospermum species, Anthemis species, Atriplex species, Brassica species, Cirsium species, Convolvulus species, Conyza species, such as horseweed (Conyza canadensis), Cassia species, Commelina species, Datura species, Euphorbia species, Geranium species, Galinsoga species, Ipomea species such as morning-glory, Lamium species, Lactuca species, Malva species, Matricaria species, Prosopis species, Rumex species, Sisymbrium species, Solanum species, Trifolium species, Xanthium species, Veronica species, Viola species such as wild pansy (Viola tricolor), common chickweed (Stellaria media), velvetleaf (Abutilon theophrasti), hemp sesbania (Sesbania exaltata Cory), Anoda cristata, Bidens pilosa, Brassica kaber, shepherd's purse (Capsella bursa-pastoris), cornflower (Centaurea cyanus or Cyanus segetum), hempnettle (Galeopsis tetrahit), cleavers (Galium aparine), Helianthus annuus, Desmodium tortuosum, kochia (Kochia scoparia), Medicago arabica, Mercurialis annua, Myosotis arvensis, common poppy (Papaver rhoeas), Raphanus raphanistrum, Russian thistle (Salsola kali), wild mustard (Sinapis arvensis), Sonchus arvensis, Thlaspi arvense, Tagetes minuta, Richardia brasiliensis, Plantago major, Plantago lanceolata, bird's-eye speedwell (Veronica persica) and speedwell.

In some embodiments, the undesirable vegetation includes velvetleaf (ABUTH, Abutilon theophrasti), pigweed (AMARE, Amaranthus retroflexus), winter rape (BRSNW, Brassica napus), shepherd's purse (CAPBP, Capsella bursa-pastoris), cornflower (CENCY, Centaurea cyanus or Cyanus segetum), lambsquarters (CHEAL, Chenopodium album), thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperus esculentus), poinsettia (EPHHL, Euphorbia heterophylla), cleavers (GALAP, Galium aparine), common sunflower (HELAN, Helianthus annuus), kochia (KCHSC, Kochia scoparia), prickly lettuce (LACSE, Lactuca serriola), purple deadnettle (LAMPU, Lamium purpureum), wild chamomile (MATCH, Matricaria chamomilla), common poppy (PAPRH, Papaver rhoeas), wild buckwheat (POLCO, Polygonum convolvulus), Russian thistle (SASKR, Salsola kali), giant foxtail (SETFA, Setaria faberi), green foxtail (SETVI, Setaria viridis), wild mustard (SINAR, Sinapis arvensis), common sorghum (SORVU, Sorghum vulgare), chickweed (STEME, Stellaria media), bird's-eye speedwell (VERPE, Veronica persica), wild pansy (VIOTR, Viola tricolor), or a combination thereof.

In some embodiments, the undesirable vegetation includes velvetleaf (ABUTH, Abutilon theophrasti), pigweed (AMARE, Amaranthus retroflexus), winter rape (BRSNW, Brassica napus), lambsquarters (CHEAL, Chenopodium album), thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperus esculentus), poinsettia (EPHHL, Euphorbia heterophylla), wild buckwheat (POLCO, Polygonum convolvulus), giant foxtail (SETFA, Setaria faberi), chickweed (STEME, Stellaria media), or a combination thereof.

The herbicidal compositions described herein can be used to control herbicide resistant or tolerant weeds. The methods employing the compositions described herein may also be employed to control herbicide resistant or tolerant weeds. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes resistant or tolerant to acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors (e.g., imidazolinones, sulfonylureas, pyrimidinylthiobenzoates, triazolopyrimidines, sulfonylaminocarbonyltriazolinones), photosystem II inhibitors (e.g., phenylcarbamates, pyridazinones, triazines, triazinones, uracils, amides, ureas, benzothiadiazinones, nitriles, phenylpyridazines), acetyl CoA carboxylase (ACCase) inhibitors (e.g., aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazolines), synthetic auxins (e.g., benzoic acids, phenoxycarboxylic acids, pyridine carboxylic acids, quinoline carboxylic acids), auxin transport inhibitors (e.g., phthalamates, semicarbazones), photosystem I inhibitors (e.g., bipyridyliums), 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors (e.g., glyphosate), glutamine synthetase inhibitors (e.g., glufosinate, bialafos), microtubule assembly inhibitors (e.g., benzamides, benzoic acids, dinitroanilines, phosphoramidates, pyridines), mitosis inhibitors (e.g., carbamates), very long chain fatty acid (VLCFA) inhibitors (e.g., acetamides, chloroacetamides, oxyacetamides, tetrazolinones), fatty acid and lipid synthesis inhibitors (e.g., phosphorodithioates, thiocarbamates, benzofuranes, chlorocarbonic acids), protoporphyrinogen oxidase (PPO) inhibitors (e.g., diphenylethers, N-phenylphthalimides, oxadiazoles, oxazolidinediones, phenylpyrazoles, pyrimidinediones, thiadiazoles, triazolinones), carotenoid biosynthesis inhibitors (e.g., clomazone, amitrole, aclonifen), phytoene desaturase (PDS) inhibitors (e.g., amides, anilidex, furanones, phenoxybutan-amides, pyridiazinones, pyridines), 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors (e.g., callistemones, isoxazoles, pyrazoles, triketones), cellulose biosynthesis inhibitors (e.g., nitriles, benzamides, quinclorac, triazolocarboxamides), herbicides with multiple modes of action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals. 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., target site resistance or metabolic resistance).

By way of non-limiting illustration, examples of certain embodiments of the present disclosure are given below. Parts and percentages are on a per weight basis unless otherwise indicated.

EXAMPLES
Example 1
Herbicidal Activity and Effect on Crop Injury on Corn/Maize and Spring Wheat (TRZAS) of Cloquintocet-Mexyl in Combination with Compounds of Formula (I) in Greenhouse Trials

Methodology—Evaluation of Postemergence Herbicidal Safening in Crops Greenhouse Trials

Seeds of the desired test plant species were planted in Sun Gro MetroMix® 306 planting mixture, which typically has a pH of 6.0 to 6.8 and an organic matter content of about 30 percent, in plastic pots with a surface area of 103.2 square centimeters (cm²). When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 7-36 days (d) in a greenhouse with an approximate 14-hour (h) photoperiod which was maintained at about 23° C. during the day and 22° C. during the night. Nutrients and water were added on a regular basis and supplemental lighting was provided with overhead metal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the second or third true leaf stage.

Weighed amounts of technical material were dissolved in a volume of 97:3 volume per volume (v/v) acetone/dimethyl sulfoxide (DMSO) to stock solutions. If the experimental compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions were diluted with an aqueous mixture of 1.5% v/v of Agri-dex crop oil concentrate to provide the appropriate application rates. Compound requirements are based upon a 12 milliliter (mL) application volume at a rate of 187 liters per hectare (L/ha). Stocks solutions of the safeners were prepared following the same procedure. Spray solutions of the safeners and experimental compound mixtures were prepared by adding the stock solutions to the appropriate amount of dilution solution to form a 12 mL spray solution in two-way combinations. Formulated compounds were applied to the plant material with an overhead Mandel track sprayer equipped with 8002E nozzles calibrated to deliver 187 L/ha over an application area of 0.503 square meters (m²) at a spray height of 18 inches (43 centimeters (cm)) above average plant canopy. Control plants were sprayed in the same manner with the solvent blank. All herbicide application (component a) rates are in g ae/ha and all safener (component b) rates are in g ai/ha.

The treated plants and control plants were placed in a greenhouse as described above and watered by sub-irrigation to prevent wash-off of the test compounds. After 20-22 d, the condition of the test plants as compared with that of the control plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complete kill. The condition of the test plants was compared with that of the control plants as determined visually and scored on a scale of 0 to 100 percent, where 0 corresponds to no injury and 100 corresponds to complete kill. Colby's equation was used to determine the herbicidal effects expected from the mixtures.

The safener cloquintocet-mexyl was combined with compound 1, compound 2, compound 4, compound 5, and compound 6, and applied to corn/maize (ZEAMX) and spring wheat (TRZAS) and the phytotoxicity of the herbicidal compositions was measured. In addition, the efficacy of the herbicidal composition on velvetleaf (ABUTH, Abutilon theophrasti), pigweed (AMARE, Amaranthus retroflexus), winter rape (BRSNW, Brassica napus), lambsquarters (CHEAL, Chenopodium album), thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperus esculentus), poinsettia (EPHHL, Euphorbia heterophylla), wild buckwheat (POLCO, Polygonum convolvulus), giant foxtail (SETFA, Setaria faberi), and chickweed (STEME, Stellaria media) was evaluated. The results are summarized in Tables 1-5.

TABLE 1

Effect (% visual injury) of compound 1 on corn/maize (ZEAMX).

Application
compound 1
35
0
35

rate (g/ha)
CQC-m
0
35
35

ZEAMX
Ob
40
0
0

Ex
—
—
40

Δ

−40

AMARE
Ob
100
0
98

Ex
—
—
100

Δ
0
0
-2

BRSNW
Ob
99
0
99

Ex
—
—
99

Δ

−1

CHEAL
Ob
100
0
95

Ex
—
—
100

Δ

−5

CYPES
Ob
80
0
75

Ex
—
—
80

Δ

−5

EPHHL
Ob
100
0
100

Ex
—
—
100

Δ

0

POLCO
Ob
99
0
96

Ex
—
—
99

Δ

−2

STEME
Ob
100
0
100

Ex
—
—
100

Δ

0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

ZEAMX = Zea mays (corn/maize)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CHEAL = Chenopodium album (lambsquarters)

CYPES = Cyperus esculentus (nutsedge)

EPHHL = Euphorbia heterophylla (poinsettia)

POLCO = Polygonum convolvulus (wild buckwheat)

STEME = Stellaria media (chickweed)

TABLE 2

Effect (% visual injury) of compound 2 on corn/maize

(ZEAMX) and spring wheat (TRZAS).

Application
compound 2
35
0
35

rate (g/ha)
CQC-m
0
35
35

ZEAMX
Ob
35
0
0

Ex
—
—
35

Δ

−35

TRZAS
Ob
15
0
0

Ex

15

Δ

−15

ABUTH
Ob
80
0
80

Ex
—
—
80

Δ

0

AMARE
Ob
100
0
100

Ex
—
—
100

Δ

0

BRSNW
Ob
100
0
100

Ex
—
—
100

Δ

0

CHEAL
Ob
97
0
93

Ex
—
—
97

Δ

−4

CIRAR
Ob
70
0
70

Ex
—
—
70

Δ

0

CYPES
Ob
30
0
30

Ex
—
—
30

Δ

0

EPHHL
Ob
100
0
100

Ex
—
—
100

Δ

0

POLCO
Ob
100
0
100

Ex
—
—
100

Δ

0

g/ha= grams per hectare

CQC-m = Cloquintocet-mexyl

ZEAMX = Zea mays (corn/maize)

TRZAS = Triticum aestivum (spring wheat)

ABUTH = Abutilon theophrasti (Velvetleaf)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CHEAL = Chenopodium album (lambsquarters)

CIRAR = Cirsium arvense (thistle)

CYPES = Cyperus esculentus (nutsedge)

EPHHL = Euphorbia heterophylla (poinsettia)

POLCO = Polygonum convolvulus (wild buckwheat)

TABLE 3

Effect (% visual injury) of compound 4 on corn/maize

(ZEAMX) and spring wheat (TRZAS).

Application
compound 4
35
0
35

rate (g/ha)
CQC-m
0
35
35

ZEAMX
Ob
35
0
0

Ex
—
—
35

Δ

−35

TRZAS
Ob
40
0
0

Ex

40

Δ

−40

ABUTH
Ob
80
0
80

Ex
—
—
80

Δ

0

AMARE
Ob
100
0
100

Ex
—
—
100

Δ

0

BRSNW
Ob
97
0
97

Ex
—
—
97

Δ

0

CHEAL
Ob
97
0
97

Ex
—
—
97

Δ

0

CIRAR
Ob
75
0
80

Ex
—
—
75

Δ

5

CYPES
Ob
0
0
0

Ex
—
—
0

Δ

0

EPHHL
Ob
100
0
100

Ex
—
—
100

Δ

0

POLCO
Ob
100
0
100

Ex
—
—
100

Δ

0

STEME
Ob
93
0
100

Ex
—
—
93

Δ

7

g/ha=grams per hectare;

CQC-m = Cloquintocet-mexyl

ZEAMX = Zea mays (corn/maize)

TRZAS = Triticum aestivum (spring wheat)

ABUTH = Abutilon theophrasti (velvetleaf)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CHEAL = Chenopodium album (lambsquarters)

CIRAR = Cirsium arvense (thistle)

CYPES = Cyperus esculentus (nutsedge)

EPHHL = Euphorbia heterophylla (poinsettia)

POLCO = Polygonum convolvulus (wild buckwheat)

STEME = Stellaria media (chickweed)

TABLE 4

Effect (% visual injury) of compound 5 on corn/maize

(ZEAMX) and spring wheat (TRZAS).

Application
compound 5
35
0
35

rate (g/ha)
CQC-m
0
35
35

ZEAMX
Ob
35
0
0

Ex
—
—
35

Δ

−35

TRZAS
Ob
45
0
0

Ex

45

Δ

−45

ABUTH
Ob
80
0
75

Ex
—
—
80

Δ

−5

AMARE
Ob
100
0
100

Ex
—
—
100

Δ

0

BRSNW
Ob
97
0
100

Ex
—
—
97

Δ

3

CHEAL
Ob
100
0
97

Ex
—
—
100

Δ

−3

CIRAR
Ob
80
0
70

Ex
—
—
80

Δ

−10

CYPES
Ob
0
0
0

Ex
—
—
0

Δ

0

EPHHL
Ob
100
0
100

Ex
—
—
100

Δ

0

POLCO
Ob
100
0
97

Ex
—
—
100

Δ

−3

SETFA
Ob
60
0
65

Ex
—
—
60

Δ

5

STEME
Ob
85
0
95

Ex
—
—
85

Δ

10

g/ha = grams per hectare;

CQC-m = Cloquintocet-mexyl;

ZEAMX = Zea mays (corn/maize);

TRZAS = Triticum aestivum (spring wheat);

ABUTH = Abutilon theophrasti (Velvetleaf);

AMARE = Amaranthus retroflexus (pigweed);

BRSNW = Brassica napus (winter rape);

CHEAL = Chenopodium album (lambsquarters);

CIRAR = Cirsium arvense (thistle);

CYPES = Cyperus esculentus (nutsedge);

EPHHL = Euphorbia heterophylla (poinsettia);

POLCO = Polygonum convolvulus (wild buckwheat);

SETFA = Setaria faberi (giant foxtail);

STEME = Stellaria media (chickweed)

TABLE 5

Effect (% visual injury) of compound 6 on corn/maize

(ZEAMX) and spring wheat (TRZAS).

Application
compound 6
35
0
35

rate (g/ha)
CQC-m
0
35
35

ZEAMX
Ob
25
0
0

Ex
—
—
25

Δ

−25

TRZAS
Ob
35
0
0

Ex

35

Δ

−35

ABUTH
Ob
80
0
80

Ex
—
—
80

Δ

0

AMARE
Ob
100
0
100

Ex
—
—
100

Δ

0

BRSNW
Ob
75
0
60

Ex
—
—
75

Δ

−15

CHEAL
Ob
100
0
95

Ex
—
—
100

Δ

−5

CIRAR
Ob
75
0
70

Ex
—
—
75

Δ

−5

CYPES
Ob
0
0
0

Ex
—
—
0

Δ

0

EPHHL
Ob
100
0
100

Ex
—
—
100

Δ

0

POLCO
Ob
97
0
95

Ex
—
—
97

Δ

−2

SETFA
Ob
10
0
10

Ex
—
—
10

Δ

0

g/ha = grams per hectare;

CQC-m = Cloquintocet-mexyl;

ZEAMX = Zea mays (corn/maize);

TRZAS = Triticum aestivum (spring wheat);

ABUTH = Abutilon theophrasti (Velvetleaf);

AMARE = Amaranthus retroflexus (pigweed);

BRSNW = Brassica napus (winter rape);

CHEAL = Chenopodium album (lambsquarters);

CIRAR = Cirsium arvense (thistle);

CYPES = Cyperus esculentus (nutsedge);

EPHHL = Euphorbia heterophylla (poinsettia);

POLCO = Polygonum convolvulus (wild buckwheat);

SETFA = Setaria faberi (giant foxtail)

Example 2
Herbicidal Activity and Effect on Crop Injury on Wheat and Barley of Cloquintocet-Mexyl in Combination with Compounds of Formula (I) in Greenhouse Trials

Methodology—Evaluation of Postemergence Herbicidal Safening in Cereal Crops Greenhouse Trials

The safener cloquintocet-mexyl was combined with compound 1, compound 2, compound 3, compound 7, compound 8, compound 9, compound 10, compound 11, compound 12, compound 13, compound 14, compound 15, compound 16, compound 17, compound 18, compound 19, and compound 20, and applied to spring wheat (TRZAS), winter wheat (TRZAW), and spring barley (HORVS) and the phytotoxicity of the herbicidal compositions was measured. In addition, the efficacy of the herbicidal composition on velvetleaf (ABUTH, Abutilon theophrasti), pigweed (AMARE, Amaranthus retroflexus), winter rape (BRSNW, Brassica napus), shepherd's purse (CAPBP, Capsella bursa-pastoris), cornflower (CENCY, Centaurea cyanus or Cyanus segetum), lambsquarters (CHEAL, Chenopodium album), thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperus esculentus), poinsettia (EPHHL, Euphorbia heterophylla), cleavers (GALAP, Galium aparine), kochia (KCHSC, Kochia scoparia), prickly lettuce (LACSE, Lactuca serriola), purple deadnettle (LAMPU, Lamium purpureum), wild chamomile (MATCH, Matricaria chamomilla), common poppy (PAPRH, Papaver rhoeas), wild buckwheat (POLCO, Polygonum convolvulus), Russian thistle (SASKR, Salsola kali), giant foxtail (SETFA, Setaria faberi), green foxtail (SETVI, Setaria viridis), wild mustard (SINAR, Sinapis arvensis), common sorghum (SORVU, Sorghum vulgare), chickweed (STEME, Stellaria media), bird's-eye speedwell (VERPE, Veronica persica), wild pansy (VIOTR, Viola tricolor) was evaluated. The results are summarized in Tables 6-22.

TABLE 6

Effect (% visual injury) of compound 1 on barley (HORVS), spring wheat (TRZAS), and winter wheat (TRZAW).

compound 1

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
13
13
24
32
41
0
0
0
0
0
2
2
4
2
6

Ex
—
—
—
—
—
—
—
—
—
—
13
13
24
32
41

Δ

−11
−12
−20
−30
−35

TRZAS
Ob
13
16
31
39
51
0
0
0
0
0
2
2
4
6
10

Ex
—
—
—
—
—
—
—
—
—
—
13
16
31
39
51

Δ

−11
−14
−27
−32
−41

TRZAW
Ob

40
50

0
0

0
0

Ex
—
—
—
—
—
—
—
—
—
—

40
50

Δ

−40
−50

AMARE
Ob
81
91
99
100
100
0
0
0
0
0
84
92
97
100
100

Ex
—
—
—
—
—
—
—
—
—
—
81
91
99
100
100

Δ

3
1
−2
0
0

BRSNW
Ob
79
84
96
99
100
0
0
0
0
0
68
86
93
100
100

Ex
—
—
—
—
—
—
—
—
—
—
79
84
96
99
100

Δ

−12
1
−3
1
0

CAPBP
Ob
70
100
100
100
100
0
0
0
0
0
70
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
100
100
100
100

Δ

0
0
0
0
0

CENCY
Ob
100
100
100
100
100
0
0
0
0
0
100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
100
100
100
100
100

Δ

0
0
0
0
0

CHEAL
Ob
86
95
99
100
100
0
0
0
0
0
81
89
98
98
100

Ex
—
—
—
—
—
—
—
—
—
—
86
95
99
100
100

Δ

−5
−7
−2
−3
0

CIRAR
Ob
35
62
80
90
96
0
0
0
0
0
33
65
82
93
97

Ex
—
—
—
—
—
—
—
—
—
—
35
62
80
90
96

Δ

−2
3
2
3
1

KCHSC
Ob
67
72
93
92
97
0
0
0
0
0
63
74
88
96
95

Ex
—
—
—
—
—
—
—
—
—
—
67
72
93
92
97

Δ

−5
3
−4
3
−3

LACSE
Ob
70
93
100
100
100
0
0
0
0
0
70
95
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
93
100
100
100

Δ

0
2
0
0
0

LAMPU
Ob
76
86
90
98
100
0
0
0
0
0
76
85
95
96
97

Ex
—
—
—
—
—
—
—
—
—
—
76
86
90
98
100

Δ

0
−1
5
−2
−3

PAPRH
Ob
97
99
100
100
100
0
0
0
0
0
96
98
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
97
99
100
100
100

Δ

−1
−1
0
0
0

SASKR
Ob
66
70
82
90
91
0
0
0
0
0
65
75
82
90
91

Ex
—
—
—
—
—
—
—
—
—
—
66
70
82
90
91

Δ

−1
5
−1
0
−1

SINAR
Ob
85
88
98
99
100
0
0
0
0
0
79
93
96
96
98

Ex
—
—
—
—
—
—
—
—
—
—
85
88
98
99
100

Δ

−6
5
−1
−3
−3

VERPE
Ob
93
95
98
99
99
0
0
0
0
0
90
94
97
99
99

Ex
—
—
—
—
—
—
—
—
—
—
93
95
98
99
99

Δ

−4
0
−1
0
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

TRZAW = Triticum aestivum (winter wheat)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CAPBP = Capsella bursa-pastoris (shepherd's purse)

CENCY = Centaurea cyanus or Cyanus segetum (cornflower)

CHEAL = Chenopodium album (lambsquarters)

CIRAR = Cirsium arvense (thistle)

KCHSC = Kochia scoparia (kochia)

LACSE = Lactuca serriola (prickly lettuce)

LAMPU = Lamium purpureum (LAMPU)

PAPRH = Papaver rhoeas (common poppy)

SASKR = Salsola kali (Russian thistle)

SINAR = Sinapis arvensis (wild mustard)

VERPE = Veronica persica (bird's-eye speedwell)

TABLE 7

Effect (% visual injury) of compound 2 on barley (HORVS), spring wheat (TRZAS), and winter wheat (TRZAW).

compound 2

Application

4.380
8.75
17.5
35
70
140
0
0
0
0
0
0
4.375
8.75
17.5
35
70
140

rate (g/ha)
CQC-m
0
0
0
0
0
0
4.380
8.75
17.5
35
70
140
4.375
8.75
17.5
35
70
140

HORVS
Ob
5
10
28
33
40

0
0
0
3
7

Ex
—
—
—
—
—
—
—
—
—
—
—
—
5
10
28
33
40

Δ

−5
−10
−28
−30
−33

TRZAS
Ob
8
15
28
40
50

0
0
0
5
10

Ex
—
—
—
—
—
—
—
—
—
—
—
—
8
15
28
40
50

Δ

−8
−15
−28
−35
−40

TRZAW
Ob

20
30
50

0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
—
—
0
0
0
20
30
50

Δ

0
0
0
−20
−30
−50

AMARE
Ob
80
95
100

80
85
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
80
95
100

Δ

0
−10
0

BRSNW
Ob
84
88
55
100
100

70
80
99
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
84
88
55
100
100

Δ

−14
−8
44
0
0

CAPBP
Ob
20
30
100
100
100

30
70
93
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
20
30
100
100
100

Δ

10
40
−7
0
0

CENCY
Ob
100
100
100
100
100

100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
100
100
100
100
100

Δ

0
0
0
0
0

CHEAL
Ob
85
95
97
100
100

80
95
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
85
95
97
100
100

Δ

−5
0
3
0
0

CIRAR
Ob
35
63
80
99
99

25
55
89
99
99

Ex
—
—
—
—
—
—
—
—
—
—
—
—
35
63
80
99
99

Δ

−10
−8
9
0
0

GALAP
Ob
20
30
93
85
97

25
40
50
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
20
30
93
85
97

Δ

5
10
−43
15
3

KCHSC
Ob
93
95
98
99
100
95

87
97
98
98
98
95

Ex
—
—
—
—
—
—
—
—
—
—
—
—
93
95
98
99
100
95

Δ

−7
2
0
−1
2
0

LACSE
Ob
40
99
99
100
100

97
97
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
40
99
99
100
100

Δ

57
−2
1
0
0

LAMPU
Ob
85
93
95
100
100

85
85
93
97
91

Ex
—
—
—
—
—
—
—
—
—
—
—
—
85
93
95
100
100

Δ

0
−8
−2
−3
−9

MATCH
Ob
30
58
91
98
100

35
68
75
93
95

Ex
—
—
—
—
—
—
—
—
—
—
—
—
30
58
91
98
100

Δ

5
10
−16
−5
−5

PAPRH
Ob
93
100
100
100
100

100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
93
100
100
100
100

Δ

7
0
0
0
0

SASKR
Ob
75
85
89
92
92

80
85
89
92
94

Ex
—
—
—
—
—
—
—
—
—
—
—
—
75
85
89
92
92

Δ

5
0
0
0
3

SETVI
Ob

100
97
98

70
100
93

Ex
—
—
—
—
—
—
—
—
—
—
—
—
0
0
0
100
97
98

Δ

0
0
0
−30
3
−5

SINAR
Ob
94
95
99
100
100

89
94
98
100
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
94
95
99
100
100

Δ

−5
−1
−2
0
0

STEME
Ob
25
68
97
100
100

15
50
75
97
94

Ex
—
—
—
—
—
—
—
—
—
—
—
—
25
68
97
100
100

Δ

−10
−18
−22
−4
−6

VERPE
Ob
75
95
100
100
100

78
93
98
99
100

Ex
—
—
—
—
—
—
—
—
—
—
—
—
75
95
100
100
100

Δ

3
−3
−3
−2
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

TRZAW = Triticum aestivum (winter wheat)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CAPBP = Capsella bursa-pastoris (shepherd's purse)

CENCY = Centaurea cyanus or Cyanus segetum (cornflower)

CHEAL = Chenopodium album (lambsquarters)

CIRAR = Cirsium arvense (thistle)

GALAP = Galium aparine (cleavers)

KCHSC = Kochia scoparia (kochia)

LACSE = Lactuca serriola (prickly lettuce)

LAMPU = Lamium purpureum (LAMPU)

MATCH = Matricaria chamomilla (wild chamomile)

PAPRH = Papaver rhoeas (common poppy)

SASKR = Salsola kali (Russian thistle)

SETVI = Setaria viridis (green foxtail)

SINAR = Sinapis arvensis (wild mustard)

STEME = Stellaria media (chickweed)

VERPE = Veronica persica (bird's-eye speedwell)

TABLE 8

Effect (% visual injury) of compound 3 on spring wheat

(TRZAS).

Application
compound 3
35
0
35

rate (g/ha)
CQC-m
0
35
35

TRZAS
Ob
30
0
10

Ex
—
—
30

Δ

−20

ABUTH
Ob
50
0
50

Ex
—
—
50

Δ

0

AMARE
Ob
95
0
90

Ex
—
—
95

Δ

−5

BRSNW
Ob
30
0
30

Ex
—
—
30

Δ

0

CHEAL
Ob
85
0
97

Ex
—
—
85

Δ

12

CIRAR
Ob
50
0
60

Ex
—
—
50

Δ

10

CYPES
Ob
10
0
0

Ex
—
—
10

Δ

−10

EPHHL
Ob
100
0
100

Ex
—
—
100

Δ

0

POLCO
Ob
97
0
97

Ex
—
—
97

Δ

0

SETFA
Ob
60
0
0

Ex
—
—
60

Δ

−60

SORVU
Ob
10
0
0

Ex
—
—
10

Δ

−10

STEME
Ob
70
0
50

Ex
—
—
70

Δ

−20

VIOTR
Ob
10
0
10

Ex
—
—
10

Δ

0

ZEAMX
Ob
0
0
0

Ex
—
—
0

Δ

0

g/ha = grams per hectare;

CQC-m = Cloquintocet-mexyl;

TRZAS = Triticum aestivum (spring wheat);

ABUTH = Abutilon theophrasti (velvetleaf);

AMARE = Amaranthus retroflexus (pigweed);

BRSNW = Brassica napus (winter rape);

CHEAL = Chenopodium album (lambsquarters);

CIRAR = Cirsium arvense (thistle);

CYPES = Cyperus esculentus (nutsedge);

EPHHL = Euphorbia heterophylla (poinsettia);

POLCO = Polygonum convolvulus (wild buckwheat);

SETFA = Setaria faberi (giant foxtail);

SORVU = Sorghum vulgare (common sorghum);

STEME = Stellaria media (chickweed);

VIOTR = Viola tricolor (wild pansy);

ZEAMX = Zea mays (corn/maize);

TABLE 9

Effect (% visual injury) of compound 7 on

barley (HORVS) and spring wheat (TRZAS).

compound 7

Application

20
0
0
0
20
20
20

rate (g/ha)
CQC-m
0
20
40
80
20
20
20

HORVS
Ob
5
0
0
0
0
0
0

Ex
—
—
—
—
5
5
5

Δ

−5
−5
−5

TRZAS
Ob
10
0
0
0
0
0
0

Ex
—
—
—
—
10
10
10

Δ

−10
−10
−10

AMARE
Ob
88
0
0
0
96
98
99

Ex
—
—
—
—
88
88
88

Δ

9
10
11

CHEAL
Ob
90
0
0
0
87
84
70

Ex
—
—
—
—
90
90
90

Δ

−4
−7
−20

KCHSC
Ob
65
0
0
0
68
75
70

Ex
—
—
—
—
65
65
65

Δ

3
10
5

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

AMARE = Amaranthus retroflexus (pigweed)

CHEAL = Chenopodium album (lambsquarters)

KCHSC = Kochia scoparia (kochia)

TABLE 10

Effect (% visual injury) of compound 8 on barley (HORVS) and spring wheat (TRZAS).

compound 8

Application

4.380
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
12
18
31
43
53
0
0
0
0
0
0
0
0
3
5

Ex
—
—
—
—
—
—
—
—
—
—
12
18
31
43
53

Δ

−12
−18
−31
−40
−48

TRZAS
Ob
7
11
35
48
60
0
0
0
0
0
0
1
5
5
10

Ex
—
—
—
—
—
—
—
—
—
—
7
11
35
48
60

Δ

−7
−10
−30
−43
−50

CHEAL
Ob
86
92
99
100
100
0
0
0
0
0
80
91
95
99
100

Ex
—
—
—
—
—
—
—
—
—
—
86
92
99
100
100

Δ

−6
−1
−4
−1
0

KCHSC
Ob
69
77
81
95
95
0
0
0
0
0
68
73
88
92
97

Ex
—
—
—
—
—
—
—
—
—
—
69
77
81
95
95

Δ

−2
−4
7
−3
2

PAPRH
Ob
97
99
100
100
100
0
0
0
0
0
95
98
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
97
99
100
100
100

Δ

−2
−1
0
0
0

POLCO
Ob
85
97
93
100
100
0
0
0
0
0
90
97
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
85
97
93
100
100

Δ

5
0
2
0
0

SASKR
Ob
61
69
83
85
90
0
0
0
0
0
46
71
81
85
87

Ex
—
—
—
—
—
—
—
—
—
—
61
69
83
85
90

Δ

−15
3
−1
0
−3

SINAR
Ob
76
82
96
99
98
0
0
0
0
0
78
83
89
92
98

Ex
—
—
—
—
—
—
—
—
—
—
76
82
96
99
98

Δ

2
1
−7
−7
1

VERPE
Ob
83
92
96
98
100
0
0
0
0
0
84
86
93
95
99

Ex
—
—
—
—
—
—
—
—
—
—
83
92
96
98
100

Δ

0
−5
−3
−3
−2

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

CHEAL = Chenopodium album (lambsquarters)

KCHSC = Kochia scoparia (kochia)

PAPRH = Papaver rhoeas (common poppy)

POLCO = Polygonum convolvulus (wild buckwheat)

SASKR = Salsola kali (Russian thistle)

SINAR = Sinapis arvensis (wild mustard)

VERPE = Veronica persica (bird's-eye speedwell)

TABLE 11

Effect (% visual injury) of compound 9 on barley (HORVS) and spring wheat (TRZAS).

compound 9

Application

4.380
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
10
20
30
40
50
0
0
0
0
0
0
0
0
0
10

Ex
—
—
—
—
—
—
—
—
—
—
10
20
30
40
50

Δ

−10
−20
−30
−40
−40

TRZAS
Ob
10
25
30
50
60
0
0
0
0
0
0
0
0
10
10

Ex
—
—
—
—
—
—
—
—
—
—
10
25
30
50
60

Δ

−10
−25
−30
−40
−50

AMARE
Ob
10
20
50

100
0
0
0
0
0
80
93
95

100

Ex
—
—
—
—
—
—
—
—
—
—
10
20
50
0
100

Δ

70
73
45
0
0

BRSNW
Ob
60
60
90
98
100
0
0
0
0
0
60
80
85
98
100

Ex
—
—
—
—
—
—
—
—
—
—
60
60
90
98
100

Δ

0
20
−5
0
0

CHEAL
Ob
85
80
95
100
100
0
0
0
0
0
75
85
95
97
100

Ex
—
—
—
—
—
—
—
—
—
—
85
80
95
100
100

Δ

−10
5
0
−3
0

CIRAR
Ob
10
30
70
95
97
0
0
0
0
0
20
30
75
90
95

Ex
—
—
—
—
—
—
—
—
—
—
10
30
70
95
97

Δ

10
0
5
−5
−2

KCHSC
Ob
60
60
85
100
100
0
0
0
0
0
50
70
85
100
100

Ex
—
—
—
—
—
—
—
—
—
—
60
60
85
100
100

Δ

−10
10
0
0
0

LAMPU
Ob
83
90
100
100
100
0
0
0
0
0
80
87
97
91
100

Ex
—
—
—
—
—
—
—
—
—
—
83
90
100
100
100

Δ

−3
−3
−3
−9
0

PAPRH
Ob
90
87
100
93
100
0
0
0
0
0
85
90
93
95
100

Ex
—
—
—
—
—
—
—
—
—
—
90
87
100
93
100

Δ

−5
3
−7
2
0

SASKR
Ob
65
70
80
85
87
0
0
0
0
0
70
80
80
85
85

Ex
—
—
—
—
—
—
—
—
—
—
65
70
80
85
87

Δ

5
10
0
0
−2

SINAR
Ob
93
95
95
100
100
0
0
0
0
0
90
90
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
93
95
95
100
100

Δ

−3
−5
0
0
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CHEAL = Chenopodium album (lambsquarters)

CIRAR = Cirsium arvense (thistle)

KCHSC = Kochia scoparia (kochia)

LAMPU = Lamium purpureum (LAMPU)

PAPRH = Papaver rhoeas (common poppy)

SASKR = Salsola kali (Russian thistle)

SINAR = Sinapis arvensis (wild mustard)

TABLE 12

Effect (% visual injury) of compound 10 on barley (HORVS) and spring wheat (TRZAS).

compound 10

Application

4.380
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
0
10
20
20
40
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
10
20
20
40

Δ

0
−10
−20
−20
−40

TRZAS
Ob
10
25
40
60
70
0
0
0
0
0
0
0
0
0
10

Ex
—
—
—
—
—
—
—
—
—
—
10
25
40
60
70

Δ

−10
−25
−40
−60
−60

BRSNW
Ob
85
95
100
100
100
0
0
0
0
0
85
95
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
85
95
100
100
100

Δ

0
0
0
0
0

CAPBP
Ob
30
60
100
100
100
0
0
0
0
0
100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
30
60
100
100
100

Δ

70
40
0
0
0

CENCY
Ob
100
100
100
100
100
0
0
0
0
0
100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
100
100
100
100
100

Δ

0
0
0
0
0

CIRAR
Ob
30
40
60
85
100
0
0
0
0
0
30
40
70
85
95

Ex
—
—
—
—
—
—
—
—
—
—
30
40
60
85
100

Δ

0
0
10
0
−5

KCHSC
Ob
80
80
100
100
100
0
0
0
0
0
80
95
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
80
80
100
100
100

Δ

0
15
−5
0
0

LACSE
Ob
95
100
100
100
100
0
0
0
0
0
85
97
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
95
100
100
100
100

Δ

−10
−3
−5
0
0

SASKR
Ob
70
80
87
90
93
0
0
0
0
0
75
80
85
85
90

Ex
—
—
—
—
—
—
—
—
—
—
70
80
87
90
93

Δ

5
0
−2
−5
−3

SINAR
Ob
90
93
97
100
100
0
0
0
0
0
90
95
95
95
100

Ex
—
—
—
—
—
—
—
—
—
—
90
93
97
100
100

Δ

0
2
−2
−5
0

VERPE
Ob
70
85
90
100
100
0
0
0
0
0
80
90
93
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
85
90
100
100

Δ

10
5
3
0
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

BRSNW = Brassica napus (winter rape)

CAPBP = Capsella bursa-pastoris (shepherd's purse)

CENCY = Centaurea cyanus or Cyanus segetum (cornflower)

CIRAR = Cirsium arvense (thistle)

KCHSC = Kochia scoparia (kochia)

LACSE = Lactuca serriola (prickly lettuce)

SASKR = Salsola kali (Russian thistle)

SINAR = Sinapis arvensis (wild mustard)

VERPE = Veronica persica (bird's-eye speedwell)

TABLE 13

Effect (% visual injury) of compound 11 on

barley (HORVS) and spring wheat (TRZAS).

compound 11

Application

17.5
35
70
0
0
0
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
17.5
35
70
17.5
35
70

HORVS
Ob
10
20
40
0
0
0
0
0
0

Ex
—
—
—
—
—
—
10
20
40

Δ

−10
−20
−40

TRZAS
Ob
10
20
40
0
0
0
0
0
10

Ex
—
—
—
—
—
—
10
20
40

Δ

−10
−20
−30

BRSNW
Ob
95
100
100
0
0
0
95
95
100

Ex
—
—
—
—
—
—
95
100
100

Δ

0
−5
0

KCHSC
Ob
70
90
90
0
0
0
60
85
85

Ex
—
—
—
—
—
—
70
90
90

Δ

−10
−5
−5

LACSE
Ob
0
10
40
0
0
0
0
50
80

Ex
—
—
—
—
—
—
0
10
40

Δ

0
40
40

SINAR
Ob
95
100
100
0
0
0
95
95
100

Ex
—
—
—
—
—
—
95
100
100

Δ

0
−5
0

VERPE
Ob
85
90
95
0
0
0
90
95
95

Ex
—
—
—
—
—
—
85
90
95

Δ

5
5
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

BRSNW = Brassica napus (winter rape)

KCHSC = Kochia scoparia (kochia)

LACSE = Lactuca serriola (prickly lettuce)

SINAR = Sinapis arvensis (wild mustard)

VERPE = Veronica persica (bird's-eye speedwell)

TABLE 14

Effect (% visual injury) of compound 12 on barley (HORVS) and spring wheat (TRZAS).

compound 12

Application

4.380
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
18
23
37
47
60
0
0
0
0
0
0
0
0
0
10

Ex
—
—
—
—
—
—
—
—
—
—
18
23
37
47
60

Δ

−18
−23
−37
−47
−50

TRZAS
Ob
15
27
42
53
70
0
0
0
0
0
0
0
8
13
20

Ex
—
—
—
—
—
—
—
—
—
—
15
27
42
53
70

Δ

−15
−27
−34
−41
−50

CAPBP
Ob
70
100
100
100
100
0
0
0
0
0
100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
100
100
100
100

Δ

30
0
0
0
0

CENCY
Ob
85
95
100
100
100
0
0
0
0
0
100
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
85
95
100
100
100

Δ

15
5
0
0
0

CHEAL
Ob
40
50
72
88
91
0
0
0
0
0
60
70
75
80
85

Ex
—
—
—
—
—
—
—
—
—
—
40
50
72
88
91

Δ

20
20
4
−8
−6

KCHSC
Ob
15
62
82
95
95
0
0
0
0
0
45
65
75
85
89

Ex
—
—
—
—
—
—
—
—
—
—
15
62
82
95
95

Δ

30
3
−7
−10
−7

LAMPU
Ob
60
75
80
90
97
0
0
0
0
0
60
70
95
97
97

Ex
—
—
—
—
—
—
—
—
—
—
60
75
80
90
97

Δ

0
−5
15
7
0

MATCH
Ob
5
3
7
10
13
0
0
0
0
0
5
5
5
5
40

Ex
—
—
—
—
—
—
—
—
—
—
5
3
7
10
13

Δ

0
2
−2
−5
27

PAPRH
Ob
90
93
95
100
100
0
0
0
0
0
85
85
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
90
93
95
100
100

Δ

−5
−8
0
0
0

SASKR
Ob
10
33
52
72
88
0
0
0
0
0
10
45
58
75
85

Ex
—
—
—
—
—
—
—
—
—
—
10
33
52
72
88

Δ

0
12
6
3
−3

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

CAPBP = Capsella bursa-pastoris (shepherd's purse)

CENCY = Centaurea cyanus or Cyanus segetum (cornflower)

CHEAL = Chenopodium album (lambsquarters)

KCHSC = Kochia scoparia (kochia)

LAMPU = Lamium purpureum (LAMPU)

MATCH = Matricaria chamomilla (wild chamomile)

PAPRH = Papaver rhoeas (common poppy)

SASKR = Salsola kali (Russian thistle)

TABLE 15

Effect (% visual injury) of compound 13 on barley (HORVS), spring wheat (TRZAS), and winter wheat (TRZAW).

compound 13

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
30
38
55
64
73
0
0
0
0
0
3
7
13
20
24

Ex
—
—
—
—
—
—
—
—
—
—
30
38
55
64
73

Δ

−27
−32
−42
−44
−49

TRZAS
Ob
40
53
67
80
87
0
0
0
0
0
15
25
35
43
52

Ex
—
—
—
—
—
—
—
—
—
—
40
53
67
80
87

Δ

−25
−28
−32
−37
−35

TRZAW
Ob

70
80

0
0

40
50

Ex
—
—
—
—
—
—
—
—
—
—

70
80

Δ

−30
−30

BRSNW
Ob
100
100
100
100
100
0
0
0
0
0
98
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
100
100
100
100
100

Δ

−2
0
0
0
0

CAPBP
Ob
85
100
100
100
100
0
0
0
0
0
70
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
85
100
100
100
100

Δ

−15
0
0
0
0

CENCY
Ob
100
100
100
100
100
0
0
0
0
0
93
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
100
100
100
100
100

Δ

−7
0
0
0
0

GALAP
Ob
40
70
80
100
100
0
0
0
0
0
60
90
93
100
100

Ex
—
—
—
—
—
—
—
—
—
—
40
70
80
100
100

Δ

20
20
13
0
0

KCHSC
Ob
55
84
89
92
93
0
0
0
0
0
67
75
88
96
97

Ex
—
—
—
—
—
—
—
—
—
—
55
84
89
92
93

Δ

12
−9
−1
4
4

LACSE
Ob
85
93
95
95
100
0
0
0
0
0
95
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
85
93
95
95
100

Δ

10
7
5
5
0

PAPRH
Ob
90
100
100
100
100
0
0
0
0
0
90
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
90
100
100
100
100

Δ

0
0
0
0
0

SASKR
Ob
50
65
77
83
91
0
0
0
0
0
47
60
75
82
91

Ex
—
—
—
—
—
—
—
—
—
—
50
65
77
83
91

Δ

−3
−5
−2
−2
0

SINAR
Ob
95
100
100
100
100
0
0
0
0
0
95
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
95
100
100
100
100

Δ

0
0
0
0
0

VERPE
Ob
85
93
98
98
100
0
0
0
0
0
78
88
92
95
95

Ex
—
—
—
—
—
—
—
—
—
—
85
93
98
98
100

Δ

−8
−5
−6
−3
−5

g/ha = grams per hectare;

CQC-m = Cloqumtocet-mexyl;

HORVS = Hordeum vulgare (spring barley);

TRZAS = Triticum aestivum (spring wheat);

TRZAW = Triticum aestivum (winter wheat);

BRSNW = Brassica napus (winter rape);

CAPBP = Capsella bursa-pastoris (shepherd's purse);

CENCY = Centaurea cyanus or Cyanus segetum (cornflower);

GALAP = Galium aparine (cleavers);

KCHSC = Kochia scoparia (kochia);

LACSE = Lactuca serriola (prickly lettuce);

PAPRH = Papaver rhoeas (common poppy);

SASKR = Salsola kali (Russian thistle);

SINAR = Sinapis arvensis (wild mustard);

VERPE = Veronica persica (bird's-eye speedwell)

TABLE 16

Effect (% visual injury) of compound 14 on barley (HORVS) and spring wheat (TRZAS).

compound 14

Application

4.380
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
0
0
10
20
40
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
0
10
20
40

Δ

0
0
−10
−20
−40

TRZAS
Ob
0
0
0
10
30
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
0
0
10
30

Δ

0
0
0
−10
−30

AMARE
Ob
10
10
20

0
0
0
0
0
10
30
50

Ex
—
—
—
—
—
—
—
—
—
—
10
10
20
0
0

Δ

0
20
30
0
0

GALAP
Ob
10
10
20
30
60
0
0
0
0
0
0
10
20
30
60

Ex
—
—
—
—
—
—
—
—
—
—
10
10
20
30
60

Δ

−10
0
0
0
0

SASKR
Ob
0
10
50
60
70
0
0
0
0
0
0
10
50
60
70

Ex
—
—
—
—
—
—
—
—
—
—
0
10
50
60
70

Δ

0
0
0
0
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

AMARE = Amaranthus retroflexus (pigweed)

GALAP = Galium aparine (cleavers)

SASKR = Salsola kali (Russian thistle)

TABLE 17

Effect (% visual injury) of compound 15 on barley (HORVS) and spring wheat (TRZAS).

compound 15

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
0
0
0
10
10
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
0
0
10
10

Δ

0
0
0
−10
−10

TRZAS
Ob
0
10
15
20
25
0
0
0
0
0
0
0
0
10
10

Ex
—
—
—
—
—
—
—
—
—
—
0
10
15
20
25

Δ

0
−10
−15
−10
−15

AMARE
Ob
70
100
100
100

0
0
0
0
0
70
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
100
100
100
0

Δ

0
0
0
0
0

BRSNW
Ob
40
40
50
70
60
0
0
0
0
0
30
40
60
70
80

Ex
—
—
—
—
—
—
—
—
—
—
40
40
50
70
60

Δ

−10
0
10
0
20

GALAP
Ob
85
85
93
93
90
0
0
0
0
0
93
93
95
97
97

Ex
—
—
—
—
—
—
—
—
—
—
85
85
93
93
90

Δ

8
8
2
4
7

KCHSC
Ob
10
10
50
60
75
0
0
0
0
0
10
50
90
90
85

Ex
—
—
—
—
—
—
—
—
—
—
10
10
50
60
75

Δ

0
40
40
30
10

LAMPU
Ob
93
95
93
93
95
0
0
0
0
0
93
93
95
95
95

Ex
—
—
—
—
—
—
—
—
—
—
93
95
93
93
95

Δ

0
−2
2
2
0

PAPRH
Ob
90
100
100
100

0
0
0
0

93
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
90
100
100
100

Δ

3
0
0
0

SASKR
Ob
10
10
10
60
70
0
0
0
0
0
10
10
50
60
80

Ex
—
—
—
—
—
—
—
—
—
—
10
10
10
60
70

Δ

0
0
40
0
10

SINAR
Ob
93
100
100
100
100
0
0
0
0
0
95
100
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
93
100
100
100
100

Δ

2
0
0
0
0

VERPE
Ob
85
85
90
93
95
0
0
0
0
0
80
90
93
93
95

Ex
—
—
—
—
—
—
—
—
—
—
85
85
90
93
95

Δ

−5
5
3
0
0

VIOTR
Ob
0
10
10
20
30
0
0
0
0
0
10
20
20
30
40

Ex
—
—
—
—
—
—
—
—
—
—
0
10
10
20
30

Δ

10
10
10
10
10

g/ha = grams per hectare;

CQC-m = Cloquintocet-mexyl;

HORVS = Hordeum vulgare (spring barley);

TRZAS = Triticum aestivum (spring wheat);

AMARE = Amaranthus retroflexus (pigweed);

BRSNW = Brassica napus (winter rape);

GALAP = Galium aparine (cleavers);

KCHSC = Kochia scoparia (kochia);

LAMPU = Lamium purpureum (LAMPU);

PAPRH = Papaver rhoeas (common poppy);

SASKR = Salsola kali (Russian thistle);

SINAR = Sinapis arvensis (wild mustard);

VERPE = Veronica persica (bird's-eye speedwell);

VIOTR = Viola tricolor (wild pansy)

TABLE 18

Effect (% visual injury) of compound 16 on barley (HORVS) and spring wheat (TRZAS).

compound 16

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
15
15
25
35
40
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
15
15
25
35
40

Δ

−15
−15
−25
−35
−40

TRZAS
Ob
10
10
20
30
40
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
10
10
20
30
40

Δ

−10
−10
−20
−30
−40

AMARE
Ob
70
80
85
100
100
0
0
0
0
0
70
70
80
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
80
85
100
100

Δ

0
−10
−5
0
0

BRSNW
Ob
30
40
65
70
90
0
0
0
0
0
40
60
70
90
95

Ex
—
—
—
—
—
—
—
—
—
—
30
40
65
70
90

Δ

10
20
5
20
5

KCHSC
Ob
60
70
85
90
90
0
0
0
0
0
50
70
85
95
95

Ex
—
—
—
—
—
—
—
—
—
—
60
70
85
90
90

Δ

−10
0
0
5
5

PAPRH
Ob
70
70
100
100
100
0
0
0
0
0
70
80
85
100
100

Ex
—
—
—
—
—
—
—
—
—
—
70
70
100
100
100

Δ

0
10
−15
0
0

SINAR
Ob
90
93
95
100
100
0
0
0
0
0
93
95
97
97
100

Ex
—
—
—
—
—
—
—
—
—
—
90
93
95
100
100

Δ

3
2
2
−3
0

VIOTR
Ob
10
10
20
30
40
0
0
0
0
0
10
10
10
10
20

Ex
—
—
—
—
—
—
—
—
—
—
10
10
20
30
40

Δ

0
0
−10
−20
−20

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

KCHSC = Kochia scoparia (kochia)

PAPRH = Papaver rhoeas (common poppy)

SINAR = Sinapis arvensis (wild mustard)

VIOTR = Viola tricolor (wild pansy)

TABLE 19

Effect (% visual injury) of compound 17 on barley (HORVS) and spring wheat (TRZAS).

compound 17

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
0
15
30
40
45
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
15
30
40
45

Δ

0
−15
−30
−40
−45

TRZAS
Ob
0
15
30
40
45
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
15
30
40
45

Δ

0
−15
−30
−40
−45

AMARE
Ob

100
100

0
0

100
100

Ex
—
—
—
—
—
—
—
—
—
—

100
100

Δ

0
0

BRSNW
Ob
60
90
95
95
97
0
0
0
0
0
80
90
97
100
100

Ex
—
—
—
—
—
—
—
—
—
—
60
90
95
95
97

Δ

20
0
2
5
3

CHEAL
Ob
40
60
70
80
85
0
0
0
0
0
40
60
70
75
85

Ex
—
—
—
—
—
—
—
—
—
—
40
60
70
80
85

Δ

0
0
0
−5
0

CIRAR
Ob
0
0
10
20
20
0
0
0
0
0
0
0
0
20
20

Ex
—
—
—
—
—
—
—
—
—
—
0
0
10
20
20

Δ

0
0
−10
0
0

GALAP
Ob
50
60
70
90
90
0
0
0
0
0
50
60
70
80
85

Ex
—
—
—
—
—
—
—
—
—
—
50
60
70
90
90

Δ

0
0
0
−10
−5

KCHSC
Ob
85
90
95
100
100
0
0
0
0
0
80
93
95
95
95

Ex
—
—
—
—
—
—
—
—
—
—
85
90
95
100
100

Δ

−5
3
0
−5
−5

PAPRH
Ob
80
85
85
95
100
0
0
0
0
0
80
90
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
80
85
85
95
100

Δ

0
5
10
5
0

SINAR
Ob
93
93
95
95
100
0
0
0
0
0
93
95
95
100
100

Ex
—
—
—
—
—
—
—
—
—
—
93
93
95
95
100

Δ

0
2
0
5
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

AMARE = Amaranthus retroflexus (pigweed)

BRSNW = Brassica napus (winter rape)

CHEAL = Chenopodium album (lambsquarters)

CIRAR = Cirsium arvense (thistle)

GALAP = Galium aparine (cleavers)

KCHSC = Kochia scoparia (kochia)

PAPRH = Papaver rhoeas (common poppy)

SINAR = Sinapis arvensis (wild mustard)

TABLE 20

Effect (% visual injury) of compound 18 on barley (HORVS) and spring wheat (TRZAS).

compound 18

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
15
25
40
50
70
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
15
25
40
50
70

Δ

−15
−25
−40
−50
−70

TRZAS
Ob
10
25
40
50
70
0
0
0
0
0
0
0
0
10
10

Ex
—
—
—
—
—
—
—
—
—
—
10
25
40
50
70

Δ

−10
−25
−40
−40
−60

KCHSC
Ob
30
40
75
93
90
0
0
0
0
0
50
70
80
93
95

Ex
—
—
—
—
—
—
—
—
—
—
30
40
75
93
90

Δ

20
30
5
0
5

PAPRH
Ob
90
90
93
93
95
0
0
0
0
0
93
93
95
95
97

Ex
—
—
—
—
—
—
—
—
—
—
90
90
93
93
95

Δ

3
3
2
2
2

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

KCHSC = Kochia scoparia (kochia)

PAPRH = Papaver rhoeas (common poppy)

TABLE 21

Effect (% visual injury) of compound 19 on barley (HORVS) and spring wheat (TRZAS).

compound 19

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
0
10
10
15
35
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
10
10
15
35

Δ

0
−10
−10
−15
−35

TRZAS
Ob
0
10
30
40
50
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
10
30
40
50

Δ

0
−10
−30
−40
−50

BRSNW
Ob
0
10
20
25
30
0
0
0
0
0
0
10
20
50
70

Ex
—
—
—
—
—
—
—
—
—
—
0
10
20
25
30

Δ

0
0
0
25
40

KCHSC
Ob
0
0
0
10
60
0
0
0
0
0
0
0
0
50
70

Ex
—
—
—
—
—
—
—
—
—
—
0
0
0
10
60

Δ

0
0
0
40
10

PAPRH
Ob
80
80
85
90
95
0
0
0
0
0
80
80
85
90
95

Ex
—
—
—
—
—
—
—
—
—
—
80
80
85
90
95

Δ

0
0
0
0
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

BRSNW = Brassica napus (winter rape)

KCHSC = Kochia scoparia (kochia)

PAPRH = Papaver rhoeas (common poppy)

TABLE 22

Effect (% visual injury) of compound 20 on barley (HORVS) and spring wheat (TRZAS).

compound 20

Application

4.375
8.75
17.5
35
70
0
0
0
0
0
4.375
8.75
17.5
35
70

rate (g/ha)
CQC-m
0
0
0
0
0
4.375
8.75
17.5
35
70
4.375
8.75
17.5
35
70

HORVS
Ob
0
10
20
30
40
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
10
20
30
40

Δ

0
−10
−20
−30
−40

TRZAS
Ob
0
0
0
10
20
0
0
0
0
0
0
0
0
0
0

Ex
—
—
—
—
—
—
—
—
—
—
0
0
0
10
20

Δ

0
0
0
−10
−20

CIRAR
Ob
0
10
20
40
70
0
0
0
0
0
0
10
20
50
65

Ex
—
—
—
—
—
—
—
—
—
—
0
10
20
40
70

Δ

0
0
0
10
−5

KCHSC
Ob
70
80
85
90
95
0
0
0
0
0
70
93
90
95
95

Ex
—
—
—
—
—
—
—
—
—
—
70
80
85
90
95

Δ

0
13
5
5
0

PAPRH
Ob
85
85
95
100
95
0
0
0
0
0
85
93
100
100
100

Ex
—
—
—
—
—
—
—
—
—
—
85
85
95
100
95

Δ

0
8
5
0
5

SASKR
Ob
20
40
60
80
80
0
0
0
0
0

65
70
80
80

Ex
—
—
—
—
—
—
—
—
—
—
20
40
60
80
80

Δ

−20
25
10
0
0

SINAR
Ob
60
60
83
80
93
0
0
0
0
0
60
70
90
90
93

Ex
—
—
—
—
—
—
—
—
—
—
60
60
83
80
93

Δ

0
10
7
10
0

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

HORVS = Hordeum vulgare (spring barley)

TRZAS = Triticum aestivum (spring wheat)

CIRAR = Cirsium arvense (thistle)

KCHSC = Kochia scoparia (kochia)

PAPRH = Papaver rhoeas (common poppy)

SASKR = Salsola kali (Russian thistle)

SINAR = Sinapis arvensis (wild mustard)

Example 3
Herbicidal Activity and Effect on Crop Injury on Wheat and Barley of Cloquintocet-Acid, -Mexyl, -Dimethylammonium Salt and -Triethylammonium Salt in Combination with Compounds of Formula (I) in Greenhouse Trials

Methodology—Evaluation of Postemergence Herbicidal Safening in Cereal Crops Greenhouse Trials

The safener cloquintocet-acid and a number of agriculturally acceptable esters and salts (-mexyl, -dimethylammonium salt and -triethylammonium salt) were combined in varying ratios with compound 1 and applied to spring wheat (TRZAS), winter wheat (TRZAW), and spring barley (HORVS), and the phytotoxicity of the herbicidal compositions was measured. In addition, the efficacy of the herbicidal composition on pigweed (AMARE, Amaranthus retroflexus), nutsedge (CYPES, Cyperus esculentus), common sunflower (HELAN, Helianthus annuus), and common sorghum (SORVU, Sorghum vulgare). The results are summarized in Tables 23-26.

TABLE 23

Effect (% visual injury) of compound 1 and cloquintocet-

acid on corn/maize (ZEAMX) and winter wheat (TRZAW).

Compound 1

20
0
0
0
20
20
20
40
0
0
0
40
40
40

CQC-acid

Application

0
5
10
20
5
10
20
0
2.5
5
10
2.5
5
10

Rate (g/ha)
Ratio (H:S)
—
—
—
—
4:1
2:1
1:1
—
—
—
—
16:1
8:1
4:1

TRZAW
Ob
13
0
0
0
0
0
0
15
0
0
0
0
0
0

Ex
—
—
—
—
13
13
13
—
—
—
—
15
15
15

Δ

−13
−13
−13

−15
−15
−15

ZEAMX
Ob
3
0
0
0
0
0
0
30
0
0
0
0
5
15

Ex
—
—
—
—
3
3
3
—
—
—
—
30
30
30

Δ

−3
−3
−3

−30
−25
−15

SORVU
Ob
18
0
0
0
0
15
18
68
0
0
0
20
65
65

Ex
—
—
—
—
18
18
18
—
—
—
—
68
68
68

Δ

−18
−3
0

−48
−3
−3

HELAN
Ob
98
0
0
0
100
100
100
100
0
0
0
100
100
100

Ex
—
—
—
—
98
98
98
—
—
—
—
100
100
100

Δ

3
3
3

0
0
0

AMARE
Ob
100
0
0
0
100
100
100
100
0
0
0
100
100
100

Ex
—
—
—
—
100
100
100
—
—
—
—
100
100
100

Δ

0
0
0

0
0
0

CYPES
Ob
35
0
0
0
33
8
43
35
0
0
0
13
45
65

Ex
—
—
—
—
35
35
35
—
—
—
—
35
35
35

Δ

−3
−28
8

−23
10
30

g/ha = grams per hectare

CQC-acid = Cloquintocet-acid

TRZAW = Triticum aestivum (winter wheat)

ZEAMX = Zea mays (corn/maize)

AMARE = Amaranthus retroflexus (pigweed)

CYPES = Cyperus esculentus (nutsedge)

HELAN = Helianthus annuus (common sunflower)

SORVU = Sorghum vulgare (common sorghum)

TABLE 24

Effect (% visual injury) of compound 1 and cloquintocet-dimethylammonium

(DMA) on corn/maize (ZEAMX) and winter wheat (TRZAW).

Compound 1

20
0
0
0
20
20
20
40
0
0
0
40
40
40

CQC-DMA

Application

0
5
10
20
5
10
20
0
2.5
5
10
2.5
5
10

Rate (g/ha)
Ratio (H:S)
—
—
—
—
4:1
2:1
1:1
—
—
—
—
16:1
8:1
4:1

TRZAW
Ob
13
0
0
0
0
0
0
15
0
0
0
0
0
0

Ex
—
—
—
—
13
13
13
—
—
—
—
15
15
15

Δ

−13
−13
−13

−15
−15
−15

ZEAMX
Ob
3
0
0
0
5
2
0
30
0
0
0
8
5
0

Ex
—
—
—
—
3
3
3
—
—
—
—
30
30
30

Δ

3
−1
−3

−23
−25
−30

SORVU
Ob
18
0
0
0
8
8
3
68
0
0
0
65
63
28

Ex
—
—
—
—
18
18
18
—
—
—
—
68
68
68

Δ

−10
−10
−15

−3
−5
−40

HELAN
Ob
98
0
0
0
100
100
100
100
0
0
0
100
100
97

Ex
—
—
—
—
98
98
98
—
—
—
—
100
100
100

Δ

3
3
3

0
0
−3

AMARE
Ob
100
0
0
0
100
100
100
100
0
0
0
100
100
100

Ex
—
—
—
—
100
100
100
—
—
—
—
100
100
100

Δ

0
0
0

0
0
0

CYPES
Ob
35
0
0
0
0
15
13
35
0
0
0
20
35
63

Ex
—
—
—
—
35
35
35
—
—
—
—
35
35
35

Δ

−35
−20
−23

−15
0
28

g/ha = grams per hectare

CQC-DMA = Cloquintocet-dimethylammonium

TRZAW = Triticum aestivum (winter wheat)

ZEAMX = Zea mays (corn/maize)

AMARE = Amaranthus retroflexus (pigweed)

CYPES = Cyperus esculentus (nutsedge)

HELAN = Helianthus annuus (common sunflower)

SORVU = Sorghum vulgare (common sorghum)

TABLE 25

Effect (% visual injury) of compound 1 and cloquintocet-

mexyl on corn/maize (ZEAMX) and winter wheat (TRZAW).

Compound 1

20
0
0
0
20
20
20
40
0
0
0
40
40
40

CQC-m

Application

0
5
10
20
5
10
20
0
2.5
5
10
2.5
5
10

Rate (g/ha)
Ratio (H:S)
—
—
—
—
4:1
2:1
1:1
—
—
—
—
16:1
8:1
4:1

TRZAW
Ob
13
0
0
0
0
0
0
15
0
0
0
0
0
0

Ex
—
—
—
—
13
12.5
13
—
—
—
—
15
15
15

Δ

−13
−13
−13

−15
−15
−15

ZEAMX
Ob
3
0
0
0
0
0
0
30
0
0
0
0
0
0

Ex
—
—
—
—
3
2.5
3
—
—
—
—
30
30
30

Δ

−3
−3
−3

−30
−30
−30

SORVU
Ob
18
0
0
0
0
0
0
68
0
0
0
15
5
15

Ex
—
—
—
—
18
17.5
18
—
—
—
—
68
67.5
68

Δ

−18
−18
−18

−53
−63
−53

HELAN
Ob
98
0
0
0
95
100
100
100
0
0
0
97
100
100

Ex
—
—
—
—
98
97.5
98
—
—
—
—
100
100
100

Δ

−3
3
3

−3
0
0

AMARE
Ob
100
0
0
0
100
100
100
100
0
0
0
100
100
100

Ex
—
—
—
—
100
100
100
—
—
—
—
100
100
100

Δ

0
0
0

0
0
0

CYPES
Ob
35
0
0
0
15
30
8
35
0
0
0
33
33
30

Ex
—
—
—
—
35
35
35
—
—
—
—
35
35
35

Δ

−20
−5
−28

−3
−3
−5

g/ha = grams per hectare

CQC-m = Cloquintocet-mexyl

TRZAW = Triticum aestivum (winter wheat)

ZEAMX = Zea mays (corn/maize)

AMARE = Amaranthus retroflexus (pigweed)

CYPES = Cyperus esculentus (nutsedge)

HELAN = Helianthus annuus (common sunflower)

SORVU = Sorghum vulgare (common sorghum)

TABLE 26

Effect (% visual injury) of compound 1 and cloquintocet-triethylammonium

(TEA) on corn/maize (ZEAMX) and winter wheat (TRZAW).

Compound 1

20
0
0
0
20
20
20
40
0
0
0
40
40
40

CQC-TEA

Application

0
5
10
20
5
10
20
0
2.5
5
10
2.5
5
10

Rate (g/ha)
Ratio (H:S)
—
—
—
—
4:1
2:1
1:1
—
—
—
—
16:1
8:1
4:1

TRZAW
Ob
13
0
0
0
0
0
0
15
0
0
0
0
0
0

Ex
—
—
—
—
13
13
13
—
—
—
—
15
15
15

Δ

−13
−13
−13

−15
−15
−15

ZEAMX
Ob
3
0
0
0
0
0
0
30
0
0
0
18
10
10

Ex
—
—
—
—
3
3
3
—
—
—
—
30
30
30

Δ

−3
−3
−3

−13
−20
−20

SORVU
Ob
18
0
0
0
23
0
0
68
0
0
0
60
63
58

Ex
—
—
—
—
18
18
18
—
—
—
—
68
68
68

Δ

5
−18
−18

−8
−5
−10

HELAN
Ob
98
0
0
0
100
100
100
100
0
0
0
100
100
100

Ex
—
—
—
—
98
98
98
—
—
—
—
100
100
100

Δ

3
3
3

0
0
0

AMARE
Ob
100
0
0
0
100
100
100
100
0
0
0
100
100
100

Ex
—
—
—
—
100
100
100
—
—
—
—
100
100
100

Δ

0
0
0

0
0
0

CYPES
Ob
35
0
0
0
55
10
8
35
0
0
0
43
65
33

Ex
—
—
—
—
35
35
35
—
—
—
—
35
35
35

Δ

20
−25
−28

8
30
−3

g/ha = grams per hectare

CQC-TEA = Cloquintocet-triethylammonium

TRZAW = Triticum aestivum (winter wheat)

ZEAMX = Zea mays (corn/maize)

AMARE = Amaranthus retroflexus (pigweed)

CYPES = Cyperus esculentus (nutsedge)

HELAN = Helianthus annuus (common sunflower)

SORVU = Sorghum vulgare (common sorghum)

The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few 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 are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches.

Number	Name	Date	Kind
6297197	Fields et al.	Oct 2001	B1
6784137	Balko et al.	Aug 2004	B2
7300907	Epp et al.	Nov 2007	B2
7314849	Balko et al.	Jan 2008	B2
7498468	Balko et al.	Mar 2009	B2
7538214	Epp et al.	May 2009	B2
7642220	Epp et al.	Jan 2010	B2
7863220	Clark et al.	Jan 2011	B2
7888287	Epp et al.	Feb 2011	B2
8288318	Epp et al.	Oct 2012	B2
8426591	Guenthenspberger et al.	Apr 2013	B2
8536331	Eckelbarger et al.	Sep 2013	B2
8609592	Guenthenspberger et al.	Dec 2013	B2
8754229	Epp et al.	Jun 2014	B2
8962523	Rosinger	Feb 2015	B2
9179676	Hoffmann	Nov 2015	B2
9408387	Satchivi	Aug 2016	B2
20030114311	Balko et al.	Jun 2003	A1
20070179059	Epp et al.	Aug 2007	A1
20080045734	Balko et al.	Feb 2008	A1
20080234262	Zask et al.	Sep 2008	A1
20090048109	Epp et al.	Feb 2009	A1
20090062121	Satchivi et al.	Mar 2009	A1
20090088322	Epp et al.	Apr 2009	A1
20090264429	Apodaca et al.	Oct 2009	A1
20100137137	Rosinger et al.	Jun 2010	A1
20100179127	Floersheim et al.	Jul 2010	A1
20100285959	Armel et al.	Nov 2010	A1
20110136666	Whittingham et al.	Jun 2011	A1
20110281873	Chiang et al.	Nov 2011	A1
20120115724	Whittingham et al.	May 2012	A1
20120184435	Bristow et al.	Jul 2012	A1
20120190549	Eckelbarger et al.	Jul 2012	A1
20120288492	Kuo et al.	Nov 2012	A1
20120292905	Slot	Nov 2012	A1
20130345240	Whitten et al.	Dec 2013	A1
20140274695	Eckelbarger et al.	Sep 2014	A1
20140274701	Eckelbarger et al.	Sep 2014	A1
20150005165	Hoffmann	Jan 2015	A1

Number	Date	Country
2842830	Jan 2013	CA
03011853	Feb 2003	WO
2005063721	Jul 2005	WO
2006121648	Nov 2006	WO
2007080382	Jul 2007	WO
2007082076	Jul 2007	WO
2007082098	Jul 2007	WO
2009007751	Jan 2009	WO
2009023438	Feb 2009	WO
2009029735	Mar 2009	WO
2009081112	Jul 2009	WO
2010060581	Jun 2010	WO
2010092339	Aug 2010	WO
2009138712	Sep 2010	WO
2010125332	Nov 2010	WO
2011080568	Jul 2011	WO
2012080187	Jun 2012	WO
2012149528	Nov 2012	WO
2013003740	Jan 2013	WO
2013014165	Jan 2013	WO

Safened herbicidal compositions comprising a pyridine carboxylic acid herbicide

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

Field of Search

CPC

International Classifications

Abstract

Description

Claims

CROSS REFERENCE TO RELATED APPLICATIONS

US Referenced Citations (39)

Foreign Referenced Citations (20)

Non-Patent Literature Citations (13)

Related Publications (1)

Provisional Applications (1)

Entry
PUBCHEM. Substance Record for SID 172846318. Deposit Date: Mar. 7, 2013. [retrieved on Dec. 1, 2015]. Retrieved from the Internet, <URL:https://pubchem.ncbl.nlm.nih.gov/substance/172846318/version/1#section=Top>. entire document.
International Search Report and Written Opinion issued in related International Application No. PCT/US2015/050122 on Jul. 5, 2016.
International Search Report and Written Opinion, issued in International Application No. PCT/US15/50203 on Jan. 14, 2016.
International Search Report and Written Opinion, issued in International Application No. PCT/US15/50205 on Jan. 14, 2016.
International Search Report and Written Opinion, issued in International Application No. PCT/US15/50209 on Jan. 14, 2016.
International Search Report and Written Opinion of the EP International Searching Authority from International Application No. PCT/EP2012/064519 mailed Sep. 28, 2012.
International Search Report and Written Opinion issued in International Application No. PCT/US2014/024745 on Jul. 7, 2014.
International Search Report and Written Opinion issued in International Application No. PCT/US2014/024749, on Jul. 10, 2014.
International Search Report and Written Opinion issued in International Application No. PCT/US2014/024752 on Jul. 7, 2014.
International Search Report and Written Opinion issued in International Application No. PCT/US2015/050190 on Dec. 29, 2015.
Abell, “Target-Site Directed Herbicide Design in, pest control with enhanced environmental safety 15-37”, 1993.
Knight, et al., “Annual Review of Phytopathology”, 1997.
Ruegg, et al., “Weed Research”, 2006.