OA17475A

OA17475A - 4-Amino-6-(4-substituted-phenyl)-picolinates and 6-amino-2-(4-substituted-phenyl)-pyrimidine4-carboxylates and their use as herbicides.

Info

Publication number: OA17475A
Application number: OA1201500357
Authority: OA
Inventors: Joseph D.; ECKELBARGER; Jeffrey B. EPP; Lindsey G. FISCHER; Natalie C. GIAMPIETRO; Nicholas M. Irvine; Jeremy. KISTER; William C. Lo; Christian T. LOWE; Jeffrey. PETKUS; Joshua. ROTH; Norbert M. Satchivi; Paul R. Schmitzer; Thomas L. Siddall; Carla N. YERKES
Original assignee: Dow Agrosciences Llc
Priority date: 2013-03-15
Filing date: 2014-03-12
Publication date: 2016-12-30

Abstract

Provided herein are 4-amino-6-(4substituted-phenyl)-picolinic acids and their derivatives, and 6-amino-2-(4-substituted-phenyl)pyrimidine-4-carboxylic acids and their derivatives, compositions comprising the acids and their derivatives, and methods of use thereof as herbicides.

Description

This application claims the benefit of U.S. Patent Application No. 13/840,233 filed March 15, 2013, the entirety of which is incorporated herein by reference.

BACKGROUND

The occurrence of undesirable végétation, e.g., weeds, is a constant problem facing famers in crops, pasture, and other settings. Weeds compete with crops and negatively impact crop yield. The use of chemical herbicides is an important tool in controlling undesirable végétation.

There remains a need for new chemical herbicides that offer a broader spectrum of weed control, selectivity, minimal crop damage, storage stability, ease of handling, higher activity against weeds, and/or a means to address herbicide-tolerance that develops with respect to herbicides currently in use.

SUMMARY

Provided herein are compounds of Formula (I):

wherein

X is N or CY, wherein Y is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, or C1-C3 haloalkylthio;

R¹ is OR¹, wherein R¹ is H, C[-C₈ alkyl, or C7-C10 arylalkyl;

R² is halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl,

C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio,

C1-C4 haloalkylthio, amino, C1-C4 alkylamino, C2-C4 haloalkylamino, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, cyano, or a group of the formula

-CR¹⁷=CR¹⁸-SiR¹⁹R²⁰R²¹, wherein R¹⁷ is hydrogen, F, or Cl; R¹⁸ is hydrogen, F, Cl,

C1-C4 alkyl, or C1-C4 haloalkyl; and R¹⁹, R²⁰, and R²¹ are each independently C1-C10 alkyl,

C3-C6 cycloalkyl, C1-C10 haloalkyl, C3-C6 halocycloalkyl, phenyl, substituted phenyl,

Ci-Cio alkoxy, or OH;

R³ and R⁴ are each independently hydrogen, Ci-Cô alkyl, Ci-Cô haloalkyl, C3-C6 alkenyl, C3Cô haloalkenyl, C3-C6 alkynyl, hydroxy, Ci-Cô alkoxy, Cj-Cô haloalkoxy, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (Ci-Cô alkoxy)carbonyl, (Cj-Cô alkyl)carbamyl, Ci-Cô alkylsulfonyl, tri(Ci-C6 alkyl)silyl, di(Ci-Cô alkyl)phosphonyl, or R³ and R⁴ together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring, or R³ and R⁴ taken together represent =CR³ R⁴, wherein R³ and R⁴ are each independently hydrogen, Ci-Cô alkyl, C3-C6 alkenyl, C3-C6 alkynyl, Ci-Cô alkoxy, or C)-C₆ alkylamino, or R³ and R⁴ together with the carbon atom to which they are attached form a 5- or 6membered saturated ring;

Ar is Arl, Ar2, Ar3, Ar4, Ar5, or Ar6:

Arl

Ar2

X·

Ar3

Ar4

Ar5

Ar6 wherein

Xi is H, F, Br, I, ethynyl, haloethynyl, CF₂H, OCF₂H, OCF₃, CN, CONH₂, CO₂H, CO₂CH₃, or NO₂;

X₂ is H, F, Cl, Br, I, ethynyl, haloethynyl, CH₃, CFH₂, CF₂H, CF₃, OCF₂H, OCF₃, CN, CONH₂, CO₂H, orNO₂;

X₃ is H, F, Br, I, ethynyl, haloethynyl, CH₃, CFH₂, CF₂H, CF₃, OCF₂H, OCF₃, CN, CONH₂,

CO₂H, orNO₂;

wherein when Ar is ^X1 , then X is N, CH, CF, CCI, or CCH₃;

with provisos that:

R² is not Cl or vinyl, when X is N;

Xi is not H, F, OCF₃, or CN, when R² is Cl and X is CH;

Xi is not F, I, CN, or ethynyl, when R² is OCH₃ and X is CF;

Xi is not H, when X is CCI; and when Ar is then X is N, CH, CF, CCI, or CCH₃;

with provisos that:

R² is not Cl, when X is N;

X₂ is not Cl, when R² is OCH₃ or vinyl and X is N;

X₂ is not Cl, when R² is Cl and X is CH;

X₂ is not Cl, Br, I, or CF₃, when R² is OCH₃ and X is CF; and when Ar is ^x3 ^F, then X is N, CH, or CF;

with provisos that:

R² is not Cl, when X is N;

X₃ is not CH₃, when R² is OCH₃ and X is N;

X₃ is not H, F, or CH₃, when R² is Cl and X is CH;

•y

X₃ is not Br or I, when R is OCH₃ and X is CF; and

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when Ar is F , then X is N, CH, or CF;

with provisos that:

R² is not Cl, when X is N;

X₂ is not Cl, when R is OCH3 or vinyl and X is N;

X₂ is not F, when R² is Cl and X is CH;

X₂ is not Cl, Br, I, or CF3, when R² is OCH3 and X is CF;

then X is N, CH, or CF;

with proviso that:

X3 is not CH3, when R² is Cl and X is N;

X3 is not Br or I, when X is CF and R² is OCH3; and

then X is N, CH, or CF;

or an N-oxide or agriculturally acceptable sait thereof.

Also provided are methods of controlling undesîrable végétation comprising (a) contacting the undesîrable végétation or area adjacent to the undesîrable végétation, or (b) pre-emergently contacting soil or water, a herbicidally effective amount of at least one compound of Formula (I) or agriculturally acceptable dérivative (e.g., agriculturally acceptable salts, solvatés, hydrates, esters, amides, N-oxides, or other dérivatives) thereof.

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DETAILED DESCRIPTION

As used herein, herbicide and herbicidal active ingrédient mean a compound that controls undesirable végétation when applied in an appropriate amount.

As used herein, control of or controlling undesirable végétation means killing or preventing the végétation, or causing some other adversely modifying effect to the végétation e.g., déviations from natural growth or development, régulation, desiccation, retardation, and the like.

As used herein, a herbicidally effective or végétation controlling amount is an amount of herbicidal active ingrédient the application of which controls the relevant undesirable végétation.

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

As used herein, plants and végétation include, but are not limited to, dormant seeds, germinant seeds, emerging seedlings, plants emerging from végétative propagules, immature végétation, and established végétation.

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.

Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnésium, and aminium cations of the formula:

R^l3R^l4R^l5R^l6N⁺ wherein R¹³, R¹⁴, R¹⁵ and R¹⁶ each, independently represents hydrogen or C1-C12 alkyl, C3-C12 alkenyl, or C3-C12 alkynyl, each of which is optionally substituted by one or more substituents such as hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, or phenyl groups, provided that R¹³, R¹⁴, R¹⁵ and R¹⁶ are sterically compatible. Additionally, any two R¹³, R¹⁴, R¹⁵ and R¹⁶together may represent an aliphatic difunctional moiety containing one to twelve carbon atoms and up to two oxygen or sulfur atoms. Salts of the compounds of Formula (I) can be prepared by treatment of compounds of Formula (I) with a métal hydroxide, such as sodium hydroxide, with an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine, or with a tetraalkylammonium hydroxide, such as tétraméthylammonium hydroxide or choline hydroxide. Amine salts of compounds of Formula (I) are useful forms or dérivatives of compounds of Formula (I) because they are water-soluble and lend themselves to the préparation of désirable aqueous based herbicidal compositions.

Other forms or dérivatives of compounds of the Formula (I) include N-oxides of compounds of Formula (I). 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 subséquent volumes to the 4th édition, volume E 7b, p. 565 f.

As used herein “acyl” includes formyl, (C1-C3 alkyl)carbonyl, and (C1-C3 haloalkyl)carbonyl.

As used herein, “alkyl” refers to saturated, straight-chained or branched hydrocarbon moieties. Unless otherwise specified, Cj-Cio alkyl groups are intended. Examples include, but are not limited to, 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, 2,3dimethyl-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 l-ethyl-2-methyl-propyl.

As used herein, “haloalkyl” refers to straight-chained or branched alkyl groups, where in these groups the hydrogen atoms may partially or entirely be substituted with one or more halogen atom(s). Unless otherwise specified, Cj-Cs groups are intended. Examples include, but are not limited to, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2-difluoroethyl, 2,2dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, and l,l,l-trifluoroprop-2-yl. As used herein, “alkenyl” refers to unsaturated, straight-chained, or branched hydrocarbon moieties contaîning one or more double bond(s). Unless otherwise specified, C2-C8 alkenyl

-617475 are intended. Alkenyl groups may contain more than one unsaturated bond. Examples include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl,

2- butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl- 1-propenyl, l-methyl-2-propenyl, 2methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2butenyl, l-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-1propenyl, l-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, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-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, l,l-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2butenyl, l,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, l,3-dimethyl-2-butenyl,

1.3- dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-

3- butenyl, l,l,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, l-ethyl-2-methyl-lpropenyl, and l-ethyl-2-methyl-2-propenyl.

As used herein, “alkynyl” represents straight-chained or branched hydrocarbon moieties contaîning one or more triple bond(s). Unless otherwise specified, C₂-C₈ alkynyl groups are intended. Alkynyl groups may contain more than one unsaturated bond. Examples include, but are not limited to, C₂-Cô-alkynyl, such as ethynyl, 1-propynyl,

2- propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l,l-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1pentynyl, l-methyl-2-pentynyl, 4-methyl-2-pentynyl, l-methyl-3-pentynyl, 2-methyl-3pentynyl, l-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, l,l-dimethyl-2butynyl, l,l-dimethyl-3-butynyl, l,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,

3.3- dimethyl-l-butynyl, 1-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1 -ethyl-1 -methyl-2-propynyl.

As used herein, “alkoxy” refers to a group of the formula R-O-, where R is alkyl as defîned above. Unless otherwise specified, alkoxy groups wherein R is a Ci-C₈ alkyl group are

-717475 intended. Examples include, but are not limited to, 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-di-methyl-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-dimethylbutoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethylbutoxy, 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, “haloalkoxy” refers to a group of the formula R-O-, where R is haloalkyl as defined above. Unless otherwise specified, haloalkoxy groups wherein R is a Cj-Cg alkyl group are intended. Examples include, but are not limited to, 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-difluoroethoxy, 2,2-dichloro-2fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and l,l,l-trifluoroprop-2-oxy. As used herein, “alkylthio” refers to a group of the formula R-S- where R is alkyl as defined above. Unless otherwise specified, alkylthio groups wherein R is a Cj-Cg alkyl group are intended. Examples include, but are not limited to, methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methyl-propylthio, 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-methyl-pentylthio,

4-methyl-pentylthio, 1,1-dimethyl butylthio, 1,2-dimethyl-butylthio, 1,3-dimethyl-butylthio,

2.2- dimethyl butylthio, 2,3-dimethyl butylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio,

2- ethylbutylthio, 1,1,2-trimethyl propylthio, 1,2,2-trimethyl propylthio, 1-ethyl-1-methyl propylthio, and 1-ethyl-2-methylpropylthio.

As used herein, “haloalkylthio” refers to an alkylthio group as defined above wherein the carbon atoms are partially or entirely substituted with one or more halogen atoms. Unless otherwise specified, haloalkylthio groups wherein R is a Ci-Cg alkyl group are intended. Examples include, but are not limited to, chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio,

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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 l,l,l-trifluoroprop-2-ylthio.

As used herein, “aryl,” as well as dérivative terms such as “aryloxy,” refers to a phenyl, indanyl, or naphthyl group. In some embodiments, phenyl is preferred. The term “heteroaryl,” as well as dérivative terms such as “heteroaryloxy,” refers to a 5- or 6membered aromatic ring containing one or more heteroatoms, e.g., 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 substituents selected from, e.g., halogen, hydroxy, nitro, cyano, formyl, Cj-Cé alkyl, C₂-Cô alkenyl, C₂-Cô alkynyl, Ci-Cô alkoxy, Cj-Cô haloalkyl, Cj-Cô haloalkoxy, Cj-Côacyl, Ci-C₆ alkylthio, C]-C₆alkylsulfinyl, Cj-Cô alkylsulfonyl, (Ci-Côalkoxy)carbonyl, Ci-Cô carbamoyl, hydroxycarbonyl, (Ci-Cô alkyl)carbonyl, aminocarbonyl, (Cj-Cô alkylamino)carbonyl, (di(Ci-C6alkyl)amino)carbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. In some embodiments, preferred substituents include, for example, halogen, Ci-C₂ alkyl, and Ci-C₂ haloalkyl.

As used herein, “alkoxycarbonyl” refers to a group of the formula ^0R wherein R is alkyl.

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

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

As used herein, “alkylsulfonyl” refers to -SO₂R, wherein R is alkyl (e.g., C]-Cio alkyl).

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

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

As used herein, “Me” refers to a methyl group.

As used herein, the term “halogen,” including dérivative terms such as “halo,” refers to fluorine, chlorine, bromine, or iodine (or fluoride, chloride, bromide, or iodide).

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As used herein, plants and végétation include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from végétative propagules, immature végétation, and established végétation.

COMPOUNDS

Provided herein are compounds of Formula (I) as defined herein (e.g., in the Summary above) and N-oxides and agriculturally acceptable salts thereof.

In some embodiments, the compound is the carboxylic acid or an agriculturally acceptable ester or sait thereof. In some embodiments, the compound is the carboxylic acid or its methyl ester.

In some embodiments:

Ar is selected from the group consisting of Arl, Ar2, Ar3, Ar4, Ar5, and Ar6;

R¹ is OR¹, wherein R¹ is H or Cj-Cs alkyl;

R² is halogen, C2-C4 alkenyl, C2-C4 haloalkenyl, C]-C₄ alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, or C1-C4 haloalkylthio;

R³ and R⁴ are each independently hydrogen, Ci-C6 alkyl, Cj-Cô haloalkyl, C3-C6 alkenyl, C3Cô haloalkenyl, C3-C6 alkynyl, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (Ci-Ce alkoxy)carbonyl, (Cj-Cô alkyl)carbamyl, tri(Ci-C6 alkyl)silyl, or R³ and R⁴ taken together represent =CR³ R⁴, wherein R³ and R⁴ are each independently hydrogen, Cj-Cô alkyl, C3-Cô alkenyl, C₃-C₆ alkynyl, Ci-Cô alkoxy, or Ci-C₆ alkylamino; and

X is N or CY, where Y is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkoxy, C1-C3 alkylthio, or C1-C3 haloalkylthio.

In one embodiment, X is N. In one embodiment, X is CY.

In one embodiment, Y is hydrogen. In one embodiment, Y is halogen (e.g., F, Cl, Br, I). In one embodiment, Y is C1-C3 alkyl (e.g., methyl, ethyl, n-propyl, z-propyl). In one embodiment, Y is C1-C3 haloalkyl (e.g., CFH₂, CF₂H, CF3, CF₂CF₃). In one embodiment, Y is C1-C3 alkoxy (e.g., OCH₃, OCH₂CH3). In one embodiment, Y is C1-C3 haloalkoxy (e.g., OCFH₂, OCF₂H, OCF₃, OCF₂CF₃). In one embodiment, Y is C,-C₃alkylthio (e.g., SCH₃, SCH₂CH₃). In one embodiment, Y is C1-C3 haloalkylthio (e.g., SCFH₂, SCF₂H, SCF₃, SCF₂CF₃).

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In some embodiments, X is N or CY, wherein Y is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkoxy, C1-C3 alkylthio, or

C1-C3 haloalkylthio.

In some embodiments, X is N or CY, wherein Y is H, halo, or C1-C3 alkyl. In some embodiments, X is N or CY, wherein Y is H or halo. In some embodiments, X is N or CY, wherein Y is H, F, Cl, or Br. In some embodiments, X is N or CY, wherein Y is H, F, or Cl. In some embodiments, X is N or CY, wherein Y is H or C1-C3 alkyl. In some embodiments, X is N or CY, wherein Y is H or CH₃. In some embodiments, X is N or CY, wherein Y is H. In some embodiments, X is N or CY, wherein Y is H, F, Cl, Br, or CH₃. In some embodiments, X is N or CY, wherein Y is H, F, Cl, or CH₃. In some embodiments, X is N or CY, wherein Y is H or F. In some embodiments, X is N or CY, wherein Y is Br. In some embodiments, X is N or CY, wherein Y is H. In some embodiments, Y is H. In some embodiments, Y is F. In some embodiments, Y is Cl. In some embodiments, Y is Br. In some embodiments, Y is CH₃. In some embodiments, Y is H, halo, or Ci-C₃ alkyl. In some embodiments, Y is H or halo. In some embodiments, Y is H, F, Cl, or Br. In some embodiments, Y is H, F, or Cl. In some embodiments, Y is H or Ci-C₃ alkyl. In some embodiments, Y is H or CH₃. In some embodiments, Y is H, F, Cl, Br, or CH₃. In some embodiments, Y is H, F, Cl, or CH₃. In some embodiments, Y is H or F. In some embodiments, Y is halo.

In one embodiment, R¹ is OR¹.

In one embodiment, R¹ is H. In one embodiment, R¹ is Ci-Cg alkyl (e.g., methyl, ethyl, «-propyl, z-propyl). In one embodiment, R¹ is C7-C10 arylalkyl (e.g., benzyl).

In some embodiments, R¹ is OR¹, wherein R¹ is H or Ci-Cg alkyl. In some embodiments, R is OR , wherein R is H or C7-C10 arylalkyl.

In some embodiments, R¹ is OR¹, wherein R¹ is H, methyl, ethyl, or benzyl. In 11'1' 1 some embodiments, R is OR , wherein R is H, methyl, or ethyl. In some embodiments, R is OR¹, wherein R¹ is H or methyl. In some embodiments, R¹ is OR¹, wherein R¹ is H or benzyl.

In one embodiment, R is halogen (e.g., F, Cl, Br, I). In one embodiment, R is C1-C4 alkyl (e.g., methyl, ethyl, propyl, butyl). In one embodiment, R² is C1-C4 haloalkyl (e.g., CFH2, CF2H, CF3, CF2CF3). In one embodiment, R² is C2-C₄ alkenyl (e.g., vinyl or ethenyl, propenyl, butenyl). In one embodiment, R is C₂-C₄ haloalkenyl. In one embodiment, R is C₂-C₄ alkynyl. In one embodiment, R is C₂-C₄ haloalkynyl. In one o o embodiment, R is C1-C4 alkoxy (e.g., OCH₃, OCH₂CH₃). In one embodiment, R is C1-C4

-1117475 haloalkoxy (e.g., OCFH2, OCF2H, OCF3, OCF2CF3). In one embodiment, R² is C1-C4 alkylthio (e.g., SCH₃, SCH2CH₃). In one embodiment, R² is C1-C4 haloalkylthio (e.g.,

SCFH2, SCF2H, SCF₃, SCF2CF₃). In one embodiment, R² is amino. In one embodiment, R² is C1-C4 alkylamino. In one embodiment, R is C2-C4 haloalkylamino. In one embodiment,

2 2 R is formyl. In one embodiment, R is (C]-C₃ alkyl)carbonyl. In one embodiment, R is (Ci-C₃ haloalkyl)carbonyl. In one embodiment, R is cyano.

In one embodiment, R² is -CR¹⁷=CR¹⁸-SiR¹⁹R²⁰R²¹.

1717

In one embodiment, R is hydrogen. In one embodiment, R is F. In one embodiment, R is Cl.

1010

In one embodiment, R is hydrogen. In one embodiment, R is F. In one

1010 embodiment, R is Cl. In one embodiment, R is C1-C4 alkyl. In one embodiment, R is C1-C4 haloalkyl.

In one embodiment, R¹⁹ is C1-C10 alkyl. In one embodiment, R¹⁹ is C3-Cô cycloalkyl. In one embodiment, R¹⁹ is C1-C10 haloalkyl. In one embodiment, R¹⁹ is C3-Cô halocycloalkyl. In one embodiment, R¹⁹ is phenyl. In one embodiment, R¹⁹ is substituted phenyl. In one embodiment, R¹⁹ is Cj-Cjo alkoxy. In one embodiment, R¹⁹ is OH.

In one embodiment, R²⁰ is Cj-Cio alkyl. In one embodiment, R²⁰ is C₃-Cô cycloalkyl. In one embodiment, R is C1-C10 haloalkyl. In one embodiment, R is C₃-C6 halocycloalkyl. In one embodiment, R is phenyl. In one embodiment, R is substituted phenyl. In one embodiment, R²⁰ is C1-C10 alkoxy. In one embodiment, R²⁰ is OH.

In one embodiment, R²¹ is C1-C10 alkyl. In one embodiment, R²¹ is C3-Cô cycloalkyl. In one embodiment, R²¹ is Ci-Cæ haloalkyl. In one embodiment, R²¹ is C3-Cô halocycloalkyl. In one embodiment, R²¹ is phenyl. In one embodiment, R²¹ is substituted phenyl. In one embodiment, R²¹ is C1-C10 alkoxy. In one embodiment, R²¹ is OH.

In some embodiments, R is halogen, C2-C4 alkenyl, C2-C4 haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, or C1-C4 haloalkylthio. In some embodiments, •y

R is halogen, C2-C4 alkenyl, C2-C4 haloalkenyl, or C1-C4 alkoxy.

Q

In some embodiments, R is halogen, C2-C4 alkenyl, or C1-C4 alkoxy. In some embodiments, R is Cl, vinyl, or OCH₃. In some embodiments, R is Cl. In some embodiments, R is vinyl. In some embodiments, R is OCH₃.

JO

In one embodiment, R is hydrogen. In one embodiment, R is Ci-Cô alkyl. In

O-J one embodiment, R is Ci-Cô haloalkyl. In one embodiment, R is C₃-Cô alkenyl. In one

J embodiment, R is C₃-Cô haloalkenyl. In one embodiment, R is C₃-Cô alkynyl. In one embodiment, R is hydroxy. In one embodiment, R is Ci-Cô alkoxy. In one embodiment,

R³ is Cj-Cô haloalkoxy. In one embodiment, R³ is formyl. In one embodiment, R³ is (C1-C3 alkyl)carbonyl. In one embodiment, R³ is (C1-C3 haloalkyl)carbonyl. In one embodiment, o 3

R is (Cj-Cô alkoxy)carbonyl. In one embodiment, R is (Cj-Cô alkyl)carbamyl. In one embodiment, R³ is Cj-C₆ alkylsulfonyl. In one embodiment, R³ is tri(Cj-Cô alkyl)silyl. In one embodiment, R is di(Ci-C6 alkyl)phosphonyl.

In one embodiment, R⁴ is hydrogen. In one embodiment, R⁴ is Cj-Cô alkyl. In one embodiment, R⁴ is Cj-Cô haloalkyl. In one embodiment, R⁴ is C3-C6 alkenyl. In one embodiment, R⁴ is C3-C6 haloalkenyl. In one embodiment, R⁴ is C3-C6 alkynyl. In one embodiment, R⁴ is hydroxy. In one embodiment, R⁴ is Cj-Cô alkoxy. In one embodiment, R⁴ is Cj-Cô haloalkoxy. In one embodiment, R⁴ is formyl. In one embodiment, R⁴ is (C1-C3 alkyl)carbonyl. In one embodiment, R⁴ is (C1-C3 haloalkyl)carbonyl. In one embodiment, R⁴ is (Cj-Cô alkoxy)carbonyl. In one embodiment, R⁴ is (Cj-Cô alkyl)carbamyl. In one embodiment, R⁴ is Cj-Cô alkylsulfonyl. In one embodiment, R⁴ is tri(Cj-Cô alkyl)silyl. In one embodiment, R⁴ is di(Cj-Cô alkyl)phosphonyl.

In one embodiment, R³ and R⁴ together with the nitrogen atom to which they are attached form a 5-membered saturated ring. In one embodiment, R³ and R⁴ together with the nitrogen atom to which they are attached form a 6-membered saturated ring.

In one embodiment, R³ and R⁴ taken together represent =CR³ R⁴.

•j» V

In one embodiment, R is hydrogen. In one embodiment, R is Cj-Cô alkyl. In one embodiment, R is C3-C6 alkenyl. In one embodiment, R is C3-C6 alkynyl. In one ·ν embodiment, R is Cj-Cô alkoxy. In one embodiment, R is Cj-Cô alkylamino.

In one embodiment, R⁴ is hydrogen. In one embodiment, R⁴ is Cj-C₆ alkyl. In one embodiment, R⁴ is C3-C6 alkenyl. In one embodiment, R⁴ is C3-C6 alkynyl. In one embodiment, R⁴ is Cj-Cô alkoxy. In one embodiment, R⁴ is Cj-Cô alkylamino.

In one embodiment, R³ and R⁴ together with the carbon atom to which they are attached form a 5- membered saturated ring. In one embodiment, R³ and R⁴ together with the carbon atom to which they are attached form a 6-membered saturated ring.

In some embodiments, R³ and R⁴ are each independently hydrogen, Cj-Cô alkyl, Cj-Cô haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (Cj-Cô alkoxy)carbonyl, (Cj-Cô alkyl)carbamyl, tri(Cj-Cô alkyl)silyl. In some embodiments, R³ and R⁴ taken together represent =CR³ R⁴, wherein R³ and R⁴ are each independently hydrogen, Cj-Cô alkyl, C3-C6 alkenyl, C3-C6 alkynyl, Cj-Cô alkoxy, or Cj-Cô alkylamino.

o

In some embodiments, R is H.

-1317475

In some embodiments, R⁴ is H.

In one embodiment, Ar is Arl.

In one embodiment, provided herein is a compound of formula (1-1 ), or an Noxide or agriculturally acceptable sait thereof:

wherein X, R¹, R², R³, R⁴, and X] are defined herein elsewhere.

In one embodiment, in a compound of formula (1-1), R is OH and R is halogen.

2

In one embodiment, in a compound of formula (I-l), R is OH and R is C2-C4 aikenyl. In one embodiment, in a compound of formula (1-1), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-1), R is OH and R is Cl. In one embodiment, in a compound of formula (1-1), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-1), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-1), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-1 ), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (1-1), R is-O-(C]-C4 alkyl) and R is C2-C4 aikenyl. In one embodiment, in a compound of formula (I-1 ), R is -O-(Ci-C₄ alkyl) and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (1-1), R is-O-(Ci-C₄ alkyl) and R is Cl. In one embodiment, in a compound of formula (1-1), R is -O-(Ci-C₄ alkyl) and R is OCH3. In one embodiment, in a compound of formula (1-1), R is -O-(Ci-C₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-1), R¹ is -O-(Ci-C₄ alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (1-1), R¹ is OCH3 and R² is î 7 halogen. In one embodiment, in a compound of formula (1-1), R is OCH3 and R is C₂-C₄aikenyl. In one embodiment, in a compound of formula (1-1), R is OCH3 and R is C]-C₄alkoxy. In one embodiment, in a compound of formula (1-1), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (1-1), R is OCH3 and R is OCH3. In one

7 embodiment, in a compound of formula (1-1), R isOCTUandR is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1 ), R is OCH3 and R is 1-propenyl.

-1417475

In one embodiment, provided herein is a compound of formula (I-la), (I-lb), (I-lc), (I-ld), or (I-le), or an N-oxide or agriculturally acceptable sait thereof:

NR³R⁴ md3d4 NR³R⁴

3 3

		NR³R⁴		NR³R⁴
	Ck	J/	H₃C_s	Yr^R2
		JL^^ri n II I		JL 7
Xi		(1-ld) ⁰ , _or 7		(I-le) °
wherein R¹, R², R³,	R⁴, and	Xi are defined herein else	where.

l9

In one embodiment, in a compound of formula (I-la), R is OH and R is halogen. In one embodiment, in a compound of formula (I-la), R is OH and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-la), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-la), R is OH and R is Cl. In one embodiment, in a compound of formula (I-la), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-la), R is OH and R is vinyl (or ethenyl). In one

9 embodiment, in a compound of formula (I-la), R is OH and R is 1-propenyl. In one

9 embodiment, in a compound of formula (I-la), R is -O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, in a compound of formula (I-la), R is -O-(Ci-C₄ alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-la), R¹ is -O-(Ci-C4 alkyl) and R is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-la), R is-O-(Ci-C4 alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-la), R¹ is -O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-la), R¹ is -O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-la), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-la), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-la), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-la), R¹ is OCH3 and R² is C]-C4 alkoxy. In one embodiment, in a compound of formula (I-la), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (I-la), R¹ is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-la), R is OCH3 and R

-1517475 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-la), R¹ is OCH3 and

R is 1-propenyl.

In one embodiment, in a compound of formula (1-1 b), R is OH and R is halogen. In one embodiment, in a compound of formula (I-lb), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-1 b), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-1 b), R is OH and R isCl. In one embodiment, in a compound of formula (1-1 b), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-lb), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-lb), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-lb), R¹ is -O-(C]-C4 alkyi) and R² is halogen. In one embodiment, in a compound of formula (I-lb), R¹ is -O-(Ci-C4 alkyi) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-lb), R¹ is -O-(Ci-C4 alkyi) and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-lb), R is -O-(Ci-C₄

1 alkyi) and R is Cl. In one embodiment, in a compound of formula (I-lb), R is -O-(Ci-C₄alkyi) and R is OCH3. In one embodiment, in a compound of formula (I-lb), R is-O-(CiC₄ alkyi) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-lb), R is -O-(Ci-C₄ alkyi) and R is 1-propenyl. In one embodiment, in a compound of formula 1 9 (I-lb), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-lb), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-lb), R isOCHsandR is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-lb), 19 1

R isOCHsandR is Cl. In one embodiment, in a compound of formula (I-lb), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-lb), R isOCHsandR is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-lb), R¹ is OCH3 and R² is 1-propenyl.

In one embodiment, in a compound of formula (I-lc), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-1 c), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-lc), R¹ is OH and R² is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-lc), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-lc), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-lc), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-lc), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-lc), R¹ is -O-(Ci-C4 alkyi) and R² is halogen. In one embodiment, in a compound of formula (I-lc), R¹ is -O-(C]-C4 alkyi) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-lc), R¹ is -O-(Ci-C4 alkyi) and

-1617475 l

R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-lc), R is-O-(Ci-C₄ alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-lc), R¹ is -O-(Ci-C₄ alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-lc), R¹ is -O-(Cio

C₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-lc), R is -O-(Ci-C₄ alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula 1 7 (I-lc), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-lc), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-lc), R is OCH3 and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-lc), 12 1

R îsOCThandR is Cl. In one embodiment, in a compound of formula (I-lc), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-lc), R isOCTLandR is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-lc), R¹ is OCH3 and n

R is 1-propenyl.

In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-ld), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-ld), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (I-ld), R¹ is -O-(Ci-C4 alkyl) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-ld), R¹ is -O-(Ci-C4 alkyl) and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-ld), R is -O-(Ci-C₄alkyl) and R is Cl. In one embodiment, in a compound of formula (I-ld), R is -O-(Ci-C₄alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-ld), R¹ is -O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-ld), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-ld), R isOCHsandR is halogen. In one embodiment, in a compound of formula (I-ld), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-ld), R isOCHsandR is C]-C₄ alkoxy. In one embodiment, in a compound of formula (I-ld), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-ld), R is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-ld), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-ld), R¹ is OCH3 and R is 1-propenyl.

?

In one embodiment, in a compound of formula (I-le), R is OH and R is

9 halogen. In one embodiment, in a compound of formula (I-le), R is OH and R is C2-C4

9 alkenyl. In one embodiment, in a compound of formula (I-le), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-le), R is OH and R isCl. In one 19 embodiment, in a compound of formula (I-le), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-le), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-le), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-le), R is -O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, in a compound of formula (I-le), R is -O-(Ci-C₄ alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-le), R¹ is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-le), R is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-le), R is-O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-le), R¹ is -O-(C]C4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-le), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-le), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-le), R¹ is OCH3 and R² is C2-C₄ alkenyl. In one embodiment, in a compound of formula (I-le), R¹ is OCH3 and R² is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-le), R isOCH₃andR is Cl. In one embodiment, in a compound of formula (I-le), R is OCH₃and R is OCH₃. In one embodiment, in a compound of formula (I-le), R is OCH₃ and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-le), R¹ is OCH3 and R² is 1-propenyl.

In one embodiment, Ar is Ar2.

In one embodiment, provided herein is a compound of formula (1-2), or an Noxide or agriculturally acceptable sait thereof:

wherein X, R¹, R², R³, R⁴, and X₂ are defined herein elsewhere.

7

In one embodiment, in a compound of formula (1-2), R is OH and R is halogen.

9

In one embodiment, in a compound of formula (1-2), R is OH and R is C2-C4 alkenyl. In

9 one embodiment, in a compound of formula (1-2), R is OH and R is C1-C4 alkoxy. In one

9 embodiment, in a compound of formula (1-2), R is OH and R is Cl. In one embodiment, in a compound of formula (1-2), R is OH and R is OCH3. In one embodiment, in a compound of formula (1-2), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-2), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (1-2), R is-O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (1-2), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-2), R is -0-(Cj-C4 alkyl) and R is Ci-C4 alkoxy. In one embodiment, in a compound of formula (1-2), R is-O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (1-2), R is -O-(Ci-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (1-2), R is -O-(Ci-C4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-2), R¹ is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (1-2), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (1-2), R is OCH3 and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-2), R is OCH3 and R is C1-C4

9 alkoxy. In one embodiment, in a compound of formula (1-2), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (1-2), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (1-2), R¹ is OCH3 and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-2), R is OCH3 and R is 1-propenyl.

In one embodiment, provided herein is a compound of formula (I-2a), (I-2b), (I-2c), (I-2d), or (I-2e), or an N-oxide or agriculturally acceptable sait thereof:

-1917475

wherein R¹, R², R³, R⁴, and X₂ are defined herein elsewhere.

t7

In one embodiment, in a compound of formula (I-2a), R is OH and R is halogen. In one embodiment, in a compound of formula (I-2a), R is OH and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-2a), R is OH and R isC]-C₄ alkoxy. In one embodiment, in a compound of formula (I-2a), R is OH and R is Cl. In one embodiment, in a compound of formula (I-2a), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-2a), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2a), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-2a), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (I-2a), R is -O-(Ci-C4 alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-2a), R¹ is -O-(Ci-C4 alkyl) and R is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-2a), R is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-2a), R is -O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-2a), R¹ is -O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2a), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-2a), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-2a), R¹ is OCH3 and R² is C2-C₄ alkenyl. In one embodiment, in a compound of formula (I-2a), R¹ is OCH3 and R² is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-2a), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-2a), R is OCH3

19 and R is OCH3. In one embodiment, in a compound of formula (I-2a), R is OCH3 and R

-2017475 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2a), R¹ is OCH3 and

R is 1-propenyl.

In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2b), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-2b), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (I-2b), R¹ is -O-(Ci-C4 alkyl) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2b), R¹ is -O-(C]-C4 alkyl) and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-2b), R is -O-(Ci-C₄alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-2b), R¹ is -O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-2b), R¹ is -O-(CiC4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2b),

2

R is-O-(Ci-C₄ alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-2b), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-2b), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-2b),

2

R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2b), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-2b), R is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-2b), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2b), R¹ is OCH3 and o

R is 1-propenyl.

In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is C]-C4 alkoxy. In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2c), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-2c), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (I-2c), R is -O-(Ci-C4 alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (1-2c), R¹ is -O-(Ci-C₄ alkyl) and

Q Ι

R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2c), R is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-2c), R is -O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-2c), R¹ is -O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2c), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-2c), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-2c), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2c), R¹ is OCH3 and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2c), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-2c), R is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-2c), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2c), R¹ is OCH3 and R is 1-propenyl.

2

In one embodiment, in a compound of formula (I-2d), R is OH and R is

9 halogen. In one embodiment, in a compound of formula (I-2d), R is OH and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2d), R is OH and R 1SC1-C4 alkoxy. In one embodiment, in a compound of formula (I-2d), R is OH and R is Cl. In one embodiment, in a compound of formula (I-2d), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-2d), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2d), R is OH and R is 1-propenyl. In one

9 embodiment, in a compound of formula (I-2d), R is-O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (I-2d), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2d), R¹ is -O-(Ci-C4 alkyl) and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2d), R¹ is -O-(Ci-C4 alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-2d), R¹ is -O-(Ci-C4 alkyl) and R isOCH3. In one embodiment, in a compound of formula (I-2d), R is-O-(Cio

C4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2d), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-2d), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-2d), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2d), R¹ is OCH3 and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2d), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (I-2d), R¹ is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-2d), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2d), R¹ is OCH3 and R² is 1-propenyl.

l 2 »

In one embodiment, in a compound of formula (I-2e), R is OH and R is

2 halogen. In one embodiment, in a compound of formula (I-2e), R is OH and R is C2-C4

2 alkenyl. In one embodiment, in a compound of formula (I-2e), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2e), R is OH and R is Cl. In one embodiment, in a compound of formula (I-2e), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-2e), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2e), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-2e), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (I-2e), R¹ is -O-(C]-C4 alkyl) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2e), R¹ is -O-(Ci-C4 alkyl) and R² is C]-C4 alkoxy. In one embodiment, in a compound of formula (I-2e), R¹ is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-2e), R is -O-(C]-C₄

1 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-2e), R is -O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2e), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-2e), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-2e), R¹ is OCH3 and R² is C2-C₄ alkenyl. In one embodiment, in a compound of formula (I-2e), R isOCH3andR is C]-C₄ alkoxy. In one embodiment, in a compound of formula (I-2e), 19 1

R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-2e), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-2e), R is OCH₃ and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2e), R¹ is OCH3 and R is 1-propenyl.

In one embodiment, Ar is Ar3.

In one embodiment, provided herein is a compound of formula (1-3), or an N-

wherein X, R¹, R², R³, R⁴, and X3 are defined herein elsewhere.

l 2

In one embodiment, in a compound of formula (1-3), R is OH and R is halogen.

9

In one embodiment, in a compound of formula (1-3), R is OH and R is C2-C4 alkenyl. In

9 one embodiment, in a compound of formula (1-3), R is OH and R is C1-C4 alkoxy. In one

9 embodiment, in a compound of formula (1-3), R is OH and R is Cl. In one embodiment, in a compound of formula (1-3), R is OH and R is OCH3. In one embodiment, in a compound of formula (1-3), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-3), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (1-3), R is -O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (1-3), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-3), R is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-3), R is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (1-3), R is -O-(Ci-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (1-3), R is -O-(Ci-C4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-3), R¹ is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (1-3), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (1-3), R is OCH3 and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-3), R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-3), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (1-3), R is OCH3 and R is OCH3. In one

9 embodiment, in a compound of formula (1-3), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-3), R is OCH3 and R is 1-propenyl.

In one embodiment, provided herein is a compound of formula (1-3 a), (I-3b), or (I-3c), or an N-oxide or agriculturally acceptable sait thereof:

5 nr³r⁴

-2417475 wherein R¹, R², R³, R⁴, and X₃ are defined herein elsewhere.

In one embodiment, in a compound of formula (1-3 a), R is OH and R is halogen. In one embodiment, in a compound of formula (1-3 a), R is OH and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3a), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-3 a), R is OH and R is Cl. In one embodiment, in a compound of formula (I-3a), R is OH and R is OCH₃. In one embodiment, in a compound of formula (I-3a), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3a), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-3a), R is -O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (1-3 a), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3a), R¹ is -O-(Ci-C4 alkyl) and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3a), R¹ is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-3a), R is -O-(Ci-C4

1 alkyl) and R is OCH₃. In one embodiment, in a compound of formula (1-3a), R is-O-(CiC4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3a), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (1-3 a), R is OCH₃ and R is halogen. In one embodiment, in a compound of formula (1-3 a), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3a), R¹ is OCH3 and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-3 a), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (1-3 a), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-3a), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3a), R¹ is OCH3 and

A

R is 1-propenyl.

In one embodiment, in a compound of formula (I-3b), R is OH and R is halogen. In one embodiment, in a compound of formula (I-3b), R is OH and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3b), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3b), R is OH and R is Cl. In one embodiment, in a compound of formula (I-3b), R is OH and R is OCH₃. In one embodiment, in a compound of formula (I-3b), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3b), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-3b), R is -O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (I-3b), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3b), R¹ is -O-(Ci-C4 alkyl) and R is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-3b), R is-O-(Ci-C4

-2517475 i

alkyl) and R is Cl. In one embodiment, in a compound of formula (I-3b), R is -O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-3b), R¹ is -O-(CiC4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3b), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-3b), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-3b), R is OCH3 and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3b), R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3b), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-3b), R is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-3b), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3b), R¹ is OCH3 and R² is 1-propenyl.

In one embodiment, in a compound of formula (1-3 c), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-3c), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3c), R¹ is OH and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3c), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-3c), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-3c), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3c), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (1-3 c), R¹ is -0-(Cj-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (1-3 c), R¹ is -O-(Ci-C4 alkyl) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3c), R¹ is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-3 c), R is -O-(Ci-C4 alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-3c), R¹ is -O-(Ci-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-3c), R is -O-(CiC4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3c), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-3c), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-3c),

R is OCH3 and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3c),

R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-3 c),

R is OCH3 and R is Cl. In one embodiment, in a compound of formula (1-3 c), R is OCH₃ and R² is OCH₃. In one embodiment, in a compound of formula (1-3 c), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3c), R¹ is OCH3 and R² is 1-propenyl.

In one embodiment, Ar is Ar4.

-263

In one embodiment, provided herein is a compound of formula (1-4), or an Noxide or agriculturally acceptable sait thereof:

wherein X, R¹, R², R³, R⁴, and X₂ are defined herein elsewhere.

9

In one embodiment, in a compound of formula (1-4), R is OH and R is halogen.

9

In one embodiment, in a compound of formula (1-4), R is OH and R is C₂-C4 alkenyl. In one embodiment, in a compound of formula (1-4), R is OH and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (1-4), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (1-4), R is OH and R is OCH3. In one embodiment, in a compound of formula (1-4), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-4), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (1-4), R¹ is -O-(C]-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (1-4), R¹ is -O-(Ci-C4 alkyl) and R² is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (1-4), R is -O-(C]-C₄ alkyl) and R is C]-C₄ alkoxy. In one

9 embodiment, in a compound of formula (1-4), R is -O-(Ci-C₄ alkyl) and R is Cl. In one

9 embodiment, in a compound of formula (1-4), R is -O-(Ci-C₄ alkyl) and R is OCH3. In one embodiment, in a compound of formula (1-4), R is -O-(Ci-C4 alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-4), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (1-4), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (1-4), R is OCH3 and R is C2-C₄alkenyl. In one embodiment, in a compound of formula (1-4), R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-4), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (1-4), R is OCH3 and R is OCH3. In one

9 embodiment, in a compound of formula (1-4), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-4), R is OCH3 and R is 1-propenyl.

In one embodiment, provided herein is a compound of formula (I-4a), (I-4b), or (I-4c), or an N-oxide or agriculturally acceptable sait thereof:

-2717475 nr³r⁴ nr³r⁴

nr³r⁴

F (l-4c) wherein R¹, R², R³, R⁴, and X2 are defined herein elsewhere.

In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4a), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-4a), R¹ is -O-(Ci-C4 alkyl) and R² is halogen. In one embodiment, in a compound of formula (I-4a), R¹ is -O-(Ci-C4 alkyl) and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4a), R¹ is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4a), R is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-4a), R is -O-(Ci-C4 alkyl) and R² is OCH3. In one embodiment, in a compound of formula (I-4a), R¹ is -O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4a), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-4a), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-4a),

R is OCH3 and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4a),

R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4a),

R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-4a), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-4a), R is OCH3 and R

-2817475 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4a), R¹ is OCH3 and

R is 1-propenyl.

2

In one embodiment, in a compound of formula (I-4b), R is OH and R is

2 halogen. In one embodiment, in a compound of formula (I-4b), R is OH and R is C2-C4

2 alkenyl. In one embodiment, in a compound of formula (I-4b), R is OH and R isCi-C4 alkoxy. In one embodiment, in a compound of formula (I-4b), R is OH and R is Cl. In one embodiment, in a compound of formula (I-4b), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-4b), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4b), R is OH and R is 1-propenyl. In one

9 embodiment, in a compound of formula (I-4b), R is -O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (I-4b), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4b), R¹ is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4b), R is -O-(Ci-C4 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-4b), R is -O-(Ci-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-4b), R is-O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4b), R¹ is -0-(Cj-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-4b), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-4b), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4b), R¹ is OCH3 and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4b), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-4b), R is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-4b), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4b), R¹ is OCH3 and o

R is 1-propenyl.

In one embodiment, in a compound of formula (I-4c), R is OH and R is halogen. In one embodiment, in a compound of formula (I-4c), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4c), R¹ is OH and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4c), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-4c), R is OH and R is OCH3. In one

9 embodiment, in a compound of formula (I-4c), R is OH and R is vinyl (or ethenyl). In one

9 embodiment, in a compound of formula (I-4c), R is OH and R is 1-propenyl. In one

9 embodiment, in a compound of formula (I-4c), R is -O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (I-4c), R is -O-(Ci-C4 alkyl) and R is C₂-C4 alkenyl. In one embodiment, in a compound of formula (I-4c), R¹ is -O-(Ci-C4 alkyl) and

-2917475 l ·

R is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-4c), R is-O-(Ci-C4

1 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-4c), R is -O-(Ci-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-4c), R is -O-(CiC4 alkyl) and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4c), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-4c), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-4c), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4c), R¹ is OCH3 and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4c), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-4c), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-4c), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4c), R¹ is OCH3 and

A

R is 1-propenyl.

In one embodiment, Ar is Ar5.

In one embodiment, provided herein is a compound of formula (1-5), or an Noxide or agriculturally acceptable sait thereof:

wherein X, R¹, R², R³, R⁴, and X3 are defined herein elsewhere.

In one embodiment, in a compound of formula (1-5), R is OH and R is halogen.

In one embodiment, in a compound of formula (1-5), R is OH and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-5), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-5), R is OH and R is Cl. In one embodiment, in a compound of formula (1-5), R is OH and R is OCH3. In one embodiment, in a compound of formula (1-5), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-5), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (1-5), R is -O-(Ci-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (1-5), R is -O-(Ci-C4 alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-5), R is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one

2 embodiment, in a compound of formula (1-5), R is -O-(Ci-C4 alkyl) and R is Cl. In one • 19 embodiment, in a compound of formula (1-5), R is-O-(Ci-C4 alkyi) and R is OCH3. In one embodiment, in a compound of formula (1-5), R is -O-(C]-C4 alkyi) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-5), R¹ is -O-(C|-C4 alkyi) and R is 1-propenyl. In one embodiment, in a compound of formula (1-5), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (1-5), R¹ is OCH3 and R² is C2-C₄alkenyl. In one embodiment, in a compound of formula (1-5), R is OCH3 and R is Ci-C₄alkoxy. In one embodiment, in a compound of formula (1-5), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (1-5), R is OCH3 and R is OCH3. In one

I 9 embodiment, in a compound of formula (1-5), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-5), R is OCH3 and R is 1-propenyl.

In one embodiment, provided herein is a compound of formula (I-5a), (I-5b), or (I-5c), or an N-oxide or agriculturally acceptable sait thereof:

NR³R⁴

wherein R¹, R², R³, R⁴, and X3 are defîned herein elsewhere.

9

In one embodiment, in a compound of formula (I-5a), R is OH and R is halogen. In one embodiment, in a compound of formula (I-5a), R¹ is OH and R² is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-5a), R is OH and R is Ci-C₄alkoxy. In one embodiment, in a compound of formula (I-5a), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-5a), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-5a), R is OH and R is vinyl (or ethenyl). In one

9 embodiment, in a compound of formula (I-5a), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-5a), R is -O-(C]-C₄ alkyi) and R is halogen. In one embodiment, in a compound of formula (I-5a), R¹ is -O-(Ci-C4 alkyi) and R² is C2-C₄ alkenyl. In one embodiment, in a compound of formula (I-5a), R¹ is -O-(Ci-C₄ alkyl) and

R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-5a), R is-O-(Ci-C4

1 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-5a), R is -O-(Ci-C₄

1 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-5a), R is -O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5a), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-5a), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-5a), R¹ is OCH3 and R² is C2-C₄ alkenyl. In one embodiment, in a compound of formula (I-5a), R¹ is OCH3 and R² is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-5a), R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-5a), R is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-5a), R¹ is OCH3 and R²is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5a), R¹ is OCH3 and o

R is 1-propenyl.

In one embodiment, in a compound of formula (I-5b), R is OH and R is halogen. In one embodiment, in a compound of formula (I-5b), R is OH and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-5b), R is OH and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-5b), R is OH and R is Cl. In one 19 embodiment, in a compound of formula (I-5b), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-5b), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5b), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-5b), R is -O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, in a compound of formula (I-5b), R is -O-(Ci-C₄ alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-5b), R¹ is -O-(Ci-C₄ alkyl) and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-5b), R is -O-(Ci-C₄

1 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-5b), R is -O-(Ci-C₄

1 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-5b), R is-O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5b), R is -O-(Ci-C₄ alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-5b), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-5b), R¹ is OCH3 and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5b), R¹ is OCH3 and R² is Ci-C4 alkoxy. In one embodiment, in a compound of formula (I-5b), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (I-5b), R¹ is OCH3 and R² is OCH3. In one embodiment, in a compound of formula (I-5b), R¹ is OCH3 and R²

-3217475 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5b), R* is OCH3 and

R² is 1-propenyl.

In one embodiment, in a compound of formula (I-5c), R is OH and R is halogen. In one embodiment, in a compound of formula (I-5c), R is OH and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5c), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-5c), R is OH and R is Cl. In one embodiment, in a compound of formula (I-5c), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-5c), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5c), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-5c), R is-O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, in a compound of formula (I-5c), R is -O-(Ci-C₄ alkyl) and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-5 c), R¹ is -O-(Ci-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-5 c), R is -O-(C]-C4 alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-5c), R¹ is -O-(Ci-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-5c), R is -O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5c), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula

9 (I-5c), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-5c), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-5c), R¹ is OCH3 and R² is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-5c), R¹ is OCH3 and R² is Cl. In one embodiment, in a compound of formula (I-5c), R¹ is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-5c), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5c), R¹ is OCH3 and R is 1-propenyl.

In one embodiment, Ar is Ar6.

In one embodiment, provided herein is a compound of formula (1-6), or an Noxide or agriculturally acceptable sait thereof:

-3317475 wherein X, R¹, R², R³, R⁴, and X2 are defined herein elsewhere.

2

In one embodiment, in a compound of formula (1-6), R is OH and R is halogen. In one embodiment, in a compound of formula (1-6), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-6), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (1-6), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (1-6), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (1-6), R¹ is OH and R² is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-6), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (1-6), R is -O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, m a compound

9 of formula (1-6), R is -O-(Ci-C₄ alkyl) and R is C2-C₄ alkenyl. In one embodiment, in a

9 compound of formula (1-6), R is -O-(Ci-C₄ alkyl) and R is Ci-C₄ alkoxy. In one

2 embodiment, in a compound of formula (1-6), R is-O-(Ci-C₄ alkyl) and R is Cl. In one embodiment, in a compound of formula (1-6), R is-O-(C]-C₄ alkyl) and R is OCH3. In one embodiment, in a compound of formula (1-6), R is -O-(Ci-C₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-6), R¹ is -O-(Cj-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (1-6), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (1-6), R is OCH3 and R is C2-C4 alkenyl. In one embodiment, in a compound of formula (1-6), R is OCH3 and R isCi-C₄

9 alkoxy. In one embodiment, in a compound of formula (1-6), R is OCH3 and R is Cl. In

9 one embodiment, in a compound of formula (1-6), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (1-6), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (1-6), R¹ is OCH3 and R² is 1-propenyl.

In one embodiment, provided herein is a compound of formula (I-6a), (I-6b), or (I-6c), or an N-oxide or agriculturally acceptable sait thereof:

-3417475

wherein R¹, R², R³, R⁴, and X₂ are defined herein elsewhere.

In one embodiment, in a compound of formula (I-6a), R¹ is OH and R² is halogen. In one embodiment, in a compound of formula (I-6a), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6a), R is OH and R is Cj-C4 alkoxy. In one embodiment, in a compound of formula (I-6a), R is OH and R is Cl. In one embodiment, in a compound of formula (I-6a), R¹ is OH and R² is OCH3. In one embodiment, in a compound of formula (I-6a), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6a), R¹ is OH and R² is 1-propenyl. In one embodiment, in a compound of formula (I-6a), R is -O-(Cj-C4 alkyl) and R is halogen. In one embodiment, in a compound of formula (I-6a), R is -O-(Ci-C₄ alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-6a), R¹ is -O-(Ci-C₄ alkyl) and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-6a), R is-O-(Ci-C₄

1 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-6a), R is -O~(Ci-C₄

1 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-6a), R is -O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6a), R is -O-(Ci-C₄ alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula 1 9 (I-6a), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-6a), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-6a), R is OCH3 and R is Ci-C₄ alkoxy. In one embodiment, in a compound of formula (I-6a), 19 1

R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-6a), R is OCH3

19 and R is OCH3. In one embodiment, in a compound of formula (I-6a), R is OCH3 and R

-3517475 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6a), R¹ is OCH3 and

R is 1-propenyl.

In one embodiment, in a compound of formula (I-6b), R is OH and R is halogen. In one embodiment, in a compound of formula (I-6b), R¹ is OH and R² is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6b), R is OH and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6b), R is OH and R is Cl. In one embodiment, in a compound of formula (I-6b), R is OH and R is OCH3. In one embodiment, in a compound of formula (I-6b), R is OH and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6b), R is OH and R is 1-propenyl. In one embodiment, in a compound of formula (I-6b), R is -O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, in a compound of formula (I-6b), R is -O-(Ci-C4 alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-6b), R¹ is -O-(C]-C4 alkyl) and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6b), R is -O-(Ci-C4 alkyl) and R² is Cl. In one embodiment, in a compound of formula (I-6b), R¹ is -O-(C]-C4 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-6b), R is-O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6b), R is -O-(Ci-C4 alkyl) and R is 1-propenyl. In one embodiment, in a compound of formula (I-6b), R¹ is OCH3 and R² is halogen. In one embodiment, in a compound of formula (I-6b), R is OCH3 and R is C₂-C₄ alkenyl. In one embodiment, in a compound of formula (I-6b), R is OCH3 and R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6b),

1

R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-6b), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-6b), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6b), R¹ is OCH3 and R is 1-propenyl.

In one embodiment, in a compound of formula (I-6c), R¹ is OH and R² is

7 halogen. In one embodiment, in a compound of formula (I-6c), R is OH and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-6c), R is OH and R isC]-C₄alkoxy. In one embodiment, in a compound of formula (I-6c), R¹ is OH and R² is Cl. In one embodiment, in a compound of formula (I-6c), R is OH and R is OCH3. In one

7 embodiment, in a compound of formula (I-6c), R is OH and R is vinyl (or ethenyl). In one

7 embodiment, in a compound of formula (I-6c), R is OH and R is 1-propenyl. In one

7 embodiment, in a compound of formula (I-6c), R is-O-(Ci-C₄ alkyl) and R is halogen. In one embodiment, in a compound of formula (I-6c), R is -O-(Ci-C₄ alkyl) and R is C₂-C₄alkenyl. In one embodiment, in a compound of formula (I-6c), R¹ is -O-(Ci-C₄ alkyl) and

-3617475

1

R is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6c), R is -O-(Ci-C₄

1 alkyl) and R is Cl. In one embodiment, in a compound of formula (I-6c), R is -O-(Ci-C4

1 alkyl) and R is OCH3. In one embodiment, in a compound of formula (I-6c), R is -O-(CiC₄ alkyl) and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6c), R¹ is -O-(Ci-C4 alkyl) and R² is 1-propenyl. In one embodiment, in a compound of formula (I-6c), R is OCH3 and R is halogen. In one embodiment, in a compound of formula (I-6c), R is OCH3 and R is C2-C4 aikenyl. In one embodiment, in a compound of formula (I-6c), R is OCH3 and R is C]-C₄ alkoxy. In one embodiment, in a compound of formula (I-6c), 17 1

R is OCH3 and R is Cl. In one embodiment, in a compound of formula (I-6c), R is OCH3 and R is OCH3. In one embodiment, in a compound of formula (I-6c), R is OCH3 and R is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6c), R¹ is OCH3 and o

R is 1-propenyl.

In one embodiment, Xi is H. In one embodiment, Xi is F. In one embodiment, Xi is Br. In one embodiment, Xi is I. In one embodiment, X, is ethynyl. In one embodiment, Xi is CF2H. In one embodiment, Xi is OCF2H. In one embodiment, Xi is OCF3. In one embodiment, X] is CN. In one embodiment, Xj is CONH2. In one embodiment, X] is CO2H. In one embodiment, Xj is CO2CH3. In one embodiment, Xi is NO₂.

In some embodiments, X] is H, F, Br, I, ethynyl, CF2H, OCF2H, OCF3, CN, CONH2, CO2CH3, orNO₂.

In some embodiments, Xi is F. In some embodiments, Xi is Br or I.

In one embodiment, X₂ is H. In one embodiment, X₂ is F. In one embodiment, X₂ is Cl. In one embodiment, X₂ is Br. In one embodiment, X₂ is I. In one embodiment, X₂is ethynyl. In one embodiment, X₂ is CH3. In one embodiment, X₂ is CFH₂. In one embodiment, X₂ is CF₂H. In one embodiment, X₂ is CF3. In one embodiment, X₂ is OCF₂H. In one embodiment, X₂ is OCF3. In one embodiment, X₂ is CN. In one embodiment, X₂ is CONH₂. In one embodiment, X₂ is CO₂H. In one embodiment, X₂ is NO₂.

In some embodiments, X₂ is H, Cl, Br, I, ethynyl, CH3, CF₂H, CF3, OCF₂H, or CN.

In some embodiments, X₂ is H, F, Br, I, ethynyl, CH3, CF3, OCF₂H, or CN.

In some embodiments, X₂ is F or Cl. In some embodiments, X₂ is Br or I.

In one embodiment, X3 is H. In one embodiment, X3 is F. In one embodiment, X3 is Br. In one embodiment, X3 is I. In one embodiment, X3 is ethynyl. In one

-3717475 embodiment, X3 is CH3. In one embodiment, X3 is CFH₂. In one embodiment, X3 is CF₂H.

In one embodiment, X3 is CF3. In one embodiment, X3 is OCF₂H. In one embodiment, X3 is OCF3. In one embodiment, X3 is CN. In one embodiment, X3 is CONH₂. In one embodiment, X3 is CO₂H. In one embodiment, X3 is NO₂.

In some embodiments, X3 is H, Br, I, ethynyl, OCF₂H, CN, or NO₂.

In some embodiments, X3 is H, F, Br, I, CH3, CF₂H, CF3, OCF₂H, or CN.

In some embodiments, X3 is F or Cl. In some embodiments, X3 is Br or I.

In one embodiment, when Ar is then X is N, CH, CF, CCI, or

CCH3, with provisos that:

R² is not Cl or vinyl, when X is N;

Xi is not H, F, OCF3, or CN, when R² is Cl and X is CH;

Xi is not F, I, CN, or ethynyl, when R² is OCH3 and X is CF; and

Xi is not H, when X is CCI.

In one embodiment, when Ar is , then X is N, CH, CF, CCI, or

CCH3, with provisos that:

R² is not Cl, when X is N;

X₂ is not Cl, when R is OCH3 or vinyl and X is N;

X₂ is not Cl, when R² is Cl and X is CH; and

X₂ is not Cl, Br, I, or CF3, when R² is OCH3 and X is CF.

In one embodiment, when Ar is ^X: then X is N, CH, or CF, with provisos that:

R² is not Cl, when X is N;

X3 is not CH3, when R² is OCH3 and X is N;

X3 is not H, F, or CH3, when R² is Cl and X is CH; and

X3 is not Br or I, when R² is OCH3 and X is CF.

In one embodiment, when Ar is F , then X is N, CH, or CF, with provisos that:

R² is not Cl, when X is N;

X2 is not Cl, when R² is OCH₃ or vinyl and X is N;

X2 is not F, when R is Cl and X is CH; and

X2 is not Cl, Br, I, or CF3, when R² is OCH₃ and X is CF.

In one embodiment, when Ar is

F

F , then X is N, CH, or CF, with proviso that:

X₃ is not CH₃, when R is Cl and X is N; and

X₃ is not Br or I, when X is CF and R² is OCH₃.

then X is N, CH, or CF.

Any ofthe combinations of Ar, X, Y, R¹, R², R³, R⁴, R¹', R¹, R²”, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R³, R⁴, Arl, Ar2, Ar3, Ar4, Ar5, Ar6, Xi, X2, and/or X₃, and/or other substituents described herein, are encompassed by this disclosure and specifically provided herein.

METHODS OF PREPARING THE COMPOUNDS

Exemplary procedures to synthesize the compounds of Formula (I) are provided below. The 3,5-disubstituted-4-amino-6-(optionally substituted phenyl)picolinic acids of Formula (I) can be prepared in a number of ways. As depicted in Scheme I, the 4-amino-6chloropicolinates of Formula (II) can be converted to the 4-amino-6-substituted-picolinates of Formula (III), wherein Ar is as herein defîned, via Suzuki coupling with a boronic acid or ester, in the presence of a base, such as potassium fluoride, and a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a polar, protic solvent mixture, such as acetonitrile-water, at a température, such as 110 °C, e.g., in a micro wave reactor (reaction

-3917475 ai). 4-Amino-6-substituted-picolinates of Formula (III) can be transformed into the 5-iodo-

4- amino-6-substituted-picolinates of Formula (IV) via a reaction with iodinating reagents, such as periodic acid and iodine, in a polar, protic solvent, such as methyl alcohol (reaction bj). Stille coupîing of the 5-iodo-4-amino-6-substituted-picolinates of Formula (IV) with a stannane, such as tetramethyltin, in the presence of a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a non-reactive solvent, such as 1,2dichloroethane, at a température, such as 120-130 °C, e.g., in a microwave reactor, provides

5- (substituted)-4-amino-6-substituted-picolinates of Formula (I-A), wherein Zi is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction ci).

Altematively, 4-amino-6-chloropicolinates of Formula (II) can be transformed into the 5iodo-4-amino-6-chloropicolinates of Formula (V) via a reaction with iodinating reagents, such as periodic acid and iodine, in a polar, protic solvent, such as methyl alcohol (reaction bi). Stille coupîing of the 5-iodo-4-amino-6-chloropicolinates of Formula (V) with a stannane, such as tetramethyltin, in the presence of a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a non-reactive solvent, such as 1,2dichloroethane, at a température, such as 120-130 °C, e.g., in a microwave reactor, provides

5-(substituted)-4-amino-6-chloropicolinates of Formula (VI), wherein Zi is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction ci). The 5-substituted-4-amino-6chloropicolinates of Formula (VI) can be converted to the 5-substituted-4-amino-6substituted-picolinates of Formula (I-A), wherein Ar is as herein defined, via Suzuki coupîing with a boronic acid or ester, in the presence of a base, such as potassium fluoride, and a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a polar, protic solvent mixture, such as acetonitrile-water, at a température, such as 110 °C, e.g., in a microwave reactor (reaction a?)·

-4017475

Scheme I

As depicted in Scheme II, the 4,5,6-trichloropicolinate of Formula (VII) can be converted to the corresponding isopropyl ester of Formula (VIII), via a reaction with isopropyl alcohol and concentrated sulfuric acid, e.g., at reflux température under Dean-Stark conditions (reaction d). The isopropyl ester of Formula (VIII) can be reacted with a fluoride ion source, such as césium fluoride, in a polar, aprotic solvent, such as dimethyl sulfoxide (DMSO), at a température, such as 80 °C, under Dean-Stark conditions, to yield the isopropyl 4,5,6trifluoropicolinate of Formula (IX) (reaction e). The isopropyl 4,5,6-trifluoropicolinate of

Formula (IX) can be aminated with a nitrogen source, such as ammonia, in a polar, aprotic solvent, such as DMSO, to produce a 4-amino-5,6-difluoropicolinate of Formula (X) (reaction f). The fluoro substituent in the 6-position of the 4-amino-5,6-difluoropicolinate of Formula (X) can be exchanged with a chloro substituent by treatment with a chloride source, such as hydrogen chloride, e.g., in dioxane, in a Parr reactor, at a température, such as 100 °C, to produce a 4-amino-5-fluoro-6-chloro-picolinate of Formula (XI) (reaction g). The 4amino-5-fluoro-6-chloropicolinate of Formula (XI) can be transesterified to the corresponding methyl ester of Formula (XII) by reaction with titanium(IV) isopropoxide in methyl alcohol at reflux température (reaction h).

-4117475

Scheme II

As depicted in Scheme III, the 4-amino-5-fluoro-6-chloropicolinate of Formula (XII) can be transformed into the 3-iodo-4-amino-5-fluoro-6-chloropicolinate of Formula (XIII) via reaction with iodinating reagents, such as periodic acid and iodine, in a polar, protic solvent, such as methyl alcohol (reaction b/). Stille coupling of the 3-iodo-4-amino-5-fluoro-6chloropicolinates of Formula (XIII) with a stannane, such as tributyl(vinyl)stannane, in the presence of a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a nonreactive solvent, such as 1,2-dichloroethane, at a température, such as 120-130 °C, e.g., in a microwave reactor, provides 3-(substituted)-4-amino-5-fluoro-6-chloropicolinates of Formula (XIV), wherein R is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction q). Altematively, the 3-iodo-4-amino-5-fluoro-6-chloropicolinates of Formula (XIII) canbe treated with césium carbonate and a catalytic amount of both copper(I) iodide and 1,10phenanthroline in the presence of a polar, protic solvent, such as methyl alcohol, at a température, such as 65 °C, to provide a 3-(substituted)-4-amino-5-fluoro-6-chloropicolinic acids of Formula (XIV), wherein R is alkoxy or haloalkoxy (reaction iî), which can be esterified to the methyl esters, e.g., by treatment with hydrogen chloride (gas) and methyl alcohol at 50 °C (reaction jî). The 3-(substituted)-4-amino-5-fluoro-6-chloropicolinates of Formula (XIV) can be converted to the 4-amino-6-substituted-picolinates of Formula (I-B), wherein Ar is as herein defined, via Suzuki coupling with a boronic acid or ester, in the presence of a base, such as potassium fluoride, and a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a polar, protic solvent mixture, such as acetonitrile-water, at a température, such as 110 °C, e.g., in a micro wave reactor (reaction a₃).

Altematively, the 4-amino-5-fluoro-6-chloropicolinates of Formula (XII) can be converted to the 4-amino-5-fluoro-6-substituted-picolinates of Formula (XV), wherein Ar is as herein defined, via Suzuki coupling with a boronic acid or ester, in the presence of a base, such as potassium fluoride, and a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a polar, protic solvent mixture, such as acetonitrile-water, at a température, such as 110 °C, e.g., in a micro wave reactor (reaction u₄). The 4-amino-5-fluoro-6-substitutedpicolinates of Formula (XV) can be transformed into the 3-iodo-4-amino-5-fluoro-6substituted-picolinates of Formula (XVI) via reaction with iodinating reagents, such as periodic acid and iodine, in a polar, protic solvent, such as methyl alcohol (reaction ô₄). Stille coupling of the 3-iodo-4-amino-5-fluoro-6-substituted-picolinates of Formula (XVI) with a stannane, such as tributyl(vinyl)stannane, in the presence of a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a non-reactive solvent, such as 1,2dichloroethane, at a température, such as 120-130 °C, e.g., in a microwave reactor, provides 3-(substituted)-4-amino-5-fluoro-6-substituted-picolinates of Formula (I-B), wherein R is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction q). Altematively, the 3-iodo-4amino-5-fluoro-6-substituted-picolinates of Formula (XVI) can be treated with césium carbonate and a catalytic amount of both copper(I) iodide and 1,10-phenanthroline in the presence of a polar, protic solvent, such as methyl alcohol, at a température, such as 65 °C, to provide a 3-(substituted)-4-amino-5-fluoro-6-substituted-picolinic acids of Formula (I-B),

A wherein R is alkoxy or haloalkoxy (reaction z₂), which can be esterified to the methyl esters, e.g., by treatment with hydrogen chloride (gas) and methyl alcohol, at a température, such as 50 °C (reaction jf).

-4317475

Scheme III

h then/?

XVI c₅or ij then jj c₄ or

As depicted in Scheme IV, the 4-acetamido-6-(trimethylstannyl)picolinates of Formula (XVII) can be converted to the 4-acetamido-6-substituted-picolinates of Formula (XVIII), wherein Ar is as herein defined, via Stille coupling with an aryl bromide or aryl iodide, in the presence of a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a solvent, such as 1,2-dichloroethane, e.g., at reflux température (reaction k). 4-Amino-6substituted-picolinates of Formula (I-C), wherein Ar is as herein defined, can be synthesized from 4-acetamido-6-substituted-picolinates of Formula (XVIII) via standard deprotecting methods, such as hydrochloric acid gas in methanol (reaction /).

Scheme IV

XVIII

As depicted in Scheme V, 2,4-dichloro-5-methoxypyrimidine (XIX) can be transformed into

2,4-dichloro-5-methoxy-6-vinylpyrimidine (XX) via a reaction with vinyl magnésium bromide, in a polar, aprotic solvent, such as tetrahydrofuran (reaction m). 2,4-Dichloro-5methoxy-6-vinylpyrimidine (XX) can be transformed into 2,6-dichloro-5methoxypyrimidine-4-carboxaldehyde (XXI) via treatment with ozone, e.g., in a dichloromethane:methanol solvent mixture (reaction n). 2,6-Dichloro-5methoxypyrimidine-4-carboxaldehyde (XXI) can be transformed into methyl 2,6-dichloro-5methoxypyrimidine-4-carboxylate (XXII) via treatment with bromine, e.g., in a methanol:water solvent mixture (reaction o). Methyl 2,6-dichloro-5-methoxypyrimidine-4carboxylate (XXII) can be transformed into methyl 6-amino-2-chloro-5-methoxypyrimidine4-carboxylate (XXIII) via treatment with ammonia (e.g., 2 équivalents) in a solvent, such as DMSO (reactionp). Finally, 6-amino-2-substituted-5-methoxypyrimidine-4-carboxylates of Formula (I-D), wherein Ar is as herein defîned, can be prepared via Suzuki coupling with a boronic acid or ester, with 6-amino-2-chloro-5-methoxypyrimidine-4-carboxylate (XXIII), in the presence of a base, such as potassium fluoride, and a catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride, in a polar, protic solvent mixture, such as acetonitrile-water, at a température, such as 110 °C, e.g., in a microwave reactor (reaction ^as)·

Scheme V

XXII

XXIII

The compounds of Formulae I-A, I-B, I-C, and I-D obtained by any of these processes, can be recovered by conventional means and purified by standard procedures, such as by recrystallization or chromatography. The compounds of Formula (I) can be prepared from compounds of Formulae I-A, I-B, I-C, and I-D using standard methods well known in the art.

-4517475

COMPOSITIONS AND METHODS

In some embodiments, the compounds provided herein are employed in mixtures containing a herbicidally effective amount of the compound along with at least one agriculturally acceptable adjuvant or carrier. Exemplary adjuvants or carriers include those that are not phytotoxic or significantly phytotoxic to valuable crops, e.g., at the concentrations employed in applying the compositions for sélective weed control in the presence of crops, and/or do not react or significantly react chemically with the compounds provided herein or other composition ingrédients. Such mixtures can be designed for application directly to weeds or their locus or can be concentrâtes or formulations that are diluted with additional carriers and adjuvants before application. They can be solids, such as, for example, dusts, granules, water dispersible granules, or wettable powders, or liquids, such as, emulsifiable concentrâtes, solutions, émulsions or suspensions. They can also be provided as a pre-mix or tank-mixed.

Suitable agricultural adjuvants and carriers that are useful in preparing the herbicidal mixtures of the disclosure are well known to those skilled in the art. Some of these adjuvants include, but are not limited to, crop oil concentrate (minerai oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quatemary ammonium sait; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-Cn alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C12-C16) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxanemethyl cap; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99.

Liquid carriers that can be employed include water and organic solvents. The organic solvents typically used include, but are not limited to, petroleum fractions or hydrocarbons such as minerai oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, com oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethylhexyl stéarate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono-, di- and poly-carboxylic acids and the like. Spécifie organic solvents include toluene, xylene, petroleum naphtha, crop oil, acetone,

-4617475 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, glycérine, 7V-methyl-2-pyrrolidinone, 7V,7V-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers, and the like. In some embodiments, water is the carrier for the dilution of concentrâtes.

Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.

In some embodiments, one or more surface-active agents are utilized in the compositions of the présent disclosure. Such surface-active agents are, in some embodiments, employed in both solid and liquid compositions, e.g., those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants conventionally used in the art of formulation and which may also be used in the présent formulations are described, inter alia, in McCutcheon ’s Détergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey, 1998, and in Encyclopedia of Surfactants, Vol. I-III, Chemical Publishing Co., New York, 1980-81. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-Cig ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-Ciô ethoxylate; soaps, such as sodium stéarate; alkylnaphthalene-sulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quatemary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stéarate; block copolymers of ethylene oxide and propylene oxide; salts of mono- and dialkyl phosphate esters; vegetable or seed oils such as soybean oil, rapeseed/canola oil, olive oil, castor oil, sunflower seed oil, coconut oil, com oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; and esters of the above vegetable oils, e.g., methyl esters.

-4717475

Oftentimes, some of these materials, such as vegetable or seed oils and their esters, can be used interchangeably as an agricultural adjuvant, as a liquid carrier or as a surface active agent.

Other adjuvants commonly used in agricultural compositions include compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, pénétration aids, sticking agents, dispersing agents, thickening agents, freezing point depressants, antimicrobial agents, and the like. The compositions may also contain other compatible components, for example, other herbicides, plant growth régulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.

The concentration of the active ingrédients in the herbicidal compositions of this disclosure is generally from about 0.001 to about 98 percent by weight. Concentrations from about 0.01 to about 90 percent by weight are often employed. In compositions designed to be employed as concentrâtes, the active ingrédient is generally présent in a concentration from about 5 to about 98 weight percent, preferably about 10 to about 90 weight percent. Such compositions are typically diluted with an inert carrier, such as water, before application. The diluted compositions usually applied to weeds or the locus of weeds generally contain about 0.0001 to about 1 weight percent active ingrédient and preferably contain about 0.001 to about 0.05 weight percent.

The présent compositions can be applied to weeds or their locus by the use of conventîonal ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation or flood water, and by other conventîonal means known to those skilled in the art.

In some embodiments, the compounds and compositions described herein are applied as a post-emergence application, pre-emergence application, in-water application to flooded paddy rice or water bodies (e.g., ponds, lakes and streams), or bum-down application. In some embodiments, the compounds and compositions provided herein are utilized to control weeds in crops, including but not limited to citrus, apple, rubber, oil, palm, forestry, direct-seeded, water-seeded and transplanted rice, wheat, barley, oats, rye, sorghum, com/maize, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, or row-crops, as well as non-crop settings, e.g., industrial végétation management (IVM) or rights-of-way. In some embodiments, the compounds and compositions are used to control woody plants, broadleaf and grass weeds, or sedges.

In some embodiments, the compounds and compositions provided herein are utilized to control undesirable végétation in rice. In certain embodiments, the undesirable végétation is Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv. (bamyardgrass, ECHCG), Echinochloa colonum (L.) LINK (junglerice, ECHCO), Echinochloa oryzoides (Ard.) Fritsch (early watergrass, ECHOR), Echinochloa oryzicola (Vasinger) Vasinger (late watergrass, ECHPH), Ischaemum rugosum Salisb. (saramollagrass, ISCRU), Leptochloa chinensis (L.) Nees (Chinese sprangletop, LEFCH), Leptochloa fascicularis (Lam.) Gray (bearded sprangletop, LEFFA), Leptochloa panicoides (Presl.) Hitchc. (Amazon sprangletop, LEFPA), Panicum dichotomiflorum (L.) Michx. (fall panicum, PANDI), Paspalum dilatatum Poir. (dallisgrass, PASDI), Cyperus difformis L. (smallflower flatsedge, CYPDI), Cyperus esculentus L. (yellow nutsedge, CYPES), Cyperus iria L. (rice flatsedge, CYPIR), Cyperus rotundus L. (purple nutsedge, CYPRO), Eleocharis species (ELOSS), Fimbristylis miliacea (L.) Vahl (globe fringerush, FIMMI), Schoenoplectus juncoides Roxb. (Japanese bulrush, SCPJU), Schoenoplectus maritimus L. (sea clubrush, SCPMA), Schoenoplectus mucronatus L. (ricefield bulrush, SCPMU), Aeschynomene species, (jointvetch, AESSS), Alternanthera philoxeroides (Mart.) Griseb. (alligatorweed, ALRPH), Alisma plantago-aquatica L. (common waterplantain, ALSPA), Amaranthus species, (pigweeds and amaranths, AMASS), Ammannia coccinea Rottb. (redstem, AMMCO), Eclipta alba (L.) Hassk. (American false daisy, ECLAL), Heteranthera limosa (SW.) Willd./Vahl (ducksalad, HETLI), Heteranthera reniformis R. & P. (roundleaf mudplantain, HETRE), Ipomoea hederacea (L.) Jacq. (ivyleaf momingglory, IPOHE), Lindernia dubia (L.) Pennell (low false pimpemel, LIDDU), Monochoria korsakowii Regel & Maack (monochoria, MOOKA), Monochoria vaginalis (Burm. F.) C. Presl ex Kuhth, (monochoria, MOOVA), Murdannia nudiflora (L.) Brenan (doveweed, MUDNU), Polygonum pensylvanicum L. (Pennsylvania smartweed, POLPY), Polygonum persicaria L. (ladysthumb, POLPE), Polygonum hydropiperoides Michx. (mild smartweed, POLHP), Rotala indica (Willd.) Koehne (Indian toothcup, ROTIN), Sagittaria species, (arrowhead, SAGSS), Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill (hemp sesbania, SEBEX), or Sphenoclea zeylanica Gaertn. (gooseweed, SPDZE).

In some embodiments, the compounds and compositions provided herein are utilized to control undesirable végétation in cereals. In certain embodiments, the undesirable végétation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Apera spica-venti (L.) Beauv. (windgrass, APESV), Avena fatua L. (wild oat, AVEFA), Bromus tectorum L.

(downy brome, BROTE), Loliurn multiflorum Lam. (Italian ryegrass, LOLMU), Phalaris minor Retz, (littleseed canarygrass, PHAMI), Poa annua L. (annual bluegrass, POAAN), Setaria pumila (Poir.) Roemer & J.A. Schultes (yellow foxtail, SETLU), Setaria viridis (L.) Beauv. (green foxtail, SETVI), Cirsium arvense (L.) Scop. (Canada thistle, CIRARj, Galium aparine L. (catchweed bedstraw, GALAP), Kochia scoparia (L.) Schrad. (kochia, KCHSC), Lamium purpureum L. (purple deadnettle , LAMPU), Matricaria recutita L. (wild chamomile, MATCH), Matricaria matricarioides (Less.) Porter (pineappleweed, MATMT), Papaver rhoeas L. (common poppy, PAPRH), Polygonum convolvulus L. (wild buckwheat, POLCO), Salsola tragus L. (Russian thistle, SASKR), Stellaria media (L.) Vill. (common chickweed, STEME), Veronica persica Poir. (Persian speedwell, VERPE), Viola arvensis Murr. (field violet, VIOAR), or Viola tricolor L. (wild violet, VIOTR).

In some embodiments, the compounds and compostions provided herein are utilized to control undesirable végétation in range and pasture. In certain embodiments, the undesirable végétation is Ambrosia artemisiifolia L. (common ragweed, AMBEL), Cassia obtusifolia (sickle pod, CASOB), Centaurea maculosa auct. non Lam. (spotted knapweed, CENMA), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), Convolvulus arvensis L. (field bindweed, CONAR), Euphorbia esula L. (leafy spurge, EPHES), Lactuca serriola L./Tom. (prickly lettuce, LACSE), Plantago lanceolata L. (buckhom plantain, PLALA), Rumex obtusifolius L. (broadleaf dock, RUMOB), Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild mustard, SINAR), Sonchus arvensis L. (perennial sowthistle, SONAR), Solidago species (goldenrod, SOOSS), Taraxacum officinale G.H. Weber ex Wiggers (dandelion, TAROF), Trifolium repens L. (white clover, TRFRE), or Urtica dioica L. (common nettle, URTDI).

In some embodiments, the compounds and compositions provided herein are utilized to control undesirable végétation found in row crops. In certain embodiments, the undesirable végétation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Avena fatua L. (wild oat, AVEFA), Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv. (bamyardgrass, ECHCG), Echinochloa colonum (L.) Link (junglerice, ECHCO), Loliurn multiflorum Lam. (Italian ryegrass, LOLMU), Panicum dichotomiflorum Michx. (fail panicum, PANDI), Panicum miliaceum L. (wild-proso millet, PANMI), Setaria faberi Herrm. (giant foxtail, SETFA), Setaria viridis (L.) Beauv. (green foxtail, SETVI), Sorghum halepense (L.) Pers. (Johnsongrass, SORHA), Sorghum bicolor (L.) Moench ssp. Arundinaceum (shattercane, SORVU), Cyperus esculentus L. (yellow nutsedge, CYPES),

-5017475

Cyperus rotundus L. (purple nutsedge, CYPRO), Abutilon theophrasti Medik. (velvetleaf, ABUTH), Amaranthus species (pigweeds and amaranths, AMAS S), Ambrosia artemisiifolia L. (common ragweed, AMBEL), Ambrosia psilostachya DC. (western ragweed, AMBPS), Ambrosia trifida L. (giant ragweed, AMBTR), Asclepias syriaca L. (common milkweed, ASCSY), Chenopodium album L. (common lambsquarters, CHEAL), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), Commelina benghalensis L. (tropical spiderwort, COMBE), Datura stramonium L. (jimsonweed, DATST), Daucus carota L. (wild carrot, DAUCA), Euphorbia heterophylla L. (wild poinsettia, EPHHL), Erigeron bonariensis L. (hairy fleabane, ERIBO), Erigeron canadensis L. (Canadian fleabane, ERICA), Helianthus annuus L. (common sunflower, HELAN), Jacquemontia tamnifolia (L.) Griseb. (smallflower momingglory, IAQTA), Ipomoea hederacea (L.) Jacq. (ivyleaf momingglory, IPOHE), Ipomoea lacunosa L. (white momingglory, IPOLA), Lactuca serriola L./Tom. (prickly lettuce, LACSE), Portulaca oleracea L. (common purslane, POROL), Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild mustard, SINAR), Solanum ptychanthum Dunal (eastem black nightshade, SOLPT), orXanthium strumarium L. (common cocklebur, XANST).

In some embodiments, application rates of about 1 to about 4,000 grams/hectare (g/ha) are employed in post-emergence operations. In some embodiments, rates of about 1 to about 4,000 g/ha are employed in pre-emergence operations.

In some embodiments, the compounds, compositions, and methods provided herein are used in conjunction with one or more other herbicides to control a wider variety of undesirable végétation. When used in conjunction with other herbicides, the presently claimed compounds can be formulated with the other herbicide or herbicides, tank-mixed with the other herbicide or herbicides or applied sequentially with the other herbicide or herbicides. Some of the herbicides that can be employed in conjunction with the compounds of the présent disclosure include: 4-CPA, 4-CPB, 4-CPP, 2,4-D, 2,4-D choline sait, 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, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuronmethyl, bensulide, benthiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac-sodium, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, 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, chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop-propargyl, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, 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, 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, DMP A, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethbenzamide, ethametsulfuron, ethidimuron, ethiolate, ethobenzamid, etobenzamid, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P-ethyl, fenoxaprop-P-ethyl + isoxadifen-ethyl, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr-ethyl, flumetsulam, flumezin, flumicloracpentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-ammonium, glyphosate, halosafen, halosulfuronmethyl, haloxydine, haloxyfop-methyl, haloxyfop-P-methyl, halauxifen-methyl, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, ΜΑΜΑ, MCPA esters and amines, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, or/Ao-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraflufen-ethyl, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, 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, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac-methyl, pyroxasulfone, pyroxsulam, 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, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr esters and amines, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vemolate and xylachlor. The compounds and compositions of the présent disclosure can generally be employed in combination with known herbicide safeners, such as benoxacor, benthiocarb, brassinolide, cloquintocet (e.g., mexyl), cyometrinil, daimuron, dichlormid, dicyclonon, dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and 7V-phenylsulfonylbenzoic acid amides, to enhance their selectivity. The compounds, compositions, and methods described herein be used to control undesîrable végétation on glyphosate-tolerant-, glufosinate-tolerant-, dicamba-tolerant-, phenoxy auxintolerant-, pyridyloxy auxin-tolerant-, aryloxyphenoxypropionate-tolerant-, acetyl CoA carboxylase (ACCase) inhibitor-tolerant-, imidazolinone-tolerant-, acetolactate synthase (ALS) inhibitor-tolerant-, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor tolérant-, protoporphyrinogen oxidase (PPO) inhibitor -tolérant-, triazine-tolerant-, and bromoxynil-tolerant- crops (such as, but not limited to, soybean, cotton, canola/oilseed râpe, rice, cereals, corn, turf, etc), for example, in conjunction with glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil. The compositions and methods may be used in controlling undesîrable végétation in crops possessing multiple or stacked traits conferring tolérance to multiple chemistries and/or inhibitors of multiple modes-of-action.

The compounds and compositions provided herein may also be employed to control herbicide résistant or tolérant weeds. Exemplary résistant or tolérant weeds include, but are not limited to, biotypes résistant or tolérant to acetolactate synthase (ALS) inhibitors, photosystem II inhibitors, acetyl CoA carboxylase (ACCase) inhibitors, synthetic auxins, photosystem I inhibitors, 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, microtubule assembly inhibitors, lipid synthesis inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, carotenoid biosynthesis inhibitors, very long chain fatty acid (VLCFA) inhibitors, phytoene desaturase (PDS) inhibitors, glutamine synthetase inhibitors, 4hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple modes-of-action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals. Exemplary résistant or tolérant weeds include, but are not limited to,

-5417475 biotypes with résistance or tolérance to multiple herbicides, multiple chemical classes, and multiple herbicide modes-of-action.

The described embodiments and following examples are for illustrative purposes and are not intended to limit the scope of the claims. Other modifications, uses, or combinations with respect to the compositions described herein will be apparent to a person of ordinary skill in the art without departing from the spirit and scope of the claimed subject matter.

EXAMPLES

SYNTHESIS OF PRECURSORS

General Considérations: Fluorine spectra were acquired at 376 MHz on a Bruker DRX400 spectrometer. The spectra were referenced to trichlorofluoromethane (CFCI3) as an external standard and were typically conducted with proton decoupling.

Example 1: Préparation of methyl 4-amino-3,6-dichloropicolinate (Head A)

NH,

Cl

O

Prepared as described in Fields et al., WO 2001051468 Al.

Example 2: Préparation of methyl 4-amino-3,6-dichloro-5-fluoropicolinate (Head B)

NH

Cl

Prepared as described in Fields et al., Tetrahedron Letters 2010, 51, 79-81.

-5517475

Example 3: Préparation of 2,6-dichloro-5-methoxy-4-vinyl pyrimidine

Cl	çh₃	Cl	çh₃
	1 _XO	N 'γ-
A 2 cr n			Ίι ch₂

To a solution of commercially available 2,6-dichloro-5-methoxy pyrimidine (100 grams (g), 0.55 moles (mol) in dry tetrahydrofuran was added dropwise 1 molar (M) vinyl magnésium bromide in tetrahydrofuran solvent (124 g, 0.94 mol) over one hour (h) at room température. The mixture was then stirred for 4 h at room température. Excess Grignard reagent was quenched by addition of acetone (200 milliliters (mL)) while the température of the mixture was maintained at a température below 20 °C. Thereafter, 2,3-dichloro-5,6-dicyano-pbenzoquinone (DDQ; 151g, 0.67 mol) was added at once and stirred ovemight. A yellow solid precipitated out. The solid was filtered and washed with ethyl acetate (500 mL). The filtrate was concentrated under reduced pressure and the resulting crude compound was diluted with ethyl acetate (2 liters (L)). The resulting undissolved, dark, semi-solid was separated by filtration using ethyl acetate. It was further concentrated under reduced pressure to provide a crude compound, which was purified by column chromatography. The compound was eluted with 5% to 10% ethyl acetate in hexanes mixture to provide the title compound (70 g, 60%): mp 60 - 61 °C; *H NMR (CDC1₃) δ 3.99 (s, 3H), 5.85 (d, 1H), 6.75 (d, 1H), 6.95 (dd, 1H).

Example 4: Préparation of 2,6-dichloro-5-methoxy-pyrimidine-4-carbaldehyde

Cl	ch₃ 1 ⁰	Cl	çh₃
	_XO		1 /O
Cl N	H	Cl^bf	il
	ch₂		II 0

A solution of 2,6-dichloro-5-methoxy-4-vinyl pyrimidine (50 g, 0.24 mol) in dichloromethane:methanol (4:1, 2L) was cooled to -78 °C. Ozone gas was bubbled through for 5 h. The reaction was quenched with dimethyl sulfide (50 mL). The mixture was slowly warmed to room température and concentrated under reduced pressure at 40 °C to provide the title compound (50.5 g, 100%).

-5617475

Example 5: Préparation of methyl 2,6-dichloro-5-methoxy-pyrimidine-4-carboxylate

Cl	çh₃	Cl	çh₃
	_xo
II		»- Il
A Y-		A. Ύ
cr n	n	cr n	Y ch₃
	0		0

A solution of 2,6-dichloro-5-methoxy-pyrimidine-4-carbaldehyde (50 g, 0.24 mol) in methanol (1 L) and water (60 mL) was prepared. To the solution, sodium bicarbonate (400 g) was added. A 2 M solution of bromine (192 g, 1.2 mol) in methanol/water (600 mL, 9:1 v/v) was added dropwise to the pyrimidine solution over 45 minutes (min) at 0 °C while stirring the mixture. The stirring was continued at the same température for 1 h. Later, the mixture was stirred at room température for 4 h. While stirring, the reaction mixture was thereafter poured onto a mixture of crushed ice (2 L), sodium bisulfite (50 g), and sodium chloride (NaCI; 200 g). The product was extracted with ethyl acetate (1 L x 2), and the combined organic layer was dried over sodium sulfate (Na₂SO₄) and filtered. Evaporation of the solvent under reduced pressure produced a thick material, which solidifîed on long standing to afford the title compound (50.8 g, 87%): ESIMS m/z 238 ([M+H]⁺).

Example 6: Préparation of methyl 6-amino-2-chloro-5-methoxy-pyrimidine-4carboxylate (Head C)

CH₃

A solution of methyl 2,6-dichloro-5-methoxy-pyrimidine-4-carboxylate (25 g, 0.1 mol) and dimethyl sulfoxide (DMSO) was prepared. To this solution was added, at 0-5 °C, a solution of ammonia (2 équivalents (equiv)) in DMSO. This mixture was stirred at the same 0-5 °C température for 10 to 15 min. Later, the mixture was diluted with ethyl acetate, and the resulting solid was filtered off. The ethyl acetate filtrate was washed with a brine solution and dried over Na₂SO₄. Upon concentration, the crude product was obtained. The crude product was stirred in a minimum amount of ethyl acetate and filtered to obtain the pure compound. Additional pure compound was obtained from the filtrate which, after concentration, was purified by flash chromatography. This produced the title compound (11

-5717475 g, 50%): mp 158 °C; 'H NMR (DMSO-Aj δ 3.71 (s, 3H), 3.86 (s, 3H), 7.65 (br s, ÎH), 8.01 (br s, 1H).

Example 7: Préparation of methyl 4-amino-3,6-dichloro-5-iodopicolinate

ch₃

Methyl 4-amino-3,6-dichloropicolinate (10.0 g, 45.2 mmol), periodic acid (3.93 g, 17.2 millimoles (mmol)), and iodine (11.44 g, 45.1 mmol) were dissolved in methanol (30 mL) and stirred at reflux at 60 °C for 27 h. The reaction mixture was concentrated, diluted with diethyl ether, and washed twice with saturated aqueous sodium bisulfite. The aqueous layers 10 were extracted once with diethyl ether, and the combined organic layers were dried over anhydrous Na2SÛ4. The product was concentrated and purified by flash chromatography (silica gel; 0-50% ethyl acetate/hexanes) to provide the title compound as a pale yellow solid (12.44 g, 79%); mp 130.0-131.5 °C; 'H NMR (400 MHz, CDC1₃) δ 5.56 (s, 2H), 3.97 (s, 3H); ¹³C NMR (101 MHz, CDC1₃) δ 163.80, 153.00, 152.75, 145.63, 112.12, 83.91,

53.21; EIMS m/z 346.

Example 8: Préparation of methyl 4-amino-3,6-dichloro-5-methylpicolinate (Head D)

nh₂	h₃c.	nh₂
			^Cl
	IL /0.
CI^X	N Y CH₃ 0	cr	N	Y ch₃ 0

A mixture of methyl 4-amino-3,6-dichloro-5-iodopicolinate (8.1 g, 23.4 mmol), tetramethylstannane (8.35 g, 46.7 mmol), and bis(triphenylphosphine)palladium(II) chloride (2.5 g, 3.5 mmol) in 1,2-dichloroethane (40 mL) was irradiated in a Biotage Initiator™ microwave at 120 °C for 30 min, with extemal infrared (IR)-sensor température monitoring from the side. The reaction mixture was loaded directly onto a silica gel cartridge and purified by flash chromatography (silica gel; 0-50% ethyl acetate/hexanes) to provide the title compound as an orange solid (4.53 g, 83%): mp 133-136 °C; *H NMR (400 MHz, CDC1₃) δ 4.92 (s, 2H), 3.96 (s, 3H), 2.29 (s, 3H); ¹³C NMR (101 MHz, CDC1₃) δ 164.34,

-5817475

150.24, 148.69, 143.94, 117.01, 114.60, 53.02, 14.40; ESIMS w/z236 ([M+H]⁺), 234 ([ΜΗ]').

Example 9: Préparation of methyl 6-amino-2,5-dichloropyrimidine-4-carboxylate (Head E)

Prepared as described in Epp et al., WO 2007082076 Al.

Example 10: Préparation of methyl 4-amino-6-chloro-5-fluoro-3-methoxypicoIinate (Head F)

Prepared as described in Epp et al., WO 2013003740 Al.

Example 11: Préparation of methyl 4-amino-6-chloro-5-fluoro-3-vinylpicoIinate (Head

G)

	nh₂		nh₂ ch₂
			1 H (l^l
Cl^		Cl^	IL N CH₃
	0		0

Methyl 4-amino-6-chloro-5-fluoro-3-iodopicolinate (7.05 g, 21.33 mmol, prepared as described in Epp et al., WO 2013003740 Al) and vinyl tri-n-butyltin (7.52 mL, 25.6 mmol) were suspended in dichloroethane (71.1 mL) and the mixture was degassed with Argon for 10 min. Bis(triphenylphosphine)palladium(II) chloride (1.497 g, 2.133 mmol) was then added, and the reaction mixture was stirred at 70 °C ovemight (clear orange solution). The reaction was monitored by gas chromatography-mass spectrometry (GC-MS). After 20 h, the reaction mixture was concentrated, adsorbed onto Celite®, and purified by column chromatography (silica gel (S1O2); hexanes/ethyl acetate gradient) to afford the title compound as a light brown solid (3.23 g, 65.7%): mp 99-100 °C; ^!H NMR (400 MHz, CDC1₃) δ 6.87 (dd, J= 18.1, 11.6 Hz, 1 H), 5.72 (dd,J= 11.5, 1.3 Hz, 1H), 5.52 (dd, J = 18.2, 1.3 Hz, 1H), 4.79 (s, 2H), 3.91 (s, 3H); ¹⁹F NMR (376 MHz, CDCI3) δ -138.79 (s); EIMS m/z 230.

Example 12: Préparation of methyl 4-amino-3,5,6-trichloropicolinate (Head H)

CH₃

Prepared as described in Finkelstein et al., WO 2006062979 Al.

Example 13: Préparation of methyl 4-amino-6-bromo-3-chloro-5-fluoropicolinate (Head I)

Prepared as described in Amdt et al., US 20120190857 Al.

Example 14: Préparation of methyl 4-amino-3-chloro-5-fluoro-6-

(trimethylstannyl)picolinate (Head J)
F.	nh₂ /L /Cl
N	Y-Y x A Z°x
Sn	N jA CH₃
/ \	O

Methyl 4-amino-6-bromo-3-chloro-5-fluoropicolinate (500 milligrams (mg), 1.8 mmol), 1,1,1,2,2,2-hexamethyldistannane (580 mg, 1.8 mmol) and bis(triphenylphosphine)palladium(II) chloride (120 mg, 0.18 mmol) were combined in dry dioxane (6 mL), sparged with a stream of nitrogen for 10 min and then heated to 80 °C for 2 h. The cooled mixture was stirred with ethyl acetate (25 mL) and saturated NaCl (25 mL) for 15 min. The organic phase was separated, filtered through diatomaceous earth, dried (Na₂SO₄) and evaporated. The residue was taken up in ethyl acetate (4 mL), stirred and treated in portions with hexanes (15 mL). The milky white solution was decanted from any solids produced, filtered through glass wool and evaporated to give the title compound as an off-white solid (660 mg, 100%): *H NMR (400 MHz, CDC1₃) δ 4.63 (d, J = 29.1 Hz, 2H), 3.97 (s, 3H), 0.39 (s, 9H); ¹⁹F NMR (376 MHz, CDC1₃) δ -130.28; EIMS m/z 366.

Example 15: Préparation of methyl 4-acetamido-3-chloro-6-(trimethylstannyl)picolinate (Head K)

O

' O

Prepared as described in Balko et al., WO 2003011853 Al.

Example 16: Préparation of methyl 4-acetamido-3,6-dichloropicolinate (Head L)

O

Prepared as described in Fields et al., WO 2001051468 Al.

Example 17: Préparation of methyl 4-amino-3-chloro-6-iodopicolinate (Head M) NH₂

O_xch₃ o

Prepared as described in Balko et al., WO 2007082098 A2.

Example 18: Préparation of methyl 4-acetamido-3-chloro-6-iodopicolinate (Head N)

O

Prepared as described in Balko et al., WO 2007082098 A2.

Example 19: Préparation of methyl 4-amino-6-bromo-3,5-difluoropicolinate (Head O)

CH₃

Prepared as described in Fields et al., WO 2001051468 Al.

Example 20: Préparation of methyl 6-amino-2-chloro-5-vinylpyrimidine-4-carboxylate (Head P)

Prepared as described in Epp et al., US 20090088322.

Example 22: Préparation of 4-bromo-2-fluorophenyl)trimethylsilane

A 2.5 M solution of n-butyllithium in hexanes («-BuLi; 900 microliters (pL), 2.2 mmol, 1.1 equiv) was added to a stirred solution of l,4-dibromo-2-fluorobenzene (500 mg, 2.0 mmol,

1.0 equiv) in diethyl ether (10 mL) at -78 °C. The resulting pale yellow solution was stirred at -78 °C for 2 h. Chlorotrimethylsilane (300 pL, 2.4 mmol, 1.2 equiv) was added and the resulting pale yellow solution was allowed to slowly warm to 23 °C, by allowing the dry ice / acetone bath to melt, and was stirred for 72 h. The reaction mixture was diluted with water (50 mL) and extracted with dichloromethane (3 x 50 mL). The combined organic layers were dried (magnésium sulfate (MgSO₄)), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a pale yellow oil (350 mg, 71%): IR (thin film) 3068 (w), 2955 (m), 2927 (m), 2855 (w), 1598 (w), 1567 (w) cm'¹; ’H NMR (400 MHz, DMSO-î/₆) δ 7.38 - 7.49 (m, 3H), 0.30 (s, 9H).

Example 23: Préparation of (2-fluor0-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyl)trimethylsilane

A 2.5 M solution of n-BuLi (8.5 mL, 21 mmol, 1.1 equiv) was added to a stirred solution of (4-bromo-2-fluorophenyl)trimethylsilane (4.8 g, 19 mmol, 1.0 equiv) in tetrahydrofuran (80 mL) at -78 °C. The resulting orange solution was stirred at -78 °C for 15 min. 2Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (4.4 mL, 21 mmol, 1.1 equiv) was added, and the cloudy orange solution was allowed to slowly warm to 23 °C, by allowing the dry ice / acetone bath to melt, and stirred for 20 h. The reaction mixture was diluted with water (200 mL), adjusted to approximately pH 4 using 1 M hydrochloric acid (HCl), and extracted with dichloromethane (3 x 100 mL). The combined organic layers were dried (MgSO₄), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a pale yellow semi-solid (6.0 g, 99%); *H NMR (400 MHz, CDCI3) δ 7.55 (dt, J= 7.5, 1 Hz, IH), 7.38 - 7.42 (m, 2H), 1.34 (s, 12H), 0.29 (d, J= 1 Hz, 9H).

The following compounds were made in accordance with the procedures disclosed in Example 23:

2-(4-(DifluoromethyI)phenyl)-4,4,5,5-tetramethyI-l,3,2-dioxaborolane

-6317475

’H NMR (400 MHz, CDCl₃) δ 7.89 (br d, J = 8 Hz, 2H), 7.50 (br d, J = 8 Hz, 2H), 6.65 (t, J = 56 Hz, 1H), 1.35 (s, 12H).

2-(4-(Difluoromethyl)-3-fluorophenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane

^!H NMR (400 MHz, CDCI3) δ 7.51 - 7.68 (m, 3H), 6.90 (t, J= 55 Hz, 1H), 1.35 (s, 12H).

Example 24: Préparation of (2,3-difluoro-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2yl)phenyl)trimethylsilane

A 2.5 M solution of n-BuLi (9.5 mL, 24 mmol, 1.1 equiv) was added to a stirred solution of (2,3-difluorophenyl)trimethylsilane (4.0 g, 21 mmol, 1.0 equiv) in tetrahydrofuran (86 mL) at -78 °C. The resulting very pale yellow solution was stirred at -78 °C for 1 h. 2Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (4.8 mL, 24 mmol, 1.1 equiv) was added, and the pale yellow solution was allowed to slowly warm to 23 °C, by allowing the dry ice / acetone bath to melt, and stirred for 20 h. The reaction mixture was diluted with water (200 mL), adjusted to approximately pH 4 using IM HCl, and extracted with dichloromethane (3 x 100 mL). The combined organic layers were dried ( MgSCU), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a white

-6417475 powder (6.4 g, 96%): *Η NMR (400 MHz, CDCl₃) δ 7.42 (ddd, J= 7.5, 4.5, 0.5 Hz, 1H),

7.09 (ddd, J= 7.5, 4, 1 Hz, 1H), 1.34 (s, 12H), 0.29 (d, J- 1 Hz, 9H).

Example 25: Préparation of (3-fluoro-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2yl)phenyl)trimethylsilane

A 2.5 M solution of w-BuLi (3.5 mL, 8.5 mmol, 1.1 equiv) was added to a stirred solution of l,4-dibromo-2-fluorobenzene (2.0 g, 7.9 mmol, 1.0 equiv) in tetrahydrofuran (THF; 26 mL) at -78 °C. The resulting bright yellow solution was stirred at -78 °C for 15 min. 2Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (1.8 mL, 8.7 mmol, 1.1 equiv) was added and the resulting pale yellow solution was stirred at -78 °C for 30 min. A 2.5 M solution of tt-BuLi (3.5 mL, 8.5 mmol, 1.1 equiv) was added and the resulting yellow/brown solution was stirred at -78 °C for 15 min. Chlorotrimethylsilane (2.2 mL, 17 mmol, 2.2 equiv) was added, and the resulting pale yellow solution was allowed to slowly warm to 23 °C, by allowîng the dry ice / acetone bath to melt, and stirred for 18 h. The reaction mixture was diluted with water (150 mL) and extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried ( MgSÛ4), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a pale yellow powder (2.3 g, 99%): IR (thin film) 3058 (w), 2981 (s), 2932 (m), 1615 (m) cm’¹; ‘H NMR (400 MHz, CDC1₃) δ 7.72 (dd, J= 7.5, 6 Hz, 1H), 7.26 (m, 1H), 7.16 (d, J= 7.5 Hz, 1H), 1.34 (s, 12H), 0.23 (s, 9H).

Example 26: Préparation of 2,3,5-trifluoro-4-iodoaniline

To a stirred solution of 2,3,5-trifluoroaniline (2.0 g, 13.605 mmol, 1.0 equiv) in dry THF (40 mL) at -78 °C, was added sec-butyllithium (10.88 mL, 13.6 mmol, 1.0 equiv) over 30 min. Stirring was continued at -78 °C for 2 h. A solution of iodine (4.14 g, 16.32 mmol, 1.2 equiv) was added dropwise, and reaction mixture was slowly warmed to 20 °C over 1 h. The reaction was quenched with 10% aqueous (aq) sodium thiosulfate (Na2S2Û₃) solution and extracted with methyl terributyl ether (MTBE; 3 x 50 mL). The combined organic extracts were washed with saturated brine solution, dried over anhydrous Na2SÛ4, filtered and evaporated to dryness under reduced pressure. The crude product was column purified over silica using 0-10% ethyl acetate (EtOAc) with hexanes as eluent to afford 2,3,5trifluoro-4-iodoaniline (1.3 g, 35%) as pink solid: ^!H NMR (400 MHz, CDCI3) δ 6.43 - 6.39 (m, IH), 3.99 (br s, 2H); ESIMS m/z 274 ([M+H]⁺).

Example 27: Préparation of 4-bromo-l-(difluoromethoxy)-2-fluorobenzene

To a 100 mL flask charged with Α,Α-dimethylformamide (DMF; 23 mL) were added sodium 2-chloro-2,2-difluoroacetate (4.79 g, 31.4 mmol), potassium carbonate (2.60 g, 18.85 mmol), 4-bromo-2-fluorophenol (3 g, 15.71 mmol). Water (5.75 mL) was added and the reaction mixture was heated to 100 °C for 3 h. Upon cooling to room température, the reaction mixture was diluted with diethyl ether (Et2Û; 100 mL) and a 2 normal (N) sodium hydroxide (NaOH) solution (100 mL). The organic layer was removed and dried over anhydrous Na2SO4. Upon filtration the organic solution was concentrated on a rotary evaporator with the water bath at 4 °C to yield the title compound as a clear oil (1 g, 13%): *H NMR (400 MHz, CDCI3) δ 7.35 (dd, J= 9.7, 2.3 Hz, IH), 7.27 (ddd, J= 8.7, 2.3, 1.5 Hz, IH), 7.19 7.04 (m, IH), 6.53 (t, 7= 73.0 Hz, IH); ESIMS m/z 242([M+H]⁺).

The following compounds were made in accordance with the procedures disclosed in Example 27.

’H NMR (400 MHz, CDCI3) δ 7.53 (dd, 7= 8.8, 7.7 Hz, IH), 6.95 (dd, 7= 9.1, 2.7 Hz, IH),

6.90 - 6.79 (m, IH), 6.50 (t, 7= 72.8 Hz, IH); IR (thin film) 781.76, 811.23, 856.78, 945.20,

-6617475

1043.80, 977.35, 1141.65, 1113.50, 1174.18, 1260.90, 1285.55, 1382.78, 1423.39, 1487.03,

1593.17, 2847.53, 2927.91, 2992.21, 3112.78 cm’¹; ESIMS m/z 242([M+H]⁺).

l-Bromo-4-(difluoromethoxy)-2,3-difluorobenzene

’H NMR (400 MHz, CDC1₃) δ 7.31 (ddd, J= 9.2, 6.9, 2.5 Hz, IH), 7.02 - 6.93 (m, IH), 6.56 (t, .7=72.4 Hz, IH); IR (thinfilm) 776.30, 811.66, 884.39, 986.70, 1100.95, 1144.65,

1211.05, 1241.96, 1266.36, 1297.59, 1383.98, 1494.35,1474.47, 1600.40, 1679.63, 3038.31, 3103.90 cm'¹; ESIMS m/z 260 ([M+H]⁺).

Example 28: Préparation of 2-(4-(difluoromethoxy)-3-fluorophenyl)-4,4,5,5tetr amethyl-1,3,2-dioxaborolane

To DMSO (10 mL) were added 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(l,3,2-dioxaborolane) (1.264 g, 4.98 mmol), PdCl₂(dppf) (0.304 g, 0.415 mmol), potassium acetate (1.222 g, 12.45 mmol), and 4-bromo-l-(difluoromethoxy)-2-fluorobenzene (1 g, 4.15 mmol). The reaction was heated to an extemal température of 80 °C for 18 h. Upon cooling, the reaction mixture was poured into ice water (50 mL). The ice water mixture was transferred to a separatory funnel and two extractions with EtOAc (50 mL) were completed. The organic layers were combined, dried over Na₂SO₄, and filtered. The solution was concentrated onto Celite® (5 g) using EtOAc as solvent. The impregnated Celite® was purified by silica gel chromatography using 0-30% EtOAc:hexanes to yield the title compound as a yellow oil (773 mg, 64%): *H NMR (400 MHz, CDC1₃) δ 7.61 - 7.53 (m, 2H), 7.25 - 7.16 (m, IH), 6.58 (t, J= 73.5 Hz, IH), 1.34 (s, 12H); ESIMS m/z 289 ([M+H]⁺).

The following compounds were made in accordance with the procedures disclosed in Example 28:

-6717475

2-(4-(Difluoromethoxy)-2-fluorophenyI)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane

’H NMR (400 MHz, CDCl₃) δ 7.74 (dd, J= 8.3, 6.8 Hz, 1H), 6.89 (dd, J= 8.3, 2.2 Hz, 1H),

6.81 (dd, J= 9.9, 2.2 Hz, 1H), 6.54 (t, J= 73.2 Hz, 1H), 1.26 (s, 12H); IR (thin film) 848.53,

961.04,1066.43, 1125.19,1172.02,1238.3, 1212.77,1330.51,1281.58, 1357.05,1372.85,

1380.73,1425.32, 1469.05,1579.31, 1621.00, 2933.42, 2982.31 cm'¹; ESIMS m/z 289 ([M+H]⁺).

2-(4-(Difluoromethoxy)-2,3-difluorophenyI)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane

’H NMR (400 MHz, CDCI3) δ 7.46 (ddd, J= 8.3, 5.8, 2.3 Hz, 1H), 7.05 - 6.95 (m, 1H), 6.59 (t,J= 72.8 Hz, 1H), 1.35 (s, 12H); IR (thin film) 673.35, 851.08, 916.78, 965.07, 1123.87,

1142.58, 1210.42, 1331.14, 1280.13, 1362.56, 1392.44, 1467.32, 1507.77, 1589.62, 1629.61,

2935.00, 2982.70 cm’¹; ESIMS m/z 307 ([M+H]⁺).

Example 29: Préparation of l,4-difluoro-2-iodo-5-(trifluoromethyl)benzene

7V-(2,5-Difluoro-4-(trifluoromethyl)phenyl)acetamide (950 mg, 4.0 mmol; Prepared according to Y. Tanabe et al, J. Org. Chem. 1988, 53, 4585-4587) was stirred in methanol (25 mL), treated with acetyl chloride (3 mL) and heated at reflux for 2 h. The volatiles were removed by évaporation, and the solid residue was dissolved in 6 N HCl (50 mL), cooled to 5 °C and treated in portions with a solution of sodium nitrite (410 mg, 6.0 mmol) in water (5 mL). After 30 min, this mixture was poured into a solution of sodium iodide (2.4 g, 16 mmol) in water (50 mL) and rapidly stirred with dichloromethane (50 mL). After 30 min, solid sodium bisulfite was added to destroy the iodine color, and the separated organic phase was washed with saturated NaCl, dried (Na₂SO4), and evaporated. The material was purified by flash chromatography (SiO₂; eluting with hexanes) to provide the title compound as a volatile clear liquid (250 mg, 20%): *H NMR (400 MHz, CDCl₃) δ 7.64 (ddd, J= 8.8, 4.8, 0.4 Hz, 1H), 7.28 (dd, J= 11.1,4.7 Hz, 1H); ¹⁹F NMR (376 MHz, CDC1₃) δ -61.92, 97.64, -97.68, -118.59, -118.63, -118.64, -118.67; EIMS m/z 308.

Example 30: Préparation of 2-(2,5-difluoro-4-(trifluoromethyl)phenyl)-4,4,5,5tetramethyl-l,3,2-dioxaborolane

l,4-Difluoro-2-iodo-5-(trifluoromethyl)benzene (500 mg, 1.6 mmol) was dissolved in dry THF (7 mL), cooled to 0 °C and treated in portions with isopropyl magnésium chloridelithium chloride complex (1.3 M; 1.4 mL, 1.8 mmol) and stirred for 40 min at 5 °C. 2Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (360 pL, 330 mg, 1.8 mmol) was added and stirring was continued for 1 h. After treating with saturated ammonium chloride (NH4CI), the mixture was shaken with ethyl acetate. The organic phase was washed with saturated NaCl, dried (Na₂SÜ4), and evaporated to give the title compound as a light brown oil (500 mg, 100%). The material was used without further purification: *H NMR (400 MHz, CDC1₃) δ 7.54 (dd, J= 9.9, 4.3 Hz, 1H), 7.27 (dd, J= 8.0, 5.2 Hz, 2H), 1.37 (s, 12H); ¹⁹F NMR (376 MHz, CDC1₃) δ -62.10, -62.13, -106.85, -106.90, -121.81, -121.87, -121.90.

Example 31: Préparation of 4-bromo-2,5-difluorobenzaldehyde

To a solution of 2,5-dibromo-l,4-difluorobenzene (10.0 g, 36.77 mmol) in diethyl ether (150 mL) at -78 °C was added π-butyl lithium (2.5 M in Hexanes, 14.86 mL, 37.15 mmol)

-6917475 dropwise under nitrogen. The reaction mixture was stirred at -78 °C for 30 min. Dry DMF (3.13 mL, 40.46 mmol) in diethyl ether (10 mL) was added dropwise and reaction was slowly warmed to room température over 2 h. The reaction was quenched with aqueous saturated NH4CI solution (25 mL) and extracted with diethyl ether. The organic phase was washed with saturated brine solution, dried (Na₂SO4), filtered, and concentrated under reduced pressure (Note: Product is highly volatile). The crude product was purified by flash chromatography (SiO₂, eluting with 2-20% ethyl acetate in hexanes) to provide the title compound as a pale yellow solid (7.0 g, 86%): *H NMR (400 MHz, CDC1₃) δ 7.50 (dd, J= 5.08, 8.92 Hz, 1H), 7.62 (dd, J= 5.80, 7.68 Hz, 1H), 10.30 (d, 2.76 Hz, 1H).

Example 32: Préparation of (£)-4-bromo-2,5-difluorobenzaldehyde oxime

A solution of 4-bromo-2,5-difluorobenzaldehyde (7.0 g, 31.67 mmol), hydroxyl amine hydrochloride (2.42 g, 34.84 mmol) in pyridine (35 mL) and éthanol (35 mL) was stirred at room température for 30 min. The reaction mixture was diluted with saturated NH4CI solution and extracted with ethyl acetate. The organic phase was washed with saturated brine solution, dried (Na₂SO4), filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (SiO₂; eluting with 5-100% ethyl acetate in hexanes) to provide the title compound as a yellow solid (4.0 g, 53%): ESIMS m/z 238 ([M+2H]⁺).

Example 33: Préparation of 4-bromo-2,5-difluorobenzonitrile

A solution of cyanuric chloride (3.12 g, 16.94 mmol) and dry DMF (8.5 mL) was stirred for min or until the formation of white solid. Disappearance of cyanuric chloride was

-7017475 confirmed by thin layer chromatography (TLC). (E)-4-Bromo-2,5-difluorobenzaldehyde oxime (4.0 g, 16.94 mmol) in DMF (26 mL) was added dropwise to the suspension and stirred for 1 h. The reaction mixture was diluted with water and extracted with hexanes. The organic extract was washed with water, washed with saturated brine solution, dried (Na2SC>4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography (S1O2; eluting with 2-20% ethyl acetate in hexanes) to provide the title compound as a white solid (2.5 g, 68%): *H NMR (400 MHz, CDCI3) δ 7.40 (dd, J= 5.36, 7.10 Hz, 1H), 7.52 (dd, J= 5.40, 7.66 Hz, 1H); EIMS m/z 218.

Example 34: Préparation of l-bromo-4-(difluoromethyl)-2,5-difluorobenzene

To a solution of 4-bromo-2,5-difluorobenzaldehyde (11.0 g, 49.77 mmol) in dichloromethane (55 mL) was added (diethylamino)sulfur trifluoride (DAST; 24.06 g, 0.15 mol) in dropwise manner at 0 °C. After the addition was complété, the cooling bath was removed and stirring was continued for 2 h at room température (rt). The reaction mixture was diluted with dichloromethane, washed with water, washed with saturated brine solution, dried (Na2SÛ4), and evaporated under reduced pressure. The crude product was purified by flash chromatography (S1O2; eluting with 0-10% ethyl acetate in hexanes) to provide the title compound as a pale brown liquid (8.39 g, 69%): ’H NMR(400 MHz, CDCI3 ) δ 6.58 (t, J= 72.32 Hz, 1H), 7.12 (t, J = 7.92 Hz, 1H), 7.44 (dd, J= 6.32, 9.18 Hz, 1H); EIMS m/z 244.

Example 35: Préparation of l-bromo-4-(difluoromethoxy)-2,5-difluorobenzene

F

In a sealed tube, a solution of 4-bromo-2,5-difluorophenol (5.0 g, 23.9 mmol) and potassium hydroxide (26.8 g, 479 mmol) in a 1:1 mixture of acetonitrile and water (110 mL) at -78 °C was treated with bromo-difluoromethyl diethylphosphonate (12.8 g, 47.9 mmol) in one portion. The sealed tube was stirred at room température ovemight. The reaction mixture was diluted with diethyl ether and the organic phase was separated. The aqueous phase was extracted with diethyl ether twice. The combined organic extracts were washed with a saturated brine solution, dried (Na₂SÛ4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography (SiO₂; eluting with 010% ethyl acetate in hexanes) to provide the title compound as a clear liquid (4.2 g, 67.8%): *H NMR(300 MHz, CDC1₃) δ 6.56 (t, J= 72.36 Hz, 1H), 7.11 (t, J= 7.32 Hz, 1H), 7.40 7.45 (m, 1H); EIMS m/z 259.

Example 36: General procedure for synthesis of boronic acids

Argon was bubbled through a solution of the bromophenyl substrate (1.0 equiv), potassium acetate (3.0 equiv), and 6zs-(pinacolato)diboron (1.1 equiv) in DMSO (enough volume to provide 0.1-0.2 M in substrate) for 15 min in a sealed tube. Pd(dppf)Cl₂ (0.1 equiv) was added and the sealed tube was recapped. The reaction mixture was heated at 80 °C for 18 h. The cooled reaction mixture was diluted with water and extracted with methyl ί-butyl ether. The organic extract was washed with water, washed with saturated brine solution, dried (Na₂SO4), filtered, and evaporated to dryness under reduced pressure. The crude boronate (1.0 equiv) was dissolved in diethyl ether (10 vol) and diethanolamine (1.1 equiv) was added. The reaction mixture was stirred at room température for 30-45 min. A white solid precipitated out after 45 min. Stirring was stopped and the solvent was decanted. Fresh ether was added to the solids followed by an excess of 1.5 N HCl. The resulting biphasic solution was stirred for 30 min. The organic phase was washed with saturated brine solution, dried (Na₂SÛ4), filtered, and evaporated to dryness under reduced pressure. The boronic acids thus obtained were used in the next step without purification.

The following compounds were made in accordance with the procedures disclosed in Example 36:

-7217475 (4-(Difluoromethoxy)-2,5-difluorophenyl)boronic acid

*H NMR(300 MHz, CDCl₃) δ 6.59 (t, .7=72.78 Hz, 1H), 6.97 (dd, J= 2.70, 9.14 Hz, 1H),

7.52 (dd, .7= 5.19,10.29 Hz, 1H).

(4-(Difluoromethyl)-2,5-difluorophenyl)boronic acid

*H NMR(400 MHz, CDC1₃) δ 6.87 (dt, J= 8.48, 54.64 Hz, 1H), 7.25 - 7.32 (m, 1H), 7.49 (dd, J= 4.08, 9.48 Hz, 1H), 7.59 - 7.60 (m, 1H).

Example 37: General procedure for synthesis of boronic acids (Method A)

To a solution of the appropriate bromophenyl substrate (1.0 equiv) in dry THF (10 vol) at 78 °C, was added n-BuLi (2.5 M in hexanes; 1.2 equiv) dropwise. After addition was complété, stirring was continued for 30 min. Trimethyl borate (1.5 equiv) was added in one portion and stirring was continued for 1 h at -78 °C. The reaction mixture was slowly warmed to room température, quenched with 1.5 N HCl, and extracted with ethyl acetate. The organic extract was washed with water, washed with saturated brine solution, dried (Na2SC>4), filtered, and evaporated to dryness under reduced pressure. The boronic acids thus obtained were used in the next step without purification.

The following compound was made in accordance with the procedures dîsclosed in Example 37:

(2,5-Difluoro-4-methylphenyl)boronic acid

-7317475

’H NMR(300 MHz, CDCl₃) δ 2.30 (s, 3H), 5.03 (br s, 2H), 6.89 (dd, J= 5.67, 10.25 Hz,

1H), 7.42 (dd, J = 5.40, 9.19 Hz, 1H).

Example 38: General procedure for synthesis of boronic acids (Method B)

To a solution of the appropriate bromophenyl substrate (1.0 equiv) in dry THF (10 vol) at 40 °C was added isopropyl magnésium chloride lithium chloride complex solution (1.3 M solution in THF; 1.05 equiv) dropwise. After addition was complété, the reaction mixture was stirred at -40 °C for 45 min then slowly warmed to 0 °C. Isopropoxyboronic acid pinacol ester (1.07 equiv) was added dropwise and stirring was continued at 0 °C for 2 h. The reaction mixture was warmed to room température, quenched with aqueous saturated NH4CI solution, and extracted with ethyl acetate. The organic extract was washed with saturated brine solution, dried (Na₂SO₄), filtered, and evaporated under reduced pressure. The boronic acids thus obtained were used in the next step without purification.

The following compound was made in accordance with the procedures disclosed in Example 38:

(4-Cyano-2,5-difluorophenyl)boronic acid

-7417475 *H NMR(300 MHz, CDCl₃ ) δ 5.15 (br s, 2H), 7.29 - 7.36 (m, IH), 7.69 (dd, J= 4.80, 8.28

Hz, IH).

Example 39: Préparation of methyl 4-amino-3-chloro-6-(3-fluoro-4(trimethylsilyl)phenyl)picolinate

To a 20-mL micro wave vessel, equipped with a stir bar, Head A (500 mg, 2.262 mmol), (2fluoro-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)trimethylsilane (997 mg, 3.39 mmol), bis(triphenylphosphine)palladium(II) dichloride (203 mg, 3.39 mmol), and césium fluoride (741 mg, 4.88 mmol) were charged. The vessel was placed under nitrogen (N2) atmosphère and acetonitrile (4.0 mL) and H2O (1.0 mL) were added. The vessel was placed on a Biotage Initiator™ micro wave reactor for 30 min at 120 °C, with extemal IR-sensor température monitoring from the side of the vessel. The reaction was poured into brine solution and extracted with ethyl acetate (3 x 75 mL). The combined organic layers were dried over anhydrous MgSCU, filtered and concentrated. The resulting residue was purified via flash chromatography (Silica gel; 0-30% EtOAc in hexanes) to afford the title compound as a yellow solid (0.328 g, 41%): ’H NMR (400 MHz, DMSO-7₆) δ 7.68 (dd, 7= 7.5, 1.4 Hz, IH), 7.61 - 7.47 (m, 2H), 7.30 (s, IH), 6.78 (s, 2H), 3.88 (s, 3H), 0.30 (d, 7= 0.8 Hz, 9H); ¹⁹F NMR (376 MHz, DMSO-7₆) δ -101.12; ESIMS m/z 353 ([M+H]⁺).

The following compounds were prepared in accordance with the procedures disclosed in Example 39:

Methyl 4-amino-3,5-dichloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate

-7517475

The title compound was prepared as described in Example 39 with Head H (500 mg, 1.96 mmol) and isolated as a white solid (0.381 g, 50%): ’H NMR (400 MHz, DMSO-î/ô) δ 7.52 (dd, J =7.6, 5.9 Hz, IH), 7.41 (dd, J =1.5, 1.3 Hz, IH), 7.30 (dd, J = 9.6, 1.4 Hz, IH), 7.11 (s, 2H), 3.87 (s, 3H), 0.33 (d, J= 0.9 Hz, 9H); ¹⁹F NMR (376 MHz, DMSO-îZ₆) δ -101.38;

ESIMS m/z 387 ([M+H]⁺).

Methyl 6-amino-2-(3-fluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4carboxylate

The title compound was prepared as described in Example 39 with Head C (0.510 g, 2.34 mmol) and isolated as a yellow solid (0.307 g, 38%): *H NMR (400 MHz, DMSO-flk) δ 8.08 -7.99(m, IH), 7.82 (dd, J= 10.3, 1.4 Hz, IH), 7.60-7.27 (m, 3H),3.91 (s, 3H), 3.74 (s, 3H), 0.32 (d, J = 0.9 Hz, 9H); ¹⁹F NMR (376 MHz, DMSO-îZ₆) δ -101.73; ESIMS m/z 350 ([M+H]⁺).

Methyl 4-acetamido-3-chloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate

The title compound was prepared as described in Example 39 with Head L (0.500 g, 1.90 mmol) in dioxane (7.0 mL) and H₂O (2.0 mL) and isolated as a yellow solid (0.433 g, 58%); *H NMR (400 MHz, DMSO-î/₆) δ 9.99 (s, IH), 8.71 (s, IH), 7.75 (dd, J= 7.6,1.5 Hz, IH), 7.63 (dd, J= 10.1, 1.5 Hz, IH), 7.56 (dd, J= 7.7, 5.9 Hz, IH), 3.94 (s, 3H), 2.24 (s, 3H), 0.30 (d, J= 0.8 Hz, 9H); ¹⁹F NMR (376 MHz, DMSO-îZ₆) δ -100.78; ESIMS m/z 396 ([M+Hf).

-7617475

Methyl 4-amino-3-chloro-6-(4-cyano-2-fluorophenyl)-5-fluoropicolinate (Compound

44)

The title compound was prepared as described in Example 39 with Head B (400 mg, 1.673 mmol) and (4-cyano-2-fluorophenyl)boronic acid (400 mg, 2.425 mmol) in dioxane (4.5 mL) and H₂O (1.2 mL) and isolated as an off-white solid (0.451 g, 83%).

Methyl 6-amino-2-(3-fluoro-4-(trifluoromethyl)phenyl)-5-vinylpyrimidine-4carboxylate (Compound 137)

The title compound was prepared as described in Example 39 with Head P (350 mg, 1.64 mmol) and (3-fluoro-4-(trifluoromethyl)phenyl)boronic acid (445 mg, 2.14 mmol) in dioxane (5.0 mL) and H₂O (1.0 mL) and isolated as a light tan solid (0.291 g, 52%).

Methyl 6-amino-2-(4-cyano-2-fluorophenyl)-5-vinylpyrimidine-4-carboxylate (Compound 98)

-7717475

The title compound was prepared as described in Example 39 with Head P (350 mg, 1.638 mmol) and (4-cyano-2-fluorophenyl)boronic acid (375 mg, 2.27 mmol) in dioxane (4.5 mL) and H₂O (1.2 mL) and isolated as a yellow solid (0.291 g, 60%).

Methyl 6-amino-2-(4-aminophenyl)-5-vinylpyrimidine-4-carboxylate

The title compound was prepared as described in Example 39 with Head P (0.800 g, 3.74 mmol) and 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)aniline (0.985 g, 4.49 mmol) in dioxane (15.6 mL) and H₂O (3.12 mL) and isolated as a yellow solid (0.400 g, 40%): *H NMR (400 MHz, DMSO-îZ₆) δ 8.08 - 7.86 (m, 2H), 6.99 (s, 2H), 6.76 - 6.51 (m, 3H), 5.61 (s, 2H), 5.49 - 5.30 (m, 2H), 3.81 (s, 3H); ESIMS m/z 271 ([M+H]⁺).

Methyl 6-amino-2-(2,3,4-trifluorophenyl)-5-vinylpyrimidine-4-carboxylate (Compound

197)

F

The title compound was prepared as described in Example 39 with Head P (0.350 g, 1.64 mmol) and (2,3,4-trifluorophenyl)boronic acid (0.346 g, 1.97 mmol) in dioxane (5.0 mL) and H₂O (1.0 mL) and isolated as a yellow solid (0.414 g, 82%).

Example 40. Préparation of methyl 4-amino-3-chloro-6-(3-fluoro-4(trifluoromethyl)phenyl)picolinate (Compound 29)

-7817475

Methyl 4-amino-3,6-dichloropicolinate (630 mg, 2.85 mmol), 2-(3-fluoro-4(trifluoromethyl)phenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (1.06 g, 3.65 mmol, 1.3 equiv), bis(triphenylphosphine)palladium(II) chloride (209 mg, 0.30 mmol, 0.1 equiv), and potassium fluoride (510 mg, 8.8 mmol, 3 equiv) in acetonitrile/water (8 mL, 3:1) was capped in a 25-mL vial on a Biotage Initiator™ microwave reactor for 20 min at 115 °C, with extemal IR-sensor température monitoring from the side of the vessel. The reaction mixture was diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate and the combined organic layers were dried over anhydrous Na2SCU, filtered, and concentrated. The crude compound was loaded onto a Celite® cartridge and dried in a vacuum oven. Purification by reverse-phase flash chromatography (0-60, 60, 60-100% acetonitrile/water) afforded the title compound as a white solid (0.57 g, 57%).

The following compounds were prepared in accordance to the procedures disclosed in Example 40:

Methyl 4-amino-3-chloro-6-(4-cyanophenyl)-5-methylpicolinate (Compound 83)

The title compound was prepared as in Example 40 with Head D and isolated as an orange solid (180 mg, 55%).

Methyl 4-amino-3-chloro-6-(4-(difluoromethoxy)phenyl)-5-methylpicolinate (Compound 111)

-7917475

The title compound was prepared as in Example 40 and isolated as a waxy yellow solid (120 mg, 32%).

Methyl 4-amino-3-chloro-5-methyl-6-(4-(trimethylsilyl)phenyl)picolinate (H₃C)₃Si

CH₃

The title compound was prepared as in Example 40 with Head D and isolated as a yellow solid (1.11g, 45%): mp 160-163 °C; *H NMR (400 MHz, CDC1₃) δ 7.57 (d, J= 8.2 Hz, 2H), 7.42 (d, J= 8.2 Hz, 2H), 4.80 (s, 2H), 3.94 (s, 3H), 2.18 (s, 3H), 0.28 (s, 9H); ¹³C NMR (101 MHz, CDC1₃) δ 167.01, 157.65, 150.16, 146.19, 141.69, 141.24, 134.39, 129.61, 117.96, 114.49, 53.95, 15.86, 1.16; ESIMS m/z 348 ([M]').

Methyl 4-amino-3-chloro-6-(3-fIuoro-4-(trimethylsilyl)phenyl)-5-methylpicolinate

The title compound was prepared as in Example 40 with Head D and isolated as a yellow solid (346 mg, 27%): mp 167 °C (dec); *H NMR (400 MHz, CDCI3) δ 7.43 (dd, J= 7.4, 5.8 Hz, IH), 7.20 (dd, J= 7.4, 0.9 Hz, IH), 7.10 (dd, J= 9.2, 1.3 Hz, IH), 4.83 (s, 2H), 3.95 (s, 3H), 2.18 (s, 3H), 0.33 (d, J= 0.8 Hz, 9H); ¹⁹F NMR (376 MHz, CDC1₃) δ -100.73; ESIMS m/z 367 ([M+H]⁺).

-8017475

Methyl 4-amino-3-chloro-6-(4-cyano-3-fluorophenyl)-5-methylpicolinate (Compound

155)

The title compound was prepared as in Example 40 with Head D and isolated as a white flaky solid (200 mg, 49%).

Methyl 4-amino-3-chloro-6-(3-fluoro-4-formylphenyl)-5-methylpicolinate

CH₃

The title compound was prepared as in Example 40 with Head D and isolated as an orange solid (747 mg, 65%): mp 114-120 °C; *H NMR (400 MHz, CDC1₃) δ 10.40 (s, IH), 7.92 (t, J= 7.5 Hz, IH), 7.38 - 7.29 (m, 2H), 4.97 (s, 2H), 3.97 (s, 3H), 2.18 (s, 3H); ¹⁹F NMR (376 MHz, CDClj) δ -121.53; ESIMS m/z 323 ([M+H]⁺).

Methyl 4-amino-3-chloro-5-fluoro-6-(2,4,5-trifluorophenyl)picolinate (Compound 200)

The title compound was prepared as in Example 40 with Head B and isolated as a white powder (370 mg, 73%).

Example 41: Préparation of methyl 4-amino-3-chloro-5-fluoro-6-(4nitrophenyl)picolinate (Compound 95)

-8117475 nh₂

II O

To a suspension of Head B (250 mg, 1.05 mmol), (4-nitrophenyl)boronic acid (192 mg, 1.15 mmol), césium fluoride (CsF; 315 mg, 2.09 mmol) and tris(3-sulfonatophenyl)phosphine hydrate sodium sait (TPPTS, 60 mg, 0.11 mmol) in a water/acetonitrile mixture (2.8/0.7 mL) was added palladium acetate (12 mg, 0.05 mmol). In a Biotage™ bench top microwave the mixture was heated at 150 °C for 5 min. The reaction mixture was then filtered through Celite®, diluted with EtOAc, washed with water and brine. The organics were then dried (Na₂SO₄), filtered, concentrated in vacuo, and then purified by silica gel chromatography eluting with 0-100% EtOAc in hexanes to afford a yellow solid (150 mg, 44%).

The following compound was made in accordance with the procedures disclosed in Example

41:

Methyl 4-acetamido-3-chloro-6-(2,3-difluoro-4-(trifluoromethyl)phenyl)picolinate

O

F F ‘H NMR (400 MHz, DMSO-d₆) δ 10.03 (s, IH), 8.79 (d, J= 1.0 Hz, IH), 7.93 - 7.84 (m, IH), 7.75 (dd, J= 8.3, 6.3 Hz, IH), 3.96 (s, 3H), 2.26 (s, 3H); ESIMS m/z 409 ([M+H]⁺).

Example 42: Préparation of methyl 4-amino-3-chloro-6-(4-cyano-3-fluorophenyl)-5fluoropicolinate (Compound 135)

Head B (0.300 g, 1.255 mmol), 4-cyano-3-fluorophenylboronic acid (0.248 g, 1.506 mmol), bis(triphenylphosphine)palladium(II) chloride (0.088 g, 0.126 mmol), and césium fluoride (0.381 g, 2.51 mmol) were combined in 1,2-dimethoxyethane (2 mL) and water (2 mL) and heated in a micro wave reactor at 110 °C for 20 min. The cooled reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried and concentrated. The product was purified by flash chromatography (SiO₂; eluting with 5-60% ethyl acetate in hexanes) to provide the title compound as a white solid (0.189 g, 46.5%).

Example 43: Préparation of methyl 4-amino-3-chloro-5-fluoro-6-(4(methoxycarbonyl)phenyl)picolinate (Compound 190)

Head B (0.4 g, 1.673 mmol), 4-(methoxycarbonyl)phenylboronic acid (0.392 g, 2.175 mmol), potassium fluoride (0.253 g, 4.35 mmol), and bis(triphenylphosphine)palladium(II) chloride (0.059 g, 0.084 mmol) were combined in acetonitrile (3 mL) and water (1 mL). The reaction mixture was then irradiated in a microwave at 110 °C in a sealed vial for 20 min. The cooled reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried and concentrated onto silica gel. This mixture was applied to the top of a silica gel column and the product was eluted with a 5-60% ethyl acetate in hexanes gradient solvent system. This process yielded the title compound as a white solid (0.230 g, 40.6%).

Example 44: Préparation of methyl 4-amino-6-(4-bromo-2,3-difluorophenyl)-3chloropicolinate (Compound 114)

-8317475

Step 1: Head N (0.600 g, 1.692 mmol), 4-bromo-2,3-difluorophenylboronic acid (0.481 g, 2.031 mmol), césium fluoride (0.617 g, 4.06 mmol), and bis(triphenylphosphine)palladium(II) chloride (0.119 g, 0.169 mmol) were combined in 1,2dimethoxyethane (4 mL) and water (4 mL) and heated in a microwave reactor for 20 min at 110 °C. The cooled reaction mixture was partitioned between ethyl acetate and water. The organic phase was separated and concentrated onto silica gel. The product was eluted with an ethyl acetate/hexanes gradient to provide methyl 4-acetamido-6-(4-bromo-2,3difluorophenyl)-3-chloropicolinate (0.515 g, 72.5%) as a white solid.

Step 2: Methyl 4-acetamido-6-(4-bromo-2,3-difluorophenyl)-3-chloropicolinate (0.515 g, 1.227 mmol) was suspended in methanol (20 mL) and acetyl chloride (1.559 mL, 21.93 mmol) was added dropwise. The reaction mixture was stirred overnight at room température and concentrated under vacuum. The residue was partitioned between ethyl acetate and 5% aqueous sodium bicarbonate solution. The organic phase was concentrated onto silica gel and purified by flash chromatography (S1O2; eluting with 5-60% ethyl acetate in hexanes) to provide the title compound as a white solid (0.231 g, 55.8%).

Example 45: Préparation of methyl 4-amino-3-chloro-6-(2,3-difluoro-4(trimethylsilyl)phenyl)-5-fluoropicolinate

Head B (2.0 g, 8.37 mmol), (2,3-difluoro-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2yl)phenyl)trimethylsilane (3.40 g, 10.88 mmol), sodium carbonate (0.887 g, 8.37 mmol) and bis(triphenylphosphine)palladium(II) chloride (0.587 g, 0.837 mmol) were combined in acetonitrile (25 mL) and water (8 mL). The reaction mixture was then heated at reflux for 4

h. The cooled reaction mixture was partitioned between ethyl acetate and water. The organic phase was washed twice more with water then concentrated onto silica gel. This mixture was purified by silica gel chromatography and the product was eluted with a 7-60% ethyl acetate in hexanes solvent system. This process yielded the title compound as a white solid (2.7 g, 83%): mp 160-162 °C; *H NMR (300 MHz, CDC1₃) δ 7.37 - 7.28 (m, 1H), 7.21 (ddd, J= Ί.Ί, 4.4,1.3 Hz, 1H), 4.96 (br s, 2H), 3.97 (s, 3H), 0.35 (s, 9H).

Example 46: Préparation of methyl 6-amino-2-(3-fluoro-4-(trifluoromethyl)phenyl)-5methoxypyrimidine-4-carboxylate (Compound 26)

To a microwave vial were added Head C (184 mg, 0.846 mmol), 2-(3-fluoro-4(trifluoromethyl)phenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (270 mg, 0.930 mmol), potassium fluoride (128 mg, 2.198 mmol), and bis(triphenylphosphine)palladium(II) chloride (59.3 mg, 0.085 mmol). Subsequently, acetonitrile (2.789 mL) and water (2.79 mL) were added. The reaction vial was then capped and placed in a Biotage™ Initiator microwave reactor for 20 min at 115 °C, with extemal IR-sensor température monitoring from the side of the vessel. The reaction mixture was cooled to room température, diluted with EtOAc, and washed with H₂O. The organics were dried over Na₂SO4, filtered, and concentrated in vacuo. The crude product was purified via flash chromatography (silica; Hexanes/EtOAc). This yielded the title compound (172 mg, 58.9%) as a white solid.

Example 47: Préparation of methyl 4-amino-3-chloro-5-fluoro-6-(4-

Head B (600 mg, 2.5 mmol, 1.0 equiv) and (4-(trimethylsilyl)phenyl)boronic acid (540 mg, 2.8 mmol, 1.1 equiv) were combined in a 20 mL vial followed by césium fluoride (420 mg, 2.8 mmol, 1.1 equiv), palladium acetate (28 mg, 0.13 mmol, 0.05 equiv), and sodium 3,3',3phosphinetriyltribenzenesulfonate (140 mg, 0.25 mmol, 0.10 equiv). A 3:1 mixture of water:acetonitrile (7.2 mL) was added and the resulting brown mixture was capped and placed in a Biotage Initiator™ microwave reactor for 5 min at 150 °C, with extemal IRsensor température monitoring from the side of the vessel. The cooled reaction mixture was diluted with water (150 mL) and extracted with dichloromethane (5 x 60 mL). The combined organic layers were dried ( MgSCU), gravity filtered, and concentrated by rotary évaporation. The residue was purified by silica gel column chromatography (33% ethyl acetate in hexanes) to afford the title compound as a pale yellow powder (700 mg, 79%): mp 148-150 °C; *H NMR (300 MHz, CDC1₃) δ 7.86 (m, 2H), 7.62 (m, 2H), 4.88 (br s, 2H), 3.98 (s, 3H), 0.29 (s, 9H); ESIMS m/z 353 ([M+H]⁺).

The following compounds were made in accordance with the procedures disclosed in Example 47:

Methyl 4-amino-3-chloro-5-fluoro-6-(2-fluoro-4-formylphenyl)picolinate

mp 151-154 °C; *HNMR (400 MHz, CDC1₃) δ 10.06 (d,J=2Hz, 1H), 7.79-7.84 (m, 2H), 7.67 (dd, J= 10, 1 Hz, 1H), 5.00 (br s, 2H), 3.99 (s, 3H); ESIMS m/z 327 ([M+H]⁺).

Methyl 6-amino-2-(2-fluoro-4-formylphenyI)-5-methoxypyrimidine-4-carboxylate

-8617475 mp 176-178 °C; *H NMR (400 MHz, CDC1₃) δ 10.03 (d, J= 2 Hz, 1H), 8.10 (t, J= 8 Hz,

1H), 7.73 (dd,J=8,1.5 Hz, 1H), 7.65 (dd,J=8, 1.5 Hz, 1 H), 5.45 (brs, 2H), 4.00 (s, 3H),

3.96 (s, 3H); ESIMS m/z 306 ([M+H]⁺).

Methyl 4-amino-3-chloro-6-(2,3-difluoro-4-formylphenyl)-5-fluoropicolinate

OMe ’H NMR (400 MHz, CDC1₃) δ 10.40 (d, J= 1 Hz, 1H), 7.74 (m, 1H), 7.52 (m, 1H), 5.01 (br s, 2H), 3.97 (s, 3H).

Methyl 6-amino-2-(2,3-difluoro-4-formylphenyl)-5-methoxypyrimidine-4-carboxylate

mp 184-186 °C; ’H NMR (400 MHz, CDC1₃) δ 10.38 (d, J= 0.5 Hz, 1H), 7.84 (m, 1H),

7.67 (ddd, J= 8, 6, 2 Hz, 1H), 5.47 (br s, 2H), 4.01 (s, 3H), 3.96 (s, 3H); ESIMS m/z 324 ([M+Hf).

Methyl 6-amino-2-(4-formylphenyl)-5-methoxypyrimidine-4-carboxylate

mp 155-156 °C; *H NMR (400 MHz, CDC1₃) δ 10.1 (s, 1H), 8.54 (d, 2H), 7.99 (d, 2H), 5.56 (s, 2H), 4.08(s, 3H), 3.99(s, 3H); ESIMS m/z 288 ([M+H]⁺).

-8717475

Methyl 4-ammo-3,5-dichloro-6-(4-formylphenyl)picolinate

mp 131-133 °C; *H NMR (400 MHz, CDC1₃) δ 10.08 (s, 1H), 7.96 (d, 2H), 7.83 (d, 2H), 5.36 (s, 2H), 3.98 (s, 3H); ESIMS m/z 325 ([M+H]⁺).

Example 48: Préparation of methyl 4-amino-3-chloro-5-fluoro-6-(3-fluoro-4(trimethylsilyl)phenyl)picolinate

OMe

Dichloro[bis(triphenylphosphino)]-palladium(II) (150 mg, 0.21 mmol, 0.10 equiv) and sodium carbonate (270 mg, 2.5 mmol, 1.2 equiv) were sequentially added to a stirred mixture of crude (2-fluoro-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2yl)phenyl)trimethylsilane (990 mg, 2.5 mmol, 1.2 equiv) and Head B (500 mg, 2.1 mmol, 1.0 equiv) in a 1:1 mixture of water:acetonitrile (7.0 mL) at 23 °C. The resulting dark orange mixture was heated to 85 °C and stirred for 4 h. The cooled reaction mixture was diluted with water (150 mL) and extracted with dichloromethane (3 x 80 mL). The combined organic layers were dried ( MgSCU), gravity fiîtered, and concentrated by rotary évaporation. The residue was purified by silica gel column chromatography (25% ethyl acetate in hexanes) to afford the title compound as a pale yellow powder (500 mg, 65%): mp 125-127 °C; IR (thin film) 3481 (m), 3350 (s), 2952 (w), 1728 (m), 1610 (m) cm’¹; *H NMR (400 MHz, CDCI3) δ 7.71 (dt, J= 6.5, 1 Hz, 1H), 7.59 (dt, J = 10,1 Hz, 1H), 7.50 (dd, J= 8, 6.5 Hz, 1H), 4.91 (br s, 2H), 3.99 (s, 3H), 0.33 (d, 9H); ESIMS m/z 3ΊΧ ([M+H]⁺).

The following compounds were made in accordance with the procedures disclosed in Example 48:

-8817475

Methyl 4-amino-3-chloro-6-(2,3-difluoro-4-(trimethylsilyl)phenyl)-5-fluoropicolinate

’H NMR (400 MHz, CDCl₃) δ 7.33 (ddd, J= 8, 4.5, 1 Hz, 1H), 7.21 (ddd, J= 8, 5, 1.5 Hz,

1H), 4.94 (br s, 2H), 3.96 (s, 3H), 0.33 (d, J= 1 Hz, 9H); ESIMS m/z 389 ([M+H]⁺).

Methyl 4-amino-3-chloro-5-fluoro-6-(2-fluoro-4-(trimethylsiiyl)phenyl)picolinate

mp 175-177 °C; *H NMR (400 MHz, CDCI3) δ 7.58 (t, J= 8 Hz, 1H), 7.39 (dd, J= 8, 1 Hz,

1H), 7.27 (m, 1H), 4.91 (br s, 2H), 3.96 (s, 3H), 0.26 (s, 9H); ESIMS m/z 371 ([M+H]⁺).

Methyl 6-amino-2-(2-fluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4carboxylate

mp 140-142 °C; *H NMR (400 MHz, CDC1₃) δ 7.85 (t, J= 8 Hz, 1H), 7.32 (dd, J= 8, 1 Hz,

1H), 7.26 (m, 1H), 5.38 (br s, 2H), 3.99 (s, 3H), 3.94 (s, 3H), 0.26 (s, 9H); ESIMS m/z 348 ([M-H]-).

Methyl 4-acetamido-3-chloro-6-(2,3-difluoro-4-(trimethylsilyl)phenyl)picolinate

-8917475

^!Η NMR (400 MHz, CDCl₃) δ 9.04 (d, J= 1 Hz, 1H), 7.99 (br s, 1H), 7.65 (m, 1H), 7.18 (m,

1H), 4.00 (s, 3H), 2.31 (s, 3H), 0.33 (d, J= 1 Hz, 9H); ESIMS m/z 413 ([M-H]').

Methyl 6-amino-5-methoxy-2-(4-(trimethylsilyl)phenyl)pyrimidine-4-carboxylate

’H NMR (400 MHz, CDCI3) δ 8.25 (m, 2H), 7.58 m, 2H), 5.35 (br s, 2H), 4.01 (s, 3H), 3.91 (s, 3H). 0.30 (s, 9H); ESIMS m/z 330 ([M-H]’).

Methyl 4-acetamido-3-chloro-6-(4-(trimethyIsilyl)phenyl)picolinate

O

(s, 3H), 2.32 (s, 3H), 0.29 (s, 9H); ESIMS m/z 375 ([M-H]').

-9017475

Example 49: Préparation of methyl 4-acetamido-6-(4-amino-2,3,6-trifliiorophenyl)-3chloropicolinate

A suspension of methyl 4-acetamido-3-chloro-6-(trimethylstannyl)picolinate (Head K; 0.502 g, 1.409 mmol, 1.0 equiv), 2,3,5-trifluoro-4-iodoaniline (0.5 g, 1.831 mmol, 1.3 equiv), bis(triphenylphosphine)palladium(II) chloride (0.098 g, 0.1401 mmol, 0.1 equiv) and Cul (26 mg, 0.1401 mmol, 0.1 equiv) in dry DMF (3 mL) was irradiated with microwave at 120 °C for 1 h. The reaction mixture was cooled to 20 °C and stirred with aqueous potassium fluoride (KF) solution (20 mL) for 15 min and then extracted with ethyl acetate (3x100 mL). The combined organic layers were dried over anhydrous Na2SO₄, filtered and evaporated to dryness under reduced pressure. The crude product was purified on silica gel (60-120 mesh) using a gradient from 0-30% EtOAc in hexanes yielded the title compound as a brown solid (280 mg, 44.8%): ’H NMR (400 MHz, DMSO-J₆) δ 9.96 (s, 1H), 8.32 (s, 1H), 6.51 - 6.46 (m, 1H), 6.22 (br s, 2H), 3.92 (s, 3H), 2.23 (s, 3H); ESIMS m/z 376 ([M+3H]⁺).

Example 50: Préparation of methyl 4-amino-3-chloro-6-(2,5-difluoro-4(trimethylsilyl)phenyl)-5-fluoropicoiinate

CH₃

In a microwave vessel, a suspension of (2,5-difluoro-4-(4,4,5,5-tetramethyl-l,3,2dioxaborolan-2-yl)phenyl)trimethylsilane (see, e.g., WO 2013003740 Al; 0.6 g, 1.922 mmol), methyl 4-amino-3,6-dichloro-5-fluoropicolinate (Head B; 0.383 g, 1.601 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.112 g, 0.160 mmol) and sodium carbonate (0.204 g, 1.922 mmol) in a 3:1 mixture of acetonitrile (4.00 mL) and water (1.334 mL) was

-9117475 stirred under micro wave irradiation (120 °C, 20 min). The reaction mixture was poured into a half saturated brine solution and was extracted with EtOAc (3x). The combined organic layers were dried over Na₂SO4, filtered and concentrated. The residue was purified by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a white solid (0.271 g, 43.5%): *H NMR (400 MHz, CDC1₃) δ 7.23 (dd, J= 7.8, 5.1 Hz, 1H), 7.13 (dd, J= 9.3, 4.0 Hz, 1H), 4.95 (s, 2H), 3.98 (s, 3H), 0.33 (d, J= 0.8 Hz, 9H); ¹⁹F NMR (376 MHz, CDC1₃) δ -106.81, -106.87, -121.20, -121.25, -121.29, -121.35, -137.32, -137.41; ESIMS m/z 389 ([M+H]⁺).

Example 51: Préparation of methyl 4-amino-3-chloro-6-(2,5-difluoro-4(trimethylsilyl)phenyl)picolinate

In a microwave vessel, a suspension of (2,5-difluoro-4-(4,4,5,5-tetramethyl-l,3,2dioxaborolan-2-yl)phenyl)trimethylsilane (see, e.g., WO 2013003740 Al) (0.6 g, 1.922 mmol), methyl 4-amino-3,6-dichloropicolinate (Head A) (0.354 g, 1.601 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.112 g, 0.160 mmol) and sodium carbonate (0.204 g, 1.922 mmol) in a 3:1 mixture of acetonitrile (4.00 mL) and water (1.334 mL) was stirred under microwave irradiation (120 °C, 20 min). The reaction mixture was poured into a half saturated brine solution and was extracted with EtOAc (3x). The combined organic layers were dried over Na₂SO4, filtered and concentrated. The residue was purified by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a white solid (0.234 g, 0.631 mmol, 39.4%): ‘H NMR (400 MHz, CDC1₃) δ 7.66 (dd, J= 8.7, 5.8 Hz, 1H), 7.25 (d, J= 1.2 Hz, 1H), 7.09 (dd, J= 10.8, 4.1 Hz, 1H), 4.84 (s, 2H), 4.00 (s, 3H), 0.32 (d, J= 0.7 Hz, 9H); ¹⁹F NMR (376 MHz, CDC1₃) δ -106.56, -106.61, -124.00, -124.06; ESIMS m/z 371 ([M+H]⁺).

Example 52: Préparation of methyl 4-acetamido-3-chloro-6-(2,5-difluoro-4(trimethylsilyl)phenyl)picolinate

-9217475

In a microwave vessel, a suspension of (2,5-difluoro-4-(4,4,5,5-tetramethyl-l,3,2dioxaborolan-2-yl)phenyl)trimethylsilane (see, e.g., WO 2013003740 Al; 1 g, 2.56 mmol), methyl 4-acetamido-3,6-dichloropicolinate (Head L; 0.562 g, 2.135 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.150 g, 0.214 mmol) and sodium carbonate (0.272 g, 2.56 mmol) in a 3:1 mixture of acetonitrile (5.34 mL) and water (1.779 mL) was stirred under microwave irradiation (120 °C, 20 min). The reaction mixture was poured into a half saturated brine solution and was extracted with EtOAc (3x). The combined organic layers were dried over Na₂SO₄, filtered and concentrated. The residue was purified by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a white solid (0.481 g, 54.6%); mp 135-137 °C; ’H NMR (400 MHz, CDC1₃) δ 9.07 (d, J= 0.8 Hz, 1H), 7.96 (s, 1H), 7.62 (dd, J= 8.5, 5.7 Hz, 1H), 7.13 (dd, J= 10.5, 4.1 Hz, 1H), 4.02 (s, 3H), 2.33 (s, 3H), 0.33 (d, J= 0.8 Hz, 9H); ¹⁹F NMR (376 MHz, CDC1₃) δ -106.66, -106.72, -123.42, -123.48; ESIMS m/z 411 ([M-H]').

Example 53: Préparation of methyl 6-amino-2-(2,5-difluoro-4-(trimethylsilyl)phenyl)5-methoxypyrimidine-4-carboxylate

In a microwave vessel, a suspension of (2,5-difluoro-4-(4,4,5,5-tetramethyl-l,3,2dioxaborolan-2-yl)phenyl)trimethylsilane (e.g., WO 2013003740 Al; 1.925 g, 5.05 mmol), methyl 6-amino-2-chloro-5-methoxypyrimidine-4-carboxylate (Head C; 1 g, 4.60 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.323 g, 0.460 mmol) and sodium carbonate (0.584 g, 5.51 mmol) in a 3:1 mixture of acetonitrile (8.62 mL) and water (2.87 mL) was

-9317475 stirred under microwave irradiation (120 °C, 20 min). The reaction mixture was poured into a half saturated brine solution and was extracted with EtOAc (3x). The combined organic layers were dried over Na2SO₄, filtered and concentrated. The residue was purified by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a white solid (0.994 g, 58.9%); mp 130-131 °C; ’H NMR (400 MHz, CDC1₃) δ 7.53 (dd, J= 8.4, 5.6 Hz, 1H), 7.10 (dd, J= 10.2, 4.1 Hz, 1H), 5.44 (s, 2H), 4.00 (s, 3H), 3.94 (s, 3H), 0.32 (d, J= 0.9 Hz, 9H); ¹⁹F NMR (376 MHz, CDCI3) δ -107.45, -107.51, -122.32, -122.37; ESIMS m/z 367 ([M]⁺).

Example 54: Préparation of methyl 4-amino-6-(2,3-difluoro-4(trifluoromethyl)phenyI)-5-fluoro-3-vinylpicolinate (Compound 53)

In a microwave vessel, a suspension of 2-(2,3-difluoro-4-(trifluoromethyl)phenyl)-4,4,5,5tetramethyl-l,3,2-dioxaborolane (commercially available; 0.641 g, 2.081 mmol), methyl 4amino-6-chloro-5-fluoro-3-vinylpicolinate (Head G; 0.4 g, 1.734 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.122 g, 0.173 mmol) and sodium carbonate (0.368 g, 3.47 mmol) in a 3:1 mixture of acetonitrile (3.25 mL) and water (1.084 mL) was stirred under microwave irradiation (120 °C, 20 min). The reaction mixture was poured into a half saturated brine solution and was extracted with EtOAc (3x). The combined organic layers were dried over Na2SO₄, filtered and concentrated. The residue was purified by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a brown solid (0.163 g, 24.98%).

-94Example 55: Préparation of methyl 4-amino-6-(4-aminophenyl)-5-fIuoro-3vinylpicolinate

yl)aniline (commercially available; 0.617 g, 2.82 mmol), methyl 4-amino-6-chloro-5-fluoro-

3-vinylpicolinate (Head G; 0.5 g, 2.168 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.152 g, 0.217 mmol) and potassium fluoride (0.327 g, 5.64 mmol) in a 1:1 mixture of acetonitrile (3.61 mL) and water (3.61 mL) was stirred under microwave irradiation (120 °C, 20 min). The reaction mixture was poured into a half saturated brine solution and was extracted with EtOAc (3x). The combined organic layers were dried over Na2SÛ4, filtered and concentrated. The residue was purified by flash column chromatography (S1O2, 24 g; hexanes/EtOAc gradient) to afford the title compound as a yellow solid (0.552 g, 89%); ’H NMR (400 MHz, DMSO-î/₆) δ 7.60 - 7.58 (m, 2H), 6.72 (dd, J= 17.7, 11.5 Hz, 1H), 6.65 - 6.58 (m, 2H), 6.24 (s, 2H), 5.47 (s, 2H), 5.45 (dd, J = 11.5, 1.2 Hz, 1H), 5.38 (dd, J= 17.7,1.2 Hz, 1H), 3.77 (s, 3H); ¹⁹FNMR(376 MHz, DMSO-îZ₆) δ -146.62; ESIMS m/z 286 ([M-H]’).

Example 56: Préparation of methyl 6-amino-2-(4-(difluoromethoxy)phenyl)-5methoxypyrimidine-4-carboxylate (Compound 106)

To a 5-mL microwave safe vial were added potassium fluoride (0.151 g, 2.59 mmol), palladium (II) acetate (0.012 g, 0.052 mmol), 2-(4-(difluoromethoxy)phenyl)-4,4,5,5tetramethyl-l,3,2-dioxaborolane (0.28 g, 1.037 mmol), methyl 6-amino-2-chloro-5methoxypyrimidine-4-carboxylate (0.226 g, 1.037 mmol), and 3,3',3phosphinetriyltribenzenesulfonate (0.052 g, 0.104 mmol). A mixture of water (1 mL) and acetonitrile (2 mL) was added, and the reaction was capped and placed in a Biotage Initiator™ microwave reactor for 6 min at 160 °C, with extemal IR-sensor température monitoring from the side of the vessel. Upon cooling to room température, the reaction

-9517475 mixture was diluted with EtOAc (50 mL) and water (50 mL). An additîonal extraction using CH2CI2 (50 mL) was combined with the EtOAc and dried over of Na₂SO4 (50 g) after the CH2CI2 layer was filtered through a cotton plug. The combined organics were concentrated on a rotary evaporator and the residue was purified using a Teledyne ISCO purification system with a gradient eluent system of CH2CI2 and EtOAc to yield the title compound as a white solid (134.4 mg, 39.8%).

Example 57: Préparation of methyl 4-amino-6-(4-cyanophenyl)-5-fluoro-3vinylpicolinate (Compound 107)

To a 5-mL microwave safe vial were added potassium fluoride (0.227 g, 3.90 mmol), methyl

4-amino-6-chloro-5-fluoro-3-vinylpicolinate (0.3 g, 1.301 mmol), bis(triphenylphosphine)palladium (II) chloride (0.091 g, 0.130 mmol) and 4-(4,4,5,5tetramethyl-l,3,2-dioxaborolan-2-yl)benzonitrile (0.313 g, 1.366 mmol. A mixture of water (1 mL) and acetonitrile (2 mL) was added, and the reaction was capped and placed in a Biotage Initiator™ microwave reactor for 20 min at 115 °C, with extemal IR-sensor température monitoring from the side of the vessel. Upon cooling to room température, the reaction mixture was diluted with CH2CI2 (25 mL) and water (25 mL), and the organic layer was filtered through a cotton plug. An additîonal extraction using EtOAc (25 mL) was combined with the CH2CI2 and dried over Na2SÛ4 (50 g). Following filtration of the combined organics through a cotton plug and concentration on a rotary evaporator, the residue was purified using a Teledyne ISCO purification system with a gradient eluent system of CH2CI2 and EtOAc to yield the title compound as a tan solid (297 mg, 76%).

-96Example 58: Préparation of methyl 4-amino-5-fluoro-6-(4-formylphenyl)-3vinylpicolinate

To a 5-mL microwave safe vial were added potassium fluoride (0.378 g, 6.50 mmol), methyl 4-amino-6-chloro-5-fluoro-3-vinylpicolinate (0.5 g, 2.168 mmol), bis(triphenylphosphine)palladium(II) chloride (0.152 g, 0.217 mmol) and 4-(4,4,5,5tetramethyl-l,3,2-dioxaborolan-2-yl)benzaldehyde (0.528 g, 2.276 mmol). A mixture of water (1 mL) and acetonitrile (2 mL) was added, and the reaction was capped and placed in a Biotage Initiator™ microwave reactor for 20 min at 115 °C, with extemal IR-sensor température monitoring from the side of the vessel. Upon cooling to room température, the reaction mixture was diluted with CH2CI2 (25 mL) and water (25 mL) and the organic layer was filtered through a cotton plug. An additional extraction using EtOAc (25 mL) was combined with the CH2CI2 and dried over Na₂SO₄ (50 g). Following filtration of the combined organics through a cotton plug and concentration on a rotary evaporator, the residue was purified using a Teledyne ISCO purification system with a gradient eluent system of CH2CI2 and EtOAc to yield the title compound as a white solid (635 mg, 98%): ^[H NMR (400 MHz, CDCI3) δ 10.08 (s, 1H), 8.13 (dd, J= 8.3, 1.6 Hz, 2H), 8.03 - 7.93 (m, 2H), 6.91 (ddd, J= 18.1, 11.6, 0.5 Hz, 1H), 5.73 (dd, J= 11.5, 1.4 Hz, 1H), 5.60 (dd, J= 18.1, 1.4 Hz, 1H), 4.77 (s, 2H), 3.94 (s, 3H); ¹⁹F NMR (376 MHz, CDC1₃) δ -143.49; ESIMS m/z 301 ([M+H]⁺).

Example 59: Préparation of methyl 4-amino-3-chloro-6-(2,5-difluoro-4(trifluoromethyl)phenyl)picolinate (Compound 70)

l,4-Difluoro-2-iodo-5-(trifluoromethyl)benzene (250 mg, 0.81 mmol), Head K (318 mg, 0.81 mmol), copper(I)iodide (0.08 mmol) and bis(triphenylphosphine)palladium(II) chloride (57 mg, 0.08 mmol) were combined in dry DMF (5 mL), deaerated with a stream of nitrogen for 10 min and heated to 75 °C. After 2 h, the mixture was cooled and partitioned between ethyl acetate and water. The organic phase was washed with saturated NaCI, dried (Na₂SO₄), and evaporated. The crude product was purified by flash chromatography (SiO₂; eluting with 0-30% ethyl acetate in hexanes) to provide 100 mg of the acetamide intermediate. This material was taken up in methanol (20 mL), treated with acetyl chloride (3 mL) and stirred for 3 days at 20 °C. After removal of volatiles under vacuum, the mixture was stirred with saturated NaHCÛ3 and ethyl acetate. The organic phase was washed with saturated NaCI, dried (Na₂SO₄), and evaporated to provide the title compound as a white solid (77 mg, 24%).

Example 60: Préparation of methyl 6-amino-2-(2,5-difluoro-4(trifiuoromethyl)phenyl)-5-methoxypyrimidine-4-carboxylate (Compound 148)

2-(2,5-Difluoro-4-(trifluoromethyl)phenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (400 mg, 1.2 mmol), Head C (250 mg 1.2 mmol), césium fluoride (360 mg, 2.3 mmol) and bis(triphenylphosphine)palladium(II) chloride (82 mg, 0.12 mmol) were combined in 1:1 volume per volume (v/v) acetonitrile-water (4 mL) and heated at 115 °C for 30 min in a microwave reactor. The mixture was partitioned between water and ethyl acetate. The organic phase was washed with saturated NaCI, dried (Na₂SO₄), and evaporated. The material was purified by flash chromatography (SiO₂; eluting with 0-30% ethyl acetate in hexanes) to provide a brown oil which was triturated with hexanes-dichloromethane to provide the title compound as a white solid (40 mg, 8.8%).

-9817475

Example 61: Préparation of methyl 6-amino-2-(2,3-difluoro-4-(trimethylsilyl)phenyl)5-methoxypyrimidine-4-carboxylate

(2,3-Difluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)trimethylsilane( 1.3 g, 4.2 mmol) (e.g., WO 2013003740 Al), Head C (750 mg, 3.5 mmol) and bis(triphenylphosphine)palladium(II) chloride (240 mg, 0.34 mmol) were combined in 1:1 v/v acetonitrile-water (10 mL) and heated to 115 °C for 30 min via microwave. The cooled mixture was partitioned between saturated NaCI and ethyl acetate. The organic phase was washed with saturated NaCI, dried (Na₂SO₄), and evaporated. The material was purified by flash chromatography (SiO₂; eluting with 0-20% ethyl acetate in hexanes) to provide the title compound as a white solid (330 mg, 26%): mp 157-159° C; ’H NMR (400 MHz, CDCI3) δ 7.60 (ddd, J =7.5, 6.0, 1.2 Hz, IH), 7.14 (ddd, J= 7.7,4.5, 1.5 Hz, 1 H), 5.48 (s, 2H), 4.00 (s, 3H), 3.95 (s, 3H), 0.34 (d, J= 0.7 Hz, 9H); ¹⁹F NMR (376 MHz, CDC1₃) δ 127.10 to -127.25 (m), -142.40 (dd, J= 22.6, 3.6 Hz); ESIMS m/z 368 ([M+H]⁺).

The following compound was made in accordance with the procedures disclosed in Example 61 from commercially available (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2yl)phenyl)trimethylsilane:

Methyl 4-amino-3,5-dichloro-6-(4-(trimethyIsilyl)phenyl)picolinate (prepared utilizing Head H)

mp 171-174 °C; *H NMR (400 MHz, CDCI3) δ 6.36(m, 4H), 5.33(2, 2H), 3.99(s, 3H), 0.307 (s, 9H); ESIMS m/z 369 ([M+H]⁺).

-9917475

The following compounds were made in accordance with the procedures dîsclosed in

Example 61 from commercially available 2-fluoro-4-(4,4,5,5-tetramethyl-l,3,2dioxaborolan-2-yl)phenyl)trimethylsilane (prepared according to WO 2013003740 Al):

Methyl 4-amino-3-chloro-6-(2-fluoro-4-(trimethylsilyl)phenyl)picolinate (prepared utilizing Head A)

.0 mp 154-156° C; *H NMR (400 MHz, CDC1₃) δ 7.97 (m, 1H), 7.30 (m, 3H), 4.84 (s, 2H), 4.01 (s, 3H), 0.293 (s, 9H); ESIMS m/z 353 ([M+H]⁺).

Methyl 4-amino-3,5-dichloro-6-(2-fluoro-4-(trimethylsilyl)phenyl)picolinate (prepared utilizing Head H)

NH₂

O mp 184-185° C; *H NMR (400 MHz, CDC1₃) δ 7.35 (m, 3H), 5.33 (s, 2H), 3.96 (s, 3H), 0.290 (s, 9H); ESIMS m/z 387 ([M+H])⁺).

Example 62: General procedure for Suzuki Coupling (Method A)

Argon was bubbled through a solution of Head A, Head B, or Head C (1.0 equiv), a boronic acid (1.0 equiv), Na2CO₃ (2.0 equiv) and Pd(PPh₃)4 (0.1 equiv) in 1:1 toluene: éthanol (20 vol) for 15 min in a sealed tube. The reaction mixture was then heated in the sealed tube at 110°C for 18 h. The cooled reaction mixture was diluted with water and extracted with ethyl acetate. (Note: The aqueous layer contained carboxylic acid products that were isolated as described below). The organic extracts was washed with water, washed with saturated brine solution, dried (Na2SO₄), filtered, and evaporated to dryness under reduced pressure. The

-10017475 crude product was purified by préparative TLC to get the pure esters. The aqueous layer was acidified to pH 2 using 1.5 N HCl and extracted with ethyl acetate. The organic extract was washed with saturated brine solution, dried (Na₂SO4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by préparative TLC to get the pure carboxylic acid dérivatives.

Example 63: General procedure for Suzuki Coupling (Method B)

Argon was bubbled through a solution of Head A, Head B or Head C (0.8 equiv), a boronic acid (1.0 equiv), NaHCO₃ (2 M solution, 1.0 equiv) and Pd(PPh3)4 (0.1 equiv) in dry dioxane (20 vol) for 15 min in a sealed tube. The sealed tube was heated at 80 °C for 18 h. The cooled reaction mixture was diluted with water and extracted with ethyl acetate. The organic extract was washed with water, washed with saturated brine solution, dried (Na₂SO4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography (SiO₂; eluting with 5^40% ethyl acetate in hexanes) to provide the pure compound.

Example 64: Préparation of methyl 4-amino-3-chloro-6-(3-fluoro-4iodophenyl)picolinate (Compound 66)

To a 250-mL round bottom flask, equipped with a stir bar, were added methyl 4-amino-3chloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate (0.328 g, 0.930 mmol), and dichloromethane (5.0 mL). To this solution iodine monochloride (0.141 mL, 2.79 mmol) was added. The reaction mixture was allowed to stir at room température for 18 h. Another portion of iodine monochloride (0.141 mL, 2.79 mmol) was added, and the reaction was allowed to stir at room température for an additional 4.5 h. The reaction mixture was poured into 1 M Na₂SO3, and the layers were partitioned. The aqueous phase was extracted with additional ethyl acetate (2x 100 mL). The combined organic layers were dried over anhydrous MgSCU, filtered and concentrated to afford the title compound as a brown solid (0.375 g, 99%);

-10117475

The following compounds were made in accordance with the procedures disclosed in

Example 64:

Methyl 4-amino-3,5-dichloro-6-(3-fluoro-4-iodophenyl)picolinate (Compound 13)

F

The title compound was prepared as described in Example 64 with methyl 4-amino-3,5dichloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate (0.381 g, 0.984 mmol) and isolated as a yellow solid (0.360 g, 83%).

Methyl 6-amino-2-(3-fluoro-4-iodophenyl)-5-methoxypyriinidine-4-carboxylate (Compound 27)

NH₂

F

The title compound was prepared as described in Example 64 with methyl 6-amino-2-(3fluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4-carboxylate (0.307 g, 0.879 mmol) 15 and isolated as a yellow solid (0.368 g).

Example 65: Préparation of methyl 4-amino-3-chloro-6-(4-iodophenyl)-5methylpicolinate (Compound 136)

NH

-10217475

To methyl 4-amino-3-chloro-5-methyl-6-(4-(trimethylsilyl)phenyl)picolinate (0.95 g, 2.72 mmol) in dichloromethane (9 mL) was added iodine monochloride (920 mg, 5.67 mmol) in dichloromethane (4.5 mL) dropwise. The reaction was stirred at room température for 4 h, then quenched with saturated aqueous sodium thiosulfate, diluted with water, and extracted with dichloromethane (3x). The organic layers were dried over anhydrous Na2SO4, filtered and concentrated. Purification by flash chromatography (0-30% ethyl acetate/hexanes) afforded the title compound as a red-orange solid (618 mg, 56%).

The following compound was made in accordance with the procedures disclosed in Example 65:

Methyl 4-amino-3-chloro-6-(3-fluoro-4-iodophenyl)-5-methylpicolinate (Compound 79)

The title compound was prepared as in Example 65 and isolated as an off-white solid (54 mg, 59%).

Example 66: Préparation of methyl 4-amino-6-(4-iodophenyl)-3-chloro-5fluoropicolinate (Compound 118)

OMe

Iodine monochloride (280 mg, 1.7 mmol, 2.0 equiv) was added to a stirred solution of methyl 4-amino-3-chloro-5-fluoro-6-(4-(trimethylsilyl)phenyl)picolinate (300 mg, 0.85 mmol, 1.0 equiv) in 1,2-dichloroethane (5.7 mL) at 23 °C. The resulting brown solution was stirred at 23 °C for 17 h. The reaction mixture was diluted with a saturated solution of sodium thiosulfate (100 mL) and extracted with dichloromethane (4 x 40 mL). The combined organic layers were dried ( MgSÛ4), gravity filtered, and concentrated by rotary

-10317475 évaporation. The residue was purified by silica gel column chromatography (33% ethyl acetate in hexanes) to afford the title compound as a pale purple powder (250 mg, 71%).

Example 66:

Methyl 4-acetamido-3-chloro-6-(2,3-difluoro-4-iodophenyl)picolinate

O

*H NMR (400 MHz, CDCI3) δ 9.06 (d, J= 1.5 Hz, IH), 7.98 (br s, IH), 7.60 (ddd, J= 9, 5, 2

Hz, IH), 7.53 (ddd, J =9, 7, 2 Hz, IH), 4.03 (s, 3H), 2.34 (s, 3H); ESIMS m/z 467 ([M+H]⁺).

Methyl 4-acetamido-3-chloro-6-(4-iodophenyI)picolinate

O

’H NMR (400 MHz, CDC1₃) δ 9.00 (s, IH), 7.77 (m, 4H), 7.25 (s, IH), 4.03 (s, 3H), 2.33 (s, 3H); ESIMS m/z 431 ([M+H]⁺).

-10417475

Example 67: Préparation of methyl 4-amino-3-chloro-6-(2,5-difluoro-4-iodophenyl)-5fluoropicolinate (Compound 55)

NH

To a solution of methyl 4-amino-3-chloro-6-(2,5-difluoro-4-(trimethylsilyl)phenyl)-5fluoropicolinate (0.280 g, 0.720 mmol) in CH2CI2 (2.88 mL) at 20 °C was added iodine monochloride (0.144 mL, 2.880 mmol). The reaction mixture was stirred at 20 °C ovemight. The mixture was then poured into a 10% aqueous solution of Na2SO₃, extracted with EtOAc (3x), dried over Na2SO4, filtered and concentrated. The residue was purified by flash column chromatography (S1O2; hexanes/EtOAc gradient) to afford the title compound as a white solid (0.237 g, 74.4%).

Methyl 4-acetamido-3-chloro-6-(2,5-difluoro-4-iodophenyI)picolinate

O ‘H NMR (400 MHz, CDC1₃) δ 9.10 (d, J = 0.7 Hz, 1H), 7.96 (s, 1H), 7.76 (dd, J= 8.4, 6.4 Hz, 1H), 7.57 (dd, J= 9.8, 5.0 Hz, 1H), 4.03 (s, 3H), 2.33 (s, 3H); ¹⁹F NMR (376 MHz, CDC1₃) δ -99.95, -100.00, -119.90, -119.95; ESIMS m/z 465 ([M-H]').

-10517475

Example 68: Préparation of methyl 6-amino-2-(2,3-difluoro-4-iodophenyl)-5methoxypyrimidine-4-carboxylate (Compound 24)

Methyl 6-arnino-2-(2,3-difluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4carboxylate (330 mg, 0.90 mmol) was stirred in 1,2-dichloroethane (5 mL), treated with iodine monochloride (1.0 g, 6.9 mmol), and heated to 70° C for 21 h. After cooling, the mixture was diluted with ethyl acetate, washed with 15% sodium bisulfite, washed with saturated NaCI, dried (Na₂SO4), and evaporated. The material was purified by RP-HPLC using 70% acetonitrile to provide the title compound as a white solid (250 mg, 66%).

Example 69: Préparation of methyl 4-acetamido-6-(4-bromo-3-fluorophenyl)-3chloropicolinate

To a 100-mL round bottom flask, equipped with a stir bar, were added methyl 4-acetamido-

3-chloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate (433 mg, 1.11 mmol), dichloromethane (10 mL) and bromine (0.225 mL, 4.39 mmol). The reaction mixture was allowed to stir at room température for 18 h. The reaction mixture was then poured into 1 N Na₂SC>3 and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over anhydrous MgSC>4, filtered and concentrated. The resulting residue was purified by flash chromatography (0-50% EtOAc in Hexanes) to afford the title compound as a light tan solid (0.440 g, 100%): ^!H NMR (400 MHz, DMSO-î/₆) δ 10.02 (s, 1H), 8.71 (s, 1H), 7.98 - 7.81 (m, 2H), 7.74 (dd, J= 8.4, 2.1 Hz, 1H), 3.94 (s, 3H), 2.23 (s, 3H); ¹⁹F NMR (376 MHz, DMSO-iZg) δ -107.44; ESIMS m/z 402 ([M+H])⁺).

-10617475

Example 69:

Methyl 4-amino-6-(4-bromo-3-fluorophenyl)-3,5-dichloropicoIinate (Compound 73)

The title compound was prepared as described in Example 69 with methyl 4-amino-3,5dichloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate (0.290 g, 0.749 mmol) and isolated as a white solid (0.250 g, 85%).

Methyl 6-amino-2-(4-bromo-3-fluorophenyl)-5-methoxypyrimidine-4-carboxylate (Compound 171)

The title compound was prepared as described in Example 69 with methyl 6-amino-2-(3fluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4-carboxylate (0.250 g, 0.715 mmol) 15 and isolated as a white solid (0.200 g, 78%).

Example 70: Préparation of methyl 4-amino-6-(4-bromophenyl)-3-chloro-5methylpicolinate (Compound 81)

-107

To methyl 4-amino-3-chloro-5-methyl-6-(4-(trimethylsilyl)phenyl)picolinate (150 mg, 0.43 mmol) and potassium carbonate (215 mg, 1.56 mmol) in 1,2-dichloroethane (DCE, 2.9 mL) was added bromine (0.03 mL, 0.58 mmol) and stirred at room température for 18 h. The DCE was concentrated off under vacuum and the crude material was partitioned between ethyl acetate and aqueous potassium carbonate. The aqueous layer was extracted with ethyl acetate (3x), washed with water, dried over anhydrous MgSO4, filtered, and adsorbed onto silica gel. Purification by flash chromatography (0-40% ethyl acetate/hexanes) afforded the title compound as a pale orange powder (68 mg, 45%).

The following compound was made in accordance with the procedures disclosed in Example 70:

Methyl 4-amino-6-(4-bromo-3-fluorophenyl)-3-chloro-5-methylpicolinate (Compound

112)

CH₃

The title compound was prepared as in Example 70 and isolated as an off-white solid (96 mg, 52%).

Example 71: Préparation of methyl 4-amino-6-(4-bromo-2,3-difluorophenyl)-3-chloro5-fluoropicolinate (Compound 109)

Methyl 4-amino-3-chloro-6-(2,3-difluoro-4-(trimethylsilyl)phenyl)-5-fluoropicolinate (2.5 g, 6.43 mmol) was dissolved in acetonitrile (32 mL) and bromine (3.31 mL, 64.3 mmol) was added. The reaction mixture was stirred at room température for 4 h at which time liquid chromatography-mass spectrometry (LC-MS) indicated the reaction was mostly complété.

-10817475

The reaction mixture was partitioned between dichloromethane and water and sodium thiosulfate (10.17 g, 64.3 mmol) was added. The aqueous phase was extracted with dichloromethane and the organic extracts were combined and concentrated under vacuum.

The product was purified by flash chromatography (S1O2; eluting with 5-40% ethyl acetate in hexanes) to provide the title compound as a light yellow solid (1.62 g, 63.7%).

Example 72: Préparation of methyl 4-amino-6-(4-bromophenyI)-3-chloro-5fluoropicolinate (Compound 138)

NH_?

OMe

Bromine (47 pL, 0.92 mmol, 1.2 equiv) was added to a stirred solution of methyl 4-amino-

3-chloro-5-fluoro-6-(4-(trimethylsilyl)phenyl)picolinate (270 mg, 0.77 mmol, 1.0 equiv) in 1,2-dichloroethane (5.1 mL) at 23 °C. The resulting dark orange solution was stirred at 23 °C for 24 h. The reaction mixture was quenched with a saturated solution of sodium thiosulfate (5 mL) and then adjusted to pH 10 using 2 M sodium hydroxide. The reaction mixture was diluted with water (50 mL) and extracted with dichloromethane (3 x 30 mL). The combined organic layers were dried ( MgSCfr), gravity fiîtered, and concentrated by rotary évaporation. The residue was purified by reverse phase column chromatography (5% acetonitrile to 100% acetonitrile gradient) to afford the title compound as a tan powder (160 mg, 57%).

The following compound was made in accordance with the procedures disclosed in Example 72.

Methyl 4-acetamido-6-(4-bromophenyl)-3-chloropicolinate

-10917475 ο

Me^ NH

OMe ‘H NMR (400 MHz, CDCl₃) δ 9.01(s, IH), 7.90 (m, 2H), 7.49 (m, 2H), 7.25 (s, IH), 4.03 (s, 3H), 2.34 (s, 3H); ESIMS m/z 385 ([M+H]⁺).

Example 73: Préparation of methyl 4-amino-6-(4-bromo-2,5-difluorophenyl)-3-chloro5-fluoropicolinate (Compound 51)

NH

Br

To a solution of methyl 4-amino-3-chloro-6-(2,5-difluoro-4-(trimethylsilyl)phenyl)-5fluoropicolinate (0.240 g, 0.617 mmol) in CH2CI2 (2.469 mL) at 20 °C was added bromine (0.127 mL, 2.469 mmol). After 24 h, the reaction mixture was poured into a saturated aqueous solution of Na2S2Û₃ and was extracted with EtOAc (3x). The combined organic layers were dried over Na2SO4, filtered and concentrated. The residue was purified by flash column chromatography (SiO2; hexanes/EtOAc gradient) to afford the title compound as a white solid (0.187 g, 77%).

73:

Methyl 4-acetamido-6-(4-bromo-2,5-difluorophenyl)-3-chloropicoIinate

-11017475

mp 177-179 °C; *H NMR (400 MHz, CDC1₃) δ 9.10 (d, J = 0.7 Hz, IH), 7.97 (s, IH), 7.85 (dd, J = 9.1, 6.6 Hz, IH), 7.40 (dd, J= 9.9, 5.5 Hz, IH), 4.03 (s, 3H), 2.33 (s, 3H); ^l9F NMR (376 MHz, CDC1₃) δ -112.76, -112.80, -119.21, -119.26; ESIMS m/z 418 ([M-H]).

Example 74: Préparation of methyl 6-amino-2-(4-bromo-2,3-difIuorophenyl)-5methoxypyrimidine-4-carboxylate (Compound 122)

Methyl 6-amino-2-(2,3-difluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4carboxylate (350 mg, 0.95 mmol) was stirred in 1,2-dichloroethane (4 mL), treated with bromine (1.0 g, 6.3 mmol) and heated to 60 °C for 6 h. After cooling, the mixture was stirred with 15% sodium bisulfite solution until négative to starch-iodine paper. The mixture was diluted with ethyl acetate, washed with saturated NaCl, dried (Na₂SO₄), and evaporated. Purification by flash chromatography (SiO₂; eluting with 0-30% ethyl acetate in hexanes) provided the title compound as white solid (75 mg, 23%).

-111Example 75: Préparation of methyl 4-amino-6-(4-bromo-3-fluorophenyl)-3chloropicolinate (Compound 115)

''CH

6-(4-bromo-3-fluorophenyl)-3-chloropicolinate (0.411 g, 1.023 mmol), methanol (5.12 mL) and acetyl chloride (1.45 mL, 20.5 mmol). The reaction mixture was allowed to stir at room température for 18 h. The solvent was removed with a rotary evaporator. The resulting solid was dissolved in 1 N NaHCO₃ and extracted with ethyl acetate (3 x 75 mL). The combined organic layers were dried over anhydrous MgSÛ4, filtered and concentrated to afford the title compound as a white solid (0.324 g, 88%).

Example 76: Préparation of methyl 4-amino-3-chloro-6-(2,3-difluoro-4iodophenyl)picolinate (Compound 129)

Acetyl chloride (1.3 mL, 18 mmol, 10 equiv) was slowly added to methanol (12 mL) and stirred at 23 °C for 30 min. Methyl 4-acetamido-3-chloro-6-(2,3-difluoro-4iodophenyl)picolinate (830 mg, 1.8 mmol, 1.0 equiv) was added and the heterogeneous white mixture was stirred at 23 °C for 18 h. The reaction mixture was concentrated by rotary évaporation. The residue was diluted with saturated sodium bicarbonate (200 mL) and extracted with dichloromethane (3 x 75 mL). The organic layer was dried ( MgSÛ4), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a white powder (720 mg, 95%).

Example 77: Préparation of methyl 4-amino-6-(4-bromo-2,5-difluorophenyl)-3chloropicolinate (Compound 127)

-11217475

ch₃

To a solution of methyl 4-acetamido-6-(4-bromo-2,5-difluorophenyl)-3-chloropicolinate (0.300 g, 0.715 mmol) in a mixture of methanol (3.57 mL) and THF (3.57 mL) was slowly added acetyl chloride (1.017 mL, 14.30 mmol). The reaction mixture was stirred at 20 °C for 2 h. The mixture was then poured into a saturated aqueous solution of NaHCO₃ and extracted with EtOAc (3x). The combined organic layers were dried over Na2SÛ4, filtered, concentrated and dried in vacuo to afford methyl 4-amino-6-(4-bromo-2,5-difluorophenyl)3-chloropicolinate (0.257 g, 95%) as a white solid.

Example 78: Préparation of methyl 4-(7V-acetylacetamido)-3-chloro-6-(2,5-difluoro-4(trimethylsilyl)phenyl)picolinate

To a solution of methyl 4-amino-3-chloro-6-(2,5-difluoro-4-(trimethylsilyl)phenyl)picolinate (0.280 g, 0.755 mmol) in dichloroethane (3.02 mL) was added 7V,7V-diisopropylethylamine (0.396 mL, 2.265 mmol) and acetyl chloride (0.107 mL, 1.510 mmol). The reaction mixture was stirred at 20 °C for 4 h and then at 60 °C for 2 h. The mixture was poured into a saturated aqueous solution of NH4CI and extracted with EtOAc (3x). The combined organic layers were washed with brine, dried over Na2SÛ4, filtered and concentrated. The residue was purified by flash column chromatography (S1O2; hexanes/EtOAc gradient) to afford the title compound as a light yellow solid (104 mg, 30.3%): mp 121-123 °C; ’H NMR (400 MHz, CDCh) δ 7.88 (d, J= 0.7 Hz, IH), 7.79 (dd, J= 8.5, 5.8 Hz, IH), 7.15 (dd, J= 10.9, 4.1 Hz, IH), 4.05 (s, 3H), 2.35 (s, 6H), 0.35 (d, J= 0.8 Hz, 9H); ESIMS m/z 455 ([M+H]⁺).

Example 79: Préparation of methyl 4-amino-6-(4-bromophenyl)-5-fluoro-3 vinylpicolinate (Compound 57)

To a 0 °C suspension of nitrosyl tetrafluoroborate (0.122 g, 1.044 mmol) in CH2CI2 (2 mL) was added a solution of methyl 4-amino-6-(4-aminophenyl)-5-fluoro-3-vinylpicolinate (0.3 g, 1.044 mmol) in a 1:1 mixture of CH2CI2 and CH3CN (10 mL). The reaction mixture was stirred at 0 °C for 30 min, then was added dropwise to a suspension of potassium bromide (0.497 g, 4.18 mmol), 18-crown-6 (0.028 g, 0.104 mmol), copper(II) bromide (0.023 g, 0.104 mmol), copper(I) bromide (0.015 g, 0.104 mmol), and 1,10-phenanthroline (0.019 g, 0.104 mmol). The mixture was stirred at 20 °C for 1 h. Additîonal copper (I) bromide (0.749 g, 5 equiv) was added and the reaction mixture was stirred at 20 °C for an additîonal 1 h. The reaction mixture was diluted with Et2Û and filtered on a short pad of Celite®. The supernatant was concentrated and purified by flash column chromatography (S1O2; hexanes/EtOAc gradient) followed by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a light brown solid (130 mg, 35.5%).

The following compound was made in accordance with the procedures disclosed in Example 79:

Methyl 4-acetamido-6-(4-bromo-2,3,6-trifluorophenyl)-3-chloropicolinate

’H NMR (400 MHz, DMSO-d₆) δ 10.08 (s, IH), 8.48 (s, IH), 7.87 - 7.84 (m, IH), 3.93 (s, 3H), 2.25 (s, 3H); ESIMS m/z 437 ([M+2H]⁺).

Example 80: Préparation of methyl 6-amino-2-(4-iodophenyl)-5-vinylpyrimidine-4carboxylate (Compound 164)

To a 50-mL round bottom flask, equipped with a stir bar, was added nitrosyl tetrafluoroborate (78 mg, 0.67 mmol) and dichloromethane (2.0 mL). The flask was cooled in a ice water bath and placed under N2 atmosphère. Then methyl 6-amino-2-(4aminophenyl)-5-vinylpyrimidine-4-carboxylate (180 mg, 0.666 mmol) in dichloromethane (2.5 mL) was added dropwise. The reaction mixture was allowed to stir for 60 min. Then sodium iodide (499 mg, 3.33 mmol) in a minimal amount of H2O was added, followed by dioxane (1.0 mL). The reaction was allowed to stir for 18 h at room température. The reaction mixture was poured into a saturated Na2SO3 solution and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over anhydrous MgSO₄, filtered and concentrated. The resulting residue was purified by flash chromatography (Silica gel; 0-30% EtOAc in Hexanes) and reverse phase chromatography to afford the title compound as a light yellow solid (0.068 g, 27%).

Example 81: Préparation of methyl 4-amino-5-fluoro-6-(4-iodophenyl)-3vinylpicolinate (Compound 139)

To a 0 °C suspension of nitrosyl tetrafluoroborate (0.041 g, 0.348 mmol) in CH2CI2 (1 mL) was added a solution of methyl 4-amino-6-(4-aminophenyl)-5-fluoro-3-vinylpicolinate (0.1 g, 0.348 mmol) in a 1:1 mixture of CH2CI2 and CH3CN (4 mL). The reaction mixture was stirred at 0 °C for 30 min, then a solution of sodium iodide (0.261 g, 1.740 mmol) dissolved in a minimum of water was added and the reaction mixture was stirred at 20 °C for 30 min. The mixture was then poured into a 10% aqueous solution of sodium sulfite and extracted with EtOAc (3x). The combined organic layers were dried over Na2SO₄, filtered and

-11517475 concentrated. The residue was purified by flash column chromatography (SiO₂;

hexanes/EtOAc gradient) foliowed by préparative reverse phase HPLC (water/acetonitrile gradient) to afford the title compound as a white solid (32 mg, 23.09%).

81:

Methyl 4-acetamido-3-chloro-6-(2,3,6-trifluoro-4-iodophenyl)picolinate

‘H NMR (400 MHz, DMSO-d₆) δ 10.07 (s, IH), 8.46 (s, IH), 7.89 - 7.85 (m, IH), 3.93 (s, 3H), 2.25 (s, 3H); ESIMS m/z 487 ([M+3H]⁺).

Example 82. Préparation of methyl 4-amino-3-chloro-5-methyl-6-(4((trimethylsilyl)ethynyl)phenyl)picolinate

A mixture of methyl 4-amino-3-chloro-6-(4-iodophenyl)-5-methylpicolinate (264 mg, 0.66 mmol), trimethyl((tributylstannyl)ethynyl)silane (280 mg, 0.72 mmol), tetrakis(triphenylphosphine)palladium(0) (75 mg, 0.065 mmol) in anhydrous DMF (1.3 mL) was heated at 90 °C for 16 h. The reaction mixture was cooled, diluted water, and extracted with ethyl acetate (2x). The organic layers were dried over anhydrous MgSO₄, filtered, and adsorbed onto silica gel. Purification by flash chromatography (0-100% ethyl acetate/hexanes) afforded the title compound as a brown solid (52 mg, 21%): mp 158-164 °C; ’H NMR (400 MHz, CDCI3) δ 7.52 (d, J= 8.5 Hz, 2H), 7.40 (d, J= 8.5 Hz, 2H), 4.83 (s,

-11617475

2H), 3.96 (s, 3H), 2.14 (s, 3H), 0.26 (s, 9H); IR (neat film) 3325, 3227, 2955, 2157, 1729,

1629,1246 cm'¹; ESIMS m/z 372 ([M]⁺).

Example 83: Préparation of methyl 4-amino-3-chloro-6-(4-ethynylphenyl)-5methylpicolinate (Compound 40)

To methyl 4-amino-3-chloro-5-methyl-6-(4-((trimethylsilyl)ethynyl)phenyl)-picolinate (50 mg, 0.13 mmol) in methanol (0.7 mL) was added potassium carbonate (24 mg, 0.17 mmol). The reaction mixture was stirred at room température for 40 min, then diluted with water and extracted with dichloromethane (4x). The organic layers were dried over anhydrous MgSÛ4, filtered and concentrated to afford the title compound as a brown oil (34 mg, 84%).

Example 84: Préparation of methyl 4-amino-3-chloro-5-fluoro-6-(4((trimethylsilyl)ethynyl)phenyl)picolinate

stirred mixture of methyl 4-amino-3-chloro-5-fluoro-6-(4-iodophenyl)picolinate (490 mg, 1.2 mmol, 1.0 equiv) and tetrakis (triphenylphosphine)palladium(O) (140 mg, 0.12 mmol, 0.10 equiv) in DMF (2.4 mL) at 23 °C. The reaction mixture was heated to 90 °C, resulting in a homogeneous yellow solution, and stirred for 20 h. The cooled reaction mixture was diluted with water (200 mL) and extracted with diethyl ether (4 x 100 mL). Hexanes (100 mL) was added to the combined organic layers and the turbid solution was washed with water (200 mL). The organic layer was dried ( MgSCL), gravity filtered, and concentrated by rotary évaporation. The residue was purified by silica gel column chromatography (25%

-11717475 ethyl acetate in hexanes) to afford the title compound as a tan powder (330 mg, 73%): mp

83-86 °C; IR (thin film) 3487 (m), 3375 (s), 2958 (s), 2159 (m), 1739 (s), 1618 (s) cm'¹; *H

NMR (300 MHz, CDC1₃) δ 7.89 (m, 2H), 7.55 (m, 2H), 4.89 (br s, 2H), 3.99 (s, 3H), 0.26 (s,

9H); ESIMS m/z 377 ([M+H]⁺).

Example 85: Préparation of methyl 4-amino-3-chloro-6-(4-ethynylphenyl)-5fluoropicolinate (Compound 7)

NH,

OMe

Potassium carbonate (100 mg, 0.74 mmol, 1.0 equiv) was added to a stirred mixture of methyl 4-amino-3-chloro-5-fluoro-6-(4-((trimethylsilyl)ethynyl)phenyl)picolinate (280 mg, 0.74 mmol, 0.10 equiv) in methanol (3.7 mL) at 23 °C. The heterogeneous pale yellow mixture was stirred at 23 °C for 30 min. The reaction mixture was diluted with water (200 mL) and extracted with dichloromethane (5 x 50 mL). The organic layers were dried ( MgSO4), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a tan powder (220 mg, 96%).

Example 86: Préparation of methyl 4-amino-3-chloro-6-(4-ethynyl-3-fluorophenyl)-5fluoropicolinate (Compound 133)

NH₂

OMe

F

Dimethyl l-diazo-2-oxopropylphosphonate (290 mg, 1.5 mmol, 1.2 equiv) was added to a stirred mixture of methyl 4-amino-3-chloro-5-fluoro-6-(3-fluoro-4-formylphenyl)picolinate (410 mg, 1.3 mmol, 1.0 equiv) and solid potassium carbonate (350 mg, 2.5 mmol, 2.0 equiv) in methanol (12 mL) at 23 °C. The resulting cloudy pale yellow mixture was stirred at 23 °C for 2 h. The reaction mixture was diluted with water (150 mL) and extracted with

-11817475 dichloromethane (4 x 60 mL). The organic layers were dried ( MgSO4), gravity filtered, and concentrated by rotary évaporation. The residue was purified by silica gel column chromatography (33% ethyl acetate in hexanes) to afford the title compound as a white powder (150 mg, 38%).

Example 87. Préparation of methyl 4-amino-3-chloro-6-(4-ethynyl-3-fluorophenyl)-5methylpicolinate (Compound 151)

To a solution of methyl 4-amino-3-chloro-6-(3-fluoro-4-formylphenyl)-5-methylpicolinate (358 mg, 1.1 mmol) and potassium carbonate (537 mg, 3.9 mmol) in methanol (11 mL) at room température was added dimethyl (l-diazo-2-oxopropyl)phosphonate (Bestmann-Ohira reagent, crude reagent; lmL), and the mixture was stirred for 3 h. The reaction was quenched with saturated aqueous sodium bicarbonate and extracted with ethyl acetate (3x). The combined organic layers were dried over anhydrous Na₂SO4, filtered, and adsorbed onto silica gel. Purification by flash chromatography (0-50% ethyl acetate/hexanes) provided the title compound as a yellow solid (245 mg, 69%).

Example 88: Préparation of methyl 4-amino-6-(4-ethynylphenyl)-5-fluoro-3vinyipicolinate (Compound 60)

To a 20 mL reaction vial was added methyl 4-amino-5-fluoro-6-(4-formylphenyl)-3vinylpicolinate (0.41 g, 1.365 mmol), potassium carbonate (0.377 g, 2.73 mmol) and methanol (10 mL). Dimethyl (l-diazo-2-oxopropyl)phosphonate (0.315 g, 1.638 mmol) was added in one portion. After stirring for 4 h, the reaction mixture was diluted with Et₂O (50 mL) and washed with a 5% solution of NaHCO3 (25 mL). The organic layer was dried over

-11917475

MgSO₄ (5 g), filtered, and concentrated on a rotary evaporator. The resulting residue was purified using a Teledyne ISCO purification System with a gradient eluent System of CH2CI2 and EtOAc to yield the title compound as a white solid (250 mg, 61%).

Example 89: Préparation of methyl 4-((tert-butoxycarbonyl)amino)-3-chloro-6-(4chloro-3-fluorophenyl)-5-fluoropicolinate

Step 1: Methyl 4-amino-3-chloro-6-(4-chloro-3-fluorophenyl)-5-fluoropicolinate (1.43 g, 4.29 mmol) was combined with di-ieri-butyl dicarbonate (2.99 mL, 12.88 mmol) and N,Ndimethylpyridin-4-amine (0.079 g, 0.644 mmol) in dichloromethane (30 mL). The reaction mixture was stirred ovemight at rt. The reaction mixture was concentrated under a stream of nitrogen and applied directly to a column of silica gel. The compound was eluted with a 220% ethyl acetate/hexanes gradient solvent System to provide methyl 4-(bis(/erZbutoxycarbonyl)amino)-3-chloro-6-(4-chloro-3-fluorophenyl)-5-fluoropicolinate (2.1 g, 92%) as a white solid.

Step 2: Methyl 4-(bis(/erZ-butoxycarbonyl)amino)-3-chloro-6-(4-chloro-3-fluorophenyl)-5fluoropicolinate (2.1 g, 3.94 mmol) was dissolved in dichloroethane (20 mL) and trifluoroacetic acid (0.598 mL, 7.76 mmol) was added at rt. The reaction mixture was stirred ovemight at rt then concentrated under vacuum. The product was purified by flash chromatography (S1O2; eluting with 2-20% ethyl acetate in dichloromethane) to provide the title compound as a white solid (1.64 g, 98%): 'H NMR (300 MHz, CDCI3) δ 7.80 (dd, J= 22.0, 8.5 Hz, 2H), 7.50 (dd, J= 8.3, 7.6 Hz, 1H), 6.51 (s, 1H), 4.02 (s, 3H), 1.56 (s, 9H); ESIMS m/z 431 ([M-H]').

Example 90: Préparation of methyl 4-ammo-6-(4-chloro-3-fluorophenyl)-5-fluoro-3vinylpicolinate (Compound 215)

-12017475

Step 1: Methyl 4-(ier/-butoxycarbonylamino)-3-chloro-6-(4-chloro-3-fluorophenyl)-5fluoropicolinate (1.5 g, 3.46 mmol), tributyl(vinyl)stannane (2.196 g, 6.92 mmol), and bis(triphenylphosphine)palladium(II) chloride (0.365 g, 0.519 mmol) were combined in 1,2dichloroethane (4.62 mL) and irradiated in a microwave at 130 °C in a sealed vial for 30 min. The cooled reaction mixture was applied directly to a silica gel column and eluted with a 5^40% ethyl acetate/hexanes gradient to provide methyl 4-(ier/-butoxycarbonylamino)-6(4-chloro-3-fluorophenyl)-5-fluoro-3-vinylpicolinate (0.966 g, 65.7%) as a white solid. Step 2: Methyl 4-(teri-butoxycarbonylamino)-6-(4-chloro-3-fluorophenyl)-5-fluoro-3vinylpicolinate (0.966 g, 2.274 mmol) was dissolved in dichloroethane (11 mL) and trifluoroacetic acid (3.50 mL, 45.5 mmol) was added. After 4 h at rt, the reaction mixture was concentrated under vacuum then coevaporated with additional dichloroethane twice more. The residue was purified by flash chromatography (SiO₂; eluting with 7-60% ethyl acetate in hexanes) to provide the title compound as a white solid (0.705 g, 95%).

Example 91: Préparation of methyl 4-amino-5-bromo-3-chloro-6-(2,5-difluoro-4(trimethylsilyl)phenyl)picolinate

To a solution of methyl 4-amino-3-chloro-6-(2,5-difluoro-4-(trimethylsilyl)phenyl)picolinate (0.210 g, 0.566 mmol) in CH2CI2 (2.265 mL) at 20 °C was added bromine (0.117 mL, 2.265 mmol). The reaction mixture was stirred at 20 °C ovemight. The mixture was then poured into a saturated aqueous solution of Na₂S₂O3 and extracted with EtOAc (3x). The combined organic layers were dried over Na₂SÛ4, filtered and concentrated. The residue was purified by flash column chromatography (SiO₂; hexanes/EtOAc gradient) to provide the title

-12117475 compound as a white solid (0.125 g, 49.1%): mp 165-166 °C; *H NMR (400 MHz, CDCI3) δ

7.10 (dd, J= 8.9, 4.0 Hz, 1H), 7.03 (dd, J= 7.6, 5.1 Hz, 1H), 5.43 (s, 2H), 3.96 (s, 3H), 0.33 (d, J= 0.7 Hz, 9H); ESIMS m/z 450 ([M+H]⁺).

Example 92: Préparation of 4-amino-3-chloro-6-(3-fluoro-4-iodophenyl)picolinic acid (Compound 77)

To a 100-mL round bottom flask, equipped with a stir bar, was added methyl 4-amino-3chloro-6-(3-fluoro-4-iodophenyl)picolinate (0.284 g, 0.699 mmol), 1.0 N sodium hydroxide (2.79 mL, 2.79 mmol) and methanol (5.0 mL). The reaction mixture was allowed to stir for 18 h at rt. The solvent was then removed with a rotary evaporator. The resulting solid was diluted with H2O, which was adjusted to pH~3.0 with 1 N HCl, and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over anhydrous MgSCU, filtered and concentrated to afford the title compound as a white solid (0.056 g, 21%). The following compounds were made in accordance with the procedures disclosed in Example 92:

4-Amino-3,5-dichloro-6-(3-fluoro-4-iodophenyl)picolinic acid (Compound 145)

The title compound was prepared as described in Example 92 with methyl 4-amino-3,5dichloro-6-(3-fluoro-4-iodophenyl)picolinate (0.197 g, 0.447 mmol) and isolated as a white solid (0.133 g, 70%).

6-Amino-2-(3-fluoro-4-iodophenyl)-5-methoxypyrimidine-4-carboxylic acid (Compound 37)

The title compound was prepared as described in Example 92 with methyl 6-amino-2-(35 fluoro-4-iodophenyl)-5-methoxypyrimidine-4-carboxylate (0.309 g, 0.766 mmol) and isolated as a white solid (0.065 g, 22%).

4-Amino-6-(4-bromo-3-fluorophenyl)-3-chloropicolinic acid (Compound 110)

The title compound was prepared as described in Example 92 with methyl 4-amino-6-(4bromo-3-fluorophenyl)-3-chloropicolinate (291 mg, 0.809 mmol) and isolated as an offwhite solid (0.247 g, 88%).

4-Amino-6-(4-bromo-3-fluorophenyl)-3,5-dichloropicolinic acid (Compound 43)

The title compound was prepared as described in Example 92 with methyl 4-amino-6-(4bromo-3-fluorophenyl)-3,5-dichloropicolinate (225 mg, 0.571 mmol) and isolated as a white solid (0.219 g, 100%).

-12315

6-Amino-2-(4-bromo-3-fluorophenyl)-5-methoxypyrimidine-4-carboxylic acid (Compound 113)

The title compound was prepared as described in Example 92 with methyl 6-amino-2-(4bromo-3-fluorophenyl)-5-methoxypyrimidine-4-carboxylate (166 mg, 0.466 mmol) and isolated as a white solid (0.056 g, 35%).

6-Amino-2-(4-cyano-2-fluorophenyl)-5-vinylpyrimidine-4-carboxylic acid (Compound

5)

The title compound was prepared as described in Example 92 with methyl 6-amino-2-(4cyano-2-fluorophenyl)-5-vinylpyrimidine-4-carboxylate (294 mg, 0.986 mmol) and isolated as a an orange solid (0.202 g, 72%).

6-Amino-2-(3-fluoro-4-(trifluoromethyl)phenyl)-5-vinylpyrimidine-4-carboxylic acid (Compound 32)

-124-

The title compound was prepared as described in Example 92 with methyl 6-amino-2-(3fluoro-4-(trifluoromethyl)phenyl)-5-vinylpyrimidine-4-carboxylate (265 mg, 0.777 mmol) and îsolated as a light yellow solid (0.234 g, 92%).

6-Amino-2-(2,3,4-trifluorophenyl)-5-vinylpyrimidine-4-carboxylic acid (Compound

191)

F

The title compound was prepared as described in Example 92 with methyl 6-amino-2-(2,3,4trifluorophenyl)-5-vinylpyrimidine-4-carboxylate (335 mg, 1.08 mmol) and îsolated as a yellow solid (0.275 g, 86%).

Example 93: Préparation of 4-amino-3-chloro-6-(4-cyano-2-fluorophenyl)-5fluoropicolinic acid (Compound 65)

In a 50-mL round bottom flask, equipped with a stir bar, methyl 4-amino-3-chloro-6-(4cyano-2-fluorophenyl)-5-fluoropicolinate (351 mg, 1.084 mmol) and lithium hydroxide hydrate (100 mg, 2.383 mmol) were dissolved in tetrahydrofuran (2.0 mL), methanol (2.0 mL) and H2O (1.0 mL). The reaction was stirred at rt for 2 h. The solvent was then removed by rotary evaporator. The resulting solid was treated with H2O, which was then

-12517475 adjusted to pH~3.0 with 1 N HCl, and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over anhydrous MgSC>4, filtered and concentrated. The resulting residue was purified by reverse phase chromatography (150 g Ci8, 0-100% acetonitrile in H₂O), as needed, to afford the title compound as a brown solid (0.058 g, 20%).

The following compound was made in accordance with the procedures disclosed in Example 93:

6-Amino-2-(4-iodophenyl)-5-vinylpyrimidine-4-carboxylic acid (Compound 123)

The title compound was prepared as described in Exampled 93 with methyl 6-amino-2-(4iodophenyl)-5-vinylpyrimidine-4-carboxylate (65 mg, 0.177 mmol) and isolated as an offwhite solid (60 mg, 92%).

Example 94. Préparation of 4-amino-3-chloro-6-(3-fluoro-4-(trifluoromethyl)phenyl)-5methylpicolinic acid (Compound 161)

To methyl 4-amino-3 -chloro-6-(3 -fluoro-4-(trifluoromethyl)phenyl)-5-methylpicolinate (0.35 g, 0.96 mmol) in methanol (6.4 mL) was added 2 N NaOH (1.93 mL, 3.9 mmol), and the reaction mixture was stirred at rt for 18 h. The solution was acidified with 2 N HCl and the precipitate was vacuum filtered to afford the title compound as a white powder (199 mg, 59%).

The following compounds were made in accordance with the procedures disclosed in Example 94:

-12617475

4-Amino-3-chloro-6-(4-(difluoromethoxy)phenyI)-5-methylpicolinic acid (Compound

94)

The title compound was prepared as in Example 94 and isolated as a yellow solid (36 mg, 68%).

4-Amino-6-(4-bromophenyl)-3-chloro-5-methylpicolinic acid (Compound 78)

The title compound was prepared as in Example 94 and isolated as a white solid (24 mg, 71%).

4-Amino-3-chloro-6-(4-iodophenyl)-5-methylpicolinic acid (Compound 116)

The title compound was prepared as in Example 94 and isolated as an orange powder (86 mg, 83%).

4-Amino-3-chloro-6-(3-fluoro-4-iodophenyl)-5-methylpicolinic acid (Compound 87)

-12717475

The title compound was prepared as in Example 94 and isolated as a white powder (120.5 mg, 88%).

The title compound was prepared as in Example 94 and isolated as a yellow powder (147 mg, 82%).

Example 95: Préparation of 4-amino-3-chloro-5-fluoro-6-(4-nitrophenyl)picolinic acid (Compound 31)

O

To a solution of methyl 4-amino-3-chloro-5-fluoro-6-(4-nitrophenyl)picolinate (88 mg, 0.27 mmol) in methanol (MeOH; 3 mL) was added 1 Normal (N) aqueous sodium hydroxide solution (NaOH; 3 mL, 3 mmol). The reaction mixture was stirred for 24 h at ambient température. The solution was then concentrated and acidifïed with 2 N aqueous HCl solution. The desired product precipitated out of solution, was colîected in a Büchner tunnel, and allowed to dry overnight to afford a tan solid (84 mg, 100%).

-12817475

Example 96: Préparation of 4-amino-3-chloro-6-(2,3-difluoro-4(trifluoromethyl)phenyl)picolinic acid (Compound 172)

To a mixture of methyl 4-acetamido-3-chloro-6-(2,3-difluoro-4(trifluoromethyl)phenyl)picolinate (115 mg, 0.28 mmol) in methanol (1 mL) was added 2 Normal (N) aqueous sodium hydroxide solution (NaOH; 1.4 mL, 2.81 mmol). The reaction solution was stirred at ambient température for 15 h. The solution was then concentrated, and acidified with a 2 N aqueous HCl solution. The desired product precipitated out of solution. This mixture was extracted (3x) with dîchloromethane, the organics were combined, dried (Na2SÜ4), filtered and the concentrated in vacuo to afford a white solid (94 mg, 90%).

Example 97: Préparation of 4-amino-3-chloro-5-fluoro-6-(4-iodophenyl)picolinic acid (Compound 45)

A 2 M solution of sodium hydroxide (740 pL, 1.5 mmol, 4.0 equiv) was added to a stirred solution of methyl 4-amino-6-(4-iodophenyl)-3-chloro-5-fluoropicolinate (150 mg, 0.37 mmol, 1.0 equiv) in methanol (3.7 mL) at 23 °C. The resulting pink solution was stirred at 23 °C for 3 h. The reaction mixture adjusted to pH 3, using concentrated HCl, and concentrated by rotary évaporation. The residue was slurried in water and vacuum filtered to afford the title compound as a pale pink powder (110 mg, 79%).

-12917475

Example 98: Préparation of 4-amino-3-chloro-6-(2,3-difluoro-4-iodophenyl)-5fluoropicolinic acid (Compound 141)

A 2 M solution of aqueous sodium hydroxide (270 pL, 0.54 mmol, 2.0 equiv) was added to a stirred suspension of methyl 4-amino-3-chloro-6-(2,3-difluoro-4-iodophenyl)-5fluoropicolinate (120 mg, 0.27 mmol, 1.0 equiv) in methanol (2.7 mL) at 23 °C. The heterogeneous white mixture was stirred at 23 °C for 18 h. The reaction mixture was adjusted to approximately pH 4 via dropwise addition of concentrated HCl and concentrated via rotary évaporation. The residue was dissolved in dichloromethane (250 mL), passed through a hydrophobie membrane phase separator, dried ( MgSO₄), gravity filtered, and concentrated by rotary évaporation to afford the title compound as a white powder (110 mg, 92%).

Example 99: Préparation of 4-amino-6-(4-bromo-2,3,6-trifluorophenyl)-3chloropicolinic acid (Compound 162)

A solution of methyl 4-acetamido-6-(4-bromo-2,3,6-trifluorophenyl)-3-chloropicolinate (50 mg, 0.122 mmol, 1.0 equiv) and sodium hydroxide (14 mg, 0.366 mmol, 3.0 equiv) in THF:MeOH:H2O (1:1:0.5; 2.5 mL) was stirred at 20 °C for 2 h. The reaction mixture was acidified to pH 4-5 using 1.5 N HCl and extracted with EtOAc (2x). The combined organic extract was dried over anhydrous Na₂SO₄ and evaporated to dryness under reduced pressure to provide the title compound as a brown solid (30 mg, 65%).

-13017475

Example 100: Préparation of 4-amino-6-(4-bromo-2,5-difluorophenyl)-3-chloro-5fluoropicolinic acid (Compound 42)

To a solution of methyl 4-amino-6-(4-bromo-2,5-difluorophenyl)-3-chloro-5fluoropicolinate (0.160 g, 0.404 mmol) in a 1:1 mixture of MeOH (0.674 mL) and acetone (0.674 mL) was added a 2 N aqueous solution of sodium hydroxide (0.607 mL, 1.213 mmol). The reaction mixture was stirred at 20 °C ovemight. The reaction mixture was concentrated, poured into a 2 N aqueous solution of HCl, and extracted with EtOAc (3x). The combined organic layers were dried over Na₂SO4, filtered, concentrated and dried in vacuo to afford the title compound as a light brown solid (126 mg, 82%).

Example 101: Préparation of 4-amino-3-chIoro-6-(4-(difluoromethoxy)-3fluorophenyl)-5-fluoropicolinic acid (Compound 92)

To a flask charged with MeOH (2 mL) was added methyl 4-amino-3-chloro-6-(4(difluoromethoxy)-3-fluorophenyl)-5-fluoropicolinate (190 mg, 0.52 mmol) and 2 M sodium hydroxide solution (1 mL, 1 mmol). Following 12 h of mechanical stirring, the reaction mixture was concentrated using a rotary evaporator with a water bath température of 40 °C. Water was added to the resulting oil and the solution was slowly acidified by the addition of concentrated HCl until a tan precipitate formed. Filtration using filter paper and a Büchner tunnel afforded the title compound as a tan solid (108 mg, 59%).

-13117475

Table 1. Compound Number, Structure, Préparation and Appearance

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		CK	/Jxl
1			A <A/O N	White Solid	42
			C\ ch₃
			nh₂
		N	^<^Οοη₃
2			'K’Y'^CHs	White Solid	73
	Br^		O
			nh₂
			Ak¹
3	F_x		Λ -Y. /OH N Y	White Solid	100
	Br	-\γΥ	O F
			nh₂
			ΙίΊ ^Cl
4			L /OH N ]<	Brown Solid	97
	F		O
			nh₂
			^ι^ίΑ^^01-12
5			JL /OH N ]<	Orange Solid	92
			O F

-13217475

Compound No.	Structure	Appearance	Prepared as in Example:
6	nh₂ ^H3^C^/A/^CIA A. /OH H ^N 1Γ ^AA ° ΗίΥ 1 F	Yellow Powder	94
7	nh₂ Vy^c1 /X JA /0^ if Y N V ^CH3^AAA o HcA	Tan Powder	85
8	nh₂ A λ \|< CH₃ /A A o Br F F	White solid	98
9	nh₂ ^fÿy^ci A A /0^ r il ^N iT ^CH3A^ A- θ r f	Off-White Powder	66
10	nh₂ x- A A /OH F ri ίΓ n r< ^F>k /AA ⁰H 0	White Solid	98
11	nh₂ Αχ. N X CH₃F\ A A\ /OH Al ^N 1Γ AA ° BU F	White Solid	100

-13317475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		R	///	^CH₂
12			N	^0	Tan Solid	42
	F	F	0	ch₃
			nh₂
		Cl.	k>!
13	fl		X. / 'N	o	Yellow Solid	64
	1^		Ck	ch₃
		F
			nh₂
		Ck	vXz	Cl
14			χΐί X. N	.0	White Solid	98
				OH

			nh₂
		CK	γ\	XI
15	H F^O'	./¼	N	.0 Ck ch₃	Yellow Solid	42
			nh₂
16	il	(i	Ay^CI -¼. N Y	Xk ch₃	Off-White Solid	42
	II		0
			nh₂
17		F. 1	X. N ]f	Xh₂ XH	Yellow Solid	100
	r		0

-13417475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
18		N' J	x° <x 'N y	ch₃zO_x ch₃	Light Yellow Oil	66
	A		0
			nh₂
					XI
19	x o LL			YD OH	White Solid	101
		F
			nh₂
		Y	γΑ/	XI		Orange-
20	Br^	Χγ '<Y	YL <X N	0	OH	Tinged White Solid	97
			nh₂
21		Y X/	ώ N	XI	OH	Off-White Powder	97
	Br^			o
		F
			nh₂
		F_x	XiT	XI
22	Υγ	X> N		O^ ch₃	White Powder	86
	yX^ H(X	F	'F	0
			nh₂	/Ci
23	F ίί ^fal JH H^XT	X-	N	0	<o T O / O	Yellow Solid	42

-13517475

Compound No.	Structure	Appearance	Prepared as in Example:
				nh₂
			N	AJ^c	ch₃
24			/Ύ JY N	/0^ ch₃	White Solid	68
	\'	/¼.		c
		F
				NH'	çh₃
				N'A	0
25			JJ	A	J,oh	Yellow Solid	98
					0
	N
				nh₂	çh₃
				N A	0
26				Λ A N	/0^ CH₃	White Solid	46
	F_x	_s JL			0
	F^x	F	F
				nh₂
				II	Ck ch₃
27		il	Yy'	LL <>L N	UD	Yellow Solid	64
		II 1^	Y		0^ ch₃
			F
				NH	2 CH₃
				N A	0
28				A A /OH f N YY	White Solid	98
			Ay		0
	HC^
				nh₂
				rV	.Cl
29			Ύζ	Λ A N	/0^ Y CH₃	White Solid	46
	Fx	_x JL	A		0
	F'	F	F

-13617475

Compound No.	Structure	Appearance	Prepared as in Example:
				nh₂ ch₃
			N	A^û
30			A	N^<J^Y°^CH₃	Yellow Solid	42
	C	A	J	0
	F'' F
				nh₂
			F^	A?^cî
31				A <A /°h ^N AT	Tan Solid	95
	o.	N^+>	u	0
		II 0
				nh₂
32		(ί	nA/^_Ch₂ /A Ά /°H N ]<	Light Yellow Solid	92
	F^	II		0
	F^	F	F
				nh₂
			Cl
33	\ o ^x7< LL LL	fAA A^A	JL ' N OH	White Solid	98
				nh₂
			Cl_x	ΪΊ θ'
34				A <A /O N	Yellow Solid	86
		\A	o_sch₃
				nh₂ ch₃
35		f	nA/° v\\|ÂAcH₃	Off-White Powder	72
	Br^	k	^'F	0

-13717475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
36		R	υΛι^οη, >L JL /OH N	Off-White Solid	101
			0
	HC^
			NH₂
		N 11	^Y°ch₃
37		II	X L\ /0 n	White Solid	92
	r	Ύ	OH
		F
			nh₂ L^CI
38			/k /OH ^N iT	White Powder	97
	r	T ^F	0
		F
			nh₂
		F_v	Ly^c'
39			A A /OH N	White Solid	98
		AA	0

			nh₂
		h₃c^	1Γί ^c'
40			Ή^γ°^χ0Η₃	Brown Oil	83
			0

			nh₂ ch₃
			X°
41		AA	/L JL /OH N ]<	Tan Powder	98
	RC?		\ o F

-13817475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
42		F- ïT^Y	Λ N	xCI OH	Light Brown Solid	100
	BY		^XF	0
			nh₂
		CI-	Υύ	XI
43			A A N	OH	White Solid	92
	Br^x	JU		0
		F
			nh₂
44		F_x	îiV Y. Y\ N	.Cl Z°x Y ch₃	Off-White Solid	39
			c	o
			Γ
			nh₂
45		F_x	N	XI OH	Pale Pink Powder	97
	r			o
			nh₂	çh₃
46		YiT		/° ^OH	Off-White Powder	98
	BY		F	0
			nh₂
		Cl·		/Cl
47			Ύ N	^.o	White Solid	74
	Br^			CY ch₃

-13917475

Compound No.	Structure	Appearance	Prepared as in Example:
		nh₂
				,ci
		il Ί
48			Αχ	OH	White Solid	98
				0
	HC^
		nh₂
		F^A^ T T	,CI		Off-White
49	\|i	aA_N^		0^ ch₃	Powder	72
	II Br^	J	0
		F
		nh₂
		F. A		,CI
		AA	T	Off-White

50				OH	Powder	98
		A^A		0
		Y F
	hcA	F
		nh₂
		r A.	„ci
		Al ί
51		AL Αχ		„O.	White Solid	73
		A^ N		ch₃
		<A	0
	Br	F
		nh₂
		r /A	zCI
		AA γ
52		Αχ A		o	White Powder	72
	Y Y N		ch₃
	/A JA	o
	Br	F
		nh₂
		^fyS	TH₂
53	F^J	A. <<λ N	0	AA ch₃	Brown Solid	54
		^F
	M
	F	F

-14017475

Compound No.	Structure	Appearance	Prepared as in Example:
			NH₂
			n^A	A A₃
54			Ά. /> N	\/^0H	White Solid	97
	BY			0
			nh₂
		F.	Af	Cl
55	F.		. <A N	lf⁰YH₃	White Solid	67
	r	a_f		O
			nh₂
				Cl
56	F.		N	Z⁰-. / ch₃	Orange Solid	77
	r	xA_f		0
			nh₂
57		R A?	Αγ . xA N	^ch₂ /A Y ch₃	Light Brown Solid	79
	BU			0
			nh₂
58		CK CT	ό N	/^Cl Y CH₃	Off-White Solid	46
		JH 'A		0
	fA F	F
			NH	2 CH₃
			N^	o
59		Αγ-	/A _x N	A A- Y CH₃	White Powder	86
	HC^		'F	o

-14117475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		R	-^X^ch₂
60			L X N J CH₃	White Solid	88
			0
	HC^
			nh₂
61	F^. F^l F	Y AA ΑγΧ F	p^ï>r^/^cH₂A <X /OH ^N ιΓ 0 F	Brown Gummy Oil	100
			nh₂
		F.	^Jx^/Cl
62			X JL /OH nv	Tan Powder	97
		XX	o
			nh₂ ch₃
			X /0 N
63		îTV	A <A /OH ^N [Γ	White Solid	96
		M	0
	fA F	F
			nh₂
		N II	'A^/0ch₃
64	f	II	X -X /Ο- Ν ]< CH₃	White Solid	41
	V LL LL	Y^F F	0
			nh₂
		F_x	/L/^Cl
65			X -X /OH N \|T	Brown Solid	93
		X/X	0 F

-14217475

Compound No.	Structure	Appearance	Prepared as in Example:
				nh₂
			S	Y
66			V	x Y/,⁰N y'	Brown Solid	64
	r	A	Y>	Ck ch₃
			F
				nh₂
67		y?	Λ	Ky ΐγγ°\Η₃	Dark Brown Viscous Oil	76
	Br^	Y		0
				nh₂
68			I J! Yv^	Αγ x /OH N lT	Off-White Solid	100
	1		T ^F	0
			F
				nh₂
			F. ]	y
69	F.	γ	1 Άγ'	X A /OH n Π	White Solid	100
	r		Y-F	O
				nh₂
			F	Æ^CI
70			ilY	/Y ΥγΟ N	White Solid	59
	R p		Y	/0 H₃c
		F	F
				nh₂
71			F. \ \|f	Yjf^cl /Y /OH N ]<	Off-White Powder	98
				0
	HC	Y	F

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂ ch₃
72		rr	AA M'_¥ ^oh	Yellow Powder	98
			o
			nh₂
		Ck	A/^ci
73		rr	k <A/O^ n rr ch₃	White Solid	69
	BU		0
		F
			nh₂
			at
74			<A /OH n rr	White Solid	98
	bA	ΆΑ	, 0 F
			nh₂
			/L· /0^ n y ch₃
76			A <A /OH n rr	White Solid	95
	F. F i F	AJ F	o F
			nh₂
			AA
77			JÎ A /0 n r^	White Solid	92
	r	Jl Ί	OH
		F
			nh₂
		h₃c	^A/^ci
78		rr	J-L <A /OH n rr	White Solid	94
	bA		0

Compound No.	Structure	Appearance	Prepared as in Example:
79	nh₂ ^h ₃ ^c^X/^CI ^N F	Off-White Solid	65
80	nh₂ Il ^N 1Γ ^CH3 '0- ₊A^\ ⁰ II 0	Yellow Solid	41
81	nh₂ H₃C^4^.CI JL -A/0^ Y N Y ch₃ _D J\<J ⁰ Br	Pale Orange Powder	70
82	nh₂ ch₃ n /A- J\ A II ^N Π ^CHs À 0	Yellow Powder	66
83	nh₂ h₃c^J^.ci hT^°'CH₃°	Orange Solid	40
84	nh₂ J\ \|< CH₃J\ Yf r il ^N iT ^CH3j^/A ⁰ <$> ΊΓ F HC^ 1 F	White Powder	86

-14517475

Compound No.	Structure	Appearance	Prepared as in Example:
		nh₂
	F. n		x-CI
85	II	N	.0^ Y ch₃	White Solid	42
	A_f		0
		nh₂
			Y^CH₂
86	[XX	zk X N		White Solid	98
			OH
	F'G T F F
		nh₂
	H₃C	Ί	/^Cl
87		N	^.OH	White Powder	94
			0
	F
		nh₂
	N		ch₃
88		. Y N	^,ΟΗ	White Solid	97
			o
		nh₂
	N	^\- II	XK ch₃
89		x. N	^,ΟΗ	White Solid	98
			0
	F
		nh₂
	1 ί		Cl
90	1 II ΠΊΓ	N	X CH₃	White Solid	77
	ιΛχ		0
	F

-14617475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
			hY	^Cl
91		I	zk 9 N		„OH	White Solid	97
	BU	ÇL	F	0
		F
			nh₂
			^z K		Cl
92	F		7 N		OH	Tan Solid	101
	F A)	Jl F		0

			nh₂
			Ύ/	.Cl
93			N	(	Αη₃	White Solid	74
	Br^^	A_f		o
			nh₂
		^H3^CA:		.ci
94	Λ		II		OH o	Yellow Solid	94
			nh₂
				^Cl
95			L JI N		.Ck ch₃	Yellow Solid	41
	+ Z / o 1	Y		0
	II 0
			nh₂
		Cl^		Cl
96		π	N	Y CH₃	Gray Solid	68
	1^			0

-147-

Compound No.	Structure	Appearance	Prepared as in Example:
		nh₂	n
		nA	ch₃	Off-White
97	YA	A d^ ' N	A CH₃	Solid	72
	„ /A-L·		0
	Br
		N H;	>
		lA	A^ch₂
98		A -x	L /O_x	Yellow Solid	39
		< N	Y ^ch3
	JL		o
	d<
	vx
		nh₂
	F.	νγ	,CI
99	\ Π	/L· N	/Ο- Υ ch₃	White Powder	66
	JL· L·		0
	i^A	F
	F
		nh₂
	Bk	Π A	.CI	Light Brown
100	^F\X\-	A A	n	67
		N	Y ch₃	solid
	Jl A		o
	r	T
		nh₂	n
		N A	ch₃
101	R	A A	Cl·	White Solid	67
			Y CH₃
	AA^A		o
		F
			nh₂ ch₃
			-L· /0
		Ν'
102	F if	γ	A /OH N γ	Yellow Solid	98
	>..J..	A	0
	F 0

-14817475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		F_x	/A /Cl
			-A Au
103	F		a aL /0^ n AU ^xch₃	Tan Solid	56
	An-		0
	F 0	F
		F
			nh₂
			/L A
			A Aa
104			A /0^	Yellow Solid	56
	f r	AA	n AU ^sch₃
			0 F
			nh₂
		eu A .ci
			Τι A
105	F		JL uA A n A^	White Solid	98
	A„		J OH
	F 0
			nh₂
			/J A. n Aa ^ch₃
106			Λ aA /0^	White Solid	56
	F r	Aa	n AU ch₃
	aJ		0
	F O
			nh₂
		F.	^Ach₂
107		Jl	s uL /0^	Tan Solid	57
	A	AA^	n AU ch₃
			0
			nh₂
		F	. /J\ /Cl
			A AA	Pale Orange	98
108			/A- A\ /OH
		Au	N AU	Powder
		Àu	X 0
	<<a		F
	HC^

-14917475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		F^,	/L· .ci
		Ji			Light Yellow
109	[j		A\ ^N n	-O\ ch₃	Solid	71
		.uk	0
	BU	F
		F
			nh₂	Cl
			n	Off-White
OH
110			N	Solid	92

	Br'	AA		0
		F
			nh₂
		h₃c.	Υί	.Cl	Waxy Yellow	40
111	F		A A N	V°ch₃	Solid
	a ,	AA		o
	F O
			nh₂
		H₃C.	1 /C
		J	γ·'·		Off-White
112		Ί	. <A N Y	.θ\ ch₃	Solid	70
	BU		O
		F
			nh₂	Cf
			nAz	ch₃
113		Av	A A N	OH	White Solid	92
	Br'	o		0
		F
			nh₂
			X .ci
		ί	Ί
114		1 ^/Υγ^/'	- A ^N n	^x ch₃	White Solid	44
	BU	\,^>A	0
	V F
		F

-150-

Compound No.	Structure	Appearance	Prepared as in Example:
115	nh₂ /^ AL /0^ r il ^N 1Γ ^CH3A o bc F	White Solid	75
116	nh₂ H₃C^X/^CIï^oh1^^ °	Orange Powder	94
117	nh₂ ^fAAa^x^^CH2 A A\ /OH Γ\|Υ N d AAA °	Light Brown Solid	100
118	nh₂ Ay^ci\⁰'^CH3 γγ ⁰	Purple Powder	66
119	nh₂ A^ ,o^ N CH₃ XFy	Yellow Solid	100
121	nh₂ FyVci /T\ .JA/Οχ. A II N CH₃ AAL ° HC^	White Powder	86

-15117475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
			II	<Ck ch₃
122		ν' Il	JL A N	.0	White Solid	74
	Br^	M F	F	Ck ch₃
			nh₂	ch₂II
123			--	Off-White Solid	93
	r			11 0
			nh₂
			îiA	.Cl
124			Y N	OH	Yellow Solid	98
	r		F	O
			NH;	?
		Cl·	y/A	Cl
125			/Y N	L.o	White Solid	98
	Br^x			OH
			nh₂
			γΑτ	^Cl
126		rfA^	-Y Ύ N	Y°^XCH3	Yellow Solid	86
		LA		0
			nh₂	Cl
127	F.		. <î>Y N	/<Y '[f ch₃	White Solid	77
	Br^			o

-15217475

Compound No.	Structure	Appearance	Prepared as in Example:
128	nh₂ f^JYY ⁰ ^F F F	White Solid	96
129	nh₂ JU /Οχ r il ^N if ^CH3J·^ À ° r f F	White Powder	76
130	nh₂ ch₃/L /0 n ίί^Ί^ Ν^γ°ΧΗ₃	White Solid	42
131	nh₂ _n<X.OH JL o	Light Brown Solid	100
132	nh₂ F.Â.CI /Jv il ^N lT ^CH3 ,Τγ¹ F	Tan Powder	66
133	nh₂ Tjf^cl Y \|[ ^N [Y ^CH3 YY HC^ 1 F	White Powder	86

-15317475

Compound No.	Structure	Appearance	Prepared as in Example:
		nh₂
	F.	x
134	X_r	JL A\ /OH N	White Solid	95
		0
	F A F
		nh₂
	F.	A^CI
135		JL J\X n X	White Solid	42
	ALA F	ch₃
		nh₂
136	H₃C	V^ci N ]< CH₃	Red-Orange Solid	65
		O
		nh₂
137		A Aa N ]< CHg 0	Light Tan Solid	39
	fX t F F
		nh₂
	F	X/^Cl
138		AL <A x nX^	Tan Powder	72
	Βι-ΆΑ	/0 hX
		nh₂
139	F. Il 1	^zxX^ch₂ k XA N ]< CHg	White Solid	81
	,AJ	0

-15417475

Compound No.	Structure	Appearance	Prepared as in Example:
140	nh₂ ΎγΟΙ J^> J\ /OH F ίΐΊ ^N lT /A JL A\ o FO^^F	Off-White Solid	101
141	t O ô \=o AL /----\ U LL }----(	White Powder	98
142	nh₂γγ\| /A J\ a. il 1^ ^{N CH}3 ALA °	Solid	42
143	nh₂ W /^ Al <A ah F A A N /A JLA o	White Solid	98
144	nh₂ _F A^Aa' Α^Αγ J\A A JL A A h₃c F 1 1 ³ F F	White Solid	60
145	nh₂ /^ JL J\A fAf ^N /A OH F	White Solid	92

-15517475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		CL	A/^Cl
146		Ar	\ <A /OH n rr	White Solid	96
	F\/	\A	0
	A	F
			NH₂
		F. \|ί	AA
147		II	x <A /OH n rr	Tan Solid	98
	Br	γζ	0
		F
			nh₂ ch₃
		F	ïV
148		Ar	A JA/Ο n r^	White Solid	60
	F^, F^ F	Ά F	χθ h₃cT
			nh₂
		F-. \|\|	rr
149	fi	II	N^y^/0^cH₃	White Solid	41
	V LL LL	LL	0
			nh₂
		F.	^V^CH₂
150		ΆΑ	A JA /OH n rr	Tan Solid	101
			0

			nh₂
		H₃C \|	Ay
151		1 ι ^ίΓ	X χθ^ n rr ch₃	Yellow Solid	87
			0
	HCT	T F

-15617475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
				„CI
152	O -f LL	A	ü. <jx N	A Y CH₃o	White Solid	56
		F
			nh₂
		Cl		.Cl
153			A L/O n	Yellow Solid	98
		AA		OH
	H(X
			nh₂
			? il	/0^ ch₃
154			A J N	xOH	Tan Powder	98
		La F	'F	O
			nh₂
		h₃c	Ax^	Cl
155		I F	A	/Οχ ch₃ 0	White Flaky Solid	40
			NH;	?
		F		.Cl
156		AA	Αχ N	Xo	White Solid	98
	A	JLJ		OH
	F
			nh₂
		F.	Al	Cl
157	(		A N	OH	Tan Powder	97
	1 r			0
		F

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
			X /Cl
			AA		Dark Brown
158		AA^	A ^N n	A ch₃	Semi-Solid	76
	r	yX	0
			nh₂
			A-ai
159		j	A-	n	White Solid	68
		aa	N H	ch₃
		\ X-	0
	r	F
			nh₂
		F^	A .ci
			il Ί
160		[ΓΥ	< X N A	A f ch₃	White Solid	41
		AA	0
	hX	1 ' F
			nh₂
		h₃c	M	xCI
161		AX	aL X N	OH	White Powder	94
	F_x	Il 1		0
	F'	F F
			nh₂	Cl
		F	A/
162		rAr	A A^ N	OH	Brown Solid	99
		JA		0
	Br Ύ	F
		F
			nh₂
		Fx	TiT	XI	Off-White
163		aa		OH	Powder	98
		X- X		0
	Br'	F

-15817475

Compound No.	Structure	Appearance	Prepared as in Example:
164	nh₂ ïl J^^CH2 ^N [f °^ch3	Light Yellow Solid	80
165	nh₂ F. Y /A A\ /0. A< Y< N Y ch₃ ^FV^ZY ⁰ ^F F	White Solid	41
166	nh₂ ch₃ n-V⁰ N^Sf° AH₃γγΑ ⁰ HCY	Yellow Solid	86
167	nh₂ FyL^cl ΥΥγΥ_ΝΥγ/0Η ΆτΆυ ⁰ ^F F F	White Solid	95
168	nh₂ Ay yAⁿ π^0Η	Brown Solid	97
169	nh₂ ΑγΟ /Y /A /Y /OH r il ^N if ΑΛ ⁰ \|Y YY^F	Off-White Powder	98

-15917475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		^Cl\	A
170	O LL LL	AA^	A A/O N γ o_xch₃	White Solid	42
			nh₂
		N^x II	Α°Αη₃
171		II A^	N γ^	White Solid	69
	Br A	A	CL ch₃
		F
			nh₂
			Αγ
172		AA^	A /OH N AA	White Solid	96
	F^T F	1 1 Άτ F	0
			nh₂
		^C\|\/	a,ci
173		Άγ^-	/OH ^N iT	Yellow Solid	98
		A	o
			nh₂
174	F\/	F	A^CI A A//O N A^ OH	Off White Solid	62
	F	F
		NH;
175		N A A /	>A < ch₃JL o	Tan Solid	57
	Γ*	r^ N	Y ch₃
			0

-16017475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
				_XCI
		F	riT
176			A A N		zO_xch₃	White Solid	63
		Y		0
	F	F
			nh₂
				.Cl
		F		A
177	F	Îl	-Z 7 N		.0^ 7 CH,	White Solid	63
	x .			0
	F 0	V F
			nh₂
			R A		zCI
		F		J	Off-White
Z.0
178		H	Y N		Solid	62
	F.	A\A		OH
	F	F
			nh₂	/Cl
		F	A ïï
179	Γ	π	A A N		ζθχ ch₃	White Solid	63
	1 H₃C7	..J		0
		F
			nh₂
			rAr	zCI
180					.OH	White Solid	101
	i		^vn^/x	0

			nh₂
		F.	Ay	Cl	ch₃	Off-White
181			<> A N		1 0	Solid	57
		A		0

-16117475

Compound No.	Structure	Appearance	Prepared as in Example:
183	nh₂ /x. A A\Ak fl ^{N CH}3 \A ⁰ F	Pale Yellow Oil	46
184	nh₂ ^{f f}Ay^ci A^ A- A Αχ A γ n ]< ch₃ A A 0 Η₃(Υγ F	White Solid	63
185	nh₂ F CH₃ AA_n Αγ° /AA 0- H₃C ch₃ F	White Solid	63
186	nh₂rAai γΆγ^ n γ/°ΥΗ₃ AA ° F F F	White Solid	41
187	nh₂f A^A⁰¹JL /A- Ax/O F II 1 ^N 1 A /AA ^0H F 0 F	White Solid	98
188	nh₂ ^f A^CIγ\- /AA ⁰ H₃c Y^ F	White Solid	62

-16217475

Compound No.	Structure	Appearance	Prepared as in Ëxample:
		nh₂
		Yy	Cl
189	F\/^	γΐ <î>\ κχ N	X ch₃	White Solid	46
			0
		nh₂
		Y	^Cl
190		fY^N	\ /Ύ Y CH₃	White Solid	43
	0^/	M	0
	/0 H₃C
		nh₂ 1
		A	^CHz
191	il		^OH	Yellow Solid	92
	H	T ^F	II 0
		F
		nh₂
		F^/L	/Cl
192	(i	'''^γ'^ι^	\ /O. Y ch₃	White Solid	43
	O^/k	A	0
	nh₂
		nh₂
		F ^Ν<\|ί	^x ch₃
193	C		\ /0^ Y CH₃	White Solid	63
		y-	0
	F	F
		nh₂
		^F Y	Cl n
194		^N	Λ,ο	White Solid	62
	H₃c	Jl 1 F	OH

-16317475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
			F. Λ	.XI Y
		F	V
195	F		/X Y N	J-Lxh	White Solid	98
	Λ		0
	F	⁰
		F
			nh₂	XI
			Ar
196		ifY	U A N	S. /<X Y ch₃	White Powder	47
		o		0
	F	F
			nh₂\|
		N II	Ί	Y₂
197	(		Ά	rf°XH₃	Yellow Solid	39
	1		0
		Y F
		F
			nh₂
		F.		/Cl
		F	YY
198		[il	-X JJ. N	. XX Y ch₃	White Solid	63
		U		0
		F
		nh₂
		^F\x^:	k/C!
199	Î\|	N y	X-. ch₃	Tan Solid	57
	Π	A_r	0
		1 ^F
		F
			nh₂
		F.	Y/	Cl
200	F.	_ Jl	X.	n	White Powder	40
			N	A ch₃
				0
	F	F

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		F	A x. X Y ch₃
201		[fA	A- A⁰	White Solid	62
	H₃C	AJ	OH
		F
			nh₂
		F	[X^ci
202		A	A A x	White Solid	63
	A	AJ F	0, ch₃
			nh₂
		F	A a XX^ CH₃
203		X	A> Α/θ N X^	White Solid	62
	F.	AA	OH
	F	F
			nh₂
		F.	X^ci
204		XX	t Ax. N CH₃	White Solid	41
	F^		O
			nh₂
		F	A
205		Ar	A Ja N X^ CH₃	White Solid	62
		AJ	o
	F	F
			nh₂
		^F-X<^CI
206		\ Ax AZ^X	Ax. N CH₃	Tan Solid	57
		X	0

-165X

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂ ch₃
			A /0
		N
207	f	T¹¹	Υγ^0Η	Tan Solid	101
		J	0
			nh₂
			A /0^
		F	CH₃
208	f\|	Αγ	A A/°- N Y CH₃	White Solid	63
	II	A	0
		F
			nh₂
			Y /Cl
			r iL·
209			A A .cl	White Powder	47
	if	Ύγ	N ]f CH₃
	F^A.	A	0
	P
			nh₂
		F	\ /A /^ci
		F	Τι ίΓ
210	R	Y/	A A /OH N ff		95
			0
	h₃A
			nh₂
			Jx/Cl Τι ιΓ
211	f\|		IL A^ N ]f CH₃	White Solid	41
	II	-îA-	0
	h₃c^	F	F
			nh₂
		F	. A /Cl
			Αί
212		AA	A /OH ^z N Y		95
		AJ	0
	HsC^	F

-16617475

Compound No.	Structure	Appearance	Prepared as in Example:
			nh₂
		F_x	A^	.Cl
213		ΓΥ	-L <^V N	A CH₃	White Solid	41
	h₃A	V		0
		F
			NH;	ch₂
		Fv	A^	H
214		Av	YL / N	Ah	White Solid	98
	ci^	O		0
		F
			nh₂	ch₂
		Fv	ΙΊ	y
215			t A N	A V ^CH3	White Solid	90
	cr			0
		F
			nh₂
		F-v	Æ	.Cl
216	Γ	A	A N	/0^ V CH₃	White Solid	42
	1 cr	J		o
		F
			NH;
		F.	A	I o ô \	Off-White
217		W	JN	Solid	97

	cr	AA		0
		F

-16717475

Table 2. Analytical Data for Compounds in Table 1

Compd. No.	mp (°C)	IR (cm¹)	Mass’	’H NMR¹	¹³C or ¹⁹F NMR
1	133.4- 134.8		ESIMS m/z 322 (1M+H]⁺)	'H NMR (400 MHz, CDC1₃) δ 7.81 (m, 4H), 5.42 (s,2H), 4.02 (s,3H)
2	186- 187		ESIMS m/z 373 ([Μ-H]' )	‘H NMR (400 MHz, CDC1₃) δ 7.78 (dd, J = 9.0, 6.5 Hz, IH), 7.37 (dd, J = 9.6, 5.6 Hz, IH), 5.43 (s, 2H), 4.01 (s, 3H), 3.95 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ-113.66,113.70, -117.53,-117.58
3	172— 174		ESIMS m/z 364 ([M+Hn	‘H NMR (400 MHz, DMSO-4₆) δ 7.897.84 (m, 2H), 7.26 (d, J= 1.2 Hz, IH), 6.85 (s, 2H)	¹⁹FNMR (376 MHz, DMSO-rf_d) δ 108.94,-108.99, -114.18,-114.22
4			ESIMS m/z 375 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-J₆) δ 7.85 (m, 2H), 7.69 (m, 2H), 7.24 (s, IH), 6.73 (br s, 2H)
5	164- 168			‘H NMR (400 MHz, DMSO-<7₆) δ 13.65 (s, IH), 8.12-7.89 (m, 2H), 7.80 (dd,J = 8.0,1.6 Hz, IH), 7.32 (d, J = 4.8 Hz, 2H), 6.66 (dd, J = 17.7, 11.4 Hz, IH), 5.75-5.41 (m,2H)	^l9FNMR (376 MHz, DMSO-i7_d) δ-111.46
6	175.0- 176.5		ESIMS m/z 303 ([Μ-H]’ )	Ή NMR (400 MHz, DMSO-<7₆) δ 13.38 (s, IH), 7.62 (t,J = 7.7 Hz, IH), 7.40 (dd, J= 10.4, 1.5 Hz, IH), 7.31 (dd,J = 7.9,1.6 Hz, IH), 6.51 (s, 2H), 4.59 (s, IH), 2.09 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-J₆) δ -111.32
7	127- 130	IR (thin film) 3478 (s), 3374 (s), 3239 (s), 2955 (w), 1731 (m), 1624 (m) cm’¹	ESIMS m/z 305 ([M+Hf)	'H NMR (300 MHz, CDCfi) δ 7.91 (m, 2H), 7.58 (m, 2H), 4.90 (br s, 2H), 3.99 (s, 3H),3.16(s, IH)
8	126128 (dec)		ESIMS m/z 360 ([Μ+ΗΠ	'H NMR (400 MHz, DMSO-<7₆) δ 13.64 (s, IH), 7.74-7.56 (m, 2H), 7.45 (s, 2H), 3.76 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-iZg) δ 131.53,-131.58, -136.08,-136.14

-16817475

Compd. No.	mp (°C)	IR (cm'¹)	Mass’	’H NMR^b	¹³C or ^,9F NMR
9	136- 138	IR (thin film) 3489 (s), 3381 (s), 3233 (m),3199 (m), 3083 (w), 3000 (w), 2954 (m), 2853 (w), 1737 (s), 1622 (s) cm'¹	ESIMS m/z 425 ([M+Hf)	*H NMR (400 MHz, CDC1₃) δ 7.88 (dd, J = 8, 1.5 Hz, 1H), 7.55 (dd, J = 10,1.5 Hz, 1H), 7.33 (dd,J = 8.5, 8 Hz, 1H), 4.94 (brs, 2H), 3.96 (s, 3H)
10	170.4- 172.1		ESIMS m/z 315 ([M+Hf)	*H NMR (400 MHz, DMSO-</₆) δ 7.97(d, 2H), 7.30(m, 5H), 6.72(s, 2H)
11	132- 133		ESIMS m/z 359 ([Μ-H]' )	'H NMR (400 MHz, DMSO-î/₆) δ 7.86 7.73 (m, 2H), 7.43 (s, 2H), 3.75 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-</₆) δ 114.36,-114.40, -116.52,-116.57
12	77-78		ESIMS m/z 359 ([M+Hf)	'H NMR (400 MHz, CDClj) δ 7.86 (dd, J = 9.0, 6.9 Hz, 2H), 7.69 (t, J =7.8 Hz, 1H), 6.90 (dd, J = 18.1, 11.6 Hz, 1H), 5.74 (dd, J= 11.6, 1.3 Hz, 1H), 5.60 (dd, J= 18.1, 1.3 Hz, 1H), 4.78 (s, 2H), 3.94 (s, 3H)
13			ESIMS m/z 442 ([M+H])	*H NMR (400 MHz, DMSO-</₆) δ 7.95 (dd, J= 8.1, 6.7 Hz, 1H), 7.47 (dd, J = 9.1, 1.9 Hz, 1H), 7.22 (dd, J =8.1, 1.9 Hz, 1H), 7.14 (s, 2H), 3.87 (s, 3H)	^,9F NMR (376 MHz, DMSO-</₆) δ-95.18
14	178.0- 179.7		ESIMS m/z 308 ([M+Hf)	‘H NMR (400 MHz, DMSO-rf₆) δ 7.95 (d, 2H), 7.80 (d, 2H), 7.09 (s, 2H)
15	102.4- 103.6		ESIMS m/z 363 ([M+Hf)	‘H NMR (400 MHz, CDCI3) δ 7.72 (d, 2H), 7.24 (d, 2H), 5.42 (s, 2H), 4.02 (s, 3H)
16			ESIMS m/z 306 ([M+Hf)	‘H NMR (400 MHz, DMSO-î/₆) δ 8.01 (m, 2H), 7.79 (dd, J = 8.1,1.5 Hz, 1H), 7.30 (d,J= 1.5 Hz, 1H), 6.96 (s, 2H), 3.89 (s, 3H)

-16917475

Compd. No.	mp (°C)	IR (cm'¹)	Mass⁸	’h nmr‘	¹³C or ¹⁹F NMR
17			ESIMS m/z ([M+Hn	‘h NMR (400 MHz, DMSO-î/₆)ô 13.12 (s, 1H), 7.87 (d, J = 8.4 Hz, 2H), 7.66 (d, 7 = 7.6 Hz, 2H), 6.75 (dd,7 = 17.8, 11.5 Hz, 1H), 6.41 (s, 2H), 5.55 (dd, 7= 14.2, 1.1 Hz, 1H), 5.52 (dd, 7 = 7.8,1.1 Hz, 1H)	¹⁹F NMR (376 MHz, DMSO-7₆) δ -145.75
18			ESIMS m/z 387 ([M+H]⁺)	‘H NMR (400 MHz, CDClj) δ 8.04 (m, 2H), 7.77 (m, 2H), 5.36 (br s, 2H),4.01 (s, 3H), 3.91 (s, 3H)
19	113- 115	IR (thin film) 1025.80, 1047.25,1126.02, 1225.15,1266.03, 1299.98, 1386.12, 1481.90, 1515.13, 1585.75, 1633.93, 1721.56, 2536.01, 3199.39,3331.39, 3471.03 cm·'	ESIMS m/z 369 ([M+H]*)	‘H NMR (400 MHz, DMSO-7₆) δ 13.70 (s, 1H), 7.47 (ddd, 7 = 9.2, 7.2,2.0 Hz, 1H), 7.40 (d, 7= 3.0 Hz, 1H), 7.37 (t, 7 = 72.3 Hz, 1H), 7.07 (s, 2H)
20	149- 152		ESIMS m/z 347 ([M+H]*)	NMR (400 MHz, DMSO-7₆) δ 7.85 7.77 (m, 2H), 7.75 7.68 (m, 2H), 6.94 (s, 2H)
21	117- 120	IR (thin film) 3468 (s), 3334 (s), 3198 (s), 1717 (w), 1629 (m), 1573 (w) cm'¹	ESIMS m/z 365 ([M+H]*)	Ή NMR (400 MHz, DMSO-7₆) δ 7.88 (dd, 7 = 9, 8 Hz, 1H), 7.82 (dd, 7=9,1.5 Hz, 1H), 7.70 (d,7 = 9 Hz, 1H), 6.73 (brs, 2H)
22	190- 192	IR (thin film) 3512 (m), 3411 (s), 3248 (s), 2954 (w), 1730 (m), 1616 (m) cm’¹	ESIMS m/z 341 ([M+H]*)	‘H NMR (400 MHz, CDC1₃) δ 7.33 - 7.35 (m, 2H), 4.98 (br s, 2H), 3.98 (s, 3H), 3.43 (s, 1H)
23	166.4169.0		ESIMS m/z 329 ([M+Hf)	‘H NMR (400 MHz, CDCI3) δ 7.95 (d, 2H), 7.31 (m, 3H), 6.85 (s, 2H), 3.92 (s, 3H)
24	169- 170		ESIMS m/z 422 ([M+H]*)	*H NMR (400 MHz, CDCI3) δ 7.58 - 7.43 (m, 2H), 5.53 (s, 2H), 4.00 (s, 3H), 3.95 (s, 3H)

-17017475

Compd. No.	mp (°C)	IR (cm¹)	Mass“	’H NMR^b	¹³C or ¹⁹F NMR
25	185.2- 186.1		ESIMS m/z 271 ([M+Hf)	'H NMR (400 MHz, DMSOY₆) δ 13.6 (s, 1H), 8.40 (d, 2H), 7.96 (d, 2H), 7.46 (s, 2H), 3.79 (s, 3H)
26		IR (thin film) 3401, 1739,1638 cm⁴	ESIMS m/z 346 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-riû) δ 8.19 (t, J= 16.1 Hz, 1H), 8.11 (d, J = 12.3 Hz, 1H), 7.92 (t,J=7.9 Hz, 1H), 7.74-7.46 (m, 2H), 3.92 (s, 3H), 3.76 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-</₆) δ -59.9,-115.7, -116.0
27			ESIMS m/z 403 ([M+H]⁺)	'H NMR (400 MHz, DMSO-îZ₆) δ 8.00 7.87 (m, 2H), 7.82 (dd, J =8.3,1.8 Hz, 1H), 7.49 (s,2H), 3.90 (s, 3H), 3.74 (s, 3H)	¹⁹FNMR (376 MHz, DMSO-<4) δ -95.51
28	170.7- 171.3		ESIMS m/z 270 ([M+H]⁺)	'H NMR (400 MHz, DMSOY) δ 13.6 (s, 1H), 8.25 (d, 2H), 7.59 (d, 2H), 7.36 (s, 2H), 4.35 (s, 1H), 3.77 (s, 3H)
29	145- 146		ESIMS m/z 349 ([M+Hf)	‘H NMR (400 MHz, CDC1₃) δ 7.79 (dd, J = 15.8,9.9 Hz, 2H), 7.66 (t, J =7.7 Hz, 1H), 7.12(s, 1H), 4.90 (s, 2H), 4.02 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -61.3,-113.9
30	122.0- 123.6		ESIMS m/z 343 ([M+H]⁺)	*H NMR (400 MHz, CDClj) δ 8.33 (d, 2H), 7.27 (d, 2H), 5.84 (s, 2H), 4.03 (s, 3H), 3.95 (s, 3H)
31	180- 181			'H NMR (400 MHz, DMSO-</₆) δ 13.71 (s, 1H), 8.40 - 8.33 (m, 2H), 8.13 (d, J = 8.3, 2H), 7.07 (s, 2H)
32	168- 171		ESIMS m/z 390 ([M+Hf)	*H NMR (400 MHz, DMSO-J₆) δ 13.68 (s, 1H), 8.28 (d, J = 8.2 Hz, 1H), 8.20 (d, J= 12.2 Hz, 1H), 7.94 (t, J =7.9 Hz, 1H), 7.35 (d, J = 27.9 Hz, 2H), 6.68 (dd, J = 17.7,11.5 Hz, 1H), 5.75 - 5.46 (m, 2H)	¹⁹F NMR (376 MHz, DMSO-4) δ -59.97 (d, J= 12.2 Hz), 115.77 (q, J= 12.2 Hz)

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	’H NMR^b	¹³C or ^WF NMR
33	146.3- 147.6		ESIMS m/z 349 ([M+H]*)	’H NMR (400 MHz, DMSO-4) δ 13.7 (s, IH), 7.68 (d, 2H), 7.32 (d, 2H), 6.96 (s, 2H)
34	164.2- 166.8		ESIMS m/z 321 ([M+H]*)	’H NMR (300 MHz, CDC1₃) δ 6.30 (m, 5H), 5.35 (s, 2H), 3.98 (s, 3H)
35	163- 165	IR (thin film) 3416 (s), 3355 (w), 3300 (m), 3162(s), 2957 (w), 1730 (s), 1637 (s) cm'¹	ESIMS m/z 358 ([M+H]*)	‘H NMR (400 MHz, CDC1₃) δ 7.84 (t, J = 9 Hz, IH), 7.31 7.37 (m, 2H), 5.41 (br s, 2H), 3.99 (s, 3H), 3.93 (s, 3H)
36			ESIMS m/z 282 ([M+H]')	’H NMR (400 MHz, CDC1₃) δ 7.93 - 7.84 (m, 2H), 7.64-7.54 (m, 2H), 6.75 (dd,J = 17.8,11.5 Hz, IH), 6.36 (s, 2H), 5.57 (dd, J = 17.8, 1.4 Hz, IH), 5.50 (dd,J = 11.5,1.4 Hz, IH), 4.31 (s, IH)	’⁹F NMR (376 MHz, CDC1₃) δ -141.43
37			ESIMS m/z 390 ([M+H]*)	‘H NMR (400 MHz, DMSO-î7₆) δ 13.57 (s, IH), 8.02-7.92 (m, 2H), 7.85 (dd,J = 8.2,1.8 Hz, IH), 7.41 (s, 2H), 3.75 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-</₆) δ -95.59.
38	288293 (dec)	IR (thin film) 3473 (s), 1588 (m) cm'¹	ESIMS m/z 411 ([M+H]*)	’H NMR (400 MHz, DMSO-</₆) δ 7.74 (m, IH), 7.55 (m, IH), 7.02 (d,J= 1.5 Hz, IH), 6.30 (brs, 2H)
39			ESIMS m/z 292 ([M+Hf)	’H NMR (400 MHz, DMSO-J₆) δ 8.08 7.92 (m, 4H), 7.03 (s, 2H)
40			ESIMS m/z 301 ([M+H]*)	’H NMR (400 MHz, CDC1₃)6 7.55 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H), 4.83 (s, 2H), 3.96 (s, 3H), 3.12 (s, IH), 2.16 (s, 3H)	’³CNMR(101 MHz, CDC1₃) δ 165.71, 155.51, 149.15, 145.10, 140.11, 132.02, 129.34, 122.02, 116.77, 113.59, 83.42,77.90, 52.87,14.65

-17217475

Compd. No.	mp (°C)	IR (cm’¹)	Mass⁸	Tl NMR^b	^,3C or ¹⁹F NMR
41	155165 (dec)	IR (thin film) 3297 (s), 3218 (s), 2938 (w), 1618 (s), 1576 (m) „ -i cm	ESIMS m/z 288 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-4) δ 7.80 (t, J =8 Hz, IH), 7.35- 7.40 (m, 2H), 6.66 (br s, 2H), 4.41 (s, IH), 3.76 (s, 3H)
42	156- 157		ESIMS m/z 382 ([M+Hf)	’H NMR (400 MHz, DMSO-7₆) δ 13.63 (s, IH), 7.92 (dd, 7 = 9.0, 5.7 Hz, IH), 7.61 (dd, 7=8.4, 6.3 Hz, IH), 7.06 (s, 2H)	¹⁹F NMR (376 MHz, DMSO-7₆) δ 113.46,-113.50, -117.37,-117.41, -117.45,-117.49, -138.28,-138.36
43			ESIMS m/z 701 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-<Z₆) δ 13.72 (s, IH), 7.82 (dd, 7 = 8.3, 7.3 Hz, IH), 7.60 (dd, 7 = 9.8,2.0 Hz, IH), 7.40 (dd, 7 = 8.3, 2.0 Hz, IH), 7.06 (s, 2H)	¹⁹F NMR (376 MHz, DMSO-J_à) δ -108.25
44			ESIMS m/z 324 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-7₆) δ 8.05 (dd,7= 10.0, 1.5 Hz, IH), 7.85 (dd,7 = 8.0,1.5 Hz, IH), 7.73 -7.81 (m, IH), 7.18 (s, 2H), 3.87 (s, 3H)	^l9F NMR (376 MHz, DMSO-7₆) δ-112.13 (d, 7 = 28.4 Hz), 137.43 (d, 7 =28.4 Hz)
45	148- 150		ESIMS m/z 393 ([M+H]⁺)	'H NMR (300 MHz, DMSO-7₆) δ 7.87 (m, 2H), 7.62 (m, 2H), 6.91 (br s, 2H)
46	133- 135	IR (thin film) 3490 (s), 3350 (s), 1753 (w), 1634 (m), 1607 (m) cm'¹	ESIMS m/z 344 ([M+HJQ	‘H NMR (400 MHz, DMSO-7₆) δ 13.60 (brs, IH), 7.81 (t,7 = 9 Hz, IH), 7.63 (dd, 7= 11,2 Hz, IH), 7.52 (dd, 7 = 9, 2 Hz, IH), 7.38 (brs, 2H), 3.76 (s, 3H)
47	159.6- 161.1		ESIMS m/z 377 ([M+H]⁺)	'H NMR (400 MHz, CDC1₃) δ 7.58 (m, 4H), 5.36 (s,2H), 3.99 (s, 3H)
48	204.2- 205.9		ESIMS m/z 273 ([M+H]*)	‘H NMR (400 MHz, DMSO-Jî) δ 13.5 (s, IH), 7.94 (d, 2H), 7.60 (d, 2H), 7.30 (s, IH), 6.69 (s, 2H)

-17317475

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	’H NMR^b	¹³C or *’F NMR
49	114- 116	IR (thin film) 3492 (s), 3378 (s), 3235 (w), 2955 (w), 2927 (w), 1736 (s), 1621 (s) cm'¹	ESIMS m/z 379 ([M+H]⁺)	’H NMR (300 MHz, CDC1₃) δ 7.76 (m, 1H), 7.60-7.68 (m, 2H), 4.94 (brs, 2H), 3.99 (s, 3H)
50	174- 176	IR (thin film) 3305 (s), 1720 (w), 1634 (m), 1586 (w) cm'¹	ESIMS m/z 327 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-i4) δ 7.53 (dd, 7=8, 7 Hz, 1H), 7.41 (m, 1H), 6.93 (brs, 2H),4.81 (s, 1H)
51	153- 154		ESIMS m/z 394 ([Μ-H]’ )	’H NMR (400 MHz, CDCI3) δ 7.42 - 7.38 (m, 2H), 4.98 (s, 2H), 3.99 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -112.74,-112.78, -116.99,-117.03, -117.09,-117.13, -137.28,-137.38
52	146- 148	IR (neat film) 3519 (m), 3473 (m), 3420 (s), 3379 (s), 3196 (w), 3075 (w), 2955 (w), 2852 (w), 1736 (s), 1616 (s) cm'¹	ESIMS m/z 379 ([M+H]⁺)	'H NMR (400 MHz, CDCI3) δ 7.50 (dd, J = 8,7 Hz, 1H), 7.42 (dd, 7 = 8, 2 Hz, 1H), 7.36 (dd, 7= 10,2 Hz, 1 H),4.93 (brs, 2H), 3.96 (s, 3H)
53	118- 120		ESIMS m/z 377 ([Μ+ΗΠ	‘H NMR (400 MHz, CDCI3) δ 7.53 - 7.45 (m ,2H), 6.91 (dd,7 = 18.1,11.6 Hz, 1H), 5.76 (dd, 7= 11.6, 1.3 Hz, 1H), 5.61 (dd, 7= 18.1, 1.3 Hz, 1H), 4.81 (s, 2H), 3.92 (s, 3H)	ⁱ⁹F NMR (376 MHz, CDCI3) δ -61.16, -61.20, -135.77,-135.83, -135.86,-135.92, -138.61,-138.65, -138.67,-138.68, -138.70,-138.72, -138.74,-138.77, -140.73,-140.82.
54			ESIMS m/z 326.07 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-7₆) δ 8.15 (m, 2H), 7.67 (m, 2H), 7.45 (brs, 2H), 3.75 (s, 3H)
55	142- 144		ESIMS m/z 443 ([M+H]⁺)	'H NMR (400 MHz, CDCI3) δ 7.56 (dd, 7 = 8.5,4.9 Hz, 1H), 7.32 (dd, 7 =7.6, 5.8 Hz, 1H), 4.97 (s, 2H), 3.98 (s, 3H)	¹⁹FNMR (376 MHz, CDCh) δ -99.87, -99.91, -117.70,-117.74, -117.80,-117.84, -137.25,-137.35.

-17417475

Compd. No.	mp (°C)	IR (cm’¹)	Mass⁸	’H NMR^b	¹³C or ¹⁹F NMR
56	142- 144		ESIMS m/z 425 ([M+Hf)	’H NMR (400 MHz, CDC1₃) δ 7.80 (dd, J = 8.5,6.5 Hz, 1H), 7.53 (dd,7 = 10.0, 5.0 Hz, 1H), 7.25 (d, J= 1.2 Hz, 1H),4.86 (s, 2H), 4.01 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -100.00, -100.05, -120.62, -120.66.
57	93-94		ESIMS m/z 352 ([M+Hf)	Ή NMR (400 MHz, CDCI3) δ 7.86 - 7.79 (m, 2H), 7.62-7.56 (m, 2H), 6.89 (dd,7 = 18.1,11.5 Hz, 1H), 5.71 (dd, 7 = 11.6, 1.4 Hz, 1H), 5.58 (dd, J= 18.1,1.4 Hz, 1H), 4.71 (s,2H), 3.93 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -144.04
58		IR (thin film) 3367, 1735, 1608 cm’¹.	ESIMS m/z 381 ([M+Hf)	‘H NMR (400 MHz, DMSO-7₆) δ 7.91 (t, J =7.8 Hz, 1H), 7.74 (d, J=11.6 Hz, 1H), 7.62 (d, 7=8.1 Hz, 1H), 7.20 (d, J = 21.4 Hz, 2H), 3.87 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-4₆) δ -59.9,-115.6, -116.3
59	203- 205	IR (thin film) 3425 (m), 3297 (m), 3245 (s), 3158 (m), 3008 (w), 2956 (w), 1729 (m), 1637 (m) cm'¹	ESIMS m/z 302 ([M+Hf)	*H NMR (400 MHz, CDC1₃)Ô7.91 (t, J = 8 Hz, 1H), 7.32 (dd,7 = 8, 1.5 Hz, 1H), 7.26 (dd, 7= 12, 1.5 Hz, 1H), 5.40 (br s, 2H), 3.99 (s, 3H), 3.93 (s, 3H), 3.15 (s, 1H)
60			ESIMS m/z 297 ([M+H]+l)	‘H NMR (400 MHz, CDCI3) δ 7.93 (ddd, 7 = 8.2,1.6,0.7 Hz, 2H), 7.65 - 7.54 (m, 2H), 6.90 (ddd, 7 = 18.1, 11.6, 0.5 Hz, 1H), 5.71 (dd, 7 = 11.5, 1.4 Hz, 1H), 5.58 (dd,7= 18.1, 1.4 Hz, 1 H), 4.71 (s, 2H), 3.93 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -143.86
61			ESIMS m/z 361 ([M-H]’ )	*H NMR (400 MHz, CDCI3) δ 7.55 - 7.45 (m, 2H), 7.25 (dd, 7 = 18.3,11.6 Hz, 1H), 5.85 (dd, 7= 11.7, 1.2 Hz, 1 H), 5.64 (dd, 7= 18.4, 1.2 Hz, 1H), 5.11 (s, 2H)	¹⁹F NMR (376 MHz, CDCI3) δ -61.22, -61.25, -135.48,-135.54, -135.57,-135.62, -137.62, -137.66, -137.68,-137.69, -137.71,-137.73, -137.75,-137.78, -137.87,-137.95

-17517475

Compd. No.	mp (°C)	IR (cm¹)	Mass’	Tl NMR	^I3C or ¹⁹F NMR
62	142147 (dec)	IR (thin film) 3317 (s), 3199 (s), 2955 (w), 2924 (w), 2870 (w), 2256 (w), 1721 (m), 1634 (m) cm'¹	ESIMS m/z 291 ([M+H]⁺)	*H NMR (300 MHz, DMSOA) δ 7.86 (m, 2H), 7.61 (m, 2H), 6.93 (br s, 2H), 4.33 (s, 1H)
63		IR (thin film) 2979, 1715 „-i cm	ESIMS m/z 332 ([M+H]⁴)	‘H NMR (400 MHz, DMSO-Jfi) δ 8.22 (t, J = 10.7 Hz, 1H), 8.17 (d, J = 12.3 Hz, 1H), 7.90 (dd,J = 21.3, 13.4 Hz, 1H), 7.56 (d, J = 44.0 Hz, 3H), 3.77 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-<7₆) δ -59.9, 115.3, -116.7
64	140- 141		ESIMS m/z 364 ([M+H]⁴)	‘H NMR (400 MHz, DMSO-4₆) δ 7.87 (t, J = 7.5 Hz, 1H), 7.72 - 7.66 (m, 1H), 7.58 (s, 2H), 3.90 (s, 3H), 3.78 (s, 3H)
65			ESIMS m/z 310 ([M+H]⁴)	'H NMR (400 MHz, DMSO-J₆) δ 13.71 (s, 1 H), 8.05 (dd, J = 9.9, 1.4 Hz, 1H), 7.86 (dd, J = 8.0,1.5 Hz, 1H), 7.75-7.81 (m, 1H), 7.09 (s, 2H)	^l9F NMR (376 MHz, DMSOA) δ-112.04 (d, J =29.9 Hz),138.35 (d, J = 29.6 Hz)
66	141- 143		ESIMS m/z 407 ([M+H]⁴)	Ή NMR (400 MHz, DMSO-<Z₆) δ 7.95 (dd, 1H), 7.77 (dd, 1H), 7.52 (dd, 1H), 7.32 (s, 1H), 6.81 (s, 2H), 3.89 (s, 3H)	¹⁹F NMR (376 MHz, DMSOA) δ -95.03
67			ESIMS m/z 341 ([M-H]*)	*H NMR (400 MHz, CDC1₃) δ 7.77 (m, 2H), 7.55 (m, 2H), 7.1 (s, 1H), 4.84 (br s, 2H), 4.00 (s, 3H)
68	170.1— 172.6		ESIMS m/z 431 ([M+3H]⁴)	‘H NMR (400 MHz, DMSOA) δ 6.85 6.77 (m, 3H), 7.79 (m, 1H)
69	159- 161		ESIMS m/z 429 ([M+H]⁴)	*H NMR (400 MHz, CDC1₃) δ 11.14 (s, 1H), 7.63 (dd,J = 8.6,4.9 Hz, 1H), 7.27 (dd, J =7.5, 5.7 Hz, 1H), 5.21 (s, 2H)	¹⁹F NMR (376 MHz, CDC1₃) δ -99.15, -99.20, -117.70,-117.74, -117.79,-117.83, -134.64,-134.71

Compd. No.	mp (°C)	IR (cm¹)	Mass’	'HNMR^b	¹³C or ”F NMR
70	114- 116		ESIMS m/z 367 ([M+H]⁺)	’H NMR (400 MHz, CDC1₃) δ 7.97 (dd,J = 10.6, 6.3 Hz, 1H), 7.39 (dd, J = 10.5, 5.6 Hz, 1H), 7.30 (d, 7= 1.2 Hz, 1H), 4.91 (s, 2H), 4.02 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -61.69, -61.73, -119.19,-119.22, -119.24,-119.27, -120.01,-120.06
71	157- 160 (dec)	IR (thin film) 3400 (s), 3300 (s), 3200 (m), 1711 (w), 1630 (m) cm’¹	ESIMS m/z 309 ([M+H]⁺)	’H NMR (400 MHz, DMSO-/₆) δ 7.68 7.78 (m, 3H), 6.76 (brs, 2H), 4.66 (s, 1H)
72	95-98	IR (thin film) 3327 (s), 2941 (w), 1718 (w), 1629 (m), 1603 (m) cm'¹	ESIMS m/z 390 ([M+H]*)	Ή NMR (400 MHz, DMSO-J₆) δ 13.67 (brs, 1H), 7.73 (dd,J = 11,1.5 Hz, 1H), 7.68 (dd,J=8.5, 1.5 Hz, 1H), 7.63 (t,J = 8.5 Hz, 1H), 7.33 (br s, 2H), 3.76 (s, 3H)
73			ESIMS m/z 395 ([M+Hn	'H NMR (400 MHz, DMSO-rffi) δ 7.82 (dd, J =8.3,7.3 Hz, 1H), 7.60 (dd, J = 9.8,2.0 Hz, 1H), 7.40 (dd, J =8.3,2.0 Hz, 1H), 7.16 (s, 2H), 3.87 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-4) δ 108.20
74	186.0- 187.3		ESIMS m/z 345 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-J₆) δ 13.6 (s, 1H), 7.87 (m, 1H), 7.72 (m, 1H), 7.57 (m,lH), 7.23 (s, 1H), 6.18 (s, 2H)
76	169- 170		ESIMS m/z 350 ((M+H]⁺)	‘H NMR (400 MHz, DMSO-</₆) δ 13.63 (s, 1H), 7.89 (t, J = 7.5 Hz, 1H), 7.69 (t, J =7.0 Hz, 1H), 7.48 (s, 2H), 3.79 (s, 3H)
77			ESIMS m/z 393 ([M+H]⁺)	'H NMR (400 MHz, DMSO-î/₆) δ 13.57 (s, 1H), 7.95 (dd,J = 8.2, 6.8 Hz, 1H), 7.74 (dd,/=9.8,2.0 Hz, 1H), 7.53 (dd, J = 8.3, 2.0 Hz, 1H), 7.28 (s, 1H), 6.71 (s, 2H)	¹⁹F NMR (376 MHz, DMSO-4₆) δ-95.12

Compd. No.	mp (°C)	IR (cm’¹)	Mass⁸	’H NMR^b	^,3C or ^,9F NMR
78	185.5- 187.0		ESIMS m/z 342 ([M+Hf)	*H NMR (400 MHz, DMSO-î/₆) δ 7.64 (d, J =8.5 Hz, 2H), 7.40 (d,J=8.5 Hz, 2H), 6.47 (s, 2H), 2.07 (s, 3H)	¹³CNMR(101 MHz, DMSO-J₆) δ 166.57, 153.45, 150.28, 138.92, 131.35, 130.86, 121.35, 115.84,109.91, 99.49, 14.91
79	121- 124		ESIMS m/z 421 ([M+H]⁺)	‘H NMR (400 MHz, CDClj) δ 7.80 (dd, J = 8.1, 6.5 Hz, IH), 7.19 (dd, J = 8.6, 1.9 Hz, IH), 7.00 (dd, J = 8.1,1.9 Hz, IH), 4.86 (s, 2H), 3.96 (s, 3H), 2.17 (s, 3H)	^l9F NMR (376 MHz, CDCI3) δ -93.62
80	170- 171		ESIMS m/z 344 ([M+Hf)	*H NMR (400 MHz, DMSO-4) δ 8.30 (dd, J = 9.8,2.1 Hz, IH), 8.22 (dd, J = 8.5, 2.2 Hz, IH), 7.87 (m, 1Η), 7.22 (s, 2H), 3.88 (s, 3H)
81	128- 130		ESIMS m/z 354 ([M-HD	'H NMR (400 MHz, CDC1₃) δ 7.56 (d, J = 8.5 Hz, 2H), 7.33 (d, J = 8.5 Hz, 2H), 4.84 (s, 2H), 3.96 (s, 3H), 2.15 (s, 3H)	¹³CNMR(101 MHz, CDCI3) δ 165.68, 155.19, 149.18, 145.09,138.57, 131.42, 131.00, 122.60, 116.69, 113.59, 52.88, 14.65
82	159- 162	IR (thin film) 3493 (s), 3352 (s), 2943 (w), 2853 (w), 1725 (m), 1602 (m) cm’¹	ESIMS m/z 404 ([M+H]⁺)	'H NMR (400 MHz, CDC1₃) δ 7.68 (t, J = 8 Hz, IH), 7.50- 7.58 (m, 2H), 5.40 (br s, 2H), 4.00 (s, 3H), 3.94 (s, 3H)
83	145— 148, 220		ESIMS m/z 302 ([M+H]*)	'H NMR (400 MHz, CDClj) δ 7.73 (d, J = 8.5 Hz, 2H), 7.58 (d, J =8.5 Hz, 2H), 4.90 (s, 2H), 3.96 (s, 3H), 2.16 (s, 3H)	¹³CNMR(101 MHz, CDCI3) δ 165.50, 154.25, 149.37, 145.36, 144.19, 132.09, 130.18, 118.67,116.71, 114.01,112.06, 52.95, 14.58

-178-

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	’H NMR^b	¹³C or ”F NMR
84	214- 217	IR (thin film) 3453 (m), 3302 (m), 3242 (s), 3170 (m), 2963 (w), 2852 (w), 2112(w), 1732 (m), 1631 (m) cm¹	ESIMS m/z 320 ([M+H]⁴)	*H NMR (400 MHz, CDC1₃) δ 7.69 (ddd, J = 9,7,2 Hz, 1H), 7.27 (m, 1H), 5.42 (br s, 2H), 4.00 (s, 3H), 3.95 (s, 3H), 3.42 (s, 1H)
85	126- 125		ESIMS m/z 347 ([M+H]⁴)	*H NMR (400 MHz, DMSO-d₆) δ 7.88 (dd, J= 8.8,1.3,2H), 7.34 (t, J =73.8, 1H), 7.31 (d, J =8.9, 2H), 7.01 (brs, 2H), 3.88 (s, 1H)
86	120- 122		ESIMS m/z 345 ([M+H]⁴)	'H NMR (400 MHz, DMSO-dô) δ 13.22 (s, 1H), 8.02 - 7.94 (m, 3H), 6.78 (dd, J = 17.7,11.6 Hz, 1H), 6.56 (s, 2H), 5.65 - 5.52 (m, 2H)	^,9F NMR (376 MHz, CDC1₃) δ -61.37, -61.41, -114.17,-114.20, -114.24,-114.27, -143.61
87	171- 172		ESIMS m/z 407 ([M+H]⁴)	‘H NMR (400 MHz, DMSO-<7₆) δ 13.36 (s, 1H), 7.91 (dd,J = 8.0,6.8 Hz, 1H), 7.35 (dd, J =9.1,1.9 Hz, 1H), 7.10 (dd, J = 8.1,1.9 Hz, 1H), 6.49 (s, 2H), 2.09 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-J₆) δ -95.45
88			ESIMS m/z 372 ([M+H]⁴)	‘H NMR (400 MHz, DMSO-<Z₆) δ 8.00 (m, 2H), 7.84 (m, 2H), 7.35 (br s, 2H), 3.11 (s, 3H)
89	119— 121			'H NMR (400 MHz, DMSO-éZ₆) δ 13.63 (s, 1H), 7.72 (ddd, J = 8.3,5.7,1.8 Hz, 1H), 7.51 (ddd, J = 8.6, 7.0,1.8 Hz, 1H), 7.43 (s, 2H), 3.76 (s, 3H)
90	176.2- 178.7		ESIMS m/z 445 ([M+2H]⁴)	'H NMR (400 MHz, DMSO-d₆) δ 3.86 (s, 3H), 6.98 - 6.94 (m, 3H), 7.89 - 7.85 (m, 1H)
91	173— 175		ESIMS m/z 363 ([M-H]’)	‘H NMR (300 MHz, DMSO-d₆)Ô 7.76 7.56 (m, 2H), 7.22 (d, J= 1.7,1H), 6.84 (s, 2H)

-17917475

Compd. No.	mp (°C)	IR (cm’)	Mass’	*H NMR^b	^,3C or ¹⁹F NMR
92	147- 149	IR (thin film)778.80, 822.34, 879.66,973.14, 1006.40, 1026.12, 1056.64, 1120.85, 1214.80.1276.30, 1389.19,1409.98, 1459.47,1496.89, 1519.03, 1592.79, 1627.42, 1720.12, 1769.38.2535.30, 3199.10,3386.23, 3501.86 cm·¹	ESIMS m/z 351 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-7₆) δ 13.63 (s, 1H), 7.83 (dd,7 = 11.8,2.1 Hz, 1H), 7.75 (t, J =72.0 Hz, 1H), 7.52 (d, J= 8.0 Hz, 1H), 7.50-7.14 (m, 1H), 6.99 (s, 2H)
93	98.9- 101.6		ESIMS m/z 359 ([M+Hf)	*H NMR (400 MHz, CDClj) δ 7.93 (m, 1H), 7.34 (m, 2H), 7.22 (s, 1H), 4.85 (s, 2H), 4.00 (s, 3H)
94	158.5- 159.5		ESIMS m/z 329 ([M+H]⁺)	'H NMR (400 MHz, DMSO-7₆) δ 7.51 (d, 7=8.6 Hz, 2H), 7.33 -7.14(m,3H), 6.61 (s, 2H), 2.09 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-J₆) δ -82.20
95			ESIMS m/z 326 ([M+H]⁺)	*H NMR (300 MHz, CDCl₃)ô8.32 (d,7 = 9.0,2H), 8.13 (dd, 7 = 9.0, 1.4, 2H), 5.02 (s, 2H), 4.01 (s, 3H)
96	187.2- 189.9		ESIMS m/z 423 ([M+H]⁺)	‘H NMR (400 MHz, CDClj) δ 7.80 (d, 2H), 7.42 (d, 2H), 5.35 (s, 2H), 3.98 (s, 3H)
97			ESIMS m/z 340 ([M+H]⁺)	‘H NMR (400 MHz, CDC1₃) δ 8.19 (m, 2H), 7.55 (m, 2H), 5.35 (br s, 2H),4.01 (s, 3H), 3.92 (s, 3H)
98			ESIMS m/z 299 ([M+H]*)	*H NMR (400 MHz, DMSO-4) δ 8.13 7.90 (m, 2H), 7.80 (dd, 7=8.0, 1.6 Hz, 1H), 7.46 (s, 2H), 6.66 (dd,7= 17.6, 11.5 Hz, 1H), 5.63- 5.43 (m, 2H), 3.82 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-J₆) δ-111.51
99	168- 170	IR (thin film) 3502 (m), 3378 (s), 2953 (w), 1739 (m), 1726 (m), 1617 (m) cm'¹	ESIMS m/z 443 ([M+H]⁺)	'H NMR (400 MHz, CDCI3) δ 7.62 (ddd, 7 = 9, 6,2 Hz, 1H), 7.16 (ddd, 7 = 9, 6.5, 2 Hz, 1H), 4.97 (br s, 2H), 3.96 (s, 3H)

-18017475

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	’H NMR^b	¹³C or ¹⁹F NMR
100	145- 147		ESIMS m/z 502 ([M-H]')	*H NMR (400 MHz, CDC1₃) δ 7.54 (dd, J = 8.2,4.9 Hz, 1H), 7.12 (dd, J = 7.4, 5.8 Hz, 1H), 5.44 (s, 2H), 3.97 (s, 3H)	¹⁹F NMR (376 MHz, CDClj) δ -99.80, -99.84, -116.84,-116.89
101	193- 194		ESIMS m/z 422 ([M+Hf)	Ή NMR (400 MHz, CDC1₃) δ 7.69 (dd, J = 8.3, 6.3 Hz, 1H), 7.54 (dd, J= 9.5, 5.0 Hz, 1H), 5.43 (s, 2H), 4.00 (s, 3H), 3.94 (s, 3H)	¹⁹F NMR (376 MHz, CDC1₃) δ -100.82, -100.86, -118.25, -118.29
102	171.0- 172.1		ESIMS m/z 330 ([M+Hf)	‘H NMR (400 MHz, DMSO-iZe) δ 7.35 (d, 2H), 7.47 (d, 2H), 7.39 (s, 2H), 3.78 (s, 3H)
103		IR (thin film) 708.67, 786.89, 824.69,939.95, 1032.81, 1120.09, 1153.46, 1204.33, 1225.97,1263.98, 1424.87,1375.02, 1445.12,1481.84, 1518.14,1615.72, 1739.13, 2959.84, 3195.90,3378.30, 3486.20 cm’¹	ESIMS m/z 383 ([M+Hf)	'H NMR (400 MHz, CDC1₃) δ 7.37 (ddd, J = 8.7,7.0,2.3 Hz, 1H), 7.19-7.11 (m, 1H), 6.61 (t, J =72.5 Hz, 1H), 4.99 (s, 2H), 3.98 (s, 3H)
104	127- 129	IR (thin film) 758.08, 793.58, 824.98, 856.60, 919.36,972.37,1014.89, 1053.05, 1122.86, 1162.89,1203.20, 1241.89,1276.59, 1369.66, 1439.27, 1480.39,1512.36 1611.65,1732.10, 2957.77, 3021.70, 3389.26,3506.76 cm¹	ESIMS m/z 366 ([M+Hf)	*H NMR (400 MHz, CDC1₃)6 7.61 (t, J = 8.3 Hz, 1H), 7.04 (ddd, J =8.6,2.3,0.8 Hz, 1H), 6.96 (dd, J = 10.5, 2.3 Hz, 1H), 6.55 (t, J = 73.0 Hz, 1H), 4.96 (s, 2H), 3.97 (s, 3H)	^l3C NMR (101 MHz, CDCI3) δ 164.70, 161.50, 158.98, 152.94,152.84, 147.17.144.60, 143.59, 143.54, 140.22, 140.08, 137.91, 137.78, 132.54, 132.53, 132.49.119.75, 119.71.119.60, 119.56,118.02, 115.77.115.75, 115.42,115.40, 115.37,112.81, 107.69,107.43, 53.07
105	141.9- 143.1		ESIMS m/z 367 ([M+H]⁺)	*H NMR (400 MHz, DMSO-î/₆) δ 13.7 (s, 1H), 7.75 (d, 2H), 7.49 (d, 2H), 7.01 (s, 2H)

Compd. No.	mp (°C)	IR (cm¹)	Mass”	’H NMR^b	¹³C or ”F NMR
106	183- 184	IR (thin film) 861.93, 886.37,962.21,984.56, 1035.97.1010.25, 1113.86.1143.26, 1173.58,1222.01, 1251.67,1294.93, 1438.95,1397.88, 1514.76,1486.42, 1595.67,1568.01, 1608.88,1645.71, 1735.15,2693.18, 2860.72,2960.57, 3179.92, 3320.20, 3406.42 cm¹	ESIMS m/z 326 ([M+H]⁴)	'H NMR (400 MHz, CDC1₃) δ 8.35 - 8.29 (m, 2H), 7.19-7.10 (m, 2H), 6.56 (t, J = 72 Hz, 1H), 5.33 (s, 3H), 4.02 (s, 3H), 3.92 (s, 3H)
107			ESIMS m/z 298 ([M+H]⁴)	‘H NMR (400 MHz, CDCI3) δ 8.08 (dd, J = 8.6,1.5 Hz, 2H), 7.78-7.71 (m, 2H), 6.89 (dd, J= 18.1, 11.6 Hz, 1 H), 5.73 (dd, 7= 11.6, 1.4 Hz, 1H), 5.59 (dd, 7 = 18.1,1.4 Hz, 1H), 4.78 (s, 2H), 3.93 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -143.64
108	165175 (dec)	IR (thin film) 3468 (s), 1621 (m) cm’¹	ESIMS m/z 309 ([M+H]⁴)	Ή NMR (400 MHz, DMSO-7₆) δ 7.55 (t, 7= 8 Hz, 1H), 7.50 (dd, 7= 11,1.5 Hz, 1H), 7.46 (dd, 7 =8, 1.5 Hz, 1H), 6.47 (br s, 2H), 4.45 (s, 1H)
109	184- 186		ESIMS m/z 393 ([M-H]’)	‘H NMR (300 MHz, CDCI3) δ 7.48 - 7.40 (m, 1H), 7.33-7.26 (m, 1H),4.99 (brs, 2H), 3.98 (s, 3H)
110			ESIMS m/z 345 ([M+H]⁴)	*H NMR (400 MHz, DMSO-7₆) δ 13.33 (s, 1H), 7.70 - 7.52 (m, 2H), 7.45 (dd,7 = 8.4,2.0 Hz, 1H), 7.06 (s, 1H), 6.52 (s, 2H)	¹⁹F NMR (376 MHz, DMSO-î/î) δ 107.95.
111			ESIMS m/z 341 ([M-H]')	‘H NMR (400 MHz, CDC1₃) δ 7.46 (d, 7 = 8.7 Hz, 2H),7.18(d, 7= 8.7 Hz, 2H), 6.53 (t, 7 =73.8 Hz, 1H), 4.84 (s, 2H), 3.95 (s, 3H), 2.16 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -80.81

-18217475

Compd. No.	mp (°C)	ER (cm¹)	Mass	'11 NMR^b	^,3C or ^,9F NMR
112	134- 137		ESIMS m/z 375 ([M+H]⁴)	*H NMR (400 MHz, CDClj) δ 7.61 (dd, J = 8.2,7.1 Hz, IH), 7.27-7.25 (m, IH), 7.13 (ddd, J =8.2, 1.9, 0.6 Hz, IH), 4.86 (s, 2H), 3.96 (s, 3H), 2.17 (s, 3H)	¹⁹FNMR(376 MHz, CDCI3) δ -107.04
113			ESIMS m/z 344 ([M+Hf)	*H NMR (400 MHz, DMSO-î/₆) δ 13.63 (s, IH), 8.07 (dd, J = 10.3,1.9 Hz, IH), 8.01 (dd,J=8.5,2.0 Hz, IH), 7.81 (dd, J = 8.4, 7.2 Hz, IH), 7.40 (s, 2H), 3.76 (s, 3H)	¹⁹FNMR(376 MHz, DMSO-<7₆) δ -108.44
114	178- 180		ESIMS m/z 379 ([M+Hn	*H NMR (400 MHz, DMSO-<Z₆) δ 7.78 7.58 (m, 2H), 7.26 (d, J= 1.6, IH), 6.95 (s, 2H), 3.89 (s, 3H)
115			ESIMS m/z 359 ([M+H]⁺)	'H NMR (400 MHz, DMSO-<7₆) δ 7.91 7.80 (m, 2H), 7.75 7.67 (m, IH), 7.35 (s, IH), 6.86 (s, 2H), 3.93 (s, 3H)	^l9F NMR (376 MHz, DMSO-</₆) δ-107.88
116	179.5- 181.0		ESIMS m/z 389 ([M+H]⁴)	‘H NMR (400 MHz, DMSO-îZ₆) δ 7.81 (d, J =8.3 Hz, 2H), 7.25 (d,J = 8.3 Hz, 2H), 6.46 (s, 2H), 2.07 (s, 3H)	¹³CNMR(101 MHz, DMSO-4) δ 166.56, 153.62, 150.28, 139.23,136.72, 131.38, 115.78, 109.86,94.48,48.57, 14.90
117	149- 151		ESIMS m/z 336 ([Μ-HD	'H NMR (400 MHz, DMSO-rf₆)ô 13.13 (s, IH), 7.82 (dd,J = 8.5, 0.9 Hz, 2H), 7.74 - 7.66 (m, 2H), 6.75 (dd, J = 17.8,11.5 Hz, IH), 6.42 (s, 2H), 5.56 (dd, J = 12.8, 1.3 Hz, IH), 5.52 (dd,J = 6.5,1.3 Hz, IH)	¹⁹F NMR (376 MHz, DMSO-îZô) δ-145.77
118	133- 135		ESIMS m/z 407 ([M+Hn	*H NMR (300 MHz, CDC1₃) δ 7.81 (m, 2H), 7.67 (m, 2H), 4.91 (brs, 2H), 3.99 (s, 3H)

-183-

Compd. No.	mp (°C)	IR (cm¹)	Mass³	Ή NMR^b	¹³C or ¹⁹F NMR
119	131- 132		ESIMS m/z 408 ([M+H]⁺)	'H NMR (400 MHz, DMSO-<Z₆) δ 7.83 (dd, J =9.6, 5.1 Hz, IH), 7.66 (dd, J = 8.5, 6.3 Hz, IH), 7.42 (s, 2H), 3.75 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-û?₆) δ 101.95, -102.00, -117.68, -117.72
121	186- 188	IR (thin film) 3500 (w), 3472 (m), 3370 (s), 3229 (m), 2955 (w), 2921 (w), 2850 (w), 1728 (m), 1622 (m) cm’¹	ESIMS m/z 323 ([M+Hf)	'H NMR (400 MHz, CDC1₃) δ 7.58 (t, J = 8 Hz, IH), 7.39 (dd, J = 8, 1.5 Hz, IH), 7.28 (m, IH), 4.94 (br s, 2H), 3.97 (s, 3H),3.17(s, IH)
122	171- 172		ESIMS m/z 374 ([M+Hf)	*H NMR (400 MHz, CDCI3) δ 7.65 (ddd, J = 9.0, 7.1,2.1 Hz, IH), 7.40-7.31 (m, IH), 5.45 (s, 2H), 4.01 (s, 3H), 3.95 (s, 3H)	^l9F NMR (376 MHz, CDCI3) δ -129.82 (s), -129.88 (s), -135.73 (s), -135.79 (s)
123	187- 190		ESIMS m/z 368 ([M+H]⁺)	‘H NMR (400 MHz, DMSO-<7₆) δ 8.01 8.09 (m, 2H), 7.827.90 (m, 2H), 7.16 (s, IH), 6.65 (dd, J = 17.7, 11.5 Hz, IH), 5.61 (dd,J = 17.7, 1.3 Hz, 1 H), 5.49 (dd, J= 11.4, 1.3 Hz, IH)
124	208.4- 210.2		ESIMS m/z 393 ([M+H]⁺)	'H NMR (400 MHz, DMSO-<7₆) δ 13.7 (s, IH), 7.78 (m, 3H), 7.23 (s, IH), 6.83 (s,2H)
125	164.9- 166.1		ESIMS m/z 363 ([M+Hf)	'H NMR (400 MHz, DMSO-4₆) δ 13.69 (s, IH), 7.67 (d, 2H) 7.55 (d, 2H), 6.99 (s, 2H)
126	158.9- 161.2		ESIMS m/z 287 ([M+H]⁺)	‘H NMR (400 MHz, CDCI3) δ 7.93 (d, 2H), 7.60 (d, 2H), 7.16 (s, 1H),4.89 (s, 2H), 4.05 (s, 3H)
127	174- 176		ESIMS m/z 376 ([M-H]')	*H NMR (400 MHz, CDCI3) δ 7.89 (dd, J = 9.2,6.7 Hz, IH), 7.36 (dd, J = 10.2, 5.5 Hz, IH), 7.25 (d, J =1.2 Hz, IH), 4.86 (s, 2H), 4.01 (s, 3H)	^,9F NMR (376 MHz, CDCI3) δ -112.80, -112.84, -119.98, -120.02

-18417475

Compd. No.	mp (°C)	IR (cm¹)	Mass“	*H NMR^b	¹³C or ¹⁹F NMR
128		IR (thin film) 3334,1722 cm’¹	ESIMS m/z 336 ([M+Hf)	'H NMR (400 MHz, DMSO-7₆) δ 8.25 (d, 7= 8.1 Hz, 2H), 8.17 (d, J=11.9 Hz, 2H), 7.95 (t, J = 7.9 Hz, 2H), 7.66 (s, 1H)	¹⁹F NMR (376 MHz, DMSO) δ -60.0,-114.7, -116.5
129	172- 174	IR (thin film) 3481 (m), 3338 (s), 3185 (w), 3096 (w), 2963 (w), 1727 (m), 1608 (m) cm'¹	ESIMS m/z 425 ([M+Hf)	¹H NMR (400 MHz, CDC1₃) δ 7.55 -7.62 (m,2H), 7.21 (d,7 = 2 Hz, 1H), 4.86 (br s, 2H), 3.99 (s, 3H)
130	185.1- 186.9		ESIMS m/z 285 ([M+Hf)	‘H NMR (400 MHz, CDClj) δ 8.45 (d, 2H), 7.75 (s, 2H), 5.84 (s, 2H), 4.03 (s, 3H), 3.96 (s, 3H)
131	173- 175		ESIMS m/z 411 ([M+Hft	*H NMR (400 MHz, DMSO-î/₆) δ 7.90 (dd, 7= 10.2, 5.1 Hz, 1H), 7.73 (dd, 7 = 8.6, 6.6 Hz, 1H), 7.26 (s, 1H), 6.83 (s, 2H)	¹⁹F NMR (376 MHz, DMSO-J₆) δ -96.56, -96.61, -115.34, -115.38
132	138- 140	IR (thin film) 3437 (w), 3352 (s), 3197 (w), 2949 (w), 1737 (m), 1614 (m) cm'¹	ESIMS m/z 425 ([M+H])	‘H NMR (400 MHz, CDCI3) δ 7.88 (dd, 7 = 9, 7 Hz, 1H), 7.73 (ddd, 7 =9,2,1 Hz, 1H), 7.55 (dt, 7 = 8.5, 2 Hz, 1H), 4.94 (br s, 2H), 4.00 (s, 3H)
133	141- 143	IR (thin film) 3385 (s), 3242 (m), 2955 (w), 2918 (w), 2856 (w), 1734 (m), 1622 (m) cm'¹	ESIMS m/z 323 ([M+H])	‘H NMR (400 MHz, CDCI3) δ 7.75 (d, 7 = 9.5 Hz, 2H), 7.57 (t, 7= 7 Hz, 1H), 4.93 (br s, 2H), 3.98 (s, 3H), 3.37 (s, 1H)
134	124- 126		ESIMS m/z 353 ([M+H]*)	'H NMR (400 MHz, DMSO-7₆) δ 7.92 (d, 7= 12.8 Hz, 3H), 7.01 (s, 2H)
135			ESIMS m/z 324 ([M+H])	'H NMR (400 MHz, CDCI3) δ 7.98 - 7.83 (m, 1H), 7.72 (dd, 7 = 8.4, 6.6, 1H), 5.01 (s, 1H), 4.01 (s, 2H)

-18517475

Compd. No.	mp (°C)	IR (cm'¹)	Mass*	’H NMR^b	¹³C or ¹⁹F NMR
136	115- 118		ESIMS m/z 403 ([M+H]*)	’H NMR (400 MHz, CDCfi) δ 7.77 (d,J = 8.5 Hz, 2H), 7.20 (d, J =8.5 Hz, 2H), 4.83 (s, 2H), 3.95 (s, 3H), 2.15 (s, 3H)	¹³CNMR(101 MHz, CDCb) δ 165.69, 155.29, 149.17, 145.12,139.19, 137.39, 131.16, 116.65,113.57, 94.30, 52.86,14.64
137			ESIMS m/z 342 ([M+H]*)	*H NMR (400 MHz, DMSO-rf₆) δ 8.26 (d, J =8.2 Hz, 1H), 8.17 (d,J= 12.2 Hz, 1H), 7.94 (t, .7 = 7.9 Hz, 1H), 7.35 (s, 2H), 6.67 (dd,J= 17.7, 11.5 Hz, 1H), 5.52 (m, 2H), 3.85 (s, 3H)	^I9F NMR (376 MHz, DMSO-rb) δ -59.99 (d, J= 12.2 Hz), -115.72 (d, J =12.2 Hz)
138			ESIMS m/z 361 ([M+H]*)	'H NMR (400 MHz, CDC1₃)Ô7.81 (m, 2H), 7.60 (m, 2H), 7.40 (d, J =2 Hz, 2H), 4.91 (brs, 2H), 3.99 (s, 3H)
139	95-96		ESIMS m/z 399 ([M+H]*)	'H NMR (400 MHz, CDC1₃) δ 7.84 - 7.75 (m, 2H), 7.73 - 7.66 (m, 2H), 6.89 (dd,J = 18.1,11.6 Hz, 1H), 5.71 (dd, .7 = 11.6, 1.4 Hz, 1H), 5.58 (dd, J= 18.1,1.4 Hz, 1H),4.71(S, 2H), 3.92 (s, 3H)	¹⁹F NMR (376 MHz, CDC1₃) δ -143.98
140	149- 151	IR (thin film) 698.09, 825.26, 869.29, 998.15, 1025.59,1050.34, 1098.57,1129.54, 1167.58,1246.97, 1386.17.1435.44, 1481.70,1515.78, 1590.42,1628.74, 1720.93.2535.45, 3198.03,3327.36, 3469.29 cm’¹	ESIMS m/z 351 ([M+H]*)	'H NMR (400 MHz, DMSO-îZ₆) δ 18.40 (s, 1H), 12.39 (t,J = 8.4 Hz, 1H), 12.16 (t, J =72.0 Hz, 1H), 12.05 (dd, J= 11.1, 2.4 Hz, 1H), 11.94 (dd, J =8.5,2.4 Hz, 1 H), 11.75 (s, 2H)
141	155- 157	IR (thin film) 3325 (s), 3193 (s), 1625 (m) cm'¹	ESIMS m/z 429 ([M+H]*)	‘H NMR (400 MHz, DMSO-<Z₆) δ 7.81 (br t, J=7Hz, 1H), 7.20 (brt, J = 7Hz, 1H), 6.64 (br s, 2H)

-18617475

Compd. No.	mp (°C)	IR (cm¹)	Mass’	'H NMR^b	^,3C or ¹⁹F NMR
142	164- 167		ESIMS m/z 306 ([M+H]*)	'H NMR (400 MHz, DMSO-7₆) δ 8.06 7.94 (m, 4H), 7.12 (brs, 2H), 3.89 (s, 3H)
143	137- 139		ESIMS m/z 333 ([M+H]*)	'H NMR (300 MHz, DMSO-îZ₆) δ 7.90 (dd,7 = 8.8,1.3,2H), 7.34 (t, J =73.8, 1H), 7.30 (d, J =8.8, 2H), 6.90 (s, 2H)
144	124- 126		ESIMS m/z -3OC ([M+H]*)	'H NMR (400 MHz, CDC1₃) δ 7.50 (dd, J = 9.8, 5.3 Hz, 1H), 7.42 (dd, 7= 8.9, 5.6 Hz, 1H), 5.03 (s, 2H), 3.99 (s, 3H)	^I9F NMR (376 MHz, CDCI3) δ -61.82,-61.85, -116.72,-116.76, -116.81,-116.86, -119.30,-119.33, -119.35,-119.38, -137.15,-137.24
145			ESIMS m/z 427 ([M+H]*)	Ή NMR (400 MHz, DMSO-J₆)Ô 13.75 (s, 1H), 7.95 (dd, 7 = 8.1,6.7 Hz, 1H), 7.48 (dd, 7=9.1,1.9 Hz, 1H), 7.25 (dd, 7 = 8.1, 1.9 Hz, 1H), 7.04 (s,2H)	¹⁹F NMR (376 MHz, DMSO-7₆) δ -95.25
146		IR (thin film) 3359, 1719, 1619 cm·'	ESIMS m/z 369 ([M+H]*)	Ή NMR (400 MHz, DMSO-Je) δ 7.90 (t, 7=7.9 Hz, 2H), 7.75 (d,7 = 11.8 Hz, 2H), 7.64 (d, 7 =8.1 Hz, 2H)	¹⁹FNMR(376 MHz, DMSO-7₆) δ -59.9, 115.3, -116.6
147	168- 170		ESIMS m/z 381 ([Μ-H]’)	'H NMR (400 MHz, DMSO-7₆) δ 7.74 7.65 (m, 1H), 7.43 - 7.32 (m, 1H), 7.00 (br s, 2H)
148	96-98		ESIMS m/z 364 ([M+H]*)	'H NMR (400 MHz, CDCI3) δ 7.84 (dd, 7 = 10.6, 5.9 Hz, 1H), 7.39 (dd, 7 = 9.8, 5.6 Hz, 1H), 5.46 (s, 2H), 4.01 (s, 3H), 3.96 (s, 3H)	¹⁹FNMR (376 MHz, CDCI3) δ -61.73,-61.76, -117.59,-117.64, -120.18,-120.21, -120.23,-120.26
149	131- 132		ESIMS m/z ([M+H]*)	'H NMR (400 MHz, DMSO-<Z₆) δ 7.77 (t, 7=7.2, 1H), 7.63 (t, 7=7.0,1H), 7.25 (s, 2H), 3.88 (s, 3H)

-18717475

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	’H NMR^b	¹³C or ¹⁹F NMR
150			ESIMS m/z 284 ([M+Hf)	‘H NMR (400 MHz, CDC1₃)ô 11.46 (s, 1H), 8.05-7.98 (m, 2H), 7.84-7.75 (m, 2H), 7.26 (ddd, J = 18.4,11.7, 1.4 Hz, 1H), 5.85 (dd, J = 11.7,1.4 Hz, 1H), 5.63 (dd, J =18.4, 1.4 Hz, 1H), 5.06 (s, 2H)	¹⁹F NMR (376 MHz, CDClj) δ -140.74
151	130- 132		ESIMS m/z 319 ([M+H]*)	‘H NMR (400 MHz, CDC1₃) δ 7.53 (dd, J = 7.9,7.3 Hz, 1H), 7.22 (ddd, J = 7.3, 6.7,1.5 Hz, 2H), 4.87 (s, 2H), 3.96 (s, 3H), 3.35 (s, lH),2.17(s, 3H)	^l9F NMR (376 MHz, CDCI3) δ -110.01
152	112- 114	IR (thin film) 751.85, 792.16, 879.37, 933.73, 1013.05,1094.15, 1058.41,1117.03, 1200.23, 1247.75, 1267.53, 1375.51, 1432.34, 1476.69, 1516.02,1611.65, 1725.02,2961.33, 3378.00, 3505.09 cm'¹	ESIMS m/z 366 ([M+H]*)	'H NMR (400 MHz, CDC1₃) δ 7.86 - 7.68 (m, 2H), 7.36 - 7.29 (m, 1H), 6.60 (t, J = 73.3 Hz, 1H), 4.95 (s, 2H), 4.00 (s, 3H)
153	160.9- 162.6		ESIMS m/z 307 ([M+H]*)	‘H NMR (400 MHz, DMSOé) δ 13.72 (s, 1H), 7.61 (m, 5H), 7.04 (s, 2H)
154	142- 144	IR (thin film) 3486 (m), 3378 (s), 3225 (s), 2940 (w), 1768 (w), 1719 (w), 1625 (m) cm'¹	ESIMS m/z 306 ([M+H]*)	'H NMR (400 MHz, DMSO-4) δ 7.72 (m, 1H), 7.46 (m, 1H), 7.11 (brs, 2H), 4.80 (s, 1H), 3.79 (m, 3H)
155	177- 180		ESIMS m/z 318 ([M-HD	‘H NMR (400 MHz, CDCI3) δ 7.78 - 7.61 (m, 1H), 7.42 - 7.29 (m, 2H), 4.92 (s, 2H), 3.97 (s, 3H), 2.17 (s, 3H)	^l3CNMR(101 MHz, CDCI3) δ 165.33, 164.23, 161.59, 152.85, 149.49, 145.46, 133.27, 125.88, 117.79, 117.58, 116.64, 114.32, 113.80, 53.01, 14.55; ¹⁹F NMR (376 MHz, CDCI3) δ -105.97

Compd. No.	mp (°C)	IR (cm¹)	Mass”	’H NMR^b	¹³C or ¹⁹F NMR
156			ESIMS m/z 310 ([M+Hn	*H NMR (300 MHz, DMSO-î/ê) δ 8.07 (dd, J = 8.1, 7.0, IH), 7.96-7.85 (m, 2H), 7.08 (s, 2H)
157	140150 (dec)	IR (thin film) 3462 (s), 3194 (s), 1610 (m) cm'¹	ESIMS m/z 411 ([M+Hf)	*H NMR (400 MHz, DMSO-î/₆) δ 7.99 (dd, J = 8,7 Hz, IH), 7.68 (dd,J= 10,1 Hz, IH), 7.53 (dt, J = 9, 1.5 Hz, IH), 6.39 (br s, 2H)
158			ESIMS m/z 387 ([M-Htt	*H NMR (400 MHz, CDC1₃) δ 7.75 (m, 2H), 7.63 (m, 2H), 7.08 (s, IH), 4.87 (br s, 2H), 4.00 (s, 3H)
159	139.8- 141.2		ESIMS m/z 407 ([Μ+ΗΠ	'H NMR (400 MHz, CDC1₃) δ 7.60 (m, 3H), 7.39 (s, IH), 5.53 (s, 2H), 4.04 (s, 3H)
160	163- 164		ESIMS m/z 342 ([M+Hf)	'H NMR (400 MHz, DMSO-4) δ 7.90 (m, IH), 7.59 (t, J = 6.8 Hz, IH), 7.25 (s, 2H), 3.87 (s, 3H)
161	170.0- 171.5		ESIMS m/z 349 ([M]⁺)	*H NMR (400 MHz, CDC1₃)Ô7.73 (t, J = 7.7 Hz, IH), 7.32 (t, J =8.9 Hz, 2H), 5.15 (s, 2H), 2.23 (s, 3H)	¹⁹F NMR (400 MHz, CDC1₃) δ -61.4,-113.3
162			ESIMS m/z 383 ([M+2H]*)	'H NMR (400 MHz, DMSO-<Z₆) δ 6.90 6.70 (br s, 3H), 7.88 (d, J =8.96 Hz, IH)
163	162- 164	IR (thin film) 3467 (s), 1609 (m) cm’¹	ESIMS m/z 365 ([M+Hf)	‘H NMR (400 MHz, DMSO-<Z₆) δ 7.75 (dd, J = 10,2 Hz, IH), 7.60 (dd, J = 8, 2Hz, IH), 7.52 (t,J = 8 Hz, IH), 6.55 (br s, 2H)
164	142- 144		ESIMS m/z 382 ([M+Hn	“H NMR (400 MHz, DMSO-4) δ 3.83 (s, 3H), 5.38 - 5.58 (m, 2H), 6.65 (dd, J = 17.6,11.5 Hz, IH), 6.98 - 7.65 (m, 2H), 7.86 (d, J =8.5 Hz, 2H), 8.03 (d, J = 8.5 Hz, 2H)
165	133- 135		ESIMS m/z 368 ([M+Hn	*H NMR (400 MHz, DMSO-4) δ 7.92 (m, 3H), 7.17 (s, 2H), 3.90 (s, 3H)

-18917475

Compd. No.	mp (°C)	IR (cm¹)	Mass	‘H NMR^b	¹³C or ¹⁹F NMR
166	148.2- 150.9		ESIMS m/z 284 ([M+Hf)	‘H NMR (400 MHz, CDC1₃) δ 7.29(d, 2H), 7.56 (d, 2H), 5.37 (s,2H), 4.02 (s, 3H), 3.93 (s, 3H) 3.18 (s,lH)
167	69-70		ESIMS m/z 369 ([M-H]’)	*H NMR (400 MHz, DMSO-rf₆) δ 13.75 (s, lH),7.77(m, IH), 7.64 (m, IH), 7.16 (s, 2H)
168			ESIMS m/z 329 ([M+H]*)	‘H NMR (400 MHz, DMSO-cZfi) δ 7.84 (m, 2H), 7.68 (m, 2H), 7.25 (s, IH), 6.72 (br s, 2H)
169	152- 155	IR (thin film) 3470 (s), 1716 (w), 1629 (m), 1606 (m) cm'¹	ESIMS m/z 411 ([M+H]*)	'H NMR (400 MHz, DMSO-d₆) δ 7.84 (dd, J= 10,1.5 Hz, IH), 7.76 (dd, J=8, 1.5 Hz, IH), 7.33 (t, J =8 Hz, IH), 6.61 (br s, 2H)
170	178.9- 180.2		ESIMS m/z 381 ([M+H]*)	‘H NMR (400 MHz, CDCI3) δ 7.75 (d, 2H), 7.32 (d, 2H), 5.40 (s, 2H), 4.02 (s, 3H)
171			ESIMS m/z 356 ([M+H]*)	‘H NMR (400 MHz, DMSO-<4) δ 8.11 7.90 (m, 2H), 7.82 (dd, J =8.3,7.2 Hz, IH), 7.67 - 7.39 (m, 2H), 3.91 (s,3H), 3.75 (s, 3H)	¹⁹FNMR(376 MHz, DMSO-î/₆) δ-108.34
172	161		ESIMS m/z 353 ([M+H]*)	“H NMR (400 MHz, DMSO-</₆) δ 13.69 (s, IH), 7.91 (t,J = 7.5 Hz, IH), 7.71 (t, J =7.2 Hz, IH), 7.30 (d, J= 1.7 Hz, IH), 6.93 (s, 2H)
173	188.7- 190.3		ESIMS m/z 409 ([M+H]*)	‘H NMR (400 MHz, DMSO-<Z₆) δ 13.79 (s, IH), 7.87 (d,2H), 7.42 (d, 2H), 7.01 (s,2H)
174	171.8- 173.9		ESIMS m/z 337 [(M+3H)*]	1H-NMR(4OO MHz, DMSO-</₆) δ 6.91 (br s,2H),7.26(t,J = 53.88 Hz, IH), 7.45 - 7.47 (m, IH), 7.68 (dd, J = 5.60, 10.64 Hz, IH), 7.87 (dd, J = 5.88,10.74 Hz, IH), 13.68 (brs, IH)

-19017475

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	'H NMR^b	¹³C or ”F NMR
175	123- 124		ESIMS m/z 260 ([M+H]⁴)	*H NMR (400 MHz, CDClj) δ 8.34 - 8.24 (m, 2H), 7.49 - 7.38 (m, 3H), 5.33 (s, 2H), 4.02 (s, 3H), 3.92 (s, 3H)
176	135.2- 136.9		ESIMS m/z 36Ί ([M+Hf)	‘H NMR (400 MHz, CDCI3) δ 7.41 (m, 2H), 6.91 (t, 1H), 5.02 (s, 2H), 4.00 (s, 3H)
177	107.5- 110.3		ESIMS m/z 365 ([M+Hf)	’H NMR (400 MHz, CDCI3) δ 7.95 (m, 1H), 7.26 (s, 1H), 7.08 (m, 1H), 6.61 (t, 1H), 4.91 (s, 2H), 4.02 (s, 3H)
178	86.1- 88.4		ESIMS m/z 354 ([M+2H]⁺)	*H NMR(400 MHz, DMSO-</₆) δ 6.99 (br s, 2H), 7.28 (t, J = 54.00 Hz, 1H), 7.607.70 (m, 2H)
179	137.2— 138.8		ESIMS m/z 313 ([M+H]⁺)	'H NMR (400 MHz, CDCI3) δ 7.73 (m, 1H), 7.76 (s, 1H), 6.95 (m, 1H), 4.85 (s, 2H), 4.01 (s, 3H), 2.30 (s, 3H)
180			ESIMS m/z 267 ([M+H]⁴)	’H NMR (400 MHz, DMSO-d₆) δ 7.82 (m, 2H), 7.55-7.44 (m, 3H), 6.88 (s, 2H)
181	105- 108		ESIMS m/z 901 ([M+H]⁴)	*H NMR (400 MHz, DMSOY) δ 7.82 (m, 2H), 7.55-7.44 (m, 3H), 6.88 (s, 2H), 3.98 (s, 3H)
183			ESIMS m/z 299 ([M+H]⁴)	*H NMR (400 MHz, DMSO-</₆) δ 7.68 (dq, ./ = 7.9,1.3 Hz, 1H), 7.58 (m, 2H), 7.33 (m, 1H), 7.06 (s, 2H), 3.89 (s, 3H)	^,9F NMR (376 MHz, DMSO-</₆) δ 112.86, -140.06
184	116.5- 118.8		ESIMS m/z 331 ([M+H]⁴)	*H NMR (400 MHz, CDCI3) δ 7.26 (m, 1H), 6.99 (m, 1H), 4.95 (s, 2H), 3.99 (s, 3H), 2.32 (s, 3H)
185	163.4- 164.8		ESIMS m/z 310 ([M+H]⁴)	‘H NMR (400 MHz, CDCI3) δ 7.62 (m, 1H), 6.97 (m, 1H), 5.45 (s, 2H), 4.01 (s, 3H), 3.95 (s, 3H), 2.30 (s, 3H)

Compd. No.	mp (°C)	IR (cm¹)	Mass“	’H NMR^b	’³C or ”F NMR
186	147- 148			‘H NMR (400 MHz, DMSO-J₆) δ 7.46 (m, 2H),7.17(s, 2H), 3.87 (s, 3H)
187	167.4- 170.2		ESIMS m/z 351 ([M+H]⁴)	*H NMR(400 MHz, CD₃OD) δ 4.89 (s, 2H), 7.02 (t,7 = 72.80 Hz, 1H), 7.33 (dd, 7=6.40, 10.80 Hz, 1H), 7.80 (dd, 7 = 7.20,11.00 Hz, 1H)
188	172.9175.0		ESIMS m/z 301 ([M+2H]⁴)	‘H NMR(400 MHz, DMSO-7₆) δ 2.28 (s, 3H), 6.80 (br s, 2H), 7.25 (s, 1H), 7.31 (dd,7=6.32, 11.58 Hz, 1H), 7.65 (dd, 7 = 6.60,10.36 Hz, 1H), 13.54 (brs, 1H)
189		IR (thin film) 3376, 1737,1615 cm·'	ESIMS m/z 3\Ί ([M+H]⁴)	‘H NMR (400 MHz, DMSO-îZ₆) δ 7.50 7.32 (m, 3H), 7.13 (s, 2H), 3.87 (d, 7=2.3 Hz, 3H)
190	163— 165		ESIMS m/z 339 ([M+H]⁴)	’H NMR (400 MHz, DMSO-<Z₆) δ 8.13 8.04 (m, 2H), 8.02 7.92 (m, 2H), 7.08 (s, 2H), 3.89 (s, 6H)
191	154- 157		ESIMS m/z 296 ([M+H]⁴)	’H NMR (400 MHz, DMSO-4) δ 7.86 7.70 (m, 1H), 7.41 (tdd, 7 = 9.5, 7.3,2.1 Hz, 3H), 6.66 (dd, 7 = 17.6,11.5 Hz, 1H), 5.63 - 5.38 (m, 2H), 3.82 (s, 3H)	¹⁹F NMR (376 MHz, DMSO-7₆) δ -132.72 (dd, 7=21.4, 8.8 Hz), -135.29 (dd, 7 = 21.0,8.7 Hz), -161.04 (t, 7 = 21.3 Hz)
192	192- 195		ESIMS m/z 324 ([M+H1Q	’H NMR (400 MHz, DMSO-7₆) δ 8.08 (br s, 1H), 7.99 (m, 2H), 7.87 (m, 2H), 7.47 (br s, 1H), 7.03 (br s, 2H), 3.89 (s, 3H)
193	127.9- 129.2		ESIMS m/z 346 ([M+H]⁴)	’H NMR (400 MHz, CDCI3) δ 7.77 (m, 1H), 7.39 (m, 1H), 6.89 (t, 1H), 5.49 (s, 2H), 4.02 (s, 3H), 3.97 (s, 3H)
194	167.4- 170.2		ESIMS m/z 3Y1 [(M+H)⁴]	’H NMR(400 MHz, DMSO-7₆) δ 2.30 (s, 3H), 6.41 (brs, 2H), 7.28-7.45 (m, 2H)

-19217475

Compd. No.	mp (°C)	IR (cm¹)	Mass⁸	’H NMR^b	^I3C or ¹⁹F NMR
195	162.0- 165.0		ESIMS m/z 369 [(M+H)⁺J	1H-NMR(4OO MHz, CDjOD) δ 4.90 (s, 2H), 7.01 (t,J = 72.72 Hz, IH), 7.29 (dd, J =6.52, 9.76 Hz, IH), 7.55 (dd, J = 6.36,10.52 Hz, IH)
196	127- 129	IR (thin film) 3480 (s), 3345 (s), 3186 (w), 2961 (w), 1717 (s), 1614 (s) cm'¹	ESIMS m/z 331 ([M+Hf)	*H NMR (300 MHz, CDC1₃) δ 7.75-7.81 (m, 2H), 7.67 (t, J = 8 Hz, IH), 7.14 (s, IH), 6.94 (t, J =55 Hz, IH), 4.90 (br s, 2H), 4.04 (s, 3H)
197	156- 158		ESIMS m/z 309 ([M+H]⁺)	'H NMR (400 MHz, DMSO-<Z₆) δ 7.86 7.70 (m, IH), 7.41 (tdd, J= 9.5, 7.3,2.1 Hz, 3H), 6.66 (dd, J = 17.6,11.5 Hz, IH), 5.63-5.38 (m, 2H), 3.82 (s, 3H)	¹⁹FNMR (376 MHz, DMSO-7₆) δ -132.72 (dd, J =21.4, 8.8 Hz), -135.29 (dd, J = 21.0,8.7 Hz), -161.04 (t, J= 21.3 Hz)
198			ESIMS m/z 342 ([M+H]⁺)	‘H NMR (400 MHz, CDCI3) δ 7.54(m, IH), 7.44(m, IH), 5.06(s, 2H), 4.00(s, 3H)	¹⁹F NMR (376 MHz, CDClj) δ -111.33,-111.38, -115.73,-115.77, -115.83,-115.89, -136.82,-136.92
199	145- 147		ESIMS m/z 317 ([M+H]⁺)	*H NMR (400 MHz, CDCI3) δ 7.36 (tt, J = 5.8, 1.7 Hz, IH), 7.29 -7.15(m, 2H), 4.97 (s, 2H), 3.98 (s, 3H)
200	143.5- 144.5	IR (thin film) 3498, 3374, 1731, 1621, 1520, 1232 cm’¹	ESIMS m/z 335 ([M+H]⁺)	‘H NMR (400 MHz, CDCI3) δ 7.57 — 7.39 (m, IH), 7.09 - 6.96 (m, IH), 4.96 (s, 2H), 4.00 (s, 3H)	^l9F NMR (400 MHz, CDCI3) δ -114.6,-131.0, -137.5,-142.0
201	135.9- 137.7		ESIMS m/z 297 ([M+H]⁺)	1H-NMR(4OO MHz, DMSO-</₆) δ 2.28 (s, 3H), 3.75 (s, 3H), 7.24 (dd, 7=6.24, 10.98 Hz, IH), 7.36 (br s, 2H), 7.58 (dd, 7 = 6.32,10.20 Hz, IH), 13.5(s,lH)
202	209.7- 211.9		ESIMS m/z 324 ([M+Hf)	'H NMR (400 MHz, CDCI3) δ 8.03 (m, IH), 7.42 (m, IH), 7.32 (s, IH), 4.96 (s, 2H), 4.03 (s, 3H)	¹⁹F NMR (376 MHz, CDCI3) δ -111.15, -119.08

-19317475

Compd. No.	mp (°C)	IR (cm¹)	Mass“	’H NMR^b	’³C or ”F NMR
203	143.7- 145.5		ESIMS m/z 332 ([M+Hf)	1H-NMR(4OO MHz, DMSO-7₆) δ 3.76 (s, 3H), 7.24 (t,J = 54.00 Hz, 1H), 7.43 (br s, 2H), 7.59 (dd, J = 5.60,10.00 Hz, 1H), 7.78 (dd, J = 5.60, 10.40 Hz, 1H)
204	131			’HNMR (400 MHz, DMSO-7₆) δ 7.87 (m, 2H), 7.35 (m, 2H), 7.01 (s, 2H), 3.89 (s, 3H)
205	141.8- 145		ESIMS m/z 349 ([M+Hn	‘H NMR (400 MHz, CDClj) δ 7.9 l(m, 1H), 7.38 (m, 1H), 7.35 (s, 1H), 6.90 (t, 1H), 4.90(s, 2H), 4.03(s, 3H)
206	159- 161		ESIMS m/z 299 ([M+Hf)	’H NMR (400 MHz, DMSO-î/₆) δ 7.55 (m, 2H), 7.39 - 7.30 (m, 2H), 7.05 (s, 2H), 3.86 (s, 3H)
207	130- 132		ESIMS m/z 246 ([M+Hf)	’H NMR (400 MHz, CDC1₃) δ 8.29 - 8.21 (m, 2H), 7.48 (m, 3H), 5.66 (s, 2H), 4.06 (s, 3H)
208	165.0- 166.5		ESIMS m/z 321 ([Μ+ΗΠ	’H NMR (400 MHz, CDClj) δ 7.88 (m, 1H), 7.42 (m, 1H), 5.51 (s, 2H), 4.03 (s, 3H), 3.98 (s, 3H)
209	113- 115	IR (thin film) 3496 (s), 3377 (s), 2954 (w), 1726 (s), 1611 (s) cm'¹	ESIMS m/z 331 ([M+Hf)	’H NMR (300 MHz, CDC1₃)6 8.O1 (brd, J= 8 Hz, 2H), 7.61 (brd, J =8 Hz, 2H), 6.70 (t, J =56 Hz, 1H),4.93 (brs,2H), 3.99 (s, 3H)
210	159 decomp		ESIMS m/z 3Y1 ([M+Hn	’H NMR (400 MHz, DMSO-cZî) δ 7.26 (m, 2H), 7.02 (s, 2H), 2.35 (d, J= 1.7 Hz, 3H)
211	167- 168		ESIMS m/z 329 ([M-H]’ )	’H NMR (300 MHz, DMSO-<4) δ 7.23 (m, 2H), 7.08 (s, 2H), 3.85 (s, 3H), 2.33 (d, J =2.1 Hz, 3H)

-19417475

Compd. No.	mp (°C)	IR (cm¹)	Mass³	‘H NMR^b	¹³C or ¹⁹F NMR
212	145- 146		ESIMS m/z 299 ([M+Hf)	'H NMR (400 MHz, DMSO-<4) δ 13.59 (s, 1H), 7.60 (m, 2H), 7.42 (m, 1H), 6.94 (s, 2H), 2.30 (s, 3H)
213	127		ESIMS m/z 313 ([M+Hf)	‘H NMR (400 MHz, DMSO-</₆) δ 7.57 (dd, J= 14.6,9.7 Hz, 2H), 7.42 (t, J =8.1 Hz, 1H), 7.02 (s, 2H), 3.89 (s, 3H), 2.30 (s, 3H)
214	151- 154		ESIMS m/z 311 ([M+Hf)	‘H NMR (400 MHz, DMSO-J₆) δ 7.87 (dd, J= 11.2, 1.6 Hz, 1H), 7.80-7.68 (m, 2H), 6.76 (dd, J = 17.6, 11.7 Hz, 1H), 6.50 (br s, 2H), 5.57 (dd, J= 7.3, 0.9 Hz, 1H), 5.53 (s, 1H)
215	97-101		ESIMS m/z 325 ([M+Hf)	‘H NMR (300 MHz, CDCI3) δ 7.83 - 7.77 (m, 1H), 7.76 - 7.69 (m, 1H), 7.48 (dd, J = 8.4, 7.6 Hz, 1H), 6.89 (dd, J= 18.0, 11.7 Hz, 1H), 5.73 (dd, J= 11.5,1.4 Hz, 1H), 5.59 (dd, J = 18.1,1.4 Hz, 1H), 4.78 (br s, 2H),3.93 (s, 3H)
216	111- 114
217	159- 161			'H NMR (400 MHz, CDClj) δ 7.80 (d, J = 10.4 Hz, 1H), 7.72 (d, J =8.4 Hz, 1H), 7.48 (m, 1H), 4.93 (s, 2H), 4.00 (s, 3H)

^a Mass spectrometry data are electrospray ionization mass spectrometry (ESIMS) unless otherwise noted.

^b Ail 'H NMR data measured in CDCI3 at 400 MHz unless otherwise noted.

Examples of Herbicidal Activities

Herbicidal évaluations were made visually on a scale of 0 to 100 where 0 represents no activity and 100 represents complété plant death. The data are displayed as indicated in

Table A.

-19517475

Table A: Percent Control Rating Conversion Table

Rating	% Control
A	95-100
B	85-94
C	75-84
D	60-74
E	45-59
F	30-44
G	0-29

Example A. Evaluation of Postemergent Herbicidal Activity

Post-Emergent Test I: Seeds of test species were obtained from commercial suppliers and planted into a 13 centimeter (cm) diameter-round pot contaîning soil-less media mix (MetroMix 360®, Sun Gro Horticulture). Postemergence treatments were planted 8-12 days (d) prior to application and cultured in a greenhouse equipped with supplémentai light sources to provide a 16 hour (h) photoperiod at 24-29 °C. Ail pots were surface irrigated.

A weighted amount, determined by the highest rate to be tested, of each compound was dîssolved in 1.3 mL acetone-dimethyl sulfoxide (DMSO; 97:3, volume per volume (v/v)) and diluted with 4.1 mL water-isopropanol-crop oil concentrate (78:20:2, v/v/v) contaîning 0.02% Triton X-155 to obtain concentrated stock solutions. Additional application rates were obtained by serial dilution of the high rate solution into a solution contaîning appropriate volume of 97:3 v/v mixture of acetone and DMSO and appropriate volume of an aqueous mixture of water, isopropyl alcohol, crop oil concentrate (78:20:2, v/v/v) contaîning 0.02% Triton X-155.

Formulated compounds were applied using a DeVilbiss® compressed air sprayer at 2—4 pounds per square inche (psi). Following treatment, pots were retumed to the greenhouse for the duration of the experiment. Ail pots were sub-irrigated as need to provide optimum growing conditions. Ail pots were fertilized one time per week by subirrigating with Peters Peat-Lite Spécial® fertilizer (20-10-20).

Phytotoxicity ratings were obtained 10 days after treatment postemergence applications. Ail évaluations were made visually on a scale of 0 to 100 where 0 represents no activity and 100 represents complété plant death and is presented as indicated in Table A.

-196Y'

Some of the compounds tested, application rates employed, plant species tested, and results are given in Table 3.

Table 3. Post-Emergent Test I Herbicidal Activity on Key Broadleaf and Grass Weed as well as Crop Species

Compound No.	Application Rate (kg ai/ha)	Visual Growth Réduction (%) 14 Days After Application
AMARE	AVEFA	ECHCG	HELAN	IPOHE	SETFA
138	4	A	C	A	A	A	A
20	4	n/t	C	A	A	B	A
135	4.04	A	D	A	A	B	C
156	4.04	A	C	A	A	A	B
16	3.84	A	G	E	A	A	D
114	3.92	A	G	A	A	B	C
85	3.76	A	F	A	A	F	B
142	3.84	A	E	A	A	A	D
118	2.32	A	A	A	A	A	A
45	3.96	A	A	A	A	B	A
143	4	A	n/t	A	A	E	A
39	2	A	C	B	A	D	n/t
209	4	A	B	A	A	B	A
199	4	A	n/t	D	A	C	B
206	4.04	A	n/t	G	A	C	G
196	3.84	A	D	A	A	B	A
181	1.76	A	G	G	A	C	G
109	4	n/t	C	A	A	B	A
147	3.96	A	C	A	A	A	A
215	3.96	n/t	F	B	A	A	G
214	4.04	n/t	D	A	A	A	B

AMARE: redroot pigwseed (Amaranthus retroflexus) AVEFA: wild oats (Avena fatua)

ECHCG: bamyardgrass (Echinochloa crus-gallî)

HELAN: sunflower (Helianthus annuus)

IPOHE: ivyleaf momingglory (Ipomoea hederecea)

-19717475

SETFA: giant foxtail (Setaria faberî) kg ai/ha: kilograms active ingrédient per hectare n/t: not tested

Example B. Evaluation of Preemergent Herbicidal Activity

Pre-Emergent Test I: Seeds of test species were planted into round plastic pots (5-inch diameter) containing sandy loam soil. After planting, ail pots were sub-irrigated 16 h prior to compound application.

Compounds were dissolved in a 97:3 v/v mixture of acetone and DMSO and diluted to the appropriate concentration in a final application solution containing water, acetone, isopropanol, DMSO and Agri-dex (crop oil concentrate) in a 59:23:15:1.0:1.5 v/v ratio and 0.02% w/v (weight/volume) of Triton X-155 to obtain the spray solution containing the highest application rate. Additional application rates were obtained by serial dilution of the high rate solution with the above application solution.

Formulated compound (2.7 mL) was pipetted evenly over the soil surface followed by incorporation with water (15 mL). Following treatment, pots were retumed to the greenhouse for the duration of the experiment. The greenhouse was programmed for an approximate 15 h photoperiod which was maintained at about 23-29°C during the day and 22-28°C during the night. Nutrients and water were added on a regular basis through surface irrigation and supplémentai lighting was provided with overhead métal halide 1000Watt lamps as necessary.

Herbicidal effect ratings were obtained 14 days after treatment. Ail évaluations were made relative to appropriate controls on a scale of 0 to 100 where 0 represents no herbicidal effect and 100 represents plant death or lack of emergence from the soil and is presented as indicated in Table A. Some of the compounds tested, application rates employed, plant species tested, and results are given in Table 4.

Table 4. Pre-Emergent Test I Herbicidal Activity on Key Broadleaf and Grass Weed as well as Crop Species

Compound No.	Application Rate (kg ai/ha)	Visual Growth Réduction (%) 14 Days After Application
AMARE	AVEFA	ECHCG	HELAN	IPOHE	SETFA
138	4	A	A	A	A	A	A
20	4	n/t	A	A	A	A	A

-1982

135	4.04	A	F	F	A	A	F
156	4.04	A	C	A	A	A	A
16	3.84	A	F	F	A	A	G
114	3.92	A	A	C	A	A	B
85	3.76	A	C	A	A	F	n/t
142	3.84	A	A	F	A	A	n/t
118	2.32	A	A	A	A	A	n/t
45	3.96	A	A	A	A	A	A
143	4	B	D	B	A	B	A
39	2	A	B	A	A	A	n/t
209	4	A	A	A	A	A	A
199	4	n/t	n/t	G	D	C	E
206	4.04	n/t	n/t	G	A	A	C
196	3.84	A	n/t	B	A	A	A
181	1.76	A	G	n/t	B	B	C
109	4	n/t	B	A	C	A	A
147	3.96	n/t	A	A	A	A	A
215	3.96	A	B	A	A	A	B
214	4.04	n/t	B	A	A	A	A

AMARE: redroot pigwseed (Amaranthus retroflexus)

AVEFA: wild oats (Avena fatua)

ECHCG: bamyardgrass (Echinochloa crus-galli)

HELAN: sunflower (Helianthus annuus)

IPOHE: ivyleaf momingglory (Ipomoea hederecea)

SETFA: giant foxtail (Setaria faberï) kg ai/ha: kilograms active ingrédient per hectare n/t: not tested

Example C. Evaluation of Postemergent Herbicidal Activity

Post-Emergent Test II: Seeds or nutlets of the desired test plant species were planted in Sun

Gro Metro-Mix® 360 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 64 square centimeters. When required to ensure good germination and healthy plants, a fongicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 7-21 d in a greenhouse with an approximate 15 h photoperiod which was maintained at

-19917475 about 23-29 °C during the day and 22-28 °C during the night. Nutrients and water were added on a regular basis and supplémentai lighting was provided with overhead métal halide

1000-Watt lamps as necessary. The plants were employed for testing when they reached the first or second true leaf stage.

A weighed amount, determined by the highest rate to be tested, of each test compound was placed in a 25 mL glass vial and was dissolved in 4 mL of a 97:3 v/v mixture of acetone and DMSO to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions obtaîned were diluted with 20 mL of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, Atplus 411F crop oil concentrate, and Triton® X-l 55 surfactant in a 48.5:39:10:1.5:1.0:0.02 v/v ratio to obtain spray solutions containing the highest application rates. Additional application rates were obtaîned by serial dilution of 12 mL of the high rate solution into a solution containing 2 mL of 97:3 v/v mixture of acetone and DMSO and 10 mL of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, Atplus 411F crop oil concentrate, and Triton X-l55 surfactant in a 48.5:39:10:1.5:1.0:0.02 v/v ratio to obtain 1/2X, 1/4X, 1/8X and 1/16X rates of the high rate. Compound requirements are based upon a 12 mL application volume at a rate of 187 liters per hectare (L/ha). 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 at a spray height of 18 inches (43 cm) above the average plant canopy height. Control plants were sprayed in the same manner with the solvent blank. The treated plants and control plants were placed in a greenhouse as described above and watered by subirrigation to prevent wash-off of the test compounds. After 14 d, the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complété kill and is presented as indicated in Table A. Some of the compounds tested, application rates employed, plant species tested, and results are given in Table 5.

-20017475

Table 5. Post-Emergent Test II Herbicidal Activity on Key Broadleaf Weed and Crop Species

Visual Growth Réduction (%) 14 Days After Application

VIOTR

<

CQ

<

Q

U-,

0

HELAN

<

C

<

EPHHL

<

m

<

0

CHEAL

<

Q

m

BRSNN

<

O

ffl

0Q

Q

o

m

0

b

m

AMARE

<

ABUTH

<

Q

o

CQ

<

Q

O

0

Application Rate (g ai/ha)

o r-

140

o r-

O T—H

o r-

140

o t-

140

o r-

140

o r-

140

o r-

140

o r-

140

Compound No.

o CN

216

217

135

156

KO

m

CO

-201-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

CQ

Φ

U

CQ

<

CQ

<

b

Φ

HELAN i 1

<

m

<

m

Q

CQ

Φ

EPHHL

<

Φ

CHEAL

<

CQ

<

PQ

cq

CQ

Q

b

BRSNN

m

CQ

<

w

Q

Φ

<

O

CQ

Q

CQ

Φ

AMARE

<

Q

CQ

Φ

P-1

ABUTH

<

CQ

<

CQ

O

Φ

Application Rate (g ai/ha)

o Γ-

140

o t·

140

o Γ

O r—<

o t-

140

o o

140

o c-

140

o Γ

140

o r-

140

Compound No.

149

r—

»r> oo

142

00

M·

Ox

143

190

-20217475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

PL

Pl

w

<

O

CQ

<

O

<

0

o

O

PL

HELAN

<

CQ

<

m

<

Q

o

U

<

EPHHL

cq

<

W

Q

<

U

Q

CQ

CHEAL

CQ

<

Q

U

<

CQ

<

BRSNN

o

(J-i

o

CQ

O

CQ

<

CQ

QQ

<

O

o

CQ

AMARE

c

m

CQ

<

CQ

<

Q

03

<

ABUTH

PL

Q

m

<

Pl

PQ

<

CQ

O

<

Application Rate (g ai/ha)

O t-

140

o o

140

o t

140

o

140 j

o Γ

140

<=> c-

140

o Γ

o M· T—<

o

140

o

140

Compound No.

C\ en

165

160

204

981

209

134

O 00

<53 03 1 ¹ <

-203-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

W

Q

O

Ό

O

U

O

o

O

<

HELAN

Q

m

CQ

<

O

<

EPHHL

<

Q

O

<

PQ

<

CHEAL

m

<

BRSNN

o

m

CQ

PQ

CQ

PQ

<

Q

CQ

<

AMARE

<

m

O

<

CQ

<

ABUTH

<

PQ

<

0

Application Rate (g ai/ha)

o r-

140

o r-

140

VO

132

o

O

o r-

140

o Γ~-

140

o

140

o t—

140

o r-

140

Compound No.

206

081

213

196

00

212

cq

109

147

-204-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

<

m

O

4—·

O

U

O

C

O

Q

W

Q

HELAN

<

m

Q

m

<

m

<

m

<

EPHHL

<

CQ

m

<

CHEAL

<

O

<

CQ

m

<

CQ

<

BRSNN

O

U

<

0

O

m

CQ

<

Q

CQ

m

<

AMARE __________________________________________________________________________________________________________________________________________________________________________________________________________________________1

<

m

<

M

U

<

ABUTH

m

CO

<

w

Q

u

<

Application Rate (g ai/ha)

o C-

140

o r-

140

o

140

o t·

140

o Γ

140

o r-

140

o Γ

O 'φ

o t-

140

o I>

140

Compound No.

210

167

215

214

ι/Ί r- H

γ~·

CT

dΌ

-20517475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

W

Q

O

<

0

o

<

HELAN

<

o

0

<

O

CQ

O

u

<

EPHHL

<

o

O

<

o

0

<

CHEAL

m

o

0

<

m

CQ

o

PQ

<

BRSNN

u

o

0

<

m

CQ

c

fe

<

AMARE

<

c

<

m

0

<

ABUTH

<

c

0

<

CQ

m

CQ

m

fe

<

Application Rate (g ai/ha)

o r·-

140

o r-~

140

o o

o ”3

o

140

o r-

140

o Τ'

140

o r-

140

o r-

140

o r-

140

Compound No.

172

106

CN

132

157

152

CO O T—

Ch Ch

-20617475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

0

O

<

o

0

b

O

C

0

fe

0

HELAN

m

<

U

O

<

U

o

<

Q

O

m

<

U

m

EPHHL

<

U

CQ

m

<

w

<

CHEAL

<

CQ

o

O

<

m

CQ

o

<

BRSNN

o

Q

U

<

o

0

u

<

m

W

m

<

AMARE

<

o

U

o

U

Q

O

ü

0

<

m

CQ

ABUTH

<

m

CQ

w

W

m

<

O

W

e

CQ

<

Application Rate (g ai/ha)

o o

140

o r-

140

o γ—·

O Tf

o r-

140

o Γ-

140

o t

140

o Γ-

140

o Γ

140

o c-

140

Compound No.

r-~

158

104

133

r-

CN

168

-207Y17475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

Q

O

m

w

Q

C

O

0

o

0

W

<

CQ

W

HELAN

U

<

m

CQ

Q

o

CQ

<

PQ

<

PQ

<

EPHHL

<

C

O

0

o

PQ

<

CHEAL

m

PQ

<

O

Q

0

Q

o

<

BRSNN ____________________________________________________________________________________________________________________________________________________________________________________________________________1

m

U

<

&

ω

O

W

CQ

m

<

AMARE

<

O

0

<

CQ

PQ

O

0

O

<

U

PQ

ABUTH

m

U

O

CQ

m

O

o

O

0

W

υ

<

C

<

Application Rate (g ai/ha)

o o

140

o t—

140

o r-

140

o r-

140

o Γ

140

o t--

140

o r-

140

o Γ'

140

o r-

140

Compound No.

Γc*

00

Xt

00 00

Ch IT)

τΓ

108

122

(N

-20817475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

<

O

0

<

O

0

Q

0

Q

m

<

HELAN

<

o

O

<

w

O

W

Q

<

EPHHL

<

o

0

<

o

<

W

<

CHEAL

<

o

U

<

ω

0

m

<

BRSNN

<

o

<

O

Q

0

m

CQ

<

AMARE

<

o

0

<

0

<

o

<

ABUTH

<

0

o

m

O

0

Q

<

m

CQ

<

Application Rate (g ai/ha) 1

o r-

140

o r-

140

o r-

140

o t-

140

o r-

140

o r-

140

o r-

O 1“^

o o

O N r-H

o r-

140

Compound No.

CN tn

Ci

en

169

CN CN

o tn

CN OO

O1 t—

tn en

-209JA

Visual Growth Réduction (%) 14 Days After Application

VIOTR

w

<

C

0

<

0

HELAN

ra

<

Q

O

U

O

m

0

m

Q

O

Q

0

EPHHL

<

o

O

<

m

CHEAL

<

o

O

0

m

<

ra

<

m

0

BRSNN

<

0

Q

m

<

Q

ra

0

AMARE

m

<

CQ

0

O

0

<

m

<

ω

Q

0

ABUTH

<

m

<

o

O

0

«

<

U

<

0

Application Rate (g ai/ha)

o Γ

140

o γ-

140

o

140

o t·-

140 |

o r-

140

o r-

140

o

O Tt

o r-

O -sfr V—H

o t-

140

Compound No.

o

00

Xt oo

154

129

oo en

en 00

ΓΊ σ\

O

-210-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

0

<

0

O

0

Q

<

0

HELAN

O

U

<

CQ

m

CQ

m

W

<

EPHHL

O

<

w

W

0

CQ

<

CHEAL

o

O

<

0

<

PQ

<

w

CQ

<

BRSNN

o

Q

<

Pu,

tu.

W

Q

0

CQ

PU

w

O

0

m

CQ

<

AMARE

0

U

<

Q

O

Q

0

w

CQ

0

CQ

<

ABUTH

O

0

<

CQ

m

CQ

Q

CQ

0

pu,

CQ

<

o

CQ

<

Application Rate (g ai/ha)

o r-

140

o

140

o r-

140

o r-

140

o r~

140

o

140

o Γ-

ο xt

o r-

140

O

140

Compound No.

00

<N

o> CN

m Ό

128

00 ι/Ί

146

xt

-21117475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

0

O

o

0

HELAN

cq

CQ

0

DQ

<

0

CQ

<

EPHHL

w

o

O

<

w

<

U

CQ

0

CHEAL

<

CQ

<

C

0

<

CQ

<

O

<

&

BRSNN

<

ω

Q

<

0

O

CQ

0

Q

CQ

<

0

AMARE

<

0

W

<

0

ABUTH

U

Q

CQ

<

CQ

Application Rate (g ai/ha)

o r-

140

o r-

O TJ v—H

o

140 1

o o-

140

o Γ

140

o t>

140

O 1—H

o

140

Compound No.

125

189

200

126

00

en rq

O

3· en

en

m

-21217475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

Φ

O

Φ

O

<

Φ

HELAN

m

<

m

CQ

m

EPHHL

O

Φ

O

Φ

<

w

W

<

CHEAL

O

Q

O

ffl

<

Q

BRSNN

Uh

Φ

c

Φ

<

ο

<

Q

Φ

AMARE

c

O

Q

Φ

<

4-»

4—»

CQ

<

ABUTH

Q

C

Φ

Q

Φ

<

m

<

m

<

œ

m

Φ

Application Rate (g ai/ha)

O

140

O Γ

140

O r-

O Tt i—4

O r-

140

O Γ

140

ο Γ-

140

ο Γ-

140

Compound No.

en CO

170

in o

-

CN

in

σ> Ό

Ό 00

100

ο

-213:

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

0

<

0

w

<

0

HELAN

0

Q

0

PQ

<

U

m

PQ

0

<

PQ

<

EPHHL

<

0

<

O

W

CHEAL

O

0

<

BRSNN

0

m

<

PQ

<

PQ

<

Q

PQ

AMARE

C

0

<

PQ

ABUTH

W

0

<

PQ

<

Application Rate (g ai/ha)

140

o C

140

o r-

140

o r-

140

o r-

140

o t-'

O XT r—<

o t·

140

o C

O ’d 1-·^

Compound No.

O en

102

(N

127

O in

en

159

124

O\

-214-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

ra

O

o

O

HELAN

<

m

CQ

<

o

ra

m

<

EPHHL

O

w

o

C

<

o

O

CHEAL

m

PQ

O

<

o

ra

<

U

ra

<

BRSNN

m

o

O

<

o

Q

m

ra

Ü

o

Q

m

ira

AMARE

CQ

<

o

w

o

<

m

ra

ABUTH

Q

ffl

o

U

m

o

<

ira

<

Application Rate (g ai/ha)

o

140

o

140

o Γ

140

o r~

140

o Γ

140

O r-

140

o Γ

140

Compound No.

00 (N

130

en UT)

m o\

o

00

136

-215-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

c

O

ra

<

C

0

ω

0

O

0

O

0

HELAN

<

m

ra

<

m

ra

U

ra

<

EPHHL

0

o

O

<

0

<

CHEAL

m

ra

m

<

m

<

ra

m

ra

BRSNN

m

<

0

o

ra

ira

ra

AMARE

ffl

<

o

ra

m

ra

<

m

<

0

ra

<

ABUTH

<

m

ra

<

o

ira

Q

u

<

ra

Application Rate (g ai/ha)

o r-

140

o r-

140

o r-

140

o r-

O r-H

o r-

140

o r-

140

o r-

140

ko ko

132

o

140

Compound No.

OO r-

ko

(N

S

-

o

107

O

150

-216Y17475

Visual Growth Réduction (%) 14 Days After Application	VIOTR	O	O	0	0	0	0	0	0	O	O	0	0	0	0	0	0	0	0
HELAN	ra	O	W	CQ	ra	ira	m	<	m	m	ra	m	Q	m	ra	ra	0	0
EPHHL	0	O	<		ra	ra	<	<		<	0	0	0	0	0	0	0	0
CHEAL	o	o	m		m	m	m	<		<	0	0	ra	Q	ra	ra	0	0
BRSNN	o	o	0	0	Q	u		<	o	Q	0	0	0	0	0	0	0	0
AMARE	u	0	<	<	ra	<		<	<	<	0	0	0	0	0	ra	0	0
ABUTH	o	0	0	0	ra	m	<		<	<	0	ra	ra	Q	0	0	0	0
Application Rate (g ai/ha)	o	140	o t-~	140	o r-	140	o r-	140	o t---	O	o r-	140	o r-	140	o r~-	140	o r-	140
Compound No.	o		Ό m		r- IT)		o		r-		en 00		-		TT ζΛ		192

-217-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

O

C

O

U

O

o

<

O

<

HELAN

<

CQ

<

CQ

<

CQ

QQ

EPHHL

o

O

<

O

b

<

Q

<

CHEAL

m

<

CQ

<

CQ

<

CQ

<

BRSNN

m

CQ

m

CQ

W

Q

m

W

CQ

Q

U

CQ

<

AMARE

Q

O

<

CQ

Q

O

<

O

<

QQ

CQ

ABUTH

<

CQ

O

CQ

<

Q

U

CQ

W

Q

W

Q

Application Rate (g ai/ha)

o F

140

Ό

132

o F~

140

o F-

140

o F'

140

o F~

140

o t-

* 140

o F~

140

o F~

140

Compound No.

CQ

Ch F-

155

m

FCQ

FF-

145

Cm

-218A

Visual Growth Réduction (%) 14 Days After Application

VIOTR

W

M

<

W

«

Q

O

w

W

Φ

O

HELAN

<

CQ

PQ

<

CQ

<

CQ

<

m

Q

EPHHL

w

Q

<

Q

<

Φ

Q

CHEAL

m

CQ

m

U

O

<

O

W

BRSNN

<

m

<

Q

o

<

CQ

<

Φ

O

AMARE

<

m

<

Φ

ABUTH

m

u

CQ

<

Q

<

U

CQ

Application Rate (g ai/ha)

o o

140 1

o r-

140

o r-

O 1—<

o fx

140

o Γχ

140

o r-

140

o ex

140

o tx

140

o (X

140

Compound No.

en r-

(χ

en xT

en

un

o

197

o>

137

-21917475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

0

Q

CQ

0

w

Q

O

0

PL

HELAN

C

0

m

CQ

PO

O

o

CQ

<

QQ

<

CQ

<

EPHHL

0

<

QQ

<

CHEAL

0

<

0

CQ

0

<

Q

CQ

Q

o

BRSNN

0

w

0

Q

CQ

<

0

Q

O

CQ

0

PL

AMARE

0

o

0

M—»

<

O

<

ABUTH

0

Q

O

0

<

CQ

0

<

PL

Q

0

Application Rate (g ai/ha)

o f-

140

o f-

140

o f-

140

o F-

140

o o

140

o F-

O

o F-

140

O F-

140

o F

140

Compound No.

00 ok

en

wn

vn

o 00

en es

O F

m KO

-22017475

Visual Growth Réduction (%) 14 Days After Application

VIOTR

Q

PQ

W

Q

<

Q

Pu

Q

O

0

W

Q

HELAN

m

<

ω

Q

Pu

Q

PQ

CQ

Q

o

<

o

W

CQ

<

EPHHL

o

CQ

PQ

O

<

W

Q

Pu

W

<

CHEAL

pq

<

CQ

<

CQ

O

0

<

BRSNN

CQ

<

W

Q

<

O

CQ

U

O

0

Q

PQ

AMARE

0

<

Q

0

<

ABUTH

PQ

U

O

PQ

CQ

PQ

CQ

<

Q

U

0

<

Application Rate (g ai/ha)

o r-

140

o r-

140

o r-

140

o r-

140

o Γ-

140

O r-

140

G r-

140

o

140

o r-

140

Compound No.

144

148

o Ch

162

00

202

198

208

205

-221-

Visual Growth Réduction (%) 14 Days After Application

VIOTR

fe

0

fe

0

W

Q

fe

0

fe

HELAN

<

Q

O

fe

0

m

CQ

O

CQ

<

Q

U

EPHHL

CQ

<

m

O

PQ

<

PQ

<

CHEAL

CQ

m

<

0

CQ

<

CQ

Q

<

<3

<

PQ

<

BRSNN

<

Q

fe

O

fe

CQ

<

fe

<

fe

AM ARE

<

o

<

Q

QQ

CQ

0

<

fe

<

ABUTH

<

Q

0

CQ

<

fe

W

0

O

fe

Application Rate (g ai/ha)

o r-

140

o

140

o

140

o V-

O ’ΤΓ

o Γ

140

o r-

140

o

140

o Γ~-

140

o

O Tt*

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------! Compound No.

176

193

177

179

184

185

174

178

203

-22217475

Visual Growth Réduction (%) 14 Days After Application	VIOTR	Φ	Φ	Ü	C	Φ	c	O	Φ	Φ	Φ
HELAN _________________________________________________________________________________________________________________________________________________________________________________________________________________1	ω	Q	Q	m	υ	o	m		Q	U
EPHHL	<		b	&	<		m	m	m	m
CHEAL	u	<	m	o	<	m	u	m	m	u
BRSNN	u	U	w	Q	Q	Q	Q	u		<
AMARE	<		O	w	<	<		<	b	Q
ABUTH	w	Q	Φ	Φ	U	<	Q	u		Q
Application Rate (g ai/ha)	o r-	140	o c-	140	o r-	140	o	140	o	140
Compound No.	187		195		OO 00 T—		194		201

m CN CN i

VIOTR: wild pansy (Viola tricolor) g ai/ha: grams active ingrédient per hectare n/t: not tested

ο

Table 6. Post-Emergent Test II Herbicidal Activity on Key Grass and Sedge Weeds as well as Grass Crops

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

<

m

CQ

<

0

U

CQ

0

TRZSS

O

U

0

Pu

0

tu

Pu

W

Q

Pu

W

0

ORYSA

Q

0

Q

0

SORVU

<

m

CQ

U

m

Q

0

SETFA

<

Pu

W

Q

o

m

<

W

Q

0

ECHCG

<

0

CQ

U

CQ

<

0

CQ

DIGSA

<

tu

0

m

Q

o

Q

0

Q

0

Q

CYPES

<

m

CQ

<

Q

CQ

<

ω

0

Application Rate (g ai/ha)

o r-

140

o

140

o r-

140

o r-

140

o fx-

140

o r-

140

o r-

O

o r-

140

Compound No.

O

216

217

135

156

C*

en

-22417475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

U

m

CQ

m

0

w

Q

m

<

PO

CQ

0

TRZSS i

PL

PO

PL

w

PL

0

PL

0

o

PO

Q

0

ORYSA

0

PL

ω

PO

Q

0

PL

0

g O <Zi

<

O

m

W

M

Q

<

0

U

CQ

0

SETFA

PL

Q

O

W

u

0

PO

Q

m

Q

CQ

0

U

0

ECHCG

<

0

m

<

0

DIGSA

PL

Q

PL

Q

o

CO

m

C0

m

O

0

CYPES

<

co

m

O

m

<

m

<

CQ

0

Application Rate (g ai/ha)

O C-

140

o o

140

o c-

140

o t—

140

o r-

140

o r-

140

o r-

140

o r-

140

o r-

140

Compound No.

149

’d^-

oo

142

00

143

190

-225Ά

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	Q	Q	O	<	C	0	O	0	0	m	0	ra	ra	Q	0	0	0	0
TRZSS		ra	ra	ra	0	0	ra	Q	Q	Q	0	0	Q	0	0	0	0	0
ORYSA	0	ü	a	c	c	C	ü	0	0	10	0	0	ra	ra	0	0	0	0
SORVU	(0	Q	o	o	o	O	o	m	Q	0		<	ra	ra	0	0	0	0
SETFA	0		Q	ira	o	C	ü	ra	0	Q	ra	0	<	<	0	0	0	0
ECHCG	ra	ra	m		o	O	<		m	<		<	<		0	0	0	0
DIGSA	0	ra	o	Q	o	O	Q	Q	ra	Q	ra	Q	0	m	0	0	0	0
CYPES	Q	u	<		Ü	0	m	ra	m	m	ra	m	<	<	0	0	0	0
Application Rate (g ai/ha)	o t>	140	o o	140	o o-	140	o Γ	140	o	140	o t-	140	o Γ	140	o r-	140	o r-	140
Compound No.	Ch en		165		160		204		186		209		134		O oo		199

-226-

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	C	0	0	0	Q	0	0	0	0	fe	0	CQ	fe	fe	CQ	CQ	<	<
TRZSS	0	0	0	0	0	0	0	0	0	0	Q	Q	0	0	fe)	Q	Q	Q
ORYSA	0	0	0	0	0	0	0	0	0	0	Q	Q	0	0	fe)	fe)	Q	0
SORVU	0	0	0	fe	0		0	O	0	fe	Q	O	0	fe	CQ		<	<
SETFA	0	0	0	0	0	0	0	0	0	0	fe)	O	fe	Q			0
ECHCG	0	0	0	0	m	CQ	<		0	0	0	CQ	fe)	CQ	<			<
DIGSA	0	0	0	0	0	0	fe)	fe)	0	0	0	fe	0	0	CQ		CQ	<
CYPES	0	0	fe	fe	0	W	CQ	CQ	<		0	fe	fe	Q	<			<
Application Rate (g ai/ha)	o t—	140	o	140	kC>	132	o r-	140	o	140	o r-	140	o t	140	o o	O ”d	O Γ--	140
Compound No.	206		081		213		196		00		212				109		147

-227-

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

O

M

O

CQ

Pu

w

CQ

0

<

0

CQ

<

0

<

TRZSS

O

0

Q

0

Pu

W

CQ

Pu

CQ

ORYSA

0

tu

0

W

0

Pu

SORVU

0

CQ

W

Q

O

CQ

0

CQ

U

Pu

CQ

SETFA

O

m

0

Pu

0

Q

<

Pu

Q

CQ

Q

ECHCG

Q

0

<

0

<

0

O

<

CQ

<

DIGSA

C

0

o

O

0

O

CQ

Q

iQ

O

CQ

CYPES

0

m

<

0

CQ

<

CQ

Q

0

Pu

Application Rate (g ai/ha)

o r-·

140

o Γ-

140

o t-

140

o t

140

o o

140

o Γ-

140

o

140

o

140

o r-

140

Compound No.

210

167

un 1——< CN

214

175

Γ·

CN

Ό

o

-22817475

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	C	<	O	0	<	<	<	<		C	<	<	<	<	0	0		<
TRZSS	w	Q	0	0	W	Q	Q	Q	0	ra	ra	ra	0	0	0	0	ra	Q
ORYSA	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
SORVU	O	O	0	0	<	<			m		02	<	ra	m	0	0	<	<
SETFA	<		0	0	Q	<	<	<	0	Q			0	ra	0	0	<	<
ECHCG			0	0	m	<	<		m	O				ira	0	0	<	<
DIGSA	O	O	0	0	Q	Q	0	0	m	02	0	02	ra	0	0	0	o	02
CYPES	<		0	0	<	W	<		ra	m	ra	ra	Q	<	0	ra		<
Application Rate (g ai/ha)	o r-	140	o t-··	140	o Γ	140	o r-	140	o t-	140	O F-	j 140	o o	140	o t-	O r—<	o r-	140
Compound No.	172		o o r—				CN		132		157		152		en O		Ch Ch

-22917475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

0

W

0

<

W

<

0

TRZSS

O

0

w

Q

0

ω

0

Q

O

U

ORYSA

0

SORVU

m

CQ

0

m

Q

0

U-,

w

W

Q

U

O

SETFA

0

<

0

W

0

Q

0

<

Q

ECHCG

CQ

<

Q

U

CQ

0

Q

CQ

0

<

O

CQ

DIGSA

Q

O

0

Q

W

0

U

O

Q

0

CYPES

<

W

m

0

<

0

w

u<

«

0

W

<

W

<

Application Rate (g ai/ha)

o r-

140

o r-

140

o

140

o r-

140

o o

O 'φ J—<

o r-

140

o

O 1—M

o r-

140

o r-

140

Compound No.

Γ

158

τΓ

104

en en

r-

168

-23017475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

<

W

M

0

W

<

TRZSS

pl

Q

b

m

ω

Q

0

PL

w

W

0

PL

ORYSA

0

O

0

SORVU

O

PL

O

Q

o

U

m

0

PL

m

SETFA

O

pl

C

0

O

u

Q

CQ

0

W

PL

<

Q

co

ECHCG

0

Q

0

m

<

O

0

W

U

CQ

<

DIGSA

w

W

c

PL

0

Q

0

Q

W

w

Q

CYPES

<

m

<

m

<

0

W

PL

<

Application Rate (g ai/ha)

o r-

140

O c-

O ”d

O r-

140

o r-

140

o r-

140

o r-

140

O

o r-

140

o r-

140

Compound No.

rOs

oo

00 00

Or in

801

122

'Φ ΓΊ

-23117475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

0

ra

Q

<

0

ra

<

Q

<

TRZSS

ra

o

0

Q

ra

ira

0

ra

Q

ra

ORYSA

0

ra

0

SORVU

<

0

ra

<

0

ra

ira

ra

Q

SETFA

ira

Ü

0

m

<

0

ra

0

m

Q

0

ira

ECHCG

Q

o

0

ra

ira

o

Q

0

ra

0

rai

CQ

<

ra

ira

DIGSA

m

ira

0

o

ra

Q

m

0

ira

0

ra

Q

ra

ira

CYPES

<

0

<

0

<

0

<

Application Rate (g ai/ha)

o o

140

o r-

140

o r-

o Φ r—4

o r-

140

o r-

140

o r-

140

o Γ

140

o o

140

o F—

140

Compound No. 1

CN ι/Ί

Ch

en

169

CN CN

O IT)

CN 00

CN r-

m en

-23217475

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	W	w	W	<	O	0	0	0	Q	0	CQ	<	0	0	Q	Q	0	0
TRZSS	m	Q	0	w	O	0	0	0	W	w	Q	Q	0	0	fe	W	0	0
ORYSA	O	O	0	Q	o	0	0	0	0	0	0	0	0	0	0	0	0	0
SORVU	w	Q	m		o	0	0	0	<	<	CQ	CQ	b	ω	fe	fe	0	0
SETFA	o	m	m	m	Ü	0	0	0				<	0	0		-4—»
ECHCG	CQ	cq	m	CQ	0	0	W	W	O	0	<	<	+—»	•4—»	4—> 'a	-4—*
DIGSA	w	o	w	Q	0	0	0	0	Q	Q	O	O	0	0	Q	Q	0	0
CYPES	<	<	w		0	0	0	0	<	•4—» 'B	<	<	0	0	0	0	0	0
Application Rate (g ai/ha)	o ta-	140	o	140	o ta-	O	o ta-	140	o ta-	140	o ta-	¹ 140	o ta-	140	o ta-	O ^“1	o ta-	140
Compound No.	Ό		o OO		00		154		129		OO m		en 00		ta)		140

-23317475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

Ü

0

Q

m

0

ira

0

Q

0

Q

m

TRZSS

0

Q

o

ra

0

Q

0

ra

Q

0

ra

ORYSA

0

ra

0

SORVU

0

<

0

ra

0

ra

0

ra

ira

ra

SETFA

0

O

0

·<—· 'à

<

U

O

ra

<

ECHCG

0

m

ra

0

Q

ira

0

Q

ffl

ra

DIGSA

0

o

m

0

ra

Q

ra

Q

O

Q

o

CYPES

0

<

ra

0

<

ra

<

Application Rate (g ai/ha)

o C

140

o c-

140

o F--

140 i

O c-

140

o

140

o

140

o

140

o Γ

140

o F'

140

Compound No.

o

00

Ό cq

Œ (N

m

128

00 m

146

ΓTh

-234-

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

Q

Φ

W

Q

Φ

0

Q

Φ

G

Φ

Q

Φ

TRZSS

Q

O

Φ

PL,

Φ

O

Φ

PL,

Φ

O

Q

Φ

ORYSA

C

Φ

O

Φ

C

Φ

c>

Φ

SORVU

Q

m

Φ

U

m

Φ

m

<

O

PL,

W

Φ

SETFA

m

<

Φ

O

m

U

Φ

o

0

Φ

w

<

U

m

O

Φ

ECHCG

4—» 73

4-» 'a

O

Φ

<

U

m

<

œ

Φ

DIGSA

Q

O

u

Φ

O

m

Q

o

O

o

Φ

PLI

W

Φ

CYPES

<

C

c

ü

«

PL,

m

Q

PL,

Φ

w

O

Φ

Q

w

Φ

Application Rate (g ai/ha)

O r-

140

o r-

140

O r-

140 |

O r-

140

o r-

140

O r-

140

o t>

O r—*

140

Compound No.

125

189

200

126

00

en CN

o

τΓ en

153

-23517475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

O

o

O

0

ra

0

Q

m

O

Q

0

ra

TRZSS

C

o

0

o

m

Q

0

<

Q

m

0

ra

Q

0

ORYSA

o

0

ra

0

ra

0

O 00

o

0

<

m

<

O

ra-<

0

SETFA

o

c

O

0

<

0

ECHCG

o

0

O

0

<

O

ira

0

DIGSA

o

0

<

0

ra

m

ra

<

0

ra

Q

0

CYPES

o

0

ra

0

<

ra

<

0

ra

Application Rate (g ai/ha)

140

O MT—M

o Γ-

140

o r-

140

o Γ

140

o r-

140

o F'

140

o t--

140

Compound No.

en en

170

105

-

un

CN N*

un U~)

o v©

00

o o

166

-23617475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

0

m

CQ

m

CQ

PQ

Q

0

TRZSS

0

Q

O

Q

0

Q

W

Q

0

ORYSA

0

fe

W

0

fe

0

fe

0

SORVU

0

O

CQ

Q

0

<

CQ

SETFA

0

<

O

<

Q

<

Q

O

ECHCG

0

<

CQ

<

CQ

<

PQ

CQ

0

Q

DIGSA

0

CQ

<

0

CQ

0

CQ

O

0

CQ

PQ

0

PQ

Q

0

CYPES

0

<

CQ

<

Application Rate (g ai/ha)

140

o r-

140

o r-

140

o o-

O Tj·

o r~~

140

o Γ~-~

140

o r-

140

o r-

140

Compound No.

O en

102

un (N

rCN 1““<

O un

en

Ch tn 1“H

124

O\

-23717475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

Q

o

Q

0

Q

0

Q

U

o

Q

O

Q

o

TRZSS

Q

0

Q

0

m

ω

W

Q

Ch

fe

W

m

ORYSA

0

U

0

SORVU

U

CQ

0

CQ

<

QQ

CQ

W

Q

O

Q

SETFA

O

m

ω

0

m

CQ

0

o

u

O

CQ

0

Q

fil

w

ECHCG

O

o

0

w

Q

0

QQ

W

Q

0

DIGSA

Q

o

Q

0

IXi

W

0

O

<

QQ

m

0

W

Q

CYPES

<

0

<

0

<

W

M

0

<

Application Rate (g ai/ha)

o r-

140

O ’rr

o •st

o F~

140

O r-

140

o F-

140

o Γ-

140

o F-

140

o F~

140

Compound No.

en r-

00 (N

130

en un

en O\

O

00

O en T—1

-23817475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

0

Pu

W

Q

O

Q

0

W

Q

TRZSS

W

PD

M

W

Pu

W

Q

M

Q

0

Pu

m

ORYSA

o

0

SORVU

0

Pu

PLI

Pu

Q

Pu

W

Q

O

Q

0

M

w

SETFA

ω

Q

W

Q

W

Q

0

Q

0

Q

ECHCG

C

0

w

Q

0

CQ

PQ

0

DIGSA

0

w

Q

W

Q

W

Q

0

CYPES

0

<

0

Q

m

W

m

W

0

Q

0

W

Application Rate (g ai/ha)

o

140

o r-

140

o Γ

140

o r-

140

o o

O 1—

o r-

140

o r-

140

va Ό

132

o r-

140

Compound No.

00 A

Ό

rq

o

-

Ch

107

O

150

-23917475

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	O	0	PL	w	0	0	Q	O	W	Q	0	0	0	0	0	0	0	0
TRZSS	O	0	W	w	0	0	PL	m	0	0	0	0	0	0	0	0	0	0
ORYSA	0	0	0	0	0	0	Q	CQ	W	W	0	0	0	0	0	0	0	0
SORVU	0	0	Q	Q	Q		m		CQ	PQ	0	0	0	0	0	0	0	0
SETFA	0	0	0	0	0	0	0	W	0	W	0	0	0	0	0	0	0	0
ECHCG	0	0	Q	O	0	0	o	CQ	Q	O	0	0	0	0	0	0	0	0
DIGSA	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
CYPES	0	0	0	<	<	<	<		<	<	0	0	0	0	0	0	0	0
Application Rate (g ai/ha)	o o	140	o	140	o	140	o r-·	140	o Γ-	140	o r-	140	o r-	140	o	140	o	140
Compound No.	o 30		V© en		Γun		Γ				en 00		r—H		^r Ch		(N

-24017475

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

Q

Φ

Q

0

Φ

0

U

Φ

w

TRZSS

W

Q

Φ

W

Q

m

W

Q

M

Q

ORYSA

o

Φ

O

Φ

O

Φ

Ü

Φ

C

Φ

SORVU

m

œ

Q

O

o

m

Φ

U-,

w

m

CQ

O

m

SETFA

m

<

U

o

Φ

o

Φ

ω

u

Φ

U

Φ

Q

ECHCG

Q

Φ

O

Q

o

Φ

G

Q

U

O

u

DIGSA

Q

Φ

Q

u

Φ

U

CQ

w

Q

CYPES

<

Φ

W

<

o

Φ

<

O

W

o

Φ

Application Rate (g ai/ha)

o tx

140

VO

132

o Γχ

140

o rx

140

o rx

140

o r-

140

o tx

140

o rx

140

o tx

140

Compound No.

eq

Ch rx

un un

o

m

tx rq

rx rx

m r—(

Γόη

-241-

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

Q

O

0

o

CQ

0

w

Q

W

Q

0

TRZSS

Q

Uh

Q

U

0

w

W

0

fx<

0

ORYSA

0

Q

0

c

<0

0

SORVU

CQ

0

m

CQ

<

CQ

Q

W

ω

0

SETFA

Q

0

Φ

Q

U

O

Q

0

O

Q

0

ECHCG

O

Q

U

Q

m

CQ

Q

U

0

O

CQ

o

0

DIGSA

0

W

0

Q

O

u

U

CQ

Q

O

W

Q

U

0

CYPES

M

m

<

C

<

W

M

Q

0

Q

W

Application Rate ! (g ai/ha)

o Γ-

140

o r-

O •’φ

o t·-

O TJ 1—H

o r-

140

o Γ-

140

o Γ

140

o r-

140

o r-

140

O

140

Compound No.

en r*

r-

en ’φ

en

m

o

r~ o

Ox

Cm

-24217475

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	O	0	W	Q	0	0	Q	0	Q	Q	m	Q	<		0	0	0	0
TRZSS	0	O	0	0	0	0	0	0	Q	Q	0	0	O	m	Pu	tu	0	0
ORYSA	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
SORVU	0	O	Q	Q	0	0	Q	Q	Q	Q	tu	Pu	m	<	0	0	0	0
SETFA	0	0	0	0	0	0	0	Q	Q	Q	0	0	Pu	Q	0	0	0	0
ECHCG	0	o	0	O	0	0	0	W	O	O	O	m	m	<	0	0	0	0
DIGSA	0	0	0	0	0	0	0	0	Q	Q	0	0	m		0	0	0	0
CYPES	O	0	0	W	0	0	0	O	0	W	0	w		<	fX-i	W	0	0
Application Rate (g ai/ha)	o o	O	o c-	140	o Γχ	140	o (X-	140	o rx	140	o rx	140	o rx	140	a rx	140	o tx	O 'φ
Compound No.	00		CN en		un		un i—-H		ΓΟΟ		en CN		o rx		Φ 'φ		un

-243-

Visual Growth Réduction (%) 14 Days After Application

ZEAMX

Q

U

0

ra

Q

0

ra

0

ra

Q

TRZSS

Q

U

ra

Q

ra

ira

ra

m

ra

Q

u

ra

0

ra

ORYSA

O

0

ra

0

ra

0

SORVU

Q

PQ

0

<

CQ

<

Q

PQ

0

Q

O

SETFA

Q

O

0

PQ

CQ

u

PQ

u

Q

0

ra

Q

ECHCG

ra

U

0

PQ

m

CQ

0

CQ

0

Q

0

PQ

CQ

DIGSA

Q

o

0

PQ

o

U

o

U-i

Q

0

ra

CYPES

CQ

Q

<

ra

<

CQ

Q

0

PQ

Application Rate (g ai/ha)

o r-

140

o o

140

o

140

o r-

140

o r-

140

o

140

o t-

140

o r-

140

o Γ

140

Compound No.

144

148

o

162

00

202

198

208

205

-24417475

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	O	CQ	O	0	0	0	0	0	0	0	0	0	0	0	0	PL	0	0
TRZSS	PL	m	0	PL	PL	Cl	0	0	0	0	0	0	0	0	PL	CQ	0	0
ORYSA	0	O	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
O 00	Q	CQ	0	W	0	W	0	CQ	0	Cl	0	0	0	0	CQ	Q	0	0
SETFA	CQ	CQ	0	m	Uh	CQ	0	0	0	0	0	0	0	CQ	CQ	CQ	0	O
ECHCG	m	CQ	0	0	0	Q	0	Cl	CQ	Q	0	0	Q	CQ	Q	CQ	0	0
DIGSA	w	Q	0	0	0	0	0	0	0	0	0	0	0	CQ	0	CQ	0	0
CYPES	CQ		PL	m	CQ	CQ	0	0	0	0	0	0	Q	CQ	CQ	CQ	0	0
Application Rate (g ai/ha)	o r-	140	O t-	140	o r-	140	o r-	140	o t-	140	o r-	O 3	o r-	140	o r-	140	o r-	140
Compound No.	176		m σ\		177		179		184		185		174		178		203

-24517475

Visual Growth Réduction (%) 14 Days After Application	ZEAMX	0	O	O	0	0	0	0	0	0	0
TRZSS	O	W	O	0	0	0	0	0	0	0
ORYSA	O	o	c	0	0	0	0	0	0	0
SORVU	O	o	Ü	0	W	0	0	0	0	fe)
SETFA	Q	U	0	0	0	fe	fe)	Q	0	fe
ECHCG	Q	Q	0	0	O	Q	0	0	Q	fe)
DIGSA	0	0	0	0	0	0	0	0	0	0
CYPES	O	fe	0	0	0	0	0	0	0	0
Application Rate (g ai/ha)	o c-	140	o t—	140	o r-	140	o Γ	140	o r—	140
Compound No.	187		195		00 00		194		201

χο •’t <Ν

Ο

Example D. Evaluation of Postemergent Herbicidal Activity in Wheat and Barley

Post-Emergent Test III. 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 •y centimeters (cm ). 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 d in a greenhouse with an approximate 14 h photoperiod which was maintained at about 18 °C during the day and 17 °C during the night. Nutrients and water were added on a regular basis and supplémentai lighting was provided with overhead métal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the second or third true leaf stage.

A weighed amount, determined by the highest rate to be tested, of each test compound was placed in a 25 mL glass vial and was dissolved in 4 mL of a 97:3 v/v mixture of acetone and DMSO to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions obtained were diluted with 20 mL of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, Agri-Dex crop oil concentrate, and X-77 surfactant in a 48:39:10:1.5:1.5:0.02 v/v ratio to obtain spray solutions containing the highest application rates. Additional application rates were obtained by serial dilution of 12 mL of the high rate solution into a solution containing 2 mL of 97:3 v/v mixture of acetone and DMSO and 10 mL of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, Agri-Dex crop oil concentrate, and X77 surfactant in a 48:39:10:1.5:1.5:0.02 v/v ratio to obtain 1/2X, 1/4X, 1/8X and 1/16X rates of the high rate. Compound requirements are based upon a 12 mL application volume at a rate of 187 liters per hectare (L/ha). 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 at a spray height of 18 inches (43 cm) above the average plant canopy height. Control plants were sprayed in the same manner with the solvent blank.

The treated plants and control plants were placed in a greenhouse as described above and watered by subirrigation to prevent wash-off of the test compounds. After 21 d, the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complété kill and is presented as indicated in Table A.

-24717475

By applying the well-accepted probit analysis as described by J. Berkson in Journal of the

American Statistical Society, 48, 565 (1953) and by D. Finney in “Probit Analysis

Cambridge University Press (1952), herbicidal injury of a spécifie compound at various rates can be used to calculate GR20, GR50, GRgo and GR90 values, which are defined as growth réduction factors that correspond to the effective dose of herbicide required to provide plant growth réduction (GR) of 20 percent, 50 percent, 80 percent and 90 percent, respectively. Probit analysis was applied to data collected from multiple dose rates of individual compounds utilizing the procedures explained in the following examples. The data for some of the dose rates and analysis of ail of the dose rates are captured in the following tables.

Some of the compounds tested, application rates employed, plant species tested, and results are given in Tables 7 through 11.

-24817475

Table 7: Activity of Herbicidal Compounds in Wheat and Barley

Visual Growth Réduction (%) 21 Days After Application

TRZSS

CQ

-

1 1

CQ

PQ

-

1 1

0

CQ

-

1 1

!

HORSS

m

CQ

<

-

i

i 1

CQ

<

-

1 1

1 l

CQ

-

1 1

1

VERPE

Q

PQ

1

CK

Q

O

i

en en

>140

W

Q

0

t 1

n en

>140

STEME

J*,

Uh

W

1 1

125

>140

O

<

1 J

oo

m n

|X|

&

0

1

rq ID

>140

SETVI

PQ

<

1 1

oo

rq en

<

1 1

o

Q

O

CQ

1 1

o CN

o

PHAMI

w

U

PQ

1

en

00 r-

PQ

CQ

PQ

1 1

>r> CN

0

b

0

1 {

>140

PAPRH

<

1 1

-

<

1 1

-

<

1

-

MATSS

Q

PQ

!

m

<

!

-

O

0

CQ

1

o

rq

LOLSS

Q

O

PQ

ί

O rq

m

Q

1

D n

>140

0

&

W

!

137

>140

LAMSS

<

1 1

-

<

1

-

1

-

KCHSC I

1 1

-

<

!

n

<

1 1

-

CN

BROTE

O

PQ

1

CN

n

Q

CQ

1

en

ΓΟΟ

W

1 1

136

>140

APESV 1

CQ

PQ

<

!

CN

CQ

PQ

*

CN

PQ

CQ

<

!

V©

o CN

ALOMY

Q

PQ

1

-

O en

O

Q

0

1 1

CN

n r-

m

Q

0

1 1

*^r in

>140

Applic -ation Rate (g ai/ha)

D en

o r-

140

o CN Pi O

O v-j ti 0

o OO Pi c

en

o

140

o S⁴Pi c

O m Pi O

<o oo Pi 0

<r> en

o t

140

o s* Pi 0

o tt! 0

O 00 Pi 0

Cpd. No.

138

O n

216

-249X

Visual Growth Réduction (%) 21 Days After Application

TRZSS

0

ira

CN

1

î

ra

KO

!

1 1

Q

T—H

1 1

1

HORSS

0

r-

!

O

ra

CN

!

i

0

ra

Q

en en

!

VERPE

Q

o

1 1

σκ

en r-

ra

1 1

>140

ra

ira

Q

1

o Ch

>140

STEME

Q

0

1

OO CN

00 00

C

0

ί

>140

0

!

o un

123

SETVI

0

1 l

O d

>140

O

0

1 1

>140

0

1 1

>140

>1401 i

1 PHAMI

m

(Ώ

ira

1 1

-

O en

O

0

!

>140

0

1

>140

PAPRH

<

!

-

<

1 1

-

ira

<

1 1

-

en

MATSS

m

CQ

ira

en

>140

0

ί

>140

0

t

00 00

>140

1 LOLSS

ω

Q

1

CN en

>140

0

t

>140

0

!

>140

LAMSS

<

1 l

-

CN

(Ώ

ffl

<

!

-

ra

m

ira

1 1

0.014

KO

KCHSC

m

<

1 f

<N

KO

Q

0

!

en

>140

0

!

>140

BROTE

0

m

ira

1 1

un

en en

0

!

>140

0

t

>140

1 APESV

m

ira

<

!

KO

un

0

1

>140

0

!

>140

ALOMY

0

m

(Ώ

1 f

CN

en

0

!

>140

0

1 1

>140

Applic -ation Rate (g ai/ha)

Un en

o

1 140

o Pi C

O VJ Pi C?

o oo Pi O

un en

o r-

140

o 04 pi O

O VJ Pi O

O 00 Pi o

un en

o r-

140

o ra 0

O VJ Pi O

G OO Pi C

Cpd. No.

217

un 00

-25017475

Visual Growth Réduction (%) 21 Days After Application

TRZSS

0

ira

>140

1 1

!

0

CQ

0.29

1 1

1

CQ

-

1

1 1

HORSS ________________________________________________________________________________________________1

0

l> Un

1 1

!

CQ

-

!

1

CQ

<

-

1

t I

VERPE ___________________________________________________________________________________________!

0

CQ

t 1

Un

o

CQ

1 1

un

F-

O

CQ

1 1

F-

O en

STEME ___________________________________________________________________________________________i

0

i

>140

ra

!

-

ra

1 1

K) F-

>140

SETVI

0

1 1

>140

0

ra

Q

1 1

03

184

Q

CQ

<

1 1

00

CN un

PHAMI

0

1 1

>140

0

Q

U

i

00 O

126

O

CQ

<

!

un

CN en

PAPRH

m

<

1 1

-

1

-

<

1

-

MATSS

0

ra

1

>140

Q

O

m

1

Tt

o 30

CQ

<

!

CN

Ch CN

LOLSS

0

1 1

>140

ra

Q

o

i

Ch Xt

CN

Q

O

CQ

1

O CN

03 30

LAMSS __________________________________________________________________________________________1

CQ

1 f

0.15

un

<

i

-

»—

CQ

<

1 (

-

30

KCHSC

cra

Q

*

F~

>140

CQ

!

en

F-

CQ

<

1 1

CN

03

BROTE

0

1

>140

Q

CQ

!

en

Tt Ό

CQ

<

1 1

en

APESV

0

1 1

>140

Q

CQ

1 1

CN CN

o 30

CQ

<

!

00

un CN

ALOMY

0

1 1

>140

Q

CQ

!

IT) CN

o 30

O

CQ

<

i

03

FCN

Applic -ation Rate (g ai/ha)

Un en

o F-

140

o s¹ C4 0

O m Pi O

C5 OO & 0

en

o F-

140

o ¢4 0

o m PÎ 0

o OO Ρί 0

un en

o F-

140

o CM 0

O W) Pi 0

O oo pî 0

Cpd. No.

142

00

un

-25117475

Visual Growth Réduction (%) 21 Days After Application

TRZSS

0

CQ

-

t 1

î

Q

0

60Ό

1 1

1

0

O

CQ

-

1 1

t 1

HORSS

U

O

CQ

-

t

1 1

Q

CQ

CS

!

t i

PL

m

Q

OO

1 l

1 1

VERPE

PL

W

f t

123

>140

PL

PQ

m

l i

Γ— OX

>140

CQ

<

1 1

1-H

CS

STEME

0

PL

m

1 1

>140

0

1 1

>140

0

cl

W

!

J-H

>140

SETVI

Q

0

O

t 1

XO

ΙΛ O t-H

W

Q

1

CM un

O 1—H Λ

Pl

M

Q

1

00 Ό

>140

PHAMI

PL

1

>140

0

PL

Q

1

CS

>140

0

PL

«

1 1

OO

>140

PAPRH

<

i

-

CQ

t

-

OO

<

1 l

-

MATSS

Q

0

CQ

I

-

un O

0

Q

!

ΓΧΟ

>140

<

!

-

LOLSS

0

1

>140

0

PL

W

1

XO

>140

PL

W

Q

t

CM 00

>140

LAMSS

1

-

en

CQ

!

-

<

!

-

KCHSC

Q

CQ

1

CS

Tt·

PL

Pl

W

!

>140

0

CQ

1

en

O

BROTE

ω

W

Cl

1

OX <S

>140

0

W

w

1*

un O\

>140

0

ί

>140

APESV

PQ

W

Q

!

ΓΧΟ

>140

Q

1

en

129

PL

m

Q

1

o r-

>140

ALOMY

PÜ

W

1

00

>140

0

Q

!

c-

>140

0

w

W

1

t—H

>140

Applic -ation Rate (g ai/ha)

un en

O r-

O

O 0

O «Λ Pi 0

O oo Pi 0

Un en

o Γ—

140

O <> Pi 0

un en

O 1—H

O s* Pü 0

Cpd. No.

σχ

143

O\ en

-25217475

Visual Growth Réduction (%) 21 Days After Application

TRZSS

Q

0

m

ta-

1

1 1

0

>140

t

1

fe

Q

νη CN

î

1 1

HORSS

fe

Q

1 1

0

m

1 1

w

Q

!

1

VERPE

Q

¹

o CM

>140

fe

W

Q

1 1

(N OO

>140

Q

1 1

o CM

Ό 00

STEME

O

Q

CQ

1 1

ta-

fe

1 I

>140

0

fe

>140

SETVI

0

fe

1 1

>140

0

!

>140

fe

W

1

o

>140

PHAMI

O

W

Q

1

100

>140

0

1 1

>140

0

!

>140

PAPRH

m

1

en

o

Q

0

1 1

-

>140

<

1 1

CM

MATSS

0

1

>140

0

*

>140

0

1 1

>140

LOLSS

0

!

>140

0

1 1

>140

0

fe

1

en O

>140

LAMSS

m

1 1

-

OO

O

CQ

!

-

ι/Ί CN

PQ

CQ

1 1

ta-

CM

KCHSC

m

<

!

CM

o

Q

1

-

>140

Q

CQ

1

CM

CN 3

BROTE

0

fe

i

>140

0

1 1

>140

0

1

00 00

>140

APESV

0

fe

Q

1 1

901

>140

0

}

>140

0

1 >

>140

ALOMY

0

ω

W

!

105

>140

0

!

>140

0

1 1

>140

Applic -ation Rate (g ai/ha)

en

o o

140

o CM Pi o

O LT) Pi o

O OO Pi O

in en

o ta-

140

o CM Pi O

O oo Pi c

in en

o ta-

o s* Pi 0

O w-) Pi o

O oo Pi 0

Cpd. No.

204

186

209

-25317475

Visual Growth Réduction (%) 21 Days After Application

TRZSS

Q

-d-

!

o

PQ

CQ

0.07 i

1 t

1 1

w

Q

’d

1 1

1

HORSS

U

m

CN

1 t

!

CQ

PQ

CQ

0.07

!

t 1

fe

O

en

1 1

VERPE

m

1 1

CN

en

W

0

Q

!

en

>140

<

1 1

-

CN

STEME

Q

1 1

-

>140

fe

Q

1

1—< o

>140

fe

1 1

>140

SETVI

υ

0

1

un

CN x!^-

Q

PQ

1 l

O

ON N^-

fe

0

1

O d

o Ch

PHAMI

<

!

<

1

’d

N

u

CQ

1

CN CN

’dd

PAPRH

<

1

-

<

1 1

-

<

!

-

MATSS

fe

i

CN

>140

<

i

o

CQ

î

^r CN

00 'd^-

LOLSS

w

fe

1

en

>140

fe

Q

i

r-

>140

0

!

>140

LAMSS

<

1 1

-

CQ

PQ

î

-

00

<

1 1

-

KCHSC

m

CQ

i

en

o

PQ

<

PQ

1 !

o

Q

O

;

en CN

CN un

BROTE

o

PQ

1 1

M^-

τφ

0

PQ

1

00 CN

fe

O

!

en 'd^-

oo

APESV

CQ

PQ

1 1

PQ

CQ

PQ

1

un

*©

O

CQ

1

O CN

NO

ALOMY

Q

0

I

CN CN

oo 00

Q

m

PQ

1

o CN

F-

fe

Q

1

FU“)

Ch

Applic -ation Rate (g ai/ha)

un en

o r-

o s¹fe 0

O VT té O

o 00 Pi o

un en

o Γ-

140

o «y fe 0

O VT ai ü

un en

o r-

o ai O

Cpd. No.

109

147

167

-254-

Visual Growth Réduction (%) 21 Days After Application	TRZSS	tu	W	Q	00	l	1
HORSS	O	tu	Q	Tt (N	1 1	1 1
VERPE	tu	Q	Q	1 j	CV va	>140
STEME	0	tu	O	1 1		>140
SETVI	0	tu	W	!	>140	>140
PHAMI	0	0	0	1	>140	>140
PAPRH	<			1	N
MATSS	O	m	m	1		N^-
LOLSS	tu	w	CQ	t		>140
LAMSS	O	u	CQ	1 1	cv	m
KCHSC	O	m	<	!	r-	CN
BROTE	O	0	0	i	>140	>140
APESV	C	tu	w	1	o	>140 1
ALOMY	tu	W	tu	1	«n O\	>140
Applic -ation Rate (g ai/ha)	IT)	o o	140	o (N PÎ O	S 0	O oo Pi o
Cpd. No.	214

-25517475

Table 8: Activity of Herbicidal Compounds in Wheat and Barley

Visual Growth Réduction (%) 21 Days After Application

TRZSS

ra

Ό

l t

>140

ira

m

-

1 1

m

ra

-

1 1

i

HORSS

O

ra

Q

C'en

î

>140

ra

-

1 1

ra

<

-

!

VIOSS

Q

0

!

en CN

>140

<

1 1

N-

r-

o

<

!

Tfr CN

<O\

VERPE

Q

0

ira

1 t

N CN

OO

ra

Q

i

en

126

0

m

t 1

o CN

o> en

SASKR

Q

!

en

>140

o

ra

1

CN

00 CN

o

m

1 1

CN

en u->

PAPRH

m

ra

<

« 1

-

<

l 1

-

<

i 1

-

MATSS

ra

rai

I 1

125

>140

<

1 1

N-

-

o

m

!

Ch

CN en

LAMSS i

U

m

ra

1 1

-

Ox

<

1

-

<

1

-

KCHSC

o

1

en

O en

<

!

CN

00

m

!

en

O\ CN

GALAP

Q

<

1

CN

oo en

1

un

t·

ira

<

1

CN

CIRAR

«

m

ra

1

-

en

Q

o

1 l

oo

en un

Q

0

î

xt CN

Application Rate (g ai/ha)

U) en

o r-

140

o & Ü

O «/·> O

o oo & o

m en

o

o s* ra 0

o té

o oo & o

m en

o

o S¹ra 0

o U~i & Ü

O oo & o

Compound No.

135

en

124

-25617475

Visual Growth Réduction (%) 21 Days After Application

TRZSS

Q

ira

cn

!

1

Q

O

-

î

!

ra

m

ra

1 1

!

HORSS

ira

m

-

!

l l

ra

ω

-

1 1

I 1

ra

<

-

!

VIOSS

o

1 t

>140

0

<

1 1

OO

rCN

o

ra

!

>140

VERPE

u

ra

1 1

CN

C'en

O

m

t i

un

CN N

m

!

-

o

SASKR

u

m

!

-

en T

Q

1

CN CN

Q

u

m

1 1

Ch

Os r-

PAPRH

<

1

-

<

!

r—H

-

<

1 1

-

MATSS

0

m

1 1

en

ra

1

109

>140

<

1 1

en

o

LAMSS

Q

1 1

CN

ra

!

-

N^-

<

!

en

KCHSC

Q

o

1 1

N CN

O r-

u

Q

1 1

OO

Q

o

î

C'en

CN

GALAP

1 1

Ν’

o

m

ira

!

un

un CN

ra

O

<

!

OO

un

CIRAR

<

t f

-

un

o

t 1

00

o

<

m

<

1 1

CN

Application Rate (g ai/ha)

un en

o r-

o S* Pi O

o U-) ra o

o oc Pi o

un en

o Γ-

s ra 0

o m Pi C

o 00 ra 0

un en

o

140

o ra 0

O m Pi O

O OO Pi o

Compound No.

o> t-

rCN

145

-257-

Visual Growth Réduction (%) 21 Days After Application

TRZSS

O

CQ

en

!

i l

0

CQ

-

1

1 1

CQ

<

-

!

1 1

HORSS

Q

U

!

t 1

w

Q

o CN

1 1

1

<

-

1

i

VIOSS

0

CQ

1 1

CN

en

<

1 1

m

o

fe)

Q

i

C'en

>140

VERPE

Q

0

!

m

k© k©

CQ

1 1

N-

ΓCN

fe

O

1

en en

>140

SASKR

ω

Q

!

en en

104

Q

U

1

CN

Γ k©

0

1

en

k©

PAPRH

<

1

-

<

I

-

<

l 1

-

MATSS

Q

!

CN

o r-

fe

1 1

>140

CQ

<

!

en

r-

LAMSS

m

i 1

-

CQ

<

*

CN

-

CQ

1 1

-

o

KCHSC

w

Q

1 1

’d en

©k

CQ

<

!

©k

en CN

Q

CQ

!

-

Ν'

GALAP

CQ

1 1

N^-

t· ¹ i en

CQ

<

!

Ok

en CN

<

!

CN

k©

CIRAR

ω

O

1

en CN

103

Q

ΐ

r-

O oo

CQ

!

0.18

en

Application Rate (g ai/ha)

m en

o r-

o & o

o w> Pi O

m en

o Γ

on en

o r-

o c¹Pi 0

Compound No.

ren

r—< F-

en

-25817475

Visual Growth Réduction (%) 21 Days After Application	TRZSS	CQ	CQ	-	1 1	1 1	CQ	CQ	-	1 1	*
HORSS	CQ		-	1 1	1 1	CQ	<	-	1	!
VIOSS	<		1 t	'φ	-	Pu	Q	1 1	un	144
VERPE	CQ	CQ	1 1	en	00	0	0	!	>140	>140
SASKR	O	CQ	1 1	un	o en	O	CQ	!	-	O en
PAPRH	<		!	-	-	<	<	1	-	-
MATSS	CQ	<	1		un	Q	CQ	1 1	o	C'en
LAMSS			1	-	•Φ	<	<	1	-	-
KCHSC	<		1 1	en	o	<	<	i	-	-
GALAP			1	un	CT	<		1	-	-
U	O	CQ	1	rx	en en	O	O	1		CN un
Application Rate (g ai/ha)	un en	o Γ	o 7 Pi 0	O m & O	o oo Pi o	un en	o tx	o ai 0	O K) Pi O	o oo PÎ 0
Compound No.	en					o

-259-

Table 9: Activity of Herbicidal Compounds in Wheat and Barley

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	KCHSC	LOLSS	SETVI	HORSS	TRZSS
76	35	C	G	F	E	D	C
	70	B	E	E	D	D	B
	GR₂o	—	—	—	—	6	4
	GR50	27	74	53	42	—	—
	GReo	52	132	133	87	—	—
172	35	F	D	G	D	D	C
	70	D	D	G	C	D	C
	GR20	—	—	—	—	3	1
	GR50	53	38	>140	25	—	—
	GRgo	124	73	>140	56	—	—
168	35	C	A	G	E	B	B
	70	B	A	E	D	A	A
	GR₂o	—	—	—	—	1	1
	GR50	21	5	108	28	—	—
	GRgo	57	15	>140	70	—	—
35	35	G	C	G	G	D	C
	70	F	B	F	F	D	C
	GR₂o	—	—	—	—	8	2
	GR50	113	8	126	79	—	—
	GRgo	>140	37	>140	>140	—	—
46	35	G	C	G	G	D	C
	70	G	B	F	F	D	C
	140	E	B	E	F	B	B
	GR₂o	—	—	—	—	8	1
	GR50	>140	10	118	>140	—	—
	GRgo	>140	45	>140	>140	—	—

-26017475

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	KCHSC	LOLSS	SETVI	HORSS	TRZSS
154	35	G	G	G	F	G	G
	70	G	G	G	D	G	F
	140	G	G	G	C	E	E
	GR20	—	—	—	—	81	49
	GR50	>140	57	>140	56	—	--
	GRgo	>140	93	>140	109	—	—
146	35	A	G	G	E	C	C
	70	A	G	G	C	B	B
	140	A	G	G	A	A	B
	GR20	—	—	—	—	1	1
	GR50	23	>140	>140	41	—	—
	GRgo	34	>140	>140	76	—	—
47	35	A	B	G	G	A	B
	70	A	C	E	C	A	A
	140	A	A	D	B	A	A
	GR₂o	—	—	—	—	1	1
	GR50	10	20	80	51	—	—
	GRgo	14	45	>140	104	—	—
125	35	C	D	G	B	B	C
	70	B	B	G	B	A	C
	140	A	A	E	B	A	B
	GR₂o	—	—	—	—	1	1
	GR50	10	8	>140	2	—	—
	GRgo	41	34	>140	16	—	—
51	35	B	B	C	C	B	B
	70	A	A	C	B	A	A
	GR₂o	—	—	—	—	1	1
	GR50	3	4	3	24	—	—
	GRgo	11	14	61	49	—	--

-26117475

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	KCHSC	LOLSS	SETVI	HORSS	TRZSS
42	35	B	B	F	B	B	B
	70	B	D	E	B	B	B
	140	A	A	C	A	A	A
	GR₂₀	—	—	--	—	1	1
	GR-50	7	1	76	1	—	—
	GR₈o	22	1	>140	19	—	—
55	35	C	B	D	C	B	B
	70	A	B	C	B	A	A
	GR₂o	—	—	—	—	1	1
	GRso	4	4	21	29	—	—
	GR₈o	18	21	50	46	—	—
159	35	B	B	E	E	B	B
	70	A	A	D	D	A	A
	GR₂₀	—	—	—	—	1	1
	GR50	11	4	36	43	—	—
	gr₈₀	25	19	89	113	—	—
96	35	F	G	E	G	B	B
	70	F	D	D	D	A	B
	140	E	D	D	C	A	A
	GR20	—	—	—	—	1	1
	GR50	125	79	48	72	—	—
	GR₈o	>140	>140	>140	128	—	—
173	35	D	F	F	F	B	C
	70	C	E	E	E	A	B
	GR20	--	—	—	—	1	1
	GR_S0	27	60	119	54	—	—
	GR₈q	59	131	>140	104	—	—

-26217475

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	KCHSC	LOLSS	SETVI	HORSS	TRZSS
28	35	G	G	G	G	G	F
	70	G	F	G	G	F	D
	GR₂o	—	—	—	—	43	17
	GR50	>140	88	>140	>140	—	—
	GR₈o	>140	>140	>140	>140	—	--
161	35	D	G	G	F	B	C
	70	C	G	G	D	B	C
	GR20	—	—	—	—	1	1
	GR50	30	>140	38	53	—	—
	GR₈o	57	>140	82	128	—	—
74	35	B	B	F	C	B	c
	70	B	A	E	B	B	c
	GR₂o	—	—	—	—	1	1
	GR50	10	3	>140	3	—	—
	GR₈o	25	11	>140	49	—	—
150	35	G	D	G	G	F	D
	70	G	D	G	F	E	D
	GR₂o	—	—	—	—	8	1
	GR50	>140	7	>140	79	—	—
	GR₈o	>140	>140	>140	>140	—	—
36	35	G	G	G	G	F	C
	70	G	G	G	F	D	c
	GR₂o	—	—	—	—	16	1
	GR50	>140	>140	>140	126	—	—
	GR₈q	>140	>140	>140	>140	—	—

-26317475

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	KCHSC	LOLSS	SETVI	HORSS	TRZSS
117	35	E	D	E	G	G	G
	70	D	C	D	D	G	F
	GR20	—	—	—	—	73	32
	GR50	41	20	41	59	—	—
	GReo	>140	67	>140	99	—	—

Table 10: Activity of Herbicidal Compounds in Wheat and Barley

Compd. No.	Application Rate (g ai/ha)	Visual Gorowth Réduction (%) 21 days After Application
KCHSC	MATSS	SASKR	VERPE	VIOSS	HORSS	TRZSS
49	35	B	D	C	E	A	C	C
	70	B	C	B	D	A	B	B
	GR20	—	—	—	—	—	1	1
	GR50	4	15	1	37	5	—	—
	GR80	18	93	30	>140	8	—	—
21	35	A	B	C	F	A	B	C
	70	A	B	B	G	A	A	B
	GR20	—	—	—	—	—	1	1
	GR50	1	5	1	130	4	—	—
	GReo	1	31	25	>140	6	—	—
132	35	B	G	C	G	A	D	D
	70	B	F	C	C	A	C	D
	140	A	F	C	B	A	A	C
	GR20	—	—	—	—	—	9	10
	GR50	4	>140	1	58	9	—	—
	GReo	20	>140	66	99	17	—	—
157	35	B	D	C	F	A	B	c
	70	B	C	B	D	A	A	c
	GR20	—	—	—	—	—	1	1
	gr₅₀	6	21	11	50	1	—	—
	GRgo	18	64	34	>140	4	—	—

-26417475

Compd. No.	Application Rate (g ai/ha)	Visual Gorowth Réduction (%) 21 days After Application
KCHSC	MATSS	SASKR	VERPE	VIOSS	HORSS	TRZSS
99	35	C	F	C	A	A	B	B
	70	B	E	C	A	A	A	B
	GR₂o	—	—	—	—	—	1	1
	GR_S0	9	63	10	8	9	—	—
	GReo	27	>140	48	17	19	—	—
141	35	C	C	C	C	A	B	C
	70	B	A	B	B	A	A	B
	GR20	—	—	—	—	—	1	1
	GR50	7	15	4	14	7	—	—
	GReo	28	33	40	43	11	—	—
108	35	G	F	G	D	F	F	C
	70	G	D	F	C	F	E	c
	GR₂o	—	—	—	—	—	16	6
	GR50	>140	58	136	22	85	—	—
	GReo	>140	>140	>140	67	>140	—	—
122	35	B	G	A	A	A	D	C
	70	A	F	A	A	A	B	B
	GR₂o	—	—	—	—	—	3	1
	GR50	5	>140	<17.5	1	10	—	—
	GReo	14	>140	<17.5	2	21	—	—
52	35	C	G	D	C	A	B	B
	70	B	D	C	A	A	A	B
	GR₂o	—	—	—	—	—	1	1
	GR50	5	62	4	20	12	—	--
	GR₈₀	38	91	84	37	19	—	—
163	35	C	C	C	C	C	B	C
	70	B	A	B	A	A	A	C
	GR₂o	—	—	—	—	—	1	1
	GR50	8	5	3	13	14	—	—
	GRso	36	24	27	30	29	—	—

-265-

Compd. No.	Application Rate (g ai/ha)	Visual Gorowth Réduction (%) 21 days After Application
KCHSC	MATSS	SASKR	VERPE	VIOSS	HORSS	TRZSS
169	37.1	D	C	D	B	c	A	C
	74.3	B	A	C	A	A	A	B
	149	B	A	B	A	A	A	B
	GR₂o	—	—	—	—	—	1	1
	GR50	8	15	5	19	21	—	—
	GReo	72	35	83	37	36	—	—
72	35	D	G	F	B	F	E	C
	70	D	F	D	A	E	D	B
	GR20	—	—	—	—	—	5	1
	GR50	27	126	48	1	67	—	—
	GReo	105	>140	106	8	>140	—	—
89	35	B	C	B	A	A	D	C
	70	B	B	B	A	A	D	B
	GR20	—	—	—	—	—	3	1
	GR50	12	14	9	3	11	—	—
	GRgo	25	36	21	6	19	—	—
129	35	B	G	C	F	C	B	C
	70	A	F	B	E	A	B	B
	GR20	—	—	—	—	—	1	1
	GR50	7	89	6	92	17	—	—
	GReo	21	131	41	>140	34	—	—
38	35	B	D	D	F	A	B	B
	70	B	B	D	D	A	B	B
	GR₂o	—	—	—	—	—	1	1
	GR50	1	21	17	42	13	—	—
	GReo	24	56	68	112	26	—	—
8	35	A	D	B	A	B	D	C
	70	A	C	B	A	B	C	B
	GR₂o	—	—	—	—	—	1	1
	GR50	3	26	1	1	13	—	—
	GRgo	6	73	16	1	28	—	—

-26617475

Compd. No.	Application Rate (g ai/ha)	Visual Gorowth Réduction (%) 21 days After Application
KCHSC	MATSS	SASKR	VERPE	VIOSS	HORSS	TRZSS
69	35	B	C	B	B	B	B	B
	70	B	B	B	A	A	A	B
	GR₂o	—	—	—	—	—	1	1
	GR50	5	5	7	1	3	—	—
	GReo	19	29	29	4	8	—	—
86	35	C	D	D	B	D	F	D
	70	C	D	C	B	D	F	D
	GR20	—	—	—	—	—	14	1
	GR50	12	22	18	15	21	—	—
	GReo	55	85	66	34	77	—	—

Table 11 : Activity of Herbicidal Compounds in Wheat and Barley

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
KCHSC	MATSS	SASKR	VIOSS	HORSS	TRZSS
149	35	F	E	D	F	D	E
	70	D	D	D	D	C	C
	gr₂₀	18	9	6	11	21	20
	GR50	56	38	24	44	—	—
	GR₈o	>140	>140	100	>140	—	—
165	35	B	G	C	F	C	D
	70	B	E	B	D	B	C
	GR₂₀	—	—	—	—	9	8
	GR50	9	81	4	55	—	—
	GR₈o	30	>140	46	>140	—	—

ALOMY: blackgrass (Alopecurus myosuroides)

APESV: bentgrass (Apera spica-venti)

BROTE: downy brome (Bromus tectorum)

HORS S: barley, including spring and winter (Hordeum vulgare)

TRZSS: wheat, including spring and winter (Triticum aestivum)

-267A17475

LOLSS: ryegrass including, Italian ryegrass (Lolium multiflorum), rigid ryegrass (Lolium rigidum), annual ryegrass (Lolium multiflorum subsp. Gaudini)

PHAMI: lesser canary grass (Phalaris minor)

SETVI: green foxtail (Setaria viridis)

KCHSC: kochia (Kochia scoparia)

LAMSS: including purple deadnettle (Lamium purpureum) and henbit (Lamium amplexicaulé)

GALAP: cleavers (Galium aparine)

VERPE: bird’s-eye speedwell (veronica persica)

PAPRH: common poppy (Papaver rhoeas)

SASKR: Russian thistle (Salsola iberica)

CIRAR: Canada thistle (Cirsium arvense)

VIOSS: wild pansy (Viola tricolor), field violet (Viola arvensis)

MATSS: scented mayweed (Matricaria chamomilla), pineappleweed (Matricaria matricarioides)

STEME: common chickweed (Stellaria media).

g ai/ha: grams active ingrédient per hectare nt: Not tested

GR20: Growth réduction of 20% of plant growth

GR50: Growth réduction of 50% of plant growth

GRgo: Growth réduction of 80% of plant growth

GR90: Growth réduction of 90% of plant growth

Example E. Evaluation of Preemergent Herbicidal Activity

Pre-Emergent Test III. Seeds of test species were planted into square plastic pots (10 cm wide) containing sandy loam soil. After planting, ail pots were sub-irrigated 16 h prior to compound application.

A weighed amount, determined by the highest rate to be tested, of each test compound was placed in a 25 mL glass vial and was dissolved in 4 mL of a 97:3 v/v mixture of acetone and DMSO to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions obtained were diluted with 20 mL of an aqueous mixture containing water and 0.02% w/v (weight/volume) of Triton X-155 to obtain spray solutions containing the highest application rates. Additional application rates were obtained by serial dilution of 12 mL of the high rate solution into a

-26817475 solution containing 2 mL of 97:3 v/v mixture of acetone and DMSO and 10 mL of an aqueous mixture containing water and 0.02% w/v (weight/volume) of Triton X-155 to obtain 1/2X, 1/4X, 1/8X and 1/16X rates of the high rate. Compound requirements are based upon a 12 mL application volume at a rate of 187 liters per hectare (L/ha). Formulated compounds were applied to the soil surface 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. Control pots were sprayed in the same manner with the solvent blank.

The treated pots and control pots were placed in a greenhouse as described above and watered through surface irrigation. After 21 d, the condition of the test pots as compared with that of the untreated pots was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no herbicidal effect and 100 corresponds to plant death or lack of emergence from the soil and is presented as indicated in Table A.

By applying the well-accepted probit analysis as described by J. Berkson in Journal of the American Statistical Society, 48, 565 (1953) and by D. Finney in “Probit Analysis” Cambridge University Press (1952), herbicidal injury of a spécifie compound at various rates can be used to calculate GR20, GR50, GRgo and GR90 values, which are defined as growth réduction factors that correspond to the effective dose of herbicide required to provide plant growth réduction (GR) of 20 percent, 50 percent, 80 percent and 90 percent, respectively. Probit analysis was applied to data collected from multiple dose rates of îndividual compounds utilizing the procedures explained in the following examples. The data for some of the dose rates and analysis of ail of the dose rates are captured in the following tables.

Some of the compounds tested, application rates employed, plant species tested, and results are given in Table 12.

Table 12: Preemergent Activity of Herbicidal Compounds in Wheat and Barley

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	LAMSS	LOLSS	SETVI	HORSS	TRZSS
20	35	A	A	G	F	F	E
	70	A	A	E	B	E	E
	GR20	—	—	—	—	17	10
	GR50	6	6	>70	32	—	—

-26917475

Compound No.	Application Rate (g ai/ha)	Visual Growth Réduction (%) 21 Days After Application
APESV	LAMSS	LOLSS	SETVI	HORSS	TRZSS
	GRso	16	9	>70	71	—	—
147	35	C	A	G	E	G	F
	70	B	A	G	C	G	F
	GR20	—	—	—	—	70	23
	GR50	19	1	52	17	—	—
	GR₈o	33	5	>70	>70	—	—
214	35	C	A	G	G	G	G
	70	A	A	E	G	G	F
	GR20	—	—	—	—	93	28
	GR50	13	1	>70	>70	—	—
	GR₈o	28	2	>70	>70	—	—
49	35	F	A	G	F	G	G
	70	E	A	G	F	G	G
	GR20	—	—	—	—	>70	>70
	GR50	>70	1	>70	>70	—	—
	GR80	>70	3	>70	>70	—	—
42	35	B	A	G	E	F	E
	70	A	A	G	D	E	E
	GR20	—	—	—	—	11	5
	GR50	12	1	>70	36	—	—
	GR₈₀	27	1	>70	>70	—	—

APESV: bentgrass (Apera spica-ventî)

LAMPU: purple deadnettle (Lamium purpureum)

LOLSS: ryegrass including, Italian ryegrass (Lolium multiflorum), rigid ryegrass (Lolium 5 rigidum), annual ryegrass (Lolium multiflorum subsp. Gaudini)

SETVI: green foxtail (Setaria viridis)

HORSS: barley, including spring and winter (Hordeum vulgaré)

TRZSS: wheat, including spring and winter (Triticum aestivum) g ai/ha: grams active ingrédient per hectare

-27017475 nt: Not tested

GR20: Growth réduction of 20% of plant growth GR50: Growth réduction of 50% of plant growth GR₈₀: Growth réduction of 80% of plant growth GR90: Growth réduction of 90% of plant growth

Example F. Evaluation of Postemergence Herbicidal Activity in Direct Seeded Rice Seeds or nutlets of the desired test plant species were planted in a soil matrix prepared by mixing a loam soil (43 percent silt, 19 percent clay, and 38 percent sand, with a pH of about 8.1 and an organic matter content of about 1.5 percent) and river sand in an 80 to 20 ratio. The soil matrix was contained in plastic pots with a surface area of 139.7 cm². When required to ensure good germination and healthy plants, a fongicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 10-17 d in a greenhouse with an approximate 14-h photoperiod which was maintained at about 29 °C during the day and 26 °C during the night. Nutrients and water were added on a regular basis and supplémentai lighting was provided with overhead métal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the second or third true leaf stage.

A weighed amount, determined by the highest rate to be tested, of each test compound was placed in 25 mL glass vials and dissolved in a volume of 97:3 v/v acetone-DMSO to obtain 12X stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions were added to the spray solutions so that the final acetone and DMSO concentrations were 16.2% and 0.5%, respectively. Spray solutions were diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.5% (v/v) Agri-dex crop oil concentrate. The final spray solutions contained 1.25% (v/v) Agri-dex crop oil concentrate. Compound requirements are based upon a 12 mL application volume at a rate of 187 L/ha. 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 cm) above average plant canopy height. Control plants were sprayed in the same manner with the solvent blank.

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, compared with that of the untreated plants, was determined

-27117475 visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complété kill and is presented as indicated in Table A.

American Statistical Society, 48, 565 (1953) and by D. Finney in “Probit Analysis”

Cambridge University Press (1952), herbicidal injury of a spécifie compound at various rates can be used to calculate GR20, GR50, GRso and GR90 values, which are defined as growth réduction factors that correspond to the effective dose of herbicide required to provide plant growth réduction (GR) of 20 percent, 50 percent, 80 percent and 90 percent, respectively. Probit analysis was applied to data collected from multiple dose rates of individual compounds utilizing the procedures explained in the following examples. The data for some of the dose rates and analysis of ail of the dose rates is captured in the following tables. Some of the application rates and ratios employed, plant species tested, and results are given in Table 13.

-27217475

Table 13: Activity of Herbicidal Compounds in Direct Seeded Ri ce

Visual Growth Réduction (%) 21 Days After Application

ORYSS

0

>70

1

w

U

G

1

!

0

>70

i

1

0

SEBEX i

<

!

-

<

1

-

<

1 1

-

<

SCPJU

<

!

-

<

!

-

r--H

CQ

!

CN

un

+-» c

LEFSS 1

CQ

<

1 1

oo

en CN

<

1 1

-

en

0

Q

1

A un

Tt

0

ECHSS

CQ

<

1

M-

un

<

!

-

U

0

1 1

r- r—4

o r-

CQ

CYPSS

CQ

!

G

G r-

<

1

Un

-

0

CQ

1 1

un

N

O

BRAPP

m

CQ

i

OO

rcv

<

1

en

un

CQ

!

N

-

CQ

Application Rate (g ai/ha)

m en

G r-

o oC 0

o u-j Pi Ü

O oo Pi 0

un en

o t

o S¹Pi 0

o m Pi 0

o oo Pi C

un en

o γ-

O (N Pi 0

o Ml Pi O

o oo Pi o

un en

Compound No

216

217

135

165

-273-

Visual Growth Réduction (%) 21 Days After Application	ORYSS	&	44	1	1 1	Q			!	!	0	0	70	!	!
SEBEX		i	-	-	<	<	!	-	-			!	-	-
SCPJU	a	1 1	1 1	I 1	•4—» G		1 1	-	-	<	<	1	-	-
LEFSS		!	24	56	<	<	!	Ό	un	0	0	(	>70	o Γ Λ
ECHSS	<	1	o	24	<	<	1 1	-	-	U	m	1		47
CYPSS	o	î	o	67			1		en r—4	<	<	}	-	-
BRAPP		1 l	CN	27		<	1	en	CN	U	m	1 t	un	42
Application Rate (g ai/ha)	70	o V OÎ <0	O un O	O oo 0	35	70	o s· & 0	s? 0	O oo Pi o	35	70	o S¹oi 0	o un té O	O oo té O
Compound No					134					122

-27417475

Visual Growth Réduction (%) 21 Days After Application

ORYSS

O

m

eq

!

I

0

>70

1

IQ

Q

00

1 l

1

0

>70

SEBEX

<

l 1

en

un

1

rq

<

!

en

Xt

<

t

SCPJU

<

1 1

-

<

l

un

oo

<

1

-

<

1 1

1 LEFSS

0

iq

1 1

o ΓA

>70

0

W

1 1

>70

o ΓA

0

Q

!

TJ· N

ΓΟΟ

Q

0

!

ECHSS 1

<

1 1

eq

VO

0

!

>70

CQ

PQ

1

r-

rq en

Ph

0

1

CYPSS

<

-

<

!

N-

00

<

1

-

<

1 1

BRAPP

<

1

N^-

<05

0

1

>70

Q

<

1

00

σ\ rq

Ph

Pp

1

Application Rate (g ai/ha)

un en

o c--

o s¹cQ 0

o m Pi O

O oo Pi 0

un en

o

o CN Ρί O

O ir> Pi Ü

O 00 Pi 0

un en

o r-

o Pi Ü

o m Pi O

o oo Pi C

un en

o r-

8 ai 0

Compound No

oo

00 un

146

r-

-275-

Visual Growth Réduction (%) 21 Days After Application

ORYSS

1 1

1

Φ

o

1

w

Q

cq

1

1 1

Q

m

-

i

1 1

Φ

SEBEX

-

!

-

<

1

-

<

!

-

<

SCPJU

-

<

1 1

-

<

1

-

<

*

-

LEFSS

>70

w

Q

1

en

>70

<

!

eq

o

<

1 1

tx

m

ECHSS

o tx Λ

>70

M

Q

1

40

>70

<

1 1

cq

Tt

<

!

cq

w

CYPSS

-

en

<

!

xr

o

<

1

rq

un

<

1 1

r—q

-

<

BRAPP

>70

W

Q

!

46

>70

<

1

en

00

<

!

OO

Q

Application Rate (g ai/ha)

S Φ

35

70

8 Φ

un en

70

un en

70

ι/Ί en

Compound No

125

159

124

96

-276-

Visual Growth Réduction (%) 21 Days After Application

ORYSS

O

130

!

î

m

Q

o

1 1

1 i

m

Q

en

1

SEBEX

<

1

-

<

1 1

-

<

1

-

SCPJU

<

!

-

<

1

-

Τ·—Γ

<

i

-

LEFSS

U

1 1

tx CM

00

w

<

1 1

'φ O1

C— *φ

<

1 1

ECHSS

m

1 l

CN

’Φ 00

o

<

i

CT

en en

<

1 1

-

CYPSS

<

!

en

<

1

CT

Φ

<

i

-

CN

BRAPP

m

1

Ch

oo

o

<

!

00

Ό CT

<

1

-

Application Rate (g ai/ha)

o tx

o & o

o o

o oo o

in en

o tx

o S* ai 0

s ai 0

O 00 O

en

o tx

o <T ai 0

O W) té O

o oo & o

Compound No

173

en O

-277-

Visual Growth Réduction (%) 21 Days After Application	ORYSS	Q	Q	Ν’	ί	ΐ	ra	ra	25	!	1 1
SEBEX	<	<	!	-	-	<	<	1 1	en	r-
SCPJU	<	<	1	-	-	<	<	!	-	-
LEFSS	<		1		en	O	0	!	175	463
ECHSS	<	<	1	-	-	m	<	!	-	25
CYPSS		<	1 1	un	o	<	<	!	-	-
BRAPP	<	<	!	-	un	Q	CQ	!	en	44
Application Rate (g ai/ha)	35	70	o S¹ra o	o u~> Pi O	o OO Pi o	35	70	o Pi O	o Pi O	O OO ra 0
Compound No	74					-

Claims

wherein

X is N or CY; wherein Y is hydrogen, halogen, C1-C3 alkyi, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, or C1-C3 haloalkylthio;

R* is OR¹,wherein R¹’ is H, CpCg alkyi, or C7-C10 arylalkyl;

R² is halogen, C1-C4 alkyi, C1-C4 haloalkyl, C2-C4 alkenyl, C₂-C₄ haloalkenyl, C₂-C₄alkynyl, C₂-C₄ haloalkynyl, C]-C₄ alkoxy, C1-C4 haloalkoxy, C]-C₄ alkylthio, C1-C4 haloalkylthio, amino, C1-C4 alkylamino, C₂-C₄ haloalkylamino, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, cyano, or a group of the formula -CR¹⁷=CR¹⁸SiR¹⁹R²⁰R²¹, wherein R¹⁷ is hydrogen, F, or Cl; R¹⁸ is hydrogen, F, Cl, C1-C4 alkyi, or C1-C4 haloalkyl; and R¹⁹, R²⁰, and R²¹ are each independently C1-C10 alkyi, C3-C6 cycloalkyl, CiC10 haloalkyl, C3-C6 halocycloalkyl, phenyl, substituted phenyl, Cj-Cio alkoxy, or OH;

R³ and R⁴ are each independently hydrogen, Ci-Cô alkyi, Cj-Cô haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C₃-Cô alkynyl, hydroxy, Ci-Ce alkoxy, Cj-Cé haloalkoxy, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (Ci-Cô alkoxy)carbonyl, (Ci-Cô alkyl)carbamyl, Cj-Cô alkylsulfonyl, tri(Ci-C6 alkyl)silyl, di(Ci-C6 alkyl)phosphonyl, or R³and R⁴ together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring, or R³ and R⁴ taken together represent =CR³ R⁴, wherein R³ and R⁴ are each independently hydrogen, Ci-Cô alkyi, C3-C6 alkenyl, C3-C6 alkynyl, Ci-Cô alkoxy, or Ci-Cô alkylamino, or R³ and R⁴ together with the carbon atom to which they are attached form a 5or 6-membered saturated ring;

-27917475

Ar is Ar2, Ar3, Ar4, Ar5, or Ar6:

Ar2

Ar3

Ar4

Ar5

Ar6 wherein

X2 is H, F, Cl, Br, I, ethynyl, haloethynyl, CH₃, CFH₂, CF2H, CF₃, OCF2H, OCF₃, CN, CONH₂, CO₂H, orNO₂;

X₃ is H, F, Br, I, ethynyl, haloethynyl, CH₃, CFH₂, CF₂H, CF₃, OCF₂H, OCF₃, CN, CONH2, CO₂H, orNO₂;

wherein

a) when Ar is then X is N, CH, CF, CCI, or CCH₃;

with provisos that:

i) R² is not Cl, when X is N;

ii) X2 is not Cl, when R² is OCH₃ or vinyl and X is N;

iii) X2 is not Cl, when R² is Cl and X is CH;

iv) X2 is not Cl, Br, I, or CF₃, when R² is OCH₃ and X is CF; and

-280b) whenAris *3

F then X is N, CH, or CF;

with provisos that:

i) R² is not Cl, when X is N;

ii) X₃ is not CH₃, when R² is OCH₃ and X is N;

iii) X₃ is not H, F, or CH₃, when R² is Cl and X is CH;

iv) X₃ is not Br or I, when R² is OCH₃ and X is CF; and

c) when Ar is F , then X is N, CH, or CF;

with provisos that:

i) R² is not Cl, when X is N;

ii) X₂ is not Cl, when R is OCH₃ or vinyl and X is N;

iii) X₂ is not F, when R² is Cl and X is CH;

iv) X₂ is not Cl, Br, I, or CF₃, when R² is OCH₃ and X is CF;

then X is N, CH, or CF;

with proviso that:

i) X₃ is not CH₃, when R² is Cl and X is N;

ii) X₃ is not Br or I, when X is CF and R² is OCH₃; and

F

e) when Ar is F , then X is N, CH, or CF;

or an N-oxide or agriculturally acceptable sait thereof.
2. The compound of claim 1, wherein Ar is Ar2, and X₂ is preferably H, Cl, Br, I, ethynyl, CH₃, CF₂H, CF₃, OCF₂H, or CN.
3. The compound of claim 1, wherein Ar is Ar3, and X₃ is preferably H, Br, I, ethynyl, OCF₂H, CN, orNO₂.
4. The compound of claim 1, wherein Ar is Ar4, and X2 is preferablyH, F, Br, I, ethynyl, CH₃, CF₃, OCF₂H, or CN.
5. The compound of claim 1, wherein Ar is Ar5, and X₃ is preferably H, F, Br, I, CH₃, CF₂H, CF₃, OCF₂H, or CN.
6. The compound of claim 1, wherein Ar is Ar6, and X2 is preferably Br or I.
7. The compound of any of claims 1-6, wherein R¹ is OR¹.
8. The compound of any of claims 1-7, wherein X is N.
9. The compound of any of claims 1-7, wherein X is CY.
10. The compound of claim any of claims 1-9, wherein R is halogen, C2-C4 alkenyl, C2-

C₄ haloalkenyl, C1-C4 alkoxy, C]-C₄ haloalkoxy, C1-C4 alkylthio, or C1-C4 haloalkylthio.
11. The compound of any of claims 1-10, wherein R³ and R⁴ are hydrogen.
12. The compound of claim 1 or an N-oxide or agriculturally acceptable sait thereof, wherein the compound is:

-282Y

-2837

-284-

O=Z

-287»

-28817475

-282^>17475

-29(g2-^
13. A herbicidal composition comprising the compound of any of claims 1-12 or an Noxide or agriculturally acceptable sait thereof, and an agriculturally acceptable adjuvant or

5 carrier, preferably further comprising at one additional herbicidal compound and/or safener.
14. A method for controlling undesirable végétation, which comprises applying the compound of any of claims 1-12, or the composition of claim 13.