4-amino-6-(4-substituted-phenyl)-picolinates and 6-amino-2-(4-substituted-phenyl)-pyrimidine-4-carboxylates and their use as herbicides
Patent Information
- Authority / Receiving Office
- CA · CA
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2014-03-12
- Publication Date
- 2026-08-04
Abstract
Description
4-AMINO-6-(4-SUBSTITUTED-PHENYL)-PICOLINATES AND 6-AMINO-2-(4- SUBSTITUTED-PHENYL)-PYRIMIDINE-4-CARBOXYLATES AND THEIR USE AS HERBICIDES
[0001] BACKGROUND
[0002] The occurrence of undesirable vegetation, 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 vegetation.
[0003] 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
[0004] Provided herein are compounds of Formula (I): [Image disponible dans le document PDF, Image available in the PDF document] (I) wherein X is N or CY, wherein Y is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkylthio, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkylthio; <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>OR1<annotation encoding="application / x-tex">OR^1< / annotation>< / semantics>, wherein <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is H, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl, or <semantics>C7<annotation encoding="application / x-tex">C_7< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> 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, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkyl; and <semantics>R19<annotation encoding="application / x-tex">R^{19}< / annotation>< / semantics>, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics>, and <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> are each independently <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkyl, C3-C6 cycloalkyl, C1-C10 haloalkyl, C3-C6 halocycloalkyl, phenyl, substituted phenyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkoxy, or OH; R3 and R4 are each independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, hydroxy, C1-C6 alkoxy, C1-C6 haloalkoxy, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (C1-C6 alkoxy)carbonyl, (C1-C6 alkyl)carbamyl, C1-C6 alkylsulfonyl, tri(C1-C6 alkyl)silyl, di(C1-C6 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, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C6 alkoxy, or C1-C6 alkylamino, or R3' and R4' together with the carbon atom to which they are attached form a 5- or 6-membered saturated ring; Ar is Ar1, Ar2, Ar3, Ar4, Ar5, or Ar6: [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] Ar1 Ar2 Ar3 [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] Ar4 Ar5 Ar6 wherein X1 is H, F, Br, I, ethynyl, haloethynyl, CF2H, OCF2H, OCF3, CN, CONH2, CO2H, <semantics>CO2CH3<annotation encoding="application / x-tex">CO_2CH_3< / annotation>< / semantics>, or <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>; X2 is H, F, Cl, Br, I, ethynyl, haloethynyl, CH3, CFH2, CF2H, CF3, OCF2H, OCF3, <semantics>CN<annotation encoding="application / x-tex">CN< / annotation>< / semantics>, <semantics>CONH2<annotation encoding="application / x-tex">CONH_2< / annotation>< / semantics>, <semantics>CO2H<annotation encoding="application / x-tex">CO_2H< / annotation>< / semantics>, or <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>; X3 is H, F, Br, I, ethynyl, haloethynyl, CH3, CFH2, CF2H, CF3, OCF2H, OCF3, CN, <semantics>CONH2<annotation encoding="application / x-tex">CONH_2< / annotation>< / semantics>, <semantics>CO2H<annotation encoding="application / x-tex">CO_2H< / annotation>< / semantics>, or <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>; wherein [Image disponible dans le document PDF, Image available in the PDF document] a) when Ar is then X is N, CH, CF, CCl, or CCH3; with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl or vinyl, when X is N; ii) <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is not H, F, OCF3, or CN, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is CH; iii) <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is not F, I, CN, or ethynyl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 and X is CF; iv) <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is not H, when X is CCl; and [Image disponible dans le document PDF, Image available in the PDF document] b) when Ar is then X is N, CH, CF, CCl, or CCH3; with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl, when X is N; ii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 or vinyl and X is N; iii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is CH; iv) X2 is not Cl, Br, I, or CF3, when R2 is OCH3 and X is CF; and [Image disponible dans le document PDF, Image available in the PDF document] c) when Ar is then X is N, CH, or CF; with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl, when X is N; ii) <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is not CH3, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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 [Image disponible dans le document PDF, Image available in the PDF document] d) when Ar is then X is N, CH, or CF; with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl, when X is N; ii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 or vinyl and X is N; iii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not F, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is CH; iv) X2 is not Cl, Br, I, or CF3, when R2 is OCH3 and X is CF; [Image disponible dans le document PDF, Image available in the PDF document] e) when Ar is , 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 [Image disponible dans le document PDF, Image available in the PDF document] f) when Ar is , then X is N, CH, or CF; or an N-oxide or agriculturally acceptable salt thereof.
[0005] Also provided are methods of controlling undesirable vegetation comprising (a) contacting the undesirable vegetation or area adjacent to the undesirable vegetation, or (b) pre-emergently contacting soil or water, a herbicidally effective amount of at least one compound of Formula (I) or agriculturally acceptable derivative (e.g., agriculturally acceptable salts, solvates, hydrates, esters, amides, N-oxides, or other derivatives) thereof. [0005a] In one embodiment, there is provided a compound of Formula (I): [Image disponible dans le document PDF, Image available in the PDF document] , (I) wherein X is CH, CF, CCl, and CCH3; <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>OR1′<annotation encoding="application / x-tex">OR^{1'}< / annotation>< / semantics>, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl, or <semantics>C7<annotation encoding="application / x-tex">C_7< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> arylalkyl; <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl; <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> and <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> are each independently hydrogen or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl; Ar is Ar2: [Image disponible dans le document PDF, Image available in the PDF document] Ar2 wherein X2 is H, Cl, Br, I, ethynyl, CH3, CFH2, CF2H, CF3, OCF2H, OCF3, or CN; with the proviso that: <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when X is CH. DETAILED DESCRIPTION
[0006] As used herein, herbicide and herbicidal active ingredient mean a compound that controls undesirable vegetation when applied in an appropriate amount.
[0007] As used herein, control of or controlling undesirable vegetation means killing or preventing the vegetation, or causing some other adversely modifying effect to the vegetation e.g., deviations from natural growth or development, regulation, desiccation, retardation, and the like.
[0008] As used herein, a herbicidally effective or vegetation controlling amount is an amount of herbicidal active ingredient the application of which controls the relevant undesirable vegetation.
[0009] As used herein, applying a herbicide or herbicidal composition means delivering it directly to the targeted vegetation or to the locus thereof or to the area where control of undesired vegetation is desired. Methods of application include, but are not limited to, pre- emergently contacting soil or water, or post-emergently contacting the undesirable vegetation or area adjacent to the undesirable vegetation.
[0010] As used herein, plants and vegetation include, but are not limited to, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.
[0011] 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.
[0012] Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and aminium cations of the formula: [Image disponible dans le document PDF, Image available in the PDF document] wherein R13, R14, R15 and R16 each, independently represents hydrogen or C1-C12 alkyl, <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C12<annotation encoding="application / x-tex">C_{12}< / annotation>< / semantics> alkenyl, or <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C12<annotation encoding="application / x-tex">C_{12}< / annotation>< / semantics> alkynyl, each of which is optionally substituted by one or more substituents such as hydroxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkylthio, or phenyl groups, provided that R13, R14, R15 and R16 are sterically compatible. Additionally, any two R13, R14, R15 and R16 together 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 metal hydroxide, such as sodium hydroxide, with an amine, such as ammonia, trimethylamine, diethanolamine, 2-methyl- thiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine, or with a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide or choline hydroxide. Amine salts of compounds of Formula (I) are useful forms or derivatives of compounds of Formula (I) because they are water-soluble and lend them- selves to the preparation of desirable aqueous based herbicidal compositions.
[0013] Other forms or derivatives 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 subsequent volumes to the 4th edition, volume E 7b, p. 565 f.
[0014] As used herein "acyl" includes formyl, <semantics>(C1−C3 alkyl)<annotation encoding="application / x-tex">(C_1-C_3 \text{ alkyl})< / annotation>< / semantics> carbonyl, and <semantics>(C1−C3 alkyl)<annotation encoding="application / x-tex">(C_1-C_3 \text{ alkyl})< / annotation>< / semantics> haloalkyl)carbonyl.
[0015] As used herein, "alkyl" refers to saturated, straight-chained or branched hydrocarbon moieties. Unless otherwise specified, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> 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, 2,3- dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl, 1-ethyl-1-methyl-propyl, and 1-ethyl-2-methyl-propyl.
[0016] 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, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> 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, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl.
[0017] As used herein, "alkenyl" refers to unsaturated, straight-chained, or branched hydrocarbon moieties containing one or more double bond(s). Unless otherwise specified, C2-C8 alkenyl 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, 1-methyl-2- propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1- butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1- propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2- butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2- butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1- butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl- 3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1- propenyl, and 1-ethyl-2-methyl-2-propenyl.
[0018] As used herein, "alkynyl" represents straight-chained or branched hydrocarbon moieties containing 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, <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics>-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1- pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3- pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2- butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2-propynyl.
[0019] As used herein, "alkoxy" refers to a group of the formula R-O-, where R is alkyl as defined above. Unless otherwise specified, alkoxy groups wherein R is a C1-C8 alkyl group are 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-dimethyl- butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl- butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy.
[0020] 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 C1-C8 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-2- fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy.
[0021] 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 C1-C8 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.
[0022] 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 C1-C8 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, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and 1,1,1-trifluoroprop-2-ylthio.
[0023] As used herein, "aryl," as well as derivative terms such as "aryloxy," refers to a phenyl, indanyl, or naphthyl group. In some embodiments, phenyl is preferred. The term "heteroaryl," as well as derivative terms such as "heteroaryloxy," refers to a 5- or 6- membered aromatic ring containing one or more heteroatoms, 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, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 acyl, C1-C6 alkylthio, C1-C6 alkylsulfinyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkylsulfonyl, <semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkoxy)carbonyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> carbamoyl, hydroxycarbonyl, (C1-C6 alkyl)carbonyl, aminocarbonyl, (C1-C6 alkylamino)carbonyl, <semantics>(di(C1−C6alkyl))<annotation encoding="application / x-tex">(di(C_1-C_6 alkyl))< / annotation>< / semantics>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, C1-C2 alkyl, and C1-C2 haloalkyl. [Image disponible dans le document PDF, Image available in the PDF document]
[0024] As used herein, "alkoxycarbonyl" refers to a group of the formula wherein R is alkyl.
[0025] 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.
[0026] As used herein, "alkylcarbamyl" refers to a carbamyl group substituted on the nitrogen with an alkyl group.
[0027] As used herein, "alkylsulfonyl" refers to <semantics>−SO2R<annotation encoding="application / x-tex">-SO_2R< / annotation>< / semantics>, wherein R is alkyl (e.g., <semantics>C1−C10<annotation encoding="application / x-tex">C_1-C_{10}< / annotation>< / semantics> alkyl).
[0028] As used herein, "carbamyl" (also referred to as carbamoyl or aminocarbonyl) [Image disponible dans le document PDF, Image available in the PDF document] refers to a group of the formula
[0029] 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.
[0030] As used herein, "Me" refers to a methyl group.
[0031] As used herein, the term "halogen," including derivative terms such as "halo," refers to fluorine, chlorine, bromine, or iodine (or fluoride, chloride, bromide, or iodide).
[0032] As used herein, plants and vegetation include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation. COMPOUNDS
[0033] Provided herein are compounds of Formula (I) as defined herein (e.g., in the Summary above) and N-oxides and agriculturally acceptable salts thereof.
[0034] In some embodiments, the compound is the carboxylic acid or an agriculturally acceptable ester or salt thereof. In some embodiments, the compound is the carboxylic acid or its methyl ester.
[0035] In some embodiments: Ar is selected from the group consisting of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6; <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>OR1′<annotation encoding="application / x-tex">OR^{1'}< / annotation>< / semantics>, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl; <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen, <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl, <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkenyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkylthio, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkylthio; R3 and R4 are each independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (C1-C6 alkoxy)carbonyl, (C1-C6 alkyl)carbamyl, tri(C1-C6 alkyl)silyl, or <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> and <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> taken together represent =<semantics>CR3′R4′<annotation encoding="application / x-tex">CR^{3'}R^{4'}< / annotation>< / semantics>, wherein <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> and <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> are each independently hydrogen, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl, <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkenyl, <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkynyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkoxy, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkylamino; and X is N or CY, where Y is hydrogen, halogen, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkylthio, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkylthio.
[0036] In one embodiment, X is N. In one embodiment, X is CY.
[0037] In one embodiment, Y is hydrogen. In one embodiment, Y is halogen (e.g., F, Cl, Br, I). In one embodiment, Y is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkyl (e.g., methyl, ethyl, n-propyl, i-propyl). In one embodiment, Y is C1-C3 haloalkyl (e.g., CFH2, CF2H, CF3, CF2CF3). In one embodiment, Y is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkoxy (e.g., OCH3, OCH2CH3). In one embodiment, Y is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkoxy (e.g., OCF2H, OCF3, OCF2CF3). In one embodiment, Y is C1-C3 alkylthio (e.g., SCH3, SCH2CH3). In one embodiment, Y is C1-C3 haloalkylthio (e.g., SCFH2, SCF2H, SCF3, SCF2CF3).
[0038] In some embodiments, X is N or CY, wherein Y is hydrogen, halogen, C1-C3 alkyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkoxy, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkylthio, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> haloalkylthio.
[0039] In some embodiments, X is N or CY, wherein Y is H, halo, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> 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 C1-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 C1-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.
[0040] In one embodiment, R1 is OR1.
[0041] In one embodiment, <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H. In one embodiment, <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl (e.g., methyl, ethyl, n-propyl, i-propyl). In one embodiment, <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is <semantics>C7<annotation encoding="application / x-tex">C_7< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> arylalkyl (e.g., benzyl).
[0042] In some embodiments, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>OR1′<annotation encoding="application / x-tex">OR^{1'}< / annotation>< / semantics>, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl. In some embodiments, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>OR1′<annotation encoding="application / x-tex">OR^{1'}< / annotation>< / semantics>, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H or <semantics>C7<annotation encoding="application / x-tex">C_7< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> arylalkyl.
[0043] In some embodiments, R1 is OR1, wherein R1 is H, methyl, ethyl, or benzyl. In some embodiments, R1 is OR1, wherein R1 is H, methyl, or ethyl. In some embodiments, R1 is <semantics>OR1′<annotation encoding="application / x-tex">OR^{1'}< / annotation>< / semantics>, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H or methyl. In some embodiments, <semantics>R1<annotation encoding="application / x-tex">R^{1}< / annotation>< / semantics> is <semantics>OR1′<annotation encoding="application / x-tex">OR^{1'}< / annotation>< / semantics>, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H or benzyl.
[0044] In one embodiment, R2 is halogen (e.g., F, Cl, Br, I). In one embodiment, R2 is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl (e.g., methyl, ethyl, propyl, butyl). In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> 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, R2 is C2-C4 haloalkenyl. In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkynyl. In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkynyl. In one embodiment, R2 is C1-C4 alkoxy (e.g., OCH3, OCH2CH3). In one embodiment, R2 is C1-C4 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 <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkylamino. In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkylamino. In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is formyl. In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>(C1−C3 alkyl)<annotation encoding="application / x-tex">(C_1-C_3 \text{ alkyl})< / annotation>< / semantics>carbonyl. In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>(C1−C3 haloalkyl)<annotation encoding="application / x-tex">(C_1-C_3 \text{ haloalkyl})< / annotation>< / semantics>carbonyl. In one embodiment, <semantics>ℝ2<annotation encoding="application / x-tex">\mathbb{R}^2< / annotation>< / semantics> is cyano.
[0045] In one embodiment, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>−CR17=CR18−SiR19R20R21<annotation encoding="application / x-tex">-CR^{17}=CR^{18}-SiR^{19}R^{20}R^{21}< / annotation>< / semantics>.
[0046] In one embodiment, R17 is hydrogen. In one embodiment, R17 is F. In one embodiment, R17 is Cl.
[0047] In one embodiment, R18 is hydrogen. In one embodiment, R18 is F. In one embodiment, <semantics>R18<annotation encoding="application / x-tex">R^{18}< / annotation>< / semantics> is Cl. In one embodiment, <semantics>R18<annotation encoding="application / x-tex">R^{18}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R18<annotation encoding="application / x-tex">R^{18}< / annotation>< / semantics> is C1-C4 haloalkyl.
[0048] In one embodiment, <semantics>R19<annotation encoding="application / x-tex">R^{19}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R19<annotation encoding="application / x-tex">R^{19}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> cycloalkyl. In one embodiment, R19 is C1-C10 haloalkyl. In one embodiment, R19 is C3-C6 halocycloalkyl. In one embodiment, R19 is phenyl. In one embodiment, R19 is substituted phenyl. In one embodiment, <semantics>R19<annotation encoding="application / x-tex">R^{19}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkoxy. In one embodiment, <semantics>R19<annotation encoding="application / x-tex">R^{19}< / annotation>< / semantics> is OH.
[0049] In one embodiment, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> cycloalkyl. In one embodiment, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> haloalkyl. In one embodiment, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> halocycloalkyl. In one embodiment, R20 is phenyl. In one embodiment, R20 is substituted phenyl. In one embodiment, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkoxy. In one embodiment, <semantics>R20<annotation encoding="application / x-tex">R^{20}< / annotation>< / semantics> is OH.
[0050] In one embodiment, <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> cycloalkyl. In one embodiment, R21 is C1-C10 haloalkyl. In one embodiment, R21 is C3-C6 halocycloalkyl. In one embodiment, <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> is phenyl. In one embodiment, <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> is substituted phenyl. In one embodiment, <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C10<annotation encoding="application / x-tex">C_{10}< / annotation>< / semantics> alkoxy. In one embodiment, <semantics>R21<annotation encoding="application / x-tex">R^{21}< / annotation>< / semantics> is OH.
[0051] In some embodiments, R2 is halogen, C2-C4 alkenyl, C2-C4 haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, or C1-C4 haloalkylthio. In some embodiments, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen, <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl, <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> haloalkenyl, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy.
[0052] In some embodiments, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen, <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In some embodiments, R2 is Cl, vinyl, or OCH3. In some embodiments, R2 is Cl. In some embodiments, R2 is vinyl. In some embodiments, R2 is OCH3.
[0053] In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is hydrogen. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> haloalkyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkenyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> haloalkenyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkynyl. In one embodiment, R3 is hydroxy. In one embodiment, R3 is C1-C6 alkoxy. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> haloalkoxy. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is formyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is <semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics> alkyl)carbonyl. In one embodiment, R3 is (C1-C3 haloalkyl)carbonyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is (C1-C6 alkoxy)carbonyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is (C1-C6 alkyl)carbamyl. In one embodiment, R3 is C1-C6 alkylsulfonyl. In one embodiment, R3 is tri(C1-C6 alkyl)silyl. In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> is di(<semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl)phosphonyl.
[0054] In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is hydrogen. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> haloalkyl. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> 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 C1-C6 alkoxy. In one embodiment, R4 is C1-C6 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, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is <semantics>(C1−C6<annotation encoding="application / x-tex">(C_1-C_6< / annotation>< / semantics> alkoxy)carbonyl. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is <semantics>(C1−C6<annotation encoding="application / x-tex">(C_1-C_6< / annotation>< / semantics> alkyl)carbamyl. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkylsulfonyl. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is tri(<semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl)silyl. In one embodiment, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> is di(<semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl)phosphonyl.
[0055] 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.
[0056] In one embodiment, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> and <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> taken together represent =<semantics>CR3′R4′<annotation encoding="application / x-tex">CR^{3'}R^{4'}< / annotation>< / semantics>.
[0057] In one embodiment, <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> is hydrogen. In one embodiment, <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkenyl. In one embodiment, <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkynyl. In one embodiment, <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkoxy. In one embodiment, <semantics>R3′<annotation encoding="application / x-tex">R^{3'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkylamino.
[0058] In one embodiment, <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> is hydrogen. In one embodiment, <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl. In one embodiment, <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkenyl. In one embodiment, <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> is <semantics>C3<annotation encoding="application / x-tex">C_3< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkynyl. In one embodiment, <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkoxy. In one embodiment, <semantics>R4′<annotation encoding="application / x-tex">R^{4'}< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkylamino.
[0059] 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.
[0060] In some embodiments, R3 and R4 are each independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, (C1-C3 alkyl)carbonyl, (C1-C3 haloalkyl)carbonyl, (C1-C6 alkoxy)carbonyl, (C1-C6 alkyl)carbamyl, <semantics>tri(C1−C6 alkyl)<annotation encoding="application / x-tex">tri(C_1-C_6 \text{ alkyl})< / annotation>< / semantics>silyl. In some embodiments, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> and <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> taken together represent =<semantics>CR3′R4′<annotation encoding="application / x-tex">CR^{3'}R^{4'}< / annotation>< / semantics>, wherein R3' and R4' are each independently hydrogen, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkoxy, or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkylamino.
[0061] In some embodiments, R3 is H.
[0062] In some embodiments, R4 is H.
[0063] In one embodiment, Ar is Ar1.
[0064] In one embodiment, provided herein is a compound of formula (I-1), or an N- oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] 2 <semantics>(I−1)<annotation encoding="application / x-tex">(I-1)< / annotation>< / semantics> wherein <semantics>X<annotation encoding="application / x-tex">X< / annotation>< / semantics>, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> are defined herein elsewhere.
[0065] In one embodiment, in a compound of formula (I-1), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-1), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OH and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-1), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-1), R1 is OH and R2 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 (I-1), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-1), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2−C4<annotation encoding="application / x-tex">C_2-C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-1), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1−C4<annotation encoding="application / x-tex">C_1-C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-1), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>OCH3<annotation encoding="application / x-tex">OCH_3< / annotation>< / semantics>. In one embodiment, in a compound of formula (I-1), R1 is -O-(C1-C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1), R1 is OCH3 and R2 is 1-propenyl.
[0066] In one embodiment, provided herein is a compound of formula (I-1a), (I-1b), (I-1c), (I-1d), or (I-1e), or an N-oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] 25 wherein <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> are defined herein elsewhere.
[0067] In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1a), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1a), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-1a), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1a), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-1a), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-1a), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-1a), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-1a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-1a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1a), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-1a), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-1a), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1a), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0068] In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1b), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-1b), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1b), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-1b), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-1b), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-1b), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-1b), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1b), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-1b), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-1b), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1b), R1 is OCH3 and <semantics>ℝ2<annotation encoding="application / x-tex">\mathbb{R}^2< / annotation>< / semantics> is 1-propenyl.
[0069] In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1c), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1c), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-1c), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-1c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-1c), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-1c), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-1c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-1c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1c), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-1c), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-1c), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1c), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0070] In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1d), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-1d), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-1d), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-1d), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1d), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-1d), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-1d), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1d), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0071] In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1e), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-1e), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1e), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-1e), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-1e), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1e), R1 is -O-(C1-C4 alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-1e), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-1e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-1e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-1e), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-1e), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-1e), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-1e), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0072] In one embodiment, Ar is Ar2.
[0073] In one embodiment, provided herein is a compound of formula (I-2), or an N- oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] , <semantics>(I−2)<annotation encoding="application / x-tex">(I-2)< / annotation>< / semantics> wherein X, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> are defined herein elsewhere.
[0074] In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-2), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-2), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2−C4<annotation encoding="application / x-tex">C_2-C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-2), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1−C4<annotation encoding="application / x-tex">C_1-C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-2), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-2), R1 is -O-(C1-C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2), R1 is -O-(C1-C4 alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2), R1 is OCH3 and R2 is 1-propenyl.
[0075] 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 salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] , wherein <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> are defined herein elsewhere.
[0076] In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2a), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-2a), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-2a), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2a), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-2a), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-2a), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-2a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2a), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-2a), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-2a), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2a), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0077] 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-2b), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-2b), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-2b), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-2b), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-2b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-2b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2b), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-2b), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-2b), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2b), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0078] 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 C1-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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-2c), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-2c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-2c), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2c), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-2c), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-2c), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2c), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0079] In one embodiment, in a compound of formula (I-2d), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-2d), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2d), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2d), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-2d), R1 is OH and R2 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), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-2d), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-2d), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2d), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-2d), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-2d), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2d), R1 is -O-(C1-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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2d), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> 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 R2 is OCH3. In one embodiment, in a compound of formula (I-2d), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2d), R1 is OCH3 and R2 is 1-propenyl.
[0080] In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2e), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-2e), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-2e), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-2e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-2e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-2e), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2e), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-2e), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-2e), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-2e), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-2e), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0081] In one embodiment, Ar is Ar3.
[0082] In one embodiment, provided herein is a compound of formula (I-3), or an N- oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] , <semantics>(I−3)<annotation encoding="application / x-tex">(I-3)< / annotation>< / semantics> wherein <semantics>X<annotation encoding="application / x-tex">X< / annotation>< / semantics>, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> are defined herein elsewhere.
[0083] In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-3), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-3), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2−C4<annotation encoding="application / x-tex">C_2-C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-3), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1−C4<annotation encoding="application / x-tex">C_1-C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3), R1 is -O-(C1-C4 alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-3), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-3), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3), R1 is -O-(C1-C4 alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3), R1 is OCH3 and R2 is 1-propenyl.
[0084] In one embodiment, provided herein is a compound of formula (I-3a), (I-3b), or (I-3c), or an N-oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] , [Image disponible dans le document PDF, Image available in the PDF document] or wherein R1, R2, R3, R4, and X3 are defined herein elsewhere.
[0085] In one embodiment, in a compound of formula (I-3a), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-3a), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OH and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3a), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-3a), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-3a), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3a), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-3a), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-3a), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-3a), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-3a), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-3a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3a), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-3a), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-3a), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3a), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0086] In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3b), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-3b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-3b), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3b), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-3b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-3b), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-3b), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-3b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3b), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-3b), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-3b), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3b), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0087] In one embodiment, in a compound of formula (I-3c), 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 (I-3c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-3c), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3c), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-3c), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-3c), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3c), R1 is -O-(C1-C4 alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-3c), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-3c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-3c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-3c), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-3c), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-3c), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-3c), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[8800] In one embodiment, Ar is Ar4.
[0089] In one embodiment, provided herein is a compound of formula (I-4), or an N- oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] , <semantics>(I−4)<annotation encoding="application / x-tex">(I-4)< / annotation>< / semantics> wherein X, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> are defined herein elsewhere.
[0090] In one embodiment, in a compound of formula (I-4), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-4), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OH and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-4), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-4), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-4), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-4), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-4), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2−C4<annotation encoding="application / x-tex">C_2-C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-4), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1−C4<annotation encoding="application / x-tex">C_1-C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-4), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-4), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-4), R1 is -O-(C1-C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4), R1 is OCH3 and R2 is 1-propenyl.
[0091] In one embodiment, provided herein is a compound of formula (I-4a), (I-4b), or (I-4c), or an N-oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] , , [Image disponible dans le document PDF, Image available in the PDF document] or wherein <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> are defined herein elsewhere.
[0092] 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 C1. 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-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-4a), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4a), R1 is -O-(C1-C4 alkyl) and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4a), R1 is -O-(C1-C4 alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-4a), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-4a), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-4a), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-4a), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-4a), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4a), R1 is OCH3 and <semantics>ℝ2<annotation encoding="application / x-tex">\mathbb{R}^2< / annotation>< / semantics> is 1-propenyl.
[0093] In one embodiment, in a compound of formula (I-4b), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-4b), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4b), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4b), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-4b), R1 is OH and R2 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), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-4b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-4b), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-4b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-4b), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-4b), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-4b), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-4b), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-4b), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4b), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0094] In one embodiment, in a compound of formula (I-4c), R1 is OH and R2 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), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-4c), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4c), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-4c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-4c), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-4c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-4c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-4c), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-4c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-4c), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-4c), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-4c), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-4c), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[0095] In one embodiment, Ar is Ar5.
[0096] In one embodiment, provided herein is a compound of formula (I-5), or an N- oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] 5 <semantics>(I−5)<annotation encoding="application / x-tex">(I-5)< / annotation>< / semantics> wherein <semantics>X<annotation encoding="application / x-tex">X< / annotation>< / semantics>, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> are defined herein elsewhere.
[0097] In one embodiment, in a compound of formula (I-5), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-5), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OH and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-5), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-5), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-5), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-5), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-5), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-5), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2−C4<annotation encoding="application / x-tex">C_2-C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-5), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1−C4<annotation encoding="application / x-tex">C_1-C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-5), R1 is -O-(C1-C4 alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-5), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>OCH3<annotation encoding="application / x-tex">OCH_3< / annotation>< / semantics>. In one embodiment, in a compound of formula (I-5), R1 is -O-(C1-C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5), R1 is OCH3 and R2 is 1-propenyl.
[0098] In one embodiment, provided herein is a compound of formula (I-5a), (I-5b), or (I-5c), or an N-oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] , or [Image disponible dans le document PDF, Image available in the PDF document] wherein <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> are defined herein elsewhere.
[0099] In one embodiment, in a compound of formula (I-5a), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-5a), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5a), R1 is OH and R2 is C1-C4 alkoxy. 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), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5a), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-5a), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-5a), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-5a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-5a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-5a), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-5a), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-5a), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-5a), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5a), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[00100] In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5b), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-5b), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-5b), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-5b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-5b), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-5b), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-5b), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-5b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-5b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> 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 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5b), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[00101] In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5c), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-5c), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-5c), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-5c), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-5c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl. In one embodiment, in a compound of formula (I-5c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-5c), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5c), R1 is -O-(C1-C4 alkyl) and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-5c), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-5c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-5c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> 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 R2 is OCH3. In one embodiment, in a compound of formula (I-5c), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-5c), R1 is OCH3 and <semantics>ℝ2<annotation encoding="application / x-tex">\mathbb{R}^2< / annotation>< / semantics> is 1-propenyl.
[00102] In one embodiment, Ar is Ar6.
[00103] In one embodiment, provided herein is a compound of formula (I-6), or an N- oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] , <semantics>(I−6)<annotation encoding="application / x-tex">(I-6)< / annotation>< / semantics> wherein <semantics>X<annotation encoding="application / x-tex">X< / annotation>< / semantics>, <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> are defined herein elsewhere.
[00104] In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-6), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4)<annotation encoding="application / x-tex">-O-(C_1-C_4)< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is halogen. In one embodiment, in a compound of formula (I-6), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-6), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-6), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-6), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6), R1 is OCH3 and R2 is 1-propenyl.
[00105] In one embodiment, provided herein is a compound of formula (I-6a), (I-6b), or (I-6c), or an N-oxide or agriculturally acceptable salt thereof: [Image disponible dans le document PDF, Image available in the PDF document] , wherein <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics>, <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics>, <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics>, <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics>, and <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> are defined herein elsewhere.
[00106] 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), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6a), R1 is OH and R2 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), R1 is OH and R2 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), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-6a), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6a), R1 is -O-(C1-C4 alkyl) and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6a), R1 is -O-(C1-C4 alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-6a), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-6a), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-6a), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-6a), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6a), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-6a), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-6a), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-6a), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6a), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[00107] In one embodiment, in a compound of formula (I-6b), R1 is OH and R2 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), R1 is OH and R2 is C1-C4 alkoxy. In one embodiment, in a compound of formula (I-6b), R1 is OH and R2 is Cl. In one embodiment, in a compound of formula (I-6b), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-6b), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6b), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-6b), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-6b), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6b), R1 is -O-(C1-C4 alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-6b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-6b), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-6b), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> 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), R1 is OCH3 and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6b), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-6b), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-6b), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-6b), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6b), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[00108] In one embodiment, in a compound of formula (I-6c), R1 is OH and R2 is halogen. In one embodiment, in a compound of formula (I-6c), R1 is OH and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6c), R1 is OH and R2 is C1-C4 alkoxy. 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), R1 is OH and R2 is OCH3. In one embodiment, in a compound of formula (I-6c), R1 is OH and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6c), R1 is OH and R2 is 1-propenyl. In one embodiment, in a compound of formula (I-6c), R1 is -O-(C1-C4 alkyl) and R2 is halogen. In one embodiment, in a compound of formula (I-6c), R1 is -O-(C1-C4 alkyl) and R2 is C2-C4 alkenyl. In one embodiment, in a compound of formula (I-6c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-6c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O<annotation encoding="application / x-tex">-O< / annotation>< / semantics>-<semantics>(C1<annotation encoding="application / x-tex">(C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkyl) and R2 is Cl. In one embodiment, in a compound of formula (I-6c), R1 is -O-(C1-C4 alkyl) and R2 is OCH3. In one embodiment, in a compound of formula (I-6c), R1 is -O-(C1- C4 alkyl) and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is <semantics>−O−(C1−C4<annotation encoding="application / x-tex">-O-(C_1-C_4< / annotation>< / semantics> alkyl) and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl. In one embodiment, in a compound of formula (I-6c), R1 is OCH3 and R2 is halogen. In one embodiment, in a compound of formula (I-6c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C2<annotation encoding="application / x-tex">C_2< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkenyl. In one embodiment, in a compound of formula (I-6c), <semantics>R1<annotation encoding="application / x-tex">R^1< / annotation>< / semantics> is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C4<annotation encoding="application / x-tex">C_4< / annotation>< / semantics> alkoxy. In one embodiment, in a compound of formula (I-6c), R1 is OCH3 and R2 is Cl. In one embodiment, in a compound of formula (I-6c), R1 is OCH3 and R2 is OCH3. In one embodiment, in a compound of formula (I-6c), R1 is OCH3 and R2 is vinyl (or ethenyl). In one embodiment, in a compound of formula (I-6c), R1 is OCH3 and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is 1-propenyl.
[00109] In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is H. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is F. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is Br. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is I. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is ethynyl. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>CF2H<annotation encoding="application / x-tex">CF_2H< / annotation>< / semantics>. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>OCF2H<annotation encoding="application / x-tex">OCF_2H< / annotation>< / semantics>. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>OCF3<annotation encoding="application / x-tex">OCF_3< / annotation>< / semantics>. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is CN. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>CONH2<annotation encoding="application / x-tex">CONH_2< / annotation>< / semantics>. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>CO2H<annotation encoding="application / x-tex">CO_2H< / annotation>< / semantics>. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>CO2CH3<annotation encoding="application / x-tex">CO_2CH_3< / annotation>< / semantics>. In one embodiment, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>.
[00110] In some embodiments, X1 is H, F, Br, I, ethynyl, CF2H, OCF3, CN, <semantics>CONH2<annotation encoding="application / x-tex">CONH_2< / annotation>< / semantics>, <semantics>CO2CH3<annotation encoding="application / x-tex">CO_2CH_3< / annotation>< / semantics>, or <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>.
[00111] In some embodiments, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is F. In some embodiments, <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is Br or I.
[00112] In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is H. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is F. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is Cl. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is Br. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is I. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is ethynyl. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is <semantics>CH3<annotation encoding="application / x-tex">CH_3< / annotation>< / semantics>. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is <semantics>CFH2<annotation encoding="application / x-tex">CFH_2< / annotation>< / semantics>. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is <semantics>CF2H<annotation encoding="application / x-tex">CF_2H< / annotation>< / semantics>. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is <semantics>CF3<annotation encoding="application / x-tex">CF_3< / annotation>< / semantics>. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is OCF2H. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is OCF3. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is CN. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is CONH2. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is CO2H. In one embodiment, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>.
[00113] In some embodiments, X2 is H, Cl, Br, I, ethynyl, CH3, CF2H, CF3, OCF2H, or CN.
[00114] In some embodiments, X2 is H, F, Br, I, ethynyl, CH3, CF3, OCF2H, or CN.
[00115] In some embodiments, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is F or Cl. In some embodiments, <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is Br or I.
[00116] In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is H. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is F. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is Br. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is I. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is ethynyl. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>CH3<annotation encoding="application / x-tex">CH_3< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>CFH2<annotation encoding="application / x-tex">CFH_2< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>CF2H<annotation encoding="application / x-tex">CF_2H< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>CF3<annotation encoding="application / x-tex">CF_3< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>OCF2H<annotation encoding="application / x-tex">OCF_2H< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is OCF3. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is CN. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>CONH2<annotation encoding="application / x-tex">CONH_2< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>CO2H<annotation encoding="application / x-tex">CO_2H< / annotation>< / semantics>. In one embodiment, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is <semantics>NO2<annotation encoding="application / x-tex">NO_2< / annotation>< / semantics>.
[00117] In some embodiments, X3 is H, Br, I, ethynyl, OCF2H, CN, or NO2.
[00118] In some embodiments, X3 is H, F, Br, I, CH3, CF2H, CF3, OCF2H, or CN.
[00119] In some embodiments, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is F or Cl. In some embodiments, <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is Br or I. [Image disponible dans le document PDF, Image available in the PDF document]
[00120] In one embodiment, when Ar is , then X is N, CH, CF, CCl, or CCH3, with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl or vinyl, when X is N; ii) <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is not H, F, OCF3, or CN, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is CH; iii) <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is not F, I, CN, or ethynyl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 and X is CF; and iv) <semantics>X1<annotation encoding="application / x-tex">X_1< / annotation>< / semantics> is not H, when X is CCl. [Image disponible dans le document PDF, Image available in the PDF document]
[00121] In one embodiment, when Ar is , then X is N, CH, CF, CCl, or CCH3, with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl, when X is N; ii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 or vinyl and X is N; iii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is CH; and iv) X2 is not Cl, Br, I, or CF3, when R2 is OCH3 and X is CF. [Image disponible dans le document PDF, Image available in the PDF document]
[00122] In one embodiment, when Ar is , then X is N, CH, or CF, with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl, when X is N; ii) <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is not <semantics>CH3<annotation encoding="application / x-tex">CH_3< / annotation>< / semantics>, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is <semantics>OCH3<annotation encoding="application / x-tex">OCH_3< / annotation>< / semantics> and <semantics>X<annotation encoding="application / x-tex">X< / annotation>< / semantics> is <semantics>N<annotation encoding="application / x-tex">N< / annotation>< / semantics>; iii) X3 is not H, F, or CH3, when R2 is Cl and X is CH; and iv) <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is not Br or I, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 and X is CF. [Image disponible dans le document PDF, Image available in the PDF document]
[00123] In one embodiment, when Ar is , then X is N, CH, or CF, with provisos that: i) <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is not Cl, when X is N; ii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not Cl, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3 or vinyl and X is N; iii) <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is not F, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is CH; and iv) X2 is not Cl, Br, I, or CF3, when R2 is OCH3 and X is CF. [Image disponible dans le document PDF, Image available in the PDF document]
[00124] In one embodiment, when Ar is , then X is N, CH, or CF, with proviso that: i) <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is not CH3, when <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl and X is N; and ii) <semantics>X3<annotation encoding="application / x-tex">X_3< / annotation>< / semantics> is not Br or I, when X is CF and <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is OCH3. [Image disponible dans le document PDF, Image available in the PDF document]
[00125] In one embodiment, when Ar is , then X is N, CH, or CF.
[00126] Any of the combinations of Ar, X, Y, R1, R2, R3, R4, R1', R1'', R2'', R17, R18, R19, R20, R21, R3', R4', Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, X1, X2, and / or X3, and / or other substituents described herein, are encompassed by this disclosure and specifically provided herein. METHODS OF PREPARING THE COMPOUNDS
[00127] Exemplary procedures to synthesize the compounds of Formula (I) are provided below.
[00128] 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-6- chloropicolinates of Formula (II) can be converted to the 4-amino-6-substituted-picolinates of Formula (III), 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 temperature, such as 110 °C, e.g., in a microwave reactor (reaction <semantics>a1<annotation encoding="application / x-tex">a_1< / annotation>< / semantics>). 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 <semantics>b1<annotation encoding="application / x-tex">b_1< / annotation>< / semantics>). Stille coupling 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 1,2- dichloroethane, at a temperature, such as 120-130 °C, e.g., in a microwave reactor, provides 5-(substituted)-4-amino-6-substituted-picolinates of Formula (I-A), wherein <semantics>Z1<annotation encoding="application / x-tex">Z_1< / annotation>< / semantics> is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction <semantics>c1<annotation encoding="application / x-tex">c_1< / annotation>< / semantics>).
[00129] Alternatively, 4-amino-6-chloropicolinates of Formula (II) can be transformed into the 5-iodo-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 <semantics>b2<annotation encoding="application / x-tex">b_2< / annotation>< / semantics>). Stille coupling 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 1,2- dichloroethane, at a temperature, such as 120-130 °C, e.g., in a microwave reactor, provides 5-(substituted)-4-amino-6-chloropicolinates of Formula (VI), wherein <semantics>Z1<annotation encoding="application / x-tex">Z_1< / annotation>< / semantics> is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction <semantics>c2<annotation encoding="application / x-tex">c_2< / annotation>< / semantics>). The 5-substituted-4-amino-6- chloropicolinates of Formula (VI) can be converted to the 5-substituted-4-amino-6- substituted-picolinates of Formula (I-A), 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 temperature, such as 110 °C, e.g., in a microwave reactor (reaction <semantics>a2<annotation encoding="application / x-tex">a_2< / annotation>< / semantics>). Scheme I [Image disponible dans le document PDF, Image available in the PDF document]
[00130] 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 temperature under Dean- Stark conditions (reaction d). The isopropyl ester of Formula (VIII) can be reacted with a fluoride ion source, such as cesium fluoride, in a polar, aprotic solvent, such as dimethyl sulfoxide (DMSO), at a temperature, such as 80 °C, under Dean-Stark conditions, to yield the isopropyl 4,5,6-trifluoropicolinate 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 temperature, such as 100 °C, to produce a 4-amino-5-fluoro-6-chloro-picolinate of Formula (XI) (reaction g). The 4-amino-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 temperature (reaction <semantics>h<annotation encoding="application / x-tex">h< / annotation>< / semantics>). Scheme II [Image disponible dans le document PDF, Image available in the PDF document]
[00131] 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 <semantics>b3<annotation encoding="application / x-tex">b_3< / annotation>< / semantics>). Stille coupling of the 3-iodo-4-amino-5- fluoro-6-chloropicolinates 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 non-reactive solvent, such as 1,2-dichloroethane, at a temperature, such as 120-130 °C, e.g., in a microwave reactor, provides 3-(substituted)-4- amino-5-fluoro-6-chloropicolinates of Formula (XIV), wherein R2 is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction <semantics>c3<annotation encoding="application / x-tex">c_3< / annotation>< / semantics>). Alternatively, the 3-iodo-4-amino-5-fluoro-6- chloropicolinates of Formula (XIII) can be treated with cesium 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 temperature, such as 65 °C, to provide a 3-(substituted)- 4-amino-5-fluoro-6-chloropicolinic acids of Formula (XIV), wherein R2 is alkoxy or haloalkoxy (reaction <semantics>i1<annotation encoding="application / x-tex">i_1< / annotation>< / semantics>), which can be esterified to the methyl esters, e.g., by treatment with hydrogen chloride (gas) and methyl alcohol at 50 °C (reaction <semantics>j1<annotation encoding="application / x-tex">j_1< / annotation>< / semantics>). 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 temperature, such as 110 °C, e.g., in a microwave reactor (reaction <semantics>a3<annotation encoding="application / x-tex">a_3< / annotation>< / semantics>).
[00132] Alternatively, 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 temperature, such as 110 °C, e.g., in a microwave reactor (reaction <semantics>a4<annotation encoding="application / x-tex">a_4< / annotation>< / semantics>). The 4-amino-5-fluoro-6- substituted-picolinates of Formula (XV) can be transformed into the 3-iodo-4-amino-5- fluoro-6-substituted-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 <semantics>b4<annotation encoding="application / x-tex">b_4< / annotation>< / semantics>). 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 1,2- dichloroethane, at a temperature, 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 R2 is alkyl, alkenyl, alkynyl, haloalkenyl and alkylthio (reaction <semantics>c4<annotation encoding="application / x-tex">c_4< / annotation>< / semantics>). Alternatively, the 3-iodo-4- amino-5-fluoro-6-substituted-picolinates of Formula (XVI) can be treated with cesium 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 temperature, such as 65 °C, to provide a 3-(substituted)-4-amino-5-fluoro-6-substituted-picolinic acids of Formula (I-B), wherein <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is alkoxy or haloalkoxy (reaction <semantics>i2<annotation encoding="application / x-tex">i_2< / annotation>< / semantics>), which can be esterified to the methyl esters, e.g., by treatment with hydrogen chloride (gas) and methyl alcohol, at a temperature, such as 50 °C (reaction <semantics>j2<annotation encoding="application / x-tex">j_2< / annotation>< / semantics>). Scheme III [Image disponible dans le document PDF, Image available in the PDF document]
[00133] 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, <semantics>e.g.<annotation encoding="application / x-tex">e.g.< / annotation>< / semantics>, at reflux temperature (reaction <semantics>k<annotation encoding="application / x-tex">k< / annotation>< / semantics>). 4-Amino-6-substituted-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 l). Scheme IV [Image disponible dans le document PDF, Image available in the PDF document]
[00134] 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 magnesium bromide, in a polar, aprotic solvent, such as tetrahydrofuran (reaction <semantics>m<annotation encoding="application / x-tex">m< / annotation>< / semantics>). 2,4- Dichloro-5-methoxy-6-vinylpyrimidine (XX) can be transformed into 2,6-dichloro-5- methoxypyrimidine-4-carboxaldehyde (XXI) via treatment with ozone, e.g., in a dichloromethane:methanol solvent mixture (reaction <semantics>n<annotation encoding="application / x-tex">n< / annotation>< / semantics>). 2,6-Dichloro-5- methoxypyrimidine-4-carboxaldehyde (XXI) can be transformed into methyl 2,6-dichloro-5- methoxypyrimidine-4-carboxylate (XXII) via treatment with bromine, e.g., in a methanol:water solvent mixture (reaction o). Methyl 2,6-dichloro-5-methoxypyrimidine-4- carboxylate (XXII) can be transformed into methyl 6-amino-2-chloro-5-methoxypyrimidine- 4-carboxylate (XXIII) via treatment with ammonia (e.g., 2 equivalents) in a solvent, such as DMSO (reaction p). Finally, 6-amino-2-substituted-5-methoxypyrimidine-4-carboxylates of Formula (I-D), wherein Ar is as herein defined, 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 temperature, such as 110 °C, e.g., in a microwave reactor (reaction <semantics>a5<annotation encoding="application / x-tex">a_{5}< / annotation>< / semantics>). Scheme V [Image disponible dans le document PDF, Image available in the PDF document]
[00135] 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. COMPOSITIONS AND METHODS
[00136] 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 selective weed control in the presence of crops, and / or do not react or significantly react chemically with the compounds provided herein or other composition ingredients. Such mixtures can be designed for application directly to weeds or their locus or can be concentrates 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 concentrates, solutions, emulsions or suspensions. They can also be provided as a pre-mix or tank-mixed.
[00137] 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 (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C11 alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C12-C16) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane- methyl cap; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99.
[00138] 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 mineral 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, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethylhexyl stearate, 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. Specific organic solvents include toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers, and the like. In some embodiments, water is the carrier for the dilution of concentrates.
[00139] 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.
[00140] In some embodiments, one or more surface-active agents are utilized in the compositions of the present 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 present formulations are described, inter alia, in McCutcheon's Detergents 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-C18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C16 ethoxylate; soaps, such as sodium stearate; 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; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; 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, corn 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.
[00141] 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.
[00142] Other adjuvants commonly used in agricultural compositions include compatibilizing agents, antifoam agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration 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 regulants, 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.
[00143] The concentration of the active ingredients 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 concentrates, the active ingredient is generally present 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 ingredient and preferably contain about 0.001 to about 0.05 weight percent.
[00144] The present compositions can be applied to weeds or their locus by the use of conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation or flood water, and by other conventional means known to those skilled in the art.
[00145] 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 burn-down application.
[00146] 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, corn / maize, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, or row-crops, as well as non-crop settings, e.g., industrial vegetation 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.
[00147] In some embodiments, the compounds and compositions provided herein are utilized to control undesirable vegetation in rice. In certain embodiments, the undesirable vegetation is Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv. (barnyardgrass, 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 morningglory, IPOHE), Lindernia dubia (L.) Pennell (low false pimpernel, 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).
[00148] In some embodiments, the compounds and compositions provided herein are utilized to control undesirable vegetation in cereals. In certain embodiments, the undesirable vegetation 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), Lolium 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, CIRAR), 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).
[00149] In some embodiments, the compounds and compostions provided herein are utilized to control undesirable vegetation in range and pasture. In certain embodiments, the undesirable vegetation 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. / Torn. (prickly lettuce, LACSE), Plantago lanceolata L. (buckhorn 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).
[00150] In some embodiments, the compounds and compositions provided herein are utilized to control undesirable vegetation found in row crops. In certain embodiments, the undesirable vegetation 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. (barnyardgrass, ECHCG), Echinochloa colonum (L.) Link (junglerice, ECHCO), Lolium multiflorum Lam. (Italian ryegrass, LOLMU), Panicum dichotomiflorum Michx. (fall 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), Cyperus rotundus L. (purple nutsedge, CYPRO), Abutilon theophrasti Medik. (velvetleaf, ABUTH), Amaranthus species (pigweeds and amaranths, AMASS), 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 morningglory, IAQTA), Ipomoea hederacea (L.) Jacq. (ivyleaf morningglory, IPOHE), Ipomoea lacunosa L. (white morningglory, IPOLA), Lactuca serriola L. / Torn. (prickly lettuce, LACSE), Portulaca oleracea L. (common purslane, POROL), Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild mustard, SINAR), Solanum ptychanthum Dunal (eastern black nightshade, SOLPT), or Xanthium strumarium L. (common cocklebur, XANST).
[00151] 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.
[00152] 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 vegetation. When used in conjunction with other herbicides, the compounds described herein 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 present disclosure include: 4-CPA, 4-CPB, 4-CPP, 2,4-D, 2,4-D choline salt, 2,4-D esters and amines, 2,4-DB, 3,4-DA, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP, 2,3,6-TBA, 2,4,5T, 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, bensulfuron-methyl, 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, chlornitrofen, 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, DMPA, 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, flumiclorac- pentyl, 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, halosulfuron- methyl, 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, MAMA, 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, ortho-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, vernolate and xylachlor.
[00153] The compounds and compositions of the present 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 N-phenylsulfonylbenzoic acid amides, to enhance their selectivity.
[00154] The compounds, compositions, and methods described herein be used to control undesirable vegetation on glyphosate-tolerant-, glufosinate-tolerant-, dicamba-tolerant-, phenoxy auxin-tolerant-, pyridyloxy auxin-tolerant-, aryloxyphenoxypropionate-tolerant-, acetyl CoA carboxylase (ACCase) inhibitor-tolerant-, imidazolinone-tolerant-, acetolactate synthase (ALS) inhibitor-tolerant-, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor -tolerant-, protoporphyrinogen oxidase (PPO) inhibitor -tolerant-, triazine-tolerant-, and bromoxynil-tolerant- crops (such as, but not limited to, soybean, cotton, canola / oilseed rape, 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 undesirable vegetation in crops possessing multiple or stacked traits conferring tolerance to multiple chemistries and / or inhibitors of multiple modes-of-action.
[00155] The compounds and compositions provided herein may also be employed to control herbicide resistant or tolerant weeds. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes resistant or tolerant to acetolactate synthase (ALS) 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, 4- hydroxyphenyl-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 resistant or tolerant weeds include, but are not limited to, biotypes with resistance or tolerance to multiple herbicides, multiple chemical classes, and multiple herbicide modes-of-action.
[00156] The described embodiments and following examples are for illustrative purposes only. The scope of the claims should not be limited by the embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole. EXAMPLES SYNTHESIS OF PRECURSORS
[00157] General Considerations: Fluorine spectra were acquired at 376 MHz on a Bruker DRX400 spectrometer. The spectra were referenced to trichlorofluoromethane (CFC13) as an external standard and were typically conducted with proton decoupling. Example 1: Preparation of methyl 4-amino-3,6-dichloropicolinate (Head A) [Image disponible dans le document PDF, Image available in the PDF document]
[00158] Prepared as described in Fields et al., WO 2001051468 Al. Example 2: Preparation of methyl 4-amino-3,6-dichloro-5-fluoropicolinate (Head B) [Image disponible dans le document PDF, Image available in the PDF document]
[00159] Prepared as described in Fields et al., Tetrahedron Letters 2010, 51, 79-81. Example 3: Preparation of 2,6-dichloro-5-methoxy-4-vinyl pyrimidine [Image disponible dans le document PDF, Image available in the PDF document]
[00160] 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 magnesium bromide in tetrahydrofuran solvent (124 g, 0.94 mol) over one hour (h) at room temperature. The mixture was then stirred for 4 h at room temperature. Excess Grignard reagent was quenched by addition of acetone (200 milliliters (mL)) while the temperature of the mixture was maintained at a temperature below 20 °C. Thereafter, 2,3-dichloro-5,6- dicyano-p-benzoquinone (DDQ; 151 g, 0.67 mol) was added at once and stirred overnight. 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 <semantics>60−61<annotation encoding="application / x-tex">60 - 61< / annotation>< / semantics> °C; 1H NMR (CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 3.99 (s, 3H), 5.85 (d, 1H), 6.75 (d, 1H), 6.95 (dd, 1H). Example 4: Preparation of 2,6-dichloro-5-methoxy-pyrimidine-4-carbaldehyde [Image disponible dans le document PDF, Image available in the PDF document]
[00161] 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 temperature and concentrated under reduced pressure at 40 °C to provide the title compound (50.5 g, 100%). Example 5: Preparation of methyl 2,6-dichloro-5-methoxy-pyrimidine-4-carboxylate [Image disponible dans le document PDF, Image available in the PDF document]
[00162] 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 temperature for 1 h. Later, the mixture was stirred at room temperature 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 (NaCl; 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 solidified on long standing to afford the title compound (50.8 g, 87%): ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 238 ([M+H]+). Example 6: Preparation of methyl 6-amino-2-chloro-5-methoxy-pyrimidine-4- carboxylate (Head C) [Image disponible dans le document PDF, Image available in the PDF document]
[00163] 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 equivalents (equiv)) in DMSO. This mixture was stirred at the same 0-5 °C temperature 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 g, 50%): mp 158 °C; 1H NMR (DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 3.71 (s, 3H), 3.86 (s, 3H), 7.65 (br s, 1H), 8.01 (br s, 1H). Example 7: Preparation of methyl 4-amino-3,6-dichloro-5-iodopicolinate [Image disponible dans le document PDF, Image available in the PDF document]
[00164] 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 were extracted once with diethyl ether, and the combined organic layers were dried over anhydrous Na2SO4. 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; 1H NMR (400 MHz, CDCl3) δ 5.56 (s, 2H), 3.97 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 163.80, 153.00, 152.75, 145.63, 112.12, 83.91, 53.21; EIMS m / z 346. Example 8: Preparation of methyl 4-amino-3,6-dichloro-5-methylpicolinate (Head D) [Image disponible dans le document PDF, Image available in the PDF document]
[00165] 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 InitiatorTM microwave at 120 °C for 30 min, with external infrared (IR)-sensor temperature 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; 1H NMR (400 MHz, CDCl3) δ 4.92 (s, 2H), 3.96 (s, 3H), 2.29 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.34, 150.24, 148.69, 143.94, 117.01, 114.60, 53.02, 14.40; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 236 ([M+H]+), 234 ([M- H]-). Example 9: Preparation of methyl 6-amino-2,5-dichloropyrimidine-4-carboxylate (Head E) [Image disponible dans le document PDF, Image available in the PDF document]
[00166] Prepared as described in Epp et al., WO 2007082076 A1. Example 10: Preparation of methyl 4-amino-6-chloro-5-fluoro-3-methoxypicolinate (Head F) [Image disponible dans le document PDF, Image available in the PDF document]
[00167] Prepared as described in Epp et al., WO 2013003740 A1. Example 11: Preparation of methyl 4-amino-6-chloro-5-fluoro-3-vinylpicolinate (Head G) [Image disponible dans le document PDF, Image available in the PDF document]
[00168] Methyl 4-amino-6-chloro-5-fluoro-3-iodopicolinate (7.05 g, 21.33 mmol, prepared as described in Epp et al., WO 2013003740 A1) 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 overnight (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 (SiO2); hexanes / ethyl acetate gradient) to afford the title compound as a light brown solid (3.23 g, 65.7%): mp 99–100 °C; 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 6.87 (dd, <semantics>J=18.1<annotation encoding="application / x-tex">J = 18.1< / annotation>< / semantics>, 11.6 Hz, 1H), 5.72 (dd, <semantics>J=11.5<annotation encoding="application / x-tex">J = 11.5< / annotation>< / semantics>, 1.3 Hz, 1H), 5.52 (dd, <semantics>J=11.5<annotation encoding="application / x-tex">J = 11.5< / annotation>< / semantics>) 18.2, 1.3 Hz, 1H), 4.79 (s, 2H), 3.91 (s, 3H); 19F NMR (376 MHz, CDCl3) δ -138.79 (s); EIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 230. Example 12: Preparation of methyl 4-amino-3,5,6-trichloropicolinate (Head H) [Image disponible dans le document PDF, Image available in the PDF document]
[00169] Prepared as described in Finkelstein et al., WO 2006062979 A1. Example 13: Preparation of methyl 4-amino-6-bromo-3-chloro-5-fluoropicolinate (Head I) [Image disponible dans le document PDF, Image available in the PDF document]
[00170] Prepared as described in Arndt et al., US 20120190857 A1. Example 14: Preparation of methyl 4-amino-3-chloro-5-fluoro-6- (trimethylstannyl)picolinate (Head J) [Image disponible dans le document PDF, Image available in the PDF document]
[00171] 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%): <semantics>1<annotation encoding="application / x-tex">{}^{1}< / annotation>< / semantics>H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 4.63 (d, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 29.1 Hz, 2H), 3.97 (s, 3H), 0.39 (s, 9H); 19F NMR (376 MHz, CDCl3) δ -130.28; EIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 366. Example 15: Preparation of methyl 4-acetamido-3-chloro-6-(trimethylstannyl)- picolinate (Head K) [Image disponible dans le document PDF, Image available in the PDF document]
[00172] Prepared as described in Balko et al., WO 2003011853 A1. Example 16: Preparation of methyl 4-acetamido-3,6-dichloropicolinate (Head L) [Image disponible dans le document PDF, Image available in the PDF document]
[00173] Prepared as described in Fields et al., WO 2001051468 A1. Example 17: Preparation of methyl 4-amino-3-chloro-6-iodopicolinate (Head M) [Image disponible dans le document PDF, Image available in the PDF document]
[00174] Prepared as described in Balko et al., WO 2007082098 A2. Example 18: Preparation of methyl 4-acetamido-3-chloro-6-iodopicolinate (Head N) [Image disponible dans le document PDF, Image available in the PDF document]
[00175] Prepared as described in Balko et al., WO 2007082098 A2. Example 19: Preparation of methyl 4-amino-6-bromo-3,5-difluoropicolinate (Head O) [Image disponible dans le document PDF, Image available in the PDF document]
[00176] Prepared as described in Fields et al., WO 2001051468 A1. Example 20: Preparation of methyl 6-amino-2-chloro-5-vinylpyrimidine-4-carboxylate (Head P) [Image disponible dans le document PDF, Image available in the PDF document]
[00177] Prepared as described in Epp et al., US 20090088322. Example 22: Preparation of 4-bromo-2-fluorophenyl)trimethylsilane [Image disponible dans le document PDF, Image available in the PDF document]
[00178] A 2.5 M solution of n-butyllithium in hexanes (n-BuLi; 900 microliters (<semantics>μ<annotation encoding="application / x-tex">\mu< / annotation>< / semantics>L), 2.2 mmol, 1.1 equiv) was added to a stirred solution of 1,4-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 μL, 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 (magnesium sulfate (MgSO4)), gravity filtered, and concentrated by rotary evaporation 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; 1H NMR (400 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.38 – 7.49 (m, 3H), 0.30 (s, 9H). Example 23: Preparation of (2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl)trimethylsilane [Image disponible dans le document PDF, Image available in the PDF document]
[00179] 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. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-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 evaporation to afford the title compound as a pale yellow semi-solid (6.0 g, 99%): 1H NMR (400 MHz, CDCl3) δ 7.55 (dt, <semantics>J=7.5<annotation encoding="application / x-tex">J = 7.5< / annotation>< / semantics>, 1 Hz, 1H), 7.38 – 7.42 (m, 2H), 1.34 (s, 12H), 0.29 (d, <semantics>J=1<annotation encoding="application / x-tex">J = 1< / annotation>< / semantics> Hz, 9H).
[00180] The following compounds were made in accordance with the procedures disclosed in Example 23: 2-(4-(Difluoromethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [Image disponible dans le document PDF, Image available in the PDF document]
[00181] 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.89 (br d, <semantics>J=8<annotation encoding="application / x-tex">J = 8< / annotation>< / semantics> Hz, 2H), 7.50 (br d, <semantics>J=8<annotation encoding="application / x-tex">J = 8< / annotation>< / semantics> Hz, 2H), 6.65 (t, <semantics>J=56<annotation encoding="application / x-tex">J = 56< / annotation>< / semantics> Hz, 1H), 1.35 (s, 12H). 2-(4-(Difluoromethyl)-3-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [Image disponible dans le document PDF, Image available in the PDF document]
[00182] 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.51 – 7.68 (m, 3H), 6.90 (t, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 55 Hz, 1H), 1.35 (s, 12H). Example 24: Preparation of (2,3-difluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl)trimethylsilane [Image disponible dans le document PDF, Image available in the PDF document]
[00183] 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. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-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 1M HCl, and extracted with dichloromethane (3 x 100 mL). The combined organic layers were dried (MgSO4), gravity filtered, and concentrated by rotary evaporation to afford the title compound as a white powder (6.4 g, 96%): 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.42 (ddd, <semantics>J=7.5<annotation encoding="application / x-tex">J = 7.5< / annotation>< / semantics>, 4.5, 0.5 Hz, 1H), 7.09 (ddd, <semantics>J=7.5<annotation encoding="application / x-tex">J = 7.5< / annotation>< / semantics>, 4, 1 Hz, 1H), 1.34 (s, 12H), 0.29 (d, <semantics>J=1<annotation encoding="application / x-tex">J = 1< / annotation>< / semantics> Hz, 9H). Example 25: Preparation of (3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl)trimethylsilane [Image disponible dans le document PDF, Image available in the PDF document]
[00184] A 2.5 M solution of n-BuLi (3.5 mL, 8.5 mmol, 1.1 equiv) was added to a stirred solution of 1,4-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. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-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 n-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 allowing 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 (MgSO4), gravity filtered, and concentrated by rotary evaporation 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; 1H NMR (400 MHz, CDCl3) δ 7.72 (dd, <semantics>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).<annotation encoding="application / x-tex">J = 7.5, 6 \text{ Hz}, 1\text{H}, 7.26 \text{ (m, 1H)}, 7.16 \text{ (d, } J = 7.5 \text{ Hz}, 1\text{H)}, 1.34 \text{ (s, 12H)}, 0.23 \text{ (s, 9H)}.< / annotation>< / semantics> Example 26: Preparation of 2,3,5-trifluoro-4-iodoaniline [Image disponible dans le document PDF, Image available in the PDF document]
[00185] 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 (Na2S2O3) solution and extracted with methyl tert-butyl ether (MTBE; 3 x 50 mL). The combined organic extracts were washed with saturated brine solution, dried over anhydrous Na2SO4, 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 2,3,5-trifluoro-4-iodoaniline (1.3 g, 35%) as pink solid: 1H NMR (400 MHz, CDCl3) δ 6.43 <semantics>−6.39<annotation encoding="application / x-tex">-6.39< / annotation>< / semantics> (m, 1H), 3.99 (br s, 2H); ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 274 ([M+H]+). Example 27: Preparation of 4-bromo-1-(difluoromethoxy)-2-fluorobenzene [Image disponible dans le document PDF, Image available in the PDF document]
[00186] To a 100 mL flask charged with N, N-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 temperature, the reaction mixture was diluted with diethyl ether (Et2O; 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%): 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.35 (dd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 9.7, 2.3 Hz, 1H), 7.27 (ddd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 8.7, 2.3, 1.5 Hz, 1H), <semantics>7.19−7.04<annotation encoding="application / x-tex">7.19 - 7.04< / annotation>< / semantics> (m, 1H), <semantics>6.53<annotation encoding="application / x-tex">6.53< / annotation>< / semantics> (t, <semantics>J=73.0<annotation encoding="application / x-tex">J = 73.0< / annotation>< / semantics> Hz, 1H); ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 242([M+H]+).
[00187] The following compounds were made in accordance with the procedures disclosed in Example 27. 1-Bromo-4-(difluoromethoxy)-2-fluorobenzene [Image disponible dans le document PDF, Image available in the PDF document]
[00188] 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.53 (dd, <semantics>J=8.8,7.7<annotation encoding="application / x-tex">J = 8.8, 7.7< / annotation>< / semantics> Hz, 1H), 6.95 (dd, <semantics>J=9.1<annotation encoding="application / x-tex">J = 9.1< / annotation>< / semantics>, 2.7 Hz, 1H), <semantics>6.90−6.79<annotation encoding="application / x-tex">6.90 - 6.79< / annotation>< / semantics> (m, 1H), <semantics>6.50<annotation encoding="application / x-tex">6.50< / annotation>< / semantics> (t, <semantics>J=72.8<annotation encoding="application / x-tex">J = 72.8< / annotation>< / semantics> Hz, 1H); IR (thin film) <semantics>781.76<annotation encoding="application / x-tex">781.76< / annotation>< / semantics>, <semantics>811.23<annotation encoding="application / x-tex">811.23< / annotation>< / semantics>, 856.78, 945.20, 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 <semantics>242([M+H]+).<annotation encoding="application / x-tex">242([M+H]^{+}).< / annotation>< / semantics> 1-Bromo-4-(difluoromethoxy)-2,3-difluorobenzene [Image disponible dans le document PDF, Image available in the PDF document]
[00189] 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.31 (ddd, <semantics>J=9.2,6.9,2.5<annotation encoding="application / x-tex">J = 9.2, 6.9, 2.5< / annotation>< / semantics> Hz, 1H), 7.02 – 6.93 (m, 1H), <semantics>6.56<annotation encoding="application / x-tex">6.56< / annotation>< / semantics> (t, <semantics>J=72.4<annotation encoding="application / x-tex">J = 72.4< / annotation>< / semantics> Hz, 1H); IR (thin film) <semantics>776.30<annotation encoding="application / x-tex">776.30< / annotation>< / semantics>, <semantics>811.66<annotation encoding="application / x-tex">811.66< / annotation>< / semantics>, <semantics>884.39<annotation encoding="application / x-tex">884.39< / annotation>< / semantics>, <semantics>986.70<annotation encoding="application / x-tex">986.70< / annotation>< / semantics>, <semantics>1100.95<annotation encoding="application / x-tex">1100.95< / annotation>< / semantics>, 1144.65, 1211.05, 1241.96, 1266.36, 1297.59, 1383.98, 1494.35, 1474.47, 1600.40, 1679.63, <semantics>3038.31,3103.90 cm−1<annotation encoding="application / x-tex">3038.31, 3103.90 \text{ cm}^{-1}< / annotation>< / semantics>; ESIMS <semantics>m / z260([M+H]+)<annotation encoding="application / x-tex">m / z 260 ([M+H]^+)< / annotation>< / semantics>. Example 28: Preparation of 2-(4-(difluoromethoxy)-3-fluorophenyl)-4,4,5,5- tetramethyl-1,3,2-dioxaborolane [Image disponible dans le document PDF, Image available in the PDF document]
[00190] To DMSO (10 mL) were added 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2- 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-1-(difluoromethoxy)-2-fluorobenzene (1 g, 4.15 mmol). The reaction was heated to an external temperature 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%): <semantics>1H<annotation encoding="application / x-tex">{}^{1}H< / annotation>< / semantics> NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.61 – 7.53 (m, 2H), <semantics>7.25−7.16<annotation encoding="application / x-tex">7.25 - 7.16< / annotation>< / semantics> (m, 1H), <semantics>6.58<annotation encoding="application / x-tex">6.58< / annotation>< / semantics> (t, <semantics>J=73.5<annotation encoding="application / x-tex">J = 73.5< / annotation>< / semantics> Hz, 1H), <semantics>1.34<annotation encoding="application / x-tex">1.34< / annotation>< / semantics> (s, 12H); ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 289 <semantics>([M+H]+).<annotation encoding="application / x-tex">([M+H]^{+}).< / annotation>< / semantics>
[00191] The following compounds were made in accordance with the procedures disclosed in Example 28: 2-(4-(Difluoromethoxy)-2-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [Image disponible dans le document PDF, Image available in the PDF document]
[00192] 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.74 (dd, <semantics>J=8.3<annotation encoding="application / x-tex">J = 8.3< / annotation>< / semantics>, 6.8 Hz, 1H), 6.89 (dd, <semantics>J=8.3<annotation encoding="application / x-tex">J = 8.3< / annotation>< / semantics>, 2.2 Hz, 1H), 6.81 (dd, <semantics>J=9.9<annotation encoding="application / x-tex">J = 9.9< / annotation>< / semantics>, 2.2 Hz, 1H), 6.54 (t, <semantics>J=73.2<annotation encoding="application / x-tex">J = 73.2< / annotation>< / semantics> 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 <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 289 ([M+H]+). 2-(4-(Difluoromethoxy)-2,3-difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [Image disponible dans le document PDF, Image available in the PDF document]
[00193] 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.46 (ddd, <semantics>J=8.3,5.8,2.3<annotation encoding="application / x-tex">J = 8.3, 5.8, 2.3< / annotation>< / semantics> Hz, 1H), 7.05 – 6.95 (m, 1H), <semantics>6.59<annotation encoding="application / x-tex">6.59< / annotation>< / semantics> (t, <semantics>J=72.8<annotation encoding="application / x-tex">J = 72.8< / annotation>< / semantics> Hz, 1H), <semantics>1.35<annotation encoding="application / x-tex">1.35< / annotation>< / semantics> (s, 12H); IR (thin film) <semantics>673.35<annotation encoding="application / x-tex">673.35< / annotation>< / semantics>, <semantics>851.08<annotation encoding="application / x-tex">851.08< / annotation>< / semantics>, <semantics>916.78<annotation encoding="application / x-tex">916.78< / annotation>< / semantics>, 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 <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 307 ([M+H]+). Example 29: Preparation of 1,4-difluoro-2-iodo-5-(trifluoromethyl)benzene [Image disponible dans le document PDF, Image available in the PDF document]
[00194] N-(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 evaporation, 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%): 1H NMR (400 MHz, CDCl3) δ 7.64 <semantics>(ddd,J=8.8,4.8,0.4Hz,1H),7.28(dd,J=11.1,4.7Hz,1H);<annotation encoding="application / x-tex">(ddd, J = 8.8, 4.8, 0.4 Hz, 1H), 7.28 (dd, J = 11.1, 4.7 Hz, 1H);< / annotation>< / semantics> 19F NMR (376 MHz, CDCl3) δ -61.92, -97.64, -97.68, -118.59, -118.63, -118.64, -118.67; EIMS m / z 308. Example 30: Preparation of 2-(2,5-difluoro-4-(trifluoromethyl)phenyl)-4,4,5,5- tetramethyl-1,3,2-dioxaborolane [Image disponible dans le document PDF, Image available in the PDF document]
[00195] 1,4-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 magnesium chloride-lithium chloride complex (1.3 M; 1.4 mL, 1.8 mmol) and stirred for 40 min at 5 °C. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (360 <semantics>μ<annotation encoding="application / x-tex">\mu< / annotation>< / semantics>L, 330 mg, 1.8 mmol) was added and stirring was continued for 1 h. After treating with saturated ammonium chloride (NH4Cl), the mixture was shaken with ethyl acetate. The organic phase was washed with saturated NaCl, dried (Na2SO4), and evaporated to give the title compound as a light brown oil (500 mg, 100%). The material was used without further purification: 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.54 (dd, <semantics>J=9.9<annotation encoding="application / x-tex">J = 9.9< / annotation>< / semantics>, 4.3 Hz, 1H), 7.27 (dd, <semantics>J=8.0<annotation encoding="application / x-tex">J = 8.0< / annotation>< / semantics>, 5.2 Hz, 2H), 1.37 (s, 12H); 19F NMR (376 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> -62.10, -62.13, -106.85, -106.90, -121.81, - 121.87, -121.90. Example 31: Preparation of 4-bromo-2,5-difluorobenzaldehyde [Image disponible dans le document PDF, Image available in the PDF document]
[00196] To a solution of 2,5-dibromo-1,4-difluorobenzene (10.0 g, 36.77 mmol) in diethyl ether (150 mL) at -78 °C was added n-butyl lithium (2.5 M in Hexanes, 14.86 mL, 37.15 mmol) 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 temperature over 2 h. The reaction was quenched with aqueous saturated NH4Cl 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%): 1H NMR (400 MHz, CDCl3) δ 7.50 (dd, <semantics>J=5.08,8.92 Hz,1H<annotation encoding="application / x-tex">J = 5.08, 8.92 \text{ Hz}, 1\text{H}< / annotation>< / semantics>), 7.62 (dd, <semantics>J=5.80,7.68 Hz,1H<annotation encoding="application / x-tex">J = 5.80, 7.68 \text{ Hz}, 1\text{H}< / annotation>< / semantics>), 10.30 (d, <semantics>J=2.76 Hz,1H<annotation encoding="application / x-tex">J = 2.76 \text{ Hz}, 1\text{H}< / annotation>< / semantics>). Example 32: Preparation of <semantics>(E)<annotation encoding="application / x-tex">(E)< / annotation>< / semantics>-4-bromo-2,5-difluorobenzaldehyde oxime [Image disponible dans le document PDF, Image available in the PDF document]
[00197] 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 ethanol (35 mL) was stirred at room temperature for 30 min. The reaction mixture was diluted with saturated NH4Cl 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 <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> <semantics>238([M+2H]+).<annotation encoding="application / x-tex">238 ([M+2H]^{+}).< / annotation>< / semantics> Example 33: Preparation of 4-bromo-2,5-difluorobenzonitrile [Image disponible dans le document PDF, Image available in the PDF document]
[00198] A solution of cyanuric chloride (3.12 g, 16.94 mmol) and dry DMF (8.5 mL) was stirred for 30 min or until the formation of white solid. Disappearance of cyanuric chloride was 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 (Na2SO4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography (SiO2; eluting with 2–20% ethyl acetate in hexanes) to provide the title compound as a white solid (2.5 g, 68%): 1H NMR <semantics>(400 MHz,CDCl3)δ7.40 (dd,J=5.36,7.10 Hz,1H),7.52 (dd,J=5.40,7.66 Hz,1H);<annotation encoding="application / x-tex">(400 \text{ MHz}, \text{CDCl}_3) \delta 7.40 \text{ (dd}, J = 5.36, 7.10 \text{ Hz}, 1\text{H}), 7.52 \text{ (dd}, J = 5.40, 7.66 \text{ Hz}, 1\text{H});< / annotation>< / semantics> EIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 218. Example 34: Preparation of 1-bromo-4-(difluoromethyl)-2,5-difluorobenzene [Image disponible dans le document PDF, Image available in the PDF document]
[00199] 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 complete, the cooling bath was removed and stirring was continued for 2 h at room temperature (rt). The reaction mixture was diluted with dichloromethane, washed with water, washed with saturated brine solution, dried (Na2SO4), and evaporated under reduced pressure. The crude product was purified by flash chromatography (SiO2; eluting with 0–10% ethyl acetate in hexanes) to provide the title compound as a pale brown liquid (8.39 g, 69%): 1H NMR(400 MHz, CDCl3 ) δ 6.58 (t, <semantics>J=72.32 Hz<annotation encoding="application / x-tex">J = 72.32 \text{ Hz}< / annotation>< / semantics>, 1H), 7.12 (t, <semantics>J=7.92 Hz<annotation encoding="application / x-tex">J = 7.92 \text{ Hz}< / annotation>< / semantics>, 1H), 7.44 (dd, <semantics>J=6.32<annotation encoding="application / x-tex">J = 6.32< / annotation>< / semantics>, 9.18 Hz, 1H); EIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 244. Example 35: Preparation of 1-bromo-4-(difluoromethoxy)-2,5-difluorobenzene [Image disponible dans le document PDF, Image available in the PDF document]
[00200] 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 temperature overnight. 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 (Na2SO4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography (SiO2; eluting with 0–10% ethyl acetate in hexanes) to provide the title compound as a clear liquid (4.2 g, 67.8%): <semantics>1<annotation encoding="application / x-tex">{}^{1}< / annotation>< / semantics>H NMR(300 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 6.56 (t, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 72.36 Hz, 1H), 7.11 (t, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 7.32 Hz, 1H), <semantics>7.40−7.45<annotation encoding="application / x-tex">7.40 - 7.45< / annotation>< / semantics> (m, 1H); EIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 259. Example 36: General procedure for synthesis of boronic acids [Image disponible dans le document PDF, Image available in the PDF document]
[00201] Argon was bubbled through a solution of the bromophenyl substrate (1.0 equiv), potassium acetate (3.0 equiv), and bis-(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 t-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 temperature 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 (Na2SO4), filtered, and evaporated to dryness under reduced pressure. The boronic acids thus obtained were used in the next step without purification.
[00202] The following compounds were made in accordance with the procedures disclosed in Example 36: (4-(Difluoromethoxy)-2,5-difluorophenyl)boronic acid [Image disponible dans le document PDF, Image available in the PDF document]
[00203] 1H NMR(300 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 6.59 (t, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> =72.78 Hz, 1H), 6.97 (dd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 2.70, 9.14 Hz, 1H), 7.52 (dd, <semantics>J=5.19<annotation encoding="application / x-tex">J = 5.19< / annotation>< / semantics>, 10.29 Hz, 1H). (4-(Difluoromethyl)-2,5-difluorophenyl)boronic acid [Image disponible dans le document PDF, Image available in the PDF document]
[00204] 1H NMR(400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 6.87 (dt, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 8.48, 54.64 Hz, 1H), 7.25 – 7.32 (m, 1H), 7.49 (dd, <semantics>J=4.08<annotation encoding="application / x-tex">J = 4.08< / annotation>< / semantics>, 9.48 Hz, 1H), 7.59 – 7.60 (m, 1H). Example 37: General procedure for synthesis of boronic acids (Method A) [Image disponible dans le document PDF, Image available in the PDF document]
[00205] 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 complete, 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 temperature, quenched with 1.5 N HCl, 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 boronic acids thus obtained were used in the next step without purification.
[00206] The following compound was made in accordance with the procedures disclosed in Example 37: (2,5-Difluoro-4-methylphenyl)boronic acid [Image disponible dans le document PDF, Image available in the PDF document]
[00207] 1H NMR(300 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 2.30 (s, 3H), 5.03 (br s, 2H), 6.89 (dd, <semantics>J=5.67<annotation encoding="application / x-tex">J = 5.67< / annotation>< / semantics>, 10.25 Hz, 1H), 7.42 (dd, <semantics>J=5.40<annotation encoding="application / x-tex">J = 5.40< / annotation>< / semantics>, 9.19 Hz, 1H). Example 38: General procedure for synthesis of boronic acids (Method B) [Image disponible dans le document PDF, Image available in the PDF document]
[00208] To a solution of the appropriate bromophenyl substrate (1.0 equiv) in dry THF (10 vol) at -40 °C was added isopropyl magnesium chloride lithium chloride complex solution (1.3 M solution in THF; 1.05 equiv) dropwise. After addition was complete, 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 temperature, quenched with aqueous saturated NH4Cl 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.
[00209] The following compound was made in accordance with the procedures disclosed in Example 38: (4-Cyano-2,5-difluorophenyl)boronic acid [Image disponible dans le document PDF, Image available in the PDF document]
[00210] 1H NMR(300 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 5.15 (br s, 2H), 7.29 – 7.36 (m, 1H), 7.69 (dd, <semantics>J=<annotation encoding="application / x-tex">J =< / annotation>< / semantics> 4.80, 8.28 Hz, 1H). Example 39: Preparation of methyl 4-amino-3-chloro-6-(3-fluoro-4- (trimethylsilyl)phenyl)picolinate [Image disponible dans le document PDF, Image available in the PDF document]
[00211] To a 20-mL microwave vessel, equipped with a stir bar, Head A (500 mg, 2.262) mmol), (2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)trimethylsilane (997 mg, 3.39 mmol), bis(triphenylphosphine)palladium(II) dichloride (203 mg, 3.39 mmol), and cesium fluoride (741 mg, 4.88 mmol) were charged. The vessel was placed under nitrogen (N2) atmosphere and acetonitrile (4.0 mL) and H2O (1.0 mL) were added. The vessel was placed on a Biotage InitiatorTM microwave reactor for 30 min at 120 °C, with external IR-sensor temperature 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 MgSO4, 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%): 1H NMR (400 MHz, DMSO-d6) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.68 (dd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 7.5, 1.4 Hz, 1H), 7.61 – 7.47 (m, 2H), 7.30 (s, 1H), 6.78 (s, 2H), 3.88 (s, 3H), 0.30 (d, <semantics>J=0.8<annotation encoding="application / x-tex">J = 0.8< / annotation>< / semantics> Hz, 9H); 19F NMR (376 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> -101.12; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 353 <semantics>([M+H]+).<annotation encoding="application / x-tex">([M+H]^{+}).< / annotation>< / semantics>
[00212] 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 [Image disponible dans le document PDF, Image available in the PDF document]
[00213] 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%): 1H NMR (400 MHz, DMSO- <semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.52 (dd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 7.6, 5.9 Hz, 1H), 7.41 (dd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 7.5, 1.3 Hz, 1H), 7.30 (dd, <semantics>J<annotation encoding="application / x-tex">J< / annotation>< / semantics> = 9.6, 1.4 Hz, 1H), 7.11 (s, 2H), 3.87 (s, 3H), 0.33 (d, <semantics>J=0.9<annotation encoding="application / x-tex">J = 0.9< / annotation>< / semantics> Hz, 9H); 19F NMR (376 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> - 101.38; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 387 ([M+H]+). Methyl 6-amino-2-(3-fluoro-4-(trimethylsilyl)phenyl)-5-methoxypyrimidine-4- carboxylate [Image disponible dans le document PDF, Image available in the PDF document]
[00214] 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%): 1H NMR (400 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ8.08−7.99<annotation encoding="application / x-tex">\delta 8.08 - 7.99< / annotation>< / semantics> (m, 1H), 7.82 (dd, <semantics>J=10.3<annotation encoding="application / x-tex">J = 10.3< / annotation>< / semantics>, 1.4 Hz, 1H), 7.60 - 7.27 (m, 3H), 3.91 (s, 3H), 3.74 (s, 3H), 0.32 (d, <semantics>J=0.9<annotation encoding="application / x-tex">J = 0.9< / annotation>< / semantics> Hz, 9H); 19F NMR (376 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> -101.73; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 350 ([M+H]+). Methyl 4-acetamido-3-chloro-6-(3-fluoro-4-(trimethylsilyl)phenyl)picolinate [Image disponible dans le document PDF, Image available in the PDF document]
[00215] 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%): 1H NMR (400 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 9.99 (s, 1H), 8.71 (s, 1H), 7.75 (dd, <semantics>J=7.6<annotation encoding="application / x-tex">J = 7.6< / annotation>< / semantics>, 1.5 Hz, 1H), 7.63 (dd, <semantics>J=10.1<annotation encoding="application / x-tex">J = 10.1< / annotation>< / semantics>, 1.5 Hz, 1H), 7.56 (dd, <semantics>J=7.7<annotation encoding="application / x-tex">J = 7.7< / annotation>< / semantics>, 5.9 Hz, 1H), 3.94 (s, 3H), 2.24 (s, 3H), 0.30 (d, <semantics>J=0.8<annotation encoding="application / x-tex">J = 0.8< / annotation>< / semantics> Hz, 9H); 19F NMR (376 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> -100.78; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 396 <semantics>([M+H]+).<annotation encoding="application / x-tex">([M+H]^{+}).< / annotation>< / semantics> Methyl 4-amino-3-chloro-6-(4-cyano-2-fluorophenyl)-5-fluoropicolinate (Compound 44) [Image disponible dans le document PDF, Image available in the PDF document]
[00216] 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-4- carboxylate (Compound 137) [Image disponible dans le document PDF, Image available in the PDF document]
[00217] 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) [Image disponible dans le document PDF, Image available in the PDF document]
[00218] 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 [Image disponible dans le document PDF, Image available in the PDF document]
[00219] 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-1,3,2-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%): 1H NMR (400 MHz, DMSO-<semantics>d6<annotation encoding="application / x-tex">d_6< / annotation>< / semantics>) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 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 <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 271 ([M+H]+). Methyl 6-amino-2-(2,3,4-trifluorophenyl)-5-vinylpyrimidine-4-carboxylate (Compound 197) [Image disponible dans le document PDF, Image available in the PDF document]
[00220] 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. Preparation of methyl 4-amino-3-chloro-6-(3-fluoro-4- (trifluoromethyl)phenyl)picolinate (Compound 29) [Image disponible dans le document PDF, Image available in the PDF document]
[00221] Methyl 4-amino-3,6-dichloropicolinate (630 mg, 2.85 mmol), 2-(3-fluoro-4- (trifluoromethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-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 InitiatorTM microwave reactor for 20 min at 115 °C, with external IR-sensor temperature 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 Na2SO4, 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%).
[00222] 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) [Image disponible dans le document PDF, Image available in the PDF document]
[00223] 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) [Image disponible dans le document PDF, Image available in the PDF document]
[00224] 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 [Image disponible dans le document PDF, Image available in the PDF document]
[00225] The title compound was prepared as in Example 40 with Head D and isolated as a yellow solid (1.11 g, 45%): mp 160–163 °C; 1H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.57 (d, <semantics>J=8.2<annotation encoding="application / x-tex">J = 8.2< / annotation>< / semantics> Hz, 2H), 7.42 (d, <semantics>J=8.2<annotation encoding="application / x-tex">J = 8.2< / annotation>< / semantics> Hz, 2H), 4.80 (s, 2H), 3.94 (s, 3H), 2.18 (s, 3H), 0.28 (s, 9H); <semantics>13<annotation encoding="application / x-tex">^{13}< / annotation>< / semantics>C NMR (101 MHz, CDCl3) 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-fluoro-4-(trimethylsilyl)phenyl)-5-methylpicolinate [Image disponible dans le document PDF, Image available in the PDF document]
[00226] 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); <semantics>1<annotation encoding="application / x-tex">{}^{1}< / annotation>< / semantics>H NMR (400 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> 7.43 (dd, <semantics>J=<annotation encoding="application / x-tex">J =< / annotation>< / semantics> 7.4, 5.8 Hz, 1H), 7.20 (dd, <semantics>J=7.4<annotation encoding="application / x-tex">J = 7.4< / annotation>< / semantics>, 0.9 Hz, 1H), 7.10 (dd, <semantics>J=9.2<annotation encoding="application / x-tex">J = 9.2< / annotation>< / semantics>, 1.3 Hz, 1H), 4.83 (s, 2H), 3.95 (s, 3H), 2.18 (s, 3H), 0.33 (d, <semantics>J=0.8<annotation encoding="application / x-tex">J = 0.8< / annotation>< / semantics> Hz, 9H); 19F NMR (376 MHz, CDCl3) <semantics>δ<annotation encoding="application / x-tex">\delta< / annotation>< / semantics> -100.73; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> 367 ([M+H]+). Methyl 4-amino-3-chloro-6-(4-cyano-3-fluorophenyl)-5-methylpicolinate (Compound 155) [Image disponible dans le document PDF, Image available in the PDF document]
[00227] 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 [Image disponible dans le document PDF, Image available in the PDF document]
[00228] 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; 1H NMR (400 MHz, CDCl3) δ 10.40 (s, 1H), <semantics>7.92<annotation encoding="application / x-tex">7.92< / annotation>< / semantics> (t, <semantics>J=7.5<annotation encoding="application / x-tex">J = 7.5< / annotation>< / semantics> Hz, 1H), <semantics>7.38−7.29<annotation encoding="application / x-tex">7.38 - 7.29< / annotation>< / semantics> (m, 2H), <semantics>4.97<annotation encoding="application / x-tex">4.97< / annotation>< / semantics> (s, 2H), <semantics>3.97<annotation encoding="application / x-tex">3.97< / annotation>< / semantics> (s, 3H), <semantics>2.18<annotation encoding="application / x-tex">2.18< / annotation>< / semantics> (s, 3H); 19F NMR (376 MHz, CDCl3) δ -121.53; ESIMS <semantics>m / z<annotation encoding="application / x-tex">m / z< / annotation>< / semantics> ...
Claims
<pat:ClaimStatement>CLAIMS:< / pat:ClaimStatement> <pat:Claims com:id="claims"> <pat:Claim com:id="CLM-00001"> <pat:ClaimNumber>1< / pat:ClaimNumber> <pat:ClaimText>1. A compound of Formula (I): [Image disponible dans le document PDF, Image available in the PDF document] (I) wherein X is CH, CF, CCl, and CCH3; R1 is OR1′, wherein R1′ is H, C1-C8 alkyl, or C7-C10 arylalkyl; <semantics>R2<annotation encoding="application / x-tex">R^2< / annotation>< / semantics> is Cl; <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> and <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> are each independently hydrogen or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C6<annotation encoding="application / x-tex">C_6< / annotation>< / semantics> alkyl; Ar is Ar2: [Image disponible dans le document PDF, Image available in the PDF document] Ar2 wherein X2 is H, Cl, Br, I, ethynyl, CH3, CFH2, CF2H, CF3, OCF2H, OCF3, or CN; with the proviso that: X2 is not Cl, when X is CH. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00002"> <pat:ClaimNumber>2< / pat:ClaimNumber> <pat:ClaimText>2. The compound of claim 1, wherein <semantics>R1′<annotation encoding="application / x-tex">R^{1'}< / annotation>< / semantics> is H or <semantics>C1<annotation encoding="application / x-tex">C_1< / annotation>< / semantics>-<semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00003"> <pat:ClaimNumber>3< / pat:ClaimNumber> <pat:ClaimText>3. The compound of claim 1, wherein R1 is H or methyl. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00004"> <pat:ClaimNumber>4< / pat:ClaimNumber> <pat:ClaimText>4. The compound of any one of claims 1 to 3, wherein X is CF or CCl. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00005"> <pat:ClaimNumber>5< / pat:ClaimNumber> <pat:ClaimText>5. The compound of any one of claims 1 to 4, wherein <semantics>R3<annotation encoding="application / x-tex">R^3< / annotation>< / semantics> and <semantics>R4<annotation encoding="application / x-tex">R^4< / annotation>< / semantics> are hydrogen. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00006"> <pat:ClaimNumber>6< / pat:ClaimNumber> <pat:ClaimText>6. The compound of any one of claims 1 to 5, wherein X2 is Br, I, CF2H, CF3, or CN. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00007"> <pat:ClaimNumber>7< / pat:ClaimNumber> <pat:ClaimText>7. The compound of any one of claims 1 to 5, wherein <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is Br, I, or CN. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00008"> <pat:ClaimNumber>8< / pat:ClaimNumber> <pat:ClaimText>8. The compound of any one of claims 1 to 5, wherein <semantics>X2<annotation encoding="application / x-tex">X_2< / annotation>< / semantics> is Br or I. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00009"> <pat:ClaimNumber>9< / pat:ClaimNumber> <pat:ClaimText>9. The compound of claim 1 wherein the compound is: NIH [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] 5 - [Image disponible dans le document PDF, Image available in the PDF document] < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00010"> <pat:ClaimNumber>10< / pat:ClaimNumber> <pat:ClaimText>10. A herbicidal composition comprising the compound of any one of claims 1 to 9 and an agriculturally acceptable adjuvant or carrier. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00011"> <pat:ClaimNumber>11< / pat:ClaimNumber> <pat:ClaimText>11. The composition of claim 10, further comprising at one additional herbicidal compound. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00012"> <pat:ClaimNumber>12< / pat:ClaimNumber> <pat:ClaimText>12. The composition of claim 10 or 11, further comprising a safener. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00013"> <pat:ClaimNumber>13< / pat:ClaimNumber> <pat:ClaimText>13. A method for controlling undesirable vegetation, which comprises applying the compound of any one of claims 1 to 9, or the composition of any one of claims 10 to 12. < / pat:ClaimText> < / pat:Claim> < / pat:Claims>