4-AMINO-6-(1,3-BENZODIOXOL)PICOLINATES, COMPOSITIONS AND METHODS COMPRISING THEM

Abstract

This document describes 4-amino-6-(1,3-benzodioxol)picolinic acids, compositions comprising 4-amino-6-(1,3-benzodioxol)picolinic acids, and the use of these compounds and compositions to control undesirable vegetation. Claim 1: A compound defined by formula (1), wherein R² is halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl, C₂₋₄ alkynyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkyl-thio, C₁₋₄ haloalkyl-thioamino, C₁₋₄ alkyl-amino, C₂₋₄ haloalkyl-amino, formyl, C₁₋₃ alkyl-carbonyl, C₁₋₃ haloalkyl-carbonyl, cyano, or a group of the formula -CR⁵=CR⁶-SiR⁷R⁸R⁹, wherein R⁵ is hydrogen, F or Cl; R⁶ is hydrogen, F, Cl, C₁₋₄ alkyl or C₁₋₄ haloalkyl; and R⁷, R⁸ and R⁹ are, independently, C₁₋₁₀ alkyl, C₃₋₆ cycloalkyl, phenyl, substituted phenyl, C₁₋₁₀ alkoxy or OH;and R³ and R⁴ are, independently, hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ alkynyl, C₃₋₆ haloalkenyl, C₃₋₆ alkynyl, formyl, C₁₋₃ alkyl carbonyl, C₁₋₃ haloalkyl carbonyl, C₁₋₆ alkoxy carbonyl, C₁₋₆ alkyl carbamyl, C₁₋₆ alkyl sulfonyl, C₁₋₆ trialkyl silyl, C₁₋₆ dialkyl phosphonyl or R³ and R⁴ taken together with N is a saturated 5- or 6-membered ring or R³ and R⁴ taken together, represent =CR³'(R⁴'), wherein R³' and R⁴' are, independently, hydrogen, C₁₋₆ alkyl, C₃₋₆ alkenyl, C₃₋₆ alkynyl, C₁₋₆ alkoxy or C₁₋₆ alkyl-amino or R³' and R⁴' taken together with =C represent a saturated 5- or 6-membered ring; or one of its salts, esters or N-oxides acceptable in agriculture.

Description

4-AMINO-6-(1,3-BENZODIOXOL)PICOLINATES AND THEIR USE AS HERBICIDES CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of provisional patent application USN° serial 62 / 670.538, filed on May 11, 2018, the entirety of which is incorporated herein by reference. BACKGROUND The emergence of unwanted vegetation, such as weeds, is a constant problem faced by farmers in crops, pastures, and other facilities. Weeds compete with crops and negatively impact crop yields. The use of chemical herbicides is an important tool in controlling unwanted vegetation. There is still a need for new chemical herbicides that offer a broader spectrum of weed control, selectivity, minimal crop damage, storage stability, ease of handling, greater weed activity, and / or a means of addressing the herbicide tolerance that develops with respect to commonly used herbicides. The compounds, IF-2019-795 32212-APN-ANP#INP1I Page 1 of 78 compositions and methods analyzed herein address these and other needs. SYNTHESIS The compounds defined by formula I are provided herein: where R2 is halogen, Ci-C4 alkyl, Ci-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, Ci-C4 alkoxy, Cx-C4 haloalkoxy, Ci-C4 alkyl thio, Cx-C4 haloalkyl ioamino, Ci-C4 alkyl amino, C2-C4 haloalkyl amino, formyl, Cx-C3 alkyl carbonyl, Ci-C3 haloalkyl carbonyl, cyano or a group of the formula -CR5= CR6SiR7R8R9, wherein R5 is hydrogen, F or Cl; R6 is hydrogen, F, C1, Cx-C4 alkyl or Ci-C4 haloalkyl; and R7, R8 and R9 are, independently, Ci-C10 alkyl, C3-C6 cycloalkyl / phenyl, substituted phenyl, CxC10 alkoxy or OH; and R3 and R4 are, independently, hydrogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C3-C6 alkenyl, IF-2019-795 32212-APN-ANP#INP? Page 2 of 78 C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, C3C3 alkyl carbonyl, C3-C3 haloalkyl carbonyl, Ci-C6 alkoxy carbonyl, Cx-C6 alkyl carbamyl, Ci-C6 alkyl sulfonyl, C3-C6 trialkyl silyl, Ci-Cg dialkyl phosphonyl or R3 and R4 taken together with N is a saturated 5 or 6-membered ring or R3 and R4 taken together, represent =CR3'(R4'), wherein R3' and R4' are, independently, hydrogen, Ci-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, Ci-C6 alkoxy or Ci-C6 alkyl amino or R3' and R4' taken together with =C represent a saturated 5 or 6-membered ring; or one of its salts, esters or N-oxides acceptable in agriculture. In some embodiments, the compound can be defined by the formula IA: (IA) where R1 is hydrogen, Ci-C8 alkyl, Ci-C8 haloalkyl, C2-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, phenyl, substituted phenyl or C7-C12 arylalkyl; IF-2019-79532212-APN-ANP#INPI Page 3 of 78 R2 is halogen, Cx-C4 alkyl, Cx-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl / Ci-C4 alkoxy, Ci-C4 haloalkoxy, Cx-C4 alkylthio, Cx-C4 haloalkylthioamino, Ci-C4 alkylamino, C2-C4 haloalkylamino, formyl, Cx-C3 alkylcarbonyl, Ci-C3 haloalkylcarbonyl, cyano or a group of the formula -CR =CR SiR7R8R9, wherein R5 is hydrogen, F or Cl; R6 is hydrogen, F, Cl, Cx-C4 alkyl or Ci-C4 haloalkyl; and R7, R8 and R9 are, independently, Cx-C10 alkyl, C3-C6 cycloalkyl, phenyl, substituted phenyl, C3C10 alkoxy or OH; and R3 and R4 are, independently, hydrogen, Cx-Ce alkyl, Ci-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, C3C3 alkyl carbonyl, Cx-C3 haloalkyl carbonyl, Cx-C6 alkoxy carbonyl, Cx-C6 alkyl carbamyl, Ox-O6 alkyl sulfonyl, trialkyl Ox-C6 silyl, dialkyl Ox-O6 phosphonyl or R3 and R4 taken together with N is a saturated 5- or 6-membered ring or R3 and R4 taken together, represent =CR3'(R4'), wherein R3' and R4' are, independently, hydrogen, Ox-O6 alkyl, C3-Ce alkenyl, C3-C6 alkynyl, alkoxy Oχ-O6o alkyl Ci-C6-amino or R3' and R4' taken together with =C represent a saturated ring of 5 or 6 members; IF-2019-79532212-ΑΡΝ-ΑΝΡ#ΙΝή Page 4 of 78 or one of its salts or N-oxides acceptable in agriculture. Herbicide compositions comprising a compound of formula I and / or formula IA and an adjuvant or carrier acceptable in agriculture are also provided. Methods for controlling undesirable vegetation are also provided, comprising applying a herbicidal quantity of a compound of formula I and / or formula IA or a herbicidal composition comprising a compound of formula I and / or formula IA and an adjuvant or carrier acceptable in agriculture. BRIEF DESCRIPTION OF THE DRAWINGS Figure IA is a graph of the activity of compounds 1-15 against selected broadleaf weed species at an application rate of 17.5 g ai / ha. Figure IB is a graph of the activity of compounds 1-15 against selected grass weed species at an application rate of 17.5 g ai / ha. Figure 2A is a graph of the activity of compounds 1-15 against leafy weed species IF-2019-795 32212-APN-ANP#INPI Page 5 of 78 selected broadleaf varieties at an application rate of 35 g ai / ha. Figure 2B is a graph of the activity of compounds 1-15 against selected grass weed species at an application rate of 35 g ai / ha. Figure 3A is a graph of the activity of compounds 1-15 against selected broadleaf weed species at an application rate of 70 g ai / ha. Figure 3B is a graph of the activity of compounds 1-15 against selected grass weed species at an application rate of 70 g ai / ha. Figure 4A is a graph of the activity of compounds 1-15 against selected broadleaf weed species at an application rate of 140 g ai / ha. Figure 4B is a graph of the activity of compounds 1-15 against selected grass weed species at an application rate of 140 g ai / ha. DETAILED DESCRIPTION Definitions As used herein, herbicide and herbicide active ingredient mean a compound that IF-2019-79532212-APN-ANP#INI^ Page 6 of 78 controls unwanted vegetation when applied in an appropriate amount. As used herein, control or control unwanted vegetation means killing or preventing vegetation or causing some other adverse modifying effect on vegetation, e.g., deviations from natural growth or development, regulation, desiccation, retardation, and the like. As used herein, a quantity of herbicidal efficacy or vegetation control is a quantity of herbicidal active ingredient, the application of which controls relevant unwanted vegetation. As used herein, the application of a herbicide or herbicidal composition means direct delivery onto the target vegetation or its locus or the area where control of unwanted vegetation is desired. Application methods include, but are not limited to, pre-emergence contact with the soil or water, post-emergence contact with the unwanted vegetation or the area adjacent to the unwanted vegetation. As used herein, plants and vegetation include, but are not limited to, dormant seeds, germinating seeds, emerging seedlings, plants that IF-2019-795 32212-A PN-A NP# IN P1 Page 7 of 78 emerge from vegetative propagules, immature vegetation and established vegetation. 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 into the reference herbicide. Appropriate agriculturally acceptable esters are those that are or can be hydrolyzed, oxidized, metabolized, or otherwise converted, for example, in plants, water, or soil, into the corresponding carboxylic acid, which, depending on the pH, may be in the dissociated or undissociated form. Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula: R13R14R15R16N+ where R13, R14, R15, and R16 each independently represent hydrogen or C1-C12 alkyl, C3-C12 alkenyl, or C3-C12 alkynyl, each of which is optionally substituted with one or more hydroxy, C1-C4 alkoxy, Cx-C4 alkyl-thio, or phenyl groups, provided that R13, R14, R15, and R16 are spherically compatible. Additionally, any two of R13, R14, R15 and R16 can together represent an aliphatic difunctional remainder IF-2019-79532212-APN-ANP#INP^ Page 8 of 78 with 1 to 12 carbon atoms and up to two oxygen or sulfur atoms. Salts of compounds of formula I can be prepared by treating compounds of formula I with a metal hydroxide, such as sodium hydroxide, with an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisalylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine, or with a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide or choline hydroxide. In certain instances, amine salts may often be preferred forms of compounds of formula I because they are water-soluble and lead to the preparation of water-based herbicidal compositions, which may be desirable for certain applications. Compounds of formula (I) include N-oxides. Pyridine N-oxides can be obtained by oxidation of the corresponding pyridines. Appropriate oxidation methods are described, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], expanded and subsequent volumes to the fourth edition, volume E 7b, p. 565 f. As used herein, unless otherwise specified, acyl refers to formyl, alkyl Ci-C3-carbonyl, and haloalkyl Ci-C3-carbonyl. IF-2019-79532212-APN-ANP#INPÍ Page 9 of 78 Ci-C6 acyl refers to formyl, alkyl Ch - C5- carbonyl and haloalkyl Ci-C5-carbonyl (the group contains a total of 1 to 6 carbon atoms). As used herein, alkyl refers to saturated hydrocarbon groups of linear or branched chain. Unless otherwise specified, alkyl groups Ci-Ci0 are intended. Examples include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl 1,2,2-trimethyl-propyl, 1-ethyl-l-methyl-propyl and 1-ethyl2-methyl-propyl. As used herein, haloalkyl refers to linear or branched-chain alkyl groups, where in these groups the hydrogen atoms may be partially or totally substituted with halogen atoms. Unless otherwise specified, Ci-C8 groups are intended. Examples include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, IF-2019-79532212-APN-ANP#ráft Page 10 of 78 fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2yl. As used herein, alkenyl refers to unsaturated hydrocarbon groups of linear or branched chain with a double bond. Unless otherwise specified, alkenyl groups are intended to be Cj-Cg. Alkenyl groups may contain more than one unsaturated bond. Examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 2-methyl-l-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-l-butenyl, 2-methyl-l-butenyl, 3-methyl-l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,l-dimethyl-2-propenyl, 1,2-dimethyl-l-propenyl 1,2dimethyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2propenyl, 1—bexenyl, 2—hexenyl, 3—hexenyl, 4 — hexenyl, 5-hexenyl, 1-methyl-l-pentenyl, 2-methyl-lIF-2019-79532212-A PN-AN P# IN^ Página 11 of 78 pentenilo, 3-methyl-l-pentenilo, 4-methyl-l-pentenilo, 1metil-2-pentenilo, 2-methyl-2-pentenilo, 3-methyl-2pentenilo, 4-methyl-2-pentenilo, l-methyl-3-pentenilo, 2metil-3-pentenilo, 3-metil-3-pentenilo, 4-methyl-3pentenilo, l-methyl-4-pentenilo, 2-methyl-4-pentenilo, 3metil-4-pentenilo, 4-metil-4-pentenilo, 1,1-dimethyl-2butenilo, 1, l-dimethyl-3-butenilo, 1,2-dimethyl-l-butenilo, 1,2-dimetil-2-butenilo, 1,2-dimetil-3-butenilo, 1,3dimetil-l-butenilo, 1,3-dimetil-2-butenilo, 1,3-dimetil3-butenilo, 2,2-dimetil-3-butenilo, 2,3-dimetil-lbutenilo, 2,3-dimetil-2-butenilo, 2,3-dimetil-3-butenilo, 3,3-dimetil-l-butenilo, 3,3-dimetil-2-butenilo, 1-etil-lbutenilo, l-etil-2-butenilo, l-etil-3-butenilo, 2-etil-lbutenilo, 2-etil-2-butenilo, 2-etil-3-butenilo, 1,1,2trimethyl-2-propenilo, 1-etil-l-methyl-2-propenilo, 1-etil2-methyl-l-propenilo y l-etil-2-methyl-2-propenilo.Vinyl refers to a group that has the structure -CH=CH2; 1-propenyl refers to a group with the structure CH=CH-CH3; and 2-propenyl refers to a group with the structure -CH2-CH=CH2. As used herein, alkynyl represents linear or branched hydrocarbon chains with a triple bond. Unless otherwise specified, C2-C8 alkynyl groups are intended. Alkynyl groups may contain more than one IF-2019-79532212-APN-ANP#INPI Page 12 of 78 unsaturated link. Examples include C2-C6 alkynyls 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-l-butynyl, l-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-l-pentynyl, 4-methyl-l-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, l-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4pentynyl, 1,l-dimethyl-2-butynyl, 1,1-dimethyl-1-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, 1-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl. As used herein, alkoxy refers to a group of the formula RO-, where R is alkyl as previously defined. Unless otherwise specified, alkoxy groups are intended where R is a Ci-Cg alkyl group. Examples include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutyloxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, and 2-methyl. IF-2019-79532212-APN-ANP#INPI Page 13 of 78 pentoxy, 3-methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethylbutoxy, 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-l-methyl-propoxy and 1-ethyl2-methyl-propoxy. As used herein, haloalkoxy refers to a group of the formula RO-, where R is a haloalkyl as previously defined. Unless otherwise specified, haloalkoxy groups are intended where R is a Ci-C8 alkyl group. Examples include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2fluoroethoxy, 2-chloro-2-difluoroethoxy, 2,2-dichloro-2fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy. As used herein, alkylthio refers to a group of the formula RS- where R is alkyl as previously defined. Unless otherwise specified, alkylthio groups are intended where R is a Ci-C8 alkyl group. Examples include 14 IF-2019-79532212-APN-ANP#INPI Page 14 of 78 methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methyl-propylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3methylbutylthio, 2,2-di-methylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethyl propylthio, 1,2-dimethyl propylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methyl-pentylthio, 4methyl-pentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethyl-butylthio, 2,2-dimethylbutylthio, 2,3dimethyl butylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2ethylbutylthio, 1,1,2-trimethyl propylthio, 1,2,2-trimethyl propylthio, 1-ethyl-1-methylpropylthio y 1-ethyl-2methylpropylthio . As used herein, haloalkylthio refers to an alkylthio group as defined above, wherein the carbon atoms are partially or fully substituted with halogen atoms. Unless otherwise specified, haloalkylthio groups are intended where R is a Ci-C8 alkyl group. Examples include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2-fluoroethylthio IF-2019-79532212-APN-ANP#INPI Page 15 of 78 difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2trichloroethylthio, pentafluoroethylthio and 1,1,1trifluoroprop-2-ylthio. As used herein, aryl, as well as derived terms such as aryloxy, refers to a phenyl, indanyl, or naphthyl group, with phenyl being preferred. The term heteroaryl, as well as derived terms such as heteroaryloxy, refers to a 5- or 6-membered aromatic ring containing one or more heteroatoms, for example, N, O, or S; these heteroaromatic rings can be fused with other aromatic systems.Aryl or heteroaryl substituents may be unsubstituted or may be substituted with one or more substituents selected from halogen, hydroxy, nitro, cyano, formyl, Ci-C6 alkyl, C2-C6 alkenyl, C2-Ce alkynyl, Ci-Ce alkoxy, Cx-C6 haloalkyl, Ci-C6 haloalkoxy, Ci-C6 acyl, Ci-C6 alkylthio, CiCg alkylsulfinyl, Ci-Cg alkylsulfonyl, (CiC6 alkoxy)carbonyl, carbamoyl, hydroxycarbonyl, (CiC6 alkyl)carbonyl, aminocarbonyl, (CxC6 alkyl)aminocarbonyl, di(Ci-C6 alkyl)aminocarbonyl, provided that the substituents are spherically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include halogen, Ci-C2 alkyl and Ci-C2 haloalkyl. IF-2019-79532212-A PN-AN P# IN^ Page 16 of 78 As used herein, alkylcarbonyl refers to an alkyl group bonded to a carbonyl group. Alkyl Ci-C3-carbonyl and haloalkyl Cx-C3-carbonyl refer to groups in which a C3-C3 alkyl group is bonded to a carbonyl group (the group contains a total of 2 to 4 carbon atoms). As used herein, alkoxycarbonyl O refers to a group of the formula ^O^ where R is alkyl. As used herein, arylalkyl refers to an alkyl group substituted with an aryl group. Arylalkyl C7-C10 refers to a group in which the total number of carbon atoms in the group is 10. As used herein, alkylamino refers to an amino group substituted with one or two alkyl groups, which may be the same or different. As used herein, haloalkylamino refers to an alkylamino group in which the alkyl carbon atoms are partially or totally substituted with halogen atoms. As used herein, alkyl Ci-C6aminocarbonyl refers to a group of the formula RNHC(O)-, where R is Ci-Cg alkyl and Ci-C6 dialkyl aminocarbonyl refers to a group of the formula IF-2019-79532212-APN-ANP#INPI Page 17 of 78 R2NC(O)-, where each R is independently a Ci-C6 alkyl. As used herein, alkylcarbamyl refers to a carbamyl group substituted at the nitrogen with an alkyl group. As used herein, alkylsulfonyl is O II refers to a group of the formula $R, where R is alkyl. As used herein, carbamyl (also referred to as carbamoyl and aminocarbonyl) refers to Or to a group of the formula H2N As used herein, dialkylphosphonyl EITHER II refers to a group of the formula OR< where R is, OR independently, alkyl in each occurrence. As used herein, trialkyl Ci-C6silyl refers to a group of the formula -SiR3, wherein each R is independently a Ci-Cg alkyl group (the group contains a total of 3 to 18 carbon atoms). As used herein, Me refers to a methyl group; OMe refers to a methoxy group; i-Pr refers to an isopropyl group. IF-2019-79532212-APN-ANP#INPI Page 18 of 78 As used herein, the term halogen, which includes derivative terms such as halo, refers to fluorine, chlorine, bromine, and iodine. As used herein, plants and vegetation include, but are not limited to, germinating seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation. Compounds The compounds of formula I are provided herein, where R2 is halogen, C4-alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, Cx-C4 alkoxy, C4-C4 haloalkoxy, C4-C4 alkylthio, C4-C4 haloalkylthioamino, C1-C4 alkylamino, C2-C4 haloalkylamino, formyl, C3-C3 alkylcarbonyl, C3-C3 haloalkylcarbonyl, cyano or a group of the formula -CR =CR SiR7R8R9, wherein R5 is hydrogen, F or Cl; R6 is IF-2019-79532212-APN-ANP#INH Page 19 of 78 hydrogen, F, Cl, alkyl Ci-C4 or haloalkyl Ci~C4; and R7, R8 and R9 are, independently, alkyl Ci-C10, cycloalkyl C3-C6, phenyl, substituted phenyl, alkoxy ChC10 or OH; and R3 and R4 are, independently, hydrogen, Ci-CG alkyl, Ci-C6 haloalkyl, C3-C6 alkenyl / C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, CxC1 alkyl carbonyl, Ci-C3 haloalkyl carbonyl, Ci-CG alkoxy carbonyl, C3-CG alkyl carbamyl, Ci-CG alkyl sulfonyl, C3-CG trialkyl silyl, C3-CG dialkyl phosphonyl or R3 and R4 taken together with N is a saturated 5- or 6-membered ring or R3 and R4 taken together represent =CR3(R4) , wherein R3 and R are, independently, hydrogen, Ci-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, Ci-Cg alkoxy or Ci-Cg alkyl amino or R and R4' taken together with =C represent a ring saturated with 5 or 6 members; as well as their salts, esters and N-oxides acceptable in agriculture. In some embodiments, the compound is the carboxylic acid or an ester or salt acceptable in agriculture. In some embodiments, the compound is the carboxylic acid or an ester acceptable in agriculture. In certain embodiments, the compound is the carboxylic acid. In certain IF-2019-79532212-APN-ANP#IN3? Page 20 of 78 embodiments, the compound may be an ester acceptable in agriculture (e.g., a methyl ester, a benzyl ester, or a propargyl ester). In some embodiments, the compound can be defined by the formula IA: where r1 is hydrogen, Ci-C8 alkyl, Ch-Cg haloalkyl, C2-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, phenyl, substituted phenyl or C7-Ci2 arylalkyl; R2 is halogen, C1-C4 alkyl, C1-C4 haloalkyl or C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, Cx-C4 alkyl thio, Cx-C4 haloalkyl thioamino, C1-C4 alkyl amino, C2-C4 haloalkyl amino, formyl, Cx-C3 alkyl carbonyl, C1-C3 haloalkyl carbonyl, cyano or a group of the formula -CR =CR SiR7R8R9, wherein R5 is hydrogen, F or Cl; R is hydrogen, F, Cl, C1-C4 alkyl or Cx-C4 haloalkyl, and R7, R8 and R9 are, independently, C1-C10 alkyl, IF-2019-79532212-APN-ANP#INPI Page 21 of 78 C3-C6 cycloalkyl, phenyl, substituted phenyl, C3C10 alkoxy OH; and R3 and R4 are, independently, hydrogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, C3C3 alkyl carbonyl, C3-C3 haloalkyl carbonyl, Ci-Cg alkoxy carbonyl, C3-Cg alkyl carbamyl, Ci-Cg alkyl sulfonyl, Ci-Cg trialkyl silyl, Ci-Cg dialkyl phosphonyl or R3 and R4 taken together with N is a saturated 5- or 6-membered ring or R and R taken together, represent =CR3(R4) , wherein R3 and R are, independently, hydrogen, Ci-C6 alkyl, C3-C6 alkenyl, C3-Cg alkynyl, Ci-Cg alkoxy or Ci-Cg alkyl amino or R and r4' taken together with =C represent a saturated ring of 5 or 6 members; or one of its salts or N-oxides acceptable in agriculture. In some embodiments of formula IA, R1 is hydrogen, C1-C8 alkyl, C2-C8 alkynyl, or C7-C10 arylalkyl. In some embodiments of formula IA, R1 is hydrogen. In some embodiments of formula IA, R1 is a C1-C8 alkyl (e.g., a methyl group). In some embodiments of formula IA, R1 is a C2-C8 alkynyl (e.g., a propargyl group). In some embodiments of IF-2019-79532212-APN-ANP#INPI Page 22 of 78 realization of 'formula IA, R1 is arylalkyl C7-Ci0 (for example, a benzyl group). In some embodiments of formula I and / or formula IA, R2 is a halogen, C2-C4 alkenyl, C2-C4c haloalkenyl, or C4-C4 alkoxy. In some embodiments of formula I and / or formula IA, R2 is a halogen, C2-C4 alkenyl, or C4-C4 alkoxy. In some embodiments of formula I and / or formula IA, R2 is Cl, OMe, vinyl, or 1-propenyl. In some embodiments of formula I and / or formula IA, R2 is Cl. In some embodiments of formula I and / or formula IA, R2 is OMe. In some embodiments of formula I and / or formula IA, R is vinyl or 1-propenyl. In some embodiments of formula I and / or formula IA, R3 and R4 are, independently, hydrogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, formyl, Ci-C3 alkylcarbonyl, C4-C3 haloalkylcarbonyl, Ci-C6 alkoxycarbonyl, Ci-C6 alkylcarbamyl, or R3 and R4 taken together represent =CR3(R4), wherein R3 and R4 are, independently, hydrogen, Ci-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, Ci-C6 alkoxy, or Ci-C6 alkylamino. In some embodiments of formula I and / or formula IA, R3 and R4 are, so IF-2019-79532212-APN-ANP#ITÍft Page 23 of 78 Independently, hydrogen, Ci-C6 alkyl, CxC6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, formyl, C1-C3 alkylcarbonyl, Cx-C3 haloalkylcarbonyl, or R3 and R4 taken together, represent =CR3'(R4), wherein R3 and R4 are, independently, hydrogen, Ci-C6 alkyl, Ci-C6 alkoxy, or Ci-C6 alkylamino. In some embodiments of formula I and / or formula IA, at least one of R3 and R4 is hydrogen. In some embodiments of formula I and / or formula IA, R3 and R4 are both hydrogen. In some embodiments of formula I and / or formula IA, R2 is C1, OMe, vinyl, or 1-propenyl; and R3 and R4 are both hydrogen. In some embodiments of formula I and / or formula IA, R2 is C1 15 and R3 and R4 are both hydrogen. In some embodiments of formula I and / or formula IA, R2 is OMe and R3 and R4 are both hydrogen. In some embodiments of formula I and / or formula IA, R is vinyl or 1-propenyl; and R3 and R4 are both hydrogen. IF-2019-79532212-APN-ANP#IN^f Page 24 of 78 In some embodiments the compound can be defined by the structure below In some embodiments, the compound can be defined by the structure below. In some embodiments, the compound can be defined by the structure below. IF-2019-795 32212-APN-ANP#INPI Page 25 of 78 In some embodiments, the compound can be defined by the structure below. Methods of preparing the compounds Example procedures for synthesizing compounds of formula I and formula IA are provided below. As shown in Scheme I, the 4,5,6-trichloropicolinate of formula (VII) can be converted to the corresponding isopropyl ester of formula (VIII) by reaction with isopropyl alcohol and concentrated sulfuric acid, for example, at reflux temperature under Dean-Stark conditions (reaction d). The isopropyl ester of formula (VIII) can then 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 isopropyl 4,5,6-trifluoropicolinate of formula (IX) (reaction e). Isopropyl 4,5,6-trifluoropicolinate IF-2019-795 32212-APN-ANP#INPI Page 26 of 78 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 at position 6 of the 4-amino-5,6-difluoropicolinate of formula (X) can be exchanged for a chlorine substituent by treatment with a chloride source, such as hydrogen chloride, for example, 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 into the corresponding methyl ester of formula (XII) by reaction with titanium(IV) isopropoxide in methyl alcohol at reflux temperature (reaction h). IF-2019-79532212-APN-ANP#INPI Page 27 of 78 Scheme I As depicted in Scheme II, the 4-amino5 5-fluoro-6-chloropicolinate of formula (XII) can be transformed into the 3-iodo-4-amino-5-fluoro-6-chloropicolinate of formula (XIII) by reaction with iodination reagents such as periodic acid and iodine, in a polar protic solvent, such as methyl alcohol 10 (reaction b3). The 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, for example, in a microwave reactor, provides 3-(substituted)-4-amino-5-fluoro-6-chloropicolinates of formula (XIV), wherein R is alkyl, alkenyl, alkynyl, haloalkenyl, and alkylthio. 28 IF-2019-79532212-APN-ANP#INPI Page 28 of 78 (reaction c3). 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 3-(substituted)-4-amino-5-fluoro-6-chloropicolinics of formula (XIV), wherein R2 is alkoxy or haloalkoxy (reaction i2), which can be esterified to the methyl esters, for example, by treatment with hydrogen chloride (gas) and methyl alcohol at 50 °C (reaction j).The 3-(substituted)-4-amino-5-fluoro-6-chloropicolinates of formula (XIV) can be converted into the 4-amino-6-substituted picolinates of formula (IB), wherein Ar is as defined herein, by 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 mixture of polar protic solvents, such as acetonitrile-water, at a temperature such as 110 °C, for example, in a microwave reactor (reaction a3). Alternatively, the 4-amino-5-fluoro-6-chloropicolinates of formula (XII) can be converted into the 4-amino-5-fluoro-6-substituted picolinates of 29 IF-2019-79532212-APN-ANP#INPI Page 29 of 78 formula (XV), wherein Ar is as defined herein, by 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, for example, in a microwave reactor (reaction a4). 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) by reaction with iodination reagents, such as periodic acid and iodine, in a polar protic solvent, such as methyl alcohol (reaction b4).The 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, for example, in a microwave reactor, gives 3-(substituted)-4-amino-5-fluoro-6-substituted picolinates of formula (IB), wherein R2 is alkyl, alkenyl, alkynyl, haloalkenyl, and alkylthio (reaction c4). Alternatively, the 3-iodo-4-amino-5-fluoro-6-substituted picolinates of formula. IF-2019-795 32212-APN-ANP#INPI (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 acid of formula (IB), wherein R2 is an alkoxy or haloalkoxy (reaction i2), which can be esterified to methyl esters, for example, by treatment with hydrogen chloride (gas) and methyl alcohol, at a temperature such as 50 °C (reaction j2). IF-2019-795 32212-APN-ANP#INPI Page 31 of 78 Scheme II Compounds of formula IB obtained by any of these processes can be recovered by conventional means and purified by standard procedures, such as recrystallization or chromatography. Many compounds of formula I and / or IA can be prepared from compounds of formula IB using well-known standard methods in the art. Other compounds of formula I and / or IA can be prepared using the methods illustrated in Scheme III. In step a of Scheme III, the 3-bromo-6-chloro15 2-fluorobenzaldehyde known from formula A (Baleo, T. William et al., International Publication No. WO 2007 / 082098, which is incorporated herein in its entirety) can be converted into 3-bromo-6-chloro-2-methoxybenzaldehyde of formula B by substitution 32 IF-2019-79532212-APN-ANP#INPI Page 32 of 78. In step b, 3-bromo-6-chloro-2-methoxybenzaldehyde of formula B can be converted to 3-bromo-6-chloro-2-hydroxybenzaldehyde of formula C by demethylation of the 2-methoxy group with a Lewis acid such as boron tribromide in an aprotic solvent such as dieloromethane. In step c, 3-bromo-6-chloro-2-hydroxybenzaldehyde of formula C can be converted to 3-bromo-6-chlorobenzene-1,2-diol of formula D by means of a Dakin reaction using an oxidizing agent such as hydrogen peroxide and an aqueous solution of a base such as sodium hydroxide.In step d, 3-bromo-6-chlorobenzene-1,2-diol of formula D can be converted to 4-bromo-7-chlorobenzo[d][1,3]dioxol of formula E by means of an intramolecular cyclization reaction with a dihalomethane alkylating agent such as bromochloromethane and a base such as cesium carbonate in a polar aprotic solvent such as dimethylformamide. In step e, 2-(7-chlorobenzo[d][1,3]dioxo1-4-11)4,4,5,5-tetramethyl-1,3,2-dioxaborolane of formula F can be prepared from 4-bromo-7-chlorobenzo[d][1,3]dioxol of formula E by means of a halogen / metal exchange reaction using a Grignard reagent such as isopropylmagnesium chloride. IF-2019-79532212-APN-ANP#IN1^ Page 33 of 78 in a solvent such as tetrahydrofuran followed by inactivation of the organomagnesium intermediate formed in situ with a borylating agent such as 2-isopropoxy4,4,5,5-tetramethyl-1,3-dioxolane. In step f, 4-amino-3-chloro-6-(7-chlorobenzo[d][1,3]dioxol-4-yl)-5-methyl fluoropicolinate of formula H can be prepared by means of a Suzuki coupling between 2(7-chlorobenzo[d][1,3]dioxol-4-11)-4,4,5,5-tetramethyl1,3,2-dioxaborolane of formula F and known methyl 4-amino-3,6-dichloro-5-fluoropicolinate of formula G (Fields, Stephen C. et al. Tetrahedron Letters, 51(1), 79-81, 2010) using a palladium(II) catalyst such as bis(triphenylphosphine)palladium(II) dichloride, a base such as cesium fluoride in a mixture of solvents such as acetonitrile and water.In step g, methyl 4-amino-3-chloroq-(7-chlorobenzo[d][1,3]dioxol-4-yl)-5-fluoropicolinate of formula H can be converted to 4-amino-3-chloro-6-(7-chlorobenzo[d][1,3]dioxol-4-yl)-5-fluoropicolinic acid of formula I by means of a saponification reaction using an aqueous solution of a base such as sodium hydroxide in a solvent mixture such as methanol and tetrahydrofuran. In step h, the picolinic ester of formula J can be prepared from 4-amino-3-chloro-6-(7-chlorobenzo[d][1,3]dioxol-4-yl)-5-fluoropicolinic acid. IF-2019-79532212-APN-ANP#IN?>f Page 34 of 78 c1orobenzo[d] [ 1,3]dioxol-4 - i1)- 5 -fluoropicolinic acid by means of an alkylation reaction using an alkylating agent such as propargyl bromide or benzyl bromide and a base such as potassium carbonate in a polar aprotic solvent such as dimethylformamide. IF-2019-79532212-APN-ANP#INPI Page 35 of 78 Scheme III COMPOSITIONS AND METHODS In some embodiments, the compounds provided herein are used in mixtures containing an amount of herbicidal efficacy of the compound along with at least one adjuvant or carrier acceptable in agriculture. Example adjuvants or carriers include those that are not phytotoxic or 36 IF-2019-795 32212-APN-ANP#INPI Page 36 of 78 These mixtures are significantly phytotoxic to valuable crops, for example, at the concentrations used in the application of compositions for selective weed control in the presence of crops, and / or do not react or react significantly with the compounds provided herein or other ingredients of the composition. These mixtures may be designed for application directly to weeds or their locus, or may be concentrates or formulations that are diluted with additional carriers and adjuvants before application. They may be solids such as, for example, powders, granules, water-dispersible granules, or wettable powders, or liquids such as emulsifiable concentrates, solutions, emulsions, or suspensions. They may also be provided as a premix or tank mix. The appropriate agricultural adjuvants and carriers that are useful in preparing the herbicide mixtures described herein 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; quaternary benzylcocoalkyldimethylammonium salt; and a mixture of petroleum hydrocarbon, alkyl esters, organophosphate, and anionic surfactant. IF-2019-79532212-APN-ANP#IN^I? Page 37 of 78 Cg-Cn alkyl polyglycoside; phosphated alcohol ethoxylate; natural (Ci2—CiE) primary alcohol ethoxylate; disec-butylphenol OE-OP block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + ammonium urea nitrate; emulsified methylated seed oil; (synthetic) tridecyl alcohol ethoxylate (8EO); tallow amine ethoxylate (15OE); PEG(400) dioleate-99. Liquid carriers that may be employed include water and organic solvents. Organic solvents typically used include, but are not limited to, petroleum or hydrocarbon fractions 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, prickly pear oil, and the like; and esters of the above vegetable oils. esters of monoalcohols or dihydric, trihydric or other lower polyalcohols (containing 4-6 hydroxy), such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, di-adipate IF-2019-795 3221 2-APN-ANP#InI? Page 38 of 78 butyl, dioctyl phthalate, and the like; esters of mono-, di-, and polycarboxylic 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, glycerin, N-methyl-2-pyrrolidinium, N,N-dimethylalkylamides, dimethyl sulfoxide, liquid fertilizers, and the like. In some embodiments, water is the carrier for diluting concentrates. Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgite clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean meal, pumice, sawdust, walnut shell meal, lignin, and the like. In some embodiments, one or more surfactants are used in the compositions described herein. Such surfactants are employed, in some embodiments, both in IF-2019-795 32212-A PN-A NP# IbM Page 39 of 78 solid as well as liquid compositions, for example, those designed to be diluted with a carrier before application. Surfactants may be anionic, cationic, or nonionic and may 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 surfactants include alkyl sulfate salts such as diethanolammonium lauryl sulfate; alkylyl sulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-CI8 ethoxylate; and alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate. C16; soaps such as sodium stearate; alkylnaphthalenesulfonate 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 IF-2019-795322 12-APN-ANP#IíÍA Page 40 of 78 lauryltrimethylammonium 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 / candlewood oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, prickly pear oil, and the like; and esters of the above vegetable oils, for example, methyl esters. Often, 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 surfactant. Other adjuvants commonly used in agricultural compositions include compatibilizing agents, antifoaming agents, sequestering agents, neutralizing agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, sticking agents, dispersing agents, thickening agents, freezing point depressants, antimicrobial agents, and the like. Compositions may also contain other components. IF-2019-795 32212-APN-ANP#INPI Page 41 of 78 compatible, for example, other herbicides, plant growth regulators, fungicides, insecticides, and the like, and can be formulated with liquid or solid fertilizers, particulate fertilizer carriers such as ammonium nitrate, urea, and the like. The concentration of active ingredients in the herbicide compositions described herein is generally from approximately 0.001 to approximately 98% by weight. Concentrations of approximately 0.01 to approximately 90% by weight are often used. In compositions designed for use as concentrates, the active ingredient is generally present at a concentration of approximately 5 to approximately 98% by weight, preferably from approximately 10 to approximately 90% by weight. These compositions are typically diluted with an inert carrier, such as water, prior to application. Diluted compositions usually applied to weeds or weed locus generally contain from approximately 0.0001 to approximately 1% by weight of active ingredient and preferably contain from approximately 0.001 to approximately 0.05% by weight. The present compositions can be applied to weeds or their locus using ground dusters. IF-2019-79532212-APN-ANP#INPI Page 42 of 78 or conventional aerial sprayers and granule applicators, by addition to irrigation or flood water and by other conventional means known to those skilled in the art. In some embodiments, the compounds and compositions described in the art are applied as post-emergence application, pre-emergence application, application in water to flooded rice paddies or bodies of water (e.g., lagoons, lakes and streams) or burn application. In some embodiments, the compounds and compositions provided herein are used to control weeds in crops including, but not limited to, citrus, apple, rubber, oil palm, forestry, no-till rice, irrigated rice and transplanted rice, wheat, barley, oats, rye, sorghum, maize, pastures, meadows, rangelands, fallow land, lawns, trees and vineyards, aquatic plants or row crops, as well as non-crop areas, for example, industrial vegetation control (IVM) or rights-of-way. In some embodiments, the compounds and compositions are used to control woody plants, broadleaf weeds, and grasses or sedges. IF-2019-79532212-APN-ANP#INPI Page 43 of 78 In some embodiments, the compounds and compositions provided herein are used to control unwanted vegetation in rice. In certain embodiments, the unwanted vegetation is Brachiaria platyphylla (Groseb.) Nash (BRAPP), Digitaria sanguinalis (L.) Scop. (DIGSA), and Echinochloa crus-galli (L.) P. Beauv. (ECHCG). Echinochloa colonum (L.) LINK (ECHCO), Echinochloa oryzoides (Ard.) Fritsch (ECHOR), Echinochloa oryz icola (Vasinger) Vasinger (ECHPH), Ischaemum rugosum Salisb. (ISCRU), Leptochloa chinensis (L.) Nees (LEFCH), Leptochloa fascicularis (Lam.) Gray (LEFFA), Leptochloa panicoides (Presl.) Hitchc. (LEFPA), Panicum dichotomiflorum (L.) Michx. (PANDI), Paspalum dilatatum Poir. (PASDI), Cyperus difformis L. (CYPDI), Cyperus esculentus L. (CYPES), Cyperus iría L. (CYPIR), Cyperus rotundus L. (CYPRO), species of Eleocharis (ELOSS), Fimbristylis miliacea (L.) Vahl (FIMMI), Schoenoplectus juncoides Roxb. (SCPJU), Schoenoplectus maritimus L. (SCPMA), Schoenoplectus mucronatas L. (SCPMU), Aeschynomene species (AESSS), Alternanthera philoxeroides (Mart.) Griseb. (ALRPH), Alisma plantago-aquatica L. (ALSPA), Amaranthus species (AMASS), Ammannia coccínea Rottb. (AMMCO), Eclipta alba (L.) Hassk. (ECLAL), Heteranthera limosa (SW.) Willd. / Vahl (HETLI), Heteranthera reniformis IF-2019-79532212-APN-ANP#INPI Page 44 of 78 R. & P. ​​(HETRE) , Ipomoea hederacea (L.) Jacq. (IPOHE), Lindernia dubia (L.) Pennell (LIDDU), Monochoria korsakowii Regel & Maack (MOOKA) , Monochoria vaginalis (Burra. F.) C. Presl ex Kuhth, (MOOVA), Murdannia nudiflora (L.) Brenan (MUDNU), Polygonum pensylvanicum L., Polygonum L., L. L. (POLPE), Polygonum hydropiperoides Michx. (POLHP) , Rot ala indica (Willd.) Koehne (ROTIN), Sagittaria species, (SAGSS), Sesbania exaltata (Raf.) Cory / Rydb. Ex Hill (SEBEX), or Sphenoclea zeylanica Gaertn. (SPDZE). In some forms of implementation, the compounds and compositions proposed herein are used to control unwanted vegetation in cereals. In certain forms of implementation, undesirable vegetation is Alopecurus myosuroides Huds. (ALOMY), Apera spica-venti (L.) Beauv. (APESV), Avena fatua L. (AVEFA), Bromus tectorum L. (BROTE), Lolium multiflorum Lam. (LOLMU) , Phalaris minor Retz . (PHAMI), Poa Annua L. (POAAN), Setaria pumila (Poir.) Roemer & JA Schultes (SETLU), Setaria viridis (L.) Beauv. (SETVI), Cirsium arvense (L.) Scop. (CIRAR), Galium aparine L. (GALAP), Kochia scoparia (L.) Schrad. (KCHSC), Lamium purpureum L. (LAMPU), Matricaria recutita L. (MATCH), Matricaria matricarioides (Less.) Porter (MATMT), Papaver rhoeas L. (PAPRH), Polygonum convolvulus IF-2019-79532212-APN-ANP#INÍ*f Page 45 of 78 L. (POLCO), Salsola tragus L. (SASKR), Stellaria media (L.) Vill. (STEM), Veronica persica Poir. (VERPE), Viola arvensis Murr. (VIOAR), or Viola tricolor L. (VIOTR). In some embodiments, the compounds and compositions provided herein are used to control unwanted vegetation in grasslands and pastures. In certain embodiments, the unwanted vegetation is Ambrosia artemisiifolia L. (AMBEL), Cassia obtusifolia (CASOB), Centaurea maculosa auct. Lam’s name. (CENMA), Cirsium arvense (L.) Scop. (CIRAR), Convolvulus arvensis L. (CONAR), Euphorbia isula L. (EPHES), Lactuca serriola L. / Torn. (LACSE), Plantago lanceolata L. (PLALA), Rumex obtusifolius L. (RUMOB), Sida spinosa L. (SIDSP), Sinapis arvensis L. (SINAR), Sonchus arvensis L. (SONAR), Solidago species (SOOSS), Taraxacum officinale GH Weber ex Wiggers (TAROF), Trifolium L. or Urtica dioica L. (URTDI). In some embodiments, the compounds and compositions provided herein are used to control unwanted vegetation found in row crops. In certain embodiments, the unwanted vegetation is Alopecurus myosuroides Huds. (ALOMY), Avena fatua L. (AVEFA), Brachiaria platyphylla (Groseb.) Nash. (BRAPP), Digitaria sanguinalis (L.) Scop. (DIGSA), Echinochloa crus-galli (L.) P. Beauv. (ECHCG). IF-2019-79532212-APN-ANP#IN^ Page 46 of 78 Echinochloa colonum (L.) Link (ECHCO), Lolium multiflorum Lam. (LOLMU), Panicum dichotomyflorum Michx. (PANDI), Panicum miliaceum L. (PANMI), Setaria faberi Herrm. (SETFA), Setaria viridis (L.) Beauv. (SETVI), Sorghum halepense (L.) Pers. (SORHA), Sorghum bicolor (L.) Moench ssp. Arundinaceum (SORVU), Cyperus esculentus L. (CYPES), Cyperus rotundus L. (CYPRO), Abutilón theophrasti Medik. (ABUTH), Amaranthus species (AMASS), Ambrosia artemisiifolia L. (AMBEL), Ambrosia psilostachya DC. (AMBPS), Ambrosia trífida L. (AMBTR), Asclepias syriaca L. (ASCSY), Chenopodium album L. (CHEAL), Cirsium arvense (L.) Scop. (CIRAR), Commelina benghalensis L. (COMBE), Datura stramonium L. (DATST), Daucus carota L. (DAUCA), Euphorbia heterophylla L. (EPHHL), Erigeron bonariensis L. (ERIBO), Erigeron canadensis L. (ERICA), Melianthus annuus L. (HELAN), Jacquemontia tamnifolia (L.) Griseb. (IAQTA), Ipomoea hederacea (L.) Jacq. (IPOHE), Ipomoea lacunosa L. (IPOLA), Lactuca serriola L. / Torn.(LACSE), Portulaca oleracea L. (POROL), Sida spinosa L. (SIDSP), Sinapis arvensis L. (SINAR), Solanum ptychanthum Dunal (SOLPT), or Xanthium strumarium L. (XANST). In some embodiments, application rates of approximately 1 to approximately 4,000 grams / hectare (g / ha) are used in post-emergence operations. In some embodiments, IF-2019-795 32212-APN-ANP#INPI Page 47 of 78 They use rates of approximately 1 to approximately 4,000 g / ha in pre-emergence operations. In some embodiments, the compounds, compositions, and methods provided herein are used in conjunction with one or more other herbicides to control a wide variety of unwanted vegetation. When used in conjunction with other herbicides, the compounds claimed herein may be formulated with the other herbicide(s), tank-mixed with the other herbicide(s), or applied sequentially with the other herbicide(s).Some of the herbicides that can be used in conjunction with the compounds described herein 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, 2,4,5-T, 2,4,5-TB, acetochlor, acifluorphen, acloniphene, acrolein, alachlor, alidochlor, aloxidim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralide, amiprophos-methyl, amitrole, ammonium sulfamate, anilophos, anisurone, asulam, atratone, atrazine, azaphenidine, azimsulfurone, aziprothrin, barban, BCPC, beflubutamide, benazoline, bencarbazone, benfluralin, benfuresate, bensulfuron48. IF-2019-79532212-APN-ANP#INPI Page 48 of 78 methyl, bensulide, bentiocarb, bentazone-sodium, benzadox, benzfendizone, benzipram, benzobicyclone, benzofenap, benzofluor, benzoylprop, benzthiazurone, bicyclopyrone, bifenox, bilanafos, bispiribac-sodium, borax, bromacil, bromobonyl, bromobutide, bromophenoxim, bromoxynyl, brompyrazone, butachlor, butafenacyl, butamiphos, butenachlor, butidazole, butyurone, butralin, butroxydim, buturone, butylate, cacodylic acid, cafenstrol, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone ethyl, CDEA, CEPC, chlormethoxyphene, chlorambene, chloranocryl, chlorazifop, chlorazine, chlorbromurone, chlorbufam, chloreturone, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazone, chlorimurone, chlornitrofen, chloropone, chlorotolurone, chloroxurone, chloroxynil, chlorpropham, chlorsulfurone, chlortal, chlortiamide, cinidone-ethyl, cinmethylline, cinosulfurone, cisanilide, clethodim, cliodinate, clodinafop-propargyl, clofop, clomazone,clomeprop, cloprop, cloproxidim, clopyralid, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumilurona, cyanathrine, cyanazine, cycloate, cyclosulfamuron, cycloxidim, cyclorurone, cihalofop-butyl, ciperquat, ciprazine, ciprazol, cypromida, daimuron, dalapon, dazomet, delachlor, desmedifam, desmethrin, di-alate, dicamba, IF-2019-79532212-APN-ANP#INPI Page 49 of 78 dichlobenyl, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, dietamquat, diethylo, diphenopenteno, difenoxurona, difenzoquat, difluíenicane, diflufenzopyr, dimefurona, dimepiperate, dimetaclor, dimethamethrin, dimethenamida, dimethenamida-P, dimexane, dimidazona, dinitramine, dinophenate, dinoprop, dinosaur, dinoseb, dinoterb, difenauiida, dipropetrin, diquat, disul, dithiopir, diurona, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbona, esprocarb, etalfluralin, etbenzamida, etametsulfuron, etidimuron, etiolate, etobenzamide, etobenzamide, ethofumesate, etoxifeno, etoxisulfuron, etinofeno, etnipromida, etobenzanida, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P-ethyl, fenoxaprop-P-ethyl + isoxadifenoethyl, fenoxasulfone, fenteracol, fentiaprop, fentrazamide, fenurone, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin,flufenacet, flufenicano, flufenpir—etilo, flumetsulam, flumezina, flumiclorac— pentilo, flumioxazina, flumipropina, fluometurona, fluorodifeno, fluoroglicofeno, fluoromidina, fluoronitrofeno, fluotiurona, flupoxam, flupropacilo, flupropanato, flupirsulfurona, fluridona, flurocloridona, fluroxipir, flurtamona, flutiacet, fomesafeno, IF-2019-795 32212-APN-ANP#INPI Page 50 of 78 foramsulfuron, fosamine, furiloxifeno, glufosinate, glufosinato-amonio, glyphosate, halosafeno, halosulfuronametilo, haloxidina, haloxifop-metilo, haloxifop-P-metilo, halauxifeno-metilo, hexacloroacetona, hexaflurato, hexazinona, imazametabenz, imazamox, imazapic, imazapir, imazaquina, imazetapir, imazosulfurona, indanofano, indaziflam, yodobonilo, yodomethane, yodosulfurona, iofensulfurona, ioxinilo, ipazina, ipfencarbazona, iprimidam, isocarbamida, isocilo, isometiozina, isonorurona, isopolinato, isopropaline, isoproturona, isouróna, isoxabeno, isoxaclortol, isoxaflutol, isoxapyrifop, karbutylate, cetospiradox, lactofeno, lenacilo, linurona, MAA, MAMA, esters and amines of MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazin, mesosulfurona, mesotriona, metam, metamifop, metamitrona, metazaclor, metazosulfurona, metflurazona, metabenzthiazurona, metalpropalin, metazol, metiobencarb, methiozoline, methiurona, metomethona,metoprothrin, methyl bromide, methyl isothiocyanate, methyldimrone, methobenzurone, metobromurone, metolachlor, metosulam, methoxurone, metribuzin, metsulfurone, molinate, monalide, monisourone, monochloroacetic acid, monolinurone, monurone, morphamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburone, nicosulfurone, IF-2019-795 32212-A PN-A NP# IN P ? Page 51 of 78 nipiraclofeno, nitralina, nitrofeno, nitrofluorfeno, norflurazona, norurona, OCH, orbencarb, orthodichlorobenceno, ortosulfamurona, orizalina, oxadiargilo, oxadiazona, oxapirazona, oxasulfurona, oxaziclomefona, oxifluorfeno, paraflufeno-etilo, paraflurona, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazona, perfluidona, petoxamida, phenisofam, phenmedifam, phenmedifam—ethyl, fenobenzurona, phenylmercury acetate, picloram, picolinafeno, pinoxadeno, piperofos, arsenito de potassium, potassium azide, potassium cyanate, pretilachlor, primisulfuron-methyl, procyazine, prodiamine, profluazol, profluralin, profoxidim, proglinazine, prohexadione-calcium, prometone, prometrine, propachlor, propanil, propaquizafop, propazine, profam, propisoclor, propoxycarbazone, propirisulfuron, propizamida, prosulfaliña, prosulfocarb, prosulfuron, proxano, prinaclor, pidanone, pyraclonilo, pyraflufen, pyrasulfotol, pyrazogilo,pyrazolinate, pyrazosulfurone—ethyl, pyrazoxifen, piribenzoxim, piributicarb, pyrichlor, pyridafol, pyridate, pyriftalide, piriminobac, pirimisulfan, pyrithiobac-methyl, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamide, quizalofop, quizalofop-P-ethyl, rodtanil, rimsulfurone, saflufenacil, S—metolachlor, sebutylazine, IF-2019-795 32212-APN-ANP#INPI Page 52 of 78 secbumetona, setoxidim, sidurona, simazine, simetona, simetrina, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotriona, sulfalate, sulfentrazona, sulforneturona, sulfosate, sulfosulfurona, sulfuric acid, sulglycapine, swep, TCA, tebutam, tebutiurona, tefuryltriona, tembotriona, tepraloxidim, terbacilo, terbucarb, terbuclor, terbumetona, terbuthylazine, terbutrin, tetraflurona, tenilchlor, thiazaflurona, thiazopyr, tidiazimine, tidiazurona, tiencarbazone-methyl, tifensulfurona, thiobencarb, thiocarbazilo, thiochlorim, topramezona, tralcoxidim, triafamona, tri-alato, triasulfurona, triaziflam, tribenurona, tricamba, asteres and triclopyr amines, tridiphane, triethazine, trifloxysulfurona, trifluralin, triflusulfurona, trifop, triphopsime, trihidroxytriazine, trimeturona, tripropindane, tritac, tritosulfurona, vernolate y xylachlor. The compounds and compositions described herein can generally be used in combination with known herbicide protectants such as benoxacor, bentiocarb, brassinolide, cloquintocet (e.g., mexyl), ciometrinil, daimurone, dichlormide, dicyclonone, dimepiperate, disulfotone, fenchlorazoletil, fenchlorim, flurazole, fluxofenim, furylazole, hairpin proteins, isoxadiphenethyl, mefenpyr53 IF-2019-79532212-APN-ANP#INPI Page 53 of 78 diethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinyl, R29148 and N-phenylsulfonylbenzoic acid amides, to improve its selectivity. The compounds, compositions, and methods described herein can be used to control unwanted vegetation in glyphosate-tolerant crops, glufosinate-tolerant crops, dicamba-tolerant crops, phenoxyauxin-tolerant crops, pyridyloxyauxin-tolerant crops, aryloxyphenoxypropionate-tolerant crops, acetyl CoA carboxylase inhibitor (ACCase)-tolerant crops, imidazolinone-tolerant crops, acetolactate synthase (ALS)-tolerant crops, 4-hydroxyphenylpyruvate dioxygenase (HPPD)-tolerant crops, protoporphyrinogen oxidase (PPO)-tolerant crops, triazine-tolerant crops, and bromoxynyl-tolerant crops (such as, but not limited to, soybeans, cotton, canola / oilseed, rice, cereals, corn, turfgrass, etc.).), for example, along with glyphosate, glufosinate, dicamba, phenoxyauxins, pyridyloxyauxins, aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil. The compositions and methods can be used in the control of unwanted vegetation in crops that possess them. IF-2019-79532212-APN-ANP#INPI Page 54 of 78 multiple 'traits stacked traits that confer tolerance to multiple chemicals and / or inhibitors of multiple modes of action. The compounds and compositions provided herein can also be used for the control of herbicide-resistant or tolerant weeds.Examples of 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-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, and herbicides with multiple modes of action. such as quinclorac and non-classified herbicides such as arylaminopropionic acids, difenzoquat, endotall and organoarsenic products.Resistant or tolerant weeds. IF-2019-79532212-APN-ANP#INPI Page 55 of 78 examples include, but are not limited to, biotypes with resistance or tolerance to multiple herbicides, multiple chemical classes, and multiple herbicide modes of action. The embodiments described and the following examples are for illustrative purposes and are not intended to limit the scope of the claims. Other modifications, uses, or combinations with respect to the compositions described herein will be obvious to a person skilled in the art without departing from the spirit and scope of the claimed subject matter. Synthesis of compounds of formula I Preparation of compounds 1, 1A, 1B and 1C. Synthesis procedure for the preparation of compounds 1, 1A, 1B and 1C as detailed below. To 3-bromo-6-chloro-2-fluorobenzaldehyde A (10 g, 42.1 mmol) (Baleo, T. William et al., International Publication No. WO 2007 / 082098, which is incorporated herein by reference in its entirety) 0.5 M sodium methoxide (93 mL, 46.3 mmol) was added. The reaction was heated at 80 °C for 5 h. The reaction IF-2019-795 32212-APN-ANP#INPI Page 56 of 78. The mixture was cooled to room temperature overnight. The methanol was removed under vacuum, and the suspension was redissolved in ethyl acetate and washed twice with water and once with brine. The organic layer was dried on sodium sulfate, filtered, and concentrated to obtain the compound (9.61 g, 90% yield) as a yellow solid. M.P. = 7377 °C; 1H NMR (300 MHz, CDC13) δ 10.41 (s, 1H), 7.68 (d, J = 8.6 Hz, 1H), 7.15 (d, J = 8.6 Hz, 1H), 3.94 (s, 3H); EIMS m / z 250. A 3-bromo-6 - chloro-2-methoxybenzaldehyde B (2.13 g, 8.54 mmol) in dichloromethane (34 mL) at -40 °C. Boron tribromide (17 mL, 17.00 mmol) was added for 10 min. After 1.5 h, the reaction was neutralized with approximately 10 mL of acetonitrile and water and stirred for 10 min. Water (50 mL) was then added, and the biphasic solution was stirred for 1 h. The organic layer was washed with brine and then filtered through a phase separator and concentrated to give the compound (1.97 g, 93% yield) as a yellow solid. m.p. 97–106 °C; τH NMR IF-2019-79532212-APN-ANP#INPI Page 57 of 78 (400 MHz, chloroform-d) δ 12.57 (s, 1H), 10.37 s, 1H), 7.69 (dd, J 8.4, 0.5 Hz, 1H), 6.90 (d, J = 8.5 Hz, 1H); EIMS m / z 236. OH D A 25 mL vial was loaded with 3-bromo-6-chloro-2-hydroxybenzaldehyde C (502 mg, 2.13 mmol) and 1 N sodium hydroxide (2.24 mL, 2.24 mmol) was added. The solid suspension was heated at 50 °C for 5 min. To a vial containing water (3.4 mL), 25 wt% hydrogen peroxide (0.34 mL, 2.77 mmol) was added. The hydrogen peroxide solution was then added to the heated suspension. The reaction was heated for 1 hour longer, then cooled to room temperature and acidified with 2 N HCl. The solution was extracted with ethyl acetate (twice), the organic layers were dried on sodium sulfate, filtered, and concentrated to give the compound (484 mg, 97% yield) as a brown viscous solid. 1H NMR (300 MHz, CDC13) δ 7.01 (dd, J = 8.8, 0.4 Hz, 1H) , 6.83 (dd, J = 8.8, 0.4 Hz, 1H) , 5.67 (s, 2H) ;13C NMR (101 MHz, CDC13) δ 141.70, 140.51, 123.56, 121.50, 119.45, 107.72; EIMS m / z 224. IF-2019-795 32212-APN-ANP#INPI Page 58 of 78 AND A microwave reaction vial was loaded with cesium carbonate (840 mg, 2.58 mmol) followed by 3 bromo-6-chlorobenzene-1,2-diol D (480 mg, 2.15 mmol) in DMF (5.4 mL) and bromochloromethyl (0.168 mL, 2.58 mmol) were added using a syringe. The reaction mixture was heated in a microwave reactor at 60 °C for 2 h. The reaction mixture was then diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate. The organic layers were washed with water and brine. The combined organic layers were dried over sodium sulfate, filtered, and concentrated, then vacuum dried to yield the compound (416 mg, 78% yield) as a brown solid. — 92 97 °C;XH NMR (400 MHz, CDC13) δ 6.92 (d, J = 8.9 Hz, 1H), 6.74 (d, J = 8.9 Hz, 1H), 6.11 (s, 2H); EIMS m / z 235. IF-2019-79532212-APN-ANP#INPI Page 59 of 78 4-Bromo-7-chlorobenzo[d][l,3]dioxol E (3.26 g, 13.6 mmol) was stirred in THF (67 mL). The solution was cooled to 0 °C. Isopropylmagnesium chloride (8.82 mL, 17.6 mmol) (2 M, Et₂O) was added by syringe over 10 minutes. The mixture was stirred at 0 °C. After 5 h, 2-isopropoxy-4,4,5,5-tetramethyl-1,3-dioxolane (3.72 mL, 17.6 mmol) was added dropwise by syringe over 5 minutes. The mixture was stirred and allowed to warm to room temperature. After 22 h, the mixture was poured into saturated NH₄Cl (50 mL). The mixture was extracted with EtOAc (200 mL). The extract was washed with brine (50 mL), dried over Na₂SO₄, filtered, and concentrated to yield the compound (3.96 g, 98% yield) as a light yellow solid. m.p. = 116–118 °C; NMR (400 MHz, chloroform-d) δ 7.15 (d, J = 8.4 Hz, 1H), 6.82 (d, J = 8.4 Hz, 1H), 6.09 (s, 2H), 1.35 (s, 12H) ; EIMS m / z 282 . IF-2019-795 32212-APN-ANP#INPI Page 60 of 78 To a nitrogen-purged solution of 2 (7 chlorobenzo[d] [1,3]dioxol-4-yl)-4,4,5,5 tetramethyl 1,3,2 dioxaborolane F (17.73 g, 62.8 mmol), methyl 4-amino-3,6-dichloro-5-fluoropicolinate G (10 g, 41.8 mmol) (Fields, Stephen C. et al. Tetrahedron Letters, 51(1), 79-81; 2010; which is incorporated herein by reference in its entirety), cesium fluoride (19.07 g, 126 mmol) in CH3CN (76 mL) and water (20 mL) Pd(PPh3)2Cl2 (2.94 g, 4.18 mmol) was added. The mixture was purged with N2 for 10 min while the solids dissolved and then heated under reflux for 4 h. After cooling the mixture to room temperature, the product crystallized. The mixture was filtered and the solid washed with acetonitrile. The filtrate was concentrated to remove most of the acetonitrile, diluted with water, and extracted with ethyl acetate.Ethyl acetate extracts were combined, washed with brine, dried over MgSO4, and concentrated under reduced pressure to give an orange solid. Acetone was added to this solid. This mixture was filtered, and the solid was washed with ether and combined with the first batch to give the compound (13 g, 85% yield) as a yellow solid. f.p. = 198–200 °C; ΔH NMR (400 MHz, chloroform-d) δ 7.10 (dd, J = 8.7, 0.6 Hz, 1H) , 6.95 (d, J = 8.7 Hz, 1H) , 6.10 (s, 2H) , 4.91 (s, 2H) . IF-2019-79532212-APN-ANP#INPI Page 61 of 78 2H), 3.98 (s, 3H) ;19F NMR (376 MHz, CDC13) δ -137.59; ESIMS m / z 360 [(M+H)+] . NH2r A / Ci To methyl 4-amino-3-chloro-6-(7-chlorobenzo[d][1,3]dioxol 4 i1)-5-fluoropicolinate 1A (158 mg, 0.440 mmol) in methanol (2.20 mL), 2 N sodium hydroxide (440 μA, 0.88 mmol) was added. The reaction was acidified with HCl. The nitrogen and methanol were extracted under a stream of nitrogen. The solid was vacuum filtered, rinsed with water, and dried in a vacuum oven to provide the compound (137 mg, 88% yield) as a white solid. f.p. 200–201 °C; ¹H NMR (400 MHz, DMSO-dg) δ 13.62 (s, 1H), 7.06 (s, 2H), 6.95 (s, 2H), 6.20 (s, 2H); ESIMS m / z 345 ( [M+H]+) . NH2r A / Ci IF-2019-79532212-APN-ANP#INPI Page 62 of 78 4-Amino-3-chloro-6-(7-chlorobenzo[d][1,3]dioxo-1-4-yl)-5-fluoropicolinic acid (102 mg, 0.296 mmol) and potassium carbonate (56 mg, 0.405 mmol) in DMF (0.985 mL) were mixed with benzyl bromide (0.042 mL, 0.355 mmol) and the reaction was heated at 60 °C for 4 h. The reaction mixture was loaded directly into a Celite cartridge with acetonitrile and dried in a vacuum oven overnight. The crude product was purified by preparative reversed-phase HPLC (acetonitrile / water gradient) to obtain the compound (89 mg, 69% yield) as a white solid. 155-157 °C;τΗ NMR (400 MHz, CDC13) δ 7.49 - 7.43 (m, 2H), 7.42 - 7.33 (m, 3H), 7.12 (d, J = 8.7 Hz, 1H), 6.94 (d, J = 8.7 Hz, 1H), 6.09 (s, 2H), 5.43 (s, 2H), 4.88 (s, 2H) ;19F NMR (376 MHz, CDC13) δ 137.76; ESIMS m / z 435 ([M+H]+). acid 4-amino-3-chloro-6-(7-chlorobenzo[d][1,3]dioxol-4-i1)-5-fluoropicholinic 1 (105 IF-2019-795 32212-APN-ANP#INPI Page 63 of 78 0.304 mmol) and potassium carbonate (75 mg, 0.543 mmol) in DMF (0.985 mL) were joined by 3-bromoprop-1-yne (0.039 mL, 0.365 mmol) and the reaction was heated to 60 °C. The reaction mixture was loaded directly into a Celite cartridge with acetonitrile and dried in a vacuum oven overnight. The crude product was purified by preparative reversed-phase HPLC (acetonitrile / water gradient) to obtain the compound (63 mg, 54% yield) as a brown solid. M.P. 163–168 °C; ''H NMR (400 MHz, CDC13) δ 7.12 (d, J = 8.6 Hz, 1H) , 6.95 (d, J = 8.7 Hz, 1H) , 6.10 (s, 2H) , 4.97 (d, J = 2.5 Hz, 2H) , 4.92 (s, 2H) , 2.53 (t, J = 2.5 Hz, 1H) ;19F NMR (376 MHz, CDC13) δ 137.10; ESIMS m / z 383 ([M+H]+) IF-2019-795 32212-APN-ANP#INPI Page 64 of 78 Compounds 2-15 were prepared as described in US Patent No. 9,149,038, which is incorporated herein by reference in its entirety. The structure of compounds 1-15 is shown in the following table. IF-2019-795 32212-APN-ANP#INPI Page 65 of 78 IF-2019-795 32212-APN-ANP#INPI Page 66 of 78 IF-2019-79532212-APN-ANP#IN^? Page 67 of 78 IF-2019-795 32212-APN-ANP#INPI Page 68 of 78 EXAMPLES Example 1. Evaluation of herbicidal activity Post-emergence trial: Seeds or nuts of the desired plant species were sown in Sun Gro Metro-Mix® 360 planting mix, which typically has a pH of 6.0 to 6.8 and an organic matter content of approximately 30%, in plastic pots with a surface area of ​​64 square centimeters (cm2). When required to ensure good germination and healthy plants, a fungicide and / or other chemical or physical treatment was applied. The plants were grown for 7–21 days in a greenhouse with an approximate photoperiod of 15 h that remained at approximately 23-29 °C during IF-2019-795 32212-APN-ANP#INPI Page 69 of 78 During the day, temperatures were kept at 22–28 °C, and at night. Nutrients and water were added regularly, and supplemental lighting was provided with several 1000-watt metal halide overhead lamps as needed. Plants were used for testing when they reached the first or second true leaf stage. A weighted amount, determined by the maximum rate to be tested, of each test compound was placed in a 25 mL glass vial and dissolved in 4 mL of a 97:3 v / v mixture of acetone and DMSO to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was heated and / or sonicated. The resulting concentrated stock solutions were diluted with 20 mL of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, Atplus 411F culture oil concentrate, and Triton0X-155 surfactant in a 48.5:39:10:1.5:1.0:0.02 v / v ratio to obtain spray solutions with the highest application rates.Additional application rates were obtained by serial dilution of 12 mL of the high rate solution into a solution containing 2 mL of 97:3 v / v acetone and DMSO mixture and 10 mL of an aqueous mixture containing acetone, water, isopropyl alcohol, DMSO, Atplus 411F culture oil concentrate and Triton X155 surfactant in a ratio of 48.5:39:10:1.5:1.0:0.02. IF-2019-795 3221 2-APN-ANP#InÍ>? Page 70 of 78 v / v to obtain rates of 1 / 2X, 1 / 4X, 1 / 8X, and 1 / 16X of the high rate. Compound requirements are based on an application volume of 12 mL at a rate of 187 liters per hectare (L / ha). The formulated compounds were applied to the plant material using a Mandel overhead bag sprayer equipped with 8002E nozzles calibrated to deliver 187 L / ha over an application area of ​​0.503 square meters at a spray height of 18 inches (43 cm) above the average height of the plant canopy. Control plants were sprayed in the same manner with the white solvent. The treated and control plants were placed in a greenhouse as previously described and irrigated by subirrigation to avoid washing off the test compounds. After 14 days, the condition of the test plants compared to that of the untreated plants was visually determined and rated on a scale of 0 to 100%, where 0 corresponds to no injury and 100 corresponds to complete death. Some of the compounds tested, application rates used, plant species tested, and results are provided in Tables 1 and 2. These results are also plotted in Figures 1A-4B. As shown in Tables 1-2 and Figures 1A-4B, IF-2019-79532212-APN-ANP#INPI Page 71 of 78 the compounds of formula I (for example, compound 1) exhibit significantly improved herbicidal activity compared to a number of compounds of similar structure (e.g., compounds 2-15). The improved activity of compounds of formula I (e.g., compound 1) compared to a number of compounds of similar structure (e.g., compounds 2-15) was unexpected. IF-2019-795 32212-APN-ANP#INPI Page 72 of 78 Table 1 Post-emergence Po herbicidal activity of compounds 1-15 on key broadleaf weed species 0 oa Application rate (g ai / ha) Visual growth reduction (%) 14 days after application ABUTH BRSNN CIRAR EPHHL IPOHE VIOTR 1 17.5 80 55 85 0 0 40 35 85 100 85 0 0 60 70 90 100 95 5 10 70 140 95 100 90 15 15 95 IA 17.5 85 78 83 3 0 53 35 90 88 83 10 0 95 70 93 95 88 13 0 75 140 95 98 93 18 0 90 IB 17.5 90 95 75 10 0 40 35 95 100 80 10 0 75 70 100 100 85 15 0 60 140 100 100 90 10 10 75 1C 17.5 100 95 70 10 0 65 35 100 97 85 10 0 65 70 100 100 90 10 0 60 140 100 100 90 25 10 65 2 17.5 50 30 60 0 0 0 35 60 40 100 0 0 0 70 75 85 98 0 10 0 140 95 90 98 0 25 10 3 17.5 60 60 70 0 0 0 35 80 80 85 0 0 15 70 95 95 95 0 0 30 140 95 98 95 0 0 35 4 17.5 70 85 80 0 0 0 IF-2019-795 32212-APN-ANP#INPI Page 73 of 78 c. No. Application Rate (g ai / ha) Visual Growth Reduction (%) 14 days after application ABUTH BRSNN CI RAR EPHHL IPOHE VIOTR 35 80 90 90 0 10 0 70 80 95 95 0 10 20 140 85 95 90 0 30 35 5 17.5 10 75 60 0 0 0 35 20 80 70 0 0 0 70 40 85 75 0 0 10 140 50 95 80 0 10 10 6 17.5 75 80 70 2 0 3 35 77 82 77 0 3 12 70 80 92 85 2 3 30 140 83 97 88 7 10 53 7 17.5 50 50 60 0 0 5 35 70 60 70 0 0 10 70 75 80 75 10 0 40 140 85 85 80 20 0 50 8 17.5 30 70 20 0 0 0 35 40 75 75 0 0 5 70 60 85 80 0 10 15 140 75 97 80 0 10 35 9 17.5 80 60 70 0 0 0 35 85 60 80 0 0 0 70 85 75 85 0 0 20 140 85 75 85 0 0 20 10 17.5 65 50 60 0 0 0 35 70 60 70 0 0 0 70 75 65 70 0 0 0 140 75 70 75 0 0 0 11 17 , 5 50 90 80 0 0 0 35 70 90 85 0 0 0 70 80 90 90 0 0 0 140 85 90 90 0 0 20 IF-2019-795 32212-APN-ANP#INPI Page 74 of 78 3 Q 0 Application rate (g ai / ha) Visual growth reduction (%) 14 days after application ABUTH BRSNN CIRAR EPHHL IPOHE VIOTR 12 17.5 0 70 65 0 0 0 35 0 80 80 0 0 0 70 70 90 85 0 0 0 140 80 100 85 0 0 0 13 17.5 30 40 50 0 0 0 35 50 60 60 0 10 0 70 75 70 80 0 20 0 140 80 80 85 0 3 0 0 14 17 , 5 43 90 78 0 3 5 35 53 95 83 0 3 13 70 73 98 85 0 8 43 140 80 100 90 10 13 58 15 17.5 70 20 80 0 0 30 35 85 40 85 0 0 60 70 90 95 90 0 0 70 140 100 100 95 0 0 80 ABUTH: Abutilon theophrasti) BRSNN: Brassica napus CIRAR: Cirsium arvense EPHHL: Euphorbia heterophylla IPOHE: Ipomoea hederacea VIOTR: Viola tricolor g ai / ha: grams of active ingredient per hectare n / t: not tested IF-2019-795 32212-APN-ANP#INPI Page 75 of 78 Table 2 Post-emergence herbicidal activity of compounds 1-15 on key grass weed species C. No. Application Rate (g ai / ha) Visual Growth Reduction (%) 14 days after application CYPES DIGSA ECHCG SETFA SORVU 1 17.5 35 0 0 10 35 35 40 20 0 10 35 70 80 30 30 35 50 140 90 50 40 50 60 IA 17.5 78 5 8 15 25 35 83 20 18 15 43 70 83 50 28 25 55 140 80 28 30 30 65 IB 17.5 75 0 0 0 25 35 85 0 0 0 50 70 85 20 0 20 60 140 90 50 0 50 85 1C 17.5 30 0 0 0 10 35 80 0 0 0 50 70 85 0 0 50 70 140 80 60 0 60 70 2 17.5 0 0 0 0 0 35 0 0 0 0 0 70 10 0 0 0 0 140 30 0 0 0 0 3 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 0 140 0 0 0 0 0 4 17.5 0 0 0 0 0 35 20 0 0 0 0 IF-2019-795 32212-APN-ANP#INPI Page 76 of 78 C.N. ° Application rate (g ai / ha) Visual growth reduction (%) 14 days after application CYPES DIGSA ECHCG SETFA SORVU 70 50 0 0 0 0 140 50 0 0 0 0 5 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 0 140 0 0 0 0 0 6 17.5 30 0 0 0 0 35 25 0 0 0 2 70 25 0 3 0 10 140 60 0 3 3 23 7 17 , 5 0 0 0 0 0 35 10 0 0 0 0 70 30 0 0 0 0 140 40 0 0 10 0 8 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 0 140 10 0 0 0 0 9 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 10 140 0 0 0 0 10 10 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 0 140 0 0 0 0 0 11 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 0 IF-2019-79532212-APN-ANP#ní?I Page 77 of 78 C . N. ° Application rate (g ai / ha) Visual growth reduction (%) 14 days after application CYPES DIGSA ECHCG SETFA SORVU 140 0 0 0 0 10 12 17.5 0 0 0 0 0 35 0 0 0 0 0 0 0 13 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 140 0 0 0 0 0 14 17.5 0 0 0 0 0 35 10 0 0 0 3 70 30 0 0 0 13 140 50 5 5 0 30 15 17.5 0 0 0 0 0 35 0 0 0 0 0 70 0 0 0 0 0 140 0 0 0 20 20 CYPES: Cyperus esculentus DIGSA: Digitaria sanguinalis ECHCG: Echinochloa crus-galli SETFA: Setaria faberi SORVU: Bicolor sorghum g ai / ha: grams of active ingredient per hectare n / t: not assayed

Claims

1. A compound characterized in that the compound is defined by formula IA: FORMULA wherein R1 is hydrogen, C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, phenyl, substituted phenyl, or C7-12 arylalkyl; R2 is a halogen; and R3 and R4 are both hydrogen; or one of their salts or N-oxides acceptable in agriculture. Nine claims follow.