Weed Control Methods

Abstract

The present invention relates to the use of a compound of formula (I) or an agriculturally acceptable salt thereof as a herbicide, wherein R1, R2, R3, R4, R5 and R6 are as defined herein. The present invention further relates to herbicidal compositions comprising a compound of formula (I) and in particular to the use of a compound of formula (I) for controlling weeds in crops of useful plants. TIFF2024518834000061.tif40105

Description

[Technical field]

[0001] This invention relates to the use of certain compounds as herbicides, to herbicidal compositions containing such compounds, and to their use, especially for controlling weeds or inhibiting the growth of plants in crops of useful plants. Summary of the Invention

[0002] The present invention is based on the finding that certain difluorophenylacetic acids of formula (I) as defined herein exhibit unexpectedly good herbicidal activity. Thus, according to the present invention, the use of difluorophenylacetic acids of formula (I) as herbicides is [ka] (In the formula, each R1, R2, R4, and R5 is independently selected from the group consisting of hydrogen, halogen, amino, cyano, nitro, hydroxyl, C1-C5 alkyl, C3-6 cycloalkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, halophenyl, C1-2 haloalkyl, C1-2 alkoxyC1-2 alkyl, C1-2 alkoxycarbonyl, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, and C1-C2 alkylsulfonyl, and only one of R1, R2, R4, and R5 is C1-C4 alkoxy; or R1 and R2 together with the carbon atom to which they are attached form a 5- or 6-membered ring, the 6-membered ring contains 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), and the 5-membered ring contains 1 or 2 heteroatoms independently selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl; R3 is selected from the group consisting of hydrogen, halogen, amino, cyano, hydroxyl, C1-C5 alkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, and halophenyl; At least one of R1, R2, R3, R4, and R5 is selected from the group consisting of amino, cyano, nitro, hydroxyl, C2-C5 alkyl, C3-6 cycloalkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, halophenyl, C2 haloalkyl, C1-2 alkoxyC1-2 alkyl, C1-2 alkoxycarbonyl, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, and C1-C2 alkylsulfonyl; or R1 and R2, together with the carbon atom to which they are attached, form a 5- or 6-membered ring, the 6-membered ring containing 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), and the 5-membered ring contains 1 or 2 heteroatoms independently selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl; and R6 is selected from the group consisting of hydrogen, benzyl and C1-C3 alkyl. or an agriculturally acceptable salt of said compound.

[0003] According to a second aspect of the present invention, there is provided an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingredient.

[0004] According to a third aspect of the present invention there is provided a method for controlling or preventing undesired plant growth, wherein a herbicidally effective amount of a compound of formula (I) or a composition comprising this compound as an active ingredient is applied to the plant, its part or its habitat. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0006] As used herein, cyano refers to the group -CN.

[0007] As used herein, hydroxy or hydroxyl refers to an --OH group.

[0008] As used herein, nitro refers to the group --NO.sub.2.

[0009] As used herein, amino refers to the group --NH.

[0010] As used herein, the term "C1-C5 alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having 1 to 5 carbon atoms, and attached to the remainder of the molecule by a single bond. C1-C3 alkyl and C1-C2 alkyl should be construed accordingly. Examples of C1-C5 alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (t-butyl).

[0011] As used herein, "C 3-8 The term "cycloalkyl" refers to a stable monocyclic ring radical that is saturated and contains 3 to 8 carbon atoms. 3-6 Cycloalkyl should be construed accordingly. 3-8 Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0012] As used herein, the term "C1-C4 alkoxy" refers to a group of the formula -OR a R refers to the group a is generally a C1-C4 alkyl group as defined above. C1-C2 alkoxy should be interpreted accordingly. 1-4Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and t-butoxy.

[0013] As used herein, "C 1-4 Alkoxy C 1-4 The term "alkyl" generally refers to a group in which Rb is C as defined above. 1-4 is an alkyl group and generally as defined above, 1-4 It refers to a group of the formula Rb-O-Ra- which is an alkylene group.

[0014] As used herein, the term "C1-C2 haloalkyl" refers to a C1-C2 alkyl group, generally as defined above, substituted by one or more identical or different halogen atoms. C2 haloalkyl should be interpreted accordingly. Examples of C1-C2 haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.

[0015] As used herein, the term "C2-C3 alkenyl" refers to a straight or branched hydrocarbon chain radical group composed solely of carbon and hydrogen atoms, containing at least one double bond which may be in either the (E) or (Z) configuration, having 2-3 carbon atoms and attached to the remainder of the molecule by a single bond. Examples of C2-C3 alkenyl include, but are not limited to, ethenyl, prop-1-enyl, and allyl (prop-2-enyl).

[0016] As used herein, the term "C2-C3 alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having 2-3 carbon atoms and attached to the rest of the molecule by a single bond. Examples of C2-C3 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, and propargyl (prop-2-ynyl).

[0017] As used herein, the term "C1-C2 haloalkoxy" refers to a C1-C2 alkoxy group as defined above substituted with one or more same or different halogen atoms. Examples of C1-C2 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

[0018] As used herein, "C 1-2 The term "alkylsulfanyl" generally refers to R a C 1-2 The alkyl group of the formula -SR a Refers to the group.

[0019] As used herein, "C 1-2 The term "alkylsulfinyl" generally refers to R a C 1-2 Alkyl groups of the formula -S(O)R a Refers to the group.

[0020] As used herein, "C 1-2 The term "alkylsulfonyl" generally refers to R a C 1-2 Alkyl groups of the formula -S(O)R a Refers to the group.

[0021] As used herein, "C 1-4 The term "alkoxycarbonyl" generally refers to an alkoxy group in which Ra is C as defined above. 1-4 It refers to a group of the formula RaOC(O)-, which is an alkyl group.

[0022] As used herein, "C 1-3 Alkoxycarbonyl C 1-3 The term "alkyl" generally refers to R a C1-3 R is an alkyl group and is generally as defined above b C 1-3 Alkylene group of formula -R b C(O)OR a Refers to the group.

[0023] The presence of one or more optionally asymmetric carbon atoms in the compounds of formula (I) means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms. Astrogenic isomers can also occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers, if present, including lactam-lactim tautomerism and keto-enol tautomerism. The present invention includes all possible tautomeric forms for the compounds of formula (I). Similarly, disubstituted alkenes, if present, can exist in E or Z form or as a mixture of both in any proportion. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I).

[0024] The compounds of formula (I) are typically provided in the form of an agriculturally acceptable salt, a zwitterion, or an agriculturally acceptable salt of a zwitterion. The present invention encompasses all such agriculturally acceptable salts, zwitterions, and mixtures thereof in all proportions.

[0025] Suitable agriculturally acceptable salts of the present invention may have cations including, but not limited to, metals, conjugate acids of amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc.Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, Examples of suitable amines include amine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine.Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

[0026] In a preferred embodiment, the agriculturally acceptable salt is selected from the group consisting of sodium, potassium, aluminum, dimethylamine (DMA), diglycolamine (DGA) and choline salts, in a particularly preferred embodiment, the agriculturally acceptable salt is a choline salt.

[0027] The following list includes substituents R related to the compounds of formula (I) according to the present invention: 1 , R 2 , R 3 , R 4 , R 5 and R 6 Definitions, including preferred definitions, are provided for: Any of the definitions given below for any one of these substituents may be combined with any definition of any other substituent given below or elsewhere in this specification.

[0028] Preferably, R 1 is hydrogen, halogen, amino, cyano, nitro, hydroxyl, C1-C5 alkyl, C3-C4 cycloalkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, halophenyl and C 1-2It is preferably selected from the group consisting of hydrogen, fluorine, chlorine, nitro, cyano, C1-C4 alkyl, cyclopropyl, methylsulfanyl, amino and C1-C3 alkoxy, most preferably hydrogen, chlorine, cyano, nitro, methoxy, ethyl, cyclopropyl, ethoxy and isopropoxy.

[0029] Preferably, R 2 is hydrogen, halogen, amino, cyano, nitro, hydroxyl, C1-C5 alkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, halophenyl and C 1-2 Alkylsulfanyl, more preferably selected from the group consisting of hydrogen, bromine, fluorine, chlorine, cyano, ethenyl, ethynyl, methyl, ethyl, methylsulfanyl, methoxy, amino and fluorophenyl, most preferably hydrogen, chlorine, cyano, ethynyl, methylsulfanyl and methoxy.

[0030] Preferably, R1 and R2 together with the carbon atom to which they are attached form a 5-membered ring containing 1 or 2 heteroatoms independently selected from the group consisting of nitrogen and oxygen, more preferably 2 oxygen atoms. Preferably, the 5-membered ring is partially saturated, most preferably the 5-membered ring is saturated. Preferably, the 5-membered ring is substituted by 1 or 2 substituents independently selected from the group consisting of fluorine, chlorine and methyl, more preferably the 5-membered ring is substituted by 2 fluorines.

[0031] Preferably, R1 and R2 together with the carbon atom to which they are attached form a 6-membered ring containing 0, 1 or 2 nitrogen atoms, with the proviso that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), more preferably the 6-membered ring contains 0 or 1 nitrogen.Preferably, the 6-membered ring is aromatic.Preferably, the 6-membered ring is substituted by 0 or 1 substituent.When substituted, the substituent is preferably chlorine.

[0032] Preferably, R3 is selected from the group consisting of hydrogen, halogen, amino, cyano, hydroxyl, C1-C5 alkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy and halophenyl, more preferably hydrogen, amino, trifluoromethoxy, methyl, tert-butyl and methoxy, and most preferably hydrogen.

[0033] Preferably, R 4 is selected from the group consisting of hydrogen, amino, fluorine, chlorine, methoxy, more preferably hydrogen.

[0034] Preferably, R 5 is selected from the group consisting of hydrogen, fluorine, chlorine, amino, nitro and methoxy, more preferably hydrogen, chlorine and methoxy.

[0035] Preferably, R 6 is selected from the group consisting of hydrogen and C1-C3 alkyl, more preferably hydrogen.

[0036] A preferred subset of compounds are Each of R1, R2, R4, and R5 is selected from the group consisting of hydrogen, halogen, amino, cyano, nitro, hydroxyl, C1-C5 alkyl, C3-6 cycloalkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, halophenyl, C1-2 alkoxyC1-2 alkyl, C1-2 alkoxycarbonyl, and C 1-2 alkylsulfanyl, and only one of R1, R2, R4, and R5 is C1-C4 alkoxy; or R1 and R2 together with the carbon atom to which they are attached form a 5- or 6-membered ring, the 6-membered ring contains 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), and the 5-membered ring contains 1 or 2 heteroatoms selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl; R3 is selected from the group consisting of hydrogen, halogen, amino, cyano, hydroxyl, C1-C5 alkyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, and halophenyl; At least one of R1, R2, R3, R4, and R5 is selected from the group consisting of amino, cyano, nitro, hydroxyl, C2-C5 alkyl, cyclopropyl, C1-C4 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 haloalkoxy, halophenyl, C1-2 alkoxyC1-2 alkyl, C1-2 alkoxycarbonyl, and C1-C2 alkylsulfanyl; or R1 and R2, together with the carbon atom to which they are attached, form a 5- or 6-membered ring, the 6-membered ring contains 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), and the 5-membered ring contains 1 or 2 heteroatoms selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl; and R6 is selected from the group consisting of hydrogen and C1-C3 alkyl.

[0037] A more preferred subset of compounds are Each R1, R2, R4, and R5 is independently selected from the group consisting of hydrogen, chlorine, cyano, nitro, methoxy, ethyl, ethoxy, isopropoxy, ethynyl, and methylsulfanyl; or R1 and R2 together with the carbon atom to which they are attached form a 5- or 6-membered ring, the 6-membered ring is aromatic and contains 0 or 1 nitrogen, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), the 5-membered ring is partially or fully saturated and contains 2 oxygens in the ring, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl; R3 is hydrogen; At least one of R1, R2, R3, R4, and R5 is selected from the group consisting of cyano, nitro, methoxy, ethyl, ethoxy, isopropoxy, ethynyl, and methylsulfanyl; or R1 and R2, together with the carbon atom to which they are attached, form a 5- or 6-membered ring, the 6-membered ring contains 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), and the 5-membered ring contains 1 or 2 heteroatoms selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl; and R6 is hydrogen.

[0038] Example Table Table 1 below lists 477 specific compounds of formula (I), designated compound numbers 1-1 through 1-477, respectively. 6 is hydrogen).

[0039] [Table 1] TIFF2024518834000004.tif250146 TIFF2024518834000005.tif251144 TIFF2024518834000006.tif249144 TIFF2024518834000007.tif249145 TIFF2024518834000008.tif249145 TIFF2024518834000009.tif250145 TIFF2024518834000010.tif249145 TIFF2024518834000011.tif250145 TIFF2024518834000012.tif249145 TIFF2024518834000013.tif250145 TIFF2024518834000014.tif250145 TIFF2024518834000015.tif249145 TIFF2024518834000016.tif249146 TIFF2024518834000017.tif250146 TIFF2024518834000018.tif134151

[0040] 477 compounds of formula (I), 6 is methyl and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 2-1 through 2-477, respectively.

[0041] 477 compounds of formula (I), 6 is ethyl and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 3-1 through 3-477, respectively.

[0042] 477 compounds of formula (I), 6 is benzyl and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 4-1 through 4-477, respectively.

[0043] 477 compounds of formula (I), 6 is lithium and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 5-1 through 5-477, respectively.

[0044] 477 compounds of formula (I), 6 is sodium and R 1 ~R5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 6-1 through 6-477, respectively.

[0045] 477 compounds of formula (I), 6 is ammonium and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 7-1 through 7-477, respectively.

[0046] 477 compounds of formula (I), 6 is diisopropylammonium, and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 8-1 through 8-477, respectively.

[0047] 477 compounds of formula (I), 6 is N,N,N-trimethylethanolammonium, and R 1 ~R 5 are as given in Table 1 for Compounds 1-1 through 1-477) are designated as Compound Nos. 9-1 through 9-477, respectively.

[0048] The compounds of the present invention can be prepared by techniques known to those skilled in the art of organic chemistry. General methods for preparing compounds of formula (I) are described below. Unless otherwise specified in the text, the substituent R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is as defined herein above. The starting materials used for the preparation of the compounds of the present invention can be purchased from ordinary commercial suppliers or prepared by known methods. The starting materials and intermediates can be purified by conventional techniques, such as chromatography, crystallization, distillation and filtration, prior to use in the next step.

[0049] Compounds of formula (I) can be prepared from esters of formula (A) as shown in Reaction Scheme 1.

[0050] Reaction Scheme 1 [ka] For example, a compound of formula (A) (wherein R6 represents methyl or ethyl) may be treated with a base, such as lithium hydroxide, in a suitable solvent, such as a mixture of ethanol and water.

[0051] Compounds of formula (A) can be prepared from an aryl halide of formula (B) and an alkyl halide of formula (C) as shown in Reaction Scheme 2.

[0052] Reaction Scheme 2 [ka] For example, a mixture of a compound of formula (B) and a compound of formula (C) (wherein R6 represents methyl or ethyl) may be treated with a metal such as copper in a suitable solvent such as dimethylsulfoxide.

[0053] The aryl bromides or aryl iodides of formula (B) are either commercially available or can be prepared by methods known in the literature.

[0054] Alkyl bromides or alkyl iodides of formula (C) are either available or can be prepared by methods known in the literature.

[0055] Alternatively, compounds of formula (A) can be prepared from ketones of formula (D) as shown in Reaction Scheme 3.

[0056] Reaction Scheme 3 [ka] For example, a compound of formula (D) may be treated with a fluorinating agent, such as diethylaminosulfur trifluoride, in a suitable solvent, such as dichloromethane.

[0057] Ketones of formula (D) can be prepared from aryl halides of formula (E) as shown in Reaction Scheme 4.

[0058] Reaction Scheme 4 [ka] For example, a mixture of compounds of formula (E) (wherein Hal represents a halogen atom, for example a chlorine, bromine or iodine atom) may be treated in a suitable solvent such as tetrahydrofuran with a base such as n-butyllithium, and a reagent such as dimethyl oxalate or oxalyl chloride followed by ethanol.

[0059] Aryl halides of formula (E) are either commercially available or can be prepared by methods known in the literature.

[0060] Compounds of formula (A) can be prepared from esters of formula (F) as shown in Reaction Scheme 5.

[0061] Reaction Scheme 5 [ka] For example, a mixture of compounds of formula (F) (wherein R6 represents methyl or ethyl) may be treated with a base, such as potassium bis(trimethylsilyl)amide, and a fluorinating agent, such as N-fluorobenzenesulfonimide, in a suitable solvent, such as tetrahydrofuran.

[0062] Compounds of formula (F) can be prepared from acids of formula (G) as shown in Reaction Scheme 6.

[0063] Reaction Scheme 6 [ka] For example, a mixture of a compound of formula (G) may be treated with a chlorinating agent, such as oxalyl chloride, and an alcohol, such as methanol, in a suitable solvent, such as dichloromethane.

[0064] Compounds of formula (G) can be prepared from acids of formula (H) as shown in Reaction Scheme 7.

[0065] Reaction Scheme 7 [ka] For example, a mixture of a compound of formula (H) can be treated with an oxidant, such as a mixture of ruthenium(III) chloride and sodium periodate in a suitable solvent, such as a mixture of water, acetonitrile and ethyl acetate, followed by the addition of sodium disulfite in a suitable solvent, such as water.

[0066] The aryl aromatic compounds of formula (H) are either commercially available or can be prepared by methods known in the literature.

[0067] Compounds of formula (I) can be prepared from esters of formula (A) as shown in Reaction Scheme 8.

[0068] Reaction Scheme 8 [ka] For example, a compound of formula (A) (wherein R6 represents methyl or ethyl) may be treated with an acid, such as concentrated HCl, in a suitable solvent, such as water.

[0069] Compounds of formula (A) can be prepared from an aryl halide of formula (B) and an alkyl halide of formula (C) as shown in Reaction Scheme 2.

[0070] Compounds of formula (A) can be prepared from aromatic compounds of formula (J) and alkyl halides of formula (C) as shown in Reaction Scheme 9.

[0071] Reaction Scheme 9 [ka] For example, a mixture of a compound of formula (C) and a compound of formula (J) may be treated with a metal complex, such as potassium phosphate, in a suitable solvent, such as dimethylsulfoxide with an iridium complex.

[0072] The phenyl compounds of formula (J) and the alkyl halides of formula (C) are either commercially available or can be prepared by methods known in the literature.

[0073] Compounds of formula (A) can be prepared from aromatic compounds of formula (J) and fluoro-alkylsilanes of formula (K) as shown in Reaction Scheme 10.

[0074] Reaction Scheme 10 [ka] For example, a mixture of a compound of formula (J) and a compound of formula (K) (wherein R6 represents methyl or ethyl) may be treated with a metal complex, such as potassium fluoride, in a suitable solvent, such as dichloromethane, together with a Lewis acid, such as silver trifluoromethanesulfonate.

[0075] Aryl species of formula (J) are either commercially available or can be prepared by methods known in the literature.

[0076] Fluoro-alkylsilanes of formula (K) are either available or can be prepared by methods known in the literature.

[0077] Compounds of formula (A) can be prepared from aromatic compounds of formula (J) and alkyl halides of formula (C) as shown in Reaction Scheme 11.

[0078] Reaction Scheme 11 [ka] For example, a compound of formula (J) and a compound of formula (C) (wherein R6 represents methyl or ethyl) may be treated with a metal complex, such as ferrocene, and hydrogen peroxide in a suitable solvent, such as dimethylsulfoxide.

[0079] Aryl species of formula (J) are either commercially available or can be prepared by methods known in the literature.

[0080] Alkyl bromides or alkyl iodides of formula (C) are either available or can be prepared by methods known in the literature. Compounds of formula (L) can be prepared from aryl bromides of formula (M) as shown in Reaction Scheme 12.

[0081] Reaction Scheme 12 [ka] For example, a compound of formula (M) may be treated with a metal, such as copper(I) iodide, and an iodine source, such as sodium iodide, in a suitable solvent, such as acetonitrile.

[0082] Aryl bromides of formula (M) are either commercially available or can be prepared by methods known in the literature.

[0083] Those skilled in the art will appreciate that it is often possible to vary the order in which the transformations described above are carried out or combine them in alternative ways to prepare a wide range of compounds of formula (I). Several steps may also be combined into a single reaction. All such variations are considered to be within the scope of the present invention.

[0084] Those skilled in the art will recognize that some reagents may be substituted with certain values ​​or substituents R as defined herein. 1 , R 2 , R 3 , R 4 , R 5 and R 6and any additional steps, such as protection and / or deprotection steps, that are necessary to achieve the desired transformation will be apparent to one of skill in the art.

[0085] The compounds according to the present invention can be used as herbicides in unmodified form, but are generally formulated into compositions in various ways using formulation auxiliaries such as carriers, solvents and surfactants.The formulations can be in various physical forms, such as dusts, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or water-miscible organic solvents as carriers), impregnated polymer films or other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010).Water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble granules are preferred.Such formulations can be used directly or can be diluted before use. Dilution can be done, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0086] The formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain a composition in the form of a finely divided solid, granules, a solution, a dispersion or an emulsion. The active ingredient can also be formulated with other auxiliaries, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.

[0087] The active ingredient can also be contained in fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules usually have a diameter of 0.1 to 500 microns. The microcapsules contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient can be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the substrate, but the microcapsules themselves are not encapsulated.

[0088] Formulation auxiliaries suitable for the preparation of the compositions according to the invention are known per se. Liquid carriers include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, Oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc. may be used.

[0089] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials.

[0090] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations which may be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic or polymeric and can be used as emulsifying agents, wetting agents or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylaryl sulfonic acids, such as calcium dodecylbenzene sulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalene sulfonic acids, such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters, such as those described in, for example, McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New York, 1989. Also included are further substances described in Jersey (1981).

[0091] Further auxiliaries which can be used in the agrochemical formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, flow regulators, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0092] The composition according to the invention may contain an additive comprising an oil of vegetable or animal origin, a mineral oil, an alkyl ester of such oil or a mixture of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally 0.01-10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture is prepared. Preferred oil additives include mineral oil or oil of vegetable origin (e.g. rapeseed oil, olive oil or sunflower oil), emulsified vegetable oil, alkyl ester of oil of vegetable origin (e.g. methyl derivatives) or oil of animal origin (e.g. fish oil or beef tallow, etc.). Preferred oil additives are C8-C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Compendium of Herbicide Adjuvants, 10 th A large number of oil derivatives are known from the Journal of Chemical Industry, Vol. 13, No. 1, 2010, Issue 1, Springer-Verlag, 2010.

[0093] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of formula (I) and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surfactant. The compositions of the invention generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of the invention and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surfactant. Commercial products may preferably be formulated as concentrates, but end users will usually use dilute formulations.

[0094] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied at a rate of 1-2000 l / ha, especially 10-1000 l / ha.

[0095] A preferred formulation may have the following composition (% by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0096] Spraying agent: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0097] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%

[0098] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0099] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0100] The composition of the present invention can further comprise at least one additional pesticide.For example, the compound according to the present invention can also be used in combination with other herbicides or plant growth regulators.In a preferred embodiment, the additional pesticide is a herbicide and / or a herbicide safener.

[0101] The compounds of the present invention can also be used in mixtures with one or more herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, aminocarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, vilanaphos, bipyrazone, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfen, Trazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clasifos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and its 2-ethylhexyl ester), 2,4-DB, desalination, Medipham, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, difluhenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epirifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, Fenpyrazone, fenquinotrion, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-p-butyl), flucarbazone (including flucarbazone-sodium), flufenacet, flumetsulam, flumioxazin, fluometuron, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron,Glufosinate (including L-glufosinate and both ammonium salts), glyphosate (including its diammonium, isopropylammonium and potassium salts), haloxifen (including haloxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium). mesosulfuron (including mesosulfuron-methyl), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozoline, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor , primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-p-ethyl and quizalofop-p-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metolac rol, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, thiaphenacyl, torpiralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazine, trifluralin, triflusulfuron, tripyrasulfone,3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethyl 4-Hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-Hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-Hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (and its agriculturally acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate prop-2-ynyl and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid prop-2-ynyl. -(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate cyanomethyl), 3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]ethyl acetate, and 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one.

[0102] The mixing partners of the compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

[0103] The compounds of formula (I) may also be used in mixtures with other agricultural chemicals such as fungicides, nematicides or insecticides (examples of which are given in The Pesticide Manual).

[0104] The mixing ratio of the compound of formula (I) to the mixing partners is preferably 1:100 to 1000:1.

[0105] The mixtures can be advantageously used in the abovementioned formulations (in which case "active ingredient" relates to the respective mixture of the compound of formula (I) with the mixing partner).

[0106] The compounds of formula (I) of the present invention may also be combined with herbicide safeners. Examples of such safeners include benoxacor, cloquintocet (including cloquintocet mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole ethyl), fenclorim, fluxofenim, furilazol, isoxadifen (including isoxadifen ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.

[0107] Mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen-ethyl), cloquintocet (including cloquintocet mexyl) and / or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide are especially preferred.

[0108] The safener of the compound of formula (I) is, for example, th Edition (BCPC), 2006. A reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, and a reference to fenchlorazole-ethyl also applies to fenchlorazole, etc., as disclosed in WO 02 / 34048.

[0109] Preferably, the mixing ratio of the compound of formula (I) to the safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0110] The mixtures may be advantageously used in the formulations described above, where "active ingredient" refers to the respective mixture of compound of formula (I) and safener.

[0111] The compounds of formula (I) of the present invention are useful as herbicides. Thus, the present invention further includes a method for controlling unwanted plants, which comprises applying an effective amount of the compounds of the present invention or a herbicidal composition containing said compounds to said plants or to the habitat containing them. "Control" means killing, reducing or retarding growth, or preventing or reducing germination. Generally, the plants to be controlled are unwanted plants (weeds). "Locus" means the area where the plants are growing or will grow.

[0112] The application rates of the compounds of formula (I) may vary within a wide range and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application in the furrow; no-tillage application, etc.), the crop plants, the weeds to be controlled, the prevailing climatic conditions, as well as the application method, time of application and other factors governed by the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of 10 to 2000 g / ha, in particular 50 to 1000 g / ha. A preferred range is 10 to 200 g / ha.

[0113] Application is generally made by spraying the composition, usually with a tractor-mounted sprayer for large areas, although other methods such as dusting (for dusts), dripping or irrigation can also be used.

[0114] Useful plants in which the compositions according to the invention can be used include crops such as cereals, e.g. barley and wheat, cotton, oilseed rape, sunflower, corn, rice, soybeans, sugar beets, sugar cane and turf.

[0115] Crop plants can also include trees such as fruit trees, palm trees, coconut trees or other nuts, as well as vines such as grapes, fruit bushes, fruit plants and vegetables.

[0116] Crops should also be understood to include crops that have been made tolerant to herbicides or classes of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional breeding methods or genetic engineering. An example of a crop that has been made tolerant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer rapeseed (canola). Examples of crops that have been made tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-tolerant corn varieties available under the trade names RoundupReady® and LibertyLink®.

[0117] It should also be understood that crops are those that have been made resistant to pests by genetic engineering methods, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the cotton weevil) and even Bt potato (resistant to the Colorado potato beetle). An example of Bt maize is the Bt176 maize hybrid from NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the Bacillus thuringiensis soil bacterium. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP 451878, EP 374753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP 427529. Examples of transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Either the plant crop or its seed material can be resistant to herbicides and at the same time resistant to insect ingestion (a "stacked" transgenic event). For example, a seed has the ability to express an insecticidal Cry3 protein and is at the same time resistant to glyphosate.

[0118] It should also be understood that crop plants include those obtained by conventional breeding or genetic engineering methods and containing so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor).

[0119] Other useful plants include turfgrasses grown commercially for turfgrass or lawns, for example, on golf courses, lawns, parks and roadsides, as well as ornamental plants such as flowers or shrubs.

[0120] The compounds and compositions of formula (I) of the present invention can generally be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can usually be controlled are Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and others. faberi and Sorghum bicolor.Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica, and others. persica and Xanthium strumarium.

[0121] The compounds of formula (I) are also useful in pre-harvest drying of crops, such as, but not limited to, potatoes, soybeans, sunflowers and cotton, which are used to dry the leaves of crops to facilitate harvesting without significant damage to the crop itself.

[0122] The compounds / compositions of the present invention are particularly useful in non-selective burn down applications and may therefore also be used to control volunteer vegetation or to ward off crop plants.

[0123] Various aspects and embodiments of the invention will now be described in further detail by way of example. It will be appreciated that modifications of detail may be made without departing from the scope of the invention. EXAMPLES

[0124] The following examples are intended to illustrate, but not limit, the present invention.

[0125] Synthesis Example Example 1 Preparation of 2-(8-chloro-1-naphthyl)-2,2-difluoro-acetic acid (compound 1-416) Step 1 Synthesis of 2-(8-chloro-1-naphthyl)-2,2-difluoro-ethyl acetate (compound 3-416) [ka] To a solution of 1-bromo-8-chloro-naphthalene (1.00 g, 4.14 mmol) in DMSO (5 mL) was added Cu powder (1.32 g, 20.7 mmol) followed by 2,2-difluoro-2-iodo-ethyl acetate (1.24 g, 4.97 mmol). The reaction mixture was stirred at room temperature for 48 h. The reaction mixture was diluted with water (20 mL) and extracted with ethyl acetate (3x30 mL). The combined organic layers were washed with brine (30 mL), dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (2% EtOAc in n-hexane) to give 2-(8-chloro-1-naphthyl)-2,2-difluoro-ethyl acetate (0.200 g, 0.632 mmol, 15%) as a colorless oil. 1 H NMR(400MHz,CDCl3):δ 8.10(d,1H),7.97(d,1H),7.81(dd,1H),7.62(dd,1H),7.53(t,1H),7.38(t,1H),4.36(q,2H),1.30(t,3H)ppm

[0126] Moreover, this general method 2-(3,7-dichloro-8-quinolyl)-2,2-difluoro-acetic acid methyl ester (compound 2-418) 1 H NMR(400MHz,CDCl3):δ 8.73(s,1H),8.14(s,1H),7.80-7.78(d,1H),7.65-7.63(m,1H),3.85(s,3H)ppm 2-[8-(2-ethoxy-1,1-difluoro-2-oxo-ethyl)-1-naphthyl]-2,2-difluoro-ethyl acetate (compound 3-419) 1 H NMR(400MHz,CDCl3):δ 8.11(d,1H),7.99(d,1H),7.90(dt,2H),7.56(t,1H),7.33(t,1H),4.38(q,4H),1.33(t,6H)ppm 2-(2-chloro-6-nitrophenyl)-2,2-difluoroethyl acetate (compound 3-67) 1 H NMR(400MHz,DMSO-d6):δ 8.03-7.99(m,2H),7.91-7.87(m,1H),4.40(q,2H),1.25(t,3H)ppm was prepared.

[0127] Step 2 Synthesis of 2-(8-chloro-1-naphthyl)-2,2-difluoro-acetic acid (compound 1-416) [ka] To a solution of 2-(8-chloro-1-naphthyl)-2,2-difluoro-ethyl acetate (200 mg, 0.632 mmol) in 2:1 THF / water (3.0 mL), LiOH·H2O (0.0531 g, 1.26 mmol) was added in portions and the reaction mixture was stirred at room temperature for 16 h. The reaction mixture was concentrated, diluted with water (20 mL) and extracted with ethyl acetate (3x30 mL). The combined organic layers were washed with 1N HCl solution (30 mL), dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by reverse phase column chromatography (product eluted with 0-50% acetonitrile in water) to give 2-(8-chloro-1-naphthyl)-2,2-difluoro-acetic acid (0.0550 g, 0.212 mmol, 34%) as an off-white solid. 1 H NMR(400MHz,DMSO-d6):δ 14.91-14.56(br s,1H),8.24(d,1H),8.10(m,2H),7.79(d,1H),7.70(t,1H),7.59(t,1H)ppm

[0128] Moreover, this general method 2-(3-chloro-2-nitro-phenyl)-2,2-difluoro-ammonium acetate (compound 7-250) 1 H NMR(400MHz,DMSO-d6)δ 7.84(t,1H),7.70-7.65(m,2H),7.19(br s,4H)ppm 2-(3,7-Dichloro-8-quinolyl)-2,2-difluoro-acetic acid (compound 1-418) 1 H NMR(400MHz,DMSO-d6)δ 14.7-14.2(br s,1H),8.93-8.92(d,1H),8.74-8.73(d,1H),8.19-8.17(d,1H),7.85-7.83(d,1H)ppm 2-(3-aminophenyl)-2,2-difluoro-acetic acid (compound 1-8) 1 H NMR(400MHz,DMSO-d6)δ 6.98(t,1H),6.74(s,1H),6.63(d,1H),6.52(d,1H),5.11(s,2H)ppm 2-(3-chloro-2-cyano-phenyl)-2,2-difluoro-acetic acid (compound 1-262) 1 H NMR(400MHz,DMSO-d6)δ 8.00(d,1H),7.90(t,1H),7.81(d,1H)ppm 2-(2-Chloro-3-ethynyl-phenyl)-2,2-difluoro-acetic acid (compound 1-208) 1 H NMR(400MHz,DMSO-d6)δ 7.66-7.60(m,2H),7.39(t,1H),4.58(s,1H)ppm 2,2-Difluoro-2-(1-naphthyl)acetic acid (compound 1-397) 1 H NMR(400MHz,DMSO-d6)δ 8.16(d,1H),8.13-8.02(m,2H),7.86(d,1H),7.75-7.55(m,3H)ppm 2,2-Difluoro-2-(quinolin-8-yl)acetic acid (compound 1-403) 1 H NMR(400MHz,DMSO-d6):δ 8.91(dd,1H),8.49(dd,1H),8.20(d,1H),8.11(d,1H),7.74(t,1H),7.64(dd,1H)ppm 2,2-Difluoro-2-(3-hydroxyphenyl)acetic acid (compound 1-5) 1 H NMR(400MHz,DMSO-d6):δ 9.87(br s,1H),7.32(t,1H),7.0-6.89(m,3H)ppm 2-(2-Chloro-6-nitrophenyl)-2,2-difluoroacetic acid (compound 1-67) 1 H NMR(400MHz,DMSO-d6):δ 7.96-7.93(m,2H),7.85-7.81(m,1H)ppm 2-(7-chloroquinolin-8-yl)-2,2-difluoroacetic acid (compound 1-407) 1 H-NMR(400MHz,DMSO-d6):δ 14.15(brs,1H),8.91-8.89(m,1H),8.52-8.50(m,1H),8.21(d,1H),7.68-7.65(m,2H)ppm 2,2-Difluoro-2-(2,3,5-trichloro-6-methoxy-phenyl)acetic acid (compound 1-82) 1 H NMR(400MHz,DMSO-d6):δ 8.17(s,1H),3.78(s,3H)ppm 2-(2,5-Dichloro-3-nitrophenyl)-2,2-difluoroacetic acid (compound 1-238) 1 H NMR(400MHz,DMSO-d6):δ 8.32(d,1H),7.84(d,1H)ppm 2-(3-Amino-2,5-dichlorophenyl)-2,2-difluoroacetic acid (compound 1-235) 1H NMR(400MHz,DMSO-d6):δ 6.99(d,1H),6.82(d,1H),5.99(brs,2H)ppm 2-(3-chloro-2-(methylthio)phenyl)-2,2-difluoroacetic acid (compound 1-356) 1 H NMR(400MHz,DMSO-d6):δ 7.81(d,1H),7.71(dd,1H),7.58(t,1H),2.29(s,3H)ppm 2-(2-Chloro-3-methylsulfanyl-phenyl)-2,2-difluoro-acetic acid (compound 1-220) 1 H NMR(400MHz,DMSO-d6):δ 7.55-7.48(m,3H),2.54(s,3H)ppm 2-(3-Amino-2,6-dichloro-phenyl)-2,2-difluoro-acetic acid (compound 1-236) 1 H NMR (400MHz, DMSO-d6): δ 7.2(d,1H),6.93(d,1H),5.87(br s,2H)ppm 2-(5-chloro-2,2-difluorobenzo[d][1,3]dioxol-4-yl)-2,2-difluoroacetic acid (compound 1-389) 1 H NMR(400MHz,DMSO-d6):δ 7.45(d,1H),7.30(d,1H)ppm 2-(4-chloro-4'-fluoro-[1,1'-biphenyl]-3-yl)-2,2-difluoroacetic acid (compound 1-64) 1 H NMR(400MHz,DMSO-d6):δ 7.92(d,1H),7.86(dd,1H),7.78(m,2H),7.69(d,1H),7.30(t,2H)ppm 2-(4,5-Dichloro-4'-fluoro-[1,1'-biphenyl]-3-yl)-2,2-difluoroacetic acid (compound 1-78) 1H NMR(400MHz,DMSO-d6):δ 7.98-7.97(d,1H),7.79-7.76(m,2H),7.73(d,1H),7.34-7.30(m,2H)ppm 2,2-Difluoro-2-(quinoxalin-5-yl)acetic acid (compound 1-409) 1 H NMR(400MHz,DMSO-d6):δ 14.50(s,1H),9.06(d,1H),8.99(d,1H),8.32(d,1H),8.22(d,1H),8.01(t,1H)ppm 2-(2-Chloro-3-ethyl-phenyl)-2,2-difluoro-acetic acid (compound 1-196) 1 H NMR (400MHz, CDCl3): δ 7.59(d,1H),7.39(d,1H),7.31(d,1H),2.76-2.81(q,2H),1.24(t,3H)ppm 2-(3-Chloro-2-ethynyl-phenyl)-2,2-difluoro-acetic acid (compound 1-291) 1 H NMR(400MHz,DMSO-d6):δ 7.78(d,1H),7.68(dd,1H),7.58(t,1H),4.98(s,1H)ppm 2-(2-Chloro-3-vinyl-phenyl)-2,2-difluoro-acetic acid (compound 1-207) 1 H NMR(400MHz,DMSO-d6):δ 7.92(dd,1H),7.70(dd,1H),7.52(t,1H),7.06(m,1H),5.96(dd,1H),5.55(dd,1H)ppm 2-(3-Chloro-2-ethyl-phenyl)-2,2-difluoro-acetic acid (compound 1-275) 1 H NMR(400MHz,DMSO-d6):δ 7.42(t,1H),7.23(t,1H),6.09(s,1H),2.88-2.82(q,2H),1.07(t,3H)ppm 2-(2-Chloro-5-hydroxyphenyl)-2,2-difluoroacetic acid (compound 1-61) 1H NMR(400MHz,DMSO-d6):δ 10.1(brs,1H),7.36(d,1H),7.09(s,1H),6.93(dd,1H)ppm 2-(2-chloro-3-nitro-phenyl)-2,2-difluoro-ammonium acetate (compound 7-237) 1 H NMR(400MHz,DMSO-d6):δ 7.9(d,1H),7.71(dd,1H),7.51(t,1H)ppm 2-(2-chloro-3-cyano-phenyl)-2,2-difluoro-ammonium acetate (compound 7-231) 1 H NMR(400MHz,DMSO-d6):δ 8.01(d,1H),7.91(d,1H),7.6(t,1H)ppm 2-(4-Bromo-3-chloro-2-methylsulfanyl-phenyl)-2,2-difluoro-acetic acid (compound 1-359) 1 H-NMR(400MHz,DMSO-d6):δ 7.59(d,1H),7.39(d,1H),2.67(s,3H)ppm 2-(2-Chloro-5-methoxyphenyl)-2,2-difluoroacetic acid (compound 1-62) 1 H NMR(400MHz,DMSO-d6):δ 14.68(br s,1H),7.61(dd,1H),7.55(d,1H),7.22(d,1H),3.71(s,3H)ppm 2,2-Difluoro-2-(2-fluoro-3-methoxy-phenyl)acetic acid (compound 1-190) 1 H NMR (500MHz, chloroform) δ = 7.34 (br s, 1H), 7.23-7.13 (m, 2H), 7.12-7.05 (m, 1H), 3.90 (s, 3H) ppm 2-(3-Cyano-2-fluoro-phenyl)-2,2-difluoro-acetic acid (compound 1-192) 1H NMR (500MHz, chloroform) δ = 8.02-7.89 (m, 1H), 7.84 (br s, 1H), 7.79 (br t, 1H), 7.40 (t, 1H) ppm 2,2-Difluoro-2-(3-methoxy-2-methyl-phenyl)acetic acid (compound 1-242) 1 H NMR (500 MHz, chloroform) δ = 7.71 (br s, 1H), 7.25-7.20 (m, 2H), 6.95 (dd, 1H), 3.83 (s, 3H), 2.27 (s, 3H) ppm 2-(3-Cyano-2-methyl-phenyl)-2,2-difluoro-acetic acid (compound 1-244) 1 H NMR (500 MHz, chloroform) δ 8.38 (br s, 1H), 7.85 (d, 1H), 7.73 (d, 1H), 7.41 (t, 1H), 2.64 (s, 3H) ppm 2-(2-Cyano-3-fluoro-phenyl)-2,2-difluoro-acetic acid (compound 1-261) 1 H NMR (500MHz, chloroform) δ = 7.92-7.53 (m, 3H), 7.52-7.32 (m, 1H) ppm 2-(2,3-Dihydrobenzofuran-4-yl)-2,2-difluoro-acetic acid (compound 1-420) 1 H NMR (500 MHz, chloroform) δ = 7.23-7.14 (m, 1H), 7.06 (d, 1H), 6.89 (d, 1H), 6.84 (br s, 1H), 4.58 (t, 2H), 3.40 (t, 2H) ppm 2-(3-Chloro-2-cyclopropyl-phenyl)-2,2-difluoro-acetic acid (compound 1-428) 1 H NMR (400 MHz, chloroform) δ = 7.60 (dd, 1H) 7.51 (d, 1H) 7.26-7.32 (m, 1H) 1.77-1.87 (m, 1H) 1.03 -1.10 (m, 2H) 0.77 (q, 2H) ppm 2-[3-Chloro-2-(methoxymethyl)phenyl]-2,2-difluoro-acetic acid (compound 1-436) 1 H NMR (400MHz, chloroform) δ = 7.53-7.62 (m, 2H) 7.35-7.41 (m, 1H) 4.93 (s, 2H) 3.47 (s, 3H) ppm 2-(3-Chloro-2-methoxycarbonyl-phenyl)-2,2-difluoro-acetic acid (compound 1-444) 1 H NMR (500 MHz, chloroform) δ = 8.17 (br s, 1H), 7.62 (d, 1H), 7.54 (d, 1H), 7.49-7.41 (m, 1H), 3.92 (s, 3H) ppm 2-[3-Chloro-2-(difluoromethoxy)phenyl]-2,2-difluoro-acetic acid (compound 1-452) 1 H NMR (500 MHz, chloroform) δ = 7.67 (dd, 1H), 7.60 (d, 1H), 7.51 (br s, 1H), 7.33 (t, 1H), 6.64 (t, 1H) ppm 2-(2,4-Difluoro-3-methoxy-phenyl)-2,2-difluoro-acetic acid (compound 1-458) 1 H NMR (500 MHz, chloroform) δ = 7.56 (br s, 1H), 7.35-7.22 (m, 1H), 7.05-6.90 (m, 1H), 4.01 (s, 3H) ppm 2-[2-Chloro-3-(difluoromethoxy)phenyl]-2,2-difluoro-acetic acid (compound 1-459) 1 H NMR (400 MHz, chloroform) δ = 9.27 (br s, 1H) 7.35-7.74 (m, 3H) 6.34-6.80 (m, 1H) ppm 2-(2-chloro-3-cyano-4-fluoro-phenyl)-2,2-difluoro-acetic acid (compound 1-460) 1 H NMR (500 MHz, chloroform) δ = 7.99 (dd, 1H), 7.62 (br s, 1H), 7.35-7.23 (m, 1H) ppm 2,2-Difluoro-2-(3-fluoro-4-methoxy-2-nitro-phenyl)acetic acid (compound 1-461) 1H NMR (500 MHz, chloroform) δ = 7.60 (br s, 1H), 7.53 (dd, 1H), 7.18 (t, 1H), 3.99 (s, 3H) ppm 2-(2-Cyano-3-methyl-phenyl)-2,2-difluoro-acetic acid (compound 1-462) 1 H NMR (500 MHz, chloroform) δ = 7.63-7.51 (m, 2H), 7.47 (d, 1H), 7.13 (br s, 1H), 2.61 (s, 3H) ppm 2,2-Difluoro-2-(2-methoxy-3-methyl-phenyl)acetic acid (compound 1-463) 1 H NMR (500 MHz, chloroform) δ = 7.78 (br s, 1H), 7.49 (d, 1H), 7.31 (d, 1H), 7.12 (t, 1H), 3.78 (s, 3H), 2.31 (s, 3H) ppm 2,2-Difluoro-2-[2-methoxy-3-(trifluoromethyl)phenyl]acetic acid (compound 1-464) 1 H NMR (500 MHz, chloroform) δ = 7.90 (d, 1H), 7.76 (d, 1H), 7.35 (t, 1H), 3.91 (s, 3H) ppm 2-[2-Chloro-4-(trifluoromethoxy)phenyl]-2,2-difluoro-acetic acid (compound 1-59) 1 H NMR (500 MHz, chloroform) δ = 7.78 (d, 1H), 7.32 (s, 1H), 7.24 (d, 1H) ppm 2,2-Difluoro-2-[2-(trifluoromethoxy)phenyl]acetic acid (compound 1-465) 1 H NMR (500MHz, chloroform) δ = 7.76 (d, 1H), 7.57-7.51 (m, 1H), 7.38 (t, 1H), 7.34 (d, 1H) ppm 2-(4-Cyanophenyl)-2,2-difluoro-acetic acid (compound 1-474) 1 H NMR(400MHz,DMSO-d6)δ=8.00(d,2H),7.76(d,2H) 2,2-Difluoro-2-(1H-indol-7-yl)acetic acid (compound 1-477) 1 H NMR(400MHz,DMSO-d6)δ=11.12(br s,1H),7.59(d,1H),7.36(d,1H),7.21(d,1H),7.00(t,1H),6.44(d,1H)ppm was prepared.

[0129] Example 2 Preparation of 2-(3-chloro-2-methoxy-phenyl)-2,2-difluoro-acetic acid (compound 1-317) Step 1 Synthesis of 2-(3-chloro-2-methoxy-phenyl)-2-oxo-ethyl acetate [ka] To a stirred solution of 1-bromo-3-chloro-2-methoxy-benzene (1.00 g, 4.52 mmol) in tetrahydrofuran (20 mL) was added n-BuLi (0.289 g, 4.52 mmol) at -78 °C and the reaction was stirred at -78 °C for 15 min. Diethyl oxalate (0.660 g, 4.52 mmol) was added and the reaction was stirred at -78 °C for 2 h. The reaction mixture was warmed to room temperature, quenched with ammonium chloride solution (20 mL) and extracted with ethyl acetate (30 mL). The organic layer was washed with brine solution (10 mL), dried over Na2SO4 and concentrated under reduced pressure to give crude 2-(3-chloro-2-methoxy-phenyl)-2-oxo-ethyl acetate (0.600 g, 2.23 mmol, 49%) as a colorless oil. 1 H NMR(400MHz,DMSO-d6):δ 7.92(d,1H),7.78(d,1H),7.39(t,1H),4.38(q,2H),3.83(s,3H),1.31(t,3H)ppm

[0130] Moreover, this general method 2-(7-fluoro-8-quinolyl)-2-oxo-ethyl acetate 1H NMR(400MHz,CDCl3):δ 9.08(m,1H),8.87(dd,1H),8.02(dd,1H),7.80(dd,1H),7.46(dd,1H),4.32(q,2H),1.37(t,3H)ppm 2-(2,2-difluoro-1,3-benzodioxol-4-yl)-2-oxo-ethyl acetate 1 H NMR(400MHz,CDCl3):δ 7.66(d,1H),7.33(d,1H),7.21(m,1H),4.46(q,2H),1.41(t,3H)ppm was prepared.

[0131] Step 2 Synthesis of 2-(3-chloro-2-methoxy-phenyl)-2,2-difluoro-ethyl acetate (compound 3-317) [ka] To a stirred solution of 2-(3-chloro-2-methoxy-phenyl)-2-oxo-ethyl acetate (680 mg, 2.52 mmol) in dichloromethane (10 mL) was added diethylaminosulfur trifluoride (0.813 g, 5.04 mmol) at 0 °C. The resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with sodium bicarbonate solution and extracted with dichloromethane. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The resulting crude product was purified by column chromatography (compound eluted with 5-10% EtOAc in n-hexane) to give 2-(3-chloro-2-methoxy-phenyl)-2,2-difluoro-ethyl acetate (0.300 g, 1.02 mmol, 40%) as a colorless oil. 1 H NMR(400MHz,CDCl3):δ 7.57(dd,1H),7.51(dd,1H),7.17(t,1H),4.34(q,2H),3.88(s,3H),1.30(t,3H)ppm

[0132] Moreover, this general method 2,2-Difluoro-2-(7-fluoro-8-quinolyl)ethyl acetate (Compound 3-406) 1 H NMR(400MHz,DMSO-d6):δ 8.92(m,1H),8.57(dd,1H),8.41(dd,1H),7.76(t,1H),7.67(dd,1H),4.31(q,2H),1.22(t,3H)ppm 2-(2,2-difluoro-1,3-benzodioxol-4-yl)-2,2-difluoro-ethyl acetate (compound 3-385) was prepared.

[0133] Step 3 Synthesis of 2-(3-chloro-2-methoxy-phenyl)-2,2-difluoro-acetic acid (compound 1-317) [ka] To a solution of 2-(3-chloro-2-methoxy-phenyl)-2,2-difluoro-ethyl acetate (220 mg, 0.83 mmol) in 1:1 THF / water (10 mL) was added lithium hydroxide monohydrate (70 mg, 1.66 mmol) and the reaction mixture was stirred at room temperature for 1 h. The reaction mixture was treated with 2N HCl solution to pH 3 and filtered. The solid was dried to give 2-(3-chloro-2-methoxy-phenyl)-2,2-difluoro-acetic acid (170 mg) as an off-white solid. 1 H NMR(400MHz,DMSO-d6):δ 14.7(br s,1H),7.72(dd,1H),7.70(dd,1H),7.32(t,1H),3.80(s,3H)ppm

[0134] Moreover, this general method 2,2-Difluoro-2-(7-fluoro-8-quinolyl)acetic acid (compound 1-406) 1 H NMR(400MHz,DMSO-d6):δ 14.57-13.99(br s,1H),8.92(d,1H),8.51(d,1H),8.31(d,1H),7.81-7.48(m,2H)ppm 2-(2,2-difluoro-1,3-benzodioxol-4-yl)-2,2-difluoro-acetic acid (compound 1-385) 1 H NMR(400MHz,DMSO-d6):δ 7.49(d,1H),7.32-7.23(m,2H)ppm 2-(2-chloro-3-methoxyphenyl)-2,2-difluoroacetic acid (compound 1-209) 1 H NMR(400MHz,DMSO-d6):δ 7.48(t,1H),7.36(d,1H),7.31(dd,1H),3.9(s,3H)ppm was prepared.

[0135] Example 3 Preparation of 2-(3,6-dichloro-2-methoxy-phenyl)-2,2-difluoro-acetic acid (compound 1-326) Step 1 Synthesis of 2-(3,6-dichloro-2-methoxy-phenyl)acetic acid [ka] Ruthenium(III) chloride (0.73 g, 3.5 mmol) was added to a solution of 2-allyl-1,4-dichloro-3-methoxy-benzene (38 g, 180 mmol) in a mixture of water (530 mL), acetonitrile (350 mL) and ethyl acetate (350 mL). Sodium periodate (190 g, 880 mmol) was added in portions over a period of 30 minutes while maintaining an internal temperature below 25° C. The mixture was stirred for 30 minutes. A solution of sodium disulfite (330 g, 1800 mmol) in water (500 mL) was prepared. The reaction mixture was cooled to 5° C. The solution of sodium disulfite was added to the reaction mixture over 2 hours at such a rate as to maintain the internal temperature below 20° C. After the addition, a starch-iodide paper test for the oxidant was negative. The mixture was diluted with brine (400 mL) and then separated. The aqueous layer was extracted with EtOAc (3x400 mL). The combined organic extracts were dried over MgSO4, filtered and concentrated in vacuo to give a black oil. The crude product was purified by flash column chromatography to give 2-(3,6-dichloro-2-methoxy-phenyl)acetic acid (30.59 g, 130.1 mmol, 74%) as an orange solid. 1 H NMR (400MHz, CDCl3): δ 7.28(d,1H),7.14(d,1H),3.93(s,2H),3.88(s,3H)ppm

[0136] Step 2 Synthesis of methyl 2-(3,6-dichloro-2-methoxy-phenyl)acetate [ka] To 2-(3,6-dichloro-2-methoxy-phenyl)acetic acid (5.00 g, 21.3 mmol) in dichloromethane (60 mL) was added oxalyl chloride (2.74 mL, 31.9 mmol) followed by a catalytic amount of dimethylformamide. The reaction mixture was stirred at room temperature. After 2 h, the reaction mixture was carefully quenched with methanol, diluted with water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and evaporated under reduced pressure. The crude material was purified by flash column chromatography to give methyl 2-(3,6-dichloro-2-methoxy-phenyl)acetate (5.27 g, 21.2 mmol, 99%). 1 H NMR(400MHz,CDCl3):δ 7.26-7.24(d,1H),7.12-7.10(d,1H),3.86(s,2H),3.84(s,3H),3.71(s,3H)ppm

[0137] Step 3 Synthesis of 2-(3,6-dichloro-2-methoxy-phenyl)-2,2-difluoro-methyl acetate (compound 2-326) [ka] To a solution of methyl 2-(3,6-dichloro-2-methoxy-phenyl)acetate (3.00 g, 12.0 mmol) in dry tetrahydrofuran (150 mL) was added potassium bis(trimethylsilyl)amide (0.50 M, 72.3 mL, 36.1 mmol) at −78° C., followed by N-fluorobenzenesulfonimide (12.2 g, 38.5 mmol). The reaction mixture was stirred at room temperature overnight. The reaction was quenched with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and evaporated under reduced pressure. The crude material was purified by flash column chromatography to give methyl 2-(3,6-dichloro-2-methoxy-phenyl)-2,2-difluoroacetate (1.97 g, 6.91 mmol, 58%). 1H NMR(400MHz,CDCl3):δ 7.42-7.40(d,1H),7.21-7.18(d,1H),3.87(s,3H),3.82(s,3H)ppm

[0138] This method also 2-(2-chloro-6-methoxy-phenyl)-2,2-difluoro-acetic acid methyl ester (compound 2-65) 1 H NMR(400MHz,CDCl3):δ 7.34-7.30(t,1H),7.09-7.07(d,1H),6.86-6.84(d,1H),3.87(s,3H),3.79(s,3H)ppm was prepared.

[0139] Step 4 Synthesis of 2-(3,6-dichloro-2-methoxy-phenyl)-2,2-difluoro-acetic acid [ka] To the compound 2-(3,6-dichloro-2-methoxy-phenyl)-2,2-difluoro-methyl acetate (1.50 g, 5.26 mmol) in dry tetrahydrofuran (15 mL) and water (15 mL) was added lithium hydroxide (0.662 g, 15.8 mmol). The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was extracted with ethyl acetate. The aqueous layer was acidified with 2N hydrochloric acid and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and evaporated under reduced pressure. The crude material was triturated with n-pentane to give 2-(3,6-dichloro-2-methoxy-phenyl)-2,2-difluoro-acetic acid (0.778 g, 2.87 mmol, 55%). 1 H NMR(400MHz,DMSO-d6):δ 15.4-14.8(br s,1H),7.75-7.73(d,1H),7.44-7.42(d,1H),3.79(s,3H)ppm

[0140] Moreover, this general method 2-(2-Chloro-6-methoxy-phenyl)-2,2-difluoro-acetic acid (compound 1-65) 1 H NMR(400MHz,DMSO-d6):δ 14.38(br s,1H),7.52-7.48(t,1H),7.19-7.15(t,2H),3.78(s,3H)ppm was prepared.

[0141] Example 4 Preparation of 2-(5-acetamido-2,3-dichlorophenyl)-2,2-difluoroacetic acid (compound 1-77) Step 1 Synthesis of N-(3-bromo-4,5-dichlorophenyl)acetamide [ka] 3-Bromo-4,5-dichloroaniline (0.70 g, 2.90 mmol) and triethylamine (0.63 mL, 4.35 mmol) in CHCl (10.0 mL) were charged with AcCl (0.31 g, 4.35 mmol) at 0° C. The reaction mixture was stirred at room temperature for 2 h. Upon completion, the reaction mixture was diluted with CHCl (50 mL), washed with HO (20 mL) followed by brine solution (20 mL) and the organic layer was dried over anhydrous NaSO, filtered and concentrated under reduced pressure to obtain the crude product. The resulting crude product was purified by column chromatography (silica gel using 30-50% EtOAc in hexanes as eluent) to obtain N-(3-bromo-4,5-dichlorophenyl)acetamide (0.70 g, 85% yield, AMRI lot#IN-KUC-A-28-1) as an off-white solid.

[0142] Step 2 Synthesis of 2-(5-acetamido-2,3-dichlorophenyl)-2,2-difluoroethyl acetate (compound 3-77) [ka] To N-(3-bromo-4,5-dichlorophenyl)-acetamide (0.61 g, 2.15 mmol) and ethyl 2,2-difluoro-2-iodoacetate (0.80 g, 3.23 mmol) in DMSO (6.0 mL) was added Cu powder (1.1 g, 17.24 mmol) at room temperature. The reaction mixture was stirred in a microwave at 60° C. for 5 h. The progress of the reaction was monitored by thin layer chromatography (TLC). Upon completion, the reaction mixture was filtered through a pad of Celite and washed with EtOAc (50.0 mL). The filtrate was washed with ice-cold H2O (2×20.0 mL), followed by brine solution (40.0 mL) and the organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to give the crude product. The resulting crude product was purified by column chromatography (silica gel using 15-30% EtOAc in hexanes as eluent) to give ethyl 2-(5-acetamido-2,3-dichlorophenyl)-2,2-difluoroacetate (0.31 g, 42% yield) as a clear liquid.

[0143] Step 3: Synthesis of 3-[carboxy(difluoro)methyl]-4,5-dichloroanilinium (compound 1-77) [ka] Ethyl 2-(5-acetamido-2,3-dichlorophenyl)-2,2-difluoroacetate (0.28 g, 0.85 mmol) in concentrated HCl:HO (3:1, 13 mL) was stirred for 16 h at 100° C. Upon completion, the excess HO was concentrated under reduced pressure to give 3-[carboxy(difluoro)methyl]-4,5-dichloroanilinium (HCl salt) (100 mg, 40% yield) as an off-white solid. 1H NMR (400MHz, DMSO-d6): δ 6.93-6.89(m,5H)ppm

[0144] Moreover, this general method 2-(5-Amino-2-chloro-phenyl)-2,2-difluoro-acetic acid (compound 1-63) 1H NMR(400MHz,DMSO-d6):δ 7.13(d,1H),6.91(s,1H),6.66(dd,1H)ppm 2-(4-amino-2,3-dichloro-phenyl)-2,2-difluoro-ammonium acetate (compound 7-75) 1 H NMR (400MHz, DMSO-d6): δ 7.3(br s,4H),7.2(d,1H),6.7(d,1H),5.84(br s,2H)ppm was prepared.

[0145] Example 5 Preparation of 2-(3,5-dimethylbenzo[d]isoxazol-4-yl)-2,2-difluoroacetic acid (Compound 1-396) Step 1 Synthesis of 2-(1-iminoethyl)-4-methylphenol [ka] 1-(2-Hydroxy-5-methylphenyl)ethanone (1.00 g, 6.66 mmol) in MeOH (5.0 mL) was charged with 7M ammonia in MeOH (10.0 mL). The reaction mixture was sealed and stirred at room temperature for 4 h. Upon completion of the reaction, formation of a yellow solid was observed. The reaction mass was filtered to give 2-(1-iminoethyl)-4-methylphenol (0.70 g, crude) as a yellow solid. 1H NMR (400MHz, CDCl3): δ 14.8(brs,1H),9.15(brs,1H),7.27(d,1H),7.14(dd,1H),6.87(d,1H),2.46(s,3H),2.28(s,3H)ppm

[0146] Step 2 Synthesis of 3,5-dimethylbenzo[d]isoxazole [ka] 2-(1-Iminoethyl)-4-methylphenol (0.65 g, crude) in THF (10.0 mL) was charged with K2CO3 (0.93 g, 6.72 mmol) and N-chlorosuccinamide (0.70 g, 5.40 mmol). The reaction mixture was stirred at room temperature for 18 h. Upon completion of the reaction, the reaction mass was diluted with H2O (20 mL) and extracted with EtOAc (2x20 mL). The combined layers were washed with brine (10 mL), dried over anhydrous Na2SO4, and concentrated under reduced pressure to give a residue. The resulting residue was purified by flash chromatography (20% EtOAc / hexane eluent) to give 3,5-dimethylbenzo[d]isoxazole (600 mg, 4.08 mmol) as an off-white solid. 1H NMR (400MHz, CDCl3): δ 7.44-7.33(m,3H),2.55(s,3H),2.47(s,3H)ppm

[0147] Step 3 Synthesis of 2-(3,5-dimethylbenzo[d]isoxazol-4-yl)-2,2-difluoroethyl acetate (compound 3-396) [ka] 3,5-Dimethylbenzo[d]isoxazole (600 mg, 4.08 mmol) in DMSO (20 mL) was charged with ethyl 2,2-difluoro-2-bromoacetate (1.66 g, 8.16 mmol), K3PO4 (1.30 g, 6.12 mmol) and fac-[Ir(PPy3)] (80 mg, 0.12 mmol). The reaction mixture was sealed and stirred at room temperature under exposure to 450-455 nm blue light for 48 h. Upon completion of the reaction, the reaction mass was diluted with H2O (20 mL) and filtered through a celite pad. The filtrate was extracted with tert-butyl methyl ether (2x10 mL). The combined layers were washed with brine (10 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure to give the crude material. The resulting residue was purified by flash chromatography (10-15% EtOAc / hexanes eluent) to afford ethyl 2-(3,5-dimethylbenzo[d]isoxazol-4-yl)-2,2-difluoroacetate (300 mg, 27%) as an off-white solid. 1H NMR (400MHz, CDCl3): δ 7.57(d,1H),7.44-7.33(m,1H),4.32(q,2H),2.67(t,3H),2.58(t,3H),1.30(t,3H)ppm

[0148] Step 4 Synthesis of 2-(3,5-dimethylbenzo[d]isoxazol-4-yl)-2,2-difluoroacetic acid (compound 1-396) [ka] 2-(3,5-dimethylbenzo[d]isoxazol-4-yl)-2,2-difluoroethyl acetate (300 mg, 1.67 mmol) in THF:HO (3:1, 12 mL) was charged with LiOH·HO (140 mg, 3.34 mmol). The reaction mixture was stirred at room temperature for 2 h. Upon completion of the reaction, the reaction mass was evaporated and diluted with HO (5 mL). The aqueous layer was then acidified to pH=3 using aqueous SN HCl and extracted into MTBE (2×15 mL). The combined layers were dried over anhydrous NaSO and concentrated under reduced pressure to give 2-(3,5-dimethylbenzo[d]isoxazol-4-yl)-2,2-difluoroacetic acid (300 mg, 75%) as an off-white solid. 1H NMR (400MHz, DMSO-d6): δ 7.83(d,1H),7.60(d,1H),2.59(t,3H),2.54(t,3H)ppm

[0149] Moreover, this general method 2,2-Difluoro-2-(3-methyl-1,2-benzoxazol-4-yl)acetic acid (compound 1-391) 1 H NMR(400MHz,DMSO-d6):δ 7.99(d,1H),7.79(t,1H),7.59(d,1H),2.60(t,3H)ppm 2-(5-chloro-3-methyl-1,2-benzoxazol-4-yl)-2,2-difluoro-acetic acid (compound 1-395) 1 H NMR(400MHz,DMSO-d6):δ 8.03(d,1H),7.86(d,1H),2.57(t,3H)ppm was prepared.

[0150] Example 6 Preparation of 2-(2-chloronaphthalen-1-yl)-2,2-difluoroacetic acid (Compound 1-401) Step 1 Synthesis of ethyl 2-(2-chloronaphthalen-1-yl)-2,2-difluoroacetate (compound 3-401) [ka] 2-Chloronaphthalene (1.00 g, 6.17 mmol) in 1,2-dichloroethane (20 mL) was charged with ethyl 2,2-difluoro-2-(trimethylsilyl)acetate (3.00 g, 15.4 mmol), AgOTf (6.34 g, 24.7 mmol) and KF (1.43 g, 24.7 mmol). The reaction mixture was sealed and exposed to microwave irradiation at 60° C. for 1 h. Upon completion of the reaction, the reaction mass was evaporated. The residue was diluted with H2O (50 mL) and extracted with EtOAc (2×50 mL). The combined layers were washed with brine (10 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure to give the crude material. The resulting crude material was purified by flash chromatography (10-20% EtOAc / hexanes as eluent) to afford ethyl 2-(2-chloronaphthalen-1-yl)-2,2-difluoroacetate (120 mg) as an off-white solid, which was used directly in the next step.

[0151] Moreover, this general method 2,2-Difluoro-2-(1-naphthyl)ethyl acetate (Compound 3-397) 1 H NMR(400MHz,DMSO-d6):δ 8.18(d,1H),8.08(dd,1H),8.02(dd,1H),7.87(d,1H),7.70-7.62(m,3H),4.32(q,2H),1.15(t,3H)ppm was prepared.

[0152] Step 2: Synthesis of 2-(2-chloronaphthalen-1-yl)-2,2-difluoroacetic acid (compound 1-401) [ka] Ethyl 2-(2-chloronaphthalen-1-yl)-2,2-difluoroacetate (150 mg, 5.28 mmol) in THF:H2O (3:1, 12 ml) was charged with LiOH·H2O (44 mg, 10.6 mmol). The reaction mixture was stirred at room temperature for 3 h. The reaction mass was then evaporated under reduced pressure and diluted with H2O (5 mL). The aqueous layer was then acidified to pH=5 using aqueous 1N HCl and evaporated under reduced pressure to obtain the crude material. The crude was purified by reverse phase column chromatography (50% CH3CN H2O as eluent) to obtain 2-(2-chloronaphthalen-1-yl)-2,2-difluoroacetic acid (15 mg, 1.1%) as an off-white solid. 1H NMR (400MHz, DMSO-d6): δ 8.42(d,1H),7.94-7.87(m,2H),7.53-7.37(m,2H),7.45(d,1H)ppm

[0153] Example 7 Preparation of 2-(2-amino-3,6-dichlorophenyl)-2,2-difluoroacetic acid (Compound 7-254) Step 1. Synthesis of ethyl 2-(2-amino-3,6-dichlorophenyl)-2,2-difluoroacetate and 4,7-dichloro-3,3-difluoroindolin-2-one [ka] To a solution of 2,5-dichloroaniline (300 mg, 2.2 mmol) in DMSO (5 mL) was added 2-bromo-2,2-difluoroethyl acetate (447 mg, 6.6 mmol) followed by ferrocene (41 mg, 0.22 mmol). The reaction mixture was cooled to 0 °C and a solution of 30% H2O2 (0.45 mL, 4.4 mmol) was added dropwise. The reaction mixture was slowly warmed to ambient temperature and kept stirring at the same temperature overnight. Upon completion of the reaction, the reaction mixture was quenched with H2O (5 mL) and washed with EtOAc (2 x 10 mL). The organic layer was washed with brine (10 mL), dried over Na2SO4 and evaporated under reduced pressure to obtain the crude material. The obtained crude material was purified by combi flash chromatography (0-15% EtOAc:Hexanes) to obtain a mixture of 1 and 2 (1:1 ratio by UPLC-MS) (0.20 g) as a yellow solid. 1H NMR (400MHz, CDCl3): δ 8.0(brs,1H),7.6(s,1H),7.38(dt,1H),7.07(d,1H),6.7(s,1H),4.34(q,2H),1.32(t,3H)ppm

[0154] Step 2 Synthesis of 2-(2-amino-3,6-dichlorophenyl)-2,2-difluoroacetic acid (compound 7-254) [ka] The starting material containing a mixture of ethyl 2-(2-amino-3,6-dichlorophenyl)-2,2-difluoroacetate and 4,7-dichloro-3,3-difluoroindolin-2-one (200 mg, 0.834 mmol) was dissolved in a three-necked round-bottom flask with THF:H2O (5.0 mL:2.5 mL). KOH pellets (237 mg, 4.21 mmol) were added to the reaction mixture. The reaction mixture was heated at 55° C. overnight. Upon completion of the reaction, the solvent was evaporated and subjected to preparative HPLC purification without any acid-base workup since the product converted back to its crystalline form in the presence of acid. In preparative HPLC, the product was purified using ammonium bicarbonate buffer and was isolated as a pale yellow solid in its ammonium salt form (0.10 g, 47%). 1 H NMR(400MHz,DMSO-d6):δ 7.2(d,1H),7.15(brs,4H),6.6(d,1H),6.12(brs,2H)ppm

[0155] Moreover, this general method 2-(3,6-Difluoro-2-methoxyphenyl)-2,2-difluoroacetic acid (compound 1-314) 1 H-NMR(400MHz,DMSO-d6):δ 7.61-7.47(m,1H),7.37-7.29(m,1H),3.90(s,3H)ppm 2,2-Difluoro-2-(3-fluoro-2-methoxy-phenyl)acetic acid (compound 1-306) 1 H-NMR(400MHz,DMSO-d6):δ 7.41-7.36(m,2H),7.33-7.29(m,1H),3.89(s,3H)ppm 2-(2-Amino-3-chloro-phenyl)-2,2-difluoro-acetic acid (compound 1-252) 1 H NMR(400MHz,DMSO-d6):δ 7.24(d,1H),7.17(d,1H),6.56-6.52(m,1H),6.10(br s,2H)ppm 2-(2-Amino-3,5,6-trichloro-phenyl)-2,2-difluoro-acetic acid (compound 1-81) 1 H NMR(400MHz,DMSO-d6):δ 7.58(s,1H),6.18(s,2H)ppm 2-(2-amino-3,5-dichloro-phenyl)-2,2-difluoro-ammonium acetate (compound 7-253) 1 H NMR(400MHz,DMSO-d6):δ 7.38(s,1H),7.13(m,1H),7.10(s,4H),6.24(s,2H)ppm 2-(2-amino-5-chloro-phenyl)-2,2-difluoro-acetate lithium (compound 5-251) 1H NMR(400MHz,DMSO-d6):δ 7.08-7.07(m,1H),7.06-7.03(m,1H),6.62-6.60(m,1H),5.95(s,2H)ppm 2-(6-amino-2,3-dichloro-phenyl)-2,2-difluoro-acetate lithium (compound 5-80) 1 H NMR(400MHz,DMSO-d6):δ 7.19(d,1H),6.61(d,1H),5.89(s,2H)ppm 2-(3,6-difluoro-2-hydroxyphenyl)-2,2-difluoroethyl acetate (compound 3-297) 1 H NMR(400MHz,DMSO-d6):δ 11.20(s,1H),7.57-7.47(m,1H),6.94-6.88(m,1H),4.33(q,2H),1.22(t,3H)ppm 2-(4,5-Dichloro-2-hydroxy-phenyl)-2,2-difluoro-acetic acid (compound 1-298) 1 H NMR(400MHz,DMSO-d6):δ 7.64(s,1H),7.27(s,1H)ppm 2-(3-chloro-6-fluoro-2-methoxyphenyl)-2,2-difluoroacetic acid (compound 7-325) 1 H NMR(400MHz,DMSO-d6):δ 7.55(s,1H),7.26(bs,4H),7.07-7.02(m,1H),3.75(s,3H)ppm 2-(5-chloro-2-fluoro-4-methoxy-phenyl)-2,2-difluoro-ammonium acetate (compound 7-31) 1 H NMR(400MHz,DMSO-d6):δ 7.43-7.41(m,1H),7.14-7.05(m,5H),3.87(s,3H)ppm was prepared.

[0156] Compounds 1-3, 1-9, 1-32, 1-263, 5-255, 1-7, 1-341, 1-304, 1-20, 1-328, 1-1, 1-305, 1-186, 1-6, 1-2 and 1-473 are available as of the priority date of this application from commercial sources such as Enamine, Accela and ChemDiv.

[0157] Formulation Examples

[0158] [Table 2]

[0159] The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to give a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0160] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0161] Emulsions of any required dilution rate which can be used for plant protection can be obtained from this concentrate by dilution with water.

[0162] [Table 3]

[0163] Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill.

[0164] Extrusion Granules Active ingredient 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0165] The combination is mixed with the auxiliaries and ground, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0166] Coated Granules Active ingredient: 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0167] In a mixer, the finely ground combination is applied uniformly to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0168] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether 6% (15 mol of ethylene oxide) Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0169] The finely ground combination is thoroughly mixed with the adjuvant to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.

[0170] Slow-release capsule suspension 28 parts of the combination are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate-mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size is achieved. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete.

[0171] The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The medium capsule diameter is 8-15 microns.

[0172] The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose.

[0173] Biological Examples Biological potency Seeds of the various test species were sown in unsterilized compost in small pots. After cultivation for 1 day (pre-emergence) or 7 days (post-emergence) in controlled conditions in a glasshouse (24 / 16°C, day / night; 14 hours light; 65% humidity), the plants were sprayed with 1 mg of active ingredient formulated in 466 μl of acetone / water / Tween 20 (49.75:49.75:0.5) solution equivalent to 1000 g / ha. After the leaves had dried, the pots were kept in a glasshouse (24 / 16°C, day / night; 14 hours light; 65% humidity) and watered twice a day. After 12 days, the tests were evaluated and scored (100=total damage to the plants, 0=no damage to the plants). The results are shown in Table 2 below.

[0174] [Table 4]

[0175] Pre-emergence biological efficacy Weed and / or crop seeds were sown in standard soil in pots. After one day of cultivation under controlled conditions in a greenhouse (24 / 19°C, day / night; 16 hours of light), the plants were sprayed with a spray solution derived from a formulation of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50g / l solution, which was then diluted using 0.2% Genapol XO80 as diluent.

[0176] The test plants were then grown under controlled conditions in a greenhouse (24 / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice a day. After 13 days, the tests were evaluated (100 = total damage to the plants; 0 = no damage to the plants). The results are shown in Table 3 below.

[0177] [Table 5] TIFF2024518834000055.tif249152 TIFF2024518834000056.tif108160

[0178] Post-emergence biological efficacy Weed and / or crop seeds were sown in standard soil in pots. After 14 days of cultivation under controlled conditions in a greenhouse (24 / 19°C, day / night; 16 hours of light), the plants were sprayed with a spray solution derived from a formulation of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50g / l solution, which was then diluted using 0.2% Genapol XO80 as diluent.

[0179] The test plants were then grown under controlled conditions in a greenhouse (24 / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice a day. After 13 days, the tests were evaluated (100 = total damage to the plants; 0 = no damage to the plants). The results are shown in Table 4 below.

[0180] [Table 6] TIFF2024518834000058.tif249151 TIFF2024518834000059.tif101159

[0181] The invention is defined by the claims.

Claims

1. Formula (I) 【Chemistry 1】 (In the formula, Each of R1, R2, R4, and R5 is hydrogen, halogen, amino, cyano, nitro, hydroxyl, C 1 ~C 5 Alkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkoxy, C 2 ~C 3 Alkenyl, C 2 ~C 3 Alkynyl, C 1 ~C 2 Haloalkoxy, halophenyl, C 1-2 Haloalkyl, C 1-2 Alkoxy C 1-2 Alkyl, C 1-2 Alkoxycarbonyl, C 1 ~C 2 Alkylsulfanyl, C 1 ~C 2 Alkylsulfinyl and C 1 ~C 2 alkylsulfonyl, and only one of R1, R2, R4, and R5 is C 1 ~C 4 Not alkoxy, or R1 and R2 together with the carbon atom to which they are attached form a 5- or 6-membered ring, the 6-membered ring containing 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), the 5-membered ring contains 1 or 2 heteroatoms independently selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is selected from hydrogen, halogen, and C. 1 ~C 2 independently selected from the group consisting of alkyl; R3 is hydrogen, halogen, amino, cyano, hydroxyl, C 1 ~C 5 Alkyl, C 1 ~C 4 Alkoxy, C 2 ~C 3 Alkenyl, C 2 ~C 3 Alkynyl, C 1 ~C 2 selected from the group consisting of haloalkoxy and halophenyl; At least one of R1, R2, R3, R4, and R5 is amino, cyano, nitro, hydroxyl, C 2 ~C 5 Alkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkoxy, C 2 ~C 3 Alkenyl, C 2 ~C 3 Alkynyl, C 1 ~C 2 Haloalkoxy, halophenyl, C 2 Haloalkyl, C 1-2 Alkoxy C 1-2 Alkyl, C 1-2 Alkoxycarbonyl, C 1 ~C 2 Alkylsulfanyl, C 1 ~C 2 Alkylsulfinyl and C 1 ~C 2 alkylsulfonyl; or R1 and R2 together with the carbon atom to which they are attached form a 5- or 6-membered ring, the 6-membered ring containing 0, 1, or 2 nitrogen atoms, provided that any nitrogen in the 6-membered ring is adjacent to the benzene ring in structure (I), the 5-membered ring contains 1 or 2 heteroatoms independently selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is selected from hydrogen, halogen, and C. 1 ~C 2 alkyl; and R6 is hydrogen, benzyl and C 1 ~C 3 alkyl) or an agriculturally acceptable salt of said compound as a herbicide.

2. The use according to claim 1, wherein in the compound of formula (I), R6 is hydrogen.

3. The use according to claim 1, wherein in the compound of formula (I), R3 is hydrogen.

4. The use according to claim 1, wherein in the compound of formula (I), each of R4 and R5 is selected from the group consisting of hydrogen and halogen.

5. In the compound of formula (I), each of R1, R2, R4, and R5 is hydrogen, halogen, cyano, nitro, C 1 ~C 2 Alkylsulfanyl, C 1 ~C 4 Alkoxy and C 1 ~C 3 2. The method of claim 1, wherein said alkyl group is independently selected from the group consisting of alkyl.

6. In the compound of formula (I), each R1 and R2 is selected from halogen, cyano, nitro, C 1 ~C 3 Alkyl, and C 1 ~C 2 independently selected from the group consisting of alkoxy; 2. The use of claim 1, wherein R1 and R2, together with the carbon atom to which they are attached, form a 5- or 6-membered ring, said 6-membered ring containing 0, 1 or 2 nitrogen atoms, with the proviso that any nitrogen in said 6-membered ring is adjacent to a benzene ring in structure (I), said 5-membered ring contains 1 or 2 heteroatoms independently selected from the group consisting of nitrogen and oxygen, and each R4 and R5 is independently selected from the group consisting of hydrogen, halogen, and C1-C2 alkyl.

7. In the compound of formula (I), one of R1 and R2 is C 1 ~C 4 2. The use according to claim 1, wherein R1 is alkoxy and the other of R1 and R2 is hydrogen.

8. The use according to claim 1, wherein in the compound of formula (I), R1 and R2 together with the carbon atom to which they are attached form a five-membered heterocycle, said five-membered heterocycle being fully saturated or partially saturated.

9. The use according to claim 1, wherein in the compound of formula (I), R1 and R2 together with the carbon atom to which they are attached form a six-membered ring, and said six-membered ring is aromatic.

10. In the compound of formula (I), R1 and R2 together with the carbon atom to which they are attached form a 5- or 6-membered ring, and the 5- or 6-membered ring is preferably free of halogen, C 1 ~C 2 Alkyl and C 1-3 Alkoxycarbonyl C 1-3 The use according to claim 1, substituted by 1 to 3 substituents independently selected from the group consisting of alkyl.

11. In said compound of formula (I), at least one of said 1 to 3 substituents is C 1 ~C 2 Alkyl or C 1-3 Alkoxycarbonyl C 1-3 11. The use according to claim 10, which is alkyl and which is substituted by one or two halogens.

12. 10. A herbicidal composition comprising (i) a compound of formula (I) as defined in claim 1 or an agriculturally acceptable salt of said compound, and (ii) an agriculturally acceptable formulation adjuvant.

13. 13. The herbicidal composition of claim 12 further comprising at least one additional pesticide.

14. 14. The herbicidal composition of claim 13, wherein the additional pesticide is a herbicide or a herbicide safener.

15. A method for controlling weeds in a locus which comprises applying to said locus a weed controlling amount of a compound of formula (I) as defined in any one of claims 1 to 11 or an agriculturally acceptable salt of said compound, or a herbicidal composition as defined in any one of claims 12 to 14.

Images