Herbicidal tetrazole compounds

Abstract

This invention relates to compounds having formula (I): (I) or an agronomically acceptable salt thereof, wherein R 1 R 2 R 3 R 4 and R 5 As described herein. The present invention further relates to compositions comprising the said compounds, methods of controlling weeds using the said compositions, and the use of compounds having formula (I) as herbicides, and intermediate compounds for manufacturing compounds having formula (I).

Description

[0001] This invention relates to novel herbicidal compounds, methods for their preparation, herbicidal compositions comprising these novel compounds, and their use for controlling weeds (particularly in useful plant crops) or for inhibiting plant growth.

[0002] N-(tetrazole-5-yl)-arylformamide is disclosed, for example, in WO 2012 / 028579. This invention relates to novel arylformamides.

[0003] Therefore, according to the present invention, a compound having formula (I) is provided:

[0004]

[0005] Or its agronomically acceptable salt.

[0006] in:-

[0007] R 1 Select from the group consisting of: C1-C4 alkyl-, C1-C4 haloalkyl-, C1-C4 alkoxy-C1-C4 alkyl- and C1-C4 haloalkoxy-C1-C4 alkyl-;

[0008] R 2 Choose from the group consisting of: halogens, C1-C6 alkyl-, C1-C3 alkoxy-, C1-C6 haloalkyl-, and -S(O). p C1-C6 alkyl groups;

[0009] R 3 It is a C1-C6 haloalkyl group;

[0010] R 4 The substituents are selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3-alkyl-, C3-C6-cycloalkyl-C1-C3 alkyl-, phenyl and heteroaryl, wherein, where chemically feasible, the phenyl or heteroaryl group may optionally be substituted by 1 to 4 substituents, the substituents being independently selected from the group consisting of: halogen, C1-C3-alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3-haloalkoxy and cyano;

[0011] R 5 It is hydrogen or C1-C3 alkyl; and

[0012] p is 0, 1, or 2.

[0013] C1-C6 alkyl and C1-C4 alkyl include, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), isobutyl (i-Bu), sec-butyl, and tert-butyl (t-Bu).

[0014] C3-C6 cycloalkyl groups include cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl).

[0015] Halogens (or halogenated) encompass fluorine, chlorine, bromine, or iodine. The above applies correspondingly to halogens in other definitional contexts, such as alkyl halogens.

[0016] C1-C6 haloalkyl groups include, for example, fluoromethyl-, difluoromethyl-, trifluoromethyl-, chloromethyl-, dichloromethyl-, trichloromethyl-, 2,2,2-trifluoroethyl-, 2,2-difluoroethyl-, 1,1-difluoroethyl-, 1,1,2,2-tetrafluoroethyl-, 2-fluoroethyl-, 2-chloroethyl-, pentafluoroethyl-, 1,1-difluoro-2,2,2-trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl-, heptafluoropropyl-, and perfluorohexyl-. C1-C4 haloalkyl groups include, for example, fluoromethyl-, difluoromethyl-, trifluoromethyl-, chloromethyl-, dichloromethyl-, trichloromethyl-, 2,2,2-trifluoroethyl-, 2-fluoroethyl-, 2-chloroethyl-, pentafluoroethyl-, 1,1-difluoro-2,2,2-trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl-, and heptafluoropropyl-.

[0017] C1-C6 alkyl-S-(alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, or tert-butylthio, preferably methylthio or ethylthio.

[0018] C1-C6 alkyl-S(O)-(alkyl sulfinyl) is, for example, methyl sulfinyl, ethyl sulfinyl, propyl sulfinyl, isopropyl sulfinyl, n-butyl sulfinyl, isobutyl sulfinyl, sec-butyl sulfinyl or tert-butyl sulfinyl, preferably methyl sulfinyl or ethyl sulfinyl.

[0019] C1-C6 alkyl-S(O)2-(alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0020] In a preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 1Choose from the group consisting of: methyl, ethyl, and n-propyl.

[0021] In another preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 2 The following groups are selected: methyl, Cl, -CF3 and -SO2 methyl, with Cl being preferred.

[0022] In another preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 3 It is either -CF3 or -CHF2.

[0023] In another preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 4 The group is selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3-alkyl-, C3-C6-cycloalkyl-C1-C3-alkyl-, phenyl and heteroaryl, wherein, where chemically feasible, the phenyl or heteroaryl group may optionally be substituted by 1 to 4, more preferably 1 to 2, substituents independently selected from the group consisting of: halogen, C1-C3-alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3-haloalkoxy and cyano.

[0024] In R 4 In the case of heteroaryl groups, suitable heteroaryl groups are selected from the following groups: Het-1, Het-2, Het-3, Het-4, Het-5, Het-6, Het-7, Het-8 and Het-9.

[0025]

[0026] Where chemically feasible, these heteroaryl groups may optionally be substituted with one to four substituents, which are independently selected from the group consisting of halogens, C1-C3-alkyl groups, C1-C3-alkoxy groups, C1-C3-haloalkyl groups, C1-C3-haloalkoxy groups, and cyano groups.

[0027] In a more preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 4The group selected is from the group consisting of: methyl, ethyl, isopropyl, n-propyl, trifluoromethyl-, methoxyethyl-, cPr, cPr-CH2-, phenyl, Het-1, Het-2, Het-3, Het-4 and Het-5, wherein, where chemically feasible, phenyl, Het-1, Het-2, Het-3, Het-4 and Het-5 may optionally be substituted by one or two substituents independently selected from the group consisting of: halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy and cyano.

[0028] In a particularly preferred embodiment, R 4 Selected from the group consisting of: C1-C6 alkyl-, C3-C6 cycloalkyl-, and C3-C6-cycloalkyl-C1-C3 alkyl-. In a more preferred embodiment, R 4 The group consisting of methyl, ethyl, n-propyl, isopropyl, c-propyl, isobutyl and c-PrCH2- is preferred, and methyl or ethyl is even more preferred.

[0029] In another preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 5 It is methyl or hydrogen, preferably hydrogen.

[0030] Compounds having formula (I) (and certain intermediate compounds used to synthesize compounds having formula (I)) may contain an asymmetric center and may exist as a single enantiomer, in any ratio of enantiomer pairs, or may contain more than one asymmetric center, containing diastereomers in all possible ratios. Typically, one of these enantiomers has enhanced biological activity compared to the other possibilities.

[0031] The present invention also includes all possible geometric and tautomer forms of compounds having formula (I).

[0032] The invention also includes agronomically acceptable salts, wherein compounds having formula (I) can form these salts with amines (e.g., ammonia, dimethylamine, and triethylamine), alkali metal and alkaline earth metal bases, or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, oxides, alcohols, and bicarbonates and carbonates used as salt-forming agents, emphasis is placed on hydroxides, alcohols, oxides, and carbonates of lithium, sodium, potassium, magnesium, and calcium, but especially those of sodium, magnesium, and calcium. Corresponding trimethylsulfonium salts may also be used.

[0033] The compounds of formula (I) according to the present invention can be used as herbicides on their own, but are typically formulated into herbicidal compositions using formulation adjuvants such as carriers, solvents, and surfactants (SFAs). Therefore, the present invention further provides a herbicidal composition comprising the herbicidal compounds of the present invention and agriculturally acceptable formulation adjuvants. The composition may be in the form of a concentrate, which is diluted prior to use, although it may also be formulated as a ready-to-use composition. Final dilution is typically carried out with water, but may be performed using, in addition to water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0034] The herbicidal composition generally comprises, by weight, from 0.1% to 99%, particularly from 0.1% to 95% of a compound having Formula I and by weight, from 1% to 99.9% of a formulation adjuvant, which preferably comprises, by weight, from 0 to 25% of a surfactant.

[0035] These compositions can be selected from a variety of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include granulated powders (DP), soluble powders (SP), water-soluble granules (SG), water-dispersible granules (WG), wettable powders (WP), granules (GR) (slow-release or fast-release), soluble concentrates (SL), oil-miscible liquids (OL), ultra-low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil-in-water (EW) and water-in-oil (EO)), microemulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS), and seed treatment formulations. In any case, the type of formulation chosen will depend on the specific intended purpose and the physical, chemical, and biological properties of the compound having formula (I).

[0036] Dustable powder (DP) can be prepared by mixing a compound having formula (I) with one or more solid diluents (e.g., natural clay, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, diatomaceous earth, chalk, calcium phosphate, calcium carbonate and magnesium carbonate, sulfur, lime, flour, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture into a fine powder.

[0037] Soluble powders (SPs) can be prepared by mixing a compound having formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate, or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants, or a mixture of said reagents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SGs).

[0038] Wettable powders (WPs) can be prepared by mixing a compound having formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersants, and optionally one or more suspending agents to promote dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WGs).

[0039] Granules (GR) can be formed by granulating a mixture of a compound having formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound having formula (I) (or a solution thereof in a suitable reagent) into a porous particulate material (such as pumice, attapulgite clay, bleaching clay, kieselguhr, diatomaceous earths, or corn cob powder), or by adsorbing a compound having formula (I) (or a solution thereof in a suitable reagent) onto a hard core material (such as sand, silicates, mineral carbonates, sulfates, or phosphates) and, if necessary, drying it to form pre-formed blank granules. Reagents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars, and vegetable oils). One or more other additives (e.g., emulsifiers, wetting agents, or dispersants) may also be included in the granules.

[0040] Dispersible concentrates (DCs) can be prepared by dissolving a compound having formula (I) in water or an organic solvent (such as a ketone, alcohol, or glycol ether). These solutions may contain surfactants (e.g., to improve water dilution or prevent crystallization in spray cans).

[0041] Emulsifiable concentrates (ECs) or oil-in-water emulsions (EWs) can be prepared by dissolving a compound having formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers, or a mixture of said reagents). Suitable organic solvents used in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150, and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone), and alcohols (such as benzyl alcohol, furfuryl alcohol, or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), and dimethylamides of fatty acids (such as C8-C...). 10 (Fatty acid dimethylamide) and chlorinated hydrocarbons. EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow for spray application using appropriate equipment.

[0042] The preparation of an emulsion (EW) involves obtaining a compound of formula (I) as a liquid (or, if not a liquid at room temperature, which can be melted at a reasonable temperature typically below 70°C) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution under high shear into water containing one or more SFAs to produce an emulsion. Suitable solvents used in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0043] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents and one or more SFAs to spontaneously produce a thermodynamically stable, isotropic liquid formulation. The compound having formula (I) is initially present in water or in a solvent / SFA blend. Suitable solvents used in MEs include those described above used in ECs or EWs. MEs can be oil-in-water or water-in-oil systems (whichever system is present can be determined by conductivity measurements) and can be used to mix water-soluble and oil-soluble biocides in the same formulation. MEs are suitable for dilution in water, maintaining as a microemulsion or forming a conventional oil-in-water emulsion.

[0044] Suspension concentrates (SCs) may comprise aqueous or non-aqueous suspensions of finely dispersed insoluble solid particles of a compound having formula (I). SCs can be prepared by ball milling or bead milling of a solid compound having formula (I) with one or more dispersants in a suitable medium to produce a fine-particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the rate of particle settling. Alternatively, a compound having formula (I) may be dry-milled and added to water containing the reagents described above to produce the desired final product.

[0045] Aerosol formulations comprise compounds having formula (I) and suitable propellants (e.g., n-butane). Compounds having formula (I) can also be dissolved or dispersed in a suitable medium (e.g., water or a water-miscible liquid, such as n-propanol) to provide compositions for use in unpressurized, manually operated spray pumps.

[0046] Capsule suspensions (CS) can be prepared in a manner similar to that used in the preparation of EW formulations, but with an additional polymerization stage, resulting in an aqueous dispersion of oil droplets, each droplet encapsulated in a polymer shell and containing a compound of formula (I) and optionally a carrier or diluent for that droplet. The polymer shell can be produced via interfacial polycondensation or via a coagulation process. These compositions can provide controlled release of compounds of formula (I) and can be used for seed treatment. Compounds of formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0047] The composition may contain one or more additives to improve the biocompatibility of the composition, for example by improving wettability, retention, or distribution on a surface; rain resistance on the treated surface; or absorption or flow of compounds having formula (I). Such additives include surfactants (SFAs), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), and blends of these with other bioenhancing adjuvants (components that may assist or modify the effects of compounds having formula (I)).

[0048] Wetting agents, dispersants, and emulsifiers can be cationic, anionic, amphoteric, or nonionic SFAs.

[0049] Suitable cationic types of SFAs include quaternary ammonium compounds (e.g., hexadecyltrimethylammonium bromide), imidazolines, and amine salts.

[0050] Suitable anionic SFAs include alkali metal salts of fatty acids, salts of aliphatic sulfate monoesters (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butyl naphthalene sulfonate, and mixtures of sodium di-isopropyl-naphthalene sulfonate and sodium tri-isopropyl-naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (products of the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), such as the reaction between lauryl alcohol and tetraphosphate; these products may also be ethoxylated), sulfosuccinates, paraffin or olefin sulfonates, taurines, and lignosulfonates.

[0051] Suitable amphoteric types of SFA include betaine, propionate, and glycine salt.

[0052] Suitable nonionic types of SFAs include condensation products of alkyl oxidases (such as ethylene oxide, propylene oxide, butane oxide, or mixtures thereof) with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long-chain fatty acids or hexyl anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); and lecithin.

[0053] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethyl cellulose) and expansive clays (such as bentonite or attapulgite).

[0054] The compounds of this invention can also be used in combination with one or more other herbicides and / or plant growth regulators. Examples of such other herbicides or plant growth regulators include acetochlor, trifluralin (including trifluralin-sodium), bensulfuron, atrazine, azoxystrobin, chlorpyrifos, chlorpyrifos, atrazine, flubutyrazole-M, quinalazine, bensulfuron-methyl (including bensulfuron-methyl), bentazon, bicyclopyranone, bispyridine, bispyribac-sodium, bixlozone, chlorpyrifos, bromobenzonitrile, butachlor, flupropylaturon, chlorpyrifos (including chlorpyrifos-ethyl), chlorpyrifos-methyl, chlorpyrifos-ethyl, chlorpyrifos, chlorpyrifos, clodinafop-methyl, clodinafop-methyl, chlorpyrifos-ethyl, chlorpyrifos, chlorpyrifos-methyl, clodinafop-methyl, clodinafop-methyl, chlorpyrifos-ethyl, chlorpyrifos ... esters), isoxaflutole, dichloropyridinic acid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, dichlorvos, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diethylene glycolamine, dimethylamine, dimethylammonium, potassium salt and sodium salt), dichlorvos, pyrfluthrin, flupyrazole, metolachlor, fenfluridine, dibromodiflubenzuron, diuron, epyrifenacil, ethylbutyrate, ethoxysulfuron, oxazolidinone (including fenfluridine) The following herbicides are listed: quizalofop-ethyl, fenoxasulfone, fenquinotrione, tetrazolium, pyrimisulfuron, diflubenzuron, florpyrauxifen (including florpyrauxifen-benzyl), quizalofop-P-ethyl (including quizalofop-butyl), flumetsulam (including flumetsulam-sodium), fluthiamethoxam, pyrimisulfuron, propyzamide, fluroxypyr, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr-meptyl (including fluroxypyr-meptyl), flufenoxuron, formamide-sulfuron, glufosinate (including L-glufosinate and the ammonium salts of both). Glyphosate (including its hydrazine, isopropylammonium, and potassium salts), halauxifen (including halauxifen-methyl), flupyridine (including flupyridine-methyl), cycloazinone, hydantocidin, methoxyfenozide (including R-methoxyfenozide), imidacloprid, metribuzin, imidacloprid, indazon, iofensulfuron (including iofensulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), iodobenzonitrile, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P (2-methyl-4-chloropropionic acid)Mesosulfuron-methyl (including mesosulfuron-methyl), mesosulfuron-methyl, bensulfuron-methyl, pyrazosulfuron, isoxaflutole, methiozolin, metolachlor, sulfadiazine, cyhalofop-p-ethyl, metsulfuron-methyl, nicosulfuron, dapoxuron, oxadiazon, cyclopyrsulfuron, ethoxysulfuron, paraquat dichlorvos, pendimethalin, penflusulfuron-methyl, bensulfuron-methyl, cyclopyr, propyrisulfuron, pendimethalin, bensulfuron-methyl, flusulfuron-methyl, propyrisulfuron, pendimethalin, bensulfuron-methyl, flusulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, flusulfuron-methyl, propyrisulfuron, pendimethalin, bensulfuron-methyl, flusulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl Pyrimisulfan, pyroxasulfone, pyrazosulfuron, quinclorac, chlorpyrifos, quizalofop-P-tefuryl (including quizalofop-ethyl and quizalofop-P-tefuryl), sulfadiazine, pyrimisulfuron, oxadiazine, simazine, metolachlor, mesosulfuron, sulfonylsulfuron, butisulfuron, terbufos, cyclosulfonone, terbutaline, terbutaline, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, bensulfuron-methyl Herbicides, triazolam, triafamone, wild valerate, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), chlorpyrifos, trifluridinesulfuron (including trifluridinesulfuron-sodium), trifludimoxazin, trifluralin, flumethrin, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazoline-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazoline-2-one [Fluoromethyl)-2-pyridyl]imidazolin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolin-2-one, 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2 ... [2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl- ... Hexane-1,3-dione, 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]cyclohexane-1,3-dione, 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazin-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid), 3-ethylthioalkyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(isopropylthioalkylmethyl)-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, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, 1-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-4,4,4-trifluoro-but-1-one, and 5-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-3-(difluoromethyl)isoxazole.

[0055] Mixtures of compounds having Formula I may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition, British Crop Protection Council, 2012.

[0056] Compounds having Formula I can also be used in mixtures with other agrochemicals, such as fungicides, nematicides, or insecticides, examples of which are given in the Handbook of Pesticides.

[0057] The mixing ratio of the compound having Formula I to the mixed formulation is preferably from 1:100 to 1000:1.

[0058] These mixtures can be advantageously used in the formulations mentioned above (in which case "active ingredient" refers to the corresponding mixture of a compound having Formula I and a mixed formulation).

[0059] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include cloquintocet, cloquintocet (including cloquinoline), cyclopropanesulfonamide, dichloropropeneamine, cloquinoxal (including cloquinoxal-ethyl), cloquinoxaline, flufenoxam, cloquinoxalic acid (including cloquinoxalic acid-ethyl), mefenpyr (including cloquinoxalic acid-diethyl), metcamifen, and cloquinoxalic acid nitrate. Particularly preferred are mixtures of compounds having formula I with cyclopropanesulfonamide, cloquinoxalic acid-ethyl, cloquinoline, and / or metcamifen.

[0060] Safeguards of compounds having formula I may also be in the form of esters or salts, as mentioned, for example, in the Handbook of Pesticides, 16th Edition (BCPC), 2012. References to quaternary ammonium salts also apply to their lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts (as disclosed in WO 02 / 34048), and references to quaternary ammonium-ethyl also apply to quaternary ammonium salts, etc.

[0061] Preferably, the mixing ratio of the compound having Formula I to the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0062] These mixtures can be advantageously used in the formulations mentioned above (in which case "active ingredient" refers to a corresponding mixture of a compound having chemical formula I and a safener).

[0063] The present invention further provides a method for controlling weeds at a site, the method comprising applying to the site a composition comprising a compound having formula (I) to control the amount of weeds. Furthermore, the present invention further provides a method for selectively controlling weeds at a site comprising crop plants and weeds, wherein the method comprises applying to the site a composition according to the invention to control the amount of weeds. 'Control' means killing, reducing, or delaying growth or preventing or reducing germination. Generally, the plant to be controlled is an unwanted plant (weed). 'Site' means an area in which plants are growing or will grow. Some crop plants may inherently tolerate the herbicidal effects of compounds having formula (I). However, in some cases, it may be necessary to engineer tolerance into crop plants, for example, through genetic engineering. Therefore, it is possible for crop plants to be conferred tolerance to HPPD inhibitors via genetic engineering. Methods for conferred tolerance to HPPD inhibitors on crop plants are known, for example, from WO 0246387. Therefore, in even more preferred embodiments, the crop plant is genetically modified with respect to a polynucleotide containing a DNA sequence encoding an HPPD inhibitor-resistant HPPD enzyme derived from bacteria (more specifically, from *Pseudomonas fluorescens* or *Shewanella colwelliana*) or from plants (more specifically, from monocotyledons or even more specifically, from barley, maize, wheat, rice, *Brachiaria*, *Cenchrus*, *Lolium*, *Festuca*, *Setaria*, *Eleusine*, *Sorghum*, or *Avena* species). Several HPPD-tolerant soybean transgenic “events” are known, including, for example, SYHT04R (WO 2012 / 082542), SYHT0H2 (WO 2012 / 082548), and FG72. Other polynucleotide sequences that can be used to provide plants tolerant to the compounds of the present invention are disclosed, for example, in WO 2010 / 085705 and WO 2011 / 068567. Crop plants in which the compositions according to the present invention can be used therefore include crops such as cereals, such as barley and wheat, cotton, rapeseed, sunflower, maize, rice, soybean, sugar beet, sugarcane, and turf.

[0064] Crop plants can also include trees, such as fruit trees, palm trees, coconut trees, or other nut-bearing plants. It also includes vines (such as grapes), shrubs, fruit trees, fruit plants, and vegetables.

[0065] The application rate of compounds having formula I can vary within a wide range and depends on soil properties, application method (pre- or post-emergence; seed dressing; application in seed furrows; no-till application, etc.), crop species, one or more weeds to be controlled, primary climatic conditions, and other factors governed by the application method, application time, and target crop. Compounds having formula I according to the invention are typically applied at rates from 10 g / ha to 2000 g / ha, particularly from 50 g / ha to 1000 g / ha.

[0066] The composition is usually applied by spraying, typically using a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or immersion can also be used.

[0067] Crop plants should be understood to include those crop plants that have been conferred tolerance to herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACC enzyme-inhibitors, and HPPD-inhibitors) through conventional breeding methods or through genetic engineering. Examples of crops conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods are... Summer rapeseed (canola). Examples of crops that have been conferred herbicide tolerance through genetic engineering include, for example, maize varieties resistant to glyphosate and glufosinate. and The trademark is available for purchase.

[0068] Crop plants should also be understood as those that have been genetically engineered to resist harmful insects, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the boll weevil), and Bt potato (resistant to the Colorado beetle). An example of Bt corn is... The Bt 176 maize hybrid (Syngenta Seeds). Bt toxin is a protein naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073, and EP-A-427 529. Examples of transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are... (Corn), Yield (corn), (cotton), (cotton), (potato), as well as Plant crops or their seed material can be both herbicide-resistant and insect-resistant (“cumulative” transgenic results). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0069] Crop plants should also be understood to include those obtained through conventional breeding or genetic engineering methods and that contain so-called exported traits (such as improved storage stability, higher nutritional value, and improved flavor).

[0070] Other useful plants include turfgrass, which is planted for lawns, such as on golf courses, lawns, parks, and roadsides, or commercially, as well as ornamental plants such as flowers or shrubs.

[0071] These compositions can be used to control unwanted plants (collectively referred to as 'weeds'). Weeds to be controlled can be monocotyledonous species, such as *Agrostis*, *Alopecurus*, *Avena*, *Brachiaria*, *Bromus*, *Cenchrus*, *Cyperus*, *Digitaria*, *Echinochloa*, *Eleusine*, *Lolium*, *Monochoria*, *Rottboellia*, *Sagittaria*, *Scirpus*, and *Setaria*. This includes species in the genera *Sorghum*, as well as dicotyledonous species such as *Abutilon*, *Amaranthus*, *Ambrosia*, *Chenopodium*, *Chrysanthemum*, *Conyza*, *Galium*, *Ipomoea*, *Nasturtium*, *Sida*, *Sinapis*, *Solanum*, *Stellaria*, *Veronica*, *Viola*, and *Xanthium*. Weeds can also include plants that could be considered crop plants but grow outside of crop areas ('escapes'), or plants that grow from seeds left from previously cultivated crops ('volunteers'). Such free-growing or wild plants can be resistant to certain other herbicides.

[0072] The compounds of the present invention can be prepared according to the following scheme.

[0073] Compounds having formula (I) can be prepared from benzoic acid having formula (II) and amine having formula (III).

[0074]

[0075] Following the above scheme, benzoic acid having formula (II) and amine having formula (III) are treated with a suitable amide coupling agent in a suitable solvent. Additives that improve the reaction rate may be optionally added. An example of a suitable amide coupling agent is thionyl chloride. An example of a suitable solvent is pyridine. An example of a suitable additive is N-methylimidazole.

[0076] Benzoic acid having formula (II) can be prepared by hydrolysis of ester having formula (IV), wherein “Alk” is defined as C1-C6 alkyl (preferably methyl or ethyl).

[0077]

[0078] According to the above scheme, benzoic acid having formula (IV) is treated with a hydroxide base (e.g., sodium hydroxide) in a suitable solvent (e.g., a 3:1 mixture of ethanol and water) to obtain a compound having formula (II).

[0079] Compounds having formula (IV) can be prepared from aniline having formula (V) and sulfonyl chloride having formula (VI).

[0080]

[0081] In a suitable solvent such as tetrahydrofuran, aniline having formula (V) is treated with a sulfonyl chloride having formula (VI). A base may be required in this reaction, depending on R. 2 R 3 and R 5 The properties of [the base]. A suitable example of a base is lithium hexamethyldisilazane.

[0082] Compounds having formula (V) can be prepared from compounds having formula (VII).

[0083]

[0084] The conditions used in this transformation will depend on R. 2 Properties. For example, in R 2 In the case of chlorine, the compound having formula (VII) is treated with thiocyanate and a catalytic amount of diisopropylamine.

[0085] Alternatively, compounds having formula (I) can be prepared from compounds having formula (VIII) and sulfonyl chlorides having formula (VI).

[0086]

[0087] In a suitable solvent such as acetonitrile, a compound having formula (VIII) is treated with a compound having formula (VI) to obtain a compound having formula (I).

[0088] Compounds having formula (VIII) can be prepared from compounds having formula (IX) and amines having formula (III).

[0089]

[0090] Compounds having formula (IX) and compounds having formula (III) are treated with a base (e.g., 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diacrylin) in a suitable solvent such as acetonitrile.

[0091] Compounds having formula (IX) can be prepared from benzoic acid having formula (X) and pentafluorophenol.

[0092]

[0093] Compounds having formula (X) are treated with pentafluorophenol and an ester coupling agent (e.g., 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) in a suitable solvent such as dichloromethane.

[0094] Compounds having formula (X) can be prepared from compounds having formula (V), where “Alk” is defined as C1-C6 alkyl.

[0095]

[0096] In a suitable solvent (e.g., a 3:1 mixture of ethanol and water), a compound having formula (V) is treated with a hydroxide base (e.g., sodium hydroxide) to obtain a compound having formula (X).

[0097] The present invention further provides a compound having formula (II).

[0098]

[0099] Where R 2 R 3 and R 5 It is as defined in compounds having formula (I), and R 4 It is a C1-C6 alkyl group.

[0100] In a preferred embodiment, a compound having formula (II) is provided, wherein R 2 It is methyl or chlorine, R 3 Is it CF3 or CHF2, R 4 The group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, c-propyl, and c-propyl-(CH2)- (more preferably methyl or ethyl) is selected, and R 5 Choose from the group consisting of: hydrogen, methyl, or ethyl.

[0101] The present invention further provides a compound having formula (IV).

[0102]

[0103] Where R 2 R 3 R 4 and R 5 It is as defined in compounds having formula (I), and "Alk" is a C1-C6 alkyl group (more preferably methyl or ethyl). In a preferred embodiment, a compound having formula (II) is provided, wherein R 2 It is methyl or chlorine, R 3 Is it CF3 or CHF2, R 4 The group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, c-propyl, and c-propyl-(CH2)- (more preferably methyl or ethyl) is selected, and R 5 Choose from the group consisting of: hydrogen, methyl, or ethyl.

[0104] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (refer to the tables provided herein).

[0105] Example P1. Preparation of compound 1.002.

[0106] Step 1: Preparation of methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate

[0107] Toluene (45 mL) and diisopropylamine (0.13 g, 1.3 mmol) were added to a round-bottom flask containing methyl 3-amino-4-(trifluoromethoxy)benzoate (3.00 g, 12.8 mmol). The reaction mixture was heated to 70 °C. Thionyl chloride (1.55 g, 11.5 mmol) was slowly added to the reaction mixture over 10 min, and the reaction mixture rapidly turned yellow and released gas. After the addition was complete, the reaction mixture was stirred for another 40 min and then cooled. Water (30 mL) was added and toluene was removed under reduced pressure. The reaction mixture was added to a separatory funnel and extracted with ethyl acetate (2 × 60 mL). The combined organic layers were washed with brine (30 mL), dried over MgSO4, and concentrated. The residue was purified by reversed-phase column chromatography (40%–80% MeCN gradient in H₂O containing 0.1% formic acid) to give methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (1.88 g, 6.97 mmol, 55%) as a yellow liquid. ¹H NMR (400 MHz, d⁴-methanol) δppm 7.19 (dq, J = 8.56, 1.55 Hz, ¹H) 7.07 (d, J = 8.80 Hz, ¹H) 3.87–3.91 (s, ³H).

[0108] Step 2: Preparation of 3-amino-2-chloro-4-(trifluoromethoxy)benzoic acid

[0109] Lithium hydroxide monohydrate (4.67 g, 111 mmol) was added to a stirred solution of methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (10.0 g, 37.1 mmol) in tetrahydrofuran (120 mL) and water (30 mL) at room temperature. The mixture was stirred at room temperature for 22 hours. The mixture was then cooled to 0 °C (ice-water bath). The reaction was quenched by the slow addition of 2 M HCl aqueous solution (100 mL). The cooling bath was removed and the mixture was warmed to room temperature. EtOAc (100 mL) and brine (50 mL) were added, and the phases were separated. The aqueous phase was extracted with EtOAc (100 mL). The combined organic phases were dried (MgSO4), filtered, and concentrated under vacuum to give 3-amino-2-chloro-4-(trifluoromethoxy)benzoic acid (9.25 g, 34.4 mmol, 93%) as a beige solid, which was used in the next step without further purification. 1H NMR (400MHz, CD3OD): δ=7.20-7.15 (m, 1H), 7.13-7.08 (m, 1H).

[0110] Step 3: Preparation of (2,3,4,5,6-pentafluorophenyl)3-amino-2-chloro-4-(trifluoromethoxy)benzoate

[0111] 3-(ethyliminomethyleneamino)-N,N-dimethyl-propane-1-amine hydrochloride (8.32 g, 43.4 mmol) was added to a stirred suspension of 3-amino-2-chloro-4-(trifluoromethoxy)benzoic acid (9.24 g, 36.2 mmol) and 2,3,4,5,6-pentafluorophenol (7.32 g, 39.8 mmol) in dichloromethane (139 mL). The mixture was stirred at room temperature for one hour. The reaction was then quenched by adding saturated aqueous NaHCO3 solution (100 mL). The mixture was stirred at room temperature for another 5 minutes. Dichloromethane (40 mL) was added, and the phases were separated. The aqueous phase was extracted with dichloromethane (50 mL). The combined organic phases were passed through a phase separation column. The filtrate was adsorbed onto silica, and the crude product was purified by rapid column chromatography (cyclohexane / EtOAc, gradient 98:2 to 93:7). The fractions containing the product were combined and concentrated under vacuum to give (2,3,4,5,6-pentafluorophenyl)3-amino-2-chloro-4-(trifluoromethoxy)benzoate (12.54 g, 29.74 mmol, 82%) as a pale yellow crystalline solid. ¹H NMR (400 MHz, CDCl₃) δ = 7.53 (d, ¹H), 7.26–7.22 (m, ¹H), 4.62 (br s, 2H).

[0112] Step 4: Preparation of 3-amino-2-chloro-N-(1-ethyltetrazole-5-yl)-4-(trifluoromethoxy)benzamide

[0113] To a stirred solution of (2,3,4,5,6-pentafluorophenyl)3-amino-2-chloro-4-(trifluoromethoxy)benzoate (6.00 g, 14.2 mmol) in acetonitrile (120 mL) at room temperature, 1-ethyltetrazole-5-amine (3.54 g, 31.3 mmol) was added, followed by 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2λ5-diazaphosphine-2-amine (9.34 mL, 31.3 mmol). The mixture was stirred at room temperature for 30 minutes. The reaction was then quenched by adding 2 M HCl aqueous solution (100 mL). The mixture was stirred at room temperature for another 5 minutes and then diluted with EtOAc (100 mL). Phase separation: The aqueous phase was extracted with EtOAc (100 mL). The combined organic phases were washed with brine (100 mL), dried (MgSO4), filtered, and adsorbed onto C18 silica. The crude product was partially purified by reversed-phase chromatography (acetonitrile + 0.1% formic acid / water + 0.1% formic acid, gradient 40:60 to 60:40). Fractions containing the product were combined, partially concentrated under vacuum to remove acetonitrile, and lyophilized to obtain a partially purified material. The partially purified material was adsorbed onto C18 silica and further purified by reversed-phase chromatography (acetonitrile + 0.1% formic acid / water + 0.1% formic acid, gradient 35:65 to 55:45). The clean fractions were combined and partially concentrated under vacuum to remove MeCN. The mixture was then diluted with brine (50 mL) and extracted with EtOAc (2 × 150 mL). The combined organic phases were dried (MgSO4), filtered, and concentrated under vacuum to give 3-amino-2-chloro-N-(1-ethyltetrazole-5-yl)-4-(trifluoromethoxy)benzamide (4.26 g, 11.5 mmol, 81%) as a white foam. ¹H NMR (400 MHz, CD3OD): δ = 7.27 (dq, 1H), 6.94 (d, 1H), 4.42 (q, 2H), 1.58 (t, 3H).

[0114] Step 5: Preparation of 2-chloro-3-(ethylsulfonylamino)-N-(1-ethyltetrazole-5-yl)-4-(trifluoromethoxy)benzamide

[0115] Ethylenesulfonyl chloride (1.28 mL, 13.5 mmol) was added to a stirred solution of 3-amino-2-chloro-N-(1-ethyltetrazole-5-yl)-4-(trifluoromethoxy)benzamide (250 mg, 0.677 mmol) in acetonitrile (2.50 mL) at room temperature. The stirred mixture was heated to mild reflux (heat plate temperature 90 °C) for 72 hours. The mixture was then cooled to room temperature. Water (1 mL) was added. The mixture was stirred at room temperature for another hour and then diluted with EtOAc (20 mL), water (10 mL), and brine (20 mL). The aqueous phase was separated. The aqueous phase was extracted with EtOAc (20 mL). The combined organic phases were dried (MgSO4), filtered, and concentrated under vacuum. The crude product was partially purified by reversed-phase rapid chromatography (acetonitrile + 0.1% formic acid / water + 0.1% formic acid, gradient 30:70 to 50:50). Fractions containing the product were combined, partially concentrated under vacuum to remove acetonitrile, and then lyophilized to obtain a partially purified material. The partially purified material was then further purified by rapid column chromatography (DCM / MeOH, gradient 99:1 to 92:8). The clean fractions were combined and concentrated under vacuum to give 2-chloro-3-(ethylsulfonylamino)-N-(1-ethyltetrazol-5-yl)-4-(trifluoromethoxy)benzamide (116 mg, 0.249 mmol, 37%) as a grayish-white solid. ¹H NMR (400 MHz, MeCN-d3): δ = 7.69 (d, 1H), 7.54–7.48 (m, 1H), 4.33 (q, 2H), 3.31 (q, 2H), 1.53 (t, 3H), 1.44 (t, 3H).

[0116] Example P2. Preparation of compound 1.003.

[0117] For example, methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate is prepared in step 1 of preparation 1.002.

[0118] Step 1: Preparation of methyl 2-chloro-3-(ethylsulfonylamino)-4-(trifluoromethoxy)benzoate

[0119] To a stirred solution of methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (1.00 g, 3.52 mmol) in tetrahydrofuran (10.0 mL, anhydrous) at -78 °C under a nitrogen atmosphere, lithium bis(trimethylsilyl)amino (1 M, 8.81 mL, 8.81 mmol in THF) was added dropwise over 15 minutes. The mixture was stirred at -78 °C for 45 minutes, followed by the dropwise addition of ethanesulfonyl chloride (0.434 mL, 4.58 mmol) over 2 minutes. The mixture was then stirred at -78 °C for another 2 hours. The reaction was then quenched by adding saturated aqueous NH4Cl solution (5 mL). The mixture was heated to room temperature. EtOAc (40 mL) and 2 M HCl aqueous solution (40 mL) were added, and the phase was separated. The aqueous phase was extracted with EtOAc (40 mL). The combined organic phases were washed with brine (60 mL), dried (MgSO4), filtered, and concentrated under vacuum. The crude product was purified by rapid column chromatography on silica (cyclohexane / EtOAc, gradient 90:10 to 60:40). The fractions containing the product were combined and concentrated under vacuum to give methyl 2-chloro-3-(ethylsulfonylamino)-4-(trifluoromethoxy)benzoate (0.686 g, 1.80 mmol, 51%) as a grayish-white solid. 1 ¹H NMR (400MHz, chloroform-d): δ=7.83(d,1H),7.33(dq,1H),6.19(s,1H),3.40(q,2H),1.55(t,3H).

[0120] Step 2: Preparation of 2-chloro-3-(ethylsulfonylamino)-4-(trifluoromethoxy)benzoic acid

[0121] Lithium hydroxide monohydrate (0.625 g, 14.9 mmol) was added to a stirred solution of methyl 2-chloro-3-(ethylsulfonylamino)-4-(trifluoromethoxy)benzoate (1.89 g, 4.96 mmol) in tetrahydrofuran (15 mL) and water (3.8 mL) at room temperature. The mixture was stirred at room temperature for 5 hours. The mixture was then cooled to 0 °C (ice-water bath) and quenched by adding 2 M HCl aqueous solution (20 mL). The mixture was stirred at 0 °C for 5 minutes, then the cooling bath was removed and the mixture was warmed to room temperature. EtOAc (50 mL) and brine (30 mL) were added, and the phase was separated. The aqueous phase was extracted with EtOAc (50 mL). The combined organic phases were dried (MgSO4), filtered, and concentrated under vacuum to give 2-chloro-3-(ethylsulfonylamino)-4-(trifluoromethoxy)benzoic acid (1.79 g, 4.89 mmol, 99%) as a pale yellow solid, which was used in the next step without further purification. 1¹H NMR (400MHz, acetonitrile-d³): δ = 7.85 (d, 1H), 7.43 (dq, 1H), 7.22 (br s, 1H), 3.29 (q, 2H), 1.42 (t, 3H).

[0122] Step 3: Preparation of 2-chloro-3-(ethylsulfonylamino)-N-(1-methyltetrazole-5-yl)-4-(trifluoromethoxy)benzamide

[0123] At room temperature, pyridine (5.8 mL) was added to a solution of 2-chloro-3-(ethylsulfonylamino)-4-(trifluoromethoxy)benzoic acid (0.578 g, 1.58 mmol) and 1-methyltetrazole-5-amine (0.188 g, 1.90 mmol) under a nitrogen atmosphere, followed by the addition of 1-methylimidazolium (0.127 mL, 1.58 mmol). The stirred mixture was cooled to 0 °C (ice-water bath) and thionyl chloride (0.232 mL, 3.16 mmol) was added dropwise. The stirred mixture was then heated to room temperature and stirred for 17 hours. The mixture was then concentrated under vacuum. The residue was dissolved in a mixture of EtOAc (40 mL) and 2 M HCl aqueous solution (40 mL). The phase was separated and the aqueous phase was extracted with EtOAc (40 mL). The combined organic phases were washed with brine (50 mL), dried (MgSO4), filtered, and concentrated under vacuum to give a crude product as a pale yellow foam. The crude product was suspended in 2-propanol (6 mL), and the mixture was heated to 100 °C. All materials were dissolved to give a pale yellow solution. The mixture was cooled to room temperature. The precipitated solid was filtered off and dried under suction. The collected solid was recombined with the filtrate and adsorbed onto silica. The material was then purified by rapid column chromatography on silica (CH2Cl2 / MeOH, gradient 99:1 to 90:10). The fractions containing the product were combined and concentrated under vacuum to give a colorless gel. MTBE was added, and the mixture was further concentrated under vacuum to give a viscous white solid. It was dissolved in DCM / MeOH and concentrated under vacuum, then further dried under high vacuum to give 2-chloro-3-(ethylsulfonylamino)-N-(1-methyltetrazole-5-yl)-4-(trifluoromethoxy)benzamide (0.085 g, 0.19 mmol, 12%) as a grayish-white solid. 1 ¹H NMR (400MHz, acetonitrile-d³): δ=7.70(d,1H), 7.56-7.48(m,1H), 3.98(s,3H), 3.31(q,2H), 1.44(t,3H).

[0124] Example P3. Preparation of compound 1.011.

[0125] Step 1: Preparation of 3-amino-2-chloro-4-(difluoromethoxy)benzoic acid

[0126] Lithium hydroxide monohydrate (7.65 g, 182 mmol) was added to a stirred solution of methyl 3-amino-2-chloro-4-(difluoromethoxy)benzoate (15.3 g, 60.7 mmol) in tetrahydrofuran (122 mL) and water (31 mL) at room temperature. The mixture was stirred at room temperature for 26 hours. The mixture was then cooled to 0 °C (ice-water bath). The reaction was then quenched by the slow addition of 2 M HCl aqueous solution (150 mL). The cooling bath was removed and the mixture was warmed to room temperature. EtOAc (150 mL) and brine (100 mL) were added, and the phases were separated. The aqueous phase was extracted with EtOAc (100 mL). The combined organic phases were dried (MgSO4), filtered, and concentrated under vacuum to give 3-amino-2-chloro-4-(difluoromethoxy)benzoic acid (14.6 g, 55.1 mmol, 91%) as a beige solid, which was used in the next step without further purification. 1 ¹H NMR (400MHz, methanol-d⁴) δ = 7.15 (d, 1H), 7.08-7.03 (m, 1H), 6.87 (t, 1H).

[0127] Step 2: Preparation of (2,3,4,5,6-pentafluorophenyl)3-amino-2-chloro-4-(difluoromethoxy)benzoate

[0128] Acetonitrile (102 mL) was added to 3-amino-2-chloro-4-(difluoromethoxy)benzoic acid (14.5 g, 55.1 mmol), and the mixture was stirred at room temperature for 5 minutes. A solution of 2,3,4,5,6-pentafluorophenol (11.2 g, 60.6 mmol) in acetonitrile (44 mL) was added, followed by 3-(ethyliminomethyleneamino)-N,N-dimethyl-prop-1-amine hydrochloride (12.7 g, 66.1 mmol). The mixture was stirred at room temperature for 2 hours. The reaction was then quenched by adding 2 M HCl aqueous solution (150 mL). The mixture was stirred at room temperature for another 5 minutes, then transferred to a separatory funnel and washed with EtOAc (3 × 20 mL). EtOAc (200 mL) and brine (150 mL) were added, and the phase was separated. The organic phase was washed with saturated NaHCO3 aqueous solution (200 mL), dried (MgSO4), and filtered. The filtrate was adsorbed onto silica (100 g) and purified on silica by rapid column chromatography (cyclohexane / EtOAc, gradient 96:4 to 80:20). Fractions containing the product were combined and concentrated under vacuum to give (2,3,4,5,6-pentafluorophenyl)3-amino-2-chloro-4-(difluoromethoxy)benzoate (19.9 g, 46.9 mmol, 85%) as a pale yellow solid. 1 ¹H NMR (400MHz, chloroform-d): δ=7.55(d,1H), 7.11(d,1H), 6.62(t,1H), 4.59(br s,2H).

[0129] Step 3: Preparation of (2,3,4,5,6-pentafluorophenyl)2-chloro-4-(difluoromethoxy)-3-(propylsulfonylamino)benzoate

[0130] To a solution of (2,3,4,5,6-pentafluorophenyl)3-amino-2-chloro-4-(difluoromethoxy)benzoate (0.8 g, 2 mmol) at -78 °C in tetrahydrofuran (8 mL), lithium bis(trimethylsilyl)amino (1 M, 5 mL, 5 mmol in THF) was added dropwise. The mixture was stirred at -78 °C for 45 min. Then, propane-1-sulfonyl chloride (0.3 mL, 3 mmol) was added dropwise. The mixture was stirred at -78 °C for 2 h. The reaction was then quenched with a saturated aqueous solution of NH4Cl. 2 NHCl was added, and the mixture was extracted three times with EtOAc. The combined organic phases were washed with brine, dried over Na2SO4, and concentrated under vacuum. The crude product was adsorbed onto silica and purified on silica by rapid column chromatography (cyclohexane / EtOAc, 70:30) to give (2,3,4,5,6-pentafluorophenyl)2-chloro-4-(difluoromethoxy)-3-(propylsulfonylamino)benzoate (0.47 g, 0.92 mmol, 50%) as a white solid. 1 H NMR (400MHz, DMSO-d6): δppm 9.61 (s, 1H), 8.22 (d, 1H), 7.32-7.73 (m, 2H), 3.17-3.26 (m, 2H), 1.86 (br d, 2H), 1.01 (t, 3H).

[0131] Step 4: Preparation of 2-chloro-4-(difluoromethoxy)-N-(1-methyltetrazole-5-yl)-3-(propylsulfonylamino)benzamide

[0132] At room temperature, 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diacrylamide (1.4 mL, 4.6 mmol) was added to a stirred solution of 1-methyltetrazole-5-amine (0.14 g, 1.4 mmol) in DMF (3 mL). The mixture was stirred at room temperature for 30 minutes. Then, a solution of (2,3,4,5,6-pentafluorophenyl)2-chloro-4-(difluoromethoxy)-3-(propylsulfonylamino)benzoate (0.47 g, 0.92 mmol) in DMF (3 mL) was added, and the mixture was stirred overnight at room temperature. The reaction was quenched with 1N HCl and extracted three times with ethyl acetate. The combined organic phases were washed three times with ice water, then with brine, dried over Na₂SO₄, and concentrated under vacuum. The obtained solid was washed three times with MTBE and dried under vacuum to give 2-chloro-4-(difluoromethoxy)-N-(1-methyltetrazole-5-yl)-3-(propylsulfonylamino)benzamide (0.16 g, 0.38 mmol, 41%) as a grayish-white solid. 1H NMR (400MHz, DMSO-d6): δppm 11.87(s,1H),9.53(s,1H)7.77(d,1H)7.41(t,1H)7.39(d,1H)4.00(s,3H)3.13-3.28(m,2H)1.82-1.92(m,2H)1.02(t,3H).

[0133] Table 1 - Examples of the herbicidal compounds of the present invention.

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152] Table 2 - Examples of intermediate compounds of the present invention.

[0153]

[0154]

[0155] Biological examples

[0156] Seeds of various test species (perennial ryegrass (Lolium perenne) (LOLPE), amaranthus retoflexus (AMARE), amaranthus palmeri (AMAPA), velvetleaf (Abutilontheophrasti) (ABUTH), setaria faberi (SETFA), barnyard grass (Echinochloa crus-galli) (ECHCG), and ipomoea hederacea (IPOHE)) were sown in standard soil in pots. Plants were sprayed with an aqueous spray solution derived from an industrial-grade formulation of the active ingredient in an acetone / water (50:50) solution containing 0.5% Tween20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) after one day (pre-emergence) or eight days (post-emergence) under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14-hour light; 65% humidity). Unless otherwise specified, the compound was applied at a rate of 130 g / h. The test plants were then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14-hour light; 65% humidity) and watered twice daily. The percentage of damage to the plants was evaluated before emergence and 13 days after emergence. The table below shows bioactivity on a five-point scale (5 = 80%-100%; 4 = 60%-79%; 3 = 40%-59%; 2 = 20%-39%; 1 = 0%-19%).

[0157] Table B1

[0158]

[0159]

[0160] "-" means that the species was not tested or no data was captured.

[0161] Table B2 - Comparison Test

[0162] Seeds of the test species were sown in standard soil in pots. After one day of cultivation under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14-hour light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from an industrial-grade active ingredient in 0.6 ml acetone and a 45 ml formulation containing 10.6% Emulsogen EL (registration number 61791-12-6), 42.2% N-methylpyrrolidone, 42.2% dipropylene glycol monomethyl ether (CAS RN 34590-94-8), and 0.2% X-77 (CAS RN 11097-66-8).

[0163] The test plants were then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice daily. After 14 days, the test was evaluated (100 = complete damage to the plant; 0 = no damage to the plant).

[0164] Test species: AMARE (Amaranthus retroflexus); ECHCG (Barnyardgrass); SETFA (Foxtail Grass); IPOHE (Bowl Flower).

[0165]

[0166] C1 is compound 4-363 disclosed in WO 2012 / 028579. It can be seen that the introduction of a 3-sulfonamide substituent onto the benzene ring provides the unexpected improvement in weed control observed.

Claims

1. A compound having formula (I): Or its agronomically acceptable salt. in: R 1 It is a C1-C4 alkyl-; R 2 Choose from the group consisting of: halogens and C1-C6 alkyl-; R 3 It is a C1-C6 haloalkyl group; R 4 Selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3-alkyl- and C3-C6-cycloalkyl-C1-C3-alkyl-; and R 5 It is hydrogen or C1-C3 alkyl.

2. The compound according to claim 1, wherein, R 1 Choose from the group consisting of: methyl, ethyl, and n-propyl.

3. The compound according to claim 1, wherein, R 2 Choose from the following groups: methyl and Cl.

4. The compound according to claim 3, wherein, R 2 It is Cl.

5. The compound according to claim 1, wherein, R 3 It is either -CF3 or -CHF2.

6. The compound according to claim 1, wherein, R 4 It is a C1-C6 alkyl group.

7. The compound according to claim 6, wherein, R 4 It is methyl or ethyl.

8. A herbicidal composition comprising the compound according to any one of claims 1 to 7 and an agriculturally acceptable formulation adjuvant.

9. The herbicidal composition according to claim 8, further comprising at least one additional pest control agent.

10. The herbicidal composition according to claim 9, wherein, The other pest control agent mentioned is a herbicide or a herbicide safener.

11. A method for controlling weeds at a site, the method comprising applying to the site a composition for controlling the amount of weeds according to any one of claims 8 to 10.

12. Use of the compound having formula (I) as defined in claim 1 as a herbicide.

13. A compound having formula (II) Where R 2 R 3 and R 5 It is as defined above in the compound having formula (I) as described in any one of claims 1 to 7, and R 4 It is a C1-C6 alkyl group.

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