Herbicidal n-heteroaryl pyrazole compounds

Abstract

The present application relates to compounds of formula (I) or to the agronomically acceptable salts of said compounds, wherein A 1 , A 2 , A 3 , Q, X, R 1 and R 2 are as defined herein. The present application further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, particularly in crops of useful plants.

Description

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

[0002] Pyrazolylpyrimidine ether compounds are disclosed, for example, in CN 107540664. This invention relates to herbicidal pyrazolylpyrimidine compounds.

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

[0004]

[0005] Or its agronomically acceptable salt.

[0006] in

[0007] A 1 A 2 and A 3 It can be CH or N independently, provided that A is present. 1 A 2 and A 3 No more than one of them is N;

[0008] X can be selected from the following groups: O, S, and CH2;

[0009] Q is a 6-membered nitrogen-containing heteroaryl group, which is optionally bonded by one or more R groups. 3 replace;

[0010] R 1 Selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy;

[0011] R 2 Selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, halogen, C1-C4 alkoxy, -S-C1-C4 alkyl and -S-C1-C4 haloalkyl;

[0012] R 3 Choose from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -CN, NO2, C2-C4 alkenyl, C2-C4 alkynyl, -S(O) p C1-C4 alkyl; and

[0013] p = 0, 1, or 2.

[0014] C1-C4 alkyl groups 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). C1-C2 alkyl groups are methyl (Me, CH3) or ethyl (Et, C2H5).

[0015] Halogens (or halogenated) include, for example, fluorine, chlorine, bromine, or iodine. The above applies correspondingly to halogens in other definitions, such as alkyl halogens.

[0016] C1-C4 and C1-C2 haloalkyl groups include, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, or 1,1-difluoro-2,2,2-trichloroethyl.

[0017] C1-C4 alkoxy and C1-C2 alkoxy include, for example, methoxy and ethoxy.

[0018] C1-C4 haloalkoxy groups include, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy, or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy, or trifluoromethoxy.

[0019] C2-C4 alkenyl groups include, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).

[0020] C2-C4 ynyl group refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one triple bond, having two to four carbon atoms, and attached to the rest of the molecule by single bonds. 2- Examples of C4 ynyl groups include, but are not limited to, prop-1-ynyl, propynyl (prop-2-ynyl), and but-1-ynyl.

[0021] C1-C4 alkyl-S-(alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, or tert-butylthio, preferably methylthio or ethylthio.

[0022] C1-C4 alkyl-S(O)-(alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0023] C1-C4 alkyl-S(O)2-(alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0024] In a preferred embodiment of the invention, a compound having formula (I) is provided, wherein X is O.

[0025] In one embodiment of the present invention, a compound having formula (I) is provided, wherein A 1 A 2 and A 3 All are CH. In another embodiment, a compound having formula (I) is provided, wherein A 1 It is N, A 2 It is CH and A 3 It is CH. In another embodiment, a compound having formula (I) is provided, wherein A 1 It is CH, A 2 It is N and A 3 It is CH. In another embodiment, a compound having formula (I) is provided, wherein A 1 It is CH, A 2 It is CH and A 3 It is N. In a preferred embodiment of the invention, A 1 It is CH, A 2 It is CH and A 3 It is CH or N.

[0026] In another embodiment of the invention, a compound having formula (I) is provided, wherein Q is selected from the group consisting of:

[0027]

[0028] Where n is 0, 1, or 2.

[0029] In embodiments where n is 1 or 2, each R 3 Independently selected from the group consisting of: halogens, C1-C4 alkyl (preferably C1-C2 alkyl), C1-C4 haloalkyl (preferably C1-C2 haloalkyl), C1-C4 alkoxy (preferably C1-C2 alkoxy-), C1-C4 haloalkoxy, -CN, NO2, C2-C4 alkenyl, C2-C4 alkynyl, -S(O) p C1-C4 alkyl. In a preferred embodiment, R 3 It is halogen.

[0030] In a preferred embodiment of the invention, a compound having formula (I) is provided, wherein Q is Q2 or Q5, and especially Q5. In a more preferred embodiment, Q is Q5, and n is 1, and R 3 Halogen is preferred.

[0031] In another preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 1 It is a C1-C4 haloalkyl (preferably a C1-C2 haloalkyl), more preferably CF3.

[0032] In another preferred embodiment of the invention, a compound having formula (I) is provided, wherein R 2 Selected from the group consisting of: halogens, C1-C4 haloalkyl (preferably C1-C2 haloalkyl (e.g. CF2H or CF3)) and C1-C4 haloalkoxy (e.g. -OCF2H, -OCF3).

[0033] In a preferred embodiment of the invention, a compound having formula (I) is provided, wherein X = O, A 1 It is CH, A 2 It is CH, A 3 It is CH or N, Q is Q2 or Q5 (preferably Q5), R 1 It is a C1-C4 haloalkyl and R 2 Selected from the group consisting of: halogens, C1-C4 haloalkyl (preferably C1-C2 haloalkyl (e.g. CF2H or CF3)) and C1-C4 haloalkoxy (e.g. -OCF2H, -OCF3).

[0034] Compounds having formula (I) may contain an asymmetric center and may exist as a single enantiomer, in any ratio of enantiomer pairs, or, in the presence of more than one asymmetric center, contain diastereomers in all possible ratios. Typically, one of these enantiomers has enhanced biological activity compared to the other possibilities.

[0035] The present invention also provides agronomically acceptable salts of compounds having formula (I). Preferably, compounds having formula (I) can form salts with: amines, including primary, secondary and tertiary amines (e.g., ammonia, dimethylamine and triethylamine), alkali metal bases and alkaline earth metal bases, transition metal bases or quaternary ammonium bases.

[0036] 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 (SAAs). Therefore, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the preceding claims and an agriculturally acceptable formulation adjuvant. 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 carried out using, in addition to water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0037] 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.

[0038] The composition can be selected from many formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersants (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), parent drug (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP), and soluble granules (SG). 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).

[0039] 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).

[0040] 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).

[0041] 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.

[0042] 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).

[0043] 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.

[0044] 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 suitable temperature typically below 70°C) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution into water containing one or more SAAs under high shear 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.

[0045] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents and one or more SAAs to spontaneously produce a thermodynamically stable, isotropic liquid formulation. The compound having formula (I) is initially present in water or in the solvent / SAA 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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 (SAAs), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), modified vegetable oils (such as methylated rapeseed oil (MRSO)), and blends of these with other bioenhancing adjuvants (components that can help or modify the effects of compounds having formula (I)).

[0050] The wetting agent, dispersant, and emulsifier can be cationic, anionic, amphoteric, or nonionic SAA.

[0051] Suitable cationic types of SAAs include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0052] Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (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, lignosulfonates, and phosphate / sulfate salts of tristyrylphenols.

[0053] Suitable amphoteric types of SAAs include betaine, propionate, and glycine salt.

[0054] Suitable nonionic types of SAAs 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); lecithin and sorbitol and their esters, alkyl polyglycosides, and tristyrylphenols.

[0055] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethyl cellulose) and expansive clays (such as bentonite or attapulgite).

[0056] The compounds of the present 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 (including chlorpyrifos-methyl), chlorpyrifos (including chlorpyrifos-ethyl), chlorpyrifos, chlorsulfuron, cyclohexane, clacyfos, clethodim, clodinafop-methyl (including... Clothiamethoxam, 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, oxazolidinyl (Including quizalofop-ethyl), fenoxasulfone, fenquinotrione, tetrazolium, pyrimisulfuron, diflubenzuron, florpyrauxifen (including florpyrauxifen-benzyl), quizalofop-butyl (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) The following are listed: ammonium salts of both; glyphosate (including its hydrazine, isopropylammonium, and potassium salts); halauxifen (including halauxifen-methyl); flupyridine (including flupyridine-methyl); cycloazinone; hydantocidin; methoxyfenozide; imidacloprid; metribuzin; imidacloprid; indazon; iosulfuron (including iosulfuron-methyl-sodium); iofensulfuron (including iofensulfuron-sodium); iodobenzonitrile; isoproturon; isoxaflutole; lancotrione; MCPA; MCPB; mecoprop-P.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.

[0057] 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.

[0058] Compounds having formula (I) can also be used in combination with other agrochemicals, such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

[0059] The mixing ratio of the compound having formula (I) to the mixed formulation is preferably from 1:100 to 1000:1.

[0060] 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) with a mixed formulation).

[0061] 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 (including cloquinoline), cyclopropanesulfonamide, dichloropropeneamine, cloquinoxal (including cloquinoxal-ethyl), cloquinoxaline, flufenoxam, cloquinoxalic acid (including cloquinoxalic acid-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen, and cloquinoxalic acid nitrate.

[0062] Particularly preferred are compounds having formula (I) and mixtures of cyclopropanesulfonamide, ethyl bis(oxazolyl) ester, antidote quinone and / or metcamifen.

[0063] Safeguards 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 (BCPC), 2012. References to antitoxin quinine also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts (as disclosed in WO 02 / 34048).

[0064] 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.

[0065] 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 can further provide 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 present invention to control the amount of weeds. 'Control' means killing, reducing, or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention exhibit significantly improved selectivity compared to known structurally similar compounds. Typically, the plant to be controlled is an unwanted plant (weed). 'Site' means an area in which the plant is growing or will grow. Application can be made to the site before and / or after the emergence of the crop plants. Some crop plants can inherently tolerate the herbicidal effects of compounds having formula (I). Preferred crop plants include maize, wheat, barley, and rice.

[0066] 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, prevailing 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 2500 g / ha, particularly from 25 g / ha to 1000 g / ha, and even more particularly from 25 g / ha to 250 g / ha.

[0067] 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.

[0068] Crop plants should be understood to also include those crop plants that have been conferred tolerance to other herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, HPPD-inhibitors, inhibitor-PDS, and ACC enzyme-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 trademarked products are commercially available. The compounds of this invention can also be used in combination with the plants disclosed in WO 2020 / 236790.

[0069] 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 events). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0070] 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).

[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*. ) and the genus Sorghum, which can also be dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola, and Xanthium.

[0072] In another aspect of the invention, the use of compounds having formula (I) as defined herein as herbicides is provided.

[0073] Method for preparing compounds having formula (I)

[0074] Methods for preparing compounds (e.g., compounds having formula (I) (which may optionally be agriculturally chemically acceptable salts)) are now described and form another aspect of the invention.

[0075]

[0076] Compounds having formula I can be prepared from compounds having formula A by reacting a compound having formula B (where LG represents a suitable leaving group, such as Br or Cl) in the presence of a suitable base and optionally in the presence of a suitable catalyst / ligand combination and in a suitable solvent. Suitable bases may include Cs₂CO₃. Suitable catalyst / ligand combinations may include Cu(I)I / 1,10-phenanthroline. Suitable solvents may include DMSO.

[0077]

[0078] A compound having formula A can be prepared from a compound having formula C by reacting it with a compound having formula D (where LG represents a suitable leaving group, such as Br or Cl) in the presence of a suitable base and optionally in the presence of a suitable catalyst / ligand combination and in a suitable solvent. A suitable base may include Cs₂CO₃. A suitable catalyst / ligand combination may include Cu(I)I / 1,10-phenanthroline. A suitable solvent may include DMSO.

[0079]

[0080] In an alternative method, a compound having formula I can be prepared from a compound having formula E by reacting it with a compound having formula D (where LG represents a suitable leaving group, such as Br or Cl) in the presence of a suitable base and optionally in the presence of a suitable catalyst / ligand combination and in a suitable solvent. A suitable base may include Cs₂CO₃. A suitable catalyst / ligand combination may include Cu(I)I / 1,10-phenanthroline. A suitable solvent may include DMSO.

[0081]

[0082] Compounds having formula E can be prepared from compounds having formula C by reacting a compound having formula B (where LG represents a suitable leaving group, such as Br or Cl) in the presence of a suitable base and optionally in the presence of a suitable catalyst / ligand combination and in a suitable solvent. Suitable bases may include Cs₂CO₃. Suitable catalyst / ligand combinations may include Cu(I)I / 1,10-phenanthroline. Suitable solvents may include DMSO.

[0083] The following non-limiting examples provide specific methods for synthesizing representative compounds used in this invention (as mentioned in Table 1 below).

[0084] Example 1: Synthesis of 2-[5-[[6-(difluoromethoxy)-2-pyridyl]oxy]-3-(trifluoromethyl)pyrazol-1-yl]-5-fluoropyrimidine (compound 1.005)

[0085] Step 1: Synthesis of 2-[5-[[6-(difluoromethoxy)-2-pyridyl]oxy]-3-(trifluoromethyl)pyrazol-1-yl]-5-fluoropyrimidine (compound 1.005)

[0086]

[0087] To a stirred solution of 3-(trifluoromethyl)-1H-pyrazole-5-ol (0.30 g, 2.0 mmol) in DMSO (8.1 mL) under N2 atmosphere, 2-bromo-6-(difluoromethoxy)pyridine (0.49 g, 2.2 mmol), Cu(I)I (0.096 g, 0.49 mmol), 1,10-phenanthroline (0.18 g, 0.99 mmol), and Cs₂CO₃ (1.90 g, 5.9 mmol) were added, and the mixture was heated to 120 °C for 18 hours. The reaction was cooled to RT, and then 2-chloro-5-fluoropyrimidine (0.49 mL, 3.9 mmol) was added, and the reaction was heated at 120 °C for 1 hour. The reaction was cooled, filtered, and then purified by reversed-phase mass-directed HPLC to give the desired product (83 mg, 11%) as a pale pink solid.

[0088] 1 H NMR (400MHz, CDCl3) δ8.58(s,2H),7.81(t,1H),6.98(t,1H),6.85(d,1H),6.67(d,1H),6.50(s,1H)

[0089] Table 1 - Examples of the herbicidal compounds of the present invention.

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097] Biological examples

[0098] Seeds of several test species (Abutilon theophrasti (ABUTH), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Ipomoeahederacea (IPOHE), and Setaria faberi (SETFA)) were sown in standard soil in pots. After one day (pre-emergence) or eight days (post-emergence) of cultivation in a greenhouse under controlled conditions (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 formulation of the active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene dehydrated sorbitol monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compound was applied at a rate of 250 g / ha. 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 assessed before emergence and 13 days after emergence. Biological activity is shown in the table below on a five-point scale (5 = 81%-100%; 4 = 61%-80%; 3 = 41%-60%; 2 = 21%-40%; 1 = 0%-20%).

[0099] Table B1 Post-emergence Tests

[0100]

[0101]

[0102] Table B2 Pre-emergence Test

[0103] NT = Untested.

Claims

1. A compound having formula (I): Or its agronomically acceptable salt. in n is 0, 1, or 2; R 2 Choose from the group consisting of: C1-C4 haloalkyl, C1-C4 haloalkoxy, and halogen; and R 3 It is halogen.

2. A herbicidal composition comprising the compound according to claim 1 and an agriculturally acceptable formulation adjuvant.

3. The herbicidal composition according to claim 2, further comprising at least one additional pest control agent.

4. The herbicidal composition according to claim 3, wherein, The other pest control agent mentioned is a herbicide or a herbicide safener.

5. A method for controlling weeds at a site, the method comprising applying to the site the composition according to claim 2 for controlling the amount of weeds.

6. Use of the compound having formula (I) according to claim 1 as a herbicide.

Images