5-membered heteroaryl and pyrazole herbicides

Abstract

The present application relates to compounds of formula (I) or to the agronomically acceptable salts of said compounds, wherein A, Q, R 1 , R 2 , R 4 and m are as defined herein. The present application further relates to herbicidal compositions comprising a compound 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 novel compounds, and their use for controlling weeds (particularly in useful plant crops) or for inhibiting plant growth.

[0002] WO 2020 / 094524 discloses herbicidal phenoxypyridine compounds. WO 2021 / 204706 discloses 5-haloalkoxy-pyrimidine compounds as herbicides. WO 2022 / 013293, WO 2022 / 101270, and WO 2023 / 099354 disclose certain herbicidal N-heteroarylpyrazole compounds. This invention relates to further herbicidal N-heteroarylpyrazole 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 is CR 5 Or N;

[0008] Q is a 5-membered heteroaryl group, optionally bounded by 1 or 2 R groups. 3 Substituent substitution,

[0009] R 1 Independently selected from the group consisting of: halogen, -CN, C1-C2 alkyl, C1-C2 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkoxy- and C1-C2 haloalkoxy-;

[0010] R 2 Choose from the following groups: halogen, -CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, -C(O)C1-C4 alkyl, -C(O)OC1-C4 alkyl, C1-C4 haloalkoxy, -S(O) p C1-C4 alkyl groups, -C(R) 6 )=NOR 7 and C3-C6 cycloalkyl groups;

[0011] R 3Independently selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl-, C1-C4 alkoxyC1-C3 alkoxy-, C1-C4 alkoxyC1-C3 alkoxyC1-C3 alkyl-, -CN, NO2, C2-C4 alkenyl, C2-C4 alkynyl, -S(O) p C1-C4 alkyl groups, -S(O) p C1-C4 haloalkyl, -C(O)OC1-C4 alkyl and -C(O)NR 8 R 9 ;

[0012] R 4 Independently selected from the group consisting of: hydrogen, 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 groups, -S(O) p C1-C4 haloalkyl, -C(O)OC1-C4 alkyl and -C(O)NR 8 R 9 ;

[0013] R 5 Choose from the following groups: hydrogen, fluorine, chlorine, and -CN;

[0014] R 6 It is hydrogen or C1-C4 alkyl;

[0015] R 7 It is hydrogen or C1-C2 alkyl;

[0016] R 8 It is hydrogen or C1-C4 alkyl;

[0017] R 9 It is hydrogen or C1-C4 alkyl;

[0018] m = 0, 1, or 2; and

[0019] p = 0, 1 or 2.

[0020] C1-C4 alkyl- and C1-C6 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). C1-C2 alkyl- are methyl (Me, CH3) or ethyl (Et, C2H5).

[0021] Halogens (or halogen groups) include, for example, fluorine, chlorine, bromine, or iodine. The above applies correspondingly to halogens in other defined contexts, such as alkyl halogens.

[0022] C1-C6 halogenated alkyl 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-tetrafluoropropyl and 2,2,2-trichloroethyl, heptafluoropropyl and perfluorohexyl. C1-C4 and C1-C2 halogenated alkyl 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.

[0023] C1-C4 alkoxy and C1-C2 alkoxy include, for example, methoxy and ethoxy.

[0024] C1-C6 haloalkoxy- and C1-C4 haloalkoxy- 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.

[0025] C2-C4 alkenyl groups include, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).

[0026] 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.

[0027] C1-C4 alkyl-S-(alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, or tert-butylthio, preferably methylthio or ethylthio.

[0028] C1-C4 alkyl-S(O)- (alkyl sulfinyl) includes, 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.

[0029] 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.

[0030] In one embodiment of the invention, A is N. In another embodiment of the invention, m is 1. Therefore, in a preferred embodiment of the invention, a compound having formula (Ia) is provided.

[0031]

[0032] Among them, Q and R 1 R 2 and R 4 It is as defined in claim 1 above.

[0033] In one embodiment of the present invention, R 1 Preferably, it is chlorine. In another embodiment of the invention, R 4 Preferably, it is hydrogen. In another embodiment of the invention, R 2 It is a C1-C4 haloalkyl group, more preferably -CF3, -CF2H or -CF2Cl.

[0034] In another embodiment of the invention, Q is preferably selected from the group consisting of:

[0035]

[0036] Where R 3 It is hydrogen or as defined in claim 1 above, R 3a Choose from the group consisting of: hydrogen, methyl, ethyl, CHF2, and cyclopropyl, and R 3b Choose from the following groups: hydrogen, fluorine, chlorine, and bromine.

[0037] In a more preferred embodiment, Q is selected from the group consisting of: Q-1, Q-2, Q-3, Q-4, Q-13, Q-14, Q-15, Q-16, Q-22, Q-23, Q-24, Q-41, Q-42, and Q-43. In an even more preferred embodiment, Q is selected from the group consisting of: Q-1, Q-3, Q-4, Q-13, Q-14, Q-15, Q-16, Q-23, Q-24, Q-41, Q-42, and Q-43. In an even more preferred embodiment, Q is Q-1 (especially where R...). 3 (It is either hydrogen or methyl and R3b is hydrogen) or Q-23 (especially where R 3 It is hydrogen and R 3a (It is methyl).

[0038] In one embodiment of the present invention, R 3 It is chlorine.

[0039] 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 case of more than one asymmetric center, in all possible ratios of diastereomers. Typically, one of these enantiomers has enhanced biological activity compared to the other possibilities.

[0040] 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.

[0041] 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 herbicidal compositions comprising the herbicidal compound according to any one of the preceding claims and an agriculturally acceptable formulation adjuvant. The compositions may be in the form of concentrates, which are diluted prior to use, although ready-to-use compositions may also be prepared. Final dilution is typically carried out with water, but may be performed using alternatives to water, such as liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0042] The herbicidal composition typically contains 0.1% to 99%, particularly 0.1% to 95% by weight of a compound having Formula I and 1% to 99.9% by weight of a formulation adjuvant, which preferably contains 0% to 25% by weight of a surfactant.

[0043] 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-miscible flow agents (OF), oil-miscible 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).

[0044] 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).

[0045] 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).

[0046] 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 earth, 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 drying it if necessary, from pre-formed blanks. Reagents typically 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 (such as emulsifiers, wetting agents, or dispersants) may also be included in the granules.

[0047] 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 a spray can).

[0048] 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.

[0049] 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 melt 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.

[0050] 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 a 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 adapted to mix water-soluble and oil-soluble biocides in the same formulation. MEs are suitable for dilution in water, maintaining as microemulsions or forming conventional oil-in-water emulsions.

[0051] Suspension concentrates (SCs) can comprise aqueous or non-aqueous suspensions of finely fragmented, insoluble solid particles of a compound having formula (I). SCs can be prepared by ball milling or bead milling 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, the compound having formula (I) can be dry-milled and added to water containing the reagents described above to produce the desired final product.

[0052] 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.

[0053] 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.

[0054] The composition may contain one or more additives to improve the biological properties of the composition, such as by improving wettability, retention, or distribution on a surface; rain resistance on the treated surface; or absorption or migration 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 bio-enhancing adjuvants (components that may assist or modify the effects of compounds having formula (I)).

[0055] The wetting agent, dispersant, and emulsifier can be cationic, anionic, amphoteric, or nonionic SAA.

[0056] Suitable cationic types of SAAs include quaternary ammonium compounds (such as cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0057] 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; additionally, these products can be ethoxylated), sulfosuccinates, paraffin or olefin sulfonates, taurine, lignin sulfonates, and phosphate / sulfate salts of tristyrylphenol.

[0058] Suitable amphoteric types of SAAs include betaine, propionate, and glycine salt.

[0059] 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.

[0060] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethyl cellulose) and expansive clays (such as bentonite or attapulgite).

[0061] The compounds of this invention can also be used in mixtures 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-methyl, atrazine, flubutyroxyfen-M, benquitrione, bensulfuron-methyl (including bensulfuron-methyl), bentazon, dicyclopyranone, bispyridine, bispyribac-methyl, bispyribac-sodium, bixlozone, broclozone, chlorpyrifos, bromobenzonitrile, butachlor, flupropyrazosulfuron, chlorpyrifos (including chlorpyrifos-ethyl), chlorpyrifos-methyl (including chlorpyrifos-methyl), and chlorpyrifos-ethyl (including chlorpyrifos-ethyl). Greenmium, chlorsulfuron, cyclohexane, clacyfos, clethodim, clodinafop-propargyl (including clodinafop-propargyl), isoxaflutole, dichloropyridinic acid, cyclopyranil, cyclopyrimorate, cycloprosulfuron, cyhalofop-butyl (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, 2,4-D propionic acid, diethylene glycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), dichlorvos, pyrfluthrin, flupyridine, metolachlor, methylphenidate, pyridaben, pyridaben Dioxopyritrione, dibromodiflubenzuron, diuron, epyrifenacil, ethylbutadiene, ethoxysulfuron, quizalofop-P-ethyl (including quizalofop-P-ethyl), fenoxasulfone, fenquinotrione, tetrazolium, pyrimisulfuron, diflubenzuron, florpyrauxifen (including florpyrauxifen-benzyl), quizalofop-P-butyl (including quizalofop-P-butyl), fluketorosulfuron (including fluketorosulfuron-sodium), fluchloraminopyr This includes fluchloraminopyr-tefuryl, flufenoximacil, flufenoximacil, pyrazosulfuron, propyzoxystrobin, fluroxypyr, flusulfanilamide, flupyrimisulfuron (including flupyrimisulfuron-methyl-sodium), fluroxypyr-meptyl (including fluroxypyr-meptyl), flusulfanilamide, flusulfanilamide, formamide-sulfuron, glufosinate (including L-glufosinate and its ammonium salts), glyphosate (including its hydrazine, isopropylammonium, and potassium salts), halauxifen (including halauxifen ester), flupyridine (including flupyridine-methyl), cyclopyridone, etc.Hydantocidin, icafolin (including isoxaflutole-methyl), methoxymethylene (including R-methoxymethylene), imidacloprid, metribuzin, imidacloprid, indazon, indolauxipyr (including indolauxipyr-cyanomethyl), iofensulfuron (including iofensulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), iofensulfuron, iptriazopyrid, isoproturon, isoxaflutole, lancotrione ), MCPA, MCPB, mecoprop-P, mesosulfuron-methyl (including mesosulfuron-methyl), nicosulfuron, bensulfuron-methyl, pyrazosulfuron, methiozolin, metolachlor, sulfadiazine, methiozoline, mesosulfuron-methyl, nicosulfuron, dapoxuron, cyclosulfuron, ethoxysulfuron, paraquat dichlorvos, pendimethalin, penflusulfuron-methyl, bensulfuron-methyl, cyclosulfuron-methyl, propyrisulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron, pyrazosulfuron, pyrazosulfuron-methyl, pyrazosulfuron-methyl (Including pyraquinate, sulfonylurea pyrazosulfuron, pyrazosulfuron, pyriflubenzoxim, pyrimisulfan, pyrrolisulfone, pyrazosulfuron, quizalofop-P-tefuryl, quizalofop-P-tefuryl (including quizalofop-Ethyl and quizalofop-P-tefuryl), rimisoxafen, sulfadiazine, pyrimisulfuron, pyrimisulfuron-methyl, simazine, S-metolachlor, metolachlor, sulfonylurea sulfonylsulfuron, butyrazosulfuron, terbufos, sulfadiazine, terbufos, tetflup yrolimet), thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, bensulfuron-methyl, triafamone, wild valerate, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), chlorpyrifos, trifluralin (including trifluralin-sodium), trifluralin, trifluralin, flusulfanilamide, triazolesulfuron, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester,4-Hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl) [Pyrazol-3-yl]imidazolidine-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methylimidazolidine-2-one, (1RS,5SR)-3-[2-methoxy-4-(prop-1-yn-1-yl)phenyl]-4-oxobicyclo[3.2.1]oct-2-en-2-yl methyl carbonate, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, 2- [2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetic acid methyl ester, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidin-4-carboxylic acid (2-fluorophenyl) methyl ester, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidin-4-carboxylic acid, 3-[ 2-Chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-cyclopentane[d]isoxazole-6a-carboxylate, 2-[(2-bromo-6-fluoro-phenyl)methoxy]-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptane, and (isopropylideneamino)6-amino-2-(4-chloro-2-fluoro-3-methoxy-phenyl)-5-methoxy-pyrimidin-4-carboxylate.

[0062] 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.

[0063] 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.

[0064] The mixing ratio of the compound having formula (I) to the mixed compatibility is preferably 1:100 to 1000:1.

[0065] 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).

[0066] 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 cloquinoxalyl ethyl ester), cloquinoxaline, flufenoxam, cloquinoxalic acid (including cloquinoxalic acid-ethyl), mefenpyr (including cloquinoxalyl ester), metcamifen, and cloquinoxalic acid nitrate.

[0067] Particularly preferred are mixtures of compounds having formula (I) with cyclopropanesulfonamide, bis(oxazolyl)-ethyl, cyclohexane and / or cyclohexanesulfonamide.

[0068] 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 antidotes also apply to their lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts, as disclosed in WO 02 / 34048.

[0069] Preferably, the mixing ratio of the compound having formula (I) to the safener is 100:1 to 1:10, especially 20:1 to 1:1.

[0070] 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 corn, wheat, barley, and rice.

[0071] 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 plants, one or more weeds to be controlled, major 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 a rate of 10 to 2500 g / ha, particularly 25 to 1000 g / ha, and even more particularly 25 to 250 g / ha.

[0072] 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.

[0073] 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. An example of a crop conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods is Clearfield® Summer Canola (Canola). Examples of crops conferred herbicide tolerance through genetic engineering include, for example, corn varieties resistant to glyphosate and glufosinate, which are commercially available under the trademarks RoundupReady® and LibertyLink®. The compounds of this invention can also be used in combination with plants disclosed in WO 2020 / 236790.

[0074] Crop plants should also be understood as those conferred resistance to harmful insects through genetic engineering, such as Bt maize (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 maize is NK®'s Bt 176 maize hybrid (SyngentaSeeds). Bt toxins are proteins naturally formed by the soil bacteria 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 KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard®, and Proteincta®. Plant crops or their seed material can be both herbicide resistant and insect-resistant (“superimposed” transgenic events). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0075] Crop plants should also be understood to include those obtained through conventional breeding or genetic engineering methods and containing so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0076] 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*. a) 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*.

[0077] In another aspect of the invention, the use of compounds having formula (I) as defined herein as herbicides is provided.

[0078] Method for preparing compounds having formula (I)

[0079] Methods for preparing compounds (e.g., compounds having formula (I) (which may optionally be salts of which are chemically acceptable for agricultural use)) are now described and form another aspect of the invention.

[0080] As shown in Scheme 1, a compound having formula (I) can be prepared by optionally heating it under acidic conditions in a suitable solvent (such as ethanol or isopropanol or a mixture of acetonitrile / water) at 100°C-180°C to decarboxylate the compound having formula (2).

[0081] Compounds of formula (2) are prepared by a nucleophilic aromatic substitution reaction of a compound of formula (4) (where LG represents a suitable leaving group, such as halogen or SO2Me) with a compound of formula (3). This reaction is carried out by heating in a suitable solvent (such as sulfolane, acetonitrile, or dimethyl sulfoxide) in the presence of a base (such as potassium carbonate, tripotassium phosphate, or sodium tert-butoxide). The reaction is typically carried out between room temperature and 100°C.

[0082] The conditions for forming pyrazole compounds of formula (3) by condensation of diketones with arylhydrazines are documented in the literature (as documented in Tetrahedron [Tetrahedron] (2013), 69(16), 3459-3464).

[0083] Option 1

[0084]

[0085] Alternatively, compounds having formula I can be prepared by the following scheme 2.

[0086] Option 2:

[0087]

[0088] In Scheme 2, a compound having Formula I can be prepared by reacting a compound having Formula VI with a reagent having Formula V (where LG1 is a halogen, preferably iodine, bromine, or chlorine (or a pseudohalogen leaving group, such as (halo)alkyl or phenyl sulfonate, for example trifluoromethanesulfonate)) in the presence of a base (such as sodium hydride or alkaline earth metal hydride, carbonate (e.g., sodium carbonate, potassium carbonate, or cesium carbonate) or hydroxide), optionally in the presence of potassium iodide, in an inert solvent (such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, N,N-dimethylacetamide, sulfolane, or acetonitrile, etc.), at a temperature between 0°C and 120°C, using a procedure well known to those skilled in the art.

[0089] Alternatively, compounds having formula I can be prepared by reacting a compound having formula VI with a compound having formula V (where LG1 is a halogen, preferably iodine, bromine, or chlorine (or a pseudohalogen leaving group, such as (halo)alkyl or phenyl sulfonate, for example, trifluoromethanesulfonate)) in the presence of a metal catalyst (such as a copper-based catalyst, such as CuI or tetra(acetonitrile)copper(I) tetrafluoroborate), optionally in the presence of a ligand (such as trans-1,2-bis(methylamino)cyclohexane or its salt (e.g., methanesulfonate) or 8-hydroxyquinoline and other similar ligands). The reaction can be carried out in the presence of a base (such as potassium carbonate, cesium carbonate, triethylamine, or pyridine and other similar substances) and a solvent (such as acetonitrile, 1,4-dioxane, or pyridine), and optionally under microwave irradiation at temperatures ranging from room temperature to 200°C.

[0090] Alternatively, compounds having formula I can be prepared by reacting a compound having formula VI with a compound having formula Va under Chan-Lam cross-coupling conditions. Such reactions are carried out in the presence of a copper-based catalyst (such as copper acetate, copper iodide, or copper bromide, and others similar) and a base (such as pyridine or 2,6-dimethylpyridine, and others similar). The reaction can be carried out in the presence of a solvent (such as dichloromethane, toluene, or acetonitrile) and in the presence of air or oxygen, at temperatures ranging from room temperature to 200°C.

[0091] Compounds having formula VI can be prepared from compounds having formula VII (where PG is an amino protecting group, such as acetyl, trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl, benzyl, p-methoxybenzyl (PMB), etc.) via a protecting group deprotection reaction. Such reactions are well known to those skilled in the art and can be carried out, for example, under base catalysis such as the use of sodium hydroxide for acetyl deprotection, or under acid catalysis such as the use of hydrochloric acid or 2,2,2-trifluoroacetic acid for the deprotection of trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl, or p-methoxybenzyl (PMB) groups.

[0092] Compounds having formula VII can be derived from compounds having formula VIII (where R... 12 It is prepared by decarboxylation of C1-C4 alkyl or phenyl groups. This reaction can be carried out using a base (such as an alkaline earth metal hydroxide or an alkali metal hydroxide like sodium hydroxide) or in the presence of an acid (such as aqueous hydrochloric acid, aqueous sulfuric acid, etc.). The reaction is typically carried out in the presence of a solvent (such as water, ethanol, methanol, tetrahydrofuran, or dioxane) or a combination of two or more solvents at a temperature ranging from room temperature to the boiling point of the solvent.

[0093] Compounds having formula VIII (where R12 The compound having formula X can be prepared by reacting a compound having formula IX with a reagent having formula IX (where LG2 is a halogen (or a pseudohalogen leaving group, such as a (halogenated) alkyl or phenyl sulfonate, for example, trifluoromethanesulfonate)) in the presence of a base (such as sodium tert-butoxide, sodium hydride or alkaline earth metal hydride, carbonate (such as sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate (such as potassium phosphate)), optionally in the presence of potassium iodide, in an inert solvent (such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile, etc.) at a temperature between 0°C and 200°C, using a procedure well known to those skilled in the art.

[0094] Compounds having formula X can be prepared by condensation reactions of compounds having formula XII with compounds having formula XI (or their hydrochloride or trifluoroacetate salts) (where PG is an amino protecting group, such as acetyl, trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl, benzyl, p-methoxybenzyl (PMB), etc.). Such reactions are well known in the literature and can optionally be carried out in the presence of an acid catalyst (such as acetic acid).

[0095] Compounds having formula XII can be produced by making compounds having formula XIV (where R...) 11 It is prepared by reacting a C1-C4 alkyl or phenyl compound with a compound having formula XIII in the presence of a base. This type of reaction is known as the Claisen condensation and is well known to those skilled in the art. The reaction can be carried out using a base (such as lithium diisopropylamino, lithium tetramethylpiperidine, sodium ethoxide, sodium hydride, etc.) in the presence of a solvent (such as tetrahydrofuran, ethanol, methanol) and at a temperature ranging from -80°C to the boiling point of the solvent.

[0096] Alternatively, compounds having formula I can be prepared by the following scheme 3.

[0097] Option 3:

[0098]

[0099] In scheme 3, compounds having formula -I are prepared by the reduction of compounds having formula XV via alcohol reduction. The reduction of such alcohols is described in detail in the literature and can be carried out using reducing agents (such as LiAlH4, DIBAL-H) ​​or triphenylphosphine in the presence of iodine and imidazole, or triethylsilane in the presence of trifluoroacetic acid. Compounds having formula XV can be prepared by reducing a compound having formula XVI (where X...) to... 1The halogen (preferably bromine or iodine) reacts with an organometallic reagent (such as a metallizing agent like BuLi or isopropyl magnesium chloride / LiCl complex) to form intermediate XVIa (where M(Ln) is a halogen). p It is the corresponding metal (such as lithium or magnesium) derived from the organometallic reagent and (Ln) p It is a group that can be optionally substituted (like chlorine), and then it reacts with a compound having formula XVII.

[0100]

[0101] Compounds having formula XVII can be prepared by reacting compounds having formula XVIII with a strong base (such as butyllithium, diisopropylaminolithium), and then with DMF. This reaction is typically carried out in the presence of a solvent (such as tetrahydrofuran, toluene, heptane) at a temperature between -80°C and the solvent's boiling point. Such reactions are well known and described in the literature. Compounds having formula XVIII can be prepared by reacting a compound having formula XIX with a compound having formula XX (where LG3 is a leaving group like a halogen (or pseudohalogen leaving group, such as (halo)alkyl or phenyl sulfonate, e.g., trifluoromethanesulfonate)) in the presence of a base (such as sodium tert-butoxide, sodium hydride or alkaline earth metal hydride, carbonate (e.g., sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate (e.g., potassium phosphate)), optionally in the presence of potassium iodide, in an inert solvent (such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile, etc.), at a temperature between 0°C and the boiling point of the solvent, using a procedure well known to those skilled in the art. Such reactions are referred to in the literature as S... N Ar reaction.

[0102] Alternatively, compounds having formula XVIII can be prepared by Chan-Lam coupling, which involves, for example, reacting a compound having formula XIX with a compound having formula XXI (where Yb1 can be a boron-derived functional group, such as B(OH)2 or B(ORb1)2, where Rb1 can be a C1-C4 alkyl group, or the two ORb1 groups can form a five-membered ring with the boron atom, such as pinacol boronic acid ester). This reaction can be catalyzed by a copper catalyst (e.g., copper-based catalysts such as Cu(OAc)2, CuI, CuBr2, CuCl, etc.) in the presence of a base (such as pyridine, sodium carbonate, tripotassium phosphate, or cesium fluoride), in a solvent or solvent mixture (e.g., a mixture of dioxane, dichloromethane, acetonitrile, N,N-dimethylformamide, 1,2-dimethoxyethane, and water, or a dioxane / water mixture, or a toluene / water mixture), under an inert atmosphere, in an oxygen atmosphere, or in air. The reaction temperature can preferably be in the range from room temperature to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. Such Chan-Lam coupling reactions are well known to those skilled in the art.

[0103] The following non-limiting examples provide specific methods for synthesizing representative compounds used in this invention (as mentioned in the table below).

[0104] Example 1: Preparation of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl]methyl]pyrimidine (1.001)

[0105] (1.001)

[0106] Step 1: Preparation of N-(tert-butoxycarbonylamino)-N-(2-methylpyrazol-3-yl)carbamate tert-butyl ester (I-1)

[0107] (I-1)

[0108] A solution of 5-iodo-1-methylpyrazole (5 g, 24.03 mmol) in tetrahydrofuran (50 mL) in a 500 mL round-bottom flask was placed under a nitrogen atmosphere cooled to -78°C. At this temperature, a solution of isopropyl magnesium chloride-lithium chloride complex (21 g, 28.8 mmol) was added dropwise. The mixture was stirred at -78°C for 10 min, then treated dropwise with a solution of di-tert-butyl azodicarbonate (6.6 g, 28.8 mmol) in tetrahydrofuran (50 mL). Note: Additions were made such that the internal temperature did not exceed -65°C. The mixture was allowed to reach room temperature and then stirred at room temperature for 2 h. The reaction mixture was quenched by the slow addition of ammonium chloride solution (50 mL) and extracted with ethyl acetate (3 x 100 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum to obtain the crude material. The crude N-(tert-butoxycarbonylamino)-N-(2-methylpyrazol-3-yl)carbamate tert-butyl ester I-1 (4.9 g, 62%), which was obtained as a yellow gel-like substance, was used directly in the next step. 1 H NMR (400MHz, CDCl3) δ = 7.41 (d, 1 H), 6.17 (br s, 1 H), 3.84 (s, 3 H), 1.47 (s, 18H)

[0109] Step 2: Preparation of ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (I-2)

[0110] (I-2)

[0111] A solution of lithium diisopropylamino in tetrahydrofuran (14 mL, 28 mmol, 2.0 mol / L) in tetrahydrofuran (16 mL) was placed in a 100 mL round-bottom flask under a nitrogen atmosphere, ice-cooled, and treated dropwise with ethyl acetoacetate (1.0 mL, 7.9 mmol). The addition was controlled so that the internal temperature did not exceed 15°C. The resulting pale yellow mixture was stirred at 0°C for 45 minutes. The mixture was cooled to -78°C and treated dropwise with ethyl difluorochloroacetate (1.3 mL, 10 mmol). The resulting reaction mixture was stirred for another 1.5 hours, then removed from the dry ice bath and stirred at room temperature for 30 minutes, during which time it was heated to approximately 0°C (internal). After completion, the mixture was quenched with 1 M hydrochloric acid (30 mL) and extracted with ethyl acetate (2 × 30 mL). The combined organic matter is passed through a hydrophobic glass frit and concentrated in a vacuum to produce ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate I-2, which is an orange oil and used in the next step.

[0112] Step 3: Preparation of ethyl 2-[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl] (I-3)

[0113] (I-3)

[0114] A solution of N-(tert-butoxycarbonylamino)-N-(2-methylpyrazol-3-yl)carbamate tert-butyl ester I-1 (2 g, 6.40 mmol) in trifluoroacetic acid (7.37 g, 64.02 mmol) was stirred overnight at room temperature. Then, a solution of ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate I-2 (1.8 g, 5.9 mmol) in acetic acid (14 mL) was added, and the reaction mixture was stirred overnight at room temperature. The reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (3 × 50 mL). The combined organic layers were washed with brine (50 mL), dried over anhydrous sodium sulfate, filtered, and evaporated to give the crude product. The crude product was purified by reversed-phase column chromatography using acetonitrile:water (40:60) as the eluent to obtain ethyl acetate 2-[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl] (0.4 g, 1.25 mmol), which was a brown oil. 1 H NMR (400 MHz, CDCl3) δ = 7.55 (d, 1 H), 6.68 (s, 1 H), 6.37 (d, 1 H)4.12 (q, 2 H), 3.72 (s, 3 H), 3.65 (s, 2 H), 1.26 (t, 3 H).

[0115] Step 4: Preparation of ethyl 2-[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl]-2-(5-chloropyrimidin-2-yl)acetate (I-4)

[0116] (I-4)

[0117] A mixture of ethyl 2-[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl]ethyl acetate I-3 (0.2 g, 0.62 mmol) in dimethyl sulfoxide (2 mL) and 2,5-dichloropyrimidine (0.28 g, 1.88 mmol) in a 25 mL round-bottom flask was placed under a nitrogen atmosphere and treated with tripotassium phosphate (0.68 g, 3.13 mmol). The mixture was heated to 80°C and stirred for 1 hour. The reaction mixture was cooled to room temperature and quenched with water (25 mL), then extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with cold water (3 x 20 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by silica gel column chromatography using 10%–12% ethyl acetate in a cyclohexane solvent system. After concentration, ethyl acetate 2-[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl]-2-(5-chloropyrimidin-2-yl)acetate I-4 (0.120 g, 44%) was obtained as a yellow oil. 1 H NMR (400 MHz, CDCl3) δ = 8.69 (s, 2H), 7.55 (d, 1 H), 6.76 (s, 1 H), 6.44 (d, 1 H), 5.30 (s, 1 H), 4.21 (q, 2H), 3.70 (s, 3 H), 1.21 (t, 3H).

[0118] Step 5: Preparation of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl]methyl]pyrimidine (1.001)

[0119] (1.001)

[0120] Add ethyl acetate I-4 (0.12 g, 0.27 mmol) in a 9:1 solution of propionitrile (0.9 mL) and water (0.1 mL) to a 10 mL microwave-safe vial. Heat the solution in a microwave at 180°C for 30 min. Cool the reaction mixture to room temperature, dilute with water, and extract with ethyl acetate (20 mL × 3). Combine the organic layers, wash with brine, dry over sodium sulfate, filter, and concentrate. Adsorb onto diatomaceous earth and purify by chromatography using 3%–3.5% tert-butyl methyl ether in a cyclohexane solvent system. After fractionation and concentration, 1.001g of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-(2-methylpyrazol-3-yl)pyrazol-3-yl]methyl]pyrimidine was obtained as a yellow gelatinous substance. 1 H NMR (400 MHz, CDCl3) δ =8.60 (s, 2 H), 7.51 (d, 1 H), 6.61 (s, 1 H), 6.39 (d, 1 H) 4.29 (s, 2 H), 3.71 (s, 3 H).

[0121] Example 2: Preparation of 5-chloro-2-[[2-(5-methyl-2-thienyl)-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (1.003)

[0122] (1.003)

[0123] Step 1: Preparation of ethyl 6,6,6-trifluoro-3,5-dioxo-hexanoate (I-5)

[0124] (I-5)

[0125] A solution of diisopropylamine (12.00 g, 118.6 mmol) in tetrahydrofuran (98 mL) was placed in a round-bottom flask under a nitrogen atmosphere, ice-cooled, and treated dropwise with n-butyllithium (2.5 M in hexane) (79 mL, 118.6 mmol). The resulting pale yellow mixture was stirred at 0°C for 30 min. At 0°C, the mixture was treated dropwise with ethyl acetoacetate (5.14 g, 39.53 mmol). An exothermic reaction was observed, and the reaction mixture turned orange. The reaction mixture was then stirred at 0°C for 30 min. The mixture was cooled to -78°C and treated dropwise with ethyl 2,2,2-trifluoroacetate (7.30 g, 51.39 mmol). The resulting reaction mixture was stirred for another 3 h, during which time it was heated to approximately 0°C and stirred overnight. The reaction mixture was quenched with ammonium chloride (100 mL), diluted with water (50 mL), and extracted with tert-butyl methyl ether (3 x 100 mL). The combined organic layers were washed with brine (150 mL), dried over sodium sulfite, filtered, and dried under vacuum to produce a crude product. A gelatinous crude product, ethyl 6,6,6-trifluoro-3,5-dioxo-hexanoate I-5, was obtained and used directly in the next step.

[0126] Step 2: Preparation of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate (I-6)

[0127] (I-6)

[0128] A solution of ethyl 6,6,6-trifluoro-3,5-dioxo-hexanoate I-5 (7 g, 23.215 mmol) in acetic acid (10 mL) was treated with (4-methoxybenzyl)hydrazine hydrochloride (4.51 g, 23.215 mmol) and stirred at room temperature for 12 h. The reaction mixture was quenched in water (100 mL) and extracted with ethyl acetate (3 × 100 mL). The combined organic layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and filtered. The solvent was removed under reduced pressure to give a crude product, which was purified by column chromatography on silica gel using ethyl acetate and cyclohexane (40:60) to obtain a colloidal substance of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]ethyl acetate I-6 (5 g, 63%). 1H NMR (400 MHz, CDCl3) δ = 7.08 (d, 2 H), 6.87 (d, 2 H), 6.51 (s, 1 H), 5.35 (s, 2H), 4.13 (q, 2 H), 3.79 (s, 3 H), 3.55 (s, 2 H), 1.24 (t, 3H).

[0129] Step 3: Preparation of ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate (I-7)

[0130] (I-7)

[0131] A mixture of 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]ethyl acetate I-6 (2.7 g, 7.9 mmol), 2,5-dichloropyrimidine (3.5 g, 24 mmol), and dimethyl sulfoxide (27 mL) in a round-bottom flask was placed under a nitrogen atmosphere and treated with tripotassium phosphate (8.5 g, 39 mmol). The mixture was heated to 80°C and stirred for 1 hour. The reaction mixture was quenched with water (100 mL) and extracted with ethyl acetate (120 mL x 3). The combined organic layers were washed with a brine solution (100 mL) and concentrated to give the crude material. The crude product was purified by silica gel column chromatography using 20% ​​ethyl acetate in cyclohexane as the eluent. After fractionation and concentration, ethyl acetate 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]-7 (3.3 g, 46%) was obtained as a pale yellow solid. 1 H NMR (400 MHz, CDCl3) δ = 8.55 (s, 2 H), 6.96 (d, 2 H), 6.78 (d, 2 H), 6.69 (s, 1 H), 5.39 (q, 1 H), 5.36 (s, 2 H) 4.14 (t, 2 H), 3.77 (s, 3 H),1.19 (t,3 H).

[0132] Step 4: Preparation of 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (I-8)

[0133] (I-8)

[0134] A solution of ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidin I-7 (3.1 g, 6.5 mmol) in 1,4-dioxane (16 mL) in a 100 mL round-bottom flask was treated with hydrochloric acid (10 mL, 6 mol / L) in deionized water (10 mL). The mixture was refluxed for 8 hours. The reaction mixture was cooled to room temperature, quenched with water (100 mL), and extracted with ethyl acetate (3 x 100 mL). The organic layer was washed with a brine solution (100 mL), dried over sodium sulfate, filtered, and concentrated to obtain crude material. The obtained crude 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidin I-8 (2.5 g, 81%), which was in a colloidal state, was used directly in the next step. 1 H NMR (400 MHz, CDCl3) δ = 8.55 (s, 2 H), 7.00 (d, 2 H), 6.79 (d, 2H), 6.48 (s, 1 H), 5.40 (s, 2 H), 4.23 (s, 2 H), 3.77 (s, 3 H)

[0135] Step 5: Preparation of 5-chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5-yl]methyl]pyrimidine (I-9)

[0136] (I-9)

[0137] A solution of 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine I-8 (2.7 g, 7.1 mmol) in 2,2,2-trifluoroacetic acid (11 mL) in a 100 mL round-bottom flask was heated to 90°C and stirred for one hour. The reaction mixture was cooled to room temperature and evaporated under vacuum to obtain the crude material. It was purified by silica gel column chromatography using ethyl acetate and cyclohexane as eluents. The desired product was collected by elution with 20%–25% ethyl acetate in cyclohexane. After concentration, 5-chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5-yl]methyl]pyrimidine I-9 (0.77 g, 38%) was obtained as a grayish-white solid. 1 H NMR (400 MHz, CDCl3) δ = 8.71 (s,2 H), 6.51 (s, 1 H), 4.41 (s, 2 H).

[0138] Step 6: Preparation of 5-chloro-2-[[2-(5-methyl-2-thienyl)-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (1.003)

[0139] (1.003)

[0140] An oven-dried 30 mL microwave-safe vial containing a mixture of 5-chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5-yl]methyl]pyrimidine I-9 (0.8 g, 3.04 mmol), potassium carbonate (4.21 g, 30.46 mmol), 2-iodo-5-methyl-thiophene (6.82 g, 30.46 mmol), and 8-hydroxyquinoline (0.134 g, 0.91 mmol) was evacuated and backfilled with nitrogen five times. Acetonitrile (8 mL) was added, and the reaction mixture was then degassed by bubbling nitrogen for 20 min. The mixture was then treated with tetra(acetonitrile)copper(i)tetrafluoroborate (0.14 g, 0.45 mmol) and heated to 120°C for 1 hour under microwave irradiation. The reaction mixture was cooled to room temperature, quenched with water (50 mL), and extracted with ethyl acetate (3 x 20 mL). The organic layer was washed with a saline solution (50 mL), dried over sodium sulfate, filtered, and concentrated to obtain the crude material. The crude product was purified by silica gel column chromatography using 5%-10% ethyl acetate and cyclohexane as eluents. After concentration, 1.003 g of 5-chloro-2-[[2-(5-methyl-2-thienyl)-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine was obtained as a brown solid. 1 ¹H NMR (400 MHz, chloroform) δ = 8.64 (s, 2 H), 6.95 (d, 1 H), 6.63 (d, 1 H), 6.53 (s, 1 H), 4.38 (s, 2 H), 2.48 (s, 3 H).

[0141] Table 1. Compounds of the present invention

[0142]

[0143] Biological examples

[0144] Seeds of various test species were sown in standard soil in pots: Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), and Setaria faberi (SETFA). The plants were incubated under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14-hour light; 65% humidity) for one day (before germination) or eight days after germination (after germination). The spray solution was derived from an industrial-grade formulation of the active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compound was applied at a rate of 250 g / ha. These test plants were then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours light; 65% humidity) and watered twice daily. The percentage of damage to the plants was evaluated 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%).

[0145] Table B1 Post-emergence Tests

[0146]

[0147] NT = Untested.

[0148] Table B2 Pre-emergence Test

[0149]

[0150] NT = Untested.

Claims

1. A compound having formula (I): Or its agronomically acceptable salt. in A is CR 5 Or N; Q is a 5-membered heteroaryl group, optionally bounded by 1 or 2 R groups. 3 Substituent substitution, R 1 Independently selected from the group consisting of: halogen, -CN, C1-C2 alkyl, C1-C2 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkoxy- and C1-C2 haloalkoxy-; R 2 Choose from the following groups: halogen, -CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, -C(O)C1-C4 alkyl, -C(O)OC1-C4 alkyl, C1-C4 haloalkoxy, -S(O) p C1-C4 alkyl groups, -C(R) 6 )=NOR 7 and C3-C6 cycloalkyl groups; R 3 Independently selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl-, C1-C4 alkoxyC1-C3 alkoxy-, C1-C4 alkoxyC1-C3 alkoxyC1-C3 alkyl-, -CN, NO2, C2-C4 alkenyl, C2-C4 alkynyl, -S(O) p C1-C4 alkyl groups, -S(O) p C1-C4 haloalkyl, -C(O)OC1-C4 alkyl and -C(O)NR 8 R 9 ; R 4 Independently selected from the group consisting of: hydrogen, 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 groups, -S(O) p C1-C4 haloalkyl, -C(O)OC1-C4 alkyl and -C(O)NR 8 R 9 ; R 5 Choose from the following groups: hydrogen, fluorine, chlorine, and -CN; R 6 It is hydrogen or C1-C4 alkyl; R 7 It is hydrogen or C1-C2 alkyl; R 8 It is hydrogen or C1-C4 alkyl; R 9 It is hydrogen or C1-C4 alkyl; m = 0, 1, or 2; and p = 0, 1 or 2.

2. The compound having formula (I) according to claim 1, wherein the compound has formula (Ia). Among them, Q and R 1 R 2 and R 4 It is as defined in claim 1 above.

3. The compound according to claim 1 or claim 2, wherein, R 4 It is hydrogen.

4. The compound according to any one of the preceding claims, wherein, R 1 It is chlorine.

5. The compound according to any one of the preceding claims, wherein, R 2 Choose from the following groups: -CF3, -CF2H, and -CF2Cl.

6. The compound according to any one of the preceding claims, wherein, Q selects a group from the following: Where R 3 It is hydrogen or as defined in claim 1 above, R 3a Choose from the group consisting of: hydrogen, methyl, ethyl, CHF2, and cyclopropyl, and R 3b Choose from the following groups: hydrogen, fluorine, chlorine, and bromine.

7. The compound according to claim 6, wherein, Q can be any of the following groups: Q-1, Q-2, Q-3, Q-4, Q-13, Q-14, Q-15, Q-16, Q-22, Q-23, Q-24, Q-41, Q-42, and Q-43.

8. The compound according to claim 6, wherein, Q is either Q-1 or Q-23.

9. A herbicidal composition comprising a compound according to any one of the preceding claims and an agriculturally acceptable formulation adjuvant.

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

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

12. 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 9 to 11.

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

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