Herbicidal pyrazole compounds

Abstract

The present invention relates to a compound having the formula (I) or an agronomically acceptable salt of said compound, wherein A, Q, R1, R2, R3 and m are as defined herein. The invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, in particular in crops of useful plants. # imgabs0 #

Description

[0001] The present invention relates to herbicidal compounds, to processes for their preparation, to herbicidal compositions comprising these compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.

[0002] Herbicidal pyrazole compounds are known, for example, from CN 105037342, WO 2022 / 013293, WO 2022 / 101270 and WO2023 / 099354. The present invention relates to alternative herbicidal pyrazole compounds. Therefore, according to the present invention, a compound having formula (I) is provided:

[0003]

[0004] or an agronomically acceptable salt thereof,

[0005] in

[0006] A is for CR 11 or N;

[0007] Q is selected from the group consisting of hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, C2-C8 haloalkynyl, C1-C4 alkoxy-C1-C3 alkyl-, C1-C4 haloalkoxy-C1-C3 alkyl-, C1-C4 alkoxy-C1-C3 haloalkyl-, C1-C8 cyanoalkyl- (e.g. -CH2CH2CN), C3-C6 cycloalkyl (optionally substituted by CN, fluorine or chlorine), -S(O) p R 4 and -(CH2) n R 10 ;

[0008] 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-;

[0009] R 2 Selected from the group consisting of: 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, -C(R 6 )=NOR 7 and C3-C6 cycloalkyl;

[0010] R 3Selected 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, -S(O) p C1-C4 haloalkyl, -C(O)OC1-C4 alkyl and -C(O)NR 8 R 9 ;

[0011] R 4 Selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C3-C6 cycloalkyl;

[0012] R 5 Selected from the group consisting of hydrogen, methyl, ethyl, -(CH2)-cyclopropyl, C2-C3 alkenyl, C2-C3 alkynyl and cyclopropyl;

[0013] R 6 selected from the group consisting of: hydrogen, methyl and ethyl;

[0014] R 7 is methyl or ethyl;

[0015] R 8 is hydrogen or C1-C4 alkyl;

[0016] R 9 is hydrogen or C1-C4 alkyl;

[0017] R 10 Selected from the group consisting of: -OH, -C(H)O, -C(O)R 4 、-S(O) p R 4 、-C(H)(OH)-CH2OH、-C(R 6 )=NOR 5 、-NR 12 R 13 , C3-C6 cycloalkyl (optionally substituted by CN, fluorine or hydroxy), a C3-C6 saturated heterocycle containing one or more oxygen atoms (e.g. tetrahydropyran and tetrahydrofuran), and a 5-membered heteroaryl containing 1 to 3 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur (e.g. pyrazolyl), wherein the heteroaryl is optionally substituted by one or two substituents independently selected from the group consisting of halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C3-C4 cycloalkyl, C1-C2 alkoxy and C1-C4 haloalkoxy;

[0018] R 11 selected from the group consisting of hydrogen, fluorine, chlorine and CN;

[0019] R 12 and R 13 Independently selected from the group consisting of: C1-C4 alkyl, C3-C4 cycloalkyl, C1-C4 alkyl-S(O) p -, C3-C4 cycloalkyl-S(O) p -, C1-C4 alkyl-C(O)- and C3-C4 cycloalkyl-C(O)-;

[0020] m = 0, 1 or 2;

[0021] n = 1, 2 or 3; and

[0022] p=0, 1 or 2.

[0023] 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 is methyl (Me, CH3) or ethyl (Et, C2H5).

[0024] Halogen (or halo) includes, for example, fluorine, chlorine, bromine or iodine. The above applies correspondingly to halogen in other defined contexts, such as haloalkyl.

[0025] C1-C8 haloalkyl-includes, 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, heptafluoro-n-propyl and perfluoro-n-hexyl. C1-C4 haloalkyl-and C1-C2 haloalkyl 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.

[0026] The C1-C4 alkoxy group and the C1-C3 alkoxy group include, for example, a methoxy group and an ethoxy group.

[0027] C1-C8 haloalkoxy- and C1-C8 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.

[0028] C2-C8 alkenyl - includes, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).

[0029] C2-C8 alkynyl - refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having two to four carbon atoms, and attached to the remainder of the molecule by a single bond. Examples of C2-C4 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

[0030] The C1-C4 alkyl-S-(alkylthio) group includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0031] The 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.

[0032] The C1-C4 alkyl-S(O)2-(alkylsulfonyl) group includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0033] In one embodiment of the present invention, A is CR 11 And R 11 Selected from the group consisting of hydrogen, fluorine, chlorine and CN, preferably fluorine or hydrogen.

[0034] In one embodiment of the present invention, A is N. In another embodiment of the present invention, m is 1. Therefore, in a preferred embodiment of the present invention, there is provided a compound having formula (Ia),

[0035]

[0036] Among them, Q, R 1 , R 2 and R 3 As defined in claim 1 above.

[0037] In one embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein R 1 It's chlorine.

[0038] In one embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein R 2It is halogen (such as Cl or Br) or C1-C4 haloalkyl (such as -CF3, -CHF2, -CF2Cl).

[0039] In one embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein R 3 is hydrogen or a halogen (eg Cl).

[0040] In a preferred embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein Q is selected from the group consisting of hydrogen, C1-C8 alkyl (e.g., methyl, -CH2CH(CH3)2, n-butyl, n-pentyl), C2-C8 alkenyl (e.g., -CH2CH2CH=CH2), C1-C8 haloalkyl (e.g., -CH2CH2CHF2, -CH2CH2CH2CHF2, -CH2CH2CF3, -CH2CH2CH2CF3), C1-C4 alkoxy-C1-C3 alkyl- (e.g., -CH2OCH3, -CH2CH2OCH3), C1-C4 haloalkoxy-C1-C3 alkyl- (e.g., -CH2OCH2CHF2, -CH2CH2OCH2CHF2), -S(O) p R 4 (e.g. -SO2CH2CH2CF3, -S-CH2CH2CF3) and -(CH2) n R 10 (e.g., -CH2CH2CH2OH, -CH2CH2C(H)(OH)CH2OH, -CH2CH2C(H)O)-OH, -CH2CH2C(H)=N-OH, -CH2CH2C(H)=NO-CH3 and -CH2CH2C(H)=NO-CH2-cPr).

[0041] In one embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein Q is -(CH2) n R 10 , n is 1, 2 or 3, and R 10 Selected from the group consisting of: -OH (e.g., -CH2CH2CH2OH), -C(H)(OH)-CH2OH (e.g., -CH2CH2C(H)(OH)CH2OH), -C(H)=NOR 5 (e.g., -CH2CH2C(H)=N-OH, -CH2CH2C(H)=NO-CH3, -CH2CH2C(H)=NO-CH2-cPr), and -NR 12 R 13 (e.g. -CH2CH2CH2N(CH3)SO2CH3).

[0042] In a preferred embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein Q is a C1-C8 alkyl group (eg, methyl, -CH2CH(CH3)2, n-butyl, n-pentyl).

[0043] In another preferred embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein Q is a C1-C8 haloalkyl group (eg, -CH2CH2CHF2, -CH2CH2CHF2, -CH2CH2CF3, -CH2CH2CH2CF3).

[0044] In another preferred embodiment of the present invention, there is provided a compound having formula (I) or formula (Ia), wherein Q is C1-C4 haloalkoxy-C1-C3 alkyl- (eg, -CH2OCH2CHF2, -CH2CH2CH2OCH2CHF2).

[0045] The present invention further relates to compounds having the formula (II-a):

[0046]

[0047] Where R 2 It is CF2H or CF2Cl.

[0048] Compounds of formula (I) may contain asymmetric centers and may exist as single enantiomers, in pairs of enantiomers in any ratio, or, in the case of more than one asymmetric center, in all possible ratios of diastereomers. Typically, one of the enantiomers has an enhanced biological activity compared to the other possibilities.

[0049] The present invention also provides agronomically acceptable salts of compounds of formula (I). Preferably, the compounds of formula (I) can form salts with: amines, including primary amines, secondary amines and tertiary amines (e.g., ammonia, dimethylamine and triethylamine); alkali metal bases and alkaline earth metal bases, transition metal bases or quaternary ammonium bases.

[0050] The compounds of formula (I) according to the invention can be used as herbicides themselves, but they are usually formulated into herbicidal compositions using formulation adjuvants such as carriers, solvents and surfactants (SAAs). Therefore, the present invention further provides herbicidal compositions comprising a 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 before use, although ready-to-use compositions may also be prepared. The final dilution is usually carried out with water, but may be carried out using, for example, liquid fertilizers, micronutrients, biological organisms, oils or solvents instead of or in addition to water.

[0051] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds of formula I and 1 to 99.9% by weight of formulation adjuvants which preferably comprise 0 to 25% by weight of surface-active substances.

[0052] The composition can be selected from a number of formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (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 flowables (OF), oil miscible liquids (OL), soluble concentrates (SL), ultra low volume suspensions (SU), ultra low volume liquids (UL), parent drugs (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP) and soluble granules (SG). In any case, the formulation type selected will depend on the specific purpose envisioned and the physical, chemical and biological properties of the compound of formula (I).

[0053] Soluble powders (SP) can be prepared by mixing a compound of 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 agents 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 (SG).

[0054] Wettable powders (WP) can be prepared by mixing a compound of 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 facilitate dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water dispersible granules (WG).

[0055] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or by absorbing the compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material such as pumice, attapulgite clay, Fuller's earth, kieselguhr, diatomaceous earth or corn cob meal, or by adsorbing the compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicates, mineral carbonates, sulfates or phosphates and drying if necessary from preformed green particles. Agents commonly used to aid absorption or adsorption include solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters and adhesives such as polyvinyl acetate, polyvinyl alcohol, dextrins, sugars and vegetable oils. One or more other additives such as emulsifiers, wetting agents or dispersants may also be included in the granules.

[0056] Dispersible concentrates (DC) can be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain a surfactant (for example to improve water dilution or to prevent crystallization in a spray tank).

[0057] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers or a mixture of said agents). Suitable organic solvents for use 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), dimethylamides of fatty acids (such as C8-C 10 EC products emulsify spontaneously when added to water, producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

[0058] The preparation of EWs involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it 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 for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents having low solubility in water.

[0059] Microemulsions (ME) 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 of formula (I) is initially present in water or in a solvent / SAA blend. Suitable solvents for use in MEs include those described above in ECs or in EWs. MEs can be oil-in-water systems or water-in-oil systems (which system is present can be determined by conductivity measurements) and can be suitable for mixing water-soluble pesticides and oil-soluble pesticides in the same formulation. MEs are suitable for dilution into water, remaining as microemulsions or forming conventional oil-in-water emulsions.

[0060] Suspension concentrates (SC) may include aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SC may be prepared by ball milling or bead milling a solid compound of 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 of formula (I) may be dry-milled and added to water containing the reagents described above to produce a desired final product.

[0061] Aerosol formulations comprise a compound of formula (I) and a suitable propellant (e.g. n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g. water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized hand-operated spray pump.

[0062] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, but with an additional polymerization stage, to obtain an aqueous dispersion of oil droplets, each of which is wrapped by a polymer shell and contains a compound of formula (I) and optionally a carrier or diluent for the oil droplet. The polymer shell can be produced by an interfacial polycondensation reaction or by a coacervation procedure. These compositions can provide controlled release of compounds of formula (I) and they 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.

[0063] The composition may include one or more additives to improve the biological performance of the composition, for example by improving wettability, retention or distribution on a surface; rain resistance on a treated surface; or absorption or mobility of a compound of 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 bioenhancement adjuvants (ingredients that can assist or modify the action of a compound of formula (I)).

[0064] The wetting agent, dispersant and emulsifier may be a cationic type, anionic type, amphoteric type or nonionic type SAA.

[0065] Suitable cationic-type SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0066] 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, butylnaphthalenesulfonate and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laureth-3-sulfate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphates (products from the reaction of one or more fatty alcohols with phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), for example the reaction of lauryl alcohol with tetraphosphoric acid; additionally, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignin sulfonates and phosphates / sulfates of tristyrylphenol.

[0067] Suitable amphoteric types of SAA include betaine, propionate and glycinate.

[0068] Suitable SAAs of the nonionic type include condensation products of alkylene oxides (such as ethylene oxide, propylene oxide, butylene 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 hexitol anhydrides; condensation products of the partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (such as fatty acid polyethylene glycol esters); amine oxides (such as lauryl dimethyl amine oxide); lecithin and sorbitan and its esters, alkyl polyglycosides and tristyrylphenol.

[0069] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0070] The compounds of the present invention may also be used in a mixture with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen sodium), bensulfuron, ametryn, amitriptyline, aminopyralid, cypermethrin, atrazine, flubutyric acid-M, quinclorac, benquitrione, benzylsulfuron-methyl (including benzylsulfuron-methyl), bentazon, bicyclpyrone, bialaphos, bispyribac-sodium, bixlozone, herbicide, bromoxynil, butachlor, flubutyric acid-butyl, mesotrione (including mesotrione-ethyl), chlorsulfuron (including chlorsulfuron-methyl), chlorsulfuron (including chlorsulfuron-ethyl), chlorotoluron, chlorsulfuron, cyproconazole, chlorpyrifos, chlorpyrifos-butyl ... lacyfos), clethodim, clodinafop-butyl (including clodinafop-butyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), bisclorac, fluazifop-butyl, fluazifop-butyl, dimethoate, dimethoate-s-propyl, dioxopyritrione, dibromdiquat , diuron, epyrifenacil, ethylbutenefluanid, ethoxyfuran, oxadiazine (including epyrifenacil-ethyl), fenoxasulfone, benzylpyridinol, fenquinotrione, tetrazoline, fluazifop-butyl, bispyribac, florpyrauxifen (including florpyrauxifen benzyl ester), fluazifop-butyl (including fluazifop-butyl-butyl), fluazifop-butyl (including fluazifop-sodium), flufenacet, fluazifop-butyl ... including fluroxypyr-meptyl), fluazifop-butyl, foramsulfuron, glufosinate (including L-glufosinate and ammonium salts of both), glyphosate (including its hydrazine, isopropyl ammonium and potassium salts), halauxifen (including halauxifen methyl), fluazifop-methyl (including fluazifop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapyr, imazapyr, imazamox, indazine fluazifop-butyl, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioboxynil,Isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methizolin, isopropylamine, sulfamethoxazole, metribuzin, metsulfuron-methyl, propamide, nicosulfuron, norfadine, oxadiazine, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, bendisulfuron, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, promethazine, propanil, oxadiazine, propyrisulfuron, propenylsulfuron, promethazine, procarb, sulfamethoxazole sulfamethoxam, pyraflufen (including pyraflufen-ethyl), pyraflufen-sulfuron, pyridasulfuron, pyrimisulfan, pyroxasulfone, pyrosulfuron, quinclorac, clomeclorac, quizalofop-ethyl (including quizalofop-P-tefuryl), rimisoxafen, sulfamethoxam, pyraflufen-sulfuron, sethoxydim, simazine, metolachlor, sulfamethoxam, sulfamethoxam, thiosulfuron, thiosulfuron, tetthiocarb, tetflupyrolimet, thiothione Thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, benpyrazone, triafamone, triafamone, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, fluralin, flufenac, triazosulfuron, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-Hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one,4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including agrochemically acceptable esters thereof, for example, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid prop-2-ynyl ester and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid cyanomethyl ester), 3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[ 4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 2- Ethyl [[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, tetrahydrofuran-2-ylmethyl ester, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]propionic acid, 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluoromethyl)benzamide, 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-propylsulfinyl-4-(trifluoromethyl)benzamide, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid (2-fluorophenyl)methyl ester and 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid.

[0071] Mixture partners of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

[0072] The compounds of formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

[0073] The mixing ratio of the compound having formula (I) to the mixing partner is preferably 1:100 to 1000:1.

[0074] These mixtures can advantageously be used in the abovementioned formulations (in this case, "active ingredient" relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0075] 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 cloquintocet-mexyl), cyclopropylsulfonamide, dichloropropene, oxadiazole (including oxadiazole ethyl), chlorpyrifos, fluazifop, oxadiazole, isoxadiazole (including isoxadiazole-ethyl), mefenpyr (including mefenpyr-butyl), metcamifen and oxadiazole.

[0076] Particularly preferred are mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen-ethyl, clofonet-mexyl and / or sulfamethoxazole.

[0077] The safeners of compounds of 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 clofonethiol also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048.

[0078] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0079] The present invention further provides a method for controlling weeds at a site, the method comprising applying a composition comprising a compound of formula (I) to the site in an amount of weed control. In addition, the present invention may further provide a method for selectively controlling weeds at a site including crop plants and weeds, wherein the method comprises applying a composition according to the present invention in an amount of weed control to the site. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention show greatly improved selectivity compared to known structurally similar compounds. Typically, the plants to be controlled are unwanted plants (weeds). 'Site' means the area where the plant is growing or will grow. Application can be applied to the site before and / or after emergence of the crop plant. Some crop plants can inherently tolerate the herbicidal effect of the compound of formula (I). Preferred crop plants include corn, wheat, barley and rice.

[0080] The application rate of the compound of formula I can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence or post-emergence; seed dressing; application to the seed furrow; no-till application, etc.), the crop plants, one or more weeds to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. The compound of formula I according to the invention is usually applied at a rate of 10 g / ha to 2500 g / ha, in particular 25 g / ha to 1000 g / ha, more particularly 25 g / ha to 250 g / ha.

[0081] Application is usually carried out by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or drenching may also be used.

[0082] Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, HPPD-inhibitors, inhibitor-PDS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones (e.g. imazamox) by conventional methods of breeding are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, maize varieties resistant to glyphosate and glufosinate, which are marketed under the trade names Roundup and and The compounds of the present invention can also be used in combination with the plants disclosed in WO 2020 / 236790.

[0083] Crop plants are also to be understood as those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to the European corn borer), Bt cotton (resistant to the boll weevil) and also Bt potato (resistant to the Colorado beetle). Examples of Bt maize are Bt 176 corn hybrid (SyngentaSeeds). Bt toxins are proteins naturally produced 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 comprising one or more genes encoding insecticide 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 resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic events). For example, seeds can have the ability to express an insecticidal Cry3 protein while being tolerant to glyphosate.

[0084] Crop plants are also to be understood as including those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (eg improved storage stability, higher nutritional value and improved flavor).

[0085] These compositions can be used to control unwanted vegetation (collectively referred to as 'weeds'). The weeds to be controlled can be monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, a) and Sorghum, and also dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0086] In a further aspect of the invention there is provided the use of a compound of formula (I) as defined herein as a herbicide.

[0087] Process for preparing compounds having formula (I)

[0088] Processes for preparing compounds such as compounds of formula (I) (which may optionally be agrochemically acceptable salts thereof) are now described and form a further aspect of the invention.

[0089] Scenario 1:

[0090]

[0091] In Scheme 1, compounds of formula I can be prepared by reacting compounds of formula II with reagents of formula III, wherein LG1 is halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group, such as (halo)alkyl or phenylsulfonate, for example trifluoromethanesulfonate), in the presence of a base such as sodium hydride or alkaline earth metal hydride, carbonate (such as 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, at a temperature between 0°C and 120°C, by procedures well known to those skilled in the art. Alternatively, compounds of formula I can be prepared by reacting compounds of formula II with compounds of formula IIIaa under Mitsunobu reaction conditions. Such reactions are well known to those skilled in the art and can be carried out in the presence of a suitable phosphine reagent (such as triphenylphosphine or tributylphosphine and similar other phosphine reagents) and in the presence of an azodicarboxylate reagent (such as diisopropyl azodicarboxylate or diethyl azodicarboxylate). The reaction is usually carried out in the presence of a solvent (such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene and similar other solvents) and preferably at a temperature ranging from -10°C to the boiling point of the solvent.

[0092] Compounds of formula II can be prepared from compounds of formula IV (wherein PG is an N-protecting group, such as an amino protecting group such as acetyl, trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl, benzyl, p-methoxybenzyl (PMB)) by a protecting group deprotection reaction. Such reactions are well known to those skilled in the art and can be carried out, for example, using base catalysis (such as deprotection of acetyl using sodium hydroxide) or acid catalysis (such as deprotection of trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl or p-methoxybenzyl (PMB) groups using hydrochloric acid or 2,2,2-trifluoroacetic acid).

[0093] It can be made from a compound having the formula V (wherein R 12 The compound of formula IV is prepared by decarboxylation reaction of a C1-C4 alkyl or phenyl group. The reaction can be carried out using a base (such as an alkaline earth metal hydroxide or an alkali metal hydroxide such as sodium hydroxide) or in the presence of an acid (such as an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, etc.). The reaction is usually carried out in the presence of a solvent (such as water, ethanol, methanol, tetrahydrofuran or dioxane) or a combination of two or more solvents and at a temperature within the range of room temperature to the boiling point of the solvent.

[0094] The compound of formula V (wherein R can be prepared by reacting a compound of formula VII with a reagent of formula VI (wherein LG2 is halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group, such as (halo)alkyl or phenylsulfonate, 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 120°C, by procedures well known to those skilled in the art. 12 is C1-C4 alkyl or phenyl).

[0095] Compounds of formula VII can be prepared by condensation reaction of compounds of formula VIII with compounds of formula XI (or their hydrochloride or trifluoroacetate) (wherein PG is an N-protecting group, such as 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 be optionally carried out in the presence of an acid catalyst such as acetic acid.

[0096] The compound of formula IX (wherein R 11 The compound of formula VIII is prepared by reacting a compound of formula X with a compound of formula X in the presence of a base. Such reactions are known as Claisen condensation reactions and are well known to those skilled in the art. The reaction can be carried out using a base (such as lithium diisopropylamide, lithium tetramethylpiperidinium, 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.

[0097] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (as mentioned in the table below).

[0098] Example 1: Preparation of 5-chloro-2-[[2-(4,4-difluorobutyl)-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (1.005)

[0099]

[0100] Step 1: Preparation of 6,6,6-trifluoro-3,5-dioxo-hexanoic acid ethyl ester (I1)

[0101]

[0102] In about 30 minutes, n-butyl lithium (2.5M in hexane, 65mL, 160mmol) was added to an ice-cooled solution of diisopropylamine (22mL, 157mmol) in THF (110mL) in a 250mL round-bottom flask. The mixture was stirred for 30 minutes, treated dropwise with ethyl acetoacetate (6.8mL, 54mmol) and stirred for another 45 minutes at 0°C. The reaction mixture was then cooled to -78°C, treated dropwise with ethyl trifluoroacetate (8.3mL, 70mmol) and stirred for 3 hours. The mixture was quenched with hydrochloric acid, diluted with water and extracted with ethyl acetate. The combined organic matter was dried and concentrated to provide 6,6,6-trifluoro-3,5-dioxo-hexanoic acid ethyl ester I1 as an oil, which was used as it is in the next step.

[0103] Step 2: Preparation of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate (I2)

[0104]

[0105] To the solution of 6,6,6-trifluoro-3,5-dioxo-hexanoic acid ethyl ester I1 (prepared in step 1) in acetic acid (90mL) in 100mL flask, (4-methoxybenzyl) hydrazine hydrochloride (10.56g, 54.29mmol) was added, and the resulting mixture was stirred at room temperature for 1.5 hours. The mixture was diluted with tert-butyl methyl ether and washed with water and brine. The organic matter was concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane to give 2-[2-[(4-methoxyphenyl) methyl]-5-(trifluoromethyl) pyrazole-3-yl] ethyl acetate I2 (11.97g, 59% yield) as a yellow oil. 1 H NMR (400MHz, CDCl3)δ=7.10-7.04(m,2H),6.88-6.83(m,2H),6.50(s,1H),5.35(s,2H),4.12(q,2H),3.79(s,3H),3.54(s,2H),1.24(t,3H)

[0106] Step 3: Preparation of ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate (I3)

[0107]

[0108] To a solution of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate I2 (4.22 g, 11.71 mmol) in dimethyl sulfoxide (40 mL) in a 250 mL flask was added 2,5-dichloropyrimidine (3.71 g, 24.9 mmol) and tripotassium phosphate (7.86 g, 36.3 mmol), and the reaction mixture was stirred at 60° C. for 3.5 hours. The mixture was allowed to stand at room temperature overnight, and then stirred at 60° C. for an additional hour. The mixture was cooled to room temperature, diluted with water and extracted with tert-butyl methyl ether. The combined organics were concentrated and subjected to column chromatography on silica gel using 0-40% ethyl acetate in cyclohexane to give ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate I3 (5.19 g, 73% yield) as a yellow oil. 1 H NMR (400MHz, CDCl3) δ = 8.55 (s, 2H), 6.98-6.92 (m, 2H), 6.79-6.74 (m, 2H), 6.6 9(s,1H),5.45-5.31(m,3H),4.20-4.11(m,2H),3.77(s,3H),1.21-1.16(m,3H)

[0109] Step 4: Preparation of 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (I4)

[0110]

[0111] To a solution of 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]ethyl acetate I3 (5.19 g, 8.56 mmol) in methanol (40 mL) in a 250 mL flask was added 2M aqueous sodium hydroxide solution (40 mL), and the reaction mixture was stirred at 60 ° C for 1.5 hours. The mixture was cooled to room temperature and concentrated to half volume. The residue was then acidified with hydrochloric acid and extracted with ethyl acetate. The combined organics were dried and concentrated to give 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine I4 (3.92 g, quantitative yield) as an orange oil. 1 H NMR (400MHz, CDCl3) δ = 8.55 (s, 2H), 7.05-6.95 (m, 2H), 6.84-6.75 (m, 2H), 6.47 (s, 1H), 5.40 (s, 2H), 4.22 (s, 2H), 3.78 (s, 3H)

[0112] Step 5: Preparation of 5-chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5-yl]methyl]pyrimidine (I5)

[0113]

[0114] A solution of 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine I4 (3.92 g, 8.56 mmol) in 2,2,2-trifluoroacetic acid (14 mL) in a 100 mL flask was stirred at 90 °C for one hour. The mixture was cooled to room temperature, slowly transferred into aqueous sodium bicarbonate solution, and then extracted with ethyl acetate. The combined organics were concentrated and subjected to column chromatography on silica gel using 0-60% ethyl acetate in cyclohexane to give 5-chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5-yl]methyl]pyrimidine I5 (2.365 g, 98% yield) as an off-white solid. 1 HNMR (400MHz, CDCl3) δ = 8.70 (s, 2H), 6.49 (s, 1H), 4.41 (s, 2H)

[0115] Step 6: Preparation of 5-chloro-2-[[2-(4,4-difluorobutyl)-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (1.005)

[0116]

[0117] 5-Chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5-yl]methyl]pyrimidine 15 (98 mg, 0.336 mmol) and potassium carbonate (129 mg, 0.933 mmol) were added to a 25 mL flask. The mixture was treated with a solution of 4-bromo-1,1-difluorobutane (90 mg, 0.520 mmol) in acetonitrile (1.5 mL) and stirred at 70 ° C for 1.5 hours. After completion, the mixture was cooled, then diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected to preparative HPLC chromatography to give 5-chloro-2-[[2-(4,4-difluorobutyl)-5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine 1.005 (27 mg, 22% yield) as a colorless oil. 1 HNMR (400MHz, CDCl3) δ = 8.65 (s, 2H), 6.43 (s, 1H), 5.83 (tt, 1H), 4.32 (s, 2H), 4.26 (t, 2H), 2.10-1.96 (m, 2H), 1.94-1.78 (m, 2H).

[0118] Example 2: Preparation of 2-[[2-butyl-5-[chloro(difluoro)methyl]pyrazol-3-yl]methyl]-5-chloro-pyrimidine (1.020)

[0119]

[0120] Step 1: Preparation of 6-chloro-6,6-difluoro-3,5-dioxo-hexanoic acid ethyl ester (I6)

[0121]

[0122] The ice-cooled solution of THF (80mL) and lithium diisopropylamide solution (2.0M in THF / heptane / ethylbenzene, 70mL, 140mmol) was treated dropwise with ethyl acetoacetate (5.10mL, 40.3mmol), and the resulting mixture was stirred at 0°C for 30 minutes. The reaction mixture was then cooled to -78°C, treated dropwise with ethyl chlorodifluoroacetate (6.60mL, 52.1mmol) and stirred for an additional 3.5 hours. The reaction mixture was warmed to room temperature over 30 minutes, then quenched with 1M hydrochloric acid (200mL) and extracted with ethyl acetate (2×80mL). The combined organics were dried and concentrated to provide 6-chloro-6,6-difluoro-3,5-dioxo-hexanoic acid ethyl ester (I6) as an oil, which was used directly in the next step.

[0123] Step 2: Preparation of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]acetate (I7)

[0124]

[0125] To a solution of 6-chloro-6,6-difluoro-3,5-dioxo-hexanoic acid ethyl ester (I6) (prepared in Example 2, step 1) in acetic acid (40 mL) in a 100 mL flask was added (4-methoxybenzyl)hydrazine hydrochloride (7.05 g, 36.3 mmol), and the resulting mixture was stirred at room temperature for 15 hours. The reaction mixture was concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane to give ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]acetate I7 ​​(7.87 g, 48% yield) as a brown oil. 1 H NMR (400 MHz, chloroform) δ=7.10-7.04 (m, 2H), 6.89-6.82 (m, 2H), 6.50 (s, 1H), 5.35 (s, 2H), 4.12 (q, 2H), 3.79 (s, 3H), 3.53 (s, 2H), 1.24 (t, 3H)

[0126] Step 3: Preparation of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]-2-(5-chloropyrimidin-2-yl)acetate (I8)

[0127]

[0128] To a solution of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]acetate I7 ​​(7.87 g, 21.9 mmol) in dimethyl sulfoxide (55 mL) in a 250 mL round bottom flask was added 2,5-dichloropyrimidine (9.85 g, 66.1 mmol) and tripotassium phosphate (19.4 g, 89.5 mmol). The reaction mixture was warmed to 70 °C and stirred for 3.5 hours. The reaction mixture was then cooled to room temperature and then diluted with 0.5 M hydrochloric acid (200 mL) and extracted with tert-butyl methyl ether (2×100 mL). The combined organic extracts were concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane to give ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]-2-(5-chloropyrimidin-2-yl)acetate I8 (6.53 g, 60%) as a brown oil. 1 H NMR (400 MHz, chloroform) δ = 8.55 (s, 2H), 6.99-6.92 (m, 2H), 6.79-6.75 (m, 2H), 6.68 (s, 1H), 5.45-5.33 (m, 3H), 4.20-4.09 (m, 2H), 3.77 (s, 3H), 1.19 (t, 3H).

[0129] Step 4: Preparation of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine (I9)

[0130]

[0131] A solution of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]-2-(5-chloropyrimidin-2-yl)acetate I8 (6.52 g, 13.8 mmol) in methanol (70 mL) in a 250 mL round-bottom flask was treated with 2M aqueous sodium hydroxide solution (70 mL, 140 mmol). The resulting mixture was warmed to 60 ° C and allowed to stir for 2 hours. The reaction mixture was cooled to room temperature, then diluted with ethyl acetate (100 mL) and neutralized with 2M hydrochloric acid (100 mL). The organic layer was then separated and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic extracts were then concentrated and subjected to column chromatography on silica gel using 0-35% ethyl acetate in cyclohexane to give 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine 19 (3.76 g) as a beige oil. 1 H NMR (400 MHz, chloroform) δ = 8.55 (s, 2H), 7.00 (d, 2H), 6.79 (d, 2H), 6.46 (s, 1H), 5.40 (s, 2H), 4.21 (s, 2H), 3.78 (s, 3H).

[0132] Step 5: Preparation of 5-chloro-2-[[3-[chloro(difluoro)methyl]-1H-pyrazol-5-yl]methyl]pyrimidine (I10)

[0133]

[0134] A solution of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine I9 (3.756 g, 9.408 mmol) in 2,2,2-trifluoroacetic acid (15 mL) in a 100 mL round bottom flask was warmed to 70 °C and allowed to stir for 3 hours. The reaction mixture was cooled to room temperature and then added to water (200 mL), resulting in the formation of a precipitate. The mixture was filtered and the aqueous filtrate was adjusted to pH>8 by adding solid potassium bicarbonate. The mixture was then extracted with ethyl acetate (2×100 mL), and the combined organics were then concentrated and then subjected to column chromatography on silica gel using 40%-70% ethyl acetate in cyclohexane to give 5-chloro-2-[[3-[chloro(difluoro)methyl]-1H-pyrazol-5-yl]methyl]pyrimidine I10 (1.211 g) as an off-white solid. 1 H NMR (400 MHz, chloroform) δ = 11.55 (br s, 1H), 8.70 (s, 2H), 6.49 (s, 1H), 4.40 (s, 2H)

[0135] Step 6: Preparation of 2-[[2-butyl-5-[chloro(difluoro)methyl]pyrazol-3-yl]methyl]-5-chloro-pyrimidine (1.020)

[0136]

[0137] To a 25 mL flask was added 5-chloro-2-[[3-[chloro(difluoro)methyl]-1H-pyrazol-5-yl]methyl]pyrimidine I10 (106 mg, 0.380 mmol) and triphenylphosphine (200 mg, 0.763 mmol). The vessel was evacuated and backfilled with nitrogen three times, then 2-methyltetrahydrofuran (2.50 mL) and 1-butanol (0.070 mL, 0.76 mmol) were added and the resulting solution was stirred and cooled to 0°C. Diisopropyl azodicarboxylate (0.140 mL, 0.711 mmol) was then added dropwise, and the resulting mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction was quenched by the addition of methanol (20 mL), and the resulting mixture was concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane. The product-rich fractions were concentrated and subjected to reverse phase column chromatography on C-18 silica gel using 60%-100% acetonitrile in water (both acetonitrile and water contained 0.1% formic acid) to give 2-[[2-butyl-5-[chloro(difluoro)methyl]pyrazol-3-yl]methyl]-5-chloro-pyrimidine 1.020 (21.1 mg) as a colorless oil. 1 HNMR (400 MHz, chloroform) δ = 8.66 (s, 2H), 6.37 (s, 1H), 4.31 (s, 2H), 4.17 (t, 2H), 1.83-1.75 (m, 2H), 1.39-1.29 (m, 2H), 0.93 (t, 3H).

[0138] Table 1. Compounds of the present invention

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149] Biological Examples

[0150] Seeds of various test species (Amaranthus palmeri (AMAPA), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA)) were sown in standard soil in pots. After one day of cultivation (pre-emergence) or after 8 days of cultivation (post-emergence) in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 h light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from a formulation of the technical grade active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise stated, the compounds were applied at 250 g / ha. Then, the test plants were grown in a greenhouse under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. Before emergence and 13 days after emergence, the percentage of damage caused to the plants by the test was evaluated. The biological activity is shown in the following table on a five-point scale (5 = 81%-100%; 4 = 61%-80%; 3 = 41%-60%; 2 = 21%-40%; 1 = 0-20%).

[0151] Table B1 Post-emergence test

[0152]

[0153]

[0154] Table B2 Pre-emergence test

[0155]

[0156]

[0157] NT = not tested.

Claims

1. A compound having formula (I): or an agronomically acceptable salt thereof, in, A is for CR 11 or N; Q is selected from the group consisting of hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, C2-C8 haloalkynyl, C1-C4 alkoxy-C1-C3 alkyl-, C1-C4 haloalkoxy-C1-C3 alkyl-, C1-C4 alkoxy-C1-C3 haloalkyl-, C1-C8 cyanoalkyl-, C3-C6 cycloalkyl (optionally substituted by CN, fluorine or chlorine), -S(O) p R 4 and -(CH2) n R 10 ; 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 Selected from the group consisting of: 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, -C(R 6 )=NOR 7 and C3-C6 cycloalkyl; R 3 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, -S(O) p C1-C4 haloalkyl, -C(O)OC1-C4 alkyl and -C(O)NR 8 R 9 ; R 4 Selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C3-C6 cycloalkyl; R 5 Selected from the group consisting of hydrogen, methyl, ethyl, -(CH2)-cyclopropyl, C2-C3 alkenyl, C2-C3 alkynyl and cyclopropyl; R 6 selected from the group consisting of: hydrogen, methyl, and ethyl; R 7 is methyl or ethyl; R 8 is hydrogen or C1-C4 alkyl; R 9 is hydrogen or C1-C4 alkyl; R 10 Selected from the group consisting of: -OH, -C(H)O, -C(O)R 4 、-S(O) p R 4 、-C(H)(OH)-CH2OH、-C(R 6 )=NOR 5 、-NR 12 R 13 , C3-C6 cycloalkyl (optionally substituted by CN, fluorine or hydroxy), a C3-C6 saturated heterocycle containing one or more oxygen atoms, and a 5-membered heteroaryl containing 1 to 3 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur, wherein the heteroaryl is optionally substituted by one or two substituents independently selected from the group consisting of halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C3-C4 cycloalkyl, C1-C2 alkoxy and C1-C4 haloalkoxy; R 11 selected from the group consisting of hydrogen, fluorine, chlorine and CN; R 12 and R 13 Independently selected from the group consisting of: C1-C4 alkyl, C3-C4 cycloalkyl, C1-C4 alkyl-S(O) p -, C3-C4 cycloalkyl-S(O) p -, C1-C4 alkyl-C(O)- and C3-C4 cycloalkyl-C(O)-; m = 0, 1 or 2; n = 1, 2 or 3; and p=0, 1 or 2.

2. The compound of claim 1 having formula (I), wherein the compound has formula (Ia) Among them, Q, R 1 , R 2 and R 3 As defined in claim 1 above.

3. A compound according to any one of the preceding claims, wherein R 1 It's chlorine.

4. A compound according to any one of the preceding claims, wherein R 2 It is halogen or C1-C4 haloalkyl.

5. A compound according to any one of the preceding claims, wherein R 3 is hydrogen or a halogen.

6. A compound according to any one of the preceding claims, wherein Q is selected from the group consisting of hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C1-C4 alkoxy-C1-C3 alkyl-, C1-C4 haloalkoxy-C1-C3 alkyl-, -S(O) p R 4 and -(CH2) n R 10 .

7. The compound according to claim 6, wherein Q is -(CH2) n R 10 , n is 1, 2 or 3 and R 10 Selected from the group consisting of: -OH, -C(H)(OH)-CH2OH and -C(H)=NOR 5 .

8. The compound according to claim 6, wherein Q is a C1-C8 alkyl group.

9. The compound according to claim 6, wherein Q is a C1-C8 haloalkyl group.

10. The compound according to claim 6, wherein Q is C1-C4 haloalkoxy-C1-C3 alkyl-.

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

12. The herbicidal composition according to claim 11, further comprising at least one additional pesticide.

13. The herbicidal composition according to claim 12, wherein The additional pesticide is a herbicide or a herbicide safener.

14. A method of controlling weeds at a locus, the method comprising applying to the locus a weed controlling amount of a composition according to any one of claims 11 to 13.

15. A compound having formula (II-a): Where R 2 It is CF2H or CF2Cl.

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

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