Herbicidal imidazole 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] Certain imidazole compounds are disclosed in the prior art, for example in CN 106317072 and WO 2022 / 015975. However, the potential herbicidal use of such imidazole compounds has never been reported.

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

[0004]

[0005] or an agronomically acceptable salt thereof,

[0006] in

[0007] A is for CR 11 or N;

[0008] Q is selected from the group consisting of C2-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 ;

[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 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;

[0011] 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 ;

[0012] R 4 Selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C3-C6 cycloalkyl;

[0013] R 5 Selected from the group consisting of hydrogen, methyl, ethyl, -(CH2)-cyclopropyl, C2-C3 alkenyl, C2-C3 alkynyl and cyclopropyl;

[0014] R 6 selected from the group consisting of: hydrogen, methyl and ethyl;

[0015] R 7 is methyl or ethyl;

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

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

[0018] 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;

[0019] R 11 selected from the group consisting of hydrogen, fluorine, chlorine and CN;

[0020] 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)-;

[0021] m = 1 or 2;

[0022] n = 1, 2 or 3; and

[0023] p=0, 1 or 2.

[0024] 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).

[0025] Halogen (or halo) includes, for example, fluorine, chlorine, bromine or iodine. The above applies correspondingly to halogen in other defined contexts, such as haloalkyl.

[0026] 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.

[0027] The C1-C4 alkoxy group and the C1-C3 alkoxy group include, for example, a methoxy group and an ethoxy group.

[0028] 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.

[0029] C2-C8 alkenyl - includes, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[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 is as defined above.

[0037] In one embodiment of the present invention, A is CR 11 And R 11 is selected from the group consisting of hydrogen, fluorine, chlorine and CN, preferably fluorine or hydrogen. Therefore, in a preferred embodiment of the present invention, there is provided a compound having formula (Ib),

[0038]

[0039] Among them, Q, R 1 , R 2 , R 3 and R 11 is as defined above.

[0040] In one embodiment of the present invention, there is provided a compound having formula (I), formula (Ia) or formula (Ib), wherein R 1 It's chlorine.

[0041] In one embodiment of the present invention, there is provided a compound having formula (I), formula (Ia) or formula (Ib), wherein R 2 It is halogen (such as Cl or Br) or C1-C4 haloalkyl (such as -CF3, -CHF2).

[0042] In one embodiment of the present invention, there is provided a compound having formula (I), formula (Ia) or formula (Ib), wherein R 3 is hydrogen or a halogen (eg Cl).

[0043] In a preferred embodiment of the present invention, a compound of formula (I), formula (Ia) or formula (Ib) is provided, wherein Q is selected from the group consisting of: C2-C8 alkyl or C2-C6 alkyl (e.g., -CH2CH(CH3)2, n-butyl, n-pentyl), C2-C8 alkenyl (e.g., -CH2CH2CH=CH2), C1-C8 haloalkyl or C1-C6 haloalkyl (e.g., -CH2CH2CHF2, -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).

[0044] In one embodiment of the present invention, there is provided a compound having formula (I), formula (Ia) or formula (Ib), wherein Q is -(CH2) n R 10 , n is 1, 2 or 3, and R 10Selected 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).

[0045] In a preferred embodiment of the present invention, a compound having formula (I), formula (Ia) or formula (Ib) is provided, wherein Q is a C2-C8 alkyl group (eg, -CH2CH(CH3)2, n-butyl, n-pentyl).

[0046] In another preferred embodiment of the present invention, there is provided a compound having formula (I), formula (Ia) or formula (Ib), wherein Q is a C1-C8 haloalkyl group (eg, -CH2CH2CHF2, -CH2CH2CF3, -CH2CH2CH2CF3).

[0047] 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, -CH2CH2OCH2CHF2).

[0048] The present invention further relates to compounds having the formula Int-1:

[0049]

[0050] Where R 2 and R 3 is as defined above for formula (I). In a preferred embodiment, R 2 is C1-C4 haloalkyl (e.g. -CHF2 or -CF3) and R 3 is hydrogen. In a more preferred embodiment, the compound having formula (Int-1) is compound I18.

[0051]

[0052] The present invention further relates to compounds having the formula (IIIa-1):

[0053]

[0054] Where R 1a is a halogen (such as F or Cl) and R14 is C1-C4 alkyl (eg ethyl). In a more preferred embodiment, the compound having formula (IIIa-1) is compound I28.

[0055]

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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).

[0061] 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).

[0062] 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).

[0063] 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.

[0064] 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).

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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)).

[0072] The wetting agent, dispersant and emulsifier may be a cationic type, anionic type, amphoteric type or nonionic type SAA.

[0073] Suitable cationic-type SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0074] 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.

[0075] Suitable amphoteric types of SAA include betaine, propionate and glycinate.

[0076] 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.

[0077] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinyl pyrrolidone or sodium carboxymethyl cellulose) and swelling clays (such as bentonite or attapulgite).

[0078] 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.

[0079] 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.

[0080] 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.

[0081] The mixing ratio of the compound having formula (I) to the mixing partner is preferably 1:100 to 1000:1.

[0082] 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).

[0083] 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.

[0084] Particularly preferred are mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen-ethyl, clofonet-mexyl and / or sulfamethoxazole.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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 (Syngenta Seeds). 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.

[0092] 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).

[0093] 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.

[0094] In a further aspect of the invention there is provided the use of a compound of formula (I) as defined herein as a herbicide.

[0095] Process for preparing compounds having formula (I)

[0096] 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.

[0097] The compound of formula I-3 is a compound of formula I, wherein Q, R 2 , A and R 1 (m) is as defined in Formula I, and wherein R 31 is a C1-C4 alkyl group and can be prepared by a Suzuki reaction involving, for example, reacting a compound having formula I-1,

[0098] Scenario 1:

[0099]

[0100] Among them, Q, R 2 , A and R 1 (m) is as defined in Formula I, and wherein X 1 is chlorine, bromine or iodine, reacted with a compound of formula II, wherein R 31 is a C1-C4 alkyl group, and wherein Yb1 can be a boron-derived functional group, such as, for example, B(OH)2 or B(ORb1)2, wherein Rb1 can be a C1-C4 alkyl group, or two ORb1 groups can form a five-membered ring together with the boron atom, such as, for example, pinacol borate (Scheme 1). The reaction can be catalyzed by a palladium-based catalyst such as tetrakis(triphenyl-phosphine)palladium(0), (1,1'bis(diphenylphosphino)ferrocene)dichloropalladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos palladacycle complex) in the presence of a base such as sodium carbonate, tripotassium phosphate or cesium fluoride in a solvent or solvent mixture such as, for example, dioxane, acetonitrile, N,N-dimethyl-formamide, a mixture of 1,2-dimethoxyethane and water or a mixture of dioxane / water or a mixture of toluene / water, preferably under an inert atmosphere. 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 Suzuki reactions are well known to those skilled in the art.

[0101] The compound of formula I-4 is a compound of formula I, wherein R 3 is CN, and can be prepared from a compound of formula I-1 by reaction with M-CN IIa (cyanidation), wherein M is a metal coordinated to cyanide. Examples of cyaniding agents include NaCN, Zn(CN)2 or potassium ferrocyanide, and the like. The reaction can be catalyzed by a palladium-based catalyst such as tetrakis(triphenylphosphine)palladium(0), (1,1'bis(diphenylphosphino)ferrocene)dichloropalladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos palladacycle complex) in the presence of a base such as sodium carbonate, tripotassium phosphate or cesium fluoride in a solvent or solvent mixture such as, for example, dioxane, acetonitrile, N,N-dimethyl-formamide, a mixture of 1,2-dimethoxyethane and water or a mixture of dioxane / water or a mixture of toluene / water, preferably under an inert atmosphere. 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 reactions are well known to those skilled in the art.

[0102] Compounds of formula I-1 can be prepared by halogenation reactions, which involve, for example, reacting a compound of formula I-2 (wherein Q, R2, A and R 1 (m) is as defined in formula I) with a halogenating agent such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS) optionally in the presence of an additive such as p-toluenesulfonic acid. Alternatively, the halogenation may involve chlorine, bromine or iodine. Such halogenation reactions are carried out in a suitable solvent such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, diethyl ether, acetonitrile or N,N-dimethylformamide at a temperature between 20°C and 200°C, preferably at room temperature to 100°C.

[0103] The compound of formula IV may be reacted with a reagent of formula III (wherein A and R 1 (m) is as defined in formula I, and wherein LG1 is halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen 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 or acetonitrile, etc.), at a temperature between 0°C and 120°C, by procedures well known to those skilled in the art to prepare a compound of formula I-2.

[0104] Alternatively, compounds of formula I-2 can be prepared according to Scheme 1a. In Scheme 1a, compounds of formula I-2 are prepared from compounds of formula IVaa.

[0105] Option 1a:

[0106]

[0107] Where R 11 It is C1-C4 alkyl, prepared via decarboxylation. Such reactions can be carried out in the presence of a base (such as sodium hydroxide, potassium hydroxide, potassium carbonate and similar other bases). Compounds of formula IVaa can be prepared by reacting a compound of formula IV with a compound of formula IIIa (wherein LG11 is a leaving group, such as chlorine or bromine) in the presence of a base (such as potassium carbonate) and in the presence of a solvent (such as acetonitrile, tetrahydrofuran, sulfolane) and at a temperature between room temperature and the boiling point of the solvent and optionally under microwave radiation.

[0108] The compound of formula IV can be prepared by condensation reaction of a compound of formula VI or a hydrated form thereof with a compound of formula V in the presence of ammonia or its substitute (such as ammonium hydroxide). The reaction can be carried out in the presence of a solvent (such as methanol, tetrahydrofuran, ethanol, etc.) and at a temperature between 20°C and 200°C, preferably room temperature to 100°C. The compound of formula VI or a hydrated form thereof (wherein R 2 is as defined in formula I) can be obtained by hydrolysis of a compound of formula VII (wherein R 2 is as defined in formula I). ​​Such two-step reactions are well known in the literature.

[0109] The compound of formula I-5 is a compound of formula I wherein Q, A and R 1 (m) is as defined in Formula I, and wherein R in Formula I 3 is H and R in Formula I 2 is a halogen, defined as X 2 (Scheme 2).

[0110] Scenario 2:

[0111]

[0112] The compound of formula VIII may be reacted with a reagent of formula III (wherein A and R 1 (m) is as defined in formula I, and wherein LG1 is halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen 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 or acetonitrile, etc.), at a temperature between 0°C and 120°C, by procedures well known to those skilled in the art to prepare a compound of formula I-5.

[0113] The compound of formula IX can be reacted with CX 2 4 XII (where X 2 The compound of formula VIII is prepared by reacting 2-(4 ...

[0114] Compounds of formula IX can be prepared by amide coupling of compounds of formula X with compounds of formula XI. The reaction can use amide coupling reagents such as 1-propanephosphonic anhydride, (1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, etc., optionally in the presence of a base (such as pyridine, triethylamine, etc.). Such reactions are well known to those skilled in the art and are described in the literature.

[0115] The compound of formula I-6 is a compound of formula I wherein Q, A and R 1 (m) is as defined in Formula I, and wherein R in Formula I 2 is a halogen and is defined as X 4 (Scheme 3).

[0116] Scenario 3:

[0117]

[0118] The compound of formula XVIII may be reacted with a reagent of formula III (wherein A and R 1 (m) is as defined in formula I, and wherein LG1 is halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen 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 or acetonitrile, etc.), at a temperature between 0°C and 120°C, by procedures well known to those skilled in the art to prepare compounds of formula I-6.

[0119] A compound of formula XVIII (wherein Q is as defined in formula I, and X 4 Is halogen) can be prepared from a compound of formula XVII (wherein PG1 is an N-protecting group, such as an amino protecting group such as acetyl, trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl, etc.) 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 or acid catalysis (such as HCl).

[0120] The compound of formula XVII can be prepared from a compound of formula XVI (wherein X 4 and X 5is halogen) by selective dehalogenation reaction. Such reactions can be carried out by metal halogen exchange using an organic metal reagent (such as butyl lithium, Grignard reagent or organic zinc reagent) and further quenching the reactant with water or an acidic aqueous solution.

[0121] The compound of formula XVI can be prepared by substitution reaction or cross-coupling reaction of the compound of formula XIV with the compound of formula XV (wherein M is an alkali metal (such as lithium or potassium), an alkaline earth metal (such as magnesium) or a transition metal (such as copper or zinc). The reaction can be optionally carried out in the presence of a metal catalyst (such as palladium or copper) and in the presence of a ligand (such as PPh3, etc., based on phosphine, or copper nitrogen-containing ligand (such as 1,2-dimethylethylenediamine, etc.). The reaction can be carried out in the presence of a solvent (such as tetrahydrofuran, dioxane or toluene, etc.). Alternatively, compounds of formula XVI can be prepared by a substitution reaction involving a metal-halogen exchange of a compound of formula XIV with an organometallic reagent such as butyllithium or a Grignard reagent and then further reacted with a compound of formula XVa wherein LG2 is a halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group such as a (halo)alkyl or phenylsulfonate, e.g., trifluoromethanesulfonate), in an inert solvent such as tetrahydrofuran, dioxane, N,N-dimethylformamide DMF, N,N-dimethylacetamide, etc., at a temperature between -80°C and 120°C by procedures well known to those skilled in the art.

[0122] Compounds with formula XIV can be prepared by installing a protecting group from compounds with formula XIII. Such reactions can be carried out in the presence of a base (such as sodium hydride, potassium carbonate, sodium carbonate), and in the presence of a suitable protecting group reagent (such as 2-(chloromethoxy)ethyl-trimethyl-silane, acetyl chloride, di-tert-butyl dicarbonate) and in the presence of a solvent (such as tetrahydrofuran, methanol, water, acetonitrile, dimethylformamide). Such reactions are well known in the literature.

[0123] The compound of formula I-7 is a compound of formula I wherein Q, A and R 1 (m) is as defined in Formula I, and wherein X 6 and X 7 is a halogen (Scheme 4).

[0124] Solution 4:

[0125]

[0126] The compound of formula I-7 can be prepared from a compound of formula XXIII (wherein X 6 and X 7Is halogen) is prepared by a procedure similar to the procedure for converting a compound of formula XVIII to a compound of formula I-6 as described in Scheme 3. A compound of formula XXIII can be prepared from a compound of formula XXII by a procedure similar to the procedure for converting a compound of formula XVII to a compound of formula XVIII as described in Scheme 3. A compound of formula XXII can be prepared by deprotonating a compound of formula XX using a suitable base (a strong base such as butyllithium or lithium diisopropylamide) followed by a substitution reaction with a compound of formula XXI (wherein LG3 is a halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group such as a (halo)alkyl or phenylsulfonate, such as trifluoromethanesulfonate)). The reaction is typically carried out in the presence of a solvent such as tetrahydrofuran or toluene and at a temperature ranging from -80°C to room temperature. A compound of formula XX can be prepared from a compound of formula XIX by a procedure similar to the procedure for converting a compound of formula XIII to a compound of formula XIV as described in Scheme 3.

[0127] Alternatively, compounds of formula I-1 can be prepared according to Scheme 5. In Scheme 5, compounds of formula I-1 can be prepared from compounds of formula XXVII via fluorination reaction using a fluorinating agent such as diethylaminosulfur trifluoride or bis(2-methoxyethyl)aminosulfur trifluoride, etc.

[0128] Scenario 5:-

[0129]

[0130] A compound having formula I (wherein R 3 is H and R 2 Yes - C(H)=NOR 7 And where R 7 is as defined in formula I above) can be represented by a compound of formula I-9. The compound of formula I-9 can be prepared by a condensation reaction of a compound of formula XXVII with a compound of formula XXVIIa. Such reactions are well known in the literature.

[0131] Compounds of formula XXVII can be prepared by reacting compounds of formula XXV with compounds of formula XXVI, wherein LG is halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group, such as (halo)alkyl or phenylsulfonate, e.g. 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, sulfolane, N,N-dimethylacetamide or acetonitrile, at a temperature between 0° C. and 120° C., by procedures well known to those skilled in the art. Compounds of formula XXV can be prepared from compounds of formula XXIV via oxidation using an oxidizing agent such as an alcohol oxidizing agent such as MnO2, SO3, pyridine, pyridinium dichromate or pyridinium chlorochromate. Compounds of formula XXIV can be prepared according to procedures reported in the literature, for example, J. Med. Chem. 1995, 38, 2251-2255.

[0132] Solution 6:

[0133]

[0134] Alternatively, compounds of formula XXV can be prepared by compounds of formula XXVIII (wherein PG3 is an N-protecting group, such as N,N-dimethylsulfamoyl, acetyl, tert-butoxycarbonyl and similar other groups) via N-deprotection reaction. Such deprotection reactions can be carried out in the presence of an acid catalyst (such as hydrochloric acid) or a base (such as sodium hydroxide or potassium carbonate). Compounds of formula XXVIII can be prepared by compounds of formula XXIX via metalation using a strong base (such as n-butyl lithium, lithium diisopropylamide) and then reacting with N,N-dimethylformamide to install aldehyde. Compounds of formula XXIX can be prepared by compounds of formula XXX via N-deprotection reaction. Examples of reagents that can be used for such N-protection reactions are di-tert-butyl decarbonate, acetyl chloride, acetic anhydride, N,N-dimethylsulfamoyl chloride and similar other reagents.

[0135] Solution 7:

[0136]

[0137] Alternatively, compounds of formula XXVII can be prepared according to Scheme 7. In Scheme 7, compounds of formula XXVII can be prepared by reacting compounds of formula XXV with compounds of formula XXVI according to the procedure described in Scheme 5. Compounds of formula XXV can be prepared by reacting compounds of formula XXXII with a suitable reducing agent such as diisobutylaluminum hydride. Compounds of formula XXXII can be prepared by reacting compounds of formula XXXI with ammonium hydroxide or similar other ammonia substitutes to convert trifluoromethyl to cyano. Such reactions are well documented in the literature (see, e.g., Matthews, DP; Whitten, JP; McCarthy, JRJ Org. Chem. [Journal of Organic Chemistry] 1986, 51, 3228). The synthesis of imidazole compounds of formula XXXI is well documented in the literature (see, for example, Journal of Medicinal Chemistry, 2000, 43, 2165 and Synthetic Communications, 2020, 50, 700).

[0138] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (as mentioned in the table below).

[0139] Example 1: Preparation of 5-chloro-2-[[4-chloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]pyrimidine (Compound 1.001)

[0140]

[0141] Step 1: Preparation of N-(cyanomethyl)-5,5,5-trifluoro-pentanamide (I1)

[0142]

[0143] To a suspension of 5,5,5-trifluoropentanoic acid (620 mg, 3.97 mmol), aminoacetonitrile hydrochloride (368 mg, 3.97 mmol) and triethylamine (1.11 mL, 7.94 mmol) in ethyl acetate (10 mL) was added 1-propanephosphonic anhydride (50% by mass in ethyl acetate; 3.07 mL, 5.16 mmol), and this mixture was stirred at room temperature overnight. The reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The organics were combined, washed with saturated aqueous sodium bicarbonate solution (2×100 mL), then with brine (100 mL), dried over magnesium sulfate and concentrated to give a crude product. The crude material was subjected to column chromatography on silica gel using 0-100% ethyl acetate in cyclohexane to give N-(cyanomethyl)-5,5,5-trifluoro-pentanamide II (210 mg, 27%) as an orange crushed foam. 1 H NMR (400MHz, CDCl3) δ = 5.90 (br s, 1H), 4.20 (d, 2H), 2.32 (t, 2H), 2.24-2.10 (m, 2H), 2.00-1.89 (m, 2H)

[0144] Step 2: Preparation of 4-chloro-2-(4,4,4-trifluorobutyl)-1H-imidazole (I2)

[0145]

[0146] Under nitrogen, carbon tetrachloride (0.39 mL, 4.00 mmol) was added to a stirred suspension of N-(cyanomethyl)-5,5,5-trifluoro-pentanamide I1 (210 mg, 1.08 mmol) and triphenylphosphine (1.07 g, 4.00 mmol) in acetonitrile (5 mL). The reaction mixture was heated at 50 ° C for 1 hour and then allowed to cool to room temperature. The reaction mixture was diluted with aqueous 2M sodium hydroxide (50 mL) and then extracted with ethyl acetate (3×50 mL). The organics were combined, washed with brine (100 mL), dried over magnesium sulfate and concentrated to give a crude product. The crude material was subjected to column chromatography on silica gel using 0-100% ethyl acetate in cyclohexane to give 4-chloro-2-(4,4,4-trifluorobutyl)-1H-imidazole I2 (88 mg, purity 70%). 1 HNMR (400MHz; CDCl3) δ = 6.69 (s, 1H), 2.63 (t, 2H), 2.08-1.92 (m, 2H), 1.92-1.80 (m, 2H)

[0147] Step 3: Preparation of 5-chloro-2-[[4-chloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]pyrimidine (1.001)

[0148]

[0149] 4-Chloro-2-(4,4,4-trifluorobutyl)-1H-imidazole I2 (88 mg), 5-chloro-2-(chloromethyl)pyrimidine hydrochloride (103 mg, 0.52 mmol), potassium carbonate (144 mg, 1.03 mmol), potassium iodide (6.9 mg, 0.041 mmol), acetonitrile (4 ml) and water (0.13 ml) were heated at 80° C. overnight. The reaction mixture was cooled to room temperature, then diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The organics were combined, washed with brine (100 mL), dried over magnesium sulfate and concentrated to give the crude product. The crude material was subjected to column chromatography on silica gel using 0-50% ethyl acetate in cyclohexane to give 5-chloro-2-[[4-chloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]pyrimidine 1.001 (50 mg, 14% over 2 steps). 1 H NMR (400MHz; CDCl3) δ=8.59(s,2H),6.77(s,1H),5.10(s,2H),2.69(t,2H),2.19-2.03(m,2H),2.00-1.89(m,2H)

[0150] Example 2: Preparation of 5-chloro-2-[[4-(trifluoromethyl)-2-(3,3,3-trifluoropropyl)imidazol-1-yl]methyl]pyrimidine (Compound 1.002)

[0151]

[0152] Step 1: Preparation of 3,3,3-trifluoro-2-oxo-propanal (I3)

[0153]

[0154] Sodium acetate (508 mg, 6.13 mmol) and water (2.4 mL) were added to a 50 mL flask. 1,1-dibromo-3,3,3-trifluoroacetone (410 μL, 2.86 mmol) was added to the above solution to give a turbid solution / suspension. The reaction mixture was then heated to 100 ° C for 30 minutes. The reaction mixture was then cooled to room temperature to provide a solution of I3, which was used as is in the next step.

[0155] Step 2: Preparation of 4-(trifluoromethyl)-2-(3,3,3-trifluoropropyl)-1H-imidazole (I4)

[0156]

[0157] 35% ammonia (2.4 mL, 21 mmol) was added to the solution of I3 prepared in step 1, followed by a solution of 4,4,4-trifluorobutyraldehyde (275 mg, 2.18 mmol) in methanol (2.4 mL). The mixture was stirred at room temperature for 17 hours. The mixture was diluted with water and extracted with ethyl acetate. The combined organic matter was concentrated and subjected to column chromatography on silica gel using 0-70% ethyl acetate in cyclohexane to give 4-(trifluoromethyl)-2-(3,3,3-trifluoropropyl)-1H-imidazole (I4) (473 mg, 89% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ = 9.18 (br s, 1H), 7.31 (s, 1H), 3.05-2.98 (m, 2H), 2.74-2.59 (m, 2H)

[0158] Step 3: Preparation of 5-chloro-2-[[4-(trifluoromethyl)-2-(3,3,3-trifluoropropyl)imidazol-1-yl]methyl]pyrimidine (1.002)

[0159]

[0160] 4-(Trifluoromethyl)-2-(3,3,3-trifluoropropyl)-1H-imidazole I4 (155 mg, 0.634 mmol), potassium carbonate (241 mg, 1.745 mmol), 5-chloro-2-(chloromethyl)pyrimidine hydrochloride (162 mg, 0.772 mmol) and potassium iodide (33 mg, 0.199 mmol) were added to a 50 mL flask. The mixture was treated with acetonitrile (2.0 mL) and water (100 μL), heated to 70 ° C and stirred for 1 hour. After completion, the mixture was cooled, then diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected to reverse phase column chromatography on C-18 silica gel using 50%-100% acetonitrile in water (both water and acetonitrile contained 0.1% formic acid) to give 5-chloro-2-[[4-(trifluoromethyl)-2-(3,3,3-trifluoropropyl)imidazol-1-yl]methyl]pyrimidine 1.002 (177 mg, 74% yield) as a beige solid. 1H NMR (400 MHz, CDCl3) δ = 8.69 (s, 2H), 7.34-7.31 (m, 1H), 5.27 (s, 2H), 3.04-2.94 (m, 2H), 2.82-2.64 (m, 2H)

[0161] Example 3: Preparation of 2-[[4-bromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine (Compound 1.003):

[0162]

[0163] Step 1 - Preparation of trimethyl-[2-[(2,4,5-tribromoimidazol-1-yl)methoxy]ethyl]silane (I5):

[0164]

[0165] 2,4,5-tribromoimidazole (5.00 g, 16.4 mmol) and potassium carbonate (6.80 g, 49.2

[0166] mmol) was added once in a rapidly stirred suspension in acetonitrile (45mL) with 2-(chloromethoxy)ethyl-trimethyl-silane (4.3mL, 25mmol). The reactant was stirred at room temperature for 16h, and then quenched with saturated NH4Cl (50mL). Ethyl acetate (50mL) was added, and each phase was separated. The aqueous phase was extracted with ethyl acetate (3×30mL), the organic matter was combined, washed with saturated brine solution (50mL), and then concentrated onto granular diatomaceous earth. The crude product was purified by flash chromatography on silica gel using ethyl acetate with a gradient of 0-30% in cyclohexane as eluent to give trimethyl-[2-[(2,4,5-tribromoimidazol-1-yl)methoxy]ethyl]silane I5 (6.78g, 95%) as a white solid. 1 H NMR (400MHz, CDCl3) δ = 5.34 (s, 2H), 3.69-3.54 (m, 2H), 1.01-0.89 (m, 2H), 0.02 (s, 9H)

[0167] Step 2-2-[[4,5-dibromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane (I6) Preparation:

[0168]

[0169] Under N2, a solution of trimethyl-[2-[(2,4,5-tribromoimidazol-1-yl)methoxy]ethyl]silane I5 (0.50 g, 1.15 mmol) in THF (10 mL) was cooled to -70 ° C, and n-BuLi (2.5 M in hexane) (0.60 mL, 1.5 mmol) was added dropwise while maintaining a constant temperature below -60 ° C. Then, the reaction mixture was stirred at -70 ° C for 0.5 h. 1,1,1-trifluoro-4-iodobutane (0.22 mL, 1.73 mmol) was added dropwise to the reaction mixture. The reactant was stirred at -70 ° C under N2 for 1 h and then allowed to slowly warm to room temperature. Stirring was continued at room temperature under N2 for 4 h. The reactant was quenched with a saturated saline solution (20 mL) and ethyl acetate (20 mL) was added. The phases were separated, and the aqueous phase was extracted with ethyl acetate (3×10 mL). The organics were combined and concentrated onto granular celite. The crude product was purified by flash chromatography on silica gel using a gradient of 0-35% ethyl acetate in cyclohexane as eluent to give 2-[[4,5-dibromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane 16 (0.25 g, 47%) as a pale yellow oil.

[0170] 1 H NMR (400 MHz, chloroform) δ=5.25 (s, 2H), 3.58-3.53 (m, 2H), 2.86-2.77 (m, 2H), 2.27-2.15 (m, 2H), 2.12-2.00 (m, 2H), 0.93-0.88 (m, 2H), 0.00 (m, 9H)

[0171] Step 3- Preparation of 2-[[4-bromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane (I7):

[0172]

[0173] Under N2, a solution of 2-[[4,5-dibromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane I6 (0.25 g, 0.54 mmol) in THF (7 mL) was cooled to -70 ° C, and n-BuLi (2.5 M in hexane, 0.30 mL, 0.75 mmol) was added dropwise while maintaining a constant temperature below -60 ° C. The reaction mixture was then stirred at -70 ° C for 0.5 h. Water (1.00 mL) was added to the reaction mixture. The reactants were stirred at -70 ° C under N2 for 1 h and then slowly warmed to room temperature. The reaction mixture was concentrated onto granular diatomaceous earth. The crude product was purified by flash chromatography on silica gel using a gradient of 0-30% ethyl acetate in cyclohexane as eluent to give 2-[[4-bromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane 17 (72 mg, 35%) as a colorless oil.

[0174] 1 H NMR (400MHz, CDCl3) δ = 6.96-6.84 (m, 1H), 5.16 (s, 2H), 3.66-3.37 (m, 2H), 2.7 9(t,2H),2.34-2.14(m,2H),2.13-2.01(m,2H),1.01-0.80(m,2H),0.01(s,9H)

[0175] Step 4 - Preparation of 4-bromo-2-(4,4,4-trifluorobutyl)-1H-imidazole; hydrochloride (I8):

[0176]

[0177] To a solution of 2-[[4-bromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane 17 (96 mg, 0.25 mmol) in ethanol (2 mL) was added 6M HCl (0.6 mL, 3.6 mmol) and the reaction mixture was heated to 70° C. for 6 h. The reaction mixture was concentrated under vacuum to give 4-bromo-2-(4,4,4-trifluorobutyl)-1H-imidazole; hydrochloride salt 18 (71 mg, 97%) as a light yellow solid. 1 H NMR (400MHz, MeOD) δ=7.60-7.52(m,1H),7.69-7.42(m,1H),3.10-2.95(m,2H),2.41-2.20(m,2H),2.13-1.95(m,2H)

[0178] Step 5-2-[[4-bromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine (Compound 1.003) Preparation:

[0179]

[0180] To a stirred suspension of 4-bromo-2-(4,4,4-trifluorobutyl)-1H-imidazole; hydrochloride I8 (0.071 g, 0.24 mmol), potassium iodide (9 mg, 0.05 mmol) and potassium carbonate (0.117 g, 0.85 mmol) in acetonitrile (5 mL) and H2O (0.5 mL) was added 5-chloro-2-(chloromethyl)pyrimidine hydrochloride (0.068 g, 0.32 mmol) in one portion. The reaction was then heated to 80°C under N2 for 16 h. The reaction was cooled to room temperature and concentrated onto granular celite. The crude product was purified by flash chromatography on silica gel using a gradient of 0-70% ethyl acetate in cyclohexane as eluent to give 2-[[4-bromo-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine 1.003 (76 mg, 82%) as a light yellow oil. 1 H NMR (400MHz, CDCl3) δ = 8.67 (s, 2H), 6.93 (s, 1H), 5.20 (s, 2H), 2.78 (t, 2H), 2.29-2.10 (m, 2H), 2.09-1.97 (m, 2H)

[0181] Example 4: Preparation of 5-chloro-2-[[4,5-dichloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]pyrimidine (Compound 1.004):

[0182]

[0183] Step 1- Preparation of 2-[(4,5-dichloroimidazol-1-yl)methoxy]ethyl-trimethyl-silane (I9):

[0184]

[0185] At room temperature, potassium carbonate (2.52 g, 18.2 mmol) was added to a solution of 4,5-dichloro-1H-imidazole (1.05 g, 7.67 mmol) in acetonitrile (10 mL). The solution turned yellow, and 2-(chloromethoxy)ethyl-trimethyl-silane (1.70 mL, 9.7 mmol) was added once, and the reaction mixture turned beige. The reactant was stirred at room temperature for 1 h and then concentrated onto granular diatomaceous earth. The crude product was purified by flash chromatography on silica gel using ethyl acetate with a gradient of 0-100% in cyclohexane as eluent to give 2-[(4,5-dichloroimidazole-1-yl)methoxy]ethyl-trimethyl-silane I9 (1.76 g, 86%) as a light yellow solid. 1 H NMR (400MHz, CDCl3) δ = 7.51 (s, 1H), 5.26 (s, 2H), 3.56 (dd, 2H), 1.04-0.76 (m, 2H), 0.01 (s, 9H)

[0186] Step 2-2-[[4,5-dichloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane (I10) Preparation:

[0187]

[0188] Under N2, a solution of 2-[(4,5-dichloroimidazol-1-yl)methoxy]ethyl-trimethyl-silane I9 (0.50 g, 1.87 mmol) in tetrahydrofuran (10 mL) was cooled to -70 ° C, and n-BuLi (2.5 M in hexane) (1.00 mL, 2.5 mmol) was added dropwise while maintaining a constant temperature below -60 ° C. Then, the reaction mixture was stirred at -70 ° C for 0.5 h. 1,1,1-trifluoro-4-iodobutane (0.36 mL, 2.8 mmol) was added dropwise to the reaction mixture. The reactants were stirred at -70 ° C under N2 for 1 h and allowed to slowly warm to room temperature. Stirring was continued at room temperature under N2 for 16 h. The reactants were quenched with methanol (10 mL), and the reaction mixture was concentrated onto granular diatomaceous earth. The crude product was purified by flash chromatography on silica gel using a gradient of 0-20% ethyl acetate in cyclohexane as eluent to give 2-[[4,5-dichloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane 110 (0.43 g, 60%) as a light yellow oil. 1H NMR (400MHz, CDCl3) δ = 5.21 (s, 2H), 3.60-3.50 (m, 2H), 2.79 (t, 2H), 2.31-2.14 (m, 2H), 2.14-1.99 (m, 2H), 0.95-0.86 (m, 2H), 0.00 (s, 9H)

[0189] Step 3 - Preparation of 4,5-dichloro-2-(4,4,4-trifluorobutyl)-1H-imidazole (I11):

[0190]

[0191] 6M HCl (2.5 mL, 15 mmol) was added to a solution of 2-[[4,5-dichloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methoxy]ethyl-trimethyl-silane I10 (0.31 g, 0.82 mmol) in ethanol (5 mL) and the reactants were heated to 60 ° C for 2 h. The reaction mixture was cooled to room temperature and then concentrated onto granular diatomaceous earth. The crude product was purified by using acetonitrile in a gradient of 50%-100% in water (with 0.1% formic acid modifier) ​​as eluent on C18 reverse phase silica to give 4,5-dichloro-2-(4,4,4-trifluorobutyl)-1H-imidazole I11 (65 mg, 32%) as a white solid. 1 H NMR (400MHz, MeOD) δ = 2.70 (t, 2H), 2.34-2.10 (m, 2H), 1.92 (quin, 2H)

[0192] Step 4 - Preparation of 5-chloro-2-[[4,5-dichloro-2-(4,4,4-trifluorobutyl)imidazol-1-yl]methyl]pyrimidine 1.004:

[0193]

[0194] To a stirred suspension of 4,5-dichloro-2-(4,4,4-trifluorobutyl)-1H-imidazole II (0.065 g, 0.26 mmol), KI (5 mg, 0.030 mmol) and potassium carbonate (0.09 g, 0.65 mmol) in acetonitrile (2 mL) and H2O (0.03 mL) was added 5-chloro-2-(chloromethyl)pyrimidine hydrochloride (0.061 g, 0.29 mmol) in one portion. The reactants were then heated to 80 °C under N2 for 1.5 h. The reactants were cooled to room temperature and concentrated onto granular diatomaceous earth. The crude product was purified by flash chromatography on silica gel using a gradient of 0-40% ethyl acetate in cyclohexane as eluent to give the desired product (70 mg, 64%) as a pale yellow oil. 1H NMR (400MHz, CDCl3) δ = 8.66 (s, 2H), 5.27 (s, 2H), 2.73 (t, 2H), 2.19 (tq, 2H), 2.00 (quin, 2H)

[0195] Example 5: Preparation of 2-[[2-butyl-4-(difluoromethyl)imidazol-1-yl]methyl]-5-chloro-3-fluoro-pyridine (1.054)

[0196]

[0197] Step 1: Preparation of 2-butyl-4-(trifluoromethyl)-1H-imidazole (I12)

[0198]

[0199] Sodium acetate (7.22 g, 87.07 mmol) and water (15 mL) were added to a 250 mL flask equipped with a reflux condenser and a thermometer, followed by 1,1-dibromo-3,3,3-trifluoroacetone (11.87 g, 41.79 mmol) to give a turbid solution. The reaction mixture was then heated to 100 ° C for 30 minutes. The reactants were cooled to room temperature, and valeraldehyde (3 g, 34.83 mmol) in methanol (60 mL) was slowly added to the solution. Ammonia (13 g, 130 mmol) was added to the above solution, and then stirred at room temperature overnight. The residue was distributed between ethyl acetate (200 mL) and water (200 mL) and the phases were separated. The aqueous phase was extracted with ethyl acetate (3×200 mL). The organics were combined, washed with saturated brine (100 mL) and concentrated onto granular diatomaceous earth. The crude material was purified by silica gel column chromatography using 0-100% ethyl acetate / cyclohexane mixtures to give 2-butyl-4-(trifluoromethyl)-1H-imidazole 112 (6 g, 89%) as an off-white solid. 1 H NMR (400MHz, CDCl3) δ = 10.83 (br s, 1H), 7.26-7.29 (m, 1H), 2.74 (t, 2H), 1.73-1.65 (m, 2H), 1.39-1.30 (m, 2H), 0.90 (t, 3H).

[0200] Step 2: Preparation of 2-butyl-1H-imidazole-4-carbonitrile (I13)

[0201]

[0202] 2-butyl-4-(trifluoromethyl)-1H-imidazole I12 (2g, 10.40mmol), methanol (10mL) and ammonia (21.8g, 156.10mmol) were added to a three-necked flask, and the reaction mixture was stirred at 70°C for 6h. After this time, the reaction mixture was cooled to room temperature and concentrated to obtain a crude material. The crude product was purified by silica gel column chromatography using 0-100% ethyl acetate / cyclohexane as eluent to obtain 2-butyl-1H-imidazole-4-carbonitrile I13 (0.66g, 42%) as an off-white solid. 1 H NMR (400 MHz, methanol-d4) δ = 7.66 (s, 1H), 2.62 (t, 2H), 1.59 (m, 2H), 1.18-1.31 (m, 2H), 0.85 (t, 3H).

[0203] Step 3: Preparation of 2-butyl-1H-imidazole-4-carbonitrile (I14)

[0204]

[0205] At -78 ° C, 2-butyl -1H-imidazole -4-carbonitrile I13 (0.66g, 4.42mmol) in anhydrous tetrahydrofuran (13.2mL) was added dropwise to a stirred solution of 1M diisobutylaluminum hydride solution in toluene (7.6g, 8.84mmol). The mixture was stirred at the same temperature for 30 minutes, and then allowed to reach 0 ° C and stirred for an additional hour. The reaction mixture was quenched by adding saturated NH4Cl (15mL) and extracted with ethyl acetate (3×50mL). The organic layer was then washed with water (30mL), brine (30mL), dried over sodium sulfate, filtered and concentrated to give a crude 2-butyl -1H-imidazole -4-carboxaldehyde I14 (0.45g, 67%) as a pale yellow solid, which was used directly in the next step without further purification. 1 H NMR (400 MHz, methanol-d4) δ = 9.55 (s, 1H), 7.68 (s, 1H), 2.54-2.69 (m, 2H), 1.54-1.66 (m, 2H), 1.17-1.32 (m, 2H), 0.80-0.88 (m, 3H)

[0206] Step 4: Preparation of 2-butyl-1-[(5-chloro-3-fluoro-2-pyridyl)methyl]imidazole-4-carbaldehyde (I15)

[0207]

[0208] In a 25mL flask equipped with a nitrogen blanket, 2-butyl-1H-imidazole-4-carboxaldehyde I14 (0.25g, 1.64mmol) is dissolved in acetonitrile (2.5mL). Potassium carbonate (0.56g, 4.10mmol) and potassium iodide (0.054g, 0.32mmol) are added thereto, followed by 5-chloro-2-(chloromethyl)-3-fluoro-pyridine (0.35g, 1.97mmol). The reaction mixture is heated to 70°C for 4h. After this time, the reaction mixture is diluted with water (50mL) and extracted with ethyl acetate (3×50mL). The combined organic layer is washed with brine (30mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography using 0-40% ethyl acetate / cyclohexane to give 2-butyl-1-[(5-chloro-3-fluoro-2-pyridinyl)methyl]imidazole-4-carbaldehyde 115 as an off-white solid (0.16 g, 33%). 1 H NMR (400MHz, CDCl3) δ = 9.81 (s, 1H), 8.40 (d, 1H), 7.66 (s, 1H), 7.54 (dd, 1H), 5.25 ( d,2H),2.74-2.81(m,2H),1.71-1.81(m,2H),1.36-1.50(m,2H),0.90-0.99(m,3H).

[0209] Step 5: Preparation of 2-[[2-butyl-4-(difluoromethyl)imidazol-1-yl]methyl]-5-chloro-3-fluoro-pyridine (1.054)

[0210]

[0211] To a 50 mL three-necked round-bottom flask with a stirring bar was added: 2-butyl-1-[(5-chloro-3-fluoro-2-pyridyl)methyl]imidazole-4-carboxaldehyde I15 (128 mg, 0.43 mmol) and cooled to 0°C. At 0°C, dichloromethane (8 mL) and diethylaminosulfur trifluoride (0.55 g, 3.46 mmol) were added thereto, and the mixture was stirred at room temperature for 16 h. The reaction mixture was quenched with the addition of sodium bicarbonate solution (20 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and evaporated to give a crude product. The crude product was purified by silica gel column chromatography using 0-50% ethyl acetate / cyclohexane as eluent to give 2-[[2-butyl-4-(difluoromethyl)imidazol-1-yl]methyl]-5-chloro-3-fluoro-pyridine 1.054 (0.085 g, 58%) as a light brown liquid. 1H NMR(400MHz, CDCl3)δ=8.40(d,1H),7.53(dd,1H),7.19(t,1H),6.66(t,1H), 5.21(d,2H),2.76-2.82(m,2H),1.69-1.78(m,2H),1.42(m,2H),0.94(t,3H).

[0212] Example 6: Preparation of [1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methanol (1.072)

[0213]

[0214] Step 1: Preparation of tert-butyl-dimethyl-[[4-(trifluoromethyl)-1H-imidazol-2-yl]-methoxy]-silane (I16)

[0215]

[0216] Sodium acetate (2.38 g, 28.68 mmol), water (10 mL) and 1,1-dibromo-3,3,3-trifluoroacetone (3.91 g, 13.769 mmol) were added to a 100 mL flask equipped with a reflux condenser and a thermometer. The resulting suspension was heated to 100 ° C for 30 minutes. The reaction mixture was cooled to room temperature, and ammonia (8.8 g, 88 mmol) was slowly added to the solution, followed by the slow addition of 2-[tert-butyl(dimethyl)silyl]oxyacetaldehyde (2 g, 11.47 mmol) in methanol (40 mL), and stirred at room temperature for 16 h. After this time, the reaction mixture was quenched by adding water (100 mL) and extracted with ethyl acetate (3×150 mL). The organic layer was washed with brine (100 mL), dried over anhydrous sodium sulfate, filtered and concentrated to obtain a crude material. The crude product was purified by silica gel column chromatography using 0-100% ethyl acetate / cyclohexane to give tert-butyl-dimethyl-[[4-(trifluoromethyl)-1H-imidazol-2-yl]methoxy]silane 116 (2.3 g, 71%) as a light yellow oil. 1 H NMR (400MHz, CDCl3): δ = 9.71 (br s, 1H), 7.34 (s, 1H), 4.83 (s, 2H), 0.93 (s, 9H), 0.12 (s, 6H).

[0217] Step 2: Preparation of tert-butyl-[[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methoxy]-dimethyl-silane (I17)

[0218]

[0219] In a 50 mL flask equipped with a nitrogen blanket, tert-butyl-dimethyl-[[4-(trifluoromethyl)-1H-imidazole-2-yl]methoxy]silane I16 (2.3 g, 8.2 mmol) was dissolved in acetonitrile (23 mL). Potassium carbonate (2.8 g, 21 mmol) and potassium iodide (0.27 g, 1.6 mmol) were added thereto, and the reaction mixture was heated to 60 ° C for 16 h. After the reaction was complete, the reaction mixture was diluted with water (150 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were washed with brine (100 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to give crude tert-butyl-[[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methoxy]-dimethyl-silane 117 (4.1 g, 98%, about 80% purity), which was used directly in the next step. 1 H NMR (400MHz, CDCl3): δ = 8.65 (s, 2H), 7.34 (s, 1H), 5.49 (s, 2H), 4.81 (s, 2H), 0.81 (s, 9H), 0.0 (s, 6H).

[0220] Step 3: Preparation of [1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methanol (1.072)

[0221]

[0222] To a 100 mL flask was added: tert-butyl-[[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methoxy]-dimethyl-silane I17 (4.1 g, 5.0 mmol), ethanol (25 mL) and hydrochloric acid in deionized water (30 mL). The mixture was stirred at room temperature for 16 h. The reaction mass was quenched with water (150 mL) and extracted with ethyl acetate (3×250 ml). The combined organic layers were washed with brine solution (100 mL), dried over anhydrous sodium sulfate, filtered and concentrated to give a crude material. It was purified by silica gel column chromatography using 0-100% ethyl acetate / cyclohexane to give [1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methanol 1.072 (1.0 g, 61%) as a yellow liquid. 1 H NMR (400MHz, CDCl3) δ = 8.68 (s, 2H), 7.33 (s, 1H), 5.47 (s, 2H), 4.79 (s, 2H).

[0223] Example 7: Preparation of 5-chloro-2-[[2-(difluoromethyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine (1.070)

[0224]

[0225] Step 1: Preparation of 1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazole-2-carbaldehyde (I18)

[0226]

[0227] In a 3-necked flask equipped with a nitrogen inlet, [1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methanol 1.072 (0.3 g, 1.02 mmol) was dissolved in acetonitrile (6 mL). The resulting reaction mass was cooled to 0 ° C, and (1,1-diacetoxy-3-oxo-1λ5,2-benzoiodine oxa-1-yl) acetate (0.67 g, 1.53 mmol) was added in batches over a period of 5 minutes. The reaction mixture was stirred at room temperature for 16 h. The reaction was quenched by adding saturated sodium thiosulfate solution (2 mL) in batches. The resulting mixture was stirred for an additional 5 minutes, and sodium bicarbonate aqueous solution (30 mL) was added. The aqueous layer was extracted with ethyl acetate (3×50 mL). The combined organic layer was washed with brine solution (50 mL), dried over anhydrous sodium sulfate, filtered and concentrated to give a crude product. It was purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane as eluent to give 1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazole-2-carbaldehyde 118 (340 mg, 68%) as a white solid. 1 H NMR (400MHz, CDCl3): δ = 9.83 (d, 1H), 8.65 (s, 2H), 7.58 (s, 1H), 5.85 (s, 2H).

[0228] Step 2: Preparation of 5-chloro-2-[[2-(difluoromethyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine (1.070)

[0229]

[0230] To a solution of 1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazole-2-carbaldehyde I18 (0.34 g, 0.93 mmol) in dichloromethane (10 mL) was added diethylaminosulfur trifluoride (1.27 g, 7.48 mmol) dropwise at 0°C. It was allowed to warm to room temperature and stirred for 16 h. After this time, the reaction mixture was cooled to 0°C and quenched with saturated bicarbonate solution (30 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (3×70 mL), washed with brine solution (30 mL), dried over sodium sulfate, filtered and concentrated to give the crude material. The crude material was purified by silica gel column chromatography using 0-100% ethyl acetate in cyclohexane to give 5-chloro-2-[[2-(difluoromethyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine 1.070 (85 mg, 29%) as a brown liquid. 1 H NMR (400MHz, CDCl3) δ = 8.69 (s, 2H), 7.52 (s, 1H), 6.78 (t, 1H), 5.56 (s, 2H).

[0231] Example 8: Preparation of 5-chloro-2-[[2-(chloromethyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine (1.071)

[0232]

[0233] At 0 ° C, under nitrogen, to a solution of [1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]methanol 1.072 (0.08 g, 0.27 mmol) in acetonitrile (0.8 mL) was added thionyl chloride (0.065 g, 0.54 mmol) and stirred for 10 minutes. The reaction mixture was allowed to warm to room temperature for 2 h. The reaction mixture was cooled to 0 ° C and then quenched with saturated sodium bicarbonate solution (20 mL). It was extracted with ethyl acetate (3×30 mL). The combined organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude material. The crude product was purified by silica gel column chromatography using 0-10% ethyl acetate in cyclohexane to give 5-chloro-2-[[2-(chloromethyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine 1.071 (0.053 g, 62%) as a gummy material. 1 H NMR (400MHz, CDCl3) δ = 8.70 (s, 2H), 7.42 (d, 1H), 5.46 (s, 2H), 4.79 (s, 2H).

[0234] Example 9: Preparation of 1-[(5-chloropyrimidin-2-yl)methyl]-2-(tetrahydrofuran-3-ylmethyl)imidazole-4-carbonitrile (1.073)

[0235]

[0236] Step 1: Preparation of 2-tetrahydrofuran-3-yl acetaldehyde (I19)

[0237]

[0238] To a solution of 3-[(E)-2-methoxyvinyl]tetrahydrofuran (1.57 g, 12.2 mmol) in acetonitrile (2 mL) was added hydrogen chloride (2.5 mL, 5.0 mmol, 2 M), and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water (50 mL) and extracted with tert-butyl dimethyl ether (3×50 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to produce a crude compound. The crude compound was purified by column using 0-5% ethyl acetate in cyclohexane to give 2-tetrahydrofuran-3-yl acetaldehyde I19 (0.9 g, 60%) as a clear liquid. 1 H NMR (400MHz, CDCl3): δ=9.79(s,1H),4.02-3.95(m,1H),3.90-3.83(m,1H),3.80-3.75(s,1H), 3.42-3.35(m,1H),2.76-2.63(m,1H),2.62-2.55(m,2H),2.25-2.10(m,1H),1.60-1.47(m,1H).

[0239] Step 2: Preparation of 2-(tetrahydrofuran-3-ylmethyl)-4-(trifluoromethyl)-1H-imidazole (I20)

[0240]

[0241] Sodium acetate (1.63 g, 19.71 mmol), water (4.5 mL) and 1,1-dibromo-3,3,3-trifluoroacetone (2.68 g, 9.46 mmol) were added to a 100 mL flask equipped with a reflux condenser. The reaction mixture was heated to 100 ° C for 30 minutes. The reaction mixture was cooled to room temperature, and a solution of 2-tetrahydrofuran-3-yl acetaldehyde I19 (0.9 g, 7.88 mmol) in methanol (18 mL) was slowly added to this solution, followed by dropwise addition of ammonia (4.5 mL) and stirring at room temperature for 16 h. The reaction mixture was extracted with ethyl acetate (3×100 mL). The combined organic layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, filtered and concentrated to obtain a crude material. The crude product was purified by column chromatography using 0-40% ethyl acetate in cyclohexane. After concentration, 2-(tetrahydrofuran-3-ylmethyl)-4-(trifluoromethyl)-1H-imidazole I20 (0.7 g, 40%) was obtained as a white solid. 1 H NMR (400MHz, CDCl3) δ=7.29-7.30(d,1H),3.75-3.96(m,3H),3.56(dd,1H),2.84-2.88(d,2H),2.76(m,1H),2.12(br dd,1H),1.66(br d,1H).

[0242] Step 3: Preparation of 2-(tetrahydrofuran-3-ylmethyl)-1H-imidazole-4-carbonitrile (I21)

[0243]

[0244] 2- (tetrahydrofuran -3- ylmethyl) -4- (trifluoromethyl) -1H- imidazole I20 (370mg, 1.68mmol), methanol (2mL) and ammonia (4mL) were added to a 15mL vial. The vial was sealed and the reaction mixture was stirred at 70 ° C for 7h. The reaction mixture was cooled to room temperature and concentrated under reduced pressure to give a crude product. The crude product was purified by silica gel column chromatography using 50%-100% ethyl acetate and cyclohexane. After concentration, 2- (tetrahydrofuran -3- ylmethyl) -1H- imidazole -4- carbonitrile I21 (220mg, 73%) was obtained as a light yellow solid. 1 H NMR(400MHz,MeOH-d4)δppm 7.78(s,1H),3.72-3.90(m,3H),3.46(m,1H),2.79(dd,2H),2.61-2.71(m,1H),2.05(m,1H),1.60-1.68(m,1H).

[0245] Step 4: Preparation of 1-[(5-chloropyrimidin-2-yl)methyl]-2-(tetrahydrofuran-3-ylmethyl)imidazole-4-carbonitrile (1.073)

[0246]

[0247] To a solution of 2-(tetrahydrofuran-3-ylmethyl)-1H-imidazole-4-carbonitrile I21 (100 mg, 0.56 mmol) in acetonitrile (1.2 mL) was added potassium carbonate (0.24 g, 1.69 mmol), potassium iodide (0.018 g, 0.11 mmol) followed by 5-chloro-2-(chloromethyl)pyrimidine (0.1 g, 0.62 mmol). The reaction mass was heated at 80 °C for 5 h. The reactant was cooled to room temperature, diluted with 100 ml of ice cold water, extracted in ethyl acetate (3 x 25 ml). The organic layer was washed with brine solution (50 mL), dried over anhydrous sodium sulfate, filtered and concentrated to get the crude material. The crude product was purified by silica gel column chromatography using 70% ethyl acetate in cyclohexane. After concentration, 1.073 (102 mg, 58.9%) of 1-[(5-chloropyrimidin-2-yl)methyl]-2-(tetrahydrofuran-3-ylmethyl)imidazole-4-carbonitrile was obtained as a white solid. 1 H NMR(400MHz, CDCl3)δ=8.67-8.70(m,2H),7.54(s,1H),5.28(s,2H),3.85-3.94(m, 2H),3.76(m,1H),3.47(m,1H),2.73-2.85(m,3H),2.15(m,1H),1.60-1.65(m,1H).

[0248] Example 10: Preparation of 1-[2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazol-4-yl]-N-methoxy-formanimine (1.076)

[0249]

[0250] Step 1: Preparation of 2-butyl-N,N-dimethyl-imidazole-1-sulfonamide (I22)

[0251]

[0252] To a stirred solution of 2-butyl-1H-imidazole (800 mg, 6.44 mmol) in dimethylformamide (20 mL) was added sodium hydride (60% in mineral oil) (0.77 g, 19.327 mmol) at 0°C, and the reaction mixture was stirred for 30 min. Dimethylsulfamoyl chloride (1.12 g, 7.73 mmol) was added dropwise to this solution, and stirring was continued for 2 h at room temperature. The reaction mixture was then carefully quenched by adding saturated NH4Cl solution (about 50 mL). It was extracted with ethyl acetate (3×50 mL). The organic layer was then washed thoroughly with water (50 mL), brine (50 mL) and dried over sodium sulfate, filtered and concentrated to give the crude compound. It was then purified by silica gel column chromatography using 30%-50% ethyl acetate in cyclohexane to give 2-butyl-N,N-dimethyl-imidazole-1-sulfonamide 122 (0.8 g, 53%) as a clear gummy oil. 1 H NMR (400MHz, CDCl3)=7.21(d,1H),6.95(d,1H),2.90-2.95(m,2H),2.89(s,6H),1.71-1.89(m,2H),1.38-1.48(m,2H),0.95(t,3H).

[0253] Step 2: Preparation of 2-butyl-4-formyl-N,N-dimethyl-imidazole-1-sulfonamide (I23)

[0254]

[0255] At -78 ° C, n-butyl lithium (3.1 mL, 7.8 mmol, 2.5 mol / L) was added dropwise to a stirred solution of 2-butyl-N, N-dimethyl-imidazole-1-sulfonamide I22 (1.5 g, 6.5 mmol) in tetrahydrofuran (30 mL) over 30 min. N, N-dimethylformamide (2.5 mL) was added to the reaction mixture at -78 ° C, and the reaction mixture was then stirred at -50 ° C under nitrogen for 30 min. The reaction mixture was quenched by carefully adding about 10 mL of 1N hydrogen chloride, and the reaction mixture was stirred at room temperature for 2 h. The pH of the reaction mixture was then adjusted to 7-8 by adding an aqueous NaHCO solution, and then extracted with ethyl acetate (3×50 mL). The organic layer was washed thoroughly with brine (50 mL), dried over sodium sulfate, filtered and concentrated to provide a crude compound. The crude product was purified by silica gel column chromatography using 30%-50% ethyl acetate in cyclohexane to give 2-butyl-4-formyl-N,N-dimethyl-imidazole-1-sulfonamide I23 (1.2 g, 71%) as a light yellow gum. 1HNMR (400MHz, CDCl3) δ = 10.04 (s, 1H), 7.78 (s, 1H), 3.00-3.05 (m, 2H), 2.94 (s, 6H), 1.79-1.88 (m, 2H), 1.40-1.50 (m, 2H), 0.97 (t, 3H).

[0256] Step 3: Preparation of 2-butyl-1H-imidazole-4-carbonitrile (I24)

[0257]

[0258] To a stirred solution of 2-butyl-4-formyl-N,N-dimethyl-imidazole-1-sulfonamide I23 (900 mg, 3.47 mmol) in methanol (0.5 mL) was added hydrochloric acid (2 mL, 36%). The mixture was stirred at 80 ° C for 1 h. After this time, the reaction mixture was cooled to room temperature and neutralized by adding saturated sodium bicarbonate solution (about 20 mL). Then, it was extracted with ethyl acetate (3×50 mL). Then, the organic layer was washed thoroughly with water (50 mL), brine (50 mL), dried over sodium sulfate, filtered and concentrated to obtain 2-butyl-1H-imidazole-4-carboxaldehyde I24 (0.46 g, 78%) as a clear gum. 1 H NMR (400MHz, CDCl3) δ = 9.66 (s, 1H), 7.75 (s, 1H), 2.81-2.85 (m, 2H), 1.69-1.83 (m, 2H), 1.31-1.46 (m, 2H), 0.89-0.97 (m, 3H).

[0259] Step 4: Preparation of 2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazole-4-carbaldehyde (I25)

[0260]

[0261] Potassium carbonate (1.25 g, 9.06 mmol) was added to a solution of 2-butyl-1H-imidazole-4-carboxaldehyde I24 (0.46 g, 3.02 mmol) in sulfolane (6.0 mL), followed by 5-chloro-2-(chloromethyl)pyrimidine (0.60 g, 3.3 mmol). The reaction mass was heated at 60 ° C for 16 h. After this time, the reaction mixture was cooled to room temperature, diluted with water (50 mL), and extracted with ethyl acetate (3×30 mL). The organic layer was washed with brine (50 mL), dried over sodium sulfate, filtered and concentrated to give a crude product. The crude product was then purified by silica gel column chromatography using 30% ethyl acetate in cyclohexane. After concentration, 2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazole-4-carboxaldehyde I25 (0.28 g, 28%) was obtained as a light yellow solid. 1 H NMR (400MHz, CDCl3) δ = 9.85 (s, 1H), 8.69 (s, 2H), 7.70 (s, 1H), 5.31 (s, 2H), 2.68-2.75 (m, 2H), 1.70-1.83 (m, 2H), 1.34-1.45 (m, 2H), 0.93 (t, 3H).

[0262] Step 5: Preparation of 1-[2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazol-4-yl]-N-methoxy-formanimine (1.076)

[0263]

[0264] To a stirred solution of 2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazole-4-carboxaldehyde I25 (75 mg, 0.26 mmol) in ethanol (2 mL) was added O-methylhydroxylamine hydrochloride (76 mg, 0.81 mmol), followed by sodium acetate (0.64 g, 0.80 mmol), and the reaction mixture was heated at 50 ° C for 16 h. After this time, the reaction mixture was concentrated. Then, the residue was diluted with ethyl acetate (20 mL) and washed thoroughly with water (3×15 mL), brine (15 mL), dried over sodium sulfate, filtered and concentrated to obtain the desired compound. After concentration, 1-[2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazole-4-yl]-N-methoxy-methylimine 1.076 (83 mg, 95%) was obtained as a gummy substance as an E / Z mixture (3.3: 1).

[0265] Main isomers: 1H NMR (400MHz, CDCl3) δ = 8.68 (s, 2H), 7.77 (s, 1H), 7.54 (s, 1H), 5.29 (s, 2H), 4.02 (s ,3H),2.70-2.74(m,2H),1.69-1.73(m,2H),1.35-1.41(m,2H),0.89-0.93(m,3H).

[0266] Minor isomers: 1 H NMR (400MHz, CDCl3) δ = 8.67 (s, 2H), 8.03 (s, 1H), 7.22 (s, 1H), 5.65 (s, 2H), 3.93 (s ,3H),2.70-2.74(m,2H),1.69-1.73(m,2H),1.35-1.41(m,2H),0.89-0.93(m,3H).

[0267] Example 11: Preparation of 2-[[2-butyl-4-(trifluoromethyl)imidazol-1-yl]methyl]-5-fluoro-pyrimidine (1.077)

[0268]

[0269] Step 1: Preparation of diethyl 2-(5-fluoropyrimidin-2-yl)malonate (I26)

[0270]

[0271] To a solution of 2-chloro-5-fluoro-pyrimidine (2g, 15.09mmol) in 1,4-dioxane (40mL), cesium carbonate (14.26g, 43.76mmol), diethyl malonate (4.537mL, 29.88mmol) are added, and then degassed by bubbling nitrogen for 15min. Cuprous oxide (cupriooxycopper) (0.432g, 2.86mmol), picolinic acid (0.731g, 5.88mmol) are added thereto, and heated at 130°C for 10h in a closed container. After this time, the reaction mixture is cooled to room temperature and distributed between ethyl acetate (70ml) and water (20ml). The water layer is re-extracted with ethyl acetate (60ml). The combined organic layer is dried over sodium sulfate, filtered and concentrated to obtain crude material. The crude material is purified by using 0-50% ethyl acetate in cyclohexane using column chromatography. After concentration, diethyl 2-(5-fluoropyrimidin-2-yl)malonate 126 (2.2 g, 40%) was obtained as a yellow oil along with the decarboxylated product. 1H NMR (400MHz, CDCl3): δ = 8.62 (s, 2H), 5.12 (s, 1H), 4.17-4.25 (m, 4H), 1.25-1.28 (m, 6H).

[0272] Step 2: Preparation of ethyl 2-(5-fluoropyrimidin-2-yl)acetate (I27)

[0273]

[0274] A solution of 2-(5-fluoropyrimidine-2-yl) diethyl malonate I26 (500mg, 1.95mmol) in dimethyl sulfoxide (5mL) and sodium chloride (0.1403g, 2.40mmol) and water (0.125mL) were heated to 150 ° C for 7h. After this time, the reaction mass was quenched by adding water (100mL) and extracted with ethyl acetate (3×200mL). The combined organic layer was dried over sodium sulfate, filtered and concentrated to obtain a crude product. The crude reaction mass was purified by column chromatography using 30% ethyl acetate in cyclohexane to obtain 2-(5-fluoropyrimidine-2-yl) ethyl acetate I27 (250mg, 69%) as a yellow jelly. 1 HNMR (400MHz, CDCl3) δ = 8.58 (s, 2H), 4.25 (q, 2H), 4.04 (s, 2H), 1.27 (t, 3H).

[0275] Step 3: Preparation of ethyl 2-bromo-2-(5-fluoropyrimidin-2-yl)acetate (I28)

[0276]

[0277] Benzoyl peroxide (0.08 g, 0.32 mmol) was added to a stirred solution of ethyl 2- (5-fluoropyrimidine -2- bases) ethyl acetate I27 (0.6 g, 3.25 mmol) in carbon tetrachloride (12 mL), followed by N- bromosuccinimide (0.66 g, 3.64 mmol) and heated to reflux for 6 h. After this time, the reaction mixture was cooled to room temperature and quenched by adding water (100 mL). It was extracted with ethyl acetate (3 × 100 mL), dried over sodium sulfate, filtered and concentrated to give a crude product. The crude reaction mass was purified by silica gel column chromatography using 30% ethyl acetate in cyclohexane to obtain ethyl 2- bromo-2- (5-fluoropyrimidine -2- bases) ethyl acetate I28 (300 mg, 35%) as a yellow oil. 1 H NMR (400MHz, CDCl3) δ = 8.63 (s, 2H), 5.69 (s, 1H), 4.30 (q, 2H), 1.31 (t, 3H).

[0278] Step 4: Preparation of ethyl 2-[2-butyl-4-(trifluoromethyl)imidazol-1-yl]-2-(5-fluoropyrimidin-2-yl)acetate (I29)

[0279]

[0280] To a solution of 2-bromo-2-(5-fluoropyrimidin-2-yl)acetate I28 (300 mg, 1.14 mmol) in sulfolane (6 mL) was added potassium carbonate (0.78 g, 5.70 mmol), followed by 2-butyl-4-(trifluoromethyl)-1H-imidazole I12 (0.21 g, 1.1404 mmol). Then, the mixture was heated to 120 ° C for 1 h. After this time, the reaction mass was quenched by adding saturated ammonium chloride solution (30 mL) and extracted with ethyl acetate (3 × 50 mL), dried over sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography using 20% ​​ethyl acetate in cyclohexane to obtain 2-[2-butyl-4-(trifluoromethyl)imidazol-1-yl]-2-(5-fluoropyrimidin-2-yl)ethyl acetate I29 (90 mg, 21%) as a colorless oil. 1 HNMR (400MHz, CDCl3) δ = 8.64 (s, 2H), 7.52-7.59 (m, 1H), 6.19 (s, 1H), 4.31 (m, 2H), 2.80(t,2H),1.70-1.79(m,2H),1.37-1.45(m,2H),1.27(t,3H),0.90-0.97(m,3H).

[0281] Step 5: Preparation of 2-[[2-butyl-4-(trifluoromethyl)imidazol-1-yl]methyl]-5-fluoro-pyrimidine (1.077)

[0282]

[0283] 2M sodium hydroxide (1.336mL) was added to a solution of 2-[2-butyl-4-(trifluoromethyl)imidazol-1-yl]-2-(5-fluoropyrimidine-2-yl)ethyl acetate 129 (50mg, 0.13mmol) in methanol (1mL), and the reaction mixture was stirred at room temperature overnight. The reaction mass was quenched by adding 2N hydrochloric acid (10mL) and diluted with water (30mL). The aqueous layer was extracted with ethyl acetate (3×50mL) and dried over sodium sulfate, filtered and concentrated. The residue was purified by silica gel column chromatography using 30% ethyl acetate in cyclohexane to obtain 2-[[2-butyl-4-(trifluoromethyl)imidazol-1-yl]methyl]-5-fluoro-pyrimidine 1.077 (12mg, 29%) as a yellow oil.1 H NMR (400MHz, CDCl3) δ = 8.59 (s, 2H), 7.31 (d, 1H), 5.28 (s, 2H), 2.69-2.75 (m, 2H), 1.71-1.78 (m, 2H), 1.38 (br d, 2H), 0.91 (t, 3H).

[0284] Example 12: Preparation of 2-[[2-butyl-4-(difluoromethyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine (1.053)

[0285]

[0286] To a stirred solution of 2-butyl-1-[(5-chloropyrimidin-2-yl)methyl]imidazole-4-carboxaldehyde I25 (100 mg, 0.3588 mmol) in dichloromethane (5 mL) was added diethylaminosulfur trifluoride (0.46 g, 2.870 mmol) at 0 ° C. and allowed to stir overnight at room temperature. After this time, the reaction mixture was carefully quenched by adding saturated sodium bicarbonate solution (about 20 mL). It was then extracted with dichloromethane (3×30 mL). The combined organic layers were thoroughly washed with water (30 mL), brine (30 mL) and dried over sodium sulfate. It was concentrated to give a crude material. It was then purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane to give 2-[[2-butyl-4-(difluoromethyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine 1.053 (55 mg, 51%) as a gummy oil. 1 H NMR (400MHz, CDCl3) δ = 8.68 (s, 2H), 7.21 (t, 1H), 6.67 (t, 1H), 5.26 (s, 2H), 2.68-2.74 (m, 2H), 1.65-1.79 (m, 2H), 1.34-1.44 (m, 2H), 0.92 (t, 3H).

[0287] Example 13: Preparation of 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]-N-methoxy-propane-1-imine (1.051)

[0288]

[0289] Step 1: Preparation of 2-but-3-enyl-4-(trifluoromethyl)-1H-imidazole (I30)

[0290]

[0291] Sodium acetate (7.4g, 89mmol), water (15mL) and 1,1-dibromo-3,3,3-trifluoroacetone (12g, 43mmol) were added to a 100mL flask equipped with a reflux condenser and a thermometer to obtain a turbid solution / suspension. The reaction mixture was heated to 100°C for 30 minutes. After this time, the reaction mixture was cooled to room temperature. 4-pentenal (3.0g, 36mmol) in methanol (60mL) was slowly added to this solution, followed by ammonia (15mL, 130mmol), and stirred at room temperature for 16h. The reactant was extracted with ethyl acetate (3×200mL). The combined organic layers were washed with saturated bicarbonate solution (100ml), and then washed with brine (100mL), dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a crude material. The crude was washed with tert-butyl dimethyl ether and dried to give 2-but-3-enyl-4-(trifluoromethyl)-1H-imidazole I30 (6.4 g, 94%) as a yellow solid. 1 HNMR (400MHz, DMSO-d6) δ = 12.37 (br s, 1H) 7.61 (s, 1H), 5.83 (m, 1H), 4.95-5.08 (m, 2H), 2.69-2.75 (m, 2H), 2.34-2.48 (m, 2H).

[0292] Step 2: Preparation of 2-[[2-but-3-enyl-4-(trifluoromethyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine (I31)

[0293]

[0294] To a solution of 2-but-3-enyl-4-(trifluoromethyl)-1H-imidazole I30 (6.4 g, 34 mmol) in sulfolane (56 mL) was added potassium carbonate (14 g, 100 mmol) followed by 5-chloro-2-(chloromethyl)pyrimidine (6.7 g, 37 mmol). The reaction mixture was heated at 100 °C for 6 h. After this time, the reaction mixture was cooled to room temperature, diluted with 100 ml of ice-cold water, and extracted with ethyl acetate (4 x 500 mL). The combined organic layers were washed with brine solution (200 mL), dried over anhydrous sodium sulfate, filtered and concentrated to give a crude material. It was purified by silica gel column chromatography using 30% ethyl acetate in cyclohexane to give 2-[[2-but-3-enyl-4-(trifluoromethyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine I31 (7.3 g, 68%) as a dark yellow oil. 1H NMR (400MHz, CDCl3): δ=8.68(s,2H),7.31(d,1H),5.84(m,1H),5.26(s,2H),4.96-5.08(m,2H),2.77-2.83(m,2H),2.47-2.55(m,2H)

[0295] Step 3: Preparation of 4-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]butane-1,2-diol (I32)

[0296]

[0297] In a 100ml flask equipped with a nitrogen inlet, 2-[[2-but-3-enyl-4-(trifluoromethyl)imidazol-1-yl]methyl]-5-chloro-pyrimidine I31 (6g, 18.95mmol) was dissolved in tetrahydrofuran (120mL) and water (60mL). At room temperature, potassium osmate (VI) dihydrate (0.1388g, 0.3789mmol) was added thereto, followed by 4-methyl-4-oxidation-morpholinium-4-ium (4.53g, 37.89mmol). After addition, the reaction mixture was stirred at room temperature overnight. The reaction mixture was quenched with 10% sodium thiosulfate solution (check the complete quenching of osmium tetroxide with starch paper), and extracted with 10% methanol (6×100ml) in ethyl acetate. The organic layer was washed with brine solution (100 ml), dried over sodium sulfate, filtered and concentrated to give 4-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]butane-1,2-diol I32 (6.6 g, 99%) as a light brown gum. 1 H NMR (400MHz, CDCl3) δ = 8.68 (s, 2H), 7.28-7.31 (m, 1H), 5.29 (s, 2H), 3.64-3.76 (m, 1H), 3.58 (dd, 1H), 3.46 (dd, 1H), 2.89 (t, 2H), 1.82-2.00 (m, 2H).

[0298] Step 4: Preparation of 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propanal (I33)

[0299]

[0300] In a 50 ml flask equipped with a nitrogen inlet, 4-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]butane-1,2-diol I32 (6.3 g, 18 mmol) was dissolved in tetrahydrofuran (130 mL) and water (63 mL). To this solution was added sodium periodate (7.7 g, 36 mmol) at room temperature, and then the reaction mass was stirred at room temperature for 2 h. A 10% sodium thiosulfate solution was added to the reaction mixture and stirred for 15 minutes. Ethyl acetate (50 mL) and water (50 mL) were added thereto. The aqueous layer was re-extracted with ethyl acetate (2×100 ml), and the obtained organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography using 20% ​​ethyl acetate in cyclohexane to give 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propanal 133 (4.8 g, 84%). 1 H NMR (400MHz, CDCl3) δ = 9.83 (s, 1H), 8.67 (s, 2H), 7.26-7.30 (m, 1H), 5.34 (s, 2H), 3.09-3.14 (m, 2H), 2.96-3.01 (m, 2H).

[0301] Step 5: Preparation of 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propan-1-ol (I34)

[0302]

[0303] To a 2-necked flask equipped with a nitrogen inlet was added 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propanal I33 (0.5 g, 1.56 mmol) in tetrahydrofuran (10 mL). It was cooled to <5 °C and sodium borohydride (0.030 g, 0.78 mmol) was added in portions. The reaction mass was stirred at room temperature for 16 h. After this time, the reaction mixture was quenched with ammonium chloride (30 mL) and stirred for 15 min. It was extracted with ethyl acetate (3×100 ml). The combined organic layers were washed with brine solution (50 mL), dried over sodium sulfate, filtered and concentrated. The residue was purified by silica gel column chromatography using 40% ethyl acetate in cyclohexane. After concentration, 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propan-1-ol I34 (0.31 g, 60%) was obtained as a gummy material. 1H NMR (400MHz, CDCl3) δ=8.68(s,2H),7.29(s,1H),5.29(s,2H),3.65-3.72(m,2H),2.86-2.91(m,2H),1.99-2.03(m,2H).

[0304] Step 6: Preparation of 5-chloro-2-[[2-(3-chloropropyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine (1.051)

[0305]

[0306] To a stirred solution of 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propan-1-ol I34 (0.135 g, 0.42 mmol) in acetonitrile (2.7 mL) at 0°C was added thionyl chloride (0.100 g, 0.84 mmol). The reaction mixture was allowed to warm to room temperature and stirred for 16 h. After this time, the reaction mixture was slowly poured into an ice-cold sodium bicarbonate solution (30 mL). The reaction mass was extracted with ethyl acetate (3×100 ml). The combined organic layers were washed with brine solution (50 mL), dried over sodium sulfate, filtered and concentrated to give the crude material. The crude product was purified by column chromatography using 20% ​​ethyl acetate in cyclohexane to give 5-chloro-2-[[2-(3-chloropropyl)-4-(trifluoromethyl)imidazol-1-yl]methyl]pyrimidine 1.051 (0.12 g, 84%). 1 H NMR (400MHz, CDCl3) δ = 8.68 (s, 2H), 7.30 (d, 1H), 5.30 (s, 2H), 3.63 (t, 2H), 2.90 (t, 2H), 2.25-2.33 (m, 2H).

[0307] Example 14: Preparation of 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)-imidazol-2-yl]-N-methoxy-propane-1-imine (1.007)

[0308]

[0309] In a clean, dry 50 mL flask equipped with a nitrogen blanket, 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propanal I33 (0.2 g, 0.62 mmol) was dissolved in acetonitrile (4 mL). To this solution was added N-methoxyammonium chloride (0.104 g, 1.25 mmol) followed by N,N-diethylethylamine (0.16 g, 1.56 mmol). The reaction mixture was stirred at room temperature for 16 h. The reaction mixture was quenched with water (15 mL) and extracted with ethyl acetate (3×80 ml). The organic layer was washed with brine solution, dried over sodium sulfate, filtered and concentrated to give the crude material. The crude product was purified by silica gel column chromatography using ethyl acetate and cyclohexane as eluents. The desired product was collected by eluting with 30% ethyl acetate in cyclohexane. After concentration, 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)-imidazol-2-yl]-N-methoxy-propan-1-imine 1.007 (0.175 g, 80%) was obtained as an off-white solid as an E / Z mixture (2:3).

[0310] Main isomers: 1 H NMR (400MHz, CDCl3) δppm 8.69(s,2H),7.45(t,1H),7.31(dd,2H),5.31(s,2H),3.80(s,3H),2.88-2.96(m,s H),2.70-2.79(m,s H).

[0311] Minor isomers: 1 H NMR (400MHz, CDCl3) δ = 8.69 (s, 2H), 7.32 (dd, 2H), 6.77 (t, 1H), 5.28 (s, 2H), 3.85 (s, 3H), 2.88-2.96 (m, s H), 2.70-2.79 (m, s H).

[0312] Example 15: Preparation of 5-chloro-2-[[2-(3,3-difluoropropyl)-4-(trifluoromethyl)-imidazol-1-yl]methyl]-pyrimidine (1.010)

[0313]

[0314] To a solution of 3-[1-[(5-chloropyrimidin-2-yl)methyl]-4-(trifluoromethyl)imidazol-2-yl]propanal I33 (0.2 g, 0.62 mmol) in toluene (2.09 mL) was added dropwise N-ethyl-N-(trifluoro-λ4-sulfanyl)ethylamine (0.26 g, 1.56 mmol) at 0°C. Allowed to reach room temperature and stirred overnight. The reaction was cooled to 0°C and quenched with saturated bicarbonate solution (30 mL). The layers were separated. The organic layer was extracted with ethyl acetate (3×50 ml), washed with brine solution (30 mL), water (30 mL), dried over sodium sulfate, filtered and concentrated to give the crude material. The crude product was purified by silica gel column chromatography using ethyl acetate and cyclohexane. The desired product was eluted with 20% ethyl acetate in cyclohexane. After concentration, 5-chloro-2-[[2-(3,3-difluoropropyl)-4-(trifluoromethyl)-imidazol-1-yl]methyl]-pyrimidine 1.010 (0.066 g, 31%) was isolated as an off-white solid. 1 H NMR (400MHz, CDCl3) δ = 8.68 (s, 2H), 7.31 (s, 1H), 5.99 (tt, 1H), 5.26 (s, 2H), 2.88 (t, 2H), 2.32-2.47 (m, 2H).

[0315] Table 1. Compounds of the present invention

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333] Biological Examples

[0334] 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) and 8 days of cultivation (post-emergence) under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 hours of 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%).

[0335] Table B1 Post-emergence test

[0336]

[0337]

[0338]

[0339] Table B2 Pre-emergence test

[0340]

[0341]

[0342]

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 C2-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 = 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: C2-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 C2-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. Use of the compound of formula (I) according to claim 1 as a herbicide.

16. A compound having the formula Int-1: Where R 2 and R 3 As defined in claim 1.

17. A compound having formula (IIIa-1): Where R 1a is a halogen and R 14 It is a C1-C4 alkyl group.

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