CN121511237A - herbicides pyrazole compounds - Google Patents

Abstract

The present invention relates to a compound having formula (I) or an agronomically acceptable salt of said compound, wherein Q, U, R ^{2 2} and R ^{3 3} 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, especially in crops of useful plants.

Description

Herbicidal pyrazole compounds

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

Herbicidal pyrazole compounds are known, for example, from WO 2022/013493, WO 2022/101270 and WO 2023/099354. The compounds of the present invention are directed to herbicidal pyrazole compounds comprising a 5 membered heteroaryl (U). Thus, according to the present invention there is provided a compound having formula (I):

Or an agronomically acceptable salt thereof,

Wherein the method comprises the steps of

Q is phenyl or C-linked 6-membered heteroaryl, wherein the phenyl or 6-membered heteroaryl is optionally substituted with one or more independent R ¹;

U is a 5 membered heteroaryl optionally substituted with one or more independent R ⁷;

R ¹ is selected from the group consisting of halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ haloalkoxy, C ₃-C₆ cycloalkyl, C ₁-C₄ alkoxyC ₁-C₃ alkyl-, C ₁-C₄ alkoxyC ₁-C₃ alkoxy-, C ₁-C₄ alkoxyC ₁-C₃ alkoxyC ₁-C₃ alkyl-, -CN, NO ₂、C₂-C₄ alkenyl, C ₂-C₄ alkynyl, -S (O) _pC₁-C₄ alkyl, -S (O) _pC₁-C₄ haloalkyl, -C (O) OC ₁-C₄ alkyl, and-C (O) NR ⁴R⁵;

R ² is selected from the group consisting of-CN, NO ₂、C₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, -C (O) C ₁-C₄ alkyl, -C (O) OC ₁-C₄ alkyl, -S (O) _pC₁-C₄ alkyl, -C (R ⁶)=NOR⁸ and C ₃-C₆ cycloalkyl;

R ³ is selected from the group consisting of hydrogen, halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, -CN, NO ₂、C₂-C₄ alkenyl, C ₂-C₄ alkynyl, -S (O) _pC₁-C₄ alkyl, -S (O) _pC₁-C₄ haloalkyl, -C (O) OC ₁-C₄ alkyl, and-C (O) NR ⁴R⁵;

r ⁴ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ⁵ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ⁶ is hydrogen or C ₁-C₂ alkyl;

R ⁷ is selected from the group consisting of halogen, C ₁-C₄ alkyl, C ₃-C₄ cycloalkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, C ₁-C₄ alkoxy C ₁-C₃ alkyl-, C ₁-C₄ alkoxy C ₁-C₃ alkoxy-, -CN, C ₂-C₄ alkenyl, C ₂-C₄ alkynyl, -S (O) _pC₁-C₄ alkyl, -S (O) _pC₁-C₄ haloalkyl, -C (O) OC ₁-C₄ alkyl, -C (O) NR ⁹R¹⁰、-NR¹¹COR¹², and-S (O) _pNR¹³R¹⁴;

r ⁸ is hydrogen or C ₁-C₂ alkyl;

r ⁹ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹⁰ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹¹ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹² is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹³ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

r ¹⁴ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl, and

P=0, 1 or 2.

C ₁-C₄ alkyl-and C ₁-C₆ alkyl-include, for example, methyl (Me, CH ₃), ethyl (Et, C ₂H₅), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), isobutyl (i-Bu), sec-butyl and tert-butyl (t-Bu). C ₁-C₂ alkyl is methyl (Me, CH ₃) or ethyl (Et, C ₂H₅).

C ₂-C₄ alkenyl-includes, for example, -ch=ch ₂ (vinyl) and-CH ₂-CH=CH₂ (allyl).

C ₂-C₄ alkynyl-refers to a straight or branched hydrocarbon chain group consisting of only 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 single bonds. Examples of C _2-C₄ alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

Halogen (or halo) includes, for example, fluorine, chlorine, bromine or iodine. The above correspondingly applies to halogens in the context of other definitions, such as haloalkyl.

C ₁-C₄ haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-trifluoroethyl 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1-difluoro-2, 2-trichloroethyl, 2, 3-tetrafluoropropyl and 2, 2-trichloroethyl and heptafluoro-n-propyl. C ₁-C₂ haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl or 1, 1-difluoro-2, 2-trichloroethyl.

C ₁-C₆ alkoxy includes methoxy and ethoxy.

C ₁-C₄ haloalkoxy-including, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2-trifluoroethoxy 1, 2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-difluoroethoxy or2, 2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.

C ₁-C₄ AlkoxyC ₁-C₃ alkyl-includes, for example, methoxymethyl-.

C ₁-C₄ Alkoxy C ₁-C₃ alkoxy-includes, for example, methoxyethoxy-.

C ₁-C₄ Alkoxy C ₁-C₃ Alkoxy C ₁-C₃ alkyl-including, for example, methoxyethoxymethyl-.

C ₃-C₆ cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.

C ₁-C₄ alkyl-S- (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

C ₁-C₄ alkyl-S (O) - (alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

C ₁-C₄ alkyl-S (O) ₂ - (alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

In a preferred embodiment of the present invention, there is provided a compound having formula (I), wherein U is selected from the group consisting of:

Wherein the method comprises the steps of

R ⁷ is hydrogen or as defined in claim 1;

R ^7a is selected from the group consisting of hydrogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl and C ₃-C₄ cycloalkyl, and

N=0, 1 or 2.

In a more preferred embodiment of the invention, U is selected from the group consisting of U20, U22, U23, U25, U26, U31 and U38.

In a more preferred embodiment of the invention, U is selected from the group consisting of U20, U22, U23, U25 and U31. In an even more preferred embodiment, U is U25 or U31.

In another embodiment of the invention, Q is preferably selected from the group consisting of Q1 to Q-11:

Wherein R ¹ is as defined above (preferably C ₁-C₂ haloalkyl or halogen), and

M is 0,1 or 2 (preferably 1 or 2, more preferably 2).

In a more preferred embodiment, Q is Q-1 or Q-3.

In a further preferred embodiment of the present invention, compounds of formula (I) selected from the group consisting of formulae (Iaa), (Iab), (Iac), iad), (Iae) and (Iaf) are provided:

In a more preferred embodiment of the invention, compounds of formula (Iaa), (Iab), (Iac), (Iad), (Iae) or (Iaf) are provided wherein m is 1 or 2 (preferably 2) and R ¹ is independently halogen or C ₁-C₂ haloalkyl (preferably halogen, more preferably fluorine and/or chlorine).

In another embodiment of the invention, compounds of formula (I), (Iaa), (Iab), (Iac), (Iad), (Iae) or (Iaf) are provided wherein R ² is C ₁-C₄ haloalkyl (preferably CF ₃、CF₂ H or CF ₂ Cl).

In another embodiment of the invention, compounds of formula (I), (Iaa), (Iab), (Iac), (Iad), (Iae) or (Iaf) are provided, wherein R ³ is hydrogen or halogen (preferably hydrogen).

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

The invention also provides agronomically acceptable salts of compounds having formula (I). Preferred are salts of the compounds of formula (I) with amines, including primary, secondary and tertiary amines (e.g. ammonia, dimethylamine and triethylamine), alkali and alkaline earth metal bases, transition metal bases or quaternary ammonium bases.

The compounds of formula (I) according to the invention may themselves be used as herbicides, but they are generally formulated into herbicidal compositions using formulation adjuvants such as carriers, solvents and Surfactants (SAA). Accordingly, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any of the preceding claims and an agriculturally acceptable formulation adjuvant. The compositions may be in the form of concentrates which are diluted prior to use, although ready-to-use compositions may also be prepared. The final dilution is usually done with water, but may be done using, for example, liquid fertilizers, micronutrients, biological organisms, oils or solvents instead of or in addition to water.

The herbicidal compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of the formula I and from 1 to 99.9% by weight of a formulation auxiliary, which preferably comprises from 0 to 25% by weight of a surface-active substance.

The composition may 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 Dispersions (OD), oil miscible flowable (OF), oil miscible liquids (OL), soluble concentrates (SL), ultra low volume Suspensions (SU), ultra low volume liquids (UL), masterbatches (TK), dispersible Concentrates (DC), soluble Powders (SP), wettable Powders (WP) and Soluble Granules (SG). In any event, the type of formulation selected will depend on the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

Soluble Powders (SP) may 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 sulphate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersing agents or mixtures of such agents to improve water dispersibility/solubility. The mixture was then ground to a fine powder. Similar compositions may also be granulated to form water Soluble Granules (SG).

Wettable Powders (WP) may be prepared by mixing a compound having formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably one or more dispersing agents and optionally one or more suspending agents to facilitate dispersion in a liquid. The mixture was then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed by granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous particulate material such as pumice, attapulgite clay, fuller's earth, diatomaceous earth (kieselguhr), diatomaceous earth (diatomaceous earth) or corncob powder, or by adsorbing a compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicate, mineral carbonate, sulphate or phosphate and drying if necessary. 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 (e.g., emulsifiers, wetting agents, or dispersants) may also be included in the granule.

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

Emulsifiable Concentrates (EC) or oil-in-water Emulsions (EW) may be prepared by dissolving a compound having formula (I) in an organic solvent, optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents. Suitable organic solvents for use in the EC 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 C ₈-C₁₀ fatty acid dimethylamides), and chlorinated hydrocarbons. The EC product may spontaneously emulsify upon addition to water, thereby producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

The preparation of EW involves obtaining a compound of formula (I) as a liquid (if it is not a liquid at room temperature, it may be melted at a suitable temperature typically below 70 ℃) 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 EW include vegetable oils, chlorinated hydrocarbons (e.g., chlorobenzene), aromatic solvents (e.g., alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents having low solubility in water.

Microemulsions (ME) may 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 ME include those described above for use in EC or in EW. The ME may be an oil-in-water system or a water-in-oil system (which system is present can be determined by conductivity measurements) and may be suitable for mixing a water-soluble pesticide and an oil-soluble pesticide in the same formulation. ME is suitable for dilution into water, either to remain as a microemulsion or to form a conventional oil-in-water emulsion.

Suspension Concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). The SC may be prepared by ball or bead milling a solid compound of formula (I), optionally together 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 suspending agents may be included to reduce the rate of particle settling. Alternatively, the compound of formula (I) may be dry milled and added to water containing the reagents described above to produce the desired end product.

The aerosol formulation comprises a compound having 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 manual spray pump.

The Capsule Suspension (CS) can be prepared in a similar manner to the preparation of the EW formulation, but with an additional polymerization stage, so as to obtain an aqueous dispersion of oil droplets, each of which is surrounded by a polymeric shell and contains a compound having formula (I) and optionally a carrier or diluent for the oil droplets. The polymer shell may be produced by interfacial polycondensation reactions or by coacervation procedures. These compositions can provide controlled release of compounds having formula (I) and they can be used for seed treatment. The compounds of formula (I) may also be formulated in biodegradable polymer matrices to provide slow, controlled release of the compounds.

The composition may contain one or more additives to improve the biological properties of the composition, for example by improving the wettability, retention or distribution on the surface, the resistance to rain on the treated surface, or the absorption or mobility of the compound of formula (I). Such additives include Surfactants (SAA), oil-based spray additives such as certain mineral or natural vegetable oils (e.g., soy and rapeseed oils), modified vegetable oils (e.g., methylated rapeseed oil (MRSO)), and blends of these with other bio-enhancing adjuvants (ingredients that can assist or alter the action of compounds having formula (I)).

Wetting agents, dispersants and emulsifiers may be SAA of cationic, anionic, amphoteric or nonionic type.

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

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 dodecyl benzene sulfonate, calcium dodecyl benzene sulfonate, butylnaphthalene sulfonate and mixtures of sodium di-isopropyl naphthalene sulfonate and sodium tri-isopropyl naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laureth-3-sulfate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), such as the reaction between lauryl alcohol and tetraphosphoric acid; alternatively, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignin sulfonates and phosphate/sulfates of trisstyrylphenols.

Suitable amphoteric types of SAAs include betaines, propionates, and glycinates.

Suitable nonionic SAAs 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 polyethylene glycol esters of fatty acids), amine oxides (such as lauryl dimethyl amine oxide), lecithins and sorbitan and esters thereof, alkylpolyglycosides and tristyrylphenols.

Suitable suspending agents include hydrocolloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

The compounds of the invention may also be used in mixtures with one or more further herbicides and/or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), benomyl, ametryn, amicarbazone, aminopyralid, clomazone, atrazine, fluobutamid-M, quinclomazone (benquitrione), bensulfuron (including bensulfuron-methyl), bentazone, dicyclopyrone, bialaphos, bispyribac-sodium, clomazone (bixlozone), bromoxaden (broclozone), fluxapyrone, bromoxynil, butachlor, flumetsulam, carfentrazone (including carfentrazone-ethyl), Clomazone (including clomazone-methyl), closulfuron (including closulfuron-ethyl), chlormeuron, chlorsulfuron, cyclohepta-methyl, clomazone (clacyfos), clethodim, clodinafop (including clodinafop), clomazone, clopyralid (cyclopyranil), cyclopyridazinyl (cyclopyrimorate), cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including choline salts and 2-ethylhexyl esters thereof), 2,4-DB, betalain, dicamba (including aluminum, aminopropyl, bis-aminopropylmethyl, hypo-methyl, Choline, 2, 4-d-propionic acid, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), sulfentrazone, diflufenican, diflufenzopyr, dimethenamid, pyridazinone (dioxopyritrione), dibromodiquat, diuron, prim (EPYRIFENACIL), ethaboxam, ethofumesate, oxazachlor (including fenoxaprop-ethyl), benoxazachlor (fenoxasulfone), benazolin, fenquidone (fenquinotrione), fentrazamide, flazasulfuron, triazophos, Diflufenican, flurbiproflumilast (florpyrauxifen) (including flurbiproflumilast-benzyl), haloxyfop-butyl (including haloxyfop-butyl), fluorone sulfon (including flurazon-sodium), fluroxypyr (fluchloraminopyr) (including furfuryl fluroxypyr (fluchloramino-tefuryl)), flufenacet, fluben (flufenoximacil), flumetsulam, flubenuron, fomesafen, fluflazasulfuron (including fluflazasulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl (fluroxypyr-meptyl)), haloxyfop-methyl, Fluofenamide, fomesafen, amosulfuron, glufosinate (including L-glufosinate and ammonium salts of both), glyphosate (including di-, iso-and potassium salts thereof), clopyralid (halauxifen) (including flucloxapride-methyl), haloxyfop-methyl (including haloxyfop-methyl), hexazinone, hydantoin (hydantocidin), isooxamide (icafolin) (including isooxamide-methyl), imazethapyr (including R-imazethapyr), imazethapyr, indenofloxacin, indoxacarb (indolauxipyr) (including indoxacarb (indolauxipyr-cyanomethyl)) Iodosulfuron (including iodosulfuron-methyl-sodium), iodofensulfuron (iofensulfuron) (including iodofensulfuron-sodium), ioxynil, triazoxamide (iptriazopyrid), isoproturon, isoxaflutole, oxapenoxsulam (lancotrione), MCPA, MCPB, MCP high dimethyltetrachloropropionic acid (mecoprop-P), methyl disulfuron (including methyl disulfuron-methyl), mesotrione, metamitron, and the like metazachlor, methiazolin (metazolin), metolachlor sulfentrazone, metribuzin, metsulfuron-methyl, and, The compositions include, but are not limited to, dichlormid, nicosulfuron, dactylon, oxadiazon, cyclosulfamuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, bendiuron, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryn, propanil, oxadiazon, propyrisulfuron (propyrisulfuron), pendinafop-propargyl, prosulfuron, pyraclonil, pyriftalid (pyraflufen) (including pyraclonil-ethyl), mequindox (pyraquinate), sulfonylgrass pyrazole, pyridate, pyriftalid (pyriflubenzoxim), Pyrifos (pyrimidafan), pyrsulfuron-ethyl, pyroxsulam, quinclorac, cloquintocet-mexyl (including quizalofop-ethyl and quizalofop-P-tefuryl (quizalofop-P-tefuryl)), pyribenzoxazole (rimisoxafen), rimsulfuron, pyribenzoxim, sethoxydim, simazine, S-metolachlor, sulfentrazone, sulfosulfuron, buturon, terfutrione, cyclosulfamuron, terbuthylazine, terbutazine (tetflupyrolimet), thidiazuron-methyl (thiencarbazone), terbuzin-ethyl, and terbuzin-ethyl, Thifesulfuron, flumetsulam (tiafenacil), pyraclostrobin (tolpyralate), topramezone, triclopyr, fluoroketosulfentrazone (triafamone), dicamba, cinosulfuron, tribenuron-methyl (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifloxysulfuron, trifluralin, trifloxysulfuron, triazosulfuron, 3- (2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4-trifluoromethyl-3, 6-dihydropyrimidine-1 (2H) -yl) phenyl) -5-methyl-4, 5-dihydro isoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3- [4- (trifluoromethyl) -2-pyridinyl ] imidazolidin-2-one, 4-hydroxy-1, 5-dimethyl-3- [4- (trifluoromethyl) -2-pyridinyl ] imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3- [4- (trifluoromethyl) -2-pyridinyl ] 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, (1 RS,5 SR) -3- [ 2-methoxy-4- (prop-1-yn-1-yl) phenyl ] -4-oxobicyclo [3.2.1] oct-2-en-2-ylmethyl carbonate, ethyl-2- [ [3- [ [ 3-chloro-5-fluoro-6- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] -2-pyridinyl ] oxy ] acetate, 2- [2- [ 2-bromo-4-fluoro-5- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] phenoxy ] -2-methoxy-acetic acid methyl ester, 6-chloro-4- (2, 7-dimethyl-1-naphthyl) -5-hydroxy-2-methyl-pyridazin-3-one, 6-amino-5-chloro-2- (4-chloro-2-fluoro-3-methoxy-phenyl) pyrimidine-4-carboxylic acid (2-fluorophenyl) methyl ester, 6-amino-5-chloro-2- (4-chloro-2-fluoro-3-methoxy-phenyl) pyrimidine-4-carboxylic acid, and 3- [ 2-chloro-5- [3, 6-dihydro-3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1 (2H) -pyrimidinyl ] -4-fluorophenyl ] -3a,4,5, 6-tetrahydro-6-methyl-6 aH-cyclopenta [ d ] isoxazole-6 a-carboxylic acid methyl ester.

The mixed compatibility of the 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 committee (British Crop Protection Council), 2012.

The compounds of formula (I) can also be used in combination with other agrochemicals, such as fungicides, nematicides or insecticides, examples of which are given in THE PESTICIDE Manual.

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

These mixtures can be advantageously used in the formulations mentioned above (in which case "active ingredient" refers to the corresponding mixture of a compound of formula (I) with a mixed compatibility).

The compounds or mixtures of the present invention may also be used in combination with one or more herbicide safeners. Examples of such safeners include clomazone, clomazone (cloquintocet) (including cloquintocet-mexyl), cyclopropanesulfonamide, dichlorvos, clomazone (including clomazone ethyl), clomazone, trifloxystrobin, clomazone, bisbenzoxazole acid (including bisbenzoxazole acid-ethyl), mefenpyr (mefenpyr) (including mefenpyr), clomazone (metcamifen), and clomazone.

Particularly preferred are mixtures of compounds of formula (I) with cyclopropanesulfonamide, bisbenzoxazole acid-ethyl, cloquintocet-mexyl and/or clomazone.

Safeners for compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in THE PESTICIDE Manual, 16 th edition (BCPC), 2012. Reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02/34048.

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

The present invention still further provides a method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a composition comprising a compound having formula (I). In addition, the present invention may further provide a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises applying to the locus a weed controlling amount of a composition according to the invention. By 'control' is meant killing, reducing or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention show a greatly improved selectivity compared to known structurally similar compounds. Typically, the plants to be controlled are unwanted plants (weeds). By 'locus' is meant the area in which plants are growing or will grow. The application may be to the locus pre-emergence and/or post-emergence of the crop plants. Some crop plants may inherently tolerate the herbicidal effect of compounds having formula (I). Preferred crop plants include corn, wheat, barley, soybean and rice.

The application rate of the compounds of the formula I can vary within wide limits and depends on the nature of the soil, the application method (pre-or post-emergence; seed dressing; application to seed furrows; no-tillage application, etc.), the crop plant, the weed or weeds to be controlled, the prevailing climatic conditions and other factors governed by the application method, the application time and the target crop. The compounds of formula I according to the invention are generally applied in a ratio of from 10 to 2500 g/ha, in particular from 25 to 1000 g/ha, more in particular from 25 to 250 g/ha.

Application is usually carried out by spraying the composition, typically by tractor mounted sprayers for large areas, but other methods such as dusting (for powders), dripping or dipping may also be used.

Crop plants are understood to also include 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 breeding methods or by genetic engineering. An example of a crop that has been rendered imidazolinone (e.g., imazethapyr) tolerant by conventional breeding methods is Clearfield summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, maize varieties with glyphosate and glufosinate resistance, which are commercially available under the trade names RoundupReady and LibertyLink. The compounds of the invention may also be used in combination with crops that are tolerant to SDPS inhibiting herbicides, such as those taught in WO 2020/236790.

Crop plants are also understood as those which have been rendered resistant to pest insects by genetic engineering methods, such as Bt maize (resistant to european corn borer), bt cotton (resistant to boll weevil) and also Bt potato (resistant to corrador beetle). An example of Bt maize is the NK cube Bt 176 maize hybrid (first just reaching seed company (SYNGENTA SEEDS)). Bt toxins are proteins naturally formed by Bacillus thuringiensis (Bacillus thuringiensis) soil bacteria. 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 expression of one or more toxins are KnockOut (corn), YIELD GARD (corn), nuCOTIN33B (cotton), bollgard (cotton), newLeaf (potato), natureGard and Protexcta. The plant crop or seed material thereof is resistant to both herbicides and insect ingestion (a "stacked" transgenic event). For example, the seed may have the ability to express an insecticidal Cry3 protein while being tolerant to glyphosate.

Crop plants are also understood to include those obtained by conventional methods of breeding or genetic engineering and containing so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

These compositions may be used to control unwanted vegetation (collectively, 'weeds'). Weeds to be controlled may be either monocotyledonous species such as Agrostis (Agrostis), myrta (Alopecurus), avena (Avena), mesona (Brachiaria), bromus (Bromus), tribulus (Cenchrus), cyperus (Cyperus), crabgrass (DIGITARIA), barnyard (Echinochloa), eleusines (Eleusine), lolium (Lolium), yujiujiu (Monochoria), legionella (Rottboellia), sagittaria (SAGITTARIA), scirpus (Scirpus), setaria (Setaria) and Sorghum (Sorghum), or dicotyledonous species such as Abutilus (Abutilon), amaranthus (Amaranthus), ambrosia (Ambrosia), chenopodium (Chenopodium), june (Chrysanthemum), echinacea (Conyza), lagranola (Galium), sweet potato (Ipomoea), sida (6724), siberia (Viola (8654), taraxacum (Viola (8654) and Taraxacum (Viola).

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

Process for preparing compounds of formula (I)

The process for preparing compounds, such as compounds of formula (I) which may alternatively be agrochemically acceptable salts thereof, is now described and forms a further aspect of the invention.

As shown in scheme 1, compounds having formula (I) can be prepared via decarboxylation of compounds having formula (2) under acidic conditions with heating at 110 ℃ in a suitable solvent such as ethanol.

Using a nucleophilic aromatic substitution reaction of a compound of formula (4) wherein LG represents a suitable leaving group, such as halogen or SO ₂ Me, with a compound of formula (3), the reaction is carried out by heating in a suitable solvent, such as sulfolane, in the presence of a base, such as sodium t-butoxide. The reaction is typically carried out at 40 ℃.

Conditions for the formation of pyrazole compounds of formula (3) via condensation of diketones with arylhydrazines are reported in the literature (as reported in Tetrahedron (2013), 69 (16), 3459-3464).

Scheme 1

Alternatively, the compound having formula I may be prepared by scheme 2 below.

Scheme 2:

In scheme 2, the compounds of formula I can be prepared by reacting a compound of formula VI with a reagent of formula V wherein LG ₁ is halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group such as a (halo) alkyl or phenyl sulfonate, e.g., triflate), 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-dimethylformamide DMF, N-dimethylacetamide, sulfolane or acetonitrile, and the like, at a temperature between 0 ℃ and 120 ℃ by procedures well known to those skilled in the art.

Alternatively, compounds of formula I may be prepared by reacting a compound of formula VI with a compound of formula V wherein LG ₁ is halogen, preferably iodine, bromine or chlorine (or a pseudohalogen leaving group such as a (halo) alkyl or phenyl sulfonate, e.g., triflate), in the presence of a metal catalyst such as a copper-based catalyst, e.g., cuI or tetra (acetonitrile) copper (I) tetrafluoroborate, optionally in the presence of a ligand such as trans-1, 2-bis (methylamino) cyclohexane or a salt thereof (e.g., mesylate) or 8-hydroxyquinoline, and the like, and other ligands. The reaction may be carried out in the presence of a base such as potassium carbonate, cesium carbonate, triethylamine or pyridine and similar other substances and in the presence of a solvent such as acetonitrile, 1, 4-dioxane or pyridine, and optionally under microwave irradiation at a temperature in the range of room temperature and 200 ℃.

Alternatively, the compound of formula I may be prepared by reacting a compound of formula VI with a compound of formula Va under Chan Lam cross-coupling reaction conditions. Such reactions are carried out in the presence of copper-based catalysts such as copper acetate or iodide or bromide and the like and in the presence of bases such as pyridine or 2, 6-lutidine and the like. The reaction may be carried out in the presence of a solvent (e.g., dichloromethane, toluene, acetonitrile) and in the presence of air or oxygen and at a temperature in the range of room temperature and 200 ℃.

The compound of formula VI may be prepared from a compound of formula VII wherein PG is an amino protecting group, such as an acetyl, trimethylsilylethoxymethyl (SEM), t-butoxycarbonyl, benzyl, p-methoxybenzyl (PMB), or the like, by deprotection of the protecting group. Such reactions are well known to those skilled in the art and may be carried out, for example, under base catalysis such as deprotection of the acetyl group using sodium hydroxide, or under acid catalysis such as deprotection of the trimethylsilylethoxymethyl (SEM), t-butoxycarbonyl or p-methoxybenzyl (PMB) group with hydrochloric acid or 2, 2-trifluoroacetic acid.

The compound of formula VII may be prepared from a compound of formula VIII (wherein R ¹² is C ₁-C₄ alkyl or phenyl) via decarboxylation. The reaction may be carried out using a base (e.g., an alkaline earth metal hydroxide or an alkali metal hydroxide such as sodium hydroxide) or in the presence of an acid (e.g., aqueous hydrochloric acid, aqueous sulfuric acid, etc.). The reaction is typically carried out in the presence of a solvent (such as water, ethanol, methanol, tetrahydrofuran, or dioxane) or a combination of two or more solvents and at a temperature in the range of room temperature to the boiling point of the solvent.

The compound of formula VIII, wherein R ¹² is C ₁-C₄ alkyl or phenyl, may be prepared by reacting a compound of formula X with a reagent of formula IX, wherein LG ₂ is halogen (or a pseudohalogen leaving group such as a (halo) alkyl or phenyl sulfonate, e.g. triflate), in the presence of a base such as sodium tert-butoxide, sodium hydride or alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate (e.g. potassium phosphate), optionally in the presence of potassium iodide, in an inert solvent such as tetrahydrofuran, dioxane, water, N-dimethylformamide DMF, N-dimethylacetamide, dimethylsulfoxide, sulfolane or acetonitrile, etc., at a temperature between 0 ℃ and 200 ℃ by procedures well known to those skilled in the art.

The compound having the formula X may be prepared by condensation reaction of a compound having the formula XII with a compound having the formula XI (or a hydrochloride or trifluoroacetate salt thereof) wherein PG is an amino protecting group such as acetyl, trimethylsilylethoxymethyl (SEM), t-butoxycarbonyl, benzyl, p-methoxybenzyl (PMB), and the like. Such reactions are well known in the literature and may optionally be carried out in the presence of an acid catalyst such as acetic acid.

The compound of formula XII can be prepared by reacting a compound of formula XIV (wherein R ¹¹ is C ₁-C₄ alkyl or phenyl) with a compound of formula XIII in the presence of a base. Such reactions are known as claisen condensation reactions and are well known to those skilled in the art. The reaction may be carried out using a base (e.g., lithium diisopropylamide, lithium tetramethylpiperidine, sodium ethoxide, sodium hydride, etc.) in the presence of a solvent (e.g., tetrahydrofuran, ethanol, methanol) and at a temperature in the range of-80 ℃ to the boiling point of the solvent.

Alternatively, the compound having formula I may be prepared by scheme 3 below.

Scheme 3:

In scheme 3, the compound having formula I is prepared from the compound having formula XV via alcohol reduction. The reduction of such alcohols is described in detail in the literature and can be carried out using reducing agents (e.g. LiAlH ₄, DIBAL-H) or triphenylphosphine in the presence of iodine and imidazole or triethylsilane in the presence of trifluoroacetic acid. The compound having formula XV may be prepared by reacting a compound having formula XVI (wherein X ¹ is halogen, preferably bromine or iodine) with an organometallic reagent (such as BuLi or isopropylmagnesium chloride/LiCl complex or the like metalating reagent) to form intermediate XVIa (wherein M (Ln) ^p is the corresponding metal (such as lithium or magnesium) from the organometallic reagent and (Ln) ^p is an optionally substituted group thereof, like chlorine), and then subsequently reacting with the compound having formula XVII.

The compound having formula XVII may be prepared by reacting a compound having formula XVIII with a strong base (e.g., butyllithium, lithium diisopropylamide), and then with DMF. The reaction is typically carried out in the presence of a solvent (e.g., tetrahydrofuran, toluene, heptane) and at a temperature between-80 ℃ and the boiling point of the solvent. Such reactions are well known and described in the literature. The compound of formula XVIII may be prepared by reacting a compound of formula XIX with a compound of formula XX, wherein LG ₃ is a leaving group like a halogen (or pseudohalogen leaving group, such as a (halo) alkyl or phenyl sulfonate, e.g. triflate), in the presence of a base, such as sodium tert-butoxide, sodium hydride or alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate (e.g. potassium phosphate), optionally in the presence of potassium iodide, in an inert solvent, such as tetrahydrofuran, dioxane, water, N-dimethylformamide DMF, N-dimethylacetamide, dimethylsulfoxide, sulfolane or acetonitrile, etc., at a temperature between 0 ℃ and the boiling point of the solvent by procedures well known to those skilled in the art. Such a reaction is referred to in the literature as the S _N Ar reaction.

Alternatively, the compounds of formula XVIII may be prepared by Chan-Lam coupling involving, for example, reacting a compound of formula XIX with a compound of formula XXI (wherein Yb ₁ may be a boron derived functional group such as, for example, B (OH) ₂ or B (ORb ₁)₂ wherein Rb ₁ may be a C ₁-C₄ alkyl group or both groups ORb ₁ may form a five membered ring with the boron atom such as, for example, pinacol borate) in the presence of a copper catalyst (e.g., cu (OAc) ₂、CuI、CuBr₂, cuCl or the like) in a solvent or solvent mixture (e.g., such as dioxane, methylene chloride, acetonitrile, N-dimethyl-formamide, a mixture of 1, 2-dimethoxyethane and water or a mixture of dioxane/water) in an inert atmosphere or in an oxygen atmosphere or at air catalytic temperature preferably in the range from room temperature to the reaction boiling point of Cham, as is well known in the art.

Formula I-1 is a compound having formula I wherein U is U23. Formula I-2 is a compound having formula I wherein U is U22. Formula I-3 is a compound having formula I wherein U is U26. Formula I-4 is a compound having formula I wherein U is U25. Compounds having the formula I-1, formula I-2, formula I-3 and formula I-4 may be prepared following scheme 4.

Scheme 4

The compounds of formula I-3 and compounds of formula I-4 may be prepared by alkylation reactions involving reacting a compound of formula I-5 with a compound of formula XXXI, wherein R ^7a is as defined above in formula I and LG _x is a leaving group like a halogen (or pseudohalogen leaving group, such as a (halo) alkyl or phenyl sulfonate, e.g. triflate), in the presence of a base, such as sodium tert-butoxide, sodium hydride or alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate (e.g. potassium phosphate), optionally in the presence of potassium iodide, in an inert solvent (e.g. tetrahydrofuran, dioxane, water, N-dimethylformamide DMF, N-dimethylacetamide, dimethylsulfoxide, sulfolane or acetonitrile, etc.), at a temperature between 0 ℃ and the solvent.

Alternatively, the compounds of formula I-3 and the compounds of formula I-4 may be prepared by reacting a compound of formula XXIX with a compound of formula XXVIII, optionally in the presence of an acid catalyst (e.g. hydrochloric acid, sulfuric acid, acetic acid) and in the presence of a solvent (e.g. acetic acid, dichloromethane, tetrahydrofuran and similar other substances).

The compounds of formula I-5 may be prepared similarly from compounds of formula XXIX following procedures analogous to those described for the synthesis of compounds of formula I-3 and compounds of formula I-4 from compounds of formula XXIX (scheme 4). The compound having formula XXIX can be prepared by reacting a compound having formula XXVII with N, N-dimethylformamide dimethyl acetal. Such reactions are well known in the literature and are described, for example, in j. Compounds having formula XXVII may be prepared from compounds having formula XXII via an amidation reaction involving reacting a compound having formula XXVII with ammonia or an ammonia substitute (such as ammonium hydroxide) in the presence of a solvent (such as methanol, ethanol, tetrahydrofuran, acetonitrile and the like) and at a temperature in the range of 0 ℃ to the boiling point of the solvent. Compounds of formula XXII can be prepared from compounds of formula XIII and compounds of formula XIV following the procedure as described in scheme 2 for the synthesis of compounds of formula X from compounds of formula XIV and compounds of formula XIII.

The compound having formula I-1 may be prepared by reacting a compound having formula XXVI with a Lawson reagent (scheme 4). Such reactions are well known in the literature and are described, for example, in Journal of Organic Chemistry [ journal of organic chemistry ], 2001, 66, 23, 7925-7929. The compounds of formula I-2 may be prepared from compounds of formula XXVI via intramolecular cyclisation reactions. Such reactions are generally carried out in the presence of acid catalysts (such as hydrochloric acid, trifluoroacetic acid and the like) or in the presence of phosphorus oxychloride and are well known in the literature, for example as described in Molecules [ molecules ], 2022, 27, 22, 7687. The compound having formula XXVI can be prepared by reacting a compound having formula XXIV with a compound having formula XXV in the presence of an amide coupling reagent such as phosphorus oxychloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and similar other substances. Alternatively, the compound having formula XXVI can be prepared by reacting a compound having formula XXIV with a compound having formula XXVa or a compound having formula XXVaa. The compound having formula XXIV may be prepared by reaction of a compound having formula XXII with hydrazine XXX or a hydrate form thereof. The reaction may be carried out in the presence of a solvent (e.g., methanol, ethanol, tetrahydrofuran, etc.).

Alternatively, compounds having formula I (wherein U is an N-linked 5-membered heteroaryl optionally substituted with one or more independent R ⁷) can be prepared following scheme 5.

Scheme 5

In scheme 5, compounds having formula I can be prepared by the substitution reaction of a compound having formula XXXIV with a compound having formula XXXV, wherein U is an N-linked 5-membered heteroaryl optionally substituted with one or more independent R ⁷. Compounds of formula XXXIV, wherein X ¹ is halogen, such as chlorine or bromine, can be prepared from compounds of formula XXXIII via halogenation reactions using halogenating reagents such as thionyl chloride or using carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine. The compound of formula XXXIII can be prepared from compounds of formula XXXII (wherein R ¹³ is C ₁-C₄ alkyl or phenyl) or from compounds of formula XVII (as prepared in scheme 3) via reduction using a reducing agent such as sodium borohydride, lithium aluminum hydride or diisobutylaluminum hydride and the like.

Scheme 6

Compounds of formula I wherein U is C-linked 5-membered heteroaryl optionally substituted with one or more independent R ⁷ can be prepared by cross-coupling a compound of formula XXXIV wherein X ¹ is halogen, e.g., bromine, chlorine or iodine, with sp ³-sp² of a compound of formula XXXVI wherein X ² is halogen, e.g., bromine, chlorine or iodine (scheme 6). Such reactions have been reported in the literature and are described, for example, in Angew.chem.int. Ed. [ International edition of German application chemistry ], 2022, 61, e202116775 and chem.Commun. [ chemical communications ], 2017,53, 9364-9367. One such method involves a palladium-catalyzed desulphation cross-coupling reaction as described in Angew, chem, int, ed. [ International Germany application chemistry edition ], 2022, 61, e 202116775. The in situ sulfinate may be prepared in this process by reacting a compound having the formula XXXIV with a masked sulfinylating reagent such as sodium 1-methyl 3-sulfinylate and with a compound having the formula XXXVI (wherein X ² is halogen, e.g., bromine, chlorine or iodine), in the presence of a base such as potassium carbonate and the like and in the presence of a ligand such as a phosphino ligand like di-tert-butyl (methyl) phosphonium tetrafluoroborate and in the presence of a palladium catalyst such as palladium acetate and in the presence of a solvent such as toluene, xylene, dimethyl sulfoxide and the like and optionally under microwave irradiation at temperatures in the range of room temperature and 200 ℃.

The following non-limiting examples provide representative specific synthetic methods for the compounds of the present invention (as set forth in table 1 below).

EXAMPLE 1 preparation of 2-chloro-5- [3- [ chloro (difluoro) methyl ] -5- (1H-1, 2, 4-triazol-3-ylmethyl) pyrazol-1-yl ] -3-fluoro-pyridine (1.006)

(1.006)

Step 1 preparation of tert-butyl N- (tert-butoxycarbonylamino) -N- (6-chloro-5-fluoro-3-pyridinyl) -carbamate (I1)

(I1)

A solution of 5-bromo-2-chloro-3-fluoropyridine (1.50 g,7.12 mmol) in tetrahydrofuran (14 mL) in a 100 mL round bottom flask was placed under nitrogen atmosphere, ice-cooled and treated with 1.3M isopropyl magnesium chloride lithium chloride complex solution (6.0 mL,7.8 mmol). The mixture was allowed to stir at 0 ℃ for 15 minutes and then treated dropwise with a solution of di-tert-butyl azodicarbonate (1.83 g,7.95 mmol) in tetrahydrofuran (4 mL) in such a way that the internal temperature did not exceed 15 ℃. The mixture was allowed to stir for 30 minutes. The reaction mixture was quenched with water (100 mL) and extracted with ethyl acetate (2×50 mL). The combined organics were washed with brine (50 mL) and concentrated in vacuo. The crude product was purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane as eluent to give tert-butyl N- (tert-butoxycarbonylamino) -N- (6-chloro-5-fluoro-3-pyridinyl) -carbamate I1 (1.80 g, 66%) as an oil which crystallized upon standing as a white solid .¹H NMR (400 MHz, CDCl₃) δ = 8.36 (s, 1H), 7.92 - 7.64 (m, 1H), 6.73 (br s, 1H), 1.55 - 1.46 (m, 18H).

Step 2 preparation of 6-chloro-6, 6-difluoro-3, 5-dioxo-hexanoic acid methyl ester (I2)

(I2)

A solution of lithium diisopropylamide in tetrahydrofuran (13 mL,26 mmol) in a 100mL round bottom flask was placed under nitrogen, cooled on ice, and treated dropwise with methyl acetoacetate (0.70 mL,6.5 mmol) in such a way that the internal temperature did not exceed 15 ℃. The resulting pale yellow mixture was allowed to stir at 0 ℃ for 30 minutes. The mixture was then cooled to-78 ℃ and treated dropwise with ethyl chlorodifluoroacetate (1.1 ml,8.7 mmol). The resulting reaction mixture was allowed to stir at this temperature for an additional 3.5 hours. It was warmed to room temperature and stirred for an additional 30 minutes. After completion, the mixture was quenched with 1M hydrochloric acid (80 mL) and extracted with ethyl acetate (2×60 mL). The combined organics were passed through a hydrophobic filter and concentrated in vacuo. Assuming quantitative conversion, the resulting oil (containing methyl 6-chloro-6, 6-difluoro-3, 5-dioxo-hexanoate I2) was used as such in the next step.

Step 3 preparation of methyl 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetate (I3)

(I3)

A solution of tert-butyl N- (tert-butoxycarbonylamino) -N- (6-chloro-5-fluoro-3-pyridinyl) carbamate I1 (1.79 g,4.71 mmol) in trifluoroacetic acid (3.6 mL) in a 100 mL round bottom flask was stirred at room temperature for 1 hour. The reaction mixture was then treated with a solution of methyl 6-chloro-6, 6-difluoro-3, 5-dioxo-hexanoate I2 (as prepared in step 2) in acetic acid (10 mL) and allowed to stir overnight at room temperature. The reaction mixture was concentrated and purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane as eluent to give a yellow oil (about 1.55 g) containing a mixture of isomers of the product. The residue was further purified by reverse phase column chromatography using 40% -100% acetonitrile in 0.1% formic acid-containing water as eluent to give methyl 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetate I3 (0.89 g, 45%) as the major isomer as a yellow oil .¹H NMR (400 MHz, CDCl₃) δ = 8.42 (d, 1H), 7.80 (dd, 1H), 6.71 (s, 1H), 3.76 (s, 2H), 3.74 (s, 3H).

Step 4 preparation of 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetamide (I4)

(I4)

A solution of methyl 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetate I3 (624 mg,1.49 mmol) in methanol (2.5 mL) was treated with 7M ammonia (2.5 mL,18 mmol) in methanol and allowed to stir at room temperature for 24 hours. The reaction mixture was concentrated in vacuo and the residue was purified by reverse phase column chromatography using 30% -100% acetonitrile in 0.1% formic acid in water as eluent to give 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetamide as a white solid I4（442 mg,83%）.¹H NMR (400 MHz, CDCl₃) δ = 8.45 (d, 1H), 7.87 (dd, 1H), 6.71 (s, 1H), 5.53 (br s, 2H), 3.68 (s, 2H).

Step 5 preparation of 2-chloro-5- [3- [ chloro (difluoro) methyl ] -5- (1H-1, 2, 4-triazol-3-ylmethyl) pyrazol-1-yl ] -3-fluoro-pyridine (1.006)

(1.006)

A solution of 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetamide I4 (337 mg,0.94 mmol) in acetonitrile (4.7 mL) in a 100mL round bottom flask was placed under nitrogen and treated with N, N-dimethylformamide dimethyl acetal (140 μl,1.05 mmol). The resulting mixture was warmed to 70 ℃ and allowed to stir for 1 hour. The reaction mixture was concentrated in vacuo. This was dissolved in acetic acid (2.5 ml,44 mmol) in a 100mL round bottom flask and treated with hydrazine hydrate (64 wt% in water) under nitrogen atmosphere (150 μl,1.973 mmol). The resulting mixture was allowed to stir at room temperature for 30 minutes. The reaction mixture was diluted with ethyl acetate (30 mL) and washed with aqueous ammonium chloride (2×20 mL), 10% aqueous ferrous sulfate (20 mL) and water (20 mL). The organic phase was concentrated in vacuo. The crude product obtained was purified by silica gel column chromatography using 0-100% ethyl acetate in cyclohexane to give 2-chloro-5- [3- [ chloro (difluoro) methyl ] -5- (1H-1, 2, 4-triazol-3-ylmethyl) -pyrazol-1-yl ] -3-fluoro-pyridine 1.006.¹H NMR (400 MHz, CDCl₃) δ = 8.54 (d, 1H), 8.22 (s, 1H), 7.93 (dd, 1H), 6.67 (s, 1H), 4.23 (s, 2H).

EXAMPLE 2 preparation of 2-chloro-5- [3- [ chloro (difluoro) methyl ] -5- [ (2-methyl-1, 2, 4-triazol-3-yl) methyl ] pyrazol-1-yl ] -3-fluoro-pyridine (1.001)

(1.001)

A mixture of 2-chloro-5- [3- [ chloro (difluoro) methyl ] -5- (1H-1, 2, 4-triazol-3-ylmethyl) pyrazol-1-yl ] -3-fluoro-pyridine 1.006 (264 mg,0.72 mmol) and potassium carbonate (228 mg,1.6497 mmol) in N, N-dimethylformamide (1.8 mL) in a 50 mL round bottom flask was placed under a nitrogen atmosphere and treated with methyl iodide (70. Mu.L, 1.10 mmol). The resulting mixture was allowed to stir at room temperature for 30 minutes. The reaction mixture was diluted with water (25 mL) and extracted with tert-butyl methyl ether (2×25 mL). The combined organics were concentrated in vacuo. The residue was purified by silica gel column chromatography using 0-70% ethyl acetate in cyclohexane to give a mixture of isomers. This mixture was further purified by reverse phase column chromatography using 40% -100% acetonitrile in 0.1% formic acid in water to give 2-chloro-5- [3- [ chloro (difluoro) methyl ] -5- [ (1-methyl-1, 2, 4-triazol-3-yl) methyl ] pyrazol-1-yl ] -3-fluoro-pyridine 1.001. ¹ H NMR (400 MHz, chloroform) δ=8.49 (d, 1H), 7.92 (dd, 1H), 7.82 (s, 1H), 6.56 (s, 1H), 4.19 (s, 2H), 3.85 (s, 3H).

EXAMPLE 3 preparation of 1- (3, 4-difluorophenyl) -5- [ (1-methylpyrazol-3-yl) methyl ] -3- (trifluoromethyl) pyrazole (1.002)

(1.002)

Step 1 preparation of ethyl 2- (3, 4-difluorophenyl) -5- (trifluoromethyl) pyrazole-3-carboxylate (I6)

(I6)

A mixture of ethyl 3- (trifluoromethyl) -1H-pyrazole-5-carboxylate (1.498 g,7.197 mmol), 3, 4-difluorophenylboronic acid (2.19 g,13.18 mmol) and copper (II) acetate (2.103 g,11.58 mmol) in a 250 mL round bottom flask was treated with acetonitrile (24 mL) and pyridine (1.2 mL,15 mmol). The reaction mixture was stirred rapidly at room temperature under air for 95 hours. The reaction mixture was concentrated and the residue was purified by silica gel column chromatography using 0-40% ethyl acetate in cyclohexane to give ethyl 2- (3, 4-difluorophenyl) -5- (trifluoromethyl) pyrazole-3-carboxylate as a white solid I6（2.360 g,92%）.¹H NMR (400 MHz, CDCl₃) δ = 7.38 - 7.32 (m, 1H), 7.31 - 7.20 (m, 3H), 4.30 (q, 2H), 1.31 (t, 3H).

Step 2 preparation of [2- (3, 4-difluorophenyl) -5- (trifluoromethyl) pyrazol-3-yl ] methanol (I7)

(I7)

A solution of ethyl 2- (3, 4-difluorophenyl) -5- (trifluoromethyl) pyrazole-3-carboxylate I6 (1.30 g,3.65 mmol) in 2-methyltetrahydrofuran (10 mL) in a 250 mL round bottom flask was placed under nitrogen atmosphere, ice-cooled and treated with 2.3M lithium aluminum hydride in 2-methyltetrahydrofuran (2.0 mL). The resulting reaction mixture was allowed to stir at 0 ℃ for 15 minutes. The reaction mixture was quenched with water (175 μl) and allowed to stir for 10 min. The mixture was then treated with 15% aqueous sodium hydroxide (175 μl), stirred for 10 minutes, and then treated with additional water (525 μl). The mixture was diluted with tert-butyl methyl ether (150 mL), dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography using 0-60% ethyl acetate in cyclohexane to give [2- (3, 4-difluorophenyl) -5- (trifluoromethyl) pyrazol-3-yl ] methanol as a white solid I7（991 mg,93%）.¹H NMR (400 MHz, CDCl₃) δ = 7.64 - 7.57 (m, 1H), 7.49 - 7.43 (m, 1H), 7.34 - 7.27 (m, 1H), 6.72 (s, 1H), 4.68 (d, 2H), 1.91 (t, 1H).

Step 3 preparation of 5- (chloromethyl) -1- (3, 4-difluorophenyl) -3- (trifluoromethyl) pyrazole (I8)

(I8)

A solution of [2- (3, 4-difluorophenyl) -5- (trifluoromethyl) pyrazol-3-yl ] methanol I7 (991 mg,3.38 mmol) in acetonitrile (11 mL) in a 100 mL round bottom flask was placed under nitrogen and treated with thionyl chloride (500 μl,6.83 mmol). The resulting reaction mixture was allowed to stir at room temperature for 1.5 hours. The reaction mixture was concentrated and the residue was subjected to silica gel column chromatography using 0-30% ethyl acetate in cyclohexane to give 5- (chloromethyl) -1- (3, 4-difluorophenyl) -3- (trifluoromethyl) pyrazole as a colorless oil I8（876 mg,83%）.¹H NMR (400 MHz, CDCl₃) δ = 7.53 - 7.45 (m, 1H), 7.41 - 7.31 (m, 2H), 6.79 (s, 1H), 4.56 (s, 2H).

Step 4 preparation of 1- (3, 4-difluorophenyl) -5- [ (1-methylpyrazol-3-yl) methyl ] -3- (trifluoromethyl) pyrazole (1.002)

(1.002)

Sodium 3-methoxy-3-oxopropane-1-sulfinate (26 mg,0.147803 mmol), potassium carbonate (38 mg,0.275 mmol), palladium (II) acetate (5 mg,0.022 mmol) and di-tert-butyl (methyl) phosphonium tetrafluoroborate (14 mg,0.055876 mmol) were added to a microwave vial equipped with a stirring bar. The vials were sealed with a microwave vial cap, evacuated and backfilled five times with nitrogen. Then, 3-bromo-1-methyl-1 h-pyrazole (0.010 mL,0.098 mmol), 5- (chloromethyl) -1- (3, 4-difluorophenyl) -3- (trifluoromethyl) pyrazole I8 (53 mg,0.17 mmol) and dimethyl sulfoxide (1.00 mL) were added, and the reaction was heated to 120 ℃ in microwaves for 3 hours. The reaction mixture was cooled to room temperature, diluted with ethyl acetate (20 mL) and washed with water (20 mL), brine (20 mL), and the organic layer was concentrated in vacuo. The crude residue was loaded onto celite and subjected to silica gel column chromatography using 0-15% ethyl acetate in cyclohexane. After concentrating the fractions, 1- (3, 4-difluorophenyl) -5- [ (1-methylpyrazol-3-yl) methyl ] -3- (trifluoromethyl) pyrazole was obtained as a yellow oil 1.002.¹H NMR (400 MHz, CDCl₃) δ = 7.39 - 7.33 (m, 1H), 7.29 (d, 1H), 7.27 - 7.24 (m, 2H), 6.49 (s, 1H), 5.99 (d, 1H), 3.99 (s, 2H), 3.86 (s, 3H).

EXAMPLE 4 preparation of 2- [ [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] methyl ] -5-methyl-1, 3, 4-thiadiazole (1.003)

Step 1 preparation of 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acethydrazide (I9)

(I9)

A solution of methyl 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acetate I3 (251 mg,0.60 mmol) in methanol (3.0 mL) in a 25 mL round bottom flask was placed under nitrogen atmosphere, ice-cooled and treated with hydrazine hydrate (64 wt%, in water) (55. Mu.L, 0.7235 mmol). The resulting reaction mixture was allowed to stir at room temperature for 2 hours. The reaction mixture was treated with additional hydrazine hydrate (64 wt% in water) (55 μl,0.72 mmol) and allowed to stir for an additional 5 hours. The reaction mixture was diluted with ethyl acetate (30 mL) and washed with dilute aqueous ammonium chloride (2×25 mL), water (20 mL) and 10% aqueous ferrous sulfate (30 mL). The organic phase was concentrated in vacuo. The residue was loaded onto celite and subjected to reverse phase column chromatography using 30% -100% acetonitrile in water containing 0.1% formic acid as eluent. After concentrating the fractions, 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acethydrazide was obtained as a white waxy solid I9（227 mg,96%）.¹H NMR (400 MHz, DMSO-d6) δ = 9.25 (s, 1H), 8.62 (d, 1H), 8.46 (dd, 1H), 6.87 (s, 1H), 4.40 (br s, 2H), 3.67 (s, 2H).

Step 2 preparation of N' -acetyl-2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acethydrazide (I10)

(I10)

A solution of 2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acethydrazide I9 (227 mg,0.57 mmol) in acetic acid (1.2 mL) in a 100mL round bottom flask was treated with acetic anhydride (110. Mu.L, 1.15 mmol). The resulting reaction mixture was allowed to stir at room temperature for 5 minutes. The reaction mixture was quenched by the addition of methanol (about 10 mL). The mixture was then concentrated in vacuo and the residue was taken up in cyclohexane and concentrated three times to give N' -acetyl-2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acethydrazide as a white solid in the form of a foam I10（232 mg,91%）.¹H NMR (400 MHz, DMSO-d6) δ = 10.03 (s, 1H), 9.82 (s, 1H), 8.60 (d, 1H), 8.40 (dd, 1H), 6.94 (s, 1H), 3.83 (s, 2H), 1.83 (s, 3H).

Step 3 preparation of 2- [ [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] methyl ] -5-methyl-1, 3, 4-thiadiazole (1.003)

(1.003)

A solution of N' -acetyl-2- [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] acethydrazide I10 (174 mg,0.39 mmol) in tetrahydrofuran (2.0 mL) was placed under nitrogen and treated with Lawsen reagent (371 mg,0.89 mmol). The reaction mixture was warmed to 50 ℃ and allowed to stir for 1.5 hours. The reaction mixture was allowed to cool to room temperature, then concentrated directly onto celite, and subjected to silica gel column chromatography using 0-10% ethyl acetate in cyclohexane as eluent. The residue obtained is further purified by reverse phase column chromatography using 40% -100% acetonitrile in 0.1% formic acid in water to give 2- [ [5- [ chloro (difluoro) methyl ] -2- (6-chloro-5-fluoro-3-pyridinyl) pyrazol-3-yl ] methyl ] -5-methyl-1, 3, 4-thiadiazole 1.003.¹H NMR (400 MHz, CDCl₃) δ = 8.45 (d, 1H), 7.84 (dd, 1H), 6.66 (s, 1H), 4.49 (s, 2H), 2.78 (s, 3H).

EXAMPLE 5 preparation of 1- (4-chlorophenyl) -5- [ (4-Chloropyrazol-1-yl) methyl ] -3- (trifluoromethyl) pyrazole (1.004)

(1.004)

Step 1 preparation of 1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole (I11)

(I11)

A mixture of 5- (trifluoromethyl) -1H-pyrazole (710 mg,5.21 mmol), 1-chloro-4-iodobenzene (1.60 g,6.71 mmol), copper (I) iodide (211 mg,1.1079 mmol) and potassium carbonate (1.48 g,10.7 mmol) in a microwave vial was treated with toluene (17 mL) and trans-N, N' -dimethyl-1, 2-diaminocyclohexane (250. Mu.L, 1.57 mmol). The vials were evacuated and backfilled three times with nitrogen and then heated to 150 ℃ for 1 hour under microwave irradiation. The reaction mixture was diluted with water (30 mL) and extracted with ethyl acetate (2×25 mL). The combined organics were concentrated in vacuo. The residue was loaded onto celite and subjected to silica gel column chromatography using 0-20% ethyl acetate in cyclohexane as eluent. The fractions were combined and concentrated in vacuo to give 1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole as a pale brown crystalline solid I11（1.1 g,82%）.¹H NMR (400 MHz, CDCl₃) δ = 7.95 - 7.90 (m, 1H), 7.69 - 7.63 (m, 2H), 7.49 - 7.43 (m, 2H), 6.73 (d, 1H).

Step 2 preparation of 2- (4-chlorophenyl) -5- (trifluoromethyl) pyrazole-3-carbaldehyde (I12)

(I12)

A solution of 1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole I11 (1.110 g,4.276 mmol) in tetrahydrofuran (14 mL) in a 100 mL round bottom flask was cooled to-78℃under a nitrogen atmosphere and treated dropwise with n-butyllithium (2.5M in hexane) (2.6 mL,6.5 mmol). The mixture was allowed to stir for 1 hour and then treated with N, N-dimethylformamide (0.7 mL,9 mmol). The mixture was then allowed to stir at room temperature for an additional 30 minutes. The reaction mixture was quenched with 1M hydrochloric acid (5 mL), diluted with water (20 mL) and extracted with ethyl acetate (2×20 mL). The combined organics were concentrated in vacuo. The crude product was purified by silica gel column chromatography using 0-25% ethyl acetate in cyclohexane as eluent to give 2- (4-chlorophenyl) -5- (trifluoromethyl) pyrazole-3-carbaldehyde as a yellow oil I12（852 mg,69%）.¹H NMR (400 MHz, CDCl₃) δ = 9.88 (s, 1H), 7.57 - 7.51 (m, 2H), 7.50 - 7.45 (m, 2H), 7.34 (s, 1H).

Step 3 preparation of [2- (4-chlorophenyl) -5- (trifluoromethyl) pyrazol-3-yl ] methanol (I13)

(I13)

A solution of 2- (4-chlorophenyl) -5- (trifluoromethyl) pyrazole-3-carbaldehyde I12 (405 mg,1.40 mmol) in ethanol (3.0 mL) in a 25 mL round bottom flask was treated with sodium borohydride (73 mg,1.85 mmol). The resulting reaction mixture was allowed to stir at room temperature overnight. The reaction mixture was quenched by dropwise addition of 2M hydrochloric acid until bubbling ceased. The mixture was diluted with water (15 mL) and extracted with ethyl acetate (2×15 mL). The combined organics were passed through a hydrophobic filter and concentrated in vacuo to give [2- (4-chlorophenyl) -5- (trifluoromethyl) pyrazol-3-yl ] methanol as an off-white solid I13（438 mg,100%）.¹H NMR (400 MHz, CDCl₃) δ = 7.63 - 7.57 (m, 2H), 7.51 - 7.45 (m, 2H), 6.73 (s, 1H), 4.68 (d, 2H), 1.87 (t, 1H).

Step 4 preparation of 5- (bromomethyl) -1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole (I14)

A mixture of [2- (4-chlorophenyl) -5- (trifluoromethyl) pyrazol-3-yl ] methanol I13 (438 mg,1.34 mmol), carbon tetrabromide (566 mg,1.67 mmol) and triphenylphosphine (443 mg,1.66 mmol) in a 50mL round bottom flask was placed under nitrogen and treated with 2-methyltetrahydrofuran (3.5 mL). The resulting mixture was allowed to stir for 30 minutes. The reaction mixture was treated with additional carbon tetrabromide (549 mg,1.62 mmol) and triphenylphosphine (424 mg,1.58 mmol) and stirred for 17 hours. The reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (2×50 mL). The combined organics were concentrated. The residue was purified by silica gel column chromatography using 0-25% ethyl acetate in cyclohexane as eluent to give a mixture of 5- (bromomethyl) -1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole I14 and 5- (chloromethyl) -1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole I15 in a ratio of 3:1, respectively (244 mg, 37%). ¹H NMR (400 MHz, CDCl₃) δ=7.57-7.51 (m, 4H), 6.81-6.77 (m, 1H), 4.41 (s, 2H) of I14.

Step 5 preparation of 1- (4-chlorophenyl) -5- [ (4-Chloropyrazol-1-yl) methyl ] -3- (trifluoromethyl) pyrazole (1.004)

(1.004)

A3:1 mixture (30 mg,0.061 mmol) of 5- (bromomethyl) -1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole I14 and 5- (chloromethyl) -1- (4-chlorophenyl) -3- (trifluoromethyl) pyrazole I15 obtained above in step 4 (example 5), 4-chloro-1 h-pyrazole (33 mg,0.32 mmol) and potassium carbonate (40 mg,0.28 mmol) were treated with acetonitrile (0.5 mL). The resulting mixture was allowed to stir at room temperature 20 h. The reaction mixture was concentrated directly onto celite and subjected to silica gel column chromatography using 0-20% ethyl acetate in cyclohexane as eluent. After concentrating the fractions, 1- (4-chlorophenyl) -5- [ (4-chloropyrazol-1-yl) methyl ] -3- (trifluoromethyl) pyrazole was obtained as a colorless oil 1.004.¹H NMR (400 MHz, CDCl₃) δ = 7.52 - 7.47 (m, 2H), 7.46 (d, 1H), 7.37 - 7.32 (m, 2H), 7.29 (d, 1H), 6.64 (s, 1H), 5.27 (s, 2H).

TABLE 1

Biological example

Seeds of various test species (amaranthus longifolius (Amaranthus palmeri) (AMAPA), amaranthus retroflexus (Amaranthus retroflexus) (AMARE), setaria faberi (SETFA), barnyard grass (Echinochloa crus-galli) (ECHCG), gomphrena (Ipomoea hederacea) (IPOHE)) were sown in standard soil in pots. These plants were sprayed under controlled conditions in a greenhouse (24 ℃ C./16 ℃ C.; day/night; 14 hours of light; 65% humidity) after one day of cultivation (pre-emergence) or after 8 days of cultivation (post-emergence), with a spray aqueous solution derived from the test compound dissolved in acetone and IF50 (11.12% Emulson EL 360. TM. + 44.44% N-methylpyrrolidone +44.44% Dowanol DPM glycol ether) and then diluted to the desired concentration using 0.2% Genapol XO80 (CAS No. 9043-30-5) in water as diluent. Test compounds are administered at the stated ratio. The test plants were then grown in a greenhouse under controlled conditions in the greenhouse (at 24/16 ℃, day/night; 14 hours light; 65% humidity) and watered twice daily. The percent damage to the plants by the test was evaluated both pre-emergence and 13 days post-emergence. The biological activities are shown in the table below in terms of the pentads (5=81% -100% >, 4=61% -80% >, 3=41% -60% >, 2=21% -40% >, 1=0-20%).

TABLE B1 post-emergence test

NT = untested

Table B2 Pre-emergence test

Nt=no test.

Claims (14)

1. A compound having the formula (I):

Or an agronomically acceptable salt thereof,

Wherein the method comprises the steps of

Q is phenyl or C-linked 6-membered heteroaryl, wherein the phenyl or 6-membered heteroaryl is optionally substituted with one or more independent R ¹;

U is a 5 membered heteroaryl optionally substituted with one or more independent R ⁷;

R ¹ is selected from the group consisting of halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ haloalkoxy, C ₃-C₆ cycloalkyl, C ₁-C₄ alkoxyC ₁-C₃ alkyl-, C ₁-C₄ alkoxyC ₁-C₃ alkoxy-, C ₁-C₄ alkoxyC ₁-C₃ alkoxyC ₁-C₃ alkyl-, -CN, NO ₂、C₂-C₄ alkenyl, C ₂-C₄ alkynyl, -S (O) _pC₁-C₄ alkyl, -S (O) _pC₁-C₄ haloalkyl, -C (O) OC ₁-C₄ alkyl, and-C (O) NR ⁴R⁵;

R ² is selected from the group consisting of-CN, NO ₂、C₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, -C (O) C ₁-C₄ alkyl, -C (O) OC ₁-C₄ alkyl, -S (O) _pC₁-C₄ alkyl, -C (R ⁶)=NOR⁸ and C ₃-C₆ cycloalkyl;

R ³ is selected from the group consisting of hydrogen, halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, -CN, NO ₂、C₂-C₄ alkenyl, C ₂-C₄ alkynyl, -S (O) _pC₁-C₄ alkyl, -S (O) _pC₁-C₄ haloalkyl, -C (O) OC ₁-C₄ alkyl, and-C (O) NR ⁴R⁵;

r ⁴ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ⁵ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ⁶ is hydrogen or C ₁-C₂ alkyl;

R ⁷ is selected from the group consisting of halogen, C ₁-C₄ alkyl, C ₃-C₄ cycloalkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, C ₁-C₄ alkoxy C ₁-C₃ alkyl-, C ₁-C₄ alkoxy C ₁-C₃ alkoxy-, -CN, C ₂-C₄ alkenyl, C ₂-C₄ alkynyl, -S (O) _pC₁-C₄ alkyl, -S (O) _pC₁-C₄ haloalkyl, -C (O) OC ₁-C₄ alkyl, -C (O) NR ⁹R¹⁰、-NR¹¹COR¹², and-S (O) _pNR¹³R¹⁴;

r ⁸ is hydrogen or C ₁-C₂ alkyl;

r ⁹ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹⁰ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹¹ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹² is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

R ¹³ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl;

r ¹⁴ is selected from the group consisting of hydrogen, C ₃-C₄ cycloalkyl, C ₁-C₄ alkyl, and C ₁-C₄ haloalkyl, and

P=0, 1 or 2.

2. The compound of claim 1, wherein U is selected from the group consisting of:

Wherein the method comprises the steps of

R ⁷ is hydrogen or as defined in claim 1;

R ^7a is selected from the group consisting of hydrogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl and C ₃-C₄ cycloalkyl, and

N=0, 1 or 2.

3. The compound of claim 2, wherein U is selected from the group consisting of U20, U22, U23, and U31.

4. The compound of any one of the preceding claims, wherein Q is selected from the group consisting of Q1 to Q-11:

Wherein R ¹ is as defined in claim 1, and

M is 0, 1 or 2.

5. The compound of claim 4, wherein Q is Q-1 or Q-3.

6. The compound of any of the preceding claims, wherein the compound of formula (I) is selected from the group consisting of formulas (Iaa), (Iab), (Iac), (Iad), (Iae) and (Iaf):

7. The compound of claim 6, wherein m is 1 or 2 and R ¹ is independently halogen or C ₁-C₂ haloalkyl.

8. A compound according to any one of the preceding claims, wherein R ² is C ₁-C₄ haloalkyl.

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

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

11. The herbicidal composition of claim 10 further comprising at least one additional pesticide.

12. The herbicidal composition according to claim 11, wherein the additional pesticide is a herbicide or herbicide safener.

13. 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 10 to 12.

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