WO2025021650A1 - Herbicidal pyrazole compounds - Google Patents

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein Q, U, R² and R³ are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

Description

HERBICIDAL PYRAZOLE COMPOUNDS The present invention relates to novel herbicidal compounds, to processes for their preparation, to herbicidal compositions which comprise the 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 from, for example, WO2022/013293, WO2022/101270 and WO2023/099354. The compounds of the present invention relate to herbicidal pyrazole compounds which comprise a 5- membered heteroaryl group (U). Thus, according to the present invention there is provided a compound of Formula (I):

or an agronomically acceptable salt thereof, wherein Q is phenyl or a C-linked 6-membered heteroaryl wherein said phenyl or 6- membered heteroaryl is optionally substituted by one or more independent R¹; U is a 5-membered heteroaryl optionally substituted by one or more independent R⁷; R¹ is selected from the group consisting of halogen, C₁-C₄ alkyl, C₁- C₄ haloalkyl, C₁-C₄ haloalkoxy, C₃-C₆cycloalkyl, C₁-C₄alkoxyC₁-C₃alkyl-, C₁- C₄alkoxyC₁-C₃alkoxy-, C₁-C₄alkoxyC₁-C₃alkoxyC₁-C₃alkyl-, -CN, NO₂, C₂- C4alkenyl, C2-C4alkynyl, -S(O)pC1-C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1- C4alkyl and -C(O)NR⁴R⁵; R² is selected from the group consisting of -CN, NO₂, C₁-C₄alkyl, C₁-

R³ is selected from the group consisting of hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, -CN, NO₂, C₂-C₄alkenyl, C₂- C₄alkynyl, -S(O)_pC₁-C₄alkyl, -S(O)_pC₁-C₄haloalkyl, -C(O)OC₁-C₄alkyl and - C(O)NR⁴R⁵; R⁴ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R⁵ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R⁶ is hydrogen or C1-C2 alkyl; R⁷ is selected from the group consisting of halogen, C1-C4 alkyl, C3- C4cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4alkoxyC1- C3alkyl-, C1-C4alkoxyC1-C3alkoxy-, -CN, C2-C4alkenyl, C2-C4alkynyl, -S(O)pC1- C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1-C4alkyl, -C(O)NR⁹R¹⁰, -NR¹¹COR¹² and -S(O)pNR¹³R¹⁴; R⁸ is hydrogen or C1-C2 alkyl; R⁹ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R¹⁰ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C₄alkyl and C₁-C₄haloalkyl; R¹¹ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C₄alkyl and C₁-C₄haloalkyl; R¹² is selected from the group consisting of hydrogen, C₃-C₄cycloalkyl, C₁- C₄alkyl and C₁-C₄haloalkyl; R¹³ is selected from the group consisting of hydrogen, C₃-C₄cycloalkyl, C₁- C₄alkyl and C₁-C₄haloalkyl; R¹⁴ is selected from the group consisting of hydrogen, C₃-C₄cycloalkyl, C₁- C₄alkyl and C₁-C₄haloalkyl; and p = 0, 1 or 2. C1-C4alkyl- and C1-C6alkyl- includes, 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-C2alkyl is methyl (Me, CH3) or ethyl (Et, C2H5). C2-C4alkenyl- includes, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl). C2-C4alkynyl- refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C2-C4alkynyl 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 same correspondingly applies to halogen in the context of other definitions, such as haloalkyl. C1-C4haloalkyl- 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 and heptafluoro-n-propyl. C1-C2haloalkyl is, 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. C₁-C₆alkoxy includes methoxy and ethoxy. C₁-C₄haloalkoxy- includes, 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. C₁-C₄alkoxyC₁-C₃alkyl- includes, for example, methoxymethyl-. C₁-C₄alkoxyC₁-C₃alkoxy- includes, for example, methoxyethoxy-. C1-C4alkoxyC1-C3alkoxyC1-C3alkyl- includes, for example, meth- oxyethoxymethyl-. C3-C6cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl. C1-C4alkyl-S- (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. C1-C4alkyl-S(O)- (alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl. C1-C4alkyl-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 of Formula (I) wherein U is selected from the group consisting of:

wherein R⁷ is hydrogen or as defined in claim 1; R^7a is selected from the group consisting of hydrogen, C₁-C₄alkyl, C₁- C₄haloalkyl and C₃-C₄cycloalkyl; and n = 0, 1 or 2. In a more preferred embodiment of the present invention, U is selected from the group consisting of U20, U22, U23, U25, U26, U31 and U38. In a more preferred embodiment of the present 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 present invention, Q is preferably selected from the group consisting of Q 1 to Q-11:

wherein R¹ is as defined above (preferably C1-C2haloalkyl 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, there is provided a compound of Formula (I) selected from the group consisting of Formula (Iaa), (Iab), (Iac), Iad), (Iae) and (Iaf): In a more preferred embodiment of the present invention, there is provided a compound of Formula (Iaa), (Iab), (Iac), (Iad), (Iae) or (Iaf) wherein m is 1 or 2 (preferably 2) and R¹ is independently halogen or C1-C2haloalkyl (preferably halogen, more preferably fluoro and / or chloro). In another embodiment of the present invention, there is provided a compound of Formula (I), (Iaa), (Iab), (Iac), (Iad), (Iae) or (Iaf) wherein R² is C₁- C₄haloalkyl (preferably CF₃, CF₂H or CF₂Cl). In another embodiment of the present invention, there is provided a compound of Formula (I), (Iaa), (Iab), (Iac), (Iad), (Iae) or (Iaf) wherein R³ is hydrogen or halogen (preferably hydrogen). Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically, one of the enantiomers has enhanced biological activity compared to the other possibilities. The present invention also provides agronomically acceptable salts of compounds of Formula (I). Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred. The compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surface- active agents (SAA). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. The composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents. The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of Formula I and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. The compositions can be chosen from a number of formulation types. These include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP) and a soluble granule (SG). The formulation type chosen in any instance will depend upon 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 a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is 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 of 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 the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG). Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre- formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent). Dispersible Concentrates (DC) may 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 surface-active agent (for example to improve water dilution or prevent crystallisation in a spray tank). Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of 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 ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), 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), dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70^oC) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant 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 chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water. Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SAA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water- soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming 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). SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, 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 at which the particles settle. Alternatively, a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product. Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane). A compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps. Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment. A compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound. The composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I). Such additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I). Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type. Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts. Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates, lignosulphonates and phosphates / sulphates of tristyrylphenols. Suitable SAAs of the amphoteric type include betaines, propionates and glycinates. Suitable SAAs of the non-ionic 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 said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols. Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite). The compounds of present invention can also be used in 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), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac- sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam- methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis- aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epyrifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P- ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), fluchloraminopyr (including fluchloramino-tefuryl), flufenacet, flufenoximacil, flumetsulam, flumioxazin, fluometuron,fomesafen flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), flusulfinam, fomesafen, foramsulfuron, glufosinate (including L-glufosinate and the ammonium salts of both), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, icafolin (including icafolin-methyl), imazamox (including R- imazamox), imazapic, imazapyr, imazethapyr, indaziflam, indolauxipyr (including indolauxipyr-cyanomethyl), iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, iptriazopyrid, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryne, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyraquinate, pyrasulfotole, pyridate, pyriftalid, pyriflubenzoxim, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S- metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron- sodium), trifludimoxazin, trifluralin, triflusulfuron, tripyrasulfone, 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, (1RS,5SR)-3-[2-methoxy-4-(prop-1- yn-1-yl)phenyl]-4-oxobicyclo[3.2.1]oct-2-en-2-yl methyl carbonate, ethyl-2-[[3-[[3- chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2- pyridyl]oxy]acetate, methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate, 6-chloro-4-(2,7- dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2-fluorophenyl)methyl 6- amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate, 6- amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid, and methyl 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)- pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-cyclopent[d]isoxazole- 6a-carboxylate. The mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012. The compound 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. The mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1: 100 to 1000:1. The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of Formula (I) with the mixing partner). 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 benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil. Particularly preferred are mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen. The safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16^th Edition (BCPC), 2012. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048. Preferably the mixing ratio of compound of Formula (I) to safener is from 100:1 to 1:10, especially from 20:1 to 1:1. The present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I). Moreover, the present invention may further provide a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention. ‘Controlling’ means killing, reducing or retarding growth or preventing or reducing germination. It is noted that the compounds of the present invention show a much-improved selectivity compared to know, structurally similar compounds. Generally the plants to be controlled are unwanted plants (weeds). ‘Locus’ means the area in which the plants are growing or will grow. The application may be applied to the locus pre-emergence and/or postemergence of the crop plant. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I). Preferred crop plants include maize, wheat, barley soybean and rice. The rates of application of compounds of Formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post- emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) 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 compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2500 g/ha, especially from 25 to 1000 g/ha, more especially from 25 to 250 g/ha. The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used. 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-, GS-, EPSPS-, PPO-, HPPD-, -PDS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. The compounds of the present invention can also be used in conjunction with crops that are tolerant to SDPS-inhibiting herbicides, such as those taught in WO2020/236790. Crop plants are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut ^ (maize), Yield Gard ^ (maize), NuCOTIN33B ^ (cotton), Bollgard ^ (cotton), NewLeaf ^ (potatoes), NatureGard ^ and Protexcta ^. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate. Crop plants are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour). The compositions can be used to control unwanted plants (collectively, ‘weeds’). The weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. In a further aspect of the present invention there is provided the use of a compound of Formula (I) as defined herein as a herbicide. Processes for preparation of compounds of Formula (I) Processes for preparation of compounds, e.g. a compound of Formula (I) (which optionally can be an agrochemically acceptable salt thereof), are now described, and form further aspects of the present invention. As shown in Scheme 1, a compound of Formula (I) can be prepared via decarboxylation of compounds of Formula (2) by heating at 110^oC under acidic conditions in a suitable solvent such as ethanol. Compounds of Formula (2) are prepared using a nucleophilic aromatic substitution reaction of compounds of Formula (4) (where LG is represents a suitable leaving group such as halogen or SO2Me) by heating in a suitable solvent, such as sulfolane in the presence of a base such as sodium t-butoxide with a compound of Formula (3). The reaction is typically conducted at 40^oC. Conditions for the formation of pyrazole compounds of Formula (3) are documented in the literature via the condensation of diketones with an arylhydrazines (as documented in Tetrahedron (2013), 69(16), 3459-3464).

Alternatively compounds of formula I can be prepared by following scheme 2. Scheme 2:

In scheme 2 compounds of formula I can be prepared by reacting compounds of formula VI, with reagents of the formula V, wherein LG1 is a halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate), in the presence of a base, such as sodium hydride or an alkali earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N- dimethylformamide DMF, N,N-dimethylacetamide, sulfolane or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art. Alternatively compounds of formula I can be prepared by reacting compounds of formula VI with compounds of formula V, wherein LG1 is a halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate) in the presence of a metal catalyst such as copper based catalyst for e.g CuI or tetrakis(acetonitrile)copper(I) tetrafluoroborate optionally in the presence of a ligand such as trans-1,2-bis(methylamino)cyclohexane or its salt (for e.g. methanesulfonate salt) or 8-hydroxyquinoline amongst similar other ligands. The reaction can be carried out in the presence of a base such as potassium carbonate, cesium carbonate, triethylamine or pyridine and similar others and in the presence of a solvent such as acetonitrile, 1,4-dioxane or pyridine and optionally under microwave irradiation at temperature in the range of room temperature and 200 ^oC. Alternatively compounds of formula I can be prepared by reacting compounds of formula VI and compounds of formula Va under Chan Lam cross-coupling reaction conditions. Such reactions are carried out in the presence of copper-based catalyst such as copper acetate or copper iodide or copper bromide and similar others and in the presence of a base such as pyridine or 2,6-lutidine and similar others. The reaction can be carried out in the presence of a solvent such as dichloromethane, toluene, acetonitrile and in the presence of air or oxygen and at temperature in the range of room temperature and 200 ^oC. Compounds of formula VI can be prepared by protecting group deprotection reaction from compounds of formula VII, wherein PG is an amino-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p- methoxybenzyl (PMB) amongst others amino protecting groups. Such reactions are well known to those skilled in the art and can be carried out for example under base catalyzed such as using sodium hydroxide for the deprotection of acetyl group or under acid catalyzed such as hydrochloric acid or 2,2,2-trifluoroacetic acid for the deprotection of trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl or p- methoxybenzyl (PMB) group. Compounds of formula VII can be prepared from compounds of formula VIII, wherein R¹² is C1-C4alkyl or phenyl via decarboxylation reaction. The reaction can be carried out using base such as alkaline earth metal hydroxide or alkali metal hydroxide like sodium hydroxide or in the presence of acid such as aqueous hydrochloric acid, sulfuric acid amongst others. The reaction is generally carried out in the presence of a solvent such as water, ethanol, methanol, tetrahydrofuran or dioxane or combination of two or more solvent and at temperature in the range of room temperature to boiling point of solvent. Compounds of formula VIII, wherein R¹² is C1-C4alkyl or phenyl can be prepared by reacting compounds of formula X, with reagents of the formula IX, wherein LG2 is a halogen, (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate), in the presence of a base, such as sodium tert-butoxide, sodium hydride or an alkali earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate such as potassium phosphate optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, N,N- dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile and the like, at temperatures between 0 and 200°C, by procedures well known to those skilled in the art. Compounds of formula X can be prepared by the condensation reaction of compounds of formula XII with compounds of formula XI (or its hydrochloric acid salt or trifluoroacetic acid salt), wherein PG is an amino-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p- methoxybenzyl (PMB) amongst others amino protecting groups. Such reactions are well known in the literature and can be carried out optionally in the presence of an acid catalyst such as acetic acid. Compounds of formula XII can be prepared by reacting compounds of formula XIV, wherein R¹¹ is C1-C4alkyl or phenyl with compounds of formula XIII in the presence of a base. Such reactions are known by the name of Claisen condensation reaction and well known to those skilled in the art. Reaction can be carried out using base such as lithium diisopropylamide, lithium tetramethylpiperidide, sodium ethoxide, sodium hydride amongst other bases in the presence of solvent such as tetrahydrofuran, ethanol, methanol and at temperature in the range of -80 ^oC to boiling point of solvent. Alternatively compounds of formula I can be prepared by following scheme 3. Scheme 3: Q-LG_{3 XX}

In Scheme 3 compounds of formula-I are prepared from compounds of formula XV via reduction of alcohol. Reduction of such alcohols are well described in literature and can be carried out using reducing agent such as LiAlH₄, DIBAL-H, or using triphenyl phosphine in the presence of iodine and imidazole or using triethyl silane in the presence of trifluoroacetic acid. Compounds of formula XV can be prepared by reacting compounds of formula XVI, wherein X¹ is a halogen preferably bromine or iodine with an organometallic reagent such as BuLi or isopropylmagnesium chloride/LiCl complex amongst other metallating reagents to form an intermediate XVIa, wherein M(Ln)^p is a corresponding metal from the organometallic reagent such as lithium or magnesium and (Ln)^p is its optionally substituted group like chloro and then subsequently reacting with compounds of formula XVII. X^VIa Compounds of formula XVII can be prepared by reacting compounds of formula XVIII with strong bases such as butyl lithium, lithium diisopropylamide and then reacting with DMF. The reaction is generally carried out in the presence of a solvent such as tetrahydrofuran, toluene, heptane and at temperature between -80 ^oC to boiling point of solvent. Such reactions are well known and described in literature. Compounds of formula XVIII can be prepared by reacting compounds of formula XIX and compounds of formula XX, wherein LG3 is a leaving group like halogen (or a pseudo- halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate) in the presence of a base, such as sodium tert-butoxide, sodium hydride or an alkali earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate such as potassium phosphate optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, N,N- dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile and the like, at temperatures between 0 ^oC and boiling point of solvent, by procedures well known to those skilled in the art. Such reactions are known in literature by name of SNAr reaction. Alternatively compounds of formula XVIII may be prepared by Chan-Lam coupling, which involves for example, reacting compounds of formula XIX, with compounds of formula XXI, 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-C₄alkyl group or the two groups ORb₁ can form together with the boron atom a five membered ring, as for example a pinacol boronic ester. The reaction may be catalyzed by a copper catalyst, for example Cu(OAc)₂, CuI, CuBr₂, CuCl amongst other copper based catalyst in presence of a base, like pyridine, sodium carbonate, tripotassium phosphate or cesium fluoride, in a solvent or a solvent mixture, like, for example dioxane, dichloromethane, acetonitrile, N,N-dimethyl-formamide, a mixture of 1,2- dimethoxyethane and water or of dioxane/water, or of toluene/water, under inert atmosphere or under oxygen atmosphere or under air. The reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation. Such Chan- Lam coupling reactions are well known to those skilled in the art. Formula I-1 is a compound of formula I wherein U is U23. Formula I-2 is a compound of formula I wherein U is U22. Formula I-3 is a compound of formula I wherein U is U26. Formula I-4 is a compound of formula I wherein U is U25. Compounds of formula I-1, formula I-2, formula I-3 and formula I-4 can be prepared following scheme 4.

Scheme 4

Compounds of formula I-3 and compounds of formula I-4 can be prepared by the alkylation reaction which involves reacting compounds of formula I-5 with compounds of formula XXXI, wherein R^7a is as defined in formula I above and LGx is a leaving group like halogen (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate) in the presence of a base, such as sodium tert- butoxide, sodium hydride or an alkali earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate such as potassium phosphate optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile and the like, at temperatures between 0 ^oC and boiling point of solvent. Alternatively compounds of formula I-3 and compounds of formula I-4 can be prepared by reacting compounds of formula XXIX and compounds of formula XXVIII optionally in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, acetic acid and in the presence of a solvent such as acetic acid, dichloromethane, tetrahydrofuran, and similar others. Compounds of formula I-5 can similarly be prepared from compounds of formula XXIX following procedure analogous to as described for the synthesis of compounds of formula I-3 and formula I-4 from compounds of formula XXIX (scheme 4). Compounds of formula XXIX, can be prepared by reacting compounds of formula XXVII with N,N-dimethylformamide dimethyl acetal. Such reactions are well known in the literature and for example described in J. Heterocyclic Chem., 2009, 46, 801. Compounds of formula XXVII can be prepared from compounds of formula XXII via amidation reaction which involves reacting compounds of formula XXVII with ammonia or surrogates of ammonia such as ammonium hydroxide in the presence of a solvent such as methanol, ethanol, tetrahydrofuran, acetonitrile, and similar others and at temperatures in the range of 0 ^oC to the boiling point of solvent. Compounds of formula XXII can be prepared from compounds of formula XIII and compounds of formula XIV following procedure as described in scheme 2 for the synthesis of compounds of formula X from compounds of formula XIV and XIII. Compounds of formula I-1 can be prepared by reacting compounds of formula XXVI with Lawesson’s reagent (scheme 4). Such reactions are well known in the literature and for example described in Journal of Organic Chemistry, 2001, 66, 23, 7925- 7929. Compounds of formula I-2 can be prepared from compounds of formula XXVI via intramolecular cyclization reaction. Such reactions are generally carried out in the presence of an acid catalyst such as hydrochloric acid, trifluoroacetic acid amongst similar others or in the presence of phosphorus oxychloride and are well known in literature for example as described in Molecules, 2022, 27, 22, 7687. Compounds of formula XXVI can be prepared by reaction of compounds of formula XXIV with compounds of formula XXV in the presence of an amide coupling reagent such as phosphorus oxychloride, 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide and similar others . Alternatively compounds of formula XXVI can be prepared by reaction of compounds of formula XXIV with either compounds of formula XXVa or compounds of formula XXVaa. Compounds of formula XXIV can be prepared by the reaction of compounds of formula XXII with hydrazine XXX or its hydrate form. The reaction can be carried out in the presence of a solvent such as methanol, ethanol, tetrahydrofuran amongst others. Alternatively compounds of formula I wherein U is a N-linked 5-membered heteroaryl optionally substituted by one or more independent R⁷ can be prepared following scheme 5. Scheme 5

In scheme 5 compounds of Formula I can be prepared by the substitution reaction of compounds of formula XXXIV with compounds of formula XXXV, wherein U is a N- linked 5-membered heteroaryl optionally substituted by one or more independent R⁷. Compounds of formula XXXIV, wherein X¹ is a halogen such as chloro or bromo can be prepared from compounds of formula XXXIII via halogenation reaction using halogenating reagents such as thionyl chloride or using carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine. Compounds of formula XXXIII can be prepared either from compounds of formula XXXII, wherein R¹³ is C₁- C₄alkyl or phenyl or from compounds of formula XVII (prepared as in scheme 3) via reduction using reducing agents such as sodium borohydride, lithium aluminium hydride or diisobutylaluminium hydride amongst similar others. Scheme 6 U-X² XXXVI sp³-sp² cross-coupling reaction

_{Formula I} Compounds of formula I, wherein U is a C-linked 5-membered heteroaryl optionally substituted by one or more independent R⁷ can be prepared by sp³-sp² cross coupling reaction of compounds of formula XXXIV, wherein X¹ is a halogen for example bromo, chloro or iodo with compounds of formula XXXVI, wherein X² is a halogen for example bromo, chloro or iodo (scheme 6). Such reactions have been reported in literature and for example described in Angew. Chem. Int. Ed., 2022, 61, e202116775 and Chem. Commun., 2017,53, 9364-9367. One such process involves palladium catalyzed desulfinative cross-coupling reaction as described in Angew. Chem. Int. Ed., 2022, 61, e202116775. An in-situ sulfinate can be prepared in this process by the reaction of compounds of formula XXXIV with masked sulfinating reagent such as Sodium 1-methyl 3-sulfinopropanoate and reacted with compounds of formula XXXVI, wherein X² is a halogen for example bromo, chloro or iodo in the presence of a base such as potassium carbonate amongst similar others and in the presence of a ligand such as phosphine based ligands 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 similar others and optionally under microwave irradiation at temperature in the range of room temperature and 200 ^oC.

The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to 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)

Step 1: Preparation of tert-butyl N-(tert-butoxycarbonylamino)-N-(6-chloro-5- fluoro-3-pyridyl)-carbamate (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 bottomed flask was placed under an atmosphere of nitrogen, cooled over ice and treated with 1.3 M isopropylmagnesium chloride lithium chloride complex solution (6.0 mL, 7.8 mmol). The mixture was allowed to stir for 15 minutes at 0 ^oC before being treated dropwise with a solution of di-tert-butyl azodicarboxylate (1.83 g, 7.95 mmol) in tetrahydrofuran (4 mL) in a manner such that the internal temperature did not exceed 15 ^oC. The mixture was allowed to stir for 30 minutes. The reaction mixture was quenched with water (100 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organics were washed with brine (50 mL) and concentrated in vacuo. The crude was purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane as eluent yielding tert- butyl N-(tert-butoxycarbonylamino)-N-(6-chloro-5-fluoro-3-pyridyl)-carbamate I1 (1.80 g, 66%) as an oil that crystallized on standing to 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 methyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (I2)

A solution of 2 M lithium diisopropylamide in tetrahydrofuran (13 mL, 26 mmol) in tetrahydrofuran (13 mL) in a 100 mL round bottomed flask was placed under an atmosphere of nitrogen, cooled over ice, and treated dropwise with methyl acetoacetate (0.70 mL, 6.5 mmol) in a manner such that the internal temperature did not exceed 15 ^oC. The resulting pale-yellow mixture was allowed to stir for 30 minutes at 0 ^oC. The mixture was then cooled to -78 ^oC and treated dropwise with ethyl chlorodifluoroacetate (1.1 mL, 8.7 mmol). The resulting reaction mixture was allowed to stir for an additional 3.5 hours at this temperature. This was warmed up to room temperature and stirred for an additional 30 minutes. Upon completion, the mixture was quenched with 1 M hydrochloric acid (80 mL) and extracted with ethyl acetate (2 x 60 mL). The combined organics were passed through a hydrophobic filter and concentrated in vacuo. The resulting oil (containing methyl 6-chloro-6,6- difluoro-3,5-dioxo-hexanoate I2) was used as is in the next step assuming quantitative conversion. Step 3: Preparation of methyl 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro- 3-pyridyl)pyrazol-3-yl]acetate (I3)

A solution of tert-butyl N-(tert-butoxycarbonylamino)-N-(6-chloro-5-fluoro-3- pyridyl)carbamate I1 (1.79 g, 4.71 mmol) in trifluoroacetic acid (3.6 mL) in a 100 mL round bottomed flask was stirred at room temperature for 1 hour. This 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 was allowed to stir at room temperature overnight. The reaction mixture was concentrated and purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane as eluent to afford a yellow oil (~1.55 g) containing an isomeric mixture of the products. This residue was further purified by reverse-phase column chromatography using 40- 100% acetonitrile in water with 0.1% formic acid as eluent to afford a yellow oil containing methyl 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3-pyridyl)pyrazol- 3-yl]acetate I3 (0.89 g, 45%) as major isomer.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- pyridyl)pyrazol-3-yl]acetamide (I4)

A solution of methyl 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3- pyridyl)pyrazol-3-yl]acetate I3 (624 mg, 1.49 mmol) in methanol (2.5 mL) was treated with 7 M ammonia in methanol (2.5 mL, 18 mmol) and was allowed to stir at room temperature for 24 hours. The reaction mixture was concentrated in vacuo and the residues was purified by reverse-phase column chromatography using 30-100% acetonitrile in water with 0.1% formic acid as eluent to afford 2-[5- [chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3-pyridyl)pyrazol-3-yl]acetamide I4 (442 mg, 83%) as a white solid.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) A solution of 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3-pyridyl)pyrazol-3- yl]acetamide I4 (337 mg, 0.94 mmol) in acetonitrile (4.7 mL) in a 100 mL round bottomed flask was placed under an atmosphere of nitrogen and treated with N,N- dimethylformamide dimethyl acetal (140 μL, 1.05 mmol). The resulting mixture was warmed to 70 ^oC and was 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 100 mL round bottomed flask and treated with hydrazine hydrate (64 wt% in water) (150 μL, 1.973 mmol) under nitrogen atmosphere. The resulting mixture was allowed to stir at room temperature for 30 minutes. The reaction mixture was diluted with ethyl acetate (30 mL) and was washed with aqueous ammonium chloride (2 x 20 mL), 10% aqueous ferrous sulphate (20 mL) and water (20 mL). The organic phase was concentrated in vacuo. The crude obtained was purified by silica gel column chromatography using 0-100% ethyl acetate in cyclohexane to afford 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)

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 bottomed flask was placed under an atmosphere of nitrogen and treated with iodomethane (70 μL, 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-butylmethyl ether (2 x 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 afford a mixture of isomers. This mixture was further purified by reverse-phase column chromatography using 40-100% acetonitrile in water with 0.1% formic acid to afford 2-chloro-5-[3- [chloro(difluoro)methyl]-5-[(1-methyl-1,2,4-triazol-3-yl)methyl]pyrazol-1-yl]-3-fluoro- pyridine 1.001.¹H 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)

Step 1: Preparation of ethyl 2-(3,4-difluorophenyl)-5-(trifluoromethyl)pyrazole-3- carboxylate (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 bottomed 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 afford ethyl 2-(3,4-difluorophenyl)-5- (trifluoromethyl)pyrazole-3-carboxylate I6 (2.360 g, 92%) as a white solid. 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)

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 bottomed flask was placed under an atmosphere of nitrogen, cooled over ice and treated with 2.3 M lithium aluminium hydride in 2-methyltetrahydrofuran (2.0 mL). The resulting reaction mixture was allowed to stir at 0 ^oC for 15 minutes. The reaction mixture was quenched with water (175 μL) and was allowed to stir for 10 minutes. 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-butylmethyl ether (150 mL), dried over anhydrous magnesium sulphate, 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 afford [2-(3,4- difluorophenyl)-5-(trifluoromethyl)pyrazol-3-yl]methanol I7 (991 mg, 93%) as a white solid.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)

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 bottomed flask was placed under an atmosphere of nitrogen 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 yielding 5- (chloromethyl)-1-(3,4-difluorophenyl)-3-(trifluoromethyl)pyrazole I8 (876 mg, 83%) as a colorless oil. 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)

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 stirrer bar. The vial was sealed with a microwave vial cap, evacuated and back-filled with nitrogen gas five times. 3-Bromo-1-methyl- 1h-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 then added, and the reaction was heated in the microwave to 120 °C 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 concentrated in vacuo. The crude residue was loaded onto celite and subjected to silica gel column chromatography using 0-15% ethyl acetate in cyclohexane. Upon concentration of the fractions, 1-(3,4-difluorophenyl)-5-[(1-methylpyrazol-3-yl)methyl]- 3-(trifluoromethyl)pyrazole 1.002 was obtained as a yellow oil. 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- pyridyl)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- pyridyl)pyrazol-3-yl]acetohydrazide (I9)

A solution of methyl 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3- pyridyl)pyrazol-3-yl]acetate I3 (251 mg, 0.60 mmol) in methanol (3.0 mL) in a 25 mL round bottomed flask was placed under an atmosphere of nitrogen, cooled over ice and treated with hydrazine hydrate (64 wt% in water) (55 μL, 0.7235 mmol). The resulting reaction mixture was allowed to stir for 2 hours at room temperature. The reaction mixture was treated with additional hydrazine hydrate (64 wt% in water) (55 μL, 0.72 mmol) and was allowed to stir for additional 5 hours. The reaction mixture was diluted with ethyl acetate (30 mL) and was washed with dilute aqueous ammonium chloride (2 x 25 mL), water (20 mL) and 10% aqueous ferrous sulphate (30 mL). The organic phase was concentrated in vacuo. The residues were loaded onto celite and subjected to reverse-phase column chromatography using 30-100% acetonitrile in water with 0.1% formic acid as eluent. Upon concentration of the fractions, 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3-pyridyl)pyrazol-3- yl]acetohydrazide I9 (227 mg, 96%) was obtained as a white waxy solid. 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-pyridyl)pyrazol-3-yl]acetohydrazide (I10)

A solution of 2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3-pyridyl)pyrazol-3- yl]acetohydrazide I9 (227 mg, 0.57 mmol) in acetic acid (1.2 mL) in a 100 mL round bottomed flask was treated with acetic anhydride (110 μL, 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 (~10 mL). The mixture was then concentrated in vacuo, and the residues were taken up in cyclohexane and concentrated three time, yielding N'-acetyl-2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5- fluoro-3-pyridyl)pyrazol-3-yl]acetohydrazide I10 (232 mg, 91%) as a foam-like white solid. 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- pyridyl)pyrazol-3-yl]methyl]-5-methyl-1,3,4-thiadiazole (1.003)

A solution of N'-acetyl-2-[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3- pyridyl)pyrazol-3-yl]acetohydrazide I10 (174 mg, 0.39 mmol) in tetrahydrofuran (2.0 mL) in a 50 mL round bottomed flask was placed under an atmosphere of nitrogen and treated with Lawesson's reagent (371 mg, 0.89 mmol). The reaction mixture was warmed to 50 ^oC and was allowed to stir for 1.5 hours. The reaction mixture was allowed to cool to room temperature before being concentrated directly onto celite and subjected to silica gel column chromatography using 0-10% ethyl acetate in cyclohexane as eluent. The residue obtained were further purified by reverse-phase column chromatography using 40-100% acetonitrile in water with 0.1% formic acid to afford 2-[[5-[chloro(difluoro)methyl]-2-(6-chloro-5-fluoro-3-pyridyl)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)

Step 1: Preparation of 1-(4-chlorophenyl)-3-(trifluoromethyl)pyrazole (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 μL, 1.57 mmol). The vial was evacuated and back-filled with nitrogen three times before being heated under microwave irradiation to 150 ^oC for 1 hour. The reaction mixture was diluted with water (30 mL) and extracted with ethyl acetate (2 x 25 mL). The combined organics were concentrated in vacuo. The residues were 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, yielding 1-(4-chlorophenyl)-3-(trifluoromethyl)pyrazole I11 (1.1 g, 82%) as a light brown crystalline solid. 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)

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 bottomed flask was placed under an atmosphere of nitrogen, cooled to -78 ^oC and treated dropwise with n-butyllithium (2.5 M in hexanes) (2.6 mL, 6.5 mmol). The mixture was allowed to stir for 1 hour before being treated with N,N-dimethylformamide (0.7 mL, 9 mmol). The mixture was then allowed to stir for a further 30 minutes at room temperature. The reaction mixture was quenched with 1M hydrochloric acid (5 mL), diluted with water (20 mL) and extracted with ethyl acetate (2 x 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 afford 2-(4- chlorophenyl)-5-(trifluoromethyl)pyrazole-3-carbaldehyde I12 (852 mg, 69%) as a yellow oil. 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)

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 bottomed flask was treated with sodium borohydride (73 mg, 1.85 mmol). The resulting reaction mixture was allowed to stir at room temperature for overnight. The reaction mixture was quenched with dropwise addition of 2 M hydrochloric acid until effervescence ceased. The mixture was diluted with water (15 mL) and extracted with ethyl acetate (2 x 15 mL). The combined organics were passed through a hydrophobic filter and concentrated in vacuo, yielding of [2-(4-chlorophenyl)-5-(trifluoromethyl)pyrazol-3-yl]methanol I13 (438 mg, 100%) as an off-white solid.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 50 mL round bottomed flask was placed under an atmosphere of 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 X 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 afford a mixture of 5-(bromomethyl)-1- (4-chlorophenyl)-3-(trifluoromethyl)pyrazole I14 and 5-(chloromethyl)-1-(4- chlorophenyl)-3-(trifluoromethyl)pyrazole I15 in 3:1 ratio respectively (244 mg, 37%). ¹H NMR (400 MHz, CDCl3) of I14 δ = 7.57 - 7.51 (m, 4H), 6.81 - 6.77 (m, 1H), 4.41 (s, 2H). Step 5: Preparation of 1-(4-chlorophenyl)-5-[(4-chloropyrazol-1-yl)methyl]-3- (trifluoromethyl)pyrazole (1.004)

A 3:1 mixture of 5-(bromomethyl)-1-(4-chlorophenyl)-3-(trifluoromethyl)pyrazole I14 and 5-(chloromethyl)-1-(4-chlorophenyl)-3-(trifluoromethyl)pyrazole I15 (30 mg, 0.061 mmol) obtained as above in step 4 (example 5), 4-chloro-1h-pyrazole (33 mg, 0.32 mmol) and potassium carbonate (40 mg, 0.28 mmol) was treated with acetonitrile (0.5 mL). The resulting mixture was allowed to stir for 20 h at room temperature. The reaction mixture was concentrated directly onto celite and subjected to silica gel column chromatography using 0-20% ethyl acetate in cyclohexane as eluent. Upon concentration of the fractions, 1-(4-chlorophenyl)-5-[(4-chloropyrazol-1-yl)methyl]-3- (trifluoromethyl)pyrazole 1.004 was obtained as colorless oil. 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 1 COMPOUND STRUCTURE HNMR (400MHz, CDCl3 unless otherwise stated) 1H NMR (400 MHz, chloroform) δ = 1.001^ 8.49 (d, 1H), 7.92 (dd, 1H), 7.82 (s, 1H), 6.56 (s, 1H), 4.19 (s, 2H), 3.85 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 7.39 - 7.33 (m, 1H), 7.29 (d, 1H), 1.002 7.27 - 7.24 (m, 2H), 6.49 (s, 1H), 5.99 (d, 1H), 3.99 (s, 2H), 3.86 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 1.003 8.45 (d, 1H), 7.84 (dd, 1H), 6.66 (s, 1H), 4.49 (s, 2H), 2.78 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 1.004 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) 1H NMR (400 MHz, chloroform) δ = 1.005 8.57 (d, 1H), 7.97 - 7.93 (m, 2H), 6.65 (s, 1H), 4.14 (s, 2H), 3.88 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 1.006 8.54 (d, 1H), 8.22 (s, 1H), 7.93 (dd, 1H), 6.67 (s, 1H), 4.23 (s, 2H) 1H NMR (400 MHz, chloroform) δ = 1.007 8.45 (d, 1H), 7.83 (dd, 1H), 6.74 (s, 1H), 4.27 (s, 2H), 2.54 (s, 3H) ¹ COMPOUND STRUCTURE HNMR (400MHz, CDCl3 unless otherwise stated) 1H NMR (400 MHz, chloroform) δ = 8.03 (s, 2H), 7.37 - 7.29 (m, 1H), 1.008 7.26 - 7.20 (m, 1H), 7.04 - 6.97 (m, 1H), 6.70 (t, 1H), 6.64 (s, 1H), 5.25 (s, 2H) 1H NMR (400 MHz, chloroform) δ = 8.01 (s, 1H), 7.97 (s, 1H), 7.41 - 7.34 1.009 (m, 1H), 7.34 - 7.28 (m, 1H), 7.24 - 7.18 (m, 1H), 6.69 (t, 1H), 6.65 (s, 1H), 5.39 (s, 2H) 1H NMR (400 MHz, chloroform) δ = 1.010 7.41 - 7.20 (m, 3H), 6.69 (t, 1H), 6.58 (s, 1H), 4.45 (s, 2H), 2.76 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 1.011 7.42 - 7.29 (m, 2H), 7.29 - 7.22 (m, 1H), 6.70 (t, 1H), 6.65 (s, 1H), 4.23 (s, 2H), 2.53 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 7.34 (s, 1H), 7.33 - 7.26 (m, 2H), 1.012 7.22 - 7.16 (m, 1H), 7.08 (s, 1H), 6.60 (s, 1H), 5.25 (s, 2H), 2.06 (s, 3H) 1H NMR (400 MHz, chloroform) δ = 1.013 7.46 (s, 1H), 7.37 - 7.27 (m, 3H), 7.21 - 7.16 (m, 1H), 6.64 (s, 1H), 5.27 (s, 2H) 1H NMR (400 MHz, chloroform) δ = 1.014 7.53 - 7.43 (m, 5H), 6.54 (s, 1H), 6.24 (d, 1H), 5.32 (s, 2H) ¹ COMPOUND STRUCTURE HNMR (400MHz, CDCl3 unless otherwise stated) 1H NMR (400 MHz, chloroform) δ = 1.015 7.52 - 7.47 (m, 2H), 7.37 - 7.32 (m, 2H), 7.20 (d, 1H), 6.64 (s, 1H), 6.20 (d, 1H), 5.25 (s, 2H) 1H NMR (400 MHz, chloroform) δ = 7.74 (d, 1H), 7.51 (d, 1H), 7.35 - 1.016 7.27 (m, 2H), 7.15 - 7.10 (m, 1H), 6.70 (t, 1H), 6.67 (s, 1H), 5.61 (s, 2H) 1H NMR (400 MHz, chloroform) δ = 7.64 (s, 2H), 7.47 - 7.40 (m, 1H), 1.017 7.34 - 7.28 (m, 2H), 6.84 - 6.54 (m, 2H), 5.63 (s, 2H). 1H NMR (500MHz, DMSO-d6) δ = 7.79 - 7.73 (m, 1H), 7.68 - 7.58 (m, 1.018 1H), 7.48 - 7.42 (m, 2H), 7.25 (s, 1H), 7.16 - 6.91 (m, 1H), 6.54 (s, 1H), 5.43 (s, 2H), 1.96 (s, 3H) 1H NMR (500MHz, DMSO-d6) δ = 7.92 - 7.83 (m, 1H), 7.75 - 7.64 (m, 1H), 7.51 (br d, 1H), 7.49 (d, 1H), 1.019 7.43 (d, 1H), 7.07 (t, 1H), 6.68 (s, 1H), 5.72 (s, 2H), 2.23 - 2.17 (m, 1H), 1.12 - 1.06 (m, 4H) 1H NMR (500MHz, DMSO-d6) δ = 8.33 (s, 1H), 7.90 (s, 1H), 7.81 - 7.74 1.020 (m, 1H), 7.67 - 7.59 (m, 1H), 7.45 - 7.38 (m, 1H), 7.06 (t, 1H), 6.72 (s, 1H), 5.61 (s, 2H), 3.16 (s, 3H) ¹ COMPOUND STRUCTURE HNMR (400MHz, CDCl3 unless otherwise stated) 1H NMR (500MHz, DMSO-d6) δ = 7.76 - 7.70 (m, 1H), 7.66 - 7.57 (m, 1H), 7.45 - 7.41 (m, 1H), 7.39 (s, 1H), 1.021 7.23 (s, 1H), 7.04 (t, 1H), 6.58 (s, 1H), 5.42 (s, 2H), 1.66 - 1.59 (m, 1H), 0.80 - 0.73 (m, 2H), 0.43 - 0.36 (m, 2H) 1H NMR (500MHz, DMSO-d6) δ = 8.16 (s, 1H), 7.83 - 7.77 (m, 1H), 7.69 1.022 - 7.62 (m, 1H), 7.53 (s, 1H), 7.49 - 7.39 (m, 1H), 7.06 (t, 1H), 6.61 (s, 1H), 5.50 (s, 2H), 4.69 (s, 1H) 1H NMR (500MHz, DMSO-d6) δ = 7.78 (s, 1H), 7.79 - 7.74 (m, 1H), 7.72 1.023 - 7.61 (m, 1H), 7.51 (s, 1H), 7.45 - 7.38 (m, 1H), 7.06 (t, 1H), 6.59 (s, 1H), 5.44 (s, 2H), 4.12 (s, 1H) 1H NMR (500MHz, DMSO-d6) δ = 7.89 (s, 1H), 7.87 - 7.78 (m, 1H), 7.72 1.024 - 7.61 (m, 1H), 7.51 - 7.41 (m, 1H), 7.14 (s, 1H), 7.05 (br t, 1H), 6.51 (s, 1H), 5.46 (s, 2H) 1H NMR (500MHz, DMSO-d6) δ = 7.79 - 7.72 (m, 1H), 7.70 - 7.61 (m, 1.025 1H), 7.49 (s, 1H), 7.43 - 7.38 (m, 1H), 7.17 (d, 1H), 7.05 (t, 1H), 6.58 (s, 1H), 5.40 (s, 2H) 1H NMR (500MHz, DMSO-d6) δ = 7.80 - 7.74 (m, 1H), 7.67 - 7.58 (m, 1.026 1H), 7.48 - 7.41 (m, 1H), 7.03 (t, 1H), 6.37 (s, 1H), 5.79 (s, 1H), 5.32 (s, 2H), 2.08 (s, 3H), 2.03 (s, 3H) 1H NMR (500MHz, DMSO-d6) δ = 7.82 (d, 1H), 7.79 - 7.75 (m, 1H), 1.027 7.69 - 7.59 (m, 1H), 7.49 (d, 1H), 7.47 - 7.43 (m, 1H), 7.05 (t, 1H), 6.60 (s, 1H), 5.45 (s, 2H) ¹ COMPOUND STRUCTURE HNMR (400MHz, CDCl3 unless otherwise stated) 1H NMR (500MHz, DMSO-d6) δ = 7.92 (s, 1H), 7.82 - 7.72 (m, 1H), 7.68 1.028 - 7.60 (m, 1H), 7.55 (s, 1H), 7.48 - 7.42 (m, 1H), 7.05 (t, 1H), 6.63 (s, 1H), 5.51 (s, 2H) 1H NMR (400 MHz, CHLOROFORM- d): δ = 7.38 (s, 1H), 7.28-7.33 (m, 1.029 2H), 7.08-7.24 (m, 1H), 6.66 (s, 1H), 6.57 (d, 1H), 5.39 ppm (s, 2H)

Biological Examples Seeds of a variety of test species are sown in standard soil in pots Amaranthus palmeri (AMAPA), Amaranthus retroflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE)). After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16^oC, day/night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the dissolution of the test compound in acetone and IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) which was then diluted to the required concentration using 0.2% Genapol XO80 (CAS No.9043-30-5) in water as the diluent. Test compounds are applied at the rates stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16^oC, day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days for pre- and post-emergence, the test is evaluated for the percentage damage caused to the plant. The biological activities are 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%). TABLE B1. Post-emergence Test Compound Rate (g/ha) AMAPA AMARE SETFA ECHCG IPOHE 1.001 250 2 1 1 1 3 1.002 250 3 3 2 2 1 1.003 250 5 5 4 3 1 1.004 250 5 4 NT 2 4 1.005 250 5 NT NT NT NT 1.006 250 2 2 1 1 1 1.007 250 5 5 4 3 2 1.008 250 1 1 1 1 1 1.009 250 1 1 1 1 1 1.010 250 1 1 1 1 1 1.011 250 1 1 1 1 1 1.012 250 4 5 4 4 3 1.013 250 5 5 4 4 4 1.014 250 1 1 NT 1 1 1.015 250 2 1 NT 1 1 1.016 250 1 1 1 1 1 1.017 250 1 1 1 1 1 1.018 250 4 4 4 4 4 1.019 250 1 1 1 1 1 1.020 250 1 3 1 1 1 1.021 250 3 4 1 1 1 Compound Rate (g/ha) AMAPA AMARE SETFA ECHCG IPOHE 1.022 250 1 2 1 1 1 1.023 250 1 1 1 1 1 1.024 250 1 2 1 1 1 1.025 250 1 1 1 1 1 1.026 250 1 1 1 1 1 1.027 250 1 1 1 1 2 1.028 250 4 5 4 4 4 1.029 250 1 1 1 1 NT NT = Not tested

TABLE B2. Pre-emergence Test Compound Rate (g/ha) AMAPA AMARE SETFA ECHCG IPOHE 1.001 250 1 1 1 1 1 1.002 250 5 5 4 4 1 1.003 250 5 5 5 4 5 1.004 250 5 4 NT 2 NT 1.005 250 5 NT NT NT NT 1.006 250 1 1 1 1 1 1.007 250 5 5 5 4 5 1.008 250 1 1 1 1 1 1.009 250 1 1 1 1 1 1.010 250 1 1 1 1 1 1.011 250 1 1 1 1 1 1.012 250 5 5 5 5 3 1.013 250 5 5 5 3 4 1.014 250 1 1 NT 1 1 1.015 250 1 1 NT 1 1 1.016 250 1 1 1 1 1 1.017 250 1 NT 1 1 1 1.018 250 5 5 4 4 1 1.019 250 1 1 1 1 1 1.020 250 1 3 1 1 1 1.021 250 4 4 1 1 3 1.022 250 1 1 1 1 1 1.023 250 1 2 1 1 1 1.024 250 1 2 1 1 1 1.025 250 1 1 1 1 1 1.029 250 1 2 1 1 1 1.027 250 4 5 2 3 2 1.028 250 5 5 5 4 3 1.029 250 1 1 1 1 NT NT = Not tested

Claims

Claims 1. A compound of Formula (I):

or an agronomically acceptable salt thereof, wherein Q is phenyl or a C-linked 6-membered heteroaryl wherein said phenyl or 6- membered heteroaryl is optionally substituted by one or more independent R¹; U is a 5-membered heteroaryl optionally substituted by one or more independent R⁷; R¹ is selected from the group consisting of halogen, C1-C4 alkyl, C1- C4 haloalkyl, C1-C4 haloalkoxy, C3-C6cycloalkyl, C1-C4alkoxyC1-C3alkyl-, C1- C4alkoxyC1-C3alkoxy-, C1-C4alkoxyC1-C3alkoxyC1-C3alkyl-, -CN, NO2, C2- C4alkenyl, C2-C4alkynyl, -S(O)pC1-C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1- C4alkyl and -C(O)NR⁴R⁵; R² is selected from the group consisting of -CN, NO2, C1-C4alkyl, C1- C4haloalkyl, C1-C4alkoxy, -C(O)C1-C4alkyl, -C(O)OC1-C4alkyl, -S(O)pC1- C4alkyl, -C(R⁶)=NOR⁸ and C3-C6cycloalkyl; R³ is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -CN, NO2, C2-C4alkenyl, C2- C4alkynyl, -S(O)pC1-C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1-C4alkyl and - C(O)NR⁴R⁵; R⁴ is selected from the group consisting of hydrogen, C₃-C₄cycloalkyl, C₁- C₄alkyl and C₁-C₄haloalkyl; R⁵ is selected from the group consisting of hydrogen, C₃-C₄cycloalkyl, C₁- C₄alkyl and C₁-C₄haloalkyl; R⁶ is hydrogen or C₁-C₂ alkyl; R⁷ is selected from the group consisting of halogen, C1-C4 alkyl, C3- C4cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4alkoxyC1- C3alkyl-, C1-C4alkoxyC1-C3alkoxy-, -CN, C2-C4alkenyl, C2-C4alkynyl, -S(O)pC1- C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1-C4alkyl, -C(O)NR⁹R¹⁰, -NR¹¹COR¹² and -S(O)pNR¹³R¹⁴; R⁸ is hydrogen or C1-C2 alkyl; R⁹ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R¹⁰ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R¹¹ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R¹² is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C4alkyl and C1-C4haloalkyl; R¹³ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C₄alkyl and C₁-C₄haloalkyl; R¹⁴ is selected from the group consisting of hydrogen, C3-C4cycloalkyl, C1- C₄alkyl and C₁-C₄haloalkyl; and p = 0, 1 or 2.

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

wherein R⁷ is hydrogen or as defined in claim 1; R^7a is selected from the group consisting of hydrogen, C₁-C₄alkyl, C₁- C₄haloalkyl and C₃-C₄cycloalkyl; and n = 0, 1 or 2.

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

4. A compound according to any one of the previous claims, wherein Q is selected from the group consisting of Q 1 to Q-11:

wherein R¹ is as defined in claim 1; and m is 0, 1 or 2.

5. A compound according to claim 4, wherein Q is Q-1 or Q-3.

6. A compound according to any one of the previous claims, wherein the compound of Formula (I) is selected from the group consisting of Formula (Iaa), (Iab), (Iac), (Iad), (Iae) and (Iaf):

7. A compound according to claim 6, wherein m is 1 or 2 and R¹ is independently halogen or C₁-C₂haloalkyl.

8. A compound according to any of the previous claims, wherein R² is is C₁- C₄haloalkyl.

9. A compound according to any one of the previous claims, wherein R³ is hydrogen or halogen.

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

11. A herbicidal composition according to claim 10, further comprising at least one additional pesticide.

12. A 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 comprising application to the locus of a weed controlling amount of a composition according to any one of claims 10 to 12.

14. Use of a compound of Formula (I) as defined in claim 1 as a herbicide.