Herbicidal pyrazole and triazole compounds

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein Q, A1, A2, R1 and R2 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

[0001] HERBICIDAL PYRAZOLE AND TRIAZOLE 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. WO2023 / 066783 discloses herbicidal imidazole compounds. WO2023 / 099354 discloses herbicidal pyrazole compounds. The present invention relates to herbicidal pyrazole and triazole compounds. 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 (e.g one or two) R4; R1is independently selected from the group consisting of halogen, cyano, NO2, C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl, - S(O)pC1-C4alkyl, C1-C4alkoxy-, -C(O)C1-C4alkyl, -C(O)OC1-C4alkyl, C1- C4haloalkoxy and C1-C4alkoxyC1-C3alkyl-; R2is selected from the group consisting of halogen, cyano, NO2, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, -C(O)C1-C4alkyl, C1-C4cyanoalkyl, -C(O)OC1- C4alkyl, C1-C4haloalkoxy, C1-C4alkoxyC1-C3alkyl-, C1-C4alkoxyC1-C3alkoxy-, C1-C4alkoxyC1-C3alkoxyC1-C3alkyl-, -S(O)pC1-C4alkyl and C3-C6cycloalkyl wherein said C3-C6cycloalkyl is optionally substituted by halogen and / or cyano; R4is selected from the group consisting of halogen, C1-C4alkyl, C1- C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkoxyC1-C3alkyl-, C1- C4alkoxyC1-C3alkoxy-, C1-C4alkoxyC1-C3alkoxyC1-C3alkyl-, cyano, NO2, C2- C4alkenyl, C2-C4alkynyl, -S(O)pC1-C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1- C4alkyl and -C(O)NR5R6; A1is N or CR7; A2is N or CR8; R5is hydrogen or C1-C4alkyl; R6is hydrogen or C1-C4alkyl; R7is selected from the group consisting of hydrogen, fluoro, chloro and cyano; R8is selected from the group consisting of hydrogen, fluoro, chloro and cyano; m = 1 or 2; 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 one embodiment of the present invention m is 1. In another embodiment of the present invention m is 2. In one embodiment of the present invention, A1is N or CR7wherein R7is halogen, preferably fluoro. In another embodiment of the present invention, A2is N or CR8wherein R8is hydrogen. Thus, in one embodiment of the present invention, there is provided a compound of Formula (I), wherein A1is CR7(wherein R7is preferably fluoro), A2is CR8wherein R8is hydrogen and m is 1 and which is of Formula (Ia) wherein Q, R1, R2and R7are as defined above. In another embodiment of the present invention, there is provided a compound of Formula (I), wherein A1is N, A2is CR8wherein R8is hydrogen and m is 1 and which is of Formula (Ib) wherein Q, R1and R2are as defined above. In another embodiment of the present invention, there is provided a compound of Formula (I), wherein A1is CR7(wherein R7is preferably fluoro), A2is N and m is 1 and which is of Formula (Ic) wherein Q, R1, R2and R7are as defined above. In another embodiment of the present invention, there is provided a compound of Formula (I), wherein A1is N, A2is N and m is 1 and which is of Formula (Id) wherein Q, R1and R2are as defined above. In a preferred embodiment of the present invention, R1is halogen (e.g fluoro or chloro, preferably chloro). In one embodiment of the present invention, R2is selected from the group consisting of halogen (e.g bromo), C1-C4alkyl (e.g methyl), C3-C6cycloalkyl (e.g c- propyl) and C1-C4haloalkyl (preferably -CF3, -CF2Cl or -CF2H). In a more preferred embodiment of the present invention, R2is halogen (e.g bromo) or C1-C4haloalkyl (preferably -CF3, -CF2Cl or -CF2H). In a still more preferred embodiment, R2is selected from the group consisting of bromo, -CF3, -CF2Cl and -CF2H.

[0002] In another embodiment of the present invention, Q is selected from the group consisting of: wherein n is 0, 1 or 2. In a preferred embodiment of the present invention, Q is Q-1 or Q-3. In a further embodiment, n is 1 or 2. In a further embodiment, each R4is independently selected from the group consisting of cyano, methyl, halogen and -CF3. In a further embodiment, R4is halogen (e.g fluoro or chloro). Thus, in a more preferred embodiment of the present invention the compound of Formula (I) is (Iaa) or (Iab): wherein R7is preferably fluoro. In another preferred embodiment of the present invention the compound of Formula (I) is (Iba) or (Ibb): In another preferred embodiment of the present invention the compound of Formula (I) is (Ica) or (Icb): wherein R7is preferably fluoro. In another preferred embodiment of the present invention the compound of Formula (I) is (Ida) or (Idb): In another preferred embodiment, n is 1. In this embodiment, R4is preferably selected from the group consisting of cyano, methyl, halogen and -CF3. In another embodiment of the present invention, in a compound of Formula (I), (Ia), (Ib), (Ic) or (Id), Q is Q-3 and n is 1 or 2. Thus, in a more preferred embodiment of the present invention Q is Q-3a: wherein R4ais halogen, preferably fluoro or chloro and R4bis halogen, preferably fluoro or chloro. In another embodiment of the present invention R4ais halogen, preferably fluoro or chloro and R4bis hydrogen. Compounds featuring Q-3a are particularly preferred in the context of the present invention as they typically exhibit improved crop selectivity, particularly in maize. 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-C10fatty 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 70oC) 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 fluchloraminopyr-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, 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, 2-[(2-bromo-6-fluoro-phenyl)methoxy]-4-isopropyl-1-methyl-7- oxabicyclo[2.2.1]heptane and (isopropylideneamino) 6-amino-2-(4-chloro-2-fluoro-3- methoxy-phenyl)-5-methoxy-pyrimidine-4-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, 16thEdition (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, in particular maize. 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. The compounds of the present invention are particularly useful in controlling Amaranthus weed species, including Amaranthus species that display resistance to one or more herbicides. 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), wherein A2is CH, can be prepared by nucleophilic substitution of an aryl pyrazole of Formula 2 with an alkylating agent of Formula 3 wherein LG1is 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 alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or caesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide (DMF), N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art. Scheme 1 Compounds of Formula 2 can be prepared, as shown in scheme 2, by a condensation reaction between a diketone of Formula 7 and hydrazine in a suitable solvent such as methanol, ethanol or acetic acid, preferably at room temperature. A diketone of Formula 7 can be prepared by reaction between an aryl ketone of Formula 4 and an acylating agent of Formula 5, wherein LG2 is a suitable leaving group such as an alkoxy group or halogen, using conditions well documented in the literature (see for example Bioorganic & Medicinal Chemistry, 2018, 26, 1418–1425). Scheme 2 Alternatively, as shown in scheme 3, compounds of Formula (I), wherein A2is CH, can be prepared by direct condensation reaction between a diketone of Formula 7 and a suitably substituted hydrazine of Formula 8, or salt thereof, in a suitable solvent such as methanol, ethanol or acetic acid, preferably at room temperature. Scheme 3 As shown in scheme 4, a compound of Formula (I), wherein A2is N, can be prepared by nucleophilic substitution of an aryl triazole of Formula 9 with an alkylating agent of Formula 3 wherein LG1is 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 alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or caesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide (DMF), N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art. Scheme 49ICompounds of Formula 9 can be prepared from an acylation and subsequent condensation between a compound of Formula 10 and an acylating agent of Formula 5 wherein LG2is a suitable leaving group such as a halogen (preferentially chlorine), alkoxy or formula 5a, using conditions documented in the literature (see for example WO2014 / 9495 and WO2018 / 60704) (Scheme 5). Scheme 5 Alternatively, as shown in scheme 6, compounds of Formula (I), can be prepared from compounds of Formula 14, wherein X2is a leaving group (for example, chlorine, bromine or iodine) using cross-coupling methods as described in literature for example in Organometallics 2019, 38, 1, 3–35, Org. Process Res. Dev.2022, 26, 8, 2240–2269, Tetrahedron 2007, 63, 4266–4270 or Chem. Rev. 2002, 102, 11, 4009–4092. Compounds of Formula 14 can be prepared by Suzuki cross-coupling reaction between compounds of Formula 12 wherein X1is a leaving group (for example, chlorine, bromine or iodine) with compounds of formula Q-Yb213 wherein Q is as defined in Formula I above and Yb2 can be a boron-derived functional group, such as for example B(OH)2 or B(ORb2)2 wherein Rb2 can be a C1-C4alkyl group or the two groups ORb2 can form together with the boron atom a five membered ring, for example a pinacol boronic ester. The reaction may be catalysed by a palladium based catalyst, for example tetrakis(triphenyl-phosphine)palladium(0), (1,1'bis(diphenylphosphino)ferrocene)dichloro-palladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'- amino-1,1'-biphenyl)]palladium(ll) (XPhos palladacycle), in presence of a base, like sodium carbonate, tripotassium phosphate or caesium fluoride, in a solvent or a solvent mixture, like, for example dioxane, 2-methyl tetrahydrofuran, acetonitrile, N,N-dimethyl-formamide, a mixture of 1,2-dimethoxyethane and water or of dioxane / water, or of toluene / water, preferably under inert atmosphere. 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 Suzuki reactions are well known to those skilled in the art. Compounds of Formula 12, can be prepared by alkylation reaction of compounds of Formula 11, with compounds of Formula 3, 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 alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or caesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, sulfolane, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120oC, by procedures well known to those skilled in the art. Scheme 6

[0003] Alternatively, compounds of the formula I wherein A2is N can be prepared following Scheme 7 via Suzuki reaction between compounds of the formula 17, wherein R2is as defined by the formula I above and X3is a leaving group (for example, chlorine, bromine or iodine) and compounds of the formula Q-Yb318 wherein Q is as defined in Formula I above and Yb3 can be a boron-derived functional group, such as for example B(OH)2 or B(ORb3)2 wherein Rb3 can be a C1-C4alkyl group or the two groups ORb3 can form together with the boron atom a five membered ring, for example a pinacol boronic ester. The reaction may be catalysed by a palladium based catalyst, for example tetrakis(triphenyl-phosphine)palladium(0), (1,1'bis(diphenylphosphino)ferrocene)dichloro-palladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'- amino-1,1'-biphenyl)]palladium(ll) (XPhos palladacycle), in presence of a base, like sodium carbonate, tripotassium phosphate or cesium fluoride, in a solvent or a solvent mixture, like, for example dioxane, 2-methyl tetrahydrofuran, acetonitrile, N,N-dimethyl-formamide, a mixture of 1,2-dimethoxyethane and water or of dioxane / water, or of toluene / water, preferably under inert atmosphere. 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 Suzuki reactions are well known to those skilled in the art. Compounds of the formula 17 can be obtained by the reaction of the compounds of the formula 16 with a Cu(I)X3or Cu(II)(X3)2salt via the diazotization methods reported in the literature such as Tetrahedron Letters 2007, 48, 2389–2393 or WO2023 / 122780. These reactions are known by the name of Sandmeyer reaction and well known to those skilled in the art. Compounds of the formula 16 can be prepared by the alkylation reaction of the compounds of the formula 15 with the compounds of the formula 3, wherein LG1is 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 alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, sulfolane, N,N- dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120oC, by procedures well known to those skilled in the art. Scheme 7 Alternatively, compounds of Formula I wherein A2is N can also be prepared following Scheme 8, via the alkylation of the compounds of formula 9 with the compounds of formula 3, 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 alkaline earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N-dimethylformamide DMF, sulfolane, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120oC, by procedures well known to those skilled in the art. Compounds of formula 9 can be prepared by reacting compounds of formula 21 or its salts wherein R9is C1-C4alkyl or phenyl, with compounds of formula 22, where R2is as defined in Formula I above, at temperatures between 0 to 120oC in the presence of a organic base such as triethyl amine or N,N-diisopropylethylamine or in the presence of inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate, sodium methoxide or sodium ethoxide in an inert solvent such as tetrahydrofuran, dioxane, N,N-dimethylformamide DMF, sulfolane, N,N- dimethylacetamide or acetonitrile or as described in the literature such as Tetrahedron Letters 2009, 50, 3809–3812 or Tetrahedron Letters 2016, 57, 990–992. Compounds of formula 21 can be prepared by the reaction of compounds of formula 18, where Q is as defined in Formula I above, with compounds of formula 20, wherein R9is C1-C4alkyl or phenyl in the presence of an acid catalyst which can be generated in situ from acyl chloride of the formula 19, wherein R10is C1-C4 alkyl. Such reactions are known by the name of Pinner reaction and well known to those skilled in the art. Scheme 8 I Compounds of formula 9 can also be prepared by reacting compounds of formula 25, wherein Q and R2are as defined in formula I, with hydrazine hydrate 26 in the presence of acetic acid in solvent like dimethyl formamide (DMF) at temperature between room temperature or 80oC. Compounds of formula 25 can be prepared in situ by reacting compounds of formula 23 with the compounds of formula 24 using amide coupling reagents such as HATU as described in the literature J. Org. Chem. 2011, 76, 1177. Scheme 9 Compounds of the formula I wherein A2is N can also be prepared by reacting compounds of the formula 25, wherein Q and R2are as defined in formula I, with compounds of the formula 27 in the presence of acetic acid in solvent like dimethyl formamide (DMF) at temperature between room temperature or 80oC. The compounds of the formula 25 can be prepared following the procedure as described above in scheme 9. Scheme 10

[0004] Thus, according to another embodiment of the present invention there is further provided a compound of Formula (II) wherein A1, R1and R2are as defined in the compound of Formula (I) above. In a preferred embodiment A1is C-F. In another preferred embodiment R1is chloro. In another preferred embodiment R2is C1-C4haloalkyl, preferably -CF3or -CHF2. In a particularly preferred embodiment, there is provide a compound of Formula (II) wherein A1is C-F, R1is chloro and R2is CF3. The present invention still further provides a compound of Formula (III) wherein A1, R1and R2are as defined in the compound of Formula (I) above. In a preferred embodiment A1is C-F. In another preferred embodiment R1is chloro. In another preferred embodiment R2is C1-C4haloalkyl, preferably -CF3or -CHF2. In a particularly preferred embodiment, there is provide a compound of Formula (III) wherein A1is C-F, R1is chloro and R2is CF3. The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table 1 below. LCMS Method 1: ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L / hr, Desolvation Gas Flow: 700 L / hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water / Methanol 9:1 + 0.1% formic acid, B= Acetonitrile + 0.1% formic acid, gradient: 0-100% B in 3.0 min; Flow (ml / min) 0.75. LCMS Method 2: Data was acquired on one of the below instruments. Agilent 1100 Series LC / MSD system with DAD\ELSD Alltech 2000ES and Agilent LC\MSD VL (G1956B), SL (G1956B) mass-spectrometer. Agilent 1200 Series LC / MSD system with DAD\ELSD Alltech 3300 and Agilent LC\MSD^G6130A, G6120B mass-spectrometer. Agilent Technologies 1260 Infinity LC / MSD system with DAD\ELSD Alltech 3300 and Agilent LC\MSDG6120B mass-spectrometer. Agilent Technologies 1260 Infinity II LC / MSD system with DAD\ELSD G7102A 1290 Infinity II and Agilent LC\MSD^G6120B mass-spectrometer. Agilent 1260 Series LC / MSD system with DAD\ELSD and Agilent LC\MSD (G6120B) mass-spectrometer. Column: Agilent Poroshell 120 SB-C184.6x30mm 2.7 µm; Column Temperature: 60°C; Mobile phase: А – water (0.1% formic acid), В – acetonitrile (0.1% formic acid); Flow rate: 3 ml / min; Gradient: 0.01 min – 1% B, 1.5 min – 100% B, 1.73 min – 100% B; MS Ionization mode: Electrospray ionization (ESI); MS Scan range: 83 – 600 m / z; UV detection: 215 nm, 254nm, 280 nm LCMS Method 3: Waters ACQUITY UPLC-MS using a Sample Organizer with Sample Manager FTN+, H-class QSM, Column Manager, 2 x Column Manager Aux, photodiode array, ELSD (Wavelength range (nm): 210 to 400) and SQD 2. Ionisation method: Electrospray positive and negative: Capillary (kV) 3.0, Cone (V) 35.0, Source Temperature (°C) 150, Cone Gas Flow (L / Hr.) 10, Desolvation Gas Flow (L / Hr.) 500, Desolvation Temperature (°C) 500. Mass range (Da): positive 95 to 800, negative 115 to 800, Column: Waters ACQUITY UPLC HSS T3 1.8μm 2.1x50mm, Solvent Gradient: Solvent A: water with 0.05% TFA; Solvent B: acetonitrile with 0.05% TFA; Flow (ml / min) 0.6. Example 1: 5-chloro-2-[[3-(difluoromethyl)-5-(3,4-difluorophenyl)pyrazol-1- yl]methyl]pyrimidine (1.001) Step 1: Preparation of 1-(3,4-difluorophenyl)-4,4-difluoro-butane-1,3-dione (I-1) A solution of 1-(3,4-difluorophenyl)ethanone (2.00 g, 12.8 mmol) in tetrahydrofuran (20 mL) was placed under an atmosphere of nitrogen, cooled over ice and treated with sodium methoxide (25% in methanol, 5.3 mL, 23.1 mmol) and ethyl difluoroacetate (1.9 mL, 19.2 mmol). The resulting mixture was stirred at room temperature for 16 hours, diluted with aqueous ammonium chloride and extracted with ethyl acetate. The combined organics were concentrated and subjected to silica gel column chromatography using ethyl acetate in cyclohexane. The fractions forming the major peak of interest were combined and concentrated in vacuo, yielding 1-(3,4-difluorophenyl)-4,4-difluoro-butane-1,3-dione I-1 (2.00 g, 53%) as an orange solid.1H NMR (400 MHz, CDCl3) δ = 7.82 - 7.70 (m, 2H), 7.32 - 7.27 (m, 1H), 6.50 (s, 1H), 6.02 (t, 1H). Step 2: Preparation of 3-(difluoromethyl)-5-(3,4-difluorophenyl)-1H-pyrazole (I- 2) A solution of 1-(3,4-difluorophenyl)-4,4-difluoro-butane-1,3-dione I-1 (1.00 g, 4.27 mmol) in acetic acid (8.5 mL) was treated with hydrazine hydrate (0.32 mL, 6.41 mmol) and was stirred at room temperature overnight. The mixture was diluted with water and extracted with ethyl acetate. The combined organics were washed with brine, dried and concentrated, yielding 3-(difluoromethyl)-5-(3,4-difluorophenyl)-1H- pyrazole I-2 (850 mg, 87%).1H NMR (400 MHz, CDCl3) δ = 7.49 - 7.40 (m, 1H), 7.39 - 7.32 (m, 1H), 7.29 - 7.20 (m, 1H), 6.74 (t, 1H), 6.72 (s, 1H). Step 3: Preparation of 5-chloro-2-[[3-(difluoromethyl)-5-(3,4- difluorophenyl)pyrazol-1-yl]methyl]pyrimidine (1.001) (1.001) A solution of 3-(difluoromethyl)-5-(3,4-difluorophenyl)-1H-pyrazole I-2 (350 mg, 1.52 mmol) in acetonitrile (3.5 mL) was treated with potassium carbonate (525 mg, 3.80 mmol), potassium iodide (51 mg, 0.30 mmol) and 5-chloro-2-(chloromethyl)pyrimidine (297 mg, 1.82 mmol) and the resulting mixture was stirred at 70oC for 2 hours. The mixture was cooled, diluted with water and extracted with ethyl acetate. The combined organics were concentrated and purified by preparative HPLC, yielding 5- chloro-2-[[3-(difluoromethyl)-5-(3,4-difluorophenyl)pyrazol-1-yl]methyl]pyrimidine 1.001.1H NMR (400 MHz, CDCl3) δ = 8.68 (s, 2H), 7.45 - 7.38 (m, 1H), 7.29 - 7.19 (m, 2H), 6.68 (t, 1H), 6.59 (s, 1H), 5.50 (s, 2H). Example 2: 5-chloro-2-[[3-(difluoromethyl)-5-(4-fluorophenyl)-1,2,4-triazol-1- yl]methyl]pyrimidine (1.028) (1.028) Step 1: Preparation of N-amino-4-fluoro-benzamidine (I-3) A solution of 4-fluorobenzamidine (2.00 g, 14.5 mmol) in methanol (14.5 mL) was treated with N,N-diisopropylethylamine (7.5 mL, 43.4 mmol) and hydrazine hydrate (0.73 mL, 14.5 mmol) and was stirred at room temperature for 16 hours. On completion, the reaction mixture was concentrated in vacuo to give 2.00 g of crude product which was used as is in the next step. Step 2: Preparation of 3-(difluoromethyl)-5-(4-fluorophenyl)-1H-1,2,4-triazole (I- 4) Crude N-amino-4-fluoro-benzamidine I-3 (1.00 g, 5.22 mmol) from previous step was dissolved in acetonitrile (10 mL) and was treated with difluoroacetic anhydride (1.00 mL, 6.80 mmol) and was stirred at 50oC for 3 hours. The reaction was cooled, diluted with ethyl acetate and washed with aqueous sodium bicarbonate solution. The combined organics were concentrated and subjected to silica gel column chromatography using ethyl acetate in cyclohexane. The fractions forming the major peak of interest were combined and concentrated in vacuo, yielding 3- (difluoromethyl)-5-(4-fluorophenyl)-1H-1,2,4-triazole I-4 (450 mg, 40%) as an off- white solid.1H NMR (400 MHz, CDCl3) δ = 8.00 - 7.94 (m, 2H), 7.20 (t, 2H), 6.82 (t, 1H). Step 3: Preparation of 5-chloro-2-[[3-(difluoromethyl)-5-(4-fluorophenyl)-1,2,4- triazol-1-yl]methyl]pyrimidine (1.028) (1.028) A solution of 3-(difluoromethyl)-5-(4-fluorophenyl)-1H-1,2,4-triazole I-4 (150 mg, 0.70 mmol) in acetonitrile (1.5 mL) was treated with potassium carbonate (243 mg, 1.76 mmol), potassium iodide (23 mg, 0.14 mmol) and 5-chloro-2-(chloromethyl)pyrimidine (138 mg, 0.84 mmol) and the resulting mixture was stirred at 70oC for 2 hours. The mixture was cooled, diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected to silica gel column chromatography using ethyl acetate in cyclohexane. The fractions forming the major peak of interest were combined and concentrated in vacuo, giving 5-chloro-2-[[3- (difluoromethyl)-5-(4-fluorophenyl)-1,2,4-triazol-1-yl]methyl]pyrimidine 1.028.1H NMR (400 MHz, CDCl3) δ = 8.70 (s, 2H), 7.80 (t, 2H), 7.18 (t, 2H), 6.73 (t, 1H), 5.63 (s, 2H). Example 3: Preparation of 2-[[3-bromo-5-(3,4-difluorophenyl)-1,2,4-triazol-1- yl]methyl]-5-chloro-pyrimidine (1.010) Step 1: Preparation of 5-chloro-2-[(3,5-dibromo-1,2,4-triazol-1- yl)methyl]pyrimidine (I-5) A mixture of 3,5-dibromo-1H-1,2,4-triazole (1.20 g, 5.29 mmol), 5-chloro-2- (chloromethyl)pyrimidine hydrochloride (1.32 g, 6.62 mmol), potassium carbonate (2.22 g, 16.1 mmol) and potassium iodide (187 mg, 1.13 mmol) in acetonitrile (27 mL) and water (1.3 mL) was stirred at 80oC for an hour. The mixture was cooled, diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected to silica gel column chromatography using ethyl acetate in cyclohexane. The fractions forming the major peak of interest were combined and concentrated in vacuo, yielding 5-chloro-2-[(3,5-dibromo-1,2,4-triazol-1- yl)methyl]pyrimidine I-5 (1.799 g, 91%) as an off-white solid.1H NMR (400 MHz, CDCl3) δ = 8.67 (s, 2H), 5.57 (s, 2H). Step 2: Preparation of 2-[[3-bromo-5-(3,4-difluorophenyl)-1,2,4-triazol-1- yl]methyl]-5-chloro-pyrimidine (1.010) (1.010) A de-gassed mixture of 5-chloro-2-[(3,5-dibromo-1,2,4-triazol-1-yl)methyl]pyrimidine I-5 (1.00 g, 2.83 mmol), (3,4-difluorophenyl)boronic acid (0.670 g, 4.24 mmol), caesium carbonate (1.84 g, 5.66 mmol), [1,1'- bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (153 mg, 0.184 mmol) and 2-methyltetrahydrofuran (10 mL) was irradiated under microwave radiation to 100oC for 30 minutes. The mixture was diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected to silica gel column chromatography using ethyl acetate in cyclohexane. The fractions forming the major peak of interest were combined and concentrated in vacuo, giving 2-[[3-bromo-5-(3,4-difluorophenyl)-1,2,4-triazol-1-yl]methyl]-5-chloro- pyrimidine 1.010.1H NMR (400 MHz, CDCl3) δ = 8.72 (s, 2H), 7.76 - 7.70 (m, 1H), 7.59 - 7.54 (m, 1H), 7.33 - 7.23 (m, 1H), 5.58 (s, 2H). Example 4: Preparation of 5-chloro-2-[[3-cyclopropyl-5-(3,4-difluorophenyl)- 1,2,4-triazol-1-yl]methyl]pyrimidine (1.021) (1.021) Step 1: Preparation of 5-chloro-2-[[3-cyclopropyl-5-(3,4-difluorophenyl)-1,2,4- triazol-1-yl]methyl]pyrimidine (1.010) (1.021) A de-gassed mixture of 2-[[3-bromo-5-(3,4-difluorophenyl)-1,2,4-triazol-1-yl]methyl]- 5-chloro-pyrimidine 1.010 (150 mg, 0.39 mmol), cyclopropylboronic acid (53 mg, 0.58 mmol), caesium carbonate (253 mg, 0.78 mmol), [1,1'- bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (32 mg, 0.038 mmol) and 2-methyltetrahydrofuran (1.5 mL) was irradiated under microwave radiation to 100oC for 1 hour. The mixture was diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected to silica gel column chromatography using ethyl acetate in cyclohexane. The fractions forming the major peak of interest were combined and concentrated in vacuo, yielding 2-[[3-bromo-5-(3,4-difluorophenyl)-1,2,4-triazol-1-yl]methyl]-5-chloro- pyrimidine 1.021.1H NMR (400 MHz, CDCl3) δ = 8.70 (s, 2H), 7.69 - 7.62 (m, 1H), 7.53 - 7.47 (m, 1H), 7.28 - 7.21 (m, 1H), 5.48 (s, 2H), 2.09 - 2.01 (m, 1H), 1.06 - 0.91 (m, 4H). Example 5: Preparation of 5-chloro-3-fluoro-2-[[5-(6-fluoro-3-pyridyl)-3- (trifluoromethyl)-1,2,4-triazol-1-yl]methyl]pyridine (1.117) Step 1: Preparation of 2-[(5-chloro-3-fluoro-2-pyridyl)methyl]-5- (trifluoromethyl)-1,2,4-triazol-3-amine (I-6) In a 250 mL two-neck round bottom flask under nitrogen atmosphere were added 3- (trifluoromethyl)-1H-1,2,4-triazol-5-amine (4.5 g, 29.59 mmol) and propanenitrile (45 mL) at room temperature. To this, potassium carbonate (6.197 g, 44.38 mmol) and potassium iodide (0.49 g, 2.95 mmol) were then added sequentially. The reaction mixture was stirred at 60oC for 10 minutes before adding 5-chloro-2-(chloromethyl)- 3-fluoro-pyridine (6.51 g, 32.54 mmol). The resulting mixture was stirred at 80oC for 1.5 hour. The reaction was then quenched by adding water and the quenched reaction mixture was extracted with ethyl acetate (3 x 150 mL). The combined organic phases were concentrated under reduced pressure to yield a gum-like residue. This residue was washed twice with tert-butyl methyl ether (15.0 mL). The solid phase and mother liquor were separated, and the mother liquor was concentrated under reduced pressure to get 2-[(5-chloro-3-fluoro-2-pyridyl)methyl]-5- (trifluoromethyl)-1,2,4-triazol-3-amine I-6 (6.7 g, 73%) as off-white solid.1H NMR (400 MHz, CDCl3) δ = 8.35 (d, 1 H), 7.54 (dd, 1 H), 5.31 (d, 2 H). Step 2: Preparation of 2-[[5-bromo-3-(trifluoromethyl)-1,2,4-triazol-1-yl]methyl]- 5-chloro-3-fluoro-pyridine (I-7) In a 500 mL two-neck round bottom flask under nitrogen atmosphere, 2-[(5-chloro-3- fluoro-2-pyridyl)methyl]-5-(trifluoromethyl)-1,2,4-triazol-3-amine I-6 (6.3 g, 21.3 mmol), was dissolved in 95 mL acetonitrile) at room temperature. Copper(II) bromide (9.52 g, 42.61 mmol) was then added and the reaction mixture was cooled to 0oC and stirred for 10 minutes. To this, tert-Butyl nitrite (4.39 g, 42.62 mmol) was added dropwise over 10 minutes. The resulting mixture was heated to 60oC and stirred at this temperature for 1 hour. After this time, the mixture was quenched by adding water (150 mL). The quenched reaction mixture was extracted with ethyl acetate (3 X 150 mL) and the combined organic phases were concentrated under reduced pressure to yield a gum-like residue. This residue was purified by silica gel column chromatography using 0-10% ethyl acetate in cyclohexane. Upon concentration, 2- [[5-bromo-3-(trifluoromethyl)-1,2,4-triazol-1-yl]methyl]-5-chloro-3-fluoro-pyridine I-7 (6.6 g, 82%) was obtained as a pale yellowish gummy material.1H NMR (400 MHz, CDCl3) δ = 8.35 (d, 1 H), 7.53 (dd, 1 H), 5.59 (d, 2 H). Step 3: Preparation of 5-chloro-3-fluoro-2-[[5-(6-fluoro-3-pyridyl)-3- (trifluoromethyl)-1,2,4-triazol-1-yl]methyl]pyridine (1.117) In a 100 mL two-neck round bottom flask, 2-[[5-bromo-3-(trifluoromethyl)-1,2,4- triazol-1-yl]methyl]-5-chloro-3-fluoro-pyridine I-7 (1.0 g, 2.78 mmol) was dissolved in 10 mL of 2-methyltetrahydrofuran. To this solution, (6-fluoro-3-pyridyl)boronic acid (0.51 g, 3.61 mmol) was added, followed by potassium carbonate (0.776 g, 5.55 mmol) and 1 mL water. The reaction mixture was degassed by bubbling nitrogen for 10 minutes. To this mixture, bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.047 g, 0.055 mmol) was added and the resulting mixture was stirred at 90°C for 4 hours. After the reaction period, the mixture was allowed to cool to room temperature and then quenched by adding water. The quenched reaction mixture was extracted with ethyl acetate (3 X 100 mL) and the combined organic phases were concentrated under reduced pressure to yield a gum-like residue. This residue was purified by silica gel column chromatography using 6-8% ethyl acetate in cyclohexane. Upon concentration of the desired fraction, 5-chloro-3-fluoro-2-[[5-(6-fluoro-3-pyridyl)-3- (trifluoromethyl)-1,2,4-triazol-1-yl]methyl]pyridine 1.117 was obtained as white solid.1H NMR (400 MHz, CDCl3) δ = 8.84 (d, 1 H), 8.37 - 8.44 (m, 2 H), 7.59 (dd, 1 H), 7.15 (dd, 1 H), 5.60 (d, 2 H). Example 6: Preparation of 5-chloro-2-[[3-(1,1-difluoroethyl)-5-(3,4- difluorophenyl)-1,2,4-triazol-1-yl]methyl]pyrimidine (1.107) (1.107) Step 1: Preparation of ethyl 3,4-difluorobenzenecarboximidate (I-8) (I-8) In a 250 mL flask 3,4-difluorobenzonitrile (10.0 g, 70.45 mmol) was dissolved in 45 mL ethanol and cooled to 0°C. To this, acetyl chloride (3.5 g, 422.7) was added dropwise. The reaction mixture was then left stirring at room temperature for 12 h. After concentration, ethyl 3,4-difluorobenzenecarboximidate I-8 (13.0 g, 97%) was obtained as hydrochloride salt.1H NMR (400 MHz, DMSO-d6) δ = 9.07 (br s, 1 H), 7.90 (br t, 1 H), 7.70 (br s, 1 H), 7.45 - 7.58 (m, 1 H), 4.21 (br s, 2 H), 1.31 (t, 3H). Step 2: Preparation of 3-(1,1-difluoroethyl)-5-(3,4-difluorophenyl)-1H-1,2,4- triazole (I-9) (I-9) In a 100 mL two-neck round bottom flask under nitrogen atmosphere, ethyl 3,4- difluorobenzenecarboximidate I-8 (1.5 g, 8.1 mmol) was dissolved in 30 mL Tetrahydrofuran. To this solution were added sodium methoxide (0.67 g, 12.15 mmol), 2,2-difluoropropanehydrazide (1.51 g, 12.15 mmol) and the resulting mixture was stirred at 80 °C for 1 hour. After the reaction period, the mixture was cooled to room temperature, quenched with water (50.0 mL) and extracted with ethyl acetate (3 X 60 mL). The combined organic phases were concentrated under reduced pressure to yield the crude product. This was then purified by silica gel column chromatography using 0-30% ethyl acetate in cyclohexane. Upon concentration of the desired fraction, the product 3-(1,1-difluoroethyl)-5-(3,4-difluorophenyl)-1H-1,2,4- triazole I-9 (0.9 g, 90%) was obtained as off-white solid.1H NMR (400 MHz, CDCl3) δ = 7.90 (m, 1 H), 7.79 (m, 1 H), 7.09 - 7.22 (m, 1 H), 2.03 (t, 3 H). Step 3: Preparation of 5-chloro-2-[[3-(1,1-difluoroethyl)-5-(3,4-difluorophenyl)- 1,2,4-triazol-1-yl]methyl]pyrimidine (1.107) (1.107) In a 100 mL two-neck round bottom flask under nitrogen atmosphere, 3-(1,1- difluoroethyl)-5-(3,4-difluorophenyl)-1H-1,2,4-triazole I-9 (0.4 g, 1.63 mmol) was dissolved in 10 mL propanenitrile. To this solution were added potassium carbonate (0.455 g, 3.25 mmol), 5-chloro-2-(chloromethyl)-3-fluoro-pyridine (0.35 g, 1.96 mmol), potassium iodide (0.027 g, 0.16 mmol) and the resulting mixture was stirred at 80 °C for 1 hour. After the reaction period, the mixture was quenched with water (15.0 mL) and extracted with ethyl acetate (3 X 30 mL). The combined organic phases was concentrated and the residue was purified by silica gel column chromatography using 0-10% ethyl acetate in cyclohexane as eluent to afford the product 5-chloro-2-[[3- (1,1-difluoroethyl)-5-(3,4-difluorophenyl)-1,2,4-triazol-1-yl]methyl]pyrimidine 1.107.1H NMR (400 MHz, CDCl3) δ = 8.70 (s, 2 H), 7.73 (m, 1 H), 7.54 - 7.59 (m, 1 H), 7.24 - 7.31 (m,1 H), 5.61 (s, 2 H), 2.08 (t, 3 H). Example 7: Preparation of 5-chloro-2-[[3-cyclopropyl-5-(6-fluoro-3-pyridyl)- 1,2,4-triazol-1-yl]methyl]pyrimidine (1.135) (1.135) Step 1: Preparation of 5-(3-cyclopropyl-1H-1,2,4-triazol-5-yl)-2-fluoro-pyridine (I- 10) (I-10) To a stirred solution of 6-fluoropyridine-3-carboxylic acid (0.50 g, 3.54 mmol) in 10 mL dimethyl formamide were added N,N-Diisopropylethylamine (1.40 g, 10.6 mmol), .cyclopropanecarboxamidine hydrochloride (0.641 g, 5.32 mmol) and HATU (1.53 g, 3.90 mmol) and the reaction mixture was stirred at room temperature overnight. To the reaction mixture hydrazine hydrate (0.266 g, 5.32 mmol) and acetic acid (2.24 g, 35.4 mmol) were added and the reaction mixture was stirred at 800C for 3 h. After this time, the reaction mixture was diluted with 10 mL ethyl acetate, neutralized with aqueous sodium bicarbonate (20 mL) and then extracted with ethyl acetate (3 X 30 mL). The combined organic layer was dried over sodium sulfate, filtered and concentrated to get the crude. The crude product was purified by silica gel column chromatography using 20-30% ethyl acetate in cyclohexane to get 5-(3-cyclopropyl- 1H-1,2,4-triazol-5-yl)-2-fluoro-pyridine I-10 (0.26 g, 37.1%) as a yellow solid.1H NMR (400 MHz, DMSO-d6) δ = 13.88 (br s, 1 H), 8.71 - 8.77 (m, 1 H), 8.43 (m, 1 H), 7.26 (dd, 1 H), 2.06 - 2.14 (m, 1 H), 1.03 - 1.11 (m, 2 H), 0.93 - 1.02 (m, 2 H). Step 2: Preparation of 5-chloro-2-[[3-cyclopropyl-5-(6-fluoro-3-pyridyl)-1,2,4- triazol-1-yl]methyl]pyrimidine (1.135) (1.135) To a stirred solution of 5-(3-cyclopropyl-1H-1,2,4-triazol-5-yl)-2-fluoro-pyridine I-10 (0.250 g, 1.22 mmol) in 2 mL acetonitrile were added potassium carbonate (0.423 g, 3.06 mmol), potassium iodide (0.041 g, 0.245 mmol), followed by 5-chloro-2- (chloromethyl)pyrimidine (0.239 g, 1.47 mmol). The reaction mixture heated to at 600C overnight. After this period, the reaction mixture was cooled to room temperature and diluted with 15 mL water and extracted using ethyl acetate (3 X 30 mL), dried over anhydrous sodium sulfate, filtered and then concentrated to get the crude product. The crude product was then purified via reverse phase column chromatography using 0-50% acetonitrile in water as eluent and the isomers were successfully separated. The fractions were then concentrated to get the desired isomer 5-chloro-2-[[3-cyclopropyl-5-(6-fluoro-3-pyridyl)-1,2,4-triazol-1- yl]methyl]pyrimidine 1.135 as a white solid.1H NMR (400 MHz, CDCl3): δ = 8.70 (s, 2H), 8.65 (d, 1H), 8.24 (m, 1H), 7.05 (dd, 1H), 5.49 (s, 2H), 2.02-2.11 (m, 1H), 0.94- 1.06 ppm (m, 4H). Example 8: Preparation of 5-chloro-2-[[5-(6-chloro-5-fluoro-3-pyridyl)-3- cyclopropyl-1,2,4-triazol-1-yl]methyl]pyrimidine (1.129) (1.129) To a stirred solution of 6-chloro-5-fluoro-pyridine-3-carboxylic acid (0.1 g, 0.57 mmol) in 10 mL dimethylformamide were added N,N-diisopropylethylamine (0.225 g, 1.71 mmol), cyclopropanecarboxamidine hydrochloride (0.10 g, 0.85 mmol), and 1- [Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide hexafluoro- phosphate (HATU) (0.24 g, 0.62 mmol). The reaction mixture was stirred at room temperature for 2 h. To this reaction mixture, (5-chloropyrimidin-2-yl)methyl- hydrazine hydrochloride (0.167 g, 0.85 mmol) and acetic acid (0.36 g, 5.69 mmol) were added and the mixture was stirred at 800C for 1 h. After this time, the reaction mixture was quenched with ice cold water (50 mL), extracted with ethyl acetate (3 X 50 ml). The combined organic layer was dried over sodium sulphate and concentrated to get the crude which was purified by silica gel column chromatography using 15-20% ethyl acetate in cyclohexane. Upon concentration, the product 5-chloro-2-[[5-(6-chloro-5-fluoro-3-pyridyl)-3-cyclopropyl-1,2,4-triazol-1- yl]methyl]pyrimidine 1.129 was obtained as white solid.1H NMR (400 MHz, CDCl3) δ = 8.71 (s, 2 H), 8.66 (d,1 H), 8.04 (dd,1 H), 5.51 (s, 2 H), 2.06 (m,1 H) 0.95 - 1.05 (m, 4 H).

[0005] TABLE 1. Compounds of the Present Invention 1 Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.68 (s, 2H), 7.45 - 7.38 (m, 1.001 1H), 7.29 - 7.19 (m, 2H), 6.68 (t, 1H), 6.59 (s, 1H), 5.50 (s, 2H) 1.002 δ = 8.65 (s, 2H), 7.47 - 7.36 (m, 4H), 6.63 (s, 1H), 5.54 (s, 2H) 1.003 δ = 8.65 (s, 2H), 7.46 (dd, 2H), 7.12 (t, 2H), 6.62 (s, 1H), 5.54 (s, 2H) δ = 8.66 (s, 2H), 7.43 - 7.34 (m, 1.004 1H), 7.25 - 7.19 (m, 2H), 6.62 (s, 1H), 5.53 (s, 2H) δ = 8.60 (s, 2H), 8.34 (d, 1H), 7.97 - 1.005 7.88 (m, 1H), 6.97 (dd, 1H), 6.63 (t, 1H), 6.58 (s, 1H), 5.42 (s, 2H) δ = 8.58 (s, 2H), 7.48 (d, 1H), 7.39 - 1.006 7.34 (m, 2H), 7.29 - 7.24 (m, 1H), 6.74 (t, 1H), 6.60 (s, 1H), 5.43 (s, 2H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.59 (s, 2H), 7.51 (d, 1H), 7.36 - 1.007 7.31 (m, 1H), 7.28 (d, 1H), 6.72 (t, 1H), 6.60 (s, 1H), 5.41 (s, 2H) δ = 8.59 (s, 2 H), 7.50 (d, 1 H), 7.37 - 1.008 7.42 (m, 2 H), 7.26 - 7.30 (m, 1 H), 6.65 (s, 1 H), 5.50 (s, 2H) δ = 8.58 (s, 2H), 7.51 (d, 1H), 7.36 - 1.009 7.31 (m, 1H), 7.28 - 7.24 (m, 1H), 6.62 (s, 1H), 5.45 (s, 2H) δ = 8.72 (s, 2H), 7.76 - 7.70 (m, 1.010 1H), 7.59 - 7.54 (m, 1H), 7.33 - 7.23 (m, 1H), 5.58 (s, 2H) δ = 8.42 (d, 1H), 7.88- 7.79 (m, 1H), 1.011 7.71 - 7.65 (m, 1H), 7.56 (dd, 1H), 7.37 - 7.29 (m, 1H), 5.51 (d, 2H) 1.012 δ = 8.71 (s, 2H), 8.69 (d, 1H), 8.07 (dd, 1H), 5.60 (s, 2H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.73 (s, 2H), 7.83 - 7.77 (m, 1.013 2H), 7.22 - 7.16 (m, 2H), 5.59 (s, 2H) δ = 8.71 (s, 2H), 7.77 - 7.69 (m, 1.014 2H), 7.50 - 7.43 (m, 2H), 5.58 (s, 2H) 1.015 δ = 8.85 (d, 1H) 8.71 (s, 2 H) 8.15 (dd, 1H) 7.49 (d, 1H) 5.59 (s, 2H) δ = 8.71 (s, 2H) 8.70 (d, 1H) 8.33 - 1.016 8.26 (m, 1H) 7.10 (dd, 1H) 5.58 (s, 2H) 1.017 δ = 8.74 (s, 2H), 7.71 (dd, 1H), 7.59 - 7.52 (m, 2H), 5.60 (s, 2H) δ = 8.71 (s, 2H), 7.94 (dd, 1H), 7.72 1.018 -7.66 (m, 1H), 7.29 - 7.23 (m, 1H), 5.56 (s, 2H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.71 (s, 2H), 8.00 (s, 1H), 7.74 1.019 – 7.66 (m, 1H), 7.58 - 7.52 (m, 1H), 7.31 - 7.24 (m, 1H), 5.61 (s, 2H) 1.020 δ = 8.70 (s, 2H), 8.05 (s, 1H), 7.93 (d, 2H), 7.75 (d, 2H), 5.64 (s, 2H) δ = 8.70 (s, 2H), 7.69 - 7.62 (m, 1.021 1H), 7.53 - 7.47 (m, 1H), 7.28 - 7.21 (m, 1H), 5.48 (s, 2H), 2.09 - 2.01 (m, 1H), 1.06 - 0.91 (m, 4H) δ = 8.39 (d, 1H), 7.77 - 7.68 (m, 1H), 7.59 - 7.52 (m, 1H), 7.49 (dd, 1.022 1H), 7.30 - 7.23 (m, 1H), 5.40 (d, 2H), 2.05 - 1.98 (m, 1H), 1.02 - 0.91 (m, 4H) δ = 8.69 (s, 2H), 7.75 - 7.66 (m, 1.023 2H), 7.16 - 7.08 (m, 2H), 5.48 (s, 2H), 2.10 - 2.01 (m, 1H), 1.06 - 0.93 (m, 4H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.74 (s, 2H), 7.78 - 7.69 (m, 1.024 1H), 7.54 - 7.59 (m, 1H), 7.29 - 7.32 (m, 1H), 5.54 (s, 2H), 2.45 (s, 3H) δ = 8.70 (s, 2 H), 7.82 - 7.74 (m, 1.025 2H), 7.22 - 7.13 (m, 2H), 5.65 (s, 2 H) δ = 8.40 (d, 1H) 7.87 - 7.80 (m, 1H), 1.026 7.71 - 7.65 (m, 1H), 7.57 (dd, 1H), 7.38 - 7.29 (m, 1H), 5.58 (d, 2H) δ = 8.72 (s, 2H), 7.79 - 7.72 (m, 1.027 1H), 7.64 - 7.55 (m, 1H), 7.34 - 7.25 (m, 1H) 6.73 (t, 1H) 5.64 (s, 2H) 1.028 δ = 8.70 (s, 2H), 7.80 (t, 2H), 7.18 (t, 2H), 6.73 (t, 1H), 5.63 (s, 2H). δ = 8.72 (s, 2H), 7.78 - 7.70 (m, 1.029 1H), 7.62 - 7.54 (m, 1H), 7.35 - 7.26 (m, 1H), 5.67 (s, 2H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.70 (s, 2H), 7.82 - 7.76 (m, 1.030 2H), 7.21 - 7.15 (m, 2H), 5.65 (s, 2H) 1.031 δ = 8.86 (dd, 1H) 8.71 (s, 2H) 8.17 (dd, 1H) 7.50 (dd, 1H) 5.67 (s, 2H) δ = 8.97 (d, 1H) 8.37 (d, 1H) 8.26 1.032 (dd, 1H) 7.57 (dd, 1H) 7.52 (dd,1H) 5.58 (d, 2H) 1.033 δ = 8.86 (dd, 1H) 8.71 (s, 2H) 8.17 (dd, 1H) 7.51 (dd, 1H) 5.68 (s, 2H) δ = 8.87 (d, 1H) 8.71 (s, 2H) 8.18 1.034 (dd, 1H) 7.56 - 7.45 (m, 1H) 6.75 (t, 1H) 5.65 (s, 2H) δ = 8.96 (dd, 1H), 8.36 (d, 1H), 8.24 1.035 (dd, 1H), 7.50-7.57 (m, 2H), 6.71 (t, 1H), 5.55 (d, 2H).1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.97 (d, 1H), 8.36 (d, 1H), 8.24 1.036 (dd, 1H), 7.56 (dd, 1H), 7.52 (d, 1H), 5.58 (d, 2H). δ = 8.40 (d, 1H), 7.84 (dd, 1H), 7.70 1.037 - 7.64 (m, 1H) 7.56 (dd, 1 H) 7.37 - 7.29 (m, 1H), 6.70 (t, 1H), 5.56 (d, 2H) 1.038 404 LCMS Method 2 1.039 383.2 LCMS Method 2 1.040 382 LCMS Method 2 1.041 402 LCMS Method 2 1.042 450.8 LCMS Method 21Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) 1.043 400 LCMS Method 2 1.044 379 LCMS Method 2 1.045 394 LCMS Method 2 1.046 415 LCMS Method 2 1.047 402 LCMS Method 2 δ = 8.71 (s, 2H), 8.39 (d, 1H), 7.66 1.048 (d, 1H), 7.48 (s, 1H), 5.69 (s, 2H), 2.09 (t, 3H) δ = 8.67 (s, 1 H), 8.46 (dd, 1 H), 1..049 8.34 - 8.41 (m, 1 H), 7.55 (dd, 1 H), 5.51 (s, 2 H), 1.42 - 1.59 (m, 2 H), 1.24 - 1.40 (m, 2 H) δ = 8.78 (d, 1H), 8.35-8.40 (m, 1H), 1.050 8.17 (dd, 1 H), 7.56 (dd, 1 H), 5.52 (s, 2 H), 1.45-1.58 (m, 2 H), 1.23- 1.42 (m, 2 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.43 (d, 1 H), 8.39 (d, 1 H), 7.78 1.051 (d, 1 H), 7.61 (s, 1 H), 7.59 (dd, 1 H), 5.63 (d, 2 H) δ = 8.40 (d, 1 H), 8.37 (d, 1 H), 7.76 1.052 (d, 1 H), 7.53 - 7.61 (m, 2 H), 5.60 (m, 2 H), 2.06 (t, 3 H). δ = 8.71 (s, 2 H), 7.48 - 7.52 (m, 1 1.053 H), 7.28 - 7.32 (m, 1 H), 7.15 (t, 1 H), 6.73 (t, 1 H), 5.64 (s, 2 H), 3.92 (s, 3 H) δ = 8.39 (d, 1 H), 7.75 (d, 1 H), 7.61 1.054 - 7.66 (dd, 1 H), 7.54 (dd, 1 H), 7.48 (d, 1 H), 6.71 (t, 1 H), 5.56 (d, 2 H), 2.36 (s, 3 H) δ = 8.77 (d, 1 H), 8.33 - 8.40 (m, 2 1.055 H), 7.55 (dd, 1 H), 7.08 - 7.12 (m, 1 H), 5.52 (d, 2 H), 1.46 - 1.59 (m, 2 H), 1.28 - 1.43 (m, 2 H) 1.056 387.02 LCMS Method 1 1.057 387.9 LCMS Method 1 1.058 387.97 LCMS Method 11Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) 1.059 372.01 LCMS Method 1 1.060 402.89 LCMS Method 1 1.061 353.99 LCMS Method 1 δ = 8.40 (d, 1 H), 7.65 - 7.74 (m, 2 1.062 H), 7.54 (dd, 1 H), 7.15 (t, 1 H), 6.72 (t, 1 H), 5.57 (d, 2 H), 2.36 (d, 3 H) δ = 8.72 (s, 2 H),7.70-7.74 (m, 1 H), 1.063 7.55 (dd, 1 H), 7.46 (d, 1 H), 6.75 (t, 1 H), 5.66 (s, 2 H), 2.44 (s, 3 H) δ = 8.71 (s, 2 H),7.67 (dd, 1 H), 1.064 7.54-7.60 (m, 1 H), 7.10 (t, 1 H), 6.74 (t, 1 H), 5.64 (s, 2 H), 2.32 (s, 3 H) δ = 8.40 (d, 1 H), 7.99 (d, 2 H), 7.57 1.065 (dd, 1 H), 6.68 (t, 1 H), 5.52 - 5.57 (m, 2 H) δ = 8.38 (d, 1 H), 7.59 (br dd, 1 H), 1.066 7.54 (br dd, 1 H), 7.40 (m, 1 H), 7.19 (dd, 1 H), 6.70 (t, 1 H), 5.54 - 5.58 (m, 2 H), 3.94 (s, 3 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) 1.067 369.12 LCMS Method 3 1.068 412.16 LCMS Method 3 1.069 402.14 LCMS Method 3 1.070 398.2 LCMS Method 3 1.071 418.12 LCMS Method 3 1.072 430.17 LCMS Method 3 1.073 353.12 LCMS Method 3 δ ppm 8.67 (s, 2H), 8.42 (d, 1H), 1.074 7.79 (dd, 1H), 6.71 (t, 1H), 5.45 (s, 2H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) 1.075 386.14 LCMS Method 3 1.076 388.16 LCMS Method 3 1.077 370.13 LCMS Method 3 1.078 371.13 LCMS Method 3 1.079 358.08 LCMS Method 3 1.080 365.11 LCMS Method 3 1.081 388.13 LCMS Method 3 1.082 371.12 LCMS Method 31Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.81 (d,1 H), 8.37 (d,1 H), 8.19 1.083 (dd, 1 H), 7.60 (dd,1 H), 5.61 (s, 2 H) 1.084 δ = 8.40 (s, 1 H), 7.94 (s, 2 H), 7.59 (dd, 1 H), 6.69 (t, 1 H), 5.60 (s, 2H) δ = 8.60 (s, 1 H), 8.38 (d, 1 H), 8.18 1.085 (dd, 1 H), 7.56 (dd, 1 H), 6.71 (t, 1 H), 5.57 (d, 2 H) 2.38 (s, 3 H) δ = 8.72 (s, 2 H), 8.50 (s, 1 H), 8.15 1.086 (dd, 1 H), 6.75 (t, 1 H), 5.67 (s, 2 H) 2.38 (s, 3 H) δ = 8.38 (d, 1 H), 7.79 - 7.85 (m, 1 1.087 H), 7.62 - 7.68 (m, 1 H), 7.53 (dd, 1 H), 7.27 - 7.34 (m, 1 H), 5.53 (d, 2 H), 2.05 (t, 3 H) δ = 8.45 (d, 1 H), 7.96 (d, 1 H), 7.64 1.088 - 7.71 (m, 1 H), 7.48 - 7.54 (m, 1 H), 7.25 - 7.32 (m, 1 H), 6.73 (t, 1 H), 5.63 (s, 2 H) δ = 8.39 (d, 1H), 7.78 (t, 1H), 7.62 1.089 (m, 1H), 7.52 (dd, 1H), 7.24-7.32 (m, 1H), 5.50 (d, 2H), 1.41-1.57 (m, 2H), 1.25-1.41 (m, 2H) δ = 8.72 (s, 2 H), 8.69 (d, 1 H), 8.11 1.090 (d, 1 H), 6.76 (t, 1 H), 5.67 (s, 2 H), 2.48 (s, 3 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.63 (s, 1 H), 8.40 (s, 1 H), 1.091 8.33 (t, 1 H), 7.60 (dd, 1 H), 6.72 (t, 1 H), 5.59 (s, 2 H) δ = 8.78 (d, 1 H), 8.36 (d, 1 H), 8.11 1.092 - 8.14 (m, 1 H), 7.55 (dd, 1 H), 6.70 (t, 1 H), 5.56 (d, 2 H), 2.47 (s, 3 H) δ = 8.41 (d, 1 H), 7.81 - 7.87 (m, 1 1.093 H), 7.65 - 7.70 (m, 1 H), 7.60 (dd,1 H), 7.37 (m, 1 H), 5.60 (d, 2 H) δ = 8.38 (d, 1 H), 7.79 (dd, 1 H), 1.094 7.62 - 7.67 (m, 1 H), 7.52 - 7.58 (m, 2 H), 6.69 (t, 1 H), 5.56 (d, 2 H) δ = 8.40 (d, 1 H), 8.02 - 8.06 (dd, 1 1.095 H), 7.81 (m, 1 H), 7.53 - 7.58 (dd, 1 H), 7.30 (t, 1 H), 6.70 (t, 1 H), 5.55 (s, 2 H) δ = 8.91 (t, 1 H), 8.39 - 8.44 (m, 2 1.096 H), 8.28 (dd,1 H), 7.74 (t,1 H), 7.56 (dd, 1 H), 6.72 (t, 1 H), 5.59 (d, 2 H). δ = 8.73 (s, 2H), 8.59-8.63 (m, 1H), 1.097 8.44 (dd, 1H), 6.74 (t, 1H), 5.66 (s, 2H) δ = 8.72 (dd, 1 H), 8.49 - 8.54 (m, 1 1.098 H), 8.38 (d, 1 H), 7.55 - 7.60 (m, 1 H), 6.70 (t, 1 H), 5.56 (d, 2 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.87 (d, 1 H), 8.66 (d, 1 H), 8.65 1.099 (s, 2 H), 8.19 (t, 1 H), 6.67 (t, 1 H), 5.60 (s, 2H) δ = 9.04 (d, 1 H), 8.76 (d,1 H), 8.39 1.100 (d, 1 H), 8.34 (t, 1 H), 7.57 (dd, 1 H), 6.72 (t, 1 H), 5.59 (d, 2 H) δ = 8.72 (s,1H), 8.71 (s, 2H), 8.29 - 1.101 8.34 (m, 1 H), 7.10 (dd,1 H), 6.74 (t, 1 H), 5.64 (s, 2 H) 1.102 δ = 8.73 (s, 2 H), 8.60 (dd, 1 H), 8.43 (dd, 1 H), 5.68 (s, 2 H) δ = 8.74 (dd, 1 H), 8.52 (dd, 1 H), 1.103 8.39 (d, 1 H), 7.59 (dd, 1 H), 5.60 (d, 2 H) δ = 8.40 (d, 1H), 8.11 - 8.19 (m, 4 1.104 H), 7.58 (dd, 1 H), 6.74 (t, 1 H), 5.60 (d, 2 H), 3.13 (s, 3 H) δ = 8.38 (d, 1 H), 8.09 - 8.18 (m, 4 1.105 H), 7.57 (dd, 1 H), 5.58 - 5.62 (m, 2 H), 3.11 (s, 3 H) δ = 8.81 (d, 1 H), 8.35 (dd, 1H), 1.106 8.37 (d, 1 H), 7.54 (d, 1 H), 7.13 (d, 1 H), 6.71 (t, 1H), 5.55 (d, 2 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.70 (s, 2 H), 7.73 (m, 1 H), 1.107 7.54 - 7.59 (m, 1 H), 7.24 - 7.31 (m, 1 H), 5.61 (s, 2 H), 2.08 (t, 3 H) δ = 8.83 (d, 1 H), 8.37 (d, 1 H), 8.22 1.108 (dd, 1 H), 7.59 (dd, 1 H), 5.60 (d, 2 H) 1.109 δ = 8.72 (s, 2H), 8.70 (d, 1 H), 8.10 (dd, 1 H), 5.69 (s, 2 H) δ = 8.83 (d, 1 H), 8.38 (d, 1 H), 8.20 1.110 - 8.23 (m, 1 H), 7.55-7.60 (m, 1H), 6.70 (t, 1 H), 5.57 (d, 2 H) 1.111 δ = 8.70-8.72 (m, 3 H), 8.11 (dd, 1 H), 6.73 (t, 1 H), 5.66 (s, 2 H) δ = 8.84 (d, 1 H), 8.39 (d, 1 H), 8.23 1.112 (dd, 1 H), 7.59 (dd, 1 H), 5.60 (d, 2 H) 1.113 δ = 8.71 (s, 2 H), 8.04-8.11 (m, 4 H), 5.69, (s, 2 H), 3.10 (s, 3 H) 1.114 δ = 8.72 (s, 2 H), 8.08 (d, 4 H), 6.76 (t, 1 H), 5.67 (s, 2 H), 3.11 (s, 3H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) 1.115 δ = 8.72 (s, 2 H), 8.04 - 8.11 (m, 4 H), 5.70 (s, 2 H), 3.11 (s, 3 H) 1.116 δ = 8.70 (s, 3 H), 8.31 (m, 1 H), 7.11 (dd, 1 H), 5.66 (s, 2 H) δ = 8.84 (d, 1 H), 8.37 - 8.44 (m, 2 1.117 H), 7.59 (dd, 1 H), 7.15 (dd, 1 H), 5.60 (d, 2 H) δ = 8.39 (d,1 H), 7.80 - 7.88 (m, 1 1.118 H), 7.64 - 7.71 (m, 1 H), 7.55 (dd, 1 H), 7.32 (m, 1 H), 5.57 (d,2 H) 1.119 δ = 8.78 (d, 1 H), 8.72 (s, 2 H), 8.38 (d, 1 H), 5.69 (s, 2 H), 4.08 (s, 3H) δ = 9.20 - 9.23 (m, 1 H), 8.43 - 8.48 1.120 (m, 1 H), 8.38 (d, 1 H), 7.83 (d,1 H) 7.54 - 7.59 (m, 1 H), 6.58-6.83 (m, 2 H), 5.59 (s, 2 H) δ = 9.20 - 9.23 (m, 1 H), 8.44 - 8.48 1.121 (m, 1 H), 8.38 (d, 1 H), 7.83 (d, 1 H), 7.54 - 7.62 (m, 1 H), 6.72 (t, 1 H), 5.60 (d, 2 H) 1.122 δ = 8.72 (s, 2 H), 8.71 (m, 1 H), 8.11 (dd, 1 H) 5.69 (s, 2 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.69 (s, 2 H) 7.70 (t, 2 H), 7.14 1.123 (t, 2 H), 5.55 (s, 2 H), 1.70 - 1.80 (m, 4 H) δ = 9.12 (d, 1 H), 8.71 (s, 2 H), 1.124 8.37 (dd, 1 H), 7.81 (d, 1 H),6.76 (t, 1 H) 6.70 (t, 1 H), 5.67 (s, 2 H) δ = 9.10 (d, 1 H), 8.72 (s, 2 H), 8.37 1.125 (dd, 1 H), 7.82 (d, 1 H), 6.70 (t, 1 H), 5.70 (s, 2 H) δ = 9.11 (d, 1 H), 8.71 (s, 2 H), 8.37 1.126 (dd, 1 H), 7.81 (d, 1 H), 6.70 (t,1 H), 5.69 (s, 2 H) 1.127 δ = 8.92 (d, 1H), 8.48 (d, 1H), 8.39 (d, 1H), 7.59 (dd, 1H), 5.59 (d, 2H) δ = 8.91 (d, 1 H), 8.48 (d, 1 H), 8.38 1.128 (d, 1 H), 7.58 (dd, 1 H), 6.71 (t, 1 H), 5.58 (d, 2 H) δ = 8.71 (s, 2 H), 8.66 (d,1 H), 8.04 1.129 (dd,1 H), 5.51 (s, 2 H), 2.06 (m,1 H), 0.95 - 1.05 (m, 4 H) δ = 8.69 (s, 2 H), 7.75 (t, 2 H), 7.12 1.130 - 7.19 (m, 2 H), 5.58 (s, 2 H), 1.44 - 1.56 (m, 2 H), 1.33 - 1.41 (m, 2H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) 1.131 δ = 8.78 (d, 1 H), 8.72 (s, 2 H), 8.38 (d, 1 H), 5.68 (s, 2 H) 1.132 δ = 8.80 (d, 1 H), 8.72 (s, 2 H), 8.40 (d, 1 H), 6.74 (t, 1 H), 5.67 (s, 2 H) 1.133 δ = 8.77 (d, 1 H), 8.72 (s, 2 H), 8.38 (d, 1 H), 5.69 (s, 2 H) δ = 8.72 (s, 2 H), 7.75 (m, 1 H), 1.134 7.58 (m, 1 H), 7.25 - 7.34 (m, 1H), 5.66 (s, 2 H) δ = 8.70 (s, 2H), 8.65 (d, 1H), 8.24 1.135 (m, 1H), 7.05 (dd, 1H), 5.49 (s, 2H), 2.02-2.11 (m, 1H), 0.94-1.06 (m, 4H). δ = 8.70 (br s, 3 H), 8.31 (m, 1 H), 1.136 7.09 (dd, 1 H), 5.63 (s, 2 H) 2.09 (t, 3 H) 1H NMR (DMSO-d6, 400 MHz) δ = 8.68 (d, 1H), 8.48 (d, 1H), 8.40 (m, 1.137 1H), 8.17 (dd, 1H), 7.39 (dd, 1H), 5.59-5.65 (m, 2H), 3.67 (t, 2H), 3.23 (s, 3H), 2.85 (t, 2H) δ = 8.78 (d, 1 H), 8.62 (s, 2 H), 8.09 1.138 (dd, 1 H), 7.41 (d, 1 H), 5.56 (s, 2 H), 2.02 (t, 3 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.79 (d, 1H), 8.40 - 8.33 (m, 1.139 2H), 7.54 (dd, 1H), 7.13 - 7.06 (m, 1H), 5.54 (d, 2H), 2.06 (t, 3H) δ = 8.70 (s, 2 H), 8.66 (d,1 H), 8.26 1.140 (m, 1 H), 7.07 (dd, 1 H), 5.59 (s, 2 H), 1.45 - 1.59 (m, 2 H) 1.29 - 1.44 (m, 2 H) δ = 8.35 (d, 1 H), 8.25 (d, 1 H) , 1.141 7.80 (m, 1 H), 7.55 (s, 1 H), 7.53 (dd, 1 H), 5.78 (s, 2 H) 1.45 - 1.60 (m, 4 H) δ = 8.96 (d, 1 H), 8.36 (d, 1 H), 8.24 1.142 (dd, 1 H), 7.55 (dd, 1 H), 7.50 (d, 1 H), 5.55 (d, 2 H), 2.07 (t, 3 H) 1.143 δ = 8.72 (s, 2 H), 8.41 (d, 1 H), 7.67 (d, 1 H), 7.49 (s, 1 H), 5.72 (s, 2 H) 1H NMR (400 MHz, DMSO-d6 ) δ = 8.68 - 8.72 (m, 1 H), 8.45 - 8.49 (m, 1.144 1 H), 8.41 (td, 1 H), 8.17 (dd, 1 H), 7.40 (dd, 1 H), 5.65 (s, 2 H), 3.80 (t, 2 H), 3.18 - 3.26 (m, 2 H) δ = 8.76 (d, 1 H), 8.31-8.39 (m, 2 1.145 H), 7.54 (dd, 1 H), 7.11 (dd, 1 H), 6.25 (t, 1 H), 5.49 (d, 2H), 3.32 (td, 2H) δ = 8.78 (d, 1 H) 8.33 - 8.40 (m, 2 1.146 H) 7.55 (dd, 1 H), 7.11 (dd, 1 H), 5.56 (d, 2 H) 2.28 - 2.44 (m, 2 H) 1.09 (t, 3 H)1Compound STRUCTURE H NMR (400 MHz, CDCl3) or LCMS (M+H) δ = 8.77 (d, 1 H), 8.34 - 8.40 (m, 2 1.147 H), 7.53 - 7.58 (m, 1 H), 7.10 - 7.14 (m, 1 H), 5.59 (d, 2H), 2.59 - 2.71 (m, 1 H), 1.10 (d, 6 H) δ = 8.36 (d, 1 H), 7.76 - 7.83 (m, 1 H), 7.60 - 7.66 (m, 1 H), 7.53 (dd, 1 1.148 H), 7.28 - 7.34 (m, 1 H), 5.55 - 5.58 (m, 2 H), 2.63 (m, 1 H), 1.07 (d, 6 H) δ ppm 8.67 (s, 2H), 8.40 (d, 1H), 1.149 7.77 (dd, 1H), 6.71 (s, 1H), 5.54 (s, 2H) δ ppm 8.71 (s, 2H), 8.45 (d, 1H), 1.150 7.83 (dd, 1H), 6.71 (t, 2H), 5.52 (s, 2H) δ = 8.82 (d, 1H), 8.37-8.42 (m, 2H), 1.151 7.57 (dd, 1H), 7.14-7.14 (m, 1H), 5.58 (d, 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 / 16oC, day / night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005- 64-5). Compounds are applied at 250 g / ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24 / 16oC, 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 5 5 5 5 NT 1.002 250 5 5 4 5 3 1.003 250 5 5 5 5 5 1.004 250 4 4 4 4 4 1.005 250 4 5 1 1 4 1.006 250 4 5 1 2 2 1.007 250 1 1 1 1 1 1.008 250 5 5 2 1 1 1.009 250 2 2 1 1 1 1.010 250 4 5 1 5 3 1.011 250 4 4 4 4 4 1.012 250 1 1 1 1 1 1.013 250 5 5 1 5 NT 1.014 250 5 5 3 5 NT 1.015 250 4 5 1 5 NT 1.016 250 3 3 1 3 NT 1.017 250 5 5 5 5 NT 1.018 250 4 5 4 4 4 1.019 250 1 2 1 2 1 1.020 250 4 3 1 3 NT 1.021 250 5 5 4 5 5 1.022 250 5 5 5 5 NT 1.023 250 5 5 1 5 NT 1.025 250 5 5 5 5 NT Compound Rate (g / ha) AMAPA AMARE SETFA ECHCG IPOHE 1.026 250 5 5 5 5 NT 1.027 250 5 5 5 5 NT 1.028 250 4 5 4 5 NT 1.029 250 5 5 5 5 NT 1.030 250 5 5 5 5 4 1.031 250 5 5 4 4 4 1.032 250 5 5 5 5 4 1.033 250 5 5 5 5 5 1.034 250 5 5 4 4 5 1.035 250 5 5 5 5 4 1.036 250 5 5 5 5 5 1.037 250 5 5 5 5 5 1.074 250 4 5 2 2 2 1.098 250 4 4 3 3 NT 1.099 250 4 4 1 1 NT 1.100 250 5 5 4 3 NT 1.101 250 5 5 1 1 NT 1.102 250 1 1 1 1 NT 1.103 250 5 5 5 4 NT 1.104 250 5 5 5 5 NT 1.105 250 5 5 5 5 NT 1.106 250 5 5 3 4 NT 1.107 250 5 5 5 5 NT 1.108 250 5 5 4 3 NT 1.109 250 4 4 1 1 NT 1.110 250 3 3 2 3 NT 1.111 250 3 2 1 1 NT 1.112 250 4 5 4 4 NT 1.113 250 5 5 5 4 NT 1.114 250 5 5 3 3 NT 1.115 250 5 5 5 4 NT 1.116 250 5 5 4 4 NT 1.117 250 5 5 5 5 NT 1.118 250 5 5 5 5 NT 1.119 250 5 5 4 3 NT 1.120 250 5 5 5 4 NT 1.121 250 5 5 5 5 NT 1.122 250 3 3 2 2 NT 1.123 250 4 4 1 1 NT 1.124 250 5 5 4 5 NT 1.125 250 5 5 5 5 NT 1.126 250 5 5 5 5 NT 1.127 250 5 5 1 1 NT 1.128 250 5 5 1 1 NT 1.129 250 4 4 1 1 NT 1.130 250 5 5 4 4 NT 1.131 250 5 5 2 1 NT 1.132 250 4 4 1 1 NT 1.133 250 5 5 2 2 NT 1.134 250 5 5 5 5 NT 1.135 250 4 4 1 1 NT Compound Rate (g / ha) AMAPA AMARE SETFA ECHCG IPOHE 1.139 250 5 NT NT NT NT 1.149 250 3 3 1 1 1 1.150 250 3 4 1 1 1 NT = Not tested TABLE B2. Pre-emergence Test Compound Rate (g / ha) AMAPA AMARE SETFA ECHCG IPOHE 1.001 250 5 5 5 5 NT 1.002 250 5 2 5 3 1 1.003 250 5 5 5 5 1 1.004 250 5 5 5 4 2 1.005 250 5 5 4 4 4 1.006 250 4 5 1 1 1 1.007 250 1 1 1 1 1 1.008 250 4 4 1 1 1 1.009 250 3 3 1 1 1 1.010 250 5 5 4 4 5 1.011 250 5 5 5 5 4 1.012 250 3 3 1 1 1 1.013 250 5 5 5 4 NT 1.014 250 5 5 5 5 NT 1.015 250 5 5 1 1 NT 1.016 250 3 4 1 1 NT 1.017 250 5 5 5 5 NT 1.018 250 5 5 5 4 3 1.019 250 3 5 3 3 2 1.020 250 4 5 3 2 NT 1.021 250 5 5 5 4 5 1.022 250 5 5 5 5 NT 1.023 250 5 5 5 4 NT 1.025 250 5 5 5 5 NT 1.026 250 5 5 5 5 NT 1.027 250 5 5 5 5 NT 1.028 250 5 5 5 5 NT 1.029 250 5 5 5 5 NT 1.030 250 5 5 5 5 5 1.031 250 5 5 5 5 4 1.032 250 5 5 5 5 4 1.033 250 5 5 5 5 5 1.034 250 5 5 5 4 5 1.035 250 5 5 5 5 5 1.036 250 5 5 5 5 5 1.037 250 5 5 5 5 5 1.038 250 5 NT 4 3 1 1.041 250 1 NT 1 1 1 1.042 250 5 NT 5 5 5 1.043 250 5 NT 5 5 5 Compound Rate (g / ha) AMAPA AMARE SETFA ECHCG IPOHE 1.044 250 5 NT 5 5 5 1.045 250 3 NT 1 1 1 1.046 250 3 NT 1 1 1 1.047 250 5 NT 2 2 3 1.048 250 5 NT 5 5 5 1.049 250 1 NT 5 4 1 1.050 250 5 NT 3 4 1 1.051 250 5 NT 5 5 5 1.052 250 5 NT 5 5 5 1.053 250 5 NT 4 4 5 1.054 250 5 NT 5 5 1 1.055 250 5 NT 5 5 5 1.056 250 1 NT 1 1 1 1.057 250 5 NT 4 4 5 1.058 250 5 NT 5 5 5 1.059 250 5 NT 5 5 5 1.060 250 3 NT 2 3 1 1.061 250 5 NT 2 3 4 1.064 250 5 NT 5 5 1 1.065 250 5 NT 5 5 4 1.066 250 5 NT 5 5 4 1.067 250 5 NT 5 3 2 1.068 250 5 NT 3 1 1 1.069 250 2 NT 1 1 NT 1.070 250 3 NT 1 1 1 1.071 250 5 NT 2 2 1 1.072 250 4 NT 1 1 4 1.073 250 5 NT 5 5 4 1.074 250 5 5 2 1 1 1.075 250 5 NT 4 4 5 1.076 250 5 NT 5 5 4 1.077 250 5 NT 5 4 4 1.078 250 5 NT 3 3 2 1.079 250 5 NT 5 5 5 1.080 250 5 NT 5 5 5 1.081 250 5 NT 4 3 3 1.082 250 5 NT 5 5 5 1.083 250 5 NT 1 2 1 1.084 250 5 NT 4 4 4 1.085 250 5 NT 5 5 4 1.086 250 5 NT 3 4 4 1.087 250 5 NT 5 5 5 1.088 250 5 NT 3 2 1 1.089 250 5 NT 5 5 5 1.090 250 5 NT 4 3 1 1.091 250 4 NT 2 1 1 1.092 250 5 NT 5 5 5 1.093 250 5 NT 4 4 2 1.094 250 5 NT 5 5 5 1.095 250 5 NT 5 5 5 1.096 250 5 NT 4 4 5 Compound Rate (g / ha) AMAPA AMARE SETFA ECHCG IPOHE 1.097 250 4 NT 1 1 1 1.098 250 5 5 5 4 2 1.099 250 5 5 5 4 5 1.100 250 5 5 5 5 5 1.101 250 5 5 5 4 5 1.102 250 4 5 2 1 1 1.103 250 5 5 5 5 3 1.104 250 5 5 5 5 5 1.105 250 5 5 5 5 5 1.106 250 5 5 5 5 5 1.107 250 5 5 5 5 5 1.108 250 5 5 4 4 3 1.109 250 5 5 2 2 1 1.110 250 5 5 3 2 3 1.111 250 5 3 1 1 3 1.112 250 5 5 5 4 2 1.113 250 5 5 5 5 5 1.114 250 5 5 4 3 5 1.115 250 5 5 5 5 5 1.116 250 5 5 5 5 5 1.117 250 5 5 5 5 5 1.118 250 5 5 5 5 4 1.119 250 5 5 5 4 2 1.120 250 5 5 5 5 5 1.121 250 5 5 5 5 5 1.122 250 5 5 2 2 1 1.123 250 5 5 2 1 4 1.124 250 5 5 5 5 5 1.125 250 5 5 5 5 5 1.126 250 5 5 5 5 5 1.127 250 5 5 4 1 1 1.128 250 5 5 1 1 1 1.129 250 5 5 1 1 NT 1.130 250 5 5 2 1 NT 1.131 250 5 5 1 1 NT 1.132 250 5 5 1 1 NT 1.133 250 5 5 1 1 NT 1.134 250 5 5 5 5 NT 1.135 250 4 4 1 1 NT 1.139 250 5 NT 5 5 NT 1.149 250 3 4 1 1 1 1.150 250 5 5 3 1 1 NT = Not tested TABLE B2 – COMPARATIVE TEST Seeds of test species were sown in standard soil in pots. After cultivation for one day under controlled conditions in a glasshouse (at 24 / 16oC, day / night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL (Registry number 61791-12-6), 42.2% N-methyl pyrrolidone, 42.2% dipropylene glycol monomethyl ether (CAS RN 34590-94-8) and 0.2 % X-77 (CAS RN 11097-66-8). The test plants were then grown in a glasshouse under controlled conditions in a glasshouse (at 24 / 16oC, day / night; 14 hours light; 65 % humidity) and watered twice daily. After 14 days, the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Test species: AMARE (Amaranthus retroflexus); AMAPA (Amatanthus palmeri); ZEAMX (Zea mays - maize). Compound PRE Application C1 Rate AMARE AMAPA ZEAMX g / ha 250 100 100 80 63 100 100 70 16 100 100 10 1.098 Rate AMARE AMAPA ZEAMX g / ha 250 100 100 10 63 100 100 0 16 80 100 0 C1 is compound 1.023 disclosed in WO2024 / 149675. As can be seen, the introduction of an additional nitrogen into the central ring causes an unexpected improvement in crop (maize) selectivity – herbicide damage on the maize is significantly reduced – whilst control of problematic Amaranthus weed species remains very good.

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 R4; R1is independently selected from the group consisting of halogen, cyano, NO2, C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl, - S(O)pC1-C4alkyl, C1-C4alkoxy-, -C(O)C1-C4alkyl, -C(O)OC1-C4alkyl, C1- C4haloalkoxy and C1-C4alkoxyC1-C3alkyl-; R2is selected from the group consisting of halogen, cyano, NO2, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, -C(O)C1-C4alkyl, C1-C4cyanoalkyl, -C(O)OC1- C4alkyl, C1-C4haloalkoxy, C1-C4alkoxyC1-C3alkyl-, C1-C4alkoxyC1-C3alkoxy-, C1-C4alkoxyC1-C3alkoxyC1-C3alkyl-, -S(O)pC1-C4alkyl and C3-C6cycloalkyl wherein said C3-C6cycloalkyl is optionally substituted by halogen and / or cyano; R4is selected from the group consisting of halogen, C1-C4 alkyl, C1- C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4alkoxyC1-C3alkyl-, C1- C4alkoxyC1-C3alkoxy-, C1-C4alkoxyC1-C3alkoxyC1-C3alkyl-, cyano, NO2, C2- C4alkenyl, C2-C4alkynyl, -S(O)pC1-C4alkyl, -S(O)pC1-C4haloalkyl, -C(O)OC1- C4alkyl and -C(O)NR5R6; A1is N or CR7;A2is N or CR8; R5is hydrogen or C1-C4alkyl; R6is hydrogen or C1-C4alkyl; R7is selected from the group consisting of hydrogen, fluoro, chloro and cyano; R8is selected from the group consisting of hydrogen, fluoro, chloro and cyano; m = 1 or 2; and p = 0, 1 or 2.

2. A compound of Formula (I) according to claim 1, selected from the group consisting of (Ia), (Ib), (Ic) and (Id):wherein Q, R1, R2and R7are as defined in claim 1 above.

3. A compound according to claim 1 or claim 2, wherein R7is fluoro.

4. A compound according to any one of the previous claims, wherein R1is chloro.

5. A compound according to any one of the previous claims, wherein R2is selected from the group consisting of bromo, -CF3, -CF2Cl and -CF2H.

6. A compound according to any one of the previous claims, wherein Q is selected from the group consisting of:wherein n is 0, 1 or 2.

7. A compound according to any one of the previous claims, wherein Q is Q-1, or Q-3.

8. A compound according to claim 7, wherein n is 1 or 2.

9. A compound according to claim 8, wherein R4is independently selected from the group consisting of cyano, methyl, halogen and -CF3.

10. A compound according to claim 9, wherein R4is halogen.

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

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

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

14. 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 11 to 13.

15. A compound of Formula (II):wherein A1, R1and R2are as defined in the compound of Formula (I) above.

16. A compound of Formula (III):wherein A1, R1and R2are as defined in the compound of Formula (I) above.

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

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