WO2018050677A1 - Herbicidal pyridines - Google Patents

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein Q, X¹, X², X³, X⁴ and R² are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I), to their use for controlling weeds, in particular in crops of useful plants.

Description

HERBICIDAL PYRIDINES

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 pyridinyl ketones are disclosed in WO 97/46530. N-(tetrazol-5-yl)- and N-(triazol-5-yl) arylcarboxamides are disclosed in, for example, WO2012/028579, WO2012/126932 and WO2013/092834. The present invention relates to novel herbicidal pyridinyl carboxamides.

Thus, according to the present invention there is provided a compound of Formula (I):

(I) or an agronomically acceptable salt thereof,

wherein :- selected from the group consisting of Ql, Q2, Q3, Q4 and Q5

(Q1 ) (02) (Q3) (Q4) (Q5) R¹ is selected from the group consisting of Ci-C6alkyl-, Ci-Cehaloalkyl- and Ci- C6alkoxy-Ci-C₃alkyl-;

R² is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci-Cehaloalkyl-, Ci- C₆alkoxy-, Ci-C6alkoxy-Ci-C6alkyl-, halogen, cyano, nitro, Ci-C6alkyl-S(0)_p- and Ci- C₆haloalkyl-S(0)_P-;

X¹ is N or CR³; X² is N or CR⁴;

X³ is N or CR⁵;

X⁴ is N or CR⁶;

R³, R⁴, R⁵ and R⁶ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -NH₂, Ci-C4alkyl-, Ci-C4alkoxy- and Ci-C4haloalkyl-; and p = 0, 1 or 2.

Ci-C6alkyl and Ci-C4alkyl groups include, for example, methyl (Me, CH₃), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (z^'-Pr), n-butyl (n- u), isobutyl (z-Bu), sec- butyl and tert-butyl (t-Bu). Halogen (or halo) encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.

Ci-C₆haloalkyl includes, for example, fluoromethyl-, difluoromethyl-, trifluoromethyl-, chloromethyl-, dichloromethyl-, trichloromethyl-, 2,2,2- trif uoroethyl-, 2-fluoroethyl-, 2-chloroethyl-, pentafluoroethyl-, l , l-difluoro-2,2,2- trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl-, heptafluoro-n-propyl and perfluoro-n-hexyl. Ci-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-tetrafluoroethyl-, 2,2,2-trichloroethyl- and heptafluoro-n- propyl-.

Ci-C6alkoxy- includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy.

Ci-C6alkoxy-Ci-C3alkyl- groups include, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxy ethyl.

Ci-C6alkyl-S- (alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

Ci-C6alkyl-S(0)- (alkylsulfmyl) is, for example, methylsulfmyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfmyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfmyl or ethylsulfinyl.

Ci-C6alkyl-S(0)2- (alkylsulfonyl) is, 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 there is provided a compound of Formula (I), wherein Q is Ql .

In another embodiment of the present invention there is provided a compound of Formula (I), wherein Q is Q2.

In another embodiment of the present invention there is provided a compound of Formula (I), wherein Q is Q3. In another embodiment of the present invention there is provided a compound of Formula (I), wherein Q is Q4.

In another embodiment of the present invention there is provided a compound of Formula (I), wherein Q is Q5.

In another embodiment of the present invention R³, R⁴, R⁵ and R⁶ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4alkyl-, Ci-C4alkoxy- and Ci-C4haloalkyl-.

In one embodiment of the present invention there is provided a compound of Formula (I) wherein X¹ is N, X² is CR⁴, X³ is CR⁵ and X⁴ is CR⁶ and wherein R⁴, R⁵ and R⁶ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4alkyl-, Ci-C4alkoxy- and Ci-C4haloalkyl-. In this context, R⁴ is preferably hydrogen or Ci-C4alkyl- (e.g methyl), R⁵ is preferably hydrogen, halogen (e.g bromine, chlorine, iodine) or Ci-C4alkyl (e.g z^'so-propyl) and R⁶ is preferably hydrogen or Ci-C4alkyl- (e.g methyl).

In another embodiment of the present invention there is provided a compound of Formula (I) wherein X¹ is N, X² is CR⁴, X³ is N and X⁴ is CR⁶ and wherein R⁴ and R⁶ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4alkyl-, Ci-C4alkoxy- and Ci-C4haloalkyl-. In this context, R⁴ is preferably hydrogen and R⁶ is preferably hydrogen. In another embodiment of the present invention there is provided a compound of Formula (I), wherein X¹ is CR³, X² is N, X³ is CR⁵ and X⁴ is CR⁶ and wherein R³, R⁵ and R⁶ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4alkyl-, Ci-C4alkoxy- and Ci-C4haloalkyl-. In this context R³ is preferably hydrogen or Ci-C4alkyl- (preferably methyl), R⁵ is preferably hydrogen and R⁶ is preferably hydrogen.

In a preferred aspect of the present invention R¹ is Ci-C4alkyl-, and in a more preferred aspect selected from the group consisting of methyl, ethyl and propyl. In one embodiment of the present invention, R² is Ci-Cehaloalkyl-, preferably trifluoromethy 1- .

Compounds of Formula (I) (and certain intermediate compounds used to synthesise compound 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.

Similarly, where there are disubstituted alkenes, these may be present in E or Z form or as mixtures of both in any proportion.

Furthermore, compounds of Formula (I) may be in equilibrium with alternative tautomeric forms. It should be appreciated that all tautomeric forms (single tautomer or mixtures thereof), racemic mixtures and single isomers are included within the scope of the present invention.

The present invention also includes agronomically acceptable salts that the compounds of Formula (I) may form with amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as salt formers, emphasis is to be given to the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium, magnesium and calcium. The corresponding trimethylsulfonium salt may also be used.

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 (SFAs). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound of the present invention 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, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. 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).

Dustable powders (DP) may be prepared by mixing a compound of Formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

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 preformed 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- Cio 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°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, 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 SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SFA 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 (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), 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 SFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs 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-z^'sopropyl- and tri-z^'sopropyl-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 and lignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs 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); and lecithins.

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

The composition of the present may further comprise at least one additional pesticide. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment the additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures are (in which T represents a compound of Formula I). I + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + ametryn, I + amicarbazone, I + amidosulfuron, I + aminopyralid, I + amitrole, I + anilofos, I + asulam, I + atrazine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bromobutide, I + bromoxynil, I + butachlor, I + butamifos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, I + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + cyanazine, I + cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop, I + cyhalofop-butyl,, I + 2,4-D, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + I + desmedipham, I + dicamba, I + dichlobenil, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclo fop- methyl, I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + dimethachlor, I + dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + endothal, I + EPTC, I + esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron-methyl, I + ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I + fenoxaprop-P, I + fenoxaprop-P-ethyl, I + fenquinotrione, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop-butyl, I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone-sodium, I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I + flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumiclorac-pentyl, I + flumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I + fluoroglyco fen-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I + fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinate-ammonium, I + glyphosate, I + halauxifen, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-P, I + hexazinone, I + imazamethabenz, I + imazamethabenz-methyl, I + imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I + imazosulfuron, I + indanofan, I + indaziflam, I + iodomethane, I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron- methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron, I + metazachlor, I + methabenzthiazuron, I + methazole, I + methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, I + metolachlor, I + S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I + metsulfuron-methyl, I + molinate, I + monolinuron, I + naproanilide, I + napropamide, I + naptalam, I + neburon, I + nicosulfuron, I + n-methyl glyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, I + pendimethalin, I + penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + pethoxamid, I + phenmedipham, I + picloram, I + picolinafen, I + pinoxaden, I + piperophos, I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I + prodiamine, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I + propisochlor, I + propoxycarbazone, I + propoxycarbazone-sodium, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen-ethyl, I + pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + pyridate, I + pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac, I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxsulam, I + quinclorac, I + quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + rimsulfuron, I + saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I + terbutryn, I + thenylchlor, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + topramezone, I + tralkoxydim, I + tri-allate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trihydroxytriazine, I + trinexapac-ethyl, I + tritosulfuron, I + [3-[2-chloro-4-fluoro-5-(l-methyl-6-trifluoromethyl-2,4-dioxo- l,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6). The compounds of the present invention may also be combined with herbicidal compounds disclosed in WO06/024820 and/or WO07/096576.

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 of Formula I according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of Formula I according to the invention with one or more further herbicides can also be used in combination with one or more safeners. The safeners can be AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, N-isopropyl- 4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4). Other possibilities include safener compounds disclosed in, for example, EP0365484 e.g N- (2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

Particularly preferred are mixtures of a compound of Formula I with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or N-(2-methoxybenzoyl)-4-[(methyl- aminocarbonyl)amino]benzenesulfonamide.

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 phos- phonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc. 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 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 safener).

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 further provides 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. Generally the plants to be controlled are unwanted plants (weeds). 'Locus' means the area in which the plants are growing or will grow. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I). However, in some instances tolerance may need to be engineered into the crop plant, for example by way of genetic engineering. Thus, it is possible that the crop plant is rendered tolerant to HPPD-inhibitors via genetic engineering. Methods of rending crop plants tolerant to HPPD-inhibitors are known, for example from WO0246387. Thus in an even more preferred embodiment the crop plant is transgenic in respect of a polynucleotide comprising a DNA sequence which encodes an HPPD- inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more particularly, from a barley, maize, wheat, rice, Brachiaria, Cenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species. Several HPPD-tolerant soybean transgenic "events" are known, and include for example SYHT04R (WO2012/082542), SYHT0H2 (WO2012/082548) and FG72. Crop plants in which the composition according to the invention can be used thus include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf. Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.

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 2000 g/ha, especially from 50 to 1000 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 herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-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®.

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-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes 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).

Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes.

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. Weeds can also include plants which may be considered crop plants but which are growing outside a crop area ('escapes'), or which grow from seed left over from a previous planting of a different crop ('volunteers'). Such volunteers or escapes may be tolerant to certain other herbicides.

The compounds of the present invention can be prepared according to the following schemes.

Scheme 1:- Activation of a carboxylic acid and reaction with a 2-amino- 1,3,4- oxadiazole

Scheme 2:- Activation of a carboxylic acid and reaction with a 3-amino- 1,2,5- oxadiazole

Scheme 3:- Activation of a carboxylic acid and reaction with a 5-amino-tetrazole

Scheme 4:- Activation of a carboxylic acid and reaction with a 5-amino-l,2,4-triazole

Scheme 5:- Activation of a carboxylic acid and reaction with a 2-amino- 1,3,4- triazole

In each of Schemes 1 - 5, PPAA is 1 -propanephosphonic acid cyclic anhydride, DMAP is 4-(dimethylamino)pyridine, the solvent is an aprotic organic solvent such as dichloromethane, ethyl acetate, tetrahydrofuran, 1 ,4-dioxane, and the reaction may be subjected to heating (optionally, by microwave irradiation). Other methods of activation of the carboxylic acids, such as acid chloride formation, or activation with carbonyldiimidazole are also applicable.

Scheme 6:- Displacement of a leaving group by a heterocyclic nucleophile

Where X is a leaving group such as chloro, bromo, iodo, trifluoromethanesulfonate etc., M+ is a metal counterion such as sodium or potassium, base is, for example, sodium hydride or potassium carbonate, solvent is, for example, 1-methylpyrrolidine (NMP) or dimethylformamide (DMF), and the reaction may be conducted at room temperature or subjected to heating (optionally, by microwave irradiation).

Scheme 7:- Preparation of heterocycle-substituted nicotinic esters and acids utilised in Schemes 1 - 5

or HCI/AcOH

Where M+ is a metal counterion, base is, for example, sodium hydride or potassium carbonate, solvent is, for example, 1-methylpyrrolidine (NMP) or dimethylformamide (DMF), and the reactions may be conducted at room temperature or subjected to heating (optionally, by microwave irradiation). R is an alkyl group such as methyl or ethyl. Scheme 8:- Preparation of amides utilised in Scheme 6

Where X is a leaving group such as chloro, bromo, iodo, trifluoromethanesulfonate etc., PPAA is 1-propanephosphonic acid cyclic anhydride, DMAP is 4- (dimethylamino)pyridine, the solvent is an aprotic organic solvent such as dichloromethane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, and the reaction may be subjected to heating (optionally, by microwave irradiation). Other methods of activation of the carboxylic acids, such as acid chloride formation, or activation with carbonyldiimidazole are also applicable. Analogous amides of 2-amino- 1,3, 4- oxadiazoles, 3-amino-l,2,5-oxadiazoles, 5-amino-l,2,4-triazoles and 2-amino- 1,3,4- triazoles may be prepared similarly.

The substituted nicotinic acids utilised in Schemes 7 and 8 are prepared by known methods, or methods analogous to known methods.

Scheme 9:- Functional group interconversion

Where Y is a leaving group such as chloro, or fluoro, NuH is a nucleophile such as an alcohol or a thiol, NuM is a metal alkoxide (such as sodium methoxide) or a metal thiolate (such as sodium thiomethoxide), the base is an optional base such as potassium carbonate or sodium carbonate, and the solvent is a non-protic solvent such as dimethylformamide, N-methyl pyrolidinone or dimethyl sulfoxide.

Scheme 10: Functional group interconversion

Where the oxidant is an oxidising agent such as hydrogen peroxide (with an optional catalytic quantity of sodium tungstate), sodium periodate or 3-chloroperoxybenzoic acid, the solvent is, for example, dichloromethane, tetrahydrofuran or ethyl acetate, n is one or two and can be controlled by the amount of oxidant used.

The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Tables 1, 2 and 3 below.

Preparative Example 1: Preparation of Compound 3.001

e/

Step 1 : A stirred solution of 2-chloro-6-(trifluoromethyl)pyridine-3-carboxylic acid (compound El : 2.64 g, 11.37 mmol) in ethanol (5.6 mL) was treated with triethyl orthoformate (3.9 mL, 23 mmol) and then sulfuric acid (cone) (0.06 mL, 1 mmol). The reaction mixture was heated to 150°C for 1 hour under microwave irradiation, when LCMS analysis showed that the reaction hadn't proceeded to completion. The reaction mixture was heated to 150°C for a further 30 minutes under microwave irradiation. The cooled reaction mixture was evaporated to dryness under reduced pressure, and the residual pale yellow liquid was dissolved in dichloromethane. The dichloromethane solution was washed with aqueous sodium bicarbonate solution, dried and evaporated under reduced pressure to afford compound E2 as a pale yellow liquid (2.40 g). 1HNMR (CDC13): δ 8.31 (d, 1H), 7.70 (d, 1H), 4.47 (q, 2H), 1.44 (t, 3H)

Step 2: A stirred solution of compound E2 (1.035 g, 4.081 mmol) in dimethylform- amide (DMF: 3 mL) was treated with 1,2,4-triazol-l-ylsodium (0.732 g, 8.034 mmol) in a microwave vial, and the reaction mixture was then heated to 100°C for 30 minutes under microwave irradiation. The cooled mixture was filtered, and the filtrate was evaporated under reduced pressure to leave a viscous red/brown residue. This residue was dissolved in ethyl acetate and washed with water. The organic layer was separated, dried and evaporated to afford compound E3 as a red/brown liquid which solidified on standing (632 mg).

1H NMR (CDC13): δ 9.09 (s, 1H), 8.21 (d, 1H), 8.10 (s, 1H), 7.79 (d, 1H), 4.40 (q, 2H), 1.30 (t, 3H)

Step 3: A stirred solution of compound E3 (454 mg, 1.5862 mmol) in 1,4-dioxane (10 mL) was treated with a solution of lithium hydroxide monohydrate (103 mg, 2.455 mmol) in water (5 mL). The resultant mixture was stirred at room temperature for 1 hour, then left to stand overnight. The mixture was evaporated to dryness under reduced pressure, and the residue was dissolved in water. This solution was washed with ethyl acetate, then acidified and extracted with ethyl acetate (x3). The combined ethyl acetate extracts of the acidified aqueous layer were dried, and evaporated to dryness under reduced pressure to afford compound E4 as a white solid (355 mg).

1H NMR (CDC13): δ 9.19 (s, 1H), 8.55 (d, 1H), 8.22 (s, 1H), 7.86 (d, 1H) Step 4: A stirred solution of compound E4 (100.0 mg, 0.387 mmol) and 2-amino-5- methyl-l,3,4-oxadiazole (53.7 mg, 0.542 mmol) in dichloromethane (3 mL) was treated with 4-(dimethylamino)pyridine (DMAP: 142.0 mg, 1.1621 mmol) followed by 1-propanephosphonic acid cyclic anhydride (PPAA (50% in ethyl acetate): 1.38 mL, 2.324 mmol). The reaction mixture was then heated to 120°C for 30 min. under microwave irradiation. The cooled mixture was evaporated to dryness under reduced pressure, and the residue was dissolved in ethyl acetate. This solution was washed with water (2 x), brine, dried and evaporated under reduced pressure. The residue was purified by silica-gel chromatography, eluting with 0 - 5% methanol in dichloromethane mixtures to afford compound 3.001 as a white solid (78.0 mg).

1H NMR (d3-MeCN) δ 9.18 - 9.12 (m, 1H), 8.41 - 8.29 (m, 1H), 8.07 (s, 1H), 7.99 (s, 1H), 2.45 (s, 3H) Preparative Example 2: Preparation of Compound 2.001

Step 1 : Using a procedure analogous to that described in Preparative Example 1 , Step 4, but using 5-amino-l -methyl- 1,2,4-triazole in place of 2-amino-5-methyl-l,3,4- oxadiazole, Compound 2.001 was obtained as a white solid.

1H NMR (d3-MeCN) δ 9.10 (s, 1H), 8.48 - 8.32 (m, 1H), 8.11 (s, 1H), 7.99 (s, 1H), 7.80 - 7.54 (m, 1H), 3.83 (s, 3H)

Preparative Example 3: Preparation of Compound 1.010

Step 1 : Using a procedure analogous to that described in Preparative Example 1 , Step 4, but using 5-amino-l -propyl-tetrazole in place of 2-amino-5-methyl-l,3,4- oxadiazole, Compound 1.010 was obtained as a white solid.

1H NMR (d3-MeCN) δ 9.40 (br s, 1H), 9.20 (s, 1H), 8.42 (d, 1H), 8.18 (s, 1H), 8.02 (d, 1H), 4.45 - 4.23 (m, 2H), 1.98 - 1.94 (m, 2H), 0.97 (t, 3H)

Preparative Example 4: preparation of Compound 1.001

1.001

Step 1 : A stirred solution of compound El (10.00 g, 44.336 mmol) and 5-amino-l- methyltetrazole (4.36 g, 44.000 mmol) in a mixture of dichloromethane (300 mL) and tetrahydrofuran (THF: 200 mL) was treated with 4-(dimethylamino)pyridine (DMAP: 10.80 g, 85.70 mmol) and the mixture was stirred at room temperature for 4 hours. 1- propanephosphonic acid cyclic anhydride (PPAA (50% in ethyl acetate): 57 mL, 95.75 mmol) was then added dropwise and the reaction mixture was stirred at room temperature for lhour, allowed to stand at room temperature overnight, stirred at room temperature for 7 hours, and again allowed to stand overnight. Water was added and the resultant mixture was shaken vigorously. The organic phase was separated, adsorbed onto silica-gel under reduced pressure, and separated by silica-gel chromatography, eluting with 10 - 40% methanol in dichloromethane mixtures, to afford compound E5 as a pale brown solid (12.47 g).

1H NMR (d6-DMSO): 12.08 (br s, 1H), 8.58 (d, 1H), 8.19 (d, 1H), 4.03 (s, 3H)

Step 2: A stirred solution of compound E5 (0.500 g, 1.63 mmol) in anhydrous 1- methylpyrrolidinone (NMP: 2.50 mL) was treated with 1,2,4-triazole, sodium salt (0.371 g, 4.08 mmol) and the mixture was heated to 100°C for 3 days. The cooled reaction mixture was allowed to stand overnight, and the thick yellow mixture was then quenched by addition of 2M HCl. The mixture was extracted with ethyl acetate (x 2) and the combined ethyl acetate extracts were washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to afford crude compound 1.001 as an off white solid. This was purified by silica-gel chromatography, eluting with 0 - 100% mixtures of ethyl acetate in iso-hexane, to afford pure compound 1.001 as a white solid (333 mg).

1H NMR (CDC13/d6-DMSO) δ 11.72 (br s, 1H), 9.06 (s, 1H), 8.21 (br d, 1H), 8.00 (s, 1H), 7.76 (d, 1H), 4.12 (br s, 3H)

Preparative Example 5: Preparation of Compound 1.012

1.012

Step 1 : A stirred solution of pyrazole (0.510 g, 7.34 mmol) in anhydrous 1- methylpyrrolidinone (NMP: 10 mL) was cooled to 0°C and treated portion wise with sodium hydride (60 mass% in oil: 0.293 g, 7.34 mmol) under a nitrogen atmosphere. The reaction mixture was allowed to warm to room temperature and stirred for 30mins, then compound E5 (0.900 g, 2.94 mmol) was added in one portion and the resultant mixture was heated to 100°C for 24hrs. The cooled reaction mixture was quenched with 2M aq. hydrochloric acid (50 mL) whereupon a white solid precipitated out. This was filtered off and dried to afford compound 1.012 as a white solid (0.650 g).

1H NMR (d6-DMSO) δ 11.78 (s, 1H), 8.61 (br s, 1H), 8.52 (br d, 1H), 8.05 (br d, 1H), 7.89 (s, 1H), 6.66 (br s, 1H), 4.10 (br s, 3H)

Preparative Example 6: Preparation of Compound 1.006

1.006 Step 1 : A vessel containing 3,5-dimethylpyrazole (34.6 mg, 0.36 mmol) was treated with potassium carbonate sesquihydrate (88.6 mg, 0.36 mmol) followed by a solution of compound E5 (46.6 mg, 0.18 mmol) in dimethylformamide (DMF: 2.0 mL). The resultant mixture was heated under reflux with stirring for 2 hours, then cooled. The mixture was evaporated to dryness under reduced pressure, and the residue was partitioned between ethyl acetate and water. The ethyl acetate layer was separated, and evaporated to dryness under reduced pressure. The residue was separated by reverse-phase chromatography to afford compound 1.006. 1H NMR (d6-DMSO) δ 12.75 (br s, 1H), 8.49 (br d, 1H), 8.08 (d, 1H), 6.40 (s, 1H), 4.02 (s, 3H), 2.49 (s, 3H), 2.22 (s, 3H)

Pre arative Example 7: Pre aration of Compound 1.002

1.002

Step 1 : Using a procedure analogous to that described in Preparative Example 6, Step 1, but using imidazole in place of 3,5-dimethylpyrazole, Compound 1.002 was obtained.

1H NMR (d6-DMSO) δ 11.90 (br, 1H), 8.94 (br s, 1H), 8.78 (br d, 1H), 8.36 (d, 1H), 7.88 (s, 1H), 7.53 (s, 1H), 3.91 (s, 3H)

Preparative Exam le 8: Preparation of compound 1.019

Step 1 : A stirred solution of compound E4 (100 mg, 0.291 mmol) and 5-amino-l-(2- methoxyethyl)tetrazole (41 mg, 0.286 mmol) in tetrahydrofuran (THF: 5 mL) was treated with triethylamine (0.16 mL, 1.1 mmol) followed by 1-propanephosphonic acid cyclic anhydride (PPAA (50% in ethyl acetate): 1.1 mL, 1.8 mmol). The reaction mixture was stirred at room temperature for 2 hours, and was then allowed to stand at room temperature overnight. Water and ethyl acetate were added, and the resulting mixture was stirred vigorously. The organic phase was then separated, washed with water and evaporated under reduced pressure to leave a pale pink oil. The residue was purified by silica-gel chromatography, eluting with 0 - 10% methanol in dichloromethane mixtures to afford compound 1.019 (21 mg).

1H NMR (CDCls) δ 9.09 (br s, 1H), 8.38 (d, 1H), 8.15 (br s, 1H), 7.84 (d, 1H), 4.37 (t, 2H), 3.78 (t, 2H), 3.42 (s, 3H)

Pre arative Example 9: Preparation of compounds 1.022 and 1.023

Step 1 : A stirred solution of compound E5 (0.150 g, 0.489 mmol) in dimethylformamide (DMF: 2.25 mL) was treated with potassium carbonate (0.169 g, 1.223 mmol) followed by lH-l,2,3-triazole (0.087 g, 1.223 mmol). The stirred mixture was heated to 100 °C for 73 hours, and was then allowed to cool. The sample was evaporated under reduced pressure and the residue was partitioned between dichloromethane and aqueous hydrochloric acid (2 M). The organic layer was separated and concentrated under reduced pressure. The resulting crude mixture of products was purified by reverse-phase HPLC to afford compound 1.022 (0.013 g)

1H NMR (CDCI₃) δ 9.00 - 8.94 (m, 1H), 8.06 (d, 1H), 8.01 - 7.95 (m, 2H), 4.10 (s, 3H) and compound 1.023 (0.018 g)

1H NMR (CDCI₃) δ 11.77 - 11.54 (m, 1H), 8.62 - 8.56 (m, 1H), 8.55 - 8.48 (m, 1H), 7.97 - 7.88 (m, 1H), 7.82 - 7.74 (m, 1H), 4.19 (s, 3H) Preparative Example 10: Preparation of compound 1.028

5-amino-1 -methyl-tetrazole

PPAA, DMAP, CH₂CI₂, 100°C

Step 1 : A mixture of compound E2 (0.400 g, 1.58 mmol) and 3-methoxy- 1,2,4- triazole; triethylammonium salt (0.632 g, 3.15 mmol) in N,N-dimethylformamide (DMF: 12.0 mL) was stirred at room temperature for 2 hours., then cesium carbonate (1.28 g, 3.94 mmol) was added followed by dimethylsulfoxide (DMSO: 2 mL). The reaction mixture was stirred for 90 minutes and then left to stand for 6 days. Water and ethyl acetate were added to the resulting mixture, and then the pH was adjusted to pH 1 with aqueous hydrochloric acid (2M). The organic phase was separated, and the aqueous layer was further extracted with ethyl acetate (x 2). The combined organic layers were washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to afford the crude product as an off- white solid. This was purified by silica-gel chromatography, eluting with 0 to 85% ethyl acetate in iso-hexane mixtures, to afford pure compound E6 as a white solid (347 mg). 1H NMR (CDC13) δ = 8.83 (s, 1H), 8.12 (d, 1H), 7.70 (d, 1H), 4.41 (q, 2H), 4.02 (s, 3H), 1.33 (t, 3H)

Step 2: A stirred mixture of compound E6 (0.320 g, 1.01 mmol), tetrahydroiuran (THF: 6.40 mL) and water (3.20 mL) was treated with lithium hydroxide hydrate (0.085 g, 2.02 mmol). The resultant solution was stirred at room temperature for 70 minutes. Tetrahydroiuran was then removed from the mixture under reduced pressure, and the residue was diluted with dichloromethane and water and acidified to pH 1 (2M HC1). The biphasic mixture was stirred vigorously for 5 minutes then the phases were separated through a phase separating cartridge. The organic phase was evaporated under reduced pressure to afford compound E7 as a white solid (288 mg).

1H NMR (CDC13) δ = 8.79 (s, IH), 8.20 (d, IH), 7.70 (d, IH), 4.01 (s, 3H)

Step 3: A stirred solution of compound E7 (0.240 g, 0.833 mmol)) and 5-amino-l- methyl-tetrazole (0.099 g, 0.999 mmol) in dichloromethane (6.7 mL) was treated with 4-(dimethylamino)pyridine (DMAP: 0.305 g, 2.50 mmol)) followed by 1- propanephosphonic acid cyclic anhydride (PPAA (50% in ethyl acetate): 2.97 mL, 5.00 mmol). The reaction mixture was then heated to 100°C for 30 min. under microwave irradiation. The cooled mixture was poured into water, whereupon a white precipitate formed. This was filtered off, washed with water and air-dried to afford compound 1.028 as a white solid.

IH NMR (DMSO-d6) δ 11.82 (br s, IH), 9.18 (s, IH), 8.61 (br d, IH), 8.15 (br d, IH), 4.03 (s, 3H), 3.85 (s, 3H)

Pre arative Exam le 11: Preparation of compound 1.037

1. CDI, 1 ,4-dioxane, heat

1. 5-amino-1-methyl-tetrazole,

DBU

1 .037

Step 1 : Using a procedure analogous to that described in Preparative Example 1 , Step 2, but using compound E8 in place of compound E2 and heating at 85 °C for 3 hours rather than 100 °C for 30 minutes, compound E9 was obtained.

1H NMR(CDC13): δ 9.00(s, IH), 8.60(dd, IH), 8.08(s, IH), 8.07(dd, IH), 7.45(dd, IH), 3.87(s, 3H) Step 2: Using a procedure analogous to that described in Preparative Example 1, Step 3, but using compound E9 in place of compound E3, compound E10 was obtained. lH NMR(CDCB): δ 9.17(s, 1H), 8.66(dd, 1H), 8.56(dd, 1H), 8.23(s, 1H), 7.55-7.52(m, 1H)

Step 3: A stirred solution of compound E10 (84 mg, 0.442 mmol) in 1,4-dioxane (7 mL) was treated with Ν,Ν'-carbonyldiimidazole (CDI: 107 mg, 0.660 mmol) under a nitrogen atmosphere, and the reaction mixture was heated to 93 °C for 1 hour. The mixture was then treated with 5-amino-l-methyltetrazole (65 mg, 0.655936 mmol) and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU: 0.07 mL, 0.5 mmol), and heating was continued for a further 45 minutes. The reaction mixture was then allowed to cool, and was left to stand overnight. Water was added and the mixture was acidified (2M HCl). The resultant mixture was extracted with ethyl acetate. LCMS analysis showed that product was present in both the organic and aqueous layers. These were evaporated under reduced pressure separately, and the residues were combined and purified by reverse-phase chromatography to afford compound 1.037 as an off- white solid (51 mg). lH NMR(d-4 MeOH): δ 9.33 (s, 1H), 8.71 (d, 1H), 8.26 (d, 1H), 8.22 (s, 1H), 7.66-7.63 (m, 1H), 4.16 (s, 3H)

Pre arative Example 12: Preparation of compound 1.038

1 . CDI, 1 ,4-dioxane, heat

1. 5-amino-1-methyl-tetrazole,

DBU

1.038

Step 1 : Using a procedure analogous to that described in Preparative Example 1 , Step

2, but using compound El 1 in place of compound E2 and conducting the reaction at - 20 °C, compound E 12 was obtained.

IH NMR (CDC13): 8.99 (s, IH), 8.09 (s, IH), 8.02 (d, IH), 7.44 (d, IH), 4.35 (q, 2H), 1.26 (t, IH)

Step 2: Using a procedure analogous to that described in Preparative Example 1, Step

3, but using compound E12 in place of compound E3, compound E13 was obtained.

IH NMR (d-4 MeOH): δ 9.10 (s, IH), 8.28 (d, IH), 8.17 (s, IH), 7.68 (d, IH)

Step 3 : Using a procedure analogous to that described in Preparative Example 11 , Step 3, but using compound E13 in place of compound E10, compound 1.038 was obtained.

IH NMR (d-4 MeOH): δ 9.32 (s, IH), 8.26 (d, IH), 8.23 (s, IH), 7.70 (d, IH), 4.15(s, 3H) Pre arative Example 13: Preparation of compound 1.040

Step 1 : A stirred solution of compound 1.039 (30 mg, 0.098 mmol), in dimethylformamide (DMF: 1.0 mL) was treated with potassium carbonate (24 mg, 0.171 mmol), and the resultant slurry was then treated with sodium thiomethoxide (12 mg, 0.163 mmol). The reaction mixture was stirred at room temperature for 1 hour, and was then left to stand overnight. LCMS analysis showed some unreacted starting material was still present, so a further amount of sodium thiomethoxide was added, and the resultant mixture was stirred at room temperature for 3 hours. Water and ethyl acetate were then added, and the mixture was stirred vigorously. The organic layer was separated, and the aqueous phase was acidified and extracted again with ethyl acetate. All ethyl acetate extracts were then combined and evaporated to dryness under reduced pressure. Trituration of the residue with a little diethyl ether afforded compound 1.040 as a white solid (29 mg).

IH NMR (d4-MeOH): δ 9.31 (s, IH), 8.20 (s, IH), 8.00 (d, IH), 7.48 (d, IH), 4.13 (s, 3H), 2.67 (s, 3H)

Pre arative Example 14: Preparation of compound 1.041

Step 1 : A stirred solution of compound 1.040 (21 mg, 0.066 mmol) in ethyl acetate (2 mL) was treated with hydrogen peroxide (0.02 mL) followed by a catalytic quantity of sodium tungstate. The reaction mixture was stirred at room temperature for 90 minutes, and was then left to stand overnight. Aqueous sodium metabisulfite was added, and the mixture was extracted with ethyl acetate. The organic extracts were tested for the absence of peroxides, and were then evaporated to dryness under reduced pressure. The residue was purified by silica-gel chromatography, eluting with 0 - 20% mixtures of methanol in dichloromethane, to afford compound 1.041 (6 mg).

1H NMR (d-4 MeOH): δ 9.52 (br s, 1H), 8.58 (d, 1H), 8.29-8.27 (m, 2H), 4.16 (br s, 3H), 3.40 (s, 3H)

TABLE 1 - Examples of herbicidal compounds of the present invention.

8.84 (s,

IH), 8.05

IH), 8.49 (br IH), 4.02 (s, 3H)

8.76 (s, IH), 8.01

8.84 (br s, - 8.01 (m,

8.49 (m,

IH), 7.72 (s, 3H)

9.20 (s, 8.02 (d, 1.98 - 1.94

9.21 (s, 8.01 (d, (t, 3H)

8.61 (br s, d, IH), 4.10 (br s,

(d, IH), (d, IH),

8.94 (m,

(m, 2H),

- 11.54 (m, - 8.48 7.82 -

- 11.70 8.87 - IH), 4.18

- 11.83 8.88 - IH), 4.10

(br s, - 8.63 4.14 -

δ 8.77

IH), 5.18

(br s, IH), 4.03

s, IH), (s, 3H),

TABLE 2 - Examples of h rbicidal compounds of the present invention.

TABLE 3 - Examples of herbicidal compounds of the present invention.

Biological Examples

Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Amaranthus retoflexus (AMARE), Abutilon theophrasti (ABUTH), 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°C, 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 R 9005-64-5). Compounds are applied at 500 g/h. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, 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 = 80-100%; 4 = 60-79%; 5=40-59%; 2=20-39%; 7=0-19%).

TABLE Bl

Compound POST Application PRE Application

AMARE ABUTH SETFA ECHCG IPOHE AMARE ABUTH SETFA ECHCG IPOHE

1.001 5 5 5 5 5 5 5 5 5 5

1.002 5 4 5 5 5 5 5 3 1 1

1.003 4 2 4 3 1 2 3 1 1 1

1.004 5 5 1 2 5 5 5 1 3 5

1.005 5 5 5 5 5 5 5 3 1 5

1.006 5 5 4 5 5 5 5 2 3 1

1.007 5 5 5 5 5 5 5 5 5 5

1.008 5 5 5 5 5 5 5 5 5 5

1.009 5 5 5 5 5 5 5 2 5 5

1.010* 5 NT 5 5 5 5 NT 5 5 5

1.011 * 5 NT 5 5 5 5 NT 5 5 5

1.012* 4 NT 5 5 5 5 NT 5 5 5

1.013 5 5 5 5 5 5 5 4 5 5

1.014 5 5 5 5 5 5 5 5 5 5

1.016 5 5 5 5 5 5 5 5 5 5

1.017 5 5 5 5 5 5 5 5 5 5

1.018 5 5 4 4 4 2 2 1 1 1

1.019 5 5 5 5 5 5 5 4 5 5

1.020 5 5 5 5 5 5 5 3 5 5

1.021 5 5 5 5 4 5 5 5 5 5

1.022 5 5 5 5 5 5 5 5 5 4

1.023 5 5 5 5 5 5 5 5 5 5

1.024 5 4 5 5 5 5 5 5 5 2

1.025 5 4 5 5 5 5 5 1 2 2

1.026 5 4 5 5 5 5 5 5 5 3 Compound POST Application PRE Application

AM ARE ABUTH SETFA ECHCG IPOHE AM ARE ABUTH SETFA ECHCG IPOHE

1.027 5 4 5 5 5 5 5 4 5 5

1.028 5 4 5 5 5 5 5 5 5 5

1.029 4 3 3 2 3 1 2 1 1 1

1.030 5 5 5 4 4 3 4 1 2 2

1.031 5 5 5 5 5 5 4 5 5 3

1.032 5 5 5 5 5 4 5 5 5 4

1.033 5 5 5 5 5 5 4 2 4 3

1.034 5 3 4 4 2 4 3 1 1 1

1.035 5 5 4 3 5 5 5 3 1 4

1.036 5 4 3 2 5 5 2 1 1 3

1.037 5 5 5 4 5 1 3 1 1 1

1.038 5 5 5 5 5 5 5 NT 5 5

1.039 4 5 5 5 5 5 5 NT 5 3

1.040 5 5 3 5 4 5 5 NT 5 5

1.041 4 3 3 4 2 2 3 2 1 2

2.001 * 5 NT 5 5 5 5 NT 5 5 4

3.001 * 5 NT 5 5 5 5 NT 5 5 5

* Applied at 1000 g/ha. NT = Not Tested.

Claims

Claims

1. A compound of Formula (I) :

or an agronomically acceptable salt thereof,

wherein :- selected from the group consisting of Ql, Q2, Q3, Q4 and Q5

(Q1 ) (Q2) (Q3) (Q4) (Q5)

R¹ is selected from the group consisting of Ci-C6alkyl-, Ci-Cehaloalkyl- and Ci-C6alkoxy-Ci-C3alkyl-;

R² is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci- C₆haloalkyl-, Ci-C6alkoxy-, Ci-C6alkoxy-Ci-C6alkyl-, halogen, cyano, nitro, Ci-C₆alkyl-S(0)_p- and Ci-C₆haloalkyl-S(0)_P-;

X¹ is N or CR³; X² is N or CR⁴;

X³ is N or CR⁵; X⁴ is N or CR⁶;

R³, R⁴, R⁵ and R⁶ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -NH₂, Ci-C4alkyl-, Ci-C4alkoxy- and Ci- C4haloalkyl-; and p = 0, 1 or 2.

2. A compound according to claim 1 , wherein Q is Q 1.

3. A compound according to claim 1, wherein Q is Q3.

4. A compound according to claim 1, wherein Q is Q4.

5. A compound according to any one of the previous claims, wherein X¹ is N, X² is CR⁴, X³ is CR⁵ and X⁴ is CR⁶.

6. A compound according to any one of claims 1 to 4, wherein X¹ is N, X² is CR⁴, X³ is N and X⁴ is CR⁶.

7. A compound according to claim 6, wherein X¹ is N, X² is CH, X³ is N and X⁴ is CH.

8. A compound according to any one of claims 1 to 4, wherein X¹ is CR³, X² is N, X³ is CR⁵ and X⁴ is CR⁶.

9. A compound according to any one of the previous claims, wherein R¹ is selected from the group consisting of methyl, ethyl and propyl.

10. A compound according to any one of the previous claims, wherein R² is Ci- C₆haloalkyl-.

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