Herbicidal compounds

Abstract

The application relates to hydroxamic acid derivatives of Formula (I) or an agronomically acceptable salt thereof, to herbicidal compositions comprising them and to their use for controlling weeds, in particular in crops of useful plants.

Description

[0001] HERBICIDAL COMPOUNDS

[0002] The present invention relates to herbicidal compounds, to processes for their preparation, to herbicidal compositions which comprise the herbicidal compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.

[0003] The present invention relates to novel methyl hydroxy amino oxo-propionate compounds, which demonstrate herbicidal activity. Thus, according to the present invention there is provided a compound of Formula (I): or an agronomically acceptable salt thereof, wherein:

[0004] A1is selected from the group consisting of CR8R9, C(0), O, S(0)pand N(R10); A2is selected from the group consisting of CR6R7, C(0), O, S(0)pand N(R10); X1is a halogen; R1is hydrogen or Ci-C4alkyl; R2and R3are both Ci-Csalkyl; R4is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci- Cealkoxy-; R5is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; or R4and R5together are =0 or -(CH2)n-; and R6is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; R7is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; or R6and R7together are -(CH2)n-; and R8is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; R9is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; R8and R9together are -(CH2)n-; R10is hydrogen or Ci-Cealkyl; n is independently 2, 3, 4 ,5 or 6; and p is independently 0, 1 or 2.

[0005] In a second aspect there is provided a herbicidal composition comprising a compound of Formula (I) as described herein, and an agriculturally acceptable formulation adjuvant.

[0006] In a third aspect the invention provides the use of a compound of Formula (I) or a composition of the invention as a herbicide. In a fourth aspect the invention provides a method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a compound of or composition as described herein.

[0007] Ci-Cealkyl- includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n- Pr), isopropyl ( / -Pr), n-butyl (n-Bu), isobutyl ( / -Bu), sec-butyl and tert-butyl (f-Bu). C1- Csalkyl includes methyl (Me, CH3), ethyl (Et, C2H5) and propyl (Pr e.g / so-propyl and n- propyl). Ci-C4alkyl includes methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl ( / -Pr), n-butyl (n-Bu), isobutyl ( / -Bu), sec-butyl and tert-butyl (f-Bu).

[0008] 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.

[0009] Ci-Cehaloalkyl- 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. Ci-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.

[0010] Ci-Cealkoxy includes methoxy, ethoxy and iso-propoxy-.

[0011] Cs-Cecycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0012] Preferred values of A1, A2, X1, R1, R2, R3, R4, and R5, as well as of the substituents comprised within these moieties (i.e. R6, R7, R8, R9, R10, n and p) are described below. A compound of Formula (I) according to, and for use in, the invention may comprise any combination of said values. The skilled man will appreciate that values of any specified set of embodiments may be combined with values of any other set of embodiments where such combinations are not mutually exclusive.

[0013] In one embodiment of the present invention, there is provided a compound of Formula (I) wherein X1is bromo, chloro or fluoro. Preferably X1is bromo or chloro.

[0014] In a preferred embodiment X1is preferably chloro.

[0015] In one preferred embodiment of the present invention, there is provided a compound of Formula (I) wherein R1is hydrogen.

[0016] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein R2and R3are both methyl.

[0017] In one embodiment of the present invention, there is provided a compound of Formula (I) wherein A1is selected from the group consisting of CH2, C(O), O, S and NH, preferably O. In another embodiment of the present invention, there is provided a compound of Formula (I) wherein A2is selected from the group consisting of CH2, C(O), O, S and NH, preferably O.

[0018] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein (i) A1and A2are O; (ii) A1is NH and A2is O; (iii) A1is O and A2is NH; (iv) A1and A2are NH; (v) A1is CH2 and A2is O; (vi) A1is O and A2is CH2; (vii) A1is CH2 and A2is CH2; (viii) A1is O and A2is S; or (ix) A1is S and A2is O.

[0019] In a preferred embodiment of the present invention, there is provided a compound of Formula (I) wherein A1and A2are O.

[0020] In the present invention, there is provided a compound of Formula (I) wherein A2is O.

[0021] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein R4and R5are independently selected from the group consisting of hydrogen, halogen and Ci-Cealkyl. In a more preferred embodiment, R4and R5are independently selected from the group consisting of hydrogen, methyl and fluoro. In another embodiment, R4and R5are halogen, preferably fluoro.

[0022] 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.

[0023] The present invention also provides agronomically acceptable salts of compounds of Formula (I), and in one embodiment, it is preferred that compounds of Formula (I) are in salt form. 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.

[0024] 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.

[0025] 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 (EG), an emulsion, oil in water (EW), a microemulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (Sil), 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).

[0026] 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).

[0027] 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).

[0028] 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).

[0029] 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).

[0030] 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 Cs-C 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.

[0031] 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 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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).

[0037] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0038] Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltri methyl ammonium bromide), imidazolines and amine salts.

[0039] 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- / sopropyl- and tri- / 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, lignosulphonates and phosphates I sulphates of tristyrylphenols.

[0040] Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.

[0041] 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.

[0042] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0043] 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-

[0044] (trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-

[0045] (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-

[0046] 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-

[0047] 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

[0048] (isopropylideneamino) 6-amino-2-(4-chloro-2-fluoro-3-methoxy-phenyl)-5-methoxy- pyrimidine-4-carboxylate.

[0049] 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, Nineteenth Edition, British Crop Protection Council, 2021.

[0050] 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.

[0051] The mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1.

[0052] 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).

[0053] 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, Nineteenth Edition, British Crop Protection Council, 2021. 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.

[0054] 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 applying to the locus 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.

[0055] 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.

[0056] 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.

[0057] 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, PPG, HPPD, PDS, SDPS 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®.

[0058] 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.

[0059] 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).

[0060] 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, Brachia ria, Bromus, Cenchrus, Cy perus, 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.

[0061] 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.

[0062] PROCESSES FOR PREPARATION OF COMPOUNDS OF FORMULA (I)

[0063] Processes for preparation of compounds, e.g. a compound of formula (I) (which optionally can be an agronomically acceptable salt thereof), are now described, and form further aspects of the present invention. The compounds of the present invention can be prepared according to the following schemes.

[0064] SCHEME 1

[0065] Compounds of formula (1) (or an agronomically acceptable salt thereof) may be prepared from compounds of formula (2).

[0066]

[0067] Compounds of formula (2) are treated with a suitable base, for example sodium hydroxide, in a suitable solvent, for example a water / methanol / 2-methyltetrahydrofuran mixture.

[0068] SCHEME 2

[0069] Compounds of formula (2) may be prepared from compounds of formula (3). For example, where R2and R3are methyl, compounds of formula (3) are treated with 2,2-dimethylmalonyl chloride and a suitable base, for example pyridine, in a suitable solvent, for example dichloromethane.

[0070] SCHEME 3 Compounds of formula (3) may be prepared from compounds of formula (4).

[0071] Compounds of formula (4) are treated with a suitable source of hydroxylamine, for example hydroxylamine hydrochloride, and optionally a suitable base, for example sodium acetate, in a suitable solvent, for example ethanol, to give compounds of formula (5). Compounds of formula (5) are treated with a suitable reducing agent, for example sodium cyanoborohydride, and a suitable acid, for example 4 M hydrochloric acid in 1 ,4-dioxane, in a suitable solvent, for example methanol, to give compounds of formula (3).

[0072] SCHEME 4 In an alternative approach, compounds of formula (3) may be prepared from compounds of formula (6), where LG represents a suitable leaving group (for example Br or Cl), according to the following scheme.

[0073] Compounds of formula (6) are treated with (terf-butoxycarbonylamino) terf-butyl carbonate (7), a suitable base, for example potassium carbonate, and optionally a suitable additive, for example 18-crown-6, in a suitable solvent, for example acetonitrile, to give compounds of formula (8). Compounds of formula (8) are treated with a suitable acid, for example hydrochloric acid, in a suitable solvent, for example 1 ,4-dioxane, to give compounds of formula (3).

[0074] SCHEME 5

[0075] In a further alternative approach, compounds of formula (2) may be prepared from compounds of formula (9). Compounds of formula (9) are treated with a suitable oxidant system, for example a mixture of trichloroisocyanuric acid and a catalytic quantity of TEMPO in a suitable solvent, for example dichloromethane.

[0076] SCHEME 6

[0077] Compounds of formula (9) may be prepared from compounds of formula (10), where PG1represents a suitable protecting group, for example -CH2CH2(Si(CH3)3).

[0078] Compounds of formula (10) are reacted under suitable deprotection conditions. For example, where PG1is -CH2CH2(Si(CH3)3) compounds of formula (10) are treated with a suitable Lewis acid source, for example boron trifluoride diethyl etherate, in a suitable solvent, for example dichloromethane.

[0079] SCHEME 7

[0080] Compounds of formula (10) may be prepared from compounds of formula (6), where LG represents a suitable leaving group (for example Br or Cl), and compounds of formula (11), where PG1represents a suitable protecting group, for example -

[0081] CH2CH2(Si(CH3)3).

[0082] Compounds of formula (6) are treated with compounds of formula (11), a carbonate base, for example potassium carbonate, and optionally a suitable additive, for example sodium iodide, in a suitable solvent, for example acetone.

[0083] SCHEME 8

[0084] Compounds of formula (11) may be prepared from compounds of formula (12) according to the following scheme. Hydroxylamine

[0085] Chlorinating source -

[0086] Solvent

[0087] (12) (13) (14)

[0088] Base

[0089] Solvent

[0090] 3,3-Dichloro-2,2-dimethylpropanoic acid (12) is treated with a suitable chlorinating agent, for example thionyl chloride, to give 3,3-dichloro-2,2-dimethylpropanoyl chloride (13). 3,3-Dichloro-2,2-dimethylpropanoyl chloride (13) is treated with a suitable source of hydroxylamine, for example hydroxylamine (50% in H2O), to give 3,3-dichloro-2,2- dimethyl-propanehydroxamic acid (14). 3,3-Dichloro-2,2-dimethyl-propanehydroxamic acid (14) is treated with compounds of formula (15), where PG1represents a suitable protecting group, for example -CH2CH2(Si(CH3)3), and a suitable base, for example 1 ,8- diazabicyclo(5.4.0)undec-7-ene, to give compounds of formula (11).

[0091] SCHEME 9

[0092] Compounds of formula (6) may be prepared from compounds of formula (16).

[0093] For example, where LG is Cl, compounds of formula (16) are treated with a chlorinating agent, for example thionyl chloride, either neat or in a suitable solvent, for example dichloromethane.

[0094] SCHEME 10

[0095] Compounds of formula (16) may be prepared from compounds of formula (17), where Z is H or O-alkyl.

[0096] For example, where Z is H, compounds of formula (17) are treated with a reducing agent, for example sodium borohydride, in a suitable solvent, for example a tetra hy d rof u ra n / m eth an ol m ixtu re .

[0097] SCHEME 11

[0098] The synthesis routes used to access compounds of formula (17) will vary depending on the nature of Z, X1, A1, A2, R4and R5. For example, compounds of formula (4) may be prepared from compounds of formula (18).

[0099] Compounds of formula (18) are reacted under suitable formylation conditions, for example by treatment with titanium tetrachloride and dichloro(methoxy)methane in a suitable solvent, for example dichloromethane.

[0100] SCHEME 12

[0101] In an alternative approach, compounds of formula (16) may be prepared from compounds of formula (19).

[0102] Halogenating agent

[0103] Solvent

[0104] Compounds of formula (19) are treated with a suitable halogenating agent, for example / V-chlorosuccinimide, in a suitable solvent, for example acetonitrile. SCHEME 13

[0105] Compounds of formula (19) may be prepared from compounds of formula (20), where Z is H or O-alkyl.

[0106] For example, where Z is H, compounds of formula (20) are treated with a reducing agent, for example sodium borohydride, in a suitable solvent, for example water.

[0107] SCHEME 14

[0108] In a further alternative approach, compounds of formula (16) may be prepared from compounds of formula (21) and compounds of formula (22) where PG2represents a suitable protecting group, for example -CH2CH2(Si(CH3)3), according to the following scheme. Compounds of formula (22) are available from commercial sources.

[0109] Compounds of formula (21) are reacted with compounds of formula (22) in the presence of a suitable catalyst system and a suitable base in a suitable solvent to give compounds of formula (23). For example, where PG2is -CH2CH2(Si(CH3)3), compounds of formula (21) are reacted with potassium trifluoro(2- trimethylsilylethoxymethyl)boranuide in the presence of a suitable (pre-)catalyst / ligand combination, for example palladium^ I) acetate and RuPhos, and a suitable base, for example cesium carbonate, in a suitable solvent, for example a 1 ,4-dioxane / water mixture. Compounds of formula (23) are reacted under suitable deprotection conditions to give compounds of formula (16). For example, compounds of formula (23) where PG2is -CH2CH2(Si(CH3)3) are treated with boron trifluoride diethyl etherate in a suitable solvent, for example dichloromethane. SCHEME 15

[0110] Compounds of formula (21) may be prepared from compounds of formula (18).

[0111] Compounds of formula (18) are treated with a suitable brominating agent, for example / V-bromosuccinimide, in a suitable solvent, for example acetonitrile.

[0112] SCHEME 16

[0113] Compounds of formula (18) may be prepared from compounds of formula (24).

[0114] Compounds of formula (24) are treated with a suitable halogenating agent, for example / V-chlorosuccinimide, in a suitable solvent, for example acetonitrile.

[0115] SCHEME 17

[0116] Compounds of formula (17), formula (18), formula (19), formula (20), formula (21) and formula (24) may be commercially available. Alternatively, they may be prepared utilising ring synthesis strategies known in the literature. The synthetic route adopted will vary depending on the nature of Z, X1, A1, A2, R4and R5. For example, compounds of formula (25) may be prepared from compounds of formula (26) according to the following scheme. Compounds of formula (26) are available from commercial sources or may be prepared according to strategies known in the literature.

[0117]

[0118] Compounds of formula (26) are treated with a suitable Grignard reagent (27) (where X2is a suitable halogen), for example methylmagnesium chloride, in a suitable solvent, for example tetrahydrofuran, to give compounds of formula (28). Compounds of formula (28) are treated with a suitable base, for example potassium terf-butoxide, in a suitable solvent, for example tetrahydrofuran, to give compounds of formula (25).

[0119] SCHEME 18

[0120] Compounds of formula (29) where R1is Ci-C4alkyl may be prepared from compounds of formula (2).

[0121] Compounds of formula (2) are treated with a metal alkoxide, for example sodium methoxide, in a suitable solvent, for example methanol.

[0122] SCHEME 19

[0123] In an alternative approach, compounds of formula (29) where R1is Ci-C4alkyl may be prepared from compounds of formula (3) and compounds of formula (30). Compounds of formula (30) are available from commercial sources.

[0124] Compounds of formula (30) are activated by converting the -OH of the carboxylic acid into a good leaving group such as -Cl, for example by treatment with a suitable chlorinating agent, for example thionyl chloride, and optionally a suitable base, for example triethylamine, either neat or in a suitable solvent, for example dichloromethane. The activated intermediates derived from compounds of formula (30) are then treated with compounds of formula (3) and a suitable base, for example triethylamine, in a suitable solvent, for example dichloromethane. Alternatively, compounds of formula (30) are reacted with compounds of formula (3) under suitable amide coupling conditions, for example by treatment with a carboxylic acid activating agent, for example 2,4,6-tripropyl- 1 ,3,5,2A5,4A5,6A5-trioxatriphosphinane 2,4,6-trioxide, and a suitable base, for example triethylamine, in a suitable solvent, for example dichloromethane.

[0125] The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table 1 below.

[0126] PREPARATION EXAMPLES

[0127] Example 1 : Preparation of Compound 1.001

[0128] Step 1: Preparation of 5-bromo-6-chloro-2,3-dihydrobenzofuran

[0129] / V-Bromosuccinimide (0.691 g, 3.89 mmol) was added to a solution of 6-chloro- 2,3-dihydrobenzofuran (0.572 g, 3.70 mmol) in acetonitrile (8.6 mL) at 0 °C. The reaction was stirred at room temperature for 4 h then ethyl acetate was added. The mixture was washed with sat. aq. NaHCOs, dried over MgSO4, filtered and concentrated. Purification by flash column chromatography (0-30% acetone in cyclohexane) afforded 5-bromo-6- chloro-2,3-dihydrobenzofuran (0.733 g, 3.14 mmol, 85%).1H NMR (400 MHz, CDCI3) 6 ppm 7.39 (t, 1 H), 6.89 (s, 1 H), 4.62 (t, 2H), 3.20 (dt, 2H).

[0130] Step 2: Preparation of 6-chloro-2,3-dihydrobenzofuran-5-carbaldehyde n-Butyllithium (2.3 M solution in hexanes, 1 .3 mL, 3.06 mmol) was added dropwise to a solution of 5-bromo-6-chloro-2,3-dihydrobenzofuran (0.595 g, 2.55 mmol) in tetra hydrofuran (6.0 mL) at -78 °C under an atmosphere of nitrogen. The mixture was stirred at -78 °C for 30 min then a solution of / V, / V-dimethylformamide (0.26 mL, 3.31 mmol) in tetrahydrofuran (1.2 mL) was added dropwise and the reaction mixture was stirred at - 78 °C for a further 1 h. The reaction was quenched by the dropwise addition of sat. aq. ammonium chloride and allowed to warm to room temperature. The mixture was extracted with ethyl acetate (x2) and the combined organic portions were washed with brine, dried over MgSC>4 and concentrated. Purification by flash column chromatography (0-50% acetone in cyclohexane) afforded 6-chloro-2,3-dihydrobenzofuran-5-carbaldehyde (0.284 g, 1.56 mmol, 61%).1H NMR (400 MHz, CDCI3) 5 ppm 10.32 (s, 1 H), 7.79 (s, 1 H), 6.83 (s, 1 H), 4.71 (t, 2H), 3.23 (t, 2H).

[0131] Step 3: Preparation of 6-chloro-2,3-dihydrobenzofuran-5-carbaldehyde oxime

[0132] To a solution of 6-chloro-2,3-dihydrobenzofuran-5-carbaldehyde (0.192 g, 1.05 mmol) in ethanol (10 mL) was added pyridine (83 mg, 0.085 mL, 1.05 mmol) and hydroxylamine hydrochloride (80 mg, 1.16 mmol). The reaction mixture was heated at reflux for 3 h then concentrated. The resulting residue was diluted in dichloromethane and washed with 1 M aqueous hydrochloric acid. The organic portion was passed through a hydrophobic frit then concentrated to afford 6-chloro-2,3-dihydrobenzofuran-5- carbaldehyde oxime (0.207 g, 1.05 mmol, 100%).1H NMR (400 MHz, CDCh) 6 ppm 8.50 (s, 1 H), 7.68 (s, 1 H), 6.81 (s, 1 H), 4.64 (t, 2H), 3.20 (t, 2H), 2.86 (br s, 1 H).

[0133] Step 4: Preparation of N-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl]hydroxylamine

[0134] Solutions of sodium cyanoborohydride (0.106 g, 1.68 mmol) in methanol (5.0 mL) and hydrochloric acid (4 M solution in 1 ,4-dioxane, 0.53 mL, 2.11 mmol) were added dropwise simultaneously over 15 min to a stirred solution of 6-chloro-2,2-dimethyl-1 ,3- benzodioxole-5-carbaldehyde oxime (0.207 g, 1.05 mmol) and a trace of methyl orange in methanol (5.0 mL) at room temperature. During the addition care was taken to keep the reaction mixture between 19 and 27 °C and the pH below 3. Upon completion of addition, the reaction mixture was stirred at room temperature for 3 h, during which time the reaction mixture was kept acidic by the addition of small amounts of hydrochloric acid (4 M solution in 1 ,4-dioxane). Subsequently, further hydrochloric acid (4 M solution in 1 ,4-dioxane, 0.26 mL, 1.05 mmol) and sodium cyanoborohydride (0.066 g, 1.05 mmol) in methanol (3.0 mL) were added. The reaction mixture was allowed to stand overnight and was then concentrated. The resulting residue was diluted in dichloromethane and water and the pH of the aqueous phase was adjusted to pH 9 through the dropwise addition of concentrated sodium hydroxide. The layers were separated and the aqueous portion was extracted with another portion of dichloromethane. The combined organics were washed with brine (x2), dried over MgSC>4, filtered and concentrated to afford / \ / -[(6-chloro-2,3-dihydrobenzofuran- 5-yl)methyl]hydroxylamine (0.210 g, 1.05 mmol, 100%).1H N MR (400 MHz, CDCI3) 5 ppm

[0135] 7.21 (s, 1 H), 6.83 (s, 1 H), 4.60 (t, 2H), 4.11 (s, 2H), 3.19 (t, 2H).

[0136] Step 5: Preparation of 2-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl]-4,4-dimethyl- isoxazolidine-3, 5-dione

[0137] A solution of / V-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl]hydroxylamine (0.200 g, 1.00 mmol) and pyridine (0.160 mg, 0.164 mL, 2.00 mmol) in dichloromethane (5.0 mL) had 2,2-dimethylpropanedioyl dichloride (0.169 g, 0.133 mL, 1.00 mmol) in dichloromethane (5.0 mL) added dropwise over 15 min at 0 °C. The reaction was stirred at room temperature for 2 h then 2 M aqueous hydrochloric acid was added and the mixture was passed through a hydrophobic frit and concentrated onto silica gel. Purification by flash column chromatography (0-40% ethyl acetate in isohexane) afforded 2-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl]-4,4-dimethyl-isoxazolidine-3, 5-dione (0.158 g, 0.53 mmol, 53%).1H NMR (400 MHz, CDCI3) 6 ppm 7.13 (s, 1 H), 6.76 (s, 1 H), 4.92 (s, 2H), 4.55 (t, 2H), 3.13 (t, 2H), 1.40 (s, 6H).

[0138] Step 6: Preparation of sodium 3-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl-hydroxy- amino]-2,2-dimethyl-3-oxo-propanoate

[0139] To a solution of 2-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl]-4,4-dimethyl- isoxazolidine-3, 5-dione (0.085 g, 0.29 mmol) in methanol (0.6 mL) and 2- methyltetrahydrofuran (0.6 mL) was added sodium hydroxide (2 M solution in water, 0.28 mmol, 0.14 mL) with stirring at room temperature. The reaction mixture was stirred at room temperature for 1 h then concentrated to dryness. The resulting residue was redissolved in water and again concentrated to dryness to afford sodium 3-[(6-chloro-2,3- dihydrobenzofuran-5-yl)methyl-hydroxy-amino]-2,2-dimethyl-3-oxo-propanoate.1H NMR (400 MHz, DMSO-d6) 5 ppm 15.51 (br s, 1 H), 7.18 (s, 1 H), 6.81 (s, 1 H), 4.62 (s, 2H), 4.53 (t, 2H), 3.12 (t, 2H), 1.30 (s, 6H).

[0140] Example 2: Preparation of Compound 1.002

[0141] Step 1: Preparation of 6-chloro-2,2-dimethyl-1 ,3-benzodioxole-5-carbaldehyde

[0142] To a solution of 5-chloro-2,2-dimethyl-1 ,3-benzodioxole (5.00 g, 26.5 mmol) in dichloromethane (50 mL) at -5 °C was added dichloro(methoxy)methane (3.74 g, 2.94 mL, 31.8 mmol) followed by titanium tetrachloride (5.59 g, 3.24 mL, 29.2 mmol). The reaction mixture was stirred for 1.5 h at 0 °C. Ice water was added and the product was extracted with dichloromethane. The organic portion was filtered through diatomaceous earth, passed through a hydrophobic frit then concentrated. Purification by flash column chromatography (0-40% ethyl acetate in isohexane) afforded 6-chloro-2,2-dimethyl-1 ,3- benzodioxole-5-carbaldehyde (1.60 g, 7.52 mmol, 28%).1H NMR (400 MHz, CDCI3) 6 ppm 10.29 (s, 1 H), 6.80 (s, 1 H), 6.78 (s, 1 H), 1.72 (s, 6H).

[0143] Step 2: Preparation of 6-chloro-2,2-dimethyl-1 ,3-benzodioxole-5-carbaldehyde oxime

[0144] Sodium acetate (0.745 g, 8.98 mmol) and hydroxylamine hydrochloride (0.624 g, 8.97 mmol) were added to a solution of 6-chloro-2,2-dimethyl-1 ,3-benzodioxole-5- carbaldehyde (1.59 g, 7.48 mmol) in ethanol (16 mL) and the mixture was stirred at reflux for 1 h. The reaction mixture was concentrated then diluted with water and dichloromethane. The layers were separated and the organic portion was passed through a hydrophobic frit then concentrated to afford 6-chloro-2,2-dimethyl-1 ,3-benzodioxole-5- carbaldehyde oxime (1.66 g, 7.29 mmol, 98%).1H NMR (400 MHz, CDCI3) 6 ppm 8.48 (s, 1 H), 7.19 (s, 1 H), 6.73 (s, 1 H), 1.68 (s, 6H).

[0145] Step 3: Preparation of N-[(6-chloro-2,2-dimethyl-1,3-benzodioxol-5- yl)methyl]hydroxylamine

[0146] Solutions of sodium cyanoborohydride (1.37 g, 21.7 mmol) in methanol (5.0 mL) and hydrochloric acid (4 M solution in 1 ,4-dioxane, 5.6 mL, 22.4 mmol) were added dropwise simultaneously over 30 min to a stirred solution of 6-chloro-2,2-dimethyl-1 ,3- benzodioxole-5-carbaldehyde oxime (1 .65 g, 7.25 mmol) and a trace of methyl orange in methanol (20 mL) at room temperature. During the addition care was taken to keep the reaction mixture between 19 and 27 °C and the pH below 3. Upon completion of addition, the reaction mixture was stirred at room temperature for 30 min, during which time the reaction mixture was kept acidic by the addition of small amounts of hydrochloric acid (4 M solution in 1 ,4-dioxane). The reaction mixture was cooled to 0 °C and the pH adjusted to 9.4 through the dropwise addition of concentrated sodium hydroxide. The reaction mixture was concentrated then ethyl acetate (25 mL) and water (50 mL) were added and the layers separated. The organic portion was dried over MgSC>4, filtered and concentrated to afford / V-[(6-chloro-2,2-dimethyl-1 ,3-benzodioxol-5- yl)methyl]hydroxylamine (1.66 g, 7.23 mmol, 100%).1H NMR (400 MHz, CDCI3) 6 ppm 6.78 (s, 1 H), 6.74 (s, 1 H), 4.04 (s, 2H), 1.67 (s, 6H).

[0147] Step 4: Preparation of 2-[(6-chloro-2,2-dimethyl-1,3-benzodioxol-5-yl)methyl]-4,4- dimethyl-isoxazolidine-3, 5-dione

[0148] 2,2-Dimethylpropanedioyl dichloride (1.22 g, 0.96 mL, 7.23 mmol) in dichloromethane (10 mL) was added dropwise over 15 min to a solution of / \ / -[(6-chloro- 2,2-dimethyl-1,3-benzodioxol-5-yl)methyl]hydroxylamine (1.66 g, 7.23 mmol) and pyridine (1.16 g, 1.18 mL, 14.5 mmol) in dichloromethane (10 mL) at O °C. The reaction was stirred at room temperature for 2 h and left to stand overnight. The reaction mixture was acidified with 2 M aqueous hydrochloric acid, passed through a hydrophobic frit and the organic portion was concentrated onto silica gel. Purification via flash column chromatography (0- 10% ethyl acetate in isohexane) afforded 2-[(6-chloro-2,2-dimethyl-1 ,3-benzodioxol-5- yl)methyl]-4,4-dimethyl-isoxazolidine-3, 5-dione (1.94 g, 5.94 mmol, 82%).1H NMR (400 MHz, CDCI3) 6 ppm 6.78 (s, 1 H), 6.71 (s, 1 H), 4.96 (s, 2H), 1.68 (s, 6H), 1.44 (s, 6H).

[0149] Step 5: Preparation of sodium 3-[(6-chloro-2,2-dimethyl-1,3-benzodioxol-5-yl)methyl- hydroxy-amino]-2,2-dimethyl-3-oxo-propanoate

[0150] To a stirred solution of 2-[(6-chloro-2,2-dimethyl-1 ,3-benzodioxol-5-yl)methyl]-4,4- dimethyl-isoxazolidine-3, 5-dione (0.196 g, 0.60 mmol) in methanol (1.2 mL) and 2- methyltetrahydrofuran (1.2 mL) was added sodium hydroxide (2 M solution in water, 0.3 mL, 0.6 mmol). The reaction mixture was stirred at room temperature for 1 h then concentrated to dryness. The resulting residue was re-dissolved in water and again concentrated to dryness to afford sodium 3-[(6-chloro-2,2-dimethyl-1 ,3-benzodioxol-5- yl)methyl-hydroxy-amino]-2,2-dimethyl-3-oxo-propanoate.1H NMR (400 MHz, DMSO-de) 5 ppm 15.54 (br s, 1 H), 6.93 (s, 1 H), 6.78 (s, 1 H), 4.59 (s, 2H), 1.63 (s, 6H), 1.32 (s, 6H).

[0151] Structures and characterising data for the Examples described above are shown in Table 1 below.

[0152] Table 1 Compounds of the present invention BIOLOGICAL EXAMPLES

[0153] Seeds of a variety of test species are sown in standard soil in pots Amaranthus palmeri (AMAPA), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG) and Ipomoea hederacea (IPOHE). After cultivation for one day (preemergence) 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 either i) the formulation of the technical active ingredient in acetone I water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5) or ii) the dissolution of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM + 44.44% N- methylpyrrolidone + 44.44% Dowanol DPM glycol ether), which was then diluted to required concentration using 0.2% Genapol XO80 (CAS No.9043-30-5) in water, as the diluent. Compounds are applied at 1000 g / ha. 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 tables on a five-point scale (5 = 81-100%; 4 = 61- 80%; 3=41-60%; 2=21-40%; 1=0-20%).

[0154] Table B1 Post-emergence Test

[0155] Table B2 Pre-emergence Test

Claims

CLAIMS1. A compound of Formula (I),or an agronomically acceptable salt thereof, wherein;A1is selected from the group consisting of CR8R9, C(0), O, S(0)pand N(R10);A2is selected from the group consisting of CR6R7, C(0), O, S(0)pand N(R10);X1is a halogen;R1is hydrogen or Ci-C4alkyl;R2and R3are both Ci-Csalkyl;R4is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; andR5is independently selected from the group consisting of hydrogen, halogen, Ci- Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; orR4and R5together are =0 or -(CH2)n-;R6is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; andR7is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-;or R6and R7together are -(CH2)n-;R8is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; andR9is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; or R8and R9together are -(CH2)n-;R10is hydrogen or Ci-Csalkyl; n is independently 2, 3, 4 ,5 or 6; and p is independently 0, 1 or 2.

2. The compound of Formula (I) according to claim 1 , wherein X1is bromo, chloro or fluoro.

3. The compound of Formula (I) according to claim 2, wherein X1is chloro.

4. The compound of Formula (I) according to any of the previous claims, wherein R2and R3are both methyl.

5. The compound according to any one of the previous claims, wherein A1and A2are O.

6. The compound according to any one of the previous claims, wherein A2is O.

7. The compound according to any of the previous claims, wherein R4and R5are independently selected from the group consisting of hydrogen, methyl and fluoro.

8. The compound according to any of the previous claims, wherein R4and R5are both methyl.

9. The compound according to any one of the previous claims 1 to 7, wherein R4and R5are both fluoro.

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

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

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

13. A method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a composition according to any one of claims 10 to 12.

14. Use of a compound of Formula (I) as defined in any one of claims 1 to 9 as a herbicide.

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