Herbicidal compounds

Abstract

The present invention relates to compounds of Formula (I) and (IC) or an agronomically acceptable salt of said compounds wherein A1, X1, X2, R2, R3, R4, R5, R6, R7, R8 and R9 are as defined herein. The invention further relates to herbicidal compositions which comprise these compounds and to the use of these compounds 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] Herbicidal 3-isoxazolidinones are known from US 4,405,357. Herbicidal isoxazolidine-3,5- diones are known from US 4,302,23. The present invention relates to novel 3-isoxazolidinone and isoxazolidine-3, 5-dione compounds. Thus, according to the present invention there is provided a compound of Formula (I): or an agronomically acceptable salt thereof, wherein:

[0004] A1is CHR1or C(O); X1is O or S; X2is a halogen; R1is selected from the group consisting of hydrogen, halogen, HO-, Ci-Cealkoxy, Ci-Cealkoxy-Ci-Cealkoxy-, Ci-C3alkyl-C(O)O-, HOC(O)Ci- Cealkoxy-, Ci-C6alkoxy-C(0)-Ci-Cealkoxy-, Ci-C3alkyl-S(O)P- and Ci-C3alkyl-S(0)PCi-C6alkoxy-; R2is Ci-Csalkyl; R3is 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 =O or -(CH2)n-; 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 =O, =CR10R11or =NOR12; or R6and R7together with the carbon atom to which they are joined form a 3-, 4-, 5-, or 6-membered saturated ring, said ring optionally comprising one or two ring oxygen atoms, and wherein the carbon atom to which both R6and R7are joined acts as a spiro- atom; R10and R11are each independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl and Ci-Cehaloalkyl; or R10and R11together are -(CH2)n-; R12is hydrogen, Ci-Cealkyl, Ci- Cehaloalkyl or Cs-Cecycloalkyl; R8is selected from the group consisting of hydrogen, halogen, Ci- Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; R9is selected from the group consisting hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy; or R8and R9together are =O or -(CH2)n-; A2and A3are independently selected from the group consisting of CR13R14, C(O), O, S(O)Pand N(R15); R13is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; R14is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy-; or R13and R14together are -(CH2)n-; R15is hydrogen or Ci-Cealkyl; n is independently 2, 3, 4 ,5 or 6; p is independently 0, 1 or 2 and q is independently is 2,3,4 or 5.

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

[0006] In a third aspect there is provided a method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a compound of Formula (I) or (IC) as defined herein, or of a herbicidal composition as described herein.

[0007] In a fourth aspect there is provided a compound of Formula (IC): or an agronomically acceptable salt thereof wherein:

[0008] X2is a halogen; R1Cis hydrogen or Ci-C4alkyl; R2Cis Ci-Cealkyl; R3Cis Ci-Cealkyl; R4is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy; R5is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy; or R4and R5together are =O or -(CH2)n-; R6is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy; R7is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy; or R6and R7together are =O, =CR10R11or =NOR12; or R6and R7together with the carbon atom to which they are joined form a 3-, 4-, 5-, or 6-membered saturated ring, said ring optionally comprising one or two ring oxygen atoms, and wherein the carbon atom to which both R6and R7are joined acts as a spiro-atom; R10and R11are each independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl and Ci-Cehaloalkyl; or R10and R11together are -(CH2)n-; R12is hydrogen, Ci-Cealkyl, Ci-Cehaloalkyl or Ce-Cecycloalkyl; R8is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy-; R9is selected from the group consisting hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy; or R8and R9together are =O or -(CH2)n-; A2and A3are independently selected from the group consisting of CR13R14, C(O), O, S(O)Pand N(R15); R13is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy-; R14is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci- Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy-; or R13and R14together are -(CH2)n-; R15is hydrogen or Ci-Cealkyl; n is independently 2, 3, 4 ,5 or 6; p is independently 0, 1 or 2 and q is independently is 2,3,4 or 5. Compounds of Formula (IC) correspond to isoxazolidine dione compounds of Formula (I) (where A1is C(O) and X1is O) wherein the isoxazolidine dione ring has been opened up to give 3- hydroxyamino-3-oxopropionate compounds.

[0009] As used herein the term 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 te / Y-butyl (f-Bu). Ci-Csalkyl includes methyl (Me, CH3), ethyl (Et, C2H5) and propyl (Pr e.g / so-propyl and n-propyl).

[0010] 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.

[0011] 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.

[0012] Ci-Cealkoxy includes methoxy, ethoxy and iso-propoxy-.

[0013] Ci-Cealkoxy-Ci-Cealkoxy- includes for example methoxymethoxy- and ethoxymethoxy-.

[0014] Ci-C3alkyl-C(O)O- includes methyl-C(O)O- and ethyl-C(O)O-.

[0015] Ci-C6alkoxy-C(0)-Ci-Cealkoxy- includes methoxy-C(0)-methoxy- and ethoxy-C(O)- methoxy-.

[0016] Ci-C3alkyl-S(0)PCi-C6alkoxy- includes methyl-S(0)Pmethoxy- and ethyl-S(0)Pmethoxy-.

[0017] Cs-Cecycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0018] Ci-C4alkyl-S- (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0019] Ci-C4alkyl-S(O)- (alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0020] Ci-C4alkyl-S(O)2- (alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tertbutylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0021] Preferred values of A1, A2, A3, X1, X2, R1C, R2C, R3C, R3, R4, R5, R6, R7, R8, and R9, as well as of the substituents comprised within these moieties (i.e. R10, R11, R12R13, R14, R15, n, p and q) are described below, and 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 for any specified set of embodiments may combined with values for any other set of embodiments where such combinations are not mutually exclusive. In one embodiment of the present invention, there is provided a compound of Formula (I) wherein X1is O.

[0022] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein X2is a halogen. In a preferred embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein X2is Br, Cl or F. In a more preferred embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein X2is Br or Cl. In the most preferred embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein X2is Cl.

[0023] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein R2and R3are methyl.

[0024] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein A1is CHR1and R1is hydrogen.

[0025] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein A1is CHR1and R1is OH or Ci-Cealkoxy.

[0026] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein A1is C(O).

[0027] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R4and R5are independently selected from the group consisting of hydrogen, methyl and fluoro. In one preferred embodiment, both R4and R5are hydrogen, in a second preferred embodiment they are both methyl, and in yet a third embodiment both R4and R5are fluoro.

[0028] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R6and R7are independently selected from the group consisting of hydrogen, methyl and fluoro. In one preferred embodiment, both R4and R5are hydrogen, in a second preferred embodiment both R4and R5are fluoro.

[0029] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R6and R7together are =O or =NOMe.

[0030] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R8and R9are independently selected from the group consisting of hydrogen, methyl and fluoro. In one preferred embodiment, both R4and R5are hydrogen, in a second preferred embodiment they are both methyl, and in yet a third embodiment both R4and R5are fluoro.

[0031] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein A2and A3are both O.

[0032] In another embodiment of the present invention, there is provided a compound of Formula (I) wherein X1is O, R4, R5, R8and R9are hydrogen, A1and A2are O.

[0033] In another embodiment of the present invention, there is provided a compound of Formula (IC) wherein R4, R5, R8and R9are hydrogen, A2and A3are O.

[0034] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R6and R7together with the carbon atom to which they are joined form a 5- membered saturated ring, and wherein the carbon atom to which both R6and R7are joined acts as a spiro-atom and said ring comprising of two oxygen atoms adjacent to the spiro-centre. In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R6and R7together with the carbon atom to which they are joined form a 4- membered saturated ring, said ring comprising one oxygen atom and wherein the carbon atom to which both R6and R7are joined acts as a spiro-atom.

[0035] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R6and R7together form =O.

[0036] In another embodiment of the present invention, there is provided a compound of Formula (I) or (IC) wherein R6and R7together form =NOR12.

[0037] In another embodiment of the present invention, there is provided a compound of Formula (IC) wherein Rlcis hydrogen.

[0038] In another embodiment of the present invention, there is provided a compound of Formula (IC) wherein R2Cis methyl.

[0039] In another embodiment of the present invention, there is provided a compound of Formula (IC) wherein R3Cis methyl.

[0040] In another embodiment of the present invention, there is provided a compound of Formula (IC) wherein Rlcis hydrogen and R2Cand R3Care both methyl.

[0041] Compounds of Formula (I) and (IC) 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.

[0042] The present invention also provides agronomically acceptable salts of compounds of Formula (I) and (IC). Salts that the compounds of Formula (I) and (IC) 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.

[0043] The compounds of Formula (I) and (IC) 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.

[0044] The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of Formula (I) or (IC) 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.

[0045] 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 micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP) and a soluble granule (SG). The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I) and Formula (IC).

[0046] Soluble powders (SP) may be prepared by mixing a compound of Formula (I) or (IC) 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).

[0047] Wettable powders (WP) may be prepared by mixing a compound of Formula (I) or (IC) 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).

[0048] Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) or (IC) 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).

[0049] Dispersible Concentrates (DC) may be prepared by dissolving a compound of Formula (I) or (IC) 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).

[0050] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) or (IC) 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 Ca-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.

[0051] Preparation of an EW involves obtaining a compound of Formula (I) or (IC) 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.

[0052] 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) or (IC) 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.

[0053] Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I) or (IC). SCs may be prepared by ball or bead milling the solid compound of Formula (I) or (IC) 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) or (IC) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

[0054] Aerosol formulations comprise a compound of Formula (I) or (IC) and a suitable propellant (for example n-butane). A compound of Formula (I) or (IC) 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.

[0055] 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) or (IC) 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) or (IC) and they may be used for seed treatment. A compound of Formula (I) or (IC) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

[0056] 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) or (IC). 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) or (IC).

[0057] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0058] Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

[0059] 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.

[0060] Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.

[0061] 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.

[0062] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0063] 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, 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), flufenacet, flumetsulam, flumioxazin, fluometuron, fomesafen, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), 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, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, 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), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, tripyrasulfone, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3,6-dihydropyrimidin-1 (2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4- hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]-imidazolidine-2-one, 5-ethoxy-4-hydroxy-1- methyl-3-[4-(trifluoromethyl)-2-pyridyl]-imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-

[0064] (trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3-[1 -methyl-5-

[0065] (trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1 -(5-tert-butylisoxazol-3-yl)-4-ethoxy-5- hydroxy-3-methyl-imidazolidin-2-one, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-

[0066] 2-carboxylic acid (including agrochemically acceptable esters thereof, for example, methyl 4-amino-

[0067] 3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5- fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro- 6-(7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylate), 3-ethyl-sulfanyl-N-(1 ,3,4-oxadiazol-2-yl)-5- (trifluoromethyl)-[1 ,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5- methyl-1 ,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1 ,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3- (isopropylsulfonyl-methyl)-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1 ,2,4]triazolo[4,3- a]-pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-5-

[0068] (trifluoromethyl)-[1 ,2,4]triazolo[4,3-a]pyridine-8-carboxamide, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3- methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate,6-chloro-4-(2,7-dimethyl-1- naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, tetrahydro-furan-2-ylmethyl(2R)-2-[(4-amino-3,5- dichloro-6-fluoro-2-pyridyl)oxy]-propanoate, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2- pyridyl)oxy]propanoic acid, tetrahydrofuran-2-ylmethyl2-[(4-amino-3,5-dichloro-6-fluoro-2- pyridyl)oxy]propanoate, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, 2-fluoro-N- (5-methyl-1 ,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluoromethyl)benzamide, 2-fluoro-N-(5- methyl-1 ,3,4-oxadiazol-2-yl)-3-propylsulfinyl-4-(trifluoromethyl)benzamide, (2-fluorophenyl)methyl6- amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxyphenyl)-pyrimidine-4-carboxylate, 6-amino-5-chloro- 2-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyrimidine-4-carboxylic acid, 3-(3-chlorophenyl)-6-(5- hydroxy-1 ,3-dimethyl-pyrazole-4-carbonyl)-1 ,5-dimethyl-quinazoline-2, 4-dione and [4-[3-(3- chlorophenyl)-1 ,5-dimethyl-2,4-dioxo-quinazoline-6-carbonyl]-2,5-dimethyl-pyrazol-3-yl]N,N- diethylcarbamate, methyl 2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-

[0069] (trifluoromethyl)pyrimidin-1-yl]phenyl] methyleneamino]oxypropanoate and methyl (2R)-2-[(E)-[2- chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl] methyleneamino] oxypropanoate.

[0070] The mixing partners of the compound of Formula (I) or (IC) 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.

[0071] The compound of Formula (I) or (IC) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

[0072] The mixing ratio of the compound of Formula (I) or (IC) to the mixing partner is preferably from 1 : 100 to 1000:1.

[0073] 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) or (IC) with the mixing partner).

[0074] 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.

[0075] Particularly preferred are mixtures of a compound of Formula (I) or (IC) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and / or metcamifen. The safeners of the compound of Formula (I) or (IC) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16thEdition (BCPC), 2012. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02 / 34048.

[0076] 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.

[0077] 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) or (IC). 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) or (IC). Preferred crop plants include maize, wheat, barley soybean and rice.

[0078] The rates of application of compounds of Formula (I) and (IC) 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) and (IC) 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.

[0079] 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.

[0080] Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, HPPD-, -PDS , -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®.

[0081] 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.

[0082] 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).

[0083] 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.

[0084] In a further aspect of the present invention there is provided the use of a compound of Formula (I) or (IC) as defined herein as a herbicide.

[0085] Processes for preparation of compounds of the invention, e.g. a compound of Formula (I) or (IC) (which optionally can be an agrochemically acceptable salt thereof), are now described, and form further aspects of the present invention.

[0086] Processes for preparation of compounds of Formula (I) and (IC)

[0087] The compounds of the present invention can be prepared according to the following schemes.

[0088] SCHEME 1

[0089] In embodiments where A1is -CHR1- and X1is O, compounds of formula (1) may be prepared from compounds of formula (2), where LG1represents a suitable leaving group (for example Br or Cl), and compounds of formula (3). Compounds of formula (2) are treated with isoxazolidinones of formula (3), a carbonate base, for example potassium carbonate, and optionally a suitable additive, for example sodium iodide, in a suitable solvent, for example acetone.

[0090] SCHEME 2

[0091] Compounds of formula (2) may be prepared from compounds of formula (4).

[0092] For example, where LG1is Cl, compounds of formula (4) are treated with a chlorinating agent, for example thionyl chloride, either neat or in a suitable solvent, for example dichloromethane.

[0093] SCHEME 3

[0094] In an alternative approach, in embodiments where A1is -CHR1- and X1is O, compounds of formula (1) may be prepared from compounds of formula (4).

[0095] Compounds of formula (4) are treated with isoxazolidinones of formula (3), triphenylphosphine and a suitable azodicarboxylate reagent, for example diisopropyl azodicarboxylate, in a suitable solvent, for example 2-methyltetrahydrofuran.

[0096] SCHEME 4

[0097] Compounds of formula (4) may be prepared from compounds of formula (5), where Z is H or O-alkyl.

[0098] For example, where Z is H, compounds of formula (5) are treated with a reducing agent, for example sodium borohydride, in a suitable solvent, for example a tetrahydrofuran / methanol mixture.

[0099] SCHEME 5 The synthesis routes used to access compounds of formula (5) will vary depending on the nature of Z, X2, A2, A3, R4, R5, R6, R7, R8and R9. For example, compounds of formula (6) may be prepared from compounds of formula (7).

[0100] Compounds of formula (7) are reacted under suitable formylation conditions, for example, by treatment with titanium tetrachloride and dichloro(methoxy)methane in a suitable solvent, for example dichloromethane.

[0101] SCHEME 6

[0102] In an alternative approach, compounds of formula (4) may be prepared from compounds of formula (8).

[0103] Compounds of formula (8) are treated with a suitable halogenating agent, for example / V- chlorosuccinimide, in a suitable solvent, for example acetonitrile. SCHEME 7

[0104] Compounds of formula (8) may be prepared from compounds of formula (9), where Z is H or O-alkyl.

[0105] For example, where Z is H, compounds of formula (9) are treated with a reducing agent, for example sodium borohydride, in a suitable solvent, for example a tetrahydrofuran / methanol mixture.

[0106] SCHEME 8

[0107] In a further alternative approach, compounds of formula (4) may be prepared from compounds of formula (10).

[0108] (10) (4)

[0109] Compounds of formula (10) are treated with tributylstannylmethanol in the presence of a suitable (pre-)catalyst / ligand combination, for example (2-dicyclohexylphosphino-2',4',6'-triisopropyl- 1 ,1 '-biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium(IC) methanesulfonate, in a suitable solvent, for example 1 ,4-dioxane.

[0110] SCHEME 9

[0111] Compounds of formula (10) may be prepared from compounds of formula (7).

[0112] (7) (10)

[0113] Compounds of formula (7) are treated with a brominating agent, for example / V- bromosuccinimide, in a suitable solvent, for example acetonitrile. SCHEME 10

[0114] Compounds of formula (7) may be prepared from compounds of formula (11).

[0115] (11 ) (7)

[0116] Compounds of formula (11) are treated with a suitable halogenating agent, for example / V- chlorosuccinimide, in a suitable solvent, for example acetonitrile.

[0117] SCHEME 11

[0118] Compounds of formula (5), formula (7), formula (8), formula (9), formula (10) and formula (1 1) may be commercially available. Alternatively, they may be prepared synthetically utilising ring synthesis strategies known in the literature. The synthetic route adopted will vary depending on the nature of Z, X2, A2, A3, R4, R5, R6, R7, R8and R9. For example, where A2and A3are O, compounds of formula (12) may be prepared from compounds of formula (13). Compounds of formula (13) are treated with compounds of formula (14), where LG2represents a suitable leaving group (for example Br, Cl or tosylate), and a base, for example potassium carbonate, in a suitable solvent, for example dimethylformamide. Compounds of formula (13) and formula (14) are available from commercial sources or may be prepared according to strategies known in the literature.

[0119] SCHEME 12

[0120] In an alternative approach, compounds of formula (15) where A2and A3are O, may be prepared from compounds of formula (16) according to the following scheme.

[0121] Compounds of formula (16) are treated with a suitable oxidative chlorinating agent, for example phosphorous pentachloride, in a suitable solvent, for example chlorobenzene, to give compounds of formula (17). Compounds of formula (17) are treated with isoxazolidinones of formula (3) and a carbonate base, for example potassium carbonate, in a suitable solvent, for example dimethylformamide, to give compounds of formula (18). Compounds of formula (18) are treated with compounds of formula (19), where LG2represents a suitable leaving group (for example Br, Cl or tosylate), and a suitable base, for example potassium carbonate, in a suitable solvent, for example dimethylformamide, to give compounds of formula (15). Compounds of formula (16) and formula (19) are available from commercial sources or may be prepared according to strategies known in the literature.

[0122] SCHEME 13

[0123] Where A1is -C(O)-, compounds of formula (20) may be prepared from compounds of formula

[0124] (21).

[0125] For example, where R2and R3are methyl, compounds of formula (21) are treated with 2,2- dimethylmalonyl chloride and a suitable base, for example pyridine, in a suitable solvent, for example dichloromethane.

[0126] SCHEME 14

[0127] Compounds of formula (21) may be prepared from compounds of formula (6) according to the following scheme.

[0128] Compounds of formula (6) 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 (22). Compounds of formula (22) 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 (21).

[0129] SCHEME 15

[0130] In an alternative approach, compounds of formula (21) may be prepared from compounds of formula (2), where LG1represents a suitable leaving group (for example Br or Cl), according to the following scheme.

[0131]

[0132] Compounds of formula (2) are treated with (te / Y-butoxycarbonylamino) te / Y-butyl carbonate (23), 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 (24). Compounds of formula (24) are treated with a suitable acid, for example hydrochloric acid, in a suitable solvent, for example 1 ,4-dioxane, to give compounds of formula (21).

[0133] SCHEME 16

[0134] Compounds of formula (3) may be commercially available. For example, the compound of formula (3) where R2and R3are methyl and R1is hydrogen is commercially available (CAS no 81778- 07-6). Alternatively, compounds of formula (3) may be prepared synthetically. For example, where R2and R3are methyl and R1is Ci-Cealkoxy, Ci-Cealkoxy-Ci-Cealkoxy-, HOC(0)Ci-Cealkoxy-, Ci- C6alkoxy-C(0)-Ci-Cealkoxy- or Ci-C3alkyl-S(0)PCi-C6alkoxy-, compounds of formula (3) may be prepared from 3,3-dichloro-2,2-dimethylpropanoic acid (25) according to the following scheme. 3,3-Dichloro-2,2-dimethylpropanoic acid (25) is treated with a suitable chlorinating agent, for example thionyl chloride, to give 3,3-dichloro-2,2-dimethylpropanoyl chloride (26). 3,3-Dichloro-2,2- dimethylpropanoyl chloride (26) is treated with a suitable source of hydroxylamine, for example hydroxylamine (50% in H2O), in a suitable solvent, for example water, to give 3,3-dichloro-2,2- dimethyl-propanehydroxamic acid (27). 3,3-Dichloro-2,2-dimethyl-propanehydroxamic acid (27) is treated with an alcohol and a suitable base, for example 1 ,8-diazabicyclo(5.4.0)undec-7-ene, to give compounds of formula (3).

[0135] SCHEME 17

[0136] Compounds of Formula (IC) may be prepared from compounds of formula (20).

[0137] Compounds of formula (20) are treated with water and a suitable base, for example sodium hydroxide, in a suitable solvent, for example a methanol / 2-methyltetrahydrofuran mixture. Alternatively, compounds of formula (20) are treated with a suitable hydroxide source, for example sodium hydroxide, in a suitable solvent, for example DMSO. Compounds of Formula (IC) may be isolated as a suitable salt, for example a sodium salt.

[0138] The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table 1 below.

[0139] PREPARATION EXAMPLES

[0140] Example 1 : Preparation of Compound 1.001

[0141] Step 1 : Preparation of [2,2-dimethyl-3-(p-tolylsulfonyloxy)propyl] 4-methylbenzenesulfonate

[0142] To a solution of 2,2-dimethyl-1 ,3-propanediol (1.092 g, 10.5 mmol) in dichloromethane (21 mL) was added 4-dimethylaminopyridine (259 mg, 2.1 mmol), triethylamine (7.34 mL, 52.4 mmol) and 4-methylbenzenesulfonyl chloride (4.80 g, 25.2 mmol). The reaction mixture was stirred at room temperature for 17 h then concentrated and partitioned between ethyl acetate and sat. aq. ammonium chloride. The organic portion was washed with 2 M hydrochloric acid (x2) and concentrated onto diatomaceous earth. Purification by flash column chromatography (0-20% acetone in cyclohexane) afforded [2,2-dimethyl-3-(p-tolylsulfonyloxy)propyl] 4- methylbenzenesulfonate (80% purity, 3.121 g, 6.053 mmol, 58%).1H NMR (400 MHz, CDCh) 6 ppm 7.72 (d, 4H), 7.34 (d, 4H), 3.71 (s, 4H), 2.45 (s, 6H), 0.87 (s, 6H). Step 2: Preparation of ethyl 3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepine-7-carboxylate

[0143] To a solution of ethyl 3,4-dihydroxybenzoate (780 mg, 4.28 mmol) in / V, / V-dimethylformamide (10 mL) was added potassium carbonate (1 .37 g, 9.42 mmol) and the mixture was heated at 40 °C for 1 h. A solution of [2,2-dimethyl-3-(p-tolylsulfonyloxy)propyl] 4-methylbenzenesulfonate (80% purity, 1 .94 g, 3.76 mmol) in / V, / V-dimethylformamide (10 mL) was then added, and the reaction was heated at 140 °C for 16 h. The reaction mixture was diluted with water and extracted with methyl te / Y-butyl ether (x3). The combined organic portions were washed with brine, dried over MgSC and concentrated onto silica gel. Purification by flash column chromatography (0-30% ethyl acetate in cyclohexane) afforded ethyl 3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepine-7-carboxylate (287 mg, 1.15 mmol, 31 %).1H NMR (400 MHz, CDCb) 6 ppm 7.62 - 7.57 (m, 2H), 6.91 (d, 1 H), 4.31 (q, 2H), 3.91 (s, 2H), 3.89 (s, 2H), 1.33 (t, 3H), 1.06 (s, 6H).

[0144] Step 3: Preparation of (3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-7-yl)methanol

[0145] Diisobutylaluminium hydride (1 M solution in hexanes, 4.5 mL, 4.5 mmol) was added dropwise to a solution of ethyl 3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepine-7-carboxylate (320 mg, 1 .28 mmol) in 2-methyltetrahydrofuran (4.0 mL) at 0 °C under an atmosphere of nitrogen. The reaction mixture was stirred at 0°C for 30 min then quenched by the dropwise addition of ethyl acetate at 0 °C. Sat. aq. potassium sodium tartrate was added and the mixture was stirred vigorously for 30 min at room temperature then extracted with ethyl acetate (x2). The combined organic portions were concentrated onto diatomaceous earth and purified via flash column chromatography (0-50% acetone in cyclohexane) to afford (3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-7-yl)methanol (236 mg, 1 .13 mmol, 89%).1H NMR (400 MHz, CDCb) 6 ppm 6.97 - 6.87 (m, 3H), 4.60 - 4.55 (m, 2H), 3.86 (s, 2H), 3.86 (s, 2H), 1.06 (s, 6H).

[0146] Step 4: Preparation of (7-chloro-3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methanol

[0147] A mixture of (3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-7-yl)methanol (229 mg, 1 .05 mmol) and / V-chlorosuccinimide (146 mg, 1.10 mmol) in acetonitrile (3.5 mL) was stirred at 70 °C for 1 h. The reaction mixture was allowed to stand at room temperature overnight and was then concentrated onto diatomaceous earth and purified via flash column chromatography (0-30% ethyl acetate in cyclohexane) to afford (7-chloro-3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-8- yl)methanol (245 mg, 0.959 mmol, 92%).1H NMR (400 MHz, CDCb) 6 ppm 7.04 (s, 1 H), 6.96 (s, 1 H), 4.65 (d, 2H), 3.85 (s, 2H), 3.85 (s, 2H), 1 .05 (s, 6H).

[0148] Step 5: Preparation of 2-[(7-chloro-3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methyl]-4,4- dimethyl-isoxazolidin-3-one To a solution of (7-chloro-3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methanol (241 mg, 0.993 mmol) in 2-methyltetrahydrofuran (3 mL) was added triphenylphosphine (319 mg, 1.19 mmol) and 4,4-dimethylisoxazolidin-3-one (137 mg, 1.19 mmol). The mixture was cooled to 0 °C and diisopropyl azodicarboxylate (0.22 mL, 1.09 mmol) was added dropwise. The reaction mixture was allowed to warm to room temperature and stir for 30 min. The reaction mixture was quenched with a few drops of water and concentrated onto diatomaceous earth. Purification by reverse phase flash column chromatography (50-80% acetonitrile in water, both modified with 0.1 % formic acid) afforded 2-[(7-chloro-3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl-isoxazolidin-3- one.1H NMR (400 MHz, CDCb) 6 ppm 6.95 (s, 1 H), 6.90 (s, 1 H), 4.71 (s, 2H), 4.02 (s, 2H), 3.85 (s, 2H), 3.84 (s, 2H), 1 .26 (s, 6H), 1 .04 (s, 6H).

[0149] Example 2: Preparation of Compound 1.002

[0150] Step 1 : Preparation of 5-chloro-6-(chloromethyl)-1 ,3-benzodioxol-2-one

[0151] A solution of chloropiperonyl alcohol (10.0 g, 53.6 mmol) in chlorobenzene (50 mL) was added slowly to a solution of phosphorous pentachloride (45.6 g, 214 mmol) in chlorobenzene (50 mL) over 10 min. The reaction was heated at reflux for 5 h then cooled to room temperature. The reaction mixture was added dropwise to water with stirring then extracted with dichloromethane (x2). The organic portions were combined, passed through a hydrophobic frit and concentrated. Purification by flash column chromatography (0-50% ethyl acetate in isohexane) afforded 5-chloro- 6-(chloromethyl)-1 ,3-benzodioxol-2-one (10.8 g, 49.4 mmol, 92%).1H NMR (400 MHz, CDCb) 6 ppm 7.42 (s, 1 H), 7.35 (s, 1 H), 4.70 (s, 2H).

[0152] Step 2: Preparation of 2-[(2-chloro-4,5-dihydroxy-phenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one

[0153] To a solution of 5-chloro-6-(chloromethyl)-1 ,3-benzodioxol-2-one (10.8 g, 49.4 mmol) in N,N- dimethylformamide (11 1 mL) was added potassium carbonate (20.7 g, 150 mmol) and 4,4- dimethylisoxazolidin-3-one (5.69 g, 49.4 mmol). The reaction was stirred at room temperature for 65 h. The reaction was acidified to pH 2 with 2 M hydrochloric acid and extracted with diethyl ether (x4). The organic portions were combined, dried over MgSC , filtered and concentrated. Purification by flash column chromatography (20-100% ethyl acetate in isohexane) afforded 2-[(2-chloro-4,5- dihydroxy-phenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one (9.95 g, 36.6 mmol, 74%).1H NMR (400 MHz, DMSO-de) 6 ppm 9.43 (br s, 1 H), 9.31 (br s, 1 H), 6.76 (s, 1 H), 6.74 (s, 1 H), 4.55 (s, 2H), 4.00 (s, 2H), 1.12 (s, 6H).

[0154] Step 3: Preparation of 2-[(7-chloro-3-methylene-1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl- isoxazolidin-3-one

[0155] To a mixture of 2-[(2-chloro-4,5-dihydroxy-phenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one (0.104 g, 0.383 mmol) and potassium carbonate (0.107 g, 0.766 mmol) in dimethylformamide (3.8 mL) was added 3-chloro-2-(chloromethyl)prop-1-ene (0.073 g, 0.062 mL, 0.574 mmol). The reaction mixture was stirred at 70 °C for 2 h then absorbed onto diatomaceous earth and purified via flash column chromatography (0-70% ethyl acetate in cyclohexane) to afford 2-[(7-chloro-3-methylene- 1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one.1H NMR (400 MHz, CDCh) 6 ppm 6.95 (s, 1 H), 6.91 (s, 1 H), 5.11 - 5.06 (m, 2H), 4.75 (s, 2H), 4.74 (s, 2H), 4.71 (s, 2H), 4.02 (s, 2H), 1 .26 (s, 6H)

[0156] Example 3: Preparation of Compound 1.003

[0157] Step 1 : Preparation of 4-bromo-5-chloro-benzene-1 ,2-diol

[0158] To a solution of 4-chlorocatechol (1.00 g, 6.71 mmol) in acetic acid (10 mL) at room temperature was added bromine (1.13 g, 0.363 mL, 7.05 mmol). The reaction was stirred for 2 h at room temperature. The reaction mixture was quenched with saturated aqueous sodium thiosulfate then ethyl acetate was added and the layers were separated. The organic phase was dried over MgSCM, filtered and concentrated to afford 4-bromo-5-chloro-benzene-1 ,2-diol (1.45 g, 6.49 mmol, 97%).1H NMR (400 MHz, CDCh) 6 ppm 7.12 (s, 1 H), 6.99 (s, 1 H).

[0159] Step 2: Preparation of 7-bromo-8-chloro-3-methylene-1 ,5-benzodioxepine

[0160] To a solution of 4-bromo-5-chloro-benzene-1 ,2-diol (1.20 g, 5.37 mmol) and potassium carbonate (1.50 g, 10.7 mmol) in / V, / V-dimethylformamide (27 mL) was added 3-chloro-2- (chloromethyl)prop-l-ene (1.03 g, 0.87 mL, 8.06 mmol). The reaction mixture was stirred at 70 °C for 2 h then absorbed onto diatomaceous earth and purified via flash column chromatography (0-5% ethyl acetate in cyclohexane) to afford 7-bromo-8-chloro-3-methylene-1 ,5-benzodioxepine (0.80 g, 2.90 mmol, 54%).1H NMR (400 MHz, CDCh) 6 ppm 7.18 (s, 1 H), 7.04 (s, 1 H), 5.12 - 5.10 (m, 2H), 4.76 - 4.73 (m, 4H).

[0161] Step 3: Preparation of 7-bromo-8-chloro-1 ,5-benzodioxepin-3-one

[0162] Ozone was bubbled through a solution of 7-bromo-8-chloro-3-methylene-1 ,5- benzodioxepine (0.80 g, 2.90 mmol) in methanol (29 mL) and dichloromethane (29 mL) at -78 °C for 1 h. The mixture was purged with air for 20 min then dimethyl sulphide (0.361 g, 0.426 mL, 5.81 mmol) was added. The reaction mixture was stirred at room temperature for 4 h. The reaction mixture was absorbed onto diatomaceous earth and purified via flash column chromatography (0-50% ethyl acetate in cyclohexane) to afford 7-bromo-8-chloro-1 ,5-benzodioxepin-3-one (0.660 g, 2.38 mmol, 82%).1H NMR (400 MHz, CDCh) 6 ppm 7.28 (s, 1 H), 7.13 (s, 1 H), 4.72 (s, 2H), 4.71 (s, 2H).

[0163] Step 4: Preparation of 7-bromo-8-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepine To a solution of 7-bromo-8-chloro-1 ,5-benzodioxepin-3-one (0.65 g, 2.34 mmol) in dichloromethane (23 mL) at 0 °C was added diethylaminosulfur trifluoride (1 .59 g, 1.30 mL, 9.37 mmol). The reaction was stirred at room temperature for 24 h. The reaction mixture was quenched with saturated aqueous sodium bicarbonate then dichloromethane was added and the layers were separated. The organic phase was dried over MgSCM, filtered and concentrated to afford 7-bromo- 8-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepine (0.690 g, 2.30 mmol, 98%).1H NMR (400 MHz, CDCb) 6 ppm 7.26 (s, 1 H), 7.1 1 (s, 1 H), 4.40 (t, 2H), 4.39 (t, 2H).

[0164] Step 5: Preparation of (7-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methanol

[0165] 7-Bromo-8-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepine (0.100 g, 0.334 mmol), (tributylstannyl)methanol (0.147 g, 0.434 mmol) and (2-dicyclohexylphosphino-2',4',6'-triisopropyl- 1 ,1 '-biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium(IC) methanesulfonate (0.029 g, 0.033 mmol) were stirred in 1 ,4-dioxane (3.3 mL) at 80 °C for 23 h. The reaction mixture was absorbed onto diatomaceous earth and purified via flash column chromatography (0-100% ethyl acetate in cyclohexane) to afford (7-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methanol (0.048 g, 0.19 mmol, 57%).1H NMR (400 MHz, CDCb) 6 ppm 7.13 (s, 1 H), 7.02 (s, 1 H), 4.67 (d, 2H), 4.40 (t, 2H), 4.39 (t, 2H).

[0166] Step 6: Preparation of 2-[(7-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methyl]-4,4- dimethyl-isoxazolidin-3-one

[0167] To a solution of (7-chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methanol (0.170 g, 0.678 mmol), 4,4-dimethylisoxazolidin-3-one (0.117 g, 1.02 mmol) and triphenylphosphine (0.270 g, 1.02 mmol) in 2-methyltetrahydrofuran (3.4 mL) at 0 °C was added diisopropyl azodicarboxylate (0.210 g, 0.204 mL, 1 .02 mmol). The reaction mixture was stirred at room temperature for 2 h. The reaction mixture was absorbed onto C-18 silica gel and purified via reverse phase flash column chromatography (50-90% acetonitrile in water, both modified with 0.1 % formic acid) to afford 2-[(7- chloro-3,3-difluoro-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one.1H NMR (400 MHz, CDCb) 6 ppm 7.03 (s, 1 H), 6.97 (s, 1 H), 4.72 (s, 2H), 4.40 (t, 2H), 4.39 (t, 2H), 4.03 (s, 2H), 1.27 (s, 6H).

[0168] Example 4: Preparation of Compound 1.004 (2-[(7-chloro-3,4-dihydro-2H-1 ,5-benzodioxepin- 8-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one)

[0169] To a solution of 7-chloro-8-(chloromethyl)-3,4-dihydro-2 / 7-1 ,5-benzodioxepine (0.30 g, 1.29 mmol) and sodium iodide (0.019 g, 0.129 mmol) in acetone (9 mL) was added potassium carbonate (0.271 g, 1 .93 mmol) and 4,4-dimethylisoxazolidin-3-one (0.178 g, 1 .54 mmol). The reaction mixture was stirred at room temperature overnight then quenched by the addition of water and extracted with ethyl acetate (x3). The organic extracts were combined, dried by passing through a hydrophobic filter paper and concentrated. Purification by flash column chromatography (0-40% ethyl acetate in cyclohexane) afforded 2-[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl- isoxazolidin-3-one.1H NMR (400 MHz, CDCb) 6 ppm 6.99 (s, 1 H), 6.94 (s, 1 H), 4.71 (s, 2H), 4.22 - 4.16 (m, 4H), 4.02 (s, 2H), 2.22 - 2.15 (m, 2H), 1.26 (s, 6H).

[0170] Example 5: Preparation of Compound 1.005

[0171] Step 1 : Preparation of A / -[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl]hydroxylamine hydrochloride

[0172] (te / Y-Butoxycarbonylamino) te / Y-butyl carbonate (540 mg, 2.25 mmol), potassium carbonate (348 mg, 2.50 mmol) and 7-chloro-8-(chloromethyl)-3,4-dihydro-2 / 7-1 ,5-benzodioxepine (540 mg, 2.32 mmol) were combined in acetonitrile (10 mL). The reaction mixture was stirred at room temperature overnight then at 60 °C for 4 h. 18-Crown-6 (62 mg, 0.23 mmol) was added and the reaction heated at 60 °C for a further 4 h. The reaction mixture was filtered and concentrated. The resulting residue had hydrochloric acid (4 M solution in 1 ,4-dioxane, 10 mL, 40 mmol) added and the mixture was stirred for 2 h then left to stand overnight. Concentration under reduced pressure afforded crude A / -[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl]hydroxylamine hydrochloride (0.938 g, contaminated with 18-crown-6).1H NMR (400 MHz, methanol-d4) 6 ppm 7.11 (s, 1 H), 7.21 (s, 1 H), 4.70 (s, 2H), 4.28 - 4.20 (m, 4H), 2.25 - 2.18 (m, 2H).

[0173] Step 2: Preparation of 2-[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl- isoxazolidine-3, 5-dione

[0174] A solution of A / -[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl]hydroxylamine hydrochloride (crude from step 1 , 0.938 g) and pyridine (0.846 g, 0.864 mL, 10.6 mmol) in dichloromethane (10 mL) had 2,2-dimethylpropanedioyl dichloride (0.596 g, 0.469 mL, 3.52 mmol) in dichloromethane (10 mL) added dropwise over 15 min at 0 °C. The reaction was stirred at room temperature for 1 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 (0-100% ethyl acetate in isohexane) afforded 2-[(7-chloro-3,4-dihydro-2 / 7-1 ,5- benzodioxepin-8-yl)methyl]-4,4-dimethyl-isoxazolidine-3, 5-dione.1H NMR (400 MHz, CDCb) 6 ppm 7.02 (s, 1 H), 6.97 (s, 1 H), 4.93 (s, 2H), 4.25 - 4.17 (m, 4H), 2.23 - 2.17 (m, 2H), 1 .45 (s, 6H).

[0175] Example 6: Preparation of Compound 1.011

[0176] Step 1 : Preparation of methyl 4-allyloxy-2-chloro-benzoate

[0177] Potassium carbonate (15.12 g, 107.2 mmol) was added to a solution of methyl 2-chloro-4- hydroxy-benzoate (10.0 g, 53.6 mmol) and 3-chloroprop-1-ene (8.20 g, 107.2 mmol) in acetonitrile (300 mL). The reaction mixture was heated to 60 °C for 18 h then diluted with water and extracted with ethyl acetate (x3). The organic portions were combined, passed through a hydrophobic frit and concentrated. Purification by flash column chromatography (5-25% ethyl acetate in cyclohexane) afforded methyl 4-allyloxy-2-chloro-benzoate (11.2 g, 46.9 mmol, 88%).1H NMR (400 MHz, CDCb) 6 ppm 7.87 (d, 1 H), 6.99 (d, 1 H), 6.83 (dd, 1 H), 6.08 - 5.98 (m, 1 H), 5.45 - 5.38 (m, 1 H), 5.36 - 5.30 (m, 1 H), 4.59 - 4.55 (m, 2H), 3.89 (s, 3H).

[0178] Step 2: Preparation of methyl 5-allyl-2-chloro-4-hydroxy-benzoate

[0179] A mixture of methyl 4-allyloxy-2-chloro-benzoate (3.0 g, 13.2 mmol) and a single drop of DMF was heated at 200 °C for 2 h by microwave irradiation. The crude product was purified by flash column chromatography (5-100% ethyl acetate in cyclohexane) to afford an uncharacterised mixture of methyl 5-allyl-2-chloro-4-hydroxy-benzoate and methyl 3-allyl-2-chloro-4-hydroxy-benzoate (5.88g).

[0180] Step 3: Preparation of methyl 5-allyl-4-allyloxy-2-chloro-benzoate

[0181] A solution of methyl 5-allyl-2-chloro-4-hydroxy-benzoate and methyl 3-allyl-2-chloro-4- hydroxy-benzoate (5.88 g) in acetonitrile (1 18 mL) had 3-chloroprop-1-ene (3.97 g, 51 .9 mmol) and potassium carbonate (7.32 g, 51 .9 mmol) added. The reaction mixture was heated to 60 °C for 18 h then diluted with water and extracted with ethyl acetate (x3). The organic portions were combined, passed through a hydrophobic frit and concentrated. Purification by flash column chromatography (5-20% ethyl acetate in cyclohexane) afforded methyl 5-allyl-4-allyloxy-2-chloro-benzoate (1.57 g,

[0182] 5.89 mmol, 23%).1H NMR (400 MHz, CDCb) 6 ppm 7.71 (s, 1 H), 6.88 (s, 1 H), 6.09 - 5.89 (m, 2H), 5.46 - 5.39 (m, 1 H), 5.35 - 5.29 (m, 1 H), 5.11 - 5.08 (m, 1 H), 5.07 - 5.03 (m, 1 H), 4.60 - 4.56 (m, 2H),

[0183] 3.89 (s, 3H), 3.39 - 3.35 (m, 2H).

[0184] Step 4: Preparation of methyl 8-chloro-2,5-dihydro-1-benzoxepine-7-carboxylate

[0185] A solution of methyl 5-allyl-4-allyloxy-2-chloro-benzoate (1 .57 g, 5.89 mmol) and Grubbs Catalyst® 2ndGeneration (0.750 g, 0.883 mmol) in dichloromethane (150 mL) was stirred at room temperature overnight under an atmosphere of nitrogen. The reaction mixture was concentrated and purified by flash column chromatography (5-10% ethyl acetate in cyclohexane) to afford methyl 8- chloro-2,5-dihydro-1 -benzoxepine-7-carboxylate (0.840 g, 3.52 mmol, 60%).1H NMR (400 MHz, CDCb) 6 ppm 7.64 (s, 1 H), 7.12 (s, 1 H), 5.92 - 5.84 (m, 1 H), 5.57 - 5.50 (m, 1 H), 4.65 - 4.60 (m, 2H),

[0186] 3.90 (s, 3H), 3.51 - 3.47 (m, 2H).

[0187] Step 5: Preparation of methyl 8-chloro-2,3,4,5-tetrahydro-1-benzoxepine-7-carboxylate

[0188] To one chamber of a 100mL COware vessel fitted with H-caps was added 5% Pd / C (50% water) (0.29 g, 0.067 mmol) and a solution of methyl 8-chloro-2,5-dihydro-1-benzoxepine-7- carboxylate (0.32 g, 1.34 mmol) in ethyl acetate (3 mL). To the second chamber of the COware vessel was added zinc (granular, 20 mesh, 1 .2 g, 18 mmol) and the vessel was purged with nitrogen. Hydrochloric acid (6.0 M, 1 .12 mL, 6.7 mmol) was added to the second chamber containing zinc, and the reaction was stirred at room temperature overnight. The contents of the substrate containing chamber were filtered through a plug of diatomaceous earth, washing with EtOAc / MeOH (1 :1). The filtrate was concentrated and purified by reverse phase preparative HPLC to afford methyl 8-chloro- 2,3,4,5-tetrahydro-1-benzoxepine-7-carboxylate (0.157 g, 0.65 mmol, 24%).1H NMR (400 MHz, CDCb) 6 ppm 7.68 (s, 1 H), 7.06 (s, 1 H), 4.06 - 4.02 (m, 2H), 3.90 (s, 3H), 2.83 - 2.78 (m, 2H), 2.01 - 1 .94 (m, 2H), 1 .78 - 1 .70 (m, 2H).

[0189] Step 6: Preparation of (8-chloro-2,3,4,5-tetrahydro-1-benzoxepin-7-yl)methanol

[0190] Diisobutylaluminium hydride (1 M solution in hexanes, 2.18 mL, 2.18 mmol) was added dropwise to a solution of methyl 8-chloro-2,3,4,5-tetrahydro-1-benzoxepine-7-carboxylate (0.150 g, 0.623 mmol) in 2-methyltetrahydrofuran (3 mL) at 0 °C under an atmosphere of nitrogen. The reaction mixture was stirred at 0 °C for 1 h then quenched by the dropwise addition of ethyl acetate. Sat. aq. potassium sodium tartrate was added and the mixture was stirred vigorously at room temperature then extracted with ethyl acetate (x3). The combined organic portions were concentrated to afford (8-chloro-2,3,4,5-tetrahydro-1-benzoxepin-7-yl)methanol (0.126 g, 0.59 mmol, 95%).1H NMR (400 MHz, CDCb) 6 ppm 7.21 (s, 1 H), 7.02 (s, 1 H), 4.70 (s, 2H), 4.01 - 3.96 (m, 2H), 2.81 - 2.77 (m, 2H), 2.00 - 1 .92 (m, 2H), 1 .88 (br s, 1 H), 1 .75 - 1 .67 (m, 2H).

[0191] Step 7: Preparation of 2-[(8-chloro-2,3,4,5-tetrahydro-1-benzoxepin-7-yl)methyl]-4,4-dimethyl- isoxazolidin-3-one

[0192] To a solution of (7-chloro-3,3-dimethyl-2,4-dihydro-1 ,5-benzodioxepin-8-yl)methanol (125 mg, 0.59 mmol) in 2-methyltetrahydrofuran (3 mL) was added triphenylphosphine (234 mg, 0.88 mmol) and 4,4-dimethylisoxazolidin-3-one (102 mg, 0.88 mmol). The mixture was cooled to 0 °C and diisopropyl azodicarboxylate (0.18 mL, 0.88 mmol) was added dropwise. The reaction mixture was allowed to warm to room temperature and stir for 3 h under an atmosphere of nitrogen. The reaction mixture was concentrated and purified by reverse phase flash column chromatography (60-100% acetonitrile in water, both modified with 0.1 % formic acid) to afford 2-[(8-chloro-2,3,4,5-tetrahydro-1- benzoxepin-7-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one (0.1 15 g, 0.37 mmol, 63%).1H NMR (400 MHz, CDCb) 6 ppm 7.09 (s, 1 H), 7.03 (s, 1 H), 4.76 (s, 2H), 4.01 (s, 2H), 4.01 - 3.97 (m, 2H), 2.80 - 2.75 (m, 2H), 1 .99 - 1 .92 (m, 2H), 1 .75 - 1 .67 (m, 2H), 1 .27 (s, 6H).

[0193] Example 7: Preparation of Compound 1.022 (sodium 3-[(7-chloro-3,4-dihydro-2H-1 ,5- benzodioxepin-8-yl)methyl-hydroxy-amino]-2,2-dimethyl-3-oxo-propanoate) To a solution of 2-[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl]-4,4-dimethyl- isoxazolidine-3, 5-dione (0.097 g, 0.30 mmol) in methanol (0.6 mL) and 2-methyltetrahydrofuran (0.6 mL) was added sodium hydroxide (2 M solution in water, 0.30 mmol, 0.15 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 re-dissolved in water and again concentrated to dryness to afford sodium 3-[(7-chloro-3,4-dihydro-2 / 7-1 ,5-benzodioxepin-8-yl)methyl-hydroxy-amino]-2,2-dimethyl-3- oxo-propanoate (0.087 g, 0.23 mmol, 76%).1H NMR (400 MHz, DMSO-d6) 6 ppm 7.00 (s, 1 H), 6.94 (s, 1 H), 4.61 (s, 2H), 4.16 - 4.08 (m, 4H), 2.15 - 2.05 (m, 2H), 1 .32 (s, 6H). Additional compounds of the invention, made in an analagous manner to those described above in Examples 1 to 5 are shown in Table 1 below.

[0194] Table 1. Compounds of the present invention

[0195] BIOLOGICAL EXAMPLES

[0196] Test 1

[0197] Seeds of a variety of test species are sown in standard soil in pots Leptochloa chinesis (LEFCH), Echinochloa crus-galli (ECHCG) and Cyperus esculentus (CYPES). After cultivation for one day (pre-emergence) or after 13 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 30 / 20°C, day / night; 18 hours light; 75% humidity), the plants are sprayed with an aqueous spray solution derived from 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 500 g / ha. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 30 / 20°C, day / night; 18 hours light; 75% humidity) and watered twice daily. After 13 days for pre and post-emergence, the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following table on a five-point scale (5 = 81-100%; 4 = 61-80%; 3=41-60%; 2=21-40%; 1 =0-20%); NT indicates not tested.

[0198] Table B1. Post-emergence Test 1

[0199] [a] Tested at 1000 g / ha

[0200] Table B2. Pre-emergence Test 1

[0201] [a] Tested at 1000 g / ha

[0202] [b] Tested at 125 g / ha

[0203] Test 2

[0204] Seeds of a variety of test species are sown in standard soil in pots Alopecurus myosuroides (ALOMY), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA), Solanum nigrum (SOLNI). 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 / 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 table on a five-point scale (5 = 81-100%; 4 = 61-80%; 3=41-60%; 2=21-40%; 1 =0-20%).

[0205] Table B3. Post-emergence Test 2

[0206] Table B4. Pre-emergence Test 2

Claims

CLAIMS1 . A compound of Formula (I),Or an agronomically acceptable salt, whereinA1is CHR1or C(O);X1is O or S;X2is a halogen;R1is selected from the group consisting of hydrogen, halogen, HO-, Ci-Cealkoxy, Ci- Cealkoxy-Ci-Cealkoxy-, Ci-C3alkyl-C(O)O-, HOC(0)Ci-Cealkoxy-, Ci-Cealkoxy-C(0)-Ci- Cealkoxy-, Ci-C3alkyl-S(O)P- and Ci-C3alkyl-S(0)PCi-Cealkoxy-;R2is Ci-Csalkyl;R3is 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; orR4and R5together are =O or -(CH2)n-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; orR6and R7together are =O, =CR10R11or =NOR12;R6and R7together with the carbon atom to which they are joined form a 3-, 4-, 5-, or 6-membered saturated ring, said ring optionally comprising one or two ring oxygen atoms, and wherein the carbon atom to which both R6and R7are joined acts as a spiro-atom;R10and R11are each independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl and Ci-Cehaloalkyl; orR10and R11together are -(CH2)n-;R12is hydrogen, Ci-Cealkyl, Ci-Cehaloalkyl or Cs-Cecycloalkyl;R8is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-;R9is selected from the group consisting hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, C3- Cecycloalkyl and Ci-Cealkoxy; orR8and R9together are =O or -(CH2)n-;A2and A3are independently selected from the group consisting of CR13R14, C(O), O, S(O)Pand N(R15);R13is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-;R14is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-; orR13and R14together are -(CH2)n-;R15is hydrogen or Ci-Csalkyl; n is independently 2, 3, 4 ,5 or 6; p is independently 0, 1 or 2; and q is independently is 2,3,4 or 5.

2. The compound of Formula (I) wherein X1is O.

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

4. The compound of Formula (I) accordingly to any one of the previous claims, wherein A1is CHR1and R1is hydrogen.

5. The compound of Formula (I) accordingly to any one of claims 1 to 4, wherein A1is CHR1and R1is OH or Ci-Cealkoxy.

6. The compound of Formula (I) accordingly to any one of claims 1 to 4, wherein A1is C(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 1 to 6, wherein R6and R7are independently selected from the group consisting of hydrogen, methyl and fluoro or R6and R7together are =O or =NOMe.

9. The compound according to claims 1 to 8, wherein R8and R9are independently selected from the group consisting of hydrogen, methyl and fluoro.

10. The compound according to any of the previous claims, wherein A2and A3are both O.1 1 . The compound according to any of the previous claims wherein X1is O, R4, R5, R8and R9are hydrogen, A1and A2are O.

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

13. The herbicidal composition according to claim 12, further comprising at least one additional pesticide.

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

15. A method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a compound as defined in any one of claims 1 to 11 or a weed controlling amount of a composition as defined in any one of claims 12 to 14.

16. Use of a compound of Formula (I) as defined in any one of claims 1 to 11 as a herbicide.

17. A compound of Formula (IC):(IC), or an agronomically acceptable salt thereof wherein:X2is a halogen;R1Cis hydrogen or Ci-C4alkyl;R2Cis Ci-Csalkyl; R3Cis 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;R4and R5together are =O or -(CH2)n-;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; orR6and R7together are =O, =CR10R11or =NOR12;R6and R7together with the carbon atom to which they are joined form a 3-, 4-, 5-, or 6-membered saturated ring, said ring optionally comprising one or two ring oxygen atoms, and wherein the carbon atom to which both R6and R7are joined acts as a spiro-atom;R10and R11are each independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl and Ci-Cehaloalkyl;R10and R11together are -(CH2)n-;R12is hydrogen, Ci-Cealkyl, Ci-Cehaloalkyl or Cs-Cecycloalkyl;R8is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ce-Cecycloalkyl and Ci-Cealkoxy-;R9is selected from the group consisting hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, C3- Cecycloalkyl and Ci-Cealkoxy;R8and R9together are =O or -(CH2)n-;A2and A3are independently selected from the group consisting of CR13R14, C(O), O, S(O)Pand N(R15);R13is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-;R14is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci-Cealkoxy-;R13and R14together are -(CH2)n-R15is hydrogen or Ci-Csalkyl;n is independently 2, 3, 4 ,5 or 6; p is independently 0, 1 or 2; and q is independently is 2,3,4 or 5.

Images