Herbicidal compounds

Abstract

The present invention relates to a compound having formula (I) or an agronomically acceptable salt of said compound, wherein A1, A2, A3, X1, R3, R4 are as defined herein. The invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, in particular in crops of useful plants. # imgabs0 #

Description

[0001] The present invention relates to herbicidal compounds, to processes for their preparation, to herbicidal compositions comprising these herbicidal compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.

[0002] The herbicide 3-isoxazolidinone is known from US 4,405,357. The herbicide isoxazolidine-3,5-dione is known from US 4,302,238. The present invention relates to novel 3-isoxazolidinone and isoxazolidine-3,5-dione compounds. Therefore, according to the present invention, there is provided a compound of formula (I):

[0003]

[0004] or an agronomically acceptable salt thereof, wherein:

[0005] A 1 Yes CR 1 R 2 or C(O);A 2 Selected from the group consisting of: C(R 5 )、N(R 6 ), S and O; A 3 Selected from the group consisting of: C(R 5 )、N(R 6 ), S and O; A 4 Selected from the group consisting of: C(R 5 )、N(R 6 ), S and O; X 1 O or S; R 1 Selected from the group consisting of hydrogen, halogen, HO-, C1-C6 alkoxy, C1-C6 alkoxy-C1-C6 alkoxy-, C1-C3 alkyl-C(O)O-, HOC(O)C1-C6 alkoxy-, C1-C6 alkoxy-C(O)-C1-C6 alkoxy-, C1-C3 alkyl-S(O) p - and C1-C3 alkyl-S(O) p C1-C6 alkoxy-; R 2 is hydrogen; R 3 is a C1-C3 alkyl group; R 4 is a C1-C3 alkyl group; R 5 is selected from the group consisting of hydrogen, halogen, C1-C3 alkyl, aryl (e.g. phenyl), C1-C3 haloalkyl, C1-C3 haloalkoxy-, C1-C3 alkoxy- and C3-C6 cycloalkyl; R 6 is selected from the group consisting of: hydrogen, C1-C3 alkyl- and C1-C3 haloalkyl; and p=0, 1 or 2.

[0006] C1-C6 alkyl - includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), isobutyl (i-Bu), sec-butyl and tert-butyl (t-Bu). C1-C3 alkyl includes methyl (Me, CH3), ethyl (Et, C2H5) and propyl (Pr, such as isopropyl and n-propyl).

[0007] Halogen (or halo) includes, for example, fluorine, chlorine, bromine or iodine. The above applies correspondingly to halogen in other defined contexts, such as haloalkyl.

[0008] C1-C6 haloalkyl - includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoropropyl and 2,2,2-trichloroethyl and heptafluoro-n-propyl. C1-C2 haloalkyl 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.

[0009] The C1-C6 alkoxy group includes methoxy, ethoxy and isopropoxy-.

[0010] C1-C6 haloalkoxy - includes, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.

[0011] The C1-C6 alkoxy-C1-C6 alkoxy- includes, for example, methoxymethoxy- and ethoxymethoxy-.

[0012] C1-C3 alkyl-C(O)O- includes methyl-C(O)O- and ethyl-C(O)O-.

[0013] C1-C6 alkoxy-C(O)-C1-C6 alkoxy- includes methoxy-C(O)-methoxy- and ethoxy-C(O)-methoxy-.

[0014] C1-C3 alkyl-S(O) p C1-C6 alkoxy - including methyl - S(O) p Methoxy- and Ethyl-S(O) p Methoxy-.

[0015] The C3-C6 cycloalkyl group includes cyclopropyl, cyclopentyl and cyclohexyl.

[0016] The C1-C4 alkyl-S-(alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0017] The C1-C4 alkyl-S(O)-(alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0018] The C1-C4 alkyl-S(O)2-(alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0019] In one embodiment of the present invention, there is provided a compound having formula (I), wherein X 1 It's O.

[0020] In another embodiment of the present invention, there is provided a compound having formula (I), wherein A 1 Yes CR 1 R 2 And R 1 Therefore, in a preferred embodiment of the present invention, there is provided a compound having formula 1a, 1b, 1c, 1d, 1e, 1f, 1g or 1h:

[0021]

[0022]

[0023] In another embodiment of the present invention, there is provided a compound having formula (I), wherein A 1 is C(O). Therefore, in a preferred embodiment of the present invention, a compound having formula 2a is provided:

[0024]

[0025] In another embodiment of the present invention, there is provided a compound having formula (I), wherein R 3 and R 4 It's methyl.

[0026] In another embodiment of the present invention, there is provided a compound having formula (I), wherein A 1 Yes CR 1 R 2 And R 1It is a C1-C6 alkoxy group.

[0027] In another embodiment of the present invention, there are provided compounds having formula (I), (1a), (1b), (1c), (1d) and (2a), wherein R 5 is selected from the group consisting of hydrogen, C1-C3 alkyl, aryl (e.g. phenyl), C1-C3 haloalkyl, C1-C3 haloalkoxy- and C1-C3 alkoxy-. More preferably, in such compounds, R 5 is selected from the group consisting of hydrogen, methyl and ethyl. Still more preferably, R 5 In another embodiment of the present invention, there are provided compounds having formula (I), (1e), (1f), (1g) and (1h), wherein R 6 It's methyl.

[0028] Compounds of formula (I) may contain asymmetric centers and may exist as single enantiomers, in pairs of enantiomers in any ratio, or, in the case of more than one asymmetric center, in all possible ratios of diastereomers. Typically, one of the enantiomers has an enhanced biological activity compared to the other possibilities.

[0029] The present invention also provides agronomically acceptable salts of compounds of formula (I). Preferably, the compounds of formula (I) can form salts with amines, including primary, secondary and tertiary amines (e.g., ammonia, dimethylamine and triethylamine), alkali metal bases and alkaline earth metal bases, transition metal bases or quaternary ammonium bases.

[0030] The compounds of formula (I) according to the invention can be used as herbicides themselves, but they are usually formulated into herbicidal compositions using formulation adjuvants such as carriers, solvents and surfactants (SAAs). Therefore, the present invention further provides herbicidal compositions comprising a herbicidal compound according to any one of the preceding claims and an agriculturally acceptable formulation adjuvant. The compositions may be in the form of concentrates which are diluted before use, although ready-to-use compositions may also be prepared. The final dilution is usually carried out with water, but may be carried out using, for example, liquid fertilizers, micronutrients, biological organisms, oils or solvents instead of or in addition to water.

[0031] The herbicidal compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of formula I and from 1 to 99.9% by weight of formulation adjuvants, which preferably include from 0 to 25% by weight of surface-active substances.

[0032] The composition can be selected from a number of formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersants (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), parent drugs (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP) and soluble granules (SG). In any case, the formulation type selected will depend on the specific purpose envisioned and the physical, chemical and biological properties of the compound of formula (I).

[0033] Soluble powders (SP) can 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 sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants or a mixture of said agents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0034] Wettable powders (WP) can 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 dispersants, and optionally, one or more suspending agents to facilitate dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water dispersible granules (WG).

[0035] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material such as pumice, attapulgite clay, Fuller's earth, kieselguhr, diatomaceous earth or corn cob meal, or from preformed blank particles by adsorbing a compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicates, mineral carbonates, sulfates or phosphates and, if necessary, drying. Agents commonly used to aid absorption or adsorption include solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters and adhesives such as polyvinyl acetate, polyvinyl alcohol, dextrins, sugars and vegetable oils. One or more other additives such as emulsifiers, wetting agents or dispersants may also be included in the granules.

[0036] Dispersible concentrates (DC) can 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 surfactant (for example to improve water dilution or to prevent crystallization in a spray tank).

[0037] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers 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 trademark), 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), dimethylamides of fatty acids (such as C8-C 10 EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

[0038] The preparation of EWs involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it can be melted at a suitable temperature, typically below 70° C.) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting 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 chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents having low solubility in water.

[0039] Microemulsions (ME) can be prepared by mixing water with a blend of one or more solvents and one or more SAAs to spontaneously produce a thermodynamically stable, isotropic liquid formulation. The compound of formula (I) is initially present in water or in a solvent / SAA blend. Suitable solvents for use in MEs include those described above for use in ECs or EWs. MEs can be oil-in-water systems or water-in-oil systems (which system is present can be determined by conductivity measurements) and can be suitable for mixing water-soluble pesticides and oil-soluble pesticides in the same formulation. MEs are suitable for dilution into water, remaining as microemulsions or forming conventional oil-in-water emulsions.

[0040] Suspension concentrates (SC) may include aqueous or non-aqueous suspensions of finely dispersed insoluble solid particles of a compound of formula (I). SC may be prepared by ball milling or bead milling a solid compound of formula (I) with one or more dispersants in a suitable medium 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 of particle settling. Alternatively, a compound of formula (I) may be dry-milled and added to water containing the reagents described above to produce a desired final product.

[0041] Aerosol formulations comprise a compound of formula (I) and a suitable propellant (e.g. n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g. water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized hand-operated spray pump.

[0042] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, but with an additional polymerization stage, so that an aqueous dispersion of oil droplets is obtained, wherein each oil droplet is wrapped by a polymer shell and contains a compound with formula (I) and optionally a carrier or diluent for the oil droplet. The polymer shell can be produced by an interfacial polycondensation reaction or by a coacervation procedure. These compositions can provide controlled release of compounds with formula (I) and they can be used for seed treatment. Compounds with formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0043] The composition may include one or more additives to improve the biological performance of the composition, for example by improving wettability, retention or distribution on a surface; rain resistance on the treated surface; or absorption or flow of the compound of formula (I). Such additives include surfactants (SAAs), oil-based spray additives, such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), modified vegetable oils (such as methylated rapeseed oil (MRSO)), and blends of these with other bioenhancement adjuvants (ingredients that can assist or modify the action of the compound of formula (I)).

[0044] The wetting agent, dispersant and emulsifier may be a cationic type, anionic type, amphoteric type or nonionic type SAA.

[0045] Suitable cationic-type SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0046] Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalenesulfonate, and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphates (products from the reaction of one or more fatty alcohols with phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), for example, the reaction of lauryl alcohol with tetraphosphoric acid; these products may additionally be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphates / sulfates of tristyrylphenol.

[0047] Suitable amphoteric types of SAA include betaine, propionate and glycinate.

[0048] Suitable SAAs of the nonionic 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 the partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (such as fatty acid polyethylene glycol esters); amine oxides (such as lauryl dimethyl amine oxide); lecithin and sorbitan and their esters, alkyl polyglycosides and tristyrylphenol.

[0049] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0050] The compounds of the present invention can also be used in admixture 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), bensulfuron, ametryn, amitriptyline, aminopyralid, cypermethrin, atrazine, flubutyric acid-M, quinclorac, benquitrione, benzylsulfuron-methyl (including benzylsulfuron-methyl), bentazon, bicyclic pyrone, bialaphos, bispyribac-sodium, bixlozone, herbicide, bromoxynil, butachlor, flubutyric acid-butyl, mesotrione (including mesotrione-ethyl), chlorsulfuron (including chlorsulfuron-methyl), chlorsulfuron (including chlorsulfuron-ethyl), chlorotoluron, chlorsulfuron, cyproconazole, chlorpyrifos-butyl ... cyfos), clethodim, clodinafop-butyl (including clodinafop-butyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), bisclorac, fluazifop-butyl, fluazifop-butyl, dimethoate, dimethoate-s-propyl, dioxopyritrione, diquat dibromide, diquat , epyrifenacil, ethoxyfluralin, oxadiazine (including oxadiazine-ethyl), fenoxasulfone, benzazin, fenquinotrione, tetrazoline, fluazifop-butyl, bispyribac, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop-butyl (including fluazifop-butyl-butyl), fluazifop-butyl (including fluazifop-sodium), flufenacet, fluazifop-butyl ... fluroxypyr-meptyl), fluazifop-butyl, foramsulfuron, glufosinate (including L-glufosinate and ammonium salts of both), glyphosate (including its hydrazine, isopropyl ammonium and potassium salts), halauxifen (including halauxifen-methyl), fluazifop-methyl (including fluazifop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapyr, imazapyr, imazamox, indazine fluazifop-butyl, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iodofensulfuron-sodium), ioboxynil, isoproturon,Isotrione, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methizolin, isopropyl metolachlor, sulfamethoxazole, metribuzin, metsulfuron-methyl, propamide, nicosulfuron, norfadine, oxadiazine, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, bendisulfuron, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, promethazine, propanil, oxadiazine, propyrisulfuron, propyrisulfuron, promethazine, procarb, prosulfuron, dimethoate pyraflufen (including pyraflufen-ethyl), pyraflufen, pyraflufen, pyrimisulfan, pyroxasulfone, pyraflufen, quinclorac, quinclorac, quizalofop-P (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, sulfasulfuron, pyraflufen ... hiencarbazone), thifensulfuron-methyl, tiafenacil, tolpyralate, benpyrazone, trimethoprim-butyl, triafamone, wild wheat chlorpyrifos, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, trifloxysulfuron, triazosulfuron, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4- Hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one,4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including agrochemically acceptable esters thereof, for example, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid prop-2-ynyl ester and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid cyanomethyl ester), 3-ethyl-sulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid methyl)-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-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl -2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]ethyl acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propionic acid tetrahydrofuran-2-ylmethyl ester, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propionic acid, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propionic acid tetrahydrofuran-2-ylmethyl ester, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propionic acid, 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, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxyphenyl)-pyrimidine-4-carboxylic acid (2-fluorophenyl)methyl ester, 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, 2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyleneamino]oxypropionic acid methyl ester, and (2R)-2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyleneamino]oxypropionic acid methyl ester.

[0051] Mixtures of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

[0052] The compounds 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.

[0053] The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1:100 to 1000:1.

[0054] These mixtures can advantageously be used in the abovementioned formulations ("active ingredient" in this case relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0055] 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 fenthiocarb, cloquintocet (including cloquintocet-mexyl), cyclopropylsulfonamide, dichloropropene, fenthiocarb (including fenthiocarb-ethyl), fenthiocarb, fluazifop, fenthiocarb, isoxadiazole (including isoxadiazole-ethyl), mefenpyr (including pyrazole oxalate-diethyl), metcamifen and fenthiocyanate.

[0056] Particularly preferred are mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen, clofometrexate and / or metcamifen.

[0057] The safeners of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition (BCPC), 2012. References to clofonethiol also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts (as disclosed in WO 02 / 34048).

[0058] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0059] The present invention further provides a method for controlling weeds in a place, the method comprising applying a composition comprising a compound of formula (I) to the place in a controlled amount of weeds. In addition, the present invention may further provide a method for selectively controlling weeds at a place including crop plants and weeds, wherein the method comprises applying a composition according to the present invention to the place in a controlled amount of weeds. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention show greatly improved selectivity compared to known structurally similar compounds. Plants to be controlled are usually unwanted plants (weeds). 'Place' means the area where the plant is growing or will grow. Application can be applied to the place before and / or after emergence of crop plants. Some crop plants can inherently tolerate the herbicidal effect of compounds with formula (I). Preferred crop plants include corn, wheat, barley, soybeans and rice.

[0060] The application rate of the compound of formula I can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence or post-emergence; seed dressing; application to the seed furrow; no-till application, etc.), the crop plants, the weed or weeds 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 compound of formula I according to the invention is usually applied at a rate of from 10 g / ha to 2500 g / ha, in particular from 25 g / ha to 1000 g / ha, more particularly from 25 g / ha to 250 g / ha.

[0061] Application is usually carried out by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or drenching may also be used.

[0062] 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-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, HPPD-inhibitors, inhibitor-PDS, inhibitor-SDPS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones (e.g. imazamox) by conventional methods of breeding are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, maize varieties resistant to glyphosate and glufosinate, which are now and It is commercially available under the trademark ANTIQUID®.

[0063] Crop plants are also to be understood as those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to the European corn borer), Bt cotton (resistant to the boll weevil) and also Bt potato (resistant to the Colorado beetle). Examples of Bt maize are Bt 176 corn hybrid (SyngentaSeeds). Bt toxins are proteins naturally produced by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing 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 encoding insecticide resistance and expressing one or more toxins are (Corn), Yield (corn), (cotton), (cotton), (potato), as well as Plant crops or their seed material can both be resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic events). For example, a seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

[0064] Crop plants are also to be understood as including those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (for example improved storage stability, higher nutritional value and improved flavor).

[0065] These compositions can be used to control unwanted vegetation (collectively referred to as 'weeds'). The weeds to be controlled may be monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria ) and Sorghum, and may also be dicotyledonous species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0066] In a further aspect of the invention there is provided the use of a compound of formula (I) as defined herein as a herbicide.

[0067] Process for preparing compounds having formula (I)

[0068] Processes for preparing compounds such as compounds of formula (I) (which optionally may be agrochemically acceptable salts thereof) are now described and form a further aspect of the invention.

[0069] The compounds of the present invention can be prepared according to the following schemes.

[0070] Solution 1

[0071] In which A 1 Yes-C(R 1 )(R 2 )-and X 1 In embodiments where is O, compounds of formula (1) can be prepared from compounds of formula (2) wherein LG represents a suitable leaving group such as Br or Cl and compounds of formula (3).

[0072]

[0073] A compound of formula (2) is treated with an isoxazolidinone of formula (3) and a carbonate base such as potassium carbonate in a suitable solvent such as acetone.

[0074] Solution 2

[0075] Compounds of formula (2) can be prepared from benzyl alcohols of formula (4).

[0076]

[0077] For example, where LG is Br, a benzyl alcohol of formula (4) is treated with phosphorus tribromide or triphenylphosphine and a suitable brominating agent such as carbon tetrabromide in a suitable solvent such as acetonitrile or dichloromethane.

[0078] Solution 3

[0079] The synthetic route used to obtain the compound of formula (4) will depend on A 2 , A 3 and A 4 In one method, compounds of formula (4) can be prepared from benzyl alcohols of formula (5).

[0080]

[0081] A compound of formula (5) is treated with a chlorinating agent such as N-chlorosuccinimide in a suitable solvent such as acetonitrile.

[0082] Solution 4

[0083] The compound having the formula (5) may be commercially available. 2 YesO,A 3 is C(CH3) and A 4 N) are commercially available (CAS No. 136663-38-2). Alternatively, they can be prepared synthetically. The synthetic route will depend on A 2 , A 3 and A 4 For example, benzyl alcohol having formula (5) can be prepared from aldehyde having formula (6).

[0084]

[0085] A compound of formula (6) is treated with a reducing agent such as sodium borohydride in a suitable solvent such as water.

[0086] Solution 5

[0087] In an alternative approach, compounds of formula (4) may be prepared from compounds of formula (7).

[0088]

[0089] A compound of formula (7) is treated with a reducing agent such as sodium borohydride in a suitable solvent such as a methanol / tetrahydrofuran mixture.

[0090] Solution 6

[0091] The synthetic route used to obtain the compound of formula (7) will depend on A 2 , A 3 and A 4 For example, a compound having formula (7) (wherein A 3 is N(R 6 ) and R 6 is a C1-C3 alkyl) can be prepared from a compound having the formula (8).

[0092]

[0093] A compound of formula (8) is treated with an alkylating agent (eg methyl iodide) and a suitable base (eg potassium tert-butoxide) in a suitable solvent (eg tetrahydrofuran).

[0094] Solution 7

[0095] In another example, the compound (A) having formula (7) 2 It is S, A 3 is C(R 5 ) and A 4 N) can be prepared from a compound of formula (9).

[0096]

[0097] A compound of formula (9) is treated with a suitable base (eg cesium carbonate) in a suitable solvent (eg N-methyl-2-pyrrolidone).

[0098] Solution 8

[0099] Compounds having formula (9) can be prepared from compounds having formula (10).

[0100]

[0101] A compound of formula (10) is treated with a thionation agent (eg phosphorus pentasulfide) in a suitable solvent (eg toluene) and optionally in the presence of a suitable additive (eg hexamethyldisiloxane).

[0102] Solution 9

[0103] Compounds of formula (10) can be prepared from methyl 5-amino-2,4-dichloro-benzoate (11). The reactants and reagents required will depend on R 5 varies with the nature of the

[0104]

[0105] For example, in R 5 In the case of methyl, the compound of formula (11) is treated with a suitable acetylating agent (such as acetic anhydride) and a suitable base (such as triethylamine) in a suitable solvent (such as dichloromethane).

[0106] Solution 10

[0107] In a further example, a compound having formula (7) (wherein A 2 YesO,A 3 is C(R 5 ) and A 4 is N) can be prepared from a compound having formula (12).

[0108]

[0109] The compound of formula (12) is dehydrated under suitable conditions, for example by treatment with a suitable acid (eg p-toluenesulfonic acid) in a suitable solvent (eg toluene).

[0110] Solution 11

[0111] Compounds of formula (12) can be prepared from methyl 5-amino-2-chloro-4-hydroxy-benzoate (13). The required reactants and reagents will depend on R 5 varies with the nature of the

[0112]

[0113] For example, in R 5 In the case of cyclopropyl, methyl 5-amino-2-chloro-4-hydroxy-benzoate (13) is treated with a suitable acylating agent (such as cyclopropanecarbonyl chloride) and a suitable base (such as triethylamine) in a suitable solvent (such as acetonitrile).

[0114] Solution 12

[0115] In an alternative approach, compounds of formula (2) may be prepared from compounds of formula (14).

[0116]

[0117] For example, where LG is Br, a compound having formula (14) is treated with a suitable brominating agent (e.g., N-bromosuccinimide) and a suitable free radical initiator (e.g., 2-[(E)-(1-cyano-1-methyl-ethyl)azo]-2-methyl-propionitrile) in a suitable solvent (e.g., acetonitrile).

[0118] Solution 13

[0119] Compounds of formula (14) may be commercially available. Alternatively, they may be prepared synthetically. The synthetic route will depend on A 2 , A 3 and A 4 For example, a compound having formula (14) (wherein A 2 Yes N, A 3 is S and A 4 N) can be prepared from 4-chloro-5-methyl-benzene-1,2-diamine (15).

[0120]

[0121] 4-Chloro-5-methyl-benzene-1,2-diamine (15) is treated with thionyl chloride and optionally, a suitable base such as triethylamine in a suitable solvent such as dichloromethane.

[0122] Solution 14

[0123] The compound of formula (3) may be commercially available. For example, the compound of formula (3) (wherein R 3 and R 4 is a methyl group, and R 1 and R 2 is hydrogen) is commercially available (CAS No. 81778-07-6). Alternatively, compounds of formula (3) can be prepared synthetically. For example, in R 1 is C1-C6 alkoxy, C1-C6 alkoxy-C1-C6 alkoxy-, HOC(O)C1-C6 alkoxy-, C1-C6 alkoxy-C(O)-C1-C6 alkoxy- or C1-C3 alkyl-S(O) p C1-C6 alkoxy-, and R 2In the case of hydrogen, the compound of formula (3) can be prepared from 3,3-dichloro-2,2-dimethylpropanoic acid (16).

[0124]

[0125] 3,3-Dichloro-2,2-dimethylpropanoic acid (16) is treated with a suitable chlorinating system such as thionyl chloride and catalyst dimethylformamide to give 3,3-dichloro-2,2-dimethylpropanoyl chloride (17). 3,3-Dichloro-2,2-dimethylpropanoyl chloride (17) is treated with a suitable hydroxylamine source such as hydroxylamine (50% in H2O) to give 3,3-dichloro-2,2-dimethyl-propane hydroxamic acid (18). 3,3-Dichloro-2,2-dimethyl-propane hydroxamic acid (18) is treated with a suitable alcohol such as 2-trimethylsilylethanol or ethanol and a suitable base such as 1,8-diazabicyclo(5.4.0)undec-7-ene to give compounds having formula (3).

[0126] Solution 15

[0127] Compounds of formula (19) can be prepared from compounds of formula (20).

[0128]

[0129] A compound of formula (20) is treated with a suitable Lewis acid source (eg boron trifluoride etherate) in a suitable solvent (eg dichloromethane).

[0130] Scheme 16

[0131] Compounds of formula (21) can be prepared from compounds of formula (19).

[0132]

[0133] A compound of formula (19) is treated with a suitable oxidant system (eg a mixture of trichloroisocyanuric acid and a catalytic amount of TEMPO) in a suitable solvent (eg dichloromethane).

[0134] Solution 17

[0135] Compounds of formula (22) wherein Z is C1-C3 alkyl can be prepared from compounds of formula (19).

[0136]

[0137] A compound of formula (19) is treated with a suitable acylating agent (eg isobutyryl chloride) and a suitable base (eg pyridine) in a suitable solvent (eg dichloromethane).

[0138] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (as mentioned in Table 1 below).

[0139] Preparation Example

[0140] Example P1: Preparation of Compound 1.001

[0141] Step 1: Preparation of (6-chloro-2-methyl-1,3-benzoxazol-5-yl)methanol

[0142] A solution of (2-methyl-1,3-benzoxazol-5-yl)methanol (0.500 g, 3.06 mmol) and N-chlorosuccinimide (0.430 g, 3.22 mmol) in acetonitrile (10.2 mL) was stirred at 70 °C for 1 h. The reaction mixture was concentrated to The mixture was added to 4% ethyl acetate and purified by flash column chromatography (0-70% ethyl acetate in cyclohexane). The product-containing fractions were combined and concentrated to give (6-chloro-2-methyl-1,3-benzoxazol-5-yl)methanol (0.268 g, 1.36 mmol, 44%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.76 (s, 1H), 7.52 (s, 1H), 4.85 (s, 2H), 2.64 (s, 3H).

[0143] Step 2: Preparation of 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzoxazole

[0144] To a solution of (6-chloro-2-methyl-1,3-benzoxazol-5-yl)methanol (0.268 g, 1.36 mmol) in dichloromethane (2.71 mL) was added carbon tetrabromide (0.540 g, 1.63 mmol) and the solution was cooled to 0°C in an ice bath. Triphenylphosphine (0.534 g, 2.03 mmol) was added and the reaction was then allowed to warm to room temperature and stirred for 3 h. The reaction mixture was concentrated to The product was concentrated to give 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzoxazole (0.213 g, 0.818 mmol, 60%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.71 (s, 1H), 7.55 (s, 1H), 4.70 (s, 2H), 2.64 (s, 3H).

[0145] Step 3: Preparation of 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one

[0146] To a solution of 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzoxazole (0.150 g, 0.576 mmol) in acetone (4.5 mL) was added potassium carbonate (0.121 g, 0.864 mmol) and 4,4-dimethylisoxazolidin-3-one (0.084 g, 0.691 mmol). The reaction was stirred at room temperature overnight. The reaction mixture was diluted with acetone (10 mL) and filtered through Filter and concentrate the mixture to On, and purified via flash column chromatography (0-50% ethyl acetate in cyclohexane). The product-containing fractions were concentrated to give 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one (0.136 g, 0.462 mmol, 80%) as a colorless gum. 1H NMR (400 MHz, CDCl3) δ ppm 7.62 (s, 1H), 7.53 (s, 1H), 4.91 (s, 2H), 4.04 (s, 2H), 2.63 (s, 3H), 1.28 (s, 6H).

[0147] Example P2: Preparation of Compound 1.002

[0148] Step 1: Preparation of 3,3-dichloro-2,2-dimethyl-propionyl chloride

[0149] 3,3-dichloro-2,2-dimethyl-propionic acid (88.0 g, 514 mmol) was added to a stirred solution of thionyl chloride (148 mL) at room temperature. The mixture was heated to 70 ° C for 5 h. Excess thionyl chloride was removed by crude distillation (75 ° C). The residue was then purified by distillation (40 ° C at 5 mbar) to obtain 3,3-dichloro-2,2-dimethyl-propionyl chloride (87.0 g, 459 mmol, 89%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ ppm 6.17 (s, 1H), 1.50 (s, 6H).

[0150] Step 2: Preparation of 3,3-dichloro-2,2-dimethyl-propane hydroxamic acid

[0151] 3,3-dichloro-2,2-dimethyl-propanoyl chloride (3.00 g, 15.8 mmol) was added dropwise to an aqueous solution (8.09 g, 7.5 mL, 122 mmol) of hydroxylamine (50% by mass). The reaction mixture was stirred at room temperature for 10 min. The reaction mixture was extracted with dichloromethane, passed through a phase separator and concentrated in vacuo to give 3,3-dichloro-2,2-dimethyl-propane hydroxamic acid (1.94 g, 10.4 mmol, 66%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 6.40 (br s, 1H), 6.12 (s, 1H), 1.40 (s, 6H).

[0152] Step 3: Preparation of 4,4-dimethyl-5-(2-trimethylsilylethoxy)isoxazolidin-3-one

[0153] A solution of 1,8-diazabicyclo (5.4.0) undec-7-ene (0.835 g, 0.82 mL, 5.38 mmol) and 3,3-dichloro-2,2-dimethyl-propane hydroxamic acid (0.500 g, 2.69 mmol) in 2-trimethylsilylethanol (5.0 mL) was heated at 75 ° C overnight. The reaction mixture was diluted with ethyl acetate and washed with 2M hydrochloric acid (x2) and then with brine. The organic portion was concentrated to give 4,4-dimethyl-5-(2-trimethylsilylethoxy)isoxazolidin-3-one (0.308 g, 1.33 mmol, 50%) as a light orange gum. This material was used crude in the next reaction without further purification.

[0154] Step 4: Preparation of 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-5-(2-trimethylsilylethoxy)isoxazolidin-3-one

[0155] To a solution of 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzoxazole (0.238 g, 0.914 mmol) in acetone (7.1 mL) was added potassium carbonate (0.256 g, 1.83 mmol) and 4,4-dimethyl-5-(2-trimethylsilylethoxy)isoxazolidin-3-one (0.317 g, 1.37 mmol). The reaction was stirred at room temperature overnight. The reaction mixture was diluted with acetone (10 mL) and filtered through Filter and concentrate the mixture to The product was concentrated to give 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-5-(2-trimethylsilylethoxy)isoxazolidin-3-one (0.106 g, 0.258 mmol, 28%) as a colorless gum. 1H NMR (400MHz, CDCl3) δppm 7.68(s,1H),7.52(s,1H),4.99(d,1H),4.89-4.85(m,2H),3.70-3.63(m,1H),3.47-3 .40(m,1H),2.62(s,3H),1.30(s,3H),1.21(s,3H),0.90-0.84(m,2H),-0.07(s,9H).

[0156] Step 5: Preparation of 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-5-hydroxy-4,4-dimethyl-isoxazolidin-3-one

[0157] At 0 ° C, to 2- [(6- chloro-2-methyl -1,3- benzoxazole -5- bases) methyl] -4,4- dimethyl -5- (2- trimethylsilylethoxy) isoxazolidin-3-one (0.106g, 0.258mmol) in dichloromethane (2.58mL) solution was added dropwise boron trifluoride etherate (0.183g, 0.16mL, 1.29mmol). The reaction mixture was stirred at room temperature under nitrogen for 48h. After this time, LCMS analysis indicated that there was still SM remaining, so other boron trifluoride etherate (0.183g, 0.16mL, 1.29mmol) was added. The reaction mixture was stirred at room temperature under nitrogen for 72h. The reaction was quenched with saturated aqueous NaHCO and the product was extracted with ethyl acetate (x3). The organic parts were merged, dried over MgSO, filtered and concentrated in vacuo. The crude material was purified by flash column chromatography (0-80% ethyl acetate in cyclohexane). The fractions containing the product were combined and concentrated to give 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-5-hydroxy-4,4-dimethyl-isoxazolidin-3-one (38.0 mg, 0.122 mmol, 47%) as a colorless gum. 1H NMR (400 MHz, CDCl3) δ ppm 7.68 (s, 1H), 7.50 (s, 1H), 5.29 (d, 1H), 5.01-4.97 (m, 1H), 4.90-4.86 (m, 1H), 3.82 (d 1H), 2.62 (s, 3H), 1.31 (s, 3H), 1.28 (s, 3H).

[0158] Step 6: Preparation of 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-isoxazolidine-3,5-dione

[0159] TEMPO (2.0 mg, 0.012 mmol) was added to a solution of 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-5-hydroxy-4,4-dimethyl-isoxazolidin-3-one (38 mg, 0.12 mmol) and 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione (34 mg, 0.15 mmol) in dichloromethane (0.61 mL). The reaction mixture was stirred at room temperature for 1.5 h. The reaction mixture was diluted with dichloromethane (10 mL) and filtered. Filter and concentrate the mixture to On, and purified via flash column chromatography (0-60% ethyl acetate in cyclohexane). The product-containing fractions were concentrated to give 2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-isoxazolidine-3,5-dione (26 mg, 0.084 mmol, 69%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.65 (s, 1H), 7.57 (s, 1H), 5.15 (s, 2H), 2.65 (s, 3H), 1.47 (s, 6H).

[0160] Example P3: Preparation of Compound 1.011

[0161] Step 1: Preparation of methyl 6-chloro-2-methyl-benzotriazole-5-carboxylate

[0162] At 0 ° C, potassium tert-butoxide (1M in tetrahydrofuran, 5.91mL, 5.91mmol) was added to a solution of methyl 6-chloro-1H-benzotriazole-5-formate (1.00g, 4.73mmol) in tetrahydrofuran (15.8mL). The reaction mixture was stirred for 30min at 0 ° C. Then iodomethane (2.01g, 0.88mL, 14.2mmol) was added. The reaction mixture was warmed to room temperature and stirred for 20h. The reaction was quenched with water and the product was extracted with ethyl acetate (x3). The organic parts were merged, dried over MgSO4, filtered and concentrated in vacuo. The crude material was purified by flash column chromatography (0-100% ethyl acetate in cyclohexane). The fractions containing the product were merged and concentrated to obtain methyl 6-chloro-2-methyl-benzotriazole-5-formate (0.141g, 0.625mmol, 13%) as a white solid. 1H NMR (400MHz, CDCl3) δppm8.35(d,1H),7.96(d,1H),4.54(s,3H),3.98(s,3H).

[0163] Step 2: Preparation of (6-chloro-2-methyl-benzotriazol-5-yl)methanol

[0164] At 0 ° C, sodium borohydride (0.171g, 4.34mmol) is added to a solution of methyl 6-chloro-2-methyl-benzotriazole-5-formate (0.145g, 0.643mmol) in methanol (1.24mL) and tetrahydrofuran (1.24mL). The reaction mixture is stirred at 70 ° C for 2h. The reaction is quenched with saturated aqueous NH4Cl and the product is extracted with ethyl acetate (x2). The organic part is merged, washed with brine, dried over MgSO4, filtered and concentrated in vacuo to obtain (6-chloro-2-methyl-benzotriazole-5-yl) methanol (0.127g, 0.643mmol, 100%) as a white solid. 1H NMR (400MHz, CDCl3) δ 7.99 (s, 1H), 7.89 (s, 1H), 4.90 (s, 2H), 4.51 (s, 3H).

[0165] Step 3: Preparation of 5-(bromomethyl)-6-chloro-2-methyl-benzotriazole

[0166] To a solution of (6-chloro-2-methyl-benzotriazol-5-yl)methanol (0.127 g, 0.643 mmol) in dichloromethane (3.21 mL) was added carbon tetrabromide (0.256 g, 0.771 mmol) and the solution was cooled to 0°C in an ice bath. Triphenylphosphine (0.253 g, 0.964 mmol) was added and the reaction was then allowed to warm to room temperature and stirred for 1 h. The reaction mixture was concentrated to 40°C. The product was concentrated to give 5-(bromomethyl)-6-chloro-2-methyl-benzotriazole (85 mg, 0.33 mmol, 51%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.98 (s, 1H), 7.94 (s, 1H), 4.73 (s, 2H), 4.51 (s, 3H).

[0167] Step 4: Preparation of 2-[(6-chloro-2-methyl-benzotriazol-5-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one

[0168] To a solution of 5-(bromomethyl)-6-chloro-2-methyl-benzotriazole (85 mg, 0.33 mmol) in acetone (2.5 mL) was added potassium carbonate (69 mg, 0.49 mmol) and 4,4-dimethylisoxazolidin-3-one (59 mg, 0.49 mmol). The reaction was stirred at room temperature overnight. The reaction mixture was diluted with acetone (10 mL) and filtered. Filter and concentrate the mixture to The product was concentrated to give 2-[(6-chloro-2-methyl-benzotriazol-5-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one (52 mg, 0.18 mmol, 54%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.91 (s, 1H), 7.84 (s, 1H), 4.94 (s, 2H), 4.51 (s, 3H), 4.08 (s, 2H), 1.31 (s, 6H).

[0169] Example P4: Preparation of Compound 1.006

[0170] Step 1: Preparation of methyl 5-acetamido-2,4-dichloro-benzoate

[0171] Under argon atmosphere, at 0 ℃, triethylamine (1.81mL, 13.0mmol) and acetic anhydride (1.32g, 13.0mmol) are added to the stirring solution of methyl 5-amino-2,4-dichloro-benzoate (2.86g, 13.0mmol) in dichloromethane (15mL).Reactant mixture is stirred to 12h at RT, then diluted with water and extracted with EtOAc (x2).The organic part merged is washed with salt water, through Na2SO4 is dried and concentrated.Methyl 5-acetamido-2,4-dichloro-benzoate (1.99g, 7.61mmol, 59%) is obtained by flash column chromatography (0-60% EtOAc in hexane). 1H NMR (400MHz, d6-DMSO) δppm 9.85 (s, 1H), 8.34 (s, 1H), 7.85 (s, 1H), 3.82 (s, 3H), 2.21 (s, 3H).

[0172] Step 2: Preparation of methyl 2,4-dichloro-5-(thioacetylamino)benzoate

[0173] Phosphorus pentasulfide (0.403g, 1.81mmol) and hexamethyldisiloxane (1.47g, 9.06mmol) are added to a stirred solution of methyl 5-acetamido-2,4-dichloro-benzoate (0.95g, 3.62mmol) in toluene (8mL).Reaction mixture is heated to 110 DEG C for 1h, then diluted with water and extracted with EtOAc (x2).The organic part merged is washed with salt water, through Na2SO4, dried and concentrated.Methyl 2,4-dichloro-5-(thioacetylamino)benzoate (0.712g, 2.56mmol, 71%) is obtained by flash column chromatography (0-60% EtOAc in hexane). 1H NMR (400MHz, d6-DMSO) δppm11.7(s,1H),7.96(s,1H),7.94(s,1H),3.90(s,3H),2.68(s,3H).

[0174] Step 3: Preparation of methyl 6-chloro-2-methyl-1,3-benzothiazole-5-carboxylate

[0175] Step 3: Preparation of methyl 6-chloro-2-methyl-1,3-benzothiazole-5-carboxylate

[0176] Cesium carbonate (1.87g, 5.75mmol) is added to a stirred solution of methyl 2,4-dichloro-5-(thioacetylamino)benzoate (0.80g, 2.88mmol) in NMP (10mL). By microwave irradiation, the reaction mixture is heated to 150 ° C for 1h, then diluted with water and extracted with EtOAc (x2). The organic portion combined is washed with brine, dried over Na2SO4 and concentrated. Methyl 6-chloro-2-methyl-1,3-benzothiazole-5-formate (0.406g, 1.68mmol, 58%) is obtained by flash column chromatography (0-50% EtOAc in hexane). 1H NMR (400MHz, d6-DMSO) δppm 8.37 (s, 1H), 8.28 (s, 1H), 3.89 (s, 3H), 2.83 (s, 3H).

[0177] Step 4: Preparation of (6-chloro-2-methyl-1,3-benzothiazol-5-yl)methanol

[0178] At -78 ° C, under an argon atmosphere, diisobutylaluminum hydride (1M solution in THF, 6.70mL, 6.70mmol) is added to a stirred solution of methyl 6-chloro-2-methyl-1,3-benzothiazole-5-formate (0.406g, 1.68mmol) in THF (30mL). The reaction mixture is maintained at -40 ° C for 1h, then quenched with methanol and water at -40 ° C and stirred for another 30min. The mixture is extracted with EtOAc (x2) and the combined organic portion is washed with brine, dried over Na2SO4 and concentrated. Purification by flash column chromatography gives (6-chloro-2-methyl-1,3-benzothiazole-5-yl) methanol (0.327g, 1.53mmol, 91%). 1HNMR (400MHz, d6-DMSO) δppm 8.16 (s, 1H), 8.00 (s, 1H), 5.52 (t, 1H), 4.64 (d, 2H), 2.79 (s, 3H).

[0179] Step 5: Preparation of 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzothiazole

[0180] At 0 ° C, under an argon atmosphere, phosphorus tribromide (0.182g, 0.674mmol) was added to a stirred solution of (6-chloro-2-methyl-1,3-benzothiazol-5-yl) methanol (0.144, 0.674mmol) in dichloromethane (12mL). The reaction mixture was stirred at room temperature for 3h, then diluted with water and extracted with dichloromethane (x2). The combined organic portion was washed with saturated aqueous NaHCO3, dried over Na2SO4 and concentrated to give 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzothiazole (0.140g, 0.51mmol, 76%). 1H NMR (400MHz, d6-DMSO) δppm 8.28 (s, 1H), 8.18 (s, 1H), 4.88 (s, 2H), 2.83 (s, 3H).

[0181] Step 6: Preparation of 2-[(6-chloro-2-methyl-1,3-benzothiazol-5-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one

[0182] Under argon atmosphere, potassium carbonate (0.160g, 1.16mmol) and 4,4-dimethylisoxazolidine-3-one (0.133g, 1.16mmol) are added to a stirred solution of 5-(bromomethyl)-6-chloro-2-methyl-1,3-benzothiazole (0.32g, 1.16mmol) in acetone (15mL). The reaction mixture is heated to 60 ° C for 2h and then concentrated. 2- [(6-chloro-2-methyl-1,3-benzothiazol-5-yl) methyl] -4,4-dimethyl-isoxazolidine-3-one (0.207g, 0.665mmol, 57%) is obtained by reverse phase flash column chromatography. 1H NMR (400MHz, d6-DMSO) δppm 8.25 (s, 1H), 7.88 (s, 1H), 4.84 (s, 2H), 4.06 (s, 2H), 2.80 (s, 3H), 1.15 (s, 6H).

[0183] Example P5: Preparation of Compound 1.024

[0184] Step 1: Preparation of 5-chloro-6-methyl-2,1,3-benzothiadiazole

[0185] At 0 ° C, under a nitrogen atmosphere, thionyl chloride (0.940mL, 1.53g, 12.85mmol) is added dropwise to a stirred solution of 4-chloro-5-methyl-benzene-1,2-diamine (1.01g, 6.42mmol) and triethylamine (3.60mL, 2.61g, 25.69mmol) in dichloromethane (20.9mL). The reaction mixture is heated to reflux for 2.5h, then quenched by adding water at room temperature. The mixture is concentrated to remove volatile organics, and the remaining aqueous solution is then acidified to pH 2 by adding 1M hydrochloric acid and extracted with EtOAc (x2). The combined organic portion is dried over MgSO4 and concentrated. Purification by flash column chromatography (0-50% acetone in cyclohexane) gives 5-chloro-6-methyl-2,1,3-benzothiadiazole (0.676g, 3.66mmol, 57%). 1H NMR (400MHz, CDCl3) δppm 8.05 (s, 1H), 7.88-7.85 (m, 1H), 2.57 (d, 3H).

[0186] Step 2: Preparation of 6-(bromomethyl)-5-chloro-2,1,3-benzothiadiazole

[0187] N-Bromosuccinimide (0.146 g, 0.819 mmol) and 2-[(E)-(1-cyano-1-methyl-ethyl)azo]-2-methyl-propionitrile (9.6 mg, 0.059 mmol) were added to a solution of 5-chloro-6-methyl-2,1,3-benzothiadiazole (0.144 g, 0.780 mmol) in acetonitrile (5 mL). The reaction mixture was heated to 80 °C overnight and then concentrated directly to Purification by flash column chromatography (0-20% acetone in cyclohexane) gave 6-(bromomethyl)-5-chloro-2,1,3-benzothiadiazole (0.177 g, 0.672 mmol, 86%). 1H NMR (400 MHz, CDCl3) δ ppm 8.14 (s, 1H), 8.13 (s, 1H), 4.75 (s, 2H).

[0188] Step 3: Preparation of 2-[(5-chloro-2,1,3-benzothiadiazol-6-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one

[0189] Potassium carbonate (0.195 g, 1.34 mmol) and 4,4-dimethyl-1,2-oxazolidin-3-one (0.116 g, 1.01 mmol) were added to a solution of 6-(bromomethyl)-5-chloro-2,1,3-benzothiadiazole (0.177 g, 0.672 mmol) in acetone (3.36 mL). The reaction mixture was stirred at room temperature for 1 h, then diluted with acetone and concentrated to On. Purification by flash column chromatography (0-30% acetone in cyclohexane) and then again by reverse phase flash column chromatography gave 2-[(5-chloro-2,1,3-benzothiadiazol-6-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one (0.111 g, 0.373 mmol, 56%). 1H NMR (400 MHz, CDCl3) δ ppm 8.10 (s, 1H), 8.01-7.98 (m, 1H), 4.98 (d, 2H), 4.13 (s, 2H), 1.34 (s, 6H).

[0190] Example P6: Preparation of Compound 1.025

[0191] Step 1: Preparation of methyl 2-chloro-5-(cyclopropanecarbonylamino)-4-hydroxy-benzoate

[0192] At 0 ℃, cyclopropanecarbonyl chloride (0.248mL, 2.73mmol) is added to the stirring solution of methyl 5-amino-2-chloro-4-hydroxy-benzoate (0.50g, 2.48mmol) and triethylamine (0.54mL, 3.72mmol) in acetonitrile (10mL).The reaction is stirred for 2h at 0 ℃, then stirred for 1.5h at room temperature.The reaction mixture is diluted with water and extracted with EtOAc (x3).The organic part merged is washed with brine, dried over MgSO4 and concentrated.The gained residue is dissolved in methanol (10mL) and potassium carbonate (0.397g, 2.84mmol) is added.The mixture is stirred for 1.5h at room temperature, then concentrated.Add water and EtOAc and separate each phase. The aqueous phase was washed with additional EtOAc (x2) and the combined organic portions were then washed with brine, dried over MgSO4 and concentrated to give methyl 2-chloro-5-(cyclopropanecarbonylamino)-4-hydroxy-benzoate (0.652 g, 2.42 mmol, 97%). 1H NMR (400 MHz, CDCl3) δ ppm 10.40 (br s, 1H), 7.81 (br s, 1H), 7.64 (s, 1H), 7.08 (s, 1H), 3.90 (s, 3H), 1.68-1.60 (m, 1H), 1.20-1.15 (m, 2H), 1.02-0.97 (m, 2H).

[0193] Step 2: Preparation of methyl 6-chloro-2-cyclopropyl-1,3-benzoxazole-5-carboxylate

[0194] 4-Methylbenzenesulfonic acid (0.193g, 1.11mmol) is added to a suspension of methyl 2-chloro-5-(cyclopropanecarbonylamino)-4-hydroxy-benzoate (0.300g, 1.11mmol) in toluene (5.56mL).The reaction mixture is heated overnight under reflux.Then Dean-Stark (Dean-Stark) device is installed, and the reaction mixture is heated overnight under reflux again.The reaction mixture is diluted with saturated aqueous NaHCO and extracted with EtOAc (x3).The organic part merged is washed with brine, dried over MgSO and concentrated.Methyl 6-chloro-2-cyclopropyl-1,3-benzoxazole-5-formate (0.139g, 0.552mmol, 50%) is obtained by flash column chromatography (0-50% EtOAc in cyclohexane). 1H NMR (400MHz, CDCl3) δppm 8.06 (s, 1H), 7.53 (s, 1H), 3.95 (s, 3H), 2.25-2.17 (m, 1H), 1.32-1.27 (m, 2H), 1.27-1.20 (m, 2H).

[0195] Step 3: Preparation of (6-chloro-2-cyclopropyl-1,3-benzoxazol-5-yl)methanol

[0196] The mixture of methyl 6-chloro-2-cyclopropyl-1,3-benzoxazole-5-formate (0.137g, 0.544mmol) and 2-methyltetrahydrofuran (2.06mL) is cooled to 0 DEG C and diisobutylaluminum hydride (1M in hexane, 1.63mL, 1.63mmol) is added. The reaction is stirred at room temperature for 3h, then cooled to 0 DEG C and quenched by dropping EtOAc. Saturated aqueous Rochelle salt is added and the mixture is vigorously stirred at room temperature for 15 minutes, then extracted with EtOAc (x2). The combined organic part is washed with brine, dried over MgSO4 and concentrated. Purified by flash column chromatography (0-70% EtOAc in cyclohexane) to obtain (6-chloro-2-cyclopropyl-1,3-benzoxazole-5-yl) methanol (0.105g, 0.469mmol, 86%). 1H NMR (400MHz, CDCl3) δppm 7.70 (s, 1H), 7.46 (s, 1H), 4.84 (d, 2H), 2.23-2.16 (m, 1H), 2.11 (brt, 1H), 1.30-1.25 (m, 2H), 1.23-1.17 (m, 2H).

[0197] Step 4: Preparation of 5-(bromomethyl)-6-chloro-2-cyclopropyl-1,3-benzoxazole

[0198] A mixture of (6-chloro-2-cyclopropyl-1,3-benzoxazol-5-yl)methanol (0.092 g, 0.41 mmol) and carbon tetrabromide (0.17 g, 0.49 mmol) in acetonitrile (1.6 mL) was cooled to 0 °C and triphenylphosphine (0.16 g, 0.62 mmol) was added portionwise. The reaction mixture was stirred at room temperature for 3 h and then concentrated to Purification by flash column chromatography (0-30% EtOAc in cyclohexane) gave 5-(bromomethyl)-6-chloro-2-cyclopropyl-1,3-benzoxazole (0.087 g, 0.30 mmol, 74%). 1H NMR (400 MHz, CDCl3) δ ppm 7.65 (s, 1H), 7.49 (s, 1H), 4.69 (s, 2H), 2.22-2.16 (m, 1H), 1.29-1.25 (m, 2H), 1.24-1.18 (m, 2H).

[0199] Step 5: Preparation of 2-[(6-chloro-2-cyclopropyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-isoxazolidin-3-one

[0200] Potassium carbonate (0.064g, 0.46mmol) and 4,4-dimethylisoxazolidine-3-one (0.042g, 0.36mmol) are added to 5-(bromomethyl)-6-chloro-2-cyclopropyl-1,3-benzoxazole (0.087g, 0.30mmol) in acetone (2.6mL) solution.Reactant mixture is stirred at room temperature overnight, then diluted with water and extracted with EtOAc (x3).The organic part merged is washed with salt water, dried over MgSO4 and concentrated.2-[(6-chloro-2-cyclopropyl-1,3-benzoxazole-5-yl) methyl]-4,4-dimethyl-isoxazolidine-3-one (0.067g, 0.21mmol, 69%) is obtained by flash column chromatography (0-40% EtOAc in cyclohexane). 1H NMR (400MHz, CDCl3) δppm 7.57(s,1H),7.47(s,1H),4.89(s,2H),4.03(s,2H),2.23-2.14(m,1H),1.29(s,6H),1.29-1.24(m,2H),1.23-1.67(m,2H).

[0201] Example P7: Preparation of Compound 1.026

[0202] Preparation of [2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-3-oxo-isoxazolidin-5-yl]2-methylpropanoate

[0203] Isobutyryl chloride (0.077mL, 0.078g, 0.70mmol) is added to 2-[(6-chloro-2-methyl-1,3-benzoxazole-5-yl) methyl]-5-hydroxy-4,4-dimethyl-isoxazolidine-3-one (0.108g, 0.35mmol) and pyridine (0.059mL, 0.058g, 0.70mmol) in dichloromethane (5mL) solution.Reaction mixture is stirred at room temperature overnight.Add other pyridine (0.059mL, 0.058g, 0.70mmol) and isobutyryl chloride (0.077mL, 0.078g, 0.70mmol) and reaction mixture is stirred for 3h.Reaction mixture is diluted with water and extracted with EtOAc (x3).Organic moieties are merged, washed with salt water, through MgSO4Dry and be concentrated on silica gel. Purification by flash column chromatography (0-50% EtOAc in cyclohexane) gave [2-[(6-chloro-2-methyl-1,3-benzoxazol-5-yl)methyl]-4,4-dimethyl-3-oxo-isoxazolidin-5-yl]2-methylpropanoate (0.132 g, 0.35 mmol, 100%). 1H NMR (400 MHz, CDCl3) δ ppm 7.61 (s, 1H), 7.50 (s, 1H), 6.16 (s, 1H), 5.01 (d, 1H), 4.88 (d, 1H), 2.61 (s, 3H), 2.59-2.49 (m, 1H), 1.37 (s, 3H), 1.23 (s, 3H), 1.13 (d, 3H), 1.10 (d, 3H).

[0204] Further compounds of the invention are shown in Table 1 below, which were prepared in a manner analogous to those described above in Examples P1 to P7.

[0205] Table 1. Compounds of the present invention

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] Biological Examples

[0215] Test B1

[0216] Seeds of various test species (Amaranthus retoflexus (AMARE), Setariafaberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE)) were sown in standard soil in pots. After one day of cultivation (pre-emergence) or after 8 days of cultivation (post-emergence) in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 h light; 65% humidity), the plants were sprayed with an aqueous spray solution obtained as follows: i) the technical active ingredient was formulated in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5), or ii) the technical active ingredient was dissolved in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) and then diluted to the desired concentration using 0.2% Genapol XO80 (CAS No. 9043-30-5) in water as diluent. Unless otherwise stated, the compounds were applied at 250 g / ha. These test plants were then grown in a greenhouse under controlled conditions in a greenhouse (at 24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. The percentage of damage caused to the plants by the test was evaluated before emergence and 13 days after emergence. The biological activity is 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.

[0217] Table B1. Post-emergence tests

[0218] Compound AMARE SETFA ECHCG IPOHE 1.001 4 4 4 3 1.002 3 4 4 3 1.003 1 2 2 2 1.004 1 3 2 2 1.005 3 4 2 1 1.006 1 4 4 1 1.007 1 1 1 1 1.008 1 4 4 1 1.009 1 2 2 1 1.010 1 2 1 1 1.011 1 4 4 1 1.015 2 NT 1 1 1.017 1 NT 1 1 1.018 1 NT 1 3 1.020 3 NT 4 3 1.021 2 NT 4 3 1.022 1 NT 4 3 1.023 1 NT 4 2 1.028 1 1 1 1 1.029 1 1 1 1 1.032 1 1 1 1 1.035 1 5 5 NT

[0219] Table B2. Pre-emergence test

[0220] Compound AMARE SETFA ECHCG IPOHE 1.001 5 5 5 4 1.002 1 1 1 1 1.003 1 2 1 1 1.004 1 1 1 1 1.005 1 3 1 1 1.006 2 4 3 1 1.007 1 1 1 1 1.008 1 4 4 1 1.009 1 1 1 1 1.010 1 2 1 1 1.011 2 5 4 1 1.015 NT NT 1 1 1.017 1 NT 1 1 1.018 1 NT 1 NT 1.020 1 NT 5 2 1.021 1 NT 5 2 1.022 1 NT 2 1 1.023 1 NT 3 1 1.028 1 1 1 1 1.029 1 1 1 1 1.032 1 1 1 1 1.035 2 2 4 NT

[0221] Test B2

[0222] Seeds of various test species (Leptochloa chinesis (LEFCH), barnyard grass (ECHCG) and Cyperus esculentus (CYPES)) were sown in standard soil in pots. After one day of cultivation (pre-emergence) or 13 days of cultivation (post-emergence) in a greenhouse under controlled conditions (at 30°C / 20°C, day / night; 18 hours of light; 75% humidity), the plants were sprayed with an aqueous spray solution obtained as follows: the technical grade active ingredient was dissolved in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether), and then diluted to the desired concentration using 0.2% Genapol XO80 (CAS No. 9043-30-5) in water as a diluent. The compound was applied at 500 g / ha. These test plants were then grown in a greenhouse under controlled conditions in a greenhouse (at 30°C / 20°C, day / night; 18 hours of light; 75% humidity) and watered twice a day. Before emergence and 13 days after emergence, the percentage of damage caused to the plants by the test was evaluated. The biological activity is 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%).

[0223] Table B3. Post-emergence testing

[0224]

[0225] Table B4. Pre-emergence test

[0226] Compound LEFCH ECHCG CYPES 1.001 5 4 1 1.006 2 5 1 1.008 3 4 1 1.011 5 4 1 1.020 5 5 2 1.021 5 5 3 1.024 5 1 1 1.025 2 4 1 1.026 1 2 1 1.027 2 3 1 1.031 1 1 1 1.033 1 1 1 1.034 4 2 1

Claims

1. A compound having formula (I), or an agronomically acceptable salt thereof, in A 1 Yes CR 1 R 2 or C(O); A 2 Selected from the group consisting of: C(R 5 )、N(R 6 ), S and O; A 3 Selected from the group consisting of: C(R 5 )、N(R 6 ), S and O; A 4 Selected from the group consisting of: C(R 5 )、N(R 6 ), S and O; X 1 is O or S; R 1 Selected from the group consisting of hydrogen, halogen, HO-, C1-C6 alkoxy, C1-C6 alkoxy-C1-C6 alkoxy-, C1-C3 alkyl-C(O)O-, HOC(O)C1-C6 alkoxy-, C1-C6 alkoxy-C(O)-C1-C6 alkoxy-, C1-C3 alkyl-S(O) p - and C1-C3 alkyl-S(O) p C1-C6 alkoxy-; R 2 It is hydrogen; R 3 is a C1-C3 alkyl group; R 4 is a C1-C3 alkyl group; R 5 Selected from the group consisting of hydrogen, halogen, C1-C3 alkyl, aryl, C1-C3 haloalkyl, C1-C3 haloalkoxy-, C1-C3 alkoxy- and C3-C6 cycloalkyl; R 6 is selected from the group consisting of: hydrogen, C1-C3 alkyl- and C1-C3 haloalkyl; and p=0, 1 or 2.

2. The compound of claim 1 having formula (I), wherein X 1 It's O.

3. A compound of formula (I) according to claim 1 or claim 2, wherein R 3 and R 4 It's methyl.

4. A compound according to any one of the preceding claims having formula (I), wherein A 1 Yes CR 1 R 2 , and R 1 It's hydrogen.

5. A compound of formula (I) according to any one of claims 1 to 3, wherein A 1 Yes CR 1 R 2 , and R 1 It is a C1-C6 alkoxy group.

6. A compound of formula (I) according to any one of claims 1 to 3, wherein A 1 It is C(O).

7. A compound according to any one of the preceding claims, wherein R 5 Selected from the group consisting of hydrogen, C1-C3 alkyl, aryl, C1-C3 haloalkyl, C1-C3 haloalkoxy- and C1-C3 alkoxy-.

8. A compound according to any one of the preceding claims, wherein R 5 Selected from the group consisting of: hydrogen, methyl and ethyl.

9. A compound according to any one of the preceding claims, wherein R 5 It's methyl.

10. A compound according to any one of claims 1 to 6, wherein R 6 Selected from the group consisting of: hydrogen, methyl and ethyl.

11. The compound according to claim 10, wherein R 6 It's methyl.

12. A herbicidal composition comprising a compound of formula (I) according to any one of the preceding 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 a herbicide safener.

15. A method of controlling weeds at a locus, the method comprising applying to the locus a weed controlling amount of a composition according to any one of claims 12 to 14.

16. Use of the compound of formula (I) according to claim 1 as a herbicide.

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