Herbicidal compounds

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein Q, Z1, Z2, Z3, Z4, R2, R3 and m are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

Description

[0001] HERBICIDAL COMPOUNDS

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

[0003] Herbicidal benzoxazines are known from W02024 / 015425. Thus, according to the present invention there is provided a compound of Formula (I): or an agronomically acceptable salt thereof, wherein

[0004] Z1is C-R4or N;

[0005] Z2is C-R5or N;

[0006] Z3is C-R6or N;

[0007] Z4is C-R7or N; provided that at least one, but not more than two of Z1, Z2, Z3and Z4is N;

[0008] Q is a 5-membered nitrogen-containing heteroaryl which is optionally substituted by one or more R1; and

[0009] R1is independently selected from the group consisting of Ci-Ce alkyl, C2-C6 alkenyl; Ci-Ce alkoxy, halogen and Ci-Ce haloalkyl;

[0010] R2is independently selected from the group consisting of Ci-Ce alkyl, Ci-Ce alkoxy, halogen and Ci-Ce haloalkyl; R3is selected from the group consisting of Ci-Ce alkyl, Ci-Ce haloalkyl and Ci- CsalkoxyCi-Csalkyl-;

[0011] R4, R5, R6and R7are each independently selected from the group consisting of hydrogen, halogen, Ci-Ce alkyl, Ci-Ce alkoxy and Ci-Ce haloalkyl; and m is 0, 1 or 2.

[0012] Ci-Cealkyl- includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl ( / -Pr), n-butyl (n-Bu), isobutyl ( / -Bu), sec-butyl and tert-butyl (f-Bu). Ci-C2alkyl is methyl (Me, CH3) or ethyl (Et, C2H5).

[0013] C2-Cealkenyl- includes, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).

[0014] 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.

[0015] 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.

[0016] Ci-Cealkoxy includes methoxy and ethoxy.

[0017] Ci-CsalkoxyCi-Csalkyl- includes, for example, methoxymethyl-.

[0018] In a preferred embodiment of the present invention, there is provided a compound of Formula (I) wherein Q is selected from the group consisting of Q-1 , Q-2, Q-3, Q-4, Q-5 and Q-6: wherein n is 0, 1 or 2 and R1a, R1band R1care independently selected from the group consisting of hydrogen, Ci-Ce alkyl, C2-C6 alkenyl; Ci-Ce alkoxy, halogen and Ci- Ce haloalkyl.

[0019] In a more preferred embodiment of the present invention, Q is Q-1 or Q-2, more preferably Q-1.

[0020] In another preferred embodiment of the present invention, Q is Q-1 , R1ais Ci-Ce alkyl (preferably 3-isopropyl or 3-tert-butyl) or Ci-Ce alkenyl (preferably isopropenyl) and R1bis hydrogen.

[0021] In another embodiment of the present invention, Z1is N, Z2is CR5, Z3is CR6and Z4is CR7; or Z1is CR4, Z2is CR5, Z3is CR6and Z4is N; or Z1is CR4, Z2is CR5, Z3is N and Z4is CR7; or Z1is CR4, Z2is N, Z3is CR6and Z4is CR7.

[0022] In another embodiment of the present invention, Z1is CR4, Z2is CR5, Z3is CR6and Z4is N; or Z1is CR4, Z2is CR5, Z3is N and Z4is CR7; orZ1is CR4, Z2is N, Z3is CR6and Z4is CR7.

[0023] In a preferred embodiment of the present invention, R4, R5and R6are hydrogen and R7is hydrogen or halogen. In an even more preferred embodiment of the present invention, Z1is CH, Z2is CH, Z3is CH and Z4is N; or Z1is CH, Z2is CH, Z3is N and Z4is CR7(wherein R7is H or Cl); or Z1is CH, Z2is N, Z3is CH and Z4is CR7(wherein R7is H or Cl).

[0024] In another embodiment of the present invention, m is 1 and R2is Ci-Ce alkyl or Ci-Ce alkoxy. In a more preferred embodiment, R2is 6-(CH3) or 6-(OCH3), preferably - (CH3).

[0025] In another embodiment of the present invention, R3is Ci-Ce alkyl, preferably methyl and even more preferably methyl (S). Thus, in one embodiment of the present invention, there is provided a compound of Formula (la):

[0026] Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities.

[0027] The present invention also provides agronomically acceptable salts of compounds of Formula (I).

[0028] The compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surface-active agents (SAA). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. The composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

[0029] The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of Formula I and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.

[0030] 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 (Sil), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP) and a soluble granule (SG). The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).

[0031] Soluble powders (SP) may be prepared by mixing a compound of Formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility / solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

[0032] Wettable powders (WP) may be prepared by mixing a compound of Formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

[0033] Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

[0034] Dispersible Concentrates (DC) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface-active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

[0035] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N- octylpyrrolidone), dimethyl amides of fatty acids (such as Cs-C fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.

[0036] Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SAAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.

[0037] Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent / SAA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in- water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oilsoluble 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.

[0038] Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I). SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

[0039] Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane). A compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.

[0040] Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment. A compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

[0041] The composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I). Such additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).

[0042] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0043] Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltri methyl ammonium bromide), imidazolines and amine salts.

[0044] 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.

[0045] Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.

[0046] 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.

[0047] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0048] The compounds of present invention can also be used in mixture with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac-sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epyrifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), fluchloraminopyr (including fluchloraminopyr-tefuryl), flufenacet, flufenoximacil, flumetsulam, flumioxazin, fluometuron, fomesafen flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), flusulfinam, fomesafen, foramsulfuron, glufosinate (including L-glufosinate and the ammonium salts of both), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, icafolin (including icafolin- methyl), imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, indolauxipyr (including indolauxipyr-cyanomethyl), iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, iptriazopyrid, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryne, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen- ethyl), pyraquinate, pyrasulfotole, pyridate, pyriftalid, pyriflubenzoxim, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P- ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, tripyrasulfone, 3-(2- chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)- yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1- methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5- dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1- methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4- (trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3-[1-methyl-5- (trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4- ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, (1RS,5SR)-3-[2-methoxy-4-(prop-1-yn- 1-yl)phenyl]-4-oxobicyclo[3.2.1]oct-2-en-2-yl methyl carbonate, ethyl-2-[[3-[[3-chloro-5- fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2- pyridyl]oxy]acetate, methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate, 6-chloro-4-(2,7- dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2-fluorophenyl)methyl 6- amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate, 6- amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid, methyl 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)- pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-cyclopent[d]isoxazole- 6a-carboxylate, 2-[(2-bromo-6-fluoro-phenyl)methoxy]-4-isopropyl-1-methyl-7- oxabicyclo[2.2.1]heptane and (isopropylideneamino) 6-amino-2-(4-chloro-2-fluoro-3- methoxy-phenyl)-5-methoxy-pyrimidine-4-carboxylate.

[0049] The mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

[0050] The compound of Formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

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

[0052] The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of Formula (I) with the mixing partner). 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.

[0053] Particularly preferred are mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and / or metcamifen.

[0054] The safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16thEdition (BCPC), 2012. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02 / 34048.

[0055] 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.

[0056] The present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I). Moreover, the present invention may further provide a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention. ‘Controlling’ means killing, reducing or retarding growth or preventing or reducing germination. It is noted that the compounds of the present invention show a much-improved selectivity compared to know, structurally similar compounds. Generally the plants to be controlled are unwanted plants (weeds). ‘Locus’ means the area in which the plants are growing or will grow. The application may be applied to the locus pre-emergence and / or postemergence of the crop plant. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I). Preferred crop plants include maize, wheat, barley soybean and rice.

[0057] The rates of application of compounds of Formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2500 g / ha, especially from 25 to 1000 g / ha, more especially from 25 to 250 g / ha.

[0058] 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.

[0059] Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, HPPD-, -PDS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinateresistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. The compounds of the present invention can also be used in conjunction with crops that are tolerant to SDPS-inhibiting herbicides, such as those taught in W02020 / 236790.

[0060] 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.

[0061] 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).

[0062] The compositions can be used to control unwanted plants (collectively, ‘weeds’). The weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachia ria, Bromus, Cenchrus, 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.

[0063] In a further aspect of the present invention there is provided the use of a compound of Formula (I) as defined herein as a herbicide.

[0064] Processes for preparation of compounds, e.g. compounds of Formula (I)

[0065] Processes for preparation of compounds, e.g. a compound of formula (I) (which optionally can be an agrochemically acceptable salt thereof), are now described, and form further aspects of the present invention.

[0066] A compound of Formula (I) may be prepared by reaction of a compound of Formula A and a compound of Formula B via an amide bond forming reaction either directly in the presence of a suitable reagent or indirectly via the formation of a suitable activated intermediate (e.g. an acid chloride) in the presence of a suitable base and in a suitable solvent. Suitable methods for formation of the activated intermediate may include oxalyl chloride, SO2CI2 or POCI3. Suitable bases may include N-ethyl-N-isopropyl-propan-2- amine. Suitable solvents may include THF, 2-Me THF or CH3CN. Formula s Formuta l

[0067] Compounds of Formula A may be prepared from a compound of Formula C via an ester hydrolysis reaction using a suitable reagent and in a suitable solvent. Suitable reagents may include NaOH or KOH. Suitable solvents may include THF, MeOH or water or combinations thereof.

[0068] Paonia la C Formula A

[0069] Compounds of Formula C may be prepared from a compound of Formula D (where Y1represents a suitable cross-coupling partner such as Br or I) and a compound of Formula E (where Y2represents a suitable cross-coupling partner to Y1such as a boronic acid or ester) via a suitable cross-coupling reaction in the presence of a suitable catalyst / ligand system and a suitable base and in a suitable solvent. Suitable catalyst / ligand systems may include Pd(dppf)Cl2.CH2Cl2. Suitable bases may include CS2CO3. Suitable solvents may include 2-Me THF. Compounds of Formula D and of Formula E are commercially available or may be prepared via methods known in the literature.

[0070] Formula D

[0071] Formula C

[0072] Compounds of Formula B may be prepared from a compound of Formula F via a reduction in a suitable solvent. Suitable reducing agents may include UAIH4. Suitable solvents may include THF or 2-Me THF.

[0073] Formula F Formula B

[0074] Compounds of Formula F may be prepared from compounds of Formula G via a reduction / cyclisation cascade in the presence of a suitable reducing agent and in a suitable solvent. Suitable reducing agents may include Fe / NF CI. Suitable solvents may include EtOH.

[0075]

[0076] Formula G

[0077] Compounds of Formula G may be prepared from compounds of Formula H (where LGi represents a suitable leaving group such as F, Cl, Br) and of Formula J (where Rarepresents a C1-6 alkyl group) via a displacement reaction in the presence of s suitable base and in a suitable solvent. Suitable bases may include NaH. Suitable solvents may include THF or 2-Me THF. Compounds of Formula H and of Formula J are commercially available or may be prepared via methods known in the literature. The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table 1 below.

[0078] Example 1 : Synthesis of [5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-phenyl]-[(3S)- 3-methyl-2,3-dihydropyrido[2,3-b][1,4]oxazin-1-yl]methanone (Compound 1.001)

[0079] Step 1 : Synthesis of methyl 5-(3-bromo-1,2,4-triazol-1-yl)-2-methyl-benzoate

[0080] To a stirred solution of (3-methoxycarbonyl-4-methyl-phenyl)boronic acid (1.79g, 8.77 mmol) and 3-bromo-1 H-1 ,2,4-triazole (1.50g, 9.64 mmol) in N,N-dimethylacetamide (25 mL) was added Na2COs (1.47g, 13.1 mmol), pyridine (0.37 mL, 4.38 mmol) and copper (II) acetate (0.398g, 2.19 mmol). The reaction was heated at 80°C for 18h, allowed to cool to RT and diluted with water (25 mL). The reaction mass was filtered through a pad of celite and then extracted with EtOAc (2 x 25 mL). The combined organic extracts were evaporated to dryness under reduced pressure and the crude product purified by flash chromatography on SiO2 using 25-30% EtOAc / hexane as eluent to give the desired product (2.50g, 67%) as a white solid.

[0081] 1H NMR (400 MHz, CDCI3) 8.39 (s, 1 H), 8.12 (d, 1 H), 7.63 (dd, 1 H), 7.34 (d, 1 H), 3.87 (s, 3H), 2.59 (s, 3H).

[0082] Step 2: Synthesis of methyl 5-(3-isopropenyl-1,2,4-triazol-1-yl)-2-methyl- benzoate

[0083] A microwave vial was charged with methyl 5-(3-bromo-1 ,2,4-triazol-1-yl)-2-methyl- benzoate (1.25g, 4.00 mmol), 2-methyl THF (8 mL), water (2 mL), 4,4,5,5-tetramethyl- 2-(prop-1-enyl)-1 ,3-2-dioxoborolane (2.85g, 16 mmol) and CS2CO3 (3.90g, 12 mmol), purged with N2 for 10 minutes and then Pd(dppf)Cl2.CH2Cl2 added (0.33g, 0.40 mmol) and the reaction heated at 120°C for 2 hours under microwave irradiation. The reaction was diluted with water (15 mL) and extracted with EtOAc (3 x 15 ml). The combined organic extracts were washed with brine (10 mL), dried over Na2SO4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on SiC>2 using 0-50% EtOAc / hexane as eluent to give the desired product (0.401g, 37%).1H NMR (400 MHz, CDCI3) 8.54 (s, 1 H), 8.22 (s, 1 H), 7.77 (d, 1 H), 7.42 (d, 1 H), 6.15 (s, 1 H), 5.37 (s, 1 H), 3.97 (s, 3H), 2.67 (s, 3H), 2.27 (s, 3H).

[0084] Step 3: Synthesis of methyl 5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-benzoate

[0085] To a stirred solution of methyl 5-(3-isopropenyl-1 ,2,4-triazol-1-yl)-2-methyl-benzoate (0.800g, 2.95 mmol) in EtOAc (15 mL) was added ammonium formate (1.90g, 29.5 mmol) and 10% Pd / C (80mg). The reaction was heated at reflux for 3h, allowed to cool to RT and filtered through a pad of celite. The filtrate was washed with water (5 mL) and evaporated to dryness under reduced pressure to give the desired product (0.800g, 94%).

[0086] 1H NMR (400MHz, CDCI3) 8.54 (s, 1 H), 8.20 (s, 1 H), 7.74 (d, 1 H), 7.41 (d, 1 H), 3.96 (s, 3H), 3.24-3.17 (m, 1 H), 2.66 (s, 3H), 1.42 (d, 6H).

[0087] Step 4: Synthesis of 5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-benzoic acid

[0088] To a stirred solution of methyl 5-(3-isopropyl-1 ,2,4-triazol-1-yl)-2-methyl-benzoate (0.800g, 3.09 mmol) in THF (6.4 mL) and MeOH (1.6 mL) was added NaOH (6.2 mL of a 2M solution in water, 12.3 mmol). The reaction was stirred at RT for 3h, evaporated to dryness under reduced pressure, the residue dissolved in water (10 mL) and washed with EtOAc (10 mL). The aqueous phase was acidified with 2M HCI and extracted with EtOAc (2 x 10 mL). The combined organic extracts were washed with water (10 mL), dried over MgSO4 and evaporated to dryness under reduced pressure to give the desired product (0.68g, 89%) as a white solid.

[0089] 1H NMR (400 MHz, DMSO-d6) 13.2 (br, 1 H), 9.19 (s, 1 H), 8.22 (d, 1 H), 7.90 (d, 1 H), 7.47 (d, 1 H), 3.10-3.00 (m, 1 H), 2.55 (s, 3H), 1.29 (d, 6H).

[0090] Step 5: Synthesis of methyl (2S)-2-(2-nitrophenoxy)propanoate

[0091] To a stirred solution of methyl (2S)-2-hydroxypropanoate (1.61g, 15.48 mmol) in 2- methyl THF (15 mL) at 0°C under an atmosphere of N2 was added NaH (0.619g of a 60% dispersion in mineral oil, 15.48 mmol). The reaction was stirred at 0°C for 15 minutes and a solution of 2-fluoro-3-nitro-pyridine (2.00g, 14.08 mmol) in 2-methyl THF (5 mL) was added dropwise. The reaction was allowed to warm to RT over 30 minutes then cooled to 0°C and quenched with saturated, aqueous NH4CI solution (15 mL). The reaction was extracted with EtOAc (2 x 10 mL), the combined organic extracts dried over Na2SO4 and evaporated to dryness under reduced pressure to give the desired product (2.80g, 70%) as a brown oil.

[0092] 1H NMR (400 MHz, CDCI3) 8.33-8.30 (m, 2H), 7.07 (d, 1 H), 5.45 (q, 1 H), 3.74 (s, 3H), 1.70 (d, 3H) Step 6: Synthesis of (3S)-3-methyl-1H-pyrido[2,3-b][1,4]oxazin-2-one

[0093] To a stirred solution of methyl (2S)-2-(2-nitrophenoxy)propanoate (2.80g, 12.0 mmol) in EtOH (28 mL) was added Fe powder (2.40g, 37 mmol) and the reaction heated to 70°C. A solution of ammonium chloride (2.0g, 37 mmol) in water (8.4 mL) was added slowly and the reaction heated at 70°C for a further 4h. The reaction was cooled to RT and filtered through a pad of celite. The filtrate was evaporated to dryness under reduced pressure, the residue dissolved in water (25 mL) and extracted with EtOAc (2 x 25 mL). The combined organic extracts were evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on SiC>2 using 15-20% EtOAc / hexane as eluent to give the desired product (0.955g, 47%).

[0094] 1H NMR (400 MHz, CDCI3) 8.78 (br, 1 H), 7.96 (d, 1 H), 7.18 (d, 1 H), 7.02-6.97 (m, 1 H), 4.94-4.88 (m, 1 H), 1.68 (d, 3H).

[0095] Step 7: Synthesis of (3S)-3-methyl-2,3-dihydro-1H-pyrido[2,3-b][1,4]oxazine

[0096] To a stirred solution of (3S)-3-methyl-1 H-pyrido[2,3-b][1 ,4]oxazin-2-one (0.955g, 5.82 mmol) in THF (5 mL) at 0°C under an atmosphere of N2 was added dropwise lithium aluminium hydride (6.98 mL of a 1M solution in THF, 6.98 mmol). The reaction was allowed to warm to RT over 3 hours, then cooled to 0°C and quenched by slow addition of EtOAc (10 mL) followed by a saturated aqueous solution of Rochelle’s salt (10 mL) and the reaction stirred at RT for 30 mins. The reaction was diluted with water (25 mL) and extracted with EtOAc (3 x 20 mL). The combined organic extracts were dried over Na2SO4 and evaporated to dryness under reduced pressure. The crude product was purified by reverse phase chromatography using 100% H2O as eluent to give the desired product (0.42g, 43%) as an off-white solid.

[0097] 1H NMR (400 MHz, CDCI3) 7.54 (dd, 1 H), 6.81 (dd, 1 H), 6.70-6.65 (m, 1 H), 4.40-4.30 (m, 1 H), 3.28 (dd, 1 H), 3.04 (dd, 1 H), 1.36 (d, 3H).

[0098] Step 8: Synthesis of [5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-phenyl]-[(3S)-3- methyl-2,3-dihydropyrido[2,3-b][1,4]oxazin-1-yl]methanone (A001)

[0099] To a stirred solution of 5-(3-isopropyl-1 ,2,4-triazol-1-yl)-2-methyl-benzoic acid (the product of Step 4) (0.10g, 0.41 mmol) in THF (2 mL) under an atmosphere of N2 was added oxalyl chloride (0.109 mL, 1.22 mmol) and DMF (1 drop) and the reaction stirred at RT for 1 hour. The reaction was evaporated to dryness under reduced pressure and the residue dissolved in CH3CN (2 mL) and a solution of (3S)-3-methyl-2,3-dihydro-1 H- pyrido[2,3-b][1 ,4]oxazine (the product of step 7) (0.073g, 0.49 mmol) in CH3CN (2 mL). The reaction was cooled to 0°C and then added N-ethyl-N-isopropyl-propan-2-amine (0.09 mL, 0.52 mmol) and the reaction allowed to warm to RT over 1 hour. The reaction was diluted with H2O (10 mL) and extracted with EtOAc (3 x 10 mL). The combined organic extracts were dried over Na2SO4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography using 80-90% EtOAc in cyclohexane in as eluent to give the desired product (0.084g, 53%).

[0100] 1H NMR (400 MHz, DMSO-d6, 80°C) 9.03 (d, 1 H), 8.10 (br, 1 H), 7.95 (d, 1 H), 7.82-7.77 (m, 2H), 7.45 (d, 1 H), 6.93 (t, 1 H), 4.56 (t, 1 H), 4.00-3.93 (m, 1 H), 3.42-3.30 (m, 1 H), 3.10-3.02 (m, 1 H), 2.29 (s, 3H), 1.36-1.25 (m, 9H).

[0101] TABLE 1. Compounds of the Present Invention

[0102] TABLE 2. Further Compounds of the Present Invention

[0103] Seeds of a variety of test species are sown in standard soil in pots Amaranthus palmeri (AMAPA), Amaranthus retroflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus- galli (ECHCG), Ipomoea hederacea (IPOHE)). After cultivation for one day (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 the formulation of the technical active ingredient in acetone I water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 1000 g / ha unless otherwise stated. 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%).

[0104] TABLE B1. Post-emergence Test

[0105] NT = Not tested

[0106] TABLE B2. Pre-emergence Test

[0107] NT = Not tested Table B3 - Comparative Test (Post-emergence).

[0108] A formulation containing 50 g / l of the “technical” (i.e. unformulated) active ingredient was prepared by dissolving the active ingredient in a mixture of organic solvents and emulsifier, details of which are provided in the table below. This foumulation was then mixed with a small, variable amount of acetone to aid dissolution, before addition of a 0.2% v / v aqueous solution of the adjuvant Genapol XO80, as the aqueous diluent, to form an aqueous spray solution which contains a predetermined concentration of the active ingredient (which varies depending on the application rate of the active ingredient to the plants).

[0109] Composition of the mixture of organic solvents and emulsifier used as a base for the instant formulation.

[0110] This aqueous spray solution was then sprayed onto the plants after about 12 days cultivation. The plants were grown from seeds sown in standard soil, placed in a glasshouse under controlled conditions (at 24 / 18°C or 20 / 16°C, day / night; 16 hours light; 65 % humidity). After spray application the plants were then grown on in a glasshouse under the same conditions and watered twice daily. After 15 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant).

[0111] The following plant species were tested

[0112] AVEFA = Avena fatua

[0113] ALOMY = Alopecurus myosuroides

[0114] LOLPE = Lolium perenne

[0115] DIGSA = Digitaria sanguinalis

[0116] STEME = Stellaria media

[0117] Bl DPI = Bidens pilosa

[0118] IPOHE = Ipomoea hederacea This comparative test shows that compounds of the present invention exhibit increased biological activity compared to compounds disclosed in WO2024 / 015425.

Claims

1. Claims1. A compound of Formula (I):or an agronomically acceptable salt thereof, whereinZ1is C-R4or N;Z2is C-R5or N;Z3is C-R6or N;Z4is C-R7or N; provided that at least one, but not more than two of Z1, Z2, Z3and Z4is N;Q is a 5-membered nitrogen-containing heteroaryl which is optionally substituted by one or more R1; andR1is independently selected from the group consisting of Ci-Ce alkyl, C2-C6 alkenyl; Ci-Ce alkoxy, halogen and Ci-Ce haloalkyl;R2is independently selected from the group consisting of Ci-Ce alkyl, Ci-Ce alkoxy, halogen and Ci-Ce haloalkyl;R3is selected from the group consisting of Ci-Ce alkyl, Ci-Ce haloalkyl and C1- CsalkoxyCi-Csalkyl-;R4, R5, R6and R7are each independently selected from the group consisting of hydrogen, halogen, Ci-Ce alkyl, Ci-Ce alkoxy and Ci-Ce haloalkyl; andm is 0, 1 or 2.

2. A compound of Formula (I) according to claim 1 , wherein Q is selected from the group consisting of Q-1 , Q-2, Q-3, Q-4, Q-5 and Q-6:wherein n is 0, 1 or 2 and R1a, R1band R1care independently selected from the group consisting of hydrogen, Ci-Ce alkyl, C2-C6 alkenyl; Ci-Ce alkoxy, halogen and Ci-Ce haloalkyl.

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

4. A compound according to claim 3, wherein Q is Q-1 , R1ais Ci-Ce alkyl or C2-C6 alkenyl and R1bis hydrogen.

5. A compound according to any one of the previous claims, wherein Z1is CR4, Z2is CR5, Z3is CR6and Z4is N; or Z1is CR4, Z2is CR5, Z3is N and Z4is CR7; or Z1is CR4, Z2is N, Z3is CR6and Z4is CR7.

6. A compound according to claim 5, wherein R4, R5and R6are hydrogen and R7is hydrogen or halogen.

7. A compound according to any one of the previous claims, wherein m is 1 and R2is Ci-Ce alkyl or Ci-Ce alkoxy.

8. A compound according to claim 7, wherein R2is 6-(CH3).

9. A compound according to any one of the previous claims, wherein R3is methyl.

10. A compound according to claim 9, wherein R3is methyl (S).

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

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

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

14. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to any one of claims 11 to 13.

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

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