HERBICIDAL COMPOUNDS

Information

  • Patent Application
  • 20230024283
  • Publication Number
    20230024283
  • Date Filed
    December 24, 2020
    3 years ago
  • Date Published
    January 26, 2023
    a year ago
Abstract
The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein R1, R2, R3 and R4 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

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.


WO96/06089 teaches substituted biphenyl derivatives and their use as herbicides. It has now been found that certain intermediates that are described in the synthesis of the biphenyl derivatives therein are themselves herbicidal. Thus, according to the present invention there is provided a compound of Formula (I):




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or an agronomically acceptable salt thereof,


wherein


X is CH or N,


R1 is selected from the group consisting of hydrogen, C1-C10alkylC(O)—, C1-C10alkylOC(O)—, C1-C10alkylSC(O)—and R5R6NC(O)—;


R2 is selected from the group consisting of halogen, NO2, CN, C1-C6haloalkylS(O)p—, C1-C6alkyl-S(O)p—, C2-C4alkenyl-, C2-C4alkynyl-, C1-C4haloalkyl and C1-C4haloalkoxy-;


R3 is selected from the group consisting of hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy- and C1-C4haloalkoxy-;


R4 is phenyl or a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the phenyl or heteroaryl may be optionally substituted by one or more substituents independently selected from the group consisting of halogen, C1-C6alkyl-, C2-C4alkenyl-, C2-C4alkynyl-, C1-C6haloalkyl-, C1-C6alkoxy-, C1-C6alkoxyC1C3-C3alkyl-, C1-C6alkoxyC1-C3alkoxy-, C1-C6haloalkoxy-, C1-C6alkyl-S(O)p—, C1-C6haloalkyl-S(O)p—, C3-C6cycloalkyl- (optionally substituted by 1 or 2 halogen), cyano and nitro; or


R4 is R4a




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and


R5 is hydrogen or C1-C10alkyl;


R6 is hydrogen or C1-C10alkyl;


R7 and R8 are independently selected from the group consisting of hydrogen and halogen; and


p=0, 1 or 2;


wherein said compound is not selected from the group consisting of 2-(3-bromo-5-cyano-2-hydroxyphenyl)pyridine, 3-chloro-2-ethoxy-4-hydroxy-5-phenyl-benzonitrile, 4-hydroxy-3-nitro-5-[3-(trifluoromethyl)phenyl]benzonitrile and 2′-fluoro-6-hydroxy-5-nitrobiphenyl-3-carbonitrile.


C1-C4alkyl- 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-C2alkyl is methyl (Me, CH3) or ethyl (Et, C2H5).


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.


C1-C6haloalkyl- 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, heptafluoro-n-propyl and perfluoro-n-hexyl. C1-C4haloalkyl- and C1-C2haloalkyl include, 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.


C1-C4alkoxy and C1-C2alkoxy includes, for example, methoxy and ethoxy.


C1-C6haloalkoxy- and C1-C4haloalkoxy- include, 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.


C2-C4alkenyl- includes, for example, —CH=CH2 (vinyl) and —CH2−CH=CH2 (allyl).


C2-C4alkynyl- refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C2-C4alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.


C1-C4alkyl-S— (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.


C1-C4alkyl-S(O)— (alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.


C1-C4alkyl-S(O)2— (alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.


C3-C6alkyl- includes, for example, cyclopropyl and cyclohexyl.


Five or six-membered heteroaryl includes, for example, furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl, oxadiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, thiadiazolyl and triazolyl.


In one embodiment of the present invention there is provided a compound of Formula (I) wherein R1 is C1-C6alkylC(O)— ( e.g CH3C(O)—, iPrC(O)—, t-butylC(O)—).


In another embodiment of the present invention there is provided a compound of Formula (I) wherein R1 is hydrogen.


In another embodiment of the present invention there is provided a compound of Formula (I) wherein R2 is selected from the group consisting of C1-C4haloalkyl, halogen and NO2, more preferably C1-C4haloalkyl (e.g C1-C4fluoroalkyl such as CF3, CF2H). In another preferred embodiment, R2 is selected from the group consisting of Br, Cl, CF2H, —CF3 and —OCF3, most preferably CF3.


In another embodiment of the present invention there is provided a compound of Formula (I) wherein R3 is selected from the group consisting of hydrogen, fluoro, chloro and methyl, most preferably hydrogen.


In another embodiment of the present invention there is provided a compound of Formula (I) wherein R4 is phenyl which is optionally substituted as outlined herein.


In another embodiment of the present invention there is provided a compound of Formula (I) wherein R4 a five or six-membered heteroaryl selected from the group consisting of furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl which is optionally substituted as defined herein. In a more preferred embodiment R4 is selected from the group consisting of phenyl, pyrazolyl (C or N linked), thiazolyl and thiophenyl which is optionally substituted as defined herein.


Where R4 is phenyl or a five or six-membered heteroaryl said phenyl or heteroaryl may be optionally substituted as described. For example, the phenyl or heteroaryl may comprise one, two, three or four substituents (depending on the nature of the heteroaryl). Where present, each substituent is preferably independently selected from the group consisting of halogen (e.g F, Cl), C1-C6haloalkyl- (e.g CF3, CF2H), C1-C6alkyl- (e.g methyl, ethyl), C3-C6cycloalkyl- (e.g cyclopropyl), cyano and C1-C6alkoxy- (e.g methoxy-, ethoxy-).


In another embodiment of the present invention R7 and R8 are independently selected from hydrogen and fluorine.


In another embodiment of the present invention there is provided a compound of Formula (I) wherein X is N.


In another embodiment of the present invention there is provided a compound of Formula (I) wherein X is CH.


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.


The present invention also provides agronomically acceptable salts of compounds of Formula (I). Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.


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


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


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


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


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


Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from 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).


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


Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-C10 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.


Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more 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.


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


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


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


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


The composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I). Such additives include surface active agents (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).


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


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


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-isopropyl- and tri-isopropyl-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/sulphates of tristyrylphenols.


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


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.


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


The herbicidal 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, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, diquat dibromide, diuron, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), flufenacet, flumetsulam, flumioxazin, fluometuron, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron, glufosinate (including the ammonium salt thereof), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox, imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryne, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), 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, ethyl 2-[[3-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]-2-pyridyl]oxy]acetate, 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, 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, 6-[6-cyclopropyl-2-(3,4-di methoxyphenyl)-3-oxo-pyridazi ne-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione, 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-[6-cyclopropyl-2-(3,4-di methoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including agrochemically acceptable esters thereof, for example, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl))pyridine-2-carboxylate).


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


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


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


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


The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.


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


The safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16th Edition (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.


Preferably the mixing ratio of compound of Formula (I) to safener is from 100:1 to 1:10, especially from 20:1 to 1:1.


The present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I):




embedded image


or an agronomically acceptable salt thereof,


wherein


X is CH or N,


R1 is selected from the group consisting of hydrogen, C1-C10alkylC(O)—, C1-C10alkylOC(O)—, C1-C10alkylSC(O)—and R5R6NC(O)—;


R2 is selected from the group consisting of halogen NO2, CN, C1-C6haloalkylS(O)p—, C1-C6alkyl-S(O)p—, C2-C4alkenyl-, C2-C4alkynyl-, C1-C4haloalkyl and C1-C4haloalkoxy-;


R3 is selected from the group consisting of hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy- and C1-C4haloalkoxy-;


R4 is phenyl or a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the phenyl or heteroaryl may be optionally substituted by one or more substituents selected from the group consisting of halogen, C1-C6alkyl-, C2-C4alkenyl-, C2-C4alkynyl-, C1-C6haloalkyl-, C1-C6alkoxy-, C1-C6alkoxyC1-C3alkyl-, C1-C6alkoxyC1-C3alkoxy-, C1-C6haloalkoxy-, C1-C6alkyl-S(O)p—, C1-C6haloalkyl-S(O)p—, C3-C6cycloalkyl- (optionally substituted by 1 or 2 halogen), cyano and nitro; or


R4 is R4a




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and


R5 is hydrogen or C1-C10alkyl;


R6 is hydrogen or C1-C10alkyl;


R7 and R8 are independently selected from the group consisting of hydrogen and halogen; and


p=0, 1 or 2;


The present invention further relates to said method featuring preferred embodiments of compounds of Formula (I) referred to herein.


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 an 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 and rice.


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.


The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.


Crop plants are to be understood as also including those crop plants which have been rendered tolerant to 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 glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.


Crop plants are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOutO (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.


Crop plants are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).


The compositions can be used to control unwanted plants (collectively, ‘weeds’). The weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.


The present invention further relates to the use of a compound of Formula (I):




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or an agronomically acceptable salt thereof,


wherein


X is CH or N,


R1 is selected from the group consisting of hydrogen, C1-C10alkylC(O)—, C1-C10alkylOC(O)—, C1-C10alkylSC(O)—and R5R6NC(O)—;


R2 is selected from the group consisting of halogen NO2, CN, C1-C6haloalkylS(O)p—, C1-C6alkyl-S(O)p—, C2-C4alkenyl-, C2-C4alkynyl-, C1-C4haloalkyl and C1-C4haloalkoxy-;


R3 is selected from the group consisting of hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy- and C1-C4haloalkoxy-;


R4 is phenyl or a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the phenyl or heteroaryl may be optionally substituted by one or more substituents selected from the group consisting of halogen, C1-C6alkyl-, C2-C4alkenyl-, C2-C4alkynyl-, C1-C6haloalkyl-, C1-C6alkoxy-, C1-C6alkoxyC1-C3alkyl-, C1-C6alkoxyC1-C3alkoxy-, C1-C6haloalkoxy-, C1-C6alkyl-S(O)p—, C1-C6haloalkyl-S(O)p—, C3- C6cycloalkyl- (optionally substituted by 1 or 2 halogen), cyano and nitro; or


R4 is R4a




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and


R5 is hydrogen or C1-C10alkyl;


R6 is hydrogen or C1-C10alkyl;


R7 and R8 are independently selected from the group consisting of hydrogen and halogen; and


p=0, 1 or 2;


as a herbicide.


The present invention further relates to said use featuring preferred embodiments of compounds of Formula (I) referred to herein.


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


(5-cyano-2-methoxy-phenyl)boronic acid can undergo cross-coupling with the desired aryl or heteroaryl halide (X can be I, Br, Cl) under palladium catalysis, employing a suitable palladium salt, ligand, base and solvent under elevated temperature. The resulting product is subjected to demethylation conditions, such as boron tribromide in a suitable solvent such as dichloromethane. The phenol can be halogenated with a suitable halogenating reagent such as N-bromosuccinimide at ambient or elevated temperatures, in a suitable solvent such as acetonitrile. The phenol can be further reacted with a range of acid chlorides, anhydrides or activated esters to afford the phenol esters.




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Alternatively, the desired substituted phenol (Scheme 2) can be halogenated with a suitable halogenating reagent such as N-bromosuccinimide, either at ambient or elevated temperatures in a suitable solvent such as acetonitrile. The halogenated phenol can undergo cross-coupling with the desired aryl or heteroaryl boronic acid or ester, under palladium catalysis, employing a suitable palladium salt, ligand, base and solvent under elevated temperature (Path A). Where R2 is also a halogen, isomeric mixtures may result which can be separated by chromatography. These phenols can be further reacted with a range of acid chlorides, anhydrides or activated esters to afford the phenol esters. Alternatively, the halogenated phenol can be reacted with the desired acid chloride, anhydride or activated ester to afford the phenol esters (Path B). These intermediates can undergo cross-coupling with the desired aryl or heteroaryl boronic acid or ester, under palladium catalysis, employing a suitable palladium salt, ligand, base and solvent under elevated temperature to afford further compounds of the invention.




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General

Alternatively, the desired substituted phenol (Scheme 3) can be halogenated with a suitable halogenating reagent such as N-bromosuccinimide, either at ambient or elevated temperatures in a suitable solvent such as acetonitrile. The halogenated phenol can then be protected with a suitable protecting group, such a benzyl or paramethoxybenzyl group, using benzyl chloride or paramethoxybenzylchloride, with a suitable base, such as potassium carbonate, in a suitable solvent such as acetone with a phase transfer catalyst such as tetrabutylammonium iodide. In a following step the bromide undergoes metalation with a Grignard reagent at low temperature in a suitable solvent such as THF. The resulting aryl Grignard is then reacted with a desired boronate, such as 2-ethoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting aryl boronate can then be coupled to a range of aryl or heteroaryl halides in a Suzuki reaction, under elevated temperature, followed by deprotection, to afford further compounds of the invention.




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Example 1. Synthesis of 3-bromo-4-hydroxy-5-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile—Compound 1.007
Step 1 Synthesis of 4-methoxy-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile



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A 25mL round bottomed flask was charged with a stirrer bar, (5-cyano-2-methoxy-phenyl)boronic acid (4.3 mmol, 0.76 g), 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole (4 mmol, 1.10 g) and bis(triphenylphosphine)palladium dichloride (0.4 mmol, 0.28 g). Acetonitrile (10 mL) was added followed by and potassium carbonate (6 mmol, 0.82927 g) and mixture was heated at reflux. After 3 h, the reaction was diluted with dichloromethane (15 mL), washed with and brine (10 mL), dried with MgSO4 and concentrated. The crude product was then purified by chromatography (gradient elution EtOAc/Hexane) to afford 4-methoxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (665 mg, 60%) as an off white solid.



1HNMR (CDCl3) δ 8.28 (d, 1H), 7.51 (dd, 1H), 7.12 (s, 1H), 7.02 (1H, d), 5.04 (3H, s), 3.59 (3H, s).


Step 2 Synthesis of 4-hydroxy-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile



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To a solution of 4-methoxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (0.65 g, 2.312 mmol) in anhydrous dichloromethane (20 mL) at 0° C. and under nitrogen was added boron tribromide (1M solution in DCM) (8.090 mL, 8.090 mmol) dropwise. Once addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for a further 2 h. The reaction was carefully quenched with water and then extracted with dichloromethane (3×10 mL). The organics were combined, washed with brine, dried over magnesium sulfate and concentrated in vacuo to afford 4-hydroxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile yellow solid (600 mg, 97%).



1HNMR (CDCl3) δ 10.80 (s, 1H), 7.82 (d, 1H), 7.51 (dd, 1H), 7.09 (1H, d), 7.01 (1H, s), 4.08 (3H, s).


Step 3 Synthesis of 3-bromo-4-hydroxy-5-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile—Compound 1.007



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To a stirred solution of 4-hydroxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (0.580 g, 2.1706 mmol,) in acetonitrile (10 mL) was added 1-bromopyrrolidine-2,5-dione (0.579 g, 3.25 mmol), in one portion, and the mixture was heated at reflux for 2 h. The mixture was then diluted with EtOAc and washed with water (10 mL) and Brine (10), dried (MgSO4) and purified by chromatography to afford 3-bromo-4-hydroxy-5-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (450 mg, 60%).



1HNMR (CDCl3) δ 11.59 (s, 1H), 7.80 (s, 1H), 7.36 (s, 1H), 7.03 (s, 1H), 4.09 (3H, s).


Example 2. Synthesis of 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (Compound 1.040) and 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (Compound 1.039)
Step 1 Synthesis of (2,4-dibromo-6-cyano-3-pyridyl) acetate



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4,6-dibromo-5-hydroxy-pyridine-2-carbonitrile (1 g, 3.5984 mmol), dichloromethane (10 mL) N,N-diethylethanamine (1.2 equiv., 4.3181 mmol) were combined in a 50mL round bottomed flask and acetyl chloride (1.1 equiv., 3.9583 mmol) was added dropwise. After stirring at room temperature for 5 h, the mixture was washed with water (15 mL) and brine (15 mL), dried (MgSO4) and concentrated to afford a 2,4-dibromo-6-cyano-3-pyridyl) acetate 1.07g (93%).



1HNMR (CDCl3) δ 7.91 (s,1H), 2.46 (s, 3H).


Step 2 Synthesis of 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile and 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile



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(2,4-dibromo-6-cyano-3-pyridyl) acetate (0.2 g, 0.625 mmol), (3-fluorophenyl)boronic acid (87 mg 0.625 mmol,) and bis(triphenylphosphine)palladium(II)dichloride (22 mg, 0.031 mmol) were weighed into a microwave vial. Acetonitrile (5 mL) was added followed by a stirrer bar and sodium carbonate (1.2502 mmol). The vial was sealed and heated for 10 min at 130° C. in the microwave. The mixture was diluted with EtOAc (15 mL) and washed with 2M HCl (10 mL), and brine (10 mL), dried with MgSO4 and concentrated. The resulting crude product was purified by RPHPLC (to afford the separated isomers 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (15 mg) and 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (10 mg).


4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile 1HNMR (DMSO-d6) δ 8.31 (s,1H), 7.73 (t, 2H), 7.53 (q, 1H), 7.29 (td, 1H).


6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile 1HNMR (DMSO-d6) δ 7.98 (s,1H), 7.58-7.48 (m, 3H), 7.28-7.24 (m,1H).


Example 3. Synthesis of 3-bromo-5-(3-fluorophenyl)-4-hydroxy-benzonitrile—Compound 1.046.
Step 1 Synthesis of (2,6-dibromo-4-cyano-phenyl) acetate



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3,5-dibromo-4-hydroxy-benzonitrile (5 g, 18.05 mmol) was weighed into a 250 ml round bottom flask and a stirrer bar added. Dichloromethane (100 mL) was added followed by triethylamine (1.1 equiv, 19.862 mmol) and the flask was cooled in an ice-bath. Acetyl chloride (1.1 equiv., 19.862 mmol) was added dropwise into the reaction mixture which was stirred for 1 h . The reaction mixture was washed with water (100ml×3) and the organic phase dried (MgSO4). The mixture was concentrated, in vacuo to afford the desired product (5.5 g, 96%).



1HNMR (CDCl3) δ 7.88 (s, 2H), 2.42 (s, 3H).


Step 2 Synthesis of 3-bromo-5-(3-fluorophenyl)-4-hydroxy-benzonitrile



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To a microwave tube, charged with a stirrer bar, was added (3-fluorophenyl)boronic acid (91 mg, 0.65 mmol), bis(triphenylphosphine)palladium (II) dichloride) (0.05 equiv., 0.0325 mmol), and (2,6-dibromo-4-cyano-phenyl) acetate (207 mg, 0.65 mmol) in acetonitrile (5 mL). A 1 molar solution of Sodium carbonate (2 eq. 1.3 mmol, 1.3 mL), was added and the tube was capped and microwaved at 150° C. for 15 mins. The reaction mixture was passed through a SiTMT SPE cartridge. The mixture was then concentrated in vacuo and the residue re-dissolved in 10% MeOH in DMSO and purified by mass directed RPHPLC to afford the 3-bromo-5-(3-fluorophenyl)-4-hydroxy-benzonitrile (32 mg, 15%).



1HNMR (CDCl3) δ 7.85 (d, 1H), 7.53 (1H, d), 7.50-7.46 (1H, m), 7.27-7.18 (3H, m), 6.20 (1H, bs).


Example 4. Synthesis of 3-chloro-4-hydroxy-5-[4-(trifluoromethyl)pyrazol-1-yl]benzonitrile—Compound 1.001



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To a stirred solution of 3-bromo-5-chloro-4-hydroxy-benzonitrile (0.100 g, 0.430 mmol) in anhydrous N,N-dimethylformamide (3.00 mL) , 4-(trifluoromethyl)-1H-pyrazole (0.0820 g, 0.602 mmol), Cesium carbonate (0.280 g, 0.860 mmol) and Copper iodide (0.0164 g, 0.0860 mmol) were added at RT. The reaction mixture was purged with nitrogen for 15 min and then heated at 120° C. in a sealed tube for 24 hrs. Then the reaction mass was diluted with EtOAc and passed through the bed of silica gel and concentrated to afford the crude product. Purification by chromatography, eluting with 0 to 20% EtOAc in hexane, affords 3-chloro-4-hydroxy-5-[4-(trifluoromethyl)pyrazol-1-yl]benzonitrile (10 mg, 8%).



1HNMR (400MHz,DMSO): δ 8.93 (s, 1H), 8.27 (s, 1H), 8.11-8.10 (m, 2H).


Example 5. Synthesis of 4-hydroxy-3-thiazol-2-yl-5-(trifluoromethyl)benzonitrile
Step 1 Synthesis of 3-bromo-4-hydroxy-5-(trifluoromethyl)benzonitrile



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To a stirred solution of 4-hydroxy-3-(trifluoromethyl)benzonitrile (4.5 g, 24 mmol,) in acetonitrile (30 mL) was added N-bromosuccinimide (4.3 g, 24 mmol), in one portion, and the mixture was heated at reflux for 1.5 h. The mixture was allowed to cool to room temperature and then dry-loaded on silica and purified by chromatography using a EtOAc/cyclohexane gradient elution to afford 3-bromo-4-hydroxy-5-(trifluoromethyl)benzonitrile (6.4 g).



1H NMR (400 MHz, chloroform) δ ppm 7.99 (d, J=1.83 Hz, 1H) 7.85 (d, J=1.34 Hz, 1H) 6.34-6.90 (br s, 1H).


Step 2 Synthesis of 3-bromo-4-[(4-methoxyphenyl)methoxy]-5-(trifluoromethyl)benzonitrile



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To a solution of 3-bromo-4-hydroxy-5-(trifluoromethyl)benzonitrile (6.4 g, 24 mmol) in acetone (64 mL) were added potassium carbonate (6.7 g, 48 mmol), tetrabutylammonium iodide (1.8 g, 4.8 mmol) and 1-(chloromethyl)-4-methoxy-benzene (5.7 g, 36 mmol). The reaction was heated at reflux. After 4 h the reaction was worked up with water and ethyl acetate were added and the phases separated. The organic phase was dried over magnesium sulphate and concentrated in vacuo. Purification by column chromatography (10% ethyl acetate in cyclohexane) afforded 3-bromo-4-[(4-methoxyphenyl)methoxy]-5-(trifluoromethyl)benzonitrile (77%, 7.18 g)



1H NMR (400 MHz, chloroform) δ ppm 8.05-8.15 (m, 1H) 7.90 (d, J=1.59 Hz, 1H) 7.40-7.54 (m, 2H) 6.91-6.99 (m, 2H) 5.09 (s, 2H) 3.84 (s, 3H).


Step 3 Synthesis of 4-[(4-methoxyphenyl)methoxy]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzonitrile



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To a stirring solution of 3-bromo-4-[(4-methoxyphenyl)methoxy]-5-(trifluoromethyl)benzonitrile (2.23 g, 5.77 mmol) and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.61 g, 8.66 mmol) in tetrahydrofuran (46.2 mL) at 0° C. was added isopropylmagnesium chloride Lithium chloride complex (1.3M in THF) (5.3 mL, 6.93 mmol) (added in a steady stream); after 45 min the reaction was quenched with sat. aq. ammonium chloride solution and extracted into ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated in vacuo to afford a 3.4:1 ratio of 4-[(4-methoxyphenyl)methoxy]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzonitrile and deborylated 4-[(4-methoxyphenyl)methoxy]-3-(trifluoromethyl)benzonitrile (3.13 g).



1H NMR (400 MHz, chloroform) δ ppm 8.24-8.34 (m, 1H) 7.93-8.05 (m, 1H) 7.43-7.48 (m, 2H) 6.90-6.95 (m, 2H) 5.09 (s, 2H) 3.83 (s, 3H) 1.39 (s, 12H).


Step 4 Synthesis of 4-hydroxy-3-thiazol-2-yl-5-(trifluoromethyl) benzonitrile



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2-bromothiazole (0.046 g, 0.28 mmol), 4-[(4-methoxyphenyl)methoxy]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzonitrile (crude material, assumed ˜60% purity, 0.17 g, 0.24 mmol), SPhos Pd G3 (0.019 g, 0.024 mmol), tripotassium phosphate trihydrate (0.076 g, 0.35 mmol), cyclopentyl methyl ether (1.7 mL) and water (0.85 mL) were combined in a microwave vial. The vial was sealed and heated in the microwave at 120° C. for 10 mins. The sample was then diluted with water/ethyl acetate, the phases were separated, and the organic phase was dried over magnesium sulphate and concentrated in vacuo. 2,2,2-trifluoroacetic acid (0.5 mL) was added to the residue and the mixture was stirred for 5 min; water and ethyl acetate were added, the phases were separated and the organic phase was dried over magnesium sulphate and concentrated in vacuo. The cured mixture was purified by RPHPLC to afford 4-hydroxy-3-thiazol-2-yl-5-(trifluoromethyl)benzonitrile (0.0142 g, 22%).



1H NMR (400 MHz, chloroform) δ ppm 8.11 (d, J=1.96 Hz, 1H) 7.92 (d, J=3.42 Hz, 1H) 7.89 (d, J=1.34 Hz, 1H) 7.50 (d, J=3.30 Hz, 1H)


The following tables provide examples of herbicidal compounds of the present invention. Mass spectrometry data was collected on a Waters Acquity UPLC-MS using a Sample Organizer with Sample Manager FTN, H-Class QSM, Column Manager, 2× Column Manager Aux, Photodiode Array (Wavelength range (nm): 210 to 400), ELSD and QDa mass spectrometer. Ionisation method: Electrospray positive and negative: Cone (V) 20.00, Source Temperature (° C.) 120, Cone Gas Flow (L/Hr.) 50. Mass range (Da): positive 100 to 800, negative 115 to 800.


Method 1) analysis was conducted using a four-minute run time, according to the following gradient table at 40° C.:


Waters Acquity UPLC HSS T3 (1.8 μm 2.1×50 mm).















Time (mins)
Solvent A (%)
Solvent B (%)
Flow (ml/mn)


















0.00
95.0
5.0
0.6


3.00
0.0
100
0.6


3.50
0.0
100
0.6


3.55
95.5
5.0
0.6


4.10
95.5
5.0
0.6









Solvent A: H2O with 0.05% TFA Solvent B: CH3CN with 0.05% TFA


Method 2) Analysis was conducted using a two-minute run time, according to the following gradient table at 40° C.:


Waters Acquity UPLC HSS T3 (1.8 μm 2.1×30 mm).















Time (mins)
Solvent A (%)
Solvent B (%)
Flow (ml/mn)


















0.00
95.0
5.0
0.7


1.75
0.0
100
0.7


1.76
0.0
100
0.7


2.00
0.0
100
0.7


2.01
95.5
5.0
0.7


2.11
95.5
5.0
0.7









Solvent A: H2O with 0.05% TFA Solvent B: CH3CN with 0.05% TFA









TABLE 1







Examples of herbicidal compounds of the present invention.














Retention
MH +/ M − H


Compound
Structure

1HNMR

Time
(observed)





1.001


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(DMSO-d6) δ 8.93 (s, 1H), 8.27 (s, 1H), 8.11-8.10 (m, 2H)







1.002


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(DMSO-d6) δ 11.34 (s, 1H), 7.95 (s 1H), 7.84 (d, 1H), 7.53-7.49 (m, 1H), 7.44-7.41 (m, 2H), 7.27-7.22 (m, 1H).







1.003


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(DMSO-d6) δ 11.16 (s, 1H), 7.85-7.82 (dd, 1H), 7.67 (s, 1H), 7.52-7.41 (m, 3H), 7.25-7.21 (m, 1H)







1.004


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(DMSO-d6) δ 10.68 (s, 1H), 8.00 (d, 1H), 7.75 (d, 1H), 7.52-7.47 (q, 1H), 7.40-7.37 (m, 2H), 7.26-7.22 (m, 1H)







1.005


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(DMSO-d6) δ 10.89 (s, 1H), 8.11-8.10 (d, 1H), 7.97-7.96 (d, 1H), 7.56-7.50 (m, 1H), 7.37-7.25 (m, 3H).







1.006


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(DMSO-d6) 8.48 (d, 1H), 8.24 (d, 1H), 2.62 (s, 3H)







1.007


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(CDCl3) δ 11.59 (s, 1H), 7.80 (s, 1H), 7.26 (s, 1H), 7.03 (s, 1H), 4.09 (3H, s).







1.008


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2.65
408.1





1.009


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2.49
371.1





1.010


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2.16
325.0





1.011


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2.06
345.0





1.012


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1.99
325.0





1.013


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2.08
309.9





1.014


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2.13
309.0





1.015


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2.47
338.1





1.016


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1.94
305.0





1.017


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1.12
274.99





1.018


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2.36
337.1





1.019


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2.34
351.0





1.020


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1.4
325.0





1.021


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1.85
310.0





1.022


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2.32
322.0





1.023


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1.64
278.0





1.024


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2.17
347.1





1.025


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2.45
318.1





1.026


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2.33
338.1





1.027


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2.51
358.1





1.028


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2.52
314.1





1.029


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2.31
339.0





1.030


embedded image



2.41
320.2





1.031


embedded image



2.39
288.6





1.032


embedded image



2.17
315.1





1.033


embedded image



2.09
297.1





1.034


embedded image



2.46
326.0





1.035


embedded image


(DMSO-d6) δ 14.36 (s, 1H), 9.19 (s, 2H), 8.68 (d, 1H), 8.32 (d, 1H)







1.036


embedded image










1.037


embedded image










1.038


embedded image










1.039


embedded image


(DMSO-d6) δ 7.98 (s,1H), 7.58-7.48 (m, 3H), 7.28-7.24 (m, 1H).







1.040


embedded image


(DMSO-d6) δ 8.31 (s, 1H), 7.73 (t, 2H), 7.53 (q, 1H), 7.29 (td, 1H).







1.041


embedded image



1.42
386.4





1.042


embedded image



1.41
360.2





1.043


embedded image



1.35
352.1





1.044


embedded image



0.87
276.2





1.045


embedded image



1.37
326.1





1.046


embedded image


(CDCl3) δ 7.85 (d, 1H), 7.53 (d, 1H), 7.50-7.46 (m, 1H), 7.27-7.18 (m 3H), 6.20 (bs, 1H).







1.047


embedded image



1.31
274.2





1.048


embedded image



2.27
292.2





1.049


embedded image



0.98
317.2





1.050


embedded image



2.5
323.2





1.051


embedded image



1.37
306.2





1.052


embedded image



2.26
293.1





1.053


embedded image



1.23
299.2





1.054


embedded image



1.41
308.2





1.055


embedded image



1.36
288.2





1.056


embedded image



2.73
352.1





1.057


embedded image



2.61
352.3





1.058


embedded image



1.45
342.2





1.059


embedded image



1.42
306.2





1.060


embedded image



1.44
342.2





1.061


embedded image



1.43
352.1





1.062


embedded image



1.28
292.2





1.063


embedded image



1.33
308.1





1.064


embedded image



1.38
338.2





1.065


embedded image



2.29
353.1





1.066


embedded image



1.39
358.2





1.067


embedded image



1.76
300.0





1.068


embedded image



1.34
324.2





1.069


embedded image



1.46
322.2





1.070


embedded image



0.93
293.1





1.071


embedded image



1.28
322.1





1.072


embedded image



1.3
391.2





1.073


embedded image



1.42
342.1





1.074


embedded image



1.44
302.1





1.075


embedded image



1.41
320.2





1.076


embedded image



1.39
318.2





1.077


embedded image










1.078


embedded image



1.98
307.0





1.079


embedded image



2.24
293.8





1.080


embedded image



2.39
306.1





1.081


embedded image



2.23
320.1





1.082


embedded image



2.53
322.0





1.083


embedded image



2.11
343.0





1.084


embedded image



2.50
302.0





1.085


embedded image



2.54
386.1





1.086


embedded image



2.08
323.0





1.087


embedded image



1.82
350.0





1.088


embedded image



2.14
321.0





1.089


embedded image



1.96
333.0





1.090


embedded image



2.20
317.1





1.091


embedded image



2.54
322.0





1.092


embedded image



1.82
352.0





1.093


embedded image



2.39
306.0





1.094


embedded image



1.90
303.0





1.095


embedded image



2.27
324.0





1.096


embedded image



2.47
359.98





1.097


embedded image



2.06
343.0





1.098


embedded image



1.82
300.1





1.099


embedded image



2.24
320.0





1.100


embedded image



2.17
316.1





1.101


embedded image



1.76
313.0





1.102


embedded image



2.37
320.9





1.103


embedded image



2.51
314.0





1.104


embedded image



2.35
327.9





1.105


embedded image



2.57
374.0





1.106


embedded image



2.60
374.0





1.107


embedded image



2.63
316.0





1.108


embedded image



2.49
332.0





1.109


embedded image



2.57
339.9





1.110


embedded image



2.49
356.0





1.111


embedded image



2.26
340.9





1.112


embedded image



2.29
310.0





1.113


embedded image



2.28
341.0





1.114


embedded image



2.60
388.0





1.115


embedded image



2.51
303.9





1.116


embedded image



2.34
365.1





1.117


embedded image



2.45
324.0





1.118


embedded image



1.80
292.0





1.119


embedded image



2.63
316.1





1.120


embedded image



2.38
338.0





1.121


embedded image



2.49
332.0





1.122


embedded image



2.44
370.1





1.123


embedded image



2.38
318.0





1.124


embedded image



2.45
358.0





1.125


embedded image



2.19
318.0





1.126


embedded image



2.31
367.0





1.127


embedded image



2.35
337.9





1.128


embedded image



2.23
303.9





1.129


embedded image



2.27
334.0





1.130


embedded image



2.29
309.9





1.131


embedded image



2.43
299.9





1.132


embedded image



2.73
330.2





1.133


embedded image



2.33
293.9





1.134


embedded image



2.15
279.9





1.135


embedded image



2.15
280.2





1.136


embedded image



2.26
313.9





1.137


embedded image



2.24
309.9





1.138


embedded image



2.36
313.9





1.139


embedded image



2.41
313.9





1.140


embedded image



2.17
299.1





1.141


embedded image



2.23
337.1





1.142


embedded image



2.36
282.1





1.143


embedded image



2.31
302.0





1.144


embedded image



2.21
305.1





1.145


embedded image



2.14
287.1





1.146


embedded image



2.34
312.1





1.147


embedded image



2.35
322.2





1.148


embedded image



2.45
314.1





1.149


embedded image



2.36
310.2





1.150


embedded image



2.30
310.1





1.151


embedded image



2.53
346.1





1.152


embedded image



2.05
293.2





1.153


embedded image



1.92
301.1





1.154


embedded image



1.96
340.1





1.155


embedded image



2.48
342.1





1.156


embedded image



2.34
331.1





1.157


embedded image


(CDCl3) δ = 8.11 (d, 1 H) 7.92 (d, H) 7.89 (d, 1H) 7.50 (d, 1H)
1.61
269.0





1.158


embedded image



2.20
331.1





1.159


embedded image



2.21
311.1





1.160


embedded image



2.43
314.1





1.161


embedded image



2.38
355.2





1.162


embedded image



2.43
294.1





1.163


embedded image



2.31
310.1





1.164


embedded image



2.15
331.1





1.165


embedded image



2.51
346.2





1.166


embedded image



1.50
293.1





1.167


embedded image



2.26
315.1





1.168


embedded image



1.88
307.1





1.169


embedded image



2.33
282.1





1.170


embedded image



2.12
299.1





1.171


embedded image



2.13
332.1





1.172


embedded image



1.98
281.1





1.173


embedded image



1.91
280.1





1.174


embedded image



2.20
268.1





1.175


embedded image



2.08
311.1





1.176


embedded image



2.41
312.1





1.177


embedded image



2.35
341.1





1.178


embedded image



2.27
306.1





1.179


embedded image



2.07
297.1





1.180


embedded image



2.29
280.1





1.181


embedded image



2.24
334.2





1.182


embedded image


(CDCl3) δ = 7.92- 7.86 (m, 1H), 7.69 (s, 1H), 7.17-7.11 (m, 2H)







1.183


embedded image


(CDCl3) δ = 7.91 (d, 1H), 7.72 (d, 1H), 7.05- 6.94 (m, 3H)







1.184


embedded image


(CDCl3) δ = 10.52 (bs, 1H), 8.89 (s, 1H), 8.05 (d, 1H), 7.98 (d, 1H)







1.185


embedded image


(CDCl3) δ = 8.11 (d, 1H) 7.92 (d, H) 7.89 (d, 1H) 7.50 (d, 1H)







1.186


embedded image


(CDCl3) δ = 7.69- 7.74 (m, 2 H) 7.79 (d, 1H) 7.96 (d, 1H) 12.79 (s, 1H).







1.187


embedded image


(CDCl3) δ = 12.24 (s. 1H) 7.94 (s, 1H) 7.84 (s, 2H) 2.32 (s, 3H)







1.188


embedded image


(CDCl3) δ = 12.68 (m, 1H), 8.07 (s, 1H), 7.82-7.80 (m, 1H), 7.78-7.77 (m, 2H)







1.189


embedded image


(CDCl3) δ = 12.02 (bs, 1H), 8.16 (d, 1H), 7.92 (d, 1H), 7.88 (d, 1H), 6.94 (d, 1H).







1.190


embedded image


(CDCl3) δ = 12.32 (s, 1H) 8.40 (s, 1H), 8.06 (s, 1H), 7.90 (d, 1H) 7.87 (d, 1H)







1.191


embedded image


(DMSO-d6) δ = 8.53 (d, 1H) 8.11 (d, 1H), 7.53 (m, 1H), 7.40 (m, 2H) 7.28 (m, 1H)







1.192


embedded image


(DMSO-d6) δ = 10.02 (s, 1H), 7.97- 8.00 (d, J = 8.0 HZ, 1H), 7.63-7.64 (d, J = 4.0 HZ, 1H), 7.46-7.52 (q, J = 4.0 HZ, 1H), 7.34-7.37 (m, J = 4.0 HZ, 2H), 7.20-7.25 (t, J = 4.0 HZ, 1H), 7.02-7.09 (dd, J = 72.0 HZ, 1H), 5.94-5.99 (d, J = 4.0 HZ, 1H), 5.40-5.43 (d, J =














4.0 HZ, 1H).















1.193


embedded image


(DMSO-d6) δ = 10.66 (s, 1H), 7.93 (d, 1H), 7.87 (d, 1H), 7.49-7.55 (m, 1H), 7.33-7.38 (m, 2H), 7.05-7.28 (m, 2H)







1.194


embedded image


(DMSO-d6) δ = 8.30 (d, 1H), 8.01 (d, 1H), 7.46-7.55 (q, J = 8.0 HZ, 1H), 7.36-7.42 (q, J = 8.0 HZ, 2H), 7.21- 7.29 (t, J = 8.0 HZ, 1H







1.195


embedded image


(DMSO-d6) δ = 8.10-8.11 (d, J = 4.0 HZ, 1H), 8.00 (d, 1H), 7.50-7.55 (q, J = 4.0 HZ, 1H), 7.36-7.43 (q, J = 8.0 HZ, 2H), 7.24-7.29 (t, J = 4.0 HZ, 1H), 3.35 (s, 3H)







1.196


embedded image


(DMSO-d6) δ = 10.02-9.98 (s, 1H), 7.60-7.59 (d, J = 4.0 HZ, 1H)7.54(d, 1H), 7.46-7.52 (q, J = 8.0 HZ, 1H), 7.33-7.36 (t, J = 4.0 HZ, 2H), 7.20-7.25 (t, J = 8.0 HZ, 1H), 2.47 (s, 3H)







1.197


embedded image



3.25
285.2





1.198


embedded image










1.199


embedded image



2.62
284.3





1.200


embedded image










1.201


embedded image



2.73
300.3





1.202


embedded image










1.203


embedded image










1.204


embedded image










1.205


embedded image



2.83
335.2





1.206


embedded image



3.15
284.3





1.207


embedded image



3.29
333.2





1.208


embedded image



2.73
265.2





1.209


embedded image



3.19
282.2





1.210


embedded image










1.211


embedded image










1.212


embedded image










1.213


embedded image










1.214


embedded image



2.81
335.2





1.215


embedded image










1.216


embedded image










1.217


embedded image



3.49
338.2





1.218


embedded image










1.219


embedded image










1.220


embedded image










1.221


embedded image










1.222


embedded image



2.60
303.2





1.223


embedded image



3.06
319.2





1.224


embedded image










1.225


embedded image



3.60
338.2





1.226


embedded image



2.79
294.3





1.227


embedded image



3.21
303.7





1.228


embedded image



2.44
270.2





1.229


embedded image



2.87
321.2





1.230


embedded image



2.92
268.2





1.231


embedded image










1.232


embedded image



3.48
321.2





1.233


embedded image










1.234


embedded image



2.74
294.3





1.235


embedded image



3.21
303.2





1.236


embedded image










1.237


embedded image



3.31
337.2





1.238


embedded image










1.239


embedded image










1.240


embedded image










1.241


embedded image



2.08
254.2





1.242


embedded image










1.243


embedded image



3.15
303.2





1.244


embedded image



2.37
268.2





1.245


embedded image



3.78
295.3





1.246


embedded image



3.60
301.7





1.247


embedded image



2.35
304.2





1.248


embedded image



3.06
297.2





1.249


embedded image



2.85
294.2





1.250


embedded image



3.26
337.6





1.251


embedded image










1.252


embedded image



3.04
292.2





1.253


embedded image










1.254


embedded image



3.12
308.3





1.255


embedded image










1.256


embedded image










1.257


embedded image



3.45
297.2





1.258


embedded image



2.21
298.2





1.259


embedded image



3.85
327.7





1.260


embedded image



3.06
253.2





1.261


embedded image



3.63
335.2





1.262


embedded image










1.263


embedded image



3.33
297.2





1.264


embedded image



2.25
331.0





1.265


embedded image


δ = 7.56-7.43 (m, 2H), 7.28-7.12 (m, 3H), 6.34 (s, 1H)







1.266


embedded image


δ = 7.61 (s, 1H), 7.45 (m, 1H), 7.26- 7.24 (m, 2H), 7.14 (m, 1H), 6.36 (s, 1H)







1.267


embedded image


δ = 7.75 (s, 1H), 7.48 (m, 1H), 7.30 (m, 2H), 7.18 (m, 1H), 6.74 (s, 1H)







1.268


embedded image


δ = 7.55 (s, 1H), 7.43 (m, 1H), 7.27- 7.25 (m, 2H), 7.11 (m, 1H), 6.28 (s, 1H), 2.68 (s, 3H)
















TABLE 2







Examples of herbicidal compounds of the present invention.









Compound
Structure

1HNMR






2.001


embedded image


(DMSO-d6) δ 8.15 − 8.13 (d, 1H), 7.95 (s, 1H), 7.58 − 7.53 (q, 1H), 7.35 − 7.29 (m, 3H), 2.24 (s, 3H)





2.002


embedded image


(DMSO-d6) δ 8.46 (s, 1H), 8.39 (s, 1H), 7.58 − 7.52 (q, 1H), 7.40 − 7.30 (m, 3H), 2.10 (s, 3H).





2.003


embedded image


(DMSO-d6) δ 8.47 (s, 1H), 8.38 (s, 1H), 7.57 − 7.52 (q, 1H), 7.35 − 7.29 (m, 3H), 2.66 − 2.50 (m, 1H), 0.96 (brs, 6H).





2.004


embedded image


(DMSO-d6) δ 8.47 (s, 1H), 8.35 (d, 1H), 7.57 − 7.52 (q, 1H), 7.34 − 7.25 (m, 3H), 1.02 (s, 9H).





2.005


embedded image


(DMSO-d6) δ 8.30 (d, 1H), 8.02 (d, 1H), 7.56 − 7.50 (q, 1H), 7.33 − 7.23 (m, 3H), 1.12 (s, 9H).





2.006


embedded image


(DMSO-d6) δ 8.30 (d, 1H), 8.03 (d, 1H), 7.56 − 7.51 (q, 1H), 7.33 − 7.25 (m, 3H), 2.77 − 2.67 (m, 1H), 1.06 − 1.04 (d, 6H)









Biological Examples

Seeds of a variety of test species are sown in standard soil in pots (Ipomoea hederacea (IPOHE), Abutilon theophrasti (ABUTH), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA)). After 8 days cultivation under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS 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 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%).









TABLE B1







Post-emergence Test












Compound
IPOHE
ABUTH
AMARE
ECHCG
SETFA















1.001
1
5
4

4


1.002
5
4
5
3
2


1.004
1
5
5
3
3


1.005
5
5
4
4
1


1.007
3
2
5

1


1.008
2
2
5

4


1.009
2
2
4

2


1.027
3
4
5

4


1.032
3
4
5

4


1.034

4
4




1.036
3
2
5
3
4


1.044
1
5
5
2
3


1.045
1
3
5
1
1


1.046
3
5
5
2
3


1.047
3
5
5
1
2


1.048
2
5
5
2
2


1.052
1
5
5
1
3


1.053
3
2
5
1
1


1.054
2
5
5
3
2


1.058
2
1
5
2
3


1.060
2
4
5
1
1


1.061
3
3
5
1
1


1.067
2
3
1
2
2


1.130
2
5
5
1
1


1.134
4
4
4
1
1


1.135
5
5
2
1
1


1.145*
3
1
1
1
1


1.148*
4
1
3
1
1


1.151
3
1
5
1
1


1.158
2
1
4
1
1


1.160
2
1
5
1
1


1.162
3
1
2
1
1


1.165
4
1
3
1
1


1.180
3
3
1
1
1


1.182
5
4
5
1
1


1.183
2
4
5
2
2


1.186
4
5
2
1
1


1.187
1
1
5
1
1


1.190
1
1
3
1
1


1.191
3
4
5
2
2


1.194
3
3
2
1
2


1.225


5




1.250
5
2
5
2
2


1.259
5
3
5
2
2


2.002
5
5
5
4
1


2.006
1
4
3
1
1





*Applied at 500 gai/ha





Claims
  • 1. A compound of Formula (I):
  • 2. A compound according to claim 1, wherein R1 is hydrogen.
  • 3. A compound according to claim 1 or claim 2, wherein R2 is selected from the group consisting of F, Cl, Br, —CF3 and —OCF3.
  • 4. A compound according to claim 3, wherein R2 is CF3.
  • 5. A compound according to any one of the previous claims, wherein R3 is hydrogen.
  • 6. A compound according to any one of claims 1 to 5, wherein R4 is phenyl.
  • 7. A compound according to any one of claims 1 to 5, wherein R4 is an optionally substituted five or six-membered heteroaryl selected from the group consisting of furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl.
  • 8. A compound according to claim 7, wherein R4 is an optionally substituted five or six-membered heteroaryl selected from the group consisting of pyrazolyl, thiazolyl and thiophenyl.
  • 9. A compound according to claim 8, wherein R4 is pyridyl or pyrazolyl.
  • 10. A compound according to any one of the previous claims, wherein X is CH.
  • 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 a composition comprising a weed controlling amount of a compound of Formula (I):
  • 15. Use of a compound of a compound of Formula (I):
Priority Claims (1)
Number Date Country Kind
2000011.3 Jan 2020 GB national
PCT Information
Filing Document Filing Date Country Kind
PCT/EP2020/087853 12/24/2020 WO