Herbicidal compounds

Abstract

The present invention relates to compounds having formula (I), wherein Q, R 2 , R 3 and R 4 is as defined herein. The present invention further relates to compositions comprising said compounds, and methods of controlling weeds using said compounds and / or compositions.

Description

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

[0002] N-(tetrazolyl-5-yl)- and N-(1,3,4-oxadiazol-2-yl)arylcarboxamides are disclosed, for example, in WO 2012 / 028579 and WO 2012 / 126932, respectively. The present invention relates to novel arylcarboxamides.

[0003] Therefore, according to the present invention, there is provided a compound having the formula (I):

[0004]

[0005] or an agronomically acceptable salt thereof,

[0006] in:-

[0007] Q is selected from the group consisting of: Q1 and Q2:

[0008]

[0009] R 1 Selected from the group consisting of C1-C4 alkyl-, C1-C4 haloalkyl-, C1-C4 alkoxy-C1-C4 alkyl- and C1-C4 haloalkoxy-C1-C4 alkyl-;

[0010] R 2 Selected from the group consisting of halogen, C1-C6 alkyl-, C1-C3 alkoxy-, C1-C6 haloalkyl-, C1-C3 haloalkoxy- and -S(O) p C1-C6 alkyl;

[0011] R 3 Selected from the group consisting of C1-C6 alkyl-, C3-C6 cycloalkyl- and C1-C6 haloalkyl-;

[0012] R 4 is a C1-C6 haloalkyl group;

[0013] and

[0014] p is 0, 1 or 2.

[0015] C1-C6 alkyl and C1-C4 alkyl include, 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).

[0016] Halogen (or halo) encompasses fluorine, chlorine, bromine or iodine. The above applies correspondingly to halogen in other definition contexts, such as haloalkyl.

[0017] The C1-C6 alkoxy C1-C3 alkyl- includes, for example, methoxyethyl- and ethoxymethyl-.

[0018] As used herein, C3-C6 cycloalkyl refers to a stable monocyclic group which is saturated and contains 3 to 6 carbon atoms. 3-6 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0019] C1-C6 haloalkyl includes, for example, fluoromethyl-, difluoromethyl-, trifluoromethyl-, chloromethyl-, dichloromethyl-, trichloromethyl-, 2,2,2-trifluoroethyl-, 2-fluoroethyl-, 2-chloroethyl-, pentafluoroethyl-, 1,1-difluoro-2,2,2-trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl-, heptafluoro n-propyl and perfluoro n-hexyl.C1-C4 haloalkyl includes, for example, fluoromethyl-, difluoromethyl-, trifluoromethyl-, chloromethyl-, dichloromethyl-, trichloromethyl-, 2,2,2-trifluoroethyl-, 2-fluoroethyl-, 2-chloroethyl-, pentafluoroethyl-, 1,1-difluoro-2,2,2-trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl- and heptafluoro n-propyl-.

[0020] C1-C6Alkyl-S-(alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0021] C1-C6Alkyl-S(O)-(alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0022] C1-C6Alkyl-S(O)2-(Alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0023] In one embodiment of the present invention, a compound of formula (I) is provided (wherein Q is Q1) (hereinafter shown as a compound of formula (Ia)). In another embodiment of the present invention, a compound of formula (I) is provided (wherein Q is Q2) (hereinafter shown as a compound of formula (Ib)).

[0024]

[0025] In a preferred embodiment of the present invention, R 1 is selected from the group consisting of: C1-C4 alkyl- (preferably methyl, ethyl or n-propyl), C1-C4 haloalkyl- (2,2-difluoroethyl or 2,2,2-trifluoroethyl) and C1-C4 alkoxy-C1-C4 alkyl- (preferably methoxyethyl-). In a more preferred embodiment, R 1 is selected from the group consisting of methyl, ethyl and n-propyl. In a particularly preferred embodiment of the present invention, R 1 It's methyl.

[0026] In one embodiment of the present invention, R 2 Selected from the group consisting of: halogen (preferably chlorine), C1-C6 alkyl- (preferably methyl), C1-C3 alkoxy- (preferably methoxy-), C1-C6 haloalkyl- (preferably -CF3), C1-C3 haloalkoxy- (preferably CF3O-) and -S(O) p C1-C6 alkyl (preferably -SO2Me). In particularly preferred embodiments, R 2 It's chlorine.

[0027] In one embodiment of the present invention, R 3 is selected from the group consisting of: C1-C6 alkyl- (preferably methyl or ethyl), C3-C6 cycloalkyl (e.g. cyclopropyl) and C1-C6 haloalkyl- (e.g. -CF3). In a preferred embodiment of the present invention, R 3 is methyl or ethyl, most preferably methyl.

[0028] In a preferred embodiment of the present invention, R 4 is selected from the group consisting of: CF3-, CHF2-, CH3CF2-, CF3CH2-, CF2HCF2- and CF3CHFCF2-. In a more preferred embodiment, R 4 It is CF3- or CHF2-, most preferably CF3-.

[0029] The present invention also includes agronomically acceptable salts, and compounds with formula (I) can form these salts with amines (e.g. ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium salt bases. Among the alkali metal and alkaline earth metal hydroxides, oxides, alcoholates and bicarbonates and carbonates used as salt-forming substances, emphasis is placed on hydroxides, alcoholates, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium, magnesium and calcium. Corresponding trimethyl sulfonium salts can also be used.

[0030] The compound with formula (I) according to the present invention can be used as herbicide by itself, but usually use preparation adjuvant (such as carrier, solvent and surfactant (SFA)) to be mixed with herbicidal composition.Therefore, the present invention further provides herbicidal composition, which comprises herbicidal compounds of the present invention and agriculturally acceptable preparation adjuvant.Composition can be in the form of concentrate, dilutes these concentrates before use, although ready-to-use composition can also be made.Usually, final dilution is carried out with water, but water can be substituted or used in addition to water, such as liquid fertilizer, micronutrient, biological organism, oil or solvent.

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

[0032] These compositions may be selected from a variety of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th edition, 1999. These include dustable powders (DP), soluble powders (SP), water-soluble granules (SG), water-dispersible granules (WG), wettable powders (WP), granules (GR) (slow-release or fast-release), soluble concentrates (SL), oil-miscible liquids (OL), ultra-low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil-in-water (EW) and water-in-oil (EO)), microemulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. In any case, the formulation type chosen will depend on the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

[0033] Dustable powders (DP) can be prepared by mixing a compound of formula (I) with one or more solid diluents (e.g., natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earth, calcium phosphate, calcium and magnesium carbonates, sulfur, lime, flour, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

[0034] Soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants or a mixture of said agents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0035] Wettable powders (WP) can be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably, one or more dispersants, and optionally, one or more suspending agents to facilitate dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water dispersible granules (WG).

[0036] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material such as pumice, attapulgite clay, Fuller's earth, kieselguhr, diatomaceous earths or corn cob meal, or from preformed blank particles by adsorbing a compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicates, mineral carbonates, sulfates or phosphates and, if necessary, drying. Agents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and adhesives (such as polyvinyl acetate, polyvinyl alcohol, dextrins, sugars and vegetable oils). One or more other additives may also be included in the granules (e.g., emulsifiers, wetting agents or dispersants).

[0037] Dispersible concentrates (DC) can be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain a surfactant (for example to improve water dilution or to prevent crystallization in a spray tank).

[0038] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (e.g. alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (e.g. cyclohexanone or methylcyclohexanone) and alcohols (e.g. benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (e.g. N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (e.g. C8-C 10 The EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

[0039] The preparation of EWs involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it can be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution into water containing one or more SFAs under high shear to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents having low solubility in water.

[0040] Microemulsion (ME) can be prepared in the following manner: water is mixed with a blend of one or more solvents and one or more SFAs to spontaneously produce a thermodynamically stable isotropic liquid formulation. The compound with formula (I) is initially present in water or in a solvent / SFA blend. The suitable solvent used in ME includes those used in EC or EW described above. ME can be an oil-in-water system or an oil-in-water system (which system exists can be measured by conductivity measurement) and can be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. ME is suitable for dilution in water, remains as a microemulsion or forms a conventional oil-in-water emulsion.

[0041] Suspension concentrates (SC) may include aqueous or non-aqueous suspensions of finely dispersed insoluble solid particles of a compound of formula (I). SC may be prepared by ball milling or bead milling a solid compound of formula (I) with one or more dispersants in a suitable medium to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the rate of particle settling. Alternatively, a compound of formula (I) may be dry-milled and added to water containing a previously described medicament to produce a desired end product.

[0042] Aerosol formulations comprise a compound of formula (I) and a suitable propellant (e.g. n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g. water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized manual spray pump.

[0043] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, but with an additional polymerization stage, so that an aqueous dispersion of oil droplets is obtained, wherein each oil droplet is wrapped by a polymer shell and contains a compound with formula (I) and optionally a carrier or diluent for the oil droplet. The polymer shell can be produced by an interfacial polycondensation reaction or by a coacervation procedure. These compositions can provide controlled release of compounds with formula (I) and they can be used for seed treatment. Compounds with formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0044] The composition may contain one or more additives to improve the biological performance of the composition, for example by improving wettability, retention or distribution on a surface; rain resistance on a treated surface; or absorption or flow of a compound of formula (I). Such additives include surfactants (SFAs), oil-based spray additives, such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), and blends of these with other bioenhancement adjuvants (ingredients that can assist or modify the action of a compound of formula (I)).

[0045] The wetting agents, dispersants and emulsifiers may be SFAs of the cationic, anionic, amphoteric or nonionic type.

[0046] Suitable SFAs of the cationic type include quaternary ammonium compounds (eg cetyltrimethylammonium bromide), imidazolines and amine salts.

[0047] Suitable anionic SFAs include alkali metal salts of fatty acids, salts of fatty sulfuric acid monoesters (e.g. sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalenesulfonate and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laureth-3-sulfate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphates (products from the reaction of one or more fatty alcohols with phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), for example the reaction of lauryl alcohol with tetraphosphoric acid; alternatively these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates and lignosulfonates.

[0048] Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

[0049] Suitable SFAs of the nonionic type include condensation products of alkylene oxides (e.g. ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) with fatty alcohols (e.g. oleyl alcohol or cetyl alcohol) or with alkylphenols (e.g. 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; monoesters (e.g. fatty acid polyethylene glycol esters); amine oxides (e.g. lauryl dimethyl amine oxide); and lecithin.

[0050] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0051] The herbicidal compounds of the present invention can also be used in mixtures 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), bennitroprop-butyl, ametryn, amitriptyline, aminopyralid, cypermethrin, atrazine, flubutyric acid-M, benzylsulfuron-methyl (including benzylsulfuron-methyl), bentazon, bicyclic pyrone, bialaphos, bispyribac-sodium, bixlozone, herbicide, bromoxynil, butachlor, flubutyric acid-butyl, mesotrione (including mesotrione-ethyl), chlorsulfuron (including chlorsulfuron-methyl), chlorsulfuron (including chlorsulfuron-ethyl), chlorotoluron, chlorsulfuron, cyproconazole, clacyfos, clethodim, clodinafop-butyl (including clodinafop-ethyl), chlorsulfuron, chlorsulfuron, cyproconazole, clacyfos, clethodim, clodinafop-butyl (including clodinafop-ethyl), chlorsulfuron, chlorsulfuron, cyproconazole, clacyfos, clethodim, clodinafop-butyl (including clodinafop-butyl), chlorsulfuron, ... esters), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, dichlorvos, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), bisclostrobin, fluazifop-butyl, fluazifop-butyl, dimethoate, dimethoate-s-propyl, diquat, diuron, ethosulfuron, oxadiazine (including oxadiazine-ethyl), benzylpyridinium chloride ( fenoxasulfone), fenquinotrione, tetrazopyralid, fluazifop-butyl, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop-butyl (including fluazifop-butyl-butyl), flufenoxasulfuron (including flufenoxasulfuron-sodium), flufenacet, fluazifop-butyl, fluometuron, flufenoxasulfuron (including flufenoxasulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron, glufosinate (including its ammonium salts), glyphosate (including its hydrazine, isopropyl ammonium and potassium salts), halauxifen (including halauxifen-methyl), haloxaline (including haloxaline-methyl), hexazinone, hydantocidin, imazamox, imazamox, imazamox, indazine fluazifop, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), iobenzonitrile, isoproturon, isoxathiapiprolon, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor,Methozolin, isopropylamine, sulfamethoxam, metribuzin, metsulfuron, propamide, nicosulfuron, norfaxan, oxadiazine, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, bendisulfuron, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, promethazine, propanil, cypermethrin, propyrisulfuron, propyrisulfuron, promethazine, prosulfuron, pyraflufen (including pyraflufen-ethyl), pyrasulfuron, pyrasulfuron, pyrasulfuron, pyrimidin, pyrimisulfan, pyroxasulfone, pyrasulfuron amine, quinclorac, clomeclorac, quizalofop-ethyl (including quizalofop-ethyl and quizalofop-P-tefuryl), sulfamethoxam, pyrimidine, sethoxydim, simazine, s-isopropylamine, sulfentrazone, sulfentrazone, sulfentrazone, buthiuron, tefuridine, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, benpyrazone, trimethoprim, triafamone, wild wheat chlorpyrifos, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), triclopyr , trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, trifluralin, ethyl 2-[[3-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]-2-pyridinyl]oxy]acetate, ethyl 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-carboxylate, ethyl 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolin-2-one, 4-hydroxy-1,5-dimethyl-3 -[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolin-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 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]- 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-dimethoxyphenyl)-3-oxo-pyridazine-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)-3-oxo-pyridazine-4-carbonyl] 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-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 its agrochemically acceptable esters, such as 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester).

[0052] Mixtures of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

[0053] The compounds of formula (I) can also be used in a mixture with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

[0054] The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1:100 to 1000:1.

[0055] These mixtures can advantageously be used in the abovementioned formulations ("active ingredient" in this case relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0056] Compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include fenthiocarb, cloquintocet-mexyl (including cloquintocet-mexyl), cyclopropylsulfonamide, dichloropropene, fenthiocarb (including fenthiocarb-ethyl), fenthiocarb, fluazifop, fenthiocarb, isoxadiazole (including isoxadiazole-ethyl), mefenpyr (including pyrazoles oxalic acid-diethyl), metcamifen and oxalonitrile.

[0057] Particularly preferred are mixtures of compounds of formula (I) with ciprosulfamide, isoxadifen-ethyl, clofometrexate and / or metcamifen.

[0058] The safeners of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition (BCPC), 2012. References to clofonethiol also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts (as disclosed in WO 02 / 34048).

[0059] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0060] The present invention further provides a method for controlling weeds at a site, the method comprising applying a composition comprising a compound of formula (I) to the site in an amount of weed control. In addition, the present invention further provides a method for selectively controlling weeds at a site including crop plants and weeds, wherein the method comprises applying a composition according to the present invention to the site in an amount of weed control. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. The plants to be controlled are usually unwanted plants (weeds). 'Site' means an area where the plant is growing or will grow. Some crop plants can inherently tolerate the herbicidal effects of compounds of formula (I). However, in some cases, tolerance may need to be designed into crop plants, such as by genetic engineering. Therefore, it is possible that crop plants are given tolerance to HPPD-inhibitors via genetic engineering. Methods for imparting tolerance to HPPD-inhibitors in crop plants are, for example, known from WO0246387. Thus, in an even more preferred embodiment, the crop plant is transgenic for a polynucleotide comprising a DNA sequence encoding an HPPD enzyme resistant to HPPD inhibitors derived from bacteria (more particularly, from Pseudomonas fluorescens or Shewanella colwelliana), or from a plant (more particularly, from a monocot or still more particularly, from a species of barley, maize, wheat, rice, Brachiaria, Cenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena). Several HPPD tolerant soybean transgenic "events" are known, and include, for example, SYHT04R (WO 2012 / 082542), SYHT0H2 (WO 2012 / 082548) and FG72. Other polynucleotide sequences that can be used to provide plants tolerant to the compounds of the invention are disclosed, for example, in WO 2010 / 085705 and WO 2011 / 068567. Crop plants in which the compositions according to the invention can be used therefore include crops such as cereals, for example barley and wheat, cotton, rapeseed, sunflower, corn, rice, soybean, sugar beet, sugar cane and turf.

[0061] Crop plants may also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines (such as grapes), shrub fruit trees, fruit plants and vegetables.

[0062] The application rate of the compound of formula I can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence or post-emergence; seed dressing; application to the seed furrow; no-till application, etc.), the crop plants, one or more weeds to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. The compound of formula I according to the invention is usually applied at a rate of from 10 g / ha to 2000 g / ha, in particular from 50 g / ha to 1000 g / ha.

[0063] Application is usually made by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or drenching may also be used.

[0064] Crop plants are to be understood as also including those crop plants which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACCase-inhibitors and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop plant which has been rendered tolerant to imidazolinones (e.g. imazamox) by conventional methods of breeding is Clearfield strychnine. Summer rapeseed (canola). Examples of crops rendered tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant corn varieties, which are available in Roundup Ready and LibertyLink It is commercially available under the trademark ANTIQUID®.

[0065] Crop plants are also to be understood as those crops which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to the European corn borer), Bt cotton (resistant to the boll weevil) and also Bt potato (resistant to the Colorado beetle). An example of Bt maize is NK Bt 176 corn hybrid (Syngenta Seeds). Bt toxins are proteins naturally produced by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP-A-427 529. An example of a transgenic plant comprising one or more genes encoding insecticide resistance and expressing one or more toxins is KnockOut (Corn), Yield Gard (maize), NuCOTIN33B (cotton), Bollgard (cotton), NewLeaf (potato), NatureGard and Protexcta Plant crops or their seed material can both be resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic results). For example, seeds can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

[0066] Crop plants are also to be understood as including those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (for example improved storage stability, higher nutritional value and improved aroma).

[0067] Other useful plants include turf grasses such as those grown commercially for lawns on golf courses, lawns, parks and roadsides, and ornamental plants such as flowers or shrubs.

[0068] These compositions can be used to control unwanted vegetation (collectively referred to as 'weeds'). The weeds to be controlled can be both monocotyledonous species such as bentgrass, alopecurus, avena, brachiaria, brome, tricholoma, sedge, crabgrass, barnyard grass, sedge, ryegrass, perennial ryegrass, sedge, cyperus, sagittaria, scabrous grass, setaria and sorghum, and dicotyledonous species such as abutilon, amaranth, ragweed, quinoa, chrysanthemum, sedum, elaeagnus, ivy, ipomoea, nasturtium, spatholobus, sinapis, solanum, chickweed, veronica, violet and xanthium. Weeds may also include plants that may be considered crop plants but that grow outside the crop area ('escapes'), or plants that grow from seeds left over from a previously grown different crop ('volunteers'). Such volunteers or escapes may be resistant to certain other herbicides.

[0069] The present invention further provides a compound having the formula (Va)

[0070]

[0071] Where R 2 , R 3 and R 4 is as defined in claim 1 above and R 5 It is hydrogen or C1-C4 alkyl.

[0072] The compounds of the present invention can be prepared according to the following schemes.

[0073] Compounds of formula (I) wherein p=2 or p=1 can be prepared from compounds of formula (I) wherein p=0.

[0074]

[0075] As shown in Scheme 1, a compound of formula (I) (wherein p=0) is treated with a suitable oxidizing agent (e.g., meta-chloroperbenzoic acid) in a suitable solvent (e.g., dichloromethane) to give a compound of formula (I) (wherein p=1). The compound of formula (I) (wherein p=1) can be further oxidized to a compound of formula (I) (wherein p=2) by treatment with a suitable oxidizing agent (e.g., meta-chloroperbenzoic acid) in a suitable solvent (e.g., dichloromethane). The skilled artisan will recognize that a compound of formula (I) (wherein p=2) can be prepared from a compound of formula (I) (wherein p=0) in one reaction by treatment with at least 2 equivalents of an oxidizing agent. The skilled person will recognize that the second oxidation (from the compound of formula (I) (where p=1) to the compound of formula (II) (where p=2)) requires a higher temperature and a longer reaction time than the first oxidation (from the compound of formula (I) (where p=0) to the compound of formula (I) (where p=1). Thus, the skilled person will be able to control the oxidation to give the compound of formula (I) they desire.

[0076] Amides of formula (I) wherein p=0 can be prepared from pentafluorophenyl esters of formula (II) and amines of formula (III) or of formula (IV).

[0077]

[0078] The pentafluorophenyl ester of formula (II) is treated with an amine of formula (III) (Q=Q1) or an amine of formula (IV) (Q=Q2) in the presence of a suitable base (e.g. 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine) and a suitable solvent (e.g. acetonitrile).

[0079] Pentafluorophenyl esters of formula (II) can be prepared from benzoic acid of formula (V).

[0080]

[0081] Benzoic acid of formula (V) is reacted with pentafluorophenol and a suitable ester coupling agent such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide in a suitable solvent such as dichloromethane.

[0082] In the embodiment of the present invention, R 2is C1-C6 alkyl-, C1-C3 alkoxy-, C1-C6 haloalkyl-, C1-C3 haloalkoxy- and -S(O) p C1-C6 alkyl, benzoic acid having formula (V) can be prepared from ester having formula (VI).

[0083]

[0084] The ester of formula (VI) is treated with sodium hydroxide in ethanol + water solvent to give the benzoic acid of formula (V).

[0085] In the embodiment of the present invention, R 2 is C1-C6 alkyl-, C1-C3 alkoxy-, C1-C6 haloalkyl-, C1-C3 haloalkoxy- or -S(O)pC1-C 6 Alkyl, the compound having formula (VI) can be composed of a compound having formula (VI) (wherein R 2 is chlorine).

[0086]

[0087] In this step, the chloro substituent is converted to a suitable R 2 The method of this reaction will depend on the R 2 The skilled person will be familiar with such transformations. For example, when R 2 When the alkyl group is C1-C6, in the presence of a suitable catalyst (e.g. [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) chloride) and a suitable base (e.g. potassium carbonate), a compound of formula (IX) is reacted with a C1-C6 alkylboronic acid or a C1-C6 alkylboroxane (e.g. trimethylboroxane, R 2 = methyl) reaction.

[0088] A compound having formula (VI) (wherein R 2 = chloro) can be prepared from a compound having formula (V) (wherein R 2 = chlorine) preparation.

[0089]

[0090] The compound of formula (V) is treated with ethanol and an acid catalyst such as sulfuric acid to give the compound of formula (VI).

[0091] Benzoic acid having formula (V) (wherein R 2 =chloro) can be prepared from a compound having formula (VII).

[0092]

[0093] A compound of formula (VII) is treated with N-formylsaccharin and a suitable catalyst such as palladium (II) acetate and Xantphos and a suitable base such as triethylamine in a suitable solvent such as N-methylpyrrolidone and water.

[0094] The compound of formula (VII) can be prepared from the compound of formula (VIII) and the compound of formula (IX).

[0095]

[0096] A compound of formula (VIII) is treated with lithium diisopropylamide (LDA) in a suitable solvent such as tetrahydrofuran and then with a compound of formula (IX).

[0097] In an alternative approach, compounds of formula (VII) may be prepared from phenols of formula (X).

[0098]

[0099] The phenol of formula X is treated with a suitable haloalkylating agent which will be selected according to R 4 For example, when R 4 When R4 is -CHF2, the phenol having formula (X) is treated with 2,2,2-triethyl trifluoromethylsulfonate and a base (such as potassium carbonate). In another example, when R4 is -CHF2, the phenol having formula (X) is treated with sodium 2-chloro-2,2-difluoro-acetate and a base (such as potassium carbonate).

[0100] Phenols of formula (X) can be prepared from compounds of formula (XI).

[0101]

[0102] The compound of formula (XI) is treated with aqueous acid (eg 2N hydrochloric acid) in methanol.

[0103] Compounds having formula (XI) can be prepared from (2-((4-bromo-3-chlorophenoxy)methoxy)ethyl)trimethylsilane.

[0104]

[0105] (2-((4-bromo-3-chlorophenoxy)methyl)ethyl)trimethylsilane is treated with lithium diisopropylamide (LDA) in a solvent such as tetrahydrofuran and then with a compound of formula (IX).

[0106] (2-((4-bromo-3-chlorophenoxy)methyl)ethyl)trimethylsilane can be prepared from 4-bromo-3-chlorophenol.

[0107]

[0108] 4-Bromo-3-chlorophenol was treated with 2-(chloromethoxy)ethyl-trimethyl-silane and N,N-diisopropylethylamine.

[0109] The following non-limiting examples provide specific synthetic methods for representative compounds of the invention (see Tables provided herein).

[0110] Example 1. Preparation of Compound 1.001.

[0111] Step 1

[0112] DCM (40mL) and N, N-diisopropylethylamine (10g, 13.5mL, 77.1mmol) are added to a flask containing 4-bromo-3-chloro-phenol (8g, 38.6mmol). At 0°C, 2-(chloromethoxy)ethyl-trimethyl-silane (7.07g, 7.4mL, 42.4mmol) is added dropwise. The reaction is stirred at room temperature overnight. The reaction is quenched by adding water and then adding saturated NaHCO3 aqueous solution, the material is extracted with ethyl acetate and the organic phase is concentrated in vacuo to give 2-[(4-bromo-3-chloro-phenoxy)methoxy]ethyl-trimethyl-silane (14.8g, quantitative %) as an orange oil. 1 H NMR (chloroform): 7.47 (d, 1H), 7.18 (d, 1H), 6.83 (dd, 1H), 5.18 (s, 2H), 3.75 (m, 2H), 0.94 (m, 2H), 0.00 (m, 9H)

[0113] Step 2

[0114] In a three-necked flask, THF (280 mL) was added and the reaction mixture was purged and filled (with N2). Diisopropylamine (6.78 g, 9.44 mL, 66.3 mmol) was added. The reaction was stirred at -78 °C for 30 min. n-Butyl lithium (16 g, 2.5 mol / L, 23 mL, 58.0 mmol) in hexane was added dropwise by a syringe pump (10 mL / min). It was stirred for 1 h, and the mixture was then allowed to warm to -40 °C, and then cooled to -78 °C. A solution of 2-[(4-bromo-3-chloro-phenoxy)methoxy]ethyl-trimethyl-silane (14 g, 41.5 mmol) in 23 mL THF was added by a syringe pump (10 mL / min) and the reaction mixture was stirred at -78 °C for 3 h. Dimethyl disulfide (7.89 g, 7.54 mL, 82.9 mmol) in 16 mL THF was added dropwise (10 mL / min) and the mixture was stirred at -78 °C for 40 min. The reaction mixture was quenched by adding it thoroughly to a stirred aqueous solution. 2M HCl was added until the mixture was acidic and the mixture was stirred for 15 min. The material was extracted with ethyl acetate and the organic phase was concentrated in vacuo to give 2-[(4-bromo-3-chloro-2-methylsulfanyl-phenoxy)methoxy]ethyl-trimethyl-silane (14.4 g, 31.1 mmol, 75%) as an orange oil. 1H NMR (chloroform): 7.50 (d, 1H), 7.01 (d, 1H), 5.31 (s, 2H), 3.79 (m, 2H), 2.42 (s, 3H), 0.95 (m, 2H), 0.00 (s, 9H)

[0115] Step 3

[0116] To a flask containing 2-[(4-bromo-3-chloro-2-methylsulfanyl-phenoxy)methoxy]ethyl-trimethyl-silane (14.4 g, 37.5 mmol) was added THF (188 mL), MeOH (113 mL) and 2M HCl aqueous solution (113 mL). The reaction was stirred at 70 ° C for 1 h. The reaction mixture was cooled to room temperature and then concentrated in vacuo. The crude material was diluted with water and extracted with ethyl acetate, and the organic phase was concentrated in vacuo. The material was purified by flash chromatography (0% to 20% EtOAc in cyclohexane) to give 4-bromo-3-chloro-2-methylsulfanyl-phenol (8.28 g, 32.6 mmol, 87%) as white crystals. 1 H NMR (chloroform): 7.50 (d, 1H), 7.09 (s, 1H), 6.85 (d, 1H), 2.34 (s, 3H)

[0117] Step 4

[0118] To a flask containing 4-bromo-3-chloro-2-methylsulfanyl-phenol (2 g, 7.89 mmol) was added DMF (20 mL). K2CO3 (1.38 g, 9.47 mmol) was added, followed by 2,2,2-trifluoroethyl trifluoromethanesulfonate (2.20 g, 1.36 mL, 9.47 mmol), and the reaction mixture was stirred at room temperature for 3.5 h. The reaction mixture was quenched by adding water and the material was extracted with ethyl acetate. The organic phase was washed with water and concentrated in vacuo. The material was purified by flash chromatography (0% to 15% EtOAc in cyclohexane) to give 1-bromo-2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzene (2.62 g, 7.81 mmol, 99%) as a colorless oil. 1H NMR (chloroform): 7.54 (d, 1H), 6.73 (d, 1H), 4.42 (q, 2H), 2.45 (s, 3H)

[0119] Step 5

[0120] To a vessel containing NMP (101 mL) was added palladium (II) acetate (0.169 g, 0.751 mmol), XantPhos (0.896 g, 1.50 mmol), N-formylsaccharin (3.57 g, 16.9 mmol) and 1-bromo-2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzene (2.52 g, 7.51 mmol). To a second vessel was added triethylamine (3.57 g, 4.71 mL, 33.8 mmol), NMP (101 mL) and water (5.04 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were pumped through a T-tube and then around a 20 mL stainless steel coil heated to 170°C. The flow rate was set so that the total residence time was 15 min. The reaction mixture was cooled to room temperature and diluted with ethyl acetate. The organic phase was washed with 2M HCl and then with water. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0% to 100% EtOAc in cyclohexane) to give 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoic acid (0.96 g, 2.87 mmol, 38%) as an orange solid. 1H NMR (methanol): 7.78 (d, 1H), 7.09 (d, 1H), 4.71 (q, 2H), 2.40 (s, 3H)

[0121] Step 6

[0122] 2,3,4,5,6-pentafluorophenol (0.750g, 4.07mmol) and DCM (16mL) were added to a flask containing 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoic acid (0.816g, 2.71mmol). 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.602g, 2.99mmol) was added and the reaction was stirred at room temperature for 2h. The reaction mixture was diluted with DCM and washed with saturated NaHCO3 aqueous solution. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0% to 10% EtOAc in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoate (0.758g, 1.62mmol, 60%) in the form of white needles. 1H NMR (chloroform): 8.07 (d, 1H), 6.91 (d, 1H), 4.54 (q, 2H), 2.46 (s, 3H)

[0123] Step 7

[0124] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoate (0.379 g, 0.812 mmol) was added acetonitrile (7.6 mL), and the mixture was stirred at room temperature. 1-Methyltetrazolyl-5-amine (88.5 Mg, 0.893 mmol) was added, followed by 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaziridine (0.506 g, 0.533 mL, 1.79 mmol), and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water and acidified with 2M HCl. The substance was then extracted with ethyl acetate. The organic phase was concentrated in vacuo. The substance was purified by flash chromatography (0% to 70% EtOAc in cyclohexane) to give a white solid. This material was crystallized from hot methanol to give 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (0.236 g, 0.544 mmol, 67%) as white crystals. 1H NMR (acetonitrile): 7.65 (d, 1H), 7.11 (d, 1H), 4.71 (q, 2H), 4.01 (s, 3H), 2.46 (s, 3H).

[0125] Example 2. Preparation of Compound 1.005.

[0126] Step 1

[0127] THF (22mL) is added to a three-necked flask and the reaction mixture is purged and filled (with N2). Diisopropylamine (1.19g, 1.65mL, 11.6mmol) is added. The reaction is stirred at -78 ° C for 30min. n-Butyl lithium (2.8g, 2.5mol / L, 4.1mL, 10.2mmol) in hexane is added dropwise. It is stirred for 1h, then the mixture is allowed to warm to -40 ° C, and then cooled to -78 ° C. A solution of 1-bromo-2-chloro-4-(trifluoromethoxy)benzene (2g, 7.26mmol) in 5mL of THF is added and the reaction mixture is stirred at -78 ° C for 1.5h. Dimethyl disulfide (1.38g, 1.32mL, 14.5mmol) is added dropwise and the mixture is stirred at -78 ° C for 1h. The reaction mixture is quenched by thoroughly adding the reaction mixture to the stirred aqueous solution. 2M HCl was added until the mixture was acidic and the mixture was stirred for 15 min. The material was extracted with diethyl ether and the organic phase was concentrated in vacuo to give 1-bromo-2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzene (2.09 g, 6.50 mmol, 90%) as a colorless oil. 1H NMR (chloroform): 7.62 (d, 1H), 7.11 (d, 1H), 2.46 (s, 3H)

[0128] Step 2

[0129] To a vessel containing NMP (47 mL) was added palladium (II) acetate (0.082 g, 0.364 mmol), XantPhos (0.434 g, 0.728 mmol), N-formylsaccharin (1.73 g, 8.19 mmol) and 1-bromo-2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzene (1.17 g, 3.64 mmol). To a second vessel was added triethylamine (1.66 g, 2.28 mL, 16.4 mmol), NMP (47 mL) and water (2.34 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were pumped through a T-tube and then around a 20 mL stainless steel coil heated to 170°C. The flow rate was set so that the total residence time was 20 min. The reaction mixture was cooled to room temperature and diluted with ethyl acetate. The organic phase was washed with 2M HCl and then with water. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0% to 100% EtOAc in cyclohexane) to give 2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzoic acid (0.691 g, 2.41 mmol, 66%) as a yellow solid. 1H NMR (methanol): 7.82 (d, 1H), 7.44 (d, 1H), 2.46 (s, 3H)

[0130] Step 3

[0131] To a flask containing 2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzoic acid (0.125 g, 0.436 mmol) was added 2,3,4,5,6-pentafluorophenol (88.2 mg, 0.480 mmol) and DCM (2.5 mL). 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.101 g, 0.501 mmol) was added and the reaction was stirred at room temperature for 1 h. The reaction mixture was diluted with DCM and washed with saturated aqueous NaHCO3. The organic phase was concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzoate (0.197 g, 0.436 mmol, 100%) as a light yellow oil which was used crude without further purification.

[0132] Step 4

[0133] DMF (2 mL) was added to a flask containing (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-(trifluoromethyl) benzoate (0.197 g, 0.436 mmol). 1-Methyltetrazolyl-5-amine (47.5 mg, 0.480 mmol) was added, followed by 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaziridine (0.271 g, 0.286 mL, 0.959 mmol), and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water and acidified with 2M HCl. The substance was then extracted with ethyl acetate. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0% to 100% EtOAc in cyclohexane) to give 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethoxy)benzamide (76.6 mg, 0.208 mmol, 48%) as an off-white solid. 1H NMR (methanol): 7.73 (d, 1H), 7.52 (d, 1H), 4.07 (s, 3H), 2.48 (s, 3H)

[0134] Example 3. Preparation of Compound 2.001.

[0135] The synthesis of the starting material phenol is described in the procedure for compound 1.001 above.

[0136] Step 1

[0137] DMF (20 mL) was added to a flask containing 4-bromo-3-chloro-2-methylsulfanyl-phenol (2 g, 7.89 mmol). K2CO3 (1.38 g, 9.47 mmol) was added followed by 2-chloro-2,2-difluoro-sodium acetate (1.45 g, 9.47 mmol). The reaction mixture was stirred at 100 ° C for 45 min behind a blast shield. The mixture was cooled to room temperature. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic phase was washed with water and then concentrated in vacuo. The material was purified by flash chromatography (0% to 15% EtOAc in cyclohexane) to give 1-bromo-2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzene (1.46 g, 4.81 mmol, 61%) as a colorless oil. 1H NMR (chloroform): 7.59 (d, 1H), 7.02 (d, 1H), 6.56 (t, 1H), 2.46 (s, 3H)

[0138] Step 2

[0139] To a vessel containing NMP (55 mL) was added palladium (II) acetate (0.101 g, 0.451 mmol), XantPhos (0.538 g, 0.903 mmol), N-formylsaccharin (2.15 g, 10.1 mmol), and 1-bromo-2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzene (1.37 g, 4.51 mmol). To a second vessel was added triethylamine (2.06 g, 2.83 mL, 20.3 mmol), NMP (55 mL) and water (2.74 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were pumped through a T-tube and then around a 20 mL stainless steel coil heated to 170°C. The flow rate was set so that the total residence time was 20 min. The reaction mixture was cooled to room temperature and diluted with ethyl acetate. The organic phase was washed with 2M HCl and then with water. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0% to 100% EtOAc in cyclohexane) to give 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoic acid (0.953 g, 3.19 mmol, 70%) as a yellow solid. 1H NMR (chloroform): 7.91 (d, 1H), 7.18 (d, 1H), 6.65 (t, 1H), 2.47 (s, 3H)

[0140] Step 3

[0141] To a flask containing 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoic acid (0.65 g, 2.42 mmol) was added 2,3,4,5,6-pentafluorophenol (0.668 g, 3.63 mmol) and DCM (13 mL). 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.537 g, 2.66 mmol) was added and the reaction mixture was stirred at room temperature for 2 h. The reaction mixture was diluted with DCM and washed with saturated NaHCO3 aqueous solution. The organic phase was concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoate (1.3 g, 3.00 mmol, 124%) as a green oil, which was used crude without further purification.

[0142] Step 4

[0143] Acetonitrile (10 mL) was added to a flask containing (2,3,4,5,6-pentafluorophenyl) 3-[dicyclopropylmethylcarbamoyl(methoxy)amino]-2-methyl-4-methylsulfonyl-benzoate (0.526 g, 1.21 mmol). 5-methyl-1,3,4-oxadiazole-2-amine (0.132 g, 1.33 mmol) was added, followed by 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaziridine (0.821 g, 0.866 mL, 2.90 mmol) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water and acidified with 2M HCl. The substance was then extracted with ethyl acetate. The organic phase was concentrated in vacuo.

[0144] The material was purified by flash chromatography (0% to 75% EtOAc in cyclohexane) to give 2-chloro-4-(difluoromethoxy)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-methylsulfanyl-benzamide (0.150 g, 0.399 mmol, 33%) as an off-white solid. 1H NMR (methanol): 7.67 (d, 1H), 7.19 (d, 1H), 6.64 (t, 1H), 2.54 (s, 3H), 2.46 (s, 3H)

[0145] Example 4. Preparation of Compound 1.002

[0146] The starting material was the product from Step 3 of Example 3.

[0147] Step 1

[0148] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoate (0.23 g, 0.53 mmol) was added acetonitrile (4.6 mL), 1-methyltetrazolyl-5-amine (0.115 g, 1.16 mmol), and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaziridine (0.35 mL, 1.2 mmol). The reaction mixture was stirred at room temperature for 30 min and then concentrated in vacuo (room temperature bath). The residue was diluted with water and washed with ethyl acetate. The aqueous phase was then acidified with 2M HCl and extracted with ethyl acetate x 2. The combined organic phases were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (0% to 40% ethyl acetate in cyclohexane) gave 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)benzamide (0.115 g, 0.329 mmol, 62%) as a white solid.

[0149] Example 5. Preparation of Compound 1.003

[0150] The starting material was compound 1.002 prepared in Example 4.

[0151] To a flask containing 2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-methylsulfanyl-4-(trifluoromethoxy)benzamide (0.15 g, 0.4289 mmol) was added DCM (6 mL) and 3-chloroperoxybenzoic acid (0.24 g, 1.1 mmol). The reaction was stirred at room temperature for 16 h. Another aliquot of 3-chloroperoxybenzoic acid (0.10 g, 0.44 mmol) was added. After stirring for an additional 2.5 h, the reaction mixture was quenched by the addition of saturated aqueous sodium metabisulfite solution and the phases were separated. The aqueous phase was extracted with DCM and the combined organic layers were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (0% to 80% ethyl acetate in cyclohexane) gave 2-chloro-4-(difluoromethoxy)-3-methylsulfonyl-N-(1-methyltetrazol-5-yl)benzamide (0.100 g, 0.263 mmol, 61%) as a white solid.

[0152] Example 6. Preparation of Compound 1.009

[0153] The starting material was prepared in step 3 from Example 1.

[0154] Steps 1 and 2

[0155] 1,2-dibromo-1,1,2,2-tetrafluoro-ethane (7.84g, 30.2mmol) and KOH (1.46g, 26.1mmol) were added to a solution of 4-bromo-3-chloro-2-methylsulfanyl-phenol (5.10g, 20.1mmol) in DMSO (50mL). The mixture was stirred at 70 ° C for 16h. The reaction mixture was cooled to room temperature and then concentrated in vacuo. The crude material was diluted with water and extracted with ethyl acetate, and the organic phase was concentrated in vacuo. The material was purified by flash chromatography (PE) to obtain a mixture of 1-bromo-4-(2-bromo-1,1,2,2-tetrafluoro-ethoxy)-2-chloro-3-methylsulfanyl-benzene and 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy) benzene as a colorless oil (total: 6.3g).

[0156] This mixture was used crude in the following steps:

[0157] To a mixture of 1-bromo-4-(2-bromo-1,1,2,2-tetrafluoro-ethoxy)-2-chloro-3-methylsulfanyl-benzene and 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (total: 6.3 g) in AcOH (15 mL) was added Zn (3.81 g, 58.3 mmol). The mixture was stirred at 70 ° C for 3 h. After cooling to room temperature, the crude material was diluted with water (80 ml) and extracted with ethyl acetate (50 ml), and the organic phase was washed with sodium bicarbonate solution (20 ml x 3) and concentrated in vacuo to give 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (3.90 g, 11.0 mmol, 2 step yield: 55%) as a colorless oil.

[0158] Step 3

[0159] To a solution of 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (10.2 g, 28.8 mmol) in ethanol (60 mL) was added Pd(OAc)2 (0.130 g, 0.577 mmol) and 1,1'-bis(diphenylphosphino)ferrocene (0.800 g, 1.44 mmol). CO (2.0 MPa) was added to the mixture and stirred at 120 °C for 6 h. After cooling to room temperature, the crude material was concentrated in vacuo and purified by flash chromatography (petroleum ether: ethyl acetate 40: 1 to 20: 1) to give ethyl 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (8.00 g, 23.1 mmol, 80%) as a yellow liquid.

[0160] Step 4

[0161] To a solution of ethyl 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (15.0 g, 43.3 mmol) in THF (30 mL) and water (30 ml) was added LiOH HO (5.45 g, 130 mmol). The mixture was stirred at room temperature and stirred for 16 h. Dilute hydrochloric acid was added to adjust the pH to 2. The mixture was extracted with ethyl acetate (50 ml), and the organic phase was concentrated in vacuo and purified by flash chromatography (petroleum ether: ethyl acetate 2: 1 to 1: 1) to give 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (11.5 g, 36.1 mmol, 83%) as a white solid.

[0162] Step 5

[0163] To a stirred suspension of 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (2.00 g, 6.28 mmol) and 2,3,4,5,6-pentafluorophenol (1.27 g, 6.90 mmol) in dichloromethane (30 mL) was added 3-(ethyliminomethyleneamino)-N,N-dimethyl-propane-1-amine hydrochloride (1.44 g, 7.51 mmol) at room temperature. The mixture was stirred at room temperature. After 5 minutes of adding EDC, the mixture was a homogeneous solution. The reaction mixture was stirred at room temperature overnight. The reaction was quenched by adding saturated NaHCO3 aqueous solution (100 mL). The mixture was stirred at room temperature for another 5 minutes. The mixture was filtered through a phase separation column and the organic matter was collected. The filtrate was adsorbed onto silica and the crude product was purified by flash column chromatography (gradient 0-10% EtOAc in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (3.42 g, 7.06 mmol) as a pale yellow oil which crystallized on standing.

[0164] Step 6

[0165] To a stirred solution of (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (0.500 g, 1.03 mmol) in acetonitrile (10 mL) was added 1-methyltetrazol-5-amine (0.225 g, 2.270 mmol) at room temperature followed by 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2-diazaphosphino-2-amine (0.64 g, 0.68 mL, 2.3 mmol). The mixture was stirred at room temperature overnight. The reaction was quenched by the addition of 2M aqueous HCl (100 mL). The mixture was stirred at room temperature for an additional 5 minutes. The mixture was diluted with EtOAc (100 mL). The phases were separated. The aqueous phase was extracted with EtOAc (100 mL). The combined organic phases were washed with brine (100 mL), dried (MgSO4) and purified by reverse phase chromatography to give 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (295 mg, 0.701 mmol, 68%). 1H NMR (400 MHz, d4-methanol): 2.45 (s, 3H) 4.07 (s, 3H) 6.30-6.63 (m, 1H) 7.49-7.55 (m, 1H) 7.66-7.75 (m, 1H).

[0166] Example 7: Preparation of Compound 1.010

[0167] The starting material was the same as produced in Step 4 of Example 6.

[0168] Step 1

[0169] To a flask containing 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (3.00 g, 9.41 mmol), dichloromethane (90 mL) and 3-chloroperoxybenzoic acid (6.32 g, 28.2 mmol) were added. The reaction was stirred at room temperature for 16 h. The reaction mixture was quenched with saturated aqueous sodium metabisulfite solution and the phases were separated. The aqueous layer was extracted with ethyl acetate. The combined organic phases were concentrated and purified by flash chromatography to give 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (2.46 g, 75%) as a white solid.

[0170] Step 2

[0171] At room temperature, 3-(ethyliminomethylamino)-N,N-dimethyl-propane-1-amine hydrochloride (1.6g, 8.3mmol) was added to a stirred suspension of 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (2.5g, 7.1mmol) and 2,3,4,5,6-pentafluorophenol (1.4g, 7.6mmol) in dichloromethane (30mL). Initially it was heterogeneous, however, within 5 minutes of adding EDC, the mixture was a homogeneous solution. The mixture was stirred at room temperature for 3 hours. The reaction was quenched by adding saturated NaHCO3 aqueous solution (100mL). The mixture was stirred at room temperature for another 5 minutes. The filtrate was adsorbed onto silica and the crude product was purified by flash column chromatography (0%-10% gradient of EtOAc in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (3.42 g, 6.62 mmol, 93%) as a colorless oil.

[0172] Step 3

[0173] At room temperature, to a stirred solution of (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (A, 300 mg, 0.5806 mmol, 100 mass%) in acetonitrile (8 mL) was added 1-methyltetrazol-5-amine (0.127 g, 1.28 mmol), followed by 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2-diazaphosphine-2-amine (0.36 g, 0.38 mL, 1.3 mmol). The mixture was stirred at room temperature for 2 h. The reaction was quenched by adding water 2M HCl aqueous solution (10 mL). The mixture was stirred at room temperature for another 5 minutes. The mixture was diluted with EtOAc (20 mL). Each phase was separated. The aqueous phase was extracted with EtOAc (10 mL). The combined organic phases were adsorbed onto C18-silica and the crude product was purified by reverse phase chromatography to give 2-chloro-3-methylsulfonyl-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (170 mg, 0.374 mmol, 64%) as a white solid.

[0174] Example 8: Preparation of Compound 1.007

[0175] The starting material was the product of step 3 in Example 1.

[0176] Step 1

[0177] A solution of 4-bromo-3-chloro-2-methylsulfanyl-phenol (2.50 g, 9.86 mmol) in sodium hydroxide (5% solution in water) (8.87 mL) was added to a cooled (ice bath) solution of dichlorothiocarbonyl (9.86 mmol, 0.752 mL, 1.13 g) in chloroform (6 mL). The reaction mixture was cleaned with bleach and stirred at 0 ° C for 2.5 h. The phases were separated. The organic layer was washed (2M aqueous HCl solution, then water), dried (MgSO4) and concentrated under vacuum to give O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl)chlorothioformate (3.07 g, 9.24 mmol, 94%) as a yellow liquid. 1H NMR (400MHz, CDCl3) δ = 7.69 (d, J = 8.7Hz, 1H), 6.98 (d, J = 8.8Hz, 1H), 2.44 (s, 3H).

[0178] Step 2

[0179] The oven-dried flask is evacuated and purged with nitrogen (x3).Add a solution of O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl) chlorothioformate (3.00g, 9.03mmol) in THF (90mL), then add cuprous cyanide (I) di(lithium chloride) complex solution (1M in THF, 9.94mL, 9.94mmol). It is cooled to -78 ° C.Methylmagnesium bromide (3M solution in THF) (9.94mmol, 3.31mL) is slowly added (temperature remains below -70 ° C during addition). After completion of addition, it is stirred at -78 ° C for 1h.The reaction mixture is warmed to 0 ° C, and it is stirred at this temperature for 1h.The reaction mixture is quenched by adding saturated NH4Cl aqueous solution.It is extracted with EtOAc (x3).The EtOAc extracts merged are dried (MgSO4) and concentrated under vacuum. The residue was purified by chromatography (0% to 10% EtOAc in cyclohexane) to give O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl)thioacetate (1.5 g, 4.8 mmol, 53%) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ = 7.65 (d, J = 8.7 Hz, 1H), 6.86 (d, J = 8.7 Hz, 1H), 2.38 (s, 3H)

[0180] Step 3

[0181] Under nitrogen, a solution of O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl)thioacetate (1.5 g, 4.8 mmol) in dichloromethane (19 mL) was stirred. This solution was treated with antimony (III) chloride (0.24 mmol, 0.055 g) and then with Deoxo-Fluor 50% solution (6.7 mmol, 3.4 mL) in toluene. Under nitrogen cover, the reaction mixture was stirred at room temperature for 24 h. The reaction mixture was quenched by adding saturated NaHCO3 aqueous solution. It was extracted with EtOAc (x3). The combined EtOAc extracts were dried (MgSO4) and concentrated under vacuum. The residue was purified by chromatography (0% to 10% EtOAc in cyclohexane) to give 1-bromo-2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzene (0.867 g, 2.73 mmol, 57% yield). 1H NMR (400MHz, CDCl3) δ = 7.56 (d, J = 8.9Hz, 1H), 7.15 (td, J = 1.3, 8.9Hz, 1H), 2.42 (s, 3H), 2.00 (t, J = 13.4Hz, 3H).

[0182] Step 4

[0183] To a vessel containing NMP (20 mL) was added palladium (II) acetate (74 mg, 0.33 mmol), XantPhos (39 mg, 0.66 mmol), N-formyl saccharin (1.57 g, 7.44 mmol), and 1-bromo-2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzene (1.05 g, 3.31 mmol). To a second vessel was added triethylamine (2.07 mL, 14.9 mmol), NMP (20 mL), and water (2.1 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were pumped through a T-tube and then around a 20 mL stainless steel coil heated to 170°C. The flow rate was set so that the total residence time was 15 min. The reaction mixture was cooled to room temperature and diluted with ethyl acetate. The organic phase was washed with 2M HCl and then with water. The organic phase was concentrated in vacuo. The material was purified by reverse phase flash chromatography to give 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoic acid (0.565 g, 2.00 mmol, 60%) as a yellow solid. 1H NMR (d4-methanol): 7.74 (d, 1H), 7.39 (m, 1H), 2.43 (s, 3H), 2.03 (m, 3H).

[0184] Step 5

[0185] To a flask containing 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoic acid (0.565 g, 2.00 mmol) was added: dichloromethane (11 mL) and 2,3,4,5,6-pentafluorophenol (0.405 g, 2.20 mmol). 3-(ethyliminomethyleneamino)-N,N-dimethyl-propane-1-amine hydrochloride (0.464 g, 2.30 mmol) was added and the reaction was stirred for 1 h. The reaction mixture was quenched by the addition of saturated aqueous sodium bicarbonate solution and the phases were separated and extracted with ethyl acetate x 2. The organic phases were combined, dried (MgSO4) and concentrated in vacuo. The crude material was purified by flash chromatography (0% to 10% ethyl acetate in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoate (604 mg, 1.23 mmol, 63%) as a yellow solid. 1H NMR (CDCl3): 8.01 (d, 1H), 7.45 (m, 1H), 2.45 (s, 3H), 2.06 (m, 3H).

[0186] Step 6

[0187] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoate (0.400 g, 0.892 mmol) was added DCM (4 mL) and 3-chlorobenzenecarboperoxoic acid (0.528 g, 2.14 mmol). After stirring for 5 h, another portion of 3-chloroperbenzoic acid (0.220 g, 0.892 mmol) was added. After stirring for 24 h, the reaction mixture was quenched by the addition of saturated aqueous sodium metabisulfite. The phases were separated and the aqueous layer was extracted with DCM. The combined organic layers were washed with saturated aqueous sodium carbonate solution x 2, dried (MgSO4) and concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfonyl-benzoate (0.411 g, 0.8550 mmol, 96%) as pale yellow crystals. 1 H NMR(CDCl3): 8.14(d,1H),7.58(m,1H),3.36(s,3H),2.08(m,3H).

[0188] Step 7

[0189] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoate (0.21 g, 0.4369 mmol) was added acetonitrile (4.2 mL) followed by 1-methyltetrazolyl-5-amine (0.09524 g, 0.9611 mmol) and 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2-diazaphosphin-2-amine (0.272 g, 0.287 mL, 0.961 mmol) and stirred at room temperature for 1 h. The reaction mixture was concentrated in vacuo, then diluted with 2M aqueous HCl and extracted with ethyl acetate. The organic phase was dried (MgSO 4 ), concentrated and purified by reverse phase chromatography to give 2-chloro-3-methylsulfonyl-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (170 mg, 0.374 mmol, 64%) as a white solid.

[0190] Table 1 - Examples of herbicidal compounds of the present invention.

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] Table 2 - Examples of herbicidal compounds of the invention.

[0205]

[0206]

[0207]

[0208]

[0209] Biological Examples

[0210] Seeds of various test species were sown in standard soil in pots (Lolium perenne (LOLPE), Amaranthus retoflexus (AMARE), Abutilon theophrasti (ABUTH), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE)). After one day (pre-emergence) or eight days (post-emergence) of cultivation under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 h light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from a formulation of technical grade active ingredient in acetone / water (50:50) solution containing 0.5% TweenTM20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Unless otherwise noted, the compound is applied at 125 g / h. The test plants are then grown in a greenhouse under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 hours of light; 65% humidity), and watered twice daily. Before and after emergence, 13 days later, the percentage of damage caused to the plant is evaluated. The following table shows biological activity with a five-point system (5 = 80%-100%; 4 = 60%-79%; 3 = 40%-59%; 2 = 20%-39%; 1 = 0%-19%).

[0211] Table B1: Pre-emergence application

[0212]

[0213]

[0214]

[0215] Table B2: Post-emergence application

[0216]

[0217]

[0218] *Applied at 250g / ha

[0219] Comparative experiments were performed to illustrate the advantages provided by the compounds of the present invention. Thus, the biological performance of the representative compound 1.004 was compared with that of compound 4-460 (of the type mentioned in WO 2012 / 028579). The results are given in terms of observed phytotoxicity (%). The results show that the compounds of the present invention exhibit greatly improved crop (ZEAMX / corn) selectivity, i.e., at equivalent application rates, the compounds of the present invention provide improved control for thorny weed species with little damage to the crop.

[0220] Table B3: Comparative Experiments

[0221]

Claims

1. A compound having formula (I): or an agronomically acceptable salt thereof, in: - Q is for Q1: R 1 is C1-C4 alkyl-; R 2 selected from the group consisting of halogen and C1-C6 alkyl-; R 3 is C1-C6 alkyl-; R 4 is a C1-C6 haloalkyl group; and p is 0, 1 or 2.

2. The compound according to claim 1, wherein Q is Q1.

3. The compound according to claim 1, wherein R 1 It's methyl.

4. The compound according to claim 1, wherein R 2 Selected from the group consisting of: chlorine and methyl.

5. The compound according to claim 4, wherein R 2 It's chlorine.

6. The compound according to claim 1, wherein R 3 It is methyl or ethyl.

7. The compound according to claim 1, wherein R 4 It is CF3 or CHF2.

8. A herbicidal composition comprising the compound according to any one of claims 1 to 7, and an agriculturally acceptable formulation adjuvant.

9. The herbicidal composition according to claim 8, further comprising at least one additional pesticide.

10. The herbicidal composition according to claim 9, wherein the additional pesticide is a herbicide or a herbicide safener.

11. A method of controlling weeds at a locus, the method comprising applying to the locus a weed controlling amount of a composition according to any one of claims 8 to 10.

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

13. A compound having formula (Va) Where R 2 , R 3 and R 4 is as defined in claim 1 above and R 5 It is hydrogen or C1-C4 alkyl.

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