3-[(HYDRAZONO)METHYL]-N-(TETRAZOL-5-YL)-BENZAMIDE AND 3-[(HYDRAZONO)METHYL]-N-(1 ,3,4-OXADIAZOL-2-YL)-BENZAMIDE DERIVATIVES AS HERBICIDES

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.

N-(tetrazol-5-yl)- and N-(1 ,3,4-oxadiazol-2-yl) arylcarboxamides are disclosed in, for example, WO2012/028579 and WO2012/126932 respectively. The present invention relates to novel hydrazone substituted benzoyl compounds.

Thus, according to the present invention there is provided a compound of Formula (I):

or an agronomically acceptable salt thereof,

wherein

R ² is selected from the group consisting of halogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ haloalkyl and -S(O) _p C ₁ -C ₆ alkyl;

R ³ is selected from the group consisting of halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl and - S(O) _p C ₁ -C ₆ alkyl;

Q is Q ¹ or Q ² ;

R ^{1 a} is C ₁ -C ₄ alkyl- or C ₁ -C ₃ -alkoxy-C ₁ -C ₃ -alkyl-;

R ^{1 b} is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl- and CrC ₃ -alkoxy-Ci- C ₃ -alkyl-;

R ⁴ is hydrogen or C ₁ -C ₆ alkyl;

R ⁵ is selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl and C ₁ -C ₆ haloalkyl;

R ⁶ is selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, cyano C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl-C ₁ -C ₃ alkyl-, C ₁ -C ₆ alkoxy-, C ₁ -C ₃ alkoxy- C ₁ -C ₃ alkyl-, Ci- C ₃ alkoxy-C ₁ -C ₃ alkoxy-, C ₂ -C ₆ -alkynyl, C ₂ -C ₆ alkenyl, phenyl and -(CH ₂ )-phenyl wherein the phenyl groups are optionally substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl and C ₁ -C ₆ alkoxy; or

R ⁵ and R ⁶ together are, -C(R ⁷ ) ₂ C(R ⁷ ) ₂ C(R ⁷ ) ₂ C(R ⁷ ) ₂ -, -C(R ⁷ ) ₂ C(R ⁷ ) ₂ C(R ⁷ ) ₂ C(R ⁷ ) ₂ C(R ⁷ ) ₂ -, - CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ S(0)pCH ₂ CH ₂ - and -CH ₂ CH ₂ N(R ⁸ )CH ₂ CH ₂ -; and

R ⁷ is independently selected from the group consisting of hydrogen, halogen and C ₁ -C ₆ alkyl;

R ⁸ is selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ -haloalkyl, C ₃ -C ₆ - cycloalkyl, -S(O) _p C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy-; and p = 0, 1 or 2. C ₁ -C ₆ alkyl and C ₁ -C ₄ alkyl groups include, for example, methyl (Me, CH ₃ ), ethyl (Et,

C ₂ H ₅ ), n-propyl (n-Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/- Bu), sec-butyl and tert- butyl (t- Bu).

C ₃ -C ₆ cycloalkyl- includes cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl).

C ₂ -C ₆ alkenyl can be in the form of straight or branched chains and, where appropriate, can be of either the (E)- or (Z)-configuration. Examples include vinyl & allyl.

C ₂ -C ₆ alkynyl can be in the form of straight or branched chains. Examples include ethynyl & propargyl.

Halogen (or halo) encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl. C ₁ -C ₆ 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. C ₁ -C ₄ 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-. C ₁ -C ₆ alkyl-S- (alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n- butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. C ₁ -C ₆ alkyl-S(0)- (alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl. C ₁ -C ₆ alkyl-S(0) ₂ - (alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert- butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl. C ₁ -C ₆ alkoxy- is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and ethoxy.

In a preferred embodiment of the present invention, R ² is selected from the group consisting of methyl, Cl, -CF ₃ and -SO ₂ methyl.

In another preferred embodiment of the present invention, R ³ is selected from the group consisting of methyl, Cl, -CF ₃ and -S0 ₂ methyl.

In one embodiment of the present invention Q is Q ¹ . In this embodiment R ^1a is preferably selected from the group consisting of methyl, ethyl and n-propyl, preferably methyl.

In another embodiment of the present invention Q is Q ² . In this embodiment, R ^{1 b} is preferably methyl.

In another embodiment of the present invention, R ⁴ is hydrogen or methyl, preferably hydrogen.

In another embodiment of the present invention, R ⁵ is hydrogen or C ₁ -C ₆ alkyl (preferably methyl or ethyl).

In another embodiment of the present invention, R ⁶ is C ₁ -C ₆ alkyl (preferably methyl or ethyl) or C ₁ -C ₆ haloalkyl (e.g. CF ₃ CH ₂ -)

In another embodiment of the present invention R ⁵ and R ⁶ together are - CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -.

Compounds of Formula (I) (and certain intermediate compounds used to synthesise compound 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 includes all possible geometric and tautomeric forms of a compound of formula (I).

The present invention also includes agronomically acceptable salts that the compounds of Formula (I) may form with amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as salt formers, emphasis is to be given to the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium, magnesium and calcium. The corresponding trimethylsulfonium salt may also be used.

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 (SFAs). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound of the present invention 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 formula tion 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, 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 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)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. 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).

Dustable powders (DP) may be prepared by mixing a compound of Formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

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 C ₈ -C ₁₀ 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 SFAs, 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 SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SFA 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 (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), 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 SFAs of the cationic, anionic, amphoteric or non-ionic type.

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

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /sopropyl- and tri-/sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3- carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.

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

Suitable SFAs 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); and lecithins.

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

The composition of the present may further comprise at least one additional pesticide. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment the additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures are (in which T represents a compound of Formula I). I + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + ametryn, I + amicarbazone, I + amidosulfuron, I + aminopyralid, I + amitrole, I + anilofos, I + asulam, I + atrazine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bromobutide, I + bromoxynil, I + butachlor, I + butamifos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, I + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid,

I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + cyanazine, I + cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop,

I + cyhalofop-butyl,, I + 2,4-D, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + I + desmedipham, I + dicamba, I + dichlobenil, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclofop-methyl, I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + dimethachlor, I + dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron,

I + endothal, I + EPTC, I + esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron- methyl, I + ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I + fenoxaprop-P, I + fenoxaprop-P-ethyl, I + fenquinotrione, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop-butyl, I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone-sodium, I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I + flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumiclorac-pentyl, I + flumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I + fluoroglycofen-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I + fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinate-ammonium, I + glyphosate, I + halauxifen, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-P, I + hexazinone,

I + imazamethabenz, I + imazamethabenz-methyl, I + imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I + imazosulfuron, I + indanofan, I + indaziflam, I + iodomethane, I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + isoproturon, I + isouron, I + isoxaben,

I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron, I + metazachlor,

I + methabenzthiazuron, I + methazole, I + methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, I + metolachlor, I + S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I + metsulfuron-methyl, I + molinate, I + monolinuron, I + naproanilide, I + napropamide, I + naptalam, I + neburon, I + nicosulfuron, I + n-methyl glyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, I + pendimethalin, I + penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + pethoxamid, I + phenmedipham, I + picloram, I + picolinafen,

I + pinoxaden, I + piperophos, I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I + prodiamine, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I + propisochlor, I + propoxycarbazone, I + propoxycarbazone-sodium, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen-ethyl, I + pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + pyridate, I + pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac, I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxsulam, I + quinclorac, I + quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + rimsulfuron, I + saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I + terbutryn, I + thenylchlor, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + topramezone, I + tralkoxydim, I + tri-allate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trihydroxytriazine, I + trinexapac-ethyl, I + tritosulfuron, I + [3-[2-chloro-4-fluoro-5-(1 -methyl-6- trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31 -6), I + 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one, I + 4-hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-

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

3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin- 2-one, I + (4R)1 -(5-tert-butylisoxazol-3- yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, I + 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3- oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, I + 2-[2-(3,4-dimethoxyphenyl)-6- methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1 ,3-dione, I + 2-[2-(3,4- dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cycloh exane-1 ,3-dione, 2-[2-(3,4- dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-d imethyl-cyclohexane-1 ,3-dione, I + 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbo nyl]-2,2,4,4-tetramethyl- cyclohexane-1 ,3,5-trione, I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbo nyl]- 5-ethyl-cyclohexane-1 ,3-dione, I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1 ,3-dione, I + 2-[6-cyclopropyl-2-(3,4- dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclo hexane-1 ,3-dione, I + 3-[6- cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbo nyl]bicyclo[3.2.1]octane-2,4- dione, I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carbonyl]-5, 5-dimethyl- cyclohexane-1 , 3-dione, I + 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1 ,3,5-trione, I + 2-[6-cyclopropyl-2-(3,4- dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1 , 3-dione, I + 4-[2-(3,4- dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6 ,6-tetramethyl-tetrahydropyran- 3,5-dione and 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carbonyl]-2, 2,6,6- tetramethyl-tetrahydropyran-3,5-dione. The compounds of the present invention may also be combined with herbicidal compounds disclosed in W006/024820 and/or WO07/096576.

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 of Formula I according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of Formula I according to the invention with one or more further herbicides can also be used in combination with one or more safeners. The safeners can be AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31 -8), dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, N- isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4). Other possibilities include safener compounds disclosed in, for example, EP0365484 e.g N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfona mide. Particularly preferred are mixtures of a compound of Formula I with cyprosulfamide, isoxadifen-ethyl, cloquintocet- mexyl and/or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenes ulfonamide.

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, 16 ^th 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, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc. 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 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 safener).

The present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I). Moreover, the present invention further provides 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. Generally the plants to be controlled are unwanted plants (weeds).‘Locus’ means the area in which the plants are growing or will grow. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I). However, in some instances tolerance may need to be engineered into the crop plant, for example by way of genetic engineering. Thus, it is possible that the crop plant is rendered tolerant to HPPD-inhibitors via genetic engineering. Methods of rending crop plants tolerant to HPPD-inhibitors are known, for example from WO0246387. Thus in an even more preferred embodiment the crop plant is transgenic in respect of a polynucleotide comprising a DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more particularly, from a barley, maize, wheat, rice, Brachiaria, Cenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species. Several HPPD-tolerant soybean transgenic “events” are known, and include for example SYHT04R (WO2012/082542), SYHT0H2 (WO2012/082548) and FG72. Other polynucleotide sequences that can be used to provide plants which are tolerant to the compounds of the present invention are disclosed in, for example, W02010/085705 and WO201 1/068567. Crop plants in which the composition according to the invention can be used thus include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.

Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.

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 2000 g/ha, especially from 50 to 1000 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 herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-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 KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

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).

Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes. 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. Weeds can also include plants which may be considered crop plants but which are growing outside a crop area (‘escapes’), or which grow from seed left over from a previous planting of a different crop (‘volunteers’). Such volunteers or escapes may be tolerant to certain other herbicides.

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

Amides of formula (I) may be prepared from benzoic acids of formula (II).

To prepare compound of formula (I) where Q=Q1 , the benzoic acid of formula (II) and amine of formula (III) are reacted by using an amide coupling agent such as N,N’-carbonyldiimidazole or phosphorous oxychloride in a suitable solvent such as 1 ,4-dioxane or N,N-dimethylformamide. To prepare compound of formula (I) where Q=Q2, the benzoic acid of formula (II) and amine of formula (IV) are reacted by using an amide coupling agent such as N,N’-carbonyldiimidazole or phosphorous oxychloride in a suitable solvent such as 1 ,4-dioxane or N,N-dimethylformamide. Benzoic acids of formula (II) may be prepared from esters of formula (V).

Where“Aik” is defined as a C ₁ -C ₆ alkyl group.

The ester of formula (V) is treated with a hydroxide base such as lithium hydroxide in a suitable solvent mixture, for example a 3:1 mixture of ethanol and water. Compounds of formula (V) may be prepared by condensation of compounds of formula (VI) with hydrazines of formula (VII).

The compound of formula (VI) is treated with the hydrazine of formula (VII) in the presence of a suitable base, for example potassium acetate, in a suitable solvent, for example ethanol. Compounds of formula (VI) may be prepared by a variety of methods depending on the nature of R ² , R ³ and R ⁴ .

For certain embodiments of the invention where R ⁴ = H, compounds of formula (VI) may be prepared from compounds of formula (VIII).

The compound of formula (VIII) is treated with N-methylmorpholine-N-oxide in the presence of a suitable solvent, for example dimethylsulfoxide.

Compounds of formula (VIII) may be prepared from compounds of formula (IX).

The compound of formula (IX) is treated with a suitable brominating reagent, for example N- bromosuccinimide, in the presence of a suitable catalyst, for example benzoylperoxide or azobisisobutyronitrile, in a suitable solvent, for example chloroform or benzotrifluoride.

Certain embodiments of compounds of formula (V) where R ² is alkyl may be prepared by from other embodiments of formula (V) where R ² is chloro.

The chloroarene is treated with an alkyl boronic acid (for example methyl boronic acid) in the presence of a suitable base, for example potassium carbonate, in a suitable solvent, for example 1 ,4-dioxane and with a suitable palladium catalyst. An example of a suitable palladium catalyst is [1 ,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyr idyl)palladium(ll) dichloride.

The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to the Table provided herein.

Example P1. Preparation of Compound 1.001

Step 1 :

Ethyl 2-chloro-3-methyl-4-(trifluoromethyl)benzoate (200 mg, 0.750 mmol) was taken in benzotrifuloride (6 ml_). To it was added NBS (0.534 g, 3.00 mmol) and benzoyl peroxide (75.0 %, 0.0484 g, 0.150 mmol) and it was heated at 120°C for 6h. The reaction mixture was cooled, then diluted with ethyl acetate, washed with sat. NaHC03 solution, dried over Na2S04 and concentrated. Chromatography (hexane to 30% ethyl acetate-hexane) gave ethyl 3- (bromomethyl)-2-chloro-4-(trifluoromethyl)benzoate as an oil. 1 H NMR (400 MHz, CDCI3): 7.71- 7.73 (d, 1 H), 7.63-7.65 (d, 1 H), 4.74 (s, 2H), 4.40-4.46 (q, 2H), 1.39-1.42 (t, 3H).

Step 2:

To a flask was added: ethyl 3-(bromomethyl)-2-chloro-4-(trichloromethyl)benzoate (0.88 g, 2.55 mmol), DIMETHYL SULFOXIDE (4.4 mL) and dichloromethane (4.4 mL). The mixture was cooled in an ice bath and charged with 4-methyl-4-oxido-morpholin-4-ium (1.23 g, 10.2 mmol) in several portions over 5 min, then stirred for 20 min at 0 °C. The reaction mixture is red solution. The mixture was concentrated to remove DCM. The resulting DMSO solution was partitioned between EtOAc and water. The organic layer was separated and concentrated. The crude was purified by flash chromatography (0% for 1 min, then 0 to 5 % ethyl acetate / cyclohexane over 14 min) to give ethyl 2-chloro-3-formyl-4-(trifluoromethyl)benzoate (0.526 mg, 1.87 mmol, 73%) as a colourless oil. NMR (19-17432-1): 1 H NMR (400 MHz, chloroform) d = 10.49 (q, J = 1.9 Hz, 1 H), 7.95 (d, J = 8.1 Hz, 1 H), 7.75 (d, J = 8.2 Hz, 1 H), 4.46 (q, J = 7.1 Hz, 2H), 1.43 (t, J = 7.2 Hz, 3H)

Step 3:

To a solution of ethyl 2-chloro-3-formyl-4-(trifluoromethyl)benzoate (280 mg, 0.998 mmol) in Ethanol (4.2 mL), was added 1 ,1 -dimethylhydrazine (66 mg, 1.10 mmol) to the reaction mass at 0 °C. Potassium acetate (147 mg, 1.50 mmol) was added and the reaction was stirred for 16 h.

The ethanol was evaporated and the residue was taken up with ethyl acetate, washed with water and brine, then dried (Na ₂ S0 ₄ ) and concentrated. The crude product was purified by chromatography (10-40 % ethylacetate in cyclohexane) to give ethyl 2-chloro-3- [(dimethylhydrazono)methyl]-4-(trifluoromethyl)benzoate (180 mg, 0.502 mmol, 50% Yield) as pale yellow gum. 1 H NMR (400 MHz, chloroform-d) d ppm 7.62 - 7.69 (m, 2 H) 7.29 - 7.34 (m, 1 H) 4.44 (q, 2 H) 3.06 (s, 6 H), 1.42 (t, 3 H). Step 4:

To a stirred suspension of ethyl 2-chloro-3-[(dimethylhydrazono)methyl]-4-

(trifluoromethyl)benzoate (0.16 g, 0.50 mmol) in ethanol (3.2 ml.) and water (1.6 ml_), was added lithium hydroxide (30 mg, 1.2 mmol) at 0 °C. The reaction mixture was stirred at RT for 1 h. The reaction was diluted with water, washed with then acidified with 1 N HCI to pH 1. It was then extracted with ethylacetate. The organic part was then washed with water, brine and dried over anhydrous Na2S04 and concentrated to give 2-chloro-3-[(dimethylhydrazono)methyl]-4-

(trifluoromethyl)benzoic acid (140 mg, 0.451 mmol, 91 % Yield) as yellow solid. 1 H NMR (400 MHz, d6-DMSO): 7.80 (1 H, d), 7.71 (1 H, d), 7.27 (1 H, s), 2.95 (6H, s).

Step 5:

2-chloro-3-[(dimethylhydrazono)methyl]-4-(trifluoromethyl)be nzoic acid (135 mg, 0.458 mmol), 1- methyltetrazol-5-amine (54 mg, 0.55 mmol) were taken in pyridine (1.35). To it, phosphorous oxychloride (86 mg, 0.55 mmol) was added at - 5 °C and slowly warmed to r.t. and stirred at RT for 1 h. The reaction mass was quenched with water, diluted with ethylacetate, organic part was washed with water, 1 N HCI solution and brine, then dried over anhydrous Na ₂ S0 ₄ , concentrated to give 2-chloro-3-[(dimethylhydrazono)methyl]-N-(1 -methyltetrazol-5-yl)-4-

(trifluoromethyl)benzamide (43 mg, 0.109 mmol, 24% Yield). 1 H NMR (400 MHz, DMSO-d6) 1 1 .95 (1 H, s), 7.89 (d, 1 H), 7.79 (br d, 1 H), 7.30 (s, 1 H), 4.01 (3H, s), 2.99 (6H, s).

Example P2. Preparation of Compound 1.005.

Step 1 :

A reactor was charged with 2-chloro-3-methyl-4-methylsulfonyl-benzoic acid (50 g, 191 mmol) and chlorobenzene (1 L), followed by 1 ,3-dibromo-5,5-dimethylhydantoin (17.23 g, 60.0 mmol). The mixture was stirred at room temperature for 10 min then heated to 100 °C. A solution of 2,2'- azo BIS(2-methylpropionitrile) (6.4 g, 38.2 mmol) in chlorobenzene (40 ml) was added dropwise and heating continued for 30 min. Every 30 min the reaction was charged with further ,3-dibromo- 5,5-dimethylhydantoin (17.23 g, 60.0 mmol), followed by 2,2'-azoBIS(2-methylpropionitrile) (6.4 g, 38.2 mmol) in chlorobenzene (40 ml). After 4 additions the reaction was judged to be complete. The mixture was cooled to room temperature and the reactor was charged with water (250 ml) and stirred for 15 min. The mixture was filtered and the solid dried to give 3-(bromomethyl)-2- chloro-4-methylsulfonyl-benzoic acid (35 g, 54%) as a white solid. 1 H NMR (400 MHz, METHANOL-d4) d = 8.10 - 8.15 (m, 1 H), 7.86 - 7.90 (m, 1 H), 5.01 - 5.84 (m, 2H), 3.33 - 3.35 (m, 3 H).

Step 2:

Step 3:

A solution of 3-(bromomethyl)-2-chloro-4-methylsulfonyl-benzoic acid (20 g, 61.05 mmol) in triethyl orthoformate (200 ml.) was heated to 120 °C for 3.5 h. The mixture was cooled to room temperature and filtered. The filtrate was concentrated thoroughly to give ethyl 3-(bromomethyl)- 2-chloro-4-methylsulfonyl-benzoate (15.5 g, 71 %) as an off white solid. 1 H NMR (400 MHz, chloroform) d = 8.12 (d, J = 8.3 Hz, 1 H), 7.79 (d, J = 8.2 Hz, 1 H), 5.97 - 4.61 (m, 2H), 4.46 (q, J = 7.2 Hz, 2H), 3.34 - 3.27 (m, 3H), 1.43 (t, J = 7.2 Hz, 3H).

To a flask was added ethyl 3-(bromomethyl)-2-chloro-4-methylsulfonyl-benzoate (6.0 g, 16.9 mmol), dimethyl sulfoxide (30 ml.) and dichloromethane (30 ml_). The mixture was cooled in an ice bath and charged with 4-methyl-4-oxido-morpholin-4-ium (8.15 g, 67.5 mmol) in several portions over 5 min, then stirred for 20 min at 0 °C. The mixture was concentrated to remove DCM. The resulting DMSO solution was partitioned between EtOAc and water. The organic layer was washed with water, then brine, dried (MgS04) and concentrated. The crude was purified by flash chromatography (silica: 120 g, cyclohexane/ethyl acetate) to give ethyl 2-chloro-3-formyl-4- methylsulfonyl-benzoate (4.5 g, 92%) as a white solid. 1 H NMR (400 MHz, chloroform) d = 10.49 (s, 1 H), 8.09 - 8.05 (m, 1 H), 8.02 - 7.98 (m, 1 H), 4.50 - 4.43 (m, 2H), 3.29 (s, 3H), 1.43 (t, J = 7.1 Hz, 3H).

Step 4:

To a solution of ethyl 2-chloro-3-formyl-4-methylsulfonyl-benzoate (1.0 g, 3.3 mmol) in ethanol (15 ml_), was added morpholin-4-amine (0.40 g, 3.9 mmol) to the reaction mass at 0 °. Then potassium acetate (0.48 g, 4.9 mmol) was added to the reaction mixture and the reaction mass was stirred at r.t. for 16 hr then concentrated. The crude was directly purified by chromatography (35 % ethylacetate in cyclohexane to give ethyl 2-chloro-4-methylsulfonyl-3-

(morpholinoiminomethyl)benzoate (1.1 g, 2.8 mmol, 85% Yield) as a pale yellow solid. 1 H NMR (400 MHz, CHLOROFORM-d) d ppm 8.10 (d, 1 H), 7.73 - 7.81 (m, 2 H), 4.44 (d, 2 H), 3.93-3.90

(4H, m), 3.29 (3H, s), 3.25-3.27 (4H, m), 1.41 (3H, t).

Step 5:

To a stirred suspension of ethyl 2-chloro-4-methylsulfonyl-3-(morpholinoiminomethyl)benzoate (1.1 g, 2.9 mmol) in ethanol (22 ml.) and water (1 1 ml_), was added lithium hydroxide (0.18 g, 7.3 mmol) at 0 °C. The reaction mixture was stirred at RT for 1 h. The reaction was diluted with water and then washed with ethylacetate. The aqueous layer was then acidified with 1 N HCI to pH 1. The aqueous layer was then extracted with ethylacetate. The organic part was then washed with water and brine solution, dried over Na2S04, concentrated to give 2-chloro-4-methylsulfonyl-3- (morpholinoiminomethyl)benzoic acid (900 mg, 2.465 mmol, 84% Yield) as pale yellow solid. 1 H NMR (400 MHz, d6-DMSO): 13.88 (1 H, brs), 8.03 (1 H, d), 7.96-7.79 (2H, m), 3.79 (3H, s), 3.48- 3.27 (4H, m), 3.17 (4H, m). Step 6:

2-chloro-4-methylsulfonyl-3-(morpholinoiminomethyl)benzoic acid (150 mg, 0.433 mmol), 1- ethyltetrazol-5-amine (59 mg, 0.52 mmol) were dissolved in pyridine (1.5 ml_). To it, phosphorous oxychloride (81 mg, 0.52 mmol) was added at - 5 °C and slowly warmed to RT and stirred for 1 h. The reaction was quenched with water, diluted with ethylacetate and the layers were separated. The organic layer was washed with water, 1 N HCI solution, brine, then dried over Na ₂ SO ₄ and concentrated. The crude product was purified by chromatograph (dichloromethane to 20 % methanol in dichloromethane to give 2-chloro-N-(1 -ethyltetrazol-5-yl)-4-methylsulfonyl-3- (morpholinoiminomethyl)benzamide (110 mg, 0.2365 mmol, 55% Yield) as a brown solid. 1 H NMR (400 MHz, methanol-d4) d ppm 8.20 (d, 1 H) 7.82 - 7.92 (m, 2 H) 4.45 (q, 2 H) 3.87 - 3.93 (m, 4 H) 3.36 (s, 3 H) 3.23 - 3.31 (m, 4 H), 1.60 (3H, t).

Preparation of Compound 1.010. Steps 1 to 3 are the same as the example preparation of Compound 1.005 above.

Step 4:

To a solution of ethyl 2-chloro-3-formyl-4-methylsulfonyl-benzoate (2.4 g, 7.8 mmol) in ethanol (36 ml_), was added 1 , 1-dimethylhydrazine (0.52 g, 8.6 mmol) to the reaction mass at 0 °C. Then potassium acetate (1.2 g, 12 mmol) was added to the reaction mixture and whole reaction mass was stirred at r.t. for 16 hrs. The reaction was quenched with water and then ethanol was evaporated and reaction mass extracted with ethylacetate and then washed with water, brine solution and dried over anhydrous Na2SO ₄ and concentrated. The crude product was purified by chromatography (10-40 % ethylacetate in cyclohexane) to give ethyl 2-chloro-3-

[(dimethylhydrazono)methyl]-4-methylsulfonyl-benzoate (2.35 g, 6.71 mmol, 86% Yield) as pale yellow gum. 1 H NMR (400 MHz, CDCI3): 8.10 (1 H, d), 7.70 (1 H, d), 4.43 (2H, q), 3.33 (3H, s), 3.07 (6H, s), 1.41 (3H, t).

Step 5:

To a stirred suspension of ethyl 2-chloro-3-[(dimethylhydrazono)methyl]-4-methylsulfonyl- benzoate (900 mg, 2.569 mmol) in ethanol (18 ml.) and water (9 ml_), was added lithium hydroxide (0.157 g, 6.42 mmol) at 0 °C. The reaction mixture was stirred at RT for 1 h. The reaction was diluted with water and then washed with ethylacetate. The aqueous layer was then acidified with 1 N HCI topH 1. It was then extracted with ethylacetate. The organic layer was then washed with water, brine solution and dried over anhydrous Na ₂ SO ₄ , concentrated to get the desired product 2-chloro-3-[(dimethylhydrazono)methyl]-4-methylsulfonyl-benz oic acid (650 mg, 2.026 mmol, 79% Yield) as yellow solid. 1 H NMR (d6-DMSO): 13.95 (1 H, brs), 8.02 (1 H, d), 7.79 (1 H, d), 7.37 (1 H, s), 3.38 (3H, s), 2.99 (6H, s).

Step 6:

2-chloro-3-[(dimethylhydrazono)methyl]-4-methylsulfonyl-benz oic acid (200 mg, 0.623 mmol), 5- methyl-1 ,3,4-oxadiazol-2-amine (74 mg, 0.1 1 1 mmol) in 3-methylpyridine (1.6 ml.) was stirred for 10 mins under nitrogen atmosphere , then 1 -methylimidazole (77 mg, 0.935 mmol) was added and stirred at RT for 1 hr. Reaction mass was then cooled to 0 °C and thionyl chloride (1 1 1 mg, 0.935 mmol) was added to it and then was stirred at r.t. for 12 h. Reaction mass was quenched with water, diluted with ethylacetate and the layers were separated. The organic part was washed with water, 1 N HCI solution and brine, dried over Na2S04 and concentrated. The crude residue was purified by chromatography (10 % methanol in dichloromethane) for 30 minutes to give 2- chloro-3-[(dimethylhydrazono)methyl]-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-4-methylsulfonyl- benzamide (45 mg, 0.1 1 1 mmol, 18%). 1 H NMR (400 MHz, METHANOL-d4) d ppm 8.14 (m, 1 H), 7.69 (d, 1 H), 7.44 (s, 1 H), 3.34 - 3.40 (m, 3 H), 3.07 (s, 6 H).

TABLE 1 - Examples of herbicidal compounds of the present invention.

Biological Examples

Seeds of a variety of test species are 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 cultivation for one day (preemergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 500 g/h unless otherwise indicated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16PC, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days for pre and postemergence, 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 = 80-100%; 4 = 60-79%; 3=40- 59%; 2=20-39%; 1=0-19%). Table B1 : Application pre-emergence

Table B2: Application post-emergence