WO2017178582A1 - Herbicidal pyridazinone compounds - Google Patents

Herbicidal pyridazinone compounds Download PDF

Info

Publication number
WO2017178582A1
WO2017178582A1 PCT/EP2017/058915 EP2017058915W WO2017178582A1 WO 2017178582 A1 WO2017178582 A1 WO 2017178582A1 EP 2017058915 W EP2017058915 W EP 2017058915W WO 2017178582 A1 WO2017178582 A1 WO 2017178582A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
methyl
oxo
ethyl
Prior art date
Application number
PCT/EP2017/058915
Other languages
French (fr)
Inventor
Paul Matthew BURTON
Steven GAULIER
Paula Rocha RZEPA
Melanie Jayne WATKINS
Mary Bernadette Aspinall
Edward John EMMETT
Original Assignee
Syngenta Participations Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB1617766.9A external-priority patent/GB201617766D0/en
Priority to EP17717174.1A priority Critical patent/EP3442962B1/en
Priority to AU2017251378A priority patent/AU2017251378B2/en
Priority to CA3019009A priority patent/CA3019009A1/en
Priority to JP2018554085A priority patent/JP6855504B2/en
Priority to CN201780023236.9A priority patent/CN108884074B/en
Priority to BR112018071154-3A priority patent/BR112018071154B1/en
Priority to MX2018012303A priority patent/MX2018012303A/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to KR1020187030965A priority patent/KR102445810B1/en
Priority to EA201892259A priority patent/EA038043B1/en
Priority to US16/093,338 priority patent/US10813354B2/en
Priority to UAA201811036A priority patent/UA122439C2/en
Publication of WO2017178582A1 publication Critical patent/WO2017178582A1/en
Priority to ZA2018/06433A priority patent/ZA201806433B/en
Priority to IL262187A priority patent/IL262187B/en
Priority to PH12018502201A priority patent/PH12018502201A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • 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.
  • Herbicidal pyridazinone compounds are disclosed in WO 2012/136703. These compounds are shown to afford effective weed control with regard to a variety of problematic weed species.
  • the present invention relates to novel herbicidal pyridazinone compounds which exhibit further improved properties.
  • the compounds of the present invention exhibit improved crop selectivity. That is, they continue to provide effective levels of weed control, whilst exhibiting a reduction in undesirable crop phytotoxicity.
  • R 1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C6alkyl-, C 3 -C6cycloalkyl-, C2-C 6 -alkenyl-, C2-C6alkynyl-, Ci-Cehaloalkyl-, Ci-C6alkoxy-, Ci-C 3 haloalkoxy-, Ci-C6alkoxy-Ci-C3alkyl-, Ci-C6alkyl-S(0)p- and Ci-C 6 haloalkyl-S(0)p-;
  • a 1 is selected from the group consisting of O, C(O) and (CRT ⁇ ;
  • R a , R b , R c , R d , R e and R f are each independently selected from the group consisting of hydrogen and Ci-C4alkyl- wherein R a and R c may together form a Ci-C3alkylene chain; and p is 0, 1 or 2.
  • Ci-C6alkyl- and Ci-C4alkyl- includes, for example, methyl (Me, CH 3 ), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (z-Pr), n-butyl (n- u), isobutyl (z ' -Bu), sec-butyl and tert-butyl (t-Bu).
  • C2-C6alkynyl- includes, for example, -C ⁇ CH (ethynyl) and -CH2-C ⁇ CH (propargyl).
  • Halogen includes, for example, fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
  • Ci-Cehaloalkyl- includes, for example, f uoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentaf uoroethyl, l , l-difluoro-2,2,2-trichloroethyl, 2,2,3, 3-tetrafluoropropyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro- n-hexyl.
  • Ci-C6alkoxy- includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy.
  • Ci-Cshaloalkoxy- includes, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
  • Ci-C6alkyl-S- (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
  • Ci-Cehaloalkyl-S- (haloalkylthio) relates to halogenated derivatives thereof.
  • Ci-C6alkyl-S(0)- (alkylsulfinyl) includes, for example, methylsulfmyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl or tert-butylsulfinyl, preferably methylsulfmyl or ethylsulfinyl.
  • Ci- Cehaloalkyl-S(O)- (haloalkylsulfinyl) relates to halogenated derivatives thereof.
  • Ci-C6alkyl-S(0)2- (alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
  • Ci- Cehaloalkyl-S(0)2- (haloalkylsulfonyl) relates to halogenated derivatives thereof.
  • Ci-C6alkoxy-Ci-C3alkyl- includes, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxy ethyl.
  • C3-C 6 cycloalkyl- includes, for example, cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl).
  • R 1 is Ci-C6alkyl- (preferably methyl) or C3- Cecycloalkyl- (preferably cyclopropyl). In a more preferred embodiment R 1 is methyl or cyclopropyl.
  • Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities. Similarly, where there are disubstituted or trisubstituted alkenes, these may be present in E or Z form or as mixtures of both in any proportion.
  • compounds of Formula (I) may be in equilibrium with alternative tautomeric forms.
  • compounds of Formula (I) are depicted in the keto form, they may also exist in the alternative enol form as depicted in Formula ( ⁇ ) below.
  • the present invention also provides agronomically acceptable salts of compounds of Formula (I).
  • Salts that the compounds of Formula (I) may form with amines including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.
  • Aluminium, calcium, cobalt, copper (copper (I), copper (II)), iron (iron (II), iron (III)), magnesium, potassium, sodium or zinc salts of compounds of Formula (I) are particularly preferred; copper, potassium and sodium being especially preferred.
  • the compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using co-formulants, such as carriers, solvents, surface-active agents (SAA) and adjuvants.
  • co-formulants such as carriers, solvents, surface-active agents (SAA) and adjuvants.
  • the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable co-formulant.
  • 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 co-formulant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • compositions can be chosen from a number of formulation types. These include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP), a ZC (combination of SC and CS) and a soluble granule (SG).
  • formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound
  • Soluble powders 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).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules 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 preformed 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.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • 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).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • 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).
  • DC Dispersible Concentrates
  • a compound of Formula (I) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates 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) and dimethyl amides of fatty acids (such as Cs-Cio fatty acid dimethylamide).
  • 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
  • alcohols such as benzyl alcohol, furfuryl alcohol or butanol
  • Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SAAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of Formula (I) is present initially in either the water or the solvent/SAA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water- soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs 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.
  • 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.
  • a suitable medium for example water or a water miscible liquid, such as n-propanol
  • Capsule suspensions 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).
  • a compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • Soluble concentrate (SL) may be prepared by dissolving the active ingredient in an aqueous liquid which optionally comprises wetting agent(s) and/or buffer(s).
  • 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).
  • additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).
  • SAAs surface active agents
  • spray additives based on oils for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).
  • co-formulants include:-
  • wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-z ' sopropyl- and tri-z ' 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
  • Suitable SAAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • partial esters derived from long chain fatty acids or hexitol anhydrides condensation products of
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • composition of the present may further comprise one or more additional pesticides.
  • the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators.
  • a herbicidal composition comprising (A) a compound of Formula (I) and (B) one or more herbicides selected from the group consisting of acetochlor, aciflurofen (acifluorfen-sodium), aclonifen, alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, anilifos, asulam, atrazine, beflubutamid, benefin, benfluralin, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bifenox, bispyribac-sodium, bromacil, bromoxynil, butachlor, butroxydim, but
  • R 1 is H, Ci-C6alkyl, Ci-C 6 haloalkyl or C4-C8 cycloalkyl;
  • R 6 is H, Ci-Cealkyl, or Ci-C 6 alkoxy
  • Q 1 is an optionally substituted ring system, selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, wherein when substituted said ring system is substituted by 1 to 3 R 4 ;
  • Q 2 is an optionally substituted ring system, selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinone, thiadazolyl, thiazolyl, and oxazolyl, wherein when substituted said ring system is substituted by 1 to 3 R 5 ;
  • each R 4 is independently halogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy,
  • each R 7 is independently Ci-C 6 alkyl, halogen, or Ci-Cehaloalkyl
  • R 8 is Ci-C4alkoxycarbonyl
  • R 1 1 is H, Ci-Cealkyl, Ci-C 6 haloalkyl or C 4 -C 8 cycloalkyl;
  • n is an integer of 0, 1 , 2, or 3;
  • p is an integer of 0, 1 , 2, or 3;
  • each R 2 is independently halogen, Ci-C 6 haloalkyl, or Ci-Cehaloalkoxy; and each R 3 is independently halogen, Ci-C 6 haloalkyl, Ci-C 6 haloalkoxy.
  • (B) is one or more herbicides selected from the group consisting of acetochlor, alachlor, ametryn, amicarbazone, atrazine, bicyclopyrone, bromoxynil, butachlor, chlorotoluron, clodinafop-propargyl, clopyralid, 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof), diflufenican, dimethachlor, dimethenamid-P, diuron, fenoxaprop-P-ethyl, fenquinotrione, florasulam, fiuazifop-P-butyl, fiuroxypyr-meptyl, flucarbazone- sodium, flufenacet, for
  • (B) is one or more herbicides selected from the group consisting of atrazine, bicyclopyrone, bromoxynil, clodinafop-propargyl, diflufenican, fenoxaprop-P-ethyl, florasulam, flufenacet, fluroxypyr-meptyl, glufosinate (including the ammonium salt thereof), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen-methyl, iodosulfuron- methyl-sodium, MCPA, mesosulfuron-methyl, mesotrione, metribuzin, metsulfuron, nicosulfuron, S-metolachlor, pinoxaden, prosulfocarb, pyroxsulam and terbuthylazine.
  • herbicides selected from the group consisting of atrazine, bicyclopyrone
  • R 11 is H, Ci-C 6 alkyl or Ci-C 6 haloalkyl, more preferably methyl, ethyl or CHF 2 , and more preferably still, H or methyl.
  • R 6 is H.
  • Q 1 is either a phenyl ring or a pyridinyl ring, each of which is optionally substituted by 1 to 3 R 4 .
  • Q 1 is a phenyl ring substituted by 1 to 2 R 4 .
  • Q 2 is a phenyl ring, optionally substituted by 1 to 3 R 5 . More preferably Q 1 is phenyl substituted by 1-3 R 5 .
  • each R 4 is independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, Ci-C3alkoxy, or Ci- Cshaloalkoxy; more preferably chloro, fluoro, bromo, Ci-C 2 haloalkyl, Ci- C 2 haloalkoxy, or Ci-C 2 alkoxy.
  • each R 5 is independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, Ci-C3alkoxy, or Ci-C3haloalkoxy; more preferably chloro, fluoro, bromo, Ci-C 2 haloalkyl, Ci-C 2 haloalkoxy, or Ci-C 2 alkoxy; more preferably still fluoro.
  • Particularly preferred compounds of formula B8 for use as component B in compositions of the invention are shown as compounds B801 to B815 below in Table B8.
  • Table B8 Compound of formula (B8) for use in compositions described herein.
  • component B is a compound of formula B9 it is preferred that p is 1, 2, or 3, more preferably 1 or 2.
  • n is 1, 2 or 3, more preferably 1 or 2.
  • R 1 is H or Ci-C6alkyl, more preferably H or methyl. In one set of embodiments R 1 1 is H.
  • each R 2 is independently chloro, fluoro, Ci-Cshaloalkyl, or Ci- Cshaloalkoxy, more preferably chloro, fluoro, Ci-fluoroalkyl (i.e. fluoromethyl, difluoromethyl, trifluoromethyl) Ci-fluoroalkoxy (i.e. trifluoromethoxy, difluoromethoxy, fluoromethoxy).
  • each R 3 is independently chloro, fluoro, Ci-Cshaloalkyl, or Ci-Cshaloalkoxy, more preferably chloro, fluoro, Ci-fluoroalkyl (i.e.
  • Ci-fluoroalkoxy i.e. trifluoromethoxy, difluoromethoxy, fluoromethoxy.
  • Particularly preferred compounds of formula B9 for use as component B in compositions of the invention are shown below in Table B9.
  • component (A) is compound 1.1. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.2. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.3. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.4. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.5. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.6. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.7.
  • component (A) is compound 1.8. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.9. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.10. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.11. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.12. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.13. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.14. Further example compositions of the invention comprise:
  • component compound 1.1 is replaced by compound 1.2. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.3. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.4. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.5. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.6. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.7. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.8.
  • component compound 1.1 is replaced by compound 1.9. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.10. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.11. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.12. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.13. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.14.
  • the mixing ratio of the compound of Formula (I) to the mixing partner B can vary depending on the nature of the mixing partner(s). Typical ratios include, for example, from 1 : 100 to 1000: 1, from 1 :50 to 50: 1, or from 1 : 10 to 10: 1.
  • compositions as defined in Tables 2 to 14 below. TABLE 2. Compositions comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.2 (see Table CI).
  • compositions comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.3 (see Table CI).
  • compositions comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.4 (see Table CI).
  • compositions of the invention can further include one or more safeners.
  • the following safeners are particularly preferred: AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, furilazome, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetnnil, naphthalic anhydride (CAS R 81-84-5), TI-35, N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)- benzamide (CAS RN 221668-34-4) and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenes
  • Particularly prefened safeners are cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl, mefenpyr-diethyl and N-(2-methoxybenzoyl)-4-
  • compositions of the invention and safeners include:
  • Compound 1.1 S-metolachlor and cloquintocet-mexyl; compound 1.1, S-metolachlor and cyprosulfamide; compound 1.1, S-metolachlor and isoxadifen-ethyl; compound 1.1, S-metolachlor and mefenpyr-diethyl; compound 1.1, S-metolachlor and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
  • compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.2. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.3. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.4. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.5. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.6. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.7.
  • compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.8. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.9. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.10. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.11. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.12. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.13. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.14.
  • the compounds of Formula I can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.
  • 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. The application may be applied to the locus pre-emergence and/or postemergence of the crop plant.
  • Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I).
  • Preferred crop plants include maize, wheat, barley and rice.
  • tolerance may need to be engineered into the crop plant, for example by way of genetic engineering.
  • the crop plant is rendered tolerant to 4-hydroxyphenylpyruvate dioxygenase (HPPD)-inhibitors via genetic engineering.
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • 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.
  • 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,
  • HPPD-tolerant soybean transgenic "events” are known, and include for example SYHT04R (WO2012/082542), SYHT0H2 (WO2012/082548) and FG72. Accordingly, the herbicidal compounds of the present invention have broad application in a number of crop plants, including 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 25 to 1000 g/ha, more especially from 25 to 250 g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, and ACCase-inhibitors
  • 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).
  • 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 PvOundupReady® 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).
  • 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.
  • 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).
  • 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).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • the compositions can be used to control unwanted plants (collectively, 'weeds').
  • the weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
  • a compound of Formula (I) as defined herein as a herbicide.
  • the compounds of the present invention can be prepared according to the following schemes.
  • Preparation of compounds Formula (I) is carried out analogously to known processes and comprises reacting a compound of Formula (He): where the definition of R 1 is as for Formula (I) and LG is a suitable leaving group, for example a halogen atom, such as chlorine, or an alkoxy or aryloxy group, such as 4- nitrophenoxy, in an inert organic solvent, such as dichloromethane or acetonitrile, in the presence of a base, such as triethylamine, with a diketone of Formula (III)
  • a 1 and R a , R b , R c , R d are as defined previously in respect of Formula (I);
  • R 1 is as defined as before and R 2 is selected from the group consisting of halogen, -OH, Ci-C 6 alkoxy, aryloxy and N-linked imdazolyl.
  • aryloxy is preferably a phenoxy group optionally substituted on the phenyl ring by one to five groups consisting of: fluoro, chloro, nitro, cyano, Ci- Csalkyl , Ci-C3alkoxy and Ci-Cshaloalkyl.
  • Specific examples of preferred aryloxy groups thus include phenoxy, 4-nitrophenoxy and 2,3,4,5, 6- pentafluorophenoxy.
  • the diketones of Formula (III) may be commercially available or, where they are not, prepared through methods detailed in the literature.
  • the preparation of the dione where A 1 is CH(ethyl) and R a , R b , R c and R d are all hydrogen is detailed in Tetrahedron, 2000, 4753-4758.
  • the preparation of the dione where A 1 is CH 2 , R a -R c is -CH 2 CH 2 - and R b and R d are both hydrogen is detailed in Tetrahedron Lett. 2013, 557-561.
  • the preparation of the dione where A 1 is CH 2 and R a , R b , R c and R d are all methyl is detailed in US5006150 Al, 1991.
  • a method of producing a compound of Formula (I) comprising (i) reacting, in an inert organic solvent and in the presence of a base, a compound of Formula (He):
  • R 1 is as for Formula (I) and LG is a suitable leaving group (for example a halogen atom, such as chlorine, or an alkoxy or aryloxy group, such as 4-nitrophenoxy), with a diketone of Formula (III)
  • LG chloro
  • the skilled person will recognise the common methods to execute this transformation such as treatment of the carboxylic acid with 1 equivalent of oxalyl chloride and a catalytic quantity of N,N-dimethylformamide in a non-polar solvent such as dichloromethane or acetonitrile.
  • Carboxylic acids of Formula (lib) may in turn be prepared from esters of Formula (Ila) by treatment with an alkoxide base such as lithium hydroxide in a suitable solvent system of a mixture of water and an organic solvent.
  • an alkoxide base such as lithium hydroxide
  • suitable esters are wherein R 2 Ci-C6alkyl-, such as methyl, ethyl, n-propyl and isopropyl.
  • suitable solvent systems are tetrahydrofuran / water (1 : 1) or ethanol / water (1 : 1).
  • Esters of formula (Ila) may be prepared from the Chan-Lam coupling between pyridazinones of formula (IV) and 3,4-dimethoxyboronic acid.
  • the Chan-Lam reaction is detailed in Tetrahedron Lett. 1998, 2933-2936. These reactions use a copper (II) or copper (I) salt such as copper (II) acetate, a non-polar solvent such as dichloromethane or 1,2-dichloroethane and an organic base, for example triethylamine or pyridine or a 1 :1 mixture of triethylamine and pyridine.
  • Super-stoichiometric equivalents of copper (I) or copper (II) salts may be used.
  • catalytic amounts of the copper catalyst for example 0.05 to 0.3 molar equivalents of copper (II) acetate, may be used instead if >1 equivalent of an oxidant is also added.
  • oxidants are pyridine-N-oxide or the bubbling of air or oxygen through the reaction mixture. The reaction can typically be performed at room temperature to achieve acceptable conversion in 2-16 h.
  • Pyridazinones of formula (IV) may be prepared by the oxidation of dihydropyridazmones of formula (VI) with a suitable oxidising agent.
  • suitable oxidising agents are bromine in a solution of acetic acid or dichloromethane, or iodobenzene diacetate in a solution of isopropanol.
  • Dihydropyridazmones of formula (VI) may be prepared through the treatment of compounds of formula (VII) with hydrazine hydrate in a suitable solvent such as ethanol under reflux conditions.
  • Compounds of Formula (VII) may be prepared via the alkylation of a commercially available dialkyl malonate (for example diethyl malonate) with a bromo-ketone of Formula (VIII) in the presence of a suitable base, for example potassium carbonate, in a suitable solvent, for example acetone.
  • a suitable base for example potassium carbonate
  • Compounds of Formula (VIII) may be commercially available, or alternatively they may be prepared via the bromination of a commercially available methyl ketone of Formula (IX) by treatment with bromine in a suitable solvent such as methanol or a mixture of water and glacial acetic acid ( ⁇ 5: 1).
  • a suitable solvent such as methanol or a mixture of water and glacial acetic acid ( ⁇ 5: 1).
  • reaction mixture was cooled to 0 °C (salt/ice bath) and triethylamine (1.77 mL, 12.7 mmol) was added dropwise over 15 minutes, then stirred for 5 minutes at 0 °C before 2,2,4,4-tetramethylcyclohexane-l,3,5-trione (0.58 g, 3.17 mmol) dissolved in minimum CH2CI2 was added dropwise over 15 minutes.
  • the resultant solution was stirred at 0 °C for 5 minutes then 1 hour at room temperature.
  • 6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carboxylic acid (1.00 g, 3.16 mmol) was taken in dry DCM (20 mL) and to it one drop of dry DMF was added. Then oxalylchloride (0.35 mL, 4.11 mmol) was added dropwise to the mixture & stirred for 1 h. The reaction mixture was concentrated under reduced pressure in nitrogen atmosphere. Then the crude reaction mass was dissolved in dry DCM (15 mL), activated molecular sieves was added & cooled the reaction mixture in ice salt bath.
  • reaction mixture was stirred at room temperature for lh. Triethylamine (2.2mL) and 25 drops of acetonecyanohydrin were added and stirred for 2h.
  • the reaction mass was purified by chromatography in with a mixed solvent system of 20:8:4:4: 1 Toluene : Dioxane : EtOH : Et 3 N : Water and then acidified by 10% HCl solution, extracted with DCM.
  • HORVW Hadeum vulgare - barley
  • ABUTH Abutilon theophrasti
  • AMARE Amaranthus retroflexus
  • ECHCG Echinochloa crus-galli

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein A1, R1, Ra, Rb, Rc and Rd are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I), to intermediate compounds used to produce compounds of Formula (I), to processes for producing compounds of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

Description

HERBICIDAL PYRIDAZINONE COMPOUNDS
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.
Herbicidal pyridazinone compounds are disclosed in WO 2012/136703. These compounds are shown to afford effective weed control with regard to a variety of problematic weed species. The present invention relates to novel herbicidal pyridazinone compounds which exhibit further improved properties. In particular, the compounds of the present invention exhibit improved crop selectivity. That is, they continue to provide effective levels of weed control, whilst exhibiting a reduction in undesirable crop phytotoxicity.
Thus, according to the present invention there is provided a compound of Formula (I):
Figure imgf000003_0001
or an agronomically acceptable salt thereof, wherein R1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C6alkyl-, C3-C6cycloalkyl-, C2-C6-alkenyl-, C2-C6alkynyl-, Ci-Cehaloalkyl-, Ci-C6alkoxy-, Ci-C3haloalkoxy-, Ci-C6alkoxy-Ci-C3alkyl-, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-S(0)p-;
A1 is selected from the group consisting of O, C(O) and (CRT^;
Ra, Rb, Rc, Rd, Re and Rf are each independently selected from the group consisting of hydrogen and Ci-C4alkyl- wherein Ra and Rc may together form a Ci-C3alkylene chain; and p is 0, 1 or 2.
Ci-C6alkyl- and Ci-C4alkyl- includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (z-Pr), n-butyl (n- u), isobutyl (z'-Bu), sec-butyl and tert-butyl (t-Bu).
C2-C6-alkenyl- includes, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2
(allyl).
C2-C6alkynyl- includes, for example, -C≡CH (ethynyl) and -CH2-C≡CH (propargyl).
Halogen (or halo) includes, for example, fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
Ci-Cehaloalkyl- includes, for example, f uoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentaf uoroethyl, l , l-difluoro-2,2,2-trichloroethyl, 2,2,3, 3-tetrafluoropropyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro- n-hexyl. Ci-C6alkoxy- includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy. Ci-Cshaloalkoxy- includes, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy. Ci-C6alkyl-S- (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Ci-Cehaloalkyl-S- (haloalkylthio) relates to halogenated derivatives thereof. Ci-C6alkyl-S(0)- (alkylsulfinyl) includes, for example, methylsulfmyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl or tert-butylsulfinyl, preferably methylsulfmyl or ethylsulfinyl. Ci- Cehaloalkyl-S(O)- (haloalkylsulfinyl) relates to halogenated derivatives thereof. Ci-C6alkyl-S(0)2- (alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl. Ci- Cehaloalkyl-S(0)2- (haloalkylsulfonyl) relates to halogenated derivatives thereof. Ci-C6alkoxy-Ci-C3alkyl- includes, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxy ethyl.
C3-C6cycloalkyl- includes, for example, cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl).
In a preferred embodiment of the present invention there is provided a compound of Formula (I), wherein R1 is Ci-C6alkyl- (preferably methyl) or C3- Cecycloalkyl- (preferably cyclopropyl). In a more preferred embodiment R1 is methyl or cyclopropyl.
In a preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is CReRf and Re and Rf are hydrogen.
In another preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is CReRf and Ra, Rb, Rc, Rd, Re and Rf are hydrogen.
In another preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is CReRf; Ra, Rb, Rc, Rd, and Re are hydrogen and Rf is methyl. In another preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is CReRf; Ra, Rb, Rc, Rd are hydrogen and Re and Rf are methyl.
In another preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is CReRf; Rb, Rd, Re and Rf are hydrogen, and Ra and Rc together form an ethylene (-CH2-CH2-) chain.
In another preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is C=0 and Ra, Rb, Rc and Rd are methyl.
In another preferred embodiment of the present invention there is provided a compound of Formula (I) wherein A1 is O and Ra, Rb, Rc and Rd are methyl.
Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities. Similarly, where there are disubstituted or trisubstituted alkenes, these may be present in E or Z form or as mixtures of both in any proportion.
Furthermore, compounds of Formula (I) may be in equilibrium with alternative tautomeric forms. Thus, whilst compounds of Formula (I) are depicted in the keto form, they may also exist in the alternative enol form as depicted in Formula (Γ) below.
Figure imgf000007_0001
All tautomeric forms (single tautomer or mixtures thereof), racemic mixtures single isomers are included within the scope of the present invention.
Table CI - Examples of herbicidal compounds of the present invention.
Figure imgf000007_0002
Cmp A1 Ra Rc Rb Rd R1 Ή NMR (400 MHz, CDCI3)
16.19 (1H, s), 7.16-7.09 (3H, m), 6.93 (1H, d),
1.1 CH2 -CH2-CH2- H H CH3 3.91 (6H, s), 3.11 (1H, t), 2.94 (1H, t), 2.42 (3H, s), 2.26 - 2.06 (3H, m), 2.04 - 1.98 (1H, m), 1.83 (1H, brm), 1.72 (1H, dt)
Figure imgf000008_0001
The present invention also provides agronomically acceptable salts of compounds of Formula (I). Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred. Aluminium, calcium, cobalt, copper (copper (I), copper (II)), iron (iron (II), iron (III)), magnesium, potassium, sodium or zinc salts of compounds of Formula (I) are particularly preferred; copper, potassium and sodium being especially preferred. The compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using co-formulants, such as carriers, solvents, surface-active agents (SAA) and adjuvants. Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable co-formulant. 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 co-formulant which preferably includes from 0 to 25 % by weight of a surface-active substance.
The compositions can be chosen from a number of formulation types. These include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP), a ZC (combination of SC and CS) and a soluble granule (SG). The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I) and any additional ingredient.
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 preformed 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) and dimethyl amides of fatty acids (such as Cs-Cio fatty acid dimethylamide). An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SAAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SAA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water- soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I). SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product. Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane). A compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of Formula (I). A compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound. Soluble concentrate (SL) may be prepared by dissolving the active ingredient in an aqueous liquid which optionally comprises wetting agent(s) and/or buffer(s).
The composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I). Such additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I). Examples of co-formulants include:-
Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts. Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-z'sopropyl- and tri-z'sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3 -sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates, lignosulphonates and phosphates / sulphates of tristyrylphenols. Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.
Suitable SAAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
The composition of the present may further comprise one or more additional pesticides. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. Thus, in a preferred embodiment there is provided a herbicidal composition comprising (A) a compound of Formula (I) and (B) one or more herbicides selected from the group consisting of acetochlor, aciflurofen (acifluorfen-sodium), aclonifen, alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, anilifos, asulam, atrazine, beflubutamid, benefin, benfluralin, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bifenox, bispyribac-sodium, bromacil, bromoxynil, butachlor, butroxydim, butafenacil, cafenstrole, carfentrazone (including carfentrazone-ethyl), chloransulam, chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinosulfuron, cinidon (including cinidon-ethyl), clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cycloxydim, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), daimuron, desmedipham, dicamba (including the aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichlorprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof), diclofop (including diclofop-methyl), diclosulam, difenzoquat, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, diquat dibromide, diuron, EPTC, esprocarb, ethametsulfuron, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenquinotrione, flazasulfuron, florasulam, fluazifop (including fiuazifop-P-butyl), flucarbazone (including flucarbazone-sodium), flufenacet, flumetralin, flumetsulam, fluormeturon, fiuoroglycofen, fiumioxazin, flupyrsulfuron (including flupyrsulfuron- methyl-sodium), fiuroxypyr (including fiuroxypyr-meptyl), flurtamone, fiuthiacet (including fiuthiacet-methyl), fomesafen, foramsulfuron, glufosinate (including the ammonium salt thereof), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen- methyl), halosulfuron (including halosulfuron-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl- sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, ipfencarbazone, isoproturon, isoxaben, isoxaflutole, lactofen, linuron, MCPA, mecoprop-P, mefenacet, mesosulfuran (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, metobromuron, metolachlor, metoxuron, metribuzin, metsulfuron, molinate, napropamide, nicosulfuron, norflurazon, orthosulfamuron, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, pethoxamid, phenmedipham, picloram, picolinafen, pinoxaden, pretilachlor, primisulfuron-methyl, prodiamine, prometryn, propachlor, propanil, propaquizafop, propham, propoxycarbazone, propyzamide, prosulfocarb, prosulfuron, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyrazolynate, pyrazosulfuran (including pyrazosulfuron-ethyl), pyribenzoxim, pyridate, pyriftalid, pyrithiobac- sodium, pyroxasulfone, pyroxsulam, quinclorac, quizalofop (including quizalofop-P- ethyl), rimsulfuron, saflufenacil, sethoxydim, simetryn, ^-metolachlor, sulcotrione, sulfentrazone, sulfometuron (including sulfometuron-methyl), sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbuthylazine, terbutryn, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, tritosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5- fluoropyridine-2-carboxylate (Compound Bl), 4-hydroxy- l-methoxy-5-methyl-3- [4- (trifluoromethyl)-2-pyridyl]imidazolidin-2-one (Compound B2), 4-hydroxy- 1 ,5- dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (Compound B3), 5- ethoxy-4-hydroxy-l-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (Compound B4), 4-hydroxy- 1 -methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin- 2-one (Compound B5), 4-hydroxy- l ,5-dimethyl-3-[ l-methyl-5-
(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one (Compound B6), (4R)l-(5-tert- butylisoxazo 1-3 -yl)-4-ethoxy-5 -hydroxy-3 -methyl- imidazo lidin-2-one (Compound B7), a compound of formula B8,
Figure imgf000015_0001
wherein,
R1 is H, Ci-C6alkyl, Ci-C6 haloalkyl or C4-C8 cycloalkyl;
R6 is H, Ci-Cealkyl, or Ci-C6alkoxy;
Q1 is an optionally substituted ring system, selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, wherein when substituted said ring system is substituted by 1 to 3 R4;
Q2 is an optionally substituted ring system, selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinone, thiadazolyl, thiazolyl, and oxazolyl, wherein when substituted said ring system is substituted by 1 to 3 R5;
each R4 is independently halogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy,
Ci-C6haloalkoxy, C3-Cscycloalkyl, cyano, Ci-C6alkylthio, Ci-C6alkylsulphinyl, Ci- Cealkylsulphonyl, SF5, NHR8, phenyl optionally substituted by 1-3 R7, or pyrazolyl optionally substituted by 1-3 R7; each R5 is independently halogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, cyano, nitro, Ci-C6alkylthio, Ci-C6alkylsulphinyl, or Ci- Cealkylsulphonyl;
each R7 is independently Ci-C6alkyl, halogen, or Ci-Cehaloalkyl; and
R8 is Ci-C4alkoxycarbonyl;
and a compound of formula B9,
Figure imgf000016_0001
wherein,
R1 1 is H, Ci-Cealkyl, Ci-C6 haloalkyl or C4-C8 cycloalkyl;
n is an integer of 0, 1 , 2, or 3;
p is an integer of 0, 1 , 2, or 3;
each R2 is independently halogen, Ci-C6haloalkyl, or Ci-Cehaloalkoxy; and each R3 is independently halogen, Ci-C6haloalkyl, Ci-C6 haloalkoxy.
More preferably, (B) is one or more herbicides selected from the group consisting of acetochlor, alachlor, ametryn, amicarbazone, atrazine, bicyclopyrone, bromoxynil, butachlor, chlorotoluron, clodinafop-propargyl, clopyralid, 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof), diflufenican, dimethachlor, dimethenamid-P, diuron, fenoxaprop-P-ethyl, fenquinotrione, florasulam, fiuazifop-P-butyl, fiuroxypyr-meptyl, flucarbazone- sodium, flufenacet, foramsulfuron, glufosinate (including the ammonium salt thereof), fomesafen, glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen-methyl, iodosulfuron-methyl-sodium, isoxaflutole, isoproturon, linuron, MCPA, mecoprop-P, mesosulfuron-methyl, mesotrione, metazachlor, S-metolachlor, metribuzin, metsulfuron, nicosulfuron, pendimethalin, pethoxamid, pinoxaden, prometryn, prosulfocarb, prosulfuron, pyrasulfatole, pyridate, pyroxasulfone, pyroxsulam, rimsulfuron, simazine, sulcotrione, sulfentrazone, tembotrione, terbuthylazine, terbutryn, thiencarbazone, tolpyralate, topramezone, triasulfuron and trifludimoxazin.
Even more preferably, (B) is one or more herbicides selected from the group consisting of atrazine, bicyclopyrone, bromoxynil, clodinafop-propargyl, diflufenican, fenoxaprop-P-ethyl, florasulam, flufenacet, fluroxypyr-meptyl, glufosinate (including the ammonium salt thereof), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen-methyl, iodosulfuron- methyl-sodium, MCPA, mesosulfuron-methyl, mesotrione, metribuzin, metsulfuron, nicosulfuron, S-metolachlor, pinoxaden, prosulfocarb, pyroxsulam and terbuthylazine. In one embodiment, wherein component B is a compound of formula B 8, it is preferred that R11 is H, Ci-C6 alkyl or Ci-C6haloalkyl, more preferably methyl, ethyl or CHF2, and more preferably still, H or methyl.
Preferably R6 is H. Preferably Q1 is either a phenyl ring or a pyridinyl ring, each of which is optionally substituted by 1 to 3 R4. Preferably Q1 is a phenyl ring substituted by 1 to 2 R4. Preferably Q2 is a phenyl ring, optionally substituted by 1 to 3 R5. More preferably Q1 is phenyl substituted by 1-3 R5. Preferably each R4 is independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, Ci-C3alkoxy, or Ci- Cshaloalkoxy; more preferably chloro, fluoro, bromo, Ci-C2haloalkyl, Ci- C2haloalkoxy, or Ci-C2alkoxy. Preferably each R5 is independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, Ci-C3alkoxy, or Ci-C3haloalkoxy; more preferably chloro, fluoro, bromo, Ci-C2haloalkyl, Ci-C2haloalkoxy, or Ci-C2alkoxy; more preferably still fluoro.
Particularly preferred compounds of formula B8 for use as component B in compositions of the invention are shown as compounds B801 to B815 below in Table B8. Table B8 Compound of formula (B8) for use in compositions described herein.
Compound Name Structure
N-(2-fluorophenyl)-2-oxo-4-[3-
B801 (trifluoromethyl)phenyl]pyrrolidine-
3-carboxamide
H
N-(2,3-difluorophenyl)-2-oxo-4-[3-
B802 (trifluoromethyl)phenyl]pyrrolidine-
3-carboxamide
H
F
2- 0X0-4- [3 -(trifluoromethyl)phenyl] -
B803 N-(2,3,4-trifluorophenyl)pyrrolidine-
3- carboxamide
H
N-(2-fluorophenyl)- 1 -methyl-2-oxo- 4-[3-
B804
(trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide ;£ ,
1
N-(2-fluorophenyl)-2-oxo-4-[4-
B805 (trifluoromethyl)phenyl]pyrrolidine-
3-carboxamide
Figure imgf000018_0001
Figure imgf000019_0001
Compound Name Structure
N-(2,3-difluorophenyl)-4-(3,4-
B811 difluorophenyl)-2-oxo-pyrrolidine-3- carboxamide
H
4-(3,4-difluorophenyl)-N-(2-
B812 fluorophenyl)-2-oxo-pyrrolidine-3- carboxamide ■ yR
H
F
N-(2,4-difluorophenyl)-4-(3,5-
B813 difluorophenyl)-2-oxo-pyrrolidine-3- carboxamide
H
N-(2,3-difluorophenyl)-4-(3-
B814 isopropylphenyl)-2-oxo-pyrrolidine-
3-carboxamide
N-(2,3-difluorophenyl)-2-oxo-4-[6-
B815 (trifluoromethyl)-3 - pyridyl]pyrrolidine-3-carboxamide
Figure imgf000020_0001
Compounds of formula B8 as described herein may be made as described in WO2015/084796 and WO 2016/094117.
In a further embodiment wherein component B is a compound of formula B9 it is preferred that p is 1, 2, or 3, more preferably 1 or 2. Preferably n is 1, 2 or 3, more preferably 1 or 2. Preferably R1 is H or Ci-C6alkyl, more preferably H or methyl. In one set of embodiments R1 1 is H.
Preferably each R2 is independently chloro, fluoro, Ci-Cshaloalkyl, or Ci- Cshaloalkoxy, more preferably chloro, fluoro, Ci-fluoroalkyl (i.e. fluoromethyl, difluoromethyl, trifluoromethyl) Ci-fluoroalkoxy (i.e. trifluoromethoxy, difluoromethoxy, fluoromethoxy). Preferably each R3 is independently chloro, fluoro, Ci-Cshaloalkyl, or Ci-Cshaloalkoxy, more preferably chloro, fluoro, Ci-fluoroalkyl (i.e. fluoromethyl, difluoromethyl, trifluoromethyl) Ci-fluoroalkoxy (i.e. trifluoromethoxy, difluoromethoxy, fluoromethoxy). Particularly preferred compounds of formula B9 for use as component B in compositions of the invention are shown below in Table B9.
Table B9. Compound of formula B9 for use in compositions described herein (unless otherwise stated, all compounds are in racemic form).
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Compounds of formula B9 as described herein may be made as described in WO2016/003997. In one embodiment, with reference to the compositions referred to above, component (A) is compound 1.1. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.2. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.3. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.4. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.5. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.6. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.7. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.8. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.9. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.10. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.11. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.12. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.13. In another embodiment, with reference to the compositions referred to above, component (A) is compound 1.14. Further example compositions of the invention comprise:
Compound 1.1 + acetochlor, compound 1.1 + acifluorfen-sodium, compound 1.1 + aclonifen, compound 1.1 + alachlor, compound 1.1 + alloxydim, compound 1.1 + ametryn, compound 1.1 + amicarbazone, compound 1.1 + amidosulfuron, compound 1.1 + aminocyclopyrachlor, compound 1.1 + aminopyralid, compound 1.1 + amitrole, compound 1.1 +asulam, compound 1.1 + atrazine, compound 1.1 + beflubutamid, compound 1.1 + benfluralin, compound 1.1 + bensulfuron-methyl, compound 1.1 + bentazone, compound 1.1 + bicyclopyrone, compound 1.1 + bifenox, compound 1.1 + bispyribac-sodium, compound 1.1 + bromacil, compound 1.1 + bromoxynil, compound 1.1 + butachlor, compound 1.1 + butroxydim, compound 1.1 + butafenacil, compound 1.1 + cafenstrole, compound 1.1 + carfentrazone-ethyl, compound 1.1 + chloransulam, compound 1.1 + chlorimuron-ethyl, compound 1.1 + chlorotoluron, compound 1.1 + chlorsulfuron, compound 1.1 + cinosulfuron, compound 1.1 + cinidon-ethyl, compound 1.1 + clethodim, compound 1.1 + clodinafop-propargyl, compound 1.1 + clomazone, compound 1.1 + clopyralid, compound 1.1 + cycloxydim, compound 1.1 + cyhalo fop-butyl, compound 1.1 + 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), compound 1.1 + daimuron, compound 1.1 + desmedipham, compound 1.1 + dicamba (including the aluminium, aminopropyl, bis- aminopropylmethyl, choline, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof), compound 1.1 + die lo fop-methyl, compound 1.1 + diclosulam, compound 1.1 + difenzoquat, compound 1.1 + diflufenican, compound 1.1 + diflufenzopyr, compound 1.1 + dimethachlor, compound 1.1 + dimethenamid-P, compound 1.1 + diquat dibromide, compound 1.1 + diuron, compound 1.1 + esprocarb, compound 1.1 + ethametsulfuron, compound 1.1 + ethofumesate, compound 1.1 + fenoxaprop-P-ethyl, compound 1.1 + fenquinotrione, compound 1.1 + fentrazamide, compound 1.1 + flazasulfuron, compound 1.1 + florasulam, compound 1.1 + fluazifop-P-butyl, compound 1.1 + flucarbazone-sodium, compound 1.1 + flufenacet, compound 1.1 + flumetralin, compound 1.1 + flumetsulam, compound 1.1 + flumioxazin, compound 1.1 + flupyrsulfuron-methyl-sodium, compound 1.1 + fluroxypyr-meptyl, compound 1.1 + flurtamone, compound 1.1 + fluthiacet-methyl, compound 1.1 + fomesafen, compound 1.1 + foramsulfuron, compound 1.1 + glufosinate (including the ammonium salt thereof), compound 1.1 + glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), compound 1.1 + halauxifen-methyl, compound 1.1 + halosulfuron-methyl, compound 1.1 + haloxyfop-methyl, compound 1.1 + hexazinone, compound 1.1 + imazamethabenz, compound 1.1 + imazamox, compound 1.1 + imazapic, compound 1.1 + imazapyr, compound 1.1 + imazaquin, compound 1.1 + imazethapyr, compound 1.1 + indaziflam, compound 1.1 + iodosulfuron-methyl-sodium, compound 1.1 + iofensulfuron, compound 1.1 + iofensulfuron-sodium, compound 1.1 + ioxynil, compound 1.1 + ipfencarbazone, compound 1.1 + isoproturon, compound 1.1 + isoxaben, compound 1.1 + isoxaflutole, compound 1.1 + lactofen, compound 1.1 + linuron, compound 1.1 + MCPA, compound 1.1 + mecoprop-P, compound 1.1 + mefenacet, compound 1.1 + mesosulfuron, compound 1.1 + mesosulfuron-methyl, compound 1.1 + mesotrione, compound 1.1 + metamitron, compound 1.1 + metazachlor, compound 1.1 + metobromuron, compound 1.1 + metolachlor, compound 1.1 + metoxuron, compound 1.1 + metribuzin, compound 1.1 + metsulfuron, compound 1.1 + molinate, compound 1.1 + napropamide, compound 1.1 + nicosulfuron, compound 1.1 + norflurazon, compound 1.1 + orthosulfamuron, compound 1.1 + oxadiargyl, compound 1.1 + oxadiazon, compound 1.1 + oxasulfuron, compound 1.1 + oxaziclomefone, compound 1.1 + oxyfluorfen, compound 1.1 + paraquat dichloride, compound 1.1 + pendimethalin, compound 1.1 + penoxsulam, compound 1.1 + pethoxamid, compound 1.1 + phenmedipham, compound 1.1 + picloram, compound 1.1 + picolinafen, compound 1.1 + pinoxaden, compound 1.1 + pretilachlor, compound 1.1 + primisulfuron-methyl, compound 1.1 + prodiamine, compound 1.1 + prometryn, compound 1.1 + propachlor, compound 1.1 + propanil, compound 1.1 + propaquizafop, compound 1.1 + propham, compound 1.1 + propoxycarbazone, compound 1.1 + propyzamide, compound 1.1 + prosulfocarb, compound 1.1 + prosulfuron, compound 1.1 + pyrasulfotole, compound 1.1 + pyrazolynate, compound 1.1 + pyrazosulfuron-ethyl, compound 1.1 + pyribenzoxim, compound 1.1 + pyridate, compound 1.1 + pyriftalid, compound 1.1 + pyrithiobac- sodium, compound 1.1 + pyroxasulfone, compound 1.1 + pyroxsulam, compound 1.1 + quinclorac, compound 1.1 + quizalofop-P-ethyl, compound 1.1 + rimsulfuron, compound 1.1 + saflufenacil, compound 1.1 + sethoxydim, compound 1.1 + S- metolachlor, compound 1.1 + sulcotrione, compound 1.1 + sulfentrazone, compound 1.1 + sulfometuron-methyl, compound 1.1 + sulfosulfuron, compound 1.1 + tebuthiuron, compound 1.1 + tefuryltrione, compound 1.1 + tembotrione, compound 1.1 + terbuthylazine, compound 1.1 + terbutryn, compound 1.1 + thiencarbazone, compound 1.1 + thifensulfuron, compound 1.1 + tiafenacil, compound 1.1 + tolpyralate, compound 1.1 + topramezone, compound 1.1 + tralkoxydim, compound 1.1 + triafamone, compound 1.1 + triallate, compound 1.1 + triasulfuron, compound 1.1 + tribenuron-methyl, compound 1.1 + triclopyr, compound 1.1 + trifloxysulfuron- sodium, compound 1.1 + trifludimoxazin, compound 1.1 + trifluralin, compound 1.1 + tritosulfuron and compound 1.1 + 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylate (Compound Bl), 1.1 + 4-fiydroxy-l- methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (Compound B2), 1.1 + 4-hydroxy-l,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2- one (Compound B3), 1.1 + 5-ethoxy-4-hydroxy-l-methyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one (Compound B4), 1.1 + 4-hydroxy-l-methyl-3-[4- (trifluoromethyl)-2-pyridyl]imidazolidin-2-one (Compound B5), 1.1 + 4-hydroxy-l,5- dimethyl-3 - [ 1 -methyl-5 -(trifluoromethyl)pyrazol-3 -yl] imidazo lidin-2-one (Compound B6), 1.1 + (4R) l-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl- imidazolidin-2-one (Compound B7); compound 1.1 + N-(2-fluorophenyl)-2-oxo-4-[3-(trifluoromethyl)phenyl]- pyrrolidine-3-carboxamide (compound B801), compound 1.1 + N-(2,3- difluorophenyl)-2-oxo-4-[3-(trifluoromethyl)phenyl]pyrrolidine-3-carboxamide (compound B802), compound 1.1 + 2-oxo-4-[3-(trifluoromethyl)phenyl]-N-(2,3,4- trifluorophenyl)pyrrolidine-3-carboxamide (compound B803), compound 1.1 + N-(2- fluorophenyl)-l-methyl-2-oxo-4-[3-(trifluoromethyl)phenyl]pyrrolidine-3- carboxamide (compound B804), compound 1.1 + N-(2-fluorophenyl)-2-oxo-4-[4- (trifluoromethyl)phenyl]pyrrolidine-3-carboxamide (compound B805), compound 1.1 + N-(2-fluorophenyl)- 1 -methyl-2-oxo-4-[4-(trifluoromethyl)phenyl]pyrrolidine-3- carboxamide (compound B806), compound 1.1 + N-(2,3-difluorophenyl)-2-oxo-4-[4- (trifluoromethyl)phenyl]pyrrolidine-3-carboxamide (compound B807), compound 1.1 + N-(2,3-difluorophenyl)- 1 -methyl-2-oxo-4-[4-(trifluoromethyl)phenyl]pyrrolidine-3- carboxamide (compound B808), compound 1.1 + 2-oxo-4-[4- (trifluoromethyl)phenyl]-N-(2,3,4-trifluorophenyl)pyrrolidine-3-carboxamide
(compound B809), compound 1.1 + N-(2-fluorophenyl)-4-(4-fluorophenyl)-l-methyl- 2-oxo-pyrrolidine-3 -carboxamide (compound B810), compound 1.1 + N-(2,3- difluorophenyl)-4-(3,4-difluorophenyl)-2-oxo-pyrrolidine-3-carboxamide (compound B811), compound 1.1 + 4-(3,4-difluorophenyl)-N-(2-fluorophenyl)-2-oxo- pyrrolidine-3 -carboxamide (compound B812), compound 1.1 + N-(2,4- difluorophenyl)-4-(3,5-difluorophenyl)-2-oxo-pyrrolidine-3-carboxamide (compound B813), compound 1.1 + N-(2,3-difluorophenyl)-4-(3-isopropylphenyl)-2-oxo- pyrrolidine-3 -carboxamide (compound B814), compound 1.1 + N-(2,3- difluorophenyl)-2-oxo-4-[6-(trifluoromethyl)-3-pyridyl]pyrrolidine-3-carboxamide (compound B815);
compound 1.1 + 4-(3,4-difluorophenyl)-2-oxo-N-[2-(trifluoromethyl)phenyl]- piperidine-3 -carboxamide (compound B901), compound 1.1 + N-(2,3- difluorophenyl)-2-oxo-4-[3-(trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B902), compound 1.1 + 2-oxo-N-[2-(trifluoromethyl)phenyl]-4-[3- (trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B903), compound 1.1 + N-(2-chlorophenyl)-2-oxo-4-[4-(trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B904), compound 1.1 + N-(2-fluorophenyl)-2-oxo-4-[4- (trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B905), compound 1.1 + (3R,4S)-N-(2,3-difluorophenyl)-2-oxo-4-[3-(trifluoromethyl)phenyl]piperidine-3- carboxamide (compound B906), compound 1.1 + (3R,4S)-N-(2,3-difluorophenyl)-2- oxo-4-[4-(trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B907), compound 1.1 + (3R,4S)-N-(3-chloro-2-fluoro-phenyl)-2-oxo-4-[3-
(trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B908), compound 1.1 + (3R,4S)-2-oxo-4-[3-(trifluoromethyl)phenyl]-N-(2,3,4-trifluorophenyl) piperidine- 3-carboxamide (compound 909), compound 1.1 + N-(2,3-difluorophenyl)-2-oxo-4- phenyl-piperidine-3-carboxamide (compound B910), compound 1.1 + N-(2- fluorophenyl)-2-oxo-4-[3-(trifluoromethoxy)phenyl]piperidine-3-carboxamide (compound B911), compound 1.1 +2-oxo-4-[3-(trifluoromethoxy)phenyl]-N-[2- (trifluoromethyl)phenyl]piperidine-3-carboxamide (compound B912), compound 1.1 + N-(2,3-difluorophenyl)-2-oxo-4-[3-(trifluoromethoxy)phenyl]piperidine-3- carboxamide (compound B913), compound 1.1 + (3R,4S)-4-(3-chlorophenyl)-N-(2,3- difluorophenyl)-2-oxo-piperidine-3-carboxamide (compound B914), compound 1.1 + 4- [3 -(difluoromethyl)phenyl] -2-oxo-N-(2,3 ,4-trifluorophenyl)piperidine-3 - carboxamide (compound B915), compound 1.1 + 4-[3-(difluoromethyl)phenyl]-N-(2- fluorophenyl)-2-oxo-piperidine-3-carboxamide (compound B916), compound 1.1 + 4- [3-(difluoromethyl)phenyl]-N-(2,3-difluorophenyl)-2-oxo-piperidine-3-carboxamide (compound B917), compound 1.1 + (3R,4S)-N-(2,3-difiuorophenyl)-4-(4- fluorophenyl)-2-oxo-piperidine-3-carboxamide (compound B918), and compound 1.1 + (3R,4S)-4-(4-fluorophenyl)-2-oxo-N-[2-(trifluoromethyl)phenyl]piperidine-3- carboxamide (compound B919).
In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.2. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.3. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.4. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.5. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.6. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.7. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.8. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.9. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.10. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.11. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.12. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.13. In another embodiment, with reference to the compositions referred to above, component compound 1.1 is replaced by compound 1.14.
The mixing ratio of the compound of Formula (I) to the mixing partner B can vary depending on the nature of the mixing partner(s). Typical ratios include, for example, from 1 : 100 to 1000: 1, from 1 :50 to 50: 1, or from 1 : 10 to 10: 1.
Whilst two-way mixtures of a compound of formula (I) and another herbicide are explicitly disclosed above, the skilled man will appreciate that the invention extends to three-way and further multiple combinations comprising the above two- way mixtures. In particular, the present invention provides compositions comprising the three-way mixtures listed in Table 1 below (CMP = compound: see Table CI):
1
CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 acetochlor ametryn 1.1 flufenacet 2.4D
1.1 acetochlor amicarbazone 1.1 flufenacet amidosulfuron
1.1 acetochlor atrazine 1.1 flufenacet bicyclopyrone
1.1 acetochlor bicyclopyrone 1.1 flufenacet bromoxynil
1.1 acetochlor bromoxynil 1.1 flufenacet dicamba
1.1 acetochlor clopyralid 1.1 flufenacet diflufenican
1.1 acetochlor 2,4D 1.1 flufenacet florasulam
1.1 acetochlor dicamba 1.1 flufenacet fluroxypy
1.1 acetochlor dimethenamid-P 1.1 flufenacet halauxifen
1.1 acetochlor fenquinotrione 1.1 flufenacet MCPA
1.1 acetochlor foramsulfuron 1.1 flufenacet metsulfuron
1.1 acetochlor glufosinate 1.1 flufenacet propoxycarbazone
1.1 acetochlor glyphosate 1.1 flufenacet prosulfuron
1.1 acetochlor isoxaflutole 1.1 flufenacet pyroxsulam
1.1 acetochlor mesotrione 1.1 flufenacet terbutryn
1.1 acetochlor metribuzin 1.1 flufenacet triasulfuron
1.1 acetochlor nicosulfuron 1.1 foramsulfuron glufosinate
1.1 acetochlor pethoxamid 1.1 foramsulfuron glyphosate
1.1 acetochlor prosulfuron 1.1 foramsulfuron isoxaflutole
1.1 acetochlor pyridate 1.1 foramsulfuron mesotrione
1.1 acetochlor pyroxasulfone 1.1 foramsulfuron metribuzin
1.1 acetochlor rimsulfuron 1.1 foramsulfuron nicosulfuron
1.1 acetochlor S-metolachor 1.1 foramsulfuron pethoxamid
1.1 acetochlor sulcotrione 1.1 foramsulfuron prosulfuron
1.1 acetochlor tembotrione 1.1 foramsulfuron pyridate
1.1 acetochlor terbuthylazine 1.1 foramsulfuron pyroxasulfone
1.1 acetochlor tolpyralate 1.1 foramsulfuron rimsulfuron
1.1 ametryn amicarbazone 1.1 foramsulfuron S-metolachor
1.1 ametryn atrazine 1.1 foramsulfuron sulcotrione
1.1 ametryn bicyclopyrone 1.1 foramsulfuron tembotrione
1.1 ametryn bromoxynil 1.1 foramsulfuron terbuthylazine
1.1 ametryn clopyralid 1.1 foramsulfuron tolpyralate
1.1 ametryn 2,4D 1.1 glufosinate butafenacil
1.1 ametryn dicamba 1.1 glufosinate diuron
1.1 ametryn dimethenamid-P 1.1 glufosinate flazasulfuron
1.1 ametryn fenquinotrione 1.1 glufosinate Flumioxazin
1.1 ametryn foramsulfuron 1.1 glufosinate hexazinone
1.1 ametryn glufosinate 1.1 glufosinate glyphosate
1.1 ametryn glyphosate 1.1 glufosinate isoxaflutole
1.1 ametryn isoxaflutole 1.1 glufosinate mesotrione
1.1 ametryn mesotrione 1.1 glufosinate metribuzin
1.1 ametryn metribuzin 1.1 glufosinate metsulfuron CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 ametryn nicosulfuron 1.1 glufosinate nicosulfuron
1.1 ametryn pethoxamid 1.1 glufosinate norflurazon
1.1 ametryn prosulfuron 1.1 glufosinate oxadiazon
1.1 ametryn pyridate 1.1 glufosinate oxyflurofen
1.1 ametryn pyroxasulfone 1.1 glufosinate pethoxamid
1.1 ametryn rimsulfuron 1.1 glufosinate prometryn
1.1 ametryn S-metolachor 1.1 glufosinate prosulfuron
1.1 ametryn sulcotrione 1.1 glufosinate pyridate
1.1 ametryn tembotrione 1.1 glufosinate pyroxasulfone
1.1 ametryn terbuthylazine 1.1 glufosinate rimsulfuron
1.1 ametryn tolpyralate 1.1 glufosinate S-metolachor
1.1 amicarbazone atrazine 1.1 glufosinate saflufenacil
1.1 amicarbazone bicyclopyrone 1.1 glufosinate simazine
1.1 amicarbazone bromoxynil 1.1 glufosinate sulcotrione
1.1 amicarbazone clopyralid 1.1 glufosinate tembotrione
1.1 amicarbazone 2,4D 1.1 glufosinate terbuthylazine
1.1 amicarbazone dicamba 1.1 glufosinate terbutryn
1.1 amicarbazone dimethenamid-P 1.1 glufosinate tolpyralate
1.1 amicarbazone fenquinotrione 1.1 glufosinate trifloxysulfuron
1.1 amicarbazone foramsulfuron 1.1 glyphosate Ametryn
1.1 amicarbazone glufosinate 1.1 glyphosate butafenacil
1.1 amicarbazone glyphosate 1.1 glyphosate diuron
1.1 amicarbazone isoxaflutole 1.1 glyphosate flazasulfuron
1.1 amicarbazone mesotrione 1.1 glyphosate Flumioxazin
1.1 amicarbazone metribuzin 1.1 glyphosate hexazinone
1.1 amicarbazone nicosulfuron 1.1 glyphosate metsulfuron
1.1 amicarbazone pethoxamid 1.1 glyphosate isoxaflutole
1.1 amicarbazone prosulfuron 1.1 glyphosate mesotrione
1.1 amicarbazone pyridate 1.1 glyphosate metribuzin
1.1 amicarbazone pyroxasulfone 1.1 glyphosate nicosulfuron
1.1 amicarbazone rimsulfuron 1.1 glyphosate norflurazon
1.1 amicarbazone S-metolachor 1.1 glyphosate oxadiazon
1.1 amicarbazone sulcotrione 1.1 glyphosate oxyflurofen
1.1 amicarbazone tembotrione 1.1 glyphosate pethoxamid
1.1 amicarbazone terbuthylazine 1.1 glyphosate prometryn
1.1 amicarbazone tolpyralate 1.1 glyphosate prosulfuron
1.1 atrazine bicyclopyrone 1.1 glyphosate pyridate
1.1 atrazine bromoxynil 1.1 glyphosate pyroxasulfone
1.1 atrazine clopyralid 1.1 glyphosate rimsulfuron
1.1 atrazine 2,4D 1.1 glyphosate S-metolachor
1.1 atrazine dicamba 1.1 glyphosate saflufenacil
1.1 atrazine dimethenamid-P 1.1 glyphosate simazine
1.1 atrazine fenquinotrione 1.1 glyphosate sulcotrione CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 atrazine foramsulfuron 1.1 glyphosate tembotrione
1.1 atrazine glufosinate 1.1 glyphosate terbuthylazine
1.1 atrazine glyphosate 1.1 glyphosate terbutryn
1.1 atrazine isoxaflutole 1.1 glyphosate tolpyralate
1.1 atrazine mesotrione 1.1 glyphosate trifloxysulfuron
1.1 atrazine metribuzin 1.1 iodosulfuron 2,4D
1.1 atrazine nicosulfuron 1.1 iodosulfuron amidosulfuron
1.1 atrazine pethoxamid 1.1 iodosulfuron bicyclopyrone
1.1 atrazine prosulfuron 1.1 iodosulfuron bromoxynil
1.1 atrazine pyridate 1.1 iodosulfuron dicamba
1.1 atrazine pyroxasulfone 1.1 iodosulfuron diflufenican
1.1 atrazine rimsulfuron 1.1 iodosulfuron florasulam
1.1 atrazine S-metolachor 1.1 iodosulfuron fluroxypy
1.1 atrazine sulcotrione 1.1 iodosulfuron halauxifen
1.1 atrazine tembotrione 1.1 iodosulfuron MCPA
1.1 atrazine terbuthylazine 1.1 iodosulfuron metsulfuron
1.1 atrazine tolpyralate 1.1 iodosulfuron propoxycarbazone
1.1 bicyclopyrone bromoxynil 1.1 iodosulfuron prosulfuron
1.1 bicyclopyrone clopyralid 1.1 iodosulfuron pyroxsulam
1.1 bicyclopyrone 2,4D 1.1 iodosulfuron terbutryn
1.1 bicyclopyrone dicamba 1.1 iodosulfuron triasulfuron
1.1 bicyclopyrone dimethenamid-P 1.1 isoxaflutole mesotrione
1.1 bicyclopyrone fenquinotrione 1.1 isoxaflutole metribuzin
1.1 bicyclopyrone foramsulfuron 1.1 isoxaflutole nicosulfuron
1.1 bicyclopyrone glufosinate 1.1 isoxaflutole pethoxamid
1.1 bicyclopyrone glyphosate 1.1 isoxaflutole prosulfuron
1.1 bicyclopyrone isoxaflutole 1.1 isoxaflutole pyridate
1.1 bicyclopyrone mesotrione 1.1 isoxaflutole pyroxasulfone
1.1 bicyclopyrone metribuzin 1.1 isoxaflutole rimsulfuron
1.1 bicyclopyrone nicosulfuron 1.1 isoxaflutole S-metolachor
1.1 bicyclopyrone pethoxamid 1.1 isoxaflutole sulcotrione
1.1 bicyclopyrone prosulfuron 1.1 isoxaflutole tembotrione
1.1 bicyclopyrone pyridate 1.1 isoxaflutole terbuthylazine
1.1 bicyclopyrone pyroxasulfone 1.1 isoxaflutole tolpyralate
1.1 bicyclopyrone rimsulfuron 1.1 mesosulfuron 2,4D
1.1 bicyclopyrone S-metolachor 1.1 mesosulfuron amidosulfuron
1.1 bicyclopyrone sulcotrione 1.1 mesosulfuron bicyclopyrone
1.1 bicyclopyrone tembotrione 1.1 mesosulfuron bromoxynil
1.1 bicyclopyrone terbuthylazine 1.1 mesosulfuron dicamba
1.1 bicyclopyrone tolpyralate 1.1 mesosulfuron diflufenican
1.1 bromoxynil clopyralid 1.1 mesosulfuron florasulam
1.1 bromoxynil 2,4D 1.1 mesosulfuron fluroxypy
1.1 bromoxynil dicamba 1.1 mesosulfuron halauxifen CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 bromoxyni dimethenamid-P 1.1 mesosulfuron MCPA
1.1 bromoxyni fenquinotrione 1.1 mesosulfuron metsulfuron
1.1 bromoxyni foramsulfuron 1.1 mesosulfuron propoxycarbazone
1.1 bromoxyni glufosinate 1.1 mesosulfuron prosulfuron
1.1 bromoxyni glyphosate 1.1 mesosulfuron pyroxsulam
1.1 bromoxyni isoxaflutole 1.1 mesosulfuron terbutryn
1.1 bromoxyni mesotrione 1.1 mesosulfuron triasulfuron
1.1 bromoxyni metribuzin 1.1 mesotrione metribuzin
1.1 bromoxyni nicosulfuron 1.1 mesotrione nicosulfuron
1.1 bromoxyni pethoxamid 1.1 mesotrione pethoxamid
1.1 bromoxyni prosulfuron 1.1 mesotrione prosulfuron
1.1 bromoxyni pyridate 1.1 mesotrione pyridate
1.1 bromoxyni pyroxasulfone 1.1 mesotrione pyroxasulfone
1.1 bromoxyni rimsulfuron 1.1 mesotrione rimsulfuron
1.1 bromoxyni S-metolachor 1.1 mesotrione S-metolachor
1.1 bromoxyni sulcotrione 1.1 mesotrione sulcotrione
1.1 bromoxyni tembotrione 1.1 mesotrione tembotrione
1.1 bromoxyni terbuthylazine 1.1 mesotrione terbuthylazine
1.1 bromoxyni tolpyralate 1.1 mesotrione tolpyralate
1.1 clodinafop 2,4D 1.1 metribuzin nicosulfuron
1.1 clodinafop amidosulfuron 1.1 metribuzin pethoxamid
1.1 clodinafop bicyclopyrone 1.1 metribuzin prosulfuron
1.1 clodinafop bromoxynil 1.1 metribuzin pyridate
1.1 clodinafop dicamba 1.1 metribuzin pyroxasulfone
1.1 clodinafop diflufenican 1.1 metribuzin rimsulfuron
1.1 clodinafop florasulam 1.1 metribuzin S-metolachor
1.1 clodinafop fluroxypy 1.1 metribuzin sulcotrione
1.1 clodinafop halauxifen 1.1 metribuzin tembotrione
1.1 clodinafop MCPA 1.1 metribuzin terbuthylazine
1.1 clodinafop metsulfuron 1.1 metribuzin tolpyralate
1.1 clodinafop propoxycarbazone 1.1 nicosulfuron pethoxamid
1.1 clodinafop prosulfuron 1.1 nicosulfuron prosulfuron
1.1 clodinafop pyroxsulam 1.1 nicosulfuron pyridate
1.1 clodinafop terbutryn 1.1 nicosulfuron pyroxasulfone
1.1 clodinafop triasulfuron 1.1 nicosulfuron rimsulfuron
1.1 clopyralid 2,4D 1.1 nicosulfuron S-metolachor
1.1 clopyralid dicamba 1.1 nicosulfuron sulcotrione
1.1 clopyralid dimethenamid-P 1.1 nicosulfuron tembotrione
1.1 clopyralid fenquinotrione 1.1 nicosulfuron terbuthylazine
1.1 clopyralid foramsulfuron 1.1 nicosulfuron tolpyralate
1.1 clopyralid glufosinate 1.1 paraquat ametryn
1.1 clopyralid glyphosate 1.1 paraquat atrazine
1.1 clopyralid isoxaflutole 1.1 paraquat bicyclopyrone CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 clopyralid mesotrione 1.1 paraquat Butafenacil
1.1 clopyralid metribuzin 1.1 paraquat dicamba
1.1 clopyralid nicosulfuron 1.1 paraquat diuron
1.1 clopyralid pethoxamid 1.1 paraquat flazasulfuron
1.1 clopyralid prosulfuron 1.1 paraquat flumioxazin
1.1 clopyralid pyridate 1.1 paraquat hexazinon
1.1 clopyralid pyroxasulfone 1.1 paraquat mesotrione
1.1 clopyralid rimsulfuron 1.1 paraquat metribuzin
1.1 clopyralid S-metolachor 1.1 paraquat metsulfuron
1.1 clopyralid sulcotrione 1.1 paraquat norflurazon
1.1 clopyralid tembotrione 1.1 paraquat oxadiazon
1.1 clopyralid terbuthylazine 1.1 paraquat oxyfluorfen
1.1 clopyralid tolpyralate 1.1 paraquat prometryn
1.1 2,4D dicamba 1.1 paraquat rimsulfuron
1.1 2,4D dimethenamid-P 1.1 paraquat saflufenacil
1.1 2,4D fenquinotrione 1.1 paraquat simazine
1.1 2,4D foramsulfuron 1.1 paraquat S-Metolachlor
1.1 2,4D glufosinate 1.1 paraquat terbuthylazine
1.1 2,4D glyphosate 1.1 paraquat terbutryn
1.1 2,4D isoxaflutole 1.1 paraquat trifloxysulfuron
1.1 2,4D mesotrione 1.1 pethoxamid prosulfuron
1.1 2,4D metribuzin 1.1 pethoxamid pyridate
1.1 2,4D nicosulfuron 1.1 pethoxamid pyroxasulfone
1.1 2,4D pethoxamid 1.1 pethoxamid rimsulfuron
1.1 2,4D prosulfuron 1.1 pethoxamid S-metolachor
1.1 2,4D pyridate 1.1 pethoxamid sulcotrione
1.1 2,4D pyroxasulfone 1.1 pethoxamid tembotrione
1.1 2,4D rimsulfuron 1.1 pethoxamid terbuthylazine
1.1 2,4D S-metolachor 1.1 pethoxamid tolpyralate
1.1 2,4D sulcotrione 1.1 pinoxaden 2.4D
1.1 2,4D tembotrione 1.1 pinoxaden amidosulfuron
1.1 2,4D terbuthylazine 1.1 pinoxaden bicyclopyrone
1.1 2,4D tolpyralate 1.1 pinoxaden bromoxynil
1.1 dicamba dimethenamid-P 1.1 pinoxaden dicamba
1.1 dicamba fenquinotrione 1.1 pinoxaden diflufenican
1.1 dicamba foramsulfuron 1.1 pinoxaden florasulam
1.1 dicamba glufosinate 1.1 pinoxaden fluroxypy
1.1 dicamba glyphosate 1.1 pinoxaden halauxifen
1.1 dicamba isoxaflutole 1.1 pinoxaden MCPA
1.1 dicamba mesotrione 1.1 pinoxaden metsulfuron
1.1 dicamba metribuzin 1.1 pinoxaden propoxycarbazone
1.1 dicamba nicosulfuron 1.1 pinoxaden prosulfuron CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 dicamba pethoxamid 1.1 pinoxaden pyroxsulam
1.1 dicamba prosulfuron 1.1 pinoxaden terbutryn
1.1 dicamba pyridate 1.1 pinoxaden triasulfuron
1.1 dicamba pyroxasulfone 1.1 prosulfocarb 2.4D
1.1 dicamba rimsulfuron 1.1 prosulfocarb amidosulfuron
1.1 dicamba S-metolachor 1.1 prosulfocarb bicyclopyrone
1.1 dicamba sulcotrione 1.1 prosulfocarb bromoxynil
1.1 dicamba tembotrione 1.1 prosulfocarb dicamba
1.1 dicamba terbuthylazine 1.1 prosulfocarb diflufenican
1.1 dicamba tolpyralate 1.1 prosulfocarb florasulam
1.1 diquat ametryn 1.1 prosulfocarb fluroxypy
1.1 diquat atrazine 1.1 prosulfocarb halauxifen
1.1 diquat bicyclopyrone 1.1 prosulfocarb MCPA
1.1 diquat butafenacil 1.1 prosulfocarb metsulfuron
1.1 diquat dicamba 1.1 prosulfocarb propoxycarbazone
1.1 diquat diuron 1.1 prosulfocarb prosulfuron
1.1 diquat flazasulfuron 1.1 prosulfocarb pyroxsulam
1.1 diquat flumioxazin 1.1 prosulfocarb terbutryn
1.1 diquat hexazinon 1.1 prosulfocarb triasulfuron
1.1 diquat mesotrione 1.1 prosulfuron pyridate
1.1 diquat metribuzin 1.1 prosulfuron pyroxasulfone
1.1 diquat metsulfuron 1.1 prosulfuron rimsulfuron
1.1 diquat norflurazon 1.1 prosulfuron S-metolachor
1.1 diquat oxadiazon 1.1 prosulfuron sulcotrione
1.1 diquat oxyfluorfen 1.1 prosulfuron tembotrione
1.1 diquat prometryn 1.1 prosulfuron terbuthylazine
1.1 diquat rimsulfuron 1.1 prosulfuron tolpyralate
1.1 diquat saflufenacil 1.1 pyridate pyroxasulfone
1.1 diquat simazine 1.1 pyridate rimsulfuron
1.1 diquat S-Metolachlor 1.1 pyridate S-metolachor
1.1 diquat terbuthylazine 1.1 pyridate sulcotrione
1.1 diquat terbutryn 1.1 pyridate tembotrione
1.1 diquat trifloxysulfuron 1.1 pyridate terbuthylazine
1.1 dimethenamid-P fenquinotrione 1.1 pyridate tolpyralate
1.1 dimethenamid-P foramsulfuron 1.1 pyroxasulfone amidosulfuron
1.1 dimethenamid-P glufosinate 1.1 pyroxasulfone diflufenican
1.1 dimethenamid-P glyphosate 1.1 pyroxasulfone florasulam
1.1 dimethenamid-P isoxaflutole 1.1 pyroxasulfone fluroxypy
1.1 dimethenamid-P mesotrione 1.1 pyroxasulfone halauxifen
1.1 dimethenamid-P metribuzin 1.1 pyroxasulfone MCPA
1.1 dimethenamid-P nicosulfuron 1.1 pyroxasulfone metsulfuron
1.1 dimethenamid-P pethoxamid 1.1 pyroxasulfone propoxycarbazone
1.1 dimethenamid-P prosulfuron 1.1 pyroxasulfone pyroxsulam CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 dimethenamid-P pyridate 1.1 pyroxasulfone rimsulfuron
1.1 dimethenamid-P pyroxasulfone 1.1 pyroxasulfone S-metolachor
1.1 dimethenamid-P rimsulfuron 1.1 pyroxasulfone sulcotrione
1.1 dimethenamid-P S-metolachor 1.1 pyroxasulfone tembotrione
1.1 dimethenamid-P sulcotrione 1.1 pyroxasulfone terbuthylazine
1.1 dimethenamid-P tembotrione 1.1 pyroxasulfone tolpyralate
1.1 dimethenamid-P terbuthylazine 1.1 pyroxasulfone terbutryn
1.1 dimethenamid-P tolpyralate 1.1 pyroxasulfone triasulfuron
1.1 fenoxaprop 2,4D 1.1 rimsulfuron S-metolachor
1.1 fenoxaprop amidosulfuron 1.1 rimsulfuron sulcotrione
1.1 fenoxaprop bicyclopyrone 1.1 rimsulfuron tembotrione
1.1 fenoxaprop bromoxynil 1.1 rimsulfuron terbuthylazine
1.1 fenoxaprop dicamba 1.1 rimsulfuron tolpyralate
1.1 fenoxaprop diflufenican 1.1 S-metolachor amidosulfuron
1.1 fenoxaprop florasulam 1.1 S-metolachor diflufenican
1.1 fenoxaprop fluroxypy 1.1 S-metolachor florasulam
1.1 fenoxaprop halauxifen 1.1 S-metolachor fluroxypy
1.1 fenoxaprop MCPA 1.1 S-metolachor halauxifen
1.1 fenoxaprop metsulfuron 1.1 S-metolachor MCPA
1.1 fenoxaprop propoxycarbazone 1.1 S-metolachor metsulfuron
1.1 fenoxaprop prosulfuron 1.1 S-metolachor propoxycarbazone
1.1 fenoxaprop pyroxsulam 1.1 S-metolachor pyroxsulam
1.1 fenoxaprop terbutryn 1.1 S-metolachor sulcotrione
1.1 fenoxaprop triasulfuron 1.1 S-metolachor tembotrione
1.1 fenquinotrione foramsulfuron 1.1 S-metolachor terbuthylazine
1.1 fenquinotrione glufosinate 1.1 S-metolachor tolpyralate
1.1 fenquinotrione glyphosate 1.1 S-metolachor terbutryn
1.1 fenquinotrione isoxaflutole 1.1 S-metolachor triasulfuron
1.1 fenquinotrione mesotrione 1.1 sulcotrione tembotrione
1.1 fenquinotrione metribuzin 1.1 sulcotrione terbuthylazine
1.1 fenquinotrione nicosulfuron 1.1 sulcotrione tolpyralate
1.1 fenquinotrione pethoxamid 1.1 tembotrione terbuthylazine
1.1 fenquinotrione prosulfuron 1.1 tembotrione tolpyralate
1.1 fenquinotrione pyridate 1.1 terbuthylazine tolpyralate
1.1 fenquinotrione pyroxasulfone 1.1 thiencarbazone 2,4D
1.1 fenquinotrione rimsulfuron 1.1 thiencarbazone amidosulfuron
1.1 fenquinotrione S-metolachor 1.1 thiencarbazone bicyclopyrone
1.1 fenquinotrione sulcotrione 1.1 thiencarbazone bromoxynil
1.1 fenquinotrione tembotrione 1.1 thiencarbazone dicamba
1.1 fenquinotrione terbuthylazine 1.1 thiencarbazone diflufenican
1.1 fenquinotrione tolpyralate 1.1 thiencarbazone florasulam
1.1 flucarbazone 2,4D 1.1 thiencarbazone fluroxypy
1.1 flucarbazone amidosulfuron 1.1 thiencarbazone halauxifen CMP Mix Partner 1 Mix Partner 2 CMP Mix Partner 1 Mix Partner 2
1.1 flucarbazone bicyclopyrone 1.1 thiencarbazone MCPA
1.1 flucarbazone bromoxynil 1.1 thiencarbazone metsulfuron
1.1 flucarbazone dicamba 1.1 thiencarbazone propoxycarbazone
1.1 flucarbazone diflufenican 1.1 thiencarbazone prosulfuron
1.1 flucarbazone florasulam 1.1 thiencarbazone pyroxsulam
1.1 flucarbazone fluroxypy 1.1 thiencarbazone terbutryn
1.1 flucarbazone halauxifen 1.1 thiencarbazone triasulfuron
1.1 flucarbazone MCPA
1.1 flucarbazone metsulfuron
1.1 flucarbazone propoxycarbazone
1.1 flucarbazone prosulfuron
1.1 flucarbazone pyroxsulam
1.1 flucarbazone terbutryn
1.1 flucarbazone triasulfuron
The present invention further provides compositions as defined in Tables 2 to 14 below. TABLE 2. Compositions comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.2 (see Table CI).
TABLE 3. Compositions comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.3 (see Table CI).
TABLE 4. Compositions comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.4 (see Table CI).
TABLE 5. Compounds comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.5 (see Table CI).
TABLE 6. Compounds comprising the three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.6 (see Table CI). TABLE 7. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.7 (see Table CI).
TABLE 8. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.8 (see Table CI).
TABLE 9. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.9 (see Table CI). TABLE 10. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.10 (see Table CI).
TABLE 11. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.11 (see Table CI). TABLE 12. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.12 (see Table CI).
TABLE 13. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.13 (see Table CI).
TABLE 14. Compounds comprising three-way mixtures listed in Table 1 above, wherein the compound 1.1 is replaced with compound 1.14 (see Tab 1 e C 1 ) .
The compositions of the invention can further include one or more safeners. In particular, the following safeners are particularly preferred: AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, furilazome, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetnnil, naphthalic anhydride (CAS R 81-84-5), TI-35, N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)- benzamide (CAS RN 221668-34-4) and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide. 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.
Particularly prefened safeners are cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl, mefenpyr-diethyl and N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide. Prefened compositions of the invention and safeners include:
Compound 1.1, atrazine and cloquintocet-mexyl; compound 1.1, atrazine and cyprosulfamide; compound 1.1, atrazine and isoxadifen-ethyl; compound 1.1, atrazine and mefenpyr-diethyl; compound 1.1, atrazine and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide. Compound 1.1, tebuthylazine and cloquintocet-mexyl; compound 1.1, tebuthylazine and cyprosulfamide; compound 1.1, tebuthylazine and isoxadifen-ethyl; compound 1.1, tebuthylazine and mefenpyr-diethyl; compound 1.1, tebuthylazine and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Compound 1.1, mesotrione and cloquintocet-mexyl; compound 1.1, mesotrione and cyprosulfamide; compound 1.1, mesotrione and isoxadifen-ethyl; compound 1.1 , mesotrione and mefenpyr-diethyl; compound 1.1, mesotrione and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, bicyclopyrone and cloquintocet-mexyl; compound 1.1, bicyclopyrone and cyprosulfamide; compound 1.1, bicyclopyrone and isoxadifen-ethyl; compound 1.1, bicyclopyrone and mefenpyr-diethyl; compound 1.1, bicyclopyrone and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, nicosulfuron and cloquintocet-mexyl; compound 1.1, nicosulfuron and cyprosulfamide; compound 1.1, nicosulfuron and isoxadifen-ethyl; compound 1.1, nicosulfuron and mefenpyr-diethyl; compound 1.1, nicosulfuron and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, S-metolachlor and cloquintocet-mexyl; compound 1.1, S-metolachlor and cyprosulfamide; compound 1.1, S-metolachlor and isoxadifen-ethyl; compound 1.1, S-metolachlor and mefenpyr-diethyl; compound 1.1, S-metolachlor and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, bromoxynil and cloquintocet-mexyl, compound 1.1, bromoxynil and cyprosulfamide, compound 1.1, bromoxynil and isoxadifen-ethyl, compound 1.1, bromoxynil and mefenpyr-diethyl, compound 1.1, bromoxynil and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Compound 1.1, pinoxaden and cloquintocet-mexyl, compound 1.1, pinoxaden and cyprosulfamide, compound 1.1, pinoxaden and isoxadifen-ethyl, compound 1.1, pinoxaden and mefenpyr-diethyl, compound 1.1, pinoxaden and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, clodinafop-propargyl and cloquintocet-mexyl, compound 1.1, clodinafop-propargyl and cyprosulfamide, compound 1.1 clodinafop-propargyl and isoxadifen-ethyl, compound 1.1, clodinafop-propargyl and mefenpyr-diethyl, compound 1.1, clodinafop-propargyl and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, fenoxaprop-P-ethyl and cloquintocet-mexyl, compound 1.1, fenoxaprop-P-ethyl and cyprosulfamide, compound 1.1 fenoxaprop-P-ethyl and isoxadifen-ethyl, compound 1.1, fenoxaprop-P-ethyl and mefenpyr-diethyl, compound 1.1, fenoxaprop-P-ethyl and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino- Jbenzenesulfonamide.
Compound 1.1, mesosulfuron and cloquintocet-mexyl, compound 1.1, mesosulfuron and cyprosulfamide, compound 1.1 mesosulfuron and isoxadifen-ethyl, compound 1.1, mesosulfuron and mefenpyr-diethyl, compound 1.1, mesosulfuron and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, iodosulfuron-methyl-sodium and cloquintocet-mexyl, compound 1.1, iodosulfuron-methyl-sodium and cyprosulfamide, compound 1.1 iodosulfuron- methyl-sodium and isoxadifen-ethyl, compound 1.1, iodosulfuron-methyl-sodium and mefenpyr-diethyl, compound 1.1, iodosulfuron-methyl-sodium and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, thiencarbazone and cloquintocet-mexyl, compound 1.1, thiencarbazone and cyprosulfamide, compound 1.1 thiencarbazone and isoxadifen- ethyl, compound 1.1, thiencarbazone and mefenpyr-diethyl, compound 1.1, thiencarbazone and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)- amino]benzenesulfonamide.
Compound 1.1, compound B2 and cloquintocet-mexyl, compound 1.1, compound B2 and cyprosulfamide, compound 1.1 compound B2 and isoxadifen-ethyl, compound 1.1, compound B2 and mefenpyr-diethyl, compound 1.1, compound B2 and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, compound B3 and cloquintocet-mexyl, compound 1.1, compound B3 and cyprosulfamide, compound 1.1 compound B3 and isoxadifen-ethyl, compound 1.1, compound B3 and mefenpyr-diethyl, compound 1.1, compound B3 and N-(2- methoxybenzoyl)-4- [(methylaminocarbonyl)amino ]benzenesulfonamide. Compound 1.1, compound B4 and cloquintocet-mexyl, compound 1.1, compound B4 and cyprosulfamide, compound 1.1 compound B2 and isoxadifen-ethyl, compound 1.1, compound B4 and mefenpyr-diethyl, compound 1.1, compound B4 and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Compound 1.1, compound B5 and cloquintocet-mexyl, compound 1.1, compound B5 and cyprosulfamide, compound 1.1 compound B5 and isoxadifen-ethyl, compound 1.1, compound B5 and mefenpyr-diethyl, compound 1.1, compound B5 and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, compound B6 and cloquintocet-mexyl, compound 1.1, compound B6 and cyprosulfamide, compound 1.1 compound B6 and isoxadifen-ethyl, compound 1.1, compound B6 and mefenpyr-diethyl, compound 1.1, compound B6 and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Compound 1.1, compound B7 and cloquintocet-mexyl, compound 1.1, compound B7 and cyprosulfamide, compound 1.1 compound B7 and isoxadifen-ethyl, compound 1.1, compound B7 and mefenpyr-diethyl, compound 1.1, compound B7 and N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.2. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.3. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.4. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.5. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.6. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.7. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.8. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.9. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.10. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.11. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.12. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.13. Further preferred compositions of the invention and safeners include compositions defined above wherein Compound 1.1 is substituted with Compound 1.14.
The compounds of Formula I can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.
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. The application may be applied to the locus pre-emergence and/or postemergence of the crop plant. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I). Preferred crop plants include maize, wheat, barley and rice. 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 4-hydroxyphenylpyruvate dioxygenase (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. Accordingly, the herbicidal compounds of the present invention have broad application in a number of crop plants, including 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 25 to 1000 g/ha, more especially from 25 to 250 g/ha.
The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate- resistant maize varieties commercially available under the trade names PvOundupReady® 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).
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. In a further aspect of the present invention there is provided the use of a compound of Formula (I) as defined herein as a herbicide.
The compounds of the present invention can be prepared according to the following schemes.
Preparation of compounds Formula (I) is carried out analogously to known processes and comprises reacting a compound of Formula (He):
Figure imgf000046_0001
where the definition of R1 is as for Formula (I) and LG is a suitable leaving group, for example a halogen atom, such as chlorine, or an alkoxy or aryloxy group, such as 4- nitrophenoxy, in an inert organic solvent, such as dichloromethane or acetonitrile, in the presence of a base, such as triethylamine, with a diketone of Formula (III)
Figure imgf000046_0002
wherein
A1 and Ra, Rb, Rc, Rd are as defined previously in respect of Formula (I);
to give an ester of Formula (IV):-
Figure imgf000046_0003
which may be rearranged using catalysts, such as 4-dimethylaminopyridine, or acetone cyanohydrin, or a metal cyanide salt, such as sodium cyanide, in the presence of a suitable base, such as triethylamine, to give compounds of Formula (I).
Thus, according to a further aspect of the present invention there is provided a compound of Formula (II)
Figure imgf000047_0001
wherein
R1 is as defined as before and R2 is selected from the group consisting of halogen, -OH, Ci-C6 alkoxy, aryloxy and N-linked imdazolyl. In this context, aryloxy is preferably a phenoxy group optionally substituted on the phenyl ring by one to five groups consisting of: fluoro, chloro, nitro, cyano, Ci- Csalkyl , Ci-C3alkoxy and Ci-Cshaloalkyl. Specific examples of preferred aryloxy groups thus include phenoxy, 4-nitrophenoxy and 2,3,4,5, 6- pentafluorophenoxy.
Table C2 - Examples of compounds of the present invention.
Figure imgf000047_0002
Figure imgf000048_0001
The diketones of Formula (III) may be commercially available or, where they are not, prepared through methods detailed in the literature. For example, the preparation of the dione where A1 is C=0 and Ra, Rb, Rc and Rd are all methyl is detailed in Tetrahedron 2013, 8559-8563. The preparation of the dione where A1 is CH(ethyl) and Ra, Rb, Rc and Rd are all hydrogen is detailed in Tetrahedron, 2000, 4753-4758. The preparation of the dione where A1 is CH2, Ra-Rc is -CH2CH2- and Rb and Rd are both hydrogen is detailed in Tetrahedron Lett. 2013, 557-561. The preparation of the dione where A1 is CH2 and Ra, Rb, Rc and Rd are all methyl is detailed in US5006150 Al, 1991.
Thus, according to a further aspect of the present invention, there is provided a method of producing a compound of Formula (I) comprising (i) reacting, in an inert organic solvent and in the presence of a base, a compound of Formula (He):
Figure imgf000049_0001
where the definition of R1 is as for Formula (I) and LG is a suitable leaving group (for example a halogen atom, such as chlorine, or an alkoxy or aryloxy group, such as 4-nitrophenoxy), with a diketone of Formula (III)
Figure imgf000049_0002
and (ii) rearrangement of the resulting product into the compound of Formula (I)-
Compounds of formula (lie) may be prepared from carboxylic acids of formula (lib)
Figure imgf000050_0001
For example, for LG = chloro, the skilled person will recognise the common methods to execute this transformation such as treatment of the carboxylic acid with 1 equivalent of oxalyl chloride and a catalytic quantity of N,N-dimethylformamide in a non-polar solvent such as dichloromethane or acetonitrile.
Figure imgf000050_0002
Carboxylic acids of Formula (lib) may in turn be prepared from esters of Formula (Ila) by treatment with an alkoxide base such as lithium hydroxide in a suitable solvent system of a mixture of water and an organic solvent. Examples of suitable esters are wherein R2 Ci-C6alkyl-, such as methyl, ethyl, n-propyl and isopropyl. Examples of suitable solvent systems are tetrahydrofuran / water (1 : 1) or ethanol / water (1 : 1).
Figure imgf000050_0003
Esters of formula (Ila) may be prepared from the Chan-Lam coupling between pyridazinones of formula (IV) and 3,4-dimethoxyboronic acid. The Chan-Lam reaction is detailed in Tetrahedron Lett. 1998, 2933-2936. These reactions use a copper (II) or copper (I) salt such as copper (II) acetate, a non-polar solvent such as dichloromethane or 1,2-dichloroethane and an organic base, for example triethylamine or pyridine or a 1 :1 mixture of triethylamine and pyridine. Super-stoichiometric equivalents of copper (I) or copper (II) salts, typically 1-3 equivalents of copper (II) acetate, may be used. Alternatively, catalytic amounts of the copper catalyst, for example 0.05 to 0.3 molar equivalents of copper (II) acetate, may be used instead if >1 equivalent of an oxidant is also added. Suitable examples of oxidants are pyridine-N-oxide or the bubbling of air or oxygen through the reaction mixture. The reaction can typically be performed at room temperature to achieve acceptable conversion in 2-16 h.
Figure imgf000051_0001
Pyridazinones of formula (IV) may be prepared by the oxidation of dihydropyridazmones of formula (VI) with a suitable oxidising agent. Examples of suitable oxidising agents are bromine in a solution of acetic acid or dichloromethane, or iodobenzene diacetate in a solution of isopropanol.
Figure imgf000051_0002
Dihydropyridazmones of formula (VI) may be prepared through the treatment of compounds of formula (VII) with hydrazine hydrate in a suitable solvent such as ethanol under reflux conditions.
Figure imgf000052_0001
Compounds of Formula (VII) may be prepared via the alkylation of a commercially available dialkyl malonate (for example diethyl malonate) with a bromo-ketone of Formula (VIII) in the presence of a suitable base, for example potassium carbonate, in a suitable solvent, for example acetone.
Figure imgf000052_0002
(Ιχ) (VIII)
Compounds of Formula (VIII) may be commercially available, or alternatively they may be prepared via the bromination of a commercially available methyl ketone of Formula (IX) by treatment with bromine in a suitable solvent such as methanol or a mixture of water and glacial acetic acid (~5: 1).
The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table CI above.
Preparative Example 1: Preparation of 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)- 3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-l,3,5-trione
(Compound 1.11 (see Table CI)). STEP 1. Preparations of 2-Bromo-l-cyclopropyl-ethanone.
Figure imgf000053_0001
To a stirred solution of 1-cyclopropylethanone (50 g, 595 mmol) in MeOH (350 mL) at 0 °C (ice bath) was added bromine (32 mL, 595 mmol) dropwise over a period of 1 hour (the initial red colour of the reaction mixture became colourless by the end of the addition of bromine). The resulting solution was then stirred below 5 °C for 4 hours, then water (175 mL) was added and the reaction mixture stirred at room temperature for 16 hours. The reaction mixture was then poured into water (1000 mL) and extracted with CH2CI2 (2 x 1000 mL). The combined organic layers was washed with saturated aqueous NaHC03 solution (500 mL), water (500 mL) and finally with brine (500 mL). The organic layer was dried over Na2S04, filtered and concentrated in vacuo to give a light-brown oil. Pure 2-bromo-l-cyclopropyl-ethanone was obtained by vacuum distillation of this crude oil at 100 °C (59 g, 61%).
XH N M (400 MHz, CDCI3) δ = 4.01 (s, 2H), 2.22-2.17 (m, 1H), 1.14-1.11 (m, 2H), 1.03-0.99 ( 2H).
STEP 2. Preparation of diethyl 2-(2-cyclopropyl-2-oxo-ethyl)propanedioate.
Figure imgf000053_0002
To a stirred solution of 2-bromo-l-cyclopropyl-ethanone (50 g, 307 mmol) in acetone (450 mL) at room temperature was added K2C03 (64 g, 460 mmol), potassium iodide (1.5 g, 9.2 mmol) and diethylmalonate (54 g, 337 mmol) and the resulting mixture was heated at reflux (75 °C) for 16 hours. The reaction mixture was filtered and the filtrate concentrated in vacuo. The crude material was purified by column chromatography, eluting with 8% EtOAc in hexane to afford diethyl 2-(2- cyclopropyl-2-oxo-ethyl)propanedioate as a light yellow oil (40 g, 54%). XH N M (400 MHz, CDCI3) δ = 4.24-4.13 (m, 4H), 3.95 (t, 1H), 3.18 (d, 2H), 1.98-1.92 (m, 1H), 1.26 (t, 6H), 1.06-1.03 (m, 2H), 0.93-0.88 (m, 2H). STEP 3. Preparation of ethyl 3-cyclopropyl-6-oxo-4,5-dihydro-lH-pyridazine-5- carboxylate.
Figure imgf000054_0001
To a stirred solution of diethyl 2-(2-cyclopropyl-2-oxo-ethyl)propanedioate (70 g, 289 mmol) in EtOH (500 mL) between 0-5 °C (ice-water bath) was added hydrazine hydrate (16 mL, 318 mmol) drop wise and the resulting solution was stirred at room temperature for 20 hours. All volatiles were removed from the reaction mixture in vacuo to afford crude ethyl 3-cyclopropyl-6-oxo-4,5-dihydro-lH-pyridazine-5- carboxylate as a thick yellow oil (52 g, crude). This crude material was used in the next step without any further purification.
STEP 4. Preparation of ethyl 3-cyclopropyl-6-oxo-lH-pyridazine-5-carboxylate.
Figure imgf000054_0002
To a stirred solution of ethyl 3-cyclopropyl-6-oxo-4,5-dihydro-lH-pyridazine-5- carboxylate (52 g crude, 247 mmol) in AcOH (500 mL) between 10-15 °C was added a solution of bromine (20 mL, 317 mmol) in AcOH (200 mL) dropwise over a period of 30 minutes. The resultant solution was then stirred at room temperature for a further 30 minutes. The AcOH was removed from the reaction mixture in vacuo. To the residue was added EtOAc (2000 mL) and water (5000 mL) and the mixture shaken thoroughly. All insoluble particles were then removed by filtration through a Celite bed and then the filtrate layers were separated. The aqueous layer was extracted further with EtOAc (1000 mL). The combined EtOAc layers was then washed with saturated aqueous NaHC03 solution (500 mL), saturated aqueous Na2S203 solution (500 mL) and finally with brine (500 mL). The organic layer was dried over Na2S04, filtered and concentrated in vacuo. The crude material was purified by column chromatography eluting with 8% EtOAc in hexane to afford desired product as a light yellow solid. The solid was further purified by triturating with a 1% solution of EtOAc in hexane to afford ethyl 3-cyclopropyl-6-oxo-lH-pyridazine-5-carboxylate as an off white solid (17 g, 28% over two steps).
XH N M (400 M Hz, CDCI3) δ = 11.17 (s, 1H), 7.65 (s, 1H), 4.40 (q, 2H), 1.92-1.85 (m, 1H), 1.38 (t, 3H), 1.02-0.98 (m, 2H), 0.92-0.88 (m, 2H). STEP 5. Preparation of ethyl 6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo- pyridazine-4-carboxylate.
Figure imgf000055_0001
To a stirred solution of ethyl 3-cyclopropyl-6-oxo-lH-pyridazine-5-carboxylate (2.00 g, 9.61 mmol) in dichloromethane (70 mL) was added, 4A molecular sieves (0.88 g), copper(II) acetate monohydrate (4.01 g, 22.1 mmol), triethylamine (2.7 mL, 19.2 mmol) and pyridine (1.6 mL, 19.2 mmol). Then (3,4-dimethoxyphenyl)boronic acid (2.6 g, 14.4 mmol) was added portionwise over 10 minutes. The reaction mixture was stirred for 4 hours at room temperature with compressed air bubbling through. After 4 hours the compressed air was switched off and stirring continued for a further 16 hours. The reaction mixture was filtered through C elite washing the residue with additional CH2CI2. The filtrate was washed with aqueous 2N HC1 solution (2 x 100 mL) and saturated brine solution (100 mL). The organic layer was dried over MgS04, filtered and concentrated in vacuo to leave a dark yellow gum. Purification by column chromatography eluting with 0-100% EtOAc in isohexane afforded ethyl 6- cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carboxylate as a bright yellow gum (2.46 g, 74%). XH N MR (400 MHz, CDCI3) δ = 7.55 (s, 1H), 7.11 (m, 2H), 6.91 (d, 1H), 4.40 (q, 2H), 3.94 (s, 3H), 3.90 (s, 3H), 1.97 (m, 1H), 1.40 (t, 3H), 1.04 (m, 2H), 0.92 (m, 2H). STEP 6. Preparation of 6-Cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carboxylic acid.
Figure imgf000056_0001
To a solution of ethyl 6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carboxylate (2.40 g, 6.97 mmol) in tetrahydrofuran (50 mL) was added water (25 mL) followed by lithium hydroxide (0.45 g, 10.5 mmol). The resultant solution was stirred at room temperature for 90 minutes. The THF was removed in vacuo and the remaining aqueous mixture diluted with water (25 mL) and washed with EtOAc (30 mL). The vigorously stirred aqueous layer was acidified until pH = 1 with cone. HC1 solution - a yellow precipitate forms in the process. This was collected by filtration affording 6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carboxylic acid as a yellow solid (1.78 g, 81%).
XH N M (400 M Hz, CDCI3) δ = 14.10 (br. s, 1H), 8.06 (s, 1H), 7.14 (m, 1H), 7.10 (m, 1H), 6.97 (d, 1H), 3.95 (s, 3H), 3.90 (s, 3H), 2.10 (m, 1H), 1.15 (m, 2H), 1.00 (m, 2H). STEP 7. Preparation of 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine- 4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-l,3,5-trione (Compound 1.11).
Figure imgf000056_0002
Under a nitrogen atmosphere, to a solution of 6-cyclopropyl-2-(3,4- dimethoxyphenyl)-3-oxo-pyridazine-4-carboxylic acid (1.00 g, 3.16 mmol) in dichloromethane (anhydrous, 20 mL) in a 100 mL 3 -neck round bottom flask was added Ν,Ν-dimethylformamide (anhydrous, 0.012 mL, 0.158 mmol) followed by oxalyl chloride (0.29 mL, 3.32 mmol) dropwise and the reaction mixture stirred at room temperature for 1 hour. The reaction mixture was cooled to 0 °C (salt/ice bath) and triethylamine (1.77 mL, 12.7 mmol) was added dropwise over 15 minutes, then stirred for 5 minutes at 0 °C before 2,2,4,4-tetramethylcyclohexane-l,3,5-trione (0.58 g, 3.17 mmol) dissolved in minimum CH2CI2 was added dropwise over 15 minutes. The resultant solution was stirred at 0 °C for 5 minutes then 1 hour at room temperature. The reaction mixture was cooled to 0 °C and further triethylamine (1.77 mL, 12.7 mmol) was added dropwise over 10 minutes followed by acetone cyanohydrin (0.044 mL, 0.475 mmol). The reaction mixture was stirred at 0 °C for 5 minutes then heated at reflux (40 °C) for 90 minutes. The reaction mixture was allowed to cool to room temperature, filtered and the filtrate concentrated in vacuo. Purification by column chromatography eluting with a mixed solvent system of 20:8:4:4: 1 Toluene : Dioxane : EtOH : Et3N : Water afforded the triethylamine salt of the desired compound. The crude oil was dissolved in MeOH and loaded onto a solid- phase-extraction SAX cartridge. The column was flushed with 3 column volumes of MeOH and then the desired product released with 1% formic acid in MeOH, concentrating in vacuo to afford 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo- pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-l,3,5-trione (0.31 g, 20%) as a crushed orange foam.
XH NM (400M Hz, CDCI3) δ = 7.13 (s, 1H), 7.12-7.06 (m, 2H), 6.91 (d, 1H), 3.91 (s, 3H), 3.88 (s, 3H), 2.00-1.92 (m, 1H), 1.52 (br. s, 6H), 1.40 (br. s, 6H), 1.05-0.98 (m, 2H), 0.98-0.91 (m, 2H).
Preparative Example 2: Preparation of 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)- 3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-l,3-dione (Compound 1.8 (see Table CI)).
Figure imgf000058_0001
6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carboxylic acid (1.00 g, 3.16 mmol) was taken in dry DCM (20 mL) and to it one drop of dry DMF was added. Then oxalylchloride (0.35 mL, 4.11 mmol) was added dropwise to the mixture & stirred for 1 h. The reaction mixture was concentrated under reduced pressure in nitrogen atmosphere. Then the crude reaction mass was dissolved in dry DCM (15 mL), activated molecular sieves was added & cooled the reaction mixture in ice salt bath. Then triethylamine (1.23 mL, 9.48 mmol) was added dropwise to the reaction mixture over 15 min. followed by 5-methyl-l,3-cyclohexane dione (479 mg, 3.79 mmol) in DCM (10 mL) was added dropwise to the reaction mixture. Stirred at room temperature for 1 h. Then triethylamine (1.23 mL, 9.48 mmol) and acetone cyanohydrin (0.22 mL, 2.37 mmol) were added and the reaction was stirred for 2.5 h. The crude was diluted with DCM & washed with 1 N HCl. Purification by column chromatography eluting with a mixed solvent system of 20:8:4:4: 1 Toluene : Dioxane : EtOH : Et3N : Water afforded the triethylamine salt of the desired compound as a brown gum. To this was added water (25 mL) and CH2CI2 (25 mL) and this was acidified to pH 1 with 2M HCl. The mixture was stirred for 5 minutes, then the phases separated through a phase separation cartridge, washing with further CH2CI2. The organic phase was concentrated to afford the desired product 2-[6-cyclopropyl-2- (3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-l,3- dione (850 mg, 2.00 mmol, 63%) as a solid.
XH N M (400MHz, CDCI3) δ = 7.14-7.10 (2H, m), 6.98 (1H, s), 6.89 (1H, d), 3.89 (3H, s), 3.87 (3H, s), 2.75-2.71 (1H, m), 2.53-2.39 (2H, m), 2.32-2.26 (1H, m), 2.18-2.12 (1H, m), 1.97-1.90 (1H, m), 1.08 (3H, d), 0.99-0.95 (2H, m), 0.93-0.87 (2H, m).
Preparative Example 3: Preparation of 2-[2-(3,4-Dimethoxyphenyl)-6-methyl-3- oxo-pyridazine-4-carbonyl]cyclohexane-l,3-dione (compound 1.3 (see Table CI)). STEP 1. Preparation of 1-Bromoprop
Figure imgf000059_0001
Acetone (150 g, 2.58 mol), water (480 mL) and glacial acetic acid (90 mL) were stirred in a two-necked round bottom flask and heated to reflux (75 °C). Bromine (73.2 mL, 2.84 mol) was added portionwise to the solution. The reaction mixture continued to be heated at 75 °C until it turned colourless. It was then cooled to 0 °C (ice-bath) and water added (100 mL) followed by sufficient Na2C03 until it was no longer acidic. The reaction mixture was transferred to a separating funnel and the bottom organic layer separated, dried over Na2S04 and filtered to afford 1- bromopropan-2-one (99.0 g, 28%).
XH N M (CDCIs, 400MHz) δ = 3.23 (s, 2H), 1.67-1.72 (m, 3H).
STEP 2. Preparation of diethyl 2-acetonylpropanedioate.
Figure imgf000059_0002
l-Bromopropan-2-one (90 g, 0.66 mol) was dissolved in acetone (740 mL) and under a nitrogen atmosphere diethylmalonate (126 mL, 0.79 mol), K2CO3 (136 g, 0.99 mol) and KI (3.27 g, 19.7 mmol) were added to the stirred solution. The reaction mixture was heated at refiux for 16 hours. The reaction mixture was filtered and the filtrate concentrated in vacuo. The crude material was dissolved in EtOAc and washed with water followed by brine. The organic layer was dried over Na2S04, filtered and concentrated in vacuo to afford a liquid. This crude product was purified by column chromatography eluting with 0-5% MeOH in CH2CI2 to afford diethyl 2- acetonylpropanedioate as a pale yellow oil (80.0 g, 56%>). XH N MR (CDCI3, 400MHz) δ = 4.21-4.04 (m, 4H), 3.78 (t, 1H), 2.99 (d, 2H), 2.20-2.06 (m, 3H), 1.27-1.13 ppm (m, 6H). STEP 3. Preparation of ethyl 3-methyl-6-oxo-4,5-dihydro-lH-pyridazine-5- carboxylate.
Figure imgf000060_0001
Diethyl 2-acetonylpropanedioate (80 g, 370 mmol) was dissolved in absolute ethanol (175 mL) and cooled to 0 °C. To the stirred solution was added hydrazine hydrate (20.4 mL, 407 mmol) dropwise. The mixture was allowed to warm to room temperature and stirred for 16 hours. The reaction mixture was concentrated in vacuo and the resultant crude ethyl 3-methyl-6-oxo-4,5-dihydro-lH-pyridazine-5- carboxylate was used directly in the next step without further purification (61.0 g crude, 90%).
STEP 4. Preparation of ethyl 3-methyl-6-oxo-lH-pyridazine-5-carboxylate.
Figure imgf000060_0002
A solution of bromine (17 mL, 662 mmol) in acetic acid (140 mL) was added portion wise to a stirred solution of ethyl 3-methyl-6-oxo-4,5-dihydro-lH-pyridazine-5- carboxylate (61 g crude, 331 mmol) in acetic acid (1250 mL). The reaction mixture was stirred at room temperature for 1 hour then concentrated in vacuo. The crude material was dissolved in EtOAc and this solution washed with water followed by brine, dried over Na2S04, filtered and concentrated in vacuo. The crude material was purified by column chromatography eluting with 0-5% MeOH in CH2C12 to afford ethyl 3-methyl-6-oxo-lH-pyridazine-5-carboxylate as an off-white solid (22.0 g, 37%).
XH N M (CDC , 400MHz) δ = 7.71 (s, 1H), 4.40 (q, 2H), 2.39 (s, 3H), 1.39 (t, 3H). STEP 5. Preparation of ethyl 2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carboxylate.
Figure imgf000061_0001
To a solution of ethyl 3-methyl-6-oxo-lH-pyridazine-5-carboxylate (5.0 g, 27.4 mmol) in dichloromethane (200 mL) was added copper(II) acetate mono hydrate (12.6 g, 63.1 mmol), 4A molecular sieves, pyridine (4.4 mL, 54.9 mmol) and triethylamine (7.7 mL, 54.9 mmol). To the stirred suspension was added (3,4-dimethoxyphenyl)boronic acid (7.0 g, 38.4 mmol) portion wise over 5 minutes and the reaction mixture stirred at room temperature for 16 hours. The reaction mixture was filtered through Celite washing the residue with further CH2CI2. The filtrate was washed with aqueous 2N HC1 solution (2 x 200 mL), dried over MgSC^, filtered and concentrated in vacuo. Purification by column chromatography eluting with 20-100% EtOAc in isohexane afforded ethyl 2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carboxylate as a pale yellow solid (5.10 g, 58%) .
XH N M (400M Hz, CDCI3) δ = 7.66 (s, 1H), 7.11 (br. s, 2H), 6.93 (d, 1H), 4.41 (q, 2H), 3.92 (s, 3H), 3.90 (s, 3H), 2.44 (s, 3H), 1.39 (t, 3H). STEP 6. Preparation of 2-(3,4-Dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carboxylic acid.
Figure imgf000061_0002
To a solution of ethyl 2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carboxylate (12.0 g, 37.7 mmol) in tetrahydrofuran (200 mL) cooled to 0 °C (ice- bath) was added a solution of lithium hydroxide monohydrate (2.37 g, 56.5 mmol) in water (100 mL). The reaction mixture was allowed to warm to room temperature and stirred for 30 minutes. The THF was removed in vacuo and the aqueous mixture washed with CH2CI2 (3 x 40 mL). The aqueous solution was cooled to 0 °C, and stirred while cone. HC1 solution was added until pH = 1 was achieved. A bright yellow solid precipitated out in the process. This solid was collected by filtration. The solid was dissolved in CH2CI2 and the solution dried over MgSC^, filtered and concentrated in vacuo to afford 2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine- 4-carboxylic acid as a bright yellow solid (9.5 g, 87%).
XH N M (400MHz, CDCI3) δ = 14.01 (br. s, 1H), 8.18 (s, 1H), 7.16 (d, 1H), 7.08 (br. s, 1H), 6.98 (d, 1H), 3.94 (app. d, 6H), 2.55 (s, 3H).
STEP 7. Preparation of 2-[2-(3,4-Dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carbonyl]cyclohexane-l,3-dione (Compound 1.3).
Figure imgf000062_0001
To a solution of 2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carboxylic acid (1.00 g, 3.44 mmol) in dichloromethane (anhydrous, 13 mL) was added 3 drops of Ν,Ν-dimethylformamide (anhydrous) followed by dropwise addition of oxalyl chloride (0.33 mL, 3.79 mmol). The reaction mixture was stirred at room temperature for 16 hours. Further DMF (1 drop) and oxalyl chloride (0.1 mL) were added and stirring continued at room temperature for 1 hour. To a cooled (0°C (ice bath)) solution of cyclohexane-l,3-dione (0.41 g, 3.62 mmol) in dichloromethane (anhydrous, 7.0 mL) was added triethylamine (1.44 mL, 10.3 mmol). The acid chloride solution was then added to the cyclohexane-l,3-dione-triethylamine solution via syringe pump over 10 minutes (70 mL/h) and the reaction mixture was stirred at 0 °C for a further 5 minutes. Further triethylamine (0.48 mL, 3.45 mmol) was added followed by acetone cyanohydrin (as a stock solution in anhydrous CH2CI2) (10 mol%, 0.34 mmol). The reaction flask was transferred to a pre-heated oil bath and heated with stirring at reflux (40 °C) for 6 hours and then left stirring at room temperature for a further 16 hours. The reaction mixture was concentrated in vacuo to afford a black residue. Purification by column chromatography eluting with a mixed solvent system of 20:8:4:4: 1 Toluene : Dioxane : EtOH : Et3N : Water afforded the triethylamine salt of the desired compound as a brown gum. To this was added water (25 mL) and CH2CI2 (25 mL) and this was acidified to pH 1 with 2M HC1. The mixture was stirred for 5 minutes, then the phases separated through a phase separation cartridge, washing with further CH2CI2. The organic phase was concentrated to afford 2-[2-(3,4- dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane- 1 ,3-dione as an orange foam (400 mg, 30% yield). XH NM (400MHz, CDCI3) δ = 16.14 (1H, s), 7.13 (1H, dd), 7.09 (2H, m), 6.92 (1H, d), 3.90 (3H, s), 3.89 (3H, s), 2.73 (3H, t), 2.46 (3H, t), 2.41 (3H, s), 2.04 (2H, quintet).
Preparative Example 4. Preparation of 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo- pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione (compound 1.1 (see Table CI)).
Figure imgf000063_0001
DMF (cat.) and oxalylchloride (0.6mL) were added to a stirred suspension of 2-(3,4- dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carboxylic acid (1.5g, 5.172mmol) in DCM (20mL). The reaction mixture was stirred at room temperature for 1.5h. TLC (after quenching with MeOH) showed a non-polar spot formed. The reaction mass was evaporated under N2 atmosphere. DCM (20mL) was added followed by a pinch of molecular sieve. TEA (2.2mL) and bicyclo[3.2.1]octane-2,4-dione (0.86g, 6.2mmol) were added to acid chloride solution. The reaction mixture was stirred at room temperature for lh. Triethylamine (2.2mL) and 25 drops of acetonecyanohydrin were added and stirred for 2h. The reaction mass was purified by chromatography in with a mixed solvent system of 20:8:4:4: 1 Toluene : Dioxane : EtOH : Et3N : Water and then acidified by 10% HCl solution, extracted with DCM. The solvent was evaporated to get crude compound which was further purified by chromatography with acetone- DCM to afford the desired product 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo- pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione (500 mg, 1.22 mmol, 24%) as a solid.
XH NM (400MHz, CDCI3) δ = 16.19 (1H, s), 7.16-7.09 (3H, m), 6.93 (1H, d), 3.91 (6H, s), 3.11 (1H, t), 2.94 (1H, t), 2.42 (3H, s), 2.26 - 2.06 (3H, m), 2.04 - 1.98 (1H, m), 1.83 (1H, brm), 1.72 (1H, dt).
Biological Examples
Seeds of a variety of test species HORVW (Hordeum vulgare - barley), ABUTH (Abutilon theophrasti), AMARE (Amaranthus retroflexus) and ECHCG (Echinochloa crus-galli) were sown in standard soil in pots. After cultivation for 10 days cultivation under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL (Registry number 61791-12-6), 42.2% N-methyl pyrrolidone, 42.2% dipropylene glycol monomethyl ether (CAS RN 34590-94-8) and 0.2 % X-77 (CAS RN 1 1097-66-8).
The test plants were then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 14 days, the test was evaluated (100 = total damage to plant; 0 = no damage to plant).
TABLE Bl
Compound Rate g/ha Plant Species
HORVW ECHCG ABUTH AMARE
1.5
250 50 90 90 90
WO 2012/136703
125 30 90 90 90
1.2
250 0 100 100 100
Present invention
125 0 100 100 100
1.3
250 40 100 100 100
WO 2012/136703
125 30 100 100 100
1.3
250 0 100 100 100
Present invention
125 0 100 100 100 These comparative results demonstrate that the dimethoxyphenyl substituted pyridazinone compounds of the present invention are surprisingly less damaging to the crop plant (barley - HORVW) than the equivalent monomethoxyphenyl compounds specifically disclosed in WO 2012/136703, whilst retaining good control of representative weed species (ECHCG, ABUTH, AMARE).
TABLE B2
Figure imgf000066_0001
These results demonstrate that the compounds of the present invention confer little if any damage when applied to the crop plant (barley - HORVW) but still provide good control of representative weed species (ECHCG, ABUTH, AMARE).

Claims

Claims
1. A compound of Formula (I) :
Figure imgf000067_0001
or an agronomically acceptable salt thereof, wherein
R1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C6alkyl-, C3-C6cycloalkyl-, C2-C6-alkenyl-, C2-C6alkynyl-, Ci-Cehaloalkyl-, Ci-C6alkoxy-, Ci-C3haloalkoxy-, Ci-C6alkoxy-Ci-C3alkyl-, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-S(0)p-;
A1 is selected from the group consisting of O, C(O) and (CR^^;
Ra, Rb, Rc, Rd, Re and Rf are each independently selected from the group consisting of hydrogen and Ci-C4alkyl- wherein Ra and Rc may together form a Ci-C3alkylene chain; and p is 0, 1 or
2.
A compound according to claim 1 , wherein R1 is Ci-C6alkyl- or C3- C6cycloalkyl-.
3. A compound according to claim 1 or claim 2, wherein R1 is methyl or cyclopropyl-.
4. A compound according to any one of the previous claims, wherein A1 is CReRf and Re and Rf are hydrogen.
5. A compound according to any one of the previous claims, wherein Ra, Rb, Rc and Rd are hydrogen.
6. A compound according to any one of previous claims 1 to 4, wherein Ra and Rc together form a -CH2-CH2- chain and Rb and Rd are hydrogen.
7. A compound according to any one of previous claims 1 to 3, wherein A1 is O and Ra, Rb, Rc and Rd are methyl.
8. A compound according to any one of the previous claims in the form of an agrochemically acceptable salt, wherein the agrochemically acceptable salt is selected from the group consisting of aluminium, calcium, cobalt, copper, iron, magnesium, potassium, sodium and zinc.
9. A herbicidal composition comprising a compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.
10. A herbicidal composition according to claim 9, further comprising at least one additional pesticide.
11. A herbicidal composition according to claim 10, wherein the additional pesticide is a herbicide or herbicide safener.
12. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to any one of claims 9 to 11.
13. A compound of Formula (II)
Figure imgf000069_0001
wherein
R1 is as defined in claim 1 , and
R2 is selected from the group consisting of halogen, -OH, Ci-C6 alkoxy-, aryloxy and N-linked imdazolyl.
A method of producing a compound of Formula (I) comprising: (i) reacting, in an inert organic solvent and in the presence of a base, a compound of Formula
(lie):
Figure imgf000069_0002
where the definition of R1 is as for Formula (I) and LG is a suitable leaving group, with a diketone of Formula (III)
Figure imgf000069_0003
rearrangement of the resulting product into the compound of Formula Use of a compound of Formula (I) as defined in claim 1 as a herbicide.
PCT/EP2017/058915 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds WO2017178582A1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
UAA201811036A UA122439C2 (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds
MX2018012303A MX2018012303A (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds.
CA3019009A CA3019009A1 (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds
JP2018554085A JP6855504B2 (en) 2016-04-15 2017-04-13 Herbicidal pyridadinone compound
KR1020187030965A KR102445810B1 (en) 2016-04-15 2017-04-13 Herbicide Pyridazinone Compound
BR112018071154-3A BR112018071154B1 (en) 2016-04-15 2017-04-13 HERBICIDIAL PYRIDAZINONE COMPOUNDS, HERBICIDIAL COMPOSITION, METHOD OF CONTROLING WEEDS AT A LOCU, METHOD OF PRODUCTION AND USE OF A COMPOUND
AU2017251378A AU2017251378B2 (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds
EP17717174.1A EP3442962B1 (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds
CN201780023236.9A CN108884074B (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds
EA201892259A EA038043B1 (en) 2016-10-20 2017-04-13 Herbicidal pyridazinone compounds
US16/093,338 US10813354B2 (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds
ZA2018/06433A ZA201806433B (en) 2016-04-15 2018-09-27 Herbicidal pyridazinone compounds
IL262187A IL262187B (en) 2016-04-15 2018-10-08 Herbicidal pyridazinone compounds
PH12018502201A PH12018502201A1 (en) 2016-04-15 2018-10-15 Herbicidal pyridazinone compounds

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB201606613 2016-04-15
GB1606613.6 2016-04-15
GB1617766.9 2016-10-20
GBGB1617766.9A GB201617766D0 (en) 2016-10-20 2016-10-20 Improvements in or relating to organic compounds

Publications (1)

Publication Number Publication Date
WO2017178582A1 true WO2017178582A1 (en) 2017-10-19

Family

ID=58544964

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/058915 WO2017178582A1 (en) 2016-04-15 2017-04-13 Herbicidal pyridazinone compounds

Country Status (15)

Country Link
US (1) US10813354B2 (en)
EP (1) EP3442962B1 (en)
JP (1) JP6855504B2 (en)
KR (1) KR102445810B1 (en)
CN (1) CN108884074B (en)
AU (1) AU2017251378B2 (en)
CA (1) CA3019009A1 (en)
CL (1) CL2018002931A1 (en)
IL (1) IL262187B (en)
MX (1) MX2018012303A (en)
PH (1) PH12018502201A1 (en)
UA (1) UA122439C2 (en)
UY (1) UY37199A (en)
WO (1) WO2017178582A1 (en)
ZA (1) ZA201806433B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019076930A1 (en) * 2017-10-18 2019-04-25 Syngenta Participations Ag Process for producing herbicidal pyridazinone compounds
WO2019076934A1 (en) * 2017-10-18 2019-04-25 Syngenta Participations Ag Process for producing herbicidal pyridazinone compounds
US10633379B2 (en) 2016-04-15 2020-04-28 Abbvie Inc. Bromodomain inhibitors
WO2020161270A1 (en) * 2019-02-08 2020-08-13 Syngenta Crop Protection Ag Herbicidal pyridazinum based compounds
WO2021241759A1 (en) 2020-05-29 2021-12-02 国立大学法人東海国立大学機構 Bacterial strain belonging to bacillus genus, and microbiological control agent using said bacterial strain
WO2022210999A1 (en) 2021-04-02 2022-10-06 クミアイ化学工業株式会社 Heterocyclic compound and use thereof
WO2022255274A1 (en) 2021-05-31 2022-12-08 国立大学法人東海国立大学機構 Strain belonging to genus lysinibacillus and promoting plant growth, and utilization thereof
US11672800B2 (en) 2017-04-21 2023-06-13 Epizyme, Inc. Combination therapies with EHMT2 inhibitors

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201618266D0 (en) * 2016-10-28 2016-12-14 Syngenta Participations Ag Improvements in or relating to organic compounds
WO2023040686A1 (en) * 2021-09-16 2023-03-23 江苏中旗科技股份有限公司 Pyridazinone compound, preparation method, herbicide composition and use thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012136703A1 (en) * 2011-04-08 2012-10-11 Syngenta Limited Herbicidal compounds

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1144719A (en) 1958-08-16 1957-10-17 Valve cap in the form of a pressure gauge, for vehicle tires, in particular for motor vehicles
DE2808193A1 (en) * 1978-02-25 1979-09-06 Basf Ag PYRIDAZONE CONNECTIONS
DE4423934A1 (en) 1993-09-02 1995-03-09 Basf Ag 3(2H)-Pyridazinone derivatives, their preparation and their use
DE19520613A1 (en) * 1995-06-06 1996-12-12 Bayer Ag Phenylpyridazinones
BR9909548A (en) * 1998-04-09 2000-12-12 Bayer Ag Substituted phenylpyridazinones
GB201117019D0 (en) * 2011-10-04 2011-11-16 Syngenta Ltd Herbicidal compounds
WO2013139760A1 (en) 2012-03-20 2013-09-26 Syngenta Limited Herbicidal compounds
CN103664795B (en) * 2012-09-06 2017-10-03 华东理工大学 Pyridazinone compound and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012136703A1 (en) * 2011-04-08 2012-10-11 Syngenta Limited Herbicidal compounds

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10633379B2 (en) 2016-04-15 2020-04-28 Abbvie Inc. Bromodomain inhibitors
US11672800B2 (en) 2017-04-21 2023-06-13 Epizyme, Inc. Combination therapies with EHMT2 inhibitors
WO2019076930A1 (en) * 2017-10-18 2019-04-25 Syngenta Participations Ag Process for producing herbicidal pyridazinone compounds
WO2019076934A1 (en) * 2017-10-18 2019-04-25 Syngenta Participations Ag Process for producing herbicidal pyridazinone compounds
US11254643B2 (en) 2017-10-18 2022-02-22 Syngenta Participations Ag Process for producing herbicidal pyridazinone compounds
AU2018351470B2 (en) * 2017-10-18 2022-10-27 Syngenta Participations Ag Process for producing herbicidal pyridazinone compounds
WO2020161270A1 (en) * 2019-02-08 2020-08-13 Syngenta Crop Protection Ag Herbicidal pyridazinum based compounds
WO2021241759A1 (en) 2020-05-29 2021-12-02 国立大学法人東海国立大学機構 Bacterial strain belonging to bacillus genus, and microbiological control agent using said bacterial strain
WO2022210999A1 (en) 2021-04-02 2022-10-06 クミアイ化学工業株式会社 Heterocyclic compound and use thereof
WO2022255274A1 (en) 2021-05-31 2022-12-08 国立大学法人東海国立大学機構 Strain belonging to genus lysinibacillus and promoting plant growth, and utilization thereof

Also Published As

Publication number Publication date
EP3442962B1 (en) 2020-10-28
CN108884074B (en) 2021-07-02
IL262187A (en) 2018-11-29
US10813354B2 (en) 2020-10-27
CN108884074A (en) 2018-11-23
MX2018012303A (en) 2019-01-14
UY37199A (en) 2019-06-28
US20190124926A1 (en) 2019-05-02
AU2017251378A1 (en) 2018-10-11
JP2019513791A (en) 2019-05-30
CA3019009A1 (en) 2017-10-19
ZA201806433B (en) 2019-07-31
PH12018502201A1 (en) 2019-09-23
KR102445810B1 (en) 2022-09-20
KR20180134353A (en) 2018-12-18
IL262187B (en) 2021-10-31
CL2018002931A1 (en) 2018-12-14
BR112018071154A2 (en) 2019-02-05
JP6855504B2 (en) 2021-04-07
AU2017251378B2 (en) 2021-08-05
EP3442962A1 (en) 2019-02-20
UA122439C2 (en) 2020-11-10

Similar Documents

Publication Publication Date Title
AU2017251378B2 (en) Herbicidal pyridazinone compounds
EP4132913B1 (en) 5-haloalkoxy-pyrimidine compounds as herbicides
EP4058438B1 (en) Herbicidal compounds
US20230002357A1 (en) 7-pyrimidine-2-yl-oxy-indazole derivatives and their use as herbicides
WO2021209383A1 (en) Herbicidal compounds
WO2021028316A1 (en) 2-phenoxy-pyrimidine derivatives as herbicidal compounds
WO2020079078A1 (en) Herbicidal compounds
WO2022238247A1 (en) Herbicidal compounds
EP4337651A1 (en) Substituted benzamides as herbicides
EP4334296A1 (en) Herbicidal compounds
WO2024017762A1 (en) Herbicidal compounds
WO2022207482A1 (en) Herbicidal compounds
GB2620577A (en) Improvements in or relating to organic compounds
WO2021074325A1 (en) Herbicidal compounds
AU2022372262A1 (en) Substituted benzamides as herbicides
EP4263510A1 (en) Herbicidal tetrazole compounds
EP4085048A1 (en) Herbicidal compounds
BR112018071154B1 (en) HERBICIDIAL PYRIDAZINONE COMPOUNDS, HERBICIDIAL COMPOSITION, METHOD OF CONTROLING WEEDS AT A LOCU, METHOD OF PRODUCTION AND USE OF A COMPOUND
EA038043B1 (en) Herbicidal pyridazinone compounds

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 3019009

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2017251378

Country of ref document: AU

Date of ref document: 20170413

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018554085

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112018071154

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 20187030965

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2017717174

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2017717174

Country of ref document: EP

Effective date: 20181115

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17717174

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112018071154

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20181015