Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/79—Acids; Esters
  • C07D213/80—Acids; Esters in position 3
• • 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
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P13/00—Herbicides; Algicides

Definitions

• the present invention relates to herbicidal pyridone derivatives, e.g., as active ingredients, which have herbicidal activity.
• the invention also relates to agrochemical compositions which comprise at least one of the pyridone derivatives, to processes of preparation of these compounds and to uses of the pyridone derivatives or compositions in agriculture or horticulture for controlling weeds, in particular in crops of useful plants.
• EP0239391 , EP0127313, EP0040082, GB2328614, and GB2182931 describe pyridone derivatives as herbicidal agents.
• R 1 is hydrogen, Ci-Cealkyl, phenyl, phenylCi-C2alkyl, heteroaryl, or heteroarylCi-C2alkyl wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R 5 ;
• R 2 is hydrogen or Ci-Cealkyl
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-Cealkyl, Ci-CealkoxyCi-Cealkyl, Ce-Cecycloalkyl, C2- Cealkenyl, or C2-Cealkynyl;
• R 4 is phenyl optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R 6 ;
• R 5 is halogen, cyano, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, Ci-Cehaloalkoxy, Ci-CealkoxyCi- Cealkyl, or nitro;
• R 6 is cyano, nitro, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, Ci-Cehaloalkoxy, C1- CealkoxyCi-Cealkyl, Ci-Cealkylsulfanyl, Ci-Cealkylsulfinyl, Ci-Cealkylsulfonyl, Ci-Cealkylsulfonamido, Ci-Cealkylcarbonyl, Ci-Cealkoxycarbonyl, Ci-Cealkylaminocarbonyl, Ce-Cecycloalkyl, C3- Cecycloalkylaminocarbonyl, or N,N-di(Ci-C4alkyl)aminocarbonyl; or a salt thereof.
• the novel compounds of Formula (I) have, for practical purposes, a very advantageous level of herbicidal activity.
• an agrochemical composition comprising a herbicidally effective amount of a compound of Formula (I) according to the present invention.
• Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
• a method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a composition comprising a compound of Formula (I).
• Ci-Cealkyl substituted by 1 , 2 or 3 halogens may include, but not be limited to, -CH2CI, -CHCh, -CCh, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups.
• Ci-Cealkoxy substituted by 1 , 2 or 3 halogens may include, but not limited to, CH2CIO-, CHCI2O-, CCI3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF20- groups.
• cyano means a -CN group.
• halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).
• hydroxy or “hydroxyl” means an -OH group.
• nitro means an -NO2 group.
• acetyl means a -C(O)CH3 group.
• Ci-Cealkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. “Ci-C4alkyl” and “C1- Csalkyl” are to be construed accordingly. Examples of Ci-Cealkyl include, but are not limited to, methyl, ethyl, n-propyl, and the isomers thereof, for example, isopropyl.
• Ci-Cealkylene refers to the corresponding definition of Ci-Cealkyl, except that such radical is attached to the rest of the molecule by two single bonds.
• the term “Ci-C2alkylene” is to be construed accordingly.
• Examples of Ci-Cealkylene include, but are not limited to, -CH2-, -CH2CH2- and -(CH2)3-.
• Ci-Cehaloalkyl refers a Ci-Cealkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
• Examples of Ci-Cehaloalkyl include, but are not limited to tri fluoromethyl.
• Ci-Cealkoxy refers to a radical of the formula -OR a where R a is a Ci- Cealkyl radical as generally defined above.
• Ci-C4alkoxy and “Ci-Csalkoxy” are to be construed accordingly.
• O-Cealkoxy include, but are not limited to, methoxy, ethoxy, 1- methylethoxy (iso-propoxy), and propoxy.
• Ci-Cehaloalkoxy refers to a O-Cealkoxy radical as generally defined above substituted by one or more of the same or different halogen atoms.
• Examples of Ci-Cehaloalkoxy include, but are not limited to trifluoromethoxy.
• C2-C6alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or ( ⁇ -configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
• C2-C3alkenyl is to be construed accordingly. Examples of C2-Cealkenyl include, but are not limited to, ethenyl (vinyl), prop-1 -enyl, prop-2-enyl (allyl), but-1-enyl.
• C2-C6alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
• C2-C3alkynyl is to be construed accordingly. Examples of C2-Cealkynyl include, but are not limited to, ethynyl, prop-1 -ynyl, but-1-ynyl.
• Ci-CealkoxyCi-Cealkyl refers to a radical of the formula RbOR a - wherein Rb is a Ci-Cealkyl radical as generally defined above, and R a is a Ci-Cealkylene radical as generally defined above.
• Rb is a Ci-Cealkyl radical as generally defined above
• R a is a Ci-Cealkylene radical as generally defined above.
• the terms “Ci-C4alkoxyCi-C4alkyl” and “Ci-CsalkoxyCi-Csalkyl” are to be construed accordingly.
• Cs-Cecycloalkyl refers to a radical which is a monocyclic saturated ring system and which contains 3 to 6 carbon atoms.
• the terms "Cs-Cscycloalkyl” and “C3-C4cycloalkyl” are to be construed accordingly.
• Examples of Cs-Cecycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
• Cs-Cecycloalkylaminocarbonyl refers to a Cs-Cecycloalkyl ring attached to the rest of the molecule through an -NHC(O)- linker.
• Examples of Cs-Cecycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).
• phenylCi-C2alkyl refers to a phenyl ring attached to the rest of the molecule through a Ci-C2alkylene linker as defined above.
• phenylCi-C2alkyl include, but are not limited to, benzyl and phenylethyl.
• heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, or 3 heteroatoms individually selected from nitrogen, oxygen, and sulfur.
• heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
• heteroarylCi-C2alkyl refers to a heteroaryl ring as generally defined above attached to the rest of the molecule through a Ci-C2alkylene linker as defined above.
• Ci-Cealkylcarbonyl refers to a radical of the formula -C(O)R a , where R a is a Ci-Cealkyl radical as generally defined above.
• Examples of Ci-Cealkylcarbonyl include, but are not limited to, acetyl.
• Ci-Cealkoxycarbonyl refers to a radical of the formula -C(O)OR a , where Ra is a Ci-Cealkyl radical as generally defined above.
• Ci-Cealkylaminocarbonyl refers to a radical of the formula -C(O)NHR a , wherein R a is a Ci-Cealkyl radical as generally defined above.
• Examples of Ci-Cealkylaminocarbonyl include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl).
• N,N-di(Ci-C4alkyl)amino“ refers to a radical of the formula -N(R a )(Rb), wherein R a and Rb are each individually a Ci-C4alkyl radical as generally defined above.
• R a and Rb are each individually a Ci-C4alkyl radical as generally defined above.
• N,N- di(Ci-C3alkyl)amino is to be construed accordingly.
• N,N-di(Ci-C4alkyl)aminocarbonyl“ refers to a radical of the formula - C(O)N(R a )(Rb), wherein R a and Rb are each individually a Ci-C4alkyl radical as generally defined above.
• the term “N,N-di(Ci-C3alkyl)aminocarbonyl” is to be construed accordingly. Examples of N,N-di(Ci- C4alkyl)aminocarbonyl include, but are not limited to, dimethylcarbamoyl (i.e. N, N- di(methyl)aminocarbonyl).
• Ci-Cealkylsulfanyl refers to a radical of the formula -SR a , where R a is a Ci-Cealkyl radical as generally defined above.
• R a is a Ci-Cealkyl radical as generally defined above.
• Ci-C4alkylsulfanyl and “Ci-Csalkylsulfanyl”, are to be construed accordingly.
• Examples of Ci-Cealkylsulfanyl include, but are not limited to methylsulfanyl.
• Ci-Cealkylsulfinyl refers to a radical of the formula -S(O)R a , where R a is a Ci-Cealkyl radical as generally defined above.
• R a is a Ci-Cealkyl radical as generally defined above.
• Ci-C4alkylsulfinyl and “Ci-Csalkylsulfinyl”, are to be construed accordingly.
• Examples of Ci-Cealkylsulfinyl include, but are not limited to methylsulfinyl.
• Ci-Cealkylsulfonyl refers to a radical of the formula -S(O)2Ra, where R a is a Ci-Cealkyl radical as generally defined above.
• R a is a Ci-Cealkyl radical as generally defined above.
• Ci-C4alkylsulfonyl and “Ci- Csalkylsulfonyl”, are to be construed accordingly.
• Examples of Ci-Cealkylsolfanyl include, but are not limited to methylsulfonyl.
• Ci-Cealkylsulfonamido refers to a radical of the formula -NHS(O)2Ra, where R a is a Ci-Cealkyl radical as generally defined above.
• the presence of one or more possible stereogenic elements in a compound of formula (I) means that the compounds may occur in optically isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond.
• Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I).
• formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for a compound of formula (I).
• the compounds of formula (I) according to the invention are in free form or in salt form, e.g., an agronomically usable salt form.
• Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.
• the compounds of Formula (I) may form chloride or 2,2,2-trifluoroacetate salts.
• R 1 is hydrogen, Ci-Cealkyl, phenyl, phenylCi-C2alkyl, heteroaryl, or heteroarylCi-C2alkyl wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R 5 .
• R 1 is hydrogen, Ci-Cealkyl, phenyl, phenylCi-C2alkyl, heteroaryl, or heteroarylCi- C2alkyl wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising 1 or 2 heteroatoms individually selected from N, O and S, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 , 2 or 3 groups, which may be the same or different, represented by R 5 .
• R 1 is hydrogen, Ci-C4alkyl, phenyl, phenylCi-C2alkyl, or heteroaryl, wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising 1 or 2 heteroatoms individually selected from N and O, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 , 2 or 3 groups, which may be the same or different, represented by R 5 .
• R 1 is hydrogen, Ci-Cealkyl, phenyl, phenylCi-C2alkyl, or heteroaryl, wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising a single nitrogen atom, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
• R 1 is hydrogen, methyl, phenyl, phenylCi-C2alkyl, or pyridyl, and wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
• R 1 is hydrogen, methyl, phenyl, phenylmethyl (benzyl), or pyridyl, and wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
• R 1 is Ci-Cealkyl, phenyl, phenylCi-C2alkyl, or heteroaryl, wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising a single nitrogen atom, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
• R 5 Preferably, methyl, phenyl, phenylO- C2alkyl, or pyridyl, and wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
• methyl, phenyl, phenylmethyl (benzyl), or pyridyl and wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
• R 1 is methyl, 4-chlorophenyl, 4-fluorophenyl, 3- trifluoromethylphenyl, 2,4-difluorophenyl, 2,4-difluorophenylmethyl, 4-chloro-2-fluorophenyl, 4-chloro-2- fluorophenylmethyl, 4-cyano-2-fluorophenyl, 4-cyano-2-fluorophenylmethyl, 2-fluoro-4- (trifluoromethyl)phenyl, 2-fluoro-4-(trifluoromethyl)phenylmethyl, 2-fluoro-3-(trifluoromethyl)phenyl, 5- chloro-3-fluoro-2-pyridyl, or 3,5-dichloro-2-pyridyl.
• R 2 is hydrogen or Ci-Cealkyl.
• R 2 is hydrogen or Ci-C4alkyl. More preferably, R 2 is hydrogen or Ci-Csalkyl. Even more preferably, R 2 is hydrogen or methyl. More preferably still, R 2 is methyl.
• R 2 is Ci-Csalkyl, preferably methyl.
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-Cealkyl, Ci-CealkoxyCi-Cealkyl, Cs-Cecycloalkyl, C2- Cealkenyl, or C2-Cealkynyl.
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-C4alkyl, C1- C4alkoxyCi-C4alkyl, Cs-Cecycloalkyl, C2-C4alkenyl, or C2-C4alkynyl.
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-C4alkyl, Ci-C4alkoxyCi-C4alkyl, Cs-Cecycloalkyl, C2-C3alkenyl, or C2- C4alkynyl. Even more preferably, R 3 is hydrogen, halogen, cyano, hydroxy, Ci-Csalkyl, Ci-C2alkoxyCi- Csalkyl, C3-C4cycloalkyl, C2-C3alkenyl, or C2-C3alkynyl.
• R 3 is hydrogen, bromo, chloro, cyano, hydroxy, methyl, ethyl, meth oxy methyl, cyclopropyl, vinyl, or prop-1 -ynyl. In one set of embodiments, R 3 is hydrogen, bromo, chloro, hydroxy, methyl, ethyl, methoxymethyl, cyclopropyl, or vinyl. In another set of embodiments, R 3 is bromo, hydroxy, methyl, methoxymethyl, cyclopropyl, or vinyl.
• R 4 is phenyl optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R 6 .
• R 4 is phenyl optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R 6 .
• R 4 is phenyl optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 6 .
• R 4 is phenyl optionally substituted with 2 groups, which may be the same or different, represented by R 6 .
• R 4 is 3,4-dichlorophenyl, 3-chloro-4-cyano-phenyl, 4-cyano-3-fluoro-phenyl, 3-chloro- 4-nitro-phenyl, or 3-fluoro-4-nitro-phenyl. In another set of embodiments, R 4 is 3,4-dichlorophenyl.
• R 5 is halogen, cyano, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, Ci-Cehaloalkoxy, Ci-CealkoxyCi- Cealkyl, or nitro.
• R 5 is halogen, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, C1- C4haloalkoxy, Ci-C4alkoxyCi-C3alkyl, or nitro.
• R 5 is halogen, cyano, Ci-Csalkyl, C1- Csalkoxy, Ci-Cshaloalkyl, Ci-Cshaloalkoxy, Ci-CsalkoxyCi-Csalkyl, or nitro. Even more preferably, R 5 is halogen, cyano, Ci-Cshaloalkyl, or Ci-Cshaloalkoxy. More preferably still, R 5 is halogen, cyano, or C1- Cshaloalkyl. In one set of embodiments, R 5 is chloro, fluoro, cyano, trifluoromethyl, or trifluoromethoxy. In another set of embodiments, R 5 is chloro, fluoro, cyano, or trifluoromethyl.
• R 6 is cyano, nitro, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, Ci-Cehaloalkoxy, C1- CealkoxyCi-Cealkyl, Ci-Cealkylsulfanyl, Ci-Cealkylsulfinyl, Ci-Cealkylsulfonyl, Ci-Cealkylsulfonamido, Ci-Cealkylcarbonyl, Ci-Cealkoxycarbonyl, Ci-Cealkylaminocarbonyl, Cs-Cecycloalkyl, C3- Cecycloalkylaminocarbonyl, or N,N-di(Ci-C4alkyl)aminocarbonyl.
• R 6 is cyano, nitro, halogen, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-CsalkoxyCi-Csalkyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4alkylsulfonamido, Ci-C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci-C4alkylaminocarbonyl, Cs-Cecycloalkyl, Cs-Cecycloalkylaminocarbonyl, or N,N-di(Ci- C3alkyl)aminocarbonyl.
• R 6 is cyano, nitro, halogen, Ci-Csalkyl, Ci-Csalkoxy, C1- C4haloalkyl, Ci-C4haloalkoxy, Ci-CsalkoxyCi-Csalkyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfinyl, C1- Csalkylsulfonyl, Ci-Csalkylsulfonamido, Ci-Csalkylcarbonyl, Ci-Csalkoxycarbonyl, C1- Csalkylaminocarbonyl, Cs-Cecycloalkyl, Cs-Cecycloalkylaminocarbonyl, or N,N-di(Ci- C3alkyl)aminocarbonyl.
• R 6 is cyano, nitro, halogen, Ci-Csalkyl, Ci-Csalkoxy, Ci- C4haloalkyl, Ci-C4haloalkoxy, Ci-CsalkoxyCi-Csalkyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfonyl, Ci- C2alkylcarbonyl, Ci-Csalkoxycarbonyl, or N,N-di(Ci-C2alkyl)aminocarbonyl.
• R 6 is cyano, nitro, or halogen, preferably, cyano, nitro, fluoro, or chloro.
• R 6 is halogen, preferably chloro.
• R 1 is hydrogen, methyl, phenyl, phenylCi-C2alkyl, or pyridyl, and wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 ;
• R 2 is hydrogen or methyl
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-Cealkyl, Ci-CealkoxyCi-Cealkyl, Ce-Cecycloalkyl, C2- Cealkenyl, or C2-Cealkynyl;
• R 4 is phenyl optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 6 ;
• R 5 is halogen, cyano, or trifluoromethyl
• R 6 is cyano, nitro, or halogen.
• R 1 is hydrogen, Ci-Cealkyl, phenyl, phenylCi-C2alkyl, heteroaryl, or heteroarylCi-C2alkyl wherein each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring comprising 1 or 2 heteroatoms individually selected from N, O and S, and wherein the phenyl and heteroaryl moieties may each be optionally substituted with 1 , 2 or 3 groups, which may be the same or different, represented by R 5 ;
• R 2 is methyl
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-Cealkyl, Ci-CealkoxyCi-Cealkyl, Ce-Cecycloalkyl, C2- Cealkenyl, or C2-Cealkynyl;
• R 4 is 3,4-dichlorophenyl
• R 5 is halogen, cyano, or trifluoromethyl.
• R 1 is hydrogen, methyl, phenyl, phenylmethyl, or pyridyl, wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 ;
• R 2 is methyl
• R 3 is hydrogen, bromo, chloro, hydroxy, methyl, ethyl, methoxymethyl, cyclopropyl, or vinyl;
• R 4 is 3,4-dichlorophenyl
• R 5 is chloro, fluoro, cyano, or trifluoromethyl.
• R 1 is methyl, phenyl, phenylmethyl, or pyridyl, wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 ;
• R 2 is methyl
• R 3 is hydrogen, halogen, cyano, hydroxy, Ci-Cealkyl, Ci-CealkoxyCi-Cealkyl, Ce-Cecycloalkyl, C2- Cealkenyl, or C2-Cealkynyl;
• R 4 is 3,4-dichlorophenyl
• R 5 is chloro, fluoro, cyano, or trifluoromethyl.
• R 1 is methyl, phenyl, phenylmethyl, or pyridyl, wherein the phenyl and pyridyl moieties may each be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 ;
• R 2 is methyl
• R 3 is bromo, chloro, hydroxy, methyl, ethyl, methoxymethyl, cyclopropyl, or vinyl;
• R 4 is 3,4-dichlorophenyl
• R 5 is chloro, fluoro, cyano, or trifluoromethyl.
• Compounds of Formula (I) may be prepared by hydrolysis of a compound of Formula A wherein R 5 is not hydrogen but any Ci-Cealkyl, with a suitable base (such as sodium hydroxide or lithium hydroxide) or with a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water).
• a base such as sodium hydroxide or lithium hydroxide
• a suitable acid such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid
• a suitable solvent such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran
• an optional co-solvent such as water
• Compounds of Formula A may be prepared from a compound of Formula B wherein X is Cl or Br by metal-catalysed cross-coupling reaction such as Suzuki-Miyaura cross-coupling in analogy to literature conditions.
• the reaction is performed by reaction of a compound of Formula B with R 3 -boronic acid, boroxine or tetrafluoro borate salt in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(ll), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, or dichloro(1 ,1 '-bis(diphenylphosphanyl)ferrocene)palladium(ll) dichloromethane adduct) or palladium diacetate optionally with a ligand (such as 2- dicyclohexylphosphino-2',6'-dimethoxybiphenyl
• a compound of Formula A wherein R 3 is cyano may be prepared from a compound of Formula B wherein X is Cl or Br by reaction with a suitable cyanating reagent such as copper cyanide, in a suitable solvent (such as /V,/V-dimethylformamide), at elevated temperature.
• a suitable cyanating reagent such as copper cyanide
• a suitable solvent such as /V,/V-dimethylformamide
• a compound of Formula A wherein R 3 is Ci-Cealkyl may be prepared from a compound of Formula A where R 3 is C2-Cealkenyl by reaction with hydrogen gas in the presence of a suitable metal catalyst (such as platinum (IV) oxide), in a suitable solvent (such as ethyl acetate), at room temperature or at elevated temperature.
• a suitable metal catalyst such as platinum (IV) oxide
• a suitable solvent such as ethyl acetate
• Compounds of Formula B wherein X is Cl, Br or I may be prepared by treatment of compounds of Formula C with a suitable halogenating agent (such as /V-iodo succinimide, /V-bromo succinimide or /V-chloro succinimide), optionally in the presence of trifluoroacetic acid in a suitable solvent (such as acetonitrile or dichloromethane), at room temperature or at elevated temperature (such as 80 °C). This is shown in Scheme 4 above.
• a suitable halogenating agent such as /V-iodo succinimide, /V-bromo succinimide or /V-chloro succinimide
• trifluoroacetic acid such as acetonitrile or dichloromethane
• Compounds of Formula C wherein R 1 is hydrogen may be prepared from a compound of Formula D wherein X is halogen (for example chloro) by metal-catalysed cross-coupling reaction such as Suzuki-Miyaura cross-coupling in analogy to literature conditions.
• X for example chloro
• reaction is performed by reaction of a compound of Formula D with R 4 -boronic acid in the presence of a suitable catalyst (such as dichloro-(chloromethylchloronio)-bis[cyclopentyl(diphenyl)phosphaniumyl]palladium(3-);iron, dichlorobis(triphenylphosphine)palladium(ll), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, or dichloro(1 ,1 '-bis(diphenylphosphanyl)ferrocene)palladium(ll) dichloromethane adduct) or palladium diacetate, optionally with a ligand (such as 2- dicyclohexylphosphino-2',6'-dimethoxybiphenyl), in the presence of a base (such as potassium or caesium carbonate or tripotassium phosphat
• Compounds of Formula A wherein R 1 is phenyl may be prepared from a compound of Formula A wherein R 1 is hydrogen by copper catalysed reaction with a phenyl boronic acid under Chan Lam conditions as reported in the literature.
• the reaction is performed by reaction with an aryl boronic acid in the presence of a base (such as pyridine or triethylamine), in the presence of a catalyst (such as copper(ll)acetate), optionally in the presence of an oxidant (typically air) and an additive (such as boric acid), in a suitable solvent (such as acetonitrile), and at elevated temperature.
• a base such as pyridine or triethylamine
• a catalyst such as copper(ll)acetate
• an oxidant typically air
• an additive such as boric acid
• a suitable solvent such as acetonitrile
• a compound of Formula A wherein R 1 is alkyl may be prepared from a compound of Formula A wherein R 1 is hydrogen by alkylation with a suitable alkylating agent (such as methyl iodide), in a suitable solvent (such as A/,/V-dimethyl formamide), in the presence of a base (such as caesium carbonate), and also in the presence of a lithium salt (such as lithium chloride).
• a suitable alkylating agent such as methyl iodide
• a suitable solvent such as A/,/V-dimethyl formamide
• a base such as caesium carbonate
• a lithium salt such as lithium chloride
• a compound of Formula (I) may be prepared from reaction of a compound of Formula E with a compound of Formula F in a suitable solvent (such as /V,/V-dimethylformamide) at elevated temperature followed by reaction with scandium triflate at room temperature.
• a suitable solvent such as /V,/V-dimethylformamide
• scandium triflate at room temperature.
• Compounds of Formula F are commercially available or may be prepared by methods reported in the literature.
• Compounds of Formula E may be prepared by methods reported in the literature. This is shown in Scheme 7 above.
• 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).
• the present invention may further provide a method of selectively controlling weeds at a locus comprising useful (crop) plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention.
• Controlling means killing, reducing or retarding growth or preventing or reducing germination. It is noted that the compounds of the present invention show a much improved selectivity compared to known, structurally similar compounds. Generally the plants to be controlled are unwanted plants (weeds).
• Locus means the area in which the plants are growing or will grow.
• the application may be applied to the locus pre-emergence and/or postemergence of the crop plant.
• the compounds of the present invention are applied to the locus post-emergence of the crop.
• Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I).
• the rates of application of compounds of Formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
• the compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2500 g/ha, especially from 25 to 1000 g/ha, more especially from 25 to 250 g/ha.
• the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
• useful plants is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as, for example, 4- Hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyrovyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen-oxidase (PPG) inhibitors as a result of conventional methods of breeding or genetic engineering.
• HPPD 4- Hydroxyphenylpyruvate dioxygenase
• ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
• 5-enol-pyrovyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors glutamine syntheta
• An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
• crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
• useful plants is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
• YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresse
• 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 compounds of Formula (I) can be used to control unwanted plants (collectively, ‘weeds’).
• 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 andXanthium.
• Compounds of Formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation to provide herbicidal compositions, using formulation adjuvants, such as carriers, solvents and surface-active agents (SAA).
• formulation adjuvants such as carriers, solvents and surface-active agents (SAA).
• SAA surface-active agents
• the invention therefore further provides a herbicidal composition, comprising at least one compound Formula (I) and an agriculturally acceptable carrier and optionally an adjuvant.
• An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art.
• the herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of Formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
• compositions can be chosen from a number of formulation types. These include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP) and a soluble granule (SG).
• formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).
• Soluble powders 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 pre-formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
• 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), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Ca-Cio fatty acid dimethylamide) and chlorinated hydrocarbons.
• An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
• Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SAAs, under high shear, to produce an emulsion.
• Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
• Microemulsions 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 nonpressurised, hand-actuated spray pumps.
• 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) and they may be used for seed treatment.
• a compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
• the composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I).
• additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).
• wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.
• Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
• Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-/sopropyl- and tri-/sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid
• Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.
• Suitable SAAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols.
• alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
• fatty alcohols such as oleyl
• 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
• the compounds of the present invention can also be used in mixture with one or more additional herbicides and/or plant growth regulators.
• additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac-sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron- ethyl), chlorotoluron, chlorsulfuron,
• the mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Ninetheenth Edition, British Crop Protection Council, 2021.
• the mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1.
• mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula (I) with the mixing partner).
• the compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners.
• herbicide safeners include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr- diethyl), metcamifen and oxabetrinil.
• mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen are particularly preferred.
• the safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 19 th Edition (BCPC), 2021 .
• the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048.
• the mixing ratio of compound of Formula (I) to safener is from 100:1 to 1 :10, especially from 20:1 to 1 :1.
• the compounds of Formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
• further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
• locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
• plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
• plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.
• Pesticidal agents referred to herein using their common name are known, for example, from "The Pesticide Manual", 19th Ed., British Crop Protection Council 2021.
• the compounds of formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end, they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
• Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
• Such carriers are for example described in WO 97/33890.
• the compounds of Formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
• further compounds can be, e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
• the compound of Formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
• An additional active ingredient may, in some cases, result in unexpected synergistic activities.
• the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
• Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
• Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
• Table A-1 provides 52 compounds A-1 .001 to A.1 .052 of Formula (I) wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1 .
• Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 %
• the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with waterto give suspensions of the desired concentration.
• Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %
• the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
• Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 %
• Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
• Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
• Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
• Active ingredient 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %
• the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
• the mixture is extruded and then dried in a stream of air.
• Active ingredient 8 % polyethylene glycol (mol. wt. 200) 3 %
• the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
• Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
• the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %
• Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
• the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• 28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
• This mixture is emulsified in a mixture of 1 .2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
• To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
• the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
• the capsule suspension formulation contains 28% of the active ingredients.
• the medium capsule diameter is 8-15 microns.
• the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
• LC/MS Liquid Chromatography Mass Spectrometry and the description of the apparatus and the methods is as follows:
• Step 1 Synthesis of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3-carboxylate
• Step 2 Synthesis of ethyl 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3- carboxylate
• reaction mixture was concentrated under reduced pressure to give a brown solid which was purified by flash chromatography on silica gel using a gradient of 5 - 100% ethyl acetate in cyclohexane as eluent to give ethyl 5-bromo- 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3-carboxylate as a white solid (0.12 g, 0.30 mmol).
• the aqueous phase was acidified to pH 1 by addition of aqueous hydrogen chloride solution (2M) and the phases were separated.
• the aqueous phase was further extracted into ethyl acetate (30 mL).
• the combined organic extracts were evaporated under reduced pressure to give a white solid which was purified by mass-directed reverse phase HPLC to give 5-bromo-4-(3,4- dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3-carboxylic acid (0.013 g, 0.035 mmol).
• Example 2 Synthesis of 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3- carboxylic acid (Compound 2) Step 1 : Synthesis of ethyl 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3- carboxylate
• Step 2 Synthesis of 5-chloro-1 -(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine- 3-carboxylic acid
• Step 1 Synthesis of ethyl 5-chloro-4-(3,4-dichlorophenyl)-1 ,6-dimethyl-2-oxo-pyridine-3- carboxylate
• Step 2 Synthesis of 5-chloro-4-(3,4-dichlorophenyl)-1 ,6-dimethyl-2-oxo-pyridine-3-carboxylic acid
• Step 1 Synthesis of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1 ,2-dihydropyridine-3- carboxylate
• the reaction mixture was stirred at 100°C for 2.5 hours under and atmosphere of nitrogen.
• the reaction mixture was extracted into dichloromethane (3 x 10 mL).
• the combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure.
• the residue was purified by chromatography on silica gel using a gradient of 25 to 50% ethyl acetate in petroleum ether as eluent to give ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1 ,2- dihydropyridine-3-carboxylate (0.020 mg, 0.011 mmol) as a white solid.
• Step 1 Synthesis of ethyl 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1 H-pyridine-3- carboxylate
• Step 1 Synthesis of ethyl 4-chloro-5,6-dimethyl-2-oxo-1 H-pyridine-3-carboxylate
• Step 2 Synthesis of ethyl 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1 H-pyridine-3-carboxylate
• Step 1 Synthesis of ethyl 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3- carboxylate
• ethyl 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1 H-pyridine-3-carboxylate (0.200 g, 0.494 mmol) in /V,/V-dimethylformamide (5.0 mL) was added copper cyanide (0.1 11 g, 1.23 mmol).
• the reaction mixture was heated with stirring at 160°C for 3 hours.
• Step 1 Synthesis of 4-(3,4-dichlorophenyl)but-3-yn-2-ol
• the cooled reaction mixture was evaporated to dryness under reduced pressure and partitioned between ethyl acetate (200 mL) and water (150 mL). The aqueous phase was extracted into ethyl acetate (200 mL). The combined organic extracts were washed with water and then brine, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure.
• Step 3 Synthesis of methyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyran-3-carboxylate
• Aluminium trichloride (0.063 g, 0.47 mmol) was added whilst blanketing the reaction mixture with nitrogen and the mixture stirred at room temperature for 18 hours.
• the reaction mixture was quenched by addition of saturated aqueous ammonium chloride solution and evaporated under reduced pressure to remove tetrahydrofuran.
• Step 4 Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo- pyridine-3-carboxylic acid
• the aqueous phase was extracted into ethyl acetate (20 mL) and the combined organic extracts were evaporated to dryness under reduced pressure.
• the crude residue was purified by mass-directed reverse phase HPLC to give 1-(4-chloro-2- fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.029 g, 0.068 mmol) as a brown solid.
• Step 1 Synthesis of methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo- pyridine-3-carboxylate
• Step 2 Synthesis of methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6- methyl-2-oxo-pyridine-3-carboxylate
• Step 3 Synthesis of 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2- oxo-pyridine-3-carboxylic acid
• Step 1 Synthesis of methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2- oxo-pyridine-3-carboxylate
• Step 2 Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo- pyridine-3-carboxylic acid
• Step 1 Synthesis of 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3- carboxylic acid
• Step 2 Synthesis of methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3- carboxylate
• Step 3 Synthesis of methyl 5-bromo-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2- oxo-pyridine-3-carboxylate
• Step 4 Synthesis of methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6- methyl-2-oxo-pyridine-3-carboxylate
• Step 5 Synthesis of 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-
• Step 1 Synthesis of 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo- pyridine-3-carboxylic acid
• Step 2 Synthesis of 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo- pyridine-3-carboxylic acid
• Step 1 Synthesis of methyl 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo- 5-prop-1-ynyl-pyridine-3-carboxylate
• Step 2 Synthesis of 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-prop-
• AMAPA Amaranthus palmeri
• AMARE Amaranthus retoflexus
• EHCG Echinochloa crus-galli
• ZEAMX Zea mays
• Ipomoea hederacea IPHE
• Setaria faberi SETFA
• the plants After 8 days cultivation under controlled conditions in a glasshouse (at 24 °C /16 °C, day/night; 14 hours light; 65 % humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64- 5). Compounds are applied at 1000 g/ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24 °C/16 °C, day/night; 14 hours light; 65 % humidity) and watered twice daily.
• an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64- 5). Compounds are applied at

Landscapes

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

Priority Applications (6)

Applications Claiming Priority (2)

Publications (1)

Family

ID=81388770

Family Applications (1)

Country Status (7)

Cited By (2)

Citations (8)

• 2023
  • 2023-04-20 EP EP23721333.5A patent/EP4514775A1/en active Pending
  • 2023-04-20 US US18/860,467 patent/US20250289787A1/en active Pending
  • 2023-04-20 CA CA3248515A patent/CA3248515A1/en active Pending
  • 2023-04-20 JP JP2024563098A patent/JP2025513597A/ja active Pending
  • 2023-04-20 AU AU2023261999A patent/AU2023261999B2/en active Active
  • 2023-04-20 CN CN202380036383.5A patent/CN119095827A/zh active Pending
  • 2023-04-20 WO PCT/EP2023/060266 patent/WO2023208710A1/en not_active Ceased

Patent Citations (8)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events