Herbicidal derivatives

Abstract

Compounds of Formula (I) wherein the substituents are as defined in claim 1. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

Description

[0001] HERBICIDAL DERIVATIVES

[0002] 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.

[0003] EP0239391 , EP0127313, EP0040082, GB2182931 , WO2022117445, and WO2022117446 describe pyridone derivatives as herbicidal agents.

[0004] According to the present invention, there is provided a compound of Formula (I): wherein

[0005] R1is Ci-Cealkyl, Ci-Cealkoxy, C2-Cealkenyl, C2-Cealkynyl, Ci-CealkoxyCi-Cealkyl, or C3- Cecycloalkyl;

[0006] R2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R5;

[0007] R3is hydrogen or Ci-Cealkyl;

[0008] R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R6;

[0009] X is hydrogen, halogen, Ci-Csalkyl, or Cs-Cecycloalkyl;

[0010] R5is 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, N,N-di(Ci-C4alkyl)aminocarbonyl, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R8;

[0011] R6is formyl, cyano, nitro, hydroxy, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, Ci- Cehaloalkoxy, Ci-Cealkylaminocarbonyl, Ci-Cealkylsulfanyl, Ci-Cealkylsulfinyl, Ci-Cealkylsulfonyl, Ci- Cealkylsulfonamido, aminosulfonylCi-Cealkyl, -C(R10)N=OR11, Ce-Cecycloalkyl, phenyl, phenylCi- Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R7; or any two adjacent R6groups together with the carbon atoms to which they are attached, may form a phenyl ring, or a heterocyclyl ring, wherein the heterocyclyl moiety is a 5- or 6-membered heterocyclyl ring comprising 1 or 2 heteroatoms selected from O and N, and wherein each phenyl and heterocyclyl moiety may be optionally substituted with 1 , 2, 3 or 4 groups, which may be the same or different, represented by R9;

[0012] R7is halogen, Ci-Cealkyl, or Ci-Cealkoxy;

[0013] R8is halogen, Ci-Cealkyl, or Ci-Cealkoxy;

[0014] R9is halogen, Ci-Cealkyl, or Ci-Cealkoxy;

[0015] R10is hydrogen or Ci-Cealkyl; and

[0016] R11is Ci-C6alkyl; or a salt or an N-oxide thereof.

[0017] Surprisingly, it has been found that the novel compounds of Formula (I) have, for practical purposes, an advantageous level of herbicidal activity.

[0018] According to a second aspect of the invention, there is provided 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.

[0019] According to a third aspect of the invention, there is provided 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).

[0020] According to a fourth aspect of the invention, there is provided the use of a compound of Formula (I) as a herbicide. Where substituents are indicated as being “optionally substituted”, this means that they may or may not carry one or more identical or different substituents, e.g., one, two or three R7substituents. For example, 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. As another example, 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.

[0021] As used herein, the term “cyano” means a -CN group.

[0022] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).

[0023] As used herein, the term “hydroxy” or “hydroxyl” refers to an -OH group.

[0024] As used herein, the term “nitro” means an -NO2 group.

[0025] As used herein, the term “acetyl” means a -C(O)CH3 group.

[0026] As used herein, the term “formyl” means a -C(O)H group.

[0027] As used herein, =O means an oxo group, e.g., as found in a carbonyl (-C(=O)-) group.

[0028] As used herein, the term "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. A “Ci-Cealkylene” group 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-.

[0029] As used herein, the term “Ci-Cehaloalkyl” refers a Ci-Cealkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. The terms “Ci-C4haloalkyl” and “C1- Cshaloalkyl”, are to be construed accordingly. Examples of Ci-Cehaloalkyl include, but are not limited to tri fluoromethyl.

[0030] As used herein, the term "Ci-Cealkoxy" refers to a radical of the formula -ORawhere Rais a Ci- Cealkyl radical as generally defined above. The terms “Ci-C4alkoxy” and “Ci-Csalkoxy” are to be construed accordingly. Examples of Ci-Cealkoxy include, but are not limited to, methoxy, ethoxy, 1- methylethoxy (iso-propoxy), and propoxy.

[0031] As used herein, the term "Ci-Cehaloalkoxy" refers to a Ci-Cealkoxy radical as generally defined above substituted by one or more of the same or different halogen atoms. The terms “Ci-C4haloalkoxy” and “Ci-Cshaloalkoxy”, are to be construed accordingly. Examples of Ci-Cehaloalkoxy include, but are not limited to trifluoromethoxy.

[0032] As used herein, the term "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. The term "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.

[0033] As used herein, the term "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. The term "C2-C3alkynyl" is to be construed accordingly. Examples of C2-Cealkynyl include, but are not limited to, ethynyl, prop-1 -ynyl, but-1-ynyl.

[0034] As used herein, the term “Ci-CealkoxyCi-Cealkyl” refers to a radical of the formula RbORa- wherein Rb is a Ci-Cealkyl radical as generally defined above, and Rais a Ci-Cealkylene radical as generally defined above. The term “Ci-C4alkoxyCi-C4alkyl” is to be construed accordingly.

[0035] As used herein, the term “Cs-Cecycloalkyl” refers to a radical which is a monocyclic saturated ring system, and which contains 3 to 6 carbon atoms. The terms "Cs-Cecycloalkyl" and "C3-C4cycloalkyl" are to be construed accordingly. Examples of Cs-Cecycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0036] As used herein, the term “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).

[0037] As used herein, the term “phenylCi-Csalkyl” refers to a phenyl ring attached to the rest of the molecule through a O-Csalkylene linker as defined above. The term phenylCi-C2alkyl is to be construed accordingly. Examples of phenylCi-Csalkyl include, but are not limited to, benzyl.

[0038] As used herein, the term “phenylCi-Csalkoxy” refers to a phenyl ring attached to the rest of the molecule through a O-Csalkoxy linker. Examples of phenylO-Csalkoxy include, but are not limited to, benzyloxy.

[0039] As used herein, the term "heterocyclyl" refers to a stable 5- or 6-membered non-aromatic monocyclic ring which comprises 1 or 2 heteroatoms, wherein the heteroatoms are individually selected from nitrogen and oxygen. The heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, tetra hydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidnyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl and thiazolidinyl.

[0040] As used herein, the term “heteroaryl” refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.

[0041] As used herein, the term “heteroarylCi-Csalkyl” refers to a heteroaryl group as defined above attached to the rest of the molecule through a O-Csalkylene linker as defined above.

[0042] As used herein, the term “heteroarylCi-Csalkoxy” refers to a heteroaryl group as defined above attached to the rest of the molecule through a O-Csalkoxy linker as defined above.

[0043] As used herein, the term “Ci-Cealkylcarbonyl” refers to a radical of the formula -C(O)Ra, where Rais a Ci-Cealkyl radical as generally defined above. Examples of Ci-Cealkylcarbonyl include, but are not limited to, acetyl.

[0044] As used herein, the term “Ci-Cealkoxycarbonyl” refers to a radical of the formula -C(O)ORa, where Rais a Ci-Cealkyl radical as generally defined above.

[0045] As used herein, the term “Ci-Cealkylaminocarbonyl” refers to a radical of the formula -C(O)NHRa, wherein Rais a Ci-Cealkyl radical as generally defined above. Examples of Ci-Cealkylaminocarbonyl include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl). As used herein, the term “N,N-di(Ci-C4alkyl)aminocarbonyl“ refers to a radical of the formula - C(O)N(Ra)(Rb), wherein Raand 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).

[0046] As used herein, the term “Ci-Cealkylsulfanyl” refers to a radical of the formula -SRa, where Rais a Ci-Cealkyl radical as generally defined above. The terms “Ci-C4alkylsulfanyl” and “Ci-Csalkylsulfanyl”, are to be construed accordingly. Examples of O-Cealkylsulfanyl include, but are not limited to methylsulfanyl.

[0047] As used herein, the term “Ci-Cealkylsulfinyl” refers to a radical of the formula -S(O)Ra, where Rais a Ci-Cealkyl radical as generally defined above. The terms “Ci-C4alkylsulfinyl” and “Ci-Csalkylsulfinyl”, are to be construed accordingly. Examples of Ci-Cealkylsulfinyl include, but are not limited to methylsulfinyl.

[0048] As used herein, the term “Ci-Cealkylsulfonyl” refers to a radical of the formula -S(O)2Ra, where Rais a Ci-Cealkyl radical as generally defined above. The terms “Ci-C4alkylsulfonyl” and “Ci- Csalkylsulfonyl”, are to be construed accordingly. Examples of Ci-Cealkylsolfanyl include, but are not limited to methylsulfonyl.

[0049] As used herein, the term “Ci-Cealkylsulfonamido” refers to a radical of the formula -NHS(O)2Ra, where Rais a Ci-Cealkyl radical as generally defined above.

[0050] 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). Likewise, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for a compound of formula (I).

[0051] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, 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. In a particularly preferred set of embodiments, the compounds of Formula (I) may form chloride or 2,2,2-trifluoroacetate salts.

[0052] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton (1991).

[0053] The following list provides definitions, including preferred definitions, for R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X with reference to compounds of Formula (I). For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document. R1is Ci-Cealkyl, O-Cealkoxy, C2-Cealkenyl, C2-Cealkynyl, Ci-CealkoxyCi-Cealkyl, or C3- Cecycloalkyl. Preferably, R1is Ci-C4alkyl, Ci-C4alkoxy, C2-C4alkenyl, C2-C4alkynyl, Ci-C4alkoxyCi- C4alkyl, or Cs-Cecycloalkyl. More preferably, R1is Ci-Csalkyl, Ci-Csalkoxy, C2-C3alkenyl, C2-C3alkynyl, Ci-CsalkoxyCi-Csalkyl, or C3-C4cycloalkyl. More preferably still, R1is methyl, ethyl, n-propyl, methoxy, 2-methoxyethyl, allyl, and prop-2-ynyl. In one set of embodiments, R1is Ci-Csalkyl, preferably methyl or ethyl, and more preferably, ethyl.

[0054] R2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R5.

[0055] Preferably, R2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R5.

[0056] More preferably, R2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R5.

[0057] More preferably still, R2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R5. Even more preferably still, R2is phenyl or pyridyl, wherein each phenyl and pyridyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R5.

[0058] In one set of embodiments, R2is phenyl optionally substituted with 1 or 2 groups, preferably 2 groups, which may be the same or different, represented by R5. In a further set of embodiments, R2is 4-cyanophenyl, 4-cyano-3-fluorophenyl, 3-chloro-4-cyanophenyl, or 3,4-dichlorophenyl. In a still further set of embodiments, R2is 3-chloro-4-cyanophenyl, or 3,4-dichlorophenyl.

[0059] R3is hydrogen or Ci-Cealkyl. Preferably, R3is hydrogen or Ci-C4alkyl, in particular, hydrogen, methyl, or tert-butyl. More preferably, R3is hydrogen or Ci-Csalkyl. More preferably still, R3is hydrogen, methyl, or ethyl. Even more preferably, R3is hydrogen.

[0060] R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3, or 4 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R6; Preferably, R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R6.

[0061] More preferably, R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

[0062] Even more preferably, wherein the heteroaryl moiety is a 5-membered aromatic ring comprising 2 or 3 heteroatoms individually selected from N, O and S, or a 6-membered aromatic ring comprising 1 or 2 nitrogen atoms, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

[0063] In one set of embodiments, R4is phenyl, pyridyl, pyrimidinyl, triazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, or oxadiazolyl, wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

[0064] In another set of embodiments, R4is phenyl, pyridyl, pyrimidinyl, triazolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, oxazolyl, or isoxazolyl, wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

[0065] In a further set of embodiments, R4is phenyl, pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, or isothiazolyl, wherein each phenyl and aforementioned heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

[0066] X is hydrogen, halogen, Ci-Csalkyl, or Cs-Cecycloalkyl. Preferably, X is hydrogen, halogen, Ci- Csalkyl, or C3-C4cycloalkyl. More preferably, X is hydrogen, halogen, methyl, ethyl, isopropyl, or cyclopropyl. In one set of embodiments, X is hydrogen.

[0067] R5is cyano, nitro, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, Ci-Cehaloalkoxy, Ci- CealkoxyCi-Cealkyl, Ci-Cealkylsulfanyl, Ci-Cealkylsulfinyl, Ci-Cealkylsulfonyl, Ci-Cealkylsulfonamido, Ci-Cealkylcarbonyl, Ci-Cealkoxycarbonyl, Ci-Cealkylaminocarbonyl, Cs-Cecycloalkyl, C3- Cecycloalkylaminocarbonyl, N,N-di(Ci-C4alkyl)aminocarbonyl, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R8.

[0068] Preferably, R5is 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, C3- Cecycloalkylaminocarbonyl, N,N-di(Ci-C3alkyl)aminocarbonyl, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R8. More preferably, R5is cyano, nitro, halogen, Ci-Csalkyl, O-Csalkoxy, Ci-C4haloalkyl, Ci- C4haloalkoxy, Ci-CsalkoxyCi-Csalkyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfinyl, Ci-Csalkylsulfonyl, Ci- Csalkylsulfonamido, O-Csalkylcarbonyl, O-Csalkoxycarbonyl, Ci-Csalkylaminocarbonyl, C3- Cecycloalkyl, Cs-Cecycloalkylaminocarbonyl, N,N-di(Ci-C3alkyl)aminocarbonyl, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R8. Even more preferably, R5is cyano, nitro, halogen, Ci-Csalkyl, O-Csalkoxy, C1- C4haloalkyl, Ci-C4haloalkoxy, Ci-CsalkoxyCi-Csalkyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfonyl, C1- C2alkylcarbonyl, O-Csalkoxycarbonyl, N,N-di(Ci-C2alkyl)aminocarbonyl, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R8.

[0069] In one set of embodiments, R5is nitro, halogen, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R8. Preferably, R5is halogen or phenyl, wherein each phenyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R8. More preferably, R5is chloro, fluoro, bromo, or phenyl, wherein each phenyl moiety may be optionally substituted with 2 groups, which may be the same or different, represented by R8. Even more preferably, R5is chloro, fluoro, bromo, or 2,4- difluorophenyl.

[0070] In one set of embodiments, R5is halogen or cyano, preferably, chloro, fluoro, or cyano. More preferably, R5is chloro or cyano.

[0071] R6is formyl, cyano, nitro, hydroxy, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, C1- Cehaloalkoxy, Ci-Cealkylaminocarbonyl, Ci-Cealkylsulfanyl, Ci-Cealkylsulfinyl, Ci-Cealkylsulfonyl, C1- Cealkylsulfonamido, aminosulfonylCi-Cealkyl, -C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi- Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein the phenyl and heteroaryl moieties may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R7; or any two adjacent R6groups together with the carbon atoms to which they are attached, may form a phenyl ring, or a 5- or 6-membered heterocyclyl ring, comprising 1 or 2 heteroatoms selected from O and N, and wherein each phenyl and heterocyclyl moiety may be optionally substituted with 1 , 2, 3 or 4 groups, which may be the same or different, represented by R9.

[0072] Preferably, R6is formyl, cyano, nitro, hydroxy, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkylaminocarbonyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfinyl, Ci-Csalkylsulfonyl, Ci-Csalkylsulfonamido, aminosulfonylCi-Csalkyl, -C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi- Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein the phenyl and heteroaryl moieties may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R7.

[0073] Preferably, R6is formyl, cyano, nitro, hydroxy, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkylaminocarbonyl, O-Csalkylsulfanyl, Ci-Csalkylsulfinyl, Ci-Csalkylsulfonyl, Ci-Csalkylsulfonamido, aminosulfonylCi-Csalkyl, -C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi- Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R7.

[0074] More preferably, R6is formyl, cyano, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4alkoxy, Ci- Cshaloalkyl, Ci-Cshaloalkoxy, Ci-Csalkylaminocarbonyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfinyl, Ci- Csalkylsulfonyl, Ci-Csalkylsulfonamido, aminosulfonylCi-Csalkyl, -C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi-Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi- Csalkoxy, wherein the heteroaryl moiety is a 6-membered aromatic ring which comprises 1 or 2 nitrogen atoms, and wherein each phenyl and heteroaryl moiety may be optionally substituted with a single group represented by R7.

[0075] In one set of embodiments, R6is cyano, halogen, Ci-C4alkyl, Ci-C4alkoxy, hydroxyCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 6-membered aromatic ring which comprises a single nitrogen atom, and wherein heteroaryl moiety may be optionally substituted with a single group represented by R7.

[0076] Preferably, R6is halogen, Ci-C4alkyl, Ci-C4alkoxy, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 6-membered aromatic ring which comprises a single nitrogen atom optionally substituted with a single group represented by R7. More preferably, R6is halogen, Ci-Csalkyl, Ci- C2alkoxy, or pyridylCi-C2alkoxy, wherein the pyridyl group is substituted with a single group represented by R7. Even more preferably, R6is chloro, fluoro, Ci-Csalkyl, methoxy, or (6-fluoro-2-pyridyl)methoxy. More preferably still, R6is chloro, fluoro, methyl, ethyl, isopropyl, methoxy, or (6-fluoro-2- pyridyl)methoxy.

[0077] R7is halogen, Ci-Csalkyl, or Ci-Csalkoxy. Preferably, R7is halogen, methyl, ethyl, methoxy, or ethoxy. More preferably, R7is fluoro, chloro, methyl, or methoxy. In one set of embodiments, R7is halogen, preferably fluoro.

[0078] R8is halogen, Ci-Csalkyl, or Ci-Csalkoxy. R8is halogen, methyl, ethyl, methoxy, or ethoxy. More preferably, R8is fluoro, chloro, methyl, or methoxy.

[0079] R9is halogen, Ci-Csalkyl, or Ci-Csalkoxy. R9is halogen, methyl, ethyl, methoxy, or ethoxy. More preferably, R9is fluoro, chloro, methyl, or methoxy.

[0080] R10is hydrogen or Ci-Cealkyl. Preferably, R10is hydrogen or Ci-Csalkyl. More preferably, R10is hydrogen or methyl. R11is Ci-Cealkyl. Preferably, R11is Ci-Csalkyl. More preferably, R11is methyl.

[0081] In a compound of formula (I) according to the present invention, preferably:

[0082] R1is Ci-C3alkyl;

[0083] R2is phenyl optionally substituted with 1 or 2 groups represented by R5;

[0084] R3is hydrogen;

[0085] R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6;

[0086] X is hydrogen;

[0087] R5is cyano or halogen;

[0088] R6is formyl, cyano, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4alkoxy, Ci-Cshaloalkyl, Ci- Cshaloalkoxy, Ci-Csalkylaminocarbonyl, Ci-Csalkylsulfanyl, Ci-Csalkylsulfinyl, Ci-Csalkylsulfonyl, Ci-Csalkylsulfonamido, aminosulfonylCi-Csalkyl, -C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi-Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi-Csalkoxy, and wherein each phenyl and heteroaryl moiety may be optionally substituted with a single group represented by R7;

[0089] R7is halogen;

[0090] R10is hydrogen or methyl; and

[0091] R11is methyl.

[0092] In another set of embodiments:

[0093] R1is ethyl;

[0094] R2is phenyl optionally substituted with 1 or 2 groups represented by R5;

[0095] R3is hydrogen;

[0096] R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6;

[0097] X is hydrogen;

[0098] R5is cyano or halogen;

[0099] R6is halogen, Ci-Csalkyl, methoxy, or heteroarylCi-C2alkoxy, and wherein each heteroaryl moiety is a 6-membered aromatic ring which comprises a single nitrogen atom, and which may be optionally substituted with a single R7group;

[0100] R7is halogen.

[0101] In another set of embodiments:

[0102] R1is ethyl;

[0103] R2is 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl; R3is hydrogen;

[0104] R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6;

[0105] X is hydrogen; and

[0106] R6is chloro, fluoro, methyl, ethyl, isopropyl, methoxy, or (6-fluoro-2-pyridyl)methoxy.

[0107] In another set of embodiments:

[0108] R1is ethyl;

[0109] R2is 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl;

[0110] R3is hydrogen;

[0111] R4is phenyl, pyridyl, pyrimidinyl, triazolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, oxazolyl, or isoxazolyl, wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6;

[0112] X is hydrogen; and

[0113] R6is chloro, fluoro, methyl, ethyl, isopropyl, methoxy, or (6-fluoro-2-pyridyl)methoxy.

[0114] Compounds of the invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of Formula (I). General methods for the production of compounds of Formula (I) are described below. Unless otherwise stated in the text, R1, R2, R3, R4, and X are as defined hereinbefore. The starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods. The starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallisation, distillation and filtration.

[0115] Scheme 1 :

[0116] Formula (A) Formula (I)

[0117] A compound of Formula (I) wherein R3is hydrogen may be prepared by hydrolysis of a compound of Formula (A) where R3is Ci-Cealkyl, with a suitable base (such as sodium hydroxide or lithium hydroxide) or with a suitable Bronsted acid (such as trifluoroacetic acid, hydrochloric acid, or sulfuric acid) or with a suitable Lewis acid (such as scandium triflate or zinc triflate) in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water). In the cases where a base is used, the product is obtained following acidification with a suitable acid (such as hydrochloric acid). Compounds of Formula (A) may additionally be prepared by methods described below.

[0118] Scheme 2:

[0119] Formula (C) Formula (B) Formula (A)

[0120] A compound of Formula (A) wherein R3is Ci-Cealkyl may be prepared by the treatment of a compound of Formula (B) where R3is Ci-Cealkyl and Y is a halogen such as chloro, bromo or iodo, with a compound of Formula (C) with a suitable base (such as sodium hydride) in a suitable solvent (such as tetra hydrofuran or 2-methyltetrahydrofuran). Compounds of Formula (C) are commercially available, and may also be prepared by methods familiar to persons skilled in the art. This is shown above in Scheme 2.

[0121] Scheme 3:

[0122] Formula (D)

[0123] Formula (B)

[0124] A compound of Formula (D) wherein R3is Ci-Cealkyl and X is hydrogen, halogen, Ci-Cealkyl, or Ce- Cecycloalkyl, may be converted to a compound of Formula (B) wherein R3is Ci-Cealkyl and Y is a halogen such as chloro, bromo or iodo, by a Sandmeyer halogenation with a suitable halogen source (such as copper (I) chloride or copper (I) bromide) in analogy to literature conditions. Typically the reaction is performed by the reaction of a compound of Formula (B) in the presence of a suitable oxidant (such as sodium nitrite or isoamyl nitrite), with a suitable halogen source (such as copper (I) chloride of potassium iodide) with a suitable acid (such as hydrogen chloride or hydrogen iodide) in a suitable solvent (such as acetonitrile or dichloromethane) with an optional co-solvent (such as water) at elevated temperature. This is shown above in Scheme 3.

[0125] Scheme 4:

[0126] Formula (E)

[0127] Formula (D)

[0128] A compound of Formula (E) wherein R3is Ci-Cealkyl and Z is a halogen suitable for cross-coupling (such as chloride, bromide or iodide), may be converted to a compound of Formula (E) wherein R3is Ci-Cealkyl and X is O-Csalkyl or Cs-Cecycloalkyl, via a metal catalysed cross-coupling with a suitable coupling partner. Typically, this reaction is performed with a Ci-Csalkyl or Cs-Cecycloalkyl boronic acid or boroxine in the presence of a suitable metal catalyst (such as palladium dichloride, palladium diacetate) in the presence of a ligand such as (2- dicyclohexylphopshino-2’,4’,6’-triisopropylbiphenyl, (4- (N,N-Dimethylamino)phenyl)di-tert-butyl phosphine), 1 ,1-bis(di-t-butylphosphino)ferrocene)(2'-amino- 1 , 1 '-biphenyl-2-yl) in the presence of a base (such as tripotassium phosphate) in a suitable organic solvent (such as toluene, acetonitrile or cyclopentyl methyl ether) optionally in the presence of water at elevated temperature. This is shown above in Scheme 4.

[0129] Scheme 5:

[0130] Formula (F) Formula (E)

[0131] A compound of Formula (E) wherein R3is Ci-Cealkyl and Z is a fluoride, chloride, bromide or iodide may be prepared by the treatment of a compound of Formula (F) where R3is Ci-Cealkyl with a suitable halogenating reagent (such as N-iodosuccinimide, N-bromosuccinimide, N-chlorosuccinimide or N- fluorobenzenesulfonamide) in a suitable solvent (such as dimethylformamide, acetonitrile, ethyl acetate or tetrahydrofuran) at elevated temperatures. Other halogenating reagents known to those skilled in the art may also be used. This is shown above in Scheme 5.

[0132] Scheme 6:

[0133] A compound of Formula (H) wherein R3is Ci-Cealkyl may be converted to a compound of Formula (F) wherein R3is Ci-Cealkyl by the addition of a suitable base (such as sodium ethoxide) in a suitable solvent (such as ethanol). This is shown above in Scheme 6. Scheme 7:

[0134] Compounds of Formula (H) may be prepared by reacting a compound of Formula (i) with a compound of Formula (J) in the presence of acetic anhydride with an optional co-solvent (such as acetonitrile) at elevated temperatures. This is shown above in Scheme 7. Compounds of Formula (J) and Formula (i) are commercially available and may also be prepared by methods familiar to persons skilled in the art.

[0135] Compounds of Formula (i) may additionally be prepared by methods described below.

[0136] Scheme 8:

[0137] Formula (i) Formula (H) Formula (F)

[0138] Compounds of Formula (i) may be prepared from reaction of p-keto esters of Formula (K) with an amine salt. The amine salts can be prepared in situ by acidification of amines of Formula (L) with a suitable acid (such as acetic acid). These amine salts may be reacted with compounds of Formula (K) in a suitable solvent (such as toluene or tetra hydrofuran) in the presence of an acid (such as acetic acid) and a drying agent (such as 4A molecular sieves). This is shown above in Scheme 8. Compounds of Formula (K) are commercially available and may also be prepared using conditions described below. Compounds of Formula (L) are commercially available and may also be prepared by methods reported in the literature.

[0139] Scheme 9:

[0140] Formula (K) Formula (J) Formula (H)

[0141] Compounds of Formula (K) may be prepared by treatment of carboxylic acids of Formula (M), wherein A is hydroxy or chloro, with an optional coupling agent (such as 1 ,1 '-carbonyldiimidazole) in a suitable solvent (such as tetrahydrofuran) at ambient temperature. The intermediate can subsequently be reacted with compounds of Formula (N) (such as potassium 3-methoxy-3-oxopropanoate) in the presence of an inorganic salt (such as magnesium chloride) in a suitable solvent (such as tetra hydrofuran or acetonitrile) at elevated temperatures. This is shown above in Scheme 9. Compounds of Formula (N) and Formula (M) are commercially available or may be prepared by methods familiar to persons skilled in the art.

[0142] 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 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 know, structurally similar compounds. Generally the plants to be controlled are unwanted plants (weeds). ‘Locus’ means the area in which the plants are growing or will grow. The application may be applied to the locus pre-emergence and / or postemergence of the crop plant. Preferably, the compounds of the present invention are applied to the locus post-emergence of the crop plant. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I).

[0143] 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.

[0144] The term "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 (PPO) inhibitors as a result of conventional methods of breeding or genetic engineering. 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). Examples of 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®.

[0145] The term "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.

[0146] Examples of such plants are: 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 expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.

[0147] 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.

[0148] 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).

[0149] The compounds of Formula (I) (or compositions comprising such) 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, Solarium, Stellaria, Veronica, Viola andXanthium.

[0150] 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). 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.

[0151] 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.

[0152] 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 (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). 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).

[0153] 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).

[0154] 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).

[0155] Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent). Dispersible Concentrates (DC) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

[0156] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment. A compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

[0162] 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).

[0163] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0164] Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

[0165] 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; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates, lignosulphonates and phosphates / sulphates of tristyrylphenols.

[0166] Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.

[0167] 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.

[0168] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite). regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, The compounds of present invention can also be used in mixture with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, 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, cinflubrolin, cinmethylin, clacyfos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), cypyrafluone, 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimesulfazet, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epyrifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, feproxydim, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), fluchloraminopyr (including fluchloraminopyr-tefuryl), flufenacet, flufenoximacil, flumetsulam, flumioxazin, fluometuron, flupyrsulfuron (including flupyrsulfuron-methyl- sodium), fluroxypyr (including fluroxypyr-meptyl), flusulfinam, fomesafen, foramsulfuron, glufosinate (including L-glufosinate and the ammonium salts of both), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, icafolin (including icafolin-methyl), imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, indolauxipyr (including indolauxipyr-cyanomethyl), iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, iptriazopyrid, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metproxybicyclone, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryne, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyraquinate, pyrasulfotole, pyridate, pyriftalid, pyriflubenzoxim, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, tripyrasulfone, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1 (2H)- yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl- 3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2- one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3- [1 -methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy- 5-hydroxy-3-methyl-imidazolidin-2-one, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-

[0169] (trifluoromethyl)-pyrimidin-1-yl]-2-pyridyl]oxy]-3-pyridyl]oxy]acetate, methyl 2-[2-[2-bromo-4-fluoro-5-[3- methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate, 6-chloro-4- (2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2-fluorophenyl)methyl 6-amino-5- chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate, 6-amino-5-chloro-2-(4-chloro- 2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid, methyl 3-[2-chloro-5-[3,6-dihydro-3-methyl- 2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH- cyclopent[d]isoxazole-6a-carboxylate, (isopropylideneamino) 6-amino-2-(4-chloro-2-fluoro-3-methoxy- phenyl)-5-methoxy-pyrimidine-4-carboxylate and ethyl 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4- (trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetate.

[0170] The mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012. The mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1.

[0171] The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of Formula (I) with the mixing partner).

[0172] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr- diethyl), metcamifen and oxabetrinil.

[0173] Particularly preferred are mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and / or metcamifen.

[0174] 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, 16thEdition (BCPC), 2012. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02 / 34048.

[0175] 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.

[0176] 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. These 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.

[0177] The term “locus” as used herein 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.

[0178] The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term “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.

[0179] Pesticidal agents referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0180] 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.

[0181] Suitable carriers and adjuvants, e.g., for agricultural use, 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.

[0182] 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. These 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.

[0183] 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.

[0184] In general, 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.

[0185] The table below illustrates examples of individual compounds of Formula (I) according to the invention:

[0186] Table 1 : Individual compounds of Formula (I) according to the invention

[0187] Table A-1 provides 38 compounds A-1.001 to A-1.038 of Formula (I) wherein R1is ethyl, R2is 3,4- dichlorophenyl, X is hydrogen, R3is hydrogen, and R4is defined in Table 1.

[0188] Table A-2 provides 38 compounds A-2.001 to A-2.038 of Formula (I) wherein R1is ethyl, R2is 3-chloro- 4-cyanophenyl, X is hydrogen, R3is hydrogen, and R4is defined in Table 1 . Table A-3 provides 38 compounds A-3.001 to A-3.038 of Formula (I) wherein R1is ethyl R2is 3,4- dichlorophenyl, X is chloro, R3is hydrogen, and R4is defined in Table 1 .

[0189] Table A-4 provides 38 compounds A-4.001 to A.4-038 of Formula (I) wherein R1is ethyl R2is 3-chloro-

[0190] 4-cyanophenyl, X is chloro, R3is hydrogen, and R4is defined in Table 1 .

[0191] Table A-5 provides 38 compounds A-5.001 to A.5-038 of Formula (I) wherein R1is ethyl R2is 3,4- dichlorophenyl, X is methyl, R3is hydrogen, and R4is defined in Table 1.

[0192] Table A-6 provides 38 compounds A-5.001 to A.5-038 of Formula (I) wherein R1is ethyl, R2is 3-chloro- 4-cyanophenyl, X is methyl, R3is hydrogen, and R4is defined in Table 1 .

[0193] Table A-7 provides 38 compounds A-7.001 to A.7-038 of Formula (I) wherein R1is ethyl R2is 3,4- dichlorophenyl, X is fluoro, R3is hydrogen, and R4is defined in Table 1 .

[0194] Table A-8 provides 38 compounds A-8.001 to A.8-038 of Formula (I) wherein R1is ethyl, R2is 3-chloro-

[0195] 4-cyanophenyl, X is fluoro, R3is hydrogen, and R4is defined in Table 1 .

[0196] Table A-9 provides 38 compounds A-9.001 to A.9-026 of Formula (I) wherein R1is ethyl, R2is 3,4- dichlorophenyl, X is cyclopropyl, R3is hydrogen, and R4is defined in Table 1.

[0197] Table A-10 provides 38 compounds A-10.001 to A.10-026 of Formula (I) wherein R1is ethyl, 3-chloro- 4-cyanophenyl, X is cyclopropyl, R3is hydrogen, and R4is defined in Table 1.

[0198] Formulation

[0199] 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 % Kaolin 62 % 27 %

[0200] 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.

[0201] 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 %

[0202] Kaolin 65 % 40 %

[0203] Talcum 20 %

[0204] 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.

[0205] Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 %

[0206] (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %

[0207] Cyclohexanone 30 % xylene mixture 50 %

[0208] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

[0209] Dusts a) b) c)

[0210] Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %

[0211] Kaolin 94 % mineral filler 96 % 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.

[0212] Extruder granules

[0213] Active ingredient [compound of formula (I)] 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %

[0214] Kaolin 82 %

[0215] 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.

[0216] Coated granules

[0217] Active ingredient [compound of formula (I)] 8 % polyethylene glycol (mol. wt. 200) 3 %

[0218] Kaolin 89 %

[0219] 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.

[0220] Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %

[0221] Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 %

[0222] Water 32 %

[0223] 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.

[0224] 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 %

[0225] 1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %

[0226] Silicone oil (in the form of a 75 % emulsion in water) 0.2 %

[0227] Water 45.3 %

[0228] 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.

[0229] Slow Release Capsule Suspension

[0230] 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.

[0231] Examples

[0232] The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table 2 below.

[0233] Throughout this description, temperatures are given in degrees Celsius (°C) and “m.p.” means melting point.

[0234] List of Abbreviations

[0235] A = angstrom, brd = broad doublet, brs = broad singlet, °C = degrees Celsius, d = doublet, dd = doublet of doublets, DMSO = dimethyl sulfoxide, M = molar, m = multiplet, MHz = megahertz, nm = nanometer, q = quartet, s = singlet, t = triplet, THF = tetra hydrofuran.

[0236] Example 1 : Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)methoxy]-4-oxo- pyridine-3-carboxylic acid (Compound 17)

[0237] Step 1 : Synthesis of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate

[0238] To a stirred solution of 1-(3,4-dichlorophenyl)ethanone (5.00 g, 26.5 mmol) and dimethyl carbonate (40 mL, 466 mmol) under nitrogen and at 0 °C was added portion-wise sodium hydride (3.17 g, 80 mmol, 60 mass%). The reaction mixture was allowed to warm to room temperature and stirred for 16 hours. Overnight the reaction mixture became a solid paste which was not possible to stir. More dimethyl carbonate (10 mL) was added in an attempt to create a mobile slurry for quenching. The reaction mixture was cooled to 0 °C and quenched by addition of water (25 mL). The reaction mixture was acidified to pH 3 by addition of 2M aqueous hydrochloric acid and then extracted into ethyl acetate. The organic extract was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel to give ethyl 3-(3,4- dichlorophenyl)-3-oxo-propanoate (mixture of tautomers) as a colourless liquid.

[0239] Enol:1H NMR (400 MHz, chloroform) 6 = 12.47 (s, 1 H), 7.87 (d, 1 H), 7.59 (m, 3H), 7.49 (d, 1 H), 5.65 (s, 1 H), 3.82 (s, 3H).

[0240] Keto:1H NMR (400 MHz, chloroform) 6 = 8.03 (d, 1 H), 7.77 (m, 1 H), 7.58 (d, 2H), 3.97 (s, 2H), 3.76 (s, 3H).

[0241] Step 2: Synthesis of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

[0242] To a stirred solution of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate (1 .65 g, 6.32 mmol) in toluene (11 mL) was added ethylammonium acetate (19.0 mmol) and acetic acid (6.32 mmol). The orange reaction mixture was heated at reflux for 6 hours. The cooled reaction mixture was diluted with ethyl acetate and washed with saturated aqueous sodium bicarbonate solution. The phases were separated and the aqueous phase extracted into ethyl acetate (x3). The organic extract was dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel to give ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate as a colourless oil.1H NMR (400 MHz, chloroform) 6 = 7.49 - 7.43 (m, 2H), 7.23 - 7.15 (m, 1 H), 4.58 - 4.50 (m, 1 H), 4.17 - 4.08 (m, 2H), 3.12 - 2.91 (m, 2H), 1.31 - 1.22 (m, 3H), 1.15 - 1.06 (m, 3H).

[0243] Step 3: Synthesis of ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo- butanoate

[0244] A solution of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (5.10 g, 17.7 mmol) and 2- cyanoacetic acid (1 .51 g, 17.7 mmol) in acetic anhydride (16 mL) was heated with stirring at 105 °C for 0.25 hours. The cooled reaction mixture was evaporated to dryness under reduced pressure. To the residue was added water (20 mL). The resultant precipitated solid was collected by filtration and purified by flash chromatography on silica gel to give ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)- (ethylamino)methylene]-3-oxo-butanoate as an off white solid.

[0245] Step 4: Synthesis of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0246] To a stirred solution of ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo- butanoate (4.50 g, 12.67 mmol) in ethanol (80 mL) at 0 °C was added sodium ethoxide (4.11 g, 12.7 mmol). The reaction mixture was heated at 50 °C for 2 hours. The cooled reaction mixture was poured into saturated aqueous ammonium chloride solution and extracted into dichloromethane. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on C-18 silica gel to give ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate as a white solid.1H NMR (400 MHz, methanol) 6 = 7.78 - 7.63 (m, 2H), 7.44 - 7.33 (m, 1 H), 5.89 - 5.80 (m, 1 H), 4.04 - 3.90 (m, 2H), 3.74 (q, 2H), 1.21 - 1.13 (m, 3H), 0.98 - 0.90 (m, 3H).

[0247] Step 5: Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0248] To a suspension of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (0.500 g, 1.41 mmol) in a mixture of acetonitrile (12 mL) and aqueous hydrogen chloride solution (2M, 1.8 mL) was added copper (I) chloride (0.167 g, 1 .69 mmol). The resultant reaction mixture was heated to 75 °C after which a solution of sodium nitrite (0.126 g, 1.83 mmol) water (1 mL) was added dropwise. The reaction mixture was heated with stirring at 75 °C for 0.25 hours. The cooled reaction mixture was poured into saturated aqueous ammonium chloride solution (30 mL) and extracted into ethyl acetate (2 x 50 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on C-18 silica gel to give ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate as a yellow solid.1H NMR (400 MHz, methanol) 6 = 7.77 (d, 1 H), 7.75 (d, 1 H), 7.46 (dd, 1 H), 6.74 (s, 1 H), 4.12 - 3.95 (m, 4H), 1 .25 (t, 3H), 0.97 (t, 3H).

[0249] Step 6: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)methoxy]-4-oxo- pyridine-3-carboxylate

[0250] To a stirred solution of (6-fluoro-3-pyridyl)methanol (41 mg, 0.32 mmol) in THF (5 mL) was added sodium hydride (7 mg, 0.32 mmol) at 0 °C whilst being stirred, ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4- oxo-pyridine-3-carboxylate (100 mg, 0.27 mmol) was then added as a solid portion whilst the reaction temperature remained at 0 °C. After 5 minutes the reaction temperature was then raised to room temperature for 1 hour. After this time, the reaction was quenched with water (20 mL) and extracted into ethyl acetate (3 x20 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The solid product was then analysed by LCMS and shown to be the desired product which was used directly in the next step.

[0251] LCMS: 2.02 mins, m / z 465.2 / 467.2

[0252] Step 7: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)methoxy]-4-oxo- pyridine-3-carboxylic acid (Compound 17)

[0253] To a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)methoxy]-4-oxo- pyridine-3-carboxylate (200 mg, 0.43 mmol) in THF (5 mL) and water (5 mL) was added Sc(OTf)3 (254 mg, 0.52 mmol), the resulting reaction mixture was then irradiated in a microwave at 100 °C for 1 hour. After this time, the reaction mixture was diluted with water (15 mL) and extracted with ethyl acetate (2 x 15 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was then purified by flash column chromatography on silica gel. The pure fractions were then combined, and the solvent removed under vacuum to give 2-(3,4-dichlorophenyl)-1 -ethyl-6-[(6-fluoro-3-pyridyl)methoxy]-4-oxo-pyridine-3- carboxylic acid as a white solid. 1 H-NMR (400 MHz, DMSO-d6) 6 = 8.45 (d, 1 H), 8.18 (ddd, 1 H), 7.77- 7.75 (m, 2H), 7.39 (dd, 1 H), 7.30 (dd, 1 H), 6.64 (s, 1 H), 5.47 (s, 2H), 3.67 (q, 2H), 1.02 (t, 3H).

[0254] Table 2:1H NMR Data for selected compounds of the invention.

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269] Biological examples

[0270] Seeds of a variety of test species are sown in standard soil in pots (Amaranthus palmeri (AMAPA), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), (Amaranthus retoflexus (AMARE), Zea mays (ZEAMX), Ipomoea hederacea (IPOHE)). 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 250 g / ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24 °CZ 16 °C, day / night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following table on a five-point scale (5 = 81-100%; 4 = 61-80%; 3=41-60%; 2=21-40%; 1 =1-20%; 0 = inactive; - = not tested).

[0271] TABLE B1 : Pre-emergence Test TABLE B2: Post-emergence Test

Claims

CLAIMS:1 . A compound of Formula (I):whereinR1is Ci-Cealkyl, Ci-Cealkoxy, C2-C6alkenyl, C2-C6alkynyl, Ci-CealkoxyCi-Cealkyl, or C3- Cecycloalkyl;R2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3, or 4 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R5;R3is hydrogen or Ci-Cealkyl;R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3, or 4 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R6;X is hydrogen, halogen, Ci-Csalkyl, or Cs-Cecycloalkyl;R5is 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, N,N-di(Ci-C4alkyl)aminocarbonyl, or phenyl, wherein each phenyl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R8;R6is formyl, cyano, nitro, hydroxy, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkyl, C1- Cehaloalkoxy, Ci-Cealkylaminocarbonyl, Ci-Cealkylsulfanyl, Ci-Cealkylsulfinyl, Ci-Cealkylsulfonyl, C1- Cealkylsulfonamido, aminosulfonylCi-Cealkyl, -C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi- Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R7; orany two adjacent R6groups together with the carbon atoms to which they are attached, may form a phenyl ring, or a heterocyclyl ring, wherein the heterocyclyl moiety is a 5- or 6-membered heterocyclyl ring comprising 1 or 2 heteroatoms selected from O and N, and wherein each phenyl and heterocyclyl moiety may be optionally substituted with 1 , 2, 3, or 4 groups, which may be the same or different, represented by R9;R7is halogen, Ci-Csalkyl, or O-Csalkoxy;R8is halogen, Ci-Csalkyl, or O-Csalkoxy;R9is halogen, Ci-Csalkyl, or O-Csalkoxy;R10is hydrogen or Ci-Cealkyl; andR11is Ci-C6alkyl; or a salt or an N-oxide thereof.

2. The compound according to claim 1 , wherein R1is Ci-Csalkyl.

3. The compound according to claim 1 or claim 2, wherein R2is phenyl, wherein each phenyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R5.

4. The compound according to any one of claims 1 to 3, wherein R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 , 2, or 3 groups, which may be the same or different, represented by R6.

5. The compound according to any one of claims 1 to 4, wherein R4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety is connected to the rest of the molecule through a carbon atom in the heteroaryl ring, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

6. The compound according to any one of claims 1 to 5, wherein R4is phenyl, pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, or isothiazolyl, wherein each phenyl and aforementioned heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R6.

7. The compound according to any one of claims 1 to 6, wherein R6is formyl, cyano, nitro, hydroxy, halogen, Ci-Cealkyl, Ci-Cealkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkylaminocarbonyl, Ci- Csalkylsulfanyl, Ci-Csalkylsulfinyl, Ci-Csalkylsulfonyl, Ci-Csalkylsulfonamido, aminosulfonylCi-Csalkyl, - C(R10)N=OR11, Cs-Cecycloalkyl, phenyl, phenylCi-Csalkyl, phenylCi-Csalkoxy, heteroaryl, heteroarylCi- Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R7.

8. The compound according to any one of claims 1 to 7, wherein R6is cyano, halogen, Ci-C4alkyl, Ci-C4alkoxy, hydroxyCi-Csalkyl, or heteroarylCi-Csalkoxy, wherein the heteroaryl moiety is a 6- membered aromatic ring which comprises a single nitrogen atom, and wherein each phenyl and heteroaryl moiety may be optionally substituted with a single group represented by R7.

9. The compound according to any one of claims 1 to 8, wherein R3is hydrogen.

10. The compound according to any one of claims 1 to 9, wherein R5is halogen or cyano.

11. A herbicidal composition comprising a compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.

12. A herbicidal composition according to claim 11 , further comprising at least one additional pesticide.

13. A herbicidal composition according to claim 12, wherein the additional pesticide is a herbicide or herbicide safener.

14. A method of controlling weeds at a locus comprising applying to the locus of a weed controlling amount of a composition according to any one of claims 1 1 to 13.

15. Use of a compound of Formula (I) according to any one of claims 1 to 10 as a herbicide.

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