Herbicidal 2-oxo-nicotinic acid derivatives

Abstract

The substituents are as defined in claim 1. [Formula 1] The present invention further relates to herbicidal compositions comprising the compounds of formula (I) and to the use of the compounds of formula (I) for controlling weeds, especially in crops of useful plants.

Description

[Technical field]

[0001] The present invention relates to herbicidal pyridone derivatives, for example as active ingredients having herbicidal activity. The present invention also relates to agrochemical compositions comprising at least one pyridone derivative, to processes for the preparation of these compounds, and to the use of the pyridone derivatives or compositions in the control of weeds in agriculture or horticulture, especially in crops of useful plants. [Background technology]

[0002] EP 0239391, EP 0127313, EP 0040082, GB 2328614 and GB 2182931 describe pyridone derivatives as herbicides. Summary of the Invention [Means for solving the problem]

[0003] According to the present invention, a compound of formula (I): [ka] (In the formula, R 1 is hydrogen, C1-C6 alkyl, phenyl, phenylC1-C2 alkyl, heteroaryl, or heteroarylC1-C2 alkyl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, where the phenyl and heteroaryl moieties are each independently selected from R 5 each optionally substituted with 1, 2, 3, or 4 groups which may be the same or different and are represented by R 2 is hydrogen or C1-C6 alkyl; R 3is hydrogen, halogen, cyano, hydroxy, C1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, or C2-C6 alkynyl; R 4 is R 6 phenyl optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by R 5 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, or nitro; R 6 is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl). or a salt thereof.

[0004] Surprisingly, it has now been found that the novel compounds of formula (I) have, for practical purposes, a highly advantageous level of herbicidal activity.

[0005] According to a second aspect of the present invention, there is provided an agricultural composition comprising a herbicidally effective amount of a compound of formula (I) according to the present invention, which may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0006] According to a third aspect of the present invention there is provided a method of controlling weeds in a locus comprising the step of applying to the locus a weed controlling amount of a composition comprising a compound of formula (I).

[0007] According to a fourth aspect of the present invention there is provided the use of a compound of formula (I) as a herbicide. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] When a substituent is described as being "optionally substituted," this includes one or more equal or different substituents, for example, one, two or three R 5 It means that it may or may not have a substituent. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens may include, but is not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, C1-C6 alkoxy substituted with 1, 2 or 3 halogens may include, but is not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.

[0009] As used herein, the term "cyano" refers to a -CN group.

[0010] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).

[0011] As used herein, the term "hydroxy" or "hydroxyl" refers to an --OH group.

[0012] As used herein, the term "nitro" refers to the group --NO.

[0013] As used herein, the term "acetyl" refers to a -C(O)CH group.

[0014] As used herein, =O refers to an oxo group such as found in a carbonyl (-C(=O)-) group.

[0015] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing no unsaturation, having 1-6 carbon atoms, and attached to the remainder of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" should be interpreted similarly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and its isomers, such as isopropyl. The group "C1-C6 alkylene" refers to the corresponding definition of C1-C6 alkyl, except that such group is attached to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" should be interpreted similarly. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0016] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group, generally as defined above, substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted similarly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0017] As used herein, the term "C1-C6 alkoxy" refers to R a is generally a C1-C6 alkyl group as defined above; a The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted similarly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0018] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group generally defined above, substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted similarly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0019] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least two double bonds which may be in the (E)- or (Z)-configuration, having 2-6 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C2-C3 alkenyl" should be interpreted similarly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), and but-1-enyl.

[0020] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting of only carbon and hydrogen atoms, containing at least two triple bonds, having 2-6 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C2-C3 alkynyl" should be interpreted similarly. Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, and but-1-ynyl.

[0021] As used herein, the term "C1-C6 alkoxy C1-C6 alkyl" refers to a group of formula R b OR a - group, where R b is generally a C1-C6 alkyl group as defined above, R ais generally a C1-C6 alkylene group as defined above. The terms "C1-C4 alkoxy C1-C4 alkyl" and "C1-C3 alkoxy C1-C3 alkyl" should be interpreted similarly.

[0022] As used herein, the term "C3-C6 cycloalkyl" refers to a group that is a monocyclic saturated ring system and contains 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted similarly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0023] As used herein, the term "C3-C6 cycloalkylaminocarbonyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule via a -NHC(O)- linker. Examples of C3-C6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0024] As used herein, the term "phenyl C1-C2 alkyl" refers to a phenyl ring attached to the remainder of the molecule via a C1-C2 alkylene linker as defined above. Examples of phenyl C1-C2 alkyl include, but are not limited to, benzyl and phenylethyl.

[0025] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing 1, 2, or 3 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, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

[0026] As used herein, the term "heteroaryl C1-C2 alkyl" refers to a heteroaryl ring generally as defined above attached to the remainder of the molecule via a C1-C2 alkylene linker as defined above.

[0027] As used herein, the term "C1-C6 alkylcarbonyl" refers to a group of the formula ~C(O)R a (wherein R a generally refers to a C1-C6 alkyl group as defined above. Examples of C1-C6 alkylcarbonyl include, but are not limited to, acetyl.

[0028] As used herein, the term "C1-C6 alkoxycarbonyl" refers to a group of the formula -C(O)OR a (wherein R a generally refers to a C1 to C6 alkyl group as defined above).

[0029] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to a group represented by the formula -C(O)NHR a (wherein R a generally refers to a C1-C6 alkyl group as defined above. Examples of C1-C6 alkylaminocarbonyl include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl).

[0030] As used herein, the term "N,N-di(C1-C4 alkyl)amino" refers to a group represented by the formula -N(R a )(R b ) group, where R a and R b each individually generally refers to a C1-C4 alkyl group as defined above. The term "N,N-di(C1-C3 alkyl)amino" should be construed similarly.

[0031] As used herein, the term "N,N-di(C1-C4 alkyl)aminocarbonyl" refers to a group represented by the formula -C(O)N(Ra )(R b ) group, where R a and R b each individually generally refers to a C1-C4 alkyl group as defined above. The term "N,N-di(C1-C3 alkyl)aminocarbonyl" should be interpreted similarly. Examples of N,N-di(C1-C4 alkyl)aminocarbonyl include, but are not limited to, dimethylcarbamoyl (i.e., N,N-di(methyl)aminocarbonyl).

[0032] As used herein, the term "C1-C6 alkylsulfanyl" refers to R a is generally a C1-C6 alkyl group as defined above a The terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be interpreted similarly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0033] As used herein, the term "C1-C6 alkylsulfinyl" refers to R a is generally a C1-C6 alkyl group as defined above a The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" should be interpreted similarly. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl.

[0034] As used herein, the term "C1-C6 alkylsulfonyl" refers to R a is generally a C1-C6 alkyl group as defined above a The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted similarly. Examples of C1-C6 alkylsolfanyl include, but are not limited to, methylsulfonyl.

[0035] As used herein, the term "C1-C6 alkylsulfonamide" refers to a compound of the formula -NHS(O)R a R refers to the group a is generally a C1-C6 alkyl group as defined above.

[0036] The presence of one or more possible stereogenic elements in the compound of formula (I) means that the compound can take optical isomeric forms, i.e., enantiomeric or diastereomeric forms. Atropisomers can also arise due to the restriction of rotation about a single bond. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof for the compound of formula (I). Similarly, formula (I) is intended to include all possible tautomeric forms. The present invention includes all possible tautomeric forms for the compound of formula (I).

[0037] In each case, the compounds of formula (I) according to the invention are in free form or in salt form, for example agriculturally usable salt form. Preferred are salts that the compounds of formula (I) can form with amines, including primary, secondary and tertiary amines (e.g. ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases. In a particularly preferred set of embodiments, the compounds of formula (I) can form chloride or 2,2,2-trifluoroacetate salts.

[0038] The following list refers to compounds of formula (I): 1 , R 2 , R 3 , R 4 , R 5 , and R 6 For any one of these substituents, any of the definitions set forth below may be combined with any of the definitions of any other substituents set forth below or elsewhere in this document.

[0039] R 1 is hydrogen, C1-C6 alkyl, phenyl, phenylC1-C2 alkyl, heteroaryl, or heteroarylC1-C2 alkyl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, where the phenyl and heteroaryl moieties are each independently selected from R 5 Each of the groups may be optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by 1 is hydrogen, C1-C6 alkyl, phenyl, phenylC1-C2 alkyl, heteroaryl, or heteroarylC1-C2 alkyl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S, where the phenyl and heteroaryl moieties are each independently selected from R 5 More preferably, R 1 is hydrogen, C1-C4 alkyl, phenyl, phenylC1-C2 alkyl, or heteroaryl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O, where the phenyl and heteroaryl moieties are each independently selected from R 5 Even more preferably, R 1 is hydrogen, C1-C3 alkyl, phenyl, phenylC1-C2 alkyl, or heteroaryl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing a single nitrogen atom, where the phenyl and heteroaryl moieties are each independently selected from R 5 Even more preferably, R 1is hydrogen, methyl, phenyl, phenyl C1-C2 alkyl, or pyridyl, where the phenyl and pyridyl moieties are 5 and more preferably, R 1 is hydrogen, methyl, phenyl, phenylmethyl (benzyl), or pyridyl, where the phenyl and pyridyl moieties are 5 Each may be optionally substituted with one or two groups which may be the same or different and are represented by

[0040] In one set of embodiments, R 1 is C1-C3 alkyl, phenyl, phenylC1-C2 alkyl, or heteroaryl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing a single nitrogen atom, where the phenyl and heteroaryl moieties are each independently selected from R 5 Preferably, each of the phenyl and pyridyl moieties is optionally substituted with one or two groups, which may be the same or different, represented by: 5 More preferably, each of the phenyl and pyridyl moieties is optionally substituted with one or two groups, which may be the same or different, represented by the formula: 5 Each may be optionally substituted with one or two groups which may be the same or different and are represented by

[0041] In another set of embodiments, R 1is 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.

[0042] R 2 is hydrogen or C1-C6 alkyl. 2 is hydrogen or C1-C4 alkyl. More preferably, R 2 is hydrogen or C1-C3 alkyl. Even more preferably, R 2 is hydrogen or methyl. Even more preferably, R 2 is methyl. In one embodiment, R 2 is C1 to C3 alkyl, preferably methyl.

[0043] R 3 is hydrogen, halogen, cyano, hydroxy, C1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, or C2-C6 alkynyl. 3 is hydrogen, halogen, cyano, hydroxy, C1-C4 alkyl, C1-C4 alkoxyC1-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkenyl, or C2-C4 alkynyl. More preferably, R 3 is hydrogen, halogen, cyano, hydroxy, C1-C4 alkyl, C1-C4 alkoxyC1-C4 alkyl, C3-C6 cycloalkyl, C2-C3 alkenyl, or C2-C4 alkynyl. Even more preferably, R 3is hydrogen, halogen, cyano, hydroxy, C1-C3 alkyl, C1-C2 alkoxyC1-C3 alkyl, C3-C4 cycloalkyl, C2-C3 alkenyl, or C2-C3 alkynyl. Even more preferably, R 3 is hydrogen, bromo, chloro, cyano, hydroxy, methyl, ethyl, methoxymethyl, cyclopropyl, vinyl, or prop-1-ynyl. 3 is hydrogen, bromo, chloro, hydroxy, methyl, ethyl, methoxymethyl, cyclopropyl, or vinyl. 3 is bromo, hydroxy, methyl, methoxymethyl, cyclopropyl, or vinyl.

[0044] R 4 is R 6 Preferably, R is phenyl, optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by 4 is R 6 More preferably, R is phenyl, optionally substituted with one, two or three groups, which may be the same or different, represented by 4 is R 6 Even more preferably, R is phenyl, optionally substituted with one or two groups, which may be the same or different, represented by 4 is R 6 In one set of embodiments, R is phenyl optionally substituted with two groups which may be the same or different and are represented by 4 In another set of embodiments, R 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. 4 is 3,4-dichlorophenyl.

[0045] R 5is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, or nitro. 5 is halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl, or nitro. More preferably, R 5 is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, or nitro. Even more preferably, R 5 is halogen, cyano, C1-C3 haloalkyl, or C1-C3 haloalkoxy. Even more preferably, R 5 is halogen, cyano, or C1-C3 haloalkyl. In one set of embodiments, R 5 In another set of embodiments, R is chloro, fluoro, cyano, trifluoromethyl, or trifluoromethoxy. 5 is chloro, fluoro, cyano, or trifluoromethyl.

[0046] R 6 is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl. Preferably, R 6is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl. More preferably, R 6 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonamido, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl. Even more preferably, R 6 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfonyl, C1-C2 alkylcarbonyl, C1-C3 alkoxycarbonyl, or N,N-di(C1-C2 alkyl)aminocarbonyl. 6 is cyano, nitro, or halogen, preferably cyano, nitro, fluoro, or chloro. In another set of embodiments, R 6 is halogen, preferably chloro.

[0047] In the compounds of formula (I) according to the invention, preferably: R 1is hydrogen, methyl, phenyl, phenyl C1-C2 alkyl, or pyridyl, where the phenyl and pyridyl moieties are 5 each optionally substituted with one or two groups, which may be the same or different, represented by R 2 is hydrogen or methyl; R 3 is hydrogen, halogen, cyano, hydroxy, C1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, or C2-C6 alkynyl; R 4 is R 6 phenyl optionally substituted with one or two groups, which may be the same or different, represented by R 5 is halogen, cyano, or trifluoromethyl; R 6 is cyano, nitro, or halogen.

[0048] In another set of embodiments, R 1 is hydrogen, C1-C6 alkyl, phenyl, phenylC1-C2 alkyl, heteroaryl, or heteroarylC1-C2 alkyl, where each heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S, where the phenyl and heteroaryl moieties are each independently selected from R 5 each optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by R 2 is methyl; R 3 is hydrogen, halogen, cyano, hydroxy, C1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, or C2-C6 alkynyl; R 4 is 3,4-dichlorophenyl; R 5 is halogen, cyano, or trifluoromethyl.

[0049] In another set of embodiments, R 1 is hydrogen, methyl, phenyl, phenylmethyl, or pyridyl, where the phenyl and pyridyl moieties are R 5 each optionally substituted with one or two groups, which may be the same or different, represented by 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.

[0050] In another set of embodiments, R 1 is methyl, phenyl, phenylmethyl, or pyridyl, where the phenyl and pyridyl moieties are R 5 each optionally substituted with one or two groups, which may be the same or different, represented by R 2 is methyl; R 3 is hydrogen, halogen, cyano, hydroxy, C1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, or C2-C6 alkynyl; R 4 is 3,4-dichlorophenyl; R 5 is chloro, fluoro, cyano, or trifluoromethyl.

[0051] In another set of embodiments, R 1is methyl, phenyl, phenylmethyl, or pyridyl, where the phenyl and pyridyl moieties are R 5 each optionally substituted with one or two groups, which may be the same or different, represented by 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.

[0052] The compounds of the present invention can be formed as shown in the following schemes, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I). General methods for producing compounds of formula (I) are described below. Unless otherwise specified in the context, R 1 , R 2 , R 3 , R 4 and R 5 is as previously defined herein. The starting materials used in the preparation of the compounds of the present invention may be purchased from ordinary commercial suppliers or may be prepared by known methods. The starting materials as well as intermediates may be purified by state-of-the-art techniques such as chromatography, crystallization, distillation and filtration before being used in the next step.

[0053] Scheme 1: [ka] Compounds of formula (I) can be prepared by reacting a compound of formula A, where R 5 can be prepared by hydrolysis of 1,2-dichlorophenyl ether (which is not hydrogen but is any C1-C6 alkyl). When a base was used, the product was obtained following acidification with a suitable acid (e.g., hydrochloric acid). This is shown in Scheme 1 above.

[0054] Scheme 2: [ka] Compounds of formula A may be prepared from compounds of formula B (where X is Cl or Br) by metal catalyzed cross-coupling reactions, for example Suzuki-Miyaura cross-coupling similar to literature conditions. Typically, the reaction is carried out by reacting compounds of formula B and R in the presence of a suitable catalyst (e.g. dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, or dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II) dichloromethane adduct) or palladium diacetate, optionally with a ligand (e.g. 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl), in the presence of a base (e.g. potassium or cesium carbonate or tripotassium phosphate), in a suitable organic solvent (e.g. 1,4-dioxane, toluene or tetrahydrofuran), and optionally in the presence of water, at elevated temperature. 3 -boronic acids, boroxines or tetrafluoroborates, as shown in Scheme 2 above.

[0055] Alternatively, a compound of formula A, 3Compounds of formula B, where X is Cl or Br, can be prepared by reaction with a suitable cyanating reagent, such as copper cyanide, in a suitable solvent, such as N,N-dimethylformamide, at elevated temperature.

[0056] Scheme 3: [ka] In another transformation, a compound of formula A, wherein R 3 is C1-C6 alkyl) can be converted to a compound of formula A, where R is a C1-C6 alkyl, 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 elevated temperature. 3 is a C2-C6 alkenyl), which is shown in Scheme 3 above.

[0057] Scheme 4: [ka] Compounds of formula B, where X is Cl, Br or I, may be prepared by treatment of compounds of formula C with a suitable halogenating agent (e.g., N-iodosuccinimide, N-bromosuccinimide or N-chlorosuccinimide), optionally in the presence of trifluoroacetic acid, in a suitable solvent (e.g., acetonitrile or dichloromethane) at room temperature or elevated temperature (e.g., 80° C.), as shown in Scheme 4 above.

[0058] Scheme 5: [ka] A compound of formula C, wherein R 1Compounds of formula D, where X is a halogen (e.g., chloro), can be prepared from compounds of formula D, where X is a halogen (e.g., chloro), by metal catalyzed cross-coupling reactions, for example Suzuki-Miyaura cross-coupling similar to literature conditions. Typically, the reaction is carried out by reacting a compound of formula D with a compound of formula R in the presence of a suitable catalyst (e.g., dichloro-(chloromethylchloronio)-bis[cyclopentyl(diphenyl)phosphaniumyl]palladium(3-); iron, dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, or dichloro(1,1′-bis(diphenylphosphanyl)ferrocene)palladium(II) dichloromethane adduct) or palladium diacetate, optionally with a ligand (e.g., 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl), in the presence of a base (e.g., potassium or cesium carbonate or tripotassium phosphate), in a suitable organic solvent (e.g., 1,4-dioxane, toluene or 2-methyltetrahydrofuran), and optionally in the presence of water, at elevated temperature. 4 -boronic acid. Compounds of formula D are commercially available or can be prepared by methods reported in the literature. This is shown in Scheme 5 above.

[0059] Scheme 6: [ka] A compound of formula A, wherein R 1 is phenyl) can be converted to a compound of formula A, where R is phenyl, by a copper catalyzed reaction with phenylboronic acid under Chan Lam conditions as reported in the literature. 1 is hydrogen). Typically, the reaction is carried out by reaction with an aryl boronic acid in the presence of a base (e.g., pyridine or triethylamine), in the presence of a catalyst (e.g., copper(II) acetate), optionally in the presence of an oxidant (typically air) and an additive (e.g., boric acid), in a suitable solvent (e.g., acetonitrile) at elevated temperature.

[0060] In a similar transformation, a compound of formula A, where R 1 is alkyl (e.g., methyl) can be converted to a compound of formula A by alkylation with a suitable alkylating agent (e.g., methyl iodide) in the presence of a base (e.g., cesium carbonate) and in the presence of a lithium salt (e.g., lithium chloride) in a suitable solvent (e.g., N,N-dimethylformamide), to give a compound of formula A (wherein R 1 is hydrogen), which is shown in Scheme 6 above.

[0061] Scheme 7: [ka] Alternatively, compounds of formula (I) can be prepared by reaction of compounds of formula E with compounds of formula F in a suitable solvent (e.g., N,N-dimethylformamide) at elevated temperature, followed by reaction with scandium triflate at room temperature. Compounds of formula F are commercially available or can be prepared by methods reported in the literature. Compounds of formula E can be prepared by methods reported in the literature. This is shown in Scheme 7 above.

[0062] The present invention further provides a method for controlling weeds in a habitat, comprising the application to the habitat of a weed-controlling amount of a composition comprising a compound of formula (I). Moreover, the present invention may further provide a method for selectively controlling weeds in a habitat containing useful (crop) plants and weeds, comprising the application to the habitat of a weed-controlling amount of a composition according to the present invention. By "control" is meant eradication, reduction or prevention of growth, or prevention or reduction of germination. It is noted that the compounds of the present invention show significantly improved selectivity compared to known structurally similar compounds. In general, the plants to be controlled are unwanted plants (weeds). By "habitat" is meant the area in which the plants are growing or will grow. Application may be made to the habitat before and / or after the emergence of the crop plants. Preferably, the compounds of the present invention are applied to the habitat after the emergence of the crop plants. Some crop plants may be inherently resistant to the herbicidal effect of the compounds of formula (I).

[0063] The application rates of the compounds of formula (I) can vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application in the sowing furrow; no-tillage application, etc.), the crop plant, the weeds to be controlled, the prevailing weather conditions, and other factors governed by the application method, application time and the target crop. The compounds of formula I according to the invention are generally applied in amounts of 10 to 2500 g / ha, in particular 25 to 1000 g / ha, in particular 25 to 250 g / ha.

[0064] Application is generally made by spraying the composition, typically with a tractor-mounted large area sprayer, although other methods such as dusting (if a powder), dripping or irrigation can also be used.

[0065] The term "useful plants" should also be understood to include useful plants that have been rendered resistant to herbicides such as bromoxynil or to a class of herbicides, such as, for example, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyroyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen-oxidase (PPO) inhibitors, by conventional breeding or genetic engineering methods. An example of a crop that has been rendered resistant to imidazolinones, such as imazamox, by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered resistant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0066] The term "useful plants" should also be understood to include useful plants which have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, especially those of the genus Bacillus.

[0067] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Root Feeders® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root-feeding nematode trait) and Protecta®.

[0068] Plant crops or their seed material can be both herbicide tolerant and insect feeding tolerant ("stacked" transgenic events) at the same time. For example, seeds can be capable of expressing an insecticidal Cry3 protein while at the same time being glyphosate tolerant.

[0069] Crop plants should also be understood to include those obtainable by conventional methods of breeding or genetic engineering and which contain so-called output traits, such as improved storage stability, higher nutritional value, and improved flavor.

[0070] The compounds of formula (I) (or compositions containing them) can be used to control unwanted plants (collectively "weeds"). The weeds controlled include, for example, Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, and Morocco. The species may be both monocotyledonous, such as Sorghum, and dicotyledonous, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0071] The compound of formula (I) can be used in unmodified form or, preferably, with formulation adjuvants such as carriers, solvents and surface active agents (SAA), together with adjuvants conventionally employed in the formulation art to provide herbicidal compositions.The present invention therefore further provides a herbicidal composition comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an adjuvant.An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use.Agricultural carriers are well known in the art.

[0072] The herbicidal compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of formula (I) and from 1 to 99.9% by weight of formulation adjuvants, preferably including from 0 to 25% by weight of a surface-active substance.

[0073] The composition can be selected from a number of formulation types, including emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), micro-emulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP) and soluble granules (SG). The formulation type selected in any case will depend on the specific purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

[0074] Soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and, optionally, one or more wetting agents, one or more dispersing agents, or a mixture of said agents to improve dispersibility / solubility in water. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0075] Wettable powders (WP) can be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersing agents and, optionally, one or more suspending agents to promote dispersibility in liquid. The mixture is then ground to a fine powder. Similar compositions may be granulated to form water-dispersible granules (WG).

[0076] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or may be formed from compacted powder granules that have been previously formed by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material (such as pumice, attapulgite clay, Fuller's earth, Kiesler's earth, diatomaceous earth, or ground corn cob), or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a hard core material (such as sand, silicic acid, carbonate minerals, sulfates, or phosphates), and optionally drying. Agents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars, and vegetable oils). One or more other additives may also be included in the granules (e.g., emulsifiers, wetting agents, or dispersants).

[0077] 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 surfactant (e.g. to improve dilution with water or to prevent crystallization in the spray tank).

[0078] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving the compound of formula (I) in an organic solvent, optionally with one or more wetting agents, one or more emulsifiers or a mixture of said agents. Organic solvents suitable for use in EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200 (SOLVESSO is a registered trademark)), 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), dimethylamides of fatty acids (C8-C10 alkyl esters such as N-methylpyrrolidone or N-octylpyrrolidone), and dimethylamides of fatty acids (C8-C10 alkyl esters such as N-methylpyrrolidone or N-octylpyrrolidone). 10 fatty acid dimethylamides, etc., and chlorinated hydrocarbons. EC products can emulsify spontaneously when added to water, resulting in an emulsion that is stable enough to allow spray application with appropriate equipment.

[0079] In preparing the EW, the compound of formula (I) is obtained as a liquid (if not liquid at room temperature it may be melted at a suitable temperature, typically below 70° C.) or in solution (by dissolving in a suitable solvent) and then the resulting liquid or solution is emulsified under high shear into water containing one or more SAA to provide an emulsion. Solvents suitable for use in EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0080] Microemulsions (MEs) can be prepared by mixing a blend of one or more solvents and one or more SAA with water to spontaneously result in a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in either water or in a solvent / SAA blend. Solvents suitable for use in MEs include those previously described for use in ECs or EWs. MEs can be either oil-in-water or water-in-oil systems (which system is present can be determined by conductivity measurements) and are suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. MEs are suitable for dilution in water, either as microemulsions or to form conventional oil-in-water emulsions.

[0081] Suspension concentrates (SC) may comprise an aqueous or insoluble suspension of fine, insoluble solid particles of the compound of formula (I). The SC may be prepared by ball milling or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to provide 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 settling rate of the particles. Alternatively, the compound of formula (I) may be dry milled and added to water containing the agents described hereinabove to provide the desired end product.

[0082] Aerosol formulations include a compound of formula (I) and a suitable propellant (e.g., n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g., water or a miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized, manual spray pump.

[0083] Capsule suspensions (CS) can be prepared similarly to the preparation of EW formulations, but with an additional polymerization stage such that an aqueous dispersion of oil droplets is obtained, each of which is encapsulated in a polymeric shell and contains the compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell can be produced by either an interfacial polycondensation reaction or a coacervation technique. The composition can provide a sustained release of the compound of formula (I) and can be used in seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymeric matrix to provide a slow sustained release of the compound.

[0084] The composition may contain one or more additives to improve the biological performance of the composition, for example by improving the wettability, retention or distribution of the compound of formula (I) on a surface; resistance to rain on the treated surface; or uptake or mobility. Such additives include surface active agents (SAA), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean oil and rapeseed oil), modified vegetable oils such as methylated rapeseed oil (MRSO), and blends of these with other bio-enhancing adjuvants (formulation components that can assist or modify the action of the compound of formula (I)).

[0085] Wetting agents, dispersing agents and emulsifying agents may be cationic, anionic, amphoteric or nonionic SAAs.

[0086] Suitable cationic SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines and amine salts.

[0087] Suitable anionic SAAs include alkali metal salts of fatty acids, sulfates of aliphatic monoesters (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butyl naphthalenesulfonate, and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3 sulfate), ether carboxylates (e.g., sodium laureth-3 carbonate), phosphate esters (e.g., products from the reaction of one or more aliphatic alcohols with phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly di-esters), such as the reaction of lauryl alcohol with tetraphosphoric acid; these products may also be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphate / sulfate salts of tristyrylphenol.

[0088] Suitable amphoteric SAAs include betaines, propionates, and glycinates.

[0089] Suitable nonionic SAAs include condensations 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 alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensations of the above partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); lecithin and its sorbitan and esters, alkyl polyglycosides, and tristyrylphenol.

[0090] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0091] The compounds of the present invention can also be used in mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, vilanaphos, bipyrazone, bispyribac-sodium, bixlozone, brocorozone, bromacil, bromoxynil, butachlor, Butafenacil, Carfentrazone (including carfentrazone-ethyl), Cloransulam (including cloransulam-methyl), Chlorimuron (including chlorimuron-ethyl), Chlorotoluron, Chlorsulfuron, Cinmethylin, Clasifos, Clethodim, Clodinafop (including clodinafop-propargyl), Clomazone, Clopyralid, Cyclopyranyl, Cyclopyrimorate, Cyclosulfamuron, Cyhalofop (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethyl) hexyl esters), 2,4-DB, desmedipham, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, difluhenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrone, diquat dibromide, diuron, epirifenacil, ethalfluralin, ethofumesate, fenoxaprop (f fenoxaprop-P-ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), fluchloraminopyr (including fluchloramino-tefuryl), flufenacet, flufenoximacil, flumetsulam, flumioxazin, fluometuron,Fomesafen, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), flusulfinam, fomesafen, foramsulfuron, glufosinate (including L-glufosinate and both ammonium salts), glyphosate (including its diammonium, isopropylammonium and potassium salts), haloxifen (including haloxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, icafolin (including icafolin-methyl), (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, indroloxypyr (including indroloxypyr-cyanomethyl), iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, iptriazopyride, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitro , metazachlor, methiozoline, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (pyraflufen- ethyl), pyraquinate, pyrasulfotole, pyridate, pyriftalid, pyriflubenzoxim, pyrimisulfan, pyroxasulfone, pyroxulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metallochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrrolimeth, thiencarbazone,Thifensulfuron, thiaphenacyl, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxadine, trifluralin, triflusulfuron, tripyrasulfone, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidine-1(2H)-isopropyl) 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, (1RS,5SR)-3-[2-methoxy-4-(prop-1-yn-1-yl)phenyl]-4-oxobicyclo[3.2.1]oct-2-en-2-ylmethyl] ethyl carbonate, ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-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, and 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-6a-cyclopenta[d]isoxazole-6a-carboxylate.

[0092] The compound of formula (I) may also be in the form of an ester or salt, for example as described in The Pesticide Manual, Nineteenth Edition, British Crop Protection Council, 2021.

[0093] Mixtures can be used to advantage in the above mentioned formulations (in which case the "active ingredient" refers to the respective mixture of the compound of formula (I) with the mixing partner).

[0094] 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.Particularly preferred is the mixture of the compound of formula I with cyprosulfamide, isoxadifen-ethyl, cloquintocet mexyl and / or metcamifen.

[0095] The safeners of the compounds of formula (I) can also be used as described, for example, in The Pesticide Manual, 19 thEdition (BCPC), 2021. Reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048.

[0096] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0097] The compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to the crop area or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, optionally with further carriers, surfactants or application-promoting adjuvants that are customarily used in the art of formulations.

[0098] As used herein, the term "habitat" refers to the field in which the plant is growing or in which the seeds of the cultivated plant have been sown or in which the seeds will be sown in the soil. It includes the soil, the seeds and seedlings, as well as established vegetation.

[0099] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0100] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, which can be used for their propagation, as well as vegetative bodies, such as cuttings or tubers, for example potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts may be mentioned. Also mentioned are sprouted plants and shoots that are to be transplanted after germination or emergence from the soil. These shoots may be protected by a complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to refer to seeds.

[0101] The pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 19th Ed., British Crop Protection Council 2021.

[0102] The compounds of formula (I) can be used in unmodified form or, preferably, together with the auxiliaries conventionally employed in the art of formulation.For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, direct-sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials.The application method, such as spraying, misting, dusting, scattering, coating, or pouring, as well as the type of composition, is selected according to the intended purpose and the current situation.The composition can also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, sources of trace elements, or other formulations for obtaining special effects.

[0103] For example, suitable carriers and adjuvants for use in agriculture may be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0104] The compounds of formula (I) are usually used in the form of compositions and can be applied to the crop area or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired with further carriers, surfactants or application-promoting adjuvants customarily used in the art of formulations.

[0105] The compound of formula (I) may be the sole active ingredient in the composition or, where appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic activity.

[0106] Typically, the formulations contain 0.01-90% by weight of active agent, 0-20% of agriculturally acceptable surfactants and 10-99.99% of solid or liquid inert compounding agents and adjuvants, the active agent being composed of at least the compound of formula (I) together with components (B) and (C) and optionally other active agents, in particular fungicides or preservatives. Concentrated forms of the composition generally contain about 2-80%, preferably about 5-70% by weight of active agent. Application forms of the formulations may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight of active agent. Commercial products will preferably be formulated as concentrates, but end users will usually utilize diluted formulations.

[0107] The following table shows the individual compounds of formula (I) according to the invention: [ka] Examples of compounds of the formula are shown below.

[0108] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4]

[0109] Table A-1 provides 52 compounds A-1.001 to A-1.052 of formula (I), in which R 1 , R 2 , R 3 and R 4 is as defined in Table 1.

[0110] Formulation Examples

[0111] [Table 2]

[0112] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain wettable powders which can be diluted with water to obtain a suspension of the desired concentration.

[0113] [Table 3]

[0114] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0115] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0116] Emulsions of any required dilution which can be used in plant protection can be obtained from this concentrate by dilution with water.

[0117] [Table 4]

[0118] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressing of seeds.

[0119] Extrusion Granules Active ingredient [compound of formula (I)] 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0120] The active ingredients are mixed and ground with the auxiliaries, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0121] Coated Granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0122] The finely ground active ingredient is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. Dust-free coated granules are thus obtained.

[0123] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0124] The finely ground active ingredient is thoroughly mixed with the adjuvants to obtain a suspension concentrate, from which suspensions of any desired dilution rate can be obtained by dilution with water, by which living plants as well as plant propagation material can be treated by spraying, pouring or immersion to protect them from microbial infestation.

[0125] Seed treatment flowable concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 10-20 moles of EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0126] The finely ground active ingredient is thoroughly mixed with the auxiliary to obtain a suspension concentrate, from which suspensions of any desired dilution rate can be obtained by dilution with water, using which living plants as well as plant propagation material can be treated by spraying, pouring or immersion to protect them from microbial infestation.

[0127] Slow-release capsule suspension 28 parts of a combination of compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a 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 is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contains 28% active ingredient. The medium capsule size is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose. EXAMPLES

[0128] The following non-limiting examples provide specific methods of synthesis of representative compounds of the invention referenced in Table 2 below.

[0129] Throughout this specification temperatures are given in degrees Celsius (° C.) and "mp" means melting point. LC / MS means liquid chromatography mass spectrometry, with a description of the apparatus and method as follows: Shimadzu LC-MS2020 using Sample Organizer with SPD-M40PDA. Mass Spectrometer-Ionization method: Electrospray (ESI), Polarity: Positive and Negative ions, Heat Block Temperature (°C) 400, DL Temperature (°C) 250, Nebulizer Gas Flow (L / min) 1.5. Instrument equipped with a HALO C18 column (column length 30 mm, column inner diameter 3.0 mm, particle size 2.7 microns). Gradient elution, 5-95% MeCN in water at 1.5 ml / min over 2.5 min. MeCN and water both containing 0.05% v / v FA.

[0130] List of abbreviations Å = Angstroms, brm = broad multiplet, brd = broad doublet, brs = broad singlet, °C = degrees Celsius, d = doublet, dd = doublet of doublets, ddd = doublet of doublets of doublets, DMSO = dimethylsulfoxide, HPLC = high performance liquid chromatography, LCMS = liquid chromatography mass spectrometry, M = mole, m = multiplet, MHz = megahertz, q = quartet, s = singlet, t = triplet.

[0131] Example 1: Synthesis of 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid (Compound 1) Step 1: Synthesis of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate [ka] To a mixture of ethyl 4-chloro-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.100 g, 0.46 mmol) and (3,4-dichlorophenyl)boronic acid (0.097 g, 0.51 mmol) in 2-methyltetrahydrofuran (2.0 mL) and water (0.37 mL) was added potassium phosphate tribasic (0.30 g, 1.39 mmol). The mixture was heated to dissolve the potassium phosphate. The mixture was degassed under a stream of nitrogen for 15 minutes. To this was added dichloro-(chloromethylchloronio)-bis[cyclopentyl(diphenyl)phosphaniumyl]palladium(3-);iron (0.038 g, 0.046 mmol) and the reaction mixture was heated with stirring at 80° C. for 18 hours. The cooled reaction mixture was diluted with ethyl acetate (10 mL) and water (10 mL) and the phases were separated. The aqueous phase was extracted twice into ethyl acetate (2×10 mL). The combined organic phase was washed with brine and concentrated under reduced pressure to give a brown solid, which was purified by mass-directed reverse phase HPLC to give ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate as a brown solid (0.090 g, 0.27 mmol). 1H NMR (400 MHz, chloroform) δ = 7.49 (d, 2H), 7.25 (brd, 1H), 6.05 (brs, 1H), 4.19 (q, 2H), 2.39 (s, 3H), 1.12 (t, 3H)

[0132] Step 2: Synthesis of ethyl 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate [ka] A solution of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.100 g, 0.31 mmol) in dichloromethane (1.0 mL) was cooled to 0° C. under nitrogen. The reaction mixture was cooled to 0° C. and 1-bromopyrrolidine-2,5-dione (0.055 g, 0.31 mmol) was added. The reaction mixture was stirred at room temperature under nitrogen for 18 hours. The 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-1H-pyridine-3-carboxylate as a white solid (0.12 g, 0.30 mmol). 1 H NMR (400 MHz, chloroform) δ = 13.48-12.92 (brm, 1H), 7.51 (d, 1H), 7.35 (s, 1H), 7.08 (dd, 1H), 4.08 (q, 2H), 2.56 (s, 3H), 1.00 (t, 3H)

[0133] Step 3: Synthesis of 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid [ka] To a solution of ethyl 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.11 g, 0.27 mmol) in ethanol (4 mL) was added a solution of lithium hydroxide (0.013 g, 0.30 mmol) in water (1.1 mL). The reaction mixture was stirred at room temperature for 18 hours. Additional lithium hydroxide (0.013 g, 0.30 mmol) in water (1.1 mL) was added and the reaction mixture was heated to reflux for 18 hours. The reaction mixture was quenched by the addition of saturated aqueous ammonium chloride solution and extracted into ethyl acetate. The aqueous phase was acidified to pH 1 by the addition of aqueous hydrogen chloride (2 M) 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-1H-pyridine-3-carboxylic acid (0.013 g, 0.035 mmol). 1 H NMR(400MHz,DMSO-d6)δ=7.71(d,1H),7.44(s,1H),7.15(d,1H),2.45(s,3H)

[0134] Example 2: Synthesis of 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid (Compound 2) Step 1: Synthesis of ethyl 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate [ka] To a solution of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.163 g, 0.500 mmol) in dichloromethane (5 mL) was added 1-chloropyrrolidine-2,5-dione (0.067 g, 0.500 mmol) at 0° C. under nitrogen atmosphere. The reaction mixture was stirred at room temperature for 14 days. The reaction mixture was evaporated to dryness under reduced pressure to give a cream solid which was purified by mass directed reverse phase HPLC to give ethyl 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate as a cream solid (0.094 g, 0.26 mmol). 1 H NMR (500 MHz, chloroform) δ = 7.51 (d, 1H), 7.34 (s, 1H), 7.08 (dd, 1H), 4.20-3.98 (m, 2H), 2.54 (s, 3H), 0.97 (t, 3H)

[0135] Step 2: Synthesis of 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid [ka] To a stirred mixture of ethyl 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.160 g, 0.444 mmol) in a mixture of tetrahydrofuran and water (4.00 mL, 1:1) was added lithium hydroxide (0.053 g, 2.22 mmol) in one portion at room temperature. The resulting mixture was heated at 65° C. with stirring for 2 h. The cooled reaction mixture was evaporated to dryness under reduced pressure. The residue was diluted with water and acidified to pH 1 by addition of aqueous hydrogen chloride (2 M) to give a white solid precipitate. The solid was filtered, washed with water (10 mL) and dried to give 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid as a white solid (0.110 g, 0.33 mmol). 1H NMR(400MHz,DMSO-d6)δ=7.72(d,1H),7.49(d,1H),7.19(dd,1H),2.42(s,3H)

[0136] Example 3: Synthesis of 5-chloro-1-(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 3) Step 1: Synthesis of ethyl 5-chloro-1-(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate [ka] To a mixture of (4-chlorophenyl)boronic acid (0.035 g, 0.22 mmol), ethyl 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.040 g, 0.11 mmol), pyridine (0.017 g, 0.19 mmol), copper(II) acetate (0.042 g, 0.22 mmol), boronic acid (0.0069 g, 0.11 mmol) and 4 Å molecular sieves (0.0027 g) was added acetonitrile (2.2 mL). Compressed air was bubbled through the reaction mixture which was heated to 50° C. for 18 hours. An additional portion of (4-chlorophenyl)boronic acid (0.035 g, 0.22 mmol) was added and heating was continued at 50° C. until LCMS showed consumption of starting material. The reaction mixture was diluted with aqueous hydrogen chloride (2M, 10 mL) and ethyl acetate (10 mL) and the phases were separated. The aqueous phase was extracted into ethyl acetate. The combined organic extracts were washed with saturated aqueous sodium bicarbonate (15 mL) and brine (15 mL) and evaporated to dryness under reduced pressure to give a brown oil which was purified by mass directed reverse phase HPLC to give ethyl 5-chloro-1-(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.012 g, 0.026 mmol). 1H NMR (400 MHz, chloroform) δ = 7.53 (d, 1H), 7.43 (d, 1H), 7.37-7.32 (m, 3H), 7.13-7.08 (m, 2H), 4.12 (q, 2H), 2.50 (s, 3H), 1.06 (t, 3H)

[0137] Step 2: Synthesis of 5-chloro-1-(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] As for 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid, it was prepared from ethyl 5-chloro-1-(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.012 g, 0.025 mmol) and lithium hydroxide (0.0021 g, 0.051 mmol) at room temperature to give 5-chloro-1-(4-chlorophenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.012 g, 0.025 mmol). 1 H NMR (400 MHz, chloroform) δ = 7.55-7.52 (m, 1H), 7.44 (d, 1H), 7.38-7.34 (m, 2H), 7.20-7.15 (m, 1H), 7.12 (d, 2H), 2.51 (s, 3H)

[0138] Example 4: Synthesis of 5-chloro-4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-pyridine-3-carboxylic acid (compound 4) Step 1: Synthesis of ethyl 5-chloro-4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-pyridine-3-carboxylate [ka] To a solution of ethyl 5-chloro-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.300 g, 0.832 mmol) in N,N-dimethylformamide (anhydrous, 5 mL) was added cesium carbonate (0.175 g, 2.08 mmol) and lithium chloride (0.106 g, 2.5 mmol), followed by portionwise addition of iodomethane (0.236 g, 1.66 mmol). The reaction mixture was heated at 45° C. with stirring for 3 h. The reaction mixture was diluted with water (30 mL) and extracted into ethyl acetate (3×15 mL). The combined organic extracts were evaporated to dryness under reduced pressure. The crude product was purified by chromatography on silica gel using a gradient of 0 to 70% ethyl acetate in petroleum ether as eluent to give ethyl 5-chloro-4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylate (100 mg, 0.27 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=7.76(d,1H),7.53(d,1H),7.25(dd,1H),3.96(d,2H),3.57(s,3H),2.58(s,3H),0.89(t,3H)

[0139] Step 2: Synthesis of 5-chloro-4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-pyridine-3-carboxylic acid [ka] To a stirred solution of ethyl 5-chloro-4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-pyridine-3-carboxylate (0.080 g, 0.214 mmol) in a mixture of methanol (1.5 mL) and water (1.5 mL) was added lithium hydroxide (0.0153 g, 0.641 mmol). The reaction mixture was heated at 65° C. for 18 h. The cooled reaction mixture was evaporated to dryness under reduced pressure and the residue was diluted with water and acidified to pH 1 by the addition of aqueous hydrogen chloride (2 M). The precipitated solid was filtered, washed with water and then purified by preparative HPLC to give 5-chloro-4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid (25.4 mg, 0.073 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=13.57(brs,1H),7.74(d,J=8.4Hz,1H),7.51(d,1H),7.22(dd,1H),3.62(s,3H),2.60(s,3H)

[0140] Example 5: Synthesis of 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1H-pyridine-3-carboxylic acid (compound 8) Step 1: Synthesis of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1,2-dihydropyridine-3-carboxylate [ka] To a stirred solution of ethyl 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (2.07 g, 5.10 mmol) in 1,4-dioxane (10 mL) and water (2 mL) was added potassium hydridotrifluoro(vinyl)borate (1.71 g, 12.8 mmol), dicesium carbonate (4.99 g, 15.3 mmol) and [1,1'-bis(diphenylphenylphosphino)ferrocene]dichloropalladium(II) (0.373 g, 0.510 mmol) at 20° C. The reaction mixture was stirred at 100° C. under nitrogen and nitrogen atmosphere for 2.5 hours.

[0141] The reaction mixture was extracted into dichloromethane (3×10 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 25-50% 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. 1 H NMR(400MHz,DMSO-d6)δ=12.26(s,1H),7.69(d,1H),7.41(d,1H),7.14(dd,1H) ,6.05(dd,1H),5.24(d,1H),4.97(d,1H),3.9(q,2H),2.31(s,3H),0.87(t,3H)

[0142] Step 2: Synthesis of 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1H-pyridine-3-carboxylic acid [ka] To a stirred solution of ethyl 4-(3,4-dichlorophenyl)-1,6-dimethyl-2-oxo-5-vinyl-pyridine-3-carboxylate (0.125 g, 0.341 mmol) in a mixture of tetrahydrofuran (4 mL), methanol (1 mL) and water (1 mL) was added lithium hydroxide (0.036 g, 0.853 mmol). The reaction mixture was stirred at room temperature for 18 h. The reaction mixture was diluted with dichloromethane (10 mL) and acidified to pH 1 by addition of aqueous hydrogen chloride (2 M). Dichloromethane was added to dissolve the precipitated solid and the phases were separated. The organic extract was washed with water (2×10 mL) and then evaporated to dryness under reduced pressure to give 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1H-pyridine-3-carboxylic acid (0.035 g, 0.11 mmol) as a white solid. 1H NMR(400MHz,DMSO-d6)δ=7.65(d,1H),7.37(s,1H),7.09(d,1H),5.95(dd,1H),5.30(m,1H),5.06(dd,1H),2.39(s,3H)

[0143] Example 6: Synthesis of 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid (compound 10) Step 1: Synthesis of ethyl 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1H-pyridine-3-carboxylate [ka] To a solution of ethyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-vinyl-1H-pyridine-3-carboxylate (0.704 g, 2.00 mmol) in ethyl acetate (10 mL) was added platinum(IV) oxide (0.0908 g, 0.400 mmol). The reaction mixture was stirred at room temperature under an atmosphere of hydrogen gas (provided via a balloon) for 1 h. The reaction mixture was filtered and the residue was washed with ethyl acetate (10 mL). The organic filtrate was dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by chromatography on silica gel using a gradient of 10-20% ethyl acetate in petroleum ether as eluent to give 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid (0.030 g, 0.085 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=12.10(s,1H),7.71(d,1H),7.48(d,1H),7.20(dd,1H),3.87(q,2H),2.11(s,3H),2.10(dd,2H),0.86-0.77(m,6H)

[0144] Step 2: Synthesis of 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid [ka] Prepared as for 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid from ethyl 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.150 g, 0.341 mmol) and lithium hydroxide (0.051 g, 1.22 mmol) at room temperature for 16 h to give 4-(3,4-dichlorophenyl)-5-ethyl-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid (0.012 g, 0.025 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=7.64(d,J=8.0Hz,1H),7.39(s,1H),7.11(d,J=8.0Hz,1H),2.39(s,3H),2.08(q,2H),0.79(t,3H)

[0145] Example 7: Synthesis of 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylic acid (compound 9) Step 1: Synthesis of ethyl 4-chloro-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylate [ka] To a solution of ethyl 4-hydroxy-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylate (0.987 g, 4.63 mmol) in acetonitrile (20 mL) at room temperature were added phosphoryl trichloride (3.90 mL, 25.5 mmol) and benzyl(triethyl)ammonium chloride (4.22 g, 18.5 mmol) successively. The reaction mixture was heated at 80° C. with stirring for 1 h. The reaction mixture was evaporated to dryness under reduced pressure, diluted with saturated aqueous sodium bicarbonate (15 mL) and extracted into dichloromethane (3×15 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness. The crude residue was purified by preparative thin layer chromatography to give ethyl 4-chloro-5,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylate (0.519 g, 2.26 mmol) as a white solid. LCMS(ESI)C 10 H 13 Calculated value for ClNO3 [M + H] + m / z 230.05, measured value 230.1

[0146] Step 2: Synthesis of ethyl 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylate [ka] To a stirred solution of ethyl 4-chloro-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylate (0.413 g, 1.80 mmol) in a mixture of 1,4-dioxane (5 mL) and water (1.2 mL) at room temperature, (3,4-dichlorophenyl)boronic acid (0.412 g, 2.16 mmol), [1,1'-bis(diphenylphosphino)ferrocene] (II) (0.132 g, 0.180 mmol) and dipotassium carbonate (0.498 g, 3.60 mmol) were added successively. The reaction mixture was heated at 85° C. with stirring under a nitrogen atmosphere for 5 hours. The cooled reaction mixture was extracted into ethyl acetate (3×15 mL) and the combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by preparative HPLC to give ethyl 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylate (0.130 g, 0.38 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=12.10(s,1H),7.72(d,1H),7.45(d,1H),7.17(dd,1H),3.87(m,2H),2.45(s,3H),1.68(s,3H),0.85(t,3H)

[0147] Step 3: Synthesis of 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylic acid [ka] To a stirred solution of ethyl 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1H-pyridine-3-carboxylate (0.200 g, 0.588 mmol) in a mixture of tetrahydrofuran (1 mL), methanol (1 mL) and water (1 mL) was added lithium hydroxide (0.070 g, 2.94 mmol) at room temperature. The reaction mixture was heated at 50° C. with stirring for 4 hours. The cooled reaction mixture was diluted with dichloromethane (10 mL) and the aqueous phase was adjusted to pH 3 by the addition of aqueous hydrogen chloride (1 M). The phases were separated and the aqueous phase was extracted into dichloromethane (3×10 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by preparative HPLC to give 4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid (0.076 g, 0.24 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=15.18(s,1H),13.24(s,1H),7.68(d,1H),7.39(d,1H),7.08(dd,1H),2.38(s,3H),1.65(s,3H)

[0148] Example 8: Synthesis of 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid (compound 11) Step 1: Synthesis of ethyl 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate [ka] To a stirred solution of ethyl 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.200 g, 0.494 mmol) in N,N-dimethylformamide (5.0 mL) was added copper cyanide (0.111 g, 1.23 mmol). The reaction mixture was heated at 160° C. with stirring for 3 h. The cooled reaction mixture was quenched by addition of water (30 mL) and extracted into ethyl acetate (3×30 mL). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by preparative HPLC to give ethyl 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.126 g, 0.36 mmol) as a white powder. 1 H NMR(400MHz,DMSO-d6)δ=7.81(d,1H),7.66(d,1H),7.36(dd,1H),3.99(q,2H),2.48(s,3H),0.92(t,3H)

[0149] Step 2: Synthesis of 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid [ka] Prepared as for 5-bromo-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid from ethyl 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylate (0.100 g, 0.285 mmol) and lithium hydroxide (0.017 mg, 0.712 mmol) at room temperature for 12 h to give 5-cyano-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-1H-pyridine-3-carboxylic acid (0.030 g, 0.093 mmol) as a white solid. 1 H NMR(400MHz,DMSO-d6)δ=7.63(d,1H),7.47(s,1H),7.18(d,1H),2.43(s,3H)

[0150] Example 9: Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 13) Step 1: Synthesis of 4-(3,4-dichlorophenyl)but-3-yn-2-ol [ka] To a solution of 4-bromo-1,2-dichloro-benzene (5.00 g, 22.1 mmol) in acetonitrile (32.5 mL) was added but-3-yn-2-ol (1.94 g, 27.7 mmol), followed by sequential addition of N,N-diethylethanamine (6.38 g, 63 mmol), triphenylphosphane (0.0581 g, 0.22 mmol), copper iodide (0.0426 g, 0.22 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.092 g, 0.078 mmol). The reaction mixture was flushed with nitrogen and heated at 60° C. for 18 h. 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, then brine, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 5-30% ethyl acetate in cyclohexane as eluent to give 4-(3,4-dichlorophenyl)but-3-yn-2-ol (3.72 g, 17.3 mmol) as a brown solid. 1 H NMR (400 MHz, chloroform) δ = 7.51 (s, 1H), 7.38 (d, 1H), 7.24 (dd, 1H), 4.80-4.68 (m, 1H), 1.96 (d, 1H), 1.55 (d, 3H)

[0151] Step 2: Synthesis of 4-(3,4-dichlorophenyl)but-3-yn-2-one [ka] To a solution of 4-(3,4-dichlorophenyl)but-3-yn-2-ol (3.71 g, 17.2 mmol) in tetrahydrofuran (52 mL) was added dioxomanganese (7.50 g, 86.2 mmol). The reaction mixture was stirred at room temperature for 3.5 h. Additional dioxomanganese (4.50 g, 51.7 mmol) was added and the reaction mixture was stirred at room temperature for an additional 18 h. The reaction mixture was filtered through diatomaceous earth and washed with ethyl acetate (300 mL). The organic filtrate was evaporated to dryness under reduced pressure and the crude residue was purified by flash chromatography on silica gel using a gradient of 1-10% ethyl acetate in cyclohexane as eluent to give 4-(3,4-dichlorophenyl)but-3-yn-2-one (2.87 g, 13.5 mmol). 1 H NMR (400 MHz, chloroform) δ = 7.66 (d, 1H), 7.48 (d, 1H), 7.40 (dd, 1H), 2.45 (s, 3H)

[0152] Step 3: Synthesis of methyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyran-3-carboxylate [ka] To a suspension of sodium hydride in mineral oil (60% by weight, 0.090 g, 2.3 mmol) was added tetrahydrofuran (17 mL) followed by dimethylpropanedioate (A, 0.71 g, 5.4 mmol, 0.62 mL) at room temperature under nitrogen. The reaction mixture was stirred at room temperature for 5 minutes followed by the addition of a solution of 4-(3,4-dichlorophenyl)but-3-yn-2-one (0.96 g, 4.5 mmol) in tetrahydrofuran (15 mL). The reaction mixture was stirred at room temperature for 18 hours. Aluminum trichloride (0.063 g, 0.47 mmol) was added while blanketing the reaction mixture with nitrogen and the mixture was stirred at room temperature for 18 hours. The reaction mixture was quenched by the addition of saturated aqueous ammonium chloride solution and evaporated under reduced pressure to remove tetrahydrofuran. Ethyl acetate (100 mL) and water (60 mL) were added and the aqueous phase was extracted into ethyl acetate (50 mL). The combined organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 5-30% ethyl acetate in cyclohexane as eluent to give methyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyran-3-carboxylate (0.76 g, 2.4 mmol) as a yellow solid. 1 H NMR (400 MHz, chloroform) δ = 7.52 (d, 1H), 7.48 (d, 1H), 7.22 (dd, 1H), 6.08 (d, 1H), 3.73 (s, 3H), 2.34 (d, 3H)

[0153] Step 4: Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] To a solution of methyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyran-3-carboxylate (0.100 g, 0.32 mmol) in N,N-dimethylformamide (1.5 mL) was added 4-chloro-2-fluoro-aniline (0.070 g, 0.48 mmol) followed by scandium triflate (0.158 g, 0.32 mmol) at room temperature under nitrogen atmosphere. The reaction mixture was stirred at room temperature for 3 days. Saturated aqueous ammonium chloride solution (4 mL) and ethyl acetate (20 mL) were added. 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. 1 H NMR (400 MHz, chloroform) δ = 14.42-13.87 (m, 1H), 7.50 (d, 1H), 7.45-7.38 (m, 3H), 7.26 (s, 1H), 7.17 (dd, 1H), 6.38 (s, 1H), 2.19 (s, 3H)

[0154] Example 10: Synthesis of 5-chloro-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 25) [ka] To a solution of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.120 g, 0.28 mmol) in acetonitrile (2.0 mL) was added 1-chloropyrrolidine-2,5-dione (0.035 g, 0.26 mmol). The reaction mixture was heated at 80° C. with stirring for 3 h. The cooled reaction mixture was evaporated to dryness under reduced pressure and purified by mass-directed reverse phase HPLC to give 5-chloro-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.32 mg, 0.069 mmol) as a cream solid. 1 H NMR (400 MHz, methanol) δ = 7.56 (dd, 1H), 7.46-7.40 (m, 3H), 7.36-7.29 (m, 1H), 7.13 (ddd, 1H), 2.34 (s, 3H)

[0155] Example 11: Synthesis of 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 21) Step 1: Synthesis of methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate [ka] To a cooled (ice bath) solution of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (1.3 g, 3.0 mmol) in dichloromethane (20 mL) was added oxalyl dichloride (0.73 g, 5.7 mmol) followed by catalytic N,N-dimethylformamide (0.2 mL). The reaction mixture was stirred at room temperature for 1 h. The resulting solution of the acid chloride was cooled to 0° C. and methanol (10 mL) was added. The reaction mixture was stirred at room temperature for 0.5 h. The reaction mixture was evaporated to dryness under reduced pressure. Water and dichloromethane were added and the phases were separated. The organic phase was evaporated to dryness under reduced pressure and the crude residue was purified by flash chromatography on silica gel using a gradient of 10-90% ethyl acetate / ethanol (3:1) in cyclohexane as eluent to give methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (1.07 g, 2.43 mmol) as a pink solid. 1 H NMR (400 MHz, chloroform) δ = 7.55 (d, 1H), 7.51 (d, 1H), 7.35-7.32 (m, 1H), 7.32-7.29 (m, 1H), 7.27 (d, 1H), 7.25-7.21 (m, 1H), 6.17 (d, 1H), 3.72 (s, 3H), 2.09 (s, 3H)

[0156] Step 2: Synthesis of methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate [ka] To a suspension of methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (1.07 g, 2.43 mmol) in acetonitrile (20 mL) was added 2,2,2-trifluoroacetic acid (0.30 g, 2.6 mmol). The suspension was heated at 80° C. to give a solution to which was added N-bromosuccinimide (0.450 g, 2.53 mmol). The reaction mixture was heated at 80° C. for 1 h. The cooled reaction mixture was evaporated to dryness under reduced pressure and purified by reverse-phase flash chromatography on C-18 silica gel using a gradient of acetonitrile in water to give methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (1.10 g, 2.1 mmol) as a cream-colored solid. 1 H NMR (400 MHz, chloroform) δ = 7.52 (dd, 1H), 7.47-7.38 (m, 1H), 7.38-7.31 (m, 2H), 7.26-7.21 (m, 1H), 7.20-7.11 (m, 1H), 3.62 (s, 3H), 2.31 (s, 3H).

[0157] Step 3: Synthesis of 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] To a solution of methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.100 g, 0.19 mmol) in methanol (3.0 mL) was added lithium hydroxide hydrate (0.040 g, 0.95 mmol) and water (1.0 mL). The reaction mixture was heated at 70° C. for 1 h. The cooled reaction mixture was diluted with water and acidified to pH 1 by the addition of aqueous hydrogen chloride solution, and the resulting precipitate was extracted into dichloromethane. The organic extracts were evaporated to dryness under reduced pressure and the crude residue was purified by reverse-phase flash chromatography on C-18 silica gel using a gradient of acetonitrile in water to give 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.030 g, 0.060 mmol) as a cream-colored solid. 1 H NMR (400 MHz, chloroform) δ = 7.55 (dd, 1H), 7.46-7.40 (m, 2H), 7.28 (brd, 1H), 7.26-7.20 (m, 1H), 6.99 (ddd, 1H), 2.43 (s, 3H)

[0158] Example 12: Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-pyridine-3-carboxylic acid (compound 26) Step 1: Synthesis of methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-pyridine-3-carboxylate [ka] To a degassed mixture of methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.200 g, 0.38 mmol) in acetonitrile (8 mL) and water (2 mL), methylboronic acid (0.040 g, 0.67 mmol), SPhos Pd G4 catalyst (0.060 g, 0.076 mmol) and potassium carbonate (0.200 g, 1.4 mmol) were added successively. The reaction mixture was purged with nitrogen and heated at 100° C. under microwave irradiation for 0.5 h. The reaction mixture was filtered through diatomaceous earth and the filtrate was diluted with water 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 reverse phase HPLC to give methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-pyridine-3-carboxylate (0.030 g, 0.059 mmol) as a deep orange gum. 1 H NMR (400 MHz, chloroform) δ = 7.52 (dd, 1H), 7.41-7.34 (m, 1H), 7.32 (td, 2H), 7.26-7.20 (m, 1H), 7.11 (ddd, 1H), 3.60 (s, 3H), 2.07 (s, 3H), 1.85 (s, 3H)

[0159] Step 2: Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-pyridine-3-carboxylic acid [ka] As for 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid, it was prepared from methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-pyridine-3-carboxylate (0.030 g, 0.059 mmol) and lithium hydroxide; hydrate (0.040 g, 0.95 mmol) at 80 ° C. to give 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5,6-dimethyl-2-oxo-pyridine-3-carboxylic acid (0.025 g, 0.051 mmol) as a cream-colored solid. 1 H NMR (400 MHz, chloroform) δ = 14.30 (brs, 1H), 7.54 (dd, 1H), 7.43-7.39 (m, 2H), 7.28-7.26 (m, 1H), 7.21 (dd, 1H), 6.96 (ddd, 1H), 2.20 (s, 3H), 1.85 (s, 3H).

[0160] Example 13: Synthesis of 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 36) Step 1: Synthesis of 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] As for 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid, it was prepared from methyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyran-3-carboxylate (0.500 g, 1.6 mmol) and 2,4-difluoroaniline (0.250 g, 1.9 mmol) in N,N-dimethylformamide (5 mL) in the presence of scandium; trifluoromethanesulfonate (0.800 g, 1.6 mmol) at room temperature to give, after purification, 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.540 g, 1.316 mmol). 1 H NMR (400 MHz, chloroform) δ = 7.50 (d, J = 8.3 Hz, 1H), 7.43 (d, 1H), 7.36-7.28 (m, 1H), 7.20-7.11 (m, 3H), 6.37 (s, 1H), 2.19 (s, 3H).

[0161] Step 2: Synthesis of methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate [ka] As for methyl 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate, it was prepared from 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (1.15 g, 2.80 mmol) and oxalyl dichloride (0.73 g, 5.7 mmol) in dichloromethane (20 mL) in the presence of catalytic N,N-dimethylformamide at room temperature, followed by quenching with methanol (10 mL) to give methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (1.07 g, 2.52 mmol) as a pink solid after purification. 1 H NMR (400 MHz, chloroform) δ = 7.56 (d, 1H), 7.51 (d, 1H), 7.32-7.26 (m, 2H), 7.09-7.01 (m, 2H), 6.17 (d, 1H), 3.72 (s, 3H), 2.09 (s, 3H)

[0162] Step 3: Synthesis of methyl 5-bromo-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate [ka] As for methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate, a mixture of methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.640 g, 1.5 mmol) and N-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate in acetonitrile (10 mL) was added. Prepared by reaction with mosuccinimide (0.280 g, 1.6 mmol) in the presence of 2,2,2-trifluoroacetic acid (0.04 mL, 0.5 mmol) at 80 °C for 1 h to give, after purification, methyl 5-bromo-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.430 g, 0.85 mmol) as a cream-colored solid. 1 H NMR (400 MHz, chloroform) δ = 7.52 (dd, 1H), 7.48-7.38 (m, 1H), 7.33-7.26 (m, 1H), 7.21-7.12 (m, 1H), 7.11-7.01 (m, 2H), 3.62 (s, 3H), 2.31 (s, 3H).

[0163] Step 4: Synthesis of methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylate [ka] To a mixture of methyl 5-bromo-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.200 g, 0.40 mmol), 11'-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with dichloromethane (0.060 g, 0.073 mmol) and potassium methoxymethyl trifluoroborate (0.150 g, 0.99 mmol) was added 1,4-dioxane (5 mL) and water (1 mL). To this stirred mixture was added cesium carbonate (0.390 g, 1.20 mmol) after which the reaction mixture was heated at 120° C. under microwave irradiation for 1 h. The cooled reaction mixture was filtered and then diluted with water and dichloromethane. The phases were separated and the organic extract was evaporated to dryness under reduced pressure. The crude residue was purified by mass directed reverse phase HPLC to give methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.020 g, 0.043 mmol) as a beige solid. 1 H NMR (400 MHz, chloroform) δ = 7.52 (d, 2H), 7.28-7.18 (m, 2H), 7.11-7.00 (m, 2H), 4.00-3.80 (m, 2H), 3.61 (s, 3H), 3.21 (d, 3H), 2.17 (s, 3H)

[0164] Step 5: Synthesis of 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] To a solution of methyl 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.017 g, 0.036 mmol) in methanol (1.0 mL) was added lithium hydroxide hydrate (0.010 g, 0.24 mmol) and water (0.1 mL). The solution was heated at 80° C. for 2 h. The reaction mixture was poured into water, acidified to pH 1 by addition of aqueous hydrogen chloride (2 M) and the resulting precipitate was extracted into dichloromethane. The phases were separated and the organic extract was evaporated to dryness under reduced pressure to give 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.015 g, 0.030 mmol) as a beige solid. 1 H NMR (400 MHz, chloroform) δ = 14.16 (brs, 1H), 7.53 (d, 1H), 7.36-7.27 (m, 2H), 7.18-7.10 (m, 2H), 7.06 (ddd, 1H), 3.97-3.77 (m, 2H), 3.15 (d, 3H), 2.28 (s, 3H)

[0165] Example 14: Synthesis of 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 37) Step 1: Synthesis of 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] To a mixture of methyl 5-bromo-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.200 g, 0.40 mmol), 11'-bis(diphenylphosphino)ferrocenedichloropalladium(ii) complex with dichloromethane (0.100 g, 0.12 mmol) and potassium cyclopropyltrifluoroborate (0.115 g, 0.78 mmol) in 1,4-dioxane (5 mL) and water (1 mL) was added cesium carbonate (0.400 g, 1.2 mmol) with stirring. The reaction mixture was heated at 120° C. under microwave irradiation for 50 min. The cooled reaction mixture was filtered and then diluted with dichloromethane and water. The phases were separated and the organic extract was evaporated to dryness under reduced pressure. The crude residue was purified by reverse-phase flash chromatography on C-18 silica gel using a gradient of acetonitrile in water to give methyl 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.090 g, 0.19 mmol) as a beige solid. 1 H NMR (400MHz, chloroform) δ = 7.56-7.43 (m, 2H), 7.26-7.14 (m, 2H), 7.09-7.00 (m, 2H), 3.63 (s, 3H), 2.23 (s, 3H), 1.54-1.46 (m, 1H), 0.66 (br s, 2H), 0.26-0.08 (m, 2H)

[0166] Step 2: Synthesis of 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid [ka] Prepared as for 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid from methyl 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.090 g, 0.19 mmol) and lithium;hydroxide;hydrate (0.050 g, 1.2 mmol) in methanol (10 mL) and water (1 mL) at 80 ° C to give 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.087 g, 0.19 mmol) as a beige solid. 1 H NMR (400 MHz, chloroform) δ = 14.35 (brs, 1H), 7.51 (dd, 1H), 7.33-7.27 (m, 2H), 7.18-7.10 (m, 2H), 7.06 (ddd, 1H), 2.33 (s, 3H), 1.50-1.37 (m, 1H), 0.79-0.54 (m, 2H), 0.31-0.12 (m, 2H)

[0167] Example 15: Synthesis of 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-prop-1-ynyl-pyridine-3-carboxylic acid (compound 40) 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 [ka] As for methyl 5-cyclopropyl-4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate, it was prepared from methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.200 g, 0.38 mmol) and potassium; trifluoro(prop-1-ynyl) boronide (0.080 g, 0.55 mmol) at 120 ° C for 1 h to give methyl 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-prop-1-ynyl-pyridine-3-carboxylate (0.025 g, 0.052 mmol) as a beige solid. 1 H NMR (400 MHz, chloroform) δ = 7.55 (d, 1H), 7.49 (d, 1H), 7.36-7.30 (m, 3H), 7.24-7.22 (m, 1H), 3.65 (s, 3H), 2.27 (s, 3H), 1.85 (s, 3H)

[0168] Step 2: Synthesis of 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-prop-1-ynyl-pyridine-3-carboxylic acid [ka] Prepared as for 4-(3,4-dichlorophenyl)-1-(2,4-difluorophenyl)-5-(methoxymethyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid from methyl 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-prop-1-ynyl-pyridine-3-carboxylate (0.020 g, 0.025 mmol) and lithium;hydroxide;hydrate (0.000 g, 0.24 mmol) in methanol (3 mL) and water (0.5 mL) at 80° C. to give 1-(3-chloro-5-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-5-prop-1-ynyl-pyridine-3-carboxylic acid (0.009 g, 0.017 mmol) as a cream-colored solid. 1 H NMR (400 MHz, chloroform) δ = 7.51 (dd, 1H), 7.44-7.39 (m, 2H), 7.34 (dd, 1H), 7.29-7.23 (m, 1H), 7.11-7.03 (m, 1H), 2.37 (s, 3H), 1.81 (s, 3H)

[0169] Example 16: Synthesis of 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5-hydroxy-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 42) [ka] To a solution of methyl 5-bromo-1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylate (0.200 g, 0.38 mmol) in methanol (5 mL) was added lithium hydroxide hydrate (0.220 g, 5.2 mmol) and water (5 mL). The reaction mixture was heated at 90° C. for 2 hours. The reaction mixture was poured into water and acidified to pH 1 by the addition of aqueous hydrogen chloride (2 M) and the resulting precipitate was extracted into dichloromethane. The organic extracts were evaporated to dryness under reduced pressure and the crude residue was purified by reverse-phase flash chromatography on C-18 silica gel using a gradient of acetonitrile in water to give 1-(4-chloro-2-fluoro-phenyl)-4-(3,4-dichlorophenyl)-5-hydroxy-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.022 g, 0.050 mmol) as a pale orange solid. 1 H NMR(400MHz,DMSO-d6)δ=7.79(dd,1H),7.73(d,1H),7.64-7.59(m,1H),7.57(d,1H),7.55-7.50(m,1H),7.31(dd,1H),2.01(s,3H)

[0170] Example 17: Synthesis of 1-[(4-chloro-2-fluoro-phenyl)methyl]-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (compound 22) [ka] To a solution of methyl 4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyran-3-carboxylate (0.200 g, 0.64 mmol) in N,N-dimethylformamide (3 mL) was added scandium; trifluoromethanesulfonate (0.320 g, 0.64 mmol) and (4-chloro-2-fluoro-phenyl)methanamine (0.105 g, 0.658 mmol). The reaction mixture was heated under microwave irradiation at 120° C. for 1 h and then for a further 2 h. The reaction mixture was poured into water, acidified to pH 1 by addition of aqueous hydrogen chloride (2 M) and extracted into dichloromethane. The organic extract was evaporated to dryness under reduced pressure to give a crude residue which was purified by reverse-phase flash chromatography on C-18 silica gel using a gradient of acetonitrile in water to give 1-[(4-chloro-2-fluoro-phenyl)methyl]-4-(3,4-dichlorophenyl)-6-methyl-2-oxo-pyridine-3-carboxylic acid (0.060 g, 0.14 mmol) as a yellow solid. 1 H NMR (400 MHz, chloroform) δ = 7.47 (d, 1H), 7.37 (d, 1H), 7.20-7.08 (m, 4H), 6.28 (s, 1H), 5.44 (s, 2H), 2.49 (s, 3H)

[0171] [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4] [Table 5-5] [Table 5-6] [Table 5-7]

Table 5-8

Table 5-9

Table 5-10

Table 5-11

Table 5-12

Table 5-13

Table 5-14

Table 5-15

Table 5-16

[0172] examples of biology Seeds of various test species are sown in standard soil in pots (Amaranthus palmeri (AMAPA), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX), Ipomoea hederacea (IPOHE), and Setaria faberi (SETFA)). After 8 days of cultivation in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity), they are sowed in 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 122631-10001) and cultured in 100% ethanol. The plants are sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 9005-64-5. Unless otherwise specified, the compounds are applied at 1000 g / ha. The test plants are then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice daily. After 13 days, the tests are evaluated for the percentage of damage caused by the plants. The biological activity is shown in the following table on a 5-point scale (5=81-100%; 4=61-80%; 3=41-60%; 2=21-40%; 1=1-20%; 0=no damage to the plants; -=not tested).

[0173] [Table 6-1] [Table 6-2]

[0174] [Table 7-1] [Table 7-2]

Claims

1. Equation (I): 【Chemistry 1】 (In the formula, R 1 is hydrogen, C 1 ~C 6 Alkyl, phenyl, phenyl C 1 ~C 2 Alkyl, heteroaryl, or heteroaryl C 1 ~C 2 It is an alkyl group, where each heteroaryl group is a five-membered or six-membered aromatic monocyclic ring containing one, two, or three heteroatoms individually selected from N, O, and S, where the phenyl and heteroaryl groups are R 5 Each of these may be arbitrarily substituted with one, two, three, or four bases, which may be identical or different; R 2 is hydrogen or C 1 to C 6 alkyl; R 3 These are hydrogen, halogen, cyano, hydroxy, and C. 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, or C 2 ~C 6 It is alkinyl; R 4 R 6 A phenyl which may be optionally substituted with one, two, three, or four groups which may be identical or different as represented by; R 5 These are halogen, cyano, and C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl or nitro; R 6 These are cyano, nitro, halogen, and C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 1 ~C 6 Alkyl sulfanyl, C 1 ~C 6 Alkyl sulfinyl, C 1 ~C 6 Alkyl sulfonyl, C 1 ~C 6 Alkyl sulfonamide, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkoxycarbonyl, C 1 ~C 6 Alkylaminocarbonyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkylaminocarbonyl, or N,N-di(C 1 ~C 4 (Alkyl)aminocarbonyl) A compound or salt thereof.

2. R 1 However, hydrogen, C 1 ~C 6 Alkyl, phenyl, phenyl C 1 ~C 2 Alkyl, heteroaryl, or heteroaryl C 1 ~C 2 It is an alkyl group, where each heteroaryl group is a five-membered or six-membered aromatic monocyclic ring containing one or two heteroatoms individually selected from N, O, and S, where the phenyl and heteroaryl groups are R 5 The compound according to claim 1, wherein each of the following groups may be arbitrarily substituted with one, two, or three groups, which may be identical or different, represented by .

3. R 1 However, hydrogen, C 1 ~C 3 Alkyl, phenyl, phenyl C 1 ~C 2 Alkyl or heteroaryl, where each heteroaryl portion is a five-membered or six-membered aromatic monocyclic ring containing a single nitrogen atom, where the phenyl and heteroaryl portions are R 5 The compound according to claim 1, wherein each of the two groups represented by may be either identical or different.

4. R 2 However, C 1 ~C 3 The compound according to claim 1, wherein it is alkyl.

5. R 3 is hydrogen, halogen, cyano, hydroxy, C 1 to C 4 alkyl, C 1 to C 4 alkoxy C 1 to C 4 alkyl, C 3 to C 6 cycloalkyl, C 2 to C 3 alkenyl, or C 2 to C 4 alkynyl, and the compound according to claim 1.

6. R 4 However, R 6 The compound according to claim 1, which is a phenyl that may be optionally substituted with one or two groups that are identical or different to the group represented by .

7. R 5 However, halogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy C 1 ~C 3 The compound according to claim 1, wherein it is alkyl or nitro.

8. R 6 However, cyano, nitro, halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Haloalkoxy, C 1 ~C 3 Alkoxy C 1 ~C 3 Alkyl, C 1 ~C 3 Alkyl sulfanyl, C 1 ~C 3 Alkyl sulfonyl, C 1 ~C 2 Alkylcarbonyl, C 1 ~C 3 Alkoxycarbonyl, or N,N-di(C) 1 ~C 2 The compound according to claim 1, wherein it is an alkyl)aminocarbonyl.

9. R 6 The compound according to claim 1, wherein the compound is cyano, nitro, or halogen.

10. R 4 The compound according to claim 1, wherein the compound is 3,4-dichlorophenyl.

11. A herbicide composition comprising the compound according to any one of claims 1 to 10 and an agriculturally acceptable compounding agent.

12. The herbicide composition according to claim 11, further comprising at least one additional pesticide.

13. The herbicide composition according to claim 12, wherein the additional pesticide is a herbicide or a herbicide toxicity mitigator.

14. A method for controlling weeds in a habitat, comprising applying the composition described in claim 11 to the habitat of the weeds in the amount required for control.

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

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