Herbicidal Inducer

Abstract

A compound of formula (I) wherein the substituents are as defined in claim 1. The present invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, especially in crops of useful plants. [Formula 1] JPEG2025541749000031.jpg36160

Description

[Technical Field]

[0001] The present invention relates to herbicidal pyridone derivatives, for example, as active ingredients, which have herbicidal activity. The present invention also relates to agrochemical compositions containing at least one pyridone derivative, to a process for preparing these compounds, and to the use of the pyridone derivatives or compositions for controlling weeds in agriculture or horticulture, especially in crops of useful plants. [Background technology]

[0002] EP 0239391, EP 0127313, EP 0040082, GB 2182931, WO 2022117445 and WO 2022117446 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 C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC1-C6 alkyl, or C3-C6 cycloalkyl; R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl moiety is R 5 optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 3 is hydrogen or C1-C6 alkyl; R 4is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each selected from R 6 optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 5 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; R 6 is cyano, nitro, halogen, oxo, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkyl arylsulfonamide, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkoxy, N,N-di(C1-C4 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, phenyl, phenoxy, or benzyloxy, wherein each cycloalkyl or phenyl moiety is R 8optionally substituted with one or two groups, which may be the same or different, represented by Any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, where the phenyl and heterocyclyl rings are R 9 optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 8 is cyano, halogen, C1-C3 alkyl, or C1-C3 alkoxy; R 9 is halogen, C1-C3 alkyl, or C1-C3 alkoxy) or a salt or N-oxide thereof.

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

[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. Such an agricultural composition 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, the method comprising 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 INVENTION

[0008] When substituents are designated as "optionally substituted," this means that they may be substituted with one or more of the same or different substituents, for example, one, two, or three R6 It means that it may or may not have a substituent. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens includes -CH2Cl, -CHCl2, -CCl 3、 Examples of halogen-substituted alkoxy include, but are not limited to, -CHF, -CHF, -CF, -CHCF, or -CFCH groups. As another example, C1-C6 alkoxy substituted with 1, 2, or 3 halogens may include, but are 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 "nitro" refers to the group --NO.sub.2.

[0012] As used herein, the term "acetyl" refers to a -C(O)CH3 group.

[0013] As used herein, =0 refers to an oxo group, such as found in a carbonyl (-C(=O)-) group.

[0014] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing no unsaturation, having 1 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" should be construed accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and isomers thereof, such as isopropyl. A "C1-C6 alkylene" group 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 construed accordingly. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0015] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, substituted with one or more of the same or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0016] As used herein, the term "C1-C6 alkoxy" refers to a group of the formula -OR a (In the formula, R a is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted accordingly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0017] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy as generally defined above, substituted with one or more of the same or different halogen atoms. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted accordingly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0018] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing at least one double bond which may be of either the (E) or (Z) configuration, having from 2 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C2-C3 alkenyl" should be construed accordingly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), and but-1-enyl.

[0019] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having 2 to 6 carbon atoms, and attached to the rest of the molecule by a single bond. The term "C2-C3 alkynyl" should be interpreted accordingly. Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, and but-1-ynyl.

[0020] As used herein, the term "C2-C6 alkenyloxy" refers to a C2-C6 alkenyl group, as generally defined above, attached to the remainder of the molecule via an oxygen atom.

[0021] As used herein, the term "C2-C6 alkynyloxy" refers to a C2-C6 alkynyl radical, as generally defined above, attached to the remainder of the molecule via an oxygen atom.

[0022] As used herein, the term "C1-C6 alkoxyC1-C6 alkyl" refers to a group of the formula R b OR a -(In the formula, R b is a C1-C6 alkyl group as generally defined above, and R a refers to a group of which C1-C6 alkylene group is a C1-C6 alkylene group as generally defined above. The term "C1-C4 alkoxy C1-C4 alkyl" should be interpreted accordingly.

[0023] As used herein, the term “C1-C6 alkoxy C1-C6 alkoxy” refers to a group of the formula R b OR a O-(wherein, R a and R b are each independently a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkoxy C1-C4 alkoxy" and "C1-C3 alkoxy C1-C3 alkoxy" should be interpreted accordingly.

[0024] As used herein, the term "C-C cycloalkyl" refers to a group that is a monocyclic saturated ring system containing from 3 to 6 carbon atoms. The terms "C-C cycloalkyl" and "C-C cycloalkyl" should be interpreted accordingly. Examples of C-C cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0025] As used herein, the term "C-C cycloalkenyl" refers to a group that is a monocyclic unsaturated ring system having 3 to 6 carbon atoms containing at least one double bond. The terms "C-C cycloalkenyl" and "C-C cycloalkenyl" should be interpreted accordingly. Examples of C-C cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0026] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule by a C1-C6 alkylene linking group, as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkyl include, but are not limited to, cyclopropylmethyl.

[0027] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkoxy" refers to a C3-C6 cycloalkyl ring attached to the rest of the molecule by a C1-C6 alkoxy linking group as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkoxy include, but are not limited to, cyclopropoxy.

[0028] As used herein, the term "C-C cycloalkylaminocarbonyl" refers to a C-C cycloalkyl ring attached to the remainder of the molecule via an -NHC(O)- linking group. Examples of C-C cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0029] As used herein, "C6-C 10 The term "aryl" refers to a 6- to 10-membered aromatic ring system, consisting solely of carbon and hydrogen atoms, which may be monocyclic, bicyclic, or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, or indenyl.

[0030] As used herein, "C6-C 10 The term "aryl C1-C3 alkyl" refers to an aryl moiety, as generally defined above, attached to the remainder of the molecule by a C1-C3 alkylene linking group, as defined above.

[0031] As used herein, the term "phenoxy" refers to a phenyl ring attached to the rest of the molecule via an oxygen atom.

[0032] As used herein, the term "benzyloxy" refers to a benzyl ring attached to the rest of the molecule via an oxygen atom.

[0033] As used herein, the term "heterocyclyl" refers to a stable 4-, 5-, or 6-membered non-aromatic monocyclic ring containing one, two, or three heteroatoms, where the heteroatoms are individually selected from nitrogen, oxygen, and sulfur. The heterocyclyl group can be attached to the remainder of the molecule through a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

[0034] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring containing 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

[0035] As used herein, the term "C1-C6 alkylcarbonyl" refers to a group of the formula -C(O)R a (In the formula, R a refers to a group of which C1-C6 alkyl is a C1-C6 alkyl group as generally defined above. Examples of C1-C6 alkylcarbonyl include, but are not limited to, acetyl.

[0036] As used herein, the term "C1-C6 alkoxycarbonyl" refers to a group of the formula -C(O)OR a (In the formula, R arefers to a group of which C1-C6 alkyl group is as generally defined above.

[0037] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to a group of the formula -C(O)NHR a (In the formula, R a refers to the group C1-C6 alkyl, as generally defined above. Examples of C1-C6 alkylaminocarbonyl include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl).

[0038] As used herein, the term "N,N-di(C1-C4 alkyl)aminocarbonyl" refers to a group of the formula -C(O)N(R a )(R b )(wherein, R a and R b and each individually refer to a C1-C4 alkyl group as generally defined above. The term "N,N-di(C1-C3 alkyl)aminocarbonyl" should be construed accordingly. Examples of N,N-di(C1-C4 alkyl)aminocarbonyl include, but are not limited to, dimethylcarbamoyl (i.e., N,N-di(methyl)aminocarbonyl).

[0039] As used herein, the term "N,N-di(C1-C4 alkyl)aminosulfonyl" refers to a group of the formula -S(O)N(R a )(R b )(wherein, R a and R b and each individually refer to a C1-C4 alkyl group as generally defined above. The term "N,N-di(C1-C3 alkyl)aminosulfonyl" should be construed accordingly. Examples of N,N-di(C1-C4 alkyl)aminosulfonyl include, but are not limited to, diethylsulfamoyl (i.e., N,N-di(methyl)aminosulfonyl).

[0040] As used herein, the term "C1-C6 alkylsulfanyl" refers to a group of the formula -SR a (In the formula, R a is a C1-C6 alkyl group as generally defined above). The terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be interpreted accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0041] As used herein, the term "C1-C6 alkylsulfinyl" refers to a group of the formula -S(O)R a (In the formula, R a is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" should be interpreted accordingly. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl.

[0042] As used herein, the term "C1-C6 alkylsulfonyl" refers to a group of the formula -S(O)R a (In the formula, R a is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfonyl.

[0043] As used herein, the term "C1-C6 alkylsulfonamide" refers to a compound of the formula -NHS(O)R a (In the formula, R a refers to a group of which C1-C6 alkyl group is as generally defined above.

[0044] The presence of one or more possible stereochemical elements in the compound of formula (I) means that the compound can exist in optically isomeric forms, i.e., enantiomeric or diastereomeric forms. Atropisomers may also occur as a result of restricted rotation around a single bond. Formula (I) is intended to encompass all such possible isomeric forms and mixtures thereof. The present invention encompasses all such possible isomeric forms and mixtures thereof for the compound of formula (I). Similarly, formula (I) is intended to encompass all possible tautomeric forms. The present invention encompasses all such possible tautomeric forms for the compound of formula (I).

[0045] In each case, the compounds of formula (I) according to the present invention are in free form, in oxidized form as N-oxides, or in salt form, for example, agriculturally useful salt form. Preferred are salts that the compounds of formula (I) can form with amines, such as primary, secondary, and tertiary amines (e.g., ammonia, dimethylamine, and triethylamine), alkali metal and alkaline earth metal bases, transition metal bases, or quaternary ammonium bases. In a particularly preferred set of embodiments, the compounds of formula (I) can form chlorides or 2,2,2-trifluoroacetic acid salts.

[0046] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton (1991).

[0047] The following list describes the substituent R in relation to compounds of formula (I): 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , and R 9Definitions, including preferred definitions, are provided for any one of these substituents. Any of the definitions set forth below for any one of these substituents may be combined with any definition of any other substituent set forth below or elsewhere in this document.

[0048] R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkyl, or C3-C6 cycloalkyl. Preferably, R 1 is C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkyl, or C3-C6 cycloalkyl. More preferably, R 1 is C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 alkyl, or C3-C4 cycloalkyl. 1 is methyl, ethyl, n-propyl, methoxy, 2-methoxyethyl, allyl, and prop-2-ynyl. In one set of embodiments, R 1 is C1 to C3 alkyl, preferably methyl or ethyl, more preferably ethyl.

[0049] R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl moiety is R 5 and optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by

[0050] Preferably, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl moiety is R 5and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by

[0051] More preferably, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and each phenyl and heteroaryl moiety is R 5 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by

[0052] More preferably, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and each phenyl and heteroaryl moiety is R 5 and optionally substituted with one or two groups, which may be the same or different, represented by R 2 is phenyl or pyridyl, where each phenyl and pyridyl moiety is R 5 and optionally substituted with one or two groups, which may be the same or different, represented by:

[0053] In one set of embodiments, R 2 is R 5 In a further set of embodiments, R is phenyl optionally substituted with one or two groups, preferably two groups, which may be the same or different, represented by 2 is 3,4-dichlorophenyl.

[0054] R 3 is hydrogen or C1-C6 alkyl. Preferably, R 3 is hydrogen or C1-C4 alkyl, more preferably hydrogen or C1-C3 alkyl. 3 is hydrogen, methyl, or ethyl. Even more preferably, R 3is hydrogen or ethyl. Even more preferably, R 3 is hydrogen.

[0055] R 4 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each selected from R 6 and optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by

[0056] Preferably, R 4 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each selected from R 6 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by

[0057] More preferably, R 4 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O, and the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each selected from R 6 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by

[0058] More preferably, R 4is phenyl or heteroaryl, where the heteroaryl moiety is a 5-membered aromatic monocyclic ring containing 1 or 2 nitrogen atoms, and the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each R 6 and optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0059] In one embodiment, R 4 is phenyl or pyrazolyl, where the phenyl and pyrazolyl moieties are R 6 and optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0060] In one set of embodiments, R 4 is R 6 Preferably, R is phenyl optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by 4 is R 6 and R is a phenyl optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by 6 is halogen, C1-C3 haloalkoxy, or C1-C6a alkoxycarbonyl. More preferably, R 4 is R 6 and R is a phenyl optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by 6 is halogen, C1-C2 haloalkoxy, or C1-C3 alkoxycarbonyl. Even more preferably, R 4 is R 6 and R is a phenyl optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by 6 is chloro, fluoro, trifluoromethoxy, or isopropyloxycarbonyl.

[0061] In another set of embodiments, R 4is 4-chlorophenyl, 4-chloro-2-fluorophenyl, 2-fluoro-5-(trifluoromethoxy)phenyl, 4-chloro-2-fluoro-5-isopropoxycarbonylphenyl, 2-chloro-5-(trifluoromethoxy)phenyl, 2-fluoro-5-isopropoxycarbonylphenyl, or 2-fluoro-3-(trifluoromethoxy)phenyl.

[0062] R 5 is cyano, nitro, halogen, oxo, 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.

[0063] Preferably, R 5 is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 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.

[0064] More preferably, R 5is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 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 or phenyl.

[0065] More preferably, R 5 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylcarbonyl, or C3-C6 cycloalkyl. Even more preferably, R 5 is cyano, nitro, chloro, fluoro, methyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2-difluoroethoxy, methoxymethyl, acetyl, or cyclopropyl.

[0066] In one set of embodiments, R 5 is cyano, nitro, or halogen, preferably cyano or halogen, more preferably halogen. Even more preferably, R 5 is chloro or fluoro, and more preferably further R 5 is chloro.

[0067] R 6is cyano, nitro, halogen, oxo, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkyl alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkoxy, N,N-di(C1-C4 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, phenoxy, or benzyloxy, wherein each cycloalkyl or phenyl moiety is selected from R 8 optionally substituted with one or two groups, which may be the same or different, represented by Any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, where the phenyl and heterocyclyl rings are R 9 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by

[0068] Preferably, R 6is cyano, nitro, halogen, oxo, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C4 alkyl, C1-C4 alkoxyC1-C4 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkyl alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C4 alkoxy, N,N-di(C1-C3 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C3 alkyl)aminocarbonyl, phenoxy, or benzyloxy, wherein each cycloalkyl or phenyl moiety is selected from R 8 optionally substituted with one or two groups, which may be the same or different, represented by Any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclyl ring containing one or two heteroatoms selected from O and N, where the phenyl and heterocyclyl rings are not R 9 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by

[0069] In one embodiment, R 6 is halogen, C1-C4 alkoxy, C1-C4 haloalkoxy, or C1-C4 alkoxycarbonyl; or any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring, where the phenyl ring is R 9 and optionally substituted with one or two groups, which may be the same or different, represented by:

[0070] In another embodiment, R 6is chloro, fluoro, methoxy, trifluoromethoxy, or isopropoxycarbonyl, or two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring, where the phenyl ring contains only one R 9 The group may be optionally substituted with a group.

[0071] In a further embodiment, R 6 is chloro, fluoro, trifluoromethoxy, or isopropoxycarbonyl.

[0072] R 8 is cyano, halogen, C1-C3 alkyl, or C1-C3 alkoxy. 8 is cyano, halogen, or C1-C3 alkoxy. More preferably, R 8 is cyano, halogen or methoxy. Even more preferably, R 8 is fluoro or methoxy.

[0073] R 9 is halogen, C1-C3 alkyl, or C1-C3 alkoxy. Preferably, R 9 is halogen or C1-C3 alkoxy. More preferably, R 9 is halogen or methoxy. Even more preferably, R 9 is fluoro or methoxy. More preferably still, R 9 is methoxy.

[0074] In the compounds of formula (I) according to the present invention, preferably R 1 is C1-C3 alkyl; R 2 is 3,4-dichlorophenyl; R 3 is hydrogen or ethyl; R 4is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring; phenyl and heteroaryl are each independently selected from R 6 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by R 6 is halogen, C1-C4 alkoxy, C1-C4 haloalkoxy, or C1-C4 alkoxycarbonyl; or any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring, where the phenyl ring is R 9 optionally substituted with one or two groups, which may be the same or different, represented by R 9 is methoxy.

[0075] In another set of embodiments, R 1 is methyl or ethyl; R 2 is 3,4-dichlorophenyl; R 3 is hydrogen or ethyl; R 4 is phenyl or pyrazolyl, where the phenyl and pyrazolyl moieties are R 6 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by R 6is cyano, nitro, halogen, oxo, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C4 alkyl, C1-C4 alkoxyC1-C4 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 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 cycloalkylC1-C4 alkoxy, N,N-di(C1-C3 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C3 alkyl)aminocarbonyl, phenoxy, or benzyloxy, wherein each cycloalkyl or phenyl moiety is selected from R 8 optionally substituted with one or two groups, which may be the same or different, represented by Any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, where the phenyl and heterocyclyl rings are R 9 and optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by R 9 is halogen or methoxy.

[0076] In a further set of embodiments, R 1 is ethyl; R 2 is 3,4-dichlorophenyl; R 3 is hydrogen; R 4 is R 6 and phenyl optionally substituted with 1, 2, or 3 groups, which may be the same or different, selected from: R 6is halogen, C1-C3 haloalkoxy, or C1-C3 alkoxycarbonyl.

[0077] The compounds of the present invention can be prepared as shown in the following schemes, in which the definition of each variable is as defined above for compounds of formula (I) unless otherwise specified. A general method for preparing compounds of formula (I) is described below. Unless otherwise specified in the context, R 1 , R 2 , R 3 , R 4 and X are as defined hereinbefore. The starting materials used for the preparation of the compounds of the present invention can be purchased from ordinary commercial suppliers or prepared by known methods. The starting materials as well as intermediates can be purified by state-of-the-art techniques such as chromatography, crystallization, distillation and filtration before use in the next step.

[0078] Scheme 1: [ka] R 3 is hydrogen, the compound of formula (I) is 3 is not hydrogen and is any other R as defined above 3 The compound of formula (I) can be prepared by hydrolysis with a suitable base (such as sodium hydroxide or lithium hydroxide) or a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water). When a base is used, the product is obtained by subsequent acidification with a suitable acid (such as hydrochloric acid). This is shown in Scheme 1 above. The compound of formula (I) can be further prepared by the methods described below.

[0079] Scheme 2: [ka] R 4 is phenyl or heteroaryl, and R 3 is hydrogen or any other R as defined above 3 Compounds of formula (I) which are groups are those in which Y is Cl, Br or I and R 3 is hydrogen or any other R as defined above 3 The group can be further prepared from a compound of formula (A) by Suzuki-Miyaura cross-coupling reaction using standard literature conditions. Typically, the reaction involves the reaction of a compound of formula (A) with R 4 -boronic acid or boroxine in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, or dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium(II) dichloromethane adduct) or palladium diacetate, optionally with a ligand (such as 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl), in the presence of a base (such as potassium or cesium carbonate or tripotassium phosphate), in a suitable organic solvent (such as 1,4-dioxane, toluene, or tetrahydrofuran), optionally in the presence of water, at elevated temperatures. This is shown in Scheme 2 above.

[0080] In an alternative transformation, compounds of formula (A) where Y is I can be converted to R by reaction under Stille conditions, for example with a heterocyclic stannane, in the presence of a catalyst (such as tetrakis(triphenylphosphine)palladium(0)) in a suitable solvent (such as toluene) at elevated temperature (such as 120° C.). 4 is a C-linked heterocycle (eg, oxazol-2-yl, etc.).

[0081] In a further alternative transformation, Y is I or Br and R 3 is hydrogen or any other R as defined above 3The compound of formula (A) can be converted to R by reaction under Ullmann conditions, for example, with a pyrazole heterocycle in the presence of a copper source (such as copper(I) iodide), in the presence of a base (such as potassium carbonate, cesium carbonate, potassium phosphate), and optionally in the presence of a ligand (such as 3,4,7,8-tetramethyl-1,10-phenanthroline, proline, 8-hydroxyquinoline, or N,N'-bis(2,6-dimethoxyphenyl)oxamide), in a suitable organic solvent (such as toluene, dioxane, dimethyl sulfoxide, or acetonitrile) at elevated temperature (such as 100°C). 4 is an N-linked heterocycle (such as pyrazol-1-yl or indazol-1-yl).

[0082] Scheme 3: [ka] R 3 Compounds of formula (A) where is hydrogen and Y is Br or I are 3 is not hydrogen and is any other R as defined above 3 The radical compound of formula (A) can be prepared by hydrolysis with a suitable base (such as sodium hydroxide or lithium hydroxide) or with a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water), as shown in Scheme 3 above.

[0083] Scheme 4: [ka] Compounds of formula (A) where Y is Br or I can be prepared by treatment of compounds of formula (B) with a suitable halogenating agent (such as N-iodohalosuccinimide or N-bromosuccinimide) in a suitable solvent (such as acetonitrile or trifluoroacetic acid), as shown in Scheme 4 above.

[0084] Scheme 5: [ka] R 1 and R 3 is the same, but R 1 is not hydrogen, can be converted to an alkyl halide (R 1 -X) (e.g., ethyl iodide, etc.), which is shown in Scheme 5 above.

[0085] If regioisomeric mixtures are produced after these reactions, the isomers can be separated by chromatography.

[0086] Scheme 6: [ka] Compounds of formula (C) can be prepared by reacting compounds of formula (D) with a formylating agent, such as that obtained from the combination of N,N-dimethylformamide and phosphorus oxychloride, under Vilsmeier-Haack reaction conditions, typically using N,N-dimethylformamide as the solvent, at elevated temperatures (e.g., 80-120°C), as shown in Scheme 6 above.

[0087] Scheme 7: [ka] Compounds of formula (D) can be prepared by reacting a β-ketoester of formula (E) with an arylnitrile of formula (F) in a metal-promoted addition reaction, for example, in the presence of tin tetrachloride, in a suitable solvent (such as toluene), optionally in the presence of a base (such as sodium bicarbonate), at elevated temperatures (e.g., 100°C). Compounds of formula (E) and formula (F) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown in Scheme 7 above.

[0088] The present invention further provides a method for controlling weeds in a habitat, the method comprising applying a controlling amount of a composition comprising a compound of formula (I) to the weed habitat. The present invention may also provide a method for selectively controlling weeds in a habitat containing useful (crop) plants and weeds, the method comprising applying a controlling amount of a composition of the present invention to the weed habitat. "Control" means killing, reducing or delaying growth, or preventing or reducing germination. It is noted that the compounds of the present invention exhibit significantly improved selectivity compared to known, structurally similar compounds. Generally, the plants to be controlled are undesirable plants (weeds). "Habitat" refers to the location where the plants are growing or will grow. Application can be made to the habitat before and / or after emergence of the crop plants. Some crop plants are inherently resistant to the herbicidal action of the compounds of formula (I).

[0089] 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-till application, etc.), the crop plant, the weeds to be controlled, the prevailing climatic conditions, and other factors determined by the method, time of application 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, more in particular 25 to 250 g / ha.

[0090] Application is generally carried out by spreading the composition, typically with a tractor-mounted broad-area spreader, although other methods such as dusting (in the case of dusts), drip irrigation or drench can also be used.

[0091] The term "useful plants" should also be understood to include useful plants that have been rendered tolerant, as a result of conventional methods of breeding or genetic engineering, to herbicides such as bromoxynil or to classes of herbicides such as 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. An example of a crop that has been rendered tolerant to imidazolinones, such as imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® rapeseed (Canola). Examples of crops that have been genetically engineered to tolerate herbicides or classes of herbicides include glyphosate- and glufosinate-tolerant corn varieties available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0092] The term "useful plants" should also be understood to include useful plants which have been transformed by the use of recombinant DNA techniques so that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, in particular from bacteria of the genus Bacillus.

[0093] Examples of such plants are YieldGard® (corn varieties expressing the CryIA(b) toxin); YieldGard Rootworm® (corn varieties expressing the CryIIIB(b1) toxin); YieldGard Plus® (corn varieties expressing the CryIA(b) and CryIIIB(b1) toxins); Starlink® (corn varieties expressing the Cry9(c) toxin); Herculex I® (corn varieties expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to glufosinate ammonium herbicides); NuCOTN 33B® (cotton varieties expressing the CryIA(c) toxin); Bollgard I® (cotton varieties expressing the CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxins); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) resistance trait), Agrisure® RW (a corn rootworm resistance trait), and Protecta®.

[0094] Plant crops or their seed material can be both herbicide-resistant and insect-feeding-resistant at the same time (a "crossover" of transformation events). For example, seeds can be capable of expressing the insecticidal Cry3 protein and also exhibit tolerance to glyphosate.

[0095] Crop plants should be understood to include those obtained by conventional methods of breeding or by genetic engineering and containing so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor).

[0096] The compounds of formula (I) (or compositions containing them) can be used to control undesirable plants (collectively "weeds"). The weeds to be controlled include monocotyledonous plant species such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, and Setaria. and Sorghum plants, as well as dicotyledonous plant species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium plants.

[0097] The compound of formula (I) can be used in unmodified form or, preferably, with formulation auxiliaries, such as carriers, solvents, and surfactants (SAA), conventionally used in the field of formulation to provide herbicidal compositions. Thus, the present invention 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.

[0098] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of a compound of formula I and 1 to 99.9% by weight of formulation adjuvants, preferably including 0 to 25% by weight of surfactants.

[0099] The composition can be selected from a number of formulation types, including emulsifiable concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), oil emulsions (EO), aqueous emulsions (EW), microemulsions (ME), oil dispersions (OD), oil-flowable formulations (OF), oil-liquid formulations (OL), soluble concentrates (SL), ultra-low-temperature suspensions (SU), ultra-low-temperature liquids (UL), technical concentrates (TK), wettable powders (DC), water-soluble dusts (SP), wettable powders (WP), and water-soluble granules (SG). The formulation type selected in each case will depend on the specific purpose envisaged and the physical, chemical, and biological properties of the compound of formula (I).

[0100] Water-soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (e.g., sodium bicarbonate, sodium carbonate, or magnesium sulfate) or one or more water-soluble organic solids (e.g., polysaccharides), and optionally with one or more wetting agents, one or more dispersing agents, or a mixture of the aforementioned agents to improve water dispersibility / solubility. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0101] 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, preferably one or more dispersing agents to facilitate dispersion in liquid, and optionally one or more suspending agents. This mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG).

[0102] Granules (GR) can be formed by granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) from preformed blank granules into a porous granular material (e.g., pumice, attapulgite clay, fuller's earth, diatomaceous earth, or ground corncob, etc.), or by adsorbing a compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material (e.g., sand, silicates, inorganic carbonates, sulfates, or phosphates, etc.), and optionally drying. Agents commonly used to aid absorption or adsorption include solvents (e.g., aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and binders (e.g., polyvinyl acetate, polyvinyl alcohol, dextrin, sugar, and vegetable oil, etc.). One or more other additives (for example, an emulsifying agent, wetting agent, or dispersing agent) may also be included in the granules.

[0103] Wettable powders (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 surfactants (e.g., to improve water dilution or prevent crystallization in the spray tank).

[0104] Emulsifiable concentrates (EC) or aqueous emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers, or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (e.g., alkylbenzenes or alkylnaphthalenes, examples of which include SOLVESSO 100, SOLVESSO 150, and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (e.g., cyclohexanone or methylcyclohexanone), and alcohols (e.g., benzyl alcohol, furfuryl alcohol, or butanol), N-alkylpyrrolidones (e.g., N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (e.g., C8-C9), and the like. 10 These include fatty acid dimethylamides and chlorinated hydrocarbons. EC products can spontaneously emulsify when added to water to produce emulsions that are stable enough for spray application via suitable equipment.

[0105] The preparation of EW involves obtaining the compound of formula (I) either as a liquid (if it is not liquid at room temperature, it can be melted at a moderate temperature, typically below 70°C) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution under high shear into water containing one or more SAAs to produce an emulsion. Suitable solvents 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.

[0106] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents and one or more SAA to spontaneously form a thermodynamically stable, isotropic liquid formulation. The compound of formula (I) is initially present either in water or in a solvent / SAA blend. Suitable solvents for use in MEs include those described herein above 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 can be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. MEs are suitable for dilution into water and either remain microemulsions or form traditional oil-in-water emulsions.

[0107] Suspension concentrates (SCs) may comprise aqueous or non-aqueous suspensions of finely divided, insoluble solid particles of the compound of formula (I). SCs may be prepared by ball milling or bead milling a solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to slow the rate at which the particles settle. Alternatively, the compound of formula (I) may be dry-milled and added to water containing the agents previously described herein to produce the desired final product.

[0108] 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 vehicle (e.g., water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized, manual spray pump.

[0109] Capsule suspensions (CS) can be prepared in a manner similar to the preparation of EW formulations, but with an additional polymerization step to obtain an aqueous dispersion of oil droplets, each oil droplet encapsulated by a polymeric shell and containing 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 compositions can provide controlled release of the compound of formula (I), and they can be used for seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymer matrix to provide a slow, controlled release of the compound.

[0110] The present compositions may contain one or more additives to improve the biological performance of the composition, for example, by improving wetting, retention, or distribution on a surface; rain resistance on the treated surface; or uptake or mobility of the compound of formula (I). Such additives include surfactants (SAA), spray additives based on oils, such as certain mineral oils or natural vegetable oils (e.g., soybean oil and rapeseed oil), modified vegetable oils such as methylated rapeseed oil (MRSO), and blends of these with other bio-enhancing adjuvants (components that may aid or modify the action of the compound of formula (I)).

[0111] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0112] Suitable SAAs of the cationic type include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0113] Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butyl naphthalene sulfonate, 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-carboxylate), phosphate esters (products from the reaction of one or more fatty alcohols with phosphoric acid (predominantly monoesters) or phosphorus pentoxide (predominantly di-esters), e.g., lauryl alcohol with tetraphosphoric acid; further, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphates / sulfates of tristyrylphenol.

[0114] Suitable SAAs of the amphoteric type include betaine, propionate and glycinate.

[0115] Suitable SAAs of the non-ionic type include the condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of the above partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (such as fatty acid polyethylene glycol esters); amine oxides (such as lauryl dimethylamine oxide); lecithin and sorbitan and their esters, alkyl polyglycosides, and tristyrylphenols.

[0116] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0117] 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 which 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, broclozone, bromacil, bromoxynil, butachlor, and bromochlor. Tafenacil, 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 (its choline salt and 2-ethyl hexyl esters), 2,4-DB, desmedipham, dicamba (aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, and their potassium and sodium salts), diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrion, diquat dibromide, diuron, epirifenacil, ethalfluralin, ethofumesate, fenoxaprop (fenoxaprop) including oxaprop-P-ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), fluchloraminopyr (including fluchloraminopyr-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), halaxifen (including haloxyfop-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, icaforin (icaforin-methyl), including R-Imazamox, Imazapic, Imazapyr, Imazethapyr, Indaziflam, Indorauxipyr (including Indorauxipyr-cyanomethyl), Iodosulfuron (including Iodosulfuron-methyl-sodium), Iofensulfuron (including Iofensulfuron-sodium), Ioxynil, Iptriazopiride, Isoproturon, Isoxaflutole, Lancotrione, MCPA, MCPB, Mecoprop-P, Mesosulfuron (including Mesosulfuron-methyl), Mesotrione, Metamitron , metazachlor, methiozoline, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (pyraflufen-ethyl) including quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metallochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbutylazine, terbutryn, tetflupyrolimet, thiencarbazone,Thifensulfuron, thiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, trialate, 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)-2-methylpropional) -4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4 -Hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-Hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-Hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy oxy-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 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, methyl 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-cyclopento[d]isoxazole-6a-carboxylate, 2-[(2-bromo-6-fluoro-phenyl)methoxy]-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptane, and (isopropylideneamino)6-amino-2-(4-chloro-2-fluoro-3-methoxy-phenyl)-5-methoxy-pyrimidine-4-carboxylate.

[0118] The compound of formula (I) may also be in the form of an ester or salt, as described, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012. The mixing ratio of the compound of formula (I) to the compound of formula (I) is preferably 1:100 to 1000:1.

[0119] This mixture can advantageously be used in the above-mentioned formulations (in which case the term "active ingredient" relates to the respective mixture of the compound of formula (I) and the mixing partner).

[0120] The compound or mixture 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 a mixture of the compound of formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl, and / or metcamifen.

[0121] The safeners of the compounds of formula (I) can also be used as described, for example, in The Pesticide Manual, 16 th Edition (BCPC), 2012. 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.

[0122] 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.

[0123] The compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to the cropland or plants to be treated simultaneously or successively with additional compounds. These additional compounds can be, for example, fertilizers or micronutrient 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 together with additional carriers, surfactants, or application-promoting adjuvants commonly used in the formulation art.

[0124] As used herein, the term "habitat" means the field in which plants are growing or where seeds of cultivated plants are sown or where seeds will be sown in the soil. It includes the soil, seeds, and seedlings, as well as established vegetation.

[0125] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0126] The term "plant propagation material" is understood to refer to plant material, such as reproductive parts such as seeds, and cuttings or tubers, for example, potatoes, which can be used for plant propagation. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts may be mentioned. Germinated plants and seedlings that will be transplanted after germination or emergence from the soil may also be mentioned. These seedlings may be protected by a complete or partial treatment by immersion before transplanting. Preferably, "plant propagation material" is understood to refer to seeds.

[0127] Pesticides referred to herein using their common names are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0128] The compounds of formula (I) can be used in unmodified form, or preferably with the adjuvants conventionally used in the technical field of formulation.For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and also, for example, encapsulated in polymeric materials.As well as the type of composition, the application method, such as spraying, spraying, dusting, granulation, coating or pouring, is selected according to the intended purpose and the circumstances at hand.The composition can also contain further adjuvants, such as stabilizers, antifoaming agents, viscosity modifiers, binders or tackifiers, as well as fertilizers, micronutrient donors or other formulations for achieving special effects.

[0129] For example, for agricultural applications, suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0130] The compound of formula (I) is usually used in the form of a composition, and can be applied to the cropland or the plants to be treated simultaneously or successively with other compounds.These other compounds can be, for example, fertilizers or micronutrient 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 together with additional carriers, surfactants or application-promoting adjuvants that are commonly used in the technical field of formulation.

[0131] The compound of formula (I) may be the sole active ingredient of 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.

[0132] Typically, the formulations contain 0.01 to 90% by weight of active agent, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of inactive substances and adjuvants for solid or liquid formulations, where the active agent consists of at least the compound of formula (I) together with components (B) and (C), and optionally other active agents, particularly biocides or preservatives. A concentrate-form composition generally contains about 2 to 80%, preferably about 5 to 70%, by weight of active agent. The application form of the formulation may contain, for example, 0.01 to 20%, preferably 0.01 to 5%, by weight of active agent. Commercially available products will preferably be formulated as concentrates, but end users will typically use diluted formulations.

[0133] The following table illustrates examples of individual compounds of formula (I) according to the present invention. [ka]

[0134] [Table 1]

[0135] Table A-1 provides 47 compounds A-1.001 to A-1.048 of formula (I), in which R 1 is methyl and R 2 is 3,4-dichlorophenyl, and R 3 is hydrogen, and R 4 are defined in Table 1.

[0136] Table A-2 provides 47 compounds of formula (I), A-2.001 to A-2.048, in which R 1 is ethyl, and R 2 is 3,4-dichlorophenyl, and R 3 is hydrogen and R 4 are defined in Table 1.

[0137] Table A-3 provides 47 compounds of formula (I), A-3.001 to A-3.048, in which R 1 is ethyl, and R 2 is 3,4-dichlorophenyl, and R 3 is methyl, and R 4 are defined in Table 1.

[0138] Table A-4 provides 47 compounds of formula (I), A-4.001 to A-4.048, in which R 1 is ethyl, and R 2 is 3-chloro-4-cyanophenyl, and R 3 is hydrogen, and R 4 are defined in Table 1.

[0139] Table A-5 provides 47 compounds of formula (I), A-5.001 to A-5.048, in which R 1 is ethyl, and R2 is 3,4-difluorophenyl, and R 3 is hydrogen, and R 4 are defined in Table 1.

[0140] Table A-6 provides 47 compounds A-6.001 to A-6.048 of formula L1, where R 1 is ethyl, and R 2 is (5,6-dichloro-3-pyridyl), and R 3 is hydrogen, and R 2 are defined in Table 1.

[0141] Formulation Examples

[0142] [Table 2]

[0143] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to give a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0144] [Table 3]

[0145] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to give a powder that can be used directly for seed treatment.

[0146] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0147] Emulsions of any desired dilution that can be used for plant protection can be obtained from this concentrate by dilution with water.

[0148] [Table 4]

[0149] Ready-to-use dusts can be obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry seed dressing.

[0150] Extruded Granules Active ingredient [compound of formula (I)] 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0151] The active ingredient is mixed with the adjuvants, milled, and the mixture is moistened with water, extruded, and then dried in a stream of air.

[0152] Coated granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0153] The finely ground active ingredient is applied uniformly in a mixer to kaolin moistened with polyethylene glycol, thus obtaining non-dusting coated granules.

[0154] 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%

[0155] The finely divided active ingredient is intimately mixed with adjuvants to give a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water. Such dilutions can be used to treat plant propagation material as well as living plants by spraying, pouring or immersion to protect them from microbial infestation.

[0156] Flowable seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrenephenol with 10-20 mol 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%

[0157] The finely divided active ingredient is intimately mixed with adjuvants to give a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water. Such dilutions can be used to treat plant propagation material as well as living plants by spraying, pouring or immersion to protect them from microbial infestation.

[0158] Sustained-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 (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size is reached. To this emulsion, a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added. 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. The capsule suspension formulation contains 28% active ingredient. The capsule median diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in a suitable device for the purpose. [Example]

[0159] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention, as referenced in Table 2 below.

[0160] Throughout this specification temperatures are given in degrees Celsius (°C) and "mp" means melting point.

[0161] List of abbreviations °C = degrees Celsius, d = doublet, dd = doublet of doublets, DMSO = dimethyl sulfoxide, M = moles, m = multiplet, MHz = megahertz, q = quartet, s = singlet, t = triplet.

[0162] Example 1: Synthesis of ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (compound 4)

[0163] Step 1: Synthesis of ethyl-2-[amino-(3,4-dichlorophenyl)methylene]-3-oxo-butanoate [ka] To a stirred solution of 3,4-dichlorobenzonitrile (20.0 g, 116 mmol) in toluene (150 mL) at 0°C and nitrogen, tetrachlorostannane (1.00 mol / L, 116 mL, 116 mmol) was added, followed by ethyl 3-oxobutanoate (14.8 mL, 116 mmol). The resulting reaction mixture was stirred at room temperature for 0.5 h and then at 100°C for 3 h. The cooled reaction mixture was diluted with ethyl acetate, and saturated aqueous sodium bicarbonate solution was added. The phases were separated, and the aqueous phase was extracted into ethyl acetate (x2). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0 to 80% ethyl acetate in cyclohexane as the eluent to give ethyl 2-[amino-(3,4-dichlorophenyl)methylene]-3-oxo-butanoate (22.5 g, 67.0 mmol) as an off-white semisolid. 1H NMR (400 MHz, DMSO-d6) δ = 7.72 (d, 1H), 7.60 (d, 1H), 7.28 (dd, 1H), 5.50 (q, 2H), 2.22 (s, 3H), 0.72 (t, 3H).

[0164] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-4-oxo-1H-pyridine-3-carboxylic acid [ka] To N,N-dimethylformamide (9.00 mL, 116 mmol) cooled to 0° C. was added phosphoryl trichloride (9.09 mL, 99.3 mmol). The mixture was stirred at 0° C. for 10 minutes and then at room temperature for 1 hour. After this time, the mixture was cooled to 0° C., and a solution of ethyl-2-[amino-(3,4-dichlorophenyl)methylene]-3-oxo-butanoate (10.0 g, 33.1 mmol) in N,N-dimethylformamide (50 mL) was slowly added. The resulting reaction mixture was stirred at 80° C. for 16 hours and then at 120° C. for 18 hours. Upon cooling, the mixture was quenched by the addition of water and extracted into ethyl acetate (×3). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0 to 10% methanol in dichloromethane to give 2-(3,4-dichlorophenyl)-4-oxo-1H-pyridine-3-carboxylic acid (5.10 g, 16.2 mmol) as a light brown solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.08 (d, 1H), 7.81 (d, 1H), 7.72 (d, 1H), 7.49 (d, 1H), 6.81 (d, 1H).

[0165] Step 3: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate [ka] To a stirred solution of 2-(3,4-dichlorophenyl)-4-oxo-1H-pyridine-3-carboxylic acid (6.00 g, 21.1 mmol) in N,N-dimethylformamide (60 mL) was added disodium carbonate (8.95 g, 84.5 mmol) followed by iodoethane (3.29 g, 21.1 mmol) at room temperature. The reaction mixture was heated at 70 °C for 3 hours. The cooled reaction mixture was diluted with water and extracted into ethyl acetate (×3). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 0–15% methanol in dichloromethane as eluent to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (1.80 g, 5.29 mmol) as a brown solid. 1H NMR(400MHz,DMSO-d6)δ=7.89(d,1H),7.83-7.81(m,2H),7.47-7.45(dd,1H) ,6.30(d,1H),3.90-3.82(m,2H),3.67-3.61(q,2H),1.09(t,3H),0.82(t,3H)

[0166] Step 4: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate [ka] To a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (1.50 g, 4.41 mmol) in acetonitrile (15.0 mL) at room temperature was added 1-iodopyrrolidine-2,5-dione (1.29 g, 5.73 mmol) and trifluoroacetic acid (0.036 mL, 0.441 mmol). The reaction mixture was heated at 80° C. for 5 hours. The cooled reaction mixture was diluted with water and extracted into ethyl acetate (×3). The combined organic extracts were washed successively with water (×3) and brine, then dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0 to 50% ethyl acetate in hexane as eluent to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate (1.35 g, 2.75 mmol) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.55 (s, 1H), 7.87-7.81 (m, 2H), 7.49 (d, 1H), 3.88-3.82 (q, 2H), 3.72-3.65 (q, 2H), 1.06 (t, 3H), 0.98 (t, 3H).

[0167] Step 5: Synthesis of ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate [ka] To a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate (200 mg, 0.408 mmol) in a mixture of acetonitrile (5 mL) and water (2 mL) at room temperature was added (4-chlorophenyl)boronic acid (64 mg, 0.41 mmol) and potassium phosphate (259 mg, 1.22 mmol). The resulting reaction mixture was purged with argon for 5 minutes, after which P(t-Bu)Pd G4 (24 mg, 0.041 mmol) was added. The reaction mixture was purged with argon for an additional 2 minutes and then heated at 100 °C for 2 hours. The cooled reaction mixture was diluted with water and extracted with ethyl acetate (×2). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0 to 100% ethyl acetate in hexanes as eluent to give ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (160 mg, 0.337 mmol) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.21 (s, 1H), 7.91-7.75 (m, 3H), 7.61-7.49 (m, 4H), 3.95-3.85 (m, 2H), 3.75 (q, 2H), 1.17 (t, 3H), 0.89 (t, 3H).

[0168] Example 2: Synthesis of 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 1) [ka] To a stirred solution of ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (150 mg, 0.333 mmol) in a mixture of tetrahydrofuran (5 mL) and water (2 mL) at room temperature was added lithium hydroxide hydrate (42 mg, 1.0 mmol). The resulting reaction mixture was heated at 80° C. for 16 hours. The reaction mixture was acidified to pH 1 by the addition of 2 M aqueous hydrogen chloride solution and extracted into ethyl acetate. The combined organic extracts were evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on reverse-phase C-18 silica gel using a gradient of 0 to 100% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to give 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (0.085 g, 0.20 mmol) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.57 (s, 1H), 7.83-7.77 (m, 4H), 7.57 (d, 2H), 7.46 (dd, 1H), 3.84-3.79 (q, 2H), 1.18 (t, 3H).

[0169] Example 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-[2-fluoro-5-(trifluoromethoxy)phenyl]-4-oxo-pyridine-3-carboxylic acid (compound 5) Step 1: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylic acid [ka] To a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate (1.30 g, 2.79 mmol) in a mixture of tetrahydrofuran (5 mL), methanol (5 mL), and water (2 mL) was added lithium hydroxide hydrate (0.35 g, 8.4 mmol). The reaction mixture was heated with stirring at 80° C. for 16 hours. The cooled reaction mixture was evaporated to dryness under reduced pressure, and to the residue was added water (20 mL) and 2 M aqueous hydrogen chloride solution (10 mL). The solid precipitate was isolated by filtration and dried under reduced pressure to give 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylic acid as a light brown solid. 1H NMR (400MHz, DMSO-d6) δ=8.84(s,1H),7.78(dd,2H),7.43(dd,1H),3.72(q,2H),1.12(t,3H).

[0170] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-[2-fluoro-5-(trifluoromethoxy)phenyl]-4-oxo-pyridine-3-carboxylic acid [ka] A stirred solution of 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylic acid (350 mg, 0.80 mmol), [2-fluoro-5-(trifluoromethoxy)phenyl]boronic acid (197 mg, 0.88 mmol), and tripotassium phosphate (509 mg, 2.40 mmol) in a mixture of acetonitrile (10 mL) and water (2 mL) was purged with argon for 2 minutes. Methanesulfonato(tri-t-butylphosphino)(2'-methylamino-1,1'-biphenyl-2-yl)palladium(II) (47 mg, 0.08 mmol) was added to the reaction mixture, which was purged with argon for 3 minutes. The resulting reaction mixture was heated at 100°C for 2 hours. The cooled reaction mixture was diluted with water, acidified by the addition of 2M aqueous hydrogen chloride, and extracted into ethyl acetate (x2). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0 to 100% ethyl acetate in hexanes as eluent to give 2-(3,4-dichlorophenyl)-1-ethyl-5-[2-fluoro-5-(trifluoromethoxy)phenyl]-4-oxo-pyridine-3-carboxylic acid as a white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.57 (s, 1H), 7.87 (d, 1H), 7.81 (d, 1H), 7.60-7.48 (m, 4H), 3.79 (q, 2H), 1.18 (t, 3H).

[0171] [Table 5-1]

[0172] [Table 5-2]

[0173] [Table 5-3]

[0174] [Table 5-4]

[0175] [Table 5-5]

[0176] Biological Examples Seeds of various test species (Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Amaranthus palmeri (AMAPA), Zea mays (ZEAMX), Amaranthus retoflexus (AMARE), Solanum nigrum (SOLNI), Lolium perenne (LOLPE), Abutilon theophrasti (ABUTH)) are sown in standard soil in pots. After 8 days of cultivation in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient in a 50:50 acetone / water solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compound is applied at 1000 g / ha. 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 of testing, the plants are evaluated for the percentage of damage caused. Biological activity is shown in the table below on a 5-point scale (5 = 81-100%; 4 = 61-80%; 3 = 41-60%; 2 = 21-40%; 1 = 0-20%).

[0177] [Table 6]

[0178] Table 7

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, R 1 is C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, or C 3 ~C 6 is cycloalkyl; R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl moiety is selected from R 5 and optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 3 is hydrogen or C 1 ~C 6 is alkyl; R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and the heteroaryl moiety may be bonded to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each selected from R 6 and optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 5 is cyano, nitro, halogen, 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 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl, C 1 ~C 6 Alkylsulfonyl, C 1 ~C 6 Alkyl sulfonamides, 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; R 6 is cyano, nitro, halogen, oxo, 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 Alkoxy C 1 ~C 6 Alkoxy, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Alkenyloxy, C 2 ~C 6 Alkynyloxy, C 1 ~C 6 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl, C 1 ~C 6 Alkylsulfonyl, C 1 ~C 6 Alkyl sulfonamides, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkoxycarbonyl, C 1 ~C 6 Alkylaminocarbonyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkyl C 1 ~C 6 Alkoxy, N,N-di(C 1 ~C 4 alkyl)aminosulfonyl, C 3 ~C 6 Cycloalkylaminocarbonyl, N,N-di(C 1 ~C 4 alkyl)aminocarbonyl, phenoxy, or benzyloxy, where each cycloalkyl or phenyl moiety is R 8 or optionally substituted with one or two groups, which may be the same or different, of the formula Any two adjacent R 6 Groups, together with the carbon atoms to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclyl ring containing one or two heteroatoms selected from O and N, wherein said phenyl and heterocyclyl rings are R 9 and optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 8 is cyano, halogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 is alkoxy; R 9 is a halogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 alkoxy) or a salt or N-oxide thereof.

2. R 1 is C 1 ~C 3 The compound of claim 1 , wherein the aryl group is alkyl.

3. R 2 is phenyl or pyridyl, where each phenyl and pyridyl moiety is 5 3. The compound of claim 1 or claim 2, optionally substituted with one or two groups, which may be the same or different, represented by:

4. R 3 is hydrogen or C 1 ~C 3 The compound according to any one of claims 1 to 3, which is alkyl.

5. R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O, and the heteroaryl moiety may be bonded to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and the phenyl and heteroaryl moieties are each selected from R 6 The compound according to any one of claims 1 to 4, optionally substituted with 1, 2 or 3 groups, which may be the same or different, and which are represented by:

6. R 4 is phenyl or pyrazoyl, wherein the phenyl and pyrazoyl moieties are each R 6 6. The compound according to any one of claims 1 to 5, optionally substituted with 1, 2 or 3 groups, which may be the same or different, and which are represented by:

7. R 6 is cyano, nitro, halogen, oxo, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkoxy C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy C 1 ~C 4 Alkoxy, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Alkenyloxy, C 2 ~C 6 Alkynyloxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Alkyl sulfonamides, C 1 ~C 4 Alkylcarbonyl, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylaminocarbonyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkyl C 1 ~C 4 Alkoxy, N,N-di(C 1 ~C 3 alkyl)aminosulfonyl, C 3 ~C 6 Cycloalkylaminocarbonyl, N,N-di(C 1 ~C 3 alkyl)aminocarbonyl, phenoxy, or benzyloxy, where each cycloalkyl or phenyl moiety is R 8 or optionally substituted with one or two groups, which may be the same or different, of the formula Any two adjacent R 6 Groups, together with the carbon atoms to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclyl ring containing one or two heteroatoms selected from O and N, wherein said phenyl and heterocyclyl rings are R 9 optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by The compound according to any one of claims 1 to 6.

8. R 6 is a halogen, C 1 ~C 4 Alkoxy, C 1 ~C 4 haloalkoxy, or C 1 ~C 4 alkoxycarbonyl; or any two adjacent R 6 The groups, together with the carbon atoms to which they are attached, can form a phenyl ring, wherein said phenyl ring is R 9 The compound according to any one of claims 1 to 7, which is optionally substituted with one or two groups, which may be the same or different, and which are represented by:

9. R 9 The compound according to any one of claims 1 to 8, wherein is halogen or methoxy.

10. R 2 The compound according to any one of claims 1 to 9, wherein is 3,4-dichlorophenyl.

11. A herbicidal composition comprising a compound according to any one of claims 1 to 10 and an agriculturally acceptable formulation adjuvant.

12. 12. The herbicidal composition of claim 11, further comprising at least one additional pesticide.

13. 13. The herbicide composition of claim 12, wherein the additional pesticide is a herbicide or a herbicide safener.

14. 14. A method of controlling weeds in a locus, comprising applying to said locus of weeds a controlling amount of a composition according to any one of claims 11 to 13.

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

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