Herbicidal Inducer

Abstract

A compound of formula (I) (wherein the formula, the substituents are as defined in claim 1). The present invention further relates to herbicidal compositions comprising a compound of formula (I), and to the use of a compound of formula (I) for controlling weeds, particularly in crops of useful plants. [Formula 1] JPEG2026514482000040.jpg37160

Description

[Technical Field]

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

[0002] European Patent No. 0239391, European Patent No. 0127313, European Patent No. 0040082, British Patent No. 2182931, British Patent No. 2328614, International Publication No. 2022117445, International Publication No. 2022117446, and International Publication No. 2023 / 110664 describe pyridone derivatives as herbicides. [Overview of the project] [Means for solving the problem]

[0003] According to the present invention, a compound of formula (I): [ka] (In the formula, R 1 These are C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkyl, or C3-C6 cycloalkyl; R 2 is a phenyl or heteroaryl group, where the heteroaryl group is a 5-membered or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl group is R 5 Represented by , which may be the same or different, and may be optionally substituted with 1, 2, 3, or 4 bases; R 3 is hydrogen or a C1-C6 alkyl group; R 4 is hydrogen or halogen; 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 alkylsulfonamide, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl; and X is a halogen; Alternatively, a salt or N-oxide thereof is provided.

[0004] A problem with many current herbicides used to control undesirable vegetation before planting crops is that they can damage subsequent crops if planted immediately after application. Therefore, a herbicide that provides good control against already sprouted weeds while being safe for crops when applied before sprouting would be a major advantage over current herbicides.

[0005] Remarkably, the novel compounds of formula (I) not only possess a highly advantageous level of herbicidal activity for practical purposes, but also show little to no damage to several major crops, such as corn (zea mays), when applied before emergence, while simultaneously providing excellent control of desirable vegetation (weeds and native crops) when applied after emergence, thus making it possible to successfully use them immediately before planting new crops. In contrast, related compounds reported in the prior art show similar control of undesirable vegetation, but cause unacceptable damage to many crops, thus hindering their use.

[0006] Surprisingly, the novel compound of formula (I) was found to possess a highly advantageous level of herbicidal activity for practical purposes.

[0007] According to a second aspect of the present invention, an agricultural composition is provided comprising a herbicidal effective amount of the 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 agriculturally acceptable diluent or carrier.

[0008] A third aspect of the present invention provides a method for controlling weeds in a habitat, comprising applying a composition containing a compound of formula (I) in a weed control amount to the habitat.

[0009] According to a fourth aspect of the present invention, the use of the compound of formula (I) as a herbicide is provided. [Modes for carrying out the invention]

[0010] When it is indicated that substituents "may be optionally substituted", this means that they may be one or more identical or different substituents, for example, 1, 2, or 3 R 6 This means that the molecule may or may not have substituents. For example, C1-C6 alkyl groups substituted with one, two, or three halogens include -CH2Cl, -CHCl2, and -CCl 3、 Examples include, but are not limited to, the -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3 groups. Another example of C1-C6 alkoxy groups substituted with one, two, or three halogens includes, but are not limited to, the CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups.

[0011] As used herein, the term "cyano" means the -CN group.

[0012] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iod).

[0013] As used herein, the term "nitro" means the -NO2 group.

[0014] As used herein, the term "acetyl" means the -C(O)CH3 group.

[0015] As used herein, =O means an oxo group, such as the carbonyl (-C(=O)-) group.

[0016] As used herein, the term "C1-C6 alkyl" refers to a linear or branched hydrocarbon chain radical consisting only of carbon and hydrogen atoms, containing no unsaturation, and having 1 to 6 carbon atoms, bonded to the remainder of the molecule by single bonds. "C1-C4 alkyl" and "C1-C3 alkyl" should be interpreted accordingly as appropriate. Examples of C1-C6 alkyls include, but are not limited to, methyl, ethyl, n-propyl, and their isomers, such as isopropyl. The "C1-C6 alkylene" group refers to the corresponding definition of C1-C6 alkyl, except that such a group is bonded to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" should be interpreted accordingly as appropriate. Examples of C1-C6 alkylenes include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0017] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl radical, as generally defined above, that is substituted by one or more of the same or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted accordingly as appropriate. Examples of C1-C6 haloalkyls include, but are not limited to, trifluoromethyl.

[0018] As used herein, the term "C1-C6 alkoxy" refers to a radical of the formula -OR a (wherein R a is a C1-C6 alkyl radical as generally defined above). The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted accordingly as appropriate. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (iso-propoxy), and propoxy.

[0019] As used herein, the term "C1-C6 haloalkoxy" refers to C1-C6 alkoxy as generally defined above, substituted by one or more of the same or different halogen atoms. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted accordingly as appropriate. An example of C1-C6 haloalkoxy includes, but is not limited to, trifluoromethoxy.

[0020] As used herein, the term "C2-C6 alkenyl" refers to a straight-chain or branched-chain hydrocarbon chain radical consisting only of carbon and hydrogen atoms, containing at least one double bond which may be in either the (E) or (Z) configuration, and having 2-6 carbon atoms, bonded to the remainder of the molecule by a single bond. The term "C2-C3 alkenyl" should be interpreted accordingly as appropriate. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), and but-1-enyl.

[0021] As used herein, the term "C2-C6 alkynyl" refers to a linear or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one triple bond, and having 2 to 6 carbon atoms, bonded to the remainder of the molecule by single bonds. The term "C2-C3 alkynyl" should be interpreted accordingly as appropriate. Examples of C2-C6 alkynyls include, but are not limited to, ethynyl, propan-1-inyl, and buta-1-inyl.

[0022] As used herein, the term "C2-C6 alkenyloxy" refers to a C2-C6 alkenyl radical, as generally defined above, that is bonded to the rest of the molecule via an oxygen atom.

[0023] As used herein, the term "C2-C6 alkynyloxy" refers to a C2-C6 alkynyl radical, as generally defined above, that is bonded to the rest of the molecule via an oxygen atom.

[0024] As used herein, the term "C1-C6 alkoxy C1-C6 alkyl" refers to the formula R b Ure a -(In the formula, R b R is a C1-C6 alkyl radical as generally defined above, a This refers to radicals of C1-C6 alkylene radicals as generally defined above. The term "C1-C4 alkoxy C1-C4 alkyl" should be interpreted accordingly.

[0025] As used herein, the term "C1-C6 alkoxy C1-C6 alkoxy" refers to the formula R b Ure a O-(wherein, R a and R b Each of these terms independently refers to a radical (which is a C1-C6 alkyl radical as generally defined above). The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted accordingly.

[0026] As used herein, the term "C3-C6 cycloalkyl" refers to a radical that is a monocyclic saturated ring system containing 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted accordingly as appropriate. Examples of C3-C6 cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0027] As used herein, the term "C3-C6 cycloalkenyl" refers to a radical that is a monocyclic unsaturated ring system having 3 to 6 carbon atoms and containing at least one double bond. The terms "C3-C5 cycloalkenyl" and "C3-C4 cycloalkenyl" should be interpreted accordingly as appropriate. Examples of C3-C6 cycloalkenyls include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0028] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkyl" refers to a C3-C6 cycloalkyl ring that is bonded to the remainder of the molecule by a C1-C6 alkylene linking group as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkyls include, but are not limited to, cyclopropylmethyl.

[0029] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkoxy" refers to a C3-C6 cycloalkyl ring that is linked to the remainder of the molecule by a C1-C6 alkoxy linking group as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkoxys include, but are not limited to, cyclopropoxy.

[0030] As used herein, the term "C3-C6 cycloalkylaminocarbonyl" refers to a C3-C6 cycloalkyl ring bonded to the remainder of the molecule via an -NHC(O)- linking group. Examples of C3-C6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0031] When used in this specification, "C6~C 10 The term "aryl" refers to a 6- to 10-membered aromatic ring system consisting only of carbon and hydrogen atoms, which may be monocyclic, bicyclic, or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, or indenyl.

[0032] When used in this specification, "C6~C 10 The term "aryl C1-C3 alkyl" refers to the aryl portion, as generally defined above, which is bonded to the remainder of the molecule by a C1-C3 alkylene linking group as defined above.

[0033] As used herein, the term "phenoxy" refers to a phenyl ring that is bonded to the rest of the molecule via an oxygen atom.

[0034] As used herein, the term "benzyloxy" refers to the benzyl ring bonded to the rest of the molecule via an oxygen atom.

[0035] As used herein, the term “heterocyclyl” refers to a stable four-membered, five-membered, or six-membered non-aromatic monocyclic ring containing one, two, or three heteroatoms, where the heteroatoms are individually selected from nitrogen, oxygen, and sulfur. Heterocyclyl radicals may be bonded to the remainder of the molecule via carbon atoms or heteroatoms. Examples of heterocyclyls include, but are not limited to, azilidinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

[0036] As used herein, the term "heteroaryl" refers to a five- or six-membered aromatic monocyclic ring radical containing one, two, three, or four heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryls include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridadinyl, pyrimidyl, or pyridyl.

[0037] As used herein, the term "C1-C6 alkylcarbonyl" refers to the formula -C(O)R a (In the formula, R a This refers to a radical of a C1-C6 alkyl radical (as generally defined above). Examples of C1-C6 alkylcarbonyls include acetyl, but are not limited to this.

[0038] As used herein, the term "C1-C6 alkoxycarbonyl" refers to the formula -C(O)OR a (In the formula, R a This refers to radicals of C1-C6 alkyl radicals as generally defined above.

[0039] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to the formula -C(O)NHR a (In the formula, Ra This refers to a radical of a C1-C6 alkyl radical as generally defined above. An example of a C1-C6 alkylaminocarbonyl is ethylcarbamoyl (i.e., ethylaminocarbonyl), but it is not limited to this.

[0040] As used herein, the term "N,N-di(C1~C4 alkyl)aminocarbonyl" refers to the formula -C(O)N(R a )(R b )(wherein, R a and R b Each of these independently refers to a radical (which is a C1-C4 alkyl radical as generally defined above). The term "N,N-di(C1-C3 alkyl)aminocarbonyl" should be interpreted accordingly. An example of an N,N-di(C1-C4 alkyl)aminocarbonyl is dimethylcarbamoyl (i.e., N,N-di(methyl)aminocarbonyl), but it is not limited to this.

[0041] As used herein, the term "N,N-di(C1-C4 alkyl)aminosulfonyl" refers to the formula -S(O)2N(R a )(R b )(wherein, R a and R b Each of these independently refers to a radical (which is a C1-C4 alkyl radical as generally defined above). The term "N,N-di(C1-C3 alkyl)aminosulfonyl" should be interpreted accordingly. An example of N,N-di(C1-C4 alkyl)aminosulfonyl is diethylsulfamoyl (i.e., N,N-di(methyl)aminosulfonyl), but it is not limited to this.

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

[0043] As used herein, the term "C1-C6 alkylsulfinyl" refers to the formula -S(O)R a (In the formula, R a This refers to radicals of C1-C6 alkyl radicals 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.

[0044] As used herein, the term "C1-C6 alkylsulfonyl" refers to the formula -S(O)2R a (In the formula, R a This refers to the radical of a C1-C6 alkyl radical (as generally defined above). The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted accordingly. Examples of C1-C6 alkylsulfonyls include, but are not limited to, methylsulfonyl.

[0045] As used herein, the term "C1-C6 alkylsulfonamide" refers to the formula -NHS(O)2R a (In the formula, R a This refers to radicals of C1-C6 alkyl radicals as generally defined above.

[0046] The presence of one or more possible stereoelements in a compound of formula (I) means that the compound may exist in optical isomeric forms, i.e., enantiomeric or diastereomeric forms. Atropisomers may also arise as a result of restricted rotation around a single bond. Formula (I) is intended to encompass all of its possible isomeric forms and mixtures thereof. The present invention encompasses all of its possible isomeric forms and mixtures thereof relating to the compound of formula (I). Similarly, formula (I) is intended to encompass all possible tautomers. The present invention encompasses all possible tautomeric forms relating to the compound of formula (I).

[0047] In each case, the compound of formula (I) according to the present invention exists in a free form, an oxidized form as an N-oxide, or a salt form, for example, an agriculturally useful salt form. It is preferable that the compound of formula (I) can form salts 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 compound of formula (I) can form a chloride or a 2,2,2-trifluoroacetate.

[0048] N-oxides are oxidation 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).

[0049] The following list relates to the compound of formula (I) and the substituent R 1 , R 2 , R 3 , R 4 , and R 5 This provides definitions, including preferred definitions, with respect to any of these substituents. Any of the definitions shown below for any one of these substituents may be combined with any other definition of substituents shown below or elsewhere in this specification.

[0050] R1 is a 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 a 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 a C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 alkyl, or C3-C4 cycloalkyl. More preferably, R 1 These are methyl, ethyl, n-propyl, methoxy, 2-methoxyethyl, ally, and propane-2-inyl. In one set embodiment, R 1 The element is a C1-C3 alkyl group, preferably methyl or ethyl, and more preferably ethyl.

[0051] R 2 is a phenyl or heteroaryl group, where the heteroaryl group is a 5-membered or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl group is R 5 It may be optionally substituted with one, two, three, or four groups, which may be the same or different, represented by .

[0052] Preferably, R 2 is a phenyl or heteroaryl compound, where the heteroaryl portion is a 5-membered or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl portion is R 5 It may be optionally substituted with one, two, or three elements, which may be the same or different, represented by .

[0053] Comfortable, R 2is a phenyl or heteroaryl compound, where the heteroaryl portion is a 5-membered or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and each phenyl and heteroaryl portion is R 5 It may be optionally substituted with one, two, or three elements, which may be the same or different, represented by .

[0054] Comfortable, R 2 is a phenyl or heteroaryl compound, where the heteroaryl portion is a 5-membered or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and each phenyl and heteroaryl portion is R 5 It may be optionally substituted with one or two groups, which may be the same or different, represented by . More preferably, R 2 is phenyl or pyridyl, where each phenyl and pyridyl portion is R 5 It may be optionally substituted with one or two elements, which may be the same or different, represented by .

[0055] In one set embodiment, R 2 R 5 A phenyl represented by , which may be optionally substituted with one or two groups, which may be the same or different. In another set of embodiments, R 2 R 5 A phenyl represented by which two groups, which may be the same or different, may be optionally substituted. In a further set of embodiments, R 2 is 3-chloro-4-cyanophenyl, 3,4-dichlorophenyl, or 3,4-difluorophenyl. In a more preferred set embodiment, R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl. In a particularly preferred set embodiment, R 2 It is 3,4-dichlorophenyl.

[0056] R 3is hydrogen or a C1-C6 alkyl group. Preferably, R 3 R is hydrogen or a C1-C4 alkyl group, more preferably hydrogen or a C1-C3 alkyl group. More preferably, R 3 is hydrogen, methyl, or ethyl. More preferably, R 3 is hydrogen or ethyl. More preferably, R 3 It is hydrogen.

[0057] R 4 is hydrogen or halogen. Preferably, R 4 is hydrogen, chloro, fluoro, or bromo. More preferably, R 4 is hydrogen or bromine. In one embodiment, R 4 It is hydrogen.

[0058] R 5 These are 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 alkylsulfonamide, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl.

[0059] Preferably, R 5 These are 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 alkylsulfonamide, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0060] Comfortable, R 5 These are 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 alkylsulfonamide, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0061] Comfortable, 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. More preferably, R 5 These are cyano, nitro, chloro, fluoro, methyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2-difluoroethoxy, methoxymethyl, acetyl, or cyclopropyl.

[0062] In one set embodiment, R 5 is cyano or halogen, preferably halogen, more preferably R 5 is cyano or chloro, more preferably R 5 It is chloroform.

[0063] X is a halogen. Preferably, X is chloro, fluoro, or iodine. More preferably, X is chloro or fluoro. Most preferably, X is chloro.

[0064] In the compound of formula (I) according to the present invention, preferably, R 1is C1-C3 alkyl; R 2 is R 5 is phenyl substituted with two groups, which may be the same or different, represented by R R 3 is C1-C3 alkyl; R 4 is hydrogen or halogen; R 5 is cyano or halogen; and X is halogen.

[0065] In another set of embodiments, R 1 is C1-C3 alkyl; R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl; R 3 is hydrogen, methyl or ethyl; R 4 is hydrogen or halogen; and X is halogen.

[0066] In another set of embodiments, R 1 is C1-C3 alkyl; R 2 is 3,4-dichlorophenyl; R 3 is hydrogen or ethyl; R 4 is hydrogen; and X is chloro, fluoro, or iodo.

[0067] In another set of embodiments, R 1 is ethyl; R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl; R 3 is hydrogen, methyl or ethyl; R 4 is hydrogen or halogen; and X is halogen.

[0068] In another set of embodiments, R 1 It is ethyl; R 2 These are 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl; R 3 is hydrogen; R 4 is hydrogen; and X is Chlorophyll.

[0069] In preferred embodiments, the compound of formula (I) is selected from 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylic acid (compound 2) and 6-chloro-2-(4-chloro-3-cyanophenyl)-1-ethyl-4-oxopyridine-3-carboxylic acid (compound 6).

[0070] The compounds of the present invention can be prepared as shown in the following scheme, and in the scheme, unless otherwise specified, the definitions of each variable are as defined above with respect to the compound of formula (I). A general method for preparing the compound of formula (I) is described below. Unless otherwise specified in the text, R 1 , R 2 , R 3 , R 4 And X are as previously defined herein. The starting materials used for the preparation of the compounds of the present invention may be purchased from a regular commercial supplier or prepared by known methods. The starting materials and intermediates may be purified by state-of-the-art techniques such as chromatography, crystallization, distillation and filtration before use in the next step. Scheme 1: [ka]

[0071] Compound of formula (I) (wherein R 3The compound of formula (A) (wherein R is hydrogen) is mixed with any cosolvent (such as water) in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate, or tetrahydrofuran) and then mixed with the compound of formula (A) (wherein R is hydrogen). 3 However, the compounds (which are C1-C6 alkyl) can be prepared by hydrolysis with a suitable base (such as sodium hydroxide or lithium hydroxide), a suitable Brønsted acid (such as trifluoroacetic acid, hydrochloric acid, or sulfuric acid), or a suitable Lewis acid (such as scandium triflate or zinc triflate). When a base is used, the product is obtained by subsequent acidification with a suitable acid (such as hydrochloric acid). Compounds of formula (A) may be further prepared by methods as described below. Scheme 2: [ka]

[0072] Compound of formula (B) (wherein R 3 The compound of formula (A) (wherein R is C1-C6 alkyl and X is a chloride) is obtained by a halogen exchange reaction using a suitable halogen source (such as trimethylsilyl bromide or tetramethylammonium fluoride) under the same conditions as in the literature. 3 However, it can be converted to a C1-C6 alkyl group (where X is a bromide or fluoride). Typically, this is carried out at high temperature in a suitable solvent (such as dimethylformamide or dichloromethane). This is shown above in Scheme 2. Scheme 3: [ka]

[0073] Compound of formula (C) (wherein R 3 However, the C1-C6 alkyl compounds can be converted to the compound of formula (B) (wherein R is R) by Sandmeyer halogenation with a suitable halogen source (such as copper(I) chloride) under the same conditions as in the literature. 3However, it can be converted to a C1-C6 alkyl group. Typically, the reaction is carried out by reacting the compound of formula (C) with an optional cosolvent (such as water) in a suitable solvent (such as acetonitrile or dichloromethane) at high temperature in the presence of a suitable halogen source (such as copper(I) chloride) and a suitable acid (such as hydrogen chloride) and a suitable oxidizing agent (such as sodium nitrite or isoamyl nitrite). This is shown above in Scheme 3. Scheme 4: [ka]

[0074] Compound of formula (D) (wherein R 3 However, the compound (C) of formula (R) (wherein R) is obtained by adding a suitable base (such as sodium ethoxide) in a suitable solvent (such as ethanol) 3 However, it can be converted to C1-C6 alkyl groups. This is shown above in Scheme 4. Scheme 5: [ka]

[0075] The compound of formula (D) can be prepared by reacting the compound of formula (E) with the compound of formula (F) at a high temperature in the presence of a solvent (such as acetic anhydride) and an optional co-solvent (such as acetonitrile). This is shown above in Scheme 5. The compounds of formula (F) and (E) are commercially available, but may also be prepared by methods well known to those skilled in the art. Scheme 6: [ka]

[0076] The compound of formula (A) can be prepared by decarboxylating the compound of formula (G) with a halogenating agent (such as iodine) at high temperature in a suitable solvent (such as dimethyl sulfoxide or acetonitrile) in the presence of an optional base (such as potassium phosphate), followed by halogenation. This is shown above in Scheme 6. Other decarboxylation-halogenation conditions from the literature may also be used. Scheme 7: [ka]

[0077] The compound of formula (G) can be prepared by oxidizing the compound of formula (H) (wherein R is an aldehyde or alcohol) (wherein R is an aldehyde or alcohol) in a suitable solvent (wherein R is an aldehyde or alcohol) in the presence of a base (wherein sodium phosphate is a suitable solvent) (wherein R Scheme 8: [ka]

[0078] Compounds of formula (I) (wherein R is an aldehyde, alcohol, or carboxylic acid) can be prepared by treating a compound of formula (J) with a suitable oxidizing agent (4-methyl-4-oxide-morpholine-4-ium) in a suitable solvent (such as acetonitrile), optionally in the presence of a base (N-ethyl-N-isopropyl-propane-2-amine). This is shown above in Scheme 8. Scheme 9: [ka]

[0079] The compound of formula (J) can be prepared by reacting the compound of formula (K) with the compound of formula (E) at a high temperature (e.g., 140°C) in the presence of an optional solvent (such as xylene). Both compounds of formula (E) and (K) are commercially available, but may also be prepared by methods well known to those skilled in the art, as shown above in Scheme 9. Scheme 10: [ka]

[0080] The compound of formula (E) can be prepared by reacting the β-ketoester of formula (M) with an amine salt. The amine salt can be prepared by acidifying the amine of formula (L) in situ with a suitable acid (such as acetic acid). This amine salt can then be reacted with the compound of formula (M) in a suitable solvent (such as toluene or tetrahydrofuran) in the presence of an acid (such as acetic acid) and a drying agent (such as a molecular sieve of 4 Å). This is shown above in Scheme 10. The compound of formula (M) is commercially available, but may also be prepared using the conditions described below in Scheme 11. The compound of formula (L) is commercially available, but may also be prepared by methods reported in the literature. Scheme 11: [ka]

[0081] The compound of formula (M) can be prepared by treating the carboxylic acid of formula (O) (wherein A is hydroxyl or Cl) with an optional coupling agent (such as 1,1'-carbonyldiimidazole) at high temperature in a suitable solvent (such as tetrahydrofuran). The intermediate can then be reacted with the compound of formula (N) (such as potassium-3-methoxy-3-oxopropanoate) at high temperature in a suitable solvent (such as tetrahydrofuran or acetonitrile) in the presence of an inorganic salt (such as magnesium chloride). This is shown above in Scheme 11. The compounds of formula (O) and formula (N) may be commercially available or prepared by methods well known to those skilled in the art.

[0082] The present invention provides a method for controlling weeds in a habitat, further comprising the application of a weed-controlling composition comprising a compound of formula (I) to the habitat. Furthermore, the present invention may further provide a method for selectively controlling weeds in a habitat containing useful (crop) plants and weeds, further comprising the application of a weed-controlling composition according to the present invention to the habitat. "Control" means killing, reducing or delaying growth, or preventing or reducing germination. It is noted that the compounds of the present invention exhibit much improved selectivity compared to known, structurally similar compounds. Generally, the plants to be controlled are undesirable plants (weeds). "Habitat" means a place where plants are growing or will grow. The application may be applied to habitats of crop plants before and / or after germination. Some crop plants are inherently resistant to the herbicidal effect of compounds of formula (I).

[0083] The application amount of the compound of formula (I) can vary over a wide range and depends on soil properties, application method (pre-germination or post-germination; seed coating; application to planting furrows; no-till application, etc.), crop plants, weeds to be controlled, prevailing climatic conditions, and other factors determined by the application method, timing, and target crop. The compound of formula (I) according to the present invention is generally applied in amounts of 10 to 2500 g / ha, particularly 25 to 1000 g / ha, and more particularly 25 to 250 g / ha.

[0084] Application is generally carried out by spreading the composition, typically using a wide-area spreader mounted on a tractor, but other methods such as powdering (in the case of powders), drip irrigation (drip), or drench may also be used.

[0085] The term "useful plants" should be understood to include useful plants that have been conferred resistance to herbicides such as bromoxynil or to herbicide classifications such as 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, prosulfuron, and trifloxysulfuron, 5-enol-pyrovir-shikimic acid-3-phosphate synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors, or protoporphyrinogen oxidase (PPO) inhibitors as a result of conventional breeding methods or genetic engineering. An example of a crop conferred resistance to imidazolinones, such as imazamox, by conventional breeding methods (mutation) is Clearfield® Canola. Examples of crops in which resistance to herbicides or certain classes of herbicides has been induced through genetic engineering include glyphosate- and glufosinate-resistant maize varieties marketed under trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0086] It should be understood that the term "useful plants" also includes useful plants that have been transformed using recombinant DNA techniques to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly Bacillus bacteria.

[0087] Examples of such plants include: YieldGard® (maize variety expressing CryIA(b) toxin); YieldGard Root-Eater Nematode® (maize variety expressing CryIIIB(b1) toxin); YieldGard Plus® (maize variety expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (maize variety expressing Cry9(c) toxin); Herculex I® (maize variety expressing CryIF(a2) toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing CryIA(c) toxin); Bollgard I® (cotton variety expressing CryIA(c) toxin); Bollgard II (registered trademark) (cotton varieties expressing CryIA(c) and CryIIA(b) toxins); VIPCOT (registered trademark) (cotton varieties expressing VIP toxin); NewLeaf (registered trademark) (potato varieties expressing CryIIIA toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT advantages (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB advantages (Bt11 corn borer (CB) trait), Agrisure (registered trademark) RW (corn root-boring nematode trait), and Protecta (registered trademark).

[0088] Both plant crops and their seed materials can possess herbicide resistance and, at the same time, insect feeding resistance (a "cross-breeding" of transformation events). For example, seeds can have the ability to express the insecticidal Cry3 protein while simultaneously exhibiting resistance to glyphosate.

[0089] Crop plants should be understood to include those obtained through conventional breeding methods or genetic engineering, as well as those possessing so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0090] 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. This can include both plants of the genus Sorghum, and dicotyledonous plant species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola, and Xanthium.

[0091] The compounds of formula (I) may be used in their unmodified form, or preferably with formulation aids such as carriers, solvents, and surfactants (SAAs), together with conventionally used formulation aids in the art for providing herbicidal compositions. Accordingly, the present invention further provides herbicidal compositions comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an aid. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art.

[0092] The herbicide composition generally comprises 0.1 to 99% by weight, particularly 0.1 to 95% by weight, of the compound of formula I, and 1 to 99.9% by weight of a compounding aid, preferably containing 0 to 25% by weight of a surfactant.

[0093] The composition can be selected from a variety of formulation types. These include emulsifying concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifying granules (EG), oily emulsions (EO), aqueous emulsions (EW), microemulsions (ME), oil dispersions (OD), oil-based flowable formulations (OF), oil-based liquid formulations (OL), soluble concentrates (SL), ULV-suspensions (SU), ULV-liquids (UL), industrial stocks (TK), wettable powders (DC), water-soluble powders (SP), wettable powders (WP), and water-soluble granules (SG). The formulation type selected in any case will depend on the specific intended purpose and the physical, chemical, and biological properties of the compound of formula (I).

[0094] 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 one or more wetting agents, one or more dispersants, or a mixture of such agents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0095] A wettable powder (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 dispersants to promote dispersion in a liquid, and optionally one or more suspending agents. This mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG).

[0096] Granules (GR) can be formed by granulating a mixture of the compound of formula (I) with one or more powdered solid diluents or carriers, or by absorbing the compound of formula (I) (or its solution in a suitable reagent) onto a porous granular material (e.g., pumice, attapulgite clay, fuller's earth, diatomaceous earth (kieselguhr), or crushed corn cob) from pre-formed blank granules, or by adsorbing the compound of formula (I) (or its solution in a suitable reagent) onto a hard core material (e.g., sand, silicates, inorganic carbonates, sulfates, or phosphates), and drying as necessary. Reagents 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, sugars, and vegetable oils). One or more other additives (e.g., emulsifiers, wetting agents, or dispersants) may also be included in the granules.

[0097] The wettable powder (DC) can be prepared by dissolving the compound of formula (I) in water or an organic solvent such as a ketone, alcohol, or glycol ether. These solutions may contain surfactants (for example, to improve water dilution or to prevent crystallization in the spraying tank).

[0098] Emulsifying concentrates (ECs) or aqueous emulsions (EWs) can be prepared by dissolving the compound of formula (I) in an organic solvent (which optionally contains one or more wetting agents, one or more emulsifiers, or a mixture of the reagents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (e.g., alkylbenzene or alkylnaphthalene, exemplified by 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), and dimethylamides of fatty acids (e.g., C8-C8). 10 Examples include fatty acid dimethylamides and chlorinated hydrocarbons. When added to water, EC products spontaneously emulsify, producing emulsions that are stable enough for spray application via appropriate equipment.

[0099] The preparation of EW involves obtaining the compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it can be melted at a moderate temperature, typically below 70°C) or as a solution (by dissolving it in a suitable solvent), and then emulsifying the obtained liquid or solution in water containing one or more SAAs under high shear to produce an emulsion. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons (e.g., chlorobenzene), aromatic solvents (e.g., alkylbenzene or alkylnaphthalene), and other suitable organic solvents with low solubility in water.

[0100] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents and one or more SAAs to spontaneously produce a thermodynamically stable, isotropic liquid formulation. The compound of formula (I) initially exists either in water or in the solvent / SAA blend. Suitable solvents for use in MEs include those described above herein for use in EC or EW. MEs can be either oil-in-water or water-in-oil (the system in which they exist can be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble biological agents in the same formulation. MEs are suitable for dilution in water and may remain as microemulsions or form conventional oil-in-water emulsions.

[0101] The suspension concentrate (SC) may comprise an aqueous or non-aqueous suspension of finely ground, 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 together with one or more dispersants, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and suspending agents may be included to slow the rate at which the particles settle. Alternatively, the compound of formula (I) may be dry-ground and added to water containing the reagents previously described herein to produce the desired final product.

[0102] The aerosol formulation comprises a compound of formula (I) and a suitable propellant (e.g., n-butane). The compound of formula (I) can also be dissolved or dispersed in a suitable medium (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.

[0103] 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 in which each oil droplet is encapsulated by a polymer shell in an aqueous dispersion, and which contains the compound of formula (I) and optionally a carrier or diluent therefor. The polymer shell can be produced by either an interfacial polycondensation reaction or a coacervation method. The compositions may 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 slow, controlled release of the compound.

[0104] The composition may contain one or more additives for improving the biological properties of the composition, for example, by improving wettability, retention, or distribution on a surface; rain resistance on the treated surface; or the uptake or mobility of the compound of formula (I). Such additives include surfactants (SAAs), oils, such as certain mineral oils or natural vegetable oils (e.g., soybean oil and rapeseed oil), spray additives based on modified vegetable oils such as methylated rapeseed oil (MRSO), and blends thereof with other bio-enhancing additives that may assist or modify the action of the compound of formula (I).

[0105] The wetting agent, dispersant, and emulsifier may be cationic, anionic, amphoteric, or nonionic SAA.

[0106] Suitable cationic SAAs include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0107] 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, butylnaphthalene sulfonate, and mixtures of sodium diisopropylnaphthalenesulfonate and sodium triisopropylnaphthalenesulfonate), 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 (mainly monoesters) or products from the reaction with phosphorus pentoxide (mainly diesters), e.g., the reaction of lauryl alcohol with tetraphosphate; these products may also be ethoxylated), sulfosuccinamates, paraffins or olefin sulfonates, taurates, lignosulfonates, and tristyrylphenol phosphates / sulfates.

[0108] Suitable amphoteric SAAs include betaine, propionate, and glycinate.

[0109] Suitable nonionic SAAs include condensation products of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, with fatty alcohols (e.g., oleyl alcohol or cetyl alcohol) or alkylphenols (e.g., octylphenol, nonylphenol, or octyl cresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; condensation products of the 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., lauryldimethylamine oxide); lecithin and sorbitan and their esters, alkyl polyglycosides, and tristyrylphenol.

[0110] Suitable suspending agents include hydrophilic colloids (e.g., polysaccharides, polyvinylpyrrolidone, or sodium carboxymethylcellulose) and swellable clays (e.g., bentonite or attapulgite).

[0111] The compounds of the present invention can also be used as mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifoulphen (including acifoulphen-sodium), acroniphen, ametrin, amicarbazone, aminopyralide, aminotriazole, atrazine, beflubutamide-M, benkytrione, bensulfuron (including bensulfuron-methyl), bentazon, bicyclopyrone, bialaphos, bipirazon, bispiribac-sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, Butaphenacil, carfentrazone (containing carfentrazone-ethyl), chloranslam (containing chloranslam-methyl), chlorimuron (containing chlorimuron-ethyl), chlorotoluron, chlorsulfuron, scinmethilin, clasifos, cretodym, clodinahop (containing clodinahop-propargyl), chromazon, clopyralide, cyclopyranil, cyclopyrimolate, cyclosulfamuron, cyhalofop (containing cyhalofop-butyl), 2,4-D (choline salt and 2-ethylhexyl (containing sil esters), 2,4-DB, Desmedifam, Dicanba (containing aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and their sodium salts), Diclothram, Diflufenican, Diflufenzopyr, Dimethachlor, Dimethenamide-P, Dioxopyritrone, Diquat dibromide, Diuron, Epirifenacil, Etalfluralin, Etofmesate, Phenoxaprop (Fe (containing noxaprop-P-ethyl), phenoxasulfone, fenpyrazone, fenquinotrione, phentrazamide, flazasulfuron, floralam, florpyrauxifen (containing florpyrauxifen-benzyl), fluazihop (containing fluazihop-P-butyl), flucarbazone (containing flucarbazone-sodium), fluchloraminopir (containing fluchloraminopir-tefuryl), fluphenacet, fluphenoximacil, flumetula, flumioxazine, fluomethron,Homesaphenflupyrusulfuron (containing flupyrusulfuron-methyl-sodium), fluroxypyr (containing fluroxypyr-meptyl), flusulfinum, homesaphen, horamsulfuron, glufosinate (containing both L-glufosinate and ammonium salts), glyphosate (containing diammonium, isopropylammonium and their potassium salts), harauxifen (containing harauxifen-methyl), haloxyhop (containing haloxyhop-methyl), hexazinone, hydantosidine, icaforin (icaforin-methyl) (including), Imazamox (including R-Imazamox), Imazapick, Imazapill, Imazetapir, Indadiflame, Indolauxipill (including Indolauxipill-cyanomethyl), Iodosulfuron (including Iodosulfuron-methyl-sodium), Iofensulfuron (including Iofensulfuron-sodium), Ioxinil, Iptriazopiride, Isoproturone, Isoxaflutol, Lancotrione, MCPA, MCPB, Mecoprop-P, Mesosulfuron (including Mesosulfuron-methyl), Mesotrione, Metamitron Metazachlor, Methiozoline, Metrachlor, Metoslam, Metrivudine, Metosulfuron, Napropamide, Nicosulfuron, Norflurazone, Oxadiazone, Oxasulfuron, Oxyfluphene, Paraquat Dichloride, Pendimethalin, Penoxuslam, Fenmedifam, Pichloram, Pinoxadene, Pretilachlor, Primisulfuron-Methyl, Promethrin, Propanil, Propaxafop, Propyrisulfuron, Propyzamide, Prosulfocarb, Prosulfuron, Pyraclonil, Pyrafluphene (Pyrafluphene-Ethyl) (including), pyrakinate, pyrasulfolol, pyridate, pyrifthalide, pyriflubenzoxime, pyrimisulfan, pyroxasulfone, piroxulam, quinchlorac, kinmelac, quizalopop (including quizalopop-P-ethyl and quizalopop-P-tefuryl), limisoxafen, limsulfuron, saflufenacil, cethoxydim, simazine, S-metallochlor, sulfenthrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tenbotrione, terbutyrazine, terbutrin, tetoflupyrrolimet, thiencarbazone,Thiafensulfuron, thiafenacil, torpylate, topramezon, tralcoxidime, triafamone, trialtar, triasulfuron, tribenuron (containing tribenuron-methyl), triclopyr, trifloxysulfuron (containing trifloxysulfuron-sodium), trifludimoxazine, trifluralin, triflusulfuron, tripyrasulfone, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidine-1(2H)- Phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidinedion-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidinedion-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidinedion-2-one, 4-hydroxy-1-methyl-3-[4- (trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazole-3-yl]imidazolidine-2-one, (4R)1-(5-tert-butylisoxazole-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidine-2-one, (1RS,5SR)-3-[2-methoxy-4-(propa-1-in-1-yl)phenyl]-4-oxobicyclo[3.2.1]octa-2-en-2-ylmethyl Calcium carbonate, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidine-1-yl]-2-pyridyl]oxy]acetate, methyl-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidine-1-yl]phenoxy]phenoxy]-2-methoxyacetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methylpyridazine-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 Examples include [nyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-cyclopenta[d]isoxazole-6a-carboxylate, 2-[(2-bromo-6-fluorophenyl)methoxy]-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptane, and (isopropylideneamino)6-amino-2-(4-chloro-2-fluoro-3-methoxyphenyl)-5-methoxypyrimidine-4-carboxylate.

[0112] 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.

[0113] This mixture can be advantageously used in the formulations described above (in which case, “active ingredient” refers to the respective mixtures of the compound of formula (I) and the mixing partner).

[0114] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide phytotoxicity reducers. Examples of such phytotoxicity reducers include benoxacol, croquintocet (including croquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenchlorim, fluxofenim, flirazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen, and oxavethrinil. Mixtures of the compound of formula (I) with cyprosulfamide, isoxadifen-ethyl, croquintocet-mexyl, and / or metcamifen are particularly preferred.

[0115] Drug-harm-reducing agents for compounds of formula (I) are also, for example, The Pesticide Manual, 16 th As stated in Edition (BCPC), 2012, it can be in the form of an ester or a salt. References to croquintoset-mexyl also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts, as disclosed in International Publication No. 02 / 34048.

[0116] Preferably, the mixing ratio of the compound of formula (I) to the drug damage mitigating agent is 100:1 to 1:10, and particularly 20:1 to 1:1.

[0117] The compounds of formula (I) are typically used in the form of pesticide compositions and can be applied simultaneously with or consecutively to the planted area or the plants to be treated with further compounds. These further compounds may be, for example, sources of fertilizers or micronutrients or other preparations that affect plant growth. They may also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericidal agents, nematicides, molluskicides, or mixtures thereof, and may include, as necessary, further carriers, surfactants or application enhancers commonly used in the art of formulation.

[0118] As used herein, the term “habitat” means a field in which plants grow or on which seeds of cultivated plants are sown or in which seeds will be sown in the soil. It includes the soil, seeds and seedlings, and established vegetation.

[0119] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0120] The term “plant propagation material” is understood to refer to plant materials, such as potatoes, including reproductive parts like seeds, and cuttings or tubers, that can be used for plant propagation. Examples include plant seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts. Germinated plants and seedlings that will be transplanted after germination or emergence from the soil may also be included. These seedlings may be protected before transplantation by full or partial treatment by immersion. Preferably, “plant propagation material” is understood to mean seeds.

[0121] The pesticides referred to herein by their common names are publicly known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0122] Compounds of formula (I) may be used in their unmodified form, or preferably, in combination with auxiliaries conventionally used in the art of formulation. For this purpose, they may be conveniently formulated in known forms into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, dilution emulsions, wettable powders, soluble powders, dusts, granules, and also, for example, encapsulations in polymeric substances. As with the type of composition, the method of application, such as spraying, misting, dusting, granulation, coating, or pouring, is selected according to the intended purpose and the circumstances at hand. The composition may also contain further auxiliaries such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, micronutrient donors, or other formulations for obtaining special effects.

[0123] For example, suitable carriers and auxiliaries for agricultural applications may be solids or liquids and are substances useful in compounding techniques, such as natural or recycled inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders, or fertilizers. Such carriers are described, for example, in International Publication No. 97 / 33890.

[0124] The compounds of formula (I) are typically used in the form of compositions and can be applied to the planting area or the plants to be treated, simultaneously or sequentially, to further compounds. These further compounds may be, for example, fertilizers or micronutrient donors or other preparations that affect plant growth. They may also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericidal agents, nematicides, molluscicides, or mixtures thereof, together with further carriers, surfactants, or application enhancers commonly used in the art of formulations, as needed.

[0125] 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 a pesticide, fungicide, synergist, herbicide, or plant growth regulator. The additional active ingredients may, in some cases, result in unexpected synergistic activity.

[0126] Generally, the formulation comprises 0.01 to 90% by weight of an activator, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of inert substances and auxiliary agents for solid or liquid formulations, wherein the activator consists of at least the compound of formula (I) together with components (B) and (C), and optionally other activators, particularly microbiotacitists or preservatives. The concentrated form of the composition generally contains about 2 to 80%, preferably about 5 to 70% by weight of the activator. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of the activator. Commercial products will preferably be formulated as concentrates, but end users will usually use diluted formulations.

[0127] The following table illustrates examples of individual compounds of formula (I) according to the present invention. [ka]

[0128] [Table 1]

[0129] Table A-1 provides 26 compounds of formula (I), A-1.001 to A-1.026, where R 1 is ethyl, X is chloro, and R 3 and R 4 Both are hydrogen, and R 2 This is defined in Table 1. Table A-2 provides 26 compounds of formula (I), A-2.001 to A-2.026, where R 1 is ethyl, X is bromo, and R 3 and R 4 Both are hydrogen, and R 2 This is defined in Table 1. Table A-3 provides 26 compounds of formula (I), A-3.001 to A-3.026, where R 1 is ethyl, X is chloro, and R 3 is hydrogen, R 4 is bromo, R 2This is defined in Table 1. Table A-4 provides 26 compounds of formula (I), A-4.001 to A.4.026, where R 1 is ethyl, X is chloro, and R 3 is ethyl, and R 4 is hydrogen, R 2 This is defined in Table 1. Table A-5 provides 26 compounds of formula (I), A-5.001 to A.5.026, where R 1 is ethyl, X is chloro, and R 3 is methyl, and R 4 is hydrogen, R 2 This is defined in Table 1.

[0130] Combination example

[0131] [Table 2]

[0132] By thoroughly mixing the active ingredient with an auxiliary agent and thoroughly grinding the mixture in a suitable pulverizer, a wettable powder can be obtained that can be diluted with water to form a suspension of the desired concentration.

[0133] [Table 3]

[0134] The active ingredient is thoroughly mixed with the auxiliary agent, and the mixture is finely ground in a suitable mill, resulting in a powder that can be used directly for seed treatment.

[0135] 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 (ethylene oxide 35 mol) 4% Cyclohexanone 30% Xylene mixture 50%

[0136] Emulsions of any required dilution suitable for plant protection can be obtained from this concentrate by dilution with water.

[0137] [Table 4]

[0138] Ready-to-use powders 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 drying and coating seeds.

[0139] Extruded granules Active ingredient [compound of formula (I)] 15% Sodium lignin sulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0140] The active ingredient is mixed with an auxiliary agent and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an airflow.

[0141] Coated granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0142] The finely ground active ingredient is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. A non-dusting coated granule is thus obtained. Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (ethylene oxide 15 mol) 6% Sodium lignin sulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0143] The finely ground active ingredient is tightly mixed with an auxiliary agent to obtain a suspension concentrate. By diluting this with water, a suspension of the desired dilution can be obtained. Using such dilutions, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism. Flowable formulation for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer Butanol PO / EO 2% Tristyrenephenol 2% with 10-20 moles of EO 1,2-Benzisothiazolin-3-one (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%

[0144] The finely ground active ingredient is tightly mixed with an auxiliary agent to obtain a suspension concentrate. By diluting this with water, a suspension of the desired dilution can be obtained. Using such dilutions, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.

[0145] Sustained-release capsule suspension 28 parts of the compound combination of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). 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 median diameter of the capsules is 8 to 15 microns. The resulting formulation is applied to seeds as an aqueous suspension using equipment suitable for the purpose. [Examples]

[0146] The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referenced in Table 2 below.

[0147] Throughout this specification, temperatures are expressed in degrees Celsius (°C), and "mp" indicates the melting point.

[0148] List of abbreviations ℃ = degrees Celsius, d = doublet, dd = doublet of doublets, DMSO = dimethyl sulfoxide, M = mole, m = multiplet, MHz = megahertz, q = quartet, qd = doublet of quartet, s = singlet, t = triplet.

[0149] Example 1: Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate (Compound 1) Step 1: Synthesis of ethyl 3-(3,4-dichlorophenyl)-3-oxopropanoate [ka] Sodium hydroxide (3.17 g, 80 mmol, 60% by mass) was added in small increments to a solution of 1-(3,4-dichlorophenyl)ethanone (5.00 g, 26.5 mmol) and dimethyl carbonate (40 mL, 466 mmol) under nitrogen and at 0°C. The reaction mixture was warmed to room temperature and stirred for 16 hours. The reaction mixture became an unstirrable paste-like solid overnight. Additional dimethyl carbonate (10 mL) was added to generate a fluid slurry for quenching. The reaction mixture was cooled to 0°C and quenched by adding water (25 mL). The reaction mixture was acidified to pH 3 by adding 2 M hydrochloric acid aqueous solution and then extracted in ethyl acetate. The organic extract was dried over magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel to obtain ethyl 3-(3,4-dichlorophenyl)-3-oxopropanoate (a mixture of tautomers) as a colorless liquid. Enol form: 1 ¹H NMR (400MHz, chloroform): δ = 12.47 (s, 1H), 7.87 (d, 1H), 7.59 (m, 3H), 7.49 (d, 1H), 5.65 (s, 1H), 3.82 (s, 3H). Keto bodies: 1 ¹H NMR (400 MHz, chloroform): δ = 8.03 (d, 1H), 7.77 (m, 1H), 7.58 (d, 2H), 3.97 (s, 2H), 3.76 (s, 3H).

[0150] Step 2: Synthesis of ethyl(Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate [ka] To a solution of ethyl 3-(3,4-dichlorophenyl)-3-oxopropanoate (1.65 g, 6.32 mmol) in toluene (11 mL), ammonium ethyl acetate (19.0 mmol) and acetic acid (6.32 mmol) were added. The orange reaction mixture was heated under reflux for 6 hours. The cooled reaction mixture was diluted with ethyl acetate and washed with saturated sodium bicarbonate aqueous solution. The phases were separated, and the aqueous phase was extracted in ethyl acetate (×3). The organic extract was dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel to obtain ethyl(Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)propanoate as a colorless oil. 1 ¹H NMR (400MHz, chloroform): δ = 7.49-7.43 (m,2H), 7.23-7.15 (m,1H), 4.58-4.50 (m,1H), 4.17-4.08 (m,2H), 3.12-2.91 (m,2H), 1.31-1.22 (m,3H), 1.15-1.06 (m,3H).

[0151] Step 3: Synthesis of ethyl(2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxobutanoate [ka] A solution of ethyl(Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)propa-2-enoate (5.10 g, 17.7 mmol) and 2-cyanoacetic acid (1.51 g, 17.7 mmol) in acetic anhydride (16 mL) was heated at 105 °C for 0.25 hours with stirring. The cooled reaction mixture was evaporated to dryness under reduced pressure. Water (20 mL) was added to the residue. The resulting precipitate was collected by filtration and purified by flash chromatography on silica gel to obtain ethyl(2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxobutanoate as a grayish-white solid.

[0152] Step 4: Synthesis of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate [ka] To a stirred solution of ethyl(2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butanoate (4.50 g, 12.67 mmol) in ethanol (80 mL), sodium ethoxide (4.11 g, 12.7 mmol) was added at 0°C. The reaction mixture was heated at 50°C for 2 hours. The cooled reaction mixture was poured into a saturated aqueous solution of ammonium chloride and extracted in dichloromethane. The combined organic extract was dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on C-18 silica gel to obtain ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate as a white solid. 1 ¹H NMR (400MHz, methanol): δ = 7.78-7.63 (m, 2H), 7.44-7.33 (m, 1H), 5.89-5.80 (m, 1H), 4.04-3.90 (m, 2H), 3.74 (q, 2H), 1.21-1.13 (m, 3H), 0.98-0.90 (m, 3H).

[0153] Step 5: Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate [ka] To a suspension of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate (0.500 g, 1.41 mmol) in a mixture of acetonitrile (12 mL) and aqueous hydrogen chloride (2 M, 1.8 mL), copper(I) chloride (0.167 g, 1.69 mmol) was added. The resulting reaction mixture was heated to 75°C, and then a solution of sodium nitrite (0.126 g, 1.83 mmol) and water (1 mL) was added dropwise. The reaction mixture was heated at 75°C for 0.25 hours with stirring. The cooled reaction mixture was poured into saturated aqueous ammonium chloride (30 mL) and extracted in ethyl acetate (2 × 50 mL). The combined organic extract was dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on C-18 silica gel to obtain ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate as a yellow solid. 1 ¹H NMR (400MHz, methanol): δ = 7.77 (d, 1H), 7.75 (d, 1H), 7.46 (dd, 1H), 6.74 (s, 1H), 4.12-3.95 (m, 4H), 1.25 (t, 3H), 0.97 (t, 3H).

[0154] Example 2: Synthesis of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylic acid (Compound 2) [ka] A mixture of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate (0.200 g, 0.53 mmol) and tris(trifluoromethylsulfonyloxy)scandium (0.276 g, 0.56 mmol) in water (2 mL) and tetrahydrofuran (2 mL) was heated at 120°C for 0.5 hours under microwave irradiation. The cooled reaction mixture was diluted with water and extracted in ethyl acetate. The combined organic extract was dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure to obtain 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylic acid. 1 ¹H NMR (400MHz, chloroform): δ = 7.62 (d, 1H), 7.38 (s, 1H), 7.14 (br d, 1H), 7.09-6.99 (s, 1H), 4.06 (m, 2H), 1.30-1.24 (m, 3H).

[0155] Example 3: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxopyridine-3-carboxylate (compound 3) Step 1: Synthesis of 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one [ka] A stirred solution of 2,2,6-trimethyl-1,3-dioxin-4-one (4.88 g, 34.3 mmol) and N-bromosuccinimide (7.94 g, 44.6 mmol) in dichloromethane (120 mL) was irradiated with 450 nm light at room temperature for 12 hours. The orange reaction mixture was washed with a 50:50 mixture of saturated sodium bicarbonate aqueous solution and saturated sodium thiosulfate aqueous solution. The organic phase was dried over magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on C-18 silica gel to obtain 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one as a yellow oil. 1 ¹H NMR (400 MHz, chloroform): δ = 5.54 (s, 1H), 3.90 (s, 2H), 1.73 (s, 6H).

[0156] Step 2: Synthesis of ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate [ka] To a stirred solution of ethyl(Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)propa-2-enoate (2.00 g, 6.94 mmol) in xylene (20.0 mL), 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one (2.30 g, 10.4 mmol) was added. The resulting reaction mixture was heated at 140 °C for 5 minutes with stirring. The cooled reaction mixture was diluted with ethyl acetate, the organic solution was washed with brine, dried over magnesium sulfate, filtered, and evaporated to dryness under reduced pressure to obtain ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate as a brown solid. 1 H NMR (400MHz, DMSO-d6) δ=7.89(s,1H),7.79(d,1H),7.49(d,1H),6.59(s,1H),4.72(s,2H),3.82-3.77(q,4H),1.11(t,3H),0.84(t,3H).

[0157] Step 3: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxopyridine-3-carboxylate [ka] To a stirred solution of ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate (6.99 g, 16.1 mmol) and N-ethyl-N-isopropyl-propane-2-amine (3.67 mL, 21.0 mmol) in acetonitrile (140 mL) at 0°C, 4-methyl-4-oxide-morpholine-4-ium (2.92 g, 24.2 mmol) was added in small amounts. The reaction mixture was stirred at 25°C for 2.5 hours. The reaction mixture was diluted with water and ethyl acetate to separate the phases. The organic phase was washed with brine, dried over magnesium sulfate, and evaporated to dryness under reduced pressure to obtain ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxopyridine-3-carboxylate as a yellow solid. ¹H NMR (400 MHz, chloroform): δ = 9.71 (s, ¹H), 7.60 (d, ¹H), 7.54 (d, ¹H), 7.30-7.27 (m, ¹H), 7.08 (s, ¹H), 4.19 (m, ²H), 4.04 (dd, ²H), 1.13 (t, ³H), 1.00 (t, ³H).

[0158] Step 4: Synthesis of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxopyridine-2-carboxylic acid [ka] To a solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxopyridine-3-carboxylate (5.67 g, 15.4 mmol) in tert-butanol (77 mL) and 2-methylbuta-2-ene (77 mL), a solution of monosodium phosphate (4.20 g, 34.7 mmol) in water (39 mL) was added. The reaction mixture was cooled to 0°C, and sodium chlorite (4.22 g, 46.2 mmol) was added in small amounts. The reaction mixture was warmed to room temperature and stirred for 2.5 hours. The resulting yellow solution was diluted with brine, methanol, and 2 M aqueous hydrochloric acid, and then extracted in ethyl acetate. The organic extract was extracted in a saturated sodium metabisulfite solution. The aqueous phase was acidified to pH 1 by adding 2 M aqueous hydrochloric acid, and extracted in dichloromethane. The organic extract was evaporated to dryness under reduced pressure to obtain 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxopyridine-2-carboxylic acid as a colorless solid. 1 H NMR (400MHz, DMSO-d6) δ=7.92(d,1H),7.82(d,1H),7.53(dd,1H),6.63(s,1H),3.95-3.68(m,4H),1.07(t,3H),0.83(t,3H).

[0159] Step 5: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxopyridine-3-carboxylate [ka] Iodine (0.281 g, 1.11 mmol) was added to a stirred solution of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxopyridine-2-carboxylic acid (1.42 g, 3.69 mmol) in methylsulfinilmethane (37 mL). The reaction mixture was heated at 120 °C for 1.5 hours, then quenched with saturated sodium thiosulfate solution and extracted into dichloromethane. The organic extract was washed with water and brine and passed through a phase separator cartridge. The organic filtrate was evaporated to dryness under reduced pressure to obtain a yellow oil, which was purified by flash chromatography on C-18 silica gel to obtain ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxopyridine-3-carboxylate as a yellow solid. 1 ¹H NMR (400MHz, chloroform): δ = 7.59 (d,1H), 7.52 (d,1H), 7.26 (dd,1H), 6.68 (s,1H), 4.06-3.98 (m,2H), 3.93 (q,2H), 1.21 (t,3H), 0.99 (t,3H).

[0160] Example 4: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-fluoro-4-oxopyridine-3-carboxylate (compound 7) [ka] A suspension of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate (0.600 g, 1.60 mmol) and tetramethylammonium fluoride (0.448 g, 4.80 mmol) in N,N-dimethylformamide (8 mL) was heated with stirring at 40°C for 40 hours. The cooled reaction mixture was diluted with ethyl acetate and washed sequentially with water and brine. The organic extract was dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on C-18 silica to obtain ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-fluoro-4-oxopyridine-3-carboxylate as a white solid. 1¹H NMR (400MHz, chloroform): δ = 7.59 (d,1H), 7.52 (d,1H), 7.26-7.23 (m,1H), 6.26 (d,1H), 4.09-4.01 (m,2H), 3.75 (qd,2H), 1.22 (t,3H), 1.00 (t,3H).

[0161] Step 5: Synthesis of ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate [ka] Ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate (500 mg, 1.33 mmol) was dissolved in acetonitrile (13 mL), and trimethylsilyl bromide (600 μL, 4.46 mmol) was added. The reaction mixture was then heated at 60°C for 3.5 hours. The cooled reaction mixture was neutralized with a saturated solution of sodium bicarbonate. The mixture was then extracted with dichloromethane, the organic extract was dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica to obtain ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylate as a pale yellow solid.

[0162] Example 6: Synthesis of 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxopyridine-3-carboxylic acid (Compound 8) [ka] Ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (40 mg, 0.10 mmol) and scandium triflate (49 mg, 0.10 mmol) were dissolved in a mixture of tetrahydrofuran (0.3 mL) and water (0.3 mL). The reaction mixture was then heated at 120°C for 45 minutes. The reaction mixture was then diluted with water and 2M HCl solution and then extracted with dichloromethane. The organic extract was dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on C-18 silica to give 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid as a white solid. 1 1H NMR (400 MHz, chloroform) δ = 5.86 (br s, 1H), 7.60 (d, 1H), 7.35 (d, 1H), 7.19 (s, 1H), 7.11 (dd, 1H), 4.09 (q, 2H), 1.25 (t, 3H).

[0163]

Table 5-1

[0164]

Table 5-2

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Table 5-3

[0166]

Table 5-4

[0167] Biological Examples Seeds of various test species were sown in standard soil in pots (Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Amaranthus palmeri (AMAPA), Zea mays (ZEAMX), Amaranthus retroflexus (AMARE)). 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 were sprayed with an aqueous spray solution derived from a formulation of the industrial active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compound was applied at 250 g / ha. Next, test plants were grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days of the experiment, the rate of damage inflicted on the plants was evaluated. The following table shows the biological activity on a 5-point scale (5=81-100%; 4=61-80%; 3=41-60%; 2=21-40%; 1=1-20%; 0=no activity; -=not tested).

[0168] [Table 6]

[0169] [Table 7]

Claims

1. Compound of formula (I): 【Chemistry 1】 (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 cycloalkyl; R 2 However, the compound is phenyl or heteroaryl, where the heteroaryl portion is a 5-membered or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl portion is R 5 The following may be arbitrarily substituted with one, two, three, or four bases, which may be the same or different: R 3 However, hydrogen or C 1 ~C 6 It is alkyl; R 4 However, it is hydrogen or halogen; R 5 However, 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 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 It is an alkyl)aminocarbonyl; and (X is a halogen); or its salt or N-oxide.

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

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

4. R 2 However, R 5 The compound according to any one of claims 1 to 3, which is a phenyl that may be optionally substituted with one or two groups that are the same or different as represented by .

5. R 3 However, hydrogen or C 1 ~C 3 A compound according to any one of claims 1 to 4, wherein it is alkyl.

6. R 4 The compound according to any one of claims 1 to 5, wherein the compound is hydrogen or bromo.

7. The compound according to any one of claims 1 to 6, wherein X is chloro, fluoro, or iodine.

8. R 5 The compound according to any one of claims 1 to 7, wherein the compound is cyano or halogen.

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

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

11. A herbicide composition comprising a 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 biological agent.

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

14. A method for controlling weeds in a habitat, comprising applying a weed control amount of the composition described in any one of claims 11 to 13 to the habitat of the weeds.

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

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