Herbicidal derivatives

Abstract

Compounds having the formula (I) wherein the substituents are as defined in claim 1 are disclosed. The invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, in particular in crops of useful plants.

Description

[0001] This invention relates to herbicidal pyridone derivatives (e.g., as active ingredients) that possess herbicidal activity. The invention also relates to agricultural chemical compositions comprising at least one of these pyridone derivatives, methods for preparing these compounds, and the use of these pyridone derivatives or compositions in agriculture or horticulture for controlling weeds, particularly in crops with beneficial plants.

[0002] EP 0239391, EP 0127313, EP 0040082, GB 2182931, GB 2328614, WO 2022117445, WO 2022117446, and WO 2023 / 110664 describe pyridinone derivatives as herbicides.

[0003] According to the present invention, a compound having formula (I) or a salt or N-oxide thereof is provided.

[0004]

[0005] in

[0006] R 1 It is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C6 alkyl, or C3-C6 cycloalkyl;

[0007] R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, 3, or 4 heteroatoms that may be the same or different from R 5 The group to be represented is substituted;

[0008] R 3 It is hydrogen or C1-C6 alkyl;

[0009] R 4 It is hydrogen or halogen;

[0010] R 5 It is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylthioalkyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl; and

[0011] X is a halogen.

[0012] Many herbicides currently used to control unwanted vegetation before crop planting have the problem of potentially damaging subsequent crops if they are planted shortly after application. Therefore, herbicides that are safe for crops when applied before emergence while providing good control of emerging weeds offer significant advantages over existing herbicides.

[0013] Surprisingly, it has been found that, for practical purposes, the novel compounds of formula (I) not only exhibit very favorable levels of herbicidal activity, but also show no or low levels of damage to several major crops such as maize (zea mays) when applied pre-emergence, while providing excellent control of unwanted vegetation (weeds and free-growing crops) when applied post-emergence, thus enabling their successful application shortly before the planting of new crops. In contrast, related compounds reported in the prior art, while showing similar control over unwanted vegetation, cause unacceptable damage to many crops, thus hindering their use.

[0014] Surprisingly, it has been found that novel compounds of formula (I) have very favorable levels of herbicidal activity for practical purposes.

[0015] According to a second aspect of the invention, an agricultural chemical composition is provided comprising a herbicidally effective amount of the compound of formula (I) according to the invention. This agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0016] According to a third aspect of the invention, a method for controlling weeds at a site is provided, the method comprising applying to the site a composition comprising a compound having formula (I) to control the amount of weeds.

[0017] According to a fourth aspect of the invention, the use of a compound having formula (I) as a herbicide is provided.

[0018] When substituents are indicated as "optionally substituted," this means that they may or may not have one or more of the same or different substituents, such as one, two, or three R. 6Substituents. For example, C1-C6 alkyl groups substituted with 1, 2, or 3 halogens may include, but are not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3 groups. As another example, C1-C6 alkoxy groups substituted with 1, 2, or 3 halogens may include, but are not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups.

[0019] As used in this article, the term "cyano" refers to the -CN group.

[0020] As used in this article, the term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0021] As used in this article, the term "nitro" refers to the -NO2 group.

[0022] As used herein, the term "acetyl" refers to the -C(O)CH3 group.

[0023] As used herein, =O refers to an oxo group, for example, as seen in carbonyl (-C(=O)-) groups.

[0024] As used herein, the term "C1-C6 alkyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, which is unsaturated, has one to six carbon atoms, and is attached to the rest of the molecule by single bonds. "C1-C4 alkyl" and "C1-C3 alkyl" should be interpreted accordingly. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, and their isomers, such as isopropyl. "C1-C6 alkylene" refers to the corresponding definition of C1-C6 alkyl, except that this group is attached to the rest of the molecule by two single bonds. The term "C1-C2 alkylene" should be interpreted accordingly. Examples of C1-C6 alkylene groups include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0025] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, wherein the group is 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.

[0026] As used herein, the term "C1-C6 alkoxy" refers to an alkoxy group having the formula -OR aThe group, wherein R a It 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 groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0027] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group 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 groups include, but are not limited to, trifluoromethoxy.

[0028] As used herein, the term "C2-C6 alkenyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one double bond that may have an (E)- or (Z)- configuration, has two to six carbon atoms, and is attached to the rest of the molecule by single bonds. The term "C2-C3 alkenyl" should be interpreted accordingly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl, propyl-1-enyl, propyl-2-enyl (allyl), and but-1-enyl.

[0029] As used herein, the term "C2-C6 ynyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one triple bond, having two to six carbon atoms, and attached to the rest of the molecule by single bonds. The term "C2-C3 ynyl" should be interpreted accordingly. Examples of C2-C6 ynyl groups include, but are not limited to, ethynyl, propynyl, and butynyl.

[0030] As used herein, the term “C2-C6 alkenyl group” refers to a C2-C6 alkenyl group as generally defined above, which is attached to the rest of the molecule by an oxygen atom.

[0031] As used herein, the term “C2-C6 alkynyl group” refers to the C2-C6 alkynyl group as generally defined above, which is attached to the rest of the molecule by an oxygen atom.

[0032] As used herein, the term "C1-C6 alkoxy-C1-C6 alkyl" refers to a compound having the formula R b OR a - groups, where R b It is a C1-C6 alkyl group as generally defined above, and R a It is a C1-C6 alkylene group as generally defined above. The term "C1-C4 alkoxy-C1-C4 alkyl" should be interpreted accordingly.

[0033] As used herein, the term "C1-C6 alkoxy" refers to a compound with the formula R b OR a O- groups, where R a and R b Each is independently a C1-C6 alkyl group as generally defined above. The terms “C1-C4 alkoxy” and “C1-C3 alkoxy” should be interpreted accordingly.

[0034] As used herein, the term "C3-C6 cycloalkyl" refers to a group containing 3 to 6 carbon atoms in a monocyclic saturated ring system. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0035] As used herein, the term "C3-C6 cycloalkenyl" refers to a monocyclic unsaturated ring system containing at least one double bond and comprising 3 to 6 carbon atoms. The terms "C3-C5 cycloalkenyl" and "C3-C4 cycloalkenyl" should be interpreted accordingly. Examples of C3-C6 cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0036] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of a molecule via a C1-C6 alkylene linker as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkyl include, but are not limited to, cyclopropylmethyl.

[0037] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkoxy" refers to a C3-C6 cycloalkyl ring attached to the remainder of a molecule via a C1-C6 alkoxy linker as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkoxy rings include, but are not limited to, cyclopropoxy rings.

[0038] As used herein, the term “C3-C6 cycloalkylaminocarbonyl” refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule via a -NHC(O)- linker. Examples of C3-C6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0039] As used in this article, the term "C6-C" 10 "Aryl" refers to a 6- to 10-membered aromatic ring system consisting only of carbon and hydrogen atoms. This aromatic ring system can be monocyclic, bicyclic, or tricyclic. Examples of such ring systems include phenyl, naphthyl, or indenyl.

[0040] As used in this article, the term "C6-C" 10"Aryl C1-C3 alkyl" refers to the aryl moiety as generally defined above, which is attached to the rest of the molecule by a C1-C3 alkylene linker as defined above.

[0041] As used herein, the term "phenoxy" refers to a phenyl ring attached to the rest of the molecule by an oxygen atom.

[0042] As used herein, the term “benzyloxy” refers to a benzyl ring attached to the rest of the molecule by an oxygen atom.

[0043] As used herein, the term "heterocyclic group" refers to a stable 4-, 5-, or 6-membered non-aromatic monocycle containing 1, 2, or 3 heteroatoms, wherein the heteroatoms are individually selected from nitrogen, oxygen, and sulfur. Heterocyclic groups can be bonded to the rest of the molecule via carbon atoms or heteroatoms. Examples of heterocyclic groups include, but are not limited to, acrylonitrile, azacyclic butyl, oxacyclic butyl, thiocyclic butyl, tetrahydrofuranyl, pyrrolyl, pyrazolyl, imidazoyl, piperidinyl, piperazinyl, morpholinyl, dioxopentyl, dithiopentyl, and thiazolyl.

[0044] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group comprising 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl groups include, but are not limited to, furanyl, pyrroleyl, thiopheneyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridinyl.

[0045] As used herein, the term "C1-C6 alkyl carbonyl" refers to an alkyl group having the formula -C(O)R a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. Examples of C1-C6 alkyl carbonyl groups include, but are not limited to, acetyl groups.

[0046] As used herein, the term "C1-C6 alkoxycarbonyl" refers to an alkoxycarbonyl group having the formula -C(O)OR a The group, wherein R a It is a C1-C6 alkyl group as generally defined above.

[0047] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to an amino group having the formula -C(O)NHR. a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. Examples of C1-C6 alkyl amino carbonyl groups include, but are not limited to, ethylcarbamoyl (i.e., ethylamino carbonyl).

[0048] As used herein, the term "N,N-di(C1-C4 alkyl)aminocarbonyl" refers to an amino group having the formula -C(O)N(R a(R) b ) groups, wherein R a and R b Each is individually a C1-C4 alkyl group as generally defined above. The term “N,N-di(C1-C3 alkyl)aminocarbonyl” should be interpreted accordingly. Examples of N,N-di(C1-C4 alkyl)aminocarbonyl include, but are not limited to, dimethylcarbamoyl (i.e., N,N-di(methyl)aminocarbonyl).

[0049] As used herein, the term "N,N-di(C1-C4 alkyl)aminosulfonyl" refers to an aminosulfonyl group having the formula -S(O)2N(R a (R) b ) groups, wherein R a and R b Each is individually a C1-C4 alkyl group as generally defined above. The term “N,N-di(C1-C3 alkyl)aminosulfonyl” should be interpreted accordingly. Examples of N,N-di(C1-C4 alkyl)aminosulfonyl include, but are not limited to, diethylaminosulfonyl (i.e., N,N-di(methyl)aminosulfonyl).

[0050] As used herein, the term "C1-C6 alkylthioalkyl" refers to a compound having the formula -SR a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkylthioalkyl" and "C1-C3 alkylthioalkyl" should be interpreted accordingly. Examples of C1-C6 alkylthioalkyl groups include, but are not limited to, methylthioalkyl.

[0051] As used herein, the term "C1-C6 alkylsulfinyl" refers to a group having the formula -S(O)R a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkyl sulfinyl" and "C1-C3 alkyl sulfinyl" should be interpreted accordingly. Examples of C1-C6 alkyl sulfinyl groups include, but are not limited to, methyl sulfinyl groups.

[0052] As used herein, the term "C1-C6 alkylsulfonyl" refers to an alkyl group having the formula -S(O)2R a The group, wherein R a It 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 alkylsulfonyl groups include, but are not limited to, methylsulfonyl groups.

[0053] As used herein, the term "C1-C6 alkylsulfonamide" refers to an amino group having the formula -NHS(O)2R a The group, wherein R aIt is a C1-C6 alkyl group as generally defined above.

[0054] The presence of one or more possible stereoisomers in a compound having formula (I) means that the compound can exist in optical isomeric form (i.e., enantiomers or diastereomers). Furthermore, as a result of restricted rotation around the single bond, hindered isomers may exist. Formula (I) is intended to include all such possible isomeric forms and mixtures thereof. This invention includes all such possible isomeric forms of compounds having formula (I) and mixtures thereof. Similarly, formula (I) is intended to include all possible tautomers. This invention includes all possible tautomeric forms of compounds having formula (I).

[0055] In each case, the compound having formula (I) according to the invention is in free form, oxidized form (such as N-oxide), or salt form (e.g., an agronomically usable salt form). Preferably, the compound having formula (I) can form salts with: amines, including primary, secondary, and tertiary amines (e.g., ammonia, dimethylamine, and triethylamine); alkali metal bases and alkaline earth metal bases, transition metal bases, or quaternary ammonium bases. In a particularly preferred set of embodiments, the compound having formula (I) can form chlorides or 2,2,2-trifluoroacetates.

[0056] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. They are described, for example, in A. Albini and S. Pietra’s book “Heterocyclic N-oxides” in CRC Press, Boca Raton (1991).

[0057] The following list provides information on the substituents R of compounds having formula (I). 1 R 2 R 3 R 4 and R 5 The definitions, including preferred definitions, are provided below. Any definition given below for any of these substituents may be combined with any definition of any other substituent given below or elsewhere in this document.

[0058] R 1 It 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 It 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 1It 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 It is methyl, ethyl, n-propyl, methoxy, 2-methoxyethyl, allyl, and prop-2-ynyl. In one set of examples, R 1 It is a C1-C3 alkyl group, preferably methyl or ethyl, and more preferably ethyl.

[0059] R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, 3, or 4 heteroatoms that may be the same or different from R 5 The group substitution is indicated.

[0060] Preferably, R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, or 3 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, or 3 heteroatoms that may be the same or different from R. 5 The group substitution is indicated.

[0061] More preferably, R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising one or two individual heteroatoms selected from N and O, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by one, two, or three atoms that may be the same or different from R. 5 The group substitution is indicated.

[0062] Even more preferably, R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising one or two heteroatoms individually selected from N and O, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by one or two atoms that may be the same or different from R. 5 The group indicated is substituted. Even more preferably, R 2 It is phenyl or pyridyl, wherein each phenyl and pyridyl moiety may optionally be composed of one or two identical or different R groups. 5 The group substitution is indicated.

[0063] In one set of embodiments, R 2 It can be optionally controlled by one or two identical or different R. 5 The group representing the substituted phenyl group. In another set of embodiments, R 2 It can be optionally controlled by two identical or different R values. 5The group representing the substituted phenyl group. In another set of embodiments, R 2 It is 3-chloro-4-cyanophenyl, 3,4-dichlorophenyl, or 3,4-difluorophenyl. In a more preferred set of embodiments, R 2 It is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl. In a particularly preferred set of embodiments, R 2 It is 3,4-dichlorophenyl.

[0064] R 3 It is hydrogen or a C1-C6 alkyl group. Preferably, R 3 It is hydrogen or C1-C4 alkyl, more preferably hydrogen or C1-C3 alkyl. Even more preferably, R 3 It is hydrogen, methyl, or ethyl. Even more preferably, R 3 It is hydrogen or ethyl. Even more preferably, R 3 It is hydrogen.

[0065] R 4 It is hydrogen or halogen. Preferably, R 4 It is hydrogen, chlorine, fluorine, or bromine. More preferably, R 4 It is either hydrogen or bromine. In one set of embodiments, R 4 It is hydrogen.

[0066] R 5 It is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylthioalkyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl.

[0067] Preferably, R 5 It is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonylamino, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0068] More preferably, R 5It is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylthioalkyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonylamino, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0069] Even more preferably, R 5 It is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkyl carbonyl, or C3-C6 cycloalkyl. Even more preferably, R 5 It is cyano, nitro, chlorine, fluorine, methyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2-difluoroethoxy, methoxymethyl, acetyl, or cyclopropyl.

[0070] In one set of embodiments, R 5 It is cyano or halogen, preferably halogen, and more preferably R. 5 It is cyano or chlorine, and more preferably, R 5 It is chlorine.

[0071] X is a halogen. Preferably, X is chlorine, fluorine, or iodine. More preferably, X is chlorine or fluorine. Most preferably, X is chlorine.

[0072] In the compounds having formula (I) according to the invention, preferably:

[0073] R 1 It is a C1-C3 alkyl group;

[0074] R 2 It is two entities that can be the same or different, determined by R. 5 The group represents a phenyl group that has been substituted.

[0075] R 3 It is a C1-C3 alkyl group;

[0076] R 4 It is hydrogen or halogen;

[0077] R 5 It is either cyano or halogen; and

[0078] X is a halogen.

[0079] In another set of embodiments, R 1 It is a C1-C3 alkyl group;

[0080] R 2 It is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl;

[0081] R 3 It is hydrogen, methyl, or ethyl;

[0082] R 4 It is hydrogen or halogen; and

[0083] X is a halogen.

[0084] In another set of embodiments, R 1 It is a C1-C3 alkyl group;

[0085] R 2 It is 3,4-dichlorophenyl;

[0086] R 3 It is hydrogen or ethyl;

[0087] R 4 It is hydrogen; and

[0088] X is chlorine, fluorine, or iodine.

[0089] In another set of embodiments, R 1 It is ethyl;

[0090] R 2 It is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl;

[0091] R 3 It is hydrogen, methyl, or ethyl;

[0092] R 4 It is hydrogen or halogen; and

[0093] X is a halogen.

[0094] In another set of embodiments, R 1 It is ethyl;

[0095] R 2 It is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl;

[0096] R 3 It is hydrogen;

[0097] R 4 It is hydrogen; and

[0098] X is chlorine.

[0099] In a preferred embodiment, the compound having formula (I) is selected from 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (compound 2) and 6-chloro-2-(4-chloro-3-cyano-phenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (compound 6).

[0100] The compounds of the present invention can be prepared as shown in the following embodiments, wherein, unless otherwise stated, each variable is defined as above for compounds having formula (I). A general method for producing compounds having formula (I) is described below. Unless otherwise stated herein, R 1 R 2 R 3 R 4 X and X are as defined above. Starting materials used to prepare the compounds of the present invention may be purchased from common commercial suppliers or may be prepared by known methods. Starting materials and intermediates may be purified by existing methods (such as chromatography, crystallization, distillation, and filtration) before use in the next step.

[0101] Option 1:

[0102]

[0103] Compounds having formula (I) (where R) 3 (It is hydrogen) can be obtained by combining a compound having formula (A) (where R is hydrogen) 3 The product is prepared by hydrolysis of a C1-C6 alkyl group in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate, or tetrahydrofuran) with an optional co-solvent (such as water) using 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 trifluoromethanesulfonate or zinc trifluoromethanesulfonate). In the case of using a base, the product is obtained after acidification with a suitable acid (such as hydrochloric acid). Compounds having formula (A) can also be prepared by the methods described below.

[0104] Option 2:

[0105]

[0106] Compounds having formula (B) (where R) 3 (where R is a C1-C6 alkyl group and X is chlorine) can be converted into a compound of formula (A) (where R is chlorine) by a halogen exchange reaction with a suitable halide source (such as trimethylbromosilane or tetramethylammonium fluoride) under similar literature conditions. 3 It is a C1-C6 alkyl group and X is bromine or fluorine. Typically, it is in a suitable solvent (such as dimethylformamide or dichloromethane) at high temperature. This is shown in Scheme 2 above.

[0107] Option 3:

[0108]

[0109] Compounds having formula (C) (where R) 3 (C1-C6 alkyl) can be converted into a compound of formula (B) (where R is C1-C6 alkyl) by Sandmeyer halogenation with a suitable halogen source (such as copper chloride (I)) under similar literature conditions. 3 (It is a C1-C6 alkyl group). Typically, the reaction is carried out by reacting a compound having formula (C) at high temperature in a suitable solvent (such as acetonitrile or dichloromethane) and optionally in a co-solvent (such as water), in the presence of a suitable oxidant (such as sodium nitrite or isoamyl nitrite), a suitable halogen source (such as copper chloride (I)), and a suitable acid (such as hydrogen chloride). This is shown in Scheme 3 above.

[0110] Option 4:

[0111]

[0112] A compound having formula (D) (where R3 is a C1-C6 alkyl group) can be converted into a compound having formula (C) (where R3 is a C1-C6 alkyl group) by adding a suitable base (such as sodium ethoxide) to a suitable solvent (such as ethanol). This is illustrated in Scheme 4 above.

[0113] Option 5:

[0114]

[0115] Compounds having formula (D) can be prepared by reacting a compound having formula (E) with a compound having formula (F) at high temperature in the presence of a solvent (such as acetic anhydride) and an optional co-solvent (such as acetonitrile). This is illustrated in Scheme 5 above. Compounds having formulas (F) and (E) are commercially available and can also be prepared by methods familiar to those skilled in the art.

[0116] Option 6:

[0117]

[0118] Compounds having formula (A) can be prepared by decarboxylating and subsequently halogenating a compound having formula (G) at high temperature in a suitable solvent (such as dimethyl sulfoxide or acetonitrile), optionally in the presence of a base (such as potassium phosphate) with a halogenating agent (such as iodine). This is shown in Scheme 6 above. Other decarboxylation-halogenation conditions from the literature can also be used.

[0119] Option 7:

[0120]

[0121] Compounds having formula (G) can be prepared by oxidizing (e.g., via Pinnick oxidation) a compound having formula (H) (where R is an aldehyde or alcohol) in a suitable solvent (such as tert-butanol or 2-methylbut-2-ene) and optionally in the presence of water, in the presence of a base (such as sodium monophosphate) with a suitable oxidant (such as sodium chlorite). This is shown in Scheme 7 above. Other oxidation conditions from the literature can also be used.

[0122] Option 8:

[0123]

[0124] Compounds having formula (i) (where R is an aldehyde, alcohol, or carboxylic acid) can be prepared by treating a compound having formula (J) in a suitable solvent (e.g., acetonitrile) and optionally in the presence of a base (e.g., N-ethyl-N-isopropyl-prop-2-amine) with a suitable oxidizing agent (e.g., 4-methyl-4-oxo-morpholin-4-onium). This is illustrated in Scheme 8 above.

[0125] Option 9:

[0126]

[0127] Compounds having formula (J) can be prepared by reacting a compound having formula (K) with a compound having formula (E) at a high temperature (e.g., 140°C), optionally in the presence of a solvent (e.g., xylene). Both compounds having formulas (E) and (K) are commercially available and can be prepared by methods familiar to those skilled in the art. This is illustrated in Scheme 9 above.

[0128] Option 10:

[0129]

[0130] Compounds having formula (E) can be prepared by reacting β-keto esters having formula (M) with amine salts. Amine salts can be prepared in situ by acidifying an amine having formula (L) with a suitable acid (such as acetic acid). These amine salts can react with compounds having formula (M) in a suitable solvent (such as toluene or tetrahydrofuran) with an acid (such as acetic acid) and a drying agent (such as... The reaction takes place in the presence of a molecular sieve. This is shown in Scheme 10 above. Compounds having formula (M) are commercially available and can also be prepared using the conditions described in Scheme 11 below. Compounds having formula (L) are commercially available and can also be prepared by methods reported in the literature.

[0131] Option 11:

[0132]

[0133] Compounds having formula (M) can be prepared by treating a carboxylic acid having formula (O) (where A is a hydroxyl group or Cl) at ambient temperature in a suitable solvent (such as tetrahydrofuran) with an optional coupling agent (such as 1,1'-carbonyldiimidazole). The intermediate can then be reacted with a compound having formula (N) (such as potassium 3-methoxy-3-oxopropionate) 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 illustrated in Scheme 11 above. Compounds having formulas (O) and (N) are commercially available or can be prepared by methods familiar to those skilled in the art.

[0134] The present invention further provides a method for controlling weeds at a site, the method comprising applying to the site a composition comprising a compound having formula (I) to control the amount of weeds. Furthermore, the present invention can further provide a method for selectively controlling weeds at a site comprising useful (crop) plants and weeds, wherein the method comprises applying to the site a composition according to the present invention to control the amount of weeds. 'Control' means killing, reducing, or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention exhibit significantly improved selectivity compared to known structurally similar compounds. Typically, the plant to be controlled is an unwanted plant (weed). 'Site' means an area in which the plant is growing or will grow. Application can be made at the site before and / or after the emergence of the crop plants. Some crop plants can inherently tolerate the herbicidal effects of compounds having formula (I).

[0135] The application rate of compounds having formula (I) can vary within a wide range and depends on soil properties, application method (pre- or post-emergence; seed dressing; application in seed furrows; no-till application, etc.), crop plant, one or more weeds to be controlled, major climatic conditions, and other factors governed by the application method, application time, and target crop. Compounds having formula (I) according to the invention are typically applied at a rate of 10 to 2500 g / ha, particularly 25 to 1000 g / ha, and even more particularly 25 to 250 g / ha.

[0136] The composition is usually applied by spraying, typically using a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or immersion can also be used.

[0137] The term "useful plant" should be understood to also include useful plants that have developed tolerance to herbicides (like bromuconazole) or herbicide classes (e.g., 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors (e.g., flusulfuron, fluprosulfuron, and triflusulfuron), 5-enol-pyruvyl-shikimate-3-phosphate synthase (EPSPS) inhibitors, glutamine synthase (GS) inhibitors, or protoporphyrinogen oxidase (PPO) inhibitors) through conventional breeding or genetic engineering methods. Examples of crops that have been induced to tolerate imidazolinones (e.g., methoxyfenozide) through conventional breeding methods (mutation) are... Summer rapeseed (Canola). Examples of crops that have been genetically engineered to be resistant to herbicides or herbicide classes include glyphosate- and glufosinate-resistant corn varieties, marketed under trade names. Herculex and Available for commercial purchase.

[0138] The term “useful plant” should be understood to also include useful plants that have been transformed by the use of recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to come from toxin-producing bacteria, especially those of the genus Bacillus.

[0139] Examples of such plants are: (A corn variety expressing CryIA(b) toxin); YieldGard (A corn variety expressing CryIIIB(b1) toxin); YieldGard (A corn variety expressing CryIA(b) and CryIIIB(b1) toxins); (A corn variety expressing Cry9(c) toxin); Herculex (A corn variety that expresses CryIF(a2) toxin and the enzyme phosphatidylcholine N-acetyltransferase (PAT) to acquire tolerance to the herbicide glufosinate-ammonium salt); NuCOTN (Cotton variety expressing CryIA(c) toxin); Bolgard (Cotton variety, expressing CryIA(c) toxin); Bolgard I (Cotton varieties expressing CryIA(c) and CryIIA(b) toxins); (Cotton variety, expressing VIP toxin); (Potato variety that expresses CryIIIA toxin); GT Advantage (GA21 glyphosate resistance) CB Advantage (Bt11 Corn Borer (CB) traits), RW (corn rootworm trait) and

[0140] Plant crops or their seed material can be both herbicide resistant and insect predation resistant (“superimposed” transgenic events). For example, seeds can express the insecticidal protein Cry3 while simultaneously being resistant to glyphosate.

[0141] Crop plants should also be understood to include those obtained through conventional breeding or genetic engineering methods and containing so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0142] Unwanted plants (collectively referred to as 'weeds') can be controlled using compounds having formula (I) (or compositions containing it). Weeds to be controlled can be monocotyledonous species, such as *Agrostis*, *Alopecurus*, *Avena*, *Brachiaria*, *Bromus*, *Cenchrus*, *Cyperus*, *Digitaria*, *Echinochloa*, *Eleusine*, *Lolium*, *Monochoria*, *Rottboellia*, *Sagittaria*, *Scirpus*, and *Setaria*. a) and the genus *Sorghum*, which can also be dicotyledonous species, such as *Abutilon*, *Amaranthus*, *Ambrosia*, *Chenopodium*, *Chrysanthemum*, *Conyza*, *Galium*, *Ipomoea*, *Nasturtium*, *Sida*, *Sinapis*, *Solanum*, *Stellaria*, *Veronica*, *Viola*, and *Xanthium*.

[0143] Compounds having formula (I) can be used in unmodified form, or preferably together with adjuvants conventionally used in the formulation field to provide a herbicidal composition, using formulation adjuvants such as carriers, solvents, and surfactants (SAAs). Therefore, the present invention further provides a herbicidal composition comprising at least one compound having formula (I) and 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.

[0144] The herbicidal composition typically contains 0.1% to 99%, particularly 0.1% to 95% by weight of a compound having Formula I and 1% to 99.9% by weight of a formulation adjuvant, which preferably contains 0% to 25% by weight of a surfactant.

[0145] The composition can be selected from many formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), parent drug (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP), and soluble granules (SG). In any case, the type of formulation chosen will depend on the specific intended purpose and the physical, chemical, and biological properties of the compound having formula (I).

[0146] Soluble powders (SPs) can be prepared by mixing a compound having formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate, or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants, or a mixture of said reagents 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 (SGs).

[0147] Wettable powders (WPs) can be prepared by mixing a compound having formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersants, and optionally one or more suspending agents to promote dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WGs).

[0148] Granules (GR) can be formed by granulating a mixture of a compound having formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound having formula (I) (or a solution thereof in a suitable reagent) into a porous particulate material (such as pumice, attapulgite clay, bleaching clay, kieselguhr, diatomaceous earth, or corn cob powder), or by adsorbing a compound having formula (I) (or a solution thereof in a suitable reagent) onto a hard core material (such as sand, silicates, mineral carbonates, sulfates, or phosphates) and drying it if necessary, from pre-formed blanks. Reagents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars, and vegetable oils). One or more other additives (such as emulsifiers, wetting agents, or dispersants) may also be included in the granules.

[0149] Dispersible concentrates (DCs) can be prepared by dissolving a compound having 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 a spray can).

[0150] Emulsifiable concentrates (ECs) or oil-in-water emulsions (EWs) can be prepared by dissolving a compound having formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers, or a mixture of said reagents). Suitable organic solvents used in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150, and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone), and alcohols (such as benzyl alcohol, furfuryl alcohol, or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), and dimethylamides of fatty acids (such as C8-C...). 10 (Fatty acid dimethylamide) and chlorinated hydrocarbons. EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow for spray application using appropriate equipment.

[0151] The preparation of an emulsion (EW) involves obtaining a compound of formula (I) as a liquid (or, if not a liquid at room temperature, which can be melted at a reasonable temperature typically below 70°C) or as a solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution into water containing one or more SAAs under high shear to produce an emulsion. Suitable solvents used in EWs 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.

[0152] 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 having formula (I) is initially present in water or in a solvent / SAA blend. Suitable solvents used in MEs include those described above used in ECs or EWs. MEs can be oil-in-water or water-in-oil systems (whichever 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 in water, maintaining as a microemulsion or forming a conventional oil-in-water emulsion.

[0153] Suspension concentrates (SCs) may comprise aqueous or non-aqueous suspensions of finely fragmented, insoluble solid particles of a compound having formula (I). SCs can be prepared by ball milling or bead milling of a solid compound having formula (I) with one or more dispersants in a suitable medium to produce a fine-particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the rate of particle settling. Alternatively, a compound having formula (I) may be dry-milled and added to water containing the reagents described above to produce the desired final product.

[0154] Aerosol formulations comprise compounds having formula (I) and suitable propellants (e.g., n-butane). Compounds having 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 compositions for use in unpressurized, manually operated spray pumps.

[0155] Capsule suspensions (CS) can be prepared in a manner similar to that used in the preparation of EW formulations, but with an additional polymerization stage, to obtain an aqueous dispersion of oil droplets, wherein each droplet is encapsulated by a polymer shell and contains a compound of formula (I) and optionally a carrier or diluent for the droplet. The polymer shell can be produced by interfacial polycondensation or by a coagulation process. These compositions can provide controlled release of compounds of formula (I) and they can be used for seed treatment. Compounds of formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0156] The composition may contain one or more additives to improve the biological properties of the composition, for example by improving wettability, retention, or distribution on a surface; rain resistance on the treated surface; or absorption or migration of compounds having formula (I). Such additives include surfactants (SAAs), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), modified vegetable oils (such as methylated rapeseed oil (MRSO)), and blends of these with other bio-enhancing adjuvants (components that may assist or modify the effects of compounds having formula (I)).

[0157] The wetting agent, dispersant, and emulsifier can be cationic, anionic, amphoteric, or nonionic SAA.

[0158] Suitable cationic types of SAAs include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0159] 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-naphthalene sulfonate and sodium tri-isopropyl-naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (products of reactions between one or more fatty alcohols and phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), such as the reaction between lauryl alcohol and tetraphosphate; additionally, these products may be ethoxylated), sulfosuccinates, paraffin or olefin sulfonates, taurine, lignin sulfonates, and phosphate / sulfate salts of tristyrylphenol.

[0160] Suitable amphoteric types of SAAs include betaine, propionate, and glycine salt.

[0161] Suitable nonionic types of SAAs include condensation products of alkyl oxidases (such as ethylene oxide, propylene oxide, butane 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 hexyl anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); lecithin and sorbitol and their esters, alkyl polyglycosides, and tristyrylphenols.

[0162] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethyl cellulose) and expansive clays (such as bentonite or attapulgite).

[0163] The compounds of the present invention can also be used in mixtures with one or more other herbicides and / or plant growth regulators. Examples of such other herbicides or plant growth regulators include acetochlor, trifluralin (including trifluralin-sodium), bensulfuron, atrazine, aminopyrrolidone, chlorpyrifos, atrazine, flubutyroxyfen-M, benquitrione, bensulfuron-methyl (including bensulfuron-methyl), bentazon, dicyclopyranone, bispyridine, bispyribac-sodium, bixlozone, broclozone, chlorpyrifos, bromobenzonitrile, butachlor, flupropyrin, chlorpyrifos (including chlorpyrifos-ethyl), chlorpyrifos-methyl (including chlorpyrifos-methyl), and chlorpyrifos-ethyl (including chlorpyrifos-ethyl). Greenmium, chlorsulfuron, cyclohexane, clacyfos, clethodim, clodinafop-propargyl (including clodinafop-propargyl), isoxaflutole, dichloropyridinic acid, cyclopyranil, cyclopyrimorate, cycloprosulfuron, cyhalofop-propargyl (including cyhalofop-propargyl-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, 2,4-D propionic acid, diethylene glycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), dichlorvos, pyrfluthrin, flupyridine, metolachlor, fenfluridine, pyridaben, pyridaben Dioxopyritrione, dibromodiflubenzuron, diuron, epyrifenacil, ethylbutadiene, ethoxysulfuron, quizalofop-P-ethyl (including quizalofop-P-ethyl), fenoxasulfone, fenquinotrione, tetrazolium, pyrimisulfuron, diflubenzuron, florpyrauxifen (including florpyrauxifen-benzyl), quizalofop-P-butyl (including quizalofop-P-butyl), fluoxetine (including fluoxetine-sodium), fluchloraminopyr This includes fluchloraminopyr-tefuryl, flufenoximacil, flufenoximacil, pyrazosulfuron, propyzoxystrobin, fluroxypyr, flusulfanilamide, flupyrimisulfuron (including flupyrimisulfuron-methyl-sodium), fluroxypyr-meptyl (including fluroxypyr-meptyl), flusulfanilamide, flusulfanilamide, formamide-sulfuron, glufosinate (including L-glufosinate and its ammonium salts), glyphosate (including its hydrazine, isopropylammonium, and potassium salts), halauxifen (including halauxifen ester), flupyridine (including flupyridine-methyl), cyclopyridone, etc.Hydantocidin, icafolin (including isoxaflutole-methyl), methoxymethylene (including R-methoxymethylene), imidacloprid, metribuzin, imidacloprid, indazon, indolauxipyr (including indolauxipyr-cyanomethyl), iofensulfuron (including iofensulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), iofensulfuron, iptriazopyrid, isoproturon, isoxaflutole, lancotrione ), MCPA, MCPB, mecoprop-P, mesosulfuron-methyl (including mesosulfuron-methyl), nicosulfuron, bensulfuron-methyl, pyrazosulfuron, methiozolin, metolachlor, sulfadiazine, cyprodinil, mesosulfuron-methyl, dichlorvos, nicosulfuron, dapoxuron, oxadiazon, cyclosulfuron, ethoxysulfuron, paraquat dichlorvos, pendimethalin, penflusulfuron-methyl, bensulfuron-methyl, propyrisulfuron, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron-methyl, propyrazosulfuron, propyrazosulfuron, propyrazosulfuron-methyl, propyrazosulfuron, propyrazosulfuron-methyl, propyrazosulfuron, propyrazosulfuron-methyl, propyrazosulfuron, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, propyrazosulfuron-methyl, pyraflufen-methyl (Including pyraquinate, sulfonylurea, pyrazosulfuron, pyriflubenzoxim, pyrimisulfan, pyrrolizumab, pyrazosulfuron, pyrazosulfuron, quizalofop-P-tefuryl, quizalofop-P-tefuryl (including quizalofop-Ethyl and quizalofop-P-tefuryl), rimisoxafen, sulfadiazine, pyrazosulfuron, silazine, simazine, S-metolachlor, metolachlor, sulfonylurea, butyrazosulfuron, terbufos, sulfadiazine, terbufos, terbufos, tetflup yrolimet), thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, bensulfuron-methyl, triafamone, wild valerate, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), chlorpyrifos, trifluralin (including trifluralin-sodium), trifluralin, trifluralin, flusulfanilamide, triazolesulfuron, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester,4-Hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl) [Pyrazol-3-yl]imidazolidine-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methylimidazolidine-2-one, (1RS,5SR)-3-[2-methoxy-4-(prop-1-yn-1-yl)phenyl]-4-oxobicyclo[3.2.1]oct-2-en-2-yl methyl carbonate, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, 2- [2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetic acid methyl ester, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidin-4-carboxylic acid (2-fluorophenyl) methyl ester, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidin-4-carboxylic acid, 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-cyclopentane[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-pyrimidin-4-carboxylate.

[0164] Mixtures of compounds having formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition, British Crop Protection Council, 2012. The mixing ratio of the compound having formula (I) to the mixture is preferably 1:100 to 1000:1.

[0165] These mixtures can be advantageously used in the formulations mentioned above (in which case, "active ingredient" refers to the corresponding mixture of a compound having formula (I) with a mixed formulation).

[0166] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include cloquintocet, cloquintocet (including cloquinoline), cyclopropanesulfonamide, dichloropropeneamine, cloquinoxal (including cloquinoline ethyl ester), cloquinoxaline, flufenoxam, cloquinoxalic acid (including cloquinoxalic acid-ethyl), mefenpyr (including cloquinoxalic acid ester), metcamifen, and cloquinoxalic acid nitrile. Particularly preferred are mixtures of compounds having formula (I) with cyclopropanesulfonamide, cloquinoxalic acid-ethyl, cloquinoline, and / or cloquinoxalic acid nitrile.

[0167] Safeguards of compounds having formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition (BCPC), 2012. References to antitoxin quinine also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts, as disclosed in WO 02 / 34048.

[0168] Preferably, the mixing ratio of the compound having formula (I) to the safener is 100:1 to 1:10, especially 20:1 to 1:1.

[0169] Compounds having formula (I) are typically used in the form of agricultural chemical compositions and can be applied simultaneously or sequentially to the crop area or plant to be treated. These additional compounds may, for example, be fertilizers or micronutrient donors or other formulations that influence plant growth. They may also be selective or non-selective herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these formulations, along with, if desired, additional carriers, surfactants, or application-promoting adjuvants commonly used in the formulation field.

[0170] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds and seedlings, and established vegetation.

[0171] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0172] The term "plant propagation material" should be understood to refer to the reproductive parts of a plant, such as seeds, which can be used for plant propagation, as well as vegetarian material, such as cuttings or tubers (e.g., potatoes). References may include, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of the plant. References may also include germinating plants and young plants that will be transplanted after germination or emergence. These young plants can be protected before transplanting by complete or partial treatment via maceration. Preferably, "plant propagation material" should be understood to mean seeds.

[0173] The pesticides mentioned in this article that use their common names are known, for example, from "The Pesticide Manual", 15th edition, British Crop Protection Council 2009.

[0174] Compounds having formula (I) can be used in their unmodified form, or preferably, together with adjuvants conventionally used in the field of formulations. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and encapsulants, for example, in polymeric substances. The method of application, such as spraying, atomizing, dusting, spreading, coating, or watering, is selected according to the intended purpose and the prevailing environment for the type of composition. The composition may also contain additional adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders or thickeners, and fertilizers, micronutrient donors, or other formulations used to achieve specific effects.

[0175] Suitable carriers and adjuvants, for example for agricultural uses, can be solid or liquid and are useful in formulation techniques, such as natural or recycled minerals, solvents, dispersants, wetting agents, thickeners, binders, or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0176] Compounds having formula (I) are typically used in the form of compositions and can be applied simultaneously or sequentially to the crop area or plant to be treated. These additional compounds may, for example, be fertilizers or micronutrient donors or other formulations that influence plant growth. They may also be selective or non-selective herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these formulations, along with, if desired, additional carriers, surfactants, or application-promoting adjuvants commonly used in the formulation field.

[0177] A compound having formula (I) may be the sole active ingredient in a composition, or, where appropriate, it may be mixed with one or more other active ingredients (such as pesticides, fungicides, synergists, herbicides, or plant growth regulators). In some cases, the additional active ingredients may produce unexpected synergistic effects.

[0178] Typically, formulations comprise 0.01% to 90% by weight of an active agent, 0% to 20% by weight of an agriculturally acceptable surfactant, and 10% to 99.99% by weight of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being at least composed of a compound having formula (I) together with components (B) and (C), and optionally other active agents (particularly microbicides or preservatives or the like). Concentrated forms of the composition typically contain between about 2% and 80% by weight of the active agent, preferably between about 5% and 70% by weight. Application forms of the formulation may, for example, contain 0.01% to 20% by weight of the active agent, preferably between 0.01% and 5% by weight. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0179] The following table shows examples of individual compounds having formula (I) according to the present invention:

[0180]

[0181] Table 1: Compounds of Formula (I) according to the present invention

[0182] Compound numbering <![CDATA[R 2 ]]> Compound numbering <![CDATA[R 2 ]]> 001 Phenyl 014 5-Chloro-2-fluorophenyl 002 2-Chlorophenyl 015 3-Fluoro-4-cyanophenyl 003 3-Chlorophenyl 016 3-Chloro-4-cyanophenyl 004 4-Chlorophenyl 017 3-Fluoro-4-methylphenyl 005 2,4-Dichlorophenyl 018 3-Chloro-4-methylphenyl 006 3,4-Dichlorophenyl 019 3-Methyl-4-fluorophenyl 007 3,5-Dichlorophenyl 020 3-Methyl-4-chlorophenyl 008 2-Fluorophenyl 021 3-Methoxy-4-chlorophenyl 009 4-Fluorophenyl 022 4-Methoxy-3-chlorophenyl 010 3,4-Difluorophenyl 023 3,5-Difluoro-4-chlorophenyl 011 3-Chloro-4-fluorophenyl 024 3,5-Difluoro-4-cyanophenyl 012 4-Chloro-3-fluorophenyl 025 3,5-Dichloro-4-cyanophenyl 013 4-Chloro-2-fluorophenyl 026 3-Chloro-4-cyano-5-fluorophenyl

[0183] Table A-1 Twenty-six compounds having formula (I) from A-1.001 to A.1.026 are provided, wherein R 1 It is ethyl, X is chlorine, R 3 and R 4 Both are hydrogen, and R 2 It is defined in Table 1.

[0184] Table A-2 Twenty-six compounds having formula (I) are provided, from A-2.001 to A.2.026, wherein R 1 It is ethyl, X is bromine, R 3 and R 4 Both are hydrogen, and R 2 It is defined in Table 1.

[0185] Table A-3 Twenty-six compounds having formula (I) from A-3.001 to A.3.026 are provided, wherein R 1 It is ethyl, X is chlorine, R3 It is hydrogen, R 4 It is bromine, and R 2 It is defined in Table 1.

[0186] Table A-4 Twenty-six compounds having formula (I) from A-4.001 to A.4.026 are provided, wherein R 1 It is ethyl, X is chlorine, R 3 It is ethyl, R 4 It is hydrogen, and R 2 It is defined in Table 1.

[0187] Table A-5 Twenty-six compounds having formula (I) are provided, ranging from A-5.001 to A.5.026, wherein R 1 It is ethyl, X is chlorine, R 3 It is methyl, R 4 It is hydrogen, and R 2 It is defined in Table 1.

[0188] Examples of preparations

[0189]

[0190] The active ingredient and excipients are thoroughly mixed and the mixture is thoroughly ground in a suitable grinder to provide a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0191]

[0192] The active ingredients and adjuvants are thoroughly mixed and the mixture is thoroughly ground in a suitable grinder to provide a powder that can be used directly for seed treatment.

[0193] Emulsifiable concentrate

[0194]

[0195] Emulsions with any required dilution that can be used in plant protection can be obtained from such concentrates by diluting them with water.

[0196]

[0197] 5. Ready-to-use dust powders are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry seed dressing.

[0198] Extruder granules

[0199]

[0200] The active ingredient and excipients are mixed and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an air stream.

[0201] Coated granules

[0202] Active ingredient [a compound having formula (I)] 8%

[0203] Polyethylene glycol (molecular weight 200) 3%

[0204] 89% Kaolin

[0205] The finely ground active ingredient is evenly applied to kaolin clay moistened with polyethylene glycol in a mixer. This process yields dust-free coated granules.

[0206] suspension concentrate

[0207]

[0208] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, which can be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants and plant propagation material can be treated and protected from microbial contamination by spraying, watering, or immersion.

[0209] Flowable concentrate for seed treatment

[0210]

[0211] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, which can be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants and plant propagation material can be treated and protected from microbial contamination by spraying, watering, or immersion.

[0212] Sustained-release capsule suspension

[0213] A mixture of 28 parts of compounds having formula (I) was mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was 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 was achieved. A mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water was added to this emulsion. The mixture was stirred until polymerization was complete. The resulting capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contained 28% of the active ingredient. The diameter of the medium capsules was 8-15 micrometers. The resulting formulation was applied to seeds as an aqueous suspension suitable for this purpose.

[0214] Example

[0215] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (mentioned in Table 2 below).

[0216] Throughout this specification, temperatures are given in degrees Celsius (°C), and “mp” indicates melting point.

[0217] List of abbreviations

[0218] ℃ = degrees Celsius, d = doublet, dd = doublet, DMSO = dimethyl sulfoxide, M = mole, m = multiplet, MHz = megahertz, q = quartet, qd = quartet, s = singlet, t = triplet.

[0219] Example 1: Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (compound 1)

[0220] Step 1: Synthesis of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propionate

[0221]

[0222] Sodium hydride (3.17 g, 80 mmol, 60% by mass) was added in portions to a stirred solution of 1-(3,4-dichlorophenyl) ethyl ketone (5.00 g, 26.5 mmol) and dimethyl carbonate (40 mL, 466 mmol) under nitrogen atmosphere and at 0 °C. The reaction mixture was heated to room temperature and stirred for 16 hours. After overnight, the reaction mixture became an unstirrable solid paste. More dimethyl carbonate (10 mL) was added in an attempt to produce a flowing 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 to ethyl acetate. The organic extract was dried over magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography to give ethyl 3-(3,4-dichlorophenyl)-3-oxo-propionate (a mixture of tautomers) as a colorless liquid.

[0223] Enols: 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).

[0224] ketone: 1 ¹H NMR (400MHz, chloroform) δ=8.03(d,1H),7.77(m,1H),7.58(d,2H),3.97(s,2H),3.76(s,3H).

[0225] Step 2: Synthesis of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

[0226]

[0227] Ethyl ethylammonium acetate (19.0 mmol) and acetic acid (6.32 mmol) were added to a stirred solution of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propionate (1.65 g, 6.32 mmol) in toluene (11 mL). The orange reaction mixture was heated under reflux for 6 hours. The cooled reaction mixture was diluted with ethyl acetate and washed with a saturated aqueous sodium bicarbonate solution. The phases were separated, and the aqueous phase was extracted into ethyl acetate (×3). The organic extract was dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel chromatography to give ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate as a colorless oil. 1¹H 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).

[0228] Step 3: Synthesis of ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butyrate

[0229]

[0230] A solution of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (5.10 g, 17.7 mmol) and 2-cyanoacetic acid (1.51 g, 17.7 mmol) in acetic anhydride (16 mL) was heated at 105 °C for 0.25 h 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 silica gel chromatography to give ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butyrate as a grayish-white solid.

[0231] Step 4: Synthesis of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0232]

[0233] Sodium ethoxide (4.11 g, 12.7 mmol) was added to a stirred solution of (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butyrate (4.50 g, 12.67 mmol) in ethanol (80 mL) 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 into dichloromethane. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by rapid C-18 silica gel chromatography to give ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate as a white solid. 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).

[0234] Step 5: Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0235]

[0236] Copper(I) chloride (0.167 g, 1.69 mmol) was added to a suspension of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (0.500 g, 1.41 mmol) in a mixture of acetonitrile (12 mL) and aqueous hydrogen chloride solution (2 M, 1.8 mL). The resulting reaction mixture was heated to 75 °C, and then a solution of sodium nitrite (0.126 g, 1.83 mmol) in water (1 mL) was added dropwise. The reaction mixture was heated at 75 °C for 0.25 h with stirring. The cooled reaction mixture was poured into a saturated aqueous ammonium chloride solution (30 mL) and extracted into ethyl acetate (2 × 50 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by C-18 silica gel rapid chromatography to obtain ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-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).

[0237] Example 2: Synthesis of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (compound 2)

[0238]

[0239] A mixture of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (0.200 g, 0.53 mmol) and tris(trifluoromethanesulfonyloxy)scandium (0.276 g, 0.56 mmol) in water (2 mL) and tetrahydrofuran (2 mL) was heated at 120 °C for 0.5 h under microwave irradiation. The cooled reaction mixture was diluted with water and extracted into ethyl acetate. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness under reduced pressure to give 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-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).

[0240] Example 3: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylate (compound 3)

[0241] Step 1: Synthesis of 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one

[0242]

[0243] 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 aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate solutions. The organic phase was dried over magnesium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by rapid C-18 silica gel chromatography to give 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one as a yellow oil. 1 ¹H NMR (400MHz, chloroform) δ = 5.54 (s, 1H), 3.90 (s, 2H), 1.73 (s, 6H).

[0244] Step 2: Synthesis of ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0245]

[0246] Add 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one (2.30 g, 10.4 mmol) to a stirred solution of (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (2.00 g, 6.94 mmol) in xylene (20.0 mL). Heat the resulting reaction mixture at 140 °C for 5 minutes with stirring. Dilute the cooled reaction mixture with ethyl acetate, wash the organic solution with brine, dry over magnesium sulfate, filter, and evaporate to dryness under reduced pressure to give 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-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).

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

[0248]

[0249] Ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (6.99 g, 16.1 mmol) and N-ethyl-N-isopropyl-prop-2-amine (3.67 mL, 21.0 mmol) in acetonitrile (140 mL) were added in portions to a stirred solution. The reaction mixture was stirred at 25 °C for 2.5 h. The reaction mixture was diluted with water and ethyl acetate, and the phases were separated. The organic phase was washed with brine, dried over magnesium sulfate, and evaporated to dryness under reduced pressure to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-carboxyyl-4-oxo-pyridine-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).

[0250] Step 4: Synthesis of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-2-carboxylic acid

[0251]

[0252] A solution of sodium monophosphate (4.20 g, 34.7 mmol) in water (39 mL) was added to a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate (5.67 g, 15.4 mmol) in tert-butanol (77 mL) and 2-methylbut-2-ene (77 mL). The reaction mixture was cooled to 0 °C and sodium chlorite (4.22 g, 46.2 mmol) was added in portions. The reaction mixture was heated to room temperature and stirred for 2.5 h. The resulting yellow solution was diluted with brine, methanol, and 2 M hydrochloric acid aqueous solution, and then extracted into ethyl acetate. The organic extract was extracted into a saturated sodium metabisulfite solution. The aqueous phase was acidified to pH 1 by adding 2 M hydrochloric acid aqueous solution and extracted into dichloromethane. The organic extract was evaporated to dryness under reduced pressure to give 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-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).

[0253] Step 5: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylate

[0254]

[0255] Iodine (0.281 g, 1.11 mmol) was added to a stirred solution of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-2-carboxylic acid (1.42 g, 3.69 mmol) in methyl sulfinylmethane (37 mL). The reaction mixture was heated at 120 °C for 1.5 h, 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. The organic filtrate was evaporated to dryness under reduced pressure to give a yellow oil, which was purified by C-18 silica gel rapid chromatography to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid as a yellow solid. 1¹H 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).

[0256] Example 4: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-fluoro-4-oxo-pyridine-3-carboxylate (compound 7)

[0257]

[0258] A suspension of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-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 at 40 °C with stirring for 40 hours. The cooled reaction mixture was diluted with ethyl acetate and washed successively 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 rapid C-18 silica chromatography to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-fluoro-4-oxo-pyridine-3-carboxylate as a white solid. 1 ¹H 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).

[0259] Example 5: Synthesis of ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0260]

[0261] Ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (500 mg, 1.33 mmol) was dissolved in acetonitrile (13 mL) and trimethylbromosilane (600 μL, 4.46 mmol) was added. The reaction mixture was then heated at 60 °C for 3.5 h. The cooled reaction mixture was neutralized with saturated sodium bicarbonate solution. The mixture was then extracted with dichloromethane, and the organic extract was dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude product was purified by rapid silica chromatography to give ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate as a pale yellow solid.

[0262] Example 6: Synthesis of 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (compound 8)

[0263]

[0264] Ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (40 mg, 0.10 mmol) and scandium trifluoromethanesulfonate (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 to 120 °C for 45 minutes. The reaction mixture was then diluted with water and 2 M HCl solution and 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 rapid chromatography using 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).

[0265] Table 2: Selected compounds of the present invention 1 H NMR data.

[0266]

[0267]

[0268]

[0269]

[0270] Biological examples

[0271] Seeds of several test species were sown in standard soil in pots (Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Amaranthus palmeri (AMAPA), ZeaMX, and Amaranthus retoflexus (AMARE)). After culturing for 8 days under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14-hour light; 65% humidity), the plants were sprayed with an aqueous solution derived from an industrial-grade formulation of the 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. These test plants were then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice daily. After 13 days, the percentage of damage to the plants caused by the test was evaluated. The table below shows biological activity on a five-point scale (5 = 81%-100%; 4 = 61%-80%; 3 = 41%-60%; 2 = 21%-40%; 1 = 1%-20%; 0 = no activity; - = not tested).

[0272] Table B1: Pre-emergence testing

[0273] Compound numbering SETFA AMARE ECHCG AMAPA ZEAMX 2 5 3 3 2 1 6 5 5 2 3 0

[0274] Table B2: Post-emergence testing

[0275] Compound numbering SETFA AMARE ECHCG AMAPA ZEAMX 2 4 1 3 1 0 6 4 0 1 0 1 .

Claims

1. A compound of Formula (I) or a salt or N-oxide thereof, R 1 is Ci-C6alkyl, Ci-C6alkoxy, C2-C6alkenyl, C2-C6alkynyl, Ci-C6alkoxyCi-C6alkyl, or C3-C6cycloalkyl; R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety can optionally be substituted by 1, 2, 3 or 4 groups, which can be the same or different, represented by R 5 ; R 3 is hydrogen or Ci-C6alkyl; R 4 is hydrogen or halogen; R 5 is cyano, nitro, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, C1-C6haloalkoxy, C1-C6alkoxyC1-C6alkyl, C1-C6alkylsulfanyl, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6alkylsulfonamido, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, C3-C6cycloalkyl, C3-C6cycloalkylaminocarbonyl, or N,N-di(C1-C4alkyl)aminocarbonyl; and X is halogen.

2. The compound of claim 1, wherein, R 1 is C1-C3 alkyl.

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

4. The compound according to any one of claims 1 to 3, wherein, R 2 is phenyl optionally substituted by 1 or 2 groups, which can be the same or different, represented by R 5 .

5. The compound according to any one of claims 1 to 4, wherein, R 3 is hydrogen or C1-C3alkyl.

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

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

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

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

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

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

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

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

14. A method of controlling weeds at a locus, the method comprising applying to the locus a weed- 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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