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. # imgabs0 #

Description

[0001] The present invention relates to herbicidal pyridone derivatives (e.g., as active ingredients), which have herbicidal activity. The present invention also relates to agrochemical compositions comprising at least one of these pyridone derivatives, methods for preparing these compounds, and the use of these pyridone derivatives or compositions for controlling weeds in agriculture or horticulture, particularly weeds in crops of useful plants.

[0002] EP 0239391, EP 0127313, EP 0040082, GB 2182931, WO 2022117445 and WO2022117446 describe pyridone derivatives as herbicides.

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

[0004]

[0005] wherein

[0006] R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC1-C6 alkyl, or C3-C6 cycloalkyl;

[0007] R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein each phenyl and heteroaryl moiety may optionally be substituted by 1, 2, 3 or 4 groups represented by R 5 ;

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

[0009] R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monoring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, wherein the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties may each optionally be substituted by 1, 2, 3 or 4 groups represented by R 6 ;

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

[0011] R 6 is cyano, nitro, halogen, oxo, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkoxy, N,N-di(C1-C4 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, phenyl, phenoxy, or benzyloxy, where each cycloalkyl or phenyl moiety may optionally be substituted by 1 or 2 groups, which may be the same or different, represented by R 8 ; or

[0012] any two adjacent R 6 groups together with the carbon atoms to which they are attached may form a phenyl ring, or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O and N, and where the phenyl ring and the heterocyclic ring may optionally be substituted by 1, 2, 3 or 4 groups, which may be the same or different, represented by R 9 ;

[0013] R 8 is cyano, halogen, C1-C3 alkyl, or C1-C3 alkoxy;

[0014] R 9 is halogen, C1-C3 alkyl, or C1-C3 alkoxy.

[0015] Surprisingly, it has been found that, for practical purposes, the novel compounds of formula (I) have a very advantageous level of herbicidal activity.

[0016] According to a second aspect of the present invention, there is provided an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) according to the present invention. Such an agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0017] According to a third aspect of the present invention, there is provided a method for controlling weeds at a site, the method comprising applying to the site a composition comprising a compound of formula (I) in an amount effective for controlling weeds.

[0018] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) as a herbicide.

[0019] When a substituent is represented as "optionally substituted", this means that they may or may not carry one or more identical or different substituents, for example one, two or three R 6 substituents. For example, a C1-C6 alkyl group substituted with 1, 2 or 3 halogens may include, but is not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, a C1-C6 alkoxy group substituted with 1, 2 or 3 halogens may include, but is not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.

[0020] As used herein, the term "cyano" means a -CN group.

[0021] As used herein, the term "halogen" refers to fluorine / fluoro, chlorine / chloro, bromine / bromo or iodine / iodo.

[0022] As used herein, the term "nitro" means a -NO2 group.

[0023] As used herein, the term "acetyl" means a -C(O)CH3 group.

[0024] As used herein, =O means an oxo group, for example, as seen in a carbonyl (-C(=O)-) group.

[0025] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, having no unsaturation, having one to six carbon atoms, and attached to the remainder of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" shall be interpreted accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and its isomers, such as isopropyl. "C1-C6 alkylene" refers to the corresponding definition of C1-C6 alkyl, except that such a group is attached to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" shall be interpreted accordingly. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0026] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl as generally defined above, which group is substituted by one or more of the same or different halogen atoms. "C1-C4 haloalkyl" and "C1-C3 haloalkyl" shall be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0027] As used herein, the term "C1-C6 alkoxy" refers to a group having the formula -OR a wherein R a is a C1-C6 alkyl as generally defined above. "C1-C4 alkoxy" and "C1-C3 alkoxy" shall be interpreted accordingly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0028] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy as generally defined above, which is substituted by one or more of the same or different halogen atoms. "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" shall be interpreted accordingly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0029] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, having at least one double bond which may have an (E)- or (Z)-configuration, having two to six carbon atoms, and attached to the remainder of the molecule by a single bond. "C2-C3 alkenyl" shall be interpreted accordingly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl / vinyl, prop-1-enyl, prop-2-enyl (allyl), but-1-enyl.

[0030] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, having at least one triple bond, having two to six carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C2-C3 alkynyl" shall be interpreted accordingly. Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.

[0031] As used herein, the term "C2-C6 alkenyloxy" refers to a C2-C6 alkenyl group as generally defined above attached to the remainder of the molecule through an oxygen atom.

[0032] As used herein, the term "C2-C6 alkynyloxy" refers to a C2-C6 alkynyl group as generally defined above attached to the remainder of the molecule through an oxygen atom.

[0033] As used herein, the term "C1-C6 alkoxy C1-C6 alkyl" refers to a group having the formula R b OR a -, where R b is a C1-C6 alkyl group as generally defined above, and R a is a C1-C6 alkylene group as generally defined above. The term "C1-C4 alkoxy C1-C4 alkyl" shall be interpreted accordingly.

[0034] As used herein, the term "C1-C6 alkoxy C1-C6 alkoxy" refers to a group having the formula R b OR a O-, where R a and R b are each independently a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkoxy C1-C4 alkoxy" and "C1-C3 alkoxy C1-C3 alkoxy" shall be interpreted accordingly.

[0035] As used herein, the term "C3-C6 cycloalkyl" refers to a group containing 3 to 6 carbon atoms that is a monocyclic saturated ring system. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" shall be interpreted accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0036] As used herein, the term "C3-C6 cycloalkenyl" refers to a group that is a monocyclic unsaturated ring system containing at least one double bond and containing 3 to 6 carbon atoms. The terms "C3-C5 cycloalkenyl" and "C3-C4 cycloalkenyl" shall be interpreted accordingly. Examples of C3-C6 cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0037] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule by a C1-C6 alkylene linking group as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkyl include, but are not limited to, cyclopropylmethyl.

[0038] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkoxy" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule by a C1-C6 alkoxy linking group as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkoxy include, but are not limited to, cyclopropoxy.

[0039] As used herein, the term "C3-C6 cycloalkylaminocarbonyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule by an -NHC(O)- linking group. Examples of C3-C6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0040] As used herein, the term "C6-C 10 aryl" refers to a 6- to 10-membered aromatic ring system consisting only of carbon and hydrogen atoms, which aromatic ring system may be monocyclic, bicyclic, or tricyclic. Examples of such ring systems include phenyl, naphthyl, or indenyl.

[0041] As used herein, the term "C6-C 10 aryl C1-C3 alkyl" refers to an aryl moiety as generally defined above, which aryl moiety is attached to the remainder of the molecule by a C1-C3 alkylene linking group as defined above.

[0042] As used herein, the term "phenoxy" refers to a phenyl ring attached to the remainder of the molecule by an oxygen atom.

[0043] As used herein, the term "benzyloxy" refers to a benzyl ring attached to the remainder of the molecule by an oxygen atom.

[0044] As used herein, the term "heterocyclyl" refers to a stable 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1, 2, or 3 heteroatoms, where the heteroatoms are independently selected from nitrogen, oxygen, and sulfur. The heterocyclyl may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, aziridinyl, azetidinyl, oxetidinyl, thietidinyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

[0045] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing 1, 2, 3, or 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl.

[0046] As used herein, the term "C1-C6 alkylcarbonyl" refers to a group having the formula -C(O)R a wherein R a is a C1-C6 alkyl as generally defined above. Examples of C1-C6 alkylcarbonyl include, but are not limited to, acetyl.

[0047] As used herein, the term "C1-C6 alkoxycarbonyl" refers to a group having the formula -C(O)OR a wherein R a is a C1-C6 alkyl as generally defined above.

[0048] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to a group having the formula -C(O)NHR a wherein R a is a C1-C6 alkyl as generally defined above. Examples of C1-C6 alkylaminocarbonyl include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl).

[0049] As used herein, the term "N,N-di(C1-C4 alkyl)aminocarbonyl" refers to a group having the formula -C(O)N(R a )(R b ) wherein R a and R b are each independently a C1-C4 alkyl 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).

[0050] As used herein, the term "N,N-di(C1-C4 alkyl)aminosulfonyl" refers to a group having the formula -S(O)2N(R a )(R b ) wherein R a and R b are each independently a C1-C4 alkyl 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).

[0051] As used herein, the term "C1-C6 alkylthio" refers to a group having the formula -SR a wherein R a is a C1-C6 alkyl as generally defined above. The terms "C1-C4 alkylthio" and "C1-C3 alkylthio" shall be interpreted accordingly. Examples of C1-C6 alkylthio include, but are not limited to, methylthio.

[0052] As used herein, the term "C1-C6 alkylsulfinyl" refers to a group having the formula -S(O)R a wherein R a is a C1-C6 alkyl as generally defined above. The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" shall be interpreted accordingly. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl.

[0053] As used herein, the term "C1-C6 alkylsulfonyl" refers to a group having the formula -S(O)2R a wherein R a is a C1-C6 alkyl as generally defined above. The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" shall be interpreted accordingly. Examples of C1-C6 alkylsulfonyl include, but are not limited to, methylsulfonyl.

[0054] As used herein, the term "C1-C6 alkylsulfonamido" refers to a group having the formula -NHS(O)2R a wherein R a is a C1-C6 alkyl as generally defined above.

[0055] The presence of one or more possible stereogenic elements in a compound of formula (I) means that the compound can exist in enantiomeric forms (i.e., enantiomers or diastereomers) and, as a result of restricted rotation about a single bond, atropisomers may exist. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof of the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of the compounds of formula (I).

[0056] In each case, the compound of formula (I) according to the invention is in free form, oxidized form (such as N-oxide), or salt form (e.g., an agriculturally acceptable salt form). Preferably, the compound of 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 group of embodiments, the compound of formula (I) can form chlorides or 2,2,2-trifluoroacetates.

[0057] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton (1991).

[0058] The following list provides definitions for the substituents R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 and R 9 of the compound of formula (I), including preferred definitions. For any one of these substituents, any definition given below can be combined with any other definition of any other substituent given below or elsewhere in this document.

[0059] R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC1-C6 alkyl, or C3-C6 cycloalkyl. Preferably, R 1 is C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxyC1-C4 alkyl, or C3-C6 cycloalkyl. More preferably, R 1 is C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyC1-C3 alkyl, or C3-C4 cycloalkyl. Even more preferably, R 1 is methyl, ethyl, n-propyl, methoxy, 2-methoxyethyl, allyl, and prop-2-ynyl. In a group of embodiments, R 1 is C1-C3 alkyl, preferably methyl or ethyl, and more preferably ethyl.

[0060] R 2is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein each phenyl and heteroaryl moiety may optionally be substituted by 1, 2, 3 or 4 groups represented by R 5 as defined below.

[0061] Preferably, R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, and wherein each phenyl and heteroaryl moiety may optionally be substituted by 1, 2 or 3 groups represented by R 5 as defined below.

[0062] More preferably, R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O, and wherein each phenyl and heteroaryl moiety may optionally be substituted by 1, 2 or 3 groups represented by R 5 as defined below.

[0063] Even more preferably, R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O, and wherein each phenyl and heteroaryl moiety may optionally be substituted by 1 or 2 groups represented by R 5 as defined below. Even even more preferably, R 2 is phenyl or pyridyl, wherein each phenyl and pyridyl moiety may optionally be substituted by 1 or 2 groups represented by R 5 as defined below.

[0064] In one set of embodiments, R 2 is phenyl optionally substituted by 1 or 2, preferably 2, groups represented by R 5 as defined below. In another set of embodiments, R 2 is 3,4-dichlorophenyl.

[0065] R 3 is hydrogen or C1-C6 alkyl. Preferably, R 3 is hydrogen or C1-C4 alkyl, more preferably hydrogen or C1-C3 alkyl. Even more preferably, R 3 is hydrogen, methyl, or ethyl. Even even more preferably, R 3 is hydrogen or ethyl. Even even even more preferably, R 3 is hydrogen.

[0066] R 4is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, wherein the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties may each optionally be substituted by 1, 2, 3 or 4 groups which may be the same or different and are represented by R 6 is substituted.

[0067] Preferably, R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, wherein the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties may each optionally be substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 6 is substituted.

[0068] More preferably, R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms independently selected from N and O, wherein the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties may each optionally be substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 6 is substituted.

[0069] Even more preferably, R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered aromatic monocyclic ring containing 1 or 2 nitrogen atoms, wherein the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties may each optionally be substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 6 is substituted.

[0070] In one embodiment, R 4 is phenyl or pyrazolyl, wherein the phenyl and pyrazolyl moieties may each optionally be substituted by 1, 2 or 3 groups which may be the same or different and are represented by R 6 is substituted.

[0071] In a set of embodiments, R 4 is phenyl optionally substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 6 Preferably, R 4 is phenyl optionally substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 6 and R 6 is halogen, C1-C3 haloalkoxy, or C1-C6 alkoxycarbonyl. Even more preferably, R4 is a phenyl group optionally substituted by 1, 2, or 3 groups, which may be the same or different, represented by R 6 and R 6 is halogen, C1-C2 haloalkoxy, or C1-C3 alkoxycarbonyl. Even more preferably, R 4 is a phenyl group optionally substituted by 1, 2, or 3 groups, which may be the same or different, represented by R 6 and R 6 is chlorine, fluorine, trifluoromethoxy, or isopropoxycarbonyl.

[0072] In another group of embodiments, R 4 is 4-chlorophenyl, 4-chloro-2-fluorophenyl, 2-fluoro-5-(trifluoromethoxy)phenyl, 4-chloro-2-fluoro-5-isopropoxycarbonylphenyl, 2-chloro-5-(trifluoromethoxy)phenyl, 2-fluoro-5-isopropoxycarbonylphenyl, or 2-fluoro-3-(trifluoromethoxy)phenyl.

[0073] 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 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-bis(C1-C4 alkyl)aminocarbonyl.

[0074] Preferably, R 5 is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-bis(C1-C3 alkyl)aminocarbonyl.

[0075] More preferably, R 5is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonamido, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0076] Even more preferably, R 5 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylcarbonyl, or C3-C6 cycloalkyl. Even more preferably, R 5 is cyano, nitro, chlorine, fluorine, methyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2-difluoroethoxy, methoxymethyl, acetyl, or cyclopropyl.

[0077] In one group of embodiments, R 5 is cyano, nitro, or halogen, preferably cyano or halogen, more preferably halogen. Even more preferably, R 5 is chlorine or fluorine, and even more preferably, R 5 is chlorine.

[0078] R 6 is cyano, nitro, halogen, oxo, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenoxy, C2-C6 alkynoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkoxy, N,N-di(C1-C4 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, phenoxy, or benzyloxy, where each cycloalkyl or phenyl moiety may optionally be substituted by 1 or 2 groups represented by R 8 ; or

[0079] Any two adjacent Rs 6The group, together with the carbon atom to which it is attached, can form a phenyl ring or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O and N, and wherein the phenyl ring and the heterocyclic ring can optionally be substituted by 1, 2, 3 or 4 groups which may be the same or different and are represented by R 9 and are substituted by the groups represented by R

[0080] Preferably, R 6 is cyano, nitro, halogen, oxo, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C4 alkyl, C1-C4 alkoxyC1-C4 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C4 alkoxy, N,N-bis(C1-C3 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-bis(C1-C3 alkyl)aminocarbonyl, phenoxy, or benzyloxy, wherein each cycloalkyl or phenyl moiety can optionally be substituted by 1 or 2 groups which may be the same or different and are represented by R 8 ; or

[0081] Any two adjacent R 6 groups, together with the carbon atom to which they are attached, can form a phenyl ring or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O and N, and wherein the phenyl ring and the heterocyclic ring can optionally be substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 9 and are substituted by the groups represented by R

[0082] In one embodiment, R 6 is halogen, C1-C4 alkoxy, C1-C4 haloalkoxy, or C1-C4 alkoxycarbonyl; or any two adjacent R 6 groups, together with the carbon atom to which they are attached, can form a phenyl ring, wherein the phenyl ring can optionally be substituted by 1 or 2 groups which may be the same or different and are represented by R 9 and are substituted by the groups represented by R

[0083] In another embodiment, R 6 is chlorine, fluorine, methoxy, trifluoromethoxy, or isopropoxycarbonyl, or two adjacent R 6 groups, together with the carbon atom to which they are attached, can form a phenyl ring, wherein the phenyl ring can optionally be substituted by a single 1 R 9 group and are substituted by the groups represented by R

[0084] In another embodiment, R 6 is chlorine, fluorine, trifluoromethoxy, or isopropoxycarbonyl.

[0085] R 8 is cyano, halogen, C1-C3 alkyl, or C1-C3 alkoxy. Preferably, R 8 is cyano, halogen or C1-C3 alkoxy. More preferably, R 8 is cyano, halogen or methoxy. Even more preferably, R 8 is fluorine or methoxy.

[0086] R 9 is halogen, C1-C3 alkyl, or C1-C3 alkoxy. Preferably, R 9 is halogen or C1-C3 alkoxy. More preferably, R 9 is halogen or methoxy. Even more preferably, R 9 is fluorine or methoxy. Even more preferably, R 9 is methoxy.

[0087] In the compounds of formula (I) according to the invention, preferably:

[0088] R 1 is C1-C3 alkyl;

[0089] R 2 is 3,4-dichlorophenyl;

[0090] R 3 is hydrogen or ethyl;

[0091] R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from N, O and S, wherein the heteroaryl moiety can be attached to the rest of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties can each optionally be substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 6 ;

[0092] R 6 is halogen, C1-C4 alkoxy, C1-C4 haloalkoxy, or C1-C4 alkoxycarbonyl; or any two adjacent R 6 groups together with the carbon atom to which they are attached can form a phenyl ring, wherein the phenyl ring can optionally be substituted by 1 or 2 groups which may be the same or different and are represented by R 9 ; and

[0093] R 9 is methoxy.

[0094] In another set of embodiments,

[0095] R 1 is methyl or ethyl;

[0096] R 2 is 3,4-dichlorophenyl;

[0097] R 3 is hydrogen or ethyl;

[0098] R 4 is phenyl or pyrazolyl, wherein the phenyl and pyrazolyl moieties may each optionally be substituted by 1, 2 or 3 groups which may be the same or different and are represented by R 6 ;

[0099] R 6 is cyano, nitro, halogen, oxo, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C4 alkyl, C1-C4 alkoxyC1-C4 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C4 alkoxy, N,N-bis(C1-C3 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-bis(C1-C3 alkyl)aminocarbonyl, phenoxy, or benzyloxy, wherein each cycloalkyl or phenyl moiety may optionally be substituted by 1 or 2 groups which may be the same or different and are represented by R 8 ; or

[0100] any two adjacent R 6 groups together with the carbon atom to which they are attached may form a phenyl ring, or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O and N, and wherein the phenyl ring and the heterocyclic ring may optionally be substituted by 1, 2, or 3 groups which may be the same or different and are represented by R 9 ; and

[0101] R 9 is halogen or methoxy.

[0102] In a further set of embodiments, R 1 is ethyl;

[0103] R 2 is 3,4-dichlorophenyl;

[0104] R 3 is hydrogen;

[0105] R4 is phenyl optionally substituted by 1, 2 or 3 groups, which may be the same or different, selected from R 6 groups;

[0106] R 6 is halogen, C1-C3 haloalkoxy, or C1-C3 alkoxycarbonyl.

[0107] The compounds of the present invention can be prepared as shown in the following schemes, wherein, unless otherwise stated, the definition of each variable is as defined above for the compounds of formula (I). A general method for producing the compounds of formula (I) is described below. Unless otherwise stated in the text, R 1 , R 2 , R 3 , R 4 , and X are as defined above. The starting materials for preparing the compounds of the present invention can be purchased from common commercial suppliers or can be prepared by known methods. The starting materials and intermediates can be purified by methods of the prior art (such as chromatography, crystallization, distillation, and filtration) before being used in the next step.

[0108] Scheme 1:

[0109]

[0110] Compounds of formula (I) wherein R 3 is hydrogen can be prepared by hydrolyzing a compound of formula (I) wherein R 3 is not hydrogen but any other R 3 group as defined above in a suitable solvent (such as methanol, ethanol, 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) or using a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid, or sulfuric acid). In the case of using a base, the product is obtained after acidification with a suitable acid (such as hydrochloric acid). This is shown in Scheme 1 above. Compounds of formula (I) can alternatively be prepared by the method described below.

[0111] Scheme 2:

[0112]

[0113] Compounds of formula (I) wherein R 4 is phenyl or heteroaryl, and R 3 is hydrogen or any other R 3 group as defined above can alternatively be prepared from a compound of formula (A) wherein Y is Cl, Br, or I, and R 3 is hydrogen or any other R as defined above using standard literature conditions.3 The group) is prepared via a Suzuki-Miyaura cross-coupling reaction. Typically, this reaction is carried out by reacting a compound of formula (A) with R 4 -boronic acid or boroxine at an elevated temperature, in a suitable organic solvent (such as 1,4-dioxane, toluene or tetrahydrofuran), optionally in the presence of water, in the presence of a base (such as potassium carbonate, cesium carbonate or tripotassium phosphate), in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, or dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloromethane adduct) or palladium diacetate, optionally in the presence of a ligand (such as 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl). This is shown in Scheme 2 above.

[0114] In an alternative transformation, a compound of formula (A) in which Y is I can be converted to a compound of formula (I) in which R 4 is a C-linked heterocycle (such as oxazol-2-yl)) by reacting with, for example, a heterocyclic stannane at an elevated temperature (such as 120 °C), in a suitable solvent (such as toluene), in the presence of a catalyst (such as tetrakis(triphenylphosphine)palladium(0)).

[0115] In another alternative transformation, a compound of formula (A) in which Y is I or Br and R 3 is hydrogen or any other R as defined above 3 group) can be converted to a compound of formula (I) in which R 4 is an N-linked heterocycle (such as pyrazol-1-yl or indazol-1-yl)) by reacting with, for example, a pyrazole heterocycle at an elevated temperature (such as 100 °C), in a suitable organic solvent (such as toluene, dioxane, dimethyl sulfoxide or acetonitrile), in the presence of a copper source (such as copper(I) iodide), in the presence of a base (such as potassium carbonate, cesium carbonate, potassium phosphate), optionally in the presence of a ligand (such as 3,4,7,8-tetramethyl-1,10-phenanthroline, proline, 8-hydroxyquinoline or N,N'-bis(2,6-dimethoxyphenyl)oxamide).

[0116] Scheme 3:

[0117]

[0118] A compound of formula (A) in which R 3 is hydrogen and Y is Br or I can be prepared by reacting a compound of formula (A) in which R 3 is not hydrogen but any other R as defined above3 is prepared by hydrolysis in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) and an optional co-solvent (such as water) with a suitable base (such as sodium hydroxide or lithium hydroxide) or with a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid). This is shown in Scheme 3 above.

[0119] Scheme 4:

[0120]

[0121] A compound of formula (A) wherein Y is Br or I can be prepared by treating a compound of formula (B) in a suitable solvent (such as acetonitrile or trifluoroacetic acid or a mixed solvent) with a suitable halogenating agent (such as N-iodosuccinimide or N-bromosuccinimide). This is shown in Scheme 4 above.

[0122] Scheme 5:

[0123]

[0124] A compound of formula (B) wherein R 1 and R 3 are the same, but R 1 is not hydrogen can be prepared from a compound of formula (C) by reaction with an alkyl halide (R 1 -X) (such as iodoethane) at an elevated temperature (such as 80 °C), in a suitable solvent (such as N,N-dimethylformamide), in the presence of a base (such as sodium carbonate). This is shown in Scheme 5 above.

[0125] In cases where a mixture of regioisomers is produced after these reactions, these isomers can be separated by chromatography.

[0126] Scheme 6:

[0127]

[0128] A compound of formula (C) can be prepared by reacting a compound of formula (D) with a formylating agent (such as obtained from the combination of N,N-dimethylformamide and phosphorus oxychloride) under Vilsmeier-Haack reaction conditions, typically using N,N-dimethylformamide as the solvent and at an elevated temperature (such as 80 °C to 120 °C). This is shown in Scheme 6 above.

[0129] Scheme 7:

[0130]

[0131] Compounds having formula (D) can be prepared by reacting a β-keto ester having formula (E) with an aryl nitrile having formula (F) in a metal-promoted addition reaction, for example in the presence of tin(IV) chloride, in a suitable solvent such as toluene, optionally in the presence of a base such as sodium bicarbonate and at an elevated temperature (e.g., 100 °C). Compounds having formula (E) and compounds having formula (F) are commercially available or can be prepared by methods familiar to those skilled in the art. This is shown in Scheme 7 above.

[0132] The present invention further provides a method for controlling weeds at a locus, the method comprising applying to the locus a composition comprising a compound having formula (I) in an amount effective to control weeds. Additionally, the present invention may further provide a method for selectively controlling weeds at a locus comprising useful (crop) plants and weeds, wherein the method comprises applying to the locus a composition according to the present invention in an amount effective to control weeds. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention show significantly improved selectivity compared to known structurally similar compounds. Generally, the plants to be controlled are unwanted plants (weeds). 'Locus' means an area in which plants are growing or will grow. Application can be made pre- and / or post-emergence of the crop plants to the locus. Some crop plants may inherently tolerate the herbicidal effect of the compounds having formula (I).

[0133] The application rate of the compounds having formula (I) can vary within wide limits and depends on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no-till application, etc.), the crop plants, the one or more weeds to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. The compounds having formula I according to the present invention are generally applied at a rate of from 10 g / ha to 2500 g / ha, especially from 25 g / ha to 1000 g / ha, more especially from 25 g / ha to 250 g / ha.

[0134] Application is generally effected by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or flooding can also be used.

[0135] The term "useful plant" should be understood to also include useful plants that have been made tolerant to herbicides (such as bromoxynil) or herbicide classes (such as 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors (such as flupyrsulfuron, prosulfuron, and trifloxysulfuron), 5-enolpyruvyl-shikimate-3-phosphate synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors, or protoporphyrinogen oxidase (PPO) inhibitors) by conventional breeding or genetic engineering methods. Examples of crops that have been made tolerant to imidazolinones (such as imazamox) by conventional breeding methods (mutation) are summer rape (Canola). Examples of crops that have been made tolerant to herbicides or herbicide classes by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties, which are commercially available under the trade names Herculex and commercially available.

[0136] The term "useful plant" should be understood to also include useful plants that have been so transformed by using recombinant DNA technology that they are capable of synthesizing one or more selectively acting toxins, such as those known, for example, from toxin-producing bacteria, in particular bacteria of the genus Bacillus.

[0137] Examples of such plants are: (maize variety expressing the CryIA(b) toxin); YieldGard (maize variety expressing the CryIIIB(b1) toxin); YieldGard (maize variety expressing the CryIA(b) and CryIIIB(b1) toxins); (maize variety expressing the Cry9(c) toxin); Herculex (maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide ammonium glufosinate); NuCOTN (cotton variety expressing the CryIA(c) toxin); Bollgard (cotton variety expressing the CryIA(c) toxin); Bollgard (cotton variety expressing the CryIA(c) and CryIIA(b) toxins); (cotton variety expressing the VIP toxin); (potato variety expressing the CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait), RW (corn rootworm trait), and

[0138] Plant crops or their seed materials can be both herbicide-resistant and at the same time resistant to insect feeding (“stacked” transgenic events). For example, the seeds can have the ability to express the insecticidal Cry3 protein while being tolerant to glyphosate.

[0139] Crop plants should also be understood to include those obtained by conventional breeding or genetic engineering methods and containing so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0140] Compounds of formula (I) (or compositions containing them) can be used to control unwanted plants (collectively referred to as ‘weeds’). The weeds to be controlled can be either monocotyledonous species such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, and Sorghum, or dicotyledonous species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola, and Xanthium.

[0141] Compounds having formula (I) can be used in unmodified form or, preferably, together with adjuvants conventionally used in the formulation art to provide a herbicidal composition, using formulation adjuvants such as carriers, solvents and surfactants (SAA). Accordingly, the present invention further provides a herbicidal composition comprising at least one compound having formula (I) and an agriculturally acceptable carrier and optionally adjuvants. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art.

[0142] The herbicidal composition generally comprises from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of the compound having formula I and from 1% to 99.9% by weight of formulation adjuvants, which preferably comprise from 0 to 25% by weight of surface-active substances.

[0143] The composition can be selected from many formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), 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), technical concentrates (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP) and soluble granules (SG). In any case, the formulation type selected will depend on the specific purpose envisaged and on the physical, chemical and biological properties of the compound having formula (I).

[0144] Soluble powders (SP) 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 sulphate or one or more water-soluble organic solids such as polysaccharides and optionally one or more wetting agents, one or more dispersing agents or a mixture of said reagents to improve the 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).

[0145] Wettable powders (WP) 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 dispersing agents, and optionally one or more suspending agents to facilitate dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG).

[0146] The granule (GR) can be formed as follows: by granulating a mixture of a compound having the formula (I) with one or more powdered solid diluents or carriers, or by absorbing the compound having the formula (I) (or its solution in a suitable reagent) into a porous granular material (such as pumice, attapulgite clay, bleaching earth, kieselguhr, diatomaceous earth or corn cob powder), or by adsorbing the compound having the formula (I) (or its solution in a suitable reagent) onto a hard core material (such as sand, silicate, mineral carbonate, sulfate or phosphate) and drying if necessary to form from preformed blank granules. Reagents commonly used to assist absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and adhesives (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugar and vegetable oil). One or more other additives (such as emulsifiers, wetting agents or dispersants) can also be included in the granule.

[0147] The dispersible concentrate (DC) can be prepared by dissolving the compound having the formula (I) in water or an organic solvent (such as a ketone, alcohol or glycol ether). These solutions can contain surfactants (such as to improve water dilution or prevent crystallization in the spray tank).

[0148] The emulsifiable concentrate (EC) or oil-in-water emulsion (EW) can be prepared by dissolving the compound having the 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 EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (such as C8-C 10 dimethylamides of fatty acids) and chlorinated hydrocarbons. The EC product can spontaneously emulsify when added to water, thus producing an emulsion with sufficient stability to allow spraying application through appropriate equipment.

[0149] The preparation of the EW involves obtaining the compound of formula (I) as a liquid (which can be melted at a reasonable temperature typically below 70 °C if it is not a liquid at room temperature) or in 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 for use in the EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0150] 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) is initially present in the water or in the solvent / SAA blend. Suitable solvents for use in the ME include those described above for use in the EC or in the EW. The ME can be an oil-in-water system or a water-in-oil system (which system is present can be determined by conductivity measurements) and can be suitable for mixing water-soluble and oil-soluble biocides in the same formulation. The ME is suitable for dilution in water, remaining as a microemulsion or forming a conventional oil-in-water type emulsion.

[0151] Suspension concentrates (SCs) can comprise an aqueous or non-aqueous suspension of finely divided insoluble solid particles of the compound of formula (I). The SC can be prepared by ball milling or bead milling the solid compound of formula (I) optionally with one or more dispersants in a suitable medium to produce a fine particle suspension of the compound. One or more wetting agents can be included in the composition, and a suspending agent can be included to reduce the rate of particle sedimentation. Alternatively, the compound of formula (I) can be dry milled and added to water containing the reagents described above to produce the desired final product.

[0152] Aerosol formulations contain the compound of formula (I) and a suitable propellant (such as n-butane). The compound of formula (I) can also be dissolved or dispersed in a suitable medium (such as water or a water-miscible liquid, such as n-propanol) to provide a composition for use in a non-pressurized hand spray pump.

[0153] A capsule suspension (CS) can be prepared in a manner similar to that for preparing an EW formulation, but with an additional polymerization step to obtain an aqueous dispersion of oil droplets, where each oil droplet is encapsulated by a polymer shell and contains a compound of formula (I) and optionally a carrier or diluent for the oil droplet. The polymer shell can be produced by an interfacial polycondensation reaction or by a coacervation procedure. These compositions can provide controlled release of the compound of formula (I) and they can be used for seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0154] The compositions can contain one or more additives to improve the biological properties of the composition, e.g., by improving wettability, retention, or distribution on the surface; rainfastness on the treated surface; or absorption or mobility of the compound of formula (I). Such additives include surfactants (SAA), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oil), modified vegetable oils (such as methylated rapeseed oil (MRSO)), and blends of these with other bioenhancing adjuvants (ingredients that can assist or modify the action of the compound of formula (I)).

[0155] Wetting agents, dispersants, and emulsifiers can be cationic, anionic, amphoteric, or nonionic types of SAA.

[0156] Suitable cationic types of SAA include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0157] Suitable anionic SAA 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, butylnaphthalenesulfonate, and mixtures of di-isopropyl-naphthalenesulfonate and tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (from the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), e.g., the product of the reaction between lauryl alcohol and tetraphosphoric acid; additionally, these products can be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphates / sulfates of triphenylvinylphenol.

[0158] Suitable amphoteric types of SAA include betaines, propionates, and glycine salts.

[0159] Suitable non-ionic types of SAA include condensation products of alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long-chain fatty acids or sorbitan; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; mono-esters (such as polyethylene glycol fatty acid esters); amine oxides (such as lauryldimethylamine oxide); lecithin and sorbitan and its esters, alkyl polyglycosides and triphenylvinylphenol.

[0160] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0161] The compounds of the present invention can also be used in mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), acibenzolar-S-methyl, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, butafenacil-M, benquitrione, bensulfuron-methyl (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bispyribac-sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone-ethyl (including carfentrazone-ethyl), chlorimuron-ethyl (including chlorimuron-ethyl), chlortoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop-propargyl (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop-butyl (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, desmedipham, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, 2,4-DP, diethylene glycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, diflufenican, flucarbazone-sodium, dimethenamid, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epyrifenacil, ethalfluralin, ethoxyfen-ethyl, fenoxaprop-p-ethyl (including fenoxaprop-p-ethyl), fenoxasulfone, flufenpyrazone, fenquinotrione, flufenacet, flazasulfuron, florpyrauxifen-benzyl (including florpyrauxifen-benzyl), fluazifop-p-butyl (including fluazifop-p-butyl), flucarbazone-sodium, fluchloraminopyr (including fluchloraminopyr-tefuryl), flufenacet, flufenoximacil, flumetsulam, flumioxazin, flupyrsulfuron-methyl-sodium, fluroxypyr (including fluroxypyr-meptyl), flurtamone, fomesafen, foramsulfuron, glufosinate-ammonium (including L-glufosinate and the ammonium salts of both), glyphosate (including its diamine, isopropylammonium and potassium salts), halauxifen-methyl (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone,Hydantocidin, Icafolin (including Icafolin-methyl), Imazamox (including R-Imazamox), Imazapic, Imazapyr, Imazethapyr, Indanofan, Indolauxipyr (including Indolauxipyr-cyanomethyl), Iodosulfuron (including Iodosulfuron-methyl-sodium), Iofensulfuron (including Iofensulfuron-sodium), Ioxynil, Iptriazopyrid, Isoproturon, Isoxazflutole, Lancotrione, MCPA, MCPB, Mecoprop-P, Mesosulfuron-methyl (including Mesosulfuron-methyl-methyl), Nicosulfuron, Oxadiargyl, Oxasulfuron, Pendimethalin, Penoxsulam, Pyridate, Pyraflufen (including Pyraflufen-ethyl), Pyraquinate, Pyrazosulfuron-ethyl, Pyridafol, Pyributicarb, Pyribenzoxim, Pyrimisulfan, Pyroxsulam, Quinclorac, Quinmerac, Quizalofop (including Quizalofop-P-ethyl and Quizalofop-P-tefuryl), Rimsulfuron, Pyribambenz-propyl, Sethoxydim, Simazine, S-Metolachlor, Sulfentrazone, Sulfosulfuron, Tebuthiuron, Tembotrione, Terbuthylazine, Terbutryn, Tetflupyrolimet, Thiencarbazone-methyl, Thifensulfuron-methyl, Tiafenacil, Tolpyralate, Topramezone, Triafamone, Triallate, Tribenuron-methyl (including Tribenuron-methyl-methyl), Triclopyr, Trifloxysulfuron (including Trifloxysulfuron-sodium), Triflusulfuron-methyl, Trifluralin, Triflusulfuron, Triazolopyrimidinesulfonamide, Ethyl 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate,4-Hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, (1RS,5SR)-3-[2-methoxy-4-(prop-1-yn-1-yl)phenyl]-4-oxabicyclo[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-pyridinyl]oxy]acetate, methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2-fluorophenyl)methyl 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxyphenyl)pyrimidine-4-carboxylate, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxyphenyl)pyrimidine-4-carboxylic acid, methyl 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-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.,

[0162] The mixing compatibility of the compound having the formula (I) can also be in the form of an ester or a salt, as mentioned, for example, in The Pesticide Manual, 16th Edition, British Crop Protection Council, 2012. The mixing ratio of the compound having the formula (I) to the mixing compatibility is preferably 1:100 to 1000:1.

[0163] These mixtures can advantageously be used in the above-mentioned formulations (in which case, the "active ingredient" relates to the corresponding mixtures of the compounds of formula (I) with the mixing compatibilities).

[0164] The compounds or mixtures of the invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include cloquintocet-mexyl, cloquintocet (including mefenpyr-diethyl), cyprosulfamide, dichlormid, isoxadifen (including isoxadifen-ethyl), isoxachlortole, flurazole, oxabetrinil, isoxaben (including isoxaben-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and dichlobenil. Particularly preferred are mixtures of the compounds of formula (I) with cyprosulfamide, isoxaben-ethyl, mefenpyr-diethyl and / or metcamifen.

[0165] The safeners of the compounds of formula (I) can also be in the form of esters or salts, as mentioned for example in The Pesticide Manual, 16th Edition (BCPC), 2012. The reference to mefenpyr-diethyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048.

[0166] Preferably, the mixing ratio of the compounds of formula (I) with the safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0167] The compounds of formula (I) are generally used in the form of agrochemical compositions and can be applied to the crop area or plants to be treated simultaneously or successively with further compounds. For example, these further compounds can be fertilizers or micronutrient donors or other preparations which influence plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting auxiliaries customarily used in the formulation art.

[0168] As used herein, the term "site" means the place where the plant grows or is growing, or the place where the seeds of the cultivated plant are sown, or the place where the seeds are to be placed in the soil. It includes the soil, the seeds and the seedlings, as well as the established vegetation.

[0169] The term "plant" means all the tangible parts of a plant, including seeds, seedlings, young trees, roots, tubers, stems, stalks, leaves and fruits.

[0170] The term "plant propagation material" shall be understood to denote the reproductive parts of plants, such as seeds, which can be used for the propagation of plants, as well as vegetative material, such as cuttings or tubers (e.g. potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Mention may also be made of germinated plants and young plants which are to be transplanted after having germinated from the soil or after emergence. These young plants can be protected before transplantation by being treated completely or partially by drenching. Preferably, "plant propagation material" shall be understood to denote seeds.

[0171] The pesticidal agents mentioned herein by their common names are known, for example, from "The Pesticide Manual", 15th Edition, British Crop Protection Council 2009.

[0172] The compounds of formula (I) can be used in unmodified form or, preferably, together with auxiliaries conventionally employed in the art of formulation. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusting powders, granules and also encapsulations, for example in polymeric substances. For the type of composition, the method of application is chosen according to the intended purpose and the circumstances prevailing at the time, such as spraying, atomizing, dusting, broadcasting, coating or watering. The compositions can also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0173] Suitable carriers and auxiliaries, for example for agricultural use, can be solid or liquid and are substances useful in the art of formulation, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0174] The compounds of formula (I) are generally used in the form of compositions and can be applied to the crop area or plants to be treated simultaneously or successively with further compounds. For example, these further compounds can be fertilizers or micronutrient donors or other preparations which influence plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting auxiliaries customarily used in the art of formulation.

[0175] The compound having formula (I) can be the sole active ingredient of the composition, or, where appropriate, it can be mixed with one or more additional active ingredients such as pest control agents, fungicides, synergists, herbicides or plant growth regulators. In some cases, the additional active ingredients can produce unexpected synergistic activity.

[0176] Generally, the formulation comprises from 0.01% to 90% by weight of active ingredient, from 0% to 20% of agriculturally acceptable surfactant and from 10% to 99.99% of solid or liquid formulation inert agents and one or more auxiliaries, the active ingredient consisting at least of the compound having formula (I) together with components (B) and (C), and optionally other active ingredients (in particular microbicides or preservatives or the like). The concentrated form of the composition generally contains from about 2% to 80% by weight, preferably from about 5% to 70% by weight, of active ingredient. The application form of the formulation can contain, for example, from 0.01% to 20% by weight, preferably from 0.01% to 5% by weight, of active ingredient. However, commercial products will preferably be formulated as concentrates and the end user will generally use diluted formulations.

[0177] The following table shows examples of individual compounds having formula (I) according to the invention:

[0178]

[0179] Table 1: Compounds having formula (I) according to the invention individually

[0180]

[0181]

[0182] Table A-1 There are provided 47 compounds having formula (I), A-1.001 to A.1.048, in which R 1 is methyl, R 2 is 3,4-dichlorophenyl, R 3 is hydrogen, and R 4 is defined in Table 1.

[0183] Table A-2 There are provided 47 compounds having formula (I), A-2.001 to A.2.048, in which R 1 is ethyl, R 2 is 3,4-dichlorophenyl, R 3 is hydrogen, and R 4 is defined in Table 1.

[0184] Table A-3Forty-seven compounds of formula (I), A-3.001 to A.3.048, are provided, wherein R 1 is ethyl, R 2 is 3,4-dichlorophenyl, R 3 is methyl, and R 4 is defined in Table 1.

[0185] Table A-4 Forty-seven compounds of formula (I), A-4.001 to A.4.048, are provided, wherein R 1 is ethyl, R 2 is 3-chloro-4-cyanophenyl, R 3 is hydrogen, and R 4 is defined in Table 1.

[0186] Table A-5 Forty-seven compounds of formula (I), A-5.001 to A.5.048, are provided, wherein R 1 is ethyl, R 2 is 3,4-difluorophenyl, R 3 is hydrogen, and R 4 is defined in Table 1.

[0187] Table A-6 Forty-seven compounds of formula (I), A-6.001 to A.6.048, are provided, wherein R 1 is ethyl, R 2 is (5,6-dichloro-3-pyridyl), R 3 is hydrogen, and R 4 is defined in Table 1.

[0188] Formulation Examples

[0189]

[0190]

[0191] The active ingredient is thoroughly mixed with adjuvants 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.

[0192]

[0193] The active ingredient is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to provide a powder that can be used directly for seed treatment.

[0194] Emulsifiable Concentrates

[0195]

[0196] An emulsion having any desired dilution that can be used in plant protection can be obtained from this concentrate by diluting it with water.

[0197]

[0198]

[0199] A ready-to-use dust powder is 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 dressing of seeds.

[0200] Extruder Granules

[0201]

[0202] The active ingredient is mixed with adjuvants and ground, and the mixture is wetted with water. The mixture is extruded and then dried in an air stream.

[0203] Coated Granules

[0204] Active ingredient [compound of formula (I)] 8%

[0205] Polyethylene glycol (molar weight 200) 3%

[0206] Kaolin 89%

[0207] The finely ground active ingredient is evenly applied in a mixer to kaolin wetted with polyethylene glycol. In this way, a dust-free coated granule is obtained.

[0208] Suspension Concentrates

[0209]

[0210] The finely ground active ingredient is intimately mixed with adjuvants to obtain a suspension concentrate, from which suspensions of any desired dilution can be obtained by diluting with water. Using such dilutions, living plants and plant propagation materials can be treated and protected against microbial infestation by spraying, watering or dipping.

[0211] Flowable Concentrates for Seed Treatment

[0212]

[0213] The finely ground active ingredient is intimately mixed with adjuvants to obtain a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against microbial infestation by spraying, watering or dipping.

[0214] Sustained Release Capsule Suspensions

[0215] 28 parts of the combination of compounds 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 part of an antifoaming agent and 51.6 parts of water until the desired particle size is reached. To this emulsion is added a mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension is stabilized by adding 0.25 part of a thickening agent and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredient. The diameter of the medium capsules is 8 - 15 μm. The obtained formulation is applied as an aqueous suspension to seeds in a device suitable for this purpose.

[0216] Examples

[0217] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (as mentioned in Table 2 below).

[0218] Throughout this specification, temperatures are given in degrees Celsius (°C), and "m.p." means melting point.

[0219] List of Abbreviations

[0220] °C = degrees Celsius, d = doublet, dd = double doublet, DMSO = dimethyl sulfoxide, M = mole, m = multiplet, MHz = megahertz, q = quartet, s = singlet, t = triplet.

[0221] Example 1: Synthesis of ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (Compound 4)

[0222] Step 1: Synthesis of ethyl 2-[amino-(3,4-dichlorophenyl)methylene]-3-oxo-butanoate

[0223]

[0224] At 0 °C and under nitrogen, tin(IV) chloride (1.00 mol / L, 116 mL, 116 mmol) was added to a stirred solution of 3,4-dichlorobenzonitrile (20.0 g, 116 mmol) in toluene (150 mL), followed by ethyl 3-oxobutanoate (14.8 mL, 116 mmol). The resulting reaction mixture was stirred at room temperature for 0.5 h and then at 100 °C for 3 h. The cooled reaction mixture was diluted in ethyl acetate and saturated aqueous sodium bicarbonate was added. The phases were separated and the aqueous phase was extracted with ethyl acetate (×2). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using ethyl acetate in hexane with a gradient of 0% to 80% as the eluent to give ethyl 2-[amino-(3,4-dichlorophenyl)methylene]-3-oxobutanoate (22.5 g, 67.0 mmol) as an off-white semi-solid. 1H NMR (400 MHz, DMSO-d6) δ = 7.72 (d, 1H), 7.60 (d, 1H), 7.28 (dd, 1H), 5.50 (q, 2H), 2.22 (s, 3H), 0.72 (t, 3H)

[0225] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-4-oxo-1H-pyridine-3-carboxylic acid

[0226]

[0227] Phosphorus oxychloride (9.09 mL, 99.3 mmol) was added to N,N-dimethylformamide (9.00 mL, 116 mmol) cooled to 0 °C. The mixture was stirred at 0 °C for 10 min and then at room temperature for 1 h. Thereafter, the mixture was cooled to 0 °C and a solution of ethyl 2-[amino-(3,4-dichlorophenyl)methylene]-3-oxobutanoate (10.0 g, 33.1 mmol) in N,N-dimethylformamide (50 mL) was added slowly. The resulting reaction mixture was stirred at 80 °C for 16 h and then at 120 °C for 18 h. The cooled reaction mixture was quenched by the addition of water and extracted with ethyl acetate (×3). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using methanol in dichloromethane with a gradient of 0% to 10% as the eluent to give 2-(3,4-dichlorophenyl)-4-oxo-1H-pyridine-3-carboxylic acid (5.10 g, 16.2 mmol) as a light brown solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.08 (d, 1H), 7.81 (d, 1H), 7.72 (d, 1H), 7.49 (d, 1H), 6.81 (d, 1H)

[0228] Step 3: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

[0229]

[0230] At room temperature, sodium carbonate (8.95 g, 84.5 mmol) was added to a stirred solution of 2-(3,4-dichlorophenyl)-4-oxo-1H-pyridine-3-carboxylic acid (6.00 g, 21.1 mmol) in N,N-dimethylformamide (60 mL), followed by the addition of iodoethane (3.29 g, 21.1 mmol). The reaction mixture was heated at 70 °C for 3 hours. The cooled reaction mixture was diluted with water and extracted into ethyl acetate (×3). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using methanol in dichloromethane with a gradient of 0% to 15% as the eluent to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (1.80 g, 5.29 mmol) as a brown solid. 1H NMR (400 MHz, DMSO-d6) δ = 7.89 (d, 1H), 7.83 - 7.81 (m, 2H), 7.47 - 7.45 (dd, 1H), 6.30 (d, 1H), 3.90 - 3.82 (m, 2H), 3.67 - 3.61 (q, 2H), 1.09 (t, 3H), 0.82 (t, 3H)

[0231] Step 4: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate

[0232]

[0233] At room temperature, 1-pyrrolidine-2,5-dione (1.29 g, 5.73 mmol) and trifluoroacetic acid (0.036 mL, 0.441 mmol) were added to a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (1.50 g, 4.41 mmol) in acetonitrile (15.0 mL). The reaction mixture was heated at 80 °C for 5 h. The cooled reaction mixture was diluted with water and extracted with ethyl acetate (×3). The combined organic extracts were washed successively with water (×3) and brine, then dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using ethyl acetate in hexane with a gradient of 0% to 50% as the eluent to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate (1.35 g, 2.75 mmol) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.55 (s, 1H), 7.87 - 7.81 (m, 2H), 7.49 (d, 1H), 3.88 - 3.82 (q, 2H), 3.72 - 3.65 (q, 2H), 1.06 (t, 3H), 0.98 (t, 3H)

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

[0235]

[0236] At room temperature, (4-chlorophenyl)boronic acid (64 mg, 0.41 mmol) and potassium phosphate (259 mg, 1.22 mmol) were added to a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate (200 mg, 0.408 mmol) in a mixture of acetonitrile (5 mL) and water (2 mL). The resulting reaction mixture was purged with argon for 5 minutes and then P(t-Bu)3Pd G4 (24 mg, 0.041 mmol) was added. The reaction mixture was purged with argon for an additional 2 minutes and then heated at 100 °C for 2 hours. The cooled reaction mixture was diluted with water and extracted into ethyl acetate (×2). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using ethyl acetate in hexane with a gradient of 0% to 100% as the eluent to give ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (160 mg, 0.337 mmol) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.21 (s, 1H), 7.91 - 7.75 (m, 3H), 7.61 - 7.49 (m, 4H), 3.95 - 3.85 (m, 2H), 3.75 (q, 2H), 1.17 (t, 3H), 0.89 (t, 3H)

[0237] Example 2: Synthesis of ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (Compound 1)

[0238]

[0239] Ethyl 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (150 mg, 0.333 mmol) was added to a stirred solution in a mixture of tetrahydrofuran (5 mL) and water (2 mL) with lithium hydroxide hydrate (42 mg, 1.0 mmol). The resulting reaction mixture was heated at 80 °C for 16 h. The reaction mixture was acidified to pH 1 by addition of 2 M aqueous hydrochloric acid and extracted into ethyl acetate. The combined organic extracts were evaporated to dryness under reduced pressure. The crude residue was purified by reverse-phase C-18 silica gel flash chromatography using acetonitrile (+0.1% formic acid) with a gradient of 0% to 100% in water (+0.1% formic acid) as the eluent to afford 5-(4-chlorophenyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid as an off-white solid (0.085 g, 0.20 mmol). 1H NMR (400 MHz, DMSO-d6) δ = 8.57 (s, 1H), 7.83 - 7.77 (m, 4H), 7.57 (d, 2H), 7.46 (dd, 1H), 3.84 - 3.79 (q, 2H), 1.18 (t, 3H)

[0240] Example 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-[2-fluoro-5-(trifluoromethoxy)phenyl]-4-oxo-pyridine-3-carboxylic acid (Compound 5)

[0241] Step 1: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylic acid

[0242]

[0243] Lithium hydroxide hydrate (0.35 g, 8.4 mmol) was added to a stirred solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylate (1.30 g, 2.79 mmol) in a mixture of tetrahydrofuran (5 mL), methanol (5 mL) and water (2 mL). The reaction mixture was heated at 80 °C for 16 h with stirring. The cooled reaction mixture was evaporated to dryness under reduced pressure and water (20 mL) and 2 M aqueous hydrochloric acid (10 mL) were added to the residue. The solid precipitate was separated by filtration and dried under reduced pressure to afford 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylic acid as a light brown solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.84 (s, 1H), 7.78 (dd, 2H), 7.43 (dd, 1H), 3.72 (q, 2H), 1.12 (t, 3H).

[0244] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-[2-fluoro-5-(trifluoromethoxy)phenyl]-4-oxo-pyridine-3-carboxylic acid

[0245]

[0246] A stirred solution of 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-4-oxo-pyridine-3-carboxylic acid (350 mg, 0.80 mmol), [2-fluoro-5-(trifluoromethoxy)phenyl]boronic acid (197 mg, 0.88 mmol) and tripotassium phosphate (509 mg, 2.40 mmol) in a mixture of acetonitrile (10 mL) and water (2 mL) was purged with argon for 2 minutes. (Tris-tert-butylphosphine)(2'-methylamino-1,1'-biphenyl-2-yl)palladium(II) methanesulfonate (47 mg, 0.08 mmol) was added to the reaction mixture, which was purged with argon for 3 minutes. The resulting reaction mixture was heated at 100 °C for 2 hours. The cooled reaction mixture was diluted with water, acidified by addition of 2 M aqueous hydrochloric acid and extracted into ethyl acetate (×2). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using ethyl acetate in hexane with a gradient of 0% to 100% as the eluent to give 2-(3,4-dichlorophenyl)-1-ethyl-5-[2-fluoro-5-(trifluoromethoxy)phenyl]-4-oxo-pyridine-3-carboxylic acid as a white solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.57 (s, 1H), 7.87 (d, 1H), 7.81 (d, 1H), 7.60 - 7.48 (m, 4H), 3.79 (q, 2H), 1.18 (t, 3H).

[0247] Table 2: 1H NMR data of the selected compounds of the present invention 1 H NMR data.

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254] Biological Examples

[0255] Seeds of multiple test species were sown in standard soil in pots (Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Amaranthus palmeri (AMAPA), Zea mays (ZEAMX), Amaranthus retroflexus (AMARE), Solanum nigrum (SOLNI), Lolium perenne (LOLPE), Abutilon theophrasti (ABUTH)). After 8 days of cultivation in a greenhouse under controlled conditions (24 °C / 16 °C, day / night; 14 h light; 65% humidity), these plants were sprayed with an aqueous spray solution derived from a formulation of an industrial-grade active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise stated, the compounds were applied at 1000 g / ha. The test plants were then grown in the greenhouse under controlled conditions in the greenhouse (24 °C / 16 °C, day / night; 14 h light; 65% humidity) and watered twice daily. After 13 days, the percentage of damage caused to the test plants was evaluated. The biological activity is shown in the following table on a five-point scale (5 = 81%-100%; 4 = 61%-80%; 3 = 41%-60%; 2 = 21%-40%; 1 = 0%-20%).

[0256] Table B1: Pre-emergence test

[0257]

[0258] Table B2: Post-emergence test

[0259]

[0260]

Claims

1. A compound of formula (I) or a salt or N-oxide thereof: wherein R 1 is a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy C1-C6 alkyl group, or a C3-C6 cycloalkyl group; R 2 is phenyl or heteroaryl, wherein said heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein each phenyl and heteroaryl moiety may optionally be substituted by 1, 2, 3 or 4 groups which may be the same or different and are represented by R 5 ; R 3 is hydrogen or a C1-C6 alkyl group; R 4 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, wherein the heteroaryl moiety may be attached to the remainder of the molecule through a carbon or nitrogen atom in the heteroaryl ring, and wherein the phenyl and heteroaryl moieties may each optionally be substituted by 1, 2, 3 or 4 groups which may be the same or different and are represented by R 6 ; 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 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-bis(C1-C4 alkyl)aminocarbonyl; R 6 is cyano, nitro, halogen, oxo, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkoxy, N,N-bis(C1-C4 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-bis(C1-C4 alkyl)aminocarbonyl, phenoxy, or benzyloxy, where each cycloalkyl or phenyl moiety may optionally be substituted by 1 or 2 groups which may be the same or different and are represented by R 8 ; or Any two adjacent Rs 6 groups together with the carbon atom to which they are attached can form a phenyl ring, or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O and N, and wherein said phenyl ring and heterocyclic ring can optionally be substituted by 1, 2, 3 or 4 groups which may be the same or different and are represented by R 9 ; R 8 is cyano, halogen, C1-C3 alkyl, or C1-C3 alkoxy; R 9 is a halogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group.

2. The compound according to claim 1, wherein R 1 is a C1-C3 alkyl group.

3. The compound according to claim 1 or claim 2, wherein, R 2 is phenyl or pyridyl, where each phenyl and pyridyl moiety may optionally be substituted by 1 or 2 groups, which may be the same or different, represented by R 5 as defined below.

4. The compound according to any one of claims 1 to 3, wherein, R 3 is hydrogen or a C1-C3 alkyl group.

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

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

7. The compound according to any one of claims 1 to 6, wherein R 6 is cyano, nitro, halogen, oxo, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C4 alkyl, C1-C4 alkoxyC1-C4 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C4 alkoxy, N,N-bis(C1-C3 alkyl)aminosulfonyl, C3-C6 cycloalkylaminocarbonyl, N,N-bis(C1-C3 alkyl)aminocarbonyl, phenoxy, or benzyloxy, where each cycloalkyl or phenyl moiety may optionally be substituted by 1 or 2 groups which may be the same or different and are represented by R 8 or Any two adjacent Rs 6 groups together with the carbon atom to which they are attached can form a phenyl ring, or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O and N, and wherein said phenyl ring and heterocyclic ring can optionally be substituted by 1, 2, or 3 groups, which can be the same or different, represented by R 9 as defined.

8. A compound according to any one of claims 1 to 7, wherein, R 6 is a halogen, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, or a C1-C4 alkoxycarbonyl group; or any two adjacent R 6 groups together with the carbon atom to which they are attached may form a phenyl ring, where the phenyl ring may optionally be substituted by 1 or 2 groups, which may be the same or different, represented by R 9 as defined above.

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

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

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, which further comprises at least one additional pesticidal agent.

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

14. A method for controlling weeds at a site, the method comprising applying to the site a composition according to any one of claims 11 to 13 in an amount effective to control weeds.

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

Images