Herbicidal derivatives

Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1. 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 invention also relates to agrochemical compositions comprising at least one of these pyridone derivatives, processes for the preparation of these compounds, and the use of these pyridone derivatives or compositions in agriculture or horticulture for controlling weeds, in particular weeds in crops of useful plants.

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

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

[0004]

[0005] in

[0006] X is O, S(O)n, or NR 11 ;

[0007] n is 0, 1, or 2;

[0008] R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC1-C6 alkyl, or C3-C6 cycloalkyl;

[0009] 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 be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 7 The group represented by is substituted;

[0010] R 3 is hydrogen or C1-C6 alkyl;

[0011] R 4 is hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl;

[0012] R 5 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally replaced by 1, 2, 3 or 4 R moieties which may be the same or different9 The group represented by is substituted;

[0013] or R 5 and R 11 Together with the nitrogen atom to which they are attached, they may form a 5-membered heterocyclyl ring, wherein the heterocyclyl moiety further comprises an additional oxygen atom, and wherein the heteroaryl moiety may be optionally substituted by 1 or 2 residues which may be the same or different and are represented by R 10 The group represented by is substituted;

[0014] R 7 is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl;

[0015] R 9 is cyano, nitro, hydroxy, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, or benzyloxy; or

[0016] Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a C3-C6 cycloalkyl ring or a phenyl ring, wherein the C3-C6 cycloalkyl and phenyl moieties may be optionally replaced by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 10 or

[0017] Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a 5- or 6-membered heteroaryl ring, 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 the heteroaryl moiety may be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are composed of R 10 or

[0018] Any two adjacent R 9The groups together with the carbon atom to which they are attached may form a 5- or 6-membered heterocyclyl ring, wherein the heterocyclyl moiety is a 5- or 6-membered ring containing 1 or 2 heteroatoms selected from O and N, and wherein the heterocyclyl ring may be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are composed of R 10 The group represented by is substituted;

[0019] R 10 is halogen, oxo, C1-C3 alkyl, or C1-C3 alkoxy;

[0020] R 11 It is hydrogen or C1-C6 alkyl.

[0021] Surprisingly, it has been found that the novel compounds of formula (I) have a very advantageous level of herbicidal activity for practical purposes.

[0022] 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.

[0023] According to a third aspect of the present invention there is provided a method of controlling weeds at a locus, the method comprising applying to the locus a weed controlling amount of a composition comprising a compound of formula (I).

[0024] According to a fourth aspect of the present invention, there is provided use of a compound of formula (I) as a herbicide.

[0025] When substituents are indicated as being "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 7 Substituents. For example, C1-C6 alkyl 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 substituted with 1, 2 or 3 halogens may include, but are not limited to CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.

[0026] As used herein, the term "cyano" refers to a -CN group.

[0027] As used herein, the term "halogen" refers to fluorine (fluorine / fluoro), chlorine (chlorine / chloro), bromine (bromine / bromo), or iodine (iodine / iodo).

[0028] As used herein, the term "hydroxy" or "hydroxyl" refers to an -OH group.

[0029] As used herein, the term "nitro" refers to a -NO2 group.

[0030] As used herein, the term "acetyl" refers to a -C(O)CH3 group.

[0031] As used herein, =0 refers to an oxo group, for example, as found in a carbonyl (-C(=0)-) group.

[0032] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon atoms and hydrogen atoms, which contains no unsaturation, has one to six carbon atoms, and is attached to the rest of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" should be interpreted accordingly. Examples of C1-C6 alkyls include, but are not limited to, methyl, ethyl, n-propyl, and isomers thereof, 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 alkylenes include, but are not limited to -CH2-, -CH2CH2- and -(CH2)3-.

[0033] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted by one or more of the same or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0034] As used herein, the term "C1-C6 alkoxy" refers to a group having the formula -OR a A group in which R a is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted accordingly. Examples of C1-C6 alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0035] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as generally defined above that is substituted with one or more halogen atoms that are the same or different. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted accordingly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0036] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one double bond which may have an (E)- or (Z)-configuration, having two to six carbon atoms, attached to the remainder of the molecule by a single bond. The term "C2-C3 alkenyl" should 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.

[0037] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing 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" should be interpreted accordingly. Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.

[0038] As used herein, the term "C1-C6 alkoxy C1-C6 alkyl" refers to a b OR a - a group, wherein R b is a C1-C6 alkyl group as generally defined above, and R a is a C1-C6 alkylene radical as generally defined above. The terms "C1-C4 alkoxy C1-C4 alkyl" and "C1-C3 alkoxy C1-C3 alkyl" should be interpreted accordingly.

[0039] As used herein, the term "C3-C6 cycloalkyl" refers to a group that is a monocyclic saturated ring system and contains 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0040] As used herein, the term "C3-C6 cycloalkenyl" refers to a group that is a partially unsaturated ring system that is a monocyclic ring and contains 3 to 6 carbon atoms, i.e., wherein the ring contains one or two double bonds. 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.

[0041] As used herein, the term "C3-C6 cycloalkylaminocarbonyl" refers to a C3-C6 cycloalkyl ring attached to the rest of the molecule via a -NHC(O)- linker. Examples of C3-C6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0042] As used herein, the term "phenyl C1-C2 alkyl" refers to a phenyl ring attached to the rest of the molecule via a C1-C2 alkylene linker as defined above. Examples of phenyl C1-C2 alkyl include, but are not limited to, benzyl and phenylethyl.

[0043] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing 1, 2 or 3 heteroatoms independently selected from nitrogen, oxygen and sulfur. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, pyrazinyl, pyridazinyl, pyrimidinyl or pyridyl.

[0044] As used herein, the term "heteroaryl C1-C2 alkyl" refers to a heteroaryl ring as generally defined above attached to the remainder of the molecule via a C1-C2 alkylene linker as defined above.

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

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

[0047] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to a group having the formula -C(O)NHR a A group in which R a is a C1-C6 alkyl radical as generally defined above. Examples of C1-C6 alkylaminocarbonyl radicals include, but are not limited to, ethylcarbamoyl (ie, ethylaminocarbonyl).

[0048] As used herein, the term "N,N-di(C1-C4 alkyl)amino" refers to a a )(R b ) group, wherein R a and R bEach individually is a C1-C4 alkyl group as generally defined above. The term "N,N-di(C1-C3 alkyl)amino" should be interpreted accordingly.

[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 ) group, 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 groups include, but are not limited to, dimethylcarbamoyl (i.e., N,N-di(methyl)aminocarbonyl).

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

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

[0052] As used herein, the term "C1-C6 alkylsulfonyl" refers to a group having the formula -S(O)2R a A group in which R a is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted accordingly. Examples of C1-C6 alkylsulfonyl groups include, but are not limited to, methylsulfonyl.

[0053] As used herein, the term "C1-C6 alkylsulfonylamino" refers to a group having the formula -NHS(O)2R a A group in which R a is a C1-C6 alkyl group as generally defined above.

[0054] The presence of one or more possible stereogenic elements in a compound of formula (I) means that the compound may exist in optical isomeric forms (i.e., enantiomers or diastereomeric forms). Also, as a result of restricted rotation around 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 compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of compounds of formula (I).

[0055] In each case, the compounds of formula (I) according to the invention are in free form or in salt form, for example, agronomically useful salt forms. Preferred are salts that the compounds of formula (I) can form with: amines, including primary, secondary and tertiary amines (for example 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 compounds of formula (I) can form chlorides or 2,2,2-trifluoroacetates.

[0056] The following list provides information about the substituents X, n, R, and 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 9 , R 10 , and R 11 For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0057] X is O, S(O)n, or NR 11 Preferably, X is O or NR 11 In one group of embodiments, X is O, in another group of embodiments, X is NR 11 In one group of embodiments, X is O, S, or NH.

[0058] n is 0, 1, or 2. Preferably, n is 0.

[0059] R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy C1-C6 alkyl, or C3-C6 cycloalkyl. 1is C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy C1-C4 alkyl, or C3-C6 cycloalkyl. More preferably, R 1 It is C1-C4 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 alkyl, or C3-C4 cycloalkyl.

[0060] In one set of embodiments, R 1 is methyl, ethyl, n-propyl, allyl, prop-2-ynyl, methoxy, methoxyethyl, or cyclopropyl. In another embodiment, R 1 It is a C1-C4 alkyl group, preferably a C1-C3 alkyl group, and more preferably an ethyl group.

[0061] 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 be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 7 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 be optionally substituted by 1, 2 or 3 residues which may be the same or different and are represented by R 7 The group represented is substituted.

[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 be optionally substituted by 1, 2 or 3 residues which may be the same or different and are represented by R 7 The group represented is substituted.

[0063] Still 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 be optionally replaced by 1 or 2 residues which may be the same or different and are represented by R 7 The group represented is substituted.

[0064] Even more preferably, R 2 is optionally replaced by 1 or 2 which may be the same or different from R 7 In one embodiment, R 2is 3-chloro-4-cyanophenyl, 3,4-dichlorophenyl or 3,4-difluorophenyl, preferably 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl. More preferably, R 2 It is 3,4-dichlorophenyl.

[0065] R 3 is hydrogen or C1-C6 alkyl. Preferably, R 3 is hydrogen or C1-C3 alkyl. More preferably, R 3 is hydrogen or methyl. Most preferably, R 3 It's hydrogen.

[0066] R 4 is hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl. 4 is hydrogen, halogen, C1-C3 alkyl, or C1-C3 haloalkyl. More preferably, R 4 is hydrogen or C1-C3 alkyl. In one embodiment, R 4 In another embodiment, R 4 It's hydrogen.

[0067] In one set of embodiments, R 4 is hydrogen or bromine, preferably hydrogen.

[0068] R 5 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally replaced by 1, 2, 3 or 4 R moieties which may be the same or different 9 or

[0069] R 5 and R 11 Together with the nitrogen atom to which they are attached, they may form a 5-membered heterocyclyl ring, wherein the heterocyclyl moiety further comprises an additional oxygen atom, and wherein the heteroaryl moiety may be optionally substituted by 1 or 2 residues which may be the same or different and are represented by R 10 The group represented is substituted.

[0070] Preferably, R 5 is C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered or 6-membered aromatic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally substituted by 1, 2 or 3 R which may be the same or different9 The group represented is substituted.

[0071] More preferably, R 5 is C1-C5 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C5-C6 cycloalkyl, C5-C6 cycloalkenyl, phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally substituted by 1, 2 or 3 residues which may be the same or different and are represented by R 9 The group represented is substituted.

[0072] Even more preferably, R 5 is C1-C4 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, cyclohexyl, cyclohexenyl, phenyl or pyridyl, wherein each cyclohexyl, cyclohexenyl, phenyl and pyridyl moiety may be optionally replaced by 1 or 2 residues which may be the same or different and are represented by R 9 The group represented is substituted.

[0073] In one set of embodiments, R 5 is C1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, 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 be optionally replaced by 1 or 2 residues which may be the same or different and are represented by R 9 The group represented is substituted.

[0074] In another set of embodiments, R 5 is methyl, C5 alkenyl, 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 be optionally replaced by 1 or 2 residues which may be the same or different and are represented by R 9 The group represented is substituted.

[0075] In another set of embodiments, R 5 is methyl, C5 alkenyl, phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridinyl, or pyridazinyl, wherein each phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridinyl, and pyridazinyl moiety may be optionally replaced by 1 or 2 residues which may be the same or different and are represented by R 9 The group represented is substituted.

[0076] In yet another set of embodiments, R 5 is C1-C3 alkyl or phenyl, wherein the phenyl is replaced by 1 or 2 R 9 Preferably, R 5is C1-C3 alkyl or phenyl, wherein the phenyl is separated by a single R 9 Preferably, R 5 is methyl or phenyl, wherein the phenyl group is replaced by a single R 9 Group substitution.

[0077] In a particularly preferred embodiment, R 5 is methyl, 2-methyl-but-2-enyloxy, 1-methylprop-2-ynyl, cyclopropyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 4-cyclopropylphenyl, 4-methylsulfonylphenyl, 3,4-dimethoxyphenyl, 3-chloro-5-methoxyphenyl, 4-chloro-2-methoxyphenyl, 4-chloro-2-fluorophenyl, 2-chloro-5-fluorophenyl, 3-fluoro-4-methylphenyl, 4-methyl-3-(trifluoromethyl)phenyl , 2-fluoro-3-pyridinyl, 6-fluoro-3-pyridinyl, 5-chloro-2-pyridinyl, 5-chloro-3-pyridinyl, 6-chloro-2-pyridinyl, 2-chloro-4-pyridinyl, 3,5-difluoro-2-pyridinyl, 6-methyl-2-pyridinyl, 1-methylpyrazolyl, 5-(difluoromethyl)-1-methylpyrazol-3-yl, 1-ethylpyrazol-3-yl, 1-ethylpyrazol-4-yl, 1-cyclopropylpyrazol-3-yl, 5-chloro-1-methylpyrazol-3-yl, 5-methylisoxazol-3-yl, 5-ethylisoxazol-3-yl, 5-cyclopropylisoxazol-3-yl, 1,2,5-thiadiazol-3-yl, or quinoxazolin-6-yl.

[0078] R 7 It is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 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.

[0079] Preferably, R 7It is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 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.

[0080] More preferably, R 7 It is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 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.

[0081] Still more preferably, R 7 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 7 is cyano, nitro, chloro, fluoro, methyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2-difluoroethoxy, methoxymethyl, acetyl, or cyclopropyl.

[0082] In one set of embodiments, R 7 is cyano, nitro, or halogen, preferably cyano or halogen, more preferably halogen, and still more preferably, R 7 is chlorine or fluorine. In one embodiment, R 7 It is cyano or chlorine.

[0083] R 9 is cyano, nitro, hydroxy, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, or benzyloxy; or

[0084] Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a C3-C6 cycloalkyl ring or a phenyl ring, wherein the C3-C6 cycloalkyl and phenyl moieties may be optionally replaced by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 10 or

[0085] Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a 5- or 6-membered heteroaryl ring, 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 the heteroaryl moiety may be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are composed of R 10 or

[0086] Any two adjacent R 9 The groups together with the carbon atom to which they are attached may form a 5- or 6-membered heterocyclyl ring, wherein the heterocyclyl moiety is a 5- or 6-membered ring containing 1 or 2 heteroatoms selected from O and N, and wherein the heterocyclyl ring may be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are composed of R 10 The group represented is substituted.

[0087] Preferably, R 9 is cyano, nitro, hydroxy, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C4 alkoxyC1-C4 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonylamino, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C3 alkyl)aminocarbonyl, or benzyloxy; or

[0088] Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a C3-C6 cycloalkyl ring or a phenyl ring, wherein the C3-C6 cycloalkyl and phenyl moieties may be optionally replaced by 1, 2 or 3 residues which may be the same or different and which are represented by R 10 or

[0089] Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a 5- or 6-membered heteroaryl ring, 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 the heteroaryl moiety may be optionally substituted by 1, 2 or 3 which may be the same or different and are composed of R10 or

[0090] Any two adjacent R 9 The groups together with the carbon atom to which they are attached may form a 5- or 6-membered heterocyclyl ring, wherein the heterocyclyl moiety is a 5- or 6-membered ring containing 1 or 2 heteroatoms selected from O and N, and wherein the heterocyclyl ring may be optionally substituted by 1, 2 or 3 residues which may be the same or different and which are composed of R 10 The group represented is substituted.

[0091] More preferably, R 9 It is cyano, nitro, hydroxy, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonylamino, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C4 cycloalkyl, C3-C4 cycloalkylaminocarbonyl, N,N-di(C1-C3 alkyl)aminocarbonyl, or benzyloxy.

[0092] Even more preferably, R 9 It is cyano, nitro, hydroxy, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C2 alkoxyC1-C2 alkyl, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkylsulfonyl, C1-C2 alkylsulfonylamino, C1-C2 alkylcarbonyl, C1-C2 alkoxycarbonyl, C1-C2 alkylaminocarbonyl, C3-C4 cycloalkyl, C3-C4 cycloalkylaminocarbonyl, N,N-di(C1-C2 alkyl)aminocarbonyl, or benzyloxy.

[0093] In one set of embodiments, R 9 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C5 cycloalkyl, or C1-C2 alkylsulfonyl. Preferably, R 9 is halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, cyclopropyl, or C1-C2 alkylsulfonyl. More preferably, R 9 It is halogen, C1-C2 alkyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy, cyclopropyl, or methylsulfonyl.

[0094] In one set of embodiments, R 9 is halogen or C1-C3 alkoxy, preferably methoxy, fluorine, or chlorine, and more preferably, R 9It is fluorine or chlorine.

[0095] R 10 is halogen, oxo, C1-C3 alkyl or C1-C3 alkoxy. 10 is halogen, C1-C3 alkyl, or C1-C3 alkoxy. 10 is halogen or C1-C3 alkoxy. More preferably, R 10 is halogen or methoxy. Even more preferably, R 10 is fluoro or methoxy. In one embodiment, R 10 is oxo, methyl, fluoro or methoxy.

[0096] R 11 is hydrogen or C1-C6 alkyl. Preferably, R 11 is hydrogen or C1-C4 alkyl. More preferably, R 11 is hydrogen or C1-C3 alkyl. In one embodiment, R 11 In another embodiment, R 11 It's hydrogen.

[0097] Among the compounds of formula (I) according to the present invention, preferably:

[0098] X is O or NR 11 ;

[0099] R 1 is C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyC1-C3 alkyl, or C3-C6 cycloalkyl;

[0100] R 2 is optionally represented by 2 which can be the same or different. 7 The group represented is substituted phenyl;

[0101] R 3 It is hydrogen;

[0102] R 4 is hydrogen or C1-C6 alkyl;

[0103] R 5 is C1-C3 alkyl, C2-C3 alkenyl, C3-C6 cycloalkenyl, or phenyl, wherein each cycloalkenyl and phenyl moiety may be optionally replaced by a single R 9 Group substitution;

[0104] R 7 is cyano or halogen;

[0105] R 9 is cyano, halogen, C1-C3 alkoxy, or methylsulfonyl; and

[0106] R 11 It is hydrogen or C1-C6 alkyl.

[0107] In another set of embodiments,

[0108] X is O or NH;

[0109] R 1 is a C1-C3 alkyl group;

[0110] R 2 is optionally represented by 2 which can be the same or different. 7 The group represented is substituted phenyl;

[0111] R 3 It is hydrogen;

[0112] R 4 It is hydrogen;

[0113] R 5 is C1-C3 alkyl or phenyl, wherein each phenyl moiety may be optionally replaced by a single R 9 Group substitution;

[0114] R 7 is a halogen; and

[0115] R 9 It's a halogen.

[0116] In another set of embodiments,

[0117] X is O, S, or NH;

[0118] R 1 It is ethyl;

[0119] R 2 is 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl;

[0120] R 3 It is hydrogen;

[0121] R 4 It is hydrogen;

[0122] R 5 is methyl, C5 alkenyl, phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridinyl, or pyridazinyl, wherein each phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridinyl, and pyridazinyl moiety may be optionally replaced by 1 or 2 residues which may be the same or different and are represented by R 9 The group represented by is substituted;

[0123] In yet another set of embodiments,

[0124] X is O, S, or NH;

[0125] R 1 It is ethyl;

[0126] R 2 is 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl;

[0127] R 3 It is hydrogen;

[0128] R 4 is hydrogen; and

[0129] R 5 is methyl, 2-methyl-but-2-enyloxy, 1-methylprop-2-ynyl, cyclopropyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 4-cyclopropylphenyl, 4-methylsulfonylphenyl, 3,4-dimethoxyphenyl, 3-chloro-5-methoxyphenyl, 4-chloro-2-methoxyphenyl, 4-chloro-2-fluorophenyl, 2-chloro-5-fluorophenyl, 3-fluoro-4-methylphenyl, 4-methyl-3- (trifluoromethyl)phenyl, 2-fluoro-3-pyridyl, 6-fluoro-3-pyridyl, 5-chloro-2-pyridyl, 5-chloro-3-pyridyl, 6-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3,5-difluoro-2-pyridyl, 6-methyl-2-pyridyl, 1-methylpyrazolyl, 5-(difluoromethyl)-1-methylpyrazol-3-yl, 1-ethylpyrazol-3-yl, 1-ethylpyrazol-4-yl, 1-cyclopropylpyrazol-3-yl, 5-chloro-1-methylpyrazol-3-yl, 5-methylisoxazol-3-yl, 5-ethylisoxazol-3-yl, 5-cyclopropylisoxazol-3-yl, 1,2,5-thiadiazol-3-yl, or quinoxalin-6-yl; and

[0130] R 9 It is halogen, C1-C2 alkyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy, cyclopropyl, or methylsulfonyl.

[0131] The compounds of the present invention can be prepared by techniques known to those skilled in the art of organic chemistry. The following describes a general method for producing compounds of formula (I). Unless otherwise specified in the text, R 1 , R 2 , R 4 , R 5, and X are as defined above. The starting materials for preparing the compounds of the present invention can be purchased from common commodity suppliers or can be prepared by known methods. Starting materials and intermediates can be purified by prior art methods (such as chromatography, crystallization, distillation and filtration) before being used in the next step.

[0132] As shown in Scheme 1, compounds of the present invention having formula (I) can be prepared from compounds having formula (A).

[0133] Scenario 1:

[0134]

[0135] The compound of formula (I) can be prepared by mixing a compound of formula (A) (wherein R 3 C1-C6 alkyl) in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional cosolvent (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) to prepare. In the case of using a base, the product is obtained after acidification with a suitable acid (such as hydrochloric acid). Compounds with formula (A) can also be prepared by the method described below.

[0136] Scenario 2:

[0137]

[0138] A compound of formula (B) wherein Y is Br, Cl or I, and X is O, S(O)n, or NR 11 ) can be converted to a compound of formula (A) by reduction using hydrogen in the presence of a suitable catalyst (such as palladium carbon or platinum carbon), in a suitable organic solvent (such as methanol, ethanol or ethyl acetate), optionally in the presence of an organic acid (such as acetic acid). This is shown in Scheme 2 above.

[0139] Alternatively, a compound of formula (B) wherein Y is Br and X is O, S(O)n, or NR 11 ) can be converted to a compound of formula (A) by transfer hydrogenation conditions using a suitable hydrogen source such as ammonium formate in an organic solvent such as acetonitrile in the presence of a suitable catalyst such as bis(triphenylphosphine)palladium(II) dichloride at elevated temperature.

[0140] Solution 3:

[0141]

[0142] Compounds of formula B, wherein Z is Br or H, and X is S, can be converted to compounds of formula (B), wherein Z is Br or H, and X is sulfoxide or sulfone, by oxidation with a suitable oxidant, such as 3-chloroperoxybenzoic acid or hydrogen peroxide, in a suitable solvent, such as dichloromethane or acetic acid. This is shown in Scheme 3 above.

[0143] Solution 4:

[0144]

[0145] In a different transformation, a compound of formula (B) wherein X is NH and Z is Br or hydrogen can be converted to a compound of formula (B) wherein X is NR by alkylation using a suitable alkylating agent such as an alkyl halide in a suitable solvent such as N,N-dimethylformamide or tetrahydrofuran in the presence of a base such as sodium hydride. 11 , and Z is Br or hydrogen). This is shown in Scheme 4 above.

[0146] Solution 5:

[0147]

[0148] Compounds of formula (C) wherein Z is Br or H, and X is I (or Cl or Br) can be converted to compounds of formula (B) wherein Z is Br or H, X is O, S or NH, and R is I (or Cl or Br)) by Ullmann cross coupling with nucleophiles such as phenol or aniline under similar conditions to those described in the literature. 5 is not hydrogen, but any other R as defined above 5 Typically, the reaction is carried out by reacting a compound having formula (C) with R 5 -nucleophile is reacted at elevated temperature in an organic solvent (such as 1,4 dioxane) in the presence of a suitable catalyst (such as copper (I) iodide) and a suitable ligand (such as 2-(dimethylamino)acetic acid) and a suitable base (such as cesium carbonate). Nucleophile is commercially available or can be prepared by methods familiar to those skilled in the art. This is shown in Scheme 5 above.

[0149] In an alternative transformation, a compound of formula (B) wherein Z is Br or hydrogen, R 5 is not hydrogen, but any other R as defined above 5Group, and X is O, S or NH) can be obtained by the following reaction: a compound of formula (C) (wherein Z is Br or H, and X is I) is reacted with a nucleophile (such as aniline or thiophenol) at elevated temperature, in a suitable organic solvent (such as 1,4-dioxane or toluene), in the presence of a base (such as cesium carbonate), in the presence of a suitable catalyst (such as [2-(2-aminophenyl)phenyl]-chloro-palladium; (5-diphenylphosphanyl-9,9-dimethyl-xanthene-4-yl)-diphenyl-phosphane) or palladium diacetate, optionally with a ligand (such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene).

[0150] Solution 6:

[0151]

[0152] Compounds of formula (C) (wherein Z is Br or hydrogen, and X is I, Br or Cl) can be prepared by decarboxylating and subsequently halogenating a compound of formula (D) at elevated 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.

[0153] Other decarboxylation-halogenation conditions from the literature may also be used.

[0154] Solution 7:

[0155]

[0156] Compounds of formula (D) wherein Z is Br or hydrogen can be prepared by oxidation (e.g. via Pinnick oxidation) of compounds of formula (E) wherein R is an aldehyde or alcohol in a suitable solvent such as tert-butyl alcohol or 2-methylbut-2-ene, optionally in the presence of water, in the presence of a base such as monosodium phosphate with a suitable oxidizing agent such as sodium chlorite. This is shown in Scheme 7 above. Other oxidation conditions from the literature may also be used.

[0157] Solution 8:

[0158]

[0159] Compounds with formula (E) (wherein Z is Br or hydrogen, and R is an aldehyde, alcohol or carboxylic acid) can be prepared by treating compounds with formula (F) (wherein Y is Br, I or Cl) in a suitable solvent (such as acetonitrile), optionally in the presence of a base (such as N-ethyl-N-isopropyl-propan-2-amine) with a suitable oxidant (such as 4-methyl-4-oxoanion-morpholin-4-ium). This is shown in Scheme 8 above.

[0160] Solution 9:

[0161]

[0162] Compounds of formula (F) wherein Y is Br (or I or Cl), and Z is Br or I can be prepared by treating a compound of formula (C) in a suitable solvent (such as acetonitrile or trifluoroacetic acid) with a suitable halogenating agent (such as N-bromosuccinimide). This is shown in Scheme 9 above.

[0163] Solution 10:

[0164]

[0165] Compounds of formula (F) (wherein Y is Br or hydrogen) can be prepared by reacting compounds of formula (H) (wherein Y is Br or hydrogen) with compounds of formula (i) at elevated temperatures (e.g. 140° C.), optionally in the presence of a solvent such as xylene. Compounds of formula (H) and (i) are both commercially available and can also be prepared by methods familiar to those skilled in the art. This is shown in Scheme 10 above.

[0166] Solution 11:

[0167]

[0168] Compounds of formula (i) can be prepared by reaction of a β-keto acid ester of formula (L) with an amine salt. Amine salts can be prepared in situ by acidifying an amine of formula (K) with a suitable acid (such as acetic acid). These amine salts can then be reacted with a compound of formula (L) in a suitable solvent (such as toluene) in the presence of an acid (such as acetic acid) and a drying agent (such as The reaction is carried out in the presence of 4-(4-(4-)-molecular sieves). This is shown in Scheme 11 above. Compounds of formula (L) are commercially available and can also be prepared using the following conditions. Compounds of formula (K) are commercially available and can also be prepared by methods reported in the literature.

[0169] Solution 12:

[0170]

[0171] Compounds of formula (L) can be prepared by treating a ketone of formula (M) with a base (such as sodium hydride) in the presence of a dialkyl carbonate (such as dimethyl carbonate) of formula (N). This is shown in Scheme 12 above. Compounds of formula (M) and formula (N) are commercially available or can be prepared by methods familiar to those skilled in the art.

[0172] Solution 13:

[0173]

[0174] Compounds of formula (L) can be prepared by treating a carboxylic acid of formula (O) (wherein A is hydroxyl or Cl) in a suitable solvent (such as tetrahydrofuran) at room temperature with an optional coupling agent (such as 1,1'-carbonyldiimidazole). The intermediate can then be reacted with a compound of formula (P) (such as potassium 3-methoxy-3-oxopropanoate) at elevated temperature, in a suitable solvent (such as tetrahydrofuran), in the presence of an inorganic salt (such as magnesium chloride). This is shown in Scheme 13 above. Compounds of formula (O) and formula (P) are commercially available or can be prepared by methods familiar to those skilled in the art.

[0175] Alternatively, compounds of the invention having formula (A) may be prepared from compounds having formula (I) as shown below in Schemes 1a to 7a.

[0176] Option 1a:

[0177]

[0178] The compound of formula (I) can be prepared by mixing a compound of formula (A) (wherein R 3 C1-C6 alkyl) in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional cosolvent (such as water) with a suitable base (such as sodium hydroxide or lithium hydroxide) or with a suitable Bronsted acid (such as trifluoroacetic acid, hydrochloric acid or sulfuric acid) or with a suitable Lewis acid (such as scandium trifluoromethanesulfonate or zinc trifluoromethanesulfonate) for hydrolysis to prepare. In the case of using a base, the product is obtained after acidification with a suitable acid (such as hydrochloric acid). Compounds with formula (A) can also be prepared by the methods described below.

[0179] Option 2a:

[0180]

[0181] Compounds of formula (C) wherein X is Cl (or F or Br or I) can be converted to compounds of formula (I) wherein X is O, S or NH and R 5 is not hydrogen, but any other R as defined above 5 Typically, the reaction is carried out by reacting a compound of formula (C) with an R5-nucleophile at elevated temperature in an organic solvent (such as acetonitrile) in the presence of a suitable base (such as cesium carbonate or potassium phosphate). Nucleophiles are commercially available or can be prepared by methods familiar to those skilled in the art. Compounds of formula (C) can additionally be prepared by methods described below.

[0182] Option 3a:

[0183]

[0184] A compound of formula (A) wherein X is Cl (or F or Br or I), and R 3 is C1-C6 alkyl) can be converted to a compound of formula (B) (wherein X is O, S or NH, and R 5 is not hydrogen, but any other R as defined above 5 Typically, the reaction is carried out by reacting a compound of formula (C) with an R5-nucleophile at elevated temperature in an organic solvent such as acetonitrile or toluene in the presence of a suitable base such as cesium carbonate or potassium phosphate. Nucleophiles are commercially available or can be prepared by methods familiar to those skilled in the art. This is shown in Scheme 3a above.

[0185] Option 4a:

[0186]

[0187] A compound of formula (C) wherein X is Cl (or F or Br or I), and R 3 C1-C6 alkyl) can be prepared by hydrolyzing a compound of formula (B) wherein X is Cl (or F or Br or I) in a suitable solvent such as dichloromethane, chloroform, ethyl acetate or tetrahydrofuran with an optional cosolvent such as water with a suitable base such as sodium hydroxide or lithium hydroxide or with a suitable Bronsted acid such as trifluoroacetic acid, hydrochloric acid or sulfuric acid or with 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. This is shown in Scheme 4a above.

[0188] Option 5a:

[0189]

[0190] Compounds with formula (D) (wherein R is C1-C6 alkyl) can be converted into compounds with formula (B) by Sandmeyer halogenation with a suitable halogen source (such as copper chloride (I) or copper bromide (I)) similar to literature conditions. Typically, the reaction is carried out by reacting a compound with formula (D) at an elevated temperature, in a suitable solvent (acetonitrile or dichloromethane) with an optional cosolvent (such as water), in the presence of a suitable oxidant (such as sodium nitrite or isoamyl nitrite) with a suitable halogen source (such as copper chloride (I) or potassium iodide) with a suitable acid (such as hydrogen chloride or hydrogen iodide). This is shown in the above scheme 5a.

[0191] Option 6a:

[0192]

[0193] A compound of formula (E) wherein R3 is C1-C6 alkyl can be converted to a compound of formula (D) wherein R3 is C1-C6 alkyl by adding a suitable base such as sodium ethoxide in a suitable solvent such as ethanol. This is shown in Scheme 6a above.

[0194] Option 7a:

[0195]

[0196] A compound having formula (E) (wherein R 4 described in the above claims) can be prepared by making a compound having the formula (F) (wherein R 4 The invention relates to a process for preparing a 2-hydroxy-2-nitropropene-1-yl ...

[0197] The present invention further provides a method for controlling weeds at a site, the method comprising applying a composition comprising a compound of formula (I) to the site in an amount of weed control. In addition, the present invention may further provide a method for selectively controlling weeds at a site including useful (crop) plants and weeds, wherein the method comprises applying a composition according to the present invention in an amount of weed control to the site. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention show greatly improved selectivity compared to known structurally similar compounds. Typically, the plants to be controlled are unwanted plants (weeds). 'Site' means the area where the plant is growing or will grow. Application can be applied to the site before and / or after emergence of crop plants. Some crop plants can inherently tolerate the herbicidal action of compounds with formula (I).

[0198] The application rate of the compound of formula (I) can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence or post-emergence; seed dressing; application to the seed furrow; no-till application, etc.), the crop plants, 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 compound of formula I according to the invention is usually applied at a rate of 10 g / ha to 2500 g / ha, especially 25 g / ha to 1000 g / ha, more especially 25 g / ha to 250 g / ha.

[0199] Application is usually carried out 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 drenching may also be used.

[0200] The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides such as bromoxynil or classes of herbicides such as, for example, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyruvyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen oxidase (PPO) inhibitors as a result of conventional methods of breeding or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones such as imazamox by conventional methods of breeding (mutagenesis) are Summer rapeseed (Canola). Examples of crops that have been rendered tolerant to herbicides or herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties sold under the trade name Roundup Herculex and Commercially available.

[0201] The term "useful plants" is to be understood as also including useful plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0202] Examples of such plants are: (maize variety expressing CryIA(b) toxin); YieldGard (maize variety expressing CryIIIB(b1) toxin); YieldGard (maize varieties expressing CryIA(b) and CryIIIB(b1) toxins); (maize variety expressing Cry9(c) toxin); Herculex (maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate ammonium); NuCOTN (cotton variety expressing CryIA(c) toxin); Bollgard (cotton variety expressing CryIA(c) toxin); Bollgard (cotton varieties expressing CryIA (c) and CryIIA (b) toxins); (cotton varieties expressing VIP toxin); (potato variety, expressing CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait), RW (corn rootworm trait) and

[0203] Plant crops or their seed material can be both resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic events). For example, seeds can have the ability to express an insecticidal Cry3 protein while being tolerant to glyphosate.

[0204] Crop plants are also to be understood as including those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (eg improved storage stability, higher nutritional value and improved flavor).

[0205] The compounds of formula (I) (or compositions comprising them) can be used to control unwanted plants (collectively referred to as 'weeds'). The weeds to be controlled may be monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, a) and Sorghum, and also dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0206] The compounds of formula (I) can be used in unmodified form or preferably together with adjuvants conventionally used in the field of formulation to provide herbicidal compositions, using formulation adjuvants, such as carriers, solvents and surfactants (SAAs). Therefore, the present invention further provides a herbicidal composition comprising at least one compound of 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.

[0207] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds of formula (I) and 1 to 99.9% by weight of formulation adjuvants which preferably comprise 0 to 25% by weight of surface-active substances.

[0208] The composition can be selected from a number of 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), master drugs (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 envisioned and the physical, chemical and biological properties of the compound of formula (I).

[0209] Soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants or mixtures of said agents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0210] Wettable powders (WP) can be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably one or more dispersants, 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).

[0211] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or by absorbing the compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material such as pumice, attapulgite clay, Fuller's earth, kieselguhr, diatomaceous earth or corn cob meal, or by adsorbing the compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicates, mineral carbonates, sulfates or phosphates and drying if necessary from preformed green particles. Agents commonly used to aid 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, dextrins, sugars and vegetable oils. One or more other additives such as emulsifiers, wetting agents or dispersants may also be included in the granules.

[0212] Dispersible concentrates (DC) can be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain a surfactant (for example to improve water dilution or to prevent crystallization in a spray tank).

[0213] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (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 EC products emulsify spontaneously when added to water, producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

[0214] The preparation of EWs involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it can be melted at a reasonable temperature, typically below 70°C) 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 EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents having low solubility in water.

[0215] Microemulsions (ME) 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 water or in a solvent / SAA blend. Suitable solvents for use in MEs include those described above for use in ECs or EWs. MEs can be oil-in-water systems or water-in-oil systems (which system is present can be determined by conductivity measurements) and can be suitable for mixing water-soluble pesticides and oil-soluble pesticides in the same formulation. MEs are suitable for dilution into water, remaining as microemulsions or forming conventional oil-in-water emulsions.

[0216] Suspension concentrates (SC) may include aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SC may be prepared by ball milling or bead milling a solid compound of 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 of formula (I) may be dry-milled and added to water containing the reagents described above to produce a desired final product.

[0217] Aerosol formulations comprise a compound of formula (I) and a suitable propellant (e.g. n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g. water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized hand-operated spray pump.

[0218] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, but with an additional polymerization stage, to obtain an aqueous dispersion of oil droplets, each of which is wrapped 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 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.

[0219] The composition may include one or more additives to improve the biological performance of the composition, for example by improving wettability, retention or distribution on a surface; rain resistance on a treated surface; or absorption or mobility of a compound of 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 bioenhancement adjuvants (ingredients that can assist or modify the action of a compound of formula (I)).

[0220] The wetting agent, dispersant and emulsifier may be a cationic type, anionic type, amphoteric type or nonionic type SAA.

[0221] Suitable cationic-type SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0222] 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, butylnaphthalenesulfonate and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laureth-3-sulfate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphates (products from the reaction of one or more fatty alcohols with phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), for example the reaction of lauryl alcohol with tetraphosphoric acid; additionally, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignin sulfonates and phosphates / sulfates of tristyrylphenol.

[0223] Suitable amphoteric types of SAA include betaine, propionate and glycinate.

[0224] Suitable SAAs of the nonionic type 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 hexitol anhydrides; condensation products of the partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (such as fatty acid polyethylene glycol esters); amine oxides (such as lauryl dimethyl amine oxide); lecithin and sorbitan and its esters, alkyl polyglycosides and tristyrylphenol.

[0225] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0226] The compounds of the present invention may also be used in admixture 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), bennitroprop-butyl, ametryn, amitriptyline, aminopyralid, cypermethrin, atrazine, flubutyric acid, quinquitrione, bensulfuron-methyl (including bensulfuron-methyl), bentazone, flupyralid, bialaphos, bispyribac-butyl, bispyribac-sodium, bixlozone, bromomethalin, herbicide, bromoxynil, butachlor, flupyralid, mesotrione (including mesotrione-ethyl), chlorsulfuron (including chlorsulfuron-methyl), chlorsulfuron (including chlorsulfuron-ethyl), chlorotoluron, chlorsulfuron, cyclohexane. cypermethrin, chlorpyrifos, clethodim, clodinafop-butyl (including clodinafop-butyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), bischlorosulfuron, fluazifop-butyl, fluazifop-butyl, dimethoate, dimethoate-s-propyl, dioxopyritrione, dibromo Diquat, diuron, epyrifenacil, ethoflufenacil, oxadiazine (including epyrifenacil-ethyl), benzenesulfuron, benazole, fenquinotrione, tetrazoline, fluazifop-butyl, bispyribac, clofopyralid (including clofopyralid-benzyl), fluazifop-butyl (including fluazifop-butyl-butyl), fluazifop-butyl (including fluazifop-sodium), fluclofenac (including fluclofenac furfuryl), flufenacet, fluazifop-butyl ... Including fluroxypyr-meptyl), fluroxypyr-meptyl, fluazifop-butyl, foramsulfuron, glufosinate (including L-glufosinate and its ammonium salts), glyphosate (including its ammonium, isopropyl ammonium and potassium salts), fluazifop-butyl (including fluazifop-methyl), fluazifop-methyl (including fluazifop-methyl), hexazinone, hydantocidin, isoxazolidinone (including isoxazolidinone methyl), imazamox (including R-imazamox), imazapic, imazapic, imazapic, indoxazolidinone, indolepyralid (including indolepyralid), iodosulfuron-methyl (including iodosulfuron-methyl-sodium),Iofensulfuron (including iofensulfuron-sodium), ioboxynil, triazole oxadiazole, isoproturon, isoxathiapiprom, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, pyraclostrobin, methiozolin, isopropylamine, sulfamethoxazole, metribuzin, metsulfuron-methyl, propamide, nicosulfuron, fluazifop, oxadiazine, oxasulfuron-methyl, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, bendisulfuron, picloram, pinoxabol, pretilachlor, primisulfuron-methyl, promethazine, propanil, oxadiazine, propyrisulfuron, propyrisulfuron, benzamid, prosulfuron, bispyribac, pyraflufen (including pyraflufen-ethyl), pyraflufen-butyl, ... Sulfurone, thiosulfuron, furansulfuron, cyproconazole, terbuthion, terbutaline, tetrafluralin, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, benpyrazone, trimethoprim, fluazifop, wild wheat chlorpyrifos, ether bensulfuron, bensulfuron (including bensulfuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifloxysulfuron, trifluralin, trifloxysulfuron, triazosulfuron, 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 esters, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one,(1RS,5SR)-3-[2-methoxy-4-(prop-1-yn-1-yl)phenyl]-4-oxobicyclo[3.2.1]oct-2-en-2-yl carbonate, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridinyl]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-dioxo- methyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, (2-fluorophenyl)methyl 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid and 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-carboxylic acid methyl ester.

[0227] The mixing partners of the compounds of formula (I) can also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 19th edition, British Crop Protection Council, 2021. The mixing ratio of the compound of formula (I) to the mixing partner is preferably 1:100 to 1000:1.

[0228] These mixtures can advantageously be used in the abovementioned formulations (in this case, "active ingredient" relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0229] 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 cloquintocet-mexyl), cyclopropylsulfonamide, dichloropropene, oxadiazole (including oxadiazole ethyl), chlorpyrifos, fluazifop, oxadiazole, isoxadiazole (including isoxadiazole-ethyl), mefenpyr (including mefenpyr-butyl), metcamifen and oxadiazole.

[0230] Particularly preferred are mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen-ethyl, clofonet-mexyl and / or sulfamethoxazole.

[0231] The safener of the compound of formula (I) may also be in the form of an ester or salt, as mentioned, for example, in The Pesticide Manual, 19th edition (BCPC), 2021. References to clofonethiol also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048.

[0232] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0233] Compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to crop areas or plants to be treated simultaneously or successively with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with other carriers, surfactants or adjuvants that are usually used in the formulation field to promote application.

[0234] As used herein, the term "locus" means a place in or on which plants grow, or where seeds of cultivated plants are sown, or where seeds are to be placed in the soil. It includes soil, seeds and seedlings, as well as established vegetation.

[0235] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0236] The term "plant propagation material" should be understood to mean the reproductive parts of a plant, such as seeds, which can be used for the propagation of a plant, and vegetative materials, such as cuttings or tubers (e.g., potatoes). For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants that will be transplanted after germination from the soil or after emergence can also be mentioned. These young plants can be protected before transplanting by being treated completely or partially via dipping. Preferably, "plant propagation material" should be understood to mean a seed.

[0237] The pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 19th edition, British Crop Protection Council 2021.

[0238] Compounds with formula (I) can be used in unmodified form, or preferably, together with conventional adjuvants used in the formulation field. For this purpose, they can be conveniently formulated as emulsifiable concentrates, pastes that can be coated, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also encapsulations, for example in polymeric substances, in a known manner. For the type of composition, according to the intended purpose and the environment at that time, the application method is selected, such as spraying, atomizing, dusting, sowing, coating or watering. Compositions can also contain other adjuvants, such as stabilizers, defoamers, viscosity modifiers, adhesives or tackifiers, and fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0239] Suitable carriers and adjuvants, for example for agricultural use, may be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, adhesives or fertilizers. Such carriers are for example described in WO 97 / 33890.

[0240] The compounds of formula (I) are usually used in the form of compositions and can be applied to crop areas or plants to be treated simultaneously or successively with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with other carriers, surfactants or adjuvants that are commonly used in the field of formulations to promote application.

[0241] The compound of formula (I) can be the sole active ingredient of the composition, or it can be mixed with one or more additional active ingredients (such as pesticides, fungicides, synergists, herbicides or plant growth regulators) when appropriate. In some cases, the additional active ingredients can produce unexpected synergistic activity.

[0242] Typically, the formulation comprises 0.01% to 90% by weight of an active agent, 0% to 20% of an agriculturally acceptable surfactant and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being at least composed of a compound with formula (I) together with components (B) and (C), and optionally other active agents (particularly microbicides or preservatives or the like). The concentrated form of the composition typically contains between about 2% and 80% by weight, preferably between about 5% and 70% of the active agent. The application form of the formulation can, for example, contain 0.01% to 20% by weight, preferably 0.01% to 5% by weight of the active agent. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0243] The following table shows examples of individual compounds of formula (I) according to the invention:

[0244]

[0245] Table 1: Individual compounds of formula (I) according to the invention

[0246]

[0247]

[0248]

[0249]

[0250] Table A-1 provides 70 compounds A-1.001 to A.1.070 having formula (I), wherein R 3 is hydrogen, and R 1 , R 2 , R 4 , R 5 , and R 6 is as defined in Table 1

[0251] Preparation Examples

[0252]

[0253] The active ingredient is mixed thoroughly with the adjuvant and the mixture is ground thoroughly in a suitable grinder to provide a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0254]

[0255]

[0256] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to provide a dust that can be used directly for seed treatment.

[0257] Emulsifiable concentrates

[0258]

[0259] Emulsions of any desired dilution which can be used for plant protection can be obtained from these concentrates by dilution with water.

[0260]

[0261] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0262] Extruder Granules

[0263]

[0264] The active ingredient is mixed with the auxiliary agent and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0265] Coated granules

[0266] Active ingredient [compound of formula (I)] 8%

[0267] Polyethylene glycol (molecular weight 200) 3%

[0268] Kaolin 89%

[0269] The finely ground active ingredient is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0270] Suspension concentrates

[0271]

[0272] The finely ground active ingredients are intimately mixed with adjuvants to give suspension concentrates from which suspension concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial infestation by spraying, pouring or immersion.

[0273] Flowable concentrate for seed treatment

[0274]

[0275] The finely ground active ingredients are intimately mixed with adjuvants to give suspension concentrates from which suspension concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial infestation by spraying, pouring or immersion.

[0276] Extended-release capsule suspension

[0277] 28 parts of a combination of compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion are added 2.8 parts of a 1,6-hexanediamine mixture 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 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0278] Examples

[0279] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (as mentioned in Table 2 below).

[0280] Throughout this specification, temperatures are given in degrees Celsius (° C.) and “mp” means melting point.

[0281] List of abbreviations

[0282] brd = broad doublet, brs = broad singlet, °C = degrees Celsius, d = doublet, dd = doublet of doublet, DMSO = dimethyl sulfoxide, M = molar, m = multiplet, MHz = megahertz, nm = nanometer, q = quartet, s = singlet, t = triplet.

[0283] Example 1: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylic acid (Compound 1)

[0284] Step 1: Synthesis of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propionate

[0285]

[0286] To 1-(3,4-dichlorophenyl) ethyl ketone (5.00g, 26.5mmol) and dimethyl carbonate (40mL, 466mmol) stirred solution under nitrogen and at 0°C, sodium hydride (3.17g, 80mmol, 60% by mass) was added in batches. The reaction mixture was warmed to room temperature and stirred for 16 hours. After overnight, the reaction mixture became a solid paste that could not be stirred. More dimethyl carbonate (10mL) 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 (25mL). The reaction mixture was acidified to pH 3 by adding 2M aqueous hydrochloric acid solution and then extracted into ethyl acetate. The organic extract was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica using a gradient of 0% to 15% ethyl acetate in isohexane as eluent to give 3-(3,4-dichlorophenyl)-3-oxo-propionic acid ethyl ester (mixture of tautomers) as a colourless liquid.

[0287] Enol: 1 H NMR (400 MHz, 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)

[0288] ketone: 1 H NMR (400 MHz, chloroform) δ=8.03 (d, 1H), 7.77 (m, 1H), 7.58 (d, 2H), 3.97 (s, 2H), 3.76 (s, 3H)

[0289] Step 2: Synthesis of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

[0290]

[0291] To a stirred solution of 3-(3,4-dichlorophenyl)-3-oxo-propionic acid ethyl ester (1.65 g, 6.32 mmol) in toluene (11 mL) was added ethylammonium; acetate (19.0 mmol) and acetic acid (6.32 mmol). The orange reaction mixture was heated under reflux for 6 hours. The cooled reaction mixture was diluted with ethyl acetate and washed with saturated sodium bicarbonate aqueous solution. The phases were separated and the aqueous phase was extracted 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 flash chromatography using a gradient of 0%-10% ethyl acetate in cyclohexane as eluent to obtain (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoic acid ethyl ester as a colorless oil. 1H NMR (400 MHz, 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)

[0292] Step 3: Synthesis of 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one

[0293]

[0294] A stirring 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 for 12 hours at room temperature. The orange reaction mixture was washed with a 50:50 mixture of saturated sodium bicarbonate aqueous solution and saturated sodium thiosulfate aqueous solution. The organic phase was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by C-18 silica gel flash chromatography using acetonitrile (+0.1% formic acid) with a gradient of 30%-60% in water (+0.1% formic acid) as eluent to obtain 6- (bromomethyl) -2,2-dimethyl-1,3-dioxin-4-one as a yellow oil. 1 H NMR (400 MHz, chloroform) δ=5.54 (s, 1H), 3.90 (s, 2H), 1.73 (s, 6H)

[0295] Step 4: Synthesis of 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester

[0296]

[0297] To a stirred solution of (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoic acid ethyl ester (2.00 g, 6.94 mmol) in xylene (20.0 mL) was added 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one (2.30 g, 10.4 mmol). The resulting reaction mixture was heated at 140 °C for 5 minutes with stirring. The cooled reaction mixture was diluted with ethyl acetate, and the organic solution was washed with brine, dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate as a brown solid.

[0298] 1H 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).

[0299] Step 5: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate

[0300]

[0301] 4-Methyl-4-oxo-morpholinium-4-ium (2.92 g, 24.2 mmol) was added in batches to a stirred solution of 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester (6.99 g, 16.1 mmol) and N-ethyl-N-isopropyl-propan-2-amine (3.67 mL, 21.0 mmol) in acetonitrile (140 mL) at 0 ° C. The reaction mixture was stirred at 25 ° C for 2.5 hours. 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 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylic acid ethyl ester 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).

[0302] Step 6: Synthesis of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-2-carboxylic acid

[0303]

[0304] To a stirred solution of 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylic acid ethyl ester (5.67g, 15.4mmol) in tert-butyl alcohol (77mL) and 2-methylbut-2-ene (77mL) was added a solution of monosodium phosphate (4.20g, 34.7mmol) in water (39mL). The reaction mixture was cooled to 0°C and sodium chlorite (4.22g, 46.2mmol) was added in batches. The reaction mixture was warmed to room temperature and stirred for 2.5 hours. The resulting yellow solution was diluted with saline, methanol and 2M aqueous hydrochloric acid solution and then extracted into ethyl acetate. The organic extract was extracted into a saturated sodium pyrosulfite solution. The aqueous phase was acidified to pH 1 and extracted into dichloromethane by adding 2M aqueous hydrochloric acid solution. 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 HNMR (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)

[0305] Step 7: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid ethyl ester

[0306]

[0307] 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 methylsulfinylmethane (37 mL). The reaction mixture was heated at 120 ° C for 1.5 hours, then quenched with a saturated sodium thiosulfate solution and extracted into dichloromethane. The organic extract was washed with water and brine and passed through a phase separator cartridge. The organic filtrate was evaporated to dryness under reduced pressure to obtain a yellow oil, which was purified by C-18 silica gel flash chromatography using acetonitrile (+0.1% formic acid) with a gradient of 30%-55% in water (+0.1% formic acid) as an eluent to obtain 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid ethyl ester as a yellow solid. 1H NMR (400 MHz, 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)

[0308] Step 8: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylate

[0309]

[0310] A mixture of 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid ethyl ester (0.091 g, 0.195 mmol), cesium carbonate (0.162 g, 0.488 mmol), [2-(2-aminophenyl)phenyl]-chloro-palladium; (5-diphenylphosphane-9,9-dimethyl-xanthene-4-yl)-diphenyl-phosphane (0.017 mg, 0.020 mmol) and 2-fluoroaniline (0.021 mL, 0.215 mmol) under nitrogen was dissolved in anhydrous 1,4-dioxane (1.4 mL). The reaction mixture was heated at 80°C for 1.5 hours. The cooled reaction mixture was diluted with water and extracted into ethyl acetate. The organic extract was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give a brown oil. The crude residue was purified by C-18 silica gel flash chromatography using a gradient of 30%-60% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylate as a cream solid. 1 H NMR (400 MHz, chloroform) δ=7.57 (d, 1H), 7.53 (d, 1H), 7.27-7.24 (m, 2H), 7.16-7.06 (m, 4H), 5.90-5.83 (m, 1H), 3.96 (m, 2H), 3.85 (q, 2H), 1.20 (t, 4H), 0.92 (t, 3H)

[0311] Step 9: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylic acid

[0312]

[0313] To a solution of 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylic acid methyl ethyl ester (0.020 g, 0.045 mmol) in a mixture of tetrahydrofuran (1.0 mL) and water (0.2 mL) was added lithium hydroxide (0.004 g, 0.178 mmol). The resulting solution was heated at reflux for 18 hours. The cooled reaction mixture was diluted with water and acidified to pH 1 by adding 2M aqueous hydrochloric acid solution and extracted into dichloromethane. The organic extracts were evaporated to dryness under reduced pressure to give a crude residue, which was purified by C-18 silica gel flash chromatography using a gradient of 40%-70% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to afford 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylic acid as a colorless oil. 1 H NMR (400 MHz, chloroform) δ=7.51 (d, 1H), 7.34 (d, 1H), 7.32-7.28 (m, 1H), 7.22-7.11 (m, 3H), 7.07 (dd, 1H), 5.94 (d, 1H), 3.89-3.82 (m, 2H), 1.21-1.15 (m, 3H)

[0314] Example 2: Synthesis of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 2)

[0315] Step 1: Synthesis of methyl 3-(3,4-dichlorophenyl)-3-oxo-propionate

[0316]

[0317] 1,1'-carbonyldiimidazole (5.60g, 34.6mmol) was added in batches to a stirred solution of 3,4-dichlorobenzoic acid (7.57g, 31.4mmol) in tetrahydrofuran (60mL) under nitrogen and at 0°C. The reaction mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was then added dropwise to a stirred solution of 3-methoxy-3-oxopropanoic acid potassium (7.41g, 47.1mmol) and magnesium chloride (4.49g, 47.1mmol) in tetrahydrofuran (60mL) at 50°C. The reaction mixture was stirred for 2 hours at 50°C. The cooled reaction mixture was quenched by addition to a 2M aqueous hydrochloric acid solution and then extracted into ethyl acetate. The organic extracts were washed with brine, dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give a crude residue, which was purified by flash chromatography on silica gel using a gradient of 0% - 20% ethyl acetate in cyclohexane as eluent to give 3-(3,4-dichlorophenyl)-3-oxo-propionic acid methyl ester (mixture of tautomers) as a colorless solid.

[0318] Enol: 1 H NMR (400 MHz, chloroform) δ=12.48 (s, 1H), 7.82-7.71 (m, 1H), 7.57-7.49 (m, 1H), 7.43 (d, 1H), 5.61 (s, 1H), 3.78 (s, 3H)

[0319] ketone: 1 H NMR (400 MHz, chloroform) δ=7.98 (d, 1H), 7.82-7.71 (m, 1H), 7.57-7.49 (m, 1H), 3.96 (s, 2H), 3.73 (s, 3H)

[0320] Step 2: Synthesis of methyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

[0321]

[0322] To a stirred solution of 3-(3,4-dichlorophenyl)-3-oxo-propionic acid methyl ester (4.03 g, 16.3 mmol) in toluene (46.8 mL) was added ethylammonium; acetate (48.9 mmol) and acetic acid (16.3 mmol). The slurry was heated under reflux for 3 hours. The cooled reaction mixture was diluted with ethyl acetate and washed with saturated aqueous sodium bicarbonate solution and then brine. The organic extract was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give a crude residue, which was purified by flash chromatography on silica gel using a gradient of 0%-10% ethyl acetate in cyclohexane as eluent to give (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoic acid methyl ester as a light yellow oil. 1 H NMR (400 MHz, chloroform) δ = 8.37 (br s, 1H), 7.50-7.45 (m, 2H), 7.20 (dd, 1H), 4.56 (s, 1H), 3.68 (s, 3H), 3.13-3.01 (m, 2H), 1.12 (t, 3H)

[0323] Step 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid methyl ester

[0324]

[0325] A stirred mixture of (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoic acid methyl ester (52.0 g, 160 mmol) and 2,2,6-trimethyl-1,3-dioxin-4-one (33.6 mL, 240 mmol) under nitrogen was heated at 120° C. for 1 hour. The cooled reaction mixture was evaporated to dryness under reduced pressure to give a crude residue which was purified by flash chromatography on silica gel using a gradient of 0%-10% methanol in dichloromethane as eluent to give methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate as a brown solid. 1 H NMR (400 MHz, chloroform) δ = 7.58-7.52 (m, 1H), 7.51-7.46 (m, 1H), 7.26-7.20 (m, 1H), 6.42-6.35 (m, 1H), 3.71 (q, 2H), 3.54 (s, 3H), 2.41 (s, 3H), 1.16-1.07 (m, 3H).

[0326] Step 4: Synthesis of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid ethyl ester

[0327]

[0328] N-bromosuccinimide (5.56 g, 31.2 mmol) was added to a suspension of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid ethyl ester (10.05 g, 28.37 mmol) in acetonitrile (100 mL) in batches over 3 minutes. After the addition was completed, the reaction mixture was heated at 40 ° C for 3 hours. The reaction mixture was diluted with acetonitrile (100 mL) and trifluoroacetic acid (3.93 g, 2.66 mL, 34 mmol) was added, followed by N-bromosuccinimide (5.05 g, 28.4 mmol) added in batches over 5 minutes. The resulting reaction mixture was heated at 80 ° C for 4 hours and then allowed to stand at room temperature for 18 hours. Acetonitrile was removed under reduced pressure, and the residue was distributed between dichloromethane and water. The organic phase was washed with saturated sodium bicarbonate aqueous solution and then brine, then dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0% to 100% ethyl acetate in cyclohexane as eluent to give 5-bromo-6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester as an off-white solid. 1 HNMR (500MHz, chloroform) δ=7.59(d,1H),7.53(d,1H),7.28(d,1H),4.72(brs,2H),4.10-3.95(m,4H),1.25(t,3H),1.04(t,3H)

[0329] Step 5: Synthesis of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylic acid methyl ester

[0330]

[0331] 4-Methyl-4-oxo-morpholinium-4-ium (5.47 g, 45.3 mmol) was added in batches to a stirred solution of 5-bromo-6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid methyl ester (15.0 g, 30.2 mmol) and N-ethyl-N-isopropyl-propan-2-amine (6.85 mL, 39.2 mmol) in acetonitrile (300 mL) at 0 ° C. The reaction mixture was stirred at 25 ° C for 2.5 hours. The reaction mixture was diluted with water and ethyl acetate. The organic extract was washed with brine, dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylic acid methyl ester as a yellow solid. 1H NMR (400 MHz, chloroform) δ = 10.36 (s, 1H), 7.60 (d, 1H), 7.50 (d, 1H), 7.24 (dd, 1H), 4.08-3.97 (m, 2H), 3.60 (s, 3H), 1.12 (t, 3H).

[0332] Step 6: Synthesis of 3-bromo-6-(3,4-dichlorophenyl)-1-ethyl-5-methoxycarbonyl-4-oxo-pyridine-2-carboxylic acid

[0333]

[0334] To a stirred solution of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-formic acid methyl ester (6.62g, 15.3mmol) in tert-butyl alcohol (76mL) and 2-methylbut-2-ene (76mL) was added a solution of monosodium phosphate (2.78g, 22.9mmol) in water (38mL). The reaction mixture was cooled to 0°C and sodium chlorite (4.19g, 45.9mmol) was added in batches. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with saline and 2M aqueous hydrochloric acid solution and extracted into ethyl acetate. The organic phase was washed with saturated sodium pyrosulfite aqueous solution and then extracted into saturated sodium bicarbonate aqueous solution. The aqueous extract was acidified to pH 1 by adding 2M aqueous hydrochloric acid solution and then extracted into dichloromethane. The organic extract was passed through a phase separator cartridge and evaporated to dryness under reduced pressure to give 3-bromo-6-(3,4-dichlorophenyl)-1-ethyl-5-methoxycarbonyl-4-oxo-pyridine-2-carboxylic acid as a colorless solid. 1 H NMR (400MHz, DMSO-d6) δ = 7.96 (d, 1H), 7.81 (d, 1H), 7.55 (dd, 1H), 3.76-3.69 (m, 2H), 3.42 (s, 3H), 1.11 (s, 3H).

[0335] Step 7: Synthesis of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid methyl ester

[0336]

[0337] To a stirred solution of 3-bromo-6-(3,4-dichlorophenyl)-1-ethyl-5-methoxycarbonyl-4-oxo-pyridine-2-carboxylic acid (2.05 g, 4.55 mmol) and dipotassium phosphate (0.79 g, 4.55 mmol) in acetonitrile (23 mL) was added iodine (11.6 g, 45.5 mmol). The reaction mixture was heated at reflux for 1.5 hours. The cooled reaction mixture was added to a saturated sodium pyrosulfite solution, extracted into ethyl acetate and washed with sodium pyrosulfite. The organic extract was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid methyl ester as an off-white solid. 1 H NMR (400 MHz, chloroform) δ = 7.58 (d, 1H), 7.48 (d, 1H), 7.22 (dd, 1H), 4.20 (q, 2H), 3.57 (s, 3H), 1.19 (t, 3H).

[0338] Step 8: Synthesis of 5-bromo-6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid methyl ester

[0339]

[0340] To a mixture of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylic acid methyl ester (0.410 g, 0.772 mmol), 3-chlorophenol (0.199 g, 1.54 mmol), 2-(dimethylamino)acetic acid (0.024 g, 0.232 mmol), copper (I) iodide (0.015 g, 0.077 mmol) and cesium carbonate (0.298 g, 1.54 mmol) under nitrogen, anhydrous 1,4-dioxane (18 mL) was added. The reaction mixture was heated at 100 ° C for 1 hour. The cooled reaction mixture was diluted with water, extracted into ethyl acetate and washed with brine. The organic extracts were dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give a crude oil, which was purified by C-18 silica gel flash chromatography using a gradient of 50%-85% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to give 5-bromo-6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid methyl ester as a colorless solid. 1H NMR (400MHz, chloroform) δ = 7.60 (d, 1H), 7.54 (d, 1H), 7.36-7.32 (m, 1H), 7.29 (dd, 1H), 7.18(dd,1H),7.01(t,1H),6.86(dd,1H),3.74(q,2H),3.61(s,3H),1.17(t,3H)

[0341] Step 9: Synthesis of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid methyl ester

[0342]

[0343] A mixture of 5-bromo-6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid methyl ester (0.085 g, 0.160 mmol), bis(triphenylphosphine)palladium dichloride (II) (0.011 g, 0.016 mmol) and ammonium formate (0.049 g, 0.784 mmol) in acetonitrile (3.4 mL) was heated at 120 ° C for 2 hours under microwave irradiation. The cooled reaction mixture was diluted with water and extracted into dichloromethane. 2,4,6-trimercaptotriazine silica gel was added to the organic extract, which was stirred for 5 minutes and then filtered. The organic filtrate was evaporated to dryness under reduced pressure to give a crude yellow oil, which was purified by C-18 silica gel flash chromatography using a gradient of 50%-80% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to afford 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid methyl ester as a colorless solid. 1 H NMR (400 MHz, chloroform) δ=7.59 (d, 1H), 7.55 (d, 1H), 7.44-7.38 (m, 1H), 7.34-7.31 (m, 1H), 7.30-7.26 (m, 1H), 7.17 (t, 1H), 7.08-7.02 (m, 1H), 5.72 (s, 1H), 3.87 (m, 2H), 3.56 (s, 3H), 1.25 (t, 3H)

[0344] Step 10: Synthesis of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid

[0345]

[0346] To a solution of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-formic acid methyl ester (0.028g, 0.062mmol) in a mixture of tetrahydrofuran (1.40mL) and water (0.28mL), lithium hydroxide (0.006g, 0.247mmol) is added. The resulting solution is heated under reflux for 18 hours. The cooled reaction mixture is diluted with water and acidified to pH 1 by adding 2M aqueous hydrochloric acid solution and then extracted into dichloromethane. The organic extract is evaporated to dryness under reduced pressure to obtain 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-formic acid as an off-white solid. 1 H NMR (400 MHz, chloroform) δ=7.61 (d, 1H), 7.49-7.44 (m, 1H), 7.43-7.37 (m, 2H), 7.22 (t, 1H), 7.16 (dd, 1H), 7.11 (m, 1H), 5.94 (s, 1H), 4.03-3.92 (m, 2H), 1.30 (t, 3H)

[0347] Example 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methoxy-4-oxo-pyridine-3-carboxylic acid (Compound 5)

[0348]

[0349] To a solution of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-formic acid methyl ester (0.030 g, 0.066 mmol) in a mixture of methanol (0.33 mL) and water (0.33 mL), lithium hydroxide (0.016 g, 0.663 mmol) was added. The resulting solution was heated at reflux for 1.5 hours. The cooled reaction mixture was diluted with water and acidified to pH 1 by adding 2M aqueous hydrochloric acid solution and then extracted into dichloromethane. The organic extracts were evaporated to dryness under reduced pressure to give a crude residue, which was purified by C-18 silica gel flash chromatography using a gradient of 45%-75% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to afford 2-(3,4-dichlorophenyl)-1-ethyl-6-methoxy-4-oxo-pyridine-3-carboxylic acid as a colorless solid. 1 H NMR (400 MHz, chloroform) δ = 7.59 (d, J = 8.2 Hz, 1H), 7.37 (d, 1H), 7.13 (dd, 1H), 6.21 (s, 1H), 4.04 (s, 3H), 3.83-3.76 (m, 2H), 1.16 (t, 3H)

[0350] Example 4: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid (Compound 52)

[0351] Step 1: Synthesis of ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butyrate

[0352]

[0353] By (Z) -3- (3,4- dichlorophenyl) -3- (ethylamino) prop-2- enoic acid ethyl ester (5.10g, 17.7mmol) and 2- cyanoacetic acid (1.51g, 17.7mmol) in acetic anhydride (16mL) solution under stirring at 105 DEG C for 0.25 hours. The cooled reaction mixture is evaporated to dryness under reduced pressure. Water (20mL) is added to the residue. The obtained precipitated solid is collected by filtration and purified by silica gel flash chromatography to obtain (2E) -4- cyano -2- [(3,4- dichlorophenyl) -(ethylamino) methylene] -3- oxo - butyric acid ethyl ester as off-white solid.

[0354] Step 2: Synthesis of 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester

[0355]

[0356] To a stirred solution of (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butyric acid ethyl ester (4.50 g, 12.67 mmol) in ethanol (80 mL) at 0 ° C was added sodium ethoxide (4.11 g, 12.7 mmol). The reaction mixture was heated at 50 ° C for 2 hours. The cooled reaction mixture was poured into a saturated aqueous ammonium chloride solution 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 C-18 silica gel flash chromatography to give 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester as a white solid. 1 H NMR (400 MHz, 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)

[0357] Step 3: Synthesis of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester

[0358]

[0359] To a suspension of 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester (0.500 g, 1.41 mmol) in a mixture of acetonitrile (12 mL) and aqueous hydrogen chloride solution (2M, 1.8 mL) was added copper (I) chloride (0.167 g, 1.69 mmol). The resulting reaction mixture was heated to 75 ° C, after which 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 hours 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 flash chromatography to give 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester as a yellow solid. 1 H NMR (400 MHz, 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)

[0360] Step 4: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid ethyl ester

[0361]

[0362] A stirred suspension of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester (0.050 g, 0.13 mmol), 6-fluoropyridin-3-ol (0.023 g, 0.20 mmol) and tripotassium phosphate (0.085 g, 0.40 mmol) in acetonitrile (2 mL) was heated at 100 °C for 16 hours. The cooled reaction mixture was extracted into ethyl acetate. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated under drying to give crude 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid ethyl ester.

[0363] Step 5: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid

[0364]

[0365] To a solution of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid ethyl ester (0.300g, 0.665mmol) in a mixture of tetrahydrofuran (10mL) and water (3mL) at room temperature, lithium hydroxide hydrate (0.084g, 2.0mmol) is added. The resulting solution is stirred at room temperature for 48 hours. The reaction mixture is diluted with water and acidified to pH 5 by adding 2M aqueous hydrochloric acid solution and then extracted into dichloromethane. The organic extract is dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure to obtain a crude residue, which is purified by C-18 silica gel flash chromatography to obtain 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid as an off-white solid. 1 H NMR (400MHz, DMSO-d6)δ=8.10(d,1H),8.09-8.06(m,1H),7.79(d,1H),7.77(d,1H),7.46-7.40(m,2H),5.83(s,1H),3.88-3.81(m,2H),1.18(t,3H)

[0366] Example 5: Synthesis of 2-(3,4-dichlorophenyl)-6-(3,4-difluorophenoxy)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 28)

[0367] Step 1: Synthesis of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid

[0368]

[0369] A mixture of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid ethyl ester (0.200g, 0.53mmol) and tris(trifluoromethylsulfonyloxy) scandium (0.276g, 0.56mmol) in water (2mL) and tetrahydrofuran (2mL) was heated at 120°C for 0.5 hours 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. 1H NMR (400 MHz, 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)

[0370] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-6-(3,4-difluorophenoxy)-1-ethyl-4-oxo-pyridine-3-carboxylic acid

[0371]

[0372] A mixture of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (0.100 g, 0.29 mmol), 3,4-difluorophenol (0.075 g, 0.58 mmol) and tripotassium phosphate (0.142 g, 0.63 mmol) in acetonitrile (2.4 mL) was heated at 90 ° C under microwave irradiation, suspended in MeCN in a 2-5 mL MW vial, and then heated at 90 ° C for 1 hour. More acetonitrile (1 mL) was added, and the reaction mixture was heated again at 120 ° C for 1 hour under microwave irradiation. The cooled reaction mixture was diluted with water, acidified to pH 1 and extracted into ethyl acetate by adding aqueous hydrogen chloride solution (2 M). 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 flash chromatography to give 2-(3,4-dichlorophenyl)-6-(3,4-difluorophenoxy)-1-ethyl-4-oxo-pyridine-3-carboxylic acid. 1 H NMR (400 MHz, chloroform) δ=7.62 (d, 1H), 7.42 (s, 1H), 7.34 (m, 1H), 7.17 (m, 1H), 7.14-7.06 (m, 1H), 7.00 (m, 1H), 5.91 (s, 1H), 3.96 (q, 2H), 1.29 (t, 3H)

[0373] Table 2: Selected compounds of the present invention 1 H NMR data.

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402]

[0403]

[0404]

[0405]

[0406]

[0407]

[0408]

[0409]

[0410] Biological Examples

[0411] Seeds of various test species were sown in standard soil in pots (Setaria faberi (SETFA), Ipomoea hederacea (IPOHE), Echinochloa crus-galli (ECHCG), Amaranthus retoflexus (AMARE), Zea mays (ZEAMX) and Amaranthus palmeri (AMAPA)). After 8 days of cultivation in a greenhouse under controlled conditions (at 24°C / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from a formulation of technical grade active ingredients in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). The application rates are shown in the table below in g / ha. These test plants were then grown in a greenhouse under controlled conditions in the greenhouse (at 24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the percentage of damage caused to the plants by the test was evaluated. The biological activity is shown in the table below on a five-point scale (5 = 81%-100%; 4 = 61%-80%; 3 = 41%-60%; 2 = 21%-40%; 1 = 0%-20%; - = not tested).

[0412] Table B1: Pre-emergence test

[0413]

[0414]

[0415]

[0416] Table B2: Post-emergence testing

[0417]

[0418]

[0419]

Claims

1. A compound having formula (I) or a salt or N-oxide thereof: X is O, S(O)n, or NR 11 ; n is 0, 1, or 2; R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC1-C6 alkyl, or C3-C6 cycloalkyl; R 2 is phenyl or heteroaryl, 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 be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and are represented by R 7 The group represented by is substituted; R 3 is hydrogen or C1-C6 alkyl; R 4 is hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl; R 5 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally replaced by 1, 2, 3 or 4 R which may be the same or different 9 or R 5 and R 11 Together with the nitrogen atom to which they are attached, they may form a 5-membered heterocyclyl ring, wherein the heterocyclyl moiety further comprises an additional oxygen atom, and wherein the heteroaryl moiety may be optionally substituted by 1 or 2 residues which may be the same or different and are represented by R 10 The group represented by is substituted; R 7 is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl; R 9 is cyano, nitro, hydroxy, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, N,N-di(C1-C4 alkyl)aminocarbonyl, or benzyloxy; or Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a C3-C6 cycloalkyl ring or a phenyl ring, wherein the C3-C6 cycloalkyl and phenyl moieties may be optionally replaced by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 10 or Any two adjacent R 9 The groups together with the carbon atoms to which they are attached may form a 5- or 6-membered heteroaryl ring, 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 the heteroaryl moiety may be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 10 or Any two adjacent R 9 The groups together with the carbon atom to which they are attached may form a 5- or 6-membered heterocyclyl ring, wherein the heterocyclyl moiety is a 5- or 6-membered ring containing 1 or 2 heteroatoms selected from O and N, and wherein the heterocyclyl ring may be optionally substituted by 1, 2, 3 or 4 residues which may be the same or different and which are represented by R 10 The group represented by is substituted; R 10 is halogen, oxo, C1-C3 alkyl, or C1-C3 alkoxy; R 11 It is hydrogen or C1-C6 alkyl.

2. The compound according to claim 1, wherein R 1 It is C1-C4 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 alkyl, or C3-C4 cycloalkyl.

3. The compound according to claim 1 or claim 2, wherein R 2 is optionally replaced by 1 or 2 which may be the same or different from R 7 The group represents a phenyl group substituted with.

4. The compound according to any one of claims 1 to 3, wherein R 4 It's hydrogen.

5. The compound according to any one of claims 1 to 4, wherein R 5 is C1-C5 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C5-C6 cycloalkyl, C5-C6 cycloalkenyl, phenyl or heteroaryl, wherein the heteroaryl moiety is a 5-membered or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally substituted by 1, 2 or 3 residues which may be the same or different and are represented by R 9 The group represented is substituted.

6. The compound according to any one of claims 1 to 5, wherein R 5 is C1-C3 alkyl or phenyl, wherein the phenyl group is replaced by 1 or 2 groups which may be the same or different and are represented by R 9 The group represented is substituted.

7. The compound according to any one of claims 1 to 6, wherein R 7 is cyano or halogen.

8. The compound according to any one of claims 1 to 7, wherein R 9 It is halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, cyclopropyl, or C1-C2 alkylsulfonyl.

9. The compound according to any one of claims 1 to 7, wherein R 11 It is hydrogen or C1-C3 alkyl.

10. The compound according to any one of claims 1 to 9, wherein R 2 It 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, 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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