Herbicidal derivative

Abstract

The substituent is as defined in claim 1, formula (I) A compound of JPEG2025523360000096.jpg43162. The present invention further relates to a herbicidal composition comprising a compound of formula (I), and to the use of a compound of formula (I) for controlling weeds in a crop of particularly useful plants.

Description

Technical Field

[0001] The present invention relates to herbicidal pyridone derivatives, for example, as active ingredients having herbicidal activity. The present invention also relates to pesticidal compositions containing at least one pyridone derivative, processes for preparing these compounds, and the use of pyridone derivatives or compositions in the control of weeds in agricultural or horticultural crops of particularly useful plants.

Background Art

[0002] European Patent No. 0239391, European Patent No. 0127313, European Patent No. 0040082, and British Patent No. 2182931 describe pyridone derivatives as herbicides.

Summary of the Invention

Means for Solving the Problems

[0003] According to the present invention, a compound of formula (I):

Chemical Formula

[0004] Surprisingly, the novel compounds of formula (I) have been found to have a very advantageous level of herbicidal activity for practical purposes.

[0005] 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.

[0006] According to a third aspect of the present invention, there is provided a method for controlling weeds in a habitat, the method comprising applying to the habitat a composition comprising a weed controlling amount of a compound of formula (I).

[0007] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) as a herbicide.

Mode for Carrying Out the Invention

[0008] When a substituent is described as "optionally substituted", this means that it may or may not have one or more identical or different substituents, for example, one, two or three Rs 7 and may or may not have substituents. For example, C1-C6 alkyl substituted by one, two or three halogens is not particularly limited, and examples thereof include -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, C1-C6 alkoxy substituted by one, two or three halogens is not particularly limited to these, and examples thereof include CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.

[0009] As used herein, the term "cyano" means a -CN group.

[0010] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).

[0011] As used herein, the term "hydroxy" or "hydroxyl" means a -OH group.

[0012] As used herein, the term "nitro" means a -NO2 group.

[0013] As used herein, the term "acetyl" means a -C(O)CH3 group.

[0014] As used herein, =O means an oxo group as found, for example, in a carbonyl (-C(=O)-) group.

[0015] As used herein, the term "C1-C6 alkyl" refers to a straight or branched chain hydrocarbon group consisting of only carbon and hydrogen atoms, containing no unsaturation, having 1 to 6 carbon atoms, and being bonded to the remainder of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" should be interpreted in the same manner. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and its isomers, such as isopropyl. The term "C1-C6 alkylene" refers to the corresponding definition of C1-C6 alkyl, except that such a group is bonded to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" should be interpreted in the same manner. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2- and -(CH2)3-.

[0016] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group, generally as defined above, substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted similarly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0017] As used herein, the term "C1-C6 alkoxy" refers to R a is generally a C1-C6 alkyl group as defined above; a The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted similarly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0018] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group generally defined above, substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted similarly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0019] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least two double bonds which may be in the (E)- or (Z)-configuration, having 2-6 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C2-C3 alkenyl" should be interpreted similarly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), and but-1-enyl.

[0020] As used herein, the term "C2-C6 alkynyl" refers to a straight-chain or branched hydrocarbon chain radical group composed of only carbon and hydrogen atoms, containing at least two triple bonds, having 2 to 6 carbon atoms, and bonded to the remainder of the molecule by a single bond. The term "C2-C3 alkynyl" should be interpreted in the same way. Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, and but-1-ynyl.

[0021] As used herein, the term "C1-C6 alkoxy C1-C6 alkyl" refers to a group of the formula R b OR a - (wherein R b is generally a C1-C6 alkyl group as defined above, and R a is generally a C1-C6 alkylene group as defined above). The terms "C1-C4 alkoxy C1-C4 alkyl" and "C1-C3 alkoxy C1-C3 alkyl" should be interpreted in the same way.

[0022] As used herein, the term "C3-C6 cycloalkyl" refers to a monocyclic saturated ring system and refers to a group containing 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted in the same way. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0023] As used herein, the term "C3-C6 cycloalkenyl" refers to a monocyclic partially saturated ring system and refers to a group containing 3 to 6 carbon atoms, i.e., the ring contains one or two double bonds. The terms "C3-C5 cycloalkenyl" and "C3-C4 cycloalkenyl" should be interpreted in the same way. Examples of C3-C6 cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0024] As used herein, the term "C3-C6 cycloalkylaminocarbonyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule via an -NHC(O)- linker. Examples of C3-C6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).

[0025] As used herein, the term "phenyl C1-C2 alkyl" refers to a phenyl ring attached to the remainder 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.

[0026] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing one, two, or three heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl.

[0027] As used herein, the term "heteroaryl C1-C2 alkyl" refers to a heteroaryl ring generally as defined above attached to the remainder of the molecule via a C1-C2 alkylene linker as defined above.

[0028] As used herein, the term "C1-C6 alkylcarbonyl" refers to a group of the formula -C(O)R a (wherein R a is a C1-C6 alkyl group generally as defined above). Examples of C1-C6 alkylcarbonyl include, but are not limited to, acetyl.

[0029] As used herein, the term "C1-C6 alkoxycarbonyl" refers to a group of the formula -C(O)OR a wherein R a is generally a C1-C6 alkyl group as defined above).

[0030] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to a group of the formula -C(O)NHR a wherein R a is generally a C1-C6 alkyl group as defined above). Examples of C1-C6 alkylaminocarbonyl include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl).

[0031] As used herein, the term "N,N-di(C1-C4 alkyl)amino" refers to a group of the formula -N(R a )(R b ) wherein R a and R b are each independently generally a C1-C4 alkyl group as defined above). The term "N,N-di(C1-C3 alkyl)amino" should be interpreted in the same manner.

[0032] As used herein, the term "N,N-di(C1-C4 alkyl)aminocarbonyl" refers to a group of the formula -C(O)N(R a )(R b ) wherein R a and R b are each independently generally a C1-C4 alkyl group as defined above). The term "N,N-di(C1-C3 alkyl)aminocarbonyl" should be interpreted in the same manner. Examples of N,N-di(C1-C4 alkyl)aminocarbonyl include, but are not limited to, dimethylcarbamoyl (i.e., N,N-di(methyl)aminocarbonyl).

[0033] As used herein, the term "C1-C6 alkylsulfanyl" refers to R aThe group of formula -SR, wherein R is generally a C1-C6 alkyl group as defined above a is meant. The terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be interpreted in the same way. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0034] As used herein, the term "C1-C6 alkylsulfinyl" refers to a group of formula -S(O)R a wherein R is generally a C1-C6 alkyl group as defined above. The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" should be interpreted in the same way. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl. a

[0035] As used herein, the term "C1-C6 alkylsulfonyl" refers to a group of formula -S(O)2R a wherein R is generally a C1-C6 alkyl group as defined above. The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted in the same way. Examples of C1-C6 alkylsulfonyl include, but are not limited to, methylsulfonyl. a

[0036] As used herein, the term "C1-C6 alkylsulfonamide" refers to a group of formula -NHS(O)2R a wherein R a is generally a C1-C6 alkyl group as defined above.

[0037] The presence of one or more possible stereogenic elements in a compound of formula (I) means that the compound can exist in optical isomeric forms, i.e., enantiomeric or diastereoisomeric forms. Also, atropisomers can arise due to restrictions on rotation about a single bond. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof of the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of the compounds of formula (I).

[0038] In each case, the compounds of formula (I) according to the present invention are in free form or in salt form, for example in an agriculturally usable salt form. Compounds of formula (I) preferably form salts with amines containing primary, secondary and tertiary amines (such as ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases. In a particularly preferred set of embodiments, the compounds of formula (I) can form chlorides or 2,2,2-trifluoroacetates.

[0039] The following list provides definitions (including preferred definitions) for substituents X, n, R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 9 、R 10 and R 11 in relation to the compounds of formula (I). For any one of these substituents, any of the definitions described below can be combined with any of the definitions of any of the other substituents described elsewhere in this document or below.

[0040] X is O, S(O)n or NR 11 . Preferably, X is O or NR 11 . In one set of embodiments, X is O, and in another set of embodiments, X is NR 11It is. In a set of embodiments, X is O, S, or NH.

[0041] n is 0, 1, or 2. Preferably, n is 0.

[0042] R 1 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC1-C6 alkyl, or C3-C6 cycloalkyl. Preferably, R 1 is C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxyC1-C4 alkyl, or C3-C6 cycloalkyl. More preferably, R 1 is C1-C4 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyC1-C3 alkyl, or C3-C4 cycloalkyl.

[0043] In a set of embodiments, R 1 is methyl, ethyl, n-propyl, allyl, prop-2-ynyl, methoxy, methoxyethyl, or cyclopropyl. In other sets of embodiments, R 1 is C1-C4 alkyl, preferably C1-C3 alkyl, and more preferably ethyl.

[0044] R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and where each phenyl and heteroaryl moiety is optionally substituted with 1, 2, 3, or 4 groups which may be the same or different as represented by R 7 . Preferably, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and where each phenyl and heteroaryl moiety is optionally substituted with 1, 2, 3, or 4 groups which may be the same or different as represented by R 7It may be optionally substituted with one, two or three groups which may be the same or different and are represented by

[0045] More preferably, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and where each phenyl and heteroaryl moiety may be optionally substituted with one, two or three groups which may be the same or different and are represented by R 7 It may be optionally substituted with one, two or three groups which may be the same or different and are represented by

[0046] Even more preferably, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and where each phenyl and heteroaryl moiety may be optionally substituted with one or two groups which may be the same or different and are represented by R 7 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0047] Even more preferably, R 2 is phenyl which may be optionally substituted with one or two groups which may be the same or different and are represented by R 7 In one set of embodiments, R 2 is 3-chloro-4-cyanophenyl, 3,4-dichlorophenyl or 3,4-difluorophenyl, preferably 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl. More preferably, R 2 is 3,4-dichlorophenyl.

[0048] 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 is hydrogen.

[0049] R4 is hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl. Preferably, R 4 is hydrogen, halogen, C1-C3 alkyl or C1-C3 haloalkyl. More preferably, R 4 is hydrogen or C1-C3 alkyl. In one set of embodiments, R 4 is hydrogen or methyl. In other sets of embodiments, R 4 is hydrogen.

[0050] In one set of embodiments, R 4 is hydrogen or bromo, preferably hydrogen.

[0051] R 5 is C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and where each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different as represented by R 9 ; or R 5 and R 11 may together with the nitrogen atom to which they are attached form a 5-membered heterocyclyl ring, where the heterocyclyl moiety further contains and additional oxygen atom, and where the heteroaryl moiety may be optionally substituted with 1 or 2 groups which may be the same or different as represented by R 10 .

[0052] Preferably, R 5is C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety is optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by R 9 and may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by R

[0053] More preferably, R 5 is C1-C5 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C5-C6 cycloalkyl, C5-C6 cycloalkenyl, phenyl or heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms individually selected from N and O, and wherein each cycloalkyl, cycloalkenyl, phenyl and heteroaryl moiety is optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by R 9 and may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by R

[0054] Even more preferably, R 5 is C1-C4 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, cyclohexyl, cyclohexenyl, phenyl or pyridyl, and wherein each cyclohexyl, cyclohexenyl, phenyl and pyridyl moiety is optionally substituted with 1 or 2 groups which may be the same or different and are represented by R 9 and may be optionally substituted with 1 or 2 groups which may be the same or different and are represented by R

[0055] In one set of embodiments, R 5 is C1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, phenyl or heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety is optionally substituted with R 9Optionally substituted with one or two groups, which may be the same or different, represented by

[0056] In other sets of embodiments, R 5 is methyl, C5 alkenyl, phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing one, two or three heteroatoms individually selected from N, O and S, and where each phenyl and heteroaryl moiety may optionally be substituted with one or two groups, which may be the same or different, represented by R 9 Optionally substituted with one or two groups, which may be the same or different, represented by

[0057] In a further set of embodiments, R 5 is methyl, C5 alkenyl, phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridyl or pyridazinyl, where each phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridyl and pyridazinyl moiety may optionally be substituted with one or two groups, which may be the same or different, represented by R 9 Optionally substituted with one or two groups, which may be the same or different, represented by

[0058] In a further set of embodiments, R 5 is C1-C3 alkyl or phenyl, where the phenyl group is substituted with one or two groups, which may be the same or different, represented by R 9 Preferably, R 5 is C1-C3 alkyl or phenyl, where the phenyl group is substituted with a single R 9 group. Preferably, R 5 is methyl or phenyl, where the phenyl group is substituted with a single R 9 group.

[0059] In a particularly preferred set of embodiments, R 5is methyl, 2-methyl-but-2-enoxy, 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.

[0060] 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 alkylsulfonamide, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl or N,N-di(C1-C4 alkyl)aminocarbonyl.

[0061] Preferably, R 7 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 alkylsulfonamide, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0062] 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 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonamide, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0063] Even 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.

[0064] In one set of embodiments, R7 is cyano, nitro or halogen, preferably cyano or halogen, more preferably halogen, and even more preferably R 7 is chloro or fluoro. In one set of embodiments, R 7 is cyano or chloro.

[0065] 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 alkylsulfonamide, 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 groups, together with the carbon atom to which they are attached, may form a C3-C6 cycloalkyl ring or a phenyl ring, where the C3-C6 cycloalkyl and phenyl moieties are optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by R 10 ; or any two adjacent R 9 groups, together with the carbon atom to which they are attached, may form a 5- or 6-membered heteroaryl ring, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and where the heteroaryl moiety is optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by R 10 ; or any two adjacent R 9The base, together with the carbon atom to which they are attached, may form a 5- or 6-membered heterocyclyl ring, wherein the heterocyclyl moiety is 5- or 6-membered and contains one or two heteroatoms selected from O and N, and wherein the heterocyclyl ring is optionally substituted with one, two, three or four groups which may be the same or different and are represented by R 10 and may be optionally substituted with one, two, three or four groups which may be the same or different and are represented by R

[0066] 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 alkylsulfonamide, 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 any two adjacent R 9 groups, together with the carbon atom 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 substituted with one, two or three groups which may be the same or different and are represented by R 10 ; or any two adjacent R 9 groups, together with the carbon atom 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 one, two or three heteroatoms individually selected from N, O and S, and wherein the heteroaryl moiety may be optionally substituted with one, two or three groups which may be the same or different and are represented by R 10 ; or any two adjacent R 9The base, together with the carbon atom to which they are attached, may form a 5- or 6-membered heterocyclyl ring, where the heterocyclyl moiety is 5- or 6-membered and contains one or two heteroatoms selected from O and N, and where the heterocyclyl ring is optionally substituted with one, two or three groups, which may be the same or different, represented by R 10 and is optionally substituted with one, two or three groups, which may be the same or different, represented by R

[0067] More preferably, R 9 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 alkylsulfonamide, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C4 cycloalkyl, C3-C4 cycloalkylaminocarbonyl, N,N-di(C1-C3 alkyl)aminocarbonyl or benzyloxy.

[0068] Even more preferably, R 9 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 alkylsulfonamide, C1-C2 alkylcarbonyl, C1-C2 alkoxycarbonyl, C1-C2 alkylaminocarbonyl, C3-C4 cycloalkyl, C3-C4 cycloalkylaminocarbonyl, N,N-di(C1-C2 alkyl)aminocarbonyl or benzyloxy.

[0069] In one set of embodiments, R 9is 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 is halogen, C1-C2 alkyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy, cyclopropyl or methylsulfonyl.

[0070] In one set of embodiments, R 9 is halogen or C1-C3 alkoxy, preferably methoxy, fluoro or chloro, and more preferably, R 9 is fluoro or chloro.

[0071] R 10 is halogen, oxo, C1-C3 alkyl or C1-C3 alkoxy. Preferably, R 10 is halogen, C1-C3 alkyl or C1-C3 alkoxy. Preferably, R 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 set of embodiments, R 10 is oxo, methyl, fluoro or methoxy.

[0072] 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 set of embodiments, R 11 is hydrogen or methyl. In other sets of embodiments, R 11 is hydrogen.

[0073] In the compound of formula (I) according to the present invention, preferably: X is O or NR 11 ; R 1 is C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyC1-C3 alkyl or C3-C6 cycloalkyl; R 2 is phenyl which may be optionally substituted with two groups which may be the same or different represented by R 7 ; R 3 is hydrogen; R 4 is hydrogen or C1-C6 alkyl; R 5 is C1-C3 alkyl, C2-C3 alkenyl, C3-C6 cycloalkenyl or phenyl, wherein each cycloalkenyl and phenyl moiety may be optionally substituted with a single R 9 group; R 7 is cyano or halogen; R 9 is cyano, halogen, C1-C3 alkoxy or methylsulfonyl; and R 11 is hydrogen or C1-C6 alkyl.

[0074] In other sets of embodiments, X is O or NH; R 1 is C1-C3 alkyl; R 2 is phenyl which may be optionally substituted with two groups which may be the same or different represented by R 7 ; R 3 is hydrogen; R 4 is hydrogen; R 5 is C1-C3 alkyl or phenyl, wherein each phenyl moiety may be optionally substituted with a single R 9 group; R 7 is a halogen; and R 9 is a halogen.

[0075] In a further set of embodiments, X is O, S or NH; R 1 is ethyl; R 2 is 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl; R 3 is hydrogen; R 4 is hydrogen; R 5 is methyl, C5 alkenyl, phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridyl or pyridazinyl, where each phenyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyridyl and pyridazinyl moiety is optionally substituted with one or two groups which may be the same or different and which are represented by R 9 .

[0076] In a further set of embodiments, X is O, S or NH; R 1 is ethyl; R 2 is 3,4-dichlorophenyl or 3-chloro-4-cyanophenyl; R 3 is hydrogen; R 4 is hydrogen; and R 5is methyl, 2-methyl-but-2-enoxy, 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 R 9 is halogen, C1-C2 alkyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy, cyclopropyl or methylsulfonyl.

[0077] The compounds of the present invention can be prepared by techniques known to those skilled in organic chemistry. General methods for producing the compounds of formula (I) are described below. Unless otherwise specified in the text, R 1 R 2 R 4 R 5And X is as already defined herein. The starting materials used in the preparation of the compounds of the present invention can be purchased from normal commercial suppliers or can be prepared by known methods. The starting materials as well as the intermediates may be purified by state-of-the-art techniques such as chromatography, crystallization, distillation and filtration before being used in the next step.

[0078] The compounds of formula (I) of the present invention can be prepared from the compounds of formula (A) as shown below in Scheme 1. Scheme 1:

Chemical formula

[0079] The compounds of formula (I) can be prepared by hydrolysis of the compounds of formula (A) (wherein R 3 is C1-C6 alkyl) in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) containing any co-solvent (such as water) with a suitable base (such as sodium hydroxide or lithium hydroxide) or a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid). When a base is used, the product is obtained by subsequent acidification with a suitable acid (such as hydrochloric acid). The compounds of formula (A) can, in addition, be prepared by the methods described below. Scheme 2:

Chemical formula

[0080] The compounds of formula (B) (wherein Y is Br, Cl or I, and X is O, S(O)n or NR 11 is) can be converted to the compounds of formula (A) by reduction with hydrogen gas in a suitable organic solvent (such as methanol, ethanol or ethyl acetate), optionally in the presence of an organic acid (such as acetic acid), in the presence of a suitable catalyst (such as palladium on carbon or platinum). This is shown above in Scheme 2.

[0081] Alternatively, the compound of formula (B) (wherein Y is Br and X is O, S(O)n or NR 11 is) can be converted to the compound of formula (A) under transfer hydrogenation conditions using a suitable hydrogen source (such as ammonium formate) at a high temperature in an organic solvent (such as acetonitrile) in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(II)).

[0082] Scheme 3:

Chemical Structure

[0083] Scheme 4:

Chemical Structure

[0084] Scheme 5:

Chemical Structure

[0085] In an alternative conversion, a compound of formula (B) (wherein Z is Br or hydrogen, R 5 is not hydrogen but any of the other R 5 groups as defined above, and X is O, S or NH) can be obtained by reaction of a compound of formula (C) (wherein Z is Br or H, and X is I) with a nucleophile (such as aniline or thiophenol) in a suitable organic solvent (such as 1,4-dioxane or toluene) at a high temperature, in the presence of a suitable catalyst ([2-(2-aminophenyl)phenyl]-chloro-palladium; (5-diphenylphosphanyl-9,9-dimethyl-xanthen-4-yl)-diphenyl-phosphane, etc.) or palladium diacetate, optionally with a ligand (such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) and in the presence of a base (such as cesium carbonate).

[0086] Scheme 6:

Chemical formula

[0087] Other decarboxylation-halogenation conditions from the literature can also be used.

[0088] Scheme 7:

Chem.

[0089] Scheme 8:

Chem.

[0090] Scheme 9:

Chem.

[0091] Scheme 10:

Chemical formula

[0092] Scheme 11:

Chemical formula

[0093] Scheme 12:

Chemical formula

[0094] Scheme 13:

Chem.

[0095] Alternatively, the compound of formula (A) of the present invention can be prepared from the compound of formula (I) as shown below in Schemes 1a to 7a. Scheme 1a:

Chem.

[0096] The compound of formula (I) is a compound of formula (A) (wherein R 3It can be prepared by hydrolysis of (wherein R is C1-C6 alkyl). When a base is used, the product is obtained by subsequent acidification with a suitable acid (such as hydrochloric acid). The compound of formula (A) can additionally be prepared by the methods described below. Scheme 2a:

Chemical formula

[0097] The compound of formula (C) (wherein X is Cl (or F or Br or I)) can be converted to the compound of formula (I) (wherein X is O, S or NH, and R 5 is not hydrogen and is any of the other R groups defined above 5 by the addition of a nucleophile (such as phenol or aniline) under conditions similar to those in the literature. Typically, this reaction is carried out by reacting the compound of formula (C) with the nucleophile R5 in an organic solvent (such as acetonitrile) at a high temperature in the presence of a suitable base (such as cesium carbonate or potassium phosphate). The nucleophile can be commercially available or can be prepared by methods known to those skilled in the art. The compound of formula (C) can additionally be prepared by the methods described below.

[0098] Scheme 3a:

Chemical formula

[0099] Scheme 4a:

Chemical formula

[0100] Scheme 5a:

Chemical formula

[0101] Scheme 6a:

Chemical formula

[0102] Scheme 7a:

Chemical formula

[0103] The present invention further provides a method for controlling weeds in a habitat, said method comprising applying to the habitat a composition comprising a compound of formula (I) in an amount effective for weed control. Moreover, the present invention may further provide a method for selectively controlling weeds in a habitat containing useful (crop) plants and weeds, wherein the method comprises applying to the habitat a composition according to the present invention in an amount effective for weed control. "Control" means extermination, reduction or inhibition of growth, or prevention or reduction of germination. It is noted that the compounds of the present invention exhibit considerably improved selectivity as compared to known structurally similar compounds. Generally, the plants to be controlled are unwanted plants (weeds). "Habitat" means an area where plants are growing or will grow. Application can be made to the habitat before and / or after germination of the crop plants. Some crop plants may be inherently resistant to the herbicidal effect of the compounds of formula (I).

[0104] 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- or post-emergence; seed dressing; application to furrows; without tillage application, etc.), the crop plants, the weeds to be controlled, the prevailing weather conditions, and other factors depending on the method of application, the time of application and the target crop. The compounds of formula I according to the present invention are generally applied in amounts of from 10 to 2500 g / ha, in particular from 25 to 1000 g / ha, especially from 25 to 250 g / ha.

[0105] Application is generally carried out by spraying the composition, typically with a large-area sprayer mounted on a tractor, but other methods such as dusting (in the case of powders), dripping or irrigation can also be used.

[0106] The term "useful plants" should also be understood to include useful plants that have been rendered tolerant to herbicides such as bromoxynil, or to certain 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, by conventional breeding or genetic engineering methods. An example of a crop rendered tolerant to imidazolinones such as imazamox by conventional breeding methods (mutation induction) is Clearfield® summer rape (canola). Examples of crops rendered tolerant to herbicides or certain classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant maize varieties marketed under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0107] The term "useful plants" should also be understood to include useful plants transformed using recombinant DNA technology so as to be capable of synthesizing one or more selectively acting toxins, known, for example, from toxin-producing bacteria, in particular those of the genus Bacillus.

[0108] Examples of such plants are YieldGard® (maize varieties expressing the CryIA(b) toxin); YieldGard Rootworm® (maize varieties expressing the CryIIIB(b1) toxin); YieldGard Plus® (maize varieties expressing the CryIA(b) and CryIIIB(b1) toxins); Starlink® (maize varieties expressing the Cry9(c) toxin); Herculex I® (maize varieties expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton varieties expressing the CryIA(c) toxin); Bollgard I® (cotton varieties expressing the CryIA(c) toxin); Bollgard II® (cotton varieties expressing the CryIA(c) and CryIIA(b) toxins); VIPCOT® (cotton varieties expressing the VIP toxin); NewLeaf® (potato varieties expressing the CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.

[0109] Both the plant crop and its seed material can be tolerant to herbicides and at the same time tolerant to insect feeding (“stacked” transgenic events). For example, the seeds can have the ability to express the insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

[0110] Crop plants can also be obtained by conventional methods involving crossing or genetic manipulation and should be understood to include those containing so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0111] The compound of formula (I) (or a composition containing the same) can be used for controlling unwanted plants (collectively referred to as "weeds"). The weeds to be controlled can be, for example, monocotyledonous species such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and also, for example, dicotyledonous species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0112] The compound of formula (I) can be used in its unmodified form or, preferably, in combination with adjuvants conventionally employed in the art of formulation to provide a herbicidal composition, using formulation adjuvants such as carriers, solvents and surface active agents (SAA). The present invention thus further provides a herbicidal composition comprising at least one compound of formula (I), an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art.

[0113] The herbicidal composition generally comprises 0.1 to 99% by weight, particularly 0.1 to 95% by weight, of the compound of formula (I) and 1 to 99.9% by weight of a formulation adjuvant preferably containing 0 to 25% by weight of a surfactant.

[0114] The composition can be selected from a number of formulation types. These include emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water-dispersible granule (WG), emulsifiable granule (EG), oil-in-water emulsion (EO), water-in-oil emulsion (EW), micro-emulsion (ME), oil dispersion (OD), miscible flowable (OF), miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical concentrate (TK), dispersible concentrate (DC), soluble powder (SP), wettable powder (WP), and soluble granule (SG). The formulation type selected in any case will depend on the specific intended purpose and on the physical, chemical, and biological properties of the compound of formula (I).

[0115] The soluble powder (SP) can be prepared by mixing the 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 dispersing agents, or a mixture of said agents, to improve the dispersibility / solubility in water. The mixture is then ground to a fine powder. A similar composition can also be granulated to form water-soluble granules (SG).

[0116] The wettable powder (WP) can be prepared by mixing the compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersing agents, and optionally one or more suspending agents, to promote dispersibility in liquids. The mixture is then ground to a fine powder. A similar composition may be granulated to form water-dispersible granules (WG).

[0117] The granules (GR) can be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable pharmaceutical) into a porous granular material (such as pumice, attapulgite clay, fuller's earth, kieselguhr, diatomaceous earth or ground corn cob), or by absorbing a compound of formula (I) (or a solution thereof in a suitable pharmaceutical) into a hard core material (such as sand, silicic acid, carbonate minerals, sulfates or phosphates), and, if necessary, drying to form from preformed compressed powder granules. Agents commonly used to assist absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and fixing agents (such as polyvinyl acetate, polyvinyl alcohol, dextrin, carbohydrates and vegetable oils). One or more other additives may also be included in the granules (such as emulsifiers, wetting agents or dispersing agents).

[0118] The dispersible concentrate (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 (such as to improve dilution with water or to prevent crystallization in the spray tank).

[0119] The emulsifiable concentrate (EC) or oil-in-water emulsion (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally having one or more wetting agents, one or more emulsifiers or a mixture of said agents). Organic solvents suitably used in EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200 (SOLVESSO is a registered trademark)), ketones (such as cyclohexanone or methylcyclohexanone), and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (C8-C 10Examples include fatty acid dimethylamides, and chlorinated hydrocarbons. When added to water, the EC product can spontaneously emulsify to yield an emulsion with sufficient stability to enable spraying applications with suitable equipment.

[0120] In the preparation of EW, the compound of formula (I) is obtained as a liquid (which may be melted at a suitable temperature, typically below 70 °C if not liquid at room temperature) or in solution (by dissolving in a suitable solvent), and then the resulting liquid or solution is emulsified under high shear into water containing one or more SAAs to yield an emulsion. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0121] Microemulsions (ME) can be prepared by mixing a blend of one or more solvents and one or more SAAs with water to spontaneously yield a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in either water or the solvent / SAA blend. Suitable solvents for use in ME include those described above for use in EC or EW. ME can be either oil-in-water or water-in-oil type systems (which can be determined by measuring the conductivity), and are suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. ME can remain as microemulsions or form conventional oil-in-water emulsions and be suitably diluted in water.

[0122] The suspension concentrate (SC) may contain an aqueous or non-aqueous suspension of fine insoluble solid particles of the compound of formula (I). The SC can be prepared by subjecting the solid compound of formula (I) in a suitable medium, optionally together with one or more dispersants, to a ball mill or bead mill to provide 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 sedimentation rate of the particles. Alternatively, the compound of formula (I) may be subjected to a dry mill and added to water containing the agents described above in the specification to provide the desired final product.

[0123] The aerosol formulation contains the 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 hydratable liquid such as n-propanol) to provide a composition for use in a non-pressurized manual spray pump.

[0124] The capsule suspension (CS) can be prepared in the same manner as the preparation of the EW formulation, but with each of the oil droplets encapsulated in a polymeric shell, and an additional polymerization stage such that an aqueous dispersion of oil droplets containing the compound of formula (I) and optionally a carrier or diluent therefor is obtained. The polymeric shell can be produced by either an interfacial polycondensation reaction or a coacervation technique. The composition can provide a sustained release of the compound of formula (I) and can be used for seed treatment. The compound of formula (I) may also be incorporated into a biodegradable polymer matrix such that the compound has a slow sustained release.

[0125] The composition may contain one or more additives in order to improve the biological performance of the composition, for example, by improving the wettability, retention or distribution on the surface of the compound of formula (I); the resistance to rain on the surface to be treated; or the uptake or mobility. Such additives include surfactants (SAA), for example, oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean oil and rapeseed oil), modified vegetable oils such as methylated rapeseed oil (MRSO), and blends of these with other bio-enhancing adjuvants (formulation components that can assist or modify the action of the compound of formula (I)).

[0126] Wetting agents, dispersants and emulsifiers can be cationic, anionic, amphoteric or nonionic SAA.

[0127] Suitable cationic SAA include quaternary ammonium compounds (such as cetyltrimethylammonium bromide), imidazolines and amine salts.

[0128] Suitable anionic SAA include alkali metal salts of fatty acids, sulfates of aliphatic monoesters (such as sodium lauryl sulfate), salts of sulfonated aromatic compounds (such as sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalenesulfonate, and a mixture of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (such as sodium laureth-3 sulfate), ether carboxylates (such as sodium laureth-3 carboxylate), phosphate esters (such as products from the reaction of one or more aliphatic alcohols with phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly di-esters), such as the reaction of lauryl alcohol with pyrophosphoric acid; and these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphates / sulfates of tristyrylphenol.

[0129] Suitable amphoteric SAAs include betaines, propionates, and glycineates.

[0130] Suitable nonionic SAAs include condensates 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 alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; condensates of said partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (such as fatty acid polyethylene glycol esters); amine oxides (such as lauryldimethylamine oxide); lecithin and its sorbitan and esters, alkyl polyglycosides, and tristyrylphenol.

[0131] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0132] The compounds of the present invention can also be used in mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), acronifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, bentriazone, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac-sodium, bispyrazoxon, bromoxynil, butachlor, butaphenacyl, carfentrazone (including carfentrazone-ethyl), chloransulam (including chloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clathrimfos, clethodim, clodinafop (including clodinafop-propargyl), chromazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, desmedipham, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, diflufenican, diflufenzoppil, dimethachlor, dimethenamid-P, dioxopyrimidon, diquat dibromide, diuron, epirifluorfen, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfuron, fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, flupyradifurone (including flupyradifurone-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), flucraminopyril (including flucraminotefuryl), flufenacet, flufenoxymasyl, flumetsulam, flumioxazin, fluometuron,Fomesafen, fluazifop (including fluazifop-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (including L-glufosinate and both ammonium salts), glyphosate (including its diammonium, isopropylammonium and potassium salts), haloxyfop (including haloxyfop-methyl), haloxydim (including haloxydim-methyl), hexazinone, hydantocidin, ikaridin (including ikaridin-methyl), imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, indoxacarb (including indoxacarb-cyanomethyl), iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium),ioxynil, iptacoprid, isoproturon, isoxaflutole, rankotriole, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metazachlor, methiopyrsulfone, metolachlor, metosulam, metribuzin, metosulfuron, napropamide,nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, fenmedifam, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyraquinate, pyrazosulfotole, pyridate, pyriftalid, pyriflubenzoxim, pyrimisulfan, pyroxasulfone, pyroxasulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimsulfuron, rimsulfuron, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thienacarbazone,Chlorsulfuron, Thiafenox, Tolfenpyrad, Topramezone, Tralkoxydim, Triafamone, Triallate, Triasulfuron, Tribenuron (including tribenuron-methyl), Triclopyr, Trifloxysulfuron (including trifloxysulfuron-sodium), Triflumizoxazin, Trifluralin, Triflusulfuron, Tripyrasulfone, Ethyl 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-carboxylate, 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-ylmethyl carbonate, Ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, Methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one,(2-Fluorophenyl)methyl 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxyphenyl)pyrimidine-4-carboxylate, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxyphenyl)pyrimidine-4-carboxylic acid, and methyl 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-3a,4,5,6-tetrahydro-6-methyl-6aH-cyclopenta[d]isoxazole-6a-carboxylate may be mentioned.

[0133] The mixing partner of the compound of formula (I) may also be in the form of an ester or a salt, for example as described in The Pesticide Manual, Nineteenth Edition, British Crop Protection Council, 2021.

[0134] The mixture can advantageously be used in the abovementioned formulations (in this case, the "active ingredient" relates to each mixture of the compound of formula (I) and the mixing partner).

[0135] 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 benoxacor, cloquintocet (including cloquintocet mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, flurxypyr, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifene and oxabetrinil.

[0136] Mixtures of the compound of formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet mexyl and / or metcamifene are particularly preferred.

[0137] The toxicity alleviant of the compound of formula (I) can also be in the form of an ester or a salt, for example, as described in The Pesticide Manual, 19 th Edition (BCPC), 2021. The reference to cloxacillin methyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in International Publication No. 02 / 34048.

[0138] Preferably, the mixing ratio of the compound of formula (I) to the toxicity alleviant is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0139] The compound of formula (I) is usually used in the form of an agrochemical composition and can be applied to the crop area or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or micronutrient donors, or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, and, if desired, can be accompanied by further carriers, surfactants or application-promoting adjuvants customary in the art of the formulation.

[0140] As used herein, the term "habitat" means a field in which plants are growing, or a field in which seeds of cultivated plants are sown, or a field in which seeds are to be sown in the soil. This includes the soil, seeds and seedlings as well as established vegetation.

[0141] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, petioles, foliage and fruits.

[0142] The term "plant propagation material" is understood to represent the reproductive parts of plants such as seeds which can be used for their propagation and vegetative parts such as cuttings or tubers such as potatoes for example. Examples can be seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Also included are germinated plants and sprouts which are to be transplanted after germination or after emerging from the soil. These sprouts can be protected by complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to represent seeds.

[0143] The pesticidal agents referred to in this specification using common names are known, for example, from "The Pesticide Manual", 19th Ed., British Crop Protection Council 2021.

[0144] The compounds of formula (I) can be used in the unmodified form or, preferably, together with adjuvants conventionally employed in the art of formulations. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules and capsules in, for example, polymeric substances. As well as the type of composition, the method of application such as spraying, atomizing, dusting, scattering, coating or pouring is selected according to the intended purpose and the circumstances at the time. The composition can also contain further adjuvants such as stabilizers, defoamers, viscosity regulators, binders or adhesives and fertilizers, sources of trace elements or other formulations for obtaining special effects.

[0145] Suitable carriers and adjuvants for use in agriculture can be solid or liquid and are substances useful in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0146] The compounds of formula (I) are usually used in the form of compositions and can be applied simultaneously or sequentially with further compounds to the crop area or plants to be treated. These further compounds can be, for example, fertilizers or trace element donors or other preparations which influence plant growth. They can also be selective or non-selective herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations and, if desired, are accompanied by further carriers, surfactants or application-promoting adjuvants customary in the art of formulating.

[0147] The compounds of formula (I) can be the sole active ingredient in the composition and can also be mixed, where appropriate, with one or more additional active ingredients such as pesticides, fungicides, synergists, herbicides or plant growth regulators. In some cases, the additional active ingredients can bring about unexpected synergistic activity.

[0148] As a rule, the formulations comprise 0.01 to 90% by weight of active ingredient, 0 to 20% of agriculturally acceptable surfactants and 10 to 99.99% of solid or liquid inert formulation constituents and auxiliaries, the active ingredient consisting at least of the compounds of formula (I) together with component (B) and (C) and optionally further active ingredients, in particular fungicides or preservatives etc. The concentrated form of the composition generally contains about 2 to 80%, preferably about 5 to 70% by weight of active ingredient. The application form of the formulation can contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of active ingredient. Commercially available products will preferably be formulated as concentrates, but the end user will usually utilize the diluted formulation.

[0149] The following table shows the individual compounds of formula (I) according to the invention:

Chemical formula

[0150]

Table 1-1

Table 1-2

Table 1-3

[0151] Table A-1 provides 70 compounds A-1.001 to A.1.070 of formula (I), where R 3 is hydrogen, and R 1 , R 2 , R 4 , R 5 and R 6 are as defined in Table 1.

[0152] Formulation Example

[0153]

Table 2

[0154] The active ingredient is thoroughly mixed with the adjuvant, and the mixture is thoroughly ground in a suitable mill and diluted with water to obtain a wettable powder that can be used to obtain a suspension of the desired concentration.

[0155]

Table 3

[0156] The active ingredient is thoroughly mixed with the adjuvant, and the mixture is thoroughly ground in a suitable mill to obtain a powder that can be directly used for seed treatment.

[0157] Emulsifiable Concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether 3% (4 - 5 moles of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 moles of ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0158] Emulsions of any required dilution that can be used for plant protection are obtainable from this concentrate by dilution with water.

[0159] [Table 4]

[0160] Ready-to-use powders are obtained by mixing the active ingredient with a carrier and grinding this mixture in a suitable mill. Such powders can also be used for the dry dressing of seeds.

[0161] Extruded granules Active ingredient [compound of formula (I)] 15% Sodium lignosulfonate 2% Carboxymethyl cellulose 1% Kaolin 82%

[0162] The active ingredient is mixed and ground with adjuvants, and this mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0163] Coated granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0164] In a mixer, the finely ground active ingredient is uniformly applied to kaolin moistened with polyethylene glycol. Coated granules that do not generate dust are thereby obtained.

[0165] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethyl cellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% Water 32%

[0166] The finely ground active ingredient is thoroughly mixed with the adjuvants to obtain a suspension concentrate, from which a suspension of any desired dilution can be obtained by dilution with water. Such dilutions can be used to treat and protect living plants and plant propagation materials against infestation by microorganisms by spraying, pouring or dipping.

[0167] Flowable concentrate for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrylphenol + 10 - 20 moles EO 2% 1,2 - Benzisothiazolin - 3 - one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0168] The finely ground active ingredient is thoroughly mixed with the adjuvants to obtain a suspension concentrate, from which a suspension having any desired dilution rate can be obtained by dilution with water. By using such dilutions, it is possible to treat living plants and plant propagation materials by spraying, pouring or dipping and protect them from ectoparasitism by microorganisms.

[0169] Sustained - release capsule suspension A combination of 28 parts of the compound of formula (I) is mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 part of a defoaming agent and 51.6 parts of water until the desired particle size is achieved. To this emulsion, a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 part of a thickening agent and 3 parts of a dispersing agent. This capsule suspension formulation contains 28% active ingredient. The medium capsule diameter is 8 - 15 microns. The resulting formulation is applied as an aqueous suspension to the seeds with a suitable device for this purpose.

Example

[0170] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention as referred to in Table 2 below.

[0171] Throughout this specification, temperatures are indicated in degrees Celsius (°C) and "m.p." means melting point.

[0172] List of Abbreviations Å = angstrom, brd = broad doublet, brs = broad singlet, °C = degrees Celsius, d = doublet, dd = doublet of doublets, DMSO = dimethyl sulfoxide, M = molar amount, m = multiplet, MHz = megahertz, nm = nanometer, q = quartet, s = singlet, t = triplet.

[0173] Example 1: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylic acid (Compound 1) Step 1: Synthesis of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate

Chem.

[0174] Step 2: Synthesis of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

Chemical Structure

[0175] Step 3: Synthesis of 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one

Chemical formula

[0176] Step 4: Synthesis of ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

Chemical formula

[0177] Step 5: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate

Chemical formula

[0178] Step 6: Synthesis of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-2-carboxylic acid

Chemical formula

[0179] Step 7: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylate

Chemical Structure

[0180] Step 8: Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylate

Chemical Structure

[0181] Step 9: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-(2-fluoroanilino)-4-oxo-pyridine-3-carboxylic acid

Chemical formula

[0182] Example 2: Synthesis of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 2) Step 1: Synthesis of methyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate

Chemical formula

[0183] Step 2: Synthesis of methyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

Chemical formula

[0184] Step 3: Synthesis of methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate

Chemical Structure

[0185] Step 4: Synthesis of Ethyl 5 - Bromo - 2 - (3,4 - dichlorophenyl) - 1 - ethyl - 6 - methyl - 4 - oxo - pyridine - 3 - carboxylate

Chemical Structure

[0186] Step 5: Synthesis of methyl 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate

Chemical formula

[0187] Step 6: Synthesis of 3-bromo-6-(3,4-dichlorophenyl)-1-ethyl-5-methoxycarbonyl-4-oxo-pyridine-2-carboxylic acid

Chemical formula

[0188] Step 7: Synthesis of methyl 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylate

Chemical formula

[0189] Step 8: Synthesis of methyl 5-bromo-6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

Chemical formula

[0190] Step 9: Synthesis of methyl 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

Chemical Structure

[0191] Step 10: Synthesis of 6-(3-chlorophenoxy)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid

Chemical Structure

[0192] Example 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methoxy-4-oxo-pyridine-3-carboxylic acid (Compound 5)

Chemical formula

[0193] Example 4: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid (Compound 52) Step 1: Synthesis of ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo-butanoate

Chemical Structure

[0194] Step 2: Synthesis of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate

Chemical formula

[0195] Step 3: Synthesis of Ethyl 6-Chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate [Chemical formula] To a suspension of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (0.500 g, 1.41 mmol) in a mixture of acetonitrile (12 mL) and aqueous hydrogen chloride solution (2 M, 1.8 mL) was added copper(I) chloride (0.167 g, 1.69 mmol). The resulting reaction mixture was heated to 75 °C, and then a solution of sodium nitrite (0.126 g, 1.83 mmol) in water (1 mL) was added dropwise. The reaction mixture was heated at 75 °C for 0.25 h with stirring. The cooled reaction mixture was poured into a saturated aqueous solution of ammonium chloride (30 mL) and extracted with 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 flash chromatography on C-18 silica gel to give ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate 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)

[0196] Step 4: Synthesis of Ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylate [Chemical formula] A stirred suspension of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (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 h. The cooled reaction mixture was extracted with ethyl acetate. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated under dryness to give crude ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylate.

[0197] Step 5: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid [Chemical formula] To a solution of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylate (0.300 g, 0.665 mmol) in a mixture of tetrahydrofuran (10 mL) and water (3 mL) was added lithium;hydroxide;hydrate (0.084 g, 2.0 mmol) at room temperature. The resulting solution was stirred at room temperature for 48 h. The reaction mixture was diluted with water, acidified to pH 5 by the addition of 2 M aqueous hydrochloric acid and then extracted with dichloromethane. The organic extract was dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure to give a crude residue which was purified by flash chromatography on C-18 silica gel to give 2-(3,4-dichlorophenyl)-1-ethyl-6-[(6-fluoro-3-pyridyl)oxy]-4-oxo-pyridine-3-carboxylic acid as an off-white solid. 11H NMR (400 MHz, 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)

[0198] Example 5: Synthesis of 2-(3,4-dichlorophenyl)-6-(3,4-difluorophenoxy)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 28) Step 1: Synthesis of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid

Chemical Structure

[0199] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-6-(3,4-difluorophenoxy)-1-ethyl-4-oxo-pyridine-3-carboxylic acid

Chemical Structure

[0200]

Table 5-1

Table 5-2

Table 5-3

Table 5-4

Table 5-5

Table 5-6

Table 5-7

Table 5-8

Table 5-9

Table 5-10

Table 5-11

Table 5-12

Table 5-13

Table 5-14

Table 5-15

Table 5-16

Table 5-17

Table 5-18

Table 5-19

Table 5-20

Table 5-21

Table 5-22

Table 5-23

Table 5-24

Table 5-25

Table 5-26

Table 5-27

Table 5-28

Table 5-29

Table 5-30

Table 5-31

Table 5-32

Table 5-33

Table 5-34

[0201] Biological Examples Seeds of various test species are 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 cultivation in a greenhouse (24°C / 16°C, day / night; 14 hours of light; 65% humidity) for 8 days under controlled conditions, an aqueous spray solution derived from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) is sprayed onto the plants. The application rates are shown in g / ha in the following table. The test plants are then greenhouse-cultivated in a greenhouse (24°C / 16°C, day / night; 14 hours of light; 65% humidity) under controlled conditions and watered twice a day. After 13 days, the test is evaluated for the percentage of damage inflicted on the plants. The biological activity is shown in the following table on a five-point scale (5 = 81 - 100%; 4 = 61 - 80%; 3 = 41 - 60%; 2 = 21 - 40%; 1 = 0 - 20%; - = not tested).

[0202]

Table 6-1

Table 6-2

[0203]

Table 7-1

Table 7-2

Claims

1. Compound of formula (I): 【Chemistry 1】 (In the formula, X is O, S(O)n or NR) 11 And; n is 0, 1, or 2; R 1 is C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 2 to C 6 alkenyl, C 2 to C 6 alkynyl, C 1 to C 6 alkoxy C 1 to C 6 alkyl or C 3 to C 6 cycloalkyl; R 2 is phenyl or heteroaryl, where the heteroaryl portion is a five-membered or six-membered aromatic ring containing one, two, three or four heteroatoms individually selected from N, O and S, and where each phenyl and heteroaryl portion is R 7 It may be arbitrarily substituted with one, two, three, or four bases, which may be identical or different, represented by; R 3 is hydrogen or C 1 ~C 6 It is alkyl; R 4 is hydrogen, halogen, C 1 ~C 6 Alkyl or C 1 ~C 6 It is a haloalkyl; R 5 C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 2 ~C 6 Alkenil, C 2 ~C 6 Alkinyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 The cycloalkenyl, phenyl, or heteroaryl group is a 5-membered or 6-membered aromatic ring containing one, two, three, or four heteroatoms individually selected from N, O, and S, and each cycloalkyl, cycloalkenyl, phenyl, and heteroaryl group is R 9 It may be arbitrarily substituted with one, two, three, or four bases, which may be identical or different, represented by; or R 5 and R 11 These, together with the nitrogen atom to which they are bonded, can form a five-membered heterocyclyl ring, where the heterocyclyl portion further comprises and an additional oxygen atom, and where the heteroaryl portion is R 10 It may be arbitrarily substituted with one or two bases, which may be identical or different, represented by; R 7 These are cyano, nitro, halogen, and C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 1 ~C 6 Alkyl sulfanyl, C 1 ~C 6 Alkyl sulfinyl, C 1 ~C 6 Alkyl sulfonyl, C 1 ~C 6 Alkyl sulfonamide, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkoxycarbonyl, C 1 ~C 6 Alkylaminocarbonyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkylaminocarbonyl or N,N-di(C 1 ~C 4 It is an alkyl)aminocarbonyl; R 9 is cyano, nitro, hydroxy, halogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 haloalkyl, C 1 to C 6 haloalkoxy, C 1 to C 6 alkoxyC 1 to C 6 alkyl, C 1 to C 6 alkylsulfanyl, C 1 to C 6 alkylsulfinyl, C 1 to C 6 alkylsulfonyl, C 1 to C 6 alkylsulfonamide, C 1 to C 6 alkylcarbonyl, C 1 to C 6 alkoxycarbonyl, C 1 to C 6 alkylaminocarbonyl, C 3 to C 6 cycloalkyl, C 3 to C 6 cycloalkylaminocarbonyl, N,N - di(C 1 to C 4 alkyl)aminocarbonyl or benzyloxy; or Any two adjacent R 9 The group, together with the carbon atom to which it is bonded, is C 3 ~C 6 A cycloalkyl ring or a phenyl ring may be formed, where the C 3 ~C 6 The cycloalkyl and phenyl portions are R 10 It may be arbitrarily substituted with one, two, three, or four bases, which may be identical or different, represented by; or Any two adjacent R 9 The groups, together with the carbon atoms to which they are bonded, can form a five-membered or six-membered heteroaryl ring, where the heteroaryl portion is a five-membered or six-membered aromatic ring containing one, two, three, or four heteroatoms individually selected from N, O, and S, and where the heteroaryl portion is R 10 It may be arbitrarily substituted with one, two, three, or four bases, which may be identical or different, represented by; or Any two adjacent R 9 The groups, together with the carbon atoms to which they are bonded, can form a five-membered or six-membered heterocyclyl ring, where the heterocyclyl portion is five-membered or six-membered and contains one or two heteroatoms selected from O and N, and where the heterocyclyl ring is R 10 It may be arbitrarily substituted with one, two, three, or four bases, which may be identical or different, represented by; R 10 These are halogen, oxo, and C 1 ~C 3 Alkyl or C 1 ~C 3 It is an alkoxy; R 11 is hydrogen or C 1 ~C 6 (It is alkyl.) Or, its salt or N-oxide.

2. R 1 C 1 ~C 4 Alkyl, C 1 ~C 3 Alkoxy, C 2 ~C 3 Alkenil, C 2 ~C 3 Alkinyl, C 1 ~C 3 Alkoxy C 1 ~C 3 Alkyl or C 3 ~C 4 The compound according to claim 1, wherein it is a cycloalkyl compound.

3. R 2 R 7 The compound according to claim 1, which is a phenyl that may be optionally substituted with one or two groups that are identical or different as represented by .

4. R 4 The compound according to claim 1, wherein is hydrogen.

5. R 5 C 1 ~C 5 Alkyl, C 2 ~C 4 Alkenil, C 2 ~C 4 Alkinyl, C 5 ~C 6 Cycloalkyl, C 5 ~C 6 The cycloalkenyl, phenyl, or heteroaryl group is a 5-membered or 6-membered aromatic ring containing one or two heteroatoms individually selected from N and O, and each cycloalkyl, cycloalkenyl, phenyl, and heteroaryl group is R 9 The compound according to claim 1, which may be optionally substituted with one, two, or three groups that are identical or different, represented by .

6. R 5 is C 1 ~C 3 Alkyl or phenyl, where the phenyl group is R 9 The compound according to claim 1, which is substituted with one or two groups that may be the same or different, represented by .

7. R 7 The compound according to claim 1, wherein is cyano or halogen.

8. R 9 is halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkoxy, cyclopropyl or C 1 ~C 2 The compound according to claim 1, wherein it is an alkylsulfonyl compound.

9. R 11 is hydrogen or C 1 ~C 3 The compound according to claim 1, wherein it is alkyl.

10. The compound according to claim 1, wherein R2 is 3,4-dichlorophenyl.

11. A herbicide composition comprising the compound described in claim 1 and an agriculturally acceptable compounding agent.

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

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

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

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

Images