Herbicidal shinorine derivatives

Abstract

Formula (I) TIFF2023526085000078.tif39161 (wherein the substituents are as defined in claim 1) The present invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds in crops of particularly useful plants.

Description

[Technical Field]

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

[0002] EP 0273325, EP 0274717 and US Pat. No. 5,183,891 describe shinorine derivatives as herbicides. Summary of the Invention [Means for solving the problem]

[0003] According to the present invention, a compound of formula (I): [ka] (In the formula, X is O, NR 13 or S; R 1 is R 7 phenyl optionally substituted with 1, 2, 3 or 4 groups which may be the same or different, represented by R 2 is halogen, cyano, cyanoC1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC2-C6 alkenyl, C2-C6 alkenyloxyC1-C6 alkyl, -CR 11 =N-OR 10, oxo-C1-C6 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 and the heteroaryl and heterocyclyl moieties may be attached to the remainder of the molecule via a carbon or nitrogen atom; R 3 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenylC1-C3 alkyl, and the phenyl portion is R 12 and optionally substituted with 1, 2, 3 or 4 groups represented by: R 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl; R 7 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl or C1-C6 alkylsulfonyl; or Any two adjacent R 7 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R7 Groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl or heteroaryl ring can be R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by: R 8 and R 9 are each independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, and C1-C3 alkoxy; R 10 and R 11 are each independently selected from hydrogen and C1-C3 alkyl; R 12 is halogen, cyano, C1-C3 alkyl or C1-C3 alkoxy; R 13 is hydrogen, C1-C3 alkyl or C1-C3 alkoxy) or a salt or N-oxide thereof.

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

[0005] According to a second aspect of the present invention, there is provided an agricultural 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 of controlling weeds in a locus, the method comprising the step of applying to the locus a weed-controlling amount of a composition comprising 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. DETAILED DESCRIPTION OF THE INVENTION

[0008] When a substituent is described as being "optionally substituted," this includes, for example, one, two, or three R 8 " means that the C1-C6 alkyl substituted with one, two, or three halogens may or may not have one or more identical or different substituents, such as substituted groups. For example, C1-C6 alkyl substituted with one, two, or three halogens may include, but is not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3 groups. As another example, C1-C6 alkoxy substituted with one, two, or three halogens may include, but is not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups.

[0009] As used herein, the term "cyano" refers to 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" refers to an --OH group.

[0012] As used herein, the term "acetyl" refers to a -C(O)CH3 group.

[0013] As used herein, the term "nitro" refers to the group NO2.

[0014] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing no unsaturation, having 1 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" should be construed accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and isomers thereof, such as isopropyl. A "C1-C6 alkylene" group refers to the corresponding definition of C1-C6 alkyl, except for groups that are attached to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" should be construed accordingly. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0015] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, substituted by one or more halogen atoms, which may be the same or different. 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.

[0016] As used herein, the term "C1-C6 dihaloalkyl" refers to a C1-C6 alkyl group, as generally defined above, substituted with two halogen atoms, which may be the same or different. The terms "C1-C4 dihaloalkyl" and "C1-C3 dihaloalkyl" should be interpreted accordingly. Examples of C1-C6 dihaloalkyl include, but are not limited to, difluoromethyl.

[0017] As used herein, the term "cyano C1-C6 alkyl" refers to a C1-C6 alkyl group, as generally defined above, substituted with one or more cyano groups, as defined above. Examples of cyano C1-C6 alkyl include, but are not limited to, 2-cyanomethyl and 2-cyanoethyl.

[0018] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as generally defined above, substituted by one or more halogen atoms, which may be 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.

[0019] As used herein, the term "C1-C6 alkoxy" refers to R a is a C1-C6 alkyl group as generally defined above, a The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be construed accordingly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

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

[0021] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain radical composed solely of carbon and hydrogen atoms, containing at least one triple bond, having 2 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C2-C3 alkynyl" should be construed accordingly. Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, and but-1-ynyl.

[0022] As used herein, the term "C1-C6 alkoxyC1-C6 alkyl" refers to a group of the formula R b OR a - refers to the group where R b is a C1-C6 alkyl group as generally defined above, and R a is a C1-C6 alkylene group as generally defined above.

[0023] As used herein, the term "cyano C1-C6 alkyl" refers to a C1-C6 alkyl group, as generally defined above, substituted with one or more cyano groups, as defined above. Examples of cyano C1-C6 alkyl include, but are not limited to, 2-cyanoethyl.

[0024] 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 construed accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0025] As used herein, the term "C3-C6 cycloalkyl C1-C6 alkyl" refers to a C3-C6 cycloalkyl ring attached to the rest of the molecule by a C1-C6 alkylene linker as defined above.

[0026] As used herein, the term “C1-C6 alkoxy C2-C6 alkenyl” refers to a group of the formula R b OR a - refers to the group where R b is a C1-C6 alkyl group as generally defined above, and R a is a C1-C6 alkene group as generally defined above. Examples of C1-C6 alkoxy C2-C6 alkenyl include, but are not limited to, 1-methoxyvinyl and 1-ethoxyvinyl.

[0027] As used herein, the term "C2-C6 alkenyloxyC1-C6 alkyl" refers to a group of the formula R b OR a - refers to the group where R b is a C2-C6 alkenyl group as generally defined above, and R a is a C1-C6 alkylene group as generally defined above.

[0028] As used herein, the term "oxo-C1-C6 alkyl" refers to R a is a C1-C6 alkene group as generally defined above, of the formula -R a It refers to the group CHO. Examples of "oxo-C1-C6 alkyl" include, but are not limited to, 2-oxoethyl.

[0029] As used herein, the term "phenoxy" refers to a phenyl ring attached to the rest of the molecule via an oxygen atom.

[0030] As used herein, the term "phenyl C1-C3 alkyl" refers to a phenyl ring attached to the rest of the molecule by a C1-C3 alkylene linker as defined above.

[0031] As used herein, the term "heterocyclyl" refers to a stable 4-, 5-, or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms, the heteroatoms being individually selected from nitrogen, oxygen, and sulfur. The heterocyclyl group can be attached to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, azetidinyl, oxetanyl, thietanyl, tetrahydrofuranyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

[0032] As used herein, the term "heterocyclyloxy" refers to a heterocyclyl ring attached to the rest of the molecule via an oxygen atom.

[0033] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing 1, 2, 3, or 4 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, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

[0034] As used herein, the term "C1-C6 alkylcarbonyl" refers to a group of the formula -C(O)R a where R a is a C1-C6 alkyl group as generally defined above.

[0035] As used herein, the term "C1-C6 alkylsulfanyl" refers to R a is a C1-C6 alkyl group as generally defined above; aThe terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be construed accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0036] As used herein, the term "C1-C6 alkylsulfinyl" refers to R a is a C1-C6 alkyl group as generally defined above, a The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" should be construed accordingly. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl.

[0037] As used herein, the term "C1-C6 alkylsulfonyl" refers to R a is a C1-C6 alkyl group as generally defined above, a The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be construed accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfonyl.

[0038] The possible presence of one or more stereogenic centers in compounds of formula (I) means that the compounds can exist in optically isomeric, i.e., enantiomeric or diastereomeric forms. Restricted rotation about a single bond can also give rise to atropisomers. Formula (I) is intended to encompass all these possible isomeric forms and mixtures thereof. The present invention encompasses all these possible isomeric forms and mixtures thereof of compounds of formula (I). Similarly, formula (I) is intended to encompass all possible tautomeric forms. The present invention encompasses all possible tautomeric forms of compounds of formula (I).

[0039] In each case, the compounds of formula (I) according to the invention may be in free form, in oxidized form as N-oxides or in salt form, e.g., agriculturally usable salt form. Preferred are the salts that the compounds of formula (I) can form with amines, including primary, secondary and tertiary amines (e.g., ammonia, dimethylamine and triethylamine), alkali metal bases and alkaline earth metal bases, transition metals or quaternary ammonium bases.

[0040] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds, as described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton (1991).

[0041] The following list describes the substituents X, R for compounds of formula (I): 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 For any one of these substituents, any of the definitions set forth below may be combined with any of the definitions of any other substituents set forth below or elsewhere in this specification.

[0042] X is O, N, or S. In one set of embodiments, X is O. In another set of embodiments, X is S. In a further set of embodiments, X is N.

[0043] R 1 is R 7 Preferably, R is optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by 1 is R 7More preferably, R is phenyl optionally substituted with 1, 2 or 3 groups which may be the same or different, represented by 1 is R 7 Even more preferably, R is phenyl optionally substituted with one or two groups, which may be the same or different, represented by 1 is R 7 Even more preferably, R 1 is R 7 and phenyl substituted at the para position with a single group represented by:

[0044] In one set of embodiments, R 1 is 4-(trifluoromethoxy)phenyl, 4-chlorophenyl, 3,4-dimethoxyphenyl, 4-methylsulfanylphenyl, 3-chloro-5-methyl-phenyl, 4-(trifluoromethyl)phenyl, 4-cyanophenyl, 7-quinolyl, 2,2-difluoro-1,3-benzodioxol-5-yl, 1-methylindazol-6-yl, 2,2,3,3-tetrafluoro-1,4-benzodioxin-6-yl, 3-chloro-4-methyl-phenyl, 3,4-dichlorophenyl, 3-cyanophenyl, 3-chlorophenyl or 3-chloro-4-fluoro-phenyl.

[0045] In another set of embodiments, R 1 In a further set of embodiments, R is 4-(trifluoromethoxy)phenyl, 4-chlorophenyl, or 3,4-dimethoxyphenyl. 1 is 4-(trifluoromethoxy)phenyl or 4-chlorophenyl.

[0046] R 2 is halogen, cyano, cyanoC1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylcarbonyl, C2-C6 alkenyl, C2-C4 alkynyl, C1-C4 alkoxyC2-C4 alkenyl, C2-C4 alkenyloxyC1-C3 alkyl, -CR 11 =N-OR10 , oxo-C1-C4 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0047] Preferably, R 2 is halogen, cyano, cyanoC1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkylcarbonyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C3 alkoxyC2-C3 alkenyl, C2-C3 alkenyloxyC1-C3 alkyl, -CR 11 =N-OR 10 , oxo-C1-C3 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0048] More preferably, R 2 is halogen, cyano, cyanoC1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkylcarbonyl, C2-C4 alkenyl, C1-C3 alkoxyC2-C3 alkenyl, -CR 11 =N-OR 10, oxo-C1-C3 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0049] Even more preferably, R 2 is halogen (preferably bromo), cyano, cyanomethyl, difluoromethyl, acetyl, vinyl, 1-methoxyvinyl, 1-ethoxyvinyl, -CR 11 =N-OR 10 , 2-oxo-ethyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with one or two groups, which may be the same or different, represented by

[0050] Even more preferably, R 2is cyano, cyanomethyl, difluoromethyl, acetyl, vinyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, N-hydroxy-C-methylcarbonimidoyl, 2-oxo-ethyl, nitro, phenyl, phenoxy, oxazolyl, isoxazolyl, pyrazolyl, triazolyl, pyrrolidinyl, piperidinyl, morpholino, and the phenyl, phenoxy, oxazolyl, isoxazolyl, pyrazolyl, and triazolyl moieties are R 8 Each may be optionally substituted with a single substituent represented by:

[0051] In a further preferred embodiment, R 2 is cyano, cyanomethyl, difluoromethyl, acetyl, vinyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, N-hydroxy-C-methylcarbonimidoyl, 2-oxo-ethyl, nitro, phenoxy, 5-oxazol-2-yl, isoxazol-3-yl, pyrazol-1-yl, triazol-1-yl, triazol-2-yl, 1-piperidinyl, morpholino, and the phenoxy, isoxazolyl, pyrazolyl, and triazolyl moieties are R 8 Each may be optionally substituted with a single substituent represented by:

[0052] In another preferred embodiment, R 2 is cyano, cyanomethyl, difluoromethyl, acetyl, vinyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, N-hydroxy-C-methyl-carbonimidoyl, 2-oxo-ethyl, nitro, phenoxy, 5-oxazol-2-yl, 5-(difluoromethyl)isoxazol-3-yl, 4-chloropyrazol-1-yl, 4-(trifluoromethyl)triazol-1-yl, 4-(trifluoromethyl)triazol-2-yl, 1-piperidinyl or morpholino.

[0053] R 2is cyano, C1-C6 alkylcarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC2-C6 alkenyl, C2-C6 alkenyloxyC1-C6 alkyl, -CR 11 =N-OR 10 , phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0054] Preferably, R 2 is cyano, C1-C6 alkylcarbonyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C6 alkoxyC2-C6 alkenyl, C3-C6 alkenyloxyC1-C4 alkyl, -CR 11 =N-OR 10 , phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing one or two heteroatoms individually selected from N, O, and S), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0055] More preferably, R 2is cyano, C1-C4 alkylcarbonyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C4 alkoxyC2-C4 alkenyl, C3-C4 alkenyloxyC1-C3 alkyl, -CR 11 =N-OR 10 , phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with one or two groups, which may be the same or different, represented by

[0056] Even more preferably, R 2 is cyano, C1-C3 alkylcarbonyl, C1-C3 alkoxyC2-C3 alkenyl, -CR 11 =N-OR 10 , phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5-membered aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), or heterocyclyl (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, and heterocyclyl moieties are selected from R 8 Each may be optionally substituted with one or two groups, which may be the same or different, represented by

[0057] Even more preferably, R 2is cyano, acetyl, propanoyl, 2-methylpropanoyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, N-ethoxy-C-methylcarbonimidoyl, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5-membered aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), or heterocyclyl (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), and the phenyl and phenoxy moieties are R 8 Each may be optionally substituted with a single group represented by:

[0058] Even more preferably, R 2 is cyano, acetyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, 4-fluorophenyl, 4-fluorophenoxy or oxazol-2-yl.

[0059] In another preferred set of embodiments, R 2 is cyanoC1-C4 alkyl, C1-C4 dihaloalkyl, C2-C6 alkenyl, C2-C4 alkynyl, C1-C4 alkoxyC2-C4 alkenyl, C2-C4 alkenyloxyC1-C3 alkyl, -CR 11 =N-OR 10 , oxo-C1-C4 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0060] In a further set of preferred embodiments, R 2 is cyanoC1-C3 alkyl, C1-C3 dihaloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyC2-C4 alkenyl, C2-C3 alkenyloxyC1-C3 alkyl, -CR 11 =N-OR 10 , oxo-C1-C3 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 Each may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by

[0061] In a further set of preferred embodiments, R 2 is cyanomethyl, difluoromethyl, vinyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, N-hydroxy-C-methyl-carbonimidoyl, 2-oxo-ethyl, phenoxy, 5-oxazol-2-yl, 5-(difluoromethyl)isoxazol-3-yl, 4-chloropyrazol-1-yl, 4-(trifluoromethyl)triazol-1-yl, 4-(trifluoromethyl)triazol-2-yl, 1-piperidinyl or morpholino.

[0062] R 3 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenylC1-C3 alkyl, and the phenyl portion is R 12Preferably, R 3 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C3 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenylC1-C2 alkyl, and the phenyl portion is R 12 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by 3 is hydrogen, C1-C6 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, phenyl, or benzyl, and the phenyl portion is R 12 Even more preferably, R 3 is hydrogen, C1-C6 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C3 alkyl, phenyl, or benzyl, and the phenyl portion is R 12 In one set of embodiments, R 3 is hydrogen or C1-C6 alkyl. Preferably, R 3 is hydrogen or C1-C4 alkyl, more preferably hydrogen or C1-C3 alkyl. Even more preferably, R 3 is hydrogen, methyl or ethyl. Even more preferably, R 3 is hydrogen or methyl.

[0063] R 4 and R 5are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl, and R 6 is hydrogen.

[0064] Preferably, R 4 and R 5 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, and C1-C4 alkylsulfonyl, and R 6 is hydrogen.

[0065] More preferably, R 4 and R 5 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, and C1-C3 alkylsulfonyl, and R 6 is hydrogen.

[0066] Even more preferably, R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, cyano, C1-C4 alkyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylsulfanyl, and methylsulfonyl, and R 6 is hydrogen.

[0067] Even more preferably, R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl, and R 6 is hydrogen.

[0068] In one embodiment, R 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl. 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, and C1-C4 alkylsulfonyl. More preferably, R 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, and C1-C3 alkylsulfonyl. Even more preferably, R 4 , R 5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, C1-C4 alkyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylsulfanyl, and methylsulfonyl. Even more preferably, R 4 , R 5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl.

[0069] In one set of embodiments, R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl; R 6 is hydrogen. In a further set of embodiments, R 4 , R5 and R 6 are all hydrogen.

[0070] R 7 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl or C1-C6 alkylsulfonyl; or Any two adjacent R 7 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 7 Groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl or heteroaryl ring can be R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0071] Preferably, R 7 is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl or C1-C3 alkylsulfonyl; or Any two adjacent R 7 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 7 Groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl or heteroaryl ring can be R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0072] More preferably, R 7is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy or C1-C3 alkylsulfanyl; or Any two adjacent R 7 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 oxygen atoms, or any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heteroaryl ring containing one or two nitrogen atoms, and the heterocyclyl or heteroaryl ring can be R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0073] Even more preferably, R 7 is chloro, cyano, methyl, methoxy, trifluoroalkyl, trifluoromethoxy, methylsulfanyl, or any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, form a quinolyl, indazolyl, 1,3-benzoxadiozolyl, or 1,4-benzodioxinyl group, which is represented by R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0074] In one set of embodiments, R 7 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl or C1-C6 alkylsulfonyl; or Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl ring can be R 9and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0075] Preferably, R 7 is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl or C1-C3 alkylsulfonyl; or Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl ring can be R 9 and optionally substituted with 1, 2 or 3 groups represented by:

[0076] More preferably, R 7 is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl or C1-C3 alkylsulfonyl.

[0077] Even more preferably, R 7 is fluoro, bromo, chloro, cyano, methyl, ethyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylsulfanyl, methylsulfinyl or methylsulfonyl; or Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl ring can be R 9 Even more preferably, R 7 is fluoro, bromo, chloro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy. More preferably, R7 is chloro, methoxy or trifluoromethoxy. Even more preferably, R 7 is chloro or trifluoromethoxy.

[0078] In a further set of embodiments, R 7 is C1-C6 haloalkoxy. Preferably, R 7 is C1-C4 haloalkoxy, more preferably R 7 is C1-C3 haloalkoxy, and even more preferably, R 7 is C1-C3 fluoroalkoxy, and even more preferably, R 7 is trifluoromethoxy.

[0079] R 8 and R 9 are each independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, and C1-C3 alkoxy.

[0080] Preferably, each R 8 are independently selected from halogen and C1-C3 haloalkyl. More preferably, each R 8 are independently selected from halogen and C1-C3 fluoroalkyl. Even more preferably, each R 8 is independently selected from fluoro, chloro, difluoromethyl and trifluoromethyl.

[0081] Preferably, each R 9 are independently selected from halogen and C1-C3 alkyl. More preferably, each R 9 is independently selected from halogen and methyl. Even more preferably, each R 9 is independently selected from fluoro and methyl.

[0082] In one set of embodiments, R 8 and R 9 are each independently selected from halogen, C1-C3 alkyl and C1-C3 alkoxy.8 and R 9 are each independently selected from halogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, or isopropoxy. More preferably, R 8 and R 9 are each independently selected from halogen, methyl or methoxy. Even more preferably, R 8 and R 9 are each independently selected from fluoro, chloro, methyl, or methoxy. In one set of embodiments, R 8 is fluoro.

[0083] R 10 and R 11 are each independently selected from hydrogen and C1-C3 alkyl. 10 and R 11 are each independently selected from hydrogen, methyl, and ethyl. In one set of embodiments, R 10 and R 11 are both methyl.

[0084] R 12 is halogen, cyano, C1-C3 alkyl or C1-C3 alkoxy. Preferably, R 12 is bromo, chloro, fluoro, cyano, methyl or methoxy.

[0085] R 13 is hydrogen, C1-C3 alkyl or C1-C3 alkoxy. Preferably, R 13 is hydrogen, methyl or methoxy. More preferably, R 13 is hydrogen.

[0086] In the compound of formula (I) according to the present invention, preferably, X is O, N or S; R 1 is R 7 phenyl optionally substituted with one or two groups, which may be the same or different, represented by R2 is cyano, acetyl, propanoyl, 2-methylpropanoyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, N-ethoxy-C-methylcarbonimidoyl, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), or heterocyclyl (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms individually selected from N and O), and the phenyl and phenoxy moieties are R 8 each optionally substituted with a single group represented by R 3 is hydrogen or C1-C3 alkyl; R 4 , R 5 and R 6 are all hydrogen; R 7 is halogen or C1-C3 haloalkoxy; and R 8 is a halogen.

[0087] In another set of embodiments, X is O; R 1 is R 7 is phenyl optionally substituted with a single group represented by R 2 is cyano, C1-C6 alkylcarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC2-C6 alkenyl, C2-C6 alkenyloxyC1-C6 alkyl, -CR 11 =N-OR 10, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 each optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by R 3 is hydrogen, methyl or ethyl; R 4 , R 5 and R 6 are all hydrogen; R 7 is halogen or C1-C3 haloalkoxy; and R 8 is a halogen.

[0088] In a further set of embodiments, X is O; R 1 is R 7 is phenyl optionally substituted with a single group represented by R 2 is cyano, acetyl, 1-methoxyvinyl, 1-ethoxyvinyl, N-methoxy-C-methylcarbonimidoyl, 4-fluorophenyl, 4-fluorophenoxy or oxazol-2-yl; R 3 is hydrogen, methyl or ethyl; R 4 , R 5 and R 6 are all hydrogen; and R 7 is halogen or C1-C3 haloalkoxy.

[0089] In a further set of embodiments, X is O; R 1 is R7 is phenyl optionally substituted with a single group represented by R 2 is halogen, cyano, cyanoC1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxyC2-C6 alkenyl, C2-C6 alkenyloxyC1-C6 alkyl, -CR 11 =N-OR 10 , oxo-C1-C6 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 and the heteroaryl and heterocyclyl moieties may be attached to the remainder of the molecule via a carbon or nitrogen atom; R 3 is hydrogen, methyl or ethyl; R 4 , R 5 and R 6 are all hydrogen; R 7 is C1-C3 haloalkoxy; R 8 is fluoro, chloro, difluoromethyl and trifluoromethyl; R 10 is hydrogen or methyl; and R 11 is methyl.

[0090] In a further set of embodiments, X is O; R 1 is R 7is phenyl optionally substituted with a single group represented by R 2 is cyanoC1-C4 alkyl, C1-C4 dihaloalkyl, C2-C6 alkenyl, C2-C4 alkynyl, C1-C4 alkoxyC2-C4 alkenyl, C2-C4 alkenyloxyC1-C3 alkyl, -CR 11 =N-OR 10 , oxo-C1-C4 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are R 8 each optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by R 3 is hydrogen, methyl or ethyl; R 4 , R 5 and R 6 are all hydrogen; R 7 is chloro, methoxy or trifluoromethoxy; R 8 is fluoro, chloro, difluoromethyl and trifluoromethyl; R 10 is hydrogen or methyl; and R 11 is methyl.

[0091] In a particularly preferred embodiment, the compound of formula (I) is selected from the group consisting of methyl 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P1), 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P2), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P3), carboxylate (P3), methyl 5-(1-methoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P4), 5-oxazol-2-yl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P5), methyl 5-(4-fluorophenyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P6), methyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl] Shinoline-3-carboxylate (P7), 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylic acid (P8), methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (P9), 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylic acid (P10), 1-(4-chlorophenyl)-5-(4-fluorophenoxy)-4-oxo-shinoline-3-carboxylic acid (P11), ethyl ethyl 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P12), 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P13), ethyl 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P14),5-[(E)-N-Hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P15), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (P16), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylic acid (P17), ethyl 4-oxo-5-(2-oxoethyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate carboxylate (P18), 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P19), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-2-yl]cinnoline-3-carboxylic acid (P20), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylic acid (P21), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylic acid (P22), fluoromethoxy)phenyl]-5-[4-(trifluoromethyl)pyrazol-1-yl]cinnoline-3-carboxylic acid (P22), 4-oxo-5-pyrrolidin-1-yl-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P23), 4-oxo-5-(1-piperidyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P24), 5-morpholino-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P25), ethyl 5-morpholino-4 -oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P26), ethyl 4-oxo-5-(1-piperidyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P27), ethyl 4-oxo-5-pyrrolidin-1-yl-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P28), ethyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P29),Ethyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P30), Ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)pyrazol-1-yl]cinnoline-3-carboxylate (P31), Ethyl 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P32 ), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylate (P33), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-2-yl]cinnoline-3-carboxylate (P34), ethyl 5-(cyanomethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline -3-carboxylate (P35), ethyl 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P36), 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P37), ethyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P38), ethyl 5-nitro-4 5-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P39), 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P40), 5-cyano-1-(3,4-dimethoxyphenyl)-4-oxo-cinnoline-3-carboxylic acid (P41) and ethyl 5-cyano-1-(3,4-dimethoxyphenyl)-4-oxo-cinnoline-3-carboxylate (P42).

[0092] In other particularly preferred embodiments, the compound of formula (I) is selected from the group consisting of methyl 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P1), 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P2), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P3), methyl 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P4), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P5), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P6), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P7), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P8), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P9), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P1), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinno silane (P3), methyl 5-(1-methoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P4), 5-oxazol-2-yl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P5), methyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P7), 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P8), Methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P9), 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P10), 1-(4-chlorophenyl)-5-(4-fluorophenoxy)-4-oxo-cinnoline-3-carboxylic acid (P11), ethyl 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate ( P12), 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P13), ethyl 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P14), 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P15),Ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (P16), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylic acid (P17), ethyl 4-oxo-5-(2-oxoethyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P18), 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carvone Acid (P19), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-2-yl]cinnoline-3-carboxylic acid (P20), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylic acid (P21), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)pyrazol-1-yl]cinnoline-3-carboxylic acid (P22), 4-oxo -5-(1-piperidyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P24), ethyl 5-morpholino-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P26), ethyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P29), ethyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P30 ), ethyl 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P32), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylate (P33), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-2-yl]cinnoline-3-carboxylate (P34),Ethyl 5-(cyanomethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P35), ethyl 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P36), 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P37), ethyl 5-cyano-4-oxo-1-[ 4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P38), ethyl 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P39), 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P40) and 5-cyano-1-(3,4-dimethoxyphenyl)-4-oxo-cinnoline-3-carboxylic acid (P41).

[0093] In a further particularly preferred embodiment, the compound of formula (I) is methyl 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P1), 5-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P2), methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P3), methyl 5-(1-methoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P4), 5-oxazol-2-yl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P5), methyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P7), 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P8), methyl 5-acetyl- 4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P9), 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P10), 1-(4-chlorophenyl)-5-(4-fluorophenoxy)-4-oxo-cinnoline-3-carboxylic acid (P11), ethyl 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P14), 5-[(E)-N -hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P15), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (P16), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylic acid (P17), ethyl 4-oxo-5-(2-oxoethyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P18),5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P19), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylic acid (P21), 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)pyrazol-1-yl]cinnoline-3-carboxylic acid (P22), 4-oxo-5-(1 -piperidyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P24), ethyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P29), ethyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P30), ethyl 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline Phosphorus-3-carboxylate (P32), ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-[4-(trifluoromethyl)triazol-1-yl]cinnoline-3-carboxylate (P33), ethyl 5-(cyanomethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P35), ethyl 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P36 ), ethyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P38), ethyl 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (P39), 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (P40) and 5-cyano-1-(3,4-dimethoxyphenyl)-4-oxo-cinnoline-3-carboxylic acid (P41).

[0094] The compounds of the present invention can be prepared as shown in the following schemes, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I). A general method for producing compounds of formula (I) is shown below. Unless otherwise specified in the context, X, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is as defined hereinabove. The starting materials used in the preparation of the compounds of the present invention can be purchased from ordinary commercial suppliers or prepared by known methods. The starting materials and intermediates can be purified by prior art methodologies such as chromatography, crystallization, distillation and filtration before being used in the next step.

[0095] Scheme 1: [ka] A compound of formula (I) wherein X is oxygen and R 3 is hydrogen) can be prepared by reacting a compound of formula (I) (wherein X is oxygen and R is hydrogen) 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) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water). 3 is not hydrogen and is any other R defined above 3 The compounds of formula (I) can also be prepared by the methods described below.

[0096] Scheme 2: [ka] Compounds of formula (I) can be prepared from compounds of formula (B) where Y is F, Cl, Br or I. In an embodiment of the invention, R 2When is phenoxy or heterocyclyloxy and Y is F, compounds of formula (I) can be prepared by the procedure described in the literature. N It can be prepared by reaction with an appropriately substituted phenol or heterocyclyl alcohol under Ar conditions. Typically, this reaction is carried out in the presence of a base (such as potassium carbonate) in an organic solvent (such as dimethylacetamide or N,N-dimethylformamide) at elevated temperatures (such as 100°C to 170°C). This is shown in Scheme 2 above. Compounds of formula (B) can be prepared by the following methods.

[0097] Scheme 3: [ka] Compounds of formula (I) can also be prepared from compounds of formula (B) where Y is Cl, Br or I. In an embodiment of the invention, R 2 When is C2-C6 alkenyloxy and Y is Br, compounds of formula (I) can be prepared in a Stille reaction by reaction with a stannane reagent in the presence of a palladium catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium) or dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium(II) dichloromethane adduct), with or without a base (such as triethylamine), in a suitable organic solvent (such as toluene, 1,4-dioxane, or N,N-dimethylformamide) at an elevated reaction temperature (e.g., 120°C). This is shown in Scheme 3 above.

[0098] Scheme 4: [ka] In subsequent transformations, R 2 The compound of formula (I) in which R is C1-C6 alkylcarbonyl is 2can be prepared from compounds of formula (I) where R is C2-C6 alkenyloxy by a hydrolysis reaction. Typically, this reaction is carried out by treatment with an aqueous acid (such as hydrochloric acid) optionally in a suitable organic solvent (such as acetone, 1,4-dioxane, or tetrahydrofuran) and at a suitable temperature (20°C to 60°C). This is shown in Scheme 4 above.

[0099] Scheme 5: [ka] In further transformations, R 2 Ga-CR 11 =N-OR 10 The compound of formula (I) is 2 can be prepared from a compound of formula (I) where R is C1-C6 alkylcarbonyl by a condensation reaction with a suitable hydroxylamine compound. Typically, this reaction involves the addition of a compound of formula HNOR as the free base or the hydrochloride salt. 10 with a compound having the formula: in a suitable organic solvent (such as ethanol, dimethyl sulfoxide, tetrahydrofuran, dimethyl ether, or methanol) with or without the addition of a base (such as sodium acetate, pyridine, or aqueous potassium hydroxide) at elevated temperatures with or without additional water. This is shown in Scheme 5 above.

[0100] Scheme 6: [ka] In an alternative transformation, compounds of formula (B) where Y is Br can be converted to R by reaction with, for example, a heterocyclic stannane under Stille conditions in the presence of a catalyst (such as Pd-PEPPSI IPent) and a base (such as cesium fluoride) in a suitable solvent (such as 1,4-dioxane) at elevated temperature (e.g., 150°C). 2 can be converted to compounds of formula (I) where is a C-linked heterocycle (such as oxazol-2-yl), as shown in Scheme 6 above.

[0101] Scheme 7: [ka] In another transformation, compounds of formula (B) where Y is Br can be afforded by Suzuki-Miyaura cross-coupling conditions similar to those described in the literature to afford R 2 is alkyl or phenyl. Typically, this reaction is carried out by reacting a compound of formula (B) with R in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium or dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium(II) dichloromethane adduct) or palladium diacetate, optionally with a ligand (such as 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl), in the presence of a base (such as potassium carbonate or cesium carbonate or tripotassium phosphate), in a suitable organic solvent (such as 1,4-dioxane, toluene or tetrahydrofuran), optionally in the presence of water, at elevated temperature. 2 -boronic acids or boroxines, as shown in Scheme 7 above.

[0102] Scheme 8: [ka] In another transformation, compounds of formula (B) where Y is Br can be converted to R 2can be converted to a compound of formula (I) in which is a nitrile. Typically, this reaction is carried out by reacting a compound of formula (B) with dicyanozinc in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, or dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium(II) dichloromethane adduct) or palladium diacetate, optionally with a ligand (such as 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl), in a suitable organic solvent (such as dimethylformamide) at elevated temperature. This is shown in Scheme 8 above.

[0103] Scheme 9: [ka] Compounds of formula (B), where Y is Br, X=O, and LG is a suitable leaving group (such as F, Cl, or Br), can be prepared from compounds of formula (C) by treatment with a base (such as a metal hydride such as sodium hydride or potassium carbonate) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at elevated temperatures (e.g., 100°C). This is shown in Scheme 9 above.

[0104] Scheme 10: [ka] Compounds of formula (C), where Y is Br and LG is a suitable leaving group (such as F, Cl, or Br), can be prepared from the reaction of a β-ketoester of formula (D) with an arenediazonium salt. The arenediazonium salt can be prepared in situ by diazotization of an aniline of formula (E) with sodium nitrite in water in the presence of an acid (such as hydrochloric acid), followed by reaction with a compound of formula (D) in the presence of a suitable base (such as sodium or potassium acetate or potassium carbonate) in a suitable solvent (water, methanol, or ethanol) at a temperature between 0° C. and 25° C. Compounds of formula (E) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 10.

[0105] Scheme 11: [ka] Dicarbonyl compounds of formula (D), where Y is BrI and LG is a suitable leaving group (such as F, Cl, or Br), can be prepared from methyl ketone compounds of formula (F) and diesters of formula (G) via Claisen condensation by treating the methyl ketone with a suitable base (such as potassium t-butoxide or sodium hydride) in a suitable solvent (such as tetrahydrofuran, N,N-dimethylformamide, toluene, or 1,4-dioxane), followed by reaction of the mixture with a carbonate ester (such as dimethyl carbonate or diethyl carbonate) at temperatures between 0°C and 110°C. Compounds of formula (F) and formula (G) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 11.

[0106] The present invention further provides a method for controlling weeds in a habitat, the method comprising applying to the habitat a weed-controlling amount of a composition comprising a compound of formula (I). The present invention may also provide a method for selectively controlling weeds in a habitat containing useful (crop) plants and weeds, the method comprising applying to the habitat a weed-controlling amount of a composition of the present invention. "Control" means eradicating, reducing or hindering growth, or preventing or reducing germination. It should be noted that the compounds of the present invention exhibit significantly improved selectivity compared to known structurally similar compounds. Generally, the plants to be controlled are undesirable plants (weeds). "Habitat" means the area where plants are growing or will grow. Application to the habitat may be carried out before and / or after emergence of the crop plants. Some crop plants may be inherently resistant to the herbicidal effect of the compounds of formula (I).

[0107] The application rates of the compounds of formula (I) can vary within wide limits and depend on the nature of the soil, the application method (pre- or post-emergence; seed dressing; application in the sowing furrow; no-till application, etc.), the crop plant, the weeds to be controlled, the prevailing weather conditions and other factors governed by the application method, time of application and target crop. The compounds of formula I according to the invention are generally applied in amounts of 10 to 2500 g / ha, in particular 25 to 1000 g / ha, in particular 25 to 250 g / ha.

[0108] Application is generally made by spraying the composition, typically with a large area sprayer mounted on a tractor, although other methods such as dusting (if powder), dripping or drench can also be used.

[0109] The term "useful plants" should also be understood to include useful plants that have been rendered tolerant by conventional breeding or genetic engineering methods to herbicides such as bromoxynil or to classes of herbicides, such as 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyroyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen oxidase (PPO) inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, such as imazamox, by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0110] The term "useful plants" should also be understood to include useful plants which have been transformed using recombinant DNA techniques so as to be able to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, in particular those of the genus Bacillus.

[0111] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Root-Feeding Nematode® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root nematode trait), and Protecta®.

[0112] A plant crop or its seed material can be both tolerant to herbicides and simultaneously resistant to insect feeding (a "stacked" transgenic event). For example, a seed can be capable of expressing an insecticidal Cry3 protein while simultaneously being tolerant to glyphosate.

[0113] Crop plants should be understood to include those obtainable by conventional methods of breeding or genetic engineering and containing so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0114] The compounds of formula (I) (or compositions containing them) can be used to control undesirable plants (collectively "weeds"), such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, and Moro. The species may be both monocotyledonous, such as Sorghum, and dicotyledonous, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola, and Xanthium.

[0115] The compound of formula (I) can be used in its unmodified form, or preferably with formulation adjuvants such as carriers, solvents, and surfactants (SAA), together with adjuvants conventionally employed in the formulation art to provide herbicidal compositions.The present invention therefore 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 use in agriculture.Agricultural carriers are well known in the art.

[0116] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of a compound of formula I and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surface-active substance.

[0117] The composition may be selected from a number of formulation types, including 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-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP), and soluble granules (SG). The formulation type selected in any case will depend on the specific purpose envisaged and the physical, chemical, and biological properties of the compound of formula (I).

[0118] To improve dispersibility / solubility in water, water-soluble granules (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 the above substances. This mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0119] 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 dispersing agents and optionally one or more suspending agents to facilitate dispersion in a liquid. This mixture is then ground to a fine powder. Similar compositions can also be granulated to form wettable granules (WG).

[0120] Granules (GR) can be formed by either granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable material) into a porous granular material (such as pumice, attapulgite clay, fuller's earth, kieselguhr, diatomaceous earth, or ground corncob), or by granulating from preformed blank granules by adsorbing a compound of formula (I) (or a solution thereof in a suitable material) onto a hard core material (such as sand, silicates, inorganic carbonates, sulfates, or phosphates) and optionally drying. Substances commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum-based solvents, alcohols, ethers, ketones, and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars, and vegetable oils). Granules may also contain one or more other additives (e.g., emulsifiers, wetting agents, or dispersing agents).

[0121] 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 can contain surfactants (e.g., to improve water dilutability or prevent crystallization in the spray tank).

[0122] 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 mixtures of the foregoing). 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 (C8-C9), and the like. 10EC products can emulsify spontaneously when added to water to produce emulsions that are stable enough to be spray-applied with appropriate equipment.

[0123] The preparation of EW involves obtaining the compound of formula (I) as a liquid (if it is not liquid at room temperature, it can be melted at a suitable temperature, typically below 70°C) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution in water containing one or more SAAs under high shear to produce an emulsion. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with poor water solubility.

[0124] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more SAA and one or more solvents to spontaneously form 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 MEs include those described above for use in ECs or EWs. MEs can be either oil-in-water or water-in-oil systems (which system is present can be determined by conductivity measurements) and can be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. MEs are suitable for dilution in water, either remaining as microemulsions or forming traditional oil-in-water emulsions.

[0125] Suspension concentrates (SCs) can comprise aqueous or non-aqueous suspensions of finely divided, insoluble solid particles of a compound of formula (I). SCs can be prepared by ball milling or bead milling a solid compound of formula (I), optionally with one or more dispersing agents, in a suitable medium to produce a fine particle suspension of the compound. One or more wetting agents can be included in the composition, and a suspending agent can be included to reduce the settling rate of the particles. Alternatively, a compound of formula (I) can be dry milled and added to water containing the materials described above to produce the desired end product.

[0126] Aerosol formulations include 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 vehicle (e.g., water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized, manually operated spray pump.

[0127] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, except that an additional polymerization step is involved, in which each oil droplet is encapsulated by a polymer shell, resulting in an aqueous dispersion of oil droplets containing the compound of formula (I) and, optionally, a carrier or diluent therefor. The polymer shell can be produced by either an interfacial polycondensation reaction or a coacervation procedure. This composition provides controlled release of the compound of formula (I) and can be used for seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymer matrix to provide delayed, controlled release of the compound.

[0128] The composition may contain one or more additives to improve the biological performance of the composition, for example, by improving wetting, retention, or dispersion on the surface; rain resistance on the treated surface; or uptake or mobility of the compound of formula (I). Such additives include surfactants (SAA), oil-based spray additives, such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oil), modified vegetable oils such as methylated rapeseed oil (MRSO), and blends of these with other bioactivity-enhancing adjuvants (formulation ingredients that can aid or modify the action of the compound of formula (I)).

[0129] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0130] Suitable cationic SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0131] Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate, and a mixture of sodium di-isopropyl- and tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylic acids (e.g., sodium laureth-3-carboxylate), phosphate esters (products from the reaction of one or more aliphatic alcohols with phosphoric acid (predominantly mono-esters) or phosphorus pentoxide (predominantly di-esters), such as the reaction product of lauryl alcohol with tetraphosphoric acid; further, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphates / sulfonates of tristyrylphenol.

[0132] Suitable amphoteric forms of SAA include betaines, propionates and glycinates.

[0133] Suitable non-ionic SAAs 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 alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; condensation products of the foregoing partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); lecithin and sorbitan and their esters, alkyl polyglycosides, and tristyrylphenols.

[0134] Suitable suspending agents include hydrocolloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0135] The compounds of the present invention may also be used in mixtures with one or more additional herbicides and / or plant growth regulators, such as acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, aminocarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, vilanaphos, bipyrazone, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, and carfent. Trazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clasifos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including choline salts and its 2-ethylhexyl ester), 2,4-DB, desulfamuron Medipham, dicamba (including aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, and their potassium and sodium salts), diclosulam, difluhenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrion, diquat dibromide, diuron, epirifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, Fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-p-butyl), flucarbazone (including flucarbazone-sodium), flufenacet, flumetsulam, flumioxazin, fluometuron, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron,Glufosinate (including L-glufosinate and both ammonium salts), glyphosate (including its diammonium, isopropylammonium, and potassium salts), halaxifen (including haloxyfop-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (iofensulfuron-sodium), mesosulfuron (including mesosulfuron-methyl), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozoline, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretiraclovir ol, primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-p-ethyl and quizalofop-p-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metola Chlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrrolimet, thiencarbazone, thifensulfuron, thiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazine, trifluralin, triflusulfuron, tripyrasulfone,3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]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-t-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (and its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate), 3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(Isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, and 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one.

[0136] The compounds or mixtures of the present invention may also be used in combination with one or more herbicide safeners, examples of which include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen, and oxabetrinil.

[0137] The compound of formula (I) may be in the form of an ester or a salt, as described, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012. The mixing ratio of the compound of formula (I) to the compound of formula (I) is preferably 1:100 to 1000:1.

[0138] Mixtures can be used to advantage in the formulations described above (in this case the "active ingredient" relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0139] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners, examples of which include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen, and oxabetrinil.

[0140] Mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and / or metcamifen are particularly preferred.

[0141] The safeners of the compounds of formula (I) are, for example, those described in The Pesticide Manual, 16 th Edition (BCPC), 2012. Reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048.

[0142] 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.

[0143] The compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to the crop areas or plants to be treated simultaneously or sequentially with additional compounds. These additional compounds can be, for example, fertilizers or trace element donors or other preparations that influence plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, optionally with additional carriers, surfactants, or application-promoting adjuvants customarily used in the formulation technology.

[0144] As used herein, the term "habitat" means the field in which the plants are growing, or the field in which the seeds of the cultivated plants are sown, or the field in which the seeds will be sown in soil. It includes the soil, seeds and seedlings, and established vegetation.

[0145] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage, and fruits.

[0146] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, that can be used for their propagation, as well as vegetative bodies, such as cuttings or tubers, e.g., potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and plant parts may be mentioned. Also included are sprouted plants and shoots that will be transplanted after germination or emergence from the soil. These shoots may be protected by a complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to refer to seeds.

[0147] Pesticides referred to herein using common names are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0148] The compounds of formula (I) can be used in their pure form or, preferably, together with adjuvants conventionally employed in the formulation art. For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials. The application method, such as spraying, misting, dusting, scattering, coating, or pouring, as well as the type of composition, are selected according to the intended purpose and the current situation. The composition can also contain further adjuvants, such as stabilizers, antifoaming agents, viscosity modifiers, binders, or adhesives, as well as fertilizers, trace element sources, or other compounds for achieving special effects.

[0149] For example, suitable carriers and adjuvants for use in agriculture can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0150] The compounds of formula (I) are usually used in the form of compositions and can be applied to the crop area or plants to be treated simultaneously or sequentially with additional compounds. These additional compounds can be, for example, fertilizers or trace element donors or other preparations that influence plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, optionally with additional carriers, surfactants, or application-promoting adjuvants customarily used in the formulation field.

[0151] The compound of formula (I) may be the sole active ingredient in the composition or, where appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic activity.

[0152] Typically, the formulations contain 0.01 to 90% by weight of active agent, 0 to 20% by weight of an agriculturally acceptable surfactant, and 10 to 99.99% by weight of solid or liquid inert compounding agents and adjuvants, where the active agent is composed of at least the compound of formula (I), together with components (B) and (C), and optionally other active agents, particularly fungicides or preservatives. Concentrated forms of the compositions generally contain about 2 to 80% by weight, preferably about 5 to 70% by weight, of the active agent. Application forms of the formulations may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of the active agent. While commercial products will preferably be formulated as concentrates, end users will typically utilize diluted formulations.

[0153] The following table shows compounds of formula (I) according to the present invention: [ka] Examples of individual compounds are illustrated below.

[0154] [Table 1-1] [Table 1-2]

[0155] Table A-1 provides 48 compounds A-1.001 to A-1.048 of formula (I), where X is oxygen and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is as defined in Table 1.

[0156] Combination example

[0157] [Table 2]

[0158] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to give a wettable powder, which can be diluted with water to give a suspension of the desired concentration.

[0159] [Table 3]

[0160] 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 used directly for seed treatment.

[0161] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0162] Emulsions of any required dilution that can be used in plant protection can be obtained from this concentrate by dilution with water.

[0163] [Table 4]

[0164] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry seed dressing.

[0165] Extruded Granules Active ingredient [compound of formula (I)] 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0166] The active ingredient is mixed and ground with the auxiliaries, the mixture is moistened with water, extruded and then dried in a stream of air.

[0167] Coated Granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0168] The finely ground active ingredient is applied uniformly in a mixer to kaolin moistened with polyethylene glycol, resulting in dust-free coated granules.

[0169] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0170] The finely ground active ingredient is thoroughly mixed with adjuvants to give a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water, which can be used to treat living plants and plant propagation material by spraying, pouring or immersion to protect them from microbial infestation.

[0171] Flowable concentrate for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 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%

[0172] The finely ground active ingredient is thoroughly mixed with adjuvants to give a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water, which can be used to treat living plants and plant propagation material by spraying, pouring or immersion to protect them from microbial infestation.

[0173] slow-release capsule suspension 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-polyphenylisocyanate 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 achieved. 2.8 parts of 1,6-diaminohexane in 5.3 parts of water are added to the emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contains 28% active ingredient. The median capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in a suitable device for this purpose. Another aspect of the present invention may be as follows. [1] Formula (I): [ka] (In the formula, X is O, NR 13 or S; R 1 is R 7 phenyl optionally substituted with 1, 2, 3 or 4 groups which may be the same or different, represented by R 2 is halogen, cyano, cyano C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkyl carbonyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkoxy C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkenyloxy C 1 ~C 6 Alkyl, -CR 11 =N-OR 10 , oxo-C 1 ~C 6 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O, and S), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are selected from R 8 wherein said heteroaryl and heterocyclyl moieties may be attached to the remainder of the molecule via a carbon or nitrogen atom; R 3 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkyl C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, phenyl or phenyl C 1 ~C 3 alkyl, and the phenyl moiety is R 12 and optionally substituted with 1, 2, 3 or 4 groups represented by: R 4 、R 5 and R 6 are each independently hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl and C 1 ~C 6 alkylsulfonyl; R 7 is halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylsulfanyl or C 1 ~C 6 alkylsulfonyl; or Any two adjacent R 7 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 7 Groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, said heterocyclyl or heteroaryl ring being R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by: R 8 and R 9 are each independently a halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl and C 1 ~C 3 selected from alkoxy; R 10 and R 11 are each independently hydrogen and C 1 ~C 3 alkyl; R 12 is halogen, cyano, C 1 ~C 3 Alkyl or C 1 ~C 3 is alkoxy; R 13 is hydrogen, C 1 ~C 3 Alkyl or C 1 ~C 3 alkoxy) or a salt or N-oxide thereof. 〔2〕R 2 is halogen, cyano, cyano C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkyl carbonyl, C 2 ~C 4 Alkenyl, C 1 ~C 3 Alkoxy C 2 ~C 3 Alkenyl, -CR 11 =N-OR 10 , oxo-C 1 ~C 3 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are selected from R 8 The compound according to [1] above, which may be optionally substituted with 1, 2 or 3 groups, which may be the same or different, and which are represented by the following formula: 〔3〕R 2 is halogen (preferably bromo), cyano, cyanomethyl, difluoromethyl, acetyl, vinyl, 1-methoxyvinyl, 1-ethoxyvinyl, -CR 11 =N-OR 10 , 2-oxo-ethyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are selected from R 8 The compound according to [1] or [2] above, which may be optionally substituted with one or two groups, which may be the same or different, represented by: 〔4〕R 2 is cyano C 1 ~C 4 Alkyl, C 1 ~C 4 Dihaloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Alkoxy C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkenyloxy C 1 ~C 3 Alkyl, -CR 11 =N-OR 10 , oxo-C 1 ~C 4 alkyl, nitro, phenyl, phenoxy, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, phenoxy, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are selected from R 8 The compound according to any one of the above [1] to [3], which is optionally substituted with 1, 2 or 3 groups, which may be the same or different, and which are represented by the following formula: 〔5〕R 3 is hydrogen or C 1 ~C 3 The compound according to any one of [1] to [4] above, which is alkyl. 〔6〕R 4 、R 5 and R 6 The compound according to any one of the above [1] to [5], wherein all of are hydrogen. 〔7〕R 7 is halogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkylsulfanyl, C 1 ~C 3 Alkylsulfinyl or C 1 ~C 3 The compound according to any one of the above [1] to [6], which is alkylsulfonyl. 〔8〕R 7 is C 1 ~C 3 The compound according to any one of [1] to [7] above, which is haloalkoxy. 〔9〕R 7 The compound according to any one of the above [1] to [7], wherein is fluoro, bromo, chloro, cyano, methyl, methoxy, trifluoromethyl, or trifluoromethoxy.

[10] The compound according to any one of the above [1] to [9], wherein X is O.

[11] A herbicidal composition comprising the compound according to any one of the above [1] to

[10] and an agriculturally acceptable formulation adjuvant.

[12] The herbicidal composition according to

[11] , further comprising at least one additional pesticide.

[13] The herbicidal composition according to

[12] , wherein the additional pesticide is a herbicide or a herbicide safener.

[14] A method for controlling the growth of undesirable plants, comprising the step of applying to the undesirable plants or their habitats the compound of formula (I) described in any one of [1] to

[10] above or the herbicidal composition described in any one of

[11] to

[13] above.

[15] Use of the compound of formula (I) described in any one of [1] to

[10] above as a herbicide. [Example]

[0174] The following non-limiting examples provide specific methods for synthesizing representative compounds of the present invention referenced in Table 2 below.

[0175] List of Abbreviations °C = degrees Celsius, CDCl3 = chloroform-d, d = doublet, DCM = dichloromethane, dppf = 1,1'-ferrocenediyl-bis(diphenylphosphine), m = multiplet, MHz = megahertz, Pd-PEPPSI IPent = dichloro[1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II), q = quartet, s = singlet.

[0176] Example 1: Synthesis of 5-(N-methoxy-C-methyl-carbonimidoyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P2) Step 1: Synthesis of methyl 3-(2-bromo-6-fluoro-phenyl)-3-oxo-propanoate [ka] Under a nitrogen atmosphere, sodium hydride (2.8 g, 69.1 mmol, 60% by weight) was added portionwise to a stirred solution of 1-(2-bromo-6-fluorophenyl)ethanone (5.0 g, 23.0 mmol) and dimethyl carbonate (37.3 g, 406 mmol) in N,N-dimethylformamide (20 mL) cooled to 0 °C. The reaction was allowed to warm to room temperature and stirred for 24 h. The reaction mixture was poured slowly onto ice and acidified to pH 3 with concentrated hydrochloric acid. The phases were separated, and the aqueous phase was re-extracted with diethyl ether. The combined organic extracts were dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0–30% ethyl acetate in cyclohexane as the eluent to give the desired product (mixture of tautomers) as a colorless liquid (3.34 g, 12.1 mmol, 52%). 1 H NMR (400 MHz, CDCl) δ = 7.46-7.36 (m, 1H), 7.33-7.28 (m, 1H), 7.15-6.98 (m, 1H), 3.98-3.90 (m, 2H), 3.79-3.61 (m, 3H) (data for keto form only)

[0177] Step 2: Synthesis of methyl (2E)-3-(2-bromo-6-fluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate [ka] To a solution of 4-(trifluoromethoxy)aniline (2.12 g, 12.0 mmol) in hydrochloric acid (10.0 mL, 60.1 mmol, 6 mol / L) was added dropwise a solution of sodium nitrite (0.921 g, 13.2 mmol) in water (2.4 mL, 12.0 mmol) at 0 °C. The reaction mixture was stirred at 0 °C for 30 minutes, and then added portionwise to a suspension of methyl 3-(2-bromo-6-fluoro-phenyl)-3-oxopropanoate (3.34 g, 12.0 mmol) and potassium acetate (6.0 g, 60.1 mmol) in water (2.4 mL), resulting in the formation of a yellow solid. The reaction mixture was stirred for 45 minutes and then allowed to warm to room temperature. After 90 minutes, the reaction mixture was filtered, and the solid was collected by filtration to give the desired product as a yellow solid (3.5 g, 7.6 mmol, 64%). 1 H NMR(400MHz,CDCl3)δ=13.25-13.07(m,1H),7.45-7.39(m,1H),7.33-7.28(m,1H),7.18-7.07(m,3H),7.02-6.92(m,2H),4.08-3.97(m,3H)

[0178] Step 3: Synthesis of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of methyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (3.53 g, 7.6 mmol) in dimethylformamide (30 mL) was added potassium carbonate (0.85 g, 8.38 mmol). The reaction mixture was heated at 100° C. for 1.5 hours. The cooled reaction mixture was poured onto ice, and a pale solid precipitated from the solution. The solid was collected by filtration to give the desired product as an off-white powder (3.3 g, 7.5 mmol, 98%). 1H NMR(400MHz,CDCl3)δ=7.61-7.53(m,3H),7.46-7.41(m,2H),7.16-7.05(m,1H),6.97-6.87(m,1H),4.01-3.94(m,3H)

[0179] Step 4: Synthesis of methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P3) [ka] To dichlorobis(triphenylphosphine)palladium(II) (0.048 g, 0.068 mmol) was added a solution of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.60 g, 1.35 mmol) in toluene (20 mL). The reaction mixture was degassed under a stream of nitrogen for 5 minutes, after which tributyl(1-ethoxyvinyl)stannane (1.47 g, 4.1 mmol) was added. The reaction mixture was heated at 120 °C for 60 minutes under microwave irradiation. The reaction mixture was evaporated to dryness under reduced pressure to give a brown gum, which was purified by flash chromatography on silica gel using a gradient of 5 to 100% ethyl acetate in cyclohexane as the eluent to give the desired product as an off-white solid (0.43 g, 0.99 mmol, 70%). 1 H NMR(400MHz,CDCl3)δ=7.62-7.52(m,3H),7.48-7.35(m,3H),7.19-7.08(m,1H),4.44-4 .39(m,1H),4.28-4.25(m,1H),4.12-4.03(m,2H),3.98-3.88(m,3H),1.41-1.31(m,3H)

[0180] Step 5: Synthesis of methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P9) [ka] To methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.416 g, 0.96 mmol) in acetone (5.5 mL) was added aqueous hydrochloric acid (2 M, 5.5 mL, 11 mmol). The reaction mixture was heated at 60° C. for 3.5 hours. The reaction mixture was evaporated under reduced pressure to remove acetone, and the solids were collected by filtration to give the desired product as an off-white powder (0.36 g, 0.87 mmol, 94%). 1 H NMR(400MHz,CDCl3)δ=7.73-7.67(m,1H),7.59-7.51(m,2H),7.52-7.42(m,2H),7.29-7.20(m,2H),4.03-3.89(m,3H),2.65-2.52(m,3H)

[0181] Step 6: Synthesis of methyl 5-(N-methoxy-C-methyl-carbonimidoyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P1) [ka] To methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.47 g, 1.16 mmol) in a mixture of methanol (5 mL) and water (1.5 mL) was added O-methylhydroxylamine hydrochloride (0.15 g, 1.7 mmol) and sodium acetate (0.14 g, 1.74 mmol). The reaction mixture was heated at reflux for 4.5 hours and then allowed to stand at room temperature for 3 days. Additional O-methylhydroxylamine hydrochloride (0.15 g, 1.74 mmol) and sodium acetate (0.14 g, 1.74 mmol) were added, and the reaction mixture was heated for 5 hours. The cooled reaction mixture was diluted with 2 M aqueous hydrochloric acid, and the precipitated solid was collected by filtration. The solid was purified by flash chromatography on silica gel using a gradient of 5-100% ethyl acetate in cyclohexane as eluent to give the desired product as a white solid (0.17 g, 0.39 mmol, 34%). 1H NMR(400MHz,CDCl3)δ=7.67-7.59(m,1H),7.58-7.51(m,2H),7.50-7.43(m,2H ),7.37-7.30(m,1H),7.23-7.15(m,1H),3.99-3.94(m,6H),2.28-2.21(m,3H)

[0182] Step 7: Synthesis of 5-(N-methoxy-C-methyl-carbonimidoyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P2) [ka] To a solution of methyl 5-(N-methoxy-C-methyl-carbonimidoyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.038 g, 0.087 mmol) in methanol (1 mL) and water (0.5 mL) was added lithium hydroxide monohydrate (0.0073 g, 0.17 mmol). The resulting solution was heated to 65° C. for 2 hours. The methanol was removed under reduced pressure, and the pH of the resulting aqueous reaction mixture was adjusted to pH 2 by the addition of concentrated hydrochloric acid. The precipitated solid was collected by filtration and washed with cyclohexane to give the desired product as a white powder (0.036 g, 0.084 mmol, 97%). 1 H NMR(400MHz,CDCl3)δ=7.86-7.74(m,1H),7.63-7.55(m,2H),7.55-7.45(m,3H),7.44-7.35(m,1H),4.06-3.95(m,3H),2.32-2.17(m,3H)

[0183] Example 2: Synthesis of 5-oxazol-2-yl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P5) [ka] A mixture of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.20 g, 0.45 mmol), Pd-PEPPSI IPent catalyst (0.029 g, 0.0361 mmol), cesium fluoride (0.14 g, 0.90 mmol), and tributyl(oxazol-2-yl)stannane (0.19 g, 0.54 mmol) in 1,4-dioxane (4 mL) was heated at 150 °C for 30 + 30 min under microwave irradiation. The reaction mixture was diluted with 2 M hydrochloric acid and extracted with ethyl acetate. The combined organics were concentrated to dryness under reduced pressure. The crude residue was purified by mass-directed reverse-phase HPLC followed by trituration with diethyl ether to give the desired product as a pale yellow powder (0.026 g, 0.063 mmol, 14%). 1 H NMR(400MHz,CDCl3)δ=7.91-7.81(m,3H),7.65-7.59(m,2H),7.58-7.47(m,3H),7.40-7.35(m,1H)

[0184] Example 3: Synthesis of 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P10) [ka] To a suspension of 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.052 g, 0.13 mmol) in methanol (1.5 mL) was added a solution of lithium hydroxide hydrate (0.026 g, 0.61 mmol) in water (0.15 mL). The reaction mixture was stirred at room temperature for 2.5 hours. The reaction mixture was acidified by the addition of 2 M aqueous hydrochloric acid, and a pale solid precipitated from the solution. The suspended solid was collected by filtration and air-dried to give the desired product as a white powder (0.052 g, 0.13 mmol, 87%). 1 H NMR(400MHz,CDCl3)δ=7.90-7.83(m,1H),7.66-7.58(m,2H),7.53-7.49(m,2H),7.47-7.43(m,2H),2.67-2.60(m,3H)

[0185] Example 4: Synthesis of methyl 5-(1-methoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P4) [ka] To dichlorobis(triphenylphosphine)palladium(II) (0.024 g, 0.034 mmol) was added a solution of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.30 g, 0.68 mmol) in toluene (5 mL). The mixture was degassed with nitrogen for 5 minutes, after which tributyl(1-methoxyvinyl)stannane (0.71 g, 2.03 mmol) was added. The reaction mixture was heated at 120 °C for 45 minutes under microwave irradiation. The cooled reaction mixture was filtered through diatomaceous earth, and the filtrate was concentrated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 5–100% ethyl acetate in cyclohexane as the eluent to give the desired product as an off-white solid (0.086 g, 0.20 mmol, 30%). 1 H NMR(400MHz,CDCl3)δ=7.58-7.49(m,3H),7.49-7.44(m,2H),7.43-7.37(m,1H),7.22-7 .10(m,1H),4.44-4.38(m,1H),4.27-4.21(m,1H),3.97-3.91(m,3H),3.86-3.79(m,3H)

[0186] Example 5: Synthesis of 1-(4-chlorophenyl)-5-(4-fluorophenoxy)-4-oxo-cinnoline-3-carboxylic acid (compound P11) Step 1: Synthesis of ethyl 3-(2,6-difluorophenyl)-3-oxo-propanoate [ka] To a solution of potassium 3-ethoxy-3-oxo-propanoate (6.11 g, 35.7 mmol) in acetonitrile (66 mL) at 0° C. and under a nitrogen atmosphere, triethylamine (3.78 g, 37.4 mmol) and dichloromagnesium (4.1 g, 42.5 mmol) were added. The reaction mixture was stirred at room temperature for 3.5 hours. The reaction mixture was cooled to 0° C., and 2,6-difluorobenzoyl chloride (3.0 g, 17 mmol) was added in several portions. The reaction mixture was stirred in ice for 1.5 hours, then at room temperature for 2 hours, and then allowed to stand for 18 hours. The reaction mixture was evaporated under reduced pressure and azeotroped with toluene. The residue was suspended in ethyl acetate (50 mL) and 2 M aqueous hydrochloric acid. The phases were separated, and the aqueous phase was re-extracted twice with ethyl acetate. The combined organic extracts were dried over magnesium sulfate and evaporated to dryness under reduced pressure to give the crude desired product (mixture of tautomers) as a pale yellow liquid (4.5 g, 20 mmol). 1 H NMR (400 MHz, CDCl) δ = 7.53-7.37 (m, 1H), 7.04-6.88 (m, 2H), 4.30-4.22 (m, 2H), 3.47-3.38 (m, 2H), 1.34-1.28 (m, 3H) (data for keto form only)

[0187] Step 2: Synthesis of ethyl (2E)-2-[(4-chlorophenyl)hydrazono]-3-(2,6-difluorophenyl)-3-oxo-propanoate [ka] Methyl (2E)-3-(2-bromo-6-fluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (Example 1; Step 2) was prepared using ethyl 3-(2,6-difluorophenyl)-3-oxopropanoate (3.0 g, 9.2 mmol) and 4-chloroaniline (1.17 g, 9.2 mmol). After 2.75 h of reaction time, the solid was collected by filtration to give the desired product as a yellow solid (2.2 g, 5.9 mmol, 64%). 1H NMR(400MHz,CDCl3)δ=13.15-13.05(m,1H),7.44-7.32(m,1H),7.27-7.23(m,3H),7.00-6.91(m,3H),4.49-4.38(m,2H),1.51-1.39(m,3H)

[0188] Step 3: Synthesis of ethyl 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylate [ka] Ethyl (2Z)-2-[(4-chlorophenyl)hydrazono]-3-(2,6-difluorophenyl)-3-oxopropanoate (2.2 g, 5.9 mmol) was used to prepare methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Example 1; Step 3). Upon completion of the reaction, the cooled reaction mixture was poured onto ice and the precipitated solid was collected by filtration to give the desired product as a yellow powder (1.8 g, 5.3 mmol, 89%). 1 H NMR(400MHz,CDCl3)δ=7.60-7.52(m,3H),7.48-7.40(m,2H),7.14-7.07(m,1H),7.00-6.87(m,1H),4.51-4.40(m,2H),1.45-1.34(m,3H)

[0189] Step 4: Synthesis of 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylic acid [ka] Ethyl 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylate (1.3 g, 3.7 mmol) was used to prepare 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Example 3) to give the desired product as an off-white solid (1.15 g, 3.6 mmol, 97%). 1H NMR(500MHz,CDCl3)δ=14.22-13.90(m,1H),7.82-7.74(m,1H),7.63-7.59(m,2H),7.51-7.37(m,2H),7.36-7.26(m,1H),7.19-7.00(m,1H)

[0190] Step 5: Synthesis of 1-(4-chlorophenyl)-5-(4-fluorophenoxy)-4-oxo-cinnoline-3-carboxylic acid [ka] To a solution of 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylic acid (0.10 g, 0.31 mmol) in dimethylacetamide was added 4-fluorophenol (0.053 g, 0.47 mmol) and potassium carbonate (0.066 g, 0.47 mmol). The reaction mixture was heated at 170° C. for 45 minutes. The cooled reaction mixture was poured onto ice, and the precipitated solid was collected by filtration and then purified by mass-directed reverse-phase HPLC to give the desired product as a white solid (0.010 g, 0.025 mmol, 8%). 1 H NMR(400MHz,CDCl3)δ=7.65-7.56(m,3H),7.53-7.44(m,2H),7.20-7.06(m,4H),7.01-6.91(m,1H),6.87-6.72(m,1H)

[0191] Example 6: Synthesis of methyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate and 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compounds 1.017 and 1.018) [ka] A mixture of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.300 g, 0.677 mmol), dicyanozinc (0.155 g, 1.32 mmol), and tetrakis(triphenylphosphine)palladium (0.079 g, 0.0677 mmol) in dimethylformamide (4 mL) was heated at 160 °C for 45 minutes under microwave irradiation. The reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organics were concentrated to dryness under reduced pressure. The crude residue was purified by mass-directed reverse-phase HPLC to give methyl 5-cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.088 g, 0.225 mmol, 33%). 1 H NMR (400 MHz, chloroform) δ = 7.93-7.86 (m, 1H), 7.77-7.70 (m, 1H), 7.61-7.55 (m, 2H), 7.50-7.41 (m, 3H), 4.03-3.91 (m, 3H)

[0192] 5-Cyano-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid was also obtained (0.016 g, 0.044 mmol, 6%). 1 H NMR (400 MHz, chloroform) δ = 8.11-8.04 (m, 1H), 7.97-7.84 (m, 1H), 7.65-7.58 (m, 3H), 7.54-7.39 (m, 3H)

[0193] Example 7: Synthesis of methyl 5-(4-fluorophenyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P6) [ka] A mixture of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.200 g, 0.451 mmol), (4-fluorophenyl)boronic acid (0.095 g, 0.677 mmol), and potassium carbonate (0.126 g, 0.903 mmol) in acetonitrile (1.00 mL) and water (0.200 mL) was heated at 100 °C for 30 min under microwave irradiation. The reaction mixture was diluted with 2 M aqueous hydrochloric acid and extracted with ethyl acetate (3 times). The combined organic extracts were evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 5 to 100% ethyl acetate in cyclohexane as the eluent to give the desired product as an off-white solid (0.075 g, 0.164 mmol, 36%). 1 H NMR (400 MHz, chloroform) δ = 7.63-7.56 (m, 3H), 7.50-7.45 (m, 2H), 7.31-7.27 (m, 3H), 7.20-7.15 (m, 1H), 7.13-7.06 (m, 2H), 3.93-3.80 (m, 3H)

[0194] Example 8: Synthesis of ethyl 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P14) and 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P15) Step 1: [ka] To a stirred solution of ethyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (50.0 mg, 0.119 mmol) in methanol (10 mL) and water (2.5 mL) at 0°C was added sodium acetate (0.088 g, 1.07 mmol) and hydroxylamine hydrochloride (0.074 g, 1.07 mmol). The reaction mixture was stirred for 5 minutes and then heated at 80°C for 6 hours. The cooled reaction mixture was poured into ice water, neutralized with 2 M aqueous hydrochloric acid, and filtered. The filtrate was evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0–10% methanol in dichloromethane as the eluent to give the desired product as an off-white solid (0.16 g, 0.37 mmol, 34%). 1 H NMR(400MHz,DMSO-d6):10.89(s,1H),7.85(d,2H),7.72(d,3H),7.30(d,1H),7.17(d,1H),4.32(m,2H),2.04(s,3H),1.28(t,3H)

[0195] Step 2: [ka] To a stirred solution of ethyl 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (150 mg, 0.33 mmol) in tetrahydrofuran (6 mL) and water (2 mL) was added lithium hydroxide monohydrate (0.055 g, 1.31 mmol) at room temperature. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was acidified by the addition of 2 M aqueous hydrochloric acid (5 mL) and extracted into dichloromethane (twice). The combined organic extracts were washed with brine, dried over sodium sulfate, and evaporated to dryness under reduced pressure to give 5-[(E)-N-hydroxy-C-methyl-carbonimidoyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.098 g, 0.24 mmol, 74%) as a light brown solid. 1H NMR(400MHz,DMSO-d6):13.9(brs,1H),10.97(s,1H),7.87(m,3H),7.72(d,2H),7.38(d,1H),7.21(d,1H),2.07(s,3H)

[0196] Example 9: Synthesis of ethyl 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P12) and 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P13) Step 1: [ka] To a stirred solution of ethyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (1.00 g, 2.38 mmol) in tetrahydrofuran (25 mL) was added a solution of sodium methoxide (0.129 g, 2.38 mmol) and methyl 2,2-difluoroacetate (0.393 g, 3.57 mmol) in methanol. The reaction mixture was stirred at room temperature for 10 hours. The reaction mixture was quenched by the addition of 1 M aqueous hydrochloric acid and extracted into ethyl acetate. The organic extract was evaporated to dryness under reduced pressure to give the crude product (0.900 g, 1.91 mmol, 80%) as a brown solid.

[0197] Step 2: [ka] To a stirred solution of 5-(4,4-difluoro-3-oxo-butanoyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.650 g, 1.38 mmol) in ethanol (5.30 mL) was added 1 M aqueous sodium hydroxide (0.75 mL), followed by hydroxylamine hydrochloride (0.144 g, 2.07 mmol). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with brine, extracted into ethyl acetate, and the combined organic extracts were evaporated to dryness under reduced pressure to give 5-[5-(difluoromethyl)-5-hydroxy-4H-isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.600 g, 1.24 mmol, 90%).

[0198] Step 3: [ka] To a stirred solution of 5-[5-(difluoromethyl)-5-hydroxy-4H-isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.600 g, 1.11 mmol) in toluene (10 mL) was added sodium p-toluenesulfonate (0.019 g, 0.11 mmol). The reaction mixture was stirred at 110 °C for 3 h. The reaction mixture was evaporated to dryness under reduced pressure, and the residue was partitioned between water and ethyl acetate. The organic extract was washed with brine and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 40–50% ethyl acetate in hexane to give 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.110 g, 0.235 mmol, 21%). 1 H NMR(400MHz,DMSO-d6):13.78(s,1H),7.91(m,3H),7.77(m,3H),7.75(m,2H),7.05(d,1H)

[0199] Step 4: [ka] To a stirred solution of 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.250 g, 0.535 mmol) in ethanol (25 mL) was added concentrated sulfuric acid (0.105 g, 1.07 mmol) at room temperature. The reaction mixture was heated with stirring at 75 °C for 6 hours. The reaction mixture was evaporated to dryness under reduced pressure. The crude residue was diluted with cold water, neutralized with saturated aqueous sodium bicarbonate, and extracted into ethyl acetate. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give ethyl 5-[5-(difluoromethyl)isoxazol-3-yl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.120 g, 0.237 mmol, 44%) as a brown semisolid. 1 H NMR(400MHz,DMSO-d6):7.86(s,1H),7.71(d,2H),7.61(m,3H),7.41(m,2H),7.03(s,1H),4.29(t,2H),1.29(q,3H)

[0200] Example 10: Synthesis of ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (Compound P16) and 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylic acid (Compound P17) Step 1: [ka] To a stirred solution of ethyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (1.80 g, 3.94 mmol) in toluene (30 mL) was added tributyl(vinyl)tin (1.87 g, 5.91 mmol) at room temperature. The mixture was purged with argon for 5 minutes, after which bis(triphenylphosphine)palladium(II) chloride (0.287 g, 0.394 mmol) was added and purged again with argon for 5 minutes. The reaction mixture was heated in a sealed tube at 110° C. for 4 hours. The cooled reaction mixture was filtered through a pad of diatomaceous earth, and the filtrate was evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 10% ethyl acetate in hexane as the eluent to give ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (1.30 g, 3.05 mmol, 78%) as an off-white solid. 1 H NMR(400MHz,CDCl3):8.14(m,1H),7.56(m,3H),7.53(d,3H),7.08(d,1H),5.65(d,1H),5.47(d,1H),4.47(q,2H),1.42(t,3H)

[0201] Step 2: [ka] To a stirred solution of ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (150 mg, 0.352 mmol) in a mixture of tetrahydrofuran (3 mL) and water (2 mL) was added lithium hydroxide monohydrate (0.059 g, 1.41 mmol) at room temperature. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was acidified by the addition of 2 M aqueous hydrochloric acid and extracted into dichloromethane. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylic acid (0.098 g, 0.247 mmol, 70%) as an off-white solid.1 H NMR(400MHz,DMSO-d6):14.08(s,1H),8.04(m,1H),7.79(m,2H),7.72(m,1H),7.64(m,2H),7.55(m,1H),7.18(d,1H),5.79(d,1H),5.74(d,1H)

[0202] Example 11: Synthesis of ethyl 4-oxo-5-(2-oxoethyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P18) Step 1: [ka] To a stirred solution of ethyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.200 g, 0.394 mmol) in toluene (4 mL) was added bis(triphenylphosphine)palladium(II) chloride (0.0287 g, 0.0394 mmol). The mixture was degassed under an argon atmosphere for 5 minutes, after which tributyl(1-ethoxyvinyl)stannane (0.178 mL, 0.492 mmol) was added. The reaction mixture was heated at 110 °C for 3 hours. The cooled reaction mixture was filtered through a pad of diatomaceous earth, and the filtrate was evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 20% ​​ethyl acetate in hexane as the eluent to give ethyl 5-[(E)-2-ethoxyvinyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.080 g, 0.178 mmol, 45%).

[0203] Step 2: [ka] To a stirred solution of ethyl 5-[(E)-2-ethoxyvinyl]-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (50%, 2.00 g, 2.23 mmol) in acetone (10 mL) was added 2 M aqueous hydrochloric acid (5.00 g). The reaction mixture was stirred for 5 minutes and then heated to 65° C. for 16 hours. The cooled reaction mixture was evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 3% methanol in dichloromethane as the eluent to give ethyl 4-oxo-5-(2-oxoethyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.200 g, 0.466 mmol, 21%) as a brown solid. 1 H NMR(400MHz,DMSO-d6):9.76(s,1H),7.87(t,2H),7.74(m,3H),7.38(d,1H),7.12(d,1H),4.30(m,4H),1.29(m,3H)

[0204] Example 12: Synthesis of ethyl 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P32) and 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P19) Step 1: [ka] To a solution of ethyl 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.500 g, 1.26 mmol) in N,N-dimethylformamide (5 mL) at 0 °C under an argon atmosphere was added potassium carbonate (124 mg, 1.26 mmol), followed by 4-chloro-1H-pyrazole (0.194 g, 1.89 mmol). The reaction mixture was stirred at 110 °C for 5 hours. The cooled reaction mixture was poured into water and extracted with ethyl acetate. The combined organic extracts were washed with water, then brine, dried over sodium 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 50% ethyl acetate in hexanes as eluent to give ethyl 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (450 mg, 0.921 mmol, 73%) as a light brown solid. 1 H NMR(400MHz,DMSO-d6):8.21(s,1H),7.87(m,4H),7.82(d,2H),7.56(d,1H),7.28(m,1H),4.29(d,2H),1.27(t,3H)

[0205] Step 2: [ka] To a stirred solution of ethyl 5-(4-chloro-2H-pyrrol-2-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (180 mg, 0.358 mmol) in a mixture of tetrahydrofuran (5 mL) and water (1.5 mL) was added lithium hydroxide monohydrate (0.060 g, 1.43 mmol) at room temperature. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was acidified with 2 M aqueous hydrochloric acid (2 mL) and extracted into dichloromethane. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give 5-(4-chloropyrazol-1-yl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.110 g, 0.245 mmol, 68%) as a yellow solid. 1 H NMR(400MHz,DMSO-d6):13.81(t,1H),8.24(s,1H),7.91(m,4H),7.72(m,2H),7.62(d,1H),7.36(d,1H)

[0206] Example 13: Synthesis of ethyl 5-(cyanomethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P35) [ka] A stirred solution of ethyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.100 g, 0.197 mmol) in mesitylene (10 mL) was degassed with argon for 5 minutes, followed by the sequential addition of (2-cyanoacetyl)oxypotassium (0.082 mL, 0.295 mmol), allylpalladium(II) chloride dimer (0.0144 g, 0.0394 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.0484 g, 0.118 mmol). The reaction mixture was degassed under argon for 2 minutes and then heated in a sealed tube at 100 °C for 5 hours. The cooled reaction mixture was filtered through diatomaceous earth, and the filtrate was evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 20–30% ethyl acetate in hexanes as the eluent to give ethyl 5-(cyanomethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.050 g, 0.120 mmol, 61%). 1 H NMR(400MHz,DMSO-d6):7.86(d,2H),7.79(m,1H),7.74(d,2H),7.65(d,1H),7.29(d,1H),4.59(s,2H),4.35(q,2H),1.30(t,3H)

[0207] Example 14: Synthesis of ethyl 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P36) Step 1: [ka] To a stirred solution of ethyl 4-oxo-1-[4-(trifluoromethoxy)phenyl]-5-vinyl-cinnoline-3-carboxylate (0.600 g, 1.41 mmol) in a mixture of tetrahydrofuran (20 mL) and water (5 mL) was added sodium periodate (0.905 g, 4.23 mmol) and potassium osmate dihydrate (0.052 g, 0.141 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 16 h. The reaction mixture was quenched by the addition of 10% aqueous sodium thiosulfate solution and extracted into ethyl acetate. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 30% ethyl acetate in hexanes as the eluent to give ethyl 5-formyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.455 g, 1.06 mmol, 76%) as an off-white solid.

[0208] Step 2: [ka] To a stirred solution of ethyl 5-formyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (300 mg, 0.70 mmol) in dichloromethane (20 mL) was added diethylaminosulfur trifluoride (0.565 g, 3.51 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was quenched by the addition of saturated aqueous sodium bicarbonate and extracted into dichloromethane. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 20% ​​ethyl acetate in hexane as the eluent to give ethyl 5-(difluoromethyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.290 g, 0.64 mmol, 92%) as a white solid. 1H NMR(400MHz,CDCl3):8.22(s,2H),7.93(t,1H),7.73(t,2H),7.45(d,2H),7.32(s,1H),4.45(q,2H),1.41(t,3H)

[0209] Example 15: Synthesis of ethyl 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P39) and 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P40) Step 1: [ka] To a stirred solution of potassium ethyl malonate (8.36 g, 49.1 mmol) in acetonitrile (150 mL) at room temperature were added 2-fluoro-6-nitrobenzoyl chloride (5.00 g, 24.6 mmol), magnesium dichloride (5.85 g, 61.4 mmol), and triethylamine (5.47 g, 54.0 mmol) sequentially. The reaction mixture was stirred at room temperature for 16 hours. The residue was suspended in ethyl acetate and 2 M aqueous hydrochloric acid. The phases were separated, and the aqueous phase was extracted with ethyl acetate (twice). The combined organic extracts were dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give the crude product as a pale yellow liquid.

[0210] Step 2: [ka] To a stirred solution of 4-(trifluoromethoxy)aniline (3.50 g, 19.8 mmol) in 2 M aqueous hydrochloric acid (10 mL) at 0° C. was added dropwise a solution of sodium nitrite (1.49 g, 21.6 mmol) in water (5 mL). The reaction mixture was stirred for 0.5 h and then added dropwise to a cooled (0° C.) solution of ethyl 3-(2-fluoro-6-nitro-phenyl)-3-oxo-propanoate (5.10 g, 18.0 mmol) and potassium acetate (8.81 g, 89.9 mmol) in water (50 mL). The reaction mixture was stirred at 0° C. for 2 h and then allowed to warm to room temperature. The reaction mixture was diluted with water and extracted into ethyl acetate (2×). The combined organic extracts were washed with water and brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give crude ethyl (2Z)-3-(2-fluoro-6-nitro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (5.00 g, 11.3 mmol, 63%) as a red liquid.

[0211] Step 3: [ka] To a stirred solution of ethyl (2Z)-3-(2-fluoro-6-nitro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (8.00 g, 16.2 mmol) in N,N-dimethylformamide (80 mL) was added potassium carbonate (4.42 g, 32.5 mmol). The reaction mixture was heated at 100 °C for 4 hours. The cooled reaction mixture was diluted with cold water and extracted with ethyl acetate (twice). The combined organic extracts were dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 20% ​​ethyl acetate in hexane as the eluent to give ethyl 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (7.00 g, 15.9 mmol, 98%) as a pale orange solid. 1H NMR(400MHz,DMSO-d6):7.95(m,4H),7.75(d,2H),7.36(m,1H),4.39(q,2H),1.23(t,3H)

[0212] Step 4: [ka] To a stirred solution of ethyl 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.200 g, 0.449 mmol) in a mixture of tetrahydrofuran (10 mL) and water (5 mL) was added lithium hydroxide monohydrate (0.075 g, 1.80 mmol) at room temperature. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was acidified with 2 M aqueous hydrochloric acid and extracted into dichloromethane (twice). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give 5-nitro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.120 g, 0.301 mmol, 67%) as a yellow solid. 1 H NMR(400MHz,DMSO-d6):13.67(s,1H),7.89(m,4H),7.72(d,2H),7.39(d,1H)

[0213] [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

[0214] examples of biology Seeds of various test species (Amaranthus retoflexus (AMARE), Solanum nigrum (SOLNI), Setaria faberi (SETFA), Lolium perenne (LOLPE), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE)) are sown in pots in standard soil. After 8 days of cultivation in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with an aqueous spray solution obtained from a combination of the technical active ingredients in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Unless otherwise stated, compounds are applied at 1000 g / h. Test plants are then grown in a greenhouse under controlled greenhouse conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) with watering twice daily. After 13 days, the test is evaluated for the percentage of damage caused to the plants. Biological activity is shown in the table below on a 5-point scale (5 = 81-100%; 4 = 61-80%; 3 = 41-60%; 2 = 21-40%; 1 = 10-20%; 0 = 0%; - = not tested).

[0215] [Table 6]

[0216] [Table 7]

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, X is O, NR 13 or S; R 1 is R 7 phenyl optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 2 is cyano C 1 ~C4 alkyl, C 1 ~C4 dihaloalkyl, C 2 ~C 6 Alkenyl, C 2 to C4 alkynyl, C 1 ~C4 alkoxy C 2 to C4 alkenyl, C 2 ~C4 alkenyloxy C 1 ~C alkyl, -CR 11 =N-OR 10 , oxo-C 1 to C alkyl, nitro, phenyl, heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from N and O), heterocyclyl, or heterocyclyloxy (wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N and O), and the phenyl, heteroaryl, heterocyclyl, and heterocyclyloxy moieties are selected from R 8 each optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by R 3 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkyl C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, phenyl or phenyl C 1 ~C 3 alkyl, and the phenyl moiety is R 12 and optionally substituted with 1, 2, 3 or 4 groups represented by R 4 , R 5 and R 6 are all hydrogen; R 7 is halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylsulfanyl or C 1 ~C 6 alkylsulfonyl; or Any two adjacent R 7 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 7 Groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, said heterocyclyl or heteroaryl ring being R 9 and optionally substituted with 1, 2, 3 or 4 groups represented by R 8 and R 9 are each independently a halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl and C 1 ~C 3 alkoxy; R 10 and R 11 are each independently hydrogen and C 1 ~C 3 alkyl; R 12 is halogen, cyano, C 1 ~C 3 Alkyl or C 1 ~C 3 is alkoxy; R 13 is hydrogen, C 1 ~C 3 Alkyl or C 1 ~C 3 alkoxy) or a salt or N-oxide thereof.

2. R 3 is hydrogen or C 1 ~C 3 The compound of claim 1 , wherein the aryl group is alkyl.

3. R 7 is halogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkylsulfanyl, C 1 ~C 3 Alkylsulfinyl or C 1 ~C 3 3. The compound of claim 1 or 2, which is an alkylsulfonyl.

4. R 7 is C 1 ~C 3 The compound of any one of claims 1 to 3, which is haloalkoxy.

5. R 7 The compound according to any one of claims 1 to 3, wherein is fluoro, bromo, chloro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy.

6. The compound of any one of claims 1 to 5, wherein X is O.

7. A herbicidal composition comprising the compound according to any one of claims 1 to 6 and an agriculturally acceptable formulation adjuvant.

8. 8. The herbicidal composition of claim 7 further comprising at least one additional pesticide.

9. 9. The herbicidal composition of claim 8, wherein the additional pesticide is a herbicide or a herbicide safener.

10. 10. A method for controlling the growth of undesired plants, comprising the step of applying to the undesired plants or their habitat a compound of formula (I) as defined in any one of claims 1 to 6 or a herbicidal composition as defined in any one of claims 7 to 9.

11. Use of a compound of formula (I) according to any one of claims 1 to 6 as a herbicide.

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