Herbicidal shinorine derivatives

Abstract

Formula (I) TIFF2023526084000110.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 10 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 S(O) n C1-C6 alkyl, S(O) n C1-C6 haloalkyl or S(O) n C3-C6 cycloalkyl; n is 0, 1 or 2; R 3 is hydrogen, C1 to C 12Alkyl, C1-C6 haloalkyl, cyanoC1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C6 alkoxycarbonylC1-C6 alkyl, N,N-di(C1-C6 alkyl)aminoC1-C6 alkyl, phenyl, phenylC1-C 12 alkyl, benzyloxyC1-C6 alkyl, heterocyclyl, 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; phenyl and heterocyclyl moieties are R 8 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, C1-C6 alkylsulfinyl 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 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, and C1-C3 alkoxy; R 10is 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 "optionally substituted," this means that it may or may not have one or more identical or different substituents, e.g., one, two, or three substituents. For example, C1-C6 alkyl substituted with one, two, or three halogens can 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 can 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, "C1-C 12 The term "alkyl" refers to a straight or branched hydrocarbon chain radical composed solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 12 carbon atoms, and attached to the rest of the molecule by a single bond. 11 "C1-C6 alkyl", "C1-C4 alkyl" and "C1-C3 alkyl" should be construed accordingly. 12 Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, and isomers thereof, such as isopropyl. 12 An alkylene group is a group consisting of C1 to C 12 refers to the corresponding definition of alkyl, except for groups that are attached to the rest of the molecule by two single bonds. The terms "C1-C6 alkylene," "C1-C3 alkylene," and "C1-C2 alkylene" should be construed accordingly. C1-C 12 Examples of alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0013] As used herein, the term "cyano C1-C6 alkyl" refers to a C1-C6 alkyl group, as generally defined above, substituted by one or more cyano groups, as defined above. Examples of cyano C1-C6 alkyl include, but are not limited to, 2-cyanoethyl.

[0014] 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 and 2,2,2-trifluoroethyl.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] As used herein, the term “C1-C6 alkoxycarbonyl C1-C6 alkyl” refers to a group of the formula R a OC(O)R b - refers to the group where R a is a C1-C6 alkyl group as generally defined above, and R b is a C1-C6 alkylene group as generally defined above.

[0019] As used herein, the term "N,N-di(C1-C6 alkyl)amino C1-C6 alkyl" refers to a group of the formula -R c N(R a )(R b ) group, where R a and R b are each individually a C1-C6 alkyl group as generally defined above, and R c is a C1-C6 alkylene group as generally defined above.

[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 haloalkenyl" refers to a C2-C6 alkenyl group as generally defined above, which is substituted with one or more halogen atoms, which may be the same or different. Examples of C2-C6 haloalkenyl include, but are not limited to, 2-chloroallyl.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] As used herein, "phenyl C1-C 12 The term "alkyl" means a C1-C2 alkyl group as defined above. 12 Refers to a phenyl ring attached to the rest of the molecule by an alkylene linker. 11 The terms "alkyl" and "phenyl C1-C3 alkyl" should be construed accordingly.

[0026] As used herein, the term "benzyloxyC1-C6 alkyl" refers to a group of the formula -R a OR b where R a is a C1-C6 alkylene group as generally defined above, and R b is a benzyl group.

[0027] As used herein, the term "C1-C6 alkylsulfanyl" refers to R a is a C1-C6 alkyl group as generally defined above; a The terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be construed accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0028] 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.

[0029] 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.

[0030] As used herein, the term "heterocyclyl" refers to a stable 5- or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms, the heteroatoms being independently selected from nitrogen and oxygen. 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, aziridinyl, azetidinyl, oxetanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, and dioxolanyl.

[0031] 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).

[0032] 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.

[0033] 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).

[0034] 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 and R 10 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.

[0035] X is O, N, or S. Preferably, X is O or S. In one set of embodiments, X is O. In another set of embodiments, X is N. In a further set of embodiments, X is S.

[0036] 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 7 More 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:

[0037] In one set of embodiments, R 1 is 4-(trifluoromethoxy)phenyl, 4-chlorophenyl, 2,4-dichlorophenyl or 4-chloro-2-fluorophenyl.

[0038] In another set of embodiments, R 1 is 4-(trifluoromethoxy)phenyl or 4-chlorophenyl.

[0039] R 2 is S(O) n C1-C6 alkyl, S(O) n C1-C6 haloalkyl or S(O) n C3-C6 cycloalkyl. Preferably, R 2 is S(O) n C1-C4 alkyl, S(O) n C1-C4 haloalkyl or S(O) n It is preferably a C3-C5 cycloalkyl. More preferably, R 2 is S(O) n C1-C3 alkyl, S(O) n C1-C3 haloalkyl or S(O) n Even more preferably, R 2 is methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylsulfanyl, ethylsulfinyl, ethylsulfonyl, n-propylsulfanyl, n-propylsulfinyl, n-propylsulfonyl, isopropylsulfanyl, isopropylsulfinyl, isopropylsulfonyl, 2,2,2-trifluoroethylsulfanyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trifluoroethylsulfonyl, cyclopropylsulfanyl, cyclopropylsulfinyl or cyclopropylsulfonyl. Even more preferably, R 2 is methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylsulfanyl, ethylsulfinyl, ethylsulfonyl, 2,2,2-trifluoroethylsulfanyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trifluoroethylsulfonyl, cyclopropylsulfanyl, cyclopropylsulfinyl or cyclopropylsulfonyl. Even more preferably, R 2is methylsulfanyl, methylsulfonyl, ethylsulfanyl, ethylsulfonyl, 2,2,2-trifluoroethylsulfanyl, 2,2,2-trifluoroethylsulfonyl, cyclopropylsulfanyl or cyclopropylsulfonyl. Even more preferably, R 2 is methylsulfanyl or methylsulfonyl.

[0040] n is 0, 1, or 2. In one set of embodiments, n is 0 or 2. In another set of embodiments, n is 0. In a further set of embodiments, n is 1. In a further set of embodiments, n is 2.

[0041] R 3 is hydrogen, C1 to C 12 Alkyl, C1-C6 haloalkyl, cyanoC1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C6 alkoxycarbonylC1-C6 alkyl, N,N-di(C1-C6 alkyl)aminoC1-C6 alkyl, phenyl, phenylC1-C 12 alkyl, benzyloxyC1-C6 alkyl, heterocyclyl, 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; phenyl and heterocyclyl moieties are R 8 and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0042] Preferably, R 3 is hydrogen, C1 to C 12Alkyl, C1-C4 haloalkyl, cyano C1-C3 alkyl, C3-C6 cycloalkyl C1-C3 alkyl, C1-C3 alkoxy C1-C6 alkyl, C2-C5 alkenyl, C2-C4 haloalkenyl, C2-C6 alkynyl, C1-C3 alkoxycarbonyl C1-C3 alkyl, N,N-di(C1-C3 alkyl)amino C1-C3 alkyl, phenyl C1-C 12 alkyl, benzyloxyC1-C4 alkyl or heterocyclyl, the heterocyclyl moiety being a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O and S.

[0043] More preferably, R 3 is hydrogen, C1 to C 12 Alkyl, C1-C3 haloalkyl, cyano C1-C3 alkyl, cyclopropyl C1-C3 alkyl, C1-C3 alkoxy C1-C5 alkyl, C2-C4 alkenyl, C2-C3 haloalkenyl, C3-C5 alkynyl, C1-C2 alkoxycarbonyl C1-C2 alkyl, N,N-di(methyl)amino C1-C3 alkyl, phenyl C1-C 12 alkyl, benzyloxyC1-C4 alkyl or heterocyclyl, the heterocyclyl moiety being a 5- or 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms individually selected from N, O and S.

[0044] Even more preferably, R 3 is hydrogen, C1 to C 11 alkyl, 2-chloroethyl, 2,2-difluoroethyl, 2-cyanoethyl, cyclopropylmethyl, 1-cyclopropylethyl, 3-methoxypropyl, 3-methoxy-3-methylbutyl, allyl, 1-methylallyl, 2-chloroallyl, prop-2-ynyl, but-3-ynyl, pent-4-ynyl, methoxycarbonylmethyl, N,N-di(methyl)aminoethyl, phenyl C3-C9 alkyl, benzyloxybutyl, or heterocyclyl, wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing a single oxygen atom.

[0045] Even more preferably, R 3 is hydrogen, methyl, ethyl, isopropyl, isobutyl, 2,2-dimethylpropyl, n-pentyl, n-hexyl, 3,3-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, n-undecyl, 2-chloroethyl, 2,2-difluoroethyl, 2-cyanoethyl, cyclopropylmethyl, 1-cyclopropylethyl, 3-methoxypropyl, 3-methoxy-3-methylbutyl, allyl, 1-methylallyl, 2-chloroallyl, prop-2-ynyl, but-3-ynyl, pent-4-ynyl, methoxycarbonylmethyl, N,N-di(methyl)aminoethyl, 9-phenylnonyl, 3-phenylpropyl, benzyloxybutyl, or tetrahydrofuran-3-yl.

[0046] In one set of embodiments, 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 alkynylphenyl or phenylC1-C3 alkyl, and the phenyl portion is R 8 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by 3 is hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl or phenylC1-C2 alkyl, and the phenyl moiety is R 8 Even more preferably, R 3 is hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, C1-C3 alkoxyC1-C3 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl or phenylC1-C2 alkyl, and the phenyl moiety is R 8Even more preferably, R 3 is hydrogen or C1-C4 alkyl. Most preferably, R 3 is hydrogen, methyl or ethyl, in particular hydrogen or methyl.

[0047] 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, isopropyl, isobutyl, methoxy, and trifluoromethyl. Even more preferably, R 4 , R5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl. Even more preferably, R 4 , R 5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, and methoxy.

[0048] 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 another set of embodiments, R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, and methoxy; R 6 is hydrogen. In a further set of embodiments, R 4 , R 5 and R 6 are all hydrogen.

[0049] In another preferred set of embodiments, R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, methyl, isobutyl, methoxy, and trifluoromethyl; R 6 is hydrogen. In another set of embodiments, R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, methyl, isobutyl, and methoxy; R 6 is hydrogen.

[0050] R 7 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl 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 9 and optionally substituted with 1, 2, 3 or 4 groups represented by:

[0051] 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:

[0052] 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.

[0053] Even more preferably, R 7 is fluoro, bromo, chloro, cyano, methyl, ethyl, isopropyl, isobutyl, 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 9Even more preferably, R 7 is fluoro, bromo, chloro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy. Even more preferably, R 7 is fluoro, chloro or trifluoromethoxy. Even more preferably, R 7 is chloro or trifluoromethoxy.

[0054] In one set of embodiments, R 7 is halogen or C1-C3 haloalkoxy.

[0055] 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 chloro, bromo, fluoro, methyl and methoxy.

[0056] R 10 is hydrogen, C1-C3 alkyl or C1-C3 alkoxy. Preferably, R 10 is hydrogen, methyl or methoxy. More preferably, R 10 is hydrogen.

[0057] In the compound of formula (I) according to the present invention, preferably, X is O; R 1 is R 7 is phenyl optionally substituted with one group represented by R 2 is S(O) n C1-C3 alkyl, S(O) n C1-C3 haloalkyl or S(O) n C3-C4 cycloalkyl; R 3 is hydrogen or C1-C4 alkyl; R4 , R 5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl; and R 7 is fluoro, bromo, chloro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy.

[0058] In another set of embodiments, X is O; R 1 is R 7 is phenyl optionally substituted with one group represented by R 2 is S(O) n C1-C3 alkyl, S(O) n C1-C3 haloalkyl or S(O) n C3-C4 cycloalkyl; R 3 is hydrogen, methyl or ethyl; R 4 and R 5 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl; R 6 is hydrogen; and R 7 is fluoro, bromo, chloro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy.

[0059] In a further set of embodiments, X is O; R 1 is 4-(trifluoromethoxy)phenyl or 4-chlorophenyl; R 2 is methylsulfanyl or methylsulfonyl; R 3 is hydrogen or methyl; R 4 , R 5 and R 6 are all hydrogen.

[0060] In a particularly preferred embodiment, the compound of formula (I) is selected from the group consisting of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P2), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P3), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P5), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P6), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P7), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P8), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P9), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P10), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P11), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P12), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P13), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P14), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo (oxy)phenyl]cinnoline-3-carboxylic acid (Compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P7), ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P8), ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P9), ethyl 6-Bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P10), ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P11), 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P12), 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P13), fluoromethoxy)phenyl]shinorine-3-carboxylic acid (Compound P13), 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (Compound P14), 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (Compound P15), 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (Compound P18),7-Methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P19), 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P21), ethyl 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P22), ethyl 5-ethylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P23), ethyl 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P24), 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P25), 5-ethylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P26), 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P27), ethyl 5-methylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P28), 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P30), Ethyl 5-cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P32), ethyl 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P33), 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P35), 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)- 1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P37), ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P38), ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfanyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P39), ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylate (compound P40), 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylic acid (compound P41), ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylate (compound P42), 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylic acid (compound P43), ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4 -oxo-cinnoline-3-carboxylate (compound P44), ethyl 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P45), ethyl 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P46), ethyl 6-cyano-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P47),Ethyl 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P49), ethyl 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P50), ethyl 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P52), ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P53), Sulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P53), ethyl 7-fluoro-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P54), ethyl 7-cyano-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P55), methyl 7-methoxy-5-methylsulfanyl-4-oxo-1- [4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P56), ethyl 7-methoxy-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P57), hexyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P59), undecyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline- 3-carboxylate (Compound P60), 2-chloroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P61), pent-4-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P62), cyclopropylmethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P63),1-Methylallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P64), isopropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P65), 2-chloroallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P66), 2,2-difluoroethyl 5-methylsulfonyl- 4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P67), 2,2-dimethylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P68), 3-methoxypropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P69), tetrahydrofuran-3-yl 5-methylsulfonyl-4-oxo-1-[ 4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P70), but-3-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P71), isobutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P72), 2-cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P73), carboxylate (Compound P73), 1-cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P74), pentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P75), 2-(dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P76),Heptyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P77), prop-2-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P78), prop-2-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P79), allyl 5-methylsulfonyl-4-oxo-1-[ 4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P80), 2-methoxy-2-oxo-ethyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P81), nonyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P82), 3-phenylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P83). (3-Methoxy-3-methyl-butyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P84), (3-Methoxy-3-methyl-butyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P85), 3,3-dimethylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P86), 2-Cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline phosphorus-3-carboxylate (Compound P87), isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P88), 4-benzyloxybutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P89), S-octyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (Compound P90),S-isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P91) and S-(3-phenylpropyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P92).

[0061] In other particularly preferred embodiments, the compound of formula (I) is selected from the group consisting of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P2), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P3), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P5), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (compound P7), ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylate (compound P8), ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylate (compound P9), Ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P10), 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P12), 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P13), 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P14), 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (compound P14), 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (compound P15), 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (compound P18), 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (compound P19),7-Fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P21), ethyl 5-ethylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P23), 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P25), 5-ethylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline- 3-carboxylic acid (Compound P26), 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P27), ethyl 5-methylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P28), 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P30), ethyl 5-cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P31). 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P32), ethyl 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P33), 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P35), 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline Phosphorus-3-carboxylic acid (compound P37), ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfanyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P39), ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P40), 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P41),Ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylate (compound P42), 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylic acid (compound P43), ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-shinoline-3-carboxylate (compound P44), ethyl 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carbox- ylate silane (Compound P46), ethyl 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P50), ethyl 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P52), ethyl 6-bromo-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P53), ethyl 7-fluoro-5- Methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P54), ethyl 7-cyano-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P55), ethyl 7-methoxy-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P57), hexyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P59), undecyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P60), 2-chloroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P61), pent-4-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P62),Cyclopropylmethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P63), 1-methylallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P64), isopropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P65), 2-chloroallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P66), -oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P66), 2,2-difluoroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P67), 2,2-dimethylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P68), 3-methoxypropyl 5-methylsulfonyl-4-oxo-1-[4- (trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P69), tetrahydrofuran-3-yl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P70), but-3-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P71), isobutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P72). Shinoline-3-carboxylate (P72), 2-cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (compound P73), 1-cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (compound P74), pentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (compound P75),2-(Dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P76), heptyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P77), prop-2-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P78), prop-2-ynyl 5-methylsulfonyl- 4-Oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P79), allyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P80), 2-methoxy-2-oxo-ethyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P81), nonyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P82). Nyl]cinnoline-3-carboxylate (Compound P82), 3-phenylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P84), (3-methoxy-3-methyl-butyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P85), 3,3-dimethylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3 -carboxylate (Compound P86), 2-cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P87), isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P88), 4-benzyloxybutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P89),S-octyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P90), S-isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P91), and S-(3-phenylpropyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P92).

[0062] In a further particularly preferred embodiment, the compound of formula (I) is selected from the group consisting of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P2), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P3), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P5), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P6), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P7), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P8), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P9), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P10), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P11), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P12), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P13), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P14), 1-(4-chlorophenyl)-5-methylsulfonyl-4-ox fluoromethoxy)phenyl]shinorine-3-carboxylic acid (Compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylic acid (Compound P7), ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylate (Compound P8), ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinorine-3-carboxylate (Compound P9). Compound P9), 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P12), 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P19), 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P21), 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P22). 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P27), ethyl 5-methylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P28), 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (compound P30), ethyl 5-cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P32),Ethyl 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P33), 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P41), ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylate (compound P42), 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylate carboxylic acid (Compound P43), ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylate (Compound P44), ethyl 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P46), ethyl 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P50), ethyl 7-fluoro-5-methylsulfonyl ethyl 7-fluoro-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P52), ethyl 7-fluoro-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P54), ethyl 7-methoxy-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P57), hexyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate phenyl]cinnoline-3-carboxylate (compound P59), undecyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P60), 2-chloroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P61), pent-4-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P62),Cyclopropylmethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P63), 1-methylallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P64), isopropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P65), 2-chloroallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P66), -oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P66), 2,2-difluoroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P67), 2,2-dimethylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P68), 3-methoxypropyl 5-methylsulfonyl-4-oxo-1-[4- (trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P69), tetrahydrofuran-3-yl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P70), but-3-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P71), isobutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (compound P72). Shinoline-3-carboxylate (P72), 2-cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (compound P73), 1-cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (compound P74), pentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]shinoline-3-carboxylate (compound P75),2-(Dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P76), heptyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P77), prop-2-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P78), prop-2-ynyl 5-methylsulfonyl- 4-Oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P79), allyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P80), 2-methoxy-2-oxo-ethyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P81), nonyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P82). Nyl]cinnoline-3-carboxylate (Compound P82), 3-phenylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P84), (3-methoxy-3-methyl-butyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P85), 3,3-dimethylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3 -carboxylate (Compound P86), 2-cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P87), isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P88), 4-benzyloxybutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P89),S-octyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P90), S-isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P91), and S-(3-phenylpropyl) 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate (compound P92).

[0063] 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.

[0064] Scheme 1: [ka] A compound of formula (I) wherein X is oxygen and R 3 is hydrogen) can be prepared by reaction of a compound of formula (I) (wherein 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) at a temperature between 0°C and 100°C. 3is not hydrogen and is any other R defined above 3 This can be prepared by hydrolysis of the aryl group, which is shown above in Scheme 1.

[0065] Scheme 2: [ka] Compounds of formula (I) can be prepared from compounds of formula (B) where Y is F, Cl, Br or I. 2 In embodiments of the invention where is SO2C1-C6 alkyl and Y is F, compounds of formula (I) may be prepared by reaction with an alkyl sulfinate salt (such as sodium methanesulfonate) in a suitable solvent (such as N,N-dimethylformamide, dimethylacetamide, or dimethylsulfoxide) at elevated temperatures (up to 130°C). This is shown above in Scheme 2.

[0066] Scheme 3: [ka] Instead, R 2 Compounds of formula (I) where Y is SC1-C6 alkyl can be prepared from compounds of formula (B) where Y is F by reaction with an alkyl thiol in the presence of a base (such as a metal carbonate such as sodium hydride or potassium carbonate) in a suitable solvent (such as N,N-dimethylformamide or N-methyl-2-pyrrolidone) at a suitable temperature. This is shown above in Scheme 3.

[0067] Scheme 4: [ka] Instead, R 2 Compounds of formula (I) where R is SO2C1-C6 alkyl can be obtained by oxidation with typical oxidizing agents (such as oxone, sodium hypochlorite or metachloroperbenzoic acid) in a suitable solvent under standard conditions to give R 2can be prepared from compounds of formula (I) where is SC1-C6 alkyl or S(O)C1-C6 alkyl. Such oxidation methods will be familiar to those skilled in the art. This is shown above in Scheme 4.

[0068] Scheme 5: [ka] Similarly, R 2 Compounds of formula (I) where R is S(O)C1-C6 alkyl can be obtained by oxidation with typical oxidizing agents (such as oxone, sodium hypochlorite or metachloroperbenzoic acid) in a suitable solvent under standard conditions to give R 2 can be prepared from compounds of formula (I) where is SC1-C6 alkyl. Such oxidation methods will be familiar to those skilled in the art. This is shown above in Scheme 5.

[0069] Scheme 6: [ka] A compound of formula (B) wherein Y is F, Cl, Br or I, X is oxygen, and R 3 is hydrogen) can be prepared by reaction of a compound of formula (B) (wherein 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) at a temperature between 0°C and 100°C. 3 is not hydrogen and is any other R defined above 3 This can be prepared by hydrolysis of the aryl group, which is shown above in Scheme 6.

[0070] Scheme 7: [ka] Compounds of formula (B), where Y is F, Cl, Br, or I, and X is oxygen, can be prepared from compounds of formula (C) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at elevated temperature (100° C.), optionally in the presence of a base (such as a metal hydride, e.g., sodium hydride, or potassium carbonate). This is shown above in Scheme 7.

[0071] Scheme 8: [ka] Compounds of formula (C), where Y is F, Cl, Br, or I, and X is oxygen, can be prepared by reacting a β-ketoester of formula (D), where LG is a suitable leaving group (such as F, Cl, or Br), with an arenediazonium salt. The arenediazonium salt can be prepared in situ by diazotizing 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 8.

[0072] Scheme 9: [ka] Dicarbonyl compounds of formula (D) (where Y is F, Cl, Br, or I, and X is oxygen) can be prepared from methyl ketone compounds of formula (F) where LG is a suitable leaving group (such as F, Cl, or Br) 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 9.

[0073] R 4 Compounds of the invention where X, R are methyl can also be prepared by the alternative routes shown in the following schemes, where, unless otherwise specified, the definition of each of the variables is as defined above for compounds of formula (I). General methods for the production of compounds of formula (I) are set forth below. Unless otherwise specified in the context, X, R 1 , R 2 and R 3 is as defined hereinabove. The starting materials used in the preparation of the compounds of the invention can be purchased from conventional commercial suppliers or prepared by known methods.

[0074] Scheme 1a: [ka] A compound of formula (I) wherein X is oxygen and R 3 is hydrogen) can be prepared by reaction of a compound of formula (I) (wherein 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) at a temperature between 0°C and 100°C.3 is not hydrogen and is any other R defined above 3 This can be prepared by hydrolysis of the aryl group, which is shown above in Scheme 1a.

[0075] Scheme 2a: [ka] A compound of formula (I) 3 is not hydrogen, and R 2 is SO2C1-C6 alkyl) can be obtained by the reaction of R 2 can be prepared from compounds of formula (Ia) where is SO2C1-C6 alkyl, as shown above in Scheme 2a.

[0076] Scheme 3a: [ka] R 2 Compounds of formula (Ia) where R is S(O)C1-C6 alkyl can be obtained by oxidation with typical oxidizing agents (such as oxone, sodium hypochlorite or metachloroperbenzoic acid) in a suitable solvent under standard conditions to give R 2 can be prepared from a compound of formula (Ib) where is SC1-C6 alkyl. Such oxidation methods will be familiar to those skilled in the art. This is shown above in Scheme 3a.

[0077] Scheme 4a: [ka] R 2Compounds of formula (Ib) where Y is SC1-C6 alkyl can be prepared from compounds of formula (Ic) where Y is F in the presence of a methanethiol salt (such as sodium methanethiol) and in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at room temperature. This is shown above in Scheme 4a.

[0078] Scheme 5a: [ka] Compounds of formula (Ic) where Y is F can be prepared from compounds of formula (DI) optionally in the presence of 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 low temperature (0° C.), as shown above in Scheme 5a.

[0079] Scheme 6a: [ka] Compounds of formula (DI), where Y is F and X is oxygen, can be prepared from the reaction of a β-ketoester of formula (BI), where LG is a suitable leaving group (such as F, Cl, or Br), 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 (EI) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 6a.

[0080] Scheme 7a: [ka] A compound of formula (BI) wherein Y is F, X is oxygen, and R 3 is not hydrogen) can be obtained by the reaction of R 3 is hydrogen. Compounds of formula (CI) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 7a.

[0081] Similarly, R 5 Compounds of the invention where X, R are methyl can also be prepared by the alternative routes shown in the following schemes, where, unless otherwise specified, the definition of each of the variables is as defined above for compounds of formula (I). General methods for the production of compounds of formula (I) are set forth below. Unless otherwise specified in the context, X, R 1 , R 2 and R 3 is as defined hereinabove. The starting materials used in the preparation of the compounds of the invention can be purchased from conventional commercial suppliers or prepared by known methods.

[0082] Scheme 1b: [ka] A compound of formula (I) wherein X is oxygen and R 3 is hydrogen) can be prepared by reaction of a compound of formula (I) (wherein 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) at a temperature between 0°C and 100°C. 3 is not hydrogen and is any other R defined above 3 This can be prepared by hydrolysis of the aryl group, which is shown above in Scheme 1b.

[0083] Scheme 2b: [ka] A compound of formula (I) 3 is not hydrogen, and R 2 is SO2C1-C6 alkyl) can be obtained by the reaction of R 2 can be prepared from compounds of formula (Ia) where is SO2C1-C6 alkyl, as shown above in Scheme 2b.

[0084] Scheme 3b: [ka] R 2 Compounds of formula (I-ai) where R is S(O)C1-C6 alkyl can be obtained by oxidation with typical oxidizing agents (such as oxone, sodium hypochlorite or metachloroperbenzoic acid) in a suitable solvent under standard conditions to give R 2 can be prepared from a compound of formula (I-ci) where is SC1-C6 alkyl. Such oxidation methods will be familiar to those skilled in the art. This is shown above in Scheme 3b.

[0085] Scheme 4b: [ka] R 2 Compounds of formula (I-ci) where LG is a SC1-C6 alkyl can be prepared from compounds of formula (D-II) where LG is a suitable leaving group such as F, optionally in the presence of 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 temperature (100°C). This is shown above in Scheme 4b.

[0086] Scheme 5b: [ka] Compounds of formula (D-II) (wherein R 2 (wherein E is an SC-C alkyl and LG is a suitable leaving group such as F) can be prepared from compounds of formula (B-II) with arenediazonium salts. The arenediazonium salts can be prepared in situ by diazotization of anilines of formula (E-II) with sodium nitrite in water in the presence of an acid (such as hydrochloric acid), followed by reaction with compounds of formula (B-II) 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 temperatures between 0°C and 25°C. Compounds of formula (E-II) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 5b.

[0087] Scheme 6b: [ka] Compounds of formula (B-II) 2 is an SC1-C6 alkyl, Y is F, and X is oxygen) can be converted to R 3 can be prepared from compounds of formula (C-II) where is hydrogen, as shown above in Scheme 6b.

[0088] Scheme 7b: [ka] Compounds of formula (C-II) 2 is an SC1-C6 alkyl, X is oxygen, and R 3is hydrogen) can be converted to R in the presence of a methanethiol salt (such as sodium methanethiol) and a suitable base (such as lithium bis(trimethylsilyl)azanide) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at elevated temperature (80° C.). 3 is hydrogen. Compounds of formula (G-II) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 7b.

[0089] 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).

[0090] 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.

[0091] 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.

[0092] 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®.

[0093] 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.

[0094] 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®.

[0095] 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.

[0096] 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).

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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).

[0101] 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).

[0102] 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).

[0103] 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).

[0104] 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).

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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)).

[0112] Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.

[0113] Suitable cationic SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0114] 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.

[0115] Suitable amphoteric forms of SAA include betaines, propionates and glycinates.

[0116] 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.

[0117] Suitable suspending agents include hydrocolloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage, and fruits.

[0125] 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.

[0126] Pesticides referred to herein using common names are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] The following table shows individual compounds of formula (I) according to the present invention: [ka] Examples of compounds of the formula are shown below.

[0133] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10] [Table 1-11] [Table 1-12] [Table 1-13] [Table 1-14] [Table 1-15] [Table 1-16] [Table 1-17]

[0134] Table A-1 provides 768 compounds A-1.001 to A-1.768 of formula (I), where R 1 is 4-(trifluoromethoxy)phenyl, and R 3 is hydrogen and R 6 is hydrogen, X is oxygen, and R 2 , R 4 and R 5 is as defined in Table 1.

[0135] Table A-2 provides 768 compounds of formula (I), A-2.001 to A-2.768, where R 1 is 4-(trifluoromethoxy)phenyl, and R 3 is methyl and R 6 is hydrogen, X is oxygen, and R 2 , R 4 and R 5 is as defined in Table 1.

[0136] Table A-3 provides 768 compounds of formula (I), A-3.001 to A-3.768, where R 1 is 4-(trifluoromethoxy)phenyl, and R 3 is ethyl, and R 6 is hydrogen, X is oxygen, and R 2 , R 4 and R 5 is as defined in Table 1.

[0137] Table A-4 provides 768 compounds of formula (I), A-4.001 to A-4.768, where R 1 is 4-chlorophenyl, and R 3 is hydrogen and R 6 is hydrogen, X is oxygen, and R 2 , R 4 and R 5 is as defined in Table 1.

[0138] Table A-5 provides 768 compounds of formula (I), A-5.001 to A-5.768, where R 1 is 4-chlorophenyl, and R 3 is methyl and R 6 is hydrogen, X is oxygen, and R 2 , R 4 and R 5 is as defined in Table 1.

[0139] Table A-6 provides 768 compounds of formula (I), A-6.001 to A-6.768, where R 1 is 4-chlorophenyl, and R 3 is ethyl, and R 6 is hydrogen, X is oxygen, and R 2 , R 4 and R 5 is as defined in Table 1.

[0140] Formulation example

[0141] [Table 2]

[0142] 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.

[0143] [Table 3]

[0144] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0145] 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%

[0146] Emulsions of any required dilution that can be used in plant protection can be obtained from this concentrate by dilution with water.

[0147] [Table 4]

[0148] 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.

[0149] Extruded Granules Active ingredient [compound of formula (I)] 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0150] 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.

[0151] Coated Granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0152] The finely ground active ingredient is applied uniformly in a mixer to kaolin moistened with polyethylene glycol, resulting in coated, dust-free granules.

[0153] 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%

[0154] 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.

[0155] 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%

[0156] 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.

[0157] 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 10 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 S(O) n C 1 ~C 6 Alkyl, S(O) n C 1 ~C 6 Haloalkyl or S(O) n C 3 ~C 6 is cycloalkyl; n is 0, 1 or 2; R 3 is hydrogen, C 1 ~C 12 Alkyl, C 1 ~C 6 Haloalkyl, Cyano C 1 ~C 6 Alkyl, 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 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkoxycarbonyl C 1 ~C 6 Alkyl, N,N-di(C 1 ~C 6 Alkyl)amino C 1 ~C 6 Alkyl, phenyl, phenyl C 1 ~C 12 Alkyl, benzyloxy C 1 ~C 6 alkyl, heterocyclyl, wherein the heterocyclyl moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms independently selected from N, O, and S; and the phenyl and heterocyclyl moieties are R 8 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, C 1 ~C 6 Alkylsulfinyl or C 1 ~C 6 alkylsulfonyl; or Any two adjacent R 7 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, said heterocyclyl 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 and C 1 ~C 3 selected from alkoxy; R 10 is hydrogen, C 1 ~C 3 Alkyl or C 1 ~C 3 alkoxy) or a salt or N-oxide thereof. 〔2〕R 1 is R 7 The compound according to [1] above, wherein the phenyl is optionally substituted with one or two groups, which may be the same or different, and is represented by the following formula: 〔3〕R 2 is S(O) n C 1 ~C 3 Alkyl, S(O) nC 1 ~C 3 Haloalkyl or S(O) n C 3 ~C 4 The compound according to [1] or [2] above, which is cycloalkyl. 〔4〕R 2 is methylsulfanyl, methylsulfonyl, ethylsulfanyl, ethylsulfonyl, 2,2,2-trifluoroethylsulfanyl, 2,2,2-trifluoroethylsulfonyl, cyclopropylsulfanyl, or cyclopropylsulfonyl. 〔5〕R 3 is hydrogen, C 1 ~C 11 Alkyl, 2-chloroethyl, 2,2-difluoroethyl, 2-cyanoethyl, cyclopropylmethyl, 1-cyclopropylethyl, 3-methoxypropyl, 3-methoxy-3-methylbutyl, allyl, 1-methylallyl, 2-chloroallyl, prop-2-ynyl, but-3-ynyl, pent-4-ynyl, methoxycarbonylmethyl, N,N-di(methyl)aminoethyl, phenyl C 3 ~C 9 The compound according to any one of [1] to [4] above, wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic monocyclic ring containing a single oxygen atom. 〔6〕R 4 、R 5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isopropyl, isobutyl, methoxy, and trifluoromethyl. 〔7〕R 4 、R 5 and R 6 The compound according to any one of the above [1] to [6], wherein all of are hydrogen. 〔8〕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 [7], which is alkylsulfonyl. 〔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]

[0158] The following non-limiting examples provide specific methods for synthesizing representative compounds of the present invention referenced in Table 2 below.

[0159] Example 1: Synthesis of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P2) [ka] Step 1: Synthesis of ethyl 3-(2,6-difluorophenyl)-3-oxo-propanoate [ka] To a solution of potassium 3-ethoxy-3-oxopropanoate (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, chloroform) 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).

[0160] Step 2: Synthesis of ethyl (2E)-3-(2,6-difluorophenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate [ka] To a solution of 4-(trifluoromethoxy)aniline (1.10 g, 6.25 mmol) in hydrochloric acid (5.2 mL, 31 mmol) was added a solution of sodium nitrite (0.48 g, 6.87 mmol) in water (1.3 mL) at 0° C. The reaction mixture was stirred at 0° C. for 30 minutes, after which it was added in several portions to a suspension of ethyl 3-(2,6-difluorophenyl)-3-oxopropanoate (2.03 g, 6.25 mmol) and potassium acetate (3.1 g, 31.2 mmol) in water (1.2 mL). The reaction mixture was stirred for 2.75 hours, after which the solution was decanted, leaving a red gum. This was dissolved in ethyl acetate, dried over magnesium sulfate, and evaporated to dryness under reduced pressure to give the desired product as a red solid (2.6 g, 6.25 mmol, 64%). 1 H NMR (400 MHz, chloroform) δ = 7.45-7.41 (m, 3H), 7.18-7.11 (m, 2H), 7.05-7.00 (m, 2H), 4.49-4.35 (m, 2H), 1.50-1.35 (m, 3H)

[0161] Step 3: Synthesis of ethyl 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of ethyl (2Z)-3-(2,6-difluorophenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (2.16 g, 5.179 mmol) in N,N-dimethylformamide (10 mL) was added potassium carbonate (0.58 g, 5.697 mmol). The reaction was heated and mixed at 100 °C for 3.5 h. The cooled reaction mixture was diluted with water and extracted twice into diethyl ether. The combined organic extracts were dried over magnesium sulfate and evaporated to dryness under reduced pressure to give a red solid. Trituration with cyclohexane gave the desired product as an off-white solid (1.2 g, 3.02 mmol, 58%).1 H NMR (500 MHz, chloroform) δ = 7.61-7.54 (m, 3H), 7.50-7.38 (m, 2H), 7.15-7.04 (m, 1H), 6.97-6.88 (m, 1H), 4.50-4.30 (m, 2H), 1.43-1.33 (m, 3H)

[0162] Step 4: Synthesis of 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid [ka] To a solution of ethyl 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (0.71 g, 1.8 mmol) in tetrahydrofuran (10 mL) was added a solution of lithium hydroxide monohydrate (0.31 g, 7.19 mmol) in water (1.8 mL). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was acidified by the addition of 2 M aqueous hydrochloric acid, and the precipitated solid was collected by filtration and air-dried to give the desired product as an off-white powder (0.65 g, 1.76 mmol, 98%). 1 H NMR (400 MHz, chloroform) δ = 7.82-7.73 (m, 1H), 7.63-7.56 (m, 2H), 7.52-7.46 (m, 2H), 7.36-7.30 (m, 1H), 7.17-7.12 (m, 1H)

[0163] Step 5: Synthesis of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid [ka] To a solution of 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.40 g, 1.1 mmol) in N,N-dimethylformamide (5 mL) was added sodium methanesulfinate (0.34 g, 3.26 mmol). The reaction mixture was heated at 80° C. for 5 hours. The cooled reaction mixture was poured onto ice, and a yellow solid precipitated from the solution. The solid was collected by filtration to give the desired product as a pale yellow powder (0.37 g, 0.85 mmol, 78%). 1 H NMR(400MHz,DMSO-d6)δ=8.34-8.25(m,1H),8.00-7.90(m,1H),7.88-7.83(m,2H),7.75-7.66(m,2H),7.59-7.52(m,1H),3.72-3.63(m,3H)

[0164] Example 2: Synthesis of 5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P1) [ka] To a solution of 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.20 g, 0.53 mmol) in N,N-dimethylformamide (2 mL) was added sodium thiomethoxide (0.11 g, 1.6 mmol) at room temperature. The reaction mixture was heated at 100° C. under microwave irradiation for 1 hour. The reaction mixture was diluted with 2 M aqueous hydrochloric acid, and the precipitated solid was collected by filtration and washed with water to give the desired product as a yellow powder (0.16 g, 0.40 mmol, 75%). 1 H NMR(400MHz,DMSO-d6)δ=7.88-7.78(m,2H),7.75-7.59(m,3H),7.37-7.31(m,1H),6.87-6.81(m,1H),2.49-2.43(m,3H)

[0165] Example 3: Synthesis of methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (Compound P3) [ka] To a suspension of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (0.20 g, 0.47 mmol) in methanol (10 mL) was added concentrated sulfuric acid (0.003 mL, 0.047 mmol). The reaction mixture was heated at 80° C. for 2 hours. Upon cooling, a pale solid precipitated from solution. The solid was collected by filtration, washed with water, and air-dried to give the desired product as an off-white powder (0.18 g, 0.40 mmol, 87%). 1 H NMR (400 MHz, chloroform) δ = 8.49-8.38 (m, 1H), 7.83-7.71 (m, 1H), 7.58-7.53 (m, 2H), 7.51-7.47 (m, 3H), 4.00-3.95 (m, 3H), 3.77-3.66 (m, 3H)

[0166] Example 4: Synthesis of 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid (compound P5) [ka] Step 1: Synthesis of ethyl (2E)-2-[(4-chlorophenyl)hydrazono]-3-(2,6-difluorophenyl)-3-oxo-propanoate [ka] 4-Chloroaniline (1.17 g, 9.2 mmol) was used to prepare ethyl (2E)-3-(2,6-difluorophenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (Example 1; Step 2). 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 (400 MHz, chloroform) 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)

[0167] Step 2: 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 ethyl 5-fluoro-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 (400 MHz, chloroform) 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)

[0168] Step 3: Synthesis of 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylic acid [ka] Prepared for 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Example 1; Step 4) using ethyl 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylate (1.29 g, 3.7 mmol) to give the desired product as an off-white solid (1.15 g, 3.6 mmol, 97%). 1H NMR (500 MHz, chloroform) 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)

[0169] Step 4: Synthesis of 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid [ka] To a solution of 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylic acid (0.20 g, 0.63 mmol) in N,N-dimethylformamide (2 mL) was added sodium methanesulfinate (0.19 g, 1.9 mmol). The reaction mixture was heated at 80° C. under microwave irradiation for 45+45 minutes. The cooled reaction mixture was poured onto ice, and the precipitated solid was collected by filtration to give a pale yellow powder, which was triturated with dichloromethane. Addition of a 9:1 dimethyl sulfoxide / methanol mixture resulted in the precipitation of a white solid, which was collected by filtration to give the desired product as a white solid (0.071 g, 0.19 mmol, 30%). 1 H NMR(400MHz,DMSO-d6)δ=8.36-8.27(m,1H),7.99-7.91(m,1H),7.82-7.68(m,4H),7.61-7.46(m,1H),3.73-3.65(m,3H)

[0170] Example 5: Synthesis of 1-(4-chlorophenyl)-5-methylsulfanyl-4-oxo-cinnoline-3-carboxylic acid [ka] A solution of 1-(4-chlorophenyl)-5-fluoro-4-oxo-cinnoline-3-carboxylic acid (0.20 g, 0.63 mmol) and sodium thiomethoxide (0.13 g, 1.9 mmol) in N,N-dimethylformamide (2 mL) was heated at 80° C. for 60+60 minutes under microwave irradiation. The cooled reaction mixture was diluted with 2 M aqueous hydrochloric acid, resulting in the precipitation of a yellow solid that was insoluble in ethyl acetate or dichloromethane upon extraction. The solid was collected from the aqueous phase by filtration to give the desired product as a bright yellow powder (0.048 g, 0.14 mmol, 22%). 1 H NMR(400MHz,DMSO-d6)δ=7.78-7.75(m,2H),7.72-7.64(m,3H),7.38-7.30(m,1H),6.88-6.84(m,1H),2.48-2.44(m,3H).

[0171] Example 6: Synthesis of 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P6) Step 1: Synthesis of ethyl 3-(3-bromo-2,6-difluoro-phenyl)-3-oxo-propanoate [ka] To a solution of 3-bromo-2,6-difluorobenzoic acid (18 g, 76.0 mmol) in tetrahydrofuran (1.85 mmol) at 0° C. was added 1,1′-carbonyldiimidazole (83.5 mmol) in several portions. The reaction mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was then added dropwise to a suspension of magnesium chloride (114.0 mmol) and potassium ethyl malonate (114.0 mmol) in tetrahydrofuran (1860 mmol). The reaction mixture was heated at 50° C. for 5 hours. The cooled reaction mixture was quenched with 2 M aqueous hydrochloric acid and extracted into ethyl acetate (3×100 mL). The combined organic extracts were washed with saturated aqueous sodium bicarbonate, then brine, dried over sodium sulfate, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-15% ethyl acetate in cyclohexane as eluent to give the desired product as a mixture of keto-enol isomers (15 g).

[0172] Step 2: Synthesis of ethyl (2E)-3-(3-bromo-2,6-difluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate [ka] To a cooled (0°C) mixture of 4-(trifluoromethoxy)aniline (52.3 mmol) in 6 M aqueous hydrochloric acid (261 mmol) was added a solution of sodium nitrite (57.5 mmol) in water (2 mL / mmol) dropwise over 10 minutes. This mixture was stirred at 0°C for 60 minutes, and then to a cooled (0°C) solution of ethyl 3-(3-bromo-2,6-difluoro-phenyl)-3-oxopropanoate (15.0 g, 48.8 mmol) and potassium acetate (244.2 mmol) in methanol (2 mL / mmol) and water (48.8 mmol, 5 mol / L) was added dropwise over 10 minutes. The reaction mixture was stirred at room temperature for 2 hours, after which the reaction mixture was diluted with water (100 mL) and extracted with t-butyl methyl ether (3 x 250 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered and evaporated to dryness under reduced pressure to give the desired product as a yellow solid (22 g).

[0173] Step 3: Synthesis of ethyl 6-bromo-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (and ethyl 8-bromo-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate) [ka] To a solution of ethyl (2Z)-3-(3-bromo-2,6-difluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (8.0 g, 16.2 mmol) in tetrahydrofuran (160 mL) was added portionwise a 60% suspension of sodium hydride in mineral oil (24.2 mmol) at 0 °C under a nitrogen atmosphere. The reaction mixture was stirred at 0 °C for 4 h. The reaction mixture was quenched by the addition of ice-cold water, acidified with 1 M aqueous hydrochloric acid, 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 ethyl acetate in cyclohexane as the eluent to give the desired product isomers (5.1 g).1 H NMR(400MHz,CDCl3):1.41(t,3H),4.45(q,2H),6.88(dd,1H),7.49-7.44(m,2H),7.58-7.53(m,2H),7.74(dd,1H)

[0174] Step 4: Synthesis of ethyl 6-bromo-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (and ethyl 5,6-bis(methylsulfanyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate) [ka] To a solution of ethyl 6-bromo-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (2.5 g, 5.3 mmol) in N,N-dimethylformamide (7 mL / g) at room temperature under a nitrogen atmosphere was added sodium methanethiol (1.2 equiv., 6.3 mmol). The reaction mixture was stirred at room temperature for 3 h. The reaction mixture was quenched by the addition of water (200 mL), acidified with 1 M aqueous hydrochloric acid, and extracted into ethyl acetate (3 × 300 mL). 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 a gradient of 0–20% ethyl acetate in cyclohexane as the eluent to give the desired product (2.0 g) as a yellow solid.

[0175] Step 5: Synthesis of ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of ethyl 6-bromo-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (5.4 g, 11 mmol) in trifluoromethylbenzene (10 mL / mmol) at room temperature under a nitrogen atmosphere was added 3-chloroperbenzoic acid (24 mmol, 70 wt). The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with water (200 mL) and extracted into ethyl acetate (3 × 200 mL). The combined organic extracts were washed with saturated bicarbonate solution (3 × 100 mL) and brine (200 mL), then dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using ethyl acetate in cyclohexane as the eluent to give the desired product (4.6 g). 1 H NMR(400MHz,CDCl3):1.40(t,3H),3.76(s,3H),4.46(q,2H),7.16(d,1H),7.38-7.63(m,4H),7.82(d,1H)

[0176] Step 6: Synthesis of ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (500 mg, 0.934 mmol) in diethylene dioxide (30 mL / g), 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (2.34 mmol), sodium carbonate (1.87 mmol), and water (1 mL / g) were added sequentially, and the resulting reaction mixture was degassed by bubbling nitrogen through for 10 minutes. PdCl(dppf).DCM (0.140 mmol) was added, and the reaction mixture was heated at 85 °C for 20 hours. The reaction mixture was poured onto ice, diluted with water (100 mL), acidified with 1 M aqueous hydrochloric acid, and extracted into ethyl acetate (3 × 50 mL). The combined organic extracts were washed with brine (100 mL), 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 0-20% ethyl acetate in cyclohexane as eluent to give the desired product (0.230 g). 1 H NMR(400MHz,CDCl3):1.40(t,3H),2.82(s,3H),3.77(s,3H),4.46(q,2H),7.24(d,1H),7.44-7.49(m,3H),7.50-7.56(m,2H)

[0177] Step 7: Synthesis of 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid [ka] To a solution of ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (180 mg, 0.383 mmol) in tetrahydrofuran (15 mL / g) was added a solution of lithium hydroxide hydrate (1.53 mmol) in water (2 mL / g). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with water (100 mL) and washed with ethyl acetate. The aqueous phase was acidified by the addition of 1 M aqueous hydrochloric acid and then 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 the desired product as a white solid (0.150 g). 1 H NMR(400MHz,DMSO-d6):2.73(s,3H),3.75(s,3H),7.34(d,1H),7.69(d,3H),7.85(d,2H),13.48-13.71(brs,1H)

[0178] Example 7: Synthesis of 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid (Compound P7) Step 1: Synthesis of 4-bromo-2-fluoro-6-methylsulfanyl-benzoic acid [ka] To a solution of 4-bromo-2,6-difluorobenzoic acid (1.0 g, 4.22 mmol) in tetrahydrofuran (10 mL / g) was added lithium bis(trimethylsilyl)azanide (4.64 mmol) at 0° C. The reaction mixture was stirred at 0° C. for 20 minutes, after which sodium methanethiol (4.64 mmol) was added. The resulting mixture was heated at 80° C. for 3 hours. The cooled reaction mixture was acidified by the addition of 1 M aqueous hydrochloric acid and diluted with ethyl acetate and water. The organic phase was washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give the desired product. 1 H NMR(400MHz,CDCl3):2.48-2.51(m,3H),7.08-7.18(m,1H),7.19(s,1H)

[0179] Step 2: Synthesis of ethyl 3-(4-bromo-2-fluoro-6-methylsulfanyl-phenyl)-3-oxo-propanoate [ka] To a solution of 4-bromo-2-fluoro-6-methylsulfanyl-benzoic acid (1.1 g) in tetrahydrofuran (100 mmol) was added 1,1'-carbonyldiimidazole (5.0 mmol) in several portions at 0 °C. The reaction mixture was warmed to room temperature and stirred for 1 h. The reaction mixture was then added to a suspension of magnesium chloride (6.2 mmol) and potassium ethyl malonate (6.2 mmol) in tetrahydrofuran (100 mmol). The reaction mixture was heated at 50 °C for 18 h. The cooled reaction mixture was quenched by the addition of 2 M aqueous hydrochloric acid and extracted into ethyl acetate. The combined organic extracts were washed with saturated aqueous sodium bicarbonate, then 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 15–20% ethyl acetate in cyclohexane as eluent to give the desired product as a colorless liquid.

[0180] Step 3: Synthesis of ethyl (2E)-3-(4-bromo-2-fluoro-6-methylsulfanyl-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate [ka] To 6 M aqueous hydrochloric acid (20.9 mmol) was added 4-(trifluoromethoxy)aniline (4.18 mmol). The resulting mixture was cooled to 0 °C and placed in an ice bath to which a solution of sodium nitrite (4.60 mmol) in water (2 mL / mmol) was added dropwise. The resulting mixture was stirred at 0 °C for 30 minutes, and then a solution of ethyl 3-(4-bromo-2-fluoro-6-methylsulfanyl-phenyl)-3-oxo-propanoate (1.0 g) and potassium acetate (14.9 mmol) in methanol (2.0 mL / mmol) and water (2.98 mmol) was added dropwise over 10 minutes at 0 °C. Upon completion of the addition, the reaction mixture was stirred at room temperature for 2 hours. The gummy brownish mass that formed was extracted into ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure to give the desired crude product.

[0181] Step 4: Synthesis of ethyl 7-bromo-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of ethyl (2Z)-3-(4-bromo-2-fluoro-6-methylsulfanyl-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazono]propanoate (900 mg) in N,N-dimethylformamide (10 mL) was added potassium carbonate (1.89 mmol). The reaction mixture was heated at 100° C. for 2.5 hours. Cold water was added to the cooled reaction mixture, and the precipitated solid was collected by filtration and air-dried to give the desired product. 1 H NMR(400MHz,DMSO-d6):1.22-1.30(m,3H),2.45-2.47(m,3H),4.30(d,2H),6.82(d,1H),7.30(d,1H),7.67(d,2H),7.83(d,2H)

[0182] Step 5: Synthesis of ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of ethyl 7-bromo-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (650 mg) in acetonitrile (20 mL) was added 3-chloroperbenzoic acid (2.84 mmol, 70% by weight) at 0 °C. The reaction mixture was stirred at room temperature for 18 h. The reaction mixture was quenched by the addition of saturated aqueous potassium carbonate (20 mL) and water (20 mL) and then 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 a gradient of 40–50% ethyl acetate in cyclohexane as eluent to give the desired product. 1 H NMR(400MHz,DMSO-d6):1.23-1.33(m,3H),3.70(s,3H),4.34(q,2H),7.63(d,1H),7.69(d,2H),7.82-7.90(m,2H),8.25(d,1H)

[0183] Step 6: Synthesis of ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate [ka] To a solution of ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (500 mg) in diethylene dioxide (30 mL / g) were added 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (2.34 mmol), sodium carbonate (1.87 mmol), and water (1 mL / g), sequentially. The reaction mixture was degassed by bubbling nitrogen through it for 15 minutes. PdCl2(dppf).DCM (0.14 mmol) was added, and the reaction mixture was heated at 100 °C for 2 hours. The reaction mixture was diluted with ethyl acetate, washed with water, then brine, then 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 40–50% ethyl acetate in cyclohexane as the eluent to give the desired product. 1 H NMR(400MHz,CDCl3):7.56-7.50(m,2H),7.49-7.44(m,3H),7.24(d,1H),4.46(q,2H),3.77(s,3H),2.82(s,3H),1.40(t,3H)

[0184] Step 7: Synthesis of 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid [ka] To a solution of ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate (200 mg) in tetrahydrofuran (10 mL) was added a suspension of lithium hydroxide hydrate (3 equivalents, 1.276 mmol) in water (1 mL / g). The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was acidified by the addition of 2 M aqueous hydrochloric acid and diluted with additional water. The precipitated solid was collected by filtration, washed with t-butyl methyl ether, and air-dried to give the desired product. 1H NMR(400MHz,DMSO-d6):14.26-13.44(m,1H),8.16-8.14(m,1H),7.70(d,2H),7.84(d,2H),7.35(s,1H),3.67(s,3H),2.49-2.47(m,3H)

[0185] Table 5-1 Table 5-2 Table 5-3 Table 5-4 Table 5-5 Table 5-6 Table 5-7 Table 5-8 Table 5-9 Table 5-10 Table 5-11 Table 5-12 Table 5-13 Table 5-14 Table 5-15 Table 5-16 Table 5-17 Table 5-18 Table 5-19 Table 5-20 Table 5-21 Table 5-22 Table 5-23 Table 5-24 Table 5-25 Table 5-26 Table 5-27 Table 5-28 Table 5-29 Table 5-30

[0186] 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), Abutilon theophrasti (ABUTH), and Zea mays (ZEAMX)) were sown in standard soil in pots. 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 formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Unless otherwise stated, the compounds are applied at 1000 g / h. The test plants are then cultivated in a greenhouse under controlled greenhouse conditions (24 ° C / 16 ° C, day / night; 14 hours of light; 65% humidity), watering twice a day. 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).

[0187] [Table 6-1] [Table 6-2]

[0188] [Table 7-1] [Table 7-2]

Claims

1. 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid, 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, ethyl 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 5-ethylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 5-ethylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, ethyl 5-methylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, ethyl 5-cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 5-cyclopropylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid, ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfanyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid, ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylate, 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylate, ethyl 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 6-cyano-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 6-bromo-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-fluoro-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-cyano-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, methyl 7-methoxy-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, ethyl 7-methoxy-5-methylsulfanyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, hexyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, undecyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2-chloroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, pent-4-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, cyclopropylmethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 1-methylallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, isopropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2-chloroallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2,2-difluoroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2,2-dimethylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 3-methoxypropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, tetrahydrofuran-3-yl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, but-3-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, isobutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2-cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 1-cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, pentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2-(dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, heptyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, prop-2-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, allyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, (2-methoxy-2-oxo-ethyl)5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, nonyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 9-phenylnonyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 3-phenylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, (3-methoxy-3-methyl-butyl)5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 3,3-dimethylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 2-cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, 4-benzyloxybutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate, S-octyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate, S-Isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate and S-(3-phenylpropyl)5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cinnoline-3-carbothioate Selected from: or a salt thereof.

2. 10. A herbicidal composition comprising the compound of claim 1 and an agriculturally acceptable formulation adjuvant.

3. 3. The herbicidal composition of claim 2 further comprising at least one additional pesticide.

4. 4. The herbicidal composition of claim 3, wherein the additional pesticide is a herbicide or a herbicide safener.

5. 10. A method for controlling undesired plant growth, comprising the step of applying to the undesired plants or their habitat a compound of claim 1 or a herbicidal composition of any one of claims 2 to 4.

6. 10. Use of the compound according to claim 1 as a herbicide.

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