Herbicidal cinnoline derivatives

Abstract

Compounds of formula (I), wherein the substituents are as defined in claim 1. The present application further relates to herbicidal compositions comprising a compound of formula (I) and to the use of compounds of formula (I) for controlling weeds, in particular in crops of useful plants.

Description

[0001] This invention relates to herbicidal oxaloline derivatives having herbicidal activity, for example, as active ingredients. The invention also relates to agricultural chemical compositions comprising at least one of these oxaloline derivatives, methods for preparing these compounds, and the use of these oxaloline derivatives or compositions in agriculture or horticulture for controlling weeds, particularly in crops with beneficial plants.

[0002] EP 0273325, EP 0274717, and US 5183891 describe cinroline derivatives as herbicides.

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

[0004]

[0005] in

[0006] X is O, NR 10 Or S;

[0007] R 1 It can be optionally assigned to 1, 2, 3, or 4 identical or different terms by R. 7 The group represents a phenyl group that has been substituted.

[0008] R 2 It is S(O) n C1-C6 alkyl groups, S(O) n C1-C6 haloalkyl, or S(O) n C3-C6 cycloalkyl;

[0009] n is 0, 1, or 2;

[0010] R 3 It is hydrogen, C1-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, benzyloxy C1-C6 alkyl, heterocyclic moiety, wherein the heterocyclic moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring comprising one or two heteroatoms individually selected from N, O, and S, and wherein the phenyl and heterocyclic moiety may optionally be surrounded by one, two, three, or four atoms that may be the same or different from R 8 The group to be represented is substituted;

[0011] R 4 R 5and R 6 Each is independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylthioalkyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl.

[0012] R 7 It is a halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylthioalkyl, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl; or

[0013] Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclic ring containing one or two heteroatoms selected from O and N, wherein the heterocyclic ring can optionally be composed of 1, 2, 3, or 4 identical or different atoms of R. 9 The group to be represented is substituted;

[0014] R 8 and R 9 Each is independently selected from halogens, C1-C3 alkyl groups, and C1-C3 alkoxy groups;

[0015] R 10 It is hydrogen, C1-C3 alkyl, or C1-C3 alkoxy;

[0016] Or its salts or N-oxides.

[0017] Surprisingly, it has been found that novel compounds of formula (I) have very favorable levels of herbicidal activity for practical purposes.

[0018] According to a second aspect of the invention, an agricultural chemical composition is provided comprising a herbicidally effective amount of the compound of formula (I) according to the invention. This agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0019] According to a third aspect of the invention, a method for controlling weeds at a site is provided, comprising applying to the site a weed-controlling amount of a composition comprising a compound having formula (I).

[0020] According to a fourth aspect of the invention, the use of a compound having formula (I) as a herbicide is provided.

[0021] When substituents are indicated as "optionally substituted," this means that they may or may not have one or more of the same or different substituents, for example, one, two, or three substituents. For example, C1-C8 alkyl groups substituted with one, two, or three halogens may include, but are not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3 groups. As another example, C1-C6 alkoxy groups substituted with one, two, or three halogens may include, but are not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups.

[0022] As used in this article, the term "cyano" refers to the -CN group.

[0023] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo).

[0024] As used in this article, the term "hydroxyl group" refers to the -OH group.

[0025] As used in this article, the term "C1-C" 12 "Alkyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, which is unsaturated, has one to twelve carbon atoms, and is attached to the remainder of the molecule by single bonds. "C1-C" 11 "alkyl", "C1-C6 alkyl", "C1-C4 alkyl", and "C1-C3 alkyl" should be interpreted accordingly. 12 Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, and their isomers, such as isopropyl. "C1-C" 12 "alkylene group" refers to C1-C 12 The corresponding definition of alkyl differs in that this group is attached to the remainder of the molecule by two single bonds. The terms "C1-C6 alkylene", "C1-C3 alkylene", and "C1-C2 alkylene" should be interpreted accordingly. C1-C 12 Examples of alkylene groups include, but are not limited to, -CH2-, -CH2CH2- and -(CH2)3-.

[0026] As used herein, the term "cyanoC1-C6 alkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted with one or more cyano groups as defined above. Cyano C 1- Examples of C6 alkyl groups include, but are not limited to, 2-cyanoethyl.

[0027] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted with one or more of the same or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted accordingly. Examples of C1-C6 haloalkyl groups include, but are not limited to, trifluoromethyl and 2,2,2-trifluoroethyl.

[0028] As used herein, the term "C1-C6 alkoxy" refers to an alkoxy group having the formula -OR a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms “C1-C4 alkoxy” and “C1-C3 alkoxy” should be interpreted accordingly. Examples of C1-C6 alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0029] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as generally defined above, substituted with one or more of the same or different halogen atoms. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted accordingly. Examples of C1-C6 haloalkoxy groups include, but are not limited to, trifluoromethoxy.

[0030] As used herein, the term "C1-C6 alkoxy-C1-C6 alkyl" refers to a compound having the formula R b OR a - groups, where R b It is a C1-C6 alkyl group as generally defined above, and R a It is a C1-C6 alkylene group as generally defined above.

[0031] As used herein, the term "C1-C6 alkoxycarbonyl C1-C6 alkyl" refers to a C1-C6 alkyl group having the formula R a OC(O)R b - groups, where R a It is a C1-C6 alkyl group as generally defined above, and R b It is a C1-C6 alkylene group as generally defined above.

[0032] As used herein, the term "N,N-di(C1-C6 alkyl)aminoC1-C6 alkyl" refers to an amino group having the formula -R c N(R a (R) b ) groups, wherein R a and R b Each is individually a C1-C6 alkyl group as generally defined above, and R c It is a C1-C6 alkylene group as generally defined above.

[0033] As used herein, the term "C2-C6 alkenyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one double bond of (E)- or (Z)- configuration, having two to six carbon atoms attached to the remainder of the molecule by single bonds. The term "C2-C3 alkenyl" should be interpreted accordingly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl, propyl-1-alkenyl, propyl-2-alkenyl, and but-1-alkenyl.

[0034] 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 of the same or different halogen atoms. Examples of C2-C6 haloalkenyl groups include, but are not limited to, 2-chloroallyl.

[0035] As used herein, the term "C2-C6 ynyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one triple bond, having two to six carbon atoms, and attached to the remainder of the molecule by single bonds. The term "C2-C3 ynyl" should be interpreted accordingly. Examples of C2-C6 ynyl groups include, but are not limited to, ethynyl, propynyl, and butynyl.

[0036] As used herein, the term "C3-C6 cycloalkyl" refers to a monocyclic saturated ring system containing 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0037] As used herein, the term “C3-C6 cycloalkyl C1-C6 alkyl” refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule via a C1-C6 alkylene linker as defined above.

[0038] As used herein, the term "phenyl C1-C" 12 "Alkyl" refers to a compound formed by C1-C as defined above. 12 An alkylene linker is attached to the remaining benzene ring of the molecule. The term "phenyl C1-C" is used. 11 "alkyl" and "phenyl C1-C3 alkyl" should be interpreted accordingly.

[0039] As used herein, the term "benzyloxy C1-C6 alkyl" refers to a compound having the formula -R a OR b The group, wherein R a It is a C1-C6 alkylene group as generally defined above, and R b It is benzyl.

[0040] As used herein, the term "C1-C6 alkylthioalkyl" refers to a compound having the formula -SR a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkylthioalkyl" and "C1-C3 alkylthioalkyl" should be interpreted accordingly. Examples of C1-C6 alkylthioalkyl groups include, but are not limited to, methylthioalkyl.

[0041] As used herein, the term "C1-C6 alkylsulfinyl" refers to a group having the formula -S(O)R a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkyl sulfinyl" and "C1-C3 alkyl sulfinyl" should be interpreted accordingly. Examples of C1-C6 alkyl sulfinyl groups include, but are not limited to, methyl sulfinyl groups.

[0042] As used herein, the term "C1-C6 alkylsulfonyl" refers to an alkyl group having the formula -S(O)2R a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted accordingly. Examples of C1-C6 alkylthioalkyl groups include, but are not limited to, methylsulfonyl.

[0043] As used herein, the term "heterocyclic group" refers to a stable 5- or 6-membered non-aromatic monocyclic ring containing one or two heteroatoms, wherein these heteroatoms are selected individually from nitrogen and oxygen. Heterocyclic groups can be bonded to the remainder of the molecule via carbon atoms or heteroatoms. Examples of heterocyclic groups include, but are not limited to, acridine, aziridine, oxadiazine, tetrahydrofuran, pyrrolidinyl, pyrazolyl, imidazoalkyl, piperidinyl, piperazinyl, morpholinyl, and dioxopentyl.

[0044] The presence of one or more possible stereoisomers in a compound having formula (I) means that the compound can exist in optical isomeric form (i.e., enantiomers or diastereomers). As a result of restricted rotation around the single bond, transisomers may also exist. Formula (I) is intended to include all such possible isomeric forms and mixtures thereof. This invention includes all such possible isomeric forms of compounds having formula (I) and mixtures thereof. Similarly, formula (I) is intended to include all possible tautomers. This invention includes all possible tautomeric forms of compounds having formula (I).

[0045] In each case, the compound having formula (I) according to the invention is in free form, oxidized form (such as N-oxide), or salt form (e.g., an agronomically usable salt form). It is preferred that the compound having formula (I) forms a salt with: amines, including primary, secondary, and tertiary amines (e.g., ammonia, dimethylamine, and triethylamine), alkali metal and alkaline earth metal bases, transition metal or quaternary ammonium bases.

[0046] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. For example, they are described by A. Albini and S. Pietra in their book "Heterocyclic N-oxides" published by CRC Press, Boca Raton (1991).

[0047] For compounds having formula (I), the following list provides information on substituents X, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 The definitions, including preferred definitions, are provided below. For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0048] 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 yet another set of embodiments, X is S.

[0049] R 1 It can be optionally assigned to 1, 2, 3, or 4 identical or different terms by R. 7 The group represented is a phenyl group that has been substituted. Preferably, R 1 It can be optionally assigned to 1, 2, or 3 identical or different terms by R. 7 The group represented is a phenyl group that has been substituted. More preferably, R 1 It is optional to be one or two that can be the same or different by R 7 The group represented is a substituted phenyl group. More preferably, R 1 It is arbitrarily assigned to one of R 7 The group represented is a phenyl group that has been substituted. Even more preferably, R 1 It is in the position that is single by R 7 The group indicated is a substituted phenyl group.

[0050] In one set of embodiments, R1 It is 4-(trifluoromethoxy)phenyl, 4-chlorophenyl, 2,4-dichlorophenyl, or 4-chloro-2-fluorophenyl.

[0051] In another set of embodiments, R 1 It is 4-(trifluoromethoxy)phenyl or 4-chlorophenyl.

[0052] R 2 It is S(O) n C1-C6 alkyl groups, S(O) n C1-C6 haloalkyl, or S(O) n C3-C6 cycloalkyl. Preferably, R 2 It is S(O) n C1-C4 alkyl groups, S(O) n C1-C4 haloalkyl, or S(O) n C 3- C5 cycloalkyl. More preferably, R 2 It is S(O) n C1-C3 alkyl groups, S(O) n C1-C3 haloalkyl, or S(O) n C3-C4 cycloalkyl. Even more preferably, R 2 It is methyl thioalkyl, methyl sulfinyl, methyl sulfonyl, ethyl thioalkyl, ethyl sulfinyl, ethyl sulfonyl, n-propyl thioalkyl, n-propyl sulfinyl, n-propyl sulfonyl, isopropyl thioalkyl, isopropyl sulfinyl, isopropyl sulfonyl, 2,2,2-trifluoroethyl thioalkyl, 2,2,2-trifluoroethyl sulfinyl, 2,2,2-trifluoroethyl sulfonyl, cyclopropyl thioalkyl, cyclopropyl sulfinyl, or cyclopropyl sulfonyl. More preferably, R 2 It is methyl thioalkyl, methyl sulfinyl, methyl sulfonyl, ethyl thioalkyl, ethyl sulfinyl, ethyl sulfonyl, 2,2,2-trifluoroethyl thioalkyl, 2,2,2-trifluoroethyl sulfinyl, 2,2,2-trifluoroethyl sulfonyl, cyclopropyl thioalkyl, cyclopropyl sulfinyl, or cyclopropyl sulfonyl. Even more preferably, R 2 It is methyl thioalkyl, methyl sulfonyl, ethyl thioalkyl, ethyl sulfonyl, 2,2,2-trifluoroethyl thioalkyl, 2,2,2-trifluoroethyl sulfonyl, cyclopropyl thioalkyl, or cyclopropyl sulfonyl. Even more preferably, R 2 It is a methylthioalkyl or methylsulfonyl group.

[0053] 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 yet another set of embodiments, n is 1. In still another set of embodiments, n is 2.

[0054] R 3It is hydrogen, C1-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, benzyloxy C1-C6 alkyl, heterocyclic moiety, wherein the heterocyclic moiety is a 4-, 5-, or 6-membered non-aromatic monocyclic ring comprising one or two heteroatoms individually selected from N, O, and S, and wherein the phenyl and heterocyclic moiety may optionally be surrounded by one, two, three, or four atoms that may be the same or different from R 8 The group substitution is indicated.

[0055] Preferably, R 3 It is hydrogen, C1-C 12 Alkyl, C1-C4 haloalkyl, cyanoC1-C3 alkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C3 alkoxyC1-C6 alkyl, C2-C5 alkenyl, C2-C4 haloalkenyl, C2-C6 alkynyl, C1-C3 alkoxycarbonylC1-C3 alkyl, N,N-di(C1-C3 alkyl)aminoC1-C3 alkyl, phenylC1-C 12 Alkyl, benzyloxy C1-C4 alkyl, or heterocyclic moiety, wherein the heterocyclic moiety is a 5- or 6-membered non-aromatic monocycle containing one or two heteroatoms individually selected from N, O, and S.

[0056] More preferably, R 3 It is hydrogen, C1-C 12 Alkyl, C1-C3 haloalkyl, cyanoC1-C3 alkyl, cyclopropylC1-C3 alkyl, C1-C3 alkoxyC1-C5 alkyl, C2-C4 alkenyl, C2-C3 haloalkenyl, C3-C5 alkynyl, C1-C2 alkoxycarbonylC1-C2 alkyl, N,N-di(methyl)aminoC1-C3 alkyl, phenylC1-C 12 Alkyl, benzyloxy C1-C4 alkyl, or heterocyclic moiety, wherein the heterocyclic moiety is a 5- or 6-membered non-aromatic monocycle containing one or two heteroatoms individually selected from N, O, and S.

[0057] Even more preferably, R 3 It is hydrogen, C1-C 11Alkyl, 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 heterocyclic, wherein the heterocyclic moiety is a 5- or 6-membered non-aromatic monocyclic ring containing a single oxygen atom.

[0058] Even more preferably, R 3 It 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, penta-4-ynyl, methoxycarbonylmethyl, N,N-di(methyl)aminoethyl, 9-phenylnonyl, 3-phenylpropyl, benzyloxybutyl, or tetrahydrofuran-3-yl.

[0059] In one set of embodiments, R 3 It is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, or phenylC1-C3 alkyl, wherein the phenyl moiety may optionally be composed of 1, 2, 3 or 4 identical or different R 8 The indicated group is substituted. More preferably, R 3 It 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, wherein the phenyl moiety may optionally be composed of 1, 2, or 3 identical or different atoms, derived from R. 8 The group indicated is substituted. Even more preferably, R 3 It 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, wherein the phenyl moiety may optionally be composed of one or two identical or different atoms, derived from R. 8 The indicated group substitution. More preferably, R 3 It is hydrogen or a C1-C4 alkyl group. Most preferably, R 3It is hydrogen, methyl, or ethyl, especially hydrogen or methyl.

[0060] R 4 R 5 and R 6 Each is independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylthioalkyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl. Preferably, R 4 R 5 and R 6 Each is independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, and C1-C4 alkylsulfonyl. More preferably, R 4 R 5 and R 6 Each is independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylthioalkyl, C1-C3 alkylsulfinyl, and C1-C3 alkylsulfonyl. More preferably, R 4 R 5 and R 6 Each is independently selected from hydrogen, fluorine, bromine, cyano, C1-C4 alkyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthioalkyl, and methylsulfonyl. Even more preferably, R 4 R 5 and R 6 Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isopropyl, isobutyl, methoxy, and trifluoromethyl. More preferably, R 4 R 5 and R 6 Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isobutyl, methoxy, and trifluoromethyl. Even more preferably, R 4 R 5 and R 6 Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isobutyl, and methoxy.

[0061] In one set of embodiments, R 4 and R 5 Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isobutyl, methoxy, and trifluoromethyl, and R 6 It is hydrogen. In another set of embodiments, R 4 and R 5Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isobutyl, and methoxy, and R 6 It is hydrogen. In another set of embodiments, R 4 R 5 and R 6 They're all hydrogen.

[0062] In another preferred embodiment, R 4 and R 5 Each is independently selected from hydrogen, fluorine, bromine, methyl, isobutyl, methoxy, and trifluoromethyl, and R 6 It is hydrogen. In another set of embodiments, R 4 and R 5 Each is independently selected from hydrogen, fluorine, bromine, methyl, isobutyl, and methoxy, and R 6 It is hydrogen.

[0063] R 7 It is a halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylthioalkyl, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl; or

[0064] Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclic ring containing one or two heteroatoms selected from O and N, wherein the heterocyclic ring can optionally be composed of 1, 2, 3, or 4 identical or different atoms, formed by R. 9 The group substitution is indicated.

[0065] Preferably, R 7 It is a halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylthioalkyl, C1-C3 alkylsulfinyl, or C1-C3 alkylsulfonyl; or

[0066] Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclic base ring containing one or two heteroatoms selected from O and N, wherein the heterocyclic base ring can optionally be composed of one, two, or three atoms that may be the same or different, formed by R. 9 The group substitution is indicated.

[0067] More preferably, R 7 It is a halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylthioalkyl, C1-C3 alkylsulfinyl, or C1-C3 alkylsulfonyl.

[0068] Even more preferably, R 7 It is fluorine, bromine, chlorine, cyano, methyl, ethyl, isopropyl, isobutyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthioalkyl, methylsulfinyl, or methylsulfonyl; or

[0069] Any two adjacent R 7 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclic base ring containing one or two heteroatoms selected from O and N, wherein the heterocyclic base ring can optionally be composed of one or two identical or different atoms of R. 9 The group indicated is substituted. Even more preferably, R 7 It is fluorine, bromine, chlorine, cyano, methyl, methoxy, trifluoromethyl, or trifluoromethoxy. Even more preferably, R 7 It is fluorine, chlorine, or trifluoromethoxy. More preferably, R 7 It is chlorine or trifluoromethoxy.

[0070] In one set of embodiments, R 7 It is a halogen or a C1-C3 haloalkoxy group.

[0071] R 8 and R 9 Each is independently selected from halogens, C1-C3 alkyl groups, and C1-C3 alkoxy groups. Preferably, R 8 and R 9 Each is independently selected from chlorine, bromine, fluorine, methyl, and methoxy.

[0072] R 10 It is hydrogen, C1-C3 alkyl, or C1-C3 alkoxy. Preferably, R 10 It is hydrogen, methyl, or methoxy. More preferably, R 10 It is hydrogen.

[0073] In the compound having formula (I) according to the invention, preferably:

[0074] X is O;

[0075] R 1 It is arbitrarily assigned to one of R 7 The group represents a phenyl group that has been substituted.

[0076] R 2 It is S(O) n C1-C3 alkyl groups, S(O) n C1-C3 haloalkyl, or S(O) n C3-C4 cycloalkyl

[0077] R 3 It is hydrogen or C1-C4 alkyl;

[0078] R 4 R 5 and R 6 Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isobutyl, methoxy, and trifluoromethyl; and

[0079] R 7 It is fluorine, bromine, chlorine, cyano, methyl, methoxy, trifluoromethyl, or trifluoromethoxy.

[0080] In another set of embodiments, X is O;

[0081] R 1 It is arbitrarily assigned to one of R 7 The group represents a phenyl group that has been substituted.

[0082] R 2 It is S(O) n C1-C3 alkyl groups, S(O) n C1-C3 haloalkyl, or S(O) n C3-C4 cycloalkyl

[0083] R 3 It is hydrogen, methyl, or ethyl;

[0084] R 4 and R 5 Each is independently selected from hydrogen, fluorine, bromine, cyano, methyl, isobutyl, methoxy, and trifluoromethyl;

[0085] R 6 It is hydrogen; and

[0086] R 7 It is fluorine, bromine, chlorine, cyano, methyl, methoxy, trifluoromethyl, or trifluoromethoxy.

[0087] In another set of embodiments,

[0088] X is O;

[0089] R 1 It is 4-(trifluoromethoxy)phenyl or 4-chlorophenyl;

[0090] R 2 It is a methyl thioalkyl or methyl sulfonyl group;

[0091] R 3 It is hydrogen or methyl;

[0092] R 4 R 5 and R 6 They're all hydrogen.

[0093] In a particularly preferred embodiment, the compound having formula (I) is selected from:

[0094] 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P2), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P3), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P5), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P7), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid, Ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P8), ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P9), ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P10), ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P11), ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P12), ethyl 7 ... [4-(trifluoromethoxy)phenyl] cenline-3-carboxylic acid (compound P13), 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cenline-3-carboxylic acid (compound P14), 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cenline-3-carboxylic acid (compound P15), 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cenline-3-carboxylic acid (compound P18), 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cenline-3-carboxylic acid (compound P19), 7-fluoro ... [5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P21), ethyl 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P22), ethyl 5-ethylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P23), ethyl 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P24), ethyl 5-ethylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P25), ethylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P26).5-Ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P27), ethyl 5-methylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P28), 5-cyclopropylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P30), ethyl 5-cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P32), ethyl 5-cyclopropylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P33), 4-oxo-5-(2,2,2-trifluoroethyl) 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P35), 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P37), 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P38), 4-oxo-5-(2,2,2-trifluoroethylthioalkyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P39), 4-oxo-5-(2,2,2-trifluoroethylsulfinyl ...5), 4-oxo- Ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P41), ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P42), ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P43), ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P44), ethyl 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P45), ethyl 7-isobutyl-5- Ethyl methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P46), ethyl 6-cyano-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P47), ethyl 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P49), ethyl 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P50), and ethyl 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P52).6-Bromo-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P53), 7-fluoro-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P54), 7-cyano-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P55), 7-methoxy-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid methyl ester (compound P56 ...4), 7-methoxy-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid methyl ester (compound P55), 7-methoxy-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid methyl Ethyl 3-carboxylate (compound P57), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P59), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate undecyl ester (compound P60), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate 2-chloroethyl ester (compound P61), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate pentyl-4-alkynyl ester (compound P62), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate pentyl-4-alkynyl ester (compound P62), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate pentyl-4-alkynyl ester Cyclopropyl methyl 5-methanesulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 1-methylallyl ester (compound P64), isopropyl 5-methanesulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P65), 2-chloroallyl 5-methanesulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P66), 2,2-difluoroethyl 5-methanesulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P67), 5-methanesulfonyl-4-oxo- 2,2-Dimethylpropyl 1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P68), 3-methoxypropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P69), tetrahydrofuran-3-yl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P70), butyl-3-ynyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P71), and isobutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P72).2-Cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P73), 1-cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P74), pentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P75), 2-(dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P76), heptyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P75). P77), 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic prop-2-alkynyl ester (compound P78), 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic prop-2-alkynyl ester (compound P79), 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic allyl ester (compound P80), 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic 2-methoxy-2-oxo-ethyl) ester (compound P81), 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline Nonyl 3-carboxylate (compound P82), 3-phenylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P84), 3-methylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (3-methoxy-3-methyl-butyl) ester (compound P85), 3,3-dimethylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P86), 2-cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P87), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate The following compounds are listed: 5-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid isopentyl ester (compound P88), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 4-benzyloxybutyl ester (compound P89), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-octyl ester (compound P90), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-isopentyl ester (compound P91), and 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-(3-phenylpropyl) ester (compound P92).

[0095] In another particularly preferred embodiment, the compound having formula (I) is selected from:

[0096] 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P2), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P3), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P5), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P7), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-( Ethyl trifluoromethoxy)phenyl]cenolin-3-carboxylate (compound P8), ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylate (compound P9), ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylate (compound P10), ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylate (compound P12), ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylate (compound P13), ethyl 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-( Trifluoromethoxyphenyl]cenolin-3-carboxylic acid (compound P14), 6-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylic acid (compound P15), 6-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylic acid (compound P18), 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylic acid (compound P19), 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylic acid (compound P21), 5-ethylthio-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenolin-3-carboxylic acid Ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P23), 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P25), 5-ethylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P26), 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P27), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P28), 5-cyclopropylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P30).5-Cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P32), 5-cyclopropylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P33), 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P35), 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P37), 4-oxo-5-(2,2,2-trifluoroethylthioalkyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid Ethyl 4-oxo-5-(2,2,2-trifluoroethylsulfonyl)-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P40), 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P41), 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid ethyl ester (compound P42), 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P43), 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid ethyl ester (compound P44), 7-isobutyl Ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P46), ethyl 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P50), ethyl 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P52), ethyl 6-bromo-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P53), ethyl 7-fluoro-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P54) ), ethyl 7-cyano-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P55), ethyl 7-methoxy-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P57), hexyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P59), undecyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P60), 2-chloroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P61).5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid pent-4-ynyl ester (compound P62), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid cyclopropyl methyl ester (compound P63), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 1-methyl allyl ester (compound P64), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid isopropyl ester (compound P65), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2-chloroene 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2,2-difluoroethyl ester (compound P67), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2,2-dimethylpropyl ester (compound P68), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3-methoxypropyl ester (compound P69), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid tetrahydrofuran-3-yl ester (compound P70), 5-methylsulfonyl-4-oxo-1-[4- [Trifluoromethoxy)phenyl] cinnamyl-3-carboxylate butyl-3-alkynyl ester (compound P71), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cinnamyl-3-carboxylate isobutyl ester (P72), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cinnamyl-3-carboxylate 2-cyanoethyl ester (compound P73), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cinnamyl-3-carboxylate 1-cyclopropylethyl ester (compound P74), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl] cinnamyl-3-carboxylate pentyl ester (compound P75), 5-methylsulfonyl-4-oxo- 1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2-(dimethylamino)ethyl ester (compound P76), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid heptyl ester (compound P77), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid prop-2-alkynyl ester (compound P78), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid prop-2-alkynyl ester (compound P79), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid allyl ester (compound P80)5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2-methoxy-2-oxo-ethyl) ester (compound P81), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid nonyl ester (compound P82), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3-phenyl propyl ester (compound P84), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (3-methoxy-3-methyl-butyl) ester (compound P85), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3,3-dimethylbutyl ester (compound P86), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3,3-dimethylbutyl ester (compound P86), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3,3-dimethylbutyl ester (compound P86), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3,3-dimethylbutyl ester (compound P85 ... 2-Cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cylin-3-carboxylic acid (compound P87), isopentyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cylin-3-carboxylic acid (compound P88), 4-benzyloxybutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cylin-3-carboxylic acid (compound P89), 5-methylsulfonyl-4-oxo-1- [4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-octyl ester (compound P90), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-isoamyl ester (compound P91), and 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-(3-phenylpropyl) ester (compound P92).

[0097] In a further particularly preferred embodiment, the compound having formula (I) is selected from:

[0098] 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P2), methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P3), 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P5), 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P6), 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline 3-Carboxylic acid (compound P7), ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P8), ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P9), 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P12), 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P19) ), 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P21), 5-ethylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P27), ethyl 5-methylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P28), 5-cyclopropylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P30), 5-cyclopropylsulfinyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid Ethyl 5-cyclopropylthio-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P32), ethyl 5-cyclopropylthio-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound P33), ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P41), ethyl 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylate (compound P42), ethyl 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid (compound P43), ethyl 1-(2,4-Dichlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid ethyl ester (compound P44), 7-isobutyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P46), 7-methoxy-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P50), 7-fluoro-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid ethyl ester (compound P52), 7 5-Fluoro-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate ethyl ester (compound P54), 7-methoxy-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate ethyl ester (compound P57), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate hexyl ester (compound P59), and 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate undecyl ester (compound P60). 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2-chloroethyl ester (compound P61), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid pent-4-ynyl ester (compound P62), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid cyclopropyl methyl ester (compound P63), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 1-methyl allyl ester ( Compound P64), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid isopropyl ester (Compound P65), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2-chloroallyl ester (Compound P66), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2,2-difluoroethyl ester (Compound P67), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2,2-Dimethylpropyl ester (compound P68), 3-methoxypropyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P69), tetrahydrofuran-3-yl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P70), butyl-3-ynyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P71), isobutyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (P72), 5 2-Cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P73), 1-Cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P74), 2-Amyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P75), 2-(dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P76), 5-methylsulfonyl-4-oxo-1- [4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid heptyl ester (compound P77), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid prop-2-alkynyl ester (compound P78), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid prop-2-alkynyl ester (compound P79), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid allyl ester (compound P80), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 2-Methoxy-2-oxo-ethyl) ester (compound P81), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid nonyl ester (compound P82), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3-phenylpropyl ester (compound P84), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (3-methoxy-3-methyl-butyl) ester (compound P85), 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3,3-Dimethylbutyl ester (compound P86), 2-cyclohexylethyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P87), isopentyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P88), 4-benzyloxybutyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P8) 9) S-octyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid (compound P90), S-isoamyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid (compound P91), and S-(3-phenylpropyl) ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid (compound P92).

[0099] The compounds of the present invention can be prepared as shown in the following embodiments, wherein, unless otherwise stated, each variable is defined as above for compounds having formula (I). A general method for producing compounds having formula (I) is described below. Unless otherwise stated herein, X, R... 1 R 2 R 3 R 4 R 5 and R 6 As defined above, the starting materials used to prepare the compounds of this invention can be purchased from common commercial suppliers or can be prepared by known methods. The starting materials and intermediates can be purified by existing methods (such as chromatography, crystallization, distillation, and filtration) before being used in the next step.

[0100] Option 1:

[0101]

[0102] Compounds having formula (I) (where X is oxygen and R) 3 (where R is hydrogen) can be hydrolyzed by using 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) and optionally in a co-solvent (such as water) at a temperature between 0°C and 100°C. 3 Not hydrogen, but any other R as defined above. 3 It is prepared by using (groups). This is shown in Scheme 1 above.

[0103] Option 2:

[0104]

[0105] Compounds having formula (I) can be prepared from compounds having formula (B) (where Y is F, Cl, Br, or I). In which R... 2 In embodiments of the invention where SO2C1-C6 alkyl and Y is F, compounds having formula (I) can be prepared by reacting with an alkyl sulfinate (such as sodium methanesulfonate) in a suitable solvent (such as N,N-dimethylformamide, dimethylacetamide, or dimethyl sulfoxide) at high temperatures (up to 130°C). This is shown in Scheme 2 above.

[0106] Option 3:

[0107]

[0108] Alternatively, compounds having formula (I) (where R) 2 The alkyl group (SC1-C6 alkyl) can be prepared from a compound having formula (B) (where Y is F) by reacting it with an alkyl thiol in the presence of a base (such as sodium hydride or a metal carbonate such as potassium carbonate) in a suitable solvent (such as N,N-dimethylformamide or N-methyl-2-pyrrolidone) at an appropriate temperature. This is shown in Scheme 3 above.

[0109] Option 4:

[0110]

[0111] Alternatively, compounds having formula (I) (where R) 2 SO2C1-C6 alkyl) can be produced by compounds having formula (I) (where R 2 It is prepared by oxidation (SC1-C6 alkyl or S(O)C1-C6 alkyl) in a suitable solvent and under standard conditions with a typical oxidizing agent (such as potassium persulfate preparation, sodium hypochlorite, or m-chloroperbenzoic acid). Such oxidation methods will be familiar to those skilled in the art. This is illustrated in Scheme 4 above.

[0112] Option 5:

[0113]

[0114] Similarly, compounds having formula (I) (where R) 2 (is an S(O)C1-C6 alkyl) can be produced from compounds having formula (I) (where R) 2(SC1-C6 alkyl) is prepared by oxidation in a suitable solvent and under standard conditions with a typical oxidizing agent (such as potassium persulfate preparations, sodium hypochlorite, or m-chloroperbenzoic acid). Such oxidation methods will be familiar to those skilled in the art. This is illustrated in Scheme 5 above.

[0115] Option 6:

[0116]

[0117] Compounds having formula (B) (where Y is F, Cl, Br, or I, X is oxygen, and R is oxygen) 3 (where R is hydrogen) can be hydrolyzed by using 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) and optionally a co-solvent (such as water) at a temperature between 0°C and 100°C. 3 Not hydrogen, but any other R as defined above. 3 It is prepared by using (groups). This is shown in Scheme 6 above.

[0118] Option 7:

[0119]

[0120] A compound having formula (B) (where Y is F, Cl, Br, or I, and X is oxygen) can optionally be prepared from a compound having formula (C) in the presence of a base (such as a metal hydride, for example, sodium hydride, or potassium carbonate) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at a high temperature (100°C). This is shown in Scheme 7 above.

[0121] Option 8:

[0122]

[0123] A compound having formula (C) (where Y is F, Cl, Br, or I, and X is oxygen) can be prepared by reacting a β-keto ester having formula (D) (where LG is a suitable leaving group (such as F, Cl, or Br)) with an aromatic diazonium salt. The aromatic diazonium salt can be prepared in situ by diazotizing an aniline having formula (E) with sodium nitrite in water in the presence of an acid (such as hydrochloric acid), followed by reaction with a compound having formula (D) in a suitable solvent (such as water, methanol, or ethanol) in the presence of a suitable base (such as sodium acetate, potassium acetate, or potassium carbonate) at a temperature between 0°C and 25°C. The compound having formula (E) is commercially available or can be prepared by methods familiar to those skilled in the art. This is illustrated in Scheme 8 above.

[0124] Option 9:

[0125]

[0126] A dicarbonyl compound having formula (D) (where Y is F, Cl, Br, or I, and X is oxygen) can be prepared by Claisen condensation of a methyl ketone compound having formula (F) (where LG is a suitable leaving group (such as F, Cl, or Br)) and a diester having formula (G), by treating the methyl ketone with a suitable base (such as potassium tert-butoxide or sodium hydride) in a suitable solvent (such as tetrahydrofuran, N,N-dimethylformamide, toluene, or 1,4-dioxane), followed by reacting the mixture with a carbonate (such as dimethyl carbonate or diethyl carbonate) at a temperature between 0°C and 110°C. The compounds having formulas (F) and (G) are commercially available or can be prepared by methods familiar to those skilled in the art. This is illustrated in Scheme 9 above.

[0127] The compounds of the present invention (wherein R) 4 (Methyl) can also be prepared by alternative routes as shown in the following scheme, wherein, unless otherwise stated, each variable is defined as above for compounds having formula (I). A general method for producing compounds having formula (I) is described below. Unless otherwise stated herein, X, R... 1 R 2 and R 3 As defined above, the starting materials used to prepare the compounds of this invention can be purchased from common commercial suppliers or can be prepared by known methods.

[0128] Option 1a:

[0129]

[0130] Compounds having formula (I) (where X is oxygen and R) 3 (where R is hydrogen) can be hydrolyzed by using 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) and optionally in a co-solvent (such as water) at a temperature between 0°C and 100°C. 3 Not hydrogen, but any other R as defined above. 3 It is prepared by using (groups). This is shown in scheme 1a above.

[0131] Option 2a:

[0132]

[0133] Compounds having formula (I) (where R) 3 It is not hydrogen, and R 2 SO2C1-C6 alkyl) can be produced by compounds having formula (Ia) (where R 2 It is prepared by reacting SO2C1-C6 alkyl groups in the presence of a cycloboroxane compound (such as trimethylcycloboroxane) and a palladium catalyst (such as PdCl2(dppf)), in a suitable solvent (such as 1,4-dioxane), and in the presence of a base (such as sodium carbonate) at a high temperature (85°C). This is shown in scheme 2a above.

[0134] Option 3a :

[0135]

[0136] Compounds having formula (Ia) (where R) 2 (S(O)C1-C6 alkyl) can be derived from compounds having formula (Ib) (where R) 2 (SC1-C6 alkyl) is prepared by oxidation in a suitable solvent and under standard conditions with a typical oxidizing agent (such as potassium persulfate preparations, sodium hypochlorite, or m-chloroperbenzoic acid). Such oxidation methods will be familiar to those skilled in the art. This is illustrated in scheme 3a above.

[0137] Option 4a:

[0138]

[0139] Compounds having formula (Ib) (where R) 2 (where Y is an alkyl group of SC1-C6) can be prepared from a compound having 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 in scheme 4a above.

[0140] Option 5a:

[0141]

[0142] Compounds having formula (Ic) (where Y is F) can be prepared from compounds having formula (DI) optionally in the presence of a base (such as a metal hydride, for example sodium hydride, or potassium carbonate) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at low temperature (0°C). This is shown in scheme 5a above.

[0143] Option 6a:

[0144]

[0145] Compounds having formula (DI) (where Y is F and X is oxygen) can be prepared by reacting a β-keto ester having formula (BI) (where LG is a suitable leaving group (such as F, Cl, or Br)) with an aromatic diazonium salt. The aromatic diazonium salt can be prepared in situ by diazotizing an aniline having formula (E) with sodium nitrite in water in the presence of an acid (such as hydrochloric acid), followed by reaction with a compound having formula (D) in a suitable solvent (such as water, methanol, or ethanol) in the presence of a suitable base (such as sodium acetate, potassium acetate, or potassium carbonate) at a temperature between 0°C and 25°C. Compounds having formula (EI) are commercially available or can be prepared by methods familiar to those skilled in the art. This is illustrated in scheme 6a above.

[0146] Option 7a:

[0147]

[0148] Compounds having the formula (BI) (where Y is F, X is oxygen, and R is oxygen) 3 (Not hydrogen) can be produced by compounds having the formula (CI) (where R) 3 The compound (C1) is prepared in the presence of magnesium chloride and an acylation agent (such as potassium monoethyl malonate) in a suitable solvent (such as tetrahydrofuran) at high temperature (50°C). The compound having formula (C1) is commercially available or can be prepared by methods familiar to those skilled in the art. This is shown in scheme 7a above.

[0149] Similarly, the compounds of the present invention (wherein R) 5 (Methyl) can also be prepared by alternative routes as shown in the following scheme, wherein, unless otherwise stated, each variable is defined as above for compounds having formula (I). A general method for producing compounds having formula (I) is described below. Unless otherwise stated herein, X, R... 1 R 2 and R 3 As defined above, the starting materials used to prepare the compounds of this invention can be purchased from common commercial suppliers or can be prepared by known methods.

[0150] Option 1b:

[0151]

[0152] Compounds having formula (I) (where X is oxygen and R) 3(where R is hydrogen) can be hydrolyzed by using 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) and optionally in a co-solvent (such as water) at a temperature between 0°C and 100°C. 3 Not hydrogen, but any other R as defined above. 3 It is prepared by using (groups). This is shown in scheme 1b above.

[0153] Option 2b:

[0154]

[0155] Compounds having formula (I) (where R) 3 It is not hydrogen, and R 2 SO2C1-C6 alkyl) can be produced by compounds having formula (Ia) (where R 2 It is prepared by reacting SO2C1-C6 alkyl groups in the presence of a cycloboroxane compound (such as trimethylcycloboroxane) and a palladium catalyst (such as PdCl2(dppf)), in a suitable solvent (such as 1,4-dioxane), and in the presence of a base (such as sodium carbonate), at a high temperature (85°C). This is shown in Scheme 2b above.

[0156] Option 3b:

[0157]

[0158] Compounds having the formula (I-ai) (where R) 2 (S(O)C1-C6 alkyl) can be derived from compounds having the formula (I-ci) (where R) 2 (SC1-C6 alkyl) is prepared by oxidation in a suitable solvent and under standard conditions with a typical oxidizing agent (such as potassium persulfate preparations, sodium hypochlorite, or m-chloroperbenzoic acid). Such oxidation methods will be familiar to those skilled in the art. This is illustrated in scheme 3b above.

[0159] Option 4b:

[0160]

[0161] Compounds having the formula (I-ci) (where R) 2The alkyl group (SC1-C6) can be prepared from a compound having the 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, for example, sodium hydride, or potassium carbonate) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide) at a high temperature (100°C). This is shown in Scheme 4b above.

[0162] Option 5b:

[0163]

[0164] Compounds having formula (D-II) (where R) 2 The alkyl group is SC1-C6, and LG is a suitable leaving group, such as F). It can be prepared from a compound having formula (B-II) with an aromatic diazonium salt. The aromatic diazonium salt can be prepared in situ by diazotizing an aniline having formula (E-II) with sodium nitrite in water in the presence of an acid (such as hydrochloric acid), followed by reaction with a compound having formula (B-II) in a suitable solvent (such as water, methanol, or ethanol) in the presence of a suitable base (such as sodium acetate, potassium acetate, or potassium carbonate) at a temperature between 0°C and 25°C. The compound having formula (E-II) is commercially available or can be prepared by methods familiar to those skilled in the art. This is shown in scheme 5b above.

[0165] Option 6b:

[0166]

[0167] Compounds having formula (B-II) (where R) 2 (where R is an SC1-C6 alkyl group, Y is F, and X is oxygen) can be produced by compounds having the formula (C-II) (where R is an alkyl group, Y is F, and X is oxygen). 3 It is prepared by reacting hydrogen with magnesium chloride and an acylation agent (such as potassium monoethyl malonate) in a suitable solvent (such as tetrahydrofuran) at high temperature (80°C). This is shown in Scheme 6b above.

[0168] Option 7b:

[0169]

[0170] Compounds having formula (C-II) (where R) 2 It is an SC1-C6 alkyl group, where X is oxygen, and R... 3 (is hydrogen) can be produced by compounds having the formula (G-II) (where R is hydrogen) 3The compound is prepared in the presence of a methanethiol salt (such as sodium methanethiol) and a suitable base (such as lithium bis(trimethylsilyl)amino), in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran, or N,N-dimethylformamide), and at a high temperature (80°C). Compounds having formula (G-II) are commercially available or can be prepared by methods familiar to those skilled in the art. This is illustrated in scheme 7b above.

[0171] The present invention further provides a method for controlling weeds at a site, the method comprising applying to the site a composition comprising a compound having formula (I) to control the amount of weeds. Furthermore, the present invention can further provide a method for selectively controlling weeds at a site comprising useful (crop) plants and weeds, wherein the method comprises applying to the site a composition according to the present invention to control the amount of weeds. 'Control' means killing, reducing, or delaying 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. Typically, the plant to be controlled is an unwanted plant (weed). 'Site' means an area in which the plant is growing or will grow. Application can be made to the site before and / or after the emergence of the crop plants. Some crop plants can inherently tolerate the herbicidal effects of compounds having formula (I).

[0172] The application rate of compounds having formula (I) can vary within a wide range and depends on soil properties, application method (pre- or post-emergence; seed dressing; application in seed furrows; no-till application, etc.), crop species, one or more weeds to be controlled, prevailing climatic conditions, and other factors governed by the application method, application time, and target crop. Compounds having formula I according to the invention are typically applied at rates from 10 g / ha to 2500 g / ha, particularly from 25 g / ha to 1000 g / ha, and even more particularly from 25 g / ha to 250 g / ha.

[0173] The composition is usually applied by spraying, typically using a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or immersion can also be used.

[0174] The term "useful plants" should be understood to also include useful plants that have developed tolerance to herbicides (like bromuconazole) or herbicide classes (e.g., 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as flusulfuron, fluprosulfuron, and triflusulfone, (5-enol-pyruvyl-shikimate-3-phosphate-synthetase) (EPSPS) inhibitors, glutamine synthase (GS) inhibitors, or protoporphyrinogen oxidase (PPO) inhibitors) through conventional breeding methods or genetic engineering. Examples of crops that have been induced to tolerate imidazolinones (e.g., methoxyfenozide) through conventional breeding methods (mutation) are... Summer rapeseed (Carnora). Examples of crops that have been genetically engineered to be resistant to herbicides or herbicides include glyphosate and glufosinate-resistant maize varieties, which are roundup... Herculex and Liberty Trademark names are available for purchase.

[0175] The term "useful plant" should be understood to also include useful plants that have been transformed by the use of recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to come from toxin-producing bacteria, especially those of the genus Bacillus.

[0176] Examples of such plants are: (Corn variety expressing CryIA(b) toxin); YieldGard (A maize variety expressing CryIIIB(b1) toxin); YieldGard (Maize variety expressing CryIA(b) and CryIIIB(b1) toxins); (A maize variety expressing the Cry9(c) toxin); Herculex (A maize variety that expresses the CryIF(a2) toxin and the enzyme phosphatidylcholine N-acetyltransferase (PAT) to acquire tolerance to the herbicide glufosinate-ammonium); NuCOTN (Cotton variety expressing CryIA(c) toxin); Bolgard (Cotton variety expressing CryIA(c) toxin); Bolgard (Cotton varieties expressing CryIA(c) and CryIIA(b) toxins); (Cotton variety, expressing VIP toxin); (Potato variety that expresses CryIIIA toxin); GT Advantage (GA21 glyphosate resistance) CBAdvantage (Bt11 corn borer (CB) traits), RW (corn rootworm trait) and

[0177] Plant crops or their seed material can be both herbicide-resistant and insect-resistant (“cumulative” transgenic events). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0178] Crop plants should also be understood to include those obtained through conventional breeding or genetic engineering methods and that contain so-called exported traits (such as improved storage stability, higher nutritional value, and improved flavor).

[0179] Unwanted plants (collectively referred to as 'weeds') can be controlled using compounds having formula (I) (or compositions containing it). Weeds to be controlled can be monocotyledonous species, such as *Agrostis*, *Alopecurus*, *Avena*, *Brachiaria*, *Bromus*, *Cenchrus*, *Cyperus*, *Digitaria*, *Echinochloa*, *Eleusine*, *Lolium*, *Monochoria*, *Rottboellia*, *Sagittaria*, *Scirpus*, and *Setaria*. ) and the genus Sorghum, which can also be dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola, and Xanthium.

[0180] Compounds having formula (I) can be used in their unmodified form, or preferably with adjuvants conventionally used in the formulation field to provide a herbicidal composition, using formulation adjuvants such as carriers, solvents, and surfactants (SAAs). Therefore, the present invention further provides a herbicidal composition comprising at least one compound having formula (I) and an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art.

[0181] These herbicidal compositions generally contain from 0.1% to 99%, particularly from 0.1% to 95% by weight, of a compound having Formula I, and from 1% to 99.9% by weight of a formulation adjuvant, which preferably includes from 0% to 25% by weight of a surfactant.

[0182] The composition can be selected from many formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersants (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), parent drug (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP), and soluble granules (SG). In any case, the type of formulation chosen will depend on the specific intended purpose and the physical, chemical, and biological properties of the compound having formula (I).

[0183] Soluble powders (SPs) can be prepared by mixing a compound having formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate, or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants, or a mixture of said reagents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SGs).

[0184] Wettable powders (WPs) can be prepared by mixing a compound having formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersants, and optionally one or more suspending agents to promote dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WGs).

[0185] Granules (GR) can be formed by granulating a mixture of a compound having formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound having formula (I) (or a solution thereof in a suitable reagent) into a porous particulate material (such as pumice, attapulgite clay, bleaching clay, kieselguhr, diatomaceous earths, or corn cob powder), or by adsorbing a compound having formula (I) (or a solution thereof in a suitable reagent) onto a hard core material (such as sand, silicates, mineral carbonates, sulfates, or phosphates) and, if necessary, drying it to form pre-formed blank granules. Reagents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars, and vegetable oils). One or more other additives (e.g., emulsifiers, wetting agents, or dispersants) may also be included in the granules.

[0186] Dispersible concentrates (DCs) can be prepared by dissolving a compound having formula (I) in water or an organic solvent (such as a ketone, alcohol, or glycol ether). These solutions may contain surfactants (e.g., to improve water dilution or to prevent crystallization in spray cans).

[0187] Emulsifiable concentrates (ECs) or oil-in-water emulsions (EWs) can be prepared by dissolving a compound having formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers, or a mixture of said reagents). Suitable organic solvents used in 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), and dimethylamides of fatty acids (such as C8-C...). 10 (Fatty acid dimethylamide) and chlorinated hydrocarbons. EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow for spray application using appropriate equipment.

[0188] The preparation of an emulsion (EW) involves obtaining a compound of formula (I) as a liquid (or, if not a liquid at room temperature, which can be melted at a reasonable temperature typically below 70°C) or as a solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution under high shear into water containing one or more SAAs to produce an emulsion. Suitable solvents used in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0189] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents and one or more SAAs to spontaneously produce a thermodynamically stable, isotropic liquid formulation. The compound having formula (I) is initially present in water or in the solvent / SAA blend. Suitable solvents used in MEs include those described above used in ECs or EWs. MEs can be oil-in-water or water-in-oil systems (whichever system is present can be determined by conductivity measurements) and can be used to mix water-soluble and oil-soluble biocides in the same formulation. MEs are suitable for dilution in water, maintaining as a microemulsion or forming a conventional oil-in-water emulsion.

[0190] Suspension concentrates (SCs) can comprise aqueous or non-aqueous suspensions of finely dispersed insoluble solid particles of a compound having formula (I). SCs can be prepared by ball milling or bead milling of a solid compound having formula (I) with one or more dispersants in a suitable medium to produce a fine-particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the rate of particle settling. Alternatively, a compound having formula (I) can be dry-milled and added to water containing the reagents described above to produce the desired final product.

[0191] Aerosol formulations comprise compounds having formula (I) and suitable propellants (e.g., n-butane). Compounds having formula (I) can also be dissolved or dispersed in a suitable medium (e.g., water or a water-miscible liquid, such as n-propanol) to provide compositions for use in unpressurized, manually operated spray pumps.

[0192] Capsule suspensions (CS) can be prepared in a manner similar to that used in the preparation of EW formulations, but with an additional polymerization stage, resulting in an aqueous dispersion of oil droplets, each droplet encapsulated in a polymer shell and containing a compound of formula (I) and optionally a carrier or diluent for that droplet. The polymer shell can be produced via interfacial polycondensation or via a coagulation process. These compositions can provide controlled release of compounds of formula (I) and can be used for seed treatment. Compounds of formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0193] The composition may contain one or more additives to improve the biocompatibility of the composition, for example by improving wettability, retention, or distribution on a surface; rain resistance on the treated surface; or absorption or flow of compounds having formula (I). Such additives include surfactants (SAAs), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), modified vegetable oils (such as methylated rapeseed oil (MRSO)), and blends of these with other bioenhancing adjuvants (components that can help or modify the effects of compounds having formula (I)).

[0194] The wetting agent, dispersant, and emulsifier can be cationic, anionic, amphoteric, or nonionic SAA.

[0195] Suitable cationic types of SAAs include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0196] 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, butyl naphthalene sulfonate, and mixtures of sodium di-isopropyl-naphthalene sulfonate and sodium tri-isopropyl-naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (products of the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), such as the reaction between lauryl alcohol and tetraphosphate; these products may also be ethoxylated), sulfosuccinates, paraffin or olefin sulfonates, taurines, lignosulfonates, and phosphate / sulfate salts of tristyrylphenols.

[0197] Suitable amphoteric types of SAAs include betaine, propionate, and glycine salt.

[0198] Suitable non-ionic types of SAAs include condensation products of alkyl oxidases (such as ethylene oxide, propylene oxide, butane oxide, or mixtures thereof) with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long-chain fatty acids or hexyl anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); lecithin and sorbitol and their esters, alkyl polyglycosides, and tristyrylphenols.

[0199] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethyl cellulose) and expansive clays (such as bentonite or attapulgite).

[0200] The compounds of the present invention can also be used in mixtures with one or more other herbicides and / or plant growth regulators. Examples of such other herbicides or plant growth regulators include acetochlor, trifluralin (including trifluralin-sodium), bensulfuron, atrazine, aminopyrrolidone, chlorpyrifos, atrazine, flubutyroxyfen-M, benquitrione, bensulfuron-methyl (including bensulfuron-methyl), bentazon, dicyclopyranone, bispyribac-sodium, bispyribac-sodium, bixlozone, chlorpyrifos, bromobenzonitrile, butachlor, flupropyrin, chlorpyrifos (including chlorpyrifos-ethyl), chlorpyrifos-methyl, chlorpyrifos-ethyl, chlorpyrifos-methyl ... Acyfos), clethodim, clodinafopyridine (including clodinafop-methyl), isoxaflutole, dichloropyridinic acid, cyclopyranil, cyclopyrimorate, cyprosulfuron-methyl, cyhalofop-butyl, 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diethylene glycolamine, dimethylamine, dimethylammonium, potassium salt and sodium salt), dichlorvos, pyrfluthrin, flupyridine, metolachlor, fenfluridine, dioxopyritrione, dibromodiphenyl ether The following are listed: diuron, epyrifenacil, ethylbutadiene, ethoxysulfuron, quizalofop-p-ethyl (including quizalofop-p-ethyl), fenoxasulfone, fenquinotrione, tetrazolium, pyrimisulfuron, diflubenzuron, florpyrauxifen (including florpyrauxifen-benzyl), quizalofop-p-butyl (including quizalofop-p-butyl), flumetsulam (including flumetsulam-sodium), fluthiamethoxam, pyrimisulfuron, propyzamide, fluroxypyrsulfuron-methyl-sodium, fluroxypyr (including florpyrsulfuron-methyl-sodium), and fluroxypyr (including florpyrsulfuron-methyl-sodium). Fluroxypyr-meptyl), flufenacet, formamide-sulfuron, glufosinate (including L-glufosinate and its ammonium salts), glyphosate (including its hydrazine, isopropylammonium, and potassium salts), halauxifen (including halauxifen-methyl), haloxyfop-methyl (including haloxyfop-methyl), cycloazinone, hydantocidin, methoxyfenozide (including R-methoxyfenozide), imidacloprid, metolachlor, imidacloprid, imidacloprid, indazon, iofensulfuron-methyl-sodium, iofensulfuron-sodium, iofensulfuron, isoproturon,Isoxazolidinone, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron-methyl (including mesosulfuron-methyl), mesosulfuron-methyl, benzimidone, pyrazosulfuron, isoxazolin, metolachlor, sulfadiazine, cyprodinil, mesosulfuron-methyl, dichlorvos, nicosulfuron, dapoxuron, oxadiazon, cyclosulfuron-methyl, ethoxysulfuron, paraquat dichlorvos, pendimethalin, penflusulfuron-methyl, benzimidone, chlorpyrifos, clodinafop-methyl, propargite, propargite, oxychlorpyrifos, propyrisulfuron, pendimethalin, benzimidone, flusulfuron-methyl, cyprodinil Pyraflufen (including pyraflufen-ethyl), sulfonylurea, pyrazosulfuron, cyclopyrazosulfuron, pyrimisulfan, pyroxasulfone, pyrazosulfuron, quinclorac, chlorpyrifos, quizalofop-P-tefuryl (including quizalofop-ethyl and quizalofop-P-tefuryl), rimisoxafen, sulfadiazine, pyrimisulfuron, oxadiazine, simazine, metolachlor, mesosulfuron, sulfonylurea, butyrazosulfuron, terbufos, terbufos, tetflupyrolimet, thiamethoxam (t... hiencarbazone), thifensulfuron, tiafenacil, tolpyralate, bensulfuron-methyl, triafamone, fensulfuron-methyl, chlorpyrifos, trifludimoxazin (including trifludimoxazin-sodium), triflurazole, flufensulfuron-methyl, trisulfuron-methyl, 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]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidine-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidine-2-one,4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid and prop-2-kyne 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid). And cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridin-2-yl carboxylate), 3-ethylthioalkyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridin-8-carboxamide, 3-(isopropylthioalkylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl) 3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazol[4,3-a]pyridine-8-carboxamide, 3-(ethyl ... -yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]ethyl acetate, and 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one.

[0201] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include cloquintocet (including cloquinoline), cyclopropanesulfonamide, dichloropropeneamine, cloquinoxal (including cloquinoxal-ethyl), cloquinoxal, flufenoxam, cloquinoxal, cloquinoxalic acid (including cloquinoxalic acid-ethyl), mefenpyr (including mefenpyr-diethyl), mecamifen, and cloquinoxalic acid.

[0202] Safeguards of compounds having formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition (BCPC), 2012. References to antitoxin quinine also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts (as disclosed in WO 02 / 34048).

[0203] Preferably, the mixing ratio of the compound having formula (I) to the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0204] Compounds having formula (I) are typically used in the form of agricultural chemical compositions and can be applied simultaneously or sequentially to crop areas or plants to be treated, along with other compounds. These other compounds may, for example, be fertilizers or micronutrient donors or other formulations that influence plant growth. They may also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures thereof, and, if desired, with additional carriers, surfactants, or application-promoting adjuvants commonly used in the formulation field.

[0205] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds, and seedlings, along with the established vegetation.

[0206] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0207] The term "plant propagation material" should be understood to refer to the reproductive parts of a plant, such as seeds, which can be used for plant propagation, as well as nutrient materials, such as cuttings or tubers (e.g., potatoes). References may include, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of the plant. References may also include germinating plants and young plants that will be transplanted after germination or emergence. These young plants may be protected before transplanting by complete or partial treatment with maceration. Preferably, "plant propagation material" should be understood to refer to seeds.

[0208] The pesticides mentioned in this article that use their common names are, for example, known from "The Pesticide Manual", 15th edition, British Crop Protection Council 2009.

[0209] Compounds having formula (I) can be used in their unmodified form, or preferably, in conjunction with adjuvants conventionally used in the field of formulations. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and encapsulants, for example, in polymeric substances. The method of application, such as spraying, atomizing, dusting, spreading, smearing, or watering, is selected according to the intended purpose and the prevailing environment for the type of composition. The composition may also contain additional adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders, or thickeners, along with fertilizers, micronutrient donors, or other formulations used to achieve specific effects.

[0210] Suitable carriers and adjuvants, for example, for agricultural use, can be solid or liquid and are substances useful in formulation techniques, such as natural or recycled minerals, solvents, dispersions, wetting agents, thickeners, binders, or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0211] Compounds having formula (I) are typically used in the form of a composition and can be applied simultaneously or sequentially with other compounds to crop areas or plants to be treated. These other compounds may, for example, be fertilizers or micronutrient donors or other formulations that influence plant growth. They may also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these formulations, and, if desired, with other carriers, surfactants, or application-promoting adjuvants commonly used in the formulation field.

[0212] A compound having formula (I) may be the sole active ingredient in a composition, or, where appropriate, it may be mixed with one or more other active ingredients (such as pest control agents, fungicides, synergists, herbicides, or plant growth regulators). In some cases, the additional active ingredients may result in unexpected synergistic activities.

[0213] Typically, formulations comprise from 0.01% to 90% by weight of the active ingredient, from 0% to 20% of an agriculturally acceptable surfactant, and from 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being a compound having at least formula (I) together with components (B) and (C), and optionally other active agents (particularly microbicides, preservatives, or the like). Concentrated forms of the composition typically contain between about 2% and 80% by weight, preferably between about 5% and 70% by weight of the active agent. Application forms of the formulation may, for example, contain from 0.01% to 20% by weight, preferably from 0.01% to 5% by weight of the active agent. However, commercially available products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0214] The following are examples of individual compounds having formula (I) according to the present invention:

[0215]

[0216] Table 1: Individual compounds of formula (I) according to the present invention

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239] Table A-1 provides 768 compounds having formula (I) from A-1.001 to A.1.768, where R 1 It is 4-(trifluoromethoxy)phenyl, R 3 It is hydrogen, R 6 It is hydrogen, X is oxygen, and R 2 R 4 and R 5 As defined in Table 1.

[0240] Table A-2 provides 768 compounds having formula (I) from A-2.001 to A.2.768, where R 1 It is 4-(trifluoromethoxy)phenyl, R 3 It is methyl, R 6 It is hydrogen, X is oxygen, and R 2 R 4 and R 5 As defined in Table 1.

[0241] Table A-3 provides 768 compounds having formula (I) from A-3.001 to A.3.768, where R 1 It is 4-(trifluoromethoxy)phenyl, R 3 It is ethyl, R 6 It is hydrogen, X is oxygen, and R 2 R 4 and R 5 As defined in Table 1.

[0242] Table A-4 provides 768 compounds having formula (I) from A-4.001 to A.4.768, where R 1 It is 4-chlorophenyl, R 3 It is hydrogen, R 6 It is hydrogen, X is oxygen, and R 2 R 4 and R 5 As defined in Table 1.

[0243] Table A-5 provides 768 compounds having formula (I) from A-5.001 to A.5.768, where R 1 It is 4-chlorophenyl, R 3 It is methyl, R 6 It is hydrogen, X is oxygen, and R 2 R 4 and R 5 As defined in Table 1.

[0244] Table A-6 provides 768 compounds having formula (I) from A-6.001 to A.6.768, where R 1 It is 4-chlorophenyl, R 3 It is ethyl, R 6 It is hydrogen, X is oxygen, and R 2 R 4 and R 5 As defined in Table 1.

[0245] Examples of preparations

[0246]

[0247] The active ingredient is thoroughly mixed with the excipients and the mixture is thoroughly ground in a suitable grinder to provide a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0248]

[0249]

[0250] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to provide a powder that can be used directly for seed treatment.

[0251] Emulsifiable concentrate

[0252]

[0253] Emulsions that can be used in plant protection with any required dilution can be obtained by diluting the concentrate with water.

[0254]

[0255] A ready-to-use dust powder is obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. This type of powder can also be used for dry seed dressing.

[0256] Extruder Particles

[0257]

[0258] The active ingredient is mixed with the excipients and ground, and the mixture is then moistened with water. The mixture is extruded and then dried in an air stream.

[0259] Coated particles

[0260] Active ingredient [a compound having formula (I)] 8%

[0261] Polyethylene glycol (molecular weight 200) 3%

[0262] 89% Kaolin

[0263] The finely ground active ingredient is evenly applied to kaolin clay moistened with polyethylene glycol in a mixer. This process yields dust-free coated particles.

[0264] Suspension concentrate

[0265]

[0266] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution. Using such a dilution, living plants along with their propagation material can be treated and protected against microbial infection by spraying, pouring, or immersion.

[0267] Flowable concentrate for seed treatment

[0268]

[0269] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution. Using such a dilution, living plants along with their propagation material can be treated and protected against microbial infection by spraying, pouring, or immersion.

[0270] Sustained-release capsule suspension

[0271] A mixture of 28 parts of compounds of formula (I) was mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water was added to this emulsion. The mixture was stirred until polymerization was complete. The resulting capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contained 28% of the active ingredient. The diameter of the medium capsule was 8-15 micrometers. The resulting formulation was applied to seeds as an aqueous suspension suitable for this purpose.

[0272] Example

[0273] The following non-limiting examples provide specific methods for synthesizing representative compounds used in this invention (as mentioned in Table 2 below).

[0274] Example 1: 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P2) Synthesis

[0275]

[0276] Step 1: Synthesis of ethyl 3-(2,6-difluorophenyl)-3-oxo-propionate

[0277]

[0278] Triethylamine (3.78 g, 37.4 mmol) and magnesium dichloride (4.1 g, 42.5 mmol) were added to a solution of potassium 3-ethoxy-3-oxopropionate (6.11 g, 35.7 mmol) in acetonitrile (66 mL) at 0 °C and under nitrogen atmosphere. The reaction mixture was stirred at room temperature for 3.5 h. The reaction mixture was cooled to 0 °C and 2,6-difluorobenzoyl chloride (3.0 g, 17 mmol) was added in portions. The reaction mixture was stirred on ice for 1.5 h, and then stirred at room temperature for 2 h, and then allowed to stand for 18 h. The reaction mixture was evaporated under reduced pressure and azeotropically reacted with toluene. The residue was suspended in an aqueous solution of ethyl acetate (50 mL) and 2 M hydrochloric acid. These phases were separated and the aqueous phase was extracted twice more with ethyl acetate. The combined organic extracts were dried over magnesium sulfate and evaporated to dryness under reduced pressure to give a crude desired product (a mixture of tautomers) (4.5 g, 20 mmol) as a pale yellow liquid. 1¹H NMR (400MHz, 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) (Keto form data only).

[0279] Step 2: Synthesis of ethyl (2E)-3-(2,6-difluorophenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate

[0280]

[0281] A solution of sodium nitrite (0.48 g, 6.87 mmol) in water (1.3 mL) was added to a solution of 4-(trifluoromethoxy)aniline (1.10 g, 6.25 mmol) in hydrochloric acid (5.2 mL, 31 mmol) at 0 °C. The reaction mixture was stirred at 0 °C for 30 min, and then added in portions to a suspension of ethyl 3-(2,6-difluorophenyl)-3-oxopropionate (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 h, and then the solution was decanted to leave a red gel. This gel was dissolved in ethyl acetate, dried over magnesium sulfate, and evaporated under reduced pressure to dryness to give the desired product as a red solid (2.6 g, 6.25 mmol, 64%). 1 ¹H NMR (400MHz, 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)

[0282] Step 3: Synthesis of ethyl 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate

[0283]

[0284] Potassium carbonate (0.58 g, 5.697 mmol) was added to a solution of ethyl (2Z)-3-(2,6-difluorophenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate (2.16 g, 5.179 mmol) in N,N-dimethylformamide (10 mL). The reaction mixture was heated at 100 °C for 3.5 h. The cooled reaction mixture was diluted with water and extracted twice in diethyl ether. The combined organic extracts were dried over magnesium sulfate and evaporated under reduced pressure to dryness to give a red solid. The solid was ground with cyclohexane to give the desired product (1.2 g, 3.02 mmol, 58%) as a grayish-white solid. 1 ¹H NMR (500MHz, 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)

[0285] Step 4: Synthesis of 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid

[0286]

[0287] A solution of lithium hydroxide hydrate (0.31 g, 7.19 mmol) in water (1.8 mL) was added to a solution of ethyl 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (0.71 g, 1.8 mmol) in tetrahydrofuran (10 mL). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was acidified by adding 2 M hydrochloric acid aqueous solution, and the precipitated solid was collected by filtration and air-dried to give the desired product (0.65 g, 1.76 mmol, 98%) as a grayish-white powder. 1 ¹H NMR (400MHz, 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)

[0288] Step 5: Synthesis of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid

[0289]

[0290] Sodium methanesulfinate (0.34 g, 3.26 mmol) was added to a solution of 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (0.40 g, 1.1 mmol) in N,N-dimethylformamide (5 mL). The reaction mixture was heated at 80 °C for 5 hours. The cooled reaction mixture was poured onto ice, at which point a yellow solid precipitated from the solution. The solid was collected by filtration to give the desired product (0.37 g, 0.85 mmol, 78%) as a pale yellow powder. 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)

[0291] Example 2: 5-Methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P1) Synthesis

[0292]

[0293] Sodium methanethiol (0.11 g, 1.6 mmol) was added to a solution of 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (0.20 g, 0.53 mmol) in N,N-dimethylformamide (2 mL) at room temperature. The reaction mixture was heated at 100 °C for 1 hour under microwave irradiation. The reaction mixture was diluted with 2 M hydrochloric acid aqueous solution, 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)

[0294] Example 3: Methyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (compound) Synthesis of substance P3

[0295]

[0296] Concentrated sulfuric acid (0.003 mL, 0.047 mmol) was added to a suspension of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (0.20 g, 0.47 mmol) in methanol (10 mL). The reaction mixture was heated at 80 °C for 2 hours. Upon cooling, a light-colored solid precipitated from the solution. The solid was collected by filtration, washed with water, and air-dried to give the desired product as a grayish-white powder (0.18 g, 0.40 mmol, 87%). 1 ¹H NMR (400MHz, 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)

[0297] Example 4: Synthesis of 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-boronline-3-carboxylic acid (compound P5)

[0298]

[0299] Step 1: Synthesis of ethyl (2E)-2-[(4-chlorophenyl)hydrazinyl]-3-(2,6-difluorophenyl)-3-oxopropionic acid

[0300]

[0301] The product was prepared using 4-chloroaniline (1.17 g, 9.2 mmol) in the manner used for (2E)-3-(2,6-difluorophenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate (Example 1; Step 2). After a reaction time of 2.75 h, the solid was collected by filtration to give the desired product (2.2 g, 5.9 mmol, 64%) as a yellow solid. 1 ¹H NMR (400MHz, 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)

[0302] Step 2: Synthesis of ethyl 1-(4-chlorophenyl)-5-fluoro-4-oxo-cenline-3-carboxylate

[0303]

[0304] The product was prepared using (2Z)-2-[(4-chlorophenyl)hydrazinyl]-3-(2,6-difluorophenyl)-3-oxopropionic acid ethyl ester (2.2 g, 5.9 mmol) in the manner used for ethyl 5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]oxo-3-carboxylate (Example 1; Step 3). After the reaction was complete, 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 ¹H NMR (400MHz, 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)

[0305] Step 3: Synthesis of 1-(4-chlorophenyl)-5-fluoro-4-oxo-boronline-3-carboxylic acid

[0306]

[0307] The product was prepared using ethyl 1-(4-chlorophenyl)-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (Example 1; step 4) to obtain the desired product as a grayish-white solid (1.15 g, 3.6 mmol, 97%). 1 ¹H NMR (500MHz, 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)

[0308] Step 4: Synthesis of 1-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cenline-3-carboxylic acid

[0309]

[0310] Sodium methanesulfinate (0.19 g, 1.9 mmol) was added to a solution of 1-(4-chlorophenyl)-5-fluoro-4-oxo-cenline-3-carboxylic acid (0.20 g, 0.63 mmol) in N,N-dimethylformamide (2 mL). The reaction mixture was heated at 80 °C for 45 ± 45 min under microwave irradiation. The cooled reaction mixture was poured onto ice and the precipitated solid was collected by filtration to give a pale yellow powder, which was ground with dichloromethane. The addition of a dimethyl sulfoxide / methanol mixture (9:1) caused a 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)

[0311] Example 5: Synthesis of 1-(4-chlorophenyl)-5-methylthioalkyl-4-oxo-cenline-3-carboxylic acid

[0312]

[0313] A solution of 1-(4-chlorophenyl)-5-fluoro-4-oxo-borono-3-carboxylic acid (0.20 g, 0.63 mmol) and sodium methanethiol (0.13 g, 1.9 mmol) in N,N-dimethylformamide (2 mL) was heated under microwave irradiation at 80 °C for 60 ± 60 min. The cooled reaction mixture was diluted with 2 M hydrochloric acid aqueous solution, producing a precipitate of a yellow solid that was insoluble upon extraction into ethyl acetate or dichloromethane. The solid was collected from the aqueous phase by filtration to give the desired product (0.048 g, 0.14 mmol, 22%) as a bright yellow powder. 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).

[0314] Example 6: Synthesis of 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P6)

[0315] Step 1: Synthesis of ethyl 3-(3-bromo-2,6-difluoro-phenyl)-3-oxo-propionate

[0316]

[0317] 1,1'-carbonyldiimidazole (83.5 mmol) was added dropwise to a solution of 3-bromo-2,6-difluorobenzoic acid (18 g, 76.0 mmol) in tetrahydrofuran (1.85 mmol) at 0 °C. The reaction mixture was heated 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 monoethyl 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 hydrochloric acid aqueous solution and extracted into ethyl acetate (3 × 100 mL). The combined organic extracts were washed with saturated sodium bicarbonate aqueous solution, then with brine, dried over sodium sulfate, and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 0–15% ethyl acetate in cyclohexane as eluent to give the desired product (15 g) of a mixture of keto-enol isomers.

[0318] Step 2: Synthesis of ethyl (2E)-3-(3-bromo-2,6-difluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate

[0319]

[0320] A solution of sodium nitrite (57.5 mmol) in water (2 mL / mmol) was added dropwise over 10 minutes to a cooled (0 °C) mixture of 4-(trifluoromethoxy)aniline (52.3 mmol) in 6 M hydrochloric acid aqueous solution (261 mmol). The mixture was stirred at 0 °C for 60 minutes, and then added dropwise over 10 minutes to a cooled (0 °C) solution of ethyl 3-(3-bromo-2,6-difluorophenyl)-3-oxopropionate (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). The reaction mixture was stirred at room temperature for 2 hours, after which the reaction mixture was diluted with water (100 mL) and extracted into tert-butyl methyl ether (3 × 250 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated under reduced pressure to dryness to give the desired product (22 g) as a yellow solid.

[0321] Step 3: Synthesis of ethyl 6-bromo-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (and ethyl 8-bromo-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate)

[0322]

[0323] A 60% suspension (24.2 mmol) of sodium hydride in mineral oil was added fractionally to a solution of ethyl (2Z)-3-(3-bromo-2,6-difluoro-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate (8.0 g, 16.2 mmol) in tetrahydrofuran (160 mL). The reaction mixture was stirred at 0 °C for 4 h. The reaction mixture was quenched by adding ice-cold water, acidified with 1 M hydrochloric acid aqueous solution, and extracted to 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 silica gel rapid chromatography using ethyl acetate in cyclohexane as eluent to give the desired product isomer (5.1 g). 1 HNMR(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)

[0324] Step 4: Synthesis of ethyl 6-bromo-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (and ethyl 5,6-bis(methylthioalkyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate)

[0325]

[0326] Sodium methanethiol (1.2 equivalents, 6.3 mmol) was added to a solution of ethyl 6-bromo-5-fluoro-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (2.5 g, 5.3 mmol) in N,N-dimethylformamide (7 mL / g) at room temperature and under nitrogen atmosphere. The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was quenched by adding water (200 mL), acidified with 1 M hydrochloric acid aqueous solution, and extracted to 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 silica gel rapid chromatography using a gradient of 0 to 20% ethyl acetate in cyclohexane as eluent to give the desired product (2.0 g) as a yellow solid.

[0327] Step 5: Synthesis of ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate

[0328]

[0329] To a solution of ethyl 6-bromo-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (5.4 g, 11 mmol) in trifluorotoluene (10 mL / mmol) at room temperature and under nitrogen atmosphere, 3-chloroperoxybenzoic acid (24 mmol, 70 μL by mass) was added. 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), dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using ethyl acetate in cyclohexane as 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)

[0330] Step 6: Synthesis of ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate

[0331]

[0332] To a solution of ethyl 6-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (500 mg, 0.934 mmol) in dioxane (30 mL / g), 2,4,6-trimethyl-1,3,5,2,4,6-trioxaborane (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 under nitrogen for 10 min. PdCl2 (dppf)·DCM (0.140 mmol) was added, and the reaction mixture was heated at 85 °C for 20 h. The reaction mixture was poured onto ice and diluted with water (100 mL), then acidified with 1 M hydrochloric acid aqueous solution 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 silica gel rapid chromatography using a gradient of 0 to 20% ethyl acetate in cyclohexane as eluent to obtain the desired product (0.230 g). 1H 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)

[0333] Step 7: Synthesis of 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid

[0334]

[0335] A solution of lithium hydroxide hydrate (1.53 mmol) in water (2 mL / g) was added to a solution of ethyl 6-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (180 mg, 0.383 mmol) in tetrahydrofuran (15 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 adding 1 M hydrochloric acid and then extracted into ethyl acetate. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated under reduced pressure to dryness to give the desired product (0.150 g) as a white solid. 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)

[0336] Example 7: Synthesis of 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (compound P7)

[0337] Step 1: Synthesis of 4-bromo-2-fluoro-6-methylthioalkylbenzoic acid

[0338]

[0339] Lithium bis(trimethylsilyl)amino (4.64 mmol) was added to a solution of 4-bromo-2,6-difluorobenzoic acid (1.0 g, 4.22 mmol) in tetrahydrofuran (10 mL / g). The reaction mixture was stirred at 0 °C for 20 min, and then sodium methanethiol (4.64 mmol) was added. The resulting mixture was heated at 80 °C for 3 h. The cooled reaction mixture was acidified by adding 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 under reduced pressure to dryness 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)

[0340] Step 2: Synthesis of ethyl 3-(4-bromo-2-fluoro-6-methylthioalkyl-phenyl)-3-oxo-propionate

[0341]

[0342] 1,1'-carbonyldiimidazole (5.0 mmol) was added fractionally to a solution of 1.1 g of 4-bromo-2-fluoro-6-methylthioalkylbenzoic acid in tetrahydrofuran (100 mmol) at 0 °C. The reaction mixture was heated to room temperature and stirred for 1 hour. The reaction mixture was then added to a suspension of magnesium chloride (6.2 mmol) and potassium monoethyl malonate (6.2 mmol) in tetrahydrofuran (100 mmol). The reaction mixture was heated at 50 °C for 18 hours. The cooled reaction mixture was quenched by adding 2 M hydrochloric acid aqueous solution and extracted into ethyl acetate. The combined organic extracts were washed with saturated sodium bicarbonate aqueous solution, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 15% to 20% ethyl acetate in cyclohexane as eluent to give the desired product as a colorless liquid.

[0343] Step 3: Synthesis of ethyl (2E)-3-(4-bromo-2-fluoro-6-methylthioalkyl-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate

[0344]

[0345] 4-(trifluoromethoxy)aniline (4.18 mmol) was added to a 6M hydrochloric acid aqueous solution (20.9 mmol). The resulting mixture was cooled to 0 °C and placed in an ice bath, and 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 min, and then added dropwise over 10 min to a solution of ethyl 3-(4-bromo-2-fluoro-6-methylthioalkyl-phenyl)-3-oxo-propionate (1.0 g) and potassium acetate (14.9 mmol) in methanol (2.0 mL / mmol) and water (2.98 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for 2 h. The resulting viscous brown substance was extracted into ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and evaporated under reduced pressure to dryness to give the crude desired product.

[0346] Step 4: Synthesis of ethyl 7-bromo-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate

[0347]

[0348] Potassium carbonate (1.89 mmol) was added to a solution of (2Z)-3-(4-bromo-2-fluoro-6-methylthioalkyl-phenyl)-3-oxo-2-[[4-(trifluoromethoxy)phenyl]hydrazine]propionate (900 mg) in N,N-dimethylformamide (10 mL). The reaction mixture was heated at 100 °C for 2.5 h. Cold water was added to the cooled reaction mixture, and the precipitated solid was collected by filtration and air-dried to obtain 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)

[0349] Step 5: Synthesis of ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate

[0350]

[0351] 3-Chloroperoxybenzoic acid (2.84 mmol, 70% by mass) was added to a solution of ethyl 7-bromo-5-methylthioalkyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (650 mg) in acetonitrile (20 mL). The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was quenched by adding saturated aqueous potassium carbonate solution (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 silica gel rapid chromatography using a gradient of 40% to 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)

[0352] Step 6: Synthesis of ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate

[0353]

[0354] To a solution of ethyl 7-bromo-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (500 mg) in dioxane (30 mL / g), 2,4,6-trimethyl-1,3,5,2,4,6-trioxaborane (2.34 mmol), sodium carbonate (1.87 mmol), and water (1 mL / g) were added sequentially. The reaction mixture was degassed by bubbling with nitrogen for 15 min. PdCl2 (dppf)·DCM (0.14 mmol) was added, and the reaction mixture was heated at 100 °C for 2 h. The reaction mixture was diluted with ethyl acetate and washed with water and then brine, dried over sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 40% to 50% ethyl acetate in cyclohexane as eluent to obtain 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)

[0355] Step 7: Synthesis of 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid

[0356]

[0357] A suspension of lithium hydroxide hydrate (3 equivalents, 1.276 mmol) in water (1 mL / g) was added to a solution of ethyl 7-methyl-5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate (200 mg) in tetrahydrofuran (10 mL). The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was acidified by adding 2 M hydrochloric acid aqueous solution and diluted with additional water. The precipitated solid was collected by filtration, washed with tert-butyl methyl ether, and air-dried to give the desired product. 1 H 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)

[0358] Table 2: Selected compounds in Table 1 1 H NMR and LC / MS data

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395] Biological examples

[0396] Seeds of various test species were sown in standard soil in pots (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)). After 8 days of cultivation under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14-hour light; 65% humidity), the plants were sprayed with an aqueous solution derived from an industrial-grade formulation of the active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compound was applied at 1000 g / ha. The test plants were then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14-hour light; 65% humidity) and watered twice daily. The percentage of damage to the plants was evaluated after 13 days. The table below shows biological activity on a five-point scale (5 = 81%-100%; 4 = 61%-80%; 3 = 41%-60%; 2 = 21%-40%; 1 = 10%-20%; 0 = 0%; - = not tested).

[0397] Table B1: Pre-emergence testing

[0398]

[0399]

[0400]

[0401]

[0402] Table B2: Post-emergence testing

[0403]

[0404]

[0405]

[0406]

Claims

1. A compound having the general formula (I): ###0001### wherein the compound is selected from: 5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; methyl 5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; l-(4-chlorophenyl)-5-methylsulfonyl-4-oxo-cinnoline-3-carboxylic acid; 6-methyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 7-methyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; ethyl 6-methyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; ethyl 7-methyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; ethyl 6-bromo-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; ethyl 7-bromo-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; 6-bromo-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 7-bromo-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 7-isobutyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 6-isobutyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 6-methoxy-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 7-methoxy-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 7-fluoro-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; ethyl 5-ethylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; ethyl 5-ethylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; ethyl 5-ethylsulfinyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; 5-ethylsulfinyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 5-ethylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; 5-ethylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; ethyl 5-methylsulfinyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylate; 5-cyclopropylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]cinnoline-3-carboxylic acid; ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 5-cyclopropylsulfinyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 5-cyclopropylsulfinyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid; 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid; 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid; 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid; 4-oxo-5-(2,2,2-trifluoroethylsulfinyl)-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid; 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-chromene-3-carboxylic acid; 1-(4-chloro-2-fluoro-phenyl)-5-methylsulfonyl-4-oxo-chromene-3-carboxylic acid ethyl ester; 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-chromene-3-carboxylic acid; 1-(2,4-dichlorophenyl)-5-methylsulfonyl-4-oxo-chromene-3-carboxylic acid ethyl ester; 6-isobutyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 7-isobutyl-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 6-cyano-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 6-methoxy-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 7-methoxy-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 7-fluoro-5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 6-bromo-5-methylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 7-fluoro-5-methylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 7-cyano-5-methylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 7-methoxy-5-methylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid methyl ester; 7-methoxy-5-methylsulfanyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid ethyl ester; 5-methylsulfonyl-4-oxo-l-[4-(trifluoromethoxy)phenyl]chromene-3-carboxylic acid hexyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid undecyl ester; 2-Chloroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid pent-4-alkynyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cyclopropyl methyl 3-carboxylic acid; 1-Methylallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; Isopropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 2-Chloroallyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 2,2-difluoroethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 2,2-dimethylpropyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 3-Methoxypropyl ester of 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]zoline-3-carboxylic acid tetrahydrofuran-3-yl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]benzyl-3-carboxylic acid butyl-3-alkynyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]zoline-3-carboxylic acid isobutyl ester; 2-Cyanoethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 1-Cyclopropylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cyclophosphino-3-carboxylic acid; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cyclophosphine-3-carboxylic acid pentyl ester; 2-(dimethylamino)ethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]denline-3-carboxylate heptyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]benzyl-3-carboxylic acid prop-2-alkynyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid allyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (2-methoxy-2-oxo-ethyl) ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylate; 9-Phenylnonyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cyclophosphine-3-carboxylic acid; 3-Phenylacetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid 3-phenylpropyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid (3-methoxy-3-methyl-butyl) ester; 3,3-dimethylbutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 2-Cyclohexylethyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-carboxylic acid; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]zoline-3-carboxylic acid isoamyl ester; 4-Benzyloxybutyl 5-methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]benzyl-3-carboxylic acid; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-octyl ester; 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-isoamyl ester; and 5-Methylsulfonyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]cenline-3-thiocarboxylic acid S-(3-phenylpropyl) ester; Or its salt.

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

3. The herbicidal composition according to claim 2, further comprising at least one additional pest control agent.

4. The herbicidal composition according to claim 3, wherein, The other pest control agent mentioned is a herbicide or a herbicide safener.

5. A method for controlling unwanted plant growth, comprising applying a compound having general formula (I) according to claim 1, or a herbicidal composition according to any one of claims 2 to 4, to the unwanted plant or its location.

6. Use of the compound having general formula (I) according to claim 1 as a herbicide.

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