Herbicidal quinolone derivatives

Abstract

A compound of formula (I), in which the substituents are as defined in claim 1. The present invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, especially in crops of useful plants. JPEG2025506046000033.jpg41167

Description

[Technical field]

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

[0002] US Patent No. 4,670,444, Med Chem Res (2016) 25, 1861-1876, and J. Chem. Soc., Perkin Trans. 1, 2002, 1232-1235 describe quinolone derivatives as antibacterial agents. In addition, CN108617661 and CN101643468 disclose the use of quinolone derivatives as agricultural chemicals, for example as insecticides, fungicides, or herbicides. Furthermore, Chem. Commun., 2018, 54, 1869 discloses fluoroquinolone analogs with herbicidal activity. Summary of the Invention [Means for solving the problem]

[0003] According to the present invention, a compound of formula (I): [ka] (In the formula, X is O; R 1 is R 10 C1-C6 alkyl or phenyl optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 2is hydrogen, phenyl, or heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl moiety is R 8 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 3 is hydrogen or C1-C6 alkyl; R 4 , R 5 , R 6 , and R 7 are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylcarbonyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, and phenyl, wherein each phenyl moiety is selected from R 9 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 8 is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl; R 9is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl; R 10 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, or C1-C6 alkylsulfonyl. or a salt or N-oxide thereof.

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

[0005] According to a second aspect of the present invention, there is provided an agricultural composition comprising a herbicidally effective amount of a compound of formula (I) according to the present invention, which may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

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

[0007] According to a fourth aspect of the present invention there is provided the use of a compound of formula (I) as a herbicide. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] When a substituent is described as being "optionally substituted," this includes one or more equal or different substituents, for example, one, two or three R 8 It means that it may or may not have a substituent. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens may include, but is not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, C1-C6 alkoxy substituted with 1, 2 or 3 halogens may include, but is not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.

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

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

[0011] As used herein, the term "nitro" refers to the group --NO.

[0012] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing no unsaturation, having 1-6 carbon atoms, and attached to the remainder of the molecule by a single bond. "C1-C4 alkyl" and "C1-C3 alkyl" should be interpreted similarly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and its isomers, such as isopropyl. The group "C1-C6 alkylene" refers to the corresponding definition of C1-C6 alkyl, except that such group is attached to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" should be interpreted similarly. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0013] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group, generally as defined above, substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted similarly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0014] As used herein, the term "C1-C6 alkoxy" refers to R a is generally a C1-C6 alkyl group as defined above; a The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted similarly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0015] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group generally defined above, substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted similarly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0016] As used herein, the term "C1-C6 alkoxyC1-C6 alkyl" refers to R b is a C1-C6 alkyl group as generally defined above, and R a is generally a C1-C6 alkylene group as defined above b OR a - refers to the group.

[0017] As used herein, the term "C1-C6 alkoxycarbonyl" refers to a group of the formula -C(O)OR a (wherein R a is a C1-C6 alkyl group as generally defined above).

[0018] As used herein, the term "C3-C6 cycloalkyl" refers to a group that is a monocyclic saturated ring system and contains 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted similarly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0019] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

[0020] As used herein, the term "C1-C6 alkylcarbonyl" refers to R a is generally a C1-C6 alkyl group as defined above, a Examples of C1-C6 alkylcarbonyl include, but are not limited to, acetyl.

[0021] As used herein, the term "C1-C6 alkylsulfanyl" refers to R a is generally a C1-C6 alkyl group as defined above a The terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be interpreted similarly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0022] As used herein, the term "C1-C6 alkylsulfinyl" refers to R a is generally a C1-C6 alkyl group as defined above a The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" should be interpreted similarly. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl.

[0023] As used herein, the term "C1-C6 alkylsulfonyl" refers to R ais generally a C1-C6 alkyl group as defined above a The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be interpreted similarly. Examples of C1-C6 alkylsolfanyl include, but are not limited to, methylsulfonyl.

[0024] As used herein, the term "C1-C6 alkylsulfonamide" refers to a compound of the formula -NHS(O)R a R refers to the group a is generally a C1-C6 alkyl group as defined above.

[0025] As used herein, the term "aminocarbonyl" refers to a group of formula -C(O)NH2.

[0026] As used herein, the term "C1-C6 alkylaminocarbonyl" refers to a group represented by the formula -C(O)NHR a (wherein R a is a C1-C6 alkyl group as generally defined above).

[0027] As used herein, the term "N,N-di(C1-C4 alkyl)aminocarbonyl" refers to a group represented by the formula -C(O)N(R a )(R b ) group, wherein R a and R b are each individually a C1-C4 alkyl group as generally defined above. The term "N,N-di(C1-C3 alkyl)aminocarbonyl" should be construed similarly.

[0028] As used herein, the term "C3-C6 cycloalkylaminocarbonyl" refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule via a -NHC(O)- linker.

[0029] The presence of one or more possible stereogenic elements in the compound of formula (I) means that the compound can take optical isomeric forms, i.e., enantiomeric or diastereomeric forms. Atropisomers can also arise due to the restriction of rotation about a single bond. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof for the compound of formula (I). Similarly, formula (I) is intended to include all possible tautomeric forms. The present invention includes all possible tautomeric forms for the compound of formula (I).

[0030] In each case, the compounds of formula (I) according to the invention may be in free form or in the form of a salt, for example an agriculturally usable salt form. Preferred are the salts which the compounds of formula (I) may form with amines, including primary, secondary and tertiary amines (e.g. ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases.

[0031] The following list refers to the compounds of formula (I) and indicates the substituents X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 For any one of these substituents, any of the definitions set forth below may be combined with any of the definitions of any other substituents set forth below or elsewhere in this document.

[0032] X is O.

[0033] R 1 is R 10 Preferably, R is C1-C6 alkyl or phenyl, optionally substituted with one or two groups, which may be the same or different, represented by1 is R 10 More preferably, R is C1-C4 alkyl or phenyl, optionally substituted with a single group represented by 1 is R 10 Even more preferably, R is C1-C3 alkyl or phenyl, optionally substituted with a single group represented by 1 is ethyl or 4-trifluoromethoxyphenyl. 1 is ethyl.

[0034] In one set of embodiments, R 1 is C1 to C6 alkyl. Preferably, R 1 is C1-C4 alkyl. More preferably, R 1 is C1-C3 alkyl. Even more preferably, R 1 is methyl, ethyl, n-propyl, or isopropyl. Even more preferably, R 1 is methyl or ethyl. Most preferably, R 1 is ethyl.

[0035] R 2 is hydrogen, phenyl, or heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and each phenyl and heteroaryl moiety is R 8 and optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0036] Preferably, R 2 is hydrogen, phenyl, or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S, and where each phenyl and heteroaryl moiety is selected from R 8 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0037] More preferably, R 2 is hydrogen, phenyl, or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O, and where each phenyl and heteroaryl moiety is independently selected from R 8 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0038] Even more preferably, R 2 is hydrogen, phenyl, or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O, and where each phenyl and heteroaryl moiety is independently selected from R 8 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0039] Even more preferably, R 2 is hydrogen or R 8 In one set of embodiments, R is substituted with one or two groups, which may be the same or different, represented by 2 is hydrogen, 3,4-dichlorophenyl, 3-chloro-4-cyanophenyl, 4-chloro-3-cyanophenyl, 4-chloro-3-fluorophenyl, or 4-fluorophenyl. In a preferred set of embodiments, R 2 is hydrogen, 3,4-dichlorophenyl or 4-fluorophenyl.

[0040] In one set of embodiments, R 2 is phenyl or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and where each phenyl and heteroaryl moiety is selected from R 8It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0041] Preferably, R 2 is phenyl or heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms individually selected from N, O, and S), and each phenyl and heteroaryl moiety is R 8 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0042] More preferably, R 2 is phenyl or heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O), and each phenyl and heteroaryl moiety is R 8 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0043] Even more preferably, R 2 is phenyl or heteroaryl (wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and O), and each phenyl and heteroaryl moiety is R 8 and optionally substituted with 1 or 2 groups, which may be the same or different, represented by

[0044] Even more preferably, R 2 is R 8 Even more preferably, R is phenyl, optionally substituted with one or two groups, which may be the same or different, represented by 2 is R 8 In one set of embodiments, R is substituted with one or two groups, which may be the same or different, represented by 2is 3,4-dichlorophenyl, 3-chloro-4-cyanophenyl, 4-chloro-3-cyanophenyl, 4-chloro-3-fluorophenyl, or 4-fluorophenyl. 2 is 3,4-dichlorophenyl or 4-fluorophenyl. 2 is 3,4-dichlorophenyl.

[0045] R 3 is hydrogen or C1-C6 alkyl. 3 is hydrogen or C1-C4 alkyl, more preferably hydrogen or C1-C3 alkyl. Even more preferably, R 3 is hydrogen, methyl, or ethyl. Even more preferably, R 3 is hydrogen.

[0046] R 4 , R 5 , R 6 , and R 7 are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylcarbonyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, and phenyl, wherein each phenyl moiety is selected from R 9 It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0047] Preferably, R 4 is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylcarbonyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, or phenyl, wherein each phenyl moiety is R 9It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0048] More preferably, R 4 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylcarbonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from R 9 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0049] Even more preferably, R 4 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylcarbonyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylaminocarbonyl, aminocarbonyl, or phenyl, wherein each phenyl moiety is R 9 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0050] Even more preferably, R 4 is hydrogen, halogen, cyano, acetyl, or C1-C3 haloalkyl. 4 is hydrogen, halogen, cyano, acetyl, or trifluoromethyl. 4 is hydrogen, chloro, bromo, cyano, acetyl, or trifluoromethyl.

[0051] In one set of embodiments, R 4is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9 It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0052] Preferably, R 4 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from R 9 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0053] More preferably, R 4 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylaminocarbonyl, aminocarbonyl, or phenyl, wherein each phenyl moiety is selected from R 9 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0054] In one set of embodiments, R 4 is hydrogen, halogen, cyano, or C1-C3 haloalkyl. 4 is hydrogen, halogen, cyano, or trifluoromethyl. 4is hydrogen, chloro, bromo, cyano, or trifluoromethyl.

[0055] R 5 is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9 It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0056] Preferably, R 5 is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C4 haloalkoxy, C1-C6 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C4 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0057] More preferably, R 5 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from R 9 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0058] In one set of embodiments, R 5is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9 In a preferred set of embodiments, R 5 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from a single R 9 In a particularly preferred set of embodiments, R 5 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from a single R 9 In an even more preferred set of embodiments, R 5 is hydrogen, chloro, fluoro, bromo, cyano, methyl, methoxy, trifluoromethyl, methylsulfanyl, methylsulfonyl, aminocarbonyl, or 4-fluorophenyl.

[0059] R 6 is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9 It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0060] Preferably, R 6is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from R 9 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0061] More preferably, R 6 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylaminocarbonyl, aminocarbonyl, or phenyl, wherein each phenyl moiety is selected from R 9 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0062] In one set of embodiments, R 6 is hydrogen, halogen, cyano, C1-C3 alkoxy, or C1-C3 haloalkyl. 6 is hydrogen, halogen, cyano, methoxy, or trifluoromethyl. 6 is hydrogen, chloro, cyano, methoxy, or trifluoromethyl.

[0063] R 7 is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0064] Preferably, R 7 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is selected from R 9 It may be optionally substituted with 1, 2 or 3 groups which may be the same or different and are represented by

[0065] More preferably, R 7 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylaminocarbonyl, aminocarbonyl, or phenyl, wherein each phenyl moiety is selected from R 9 It may be optionally substituted with one or two groups which may be the same or different and are represented by

[0066] In one set of embodiments, R 7 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, or C1-C3 haloalkyl. 7 is hydrogen.

[0067] In one set of embodiments, R 4 , R 6 , and R 7 are each independently selected from hydrogen, halogen, cyano, C1-C3 alkoxy, and C1-C3 haloalkyl, R 5is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfonyl, aminocarbonyl, or phenyl, where the phenyl portion is selected from a single R 9 In another set of embodiments, R 4 , R 6 , and R 7 are each independently selected from hydrogen, halogen, cyano, methoxy, and trifluoromethyl, R 5 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfonyl, aminocarbonyl, or phenyl, where the phenyl portion is selected from a single R 9 The group may be optionally substituted with a group.

[0068] R 8 is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C4 alkyl)aminocarbonyl.

[0069] Preferably, R 8is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl, or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0070] More preferably, R 8 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C2 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonamido, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C4 cycloalkyl, C3-C4 cycloalkylaminocarbonyl, or N,N-di(C1-C2 alkyl)aminocarbonyl.

[0071] In a preferred set of embodiments, R 8 is cyano or halogen. In a particularly preferred set of embodiments, R 8 is halogen, preferably chloro or fluoro. Most preferably, R 8 is fluoro.

[0072] R 9is cyano, nitro, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonamido, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl or N,N-di(C1-C4 alkyl)aminocarbonyl.

[0073] Preferably, R 9 is cyano, nitro, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxyC1-C3 alkyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonamido, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylaminocarbonyl or N,N-di(C1-C3 alkyl)aminocarbonyl.

[0074] More preferably, R 9 is cyano, nitro, halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxyC1-C2 alkyl, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonamido, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylaminocarbonyl, C3-C4 cycloalkyl, C3-C4 cycloalkylaminocarbonyl or N,N-di(C1-C2 alkyl)aminocarbonyl.

[0075] In a preferred set of embodiments, R 9 is halogen. In a particularly preferred set of embodiments, R 9is chloro, fluoro or bromo, preferably fluoro.

[0076] R 10 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, or C1-C6 alkylsulfonyl. 10 is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, or C1-C3 alkylsulfonyl. More preferably, R 10 is halogen, cyano, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, methylsulfanyl, or methylsulfonyl. Even more preferably, R 10 is trifluoromethoxy.

[0077] In the compounds of formula (I) according to the invention, preferably: X is O; R 1 is R 10 is an ethyl or phenyl substituted with a single group represented by R 2 is hydrogen or R 8 is phenyl substituted with one or two groups, which may be the same or different, represented by R 3 is hydrogen; R 4 , R 5 , R 6 , and R 7 are each independently selected from hydrogen, halogen, cyano, methyl, methoxy, trifluoromethyl, methylsulfanyl, methylsulfonyl, aminocarbonyl, and 4-fluorophenyl; R 8 is a halogen; R 10 is a C1-C3 haloalkoxy.

[0078] In one embodiment, in the compounds of formula (I) according to the invention, preferably: X is O; R 1 is ethyl or 4-trifluoromethoxyphenyl; R 2 is hydrogen, 3,4-dichlorophenyl or 4-fluorophenyl; R 3 is hydrogen; R 4 , R 5 , R 6 , and R 7 are each independently selected from hydrogen, halogen, cyano, methyl, methoxy, trifluoromethyl, methylsulfanyl, methylsulfonyl, aminocarbonyl, and 4-fluorophenyl.

[0079] In one embodiment, in the compounds of formula (I) according to the invention, preferably: X is O; R 1 is ethyl or 4-trifluoromethoxyphenyl; R 2 is hydrogen, 3,4-dichlorophenyl or 4-fluorophenyl; R 3 is hydrogen; R 4 is hydrogen, halogen, cyano, or trifluoromethyl; R 5 is hydrogen, halogen, cyano, methyl, methoxy, trifluoromethyl, methylsulfanyl, methylsulfonyl, aminocarbonyl, or 4-fluorophenyl; R 6 is hydrogen, chloro, cyano, methoxy, or trifluoromethyl; R 7 is hydrogen.

[0080] In another embodiment, in the compounds of formula (I) according to the invention, preferably: X is O; R1 is ethyl or 4-trifluoromethoxyphenyl; R 2 is hydrogen, 3,4-dichlorophenyl or 4-fluorophenyl; R 3 is hydrogen; R 4 is hydrogen, trifluoromethyl, bromo, cyano, or acetyl; R 5 is hydrogen, bromo, chloro, fluoro, cyano, methyl, methoxy, trifluoromethyl, aminocarbonyl, methylsulfanyl, or methylsulfonyl; R 6 is hydrogen, methoxy, or trifluoromethyl; R 7 is hydrogen.

[0081] In another embodiment, in the compounds of formula (I) according to the invention, preferably: X is O; R 1 is ethyl; R 2 is 3,4-dichlorophenyl or 4-fluorophenyl; R 3 is hydrogen; R 4 is hydrogen, trifluoromethyl, bromo, or cyano; R 5 is hydrogen, bromo, chloro, fluoro, cyano, methyl, methoxy, trifluoromethyl, aminocarbonyl, methylsulfanyl, or methylsulfonyl; R 6 is hydrogen, methoxy, or trifluoromethyl; R 7 is hydrogen.

[0082] In another embodiment, in the compounds of formula (I) according to the invention, preferably: X is O; R 1 is ethyl; R2 is 3,4-dichlorophenyl; R 3 is hydrogen; R 4 is hydrogen, trifluoromethyl, bromo, or cyano; R 5 is hydrogen, bromo, chloro, fluoro, cyano, methyl, methoxy, trifluoromethyl, aminocarbonyl, methylsulfanyl, or methylsulfonyl; R 6 is hydrogen, methoxy, or trifluoromethyl; R 7 is hydrogen.

[0083] The compounds of the present invention can be formed as shown in the following schemes, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I). General methods for producing compounds of formula (I) are described below. Unless otherwise specified in the context, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and X are as previously defined herein. The starting materials used in the preparation of the compounds of the present invention may be purchased from ordinary commercial suppliers or may be prepared by known methods. The starting materials as well as intermediates may be purified by state-of-the-art techniques such as chromatography, crystallization, distillation and filtration before being used in the next step.

[0084] Compounds of formula (I) of the present invention may be prepared from compounds of formula (A) as shown in Scheme 1.

[0085] Scheme 1: [ka] X is O and R 3Compounds of formula (I), where X is O and R is H, can be prepared by reaction of compounds of formula (A), where X is O and R is H, with a suitable base (such as sodium hydroxide or lithium hydroxide) or a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water). 3 is not H and is any other R defined above 3 When a base is used, the product is obtained after acidification with a suitable acid (such as hydrochloric acid). 4 When is pyridyl or pyridazinyl, the product was obtained as the equivalent salt (such as the hydrochloride salt). This is shown in Scheme 1 above.

[0086] A compound of formula (A) 4 , R 5 , R 6 or R 7 is a halogen (e.g., in the formula, R 4 , R 5 , R 6 or R 7 is Cl, Br or I) can be converted to novel compounds of formula (A), 4 , R 5 , R 6 or R 7 is not a halogen (e.g., in the formula, R 4 , R 5 , R 6 or R 7 In a further transformation, a compound of formula (A), where R 4 , R 5 , R 6 or R 7 is a halogen (e.g., in the formula, R 4 , R 5 , R 6 or R 7is Cl, Br or I) can be cross-coupled with an alkenylstannane reagent under Stille coupling conditions, followed by hydrolysis to give novel compounds of formula (A), 4 , R 5 , R 6 or R 7 is C1-C6 alkylcarbonyl). The above and related C-Hal to CR conversions are known to those skilled in the art.

[0087] Scheme 2: [ka] A compound of formula (A) 3 is not H but any other R as defined above 3 The aryl group, aryloxyethyl ether (R) (which is a aryl group), can be prepared from the reaction of a compound of formula (B) with a compound of formula (C) in a suitable solvent (e.g., tetrahydrofuran, N,N-dimethylformamide, dimethylacetamide or water) with a suitable base (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, potassium bis(trimethylsilyl)amide, potassium carbonate or sodium hydride) at a given temperature (-80°C to reflux). This is shown in Scheme 2 above.

[0088] Scheme 3: [ka] A compound of formula (B), 1 is not H but any other R as defined above 1 group) can be converted to a compound of formula (D) (wherein R is an alkyl group) by alkylation with a suitable alkylating agent (e.g., an alkyl halide or a dialkyl sulfate) in the presence of a suitable base (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylethylamine, sodium carbonate, potassium hydroxide or sodium hydride) in a suitable solvent (e.g., tetrahydrofuran, dimethylacetamide or N,N-dimethylformamide) at a given temperature (e.g., room temperature to 50° C.). 3is H). Such transformations have been described in the scientific literature. This is shown in Scheme 3 above.

[0089] Scheme 4: [ka] Compounds of formula D can be prepared by reacting the compounds of formula D with CO in a suitable solvent (e.g., tetrahydrofuran, toluene, 1,4-dioxane, acetonitrile or dichloromethane), optionally in the presence of a base (e.g., pyridine, triethylamine or sodium hydroxide), and optionally in the presence of a catalyst (e.g., 4-dimethylaminopyridine). 2+ These reactions can be carried out at room temperature or at elevated temperatures. This is shown in Scheme 4 above.

[0090] Alternatively, compounds of formula (D) may be obtained from compounds of formula (E) by reaction with a CO source (e.g., carbon monoxide) in the presence of a palladium catalyst (e.g., palladium(II) acetate) and a copper source (e.g., copper(II) acetate) in the presence of potassium iodide in a suitable solvent (e.g., acetonitrile) at elevated temperature (e.g., 60° C.). Compounds of formula (E) are commercially available or may be prepared by methods reported in the literature.

[0091] Scheme 5: [ka] Compounds of formula (C) may be prepared by treatment of a ketone of formula (F) with a base (e.g., sodium hydride) in the presence of a dialkyl carbonate of formula (G) (e.g., dimethyl carbonate). Compounds of formula (F) and formula (G) are commercially available or may be prepared by methods well known to those skilled in the art. This is shown in Scheme 5 above.

[0092] The present invention further provides a method for controlling weeds in a habitat, comprising the application to the habitat of a weed-controlling amount of a composition comprising a compound of formula (I). Moreover, the present invention may further provide a method for selectively controlling weeds in a habitat containing useful (crop) plants and weeds, comprising the application to the habitat of a weed-controlling amount of a composition according to the present invention. By "control" is meant eradication, reduction or prevention of growth, or prevention or reduction of germination. It is noted that the compounds of the present invention show significantly improved selectivity compared to known structurally similar compounds. In general, the plants to be controlled are unwanted plants (weeds). By "habitat" is meant the area in which the plants are growing or will grow. Application may be made to the habitat before and / or after the emergence of the crop plants. Preferably, the compounds of the present invention are applied to the habitat after the emergence of the crop plants. Some crop plants may be inherently resistant to the herbicidal effect of the compounds of formula (I).

[0093] The application rates of the compounds of formula (I) can vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application in the sowing furrow; no-tillage application, etc.), the crop plant, the weeds to be controlled, the prevailing weather conditions, and other factors governed by the application method, application time and the target crop. The compounds of formula (I) according to the invention are generally applied in amounts of 10 to 2500 g / ha, in particular 25 to 1000 g / ha, in particular 25 to 250 g / ha.

[0094] Application is generally made by spraying the composition, typically with a tractor-mounted large area sprayer, although other methods such as dusting (if a powder), dripping or irrigation can also be used.

[0095] The term "useful plants" should also be understood to include useful plants that have been rendered resistant to herbicides such as bromoxynil or to a class of herbicides, such as, for example, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyroyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen-oxidase (PPO) inhibitors, by conventional breeding or genetic engineering methods. An example of a crop that has been rendered resistant to imidazolinones, such as imazamox, by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered resistant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0096] The term "useful plants" should also be understood to include useful plants which have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, especially those of the genus Bacillus.

[0097] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Root Feeders® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root-feeding nematode trait) and Protecta®.

[0098] Plant crops or their seed material can be both herbicide tolerant and insect feeding tolerant ("stacked" transgenic events) at the same time. For example, seeds can be capable of expressing an insecticidal Cry3 protein while at the same time being glyphosate tolerant.

[0099] Crop plants should also be understood to include those obtainable by conventional methods of breeding or genetic engineering and which contain so-called output traits, such as improved storage stability, higher nutritional value, and improved flavor.

[0100] The compounds of formula (I) (or compositions containing them) can be used to control unwanted plants (collectively "weeds"). The weeds controlled include, for example, Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, and Morocco. The species may be both monocotyledonous, such as Sorghum, and dicotyledonous, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0101] The compound of formula (I) can be used in unmodified form or, preferably, with formulation adjuvants such as carriers, solvents and surface active agents (SAA), together with adjuvants conventionally employed in the formulation art to provide herbicidal compositions.The present invention therefore further provides a herbicidal composition comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an adjuvant.An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use.Agricultural carriers are well known in the art.

[0102] The herbicidal compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of formula I and from 1 to 99.9% by weight of formulation adjuvants, preferably including from 0 to 25% by weight of a surface-active substance.

[0103] The composition can be selected from a number of formulation types, including emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), micro-emulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP) and soluble granules (SG). The formulation type selected in any case will depend on the specific purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

[0104] Soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and, optionally, one or more wetting agents, one or more dispersing agents, or a mixture of said agents to improve dispersibility / solubility in water. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0105] Wettable powders (WP) can be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersing agents and, optionally, one or more suspending agents to promote dispersibility in liquid. The mixture is then ground to a fine powder. Similar compositions may be granulated to form water-dispersible granules (WG).

[0106] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or may be formed from compacted powder granules that have been previously formed by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material (such as pumice, attapulgite clay, Fuller's earth, Kiesler's earth, diatomaceous earth, or ground corn cob), or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a hard core material (such as sand, silicic acid, carbonate minerals, sulfates, or phosphates), and optionally drying. Agents 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 may also be included in the granules (e.g., emulsifiers, wetting agents, or dispersants).

[0107] Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain a surfactant (e.g. to improve dilution with water or to prevent crystallization in the spray tank).

[0108] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving the compound of formula (I) in an organic solvent, optionally with one or more wetting agents, one or more emulsifiers or a mixture of said agents. Organic solvents suitable for use in EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200 (SOLVESSO is a registered trademark)), ketones (such as cyclohexanone or methylcyclohexanone), and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (C8-C10 alkyl esters such as N-methylpyrrolidone or N-octylpyrrolidone), and dimethylamides of fatty acids (C8-C10 alkyl esters such as N-methylpyrrolidone or N-octylpyrrolidone). 10fatty acid dimethylamides, etc., and chlorinated hydrocarbons. EC products can emulsify spontaneously when added to water, resulting in an emulsion that is stable enough to allow spray application with appropriate equipment.

[0109] In preparing the EW, the compound of formula (I) is obtained as a liquid (if not liquid at room temperature it may be melted at a suitable temperature, typically below 70° C.) or in solution (by dissolving in a suitable solvent) and then the resulting liquid or solution is emulsified under high shear into water containing one or more SAA to provide an emulsion. Solvents suitable for use in EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0110] Microemulsions (MEs) can be prepared by mixing a blend of one or more solvents and one or more SAA with water to spontaneously result in a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in either water or in a solvent / SAA blend. Solvents suitable for use in MEs include those previously described for use in ECs or EWs. MEs can be either oil-in-water or water-in-oil systems (which system is present can be determined by conductivity measurements) and are suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. MEs are suitable for dilution in water, either as microemulsions or to form conventional oil-in-water emulsions.

[0111] Suspension concentrates (SC) may comprise an aqueous or insoluble suspension of fine, insoluble solid particles of the compound of formula (I). The SC may be prepared by ball milling or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to provide a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the settling rate of the particles. Alternatively, the compound of formula (I) may be dry milled and added to water containing the agents described hereinabove to provide the desired end product.

[0112] Aerosol formulations include a compound of formula (I) and a suitable propellant (e.g., n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g., water or a miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized, manual spray pump.

[0113] Capsule suspensions (CS) can be prepared similarly to the preparation of EW formulations, but with an additional polymerization stage such that an aqueous dispersion of oil droplets is obtained, each of which is encapsulated in a polymeric shell and contains the compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell can be produced by either an interfacial polycondensation reaction or a coacervation technique. The composition can provide a sustained release of the compound of formula (I) and can be used in seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymeric matrix to provide a slow sustained release of the compound.

[0114] The composition may contain one or more additives to improve the biological performance of the composition, for example by improving the wettability, retention or distribution of the compound of formula (I) on a surface; resistance to rain on the treated surface; or uptake or mobility. Such additives include surface active agents (SAA), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean oil and rapeseed oil), modified vegetable oils such as methylated rapeseed oil (MRSO), and blends of these with other bio-enhancing adjuvants (formulation components that can assist or modify the action of the compound of formula (I)).

[0115] Wetting agents, dispersing agents and emulsifying agents may be cationic, anionic, amphoteric or nonionic SAAs.

[0116] Suitable cationic SAAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines and amine salts.

[0117] Suitable anionic SAAs include alkali metal salts of fatty acids, sulfates of aliphatic monoesters (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butyl naphthalenesulfonate, and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3 sulfate), ether carboxylates (e.g., sodium laureth-3 carbonate), phosphate esters (e.g., products from the reaction of one or more aliphatic alcohols with phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly di-esters), such as the reaction of lauryl alcohol with tetraphosphoric acid; these products may also be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphate / sulfate salts of tristyrylphenol.

[0118] Suitable amphoteric SAAs include betaines, propionates, and glycinates.

[0119] Suitable nonionic SAAs include condensation products of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of the above partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (such as fatty acid polyethylene glycol esters); amine oxides (such as lauryl dimethylamine oxide); lecithin and its sorbitan and esters, alkyl polyglycosides, and tristyrylphenols. Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0120] The compounds of the present invention can also be used in mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, aminocarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, vilanaphos, bipyrazone, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfen, Trazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clasifos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, dextran, cyclosulfuron ... Smedipham, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, difluhenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epirifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone , fenpyrazone, fenquinotrion, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-p-butyl), flucarbazone (including flucarbazone-sodium), flufenacet, flumetsulam, flumioxazin, fluometuron, fomesafen, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen,Foramsulfuron, glufosinate (including L-glufosinate and both ammonium salts), glyphosate (including its diammonium, isopropylammonium and potassium salts), haloxifen (including haloxyfop-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-methyl-sodium), (including mesosulfuron-sodium), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozoline, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, Pretilachlor, primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metolachlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrrolimeth, thiencarbazone, thifensulfuron, thiaphenacyl, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazine, trifluralin,Triflusulfuron, tripyrasulfone, [(E)-[2-(trifluoromethyl)phenyl]methyleneamino]2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-( trifluoromethyl)-2-pyridyl] imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl] imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl] imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl] imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)-2-pyridyl] imidazolidin-2-one (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including its agrochemically acceptable esters, e.g., methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2- carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate), 3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide diazolyl-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, tetrahydrofuran-2-ylmethyl(2R)-2-[(4-amino-3 ,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, tetrahydrofuran-2-ylmethyl 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(R )-propylsulfinyl]-4-(trifluoromethyl)benzamide, 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-propylsulfinyl-4-(trifluoromethyl)benzamide, (2-fluorophenyl)methyl 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid,3-(3-chlorophenyl)-6-(5-hydroxy-1,3-dimethyl-pyrazole-4-carbonyl)-1,5-dimethyl-quinazoline-2,4-dione and [4-[3-(3-chlorophenyl)-1,5-dimethyl-2,4-dioxo-quinazoline-6-carbonyl]-2,5-dimethyl-pyrazol-3-yl]N,N-diethylcarbamate, methyl 2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyleneamino]oxypropanoate and methyl (2R)-2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyleneamino]oxypropanoate.

[0121] The mixing partners of the compounds of formula (I) may also be in the form of esters or salts, for example as described in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

[0122] Mixtures can be used to advantage in the above mentioned formulations (in which case the "active ingredient" refers to the respective mixture of the compound of formula (I) with the mixing partner).

[0123] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners.Examples of such safeners include benoxacor, cloquintocet (including cloquintocet mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.Particularly preferred is the mixture of the compound of formula I with cyprosulfamide, isoxadifen-ethyl, cloquintocet mexyl and / or metcamifen.

[0124] The safeners of the compounds of formula (I) can also be used as described, for example, in The Pesticide Manual, 16 th Edition (BCPC), 2012. Reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048.

[0125] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0126] The compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to the crop area or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, optionally with further carriers, surfactants or application-promoting adjuvants that are customarily used in the art of formulations.

[0127] As used herein, the term "habitat" refers to the field in which the plant is growing or in which the seeds of the cultivated plant have been sown or in which the seeds will be sown in the soil. It includes the soil, the seeds and seedlings, as well as established vegetation.

[0128] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0129] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, which can be used for their propagation, as well as vegetative bodies, such as cuttings or tubers, for example potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts may be mentioned. Also mentioned are sprouted plants and shoots that are to be transplanted after germination or emergence from the soil. These shoots may be protected by a complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to refer to seeds.

[0130] Pesticides referred to herein using common names are known, for example from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0131] The compounds of formula (I) can be used in unmodified form or, preferably, together with the auxiliaries conventionally employed in the art of formulation.For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, direct-sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials.The application method, such as spraying, misting, dusting, scattering, coating, or pouring, as well as the type of composition, is selected according to the intended purpose and the current situation.The composition can also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, sources of trace elements, or other formulations for obtaining special effects.

[0132] For example, suitable carriers and adjuvants for use in agriculture may be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0133] The compounds of formula (I) are usually used in the form of compositions and can be applied to the crop area or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired with further carriers, surfactants or application-promoting adjuvants customarily used in the art of formulations.

[0134] The compound of formula (I) may be the sole active ingredient in the composition or, where appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic activity.

[0135] Typically, the formulations contain 0.01-90% by weight of active agent, 0-20% of agriculturally acceptable surfactants and 10-99.99% of solid or liquid inert compounding agents and adjuvants, the active agent being composed of at least the compound of formula (I) together with components (B) and (C) and optionally other active agents, in particular fungicides or preservatives. Concentrated forms of the composition generally contain about 2-80%, preferably about 5-70% by weight of active agent. Application forms of the formulations may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight of active agent. Commercial products will preferably be formulated as concentrates, but end users will usually utilize diluted formulations.

[0136] The following table shows individual compounds of formula (I) according to the invention: [ka] An example of the above is illustrated.

[0137] [Table 1] JPEG2025506046000010.jpg156166

[0138] Table A-1 provides 34 compounds A-1.001 to A-1.034 of formula (I), where X is oxygen and R 3 and R 7 is hydrogen and R 1 , R 2 , R 4 , R 5 , and R 6 is as defined in Table 1.

[0139] [Table 2]

[0140] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain wettable powders which can be diluted with water to obtain a suspension of the desired concentration.

[0141] [Table 3]

[0142] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain a powder which is ready for use in seed treatment.

[0143] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0144] Emulsions of any required dilution which can be used in plant protection can be obtained from this concentrate by dilution with water.

[0145] [Table 4]

[0146] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressing of seeds.

[0147] Extrusion Granules Active ingredient [compound of formula (I)] 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0148] The active ingredients are mixed and ground with the auxiliaries, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0149] Coated Granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0150] The finely ground active ingredient is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. Dust-free coated granules are thus obtained.

[0151] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0152] The finely ground active ingredient is thoroughly mixed with the adjuvants to obtain a suspension concentrate, from which suspensions of any desired dilution rate can be obtained by dilution with water, by which living plants as well as plant propagation material can be treated by spraying, pouring or immersion to protect them from microbial infestation.

[0153] Seed treatment flowable concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 10-20 moles of EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0154] The finely ground active ingredient is thoroughly mixed with the auxiliary to obtain a suspension concentrate, from which suspensions of any desired dilution rate can be obtained by dilution with water, using which living plants as well as plant propagation material can be treated by spraying, pouring or immersion to protect them from microbial infestation.

[0155] Slow-release capsule suspension 28 parts of a combination of compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contains 28% active ingredient. The medium capsule size is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose. EXAMPLES

[0156] The following non-limiting examples provide specific methods of synthesis of representative compounds of the invention referenced in Table 2 below.

[0157] List of abbreviations °C = degrees Celsius, d = doublet, dd = doublet of doublets, DMSO = dimethylsulfoxide, M = mole, m = multiplet, MHz = megahertz, q = quartet, s = singlet, t = triplet.

[0158] Example 1: Synthesis of 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylic acid (compound 8) Step 1: Synthesis of methyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate [ka] To a solution of 3,4-dichlorobenzoic acid (10.0 g, 52 mmol) in tetrahydrofuran (40 mL) at 0° C. and under nitrogen, 1,1′-carbonyldiimidazole (9.3 g, 57 mmol) was added portionwise while maintaining the internal temperature at <10° C. Once the addition was complete, the cooling bath was removed and the reaction mixture was stirred at room temperature for 1 h, giving a yellow solution. This solution was added dropwise to a suspension of potassium; 3-methoxy-3-oxo-propanoic acid (12.2 g, 77.6 mmol) and magnesium chloride (7.4 g, 78 mmol) in tetrahydrofuran (30 mL) at room temperature, giving a thick precipitate. The mixture was heated at 70° C. for 2 h and then at 50° C. for a further 2 h. The cooled reaction mixture was partitioned between aqueous hydrogen chloride (2 M) and diethyl ether. The organic extract was washed with saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. The crude product is purified by flash chromatography on silica gel using a gradient of 0-20% ethyl acetate in cyclohexane as eluent to give methyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate (mixture of tautomers) as a colorless liquid (10.0 g, 40.5 mmol). 1 H NMR (400 MHz, chloroform) δ = 12.47 (s, 1H), 7.87 (d, 1H), 7.59 (m, 3H), 7.49 (d, 1H), 5.65 (s, 1H), 3.82 (s, 3H). Keto: 1 H NMR (400 MHz, chloroform) δ = 8.03 (d, 1H), 7.77 (m, 1H), 7.58 (d, 2H), 3.97 (s, 2H), 3.76 (s, 3H).

[0159] Step 1': Synthesis of 6-bromo-1H-3,1-benzoxazine-2,4-dione [ka] A solution of 2-amino-5-bromo-benzoic acid (1.00 g, 4.6 mmol) in tetrahydrofuran (20 mL) was cooled to 0° C. and triphosgene (bis(trichloromethyl)carbonate (1.6 g, 5.2 mmol) was added portionwise to give a cloudy suspension. After 0.25 h, the reaction mixture was warmed to room temperature, whereupon the suspension dissolved. The resulting reaction mixture was stirred at room temperature for 2 h, after which it was poured into water and extracted into dichloromethane. The organic extract was dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give 6-bromo-1H-3,1-benzoxazine-2,4-dione as a light grey solid (1.11 g, 4.59 mmol). 1H NMR (400 MHz, methanol) δ = 8.15 (d, 1H), 7.81 (dd, 1H), 7.09 (d, 1H).

[0160] Step 2: Synthesis of 6-bromo-1-ethyl-3,1-benzoxazine-2,4-dione [ka] To a solution of 6-bromo-1H-3,1-benzoxazine-2,4-dione (2.22 g, 9.17 mmol) in tetrahydrofuran (50 mL) was added iodoethane (1.5 mL, 19 mmol) followed by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 1.6 mL, 10 mmol). The resulting solution was stirred at room temperature for 0.25 h and then heated at 50° C. for 3 h. The resulting reaction mixture was poured into aqueous hydrogen chloride (2 M), extracted into dichloromethane, and evaporated to dryness under reduced pressure. The crude product was purified by reverse-phase flash chromatography on C-18 silica gel using a gradient of acetonitrile in water to give 6-bromo-1-ethyl-3,1-benzoxazine-2,4-dione as a tan solid (2.15 g, 7.96 mmol). 1H NMR (400 MHz, chloroform) δ = 8.28 (d, 1H), 7.85 (dd, 1H), 7.09 (d, 1H), 4.13 (q, 2H), 1.38 (t, 3H).

[0161] Step 2': Synthesis of methyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylate [ka] To a solution of 6-bromo-1-ethyl-3,1-benzoxazine-2,4-dione (2.15 g, 7.96 mmol) and methyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate (2.2 g, 8.9 mmol) in tetrahydrofuran (50 mL) at 0° C. was added 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 2.7 mL, 18 mmol) dropwise. After 5 min, the cooling was removed and the reaction mixture was heated at 50° C. for 3 h. The cooled reaction mixture was evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-80% ethyl acetate in cyclohexane as eluent to give methyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylate as a cream-colored solid (1.77 g, 3.89 mmol). 1H NMR (400 MHz, chloroform) δ = 8.64 (d, 1H), 7.81 (dd, 1H), 7.60 (d, 1H), 7.54 (d, 1H), 7.44 (d, 1H), 7.28 (dd, 1H), 4.01 (q, 2H), 3.59 (s, 3H), 1.28 (t, 3H).

[0162] Step 3: Synthesis of 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylic acid (compound 8) [ka] To a solution of methyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylate (0.80 g, 1.8 mmol) in a mixture of methanol (10 mL) and water (5 mL) was added lithium hydroxide (0.30 g, 7.1 mmol). The resulting reaction mixture was heated at 90' for 3 h. The cooled reaction mixture was evaporated to dryness under reduced pressure and the crude product was suspended in water. The mixture was acidified to pH 1 using dilute aqueous hydrogen chloride solution (2 M) and the precipitated solid was extracted into dichloromethane and evaporated to dryness under reduced pressure to give 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylic acid as a cream solid (0.71 g, 1.6 mmol). 1H NMR (400 MHz, chloroform) δ = 15.54 (brs, 1H), 8.77 (d, 1H), 7.96 (dd, 1H), 7.64 (d, 1H), 7.61 (d, 1H), 7.39 (d, 1H), 7.15 (dd, 1H), 4.14 (q, 2H), 1.33 (t, 3H).

[0163] Example 2: Synthesis of 6-cyano-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylic acid (compound 7) [ka] A solution of 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylic acid (0.200 g, 0.45 mmol) in N,N-dimethylformamide (10 mL) was added to zinc cyanide (0.105 g, 0.894 mmol) and tetrakis(triphenyl-λ 5(-phosphanyl)palladium (0.050 g, 0.043 mmol) was added and the reaction mixture was heated under microwave irradiation at 160° C. for 0.75 h. The cooled reaction mixture was partitioned between water and dichloromethane. The organic extracts were evaporated to dryness under reduced pressure and the crude residue was purified by flash chromatography on silica gel using a gradient of 0-100% ethyl acetate in cyclohexane as eluent to give 6-cyano-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-quinoline-3-carboxylic acid as a cream solid (0.060 g, 0.15 mmol). 1H NMR (400 MHz, chloroform) δ = 15.12 (brd, 1H), 8.96 (d, 1H), 8.07 (dd, 1H), 7.83 (d, 1H), 7.66 (d, 1H), 7.40 (d, 1H), 7.16 (dd, 1H), 4.18 (q, 2H), 1.36 (t, 3H).

[0164] Example 3: Synthesis of 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylic acid (compound 19) Step 1: Synthesis of methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate [ka] To a stirred solution of methyl 5-bromo-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate (500 mg, 1.07 mmol) in toluene (15 mL) was added tributyl(1-ethoxyvinyl)stannane (0.55 mL, 1.6 mmol) at room temperature. The resulting reaction mixture was purged with argon for 5 minutes, followed by the addition of bis(triphenylphosphine)palladium(II) chloride (0.078 g, 0.11 mmol). The resulting reaction mixture was purged with argon and then heated with stirring at 100° C. for 1 hour. The cooled reaction mixture was filtered through diatomaceous earth and the filtrate was evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 10% ethyl acetate in hexane as eluent to give methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate as a yellow solid. 1H NMR (400 MHz, DMSO-d6) δ = 8.40 (s, 1H), 7.81 (d, 2H), 7.68 (d, 2H), 7.57 (t, 1H), 7.26 (d, 1H), 6.92 (d, 1H), 4.26 (s, 1H), 4.05 (s, 1H), 3.94-3.89 (m, 2H), 3.72 (s, 3H), 1.21 (t, 3H).

[0165] Step 2: Synthesis of methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate [ka] To a stirred solution of methyl 5-(1-ethoxyvinyl)-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate (890 mg, 2.05 mmol) in acetone (15 mL) at room temperature was added diluted aqueous hydrogen chloride (2 M, 5 mL). The resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was evaporated under reduced pressure and the crude residue was purified by flash chromatography on silica gel using a gradient of 0-75% ethyl acetate in hexanes as eluent to give methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate as an off-white solid. 1H NMR(400MHz,DMSO-d6)δ=8.64(s,1H),7.86(d,2H),7.71(t,3H),7.26(d,1H),7.04(d,1H),3.72(s,3H),2.39(s,3H)

[0166] Step 3: Synthesis of 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylic acid (compound 19) [ka] To a stirred solution of methyl 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylate (100 mg, 0.22 mmol) in tetrahydrofuran (5 mL) at room temperature was added a solution of lithium hydroxide hydrate (0.019 g, 0.44 mmol) in water (1 mL). The resulting reaction mixture was stirred at room temperature for 1 h. The reaction mixture was evaporated to dryness under reduced pressure and the crude product was suspended in water (20 mL). The mixture was neutralized by the addition of dilute aqueous hydrogen chloride solution (2 M, 5 mL) and the precipitated solid was filtered and dried under reduced pressure to give 5-acetyl-4-oxo-1-[4-(trifluoromethoxy)phenyl]quinoline-3-carboxylic acid. 1H NMR (400MHz, chloroform) δ = 14.01 (s, 1H), 8.78 (s, 1H), 7.74-7.70 (m, 1H), 7.56-7.51 (m, 4H), 7.33-7.31 (dd, 1H), 7.17-7.14 (dd, 1H), 2.61 (s, 3H)

[0167] [Table 5] JPEG2025506046000024.jpg246161 JPEG2025506046000025.jpg249165 JPEG2025506046000026.jpg241168 JPEG2025506046000027.jpg231165 JPEG2025506046000028.jpg249163 JPEG2025506046000029.jpg131158

[0168] Biological Examples Seeds of various test species are sown in standard soil in pots (Abutilon theophrasti (ABUTH), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX), Amaranthus retoflexus (AMARE), Solanum nigrum (SOLNI), Lolium perenne (LOLPE), Amaranthus palmeri (AMAPA)). After 8 days of cultivation in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with an aqueous spray solution from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compounds are applied at 1000 g / ha. The test plants are then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice daily. After 13 days, the tests are evaluated for the percentage of damage caused by the plants. The biological activity is shown in the following table on a 5-point scale (5=81-100%; 4=61-80%; 3=41-60%; 2=21-40%; 1=0-20%, -=not tested).

[0169] [Table 6]

[0170] [Table 7]

Claims

1. Formula (I) 【Chemistry 1】 (In the formula, X is O; R 1 is R 10 C which may be optionally substituted with one or two groups which may be the same or different and which are represented by 1 ~C 6 alkyl or phenyl; R 2 is hydrogen, phenyl, or heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and where each phenyl and heteroaryl moiety is selected from R 8 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 3 is hydrogen or C 1 ~C 6 is alkyl; R 4 , R 5 , R 6 , and R 7 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl, C 1 ~C 6 Alkylsulfonyl, C 1 ~C 6 alkylaminocarbonyl, aminocarbonyl, and phenyl, where each phenyl moiety is independently selected from R 9 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 8 is cyano, nitro, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 1 ~C 6 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl, C 1 ~C 6 Alkylsulfonyl, C 1 ~C 6 Alkyl sulfonamides, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkoxycarbonyl, C 1 ~C 6 Alkylaminocarbonyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkylaminocarbonyl, or N,N-di(C 1 ~C 4 alkyl)aminocarbonyl; R 9 is cyano, nitro, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 1 ~C 6 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl, C 1 ~C 6 Alkylsulfonyl, C 1 ~C 6 Alkyl sulfonamides, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkoxycarbonyl, C 1 ~C 6 Alkylaminocarbonyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkylaminocarbonyl, or N,N-di(C 1 ~C 4 alkyl)aminocarbonyl; R 10 is halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylsulfanyl, or C 1 ~C 6 alkylsulfonyl) or a salt or N-oxide thereof.

2. R 1 But, R 10 C optionally substituted with a single group represented by 1 ~C 3 The compound of claim 1 , which is alkyl or phenyl.

3. R 2 is hydrogen or R 8 3. The compound according to claim 1 or claim 2, wherein the phenyl is substituted with one or two groups, which may be the same or different, represented by

4. R 2 But, R 8 The compound according to any one of claims 1 to 3, wherein the phenyl is substituted with one or two groups, which may be the same or different, represented by

5. R 3 The compound according to any one of claims 1 to 4, wherein is hydrogen.

6. R 5 is hydrogen, halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 3 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 alkylaminocarbonyl, aminocarbonyl, or phenyl, where each phenyl moiety is R 9 The compound according to any one of claims 1 to 5, optionally substituted with one or two groups, which may be the same or different, represented by

7. R 4 , R 6 , and R 7 is hydrogen, halogen, cyano, C 1 ~C 3 Alkoxy, and C 1 ~C 3 haloalkyl, R 5 is hydrogen, halogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkylsulfanyl, C 1 ~C 3 alkylsulfonyl, aminocarbonyl, or phenyl, wherein the phenyl moiety is a single R 9 The compound according to any one of claims 1 to 6, optionally substituted with a group.

8. R 4 The compound according to any one of claims 1 to 7, wherein is hydrogen, halogen, cyano, acetyl, or trifluoromethyl.

9. R 8 The compound according to any one of claims 1 to 8, wherein is halogen.

10. X is O; R 1 is ethyl or 4-trifluoromethoxyphenyl; R 2 is hydrogen, 3,4-dichlorophenyl or 4-fluorophenyl; R 3 is hydrogen; R 4 , R 5 , R 6 , and R 7 The compound of any one of claims 1 to 9, wherein are each independently selected from hydrogen, halogen, cyano, methyl, methoxy, trifluoromethyl, methylsulfanyl, methylsulfonyl, aminocarbonyl, and 4-fluorophenyl.

11. A herbicidal composition comprising a compound according to any one of claims 1 to 10 and an agriculturally acceptable formulation adjuvant.

12. 12. The herbicidal composition of claim 11 further comprising at least one additional pesticide.

13. 13. The herbicidal composition of claim 12, wherein the additional pesticide is a herbicide or a herbicide safener.

14. A method for controlling the growth of unwanted plants, comprising the step of applying a compound of formula (I) as defined in any one of claims 1 to 10 or a herbicidal composition as defined in any one of claims 11 to 13 to said unwanted plants or their habitat.

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

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