Herbicidal derivatives

Abstract

Compounds of formula (I) [Formula 1] TIFF2024541080000059.tif41160, wherein the substituents are as defined in claim 1. The present invention further relates to herbicidal compositions comprising the compounds of formula (I) and to the use of the compounds of formula (I) for controlling weeds in crops of particularly useful plants.

Description

[Technical field]

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

[0002] EP 0273325, EP 0274717, U.S. Pat. No. 5,183,891, WO 2021 / 233786, and WO 2021 / 233787 describe shinorine derivatives as herbicides. Summary of the Invention [Means for solving the problem]

[0003] According to the present invention, a compound of formula (I): [ka] (In the formula, X is O, NR 7 or S; R 1 is heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms independently selected from N, O, and S, and the heteroaryl moiety being R 8 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 2 is halogen, cyano, cyano C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy C2-C6 alkenyl, C2-C6 alkenyloxy C1-C6 alkyl, -CR 11 =N-OR 10 , Nitro, S(O) nC1-C6 alkyl, S(O) n C1-C6 haloalkyl or S(O) n C3-C6 cycloalkyl; R 3 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenylC1-C3 alkyl, and the phenyl portion is R 12 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl; R 7 is hydrogen, C1-C3 alkyl or C1-C3 alkoxy; R 8 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, or C1-C6 alkylsulfonyl; or Any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a six-membered aryl ring, or any two adjacent R 8 Groups may, together with the carbon atom to which they are attached, form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 8 Groups may be taken together with the carbon atom to which they are attached to form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the aryl, heterocyclyl or heteroaryl ring may be selected from R 9and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by n is 0, 1 or 2; R 9 is halogen, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy; R 10 and R 11 are each independently selected from hydrogen and C1-C3 alkyl; R 12 is halogen, cyano, C1-C3 alkyl or C1-C3 alkoxy. Or, a salt or N-oxide thereof is provided.

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

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

[0006] According to a third aspect of the present invention there is provided a method of controlling weeds in a locus 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, for example, one, two, or three R 8It means that the alkyl group may or may not have one or more identical or different substituents such as aryl, ...

[0009] As used herein, the terms "cyano" and "nitrile" refer to a -CN group.

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

[0011] As used herein, the term "hydroxy" refers to an --OH group.

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

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

[0014] 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 construed accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, and their isomers, such as iso-propyl. A "C1-C6 alkylene" group refers to the corresponding definition of C1-C6 alkyl, except for groups that are attached to the remainder of the molecule by two single bonds. The term "C1-C2 alkylene" should be construed accordingly. Examples of C1-C6 alkylene include, but are not limited to, -CH2-, -CH2CH2-, and -(CH2)3-.

[0015] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, substituted by one or more halogen atoms, which may be the same or different. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoromethyl.

[0016] As used herein, the term "cyano C1-C6 alkyl" refers to a C1-C6 alkyl group, as generally defined above, substituted with one or more cyano groups, as defined above. Examples of cyano C1-C6 alkyl include, but are not limited to, 2-cyanomethyl and 2-cyanoethyl.

[0017] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as generally defined above, substituted by one or more halogen atoms, which may be the same or different. The terms "C1-C4 haloalkoxy" and "C1-C3 haloalkoxy" should be interpreted accordingly. Examples of C1-C6 haloalkoxy include, but are not limited to, trifluoromethoxy.

[0018] As used herein, the term "C1-C6 alkoxy" refers to R a is a C1-C6 alkyl group as generally defined above; a The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be construed accordingly. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

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

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

[0021] As used herein, the term “C1-C6 alkoxy C1-C6 alkyl” refers to a group of formula R b OR a -, where R b is a C1-C6 alkyl group as generally defined above, and R a is a C1-C6 alkylene group as generally defined above. Examples of C1-C6 alkoxyC1-C6 alkyl include, but are not limited to, methoxymethyl, methoxyethyl, and ethoxymethyl.

[0022] 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 accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0023] 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 by a C1-C6 alkylene linker as defined above. Examples of C3-C6 cycloalkyl C1-C6 alkyl include, but are not limited to, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, and cyclohexylmethyl.

[0024] As used herein, the term “C1-C6 alkoxy C2-C6 alkenyl” refers to a group of formula R b OR a -, where R b is a C1-C6 alkyl group as generally defined above, and R a is a C1-C6 alkene group as generally defined above. Examples of C1-C6 alkoxy C2-C6 alkenyl include, but are not limited to, 1-methoxyvinyl and 1-ethoxyvinyl.

[0025] As used herein, the term “C2-C6 alkenyloxy C1-C6 alkyl” refers to a group of the formula R b OR a -, where R b is a C2-C6 alkenyl group as generally defined above, and R a is a C1-C6 alkylene group as generally defined above.

[0026] As used herein, the term "phenoxy" refers to a phenyl ring attached to the remainder of the molecule via an oxygen atom.

[0027] As used herein, the term "phenyl C1-C3 alkyl" refers to a phenyl ring attached to the remainder of the molecule by a C1-C3 alkylene linker as defined above.

[0028] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S. Heteroaryl groups can be attached to the remainder of the molecule through a carbon atom or a heteroatom. Examples of heteroaryl include, but are not limited to, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, benzothiazolyl, imidazolyl, benzimidazolyl, oxadiazolyl, pyridyl, pyrrolyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, indazolyl, pyrazolyl, thiazolyl, oxazolyl, benzoxazolyl, pyridazinyl, cinnolinyl, pyrimidinyl, and quinazolinyl.

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

[0030] As used herein, the term "C1-C6 alkylsulfanyl" refers to R a is a C1-C6 alkyl group as generally defined above; a The terms "C1-C4 alkylsulfanyl" and "C1-C3 alkylsulfanyl" should be construed accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfanyl.

[0031] As used herein, the term "C1-C6 alkylsulfinyl" refers to R a is a C1-C6 alkyl group as generally defined above; a The terms "C1-C4 alkylsulfinyl" and "C1-C3 alkylsulfinyl" should be construed accordingly. Examples of C1-C6 alkylsulfinyl include, but are not limited to, methylsulfinyl.

[0032] As used herein, the term "C1-C6 alkylsulfonyl" refers to R a is a C1-C6 alkyl group as generally defined above; a The terms "C1-C4 alkylsulfonyl" and "C1-C3 alkylsulfonyl" should be construed accordingly. Examples of C1-C6 alkylsulfanyl include, but are not limited to, methylsulfonyl.

[0033] The possible presence of one or more stereogenic centers in the compounds of formula (I) means that the compounds can be in optical isomeric, i.e. enantiomeric or diastereomeric form. Also, the restriction of rotation about a single bond can give rise to atropisomers. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof of the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of the compounds of formula (I). In each case, the compounds of formula (I) according to the present invention are in the free form, in the oxidized form as N-oxides or in the salt form, for example in the form of an agriculturally usable salt. Preferred are the salts that the compounds of formula (I) can form with amines, including primary, secondary and tertiary amines (e.g. ammonia, dimethylamine and triethylamine), alkali metal bases and alkaline earth metal bases, transition metals or quaternary ammonium bases. N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds. They are described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton (1991).

[0034] The following list describes the substituents X, R for compounds of formula (I): 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , n, R 8 , R 9 , R 10 , R 11 , and R 12 Definitions are provided below, including preferred definitions for: For any one of these substituents, any of the definitions given below may be combined with any of the definitions of any other substituents given below or elsewhere in this specification.

[0035] X is O, NR 7 or S. In one set of embodiments, X is O. In another set of embodiments, X is S. In a further set of embodiments, X is NR 7 It is.

[0036] R 1 is heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms independently selected from N, O, and S, and the heteroaryl moiety being R 8 Preferably, R 1 is heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms independently selected from N, O, and S, and the heteroaryl moiety being R 8 More preferably, R 1 is heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms independently selected from N, O, and S, and the heteroaryl moiety being R 8 Even more preferably, R 1is heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and S, and the heteroaryl moiety being R 8 Even more preferably, R 1 is heteroaryl, the heteroaryl moiety being a 6-membered aromatic ring containing 1 or 2 nitrogen heteroatoms, and the heteroaryl moiety being R 8 It may be optionally substituted with one or two groups, which may be the same or different, represented by

[0037] In one embodiment, R 1 is pyridyl or pyrimidinyl, each pyridyl or pyrimidinyl moiety being R 8 In another embodiment, R 1 is pyridyl or pyrimidinyl, each pyridyl moiety being R 8 and each of the substituted aryl groups is substituted with one or two groups which may be the same or different and are represented by the following formula:

[0038] R 2 is halogen, cyano, cyano C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy C2-C6 alkenyl, C2-C6 alkenyloxy C1-C6 alkyl, -CR 11 =N-OR 10 , Nitro, S(O) n C1-C6 alkyl, S(O) n C1-C6 haloalkyl or S(O) n C3-C6 cycloalkyl. Preferably, R 2 is halogen, cyano, cyano C1-C4 alkyl, C1-C4 haloalkyl, C1-C6 alkylcarbonyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C6 alkoxy C2-C6 alkenyl, C2-C4 alkenyloxy C1-C4 alkyl, -CR11 =N-OR 10 , Nitro, S(O) n C1-C6 alkyl, S(O) n C1-C4 haloalkyl or S(O) n More preferably, R 2 is halogen, cyano, C1-C6 alkylcarbonyl, C1-C6 alkoxyC2-C6 alkenyl, -CR 11 =N-OR 10 Or S(O) n More preferably, R 2 is halogen, cyano, C1-C4 alkylcarbonyl, C1-C4 alkoxy, C2-C4 alkenyl, -CR 11 =N-OR 10 Or S(O)2C1-C4 alkyl.

[0039] In one set of embodiments, R 2 is halogen, cyano, acetyl, 1-methoxyvinyl, 1-ethoxyvinyl, methylsulfonyl, or N-methoxy-C-methyl-carbonimidoyl. 2 is halogen, cyano, acetyl, or N-methoxy-C-methyl-carbonimidoyl. 2 is bromo, cyano, acetyl, or N-methoxy-C-methyl-carbonimidoyl. 2 is halogen or cyano, preferably bromo or cyano.

[0040] R 3 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenylC1-C3 alkyl, and the phenyl portion is R 12 Preferably, R 3is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C3 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenylC1-C2 alkyl, and the phenyl portion is R 12 More preferably, R 3 is hydrogen, C1-C6 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C1-C4 alkoxy C1-C3 alkyl, phenyl or benzyl, and the phenyl portion is R 12 Even more preferably, R 3 is hydrogen or C1-C4 alkyl. Even more preferably, R 3 is hydrogen or C1-C3 alkyl. 3 It is particularly preferred when R is hydrogen, methyl or ethyl. In one set of embodiments, R 3 is hydrogen or ethyl.

[0041] R 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl. 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, C1-C3 alkylsulfinyl, and C1-C3 alkylsulfonyl. More preferably, R 4 , R 5 and R 6are each independently selected from hydrogen, fluoro, bromo, cyano, C1-C4 alkyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylsulfanyl, and methylsulfonyl. Even more preferably, R 4 , R 5 and R 6 are each independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl. Even more preferably, R 4 , R 5 and R 6 is independently selected from hydrogen, fluoro, bromo, cyano, methyl, isobutyl, methoxy, and trifluoromethyl. 4 , R 5 and R 6 are all hydrogen.

[0042] R 7 is hydrogen, C1-C3 alkyl or C1-C3 alkoxy. 7 is hydrogen, methyl or methoxy. More preferably, R 7 is hydrogen.

[0043] R 8 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, or C1-C6 alkylsulfonyl; or Any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a six-membered aryl ring, or any two adjacent R 8 Groups may, together with the carbon atom to which they are attached, form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 8 Groups may be taken together with the carbon atom to which they are attached to form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the aryl, heterocyclyl or heteroaryl ring may be selected from R 9It may be optionally substituted with 1, 2, 3 or 4 groups which may be the same or different and are represented by

[0044] Preferably, R 8 is halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkylsulfanyl, or C1-C3 alkylsulfonyl; or Any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a six-membered aryl ring, or any two adjacent R 8 Groups may, together with the carbon atom to which they are attached, form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 8 Groups may be taken together with the carbon atom to which they are attached to form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl or heteroaryl ring may be 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

[0045] More preferably, R 8 is halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or C1-C3 alkylsulfanyl; or Any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a six-membered aryl ring, or any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 oxygen atoms, or any two adjacent R 8 The groups, together with the carbon atom to which they are attached, can form a 5- or 6-membered heteroaryl ring containing 1 or 2 nitrogen atoms, and the heterocyclyl or heteroaryl ring can be selected from R 9It may be optionally substituted with one or two groups, which may be the same or different, represented by

[0046] Even more preferably, R 8 is halogen, C1-C3 alkyl, C1-C3 alkoxy, or C1-C3 haloalkyl; or Any two adjacent R 8 The groups, together with the carbon atoms to which they are attached, can form a 5- or 6-membered heterocyclyl ring containing 1 or 2 oxygen atoms, and the heterocyclyl ring can be selected from R 9 It may be optionally substituted with one or two groups, which may be the same or different, represented by

[0047] Even more preferably, R 8 is chloro, bromo, fluoro, methyl, methoxy or trifluoromethyl; or any two adjacent R 8 The groups, together with the carbon atom to which they are attached, can form a 5-membered heterocyclyl ring containing two oxygen atoms and the heterocyclyl ring is substituted with two fluoro groups.

[0048] In one set of embodiments, R 8 is halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, or C1-C3 haloalkoxy; or difluoromethoxy; or any two adjacent R 8 The groups, together with the carbon atom to which they are attached, can form a 5-membered heterocyclyl ring containing two oxygen atoms and the heterocyclyl ring is substituted with two fluoro groups.

[0049] In another set of embodiments, R 8 is halogen, methyl, methoxy, difluoromethyl or difluoromethoxy; or any two adjacent R 8 The groups, together with the carbon atom to which they are attached, can form a 5-membered heterocyclyl ring containing two oxygen atoms and the heterocyclyl ring is substituted with two fluoro groups.

[0050] R 9 is halogen, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy. 9 is halogen, cyano, methyl or methoxy. More preferably, R 9 is halogen, methyl or methoxy. Even more preferably, R 9 is halogen. Even more preferably, R 9 is fluoro.

[0051] R 10 and R 11 are each independently selected from hydrogen and C1-C3 alkyl. 10 and R 11 Each is independently selected from hydrogen, methyl, and ethyl. In one set of embodiments, R 10 and R 11 are both methyl.

[0052] R 12 is halogen, cyano, C1-C3 alkyl or C1-C3 alkoxy. 12 is bromo, chloro, fluoro, cyano, methyl or methoxy.

[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 a further set of embodiments, n is 1. In a further set of embodiments, n is 2.

[0054] In the compounds of formula (I) according to the present invention, X is O, NR 7 and; R 1 is heteroaryl, the heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N, O and S, and the heteroaryl moiety being R 8and optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by R 2 is bromo or cyano; R 3 is hydrogen or C1-C3 alkyl; R 4 , R 5 and R 6 are all hydrogen; R 7 is hydrogen, C1-C3 alkyl; and R 8 is halogen, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, or C1-C6 alkylsulfonyl; or Any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a six-membered aryl ring, or any two adjacent R 8 Groups may, together with the carbon atom to which they are attached, form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 8 Groups may be taken together with the carbon atom to which they are attached to form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the aryl, heterocyclyl or heteroaryl ring may be selected from R 9 and optionally substituted with 1, 2 or 3 groups, which may be the same or different, represented by R 9 is a halogen.

[0055] In another set of embodiments, X is O; R 1 is heteroaryl, the heteroaryl moiety being a 6-membered aromatic monocyclic ring containing 1 or 2 nitrogen atoms, and the heteroaryl moiety being R 8 and optionally substituted with one or two groups, which may be the same or different, represented by R2 is bromo or cyano; R 3 is hydrogen, methyl or ethyl; R 4 , R 5 and R 6 are all hydrogen; R 8 is halogen, methyl, methoxy or trifluoromethyl; or Any two adjacent R 8 The groups, together with the carbon atom to which they are attached, can form a 5-membered heterocyclyl ring containing two oxygen atoms and the heterocyclyl ring is substituted with two fluoro groups.

[0056] In a further set of embodiments, X is O; R 1 is pyridyl or pyrimidinyl, each pyridyl or pyrimidinyl moiety being R 8 and optionally substituted with one or two groups, which may be the same or different, represented by R 2 is bromo, cyano, acetyl or N-methoxy-C-methyl-carbonimidoyl; R 3 is hydrogen or ethyl; R 4 , R 5 and R 6 are all hydrogen; R 8 is halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, or C1-C3 haloalkoxy; or Any two adjacent R 8 The groups, together with the carbon atom to which they are attached, can form a 5-membered heterocyclyl ring containing two oxygen atoms and the heterocyclyl ring is substituted with two fluoro groups.

[0057] Preferably, the compound of formula (I) is: 5-Cyano-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylic acid (Compound 1); Ethyl 5-bromo-1-(2-chloro-4-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 3); Ethyl 5-bromo-1-(6-methoxy-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 4); Ethyl 5-bromo-1-(5-chloro-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 5); Ethyl 5-bromo-1-(2-methoxy-4-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 9); Ethyl 5-bromo-1-(2-bromo-4-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 10); Ethyl 5-cyano-1-(6-fluoro-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 11); Ethyl 5-bromo-1-(6-fluoro-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 23); Ethyl 5-bromo-1-(2,2-difluoro-[1,3]dioxolo[4,5-b]pyridin-6-yl)-4-oxo-cinnoline-3-carboxylate (compound 24); Ethyl 5-bromo-1-(6-chloro-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 26); Ethyl 5-bromo-1-(6-methoxy-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 29); Ethyl 5-bromo-1-[6-(difluoromethyl)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 30); Ethyl 5-bromo-1-(6-methoxypyrimidin-4-yl)-4-oxo-cinnoline-3-carboxylate (compound 32); Ethyl 5-bromo-1-(5-chloro-3-cyano-2-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 33); Ethyl 5-cyano-1-[6-(difluoromethoxy)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 35); Ethyl 5-bromo-1-[6-(difluoromethoxy)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 36); Ethyl 5-acetyl-1-[6-(difluoromethoxy)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 37); Ethyl 5-bromo-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 38); Ethyl 5-acetyl-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 40); and Ethyl 1-[2-(difluoromethoxy)-4-pyridyl]-5-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-cinnoline-3-carboxylate (compound 41) is selected from.

[0058] More preferably, the compound of formula (I) is: 5-Cyano-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylic acid (Compound 1); Ethyl 5-bromo-1-(2-chloro-4-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 3); Ethyl 5-bromo-1-(6-methoxy-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 4); Ethyl 5-bromo-1-(5-chloro-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 5); Ethyl 5-bromo-1-(2-bromo-4-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 10); Ethyl 5-cyano-1-(6-fluoro-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 11); Ethyl 5-bromo-1-(6-fluoro-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 23); Ethyl 5-bromo-1-(2,2-difluoro-[1,3]dioxolo[4,5-b]pyridin-6-yl)-4-oxo-cinnoline-3-carboxylate (compound 24); Ethyl 5-bromo-1-(6-chloro-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 26); Ethyl 5-bromo-1-(6-methoxy-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 29); Ethyl 5-bromo-1-[6-(difluoromethyl)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 30); Ethyl 5-bromo-1-[6-(difluoromethoxy)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 36); Ethyl 5-acetyl-1-[6-(difluoromethoxy)-3-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 37); Ethyl 5-bromo-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 38); Ethyl 5-acetyl-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 40); and Ethyl 1-[2-(difluoromethoxy)-4-pyridyl]-5-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-cinnoline-3-carboxylate (compound 41) is selected from.

[0059] The compounds of the present invention can be prepared as shown in the following schemes, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I). A general method for producing compounds of formula (I) is shown below. Unless otherwise specified in the text, X, R 1 , R 2 , R 3 , R 4 , R 5 and R 6is as defined hereinabove. The starting materials used in the preparation of the compounds of the present invention can be purchased from ordinary commercial suppliers or prepared by known methods. The starting materials and intermediates can be purified by prior art methodologies such as chromatography, crystallization, distillation and filtration before being used in the next step.

[0060] Scheme 1: [ka] A compound of formula (I) wherein X is oxygen and R 3 is hydrogen) with a suitable base (such as sodium hydroxide or lithium hydroxide) or a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as water), to prepare a compound of formula (I) (wherein X is oxygen and R 3 is not hydrogen and is any other R defined above 3 This is shown in Scheme 1 above. Compounds of formula (I) may also be prepared by the methods described below.

[0061] Scheme 2: [ka] Compounds of formula (I) may also be prepared from compounds of formula (B) where Y is Cl, Br or I. In an embodiment of the invention, R 2When is C2-C6 alkenyloxy and Y is Br, compounds of formula (I) can be prepared in a Stille reaction by reaction with a stannane reagent in the presence of a palladium catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium) or dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium(ll) dichloromethane adduct) in a suitable organic solvent (such as toluene, 1,4-dioxane or N,N-dimethylformamide) with or without a base (such as triethylamine) at an elevated reaction temperature (e.g. 120°C). This is shown in Scheme 2 above.

[0062] Scheme 3: [ka] In the subsequent transformation, R 2 The compound of formula (I) in which R is C1-C6 alkylcarbonyl is 2 can be prepared from a compound of formula (I) where is C2-C6 alkenyloxy by a hydrolysis reaction. Typically, this reaction is carried out by treatment with an aqueous acid (such as hydrochloric acid) optionally in a suitable organic solvent (such as acetone, 1,4-dioxane or tetrahydrofuran) and at a suitable temperature (20° C. to 60° C.). This is shown in Scheme 3 above.

[0063] Scheme 4: [ka] In further transformations, R 2 -CR 11 =N-OR 10 The compound of formula (I) is R 2 can be prepared from a compound of formula (I) where R is C1-C6 alkylcarbonyl by a condensation reaction with a suitable hydroxylamine compound. Typically, this reaction is carried out by reacting a compound of formula "H2NOR 10" with or without the addition of a base (such as sodium acetate, pyridine or aqueous potassium hydroxide) in a suitable organic solvent (such as ethanol, dimethylsulfoxide, tetrahydrofuran, dimethyl ether or methanol) at elevated temperature with or without additional water. This is shown in Scheme 4 above.

[0064] Scheme 5: [ka] In another transformation, compounds of formula (B) where Y is Br can be converted to R 2 can be converted to a compound of formula (I) in which is a nitrile. Typically, this reaction is carried out by reaction of a compound of formula (B) with dicyanozinc in the presence of a suitable catalyst (such as dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium), tris(dibenzylideneacetone)dipalladium, dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium(ll) dichloromethane adduct, or palladium diacetate, optionally with a ligand (such as 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl), in a suitable organic solvent (such as dimethylformamide) at elevated temperature. This is shown in Scheme 5 above.

[0065] Scheme 6: [ka] In another transformation, a compound of formula (Ia), 2 is Br or CN, and R 1 is hydrogen) is the same as the known literature conditions, S N Reaction with heteroaryl halides under Ar conditions gives compounds of formula (I), 1is heteroaryl). Typically, this reaction is carried out in the presence of a base (such as potassium carbonate) in an organic solvent (such as dimethylacetamide or N,N-dimethylformamide) at elevated temperatures (such as 100° C.-170° C.). This is shown in Scheme 6 above.

[0066] Scheme 7: [ka] In another transformation, compounds of formula (Ia) can be converted to compounds of formula (I), where R 1 is heteroaryl). Typically, this reaction is carried out by reacting a compound of formula (Ia) with R in the presence of a suitable copper catalyst (such as copper(II) acetate), optionally in the presence of a base (such as triethylamine, pyridine, N,N-diethylethanamine or sodium carbonate), in a suitable organic solvent (such as acetonitrile, dimethylsulfoxide, dichloroethane or toluene), optionally in a compressed air stream or in the presence of an additional oxidizing agent (such as boronic acid, pyridine N-oxide or di-tert-butylperoxide). 1 -boronic acids or boroxines, which is shown in Scheme 7 above.

[0067] Scheme 8: [ka] In a different transformation, the compound of formula (Ia), 2 is Br) can be converted to compounds of formula (Ia), where R 2 is CN), which is shown in Scheme 8 above.

[0068] Scheme 9: [ka] Compounds of formula (Ia) can be prepared from compounds of formula (Ca) (wherein LG is a suitable leaving group such as F, Cl or Br) by treatment with a base (such as a metal hydride such as sodium hydride or potassium carbonate) in a suitable solvent (such as bis(2-methoxyethyl)ether, 1,4-dioxane, tetrahydrofuran or N,N-dimethylformamide) at elevated temperature (e.g. 150° C.) or in the absence of a base. This is shown in Scheme 9 above.

[0069] Scheme 10: [ka] Compounds of formula (B), where Y is Br, X is O and LG is a suitable leaving group (such as F, Cl or Br), can be prepared from compounds of formula (C) by treatment with a base (such as a metal hydride such as sodium hydride or potassium carbonate) in a suitable solvent (such as 1,4-dioxane, tetrahydrofuran or N,N-dimethylformamide) at elevated temperature (for example 100° C.). This is shown in Scheme 10 above.

[0070] Scheme 11: [ka] Compounds of formula (C), where Y is Br and LG is a suitable leaving group (such as F, Cl or Br), can be prepared from the reaction of a β-ketoester of formula (D) with an arenediazonium salt. The arenediazonium salt can be prepared in situ by diazotization of an aniline of formula (E) with sodium nitrite in water in the presence of an acid (such as hydrochloric acid), followed by reaction with a compound of formula (D) in the presence of a suitable base (such as sodium or potassium acetate or potassium carbonate) in a suitable solvent (water, methanol or ethanol) at a temperature between 0° C. and 25° C. Compounds of formula (E) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 11.

[0071] Scheme 12: [ka] Dicarbonyl compounds of formula (D), where Y is Br and LG is a suitable leaving group (such as F, Cl or Br), can be prepared from methyl ketone compounds of formula (F) and diesters of formula (G) via Claisen condensation by treatment of the methyl ketone with a suitable base (such as potassium t-butoxide or sodium hydride) in a suitable solvent (such as tetrahydrofuran, N,N-dimethylformamide, toluene or 1,4-dioxane), followed by reaction of the mixture with a carbonate ester (such as dimethyl carbonate or diethyl carbonate) at a temperature between 0° C. and 110° C. Compounds of formula (F) and formula (G) are commercially available or can be prepared by methods well known to those skilled in the art. This is shown above in Scheme 12.

[0072] 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). The present invention may also 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 obstruction of growth, or prevention or reduction of germination. It is noted that the compounds of the present invention show a significantly improved selectivity compared to known structurally similar compounds. In general, the plants to be controlled are undesirable plants (weeds). By "habitat" is meant the area in which the plants are growing or will grow. The application may be carried out 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).

[0073] 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.

[0074] Application is generally accomplished 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.

[0075] 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 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®.

[0076] 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, in particular those of the genus Bacillus.

[0077] 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®.

[0078] A plant crop or its seed material can be both tolerant to herbicides and tolerant to insect feeding (a "stacked" transgenic event) at the same time. For example, a seed can be capable of expressing an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

[0079] Crop plants are to be understood to include those obtainable by conventional methods of breeding or genetic engineering and containing so-called output traits (e.g., improved storage stability, higher nutritional value and improved flavor).

[0080] The compounds of formula (I) (or compositions containing them) can be used to control undesirable plants (collectively "weeds"), such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, and Moro. They may be both monocotyledonous species, such as Sorghum, and dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

[0081] 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 use in agriculture.Agricultural carriers are well known in the art.

[0082] 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 auxiliaries, preferably including from 0 to 25% by weight of surface-active substances.

[0083] The composition may be selected from a number of formulation types, including emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water-dispersible granule (WG), emulsifiable granule (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), micro-emulsion (ME), oil dispersion (OD), oil-miscible flowable (OF), oil-miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical concentrate (TK), dispersible concentrate (DC), soluble powder (SP), wettable powder (WP) and soluble granule (SG). The formulation type selected in any case will depend on the specific purpose envisaged and the physical, chemical and biological properties of the compound of formula (I). Water-soluble powders (SP) can be prepared by mixing the compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersing agents or a mixture of said substances to improve dispersibility / solubility in water. This mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG). Wettable powders (WP) can be prepared by mixing the compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably one or more dispersing agents and optionally one or more suspending agents to promote dispersion in liquid. This mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG). Granules (GR) may be formed either by granulating a mixture of the compound of formula (I) with one or more powdered solid diluents or carriers, or by absorbing the compound of formula (I) (or a solution thereof in a suitable material) into a porous granular material (such as pumice, attapulgite clay, fuller's earth, kieselguhr, diatomaceous earth or ground corn cob), or by granulating from preformed blank granules by adsorbing the compound of formula (I) (or a solution thereof in a suitable material) onto a hard core material (such as sand, silicates, inorganic carbonates, sulfates or phosphates) and optionally drying.Substances commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum-based solvents, alcohols, ethers, ketones and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars and vegetable oils). One or more other additives may also be included in the granules (e.g., emulsifiers, wetting agents or dispersants). Dispersible concentrates (DC) may be prepared by dissolving the 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 water dilutability or prevent crystallization in the spray tank). Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving the compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers or a mixture of the above substances). Suitable organic solvents for use in the 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-C9, etc.). 10dimethylamides of fatty acids) and chlorinated hydrocarbons. EC products can be spontaneously emulsified when added to water to produce emulsions that are stable enough to be spray-applied by appropriate equipment. The preparation of EW involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it can be melted at an appropriate temperature, typically below 70° C.) or in solution (by dissolving it in a suitable solvent) and then emulsifying the resulting liquid or solution in water containing one or more SAA under high shear to produce 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 water solubility. Microemulsions (MEs) can be prepared by mixing water with a blend of one or more SAA and one or more solvents to spontaneously produce a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in either the water or the solvent / SAA blend. Suitable solvents for use in ME include those mentioned above for use in EC or EW. ME can be either an oil-in-water or water-in-oil system (which system is present can be determined by conductivity measurements) and can be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. ME is suitable for dilution in water, remaining a microemulsion or forming a conventional oil-in-water emulsion. Suspension concentrates (SC) can include aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SC can be prepared by ball milling or bead milling a solid compound of formula (I) in a suitable medium, optionally with one or more dispersants, to produce a fine particle suspension of the compound. One or more wetting agents can be included in the composition, and a suspending agent can be included to reduce the settling rate of the particles. Alternatively, the compound of formula (I) can be dry milled and added to water containing the materials mentioned above to produce the desired end product. Aerosol formulations contain a compound of formula (I) and a suitable propellant (eg, n-butane).The compound of 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 obtain a composition for use in a non-pressurized, manual spray pump. Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, except with an additional polymerization step in which each oil droplet is encapsulated by a polymeric shell and an aqueous dispersion of oil droplets containing the compound of formula (I) and, optionally, a carrier or diluent therefor is obtained. The polymeric shell can be produced by either an interfacial polycondensation reaction or a coacervation procedure. This composition provides a controlled release of the compound of formula (I) and can be used for seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymer matrix to provide a delayed controlled release of the compound.

[0084] The composition may contain one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on a surface; rain resistance on a treated surface; or uptake or mobility of the compound of formula (I). Such additives include surface active agents (SAA), oil-based spray additives, such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oil), modified vegetable oils such as methylated rapeseed oil (MRSO), and blends of these with other bioactivity enhancing adjuvants (formulation ingredients that may aid or modify the action of the compound of formula (I)).

[0085] Wetting agents, dispersing agents and emulsifying agents can be SAAs of the cationic, anionic, amphoteric or non-ionic type.Suitable SAAs of the cationic type include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines and amine salts. Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate, and a mixture of di-isopropyl- and tri-isopropyl-naphthalenesulfonates), sulfate ethers, sulfate alcohol ethers (e.g., sodium laureth-3 sulfate), carboxylate ethers (e.g., sodium laureth-3 carboxylate), phosphate esters (products from the reaction of one or more aliphatic alcohols with phosphoric acid (mainly mono-esters) or phosphorus pentoxide (mainly di-esters), such as the reaction of lauryl alcohol with tetraphosphoric acid; furthermore, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignosulfonates, and phosphates / sulfonates of tristyrylphenol. Suitable amphoteric SAAs include betaines, propionates, and glycinates. Suitable non-ionic SAAs include the 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 said partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); lecithin and sorbitan and their esters, alkyl polyglycosides and tristyrylphenols.

[0086] Suitable suspending agents include hydrocolloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0087] The compounds of the present invention may 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 aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, and their potassium and sodium salts), Diclosulam, Difluhenican, Diflufenzopyr, Dimethachlor, Dimethenamid-P, Dioxopyritrio, 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 (iofensulfuron-methyl-sodium), mesosulfuron (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, pinoxa den, 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, cyanosulfonyl ... mazin, S-metallochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrrolimeth, thiencarbazone, thifensulfuron, thiaphenacyl, torpiralate, 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)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazole- 3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (and its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate and schizolinyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate. including anomethyl 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, Ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl) 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]propanoic acid lysyl)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 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,Examples of the compound of formula (I) include 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. The compound of formula (I) may also be in the form of an ester or salt, as described, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012. The mixing ratio of the compound of formula (I) to the compound of formula (I) is preferably 1:100 to 1000:1.

[0088] Mixtures can be used to advantage in the above mentioned formulations (in this case the "active ingredient" refers to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0089] 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. Safeners of the compounds of formula (I) are 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.

[0090] 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.

[0091] The compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to the crop areas or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that influence plant growth. They can also be selective or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if necessary with further carriers, surfactants or application-promoting adjuvants customarily used in the technical field of formulations.

[0092] 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.

[0093] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0094] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, that can be used for their propagation, as well as vegetative bodies, such as cuttings or tubers, 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.

[0095] The pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0096] The compounds of formula (I) can be used in their original form or preferably together with the auxiliaries that are conveniently employed in the field of formulation technology.To this end, 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 situation at hand.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 compounds for obtaining special effects.

[0097] 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.

[0098] 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 necessary with further carriers, surfactants or application-promoting adjuvants customarily used in the field of formulations.

[0099] 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.

[0100] 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.

[0101] The following table shows individual compounds of formula (I) according to the invention: [ka] Here is an example:

[0102] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5]

[0103] Table A-1 provides 150 compounds of formula (I), A-1.001 to A-1.150, where X is oxygen and R 4 , R 5 and R 6 is hydrogen, and R 1 , R 2 and R 3 is as defined in Table 1.

[0104] Formulation example

[0105] [Table 2]

[0106] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder, which can be diluted with water to obtain a suspension of the desired concentration.

[0107] [Table 3]

[0108] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0109] 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%

[0110] Emulsions of any required dilution which can be used in plant protection can be obtained from this concentrate by dilution with water.

[0111] [Table 4]

[0112] Ready-to-use dusts can be 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.

[0113] Extrusion Granules Active ingredient [compound of formula (I)] 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0114] 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.

[0115] Coated Granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0116] 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.

[0117] 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%

[0118] 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, which allows living plants as well as plant propagation material to be treated by spraying, pouring or immersion to protect them from microbial infestation.

[0119] Flowable concentrates for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 10-20 mole 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%

[0120] 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, which allows living plants as well as plant propagation material to be treated by spraying, pouring or immersion to protect them from microbial infestation.

[0121] 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). The 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. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The median capsule diameter is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose. EXAMPLES

[0122] The following non-limiting examples provide specific methods for the synthesis of representative compounds of the invention referenced in Table 2 below.

[0123] List of Abbreviations °C = degrees Celsius, Å = angstroms, CDCl3 = chloroform-d, d = doublet, dd = doublet of doublet, DMSO = dimethylsulfoxide, m = multiplet, M = moles, MHz = megahertz, q = quartet, s = singlet, t = triplet

[0124] Example 1: Synthesis of 5-cyano-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylic acid (Compound 1) Step 1: Synthesis of methyl 3-(2-bromo-6-fluoro-phenyl)-3-oxo-propanoate [ka] Sodium hydride (2.8 g, 69.1 mmol, 60% by weight) was added in portions to a stirred solution of 1-(2-bromo-6-fluoro-phenyl)ethanone (5.0 g, 23.0 mmol) and dimethyl carbonate (37.3 g, 406 mmol) in N,N-dimethylformamide (20 mL) cooled to 0° C. under a nitrogen atmosphere. The reaction was allowed to warm to room temperature and stirred for 24 h. The reaction mixture was poured slowly onto ice and acidified to pH 3 with concentrated hydrochloric acid. The phases were separated and the aqueous phase was re-extracted with diethyl ether. The combined organic extracts were dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-30% ethyl acetate in cyclohexane as eluent to give the desired product (mixture of tautomers) as a colorless liquid. Keto form: 1 H NMR(400MHz,CDCl3)δ=7.46-7.36(m,1H),7.33-7.28(m,1H),7.15-6.98(m,1H),3.98-3.90(m,2H),3.79-3.61(m,3H)

[0125] Step 2: Synthesis of methyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-hydrazinylidene-3-oxo-propanoate [ka] To a cooled (0° C.) solution of methyl 3-(2-bromo-6-fluoro-phenyl)-3-oxo-propanoate (1.00 g, 3.27 mmol) in acetonitrile (10 mL) under nitrogen atmosphere was added triethylamine (2.30 mL, 16.4 mmol), followed by dropwise addition of a solution of 4-acetamidobenzenesulfonyl azide (0.785 g, 3.27 mmol) in acetonitrile (5 mL). The reaction mixture was stirred in an ice bath for 15 minutes and then at room temperature for 2 hours. After this time, the resulting reaction mixture was cooled to 0° C. and tributylphosphine (0.826 mL, 3.27 mmol) was added dropwise. The reaction mixture was stirred for 2 hours. The reaction mixture was partitioned between water and ethyl acetate (50 mL). The phases were separated and the aqueous phase was extracted into ethyl acetate (2×50 mL). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-30% ethyl acetate in hexanes as eluent to give the desired product as a light brown solid. 1 H NMR(400MHz,DMSO-d6)δ=10.8(s,1H),10.6(s,1H),7.47(d,1H),7.38-7.26(m,2H),3.80(s,3H).

[0126] Step 3: Synthesis of methyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate [ka] A solution of methyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-hydrazinylidene-3-oxo-propanoate (0.700 g, 2.19 mmol) in diglyme (1.5 mL) was heated at 150° C. for 4 h. After this time, methyl tert-butyl ether (20 mL) was added to cool the reaction mixture, and the mixture was stirred for 20 min. The resulting precipitate was filtered and the solid was air-dried to give methyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate as a brown solid. 1H NMR(400MHz,DMSO-d6)δ=13.8(s,1H),7.71-7.64(m,3H),3.83(s,3H).

[0127] Step 4: Synthesis of methyl 5-bromo-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylate [ka] To a mixture of methyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate (0.700 g, 2.47 mmol) in acetonitrile (30 mL) was added triethylamine (1.43 mL, 9.89 mmol), copper(II) acetate (0.494 g, 2.72 mmol) and pyrimidin-5-ylboronic acid (0.613 g, 4.95 mmol). The resulting solution was heated at 65° C. for 16 h. The reaction mixture was filtered through diatomaceous earth and partitioned between water and dichloromethane. The aqueous phase was extracted into dichloromethane (twice) and the combined organic extracts were washed successively with water and brine, dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-50% ethyl acetate in hexanes as eluent to give the desired product as a brown solid. 1 H NMR(400MHz,DMSO-d6)δ=7.83(d,1H),7.71-7.69(m,1H),7.62-7.61(m,2H),7.59(t,1H),7.32(d,1H),3.83(s,3H).

[0128] Step 5: Synthesis of methyl 5-cyano-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylate [ka] A mixture of methyl 5-bromo-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylate (0.140 g, 0.330 mmol), dicyanozinc (0.077 g, 0.659 mmol) and tetrakis(triphenylphosphine)palladium (0.038 g, 0.033 mmol) in dimethylformamide (5 mL) was purged with argon and then heated at 160° C. for 1 h under microwave irradiation. The reaction mixture was filtered through diatomaceous earth and concentrated to dryness under reduced pressure. 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 the desired product as a brown solid. 1 H NMR(400MHz,DMSO-d6)δ=9.46(s,1H),9.20(s,2H),8.14(d,1H),7.91(t,1H),7.72(d,1H),3.87(s,3H).

[0129] Step 6: Synthesis of 5-cyano-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylic acid (compound 1) [ka] To a solution of methyl 5-cyano-4-oxo-1-pyrimidin-5-yl-cinnoline-3-carboxylate (0.088 g, 0.200 mmol) in tetrahydrofuran (5 mL) was added a solution of lithium hydroxide monohydrate (0.0073 g, 0.17 mmol) in water (1 mL). The resulting solution was stirred at ambient temperature for 1 h. The solvent was removed under reduced pressure and the residue was diluted with water (20 mL). The pH of the resulting aqueous mixture was adjusted to pH 2 by the addition of concentrated hydrochloric acid. The precipitated solid was collected by filtration and dried under reduced pressure to give the desired product as a light brown solid. 1 H NMR(400MHz,DMSO-d6)δ=9.46(s,1H),9.20(s,2H),8.13(d,1H),7.91(t,1H),7.43(d,1H).

[0130] Example 2: Synthesis of methyl 5-bromo-4-oxo-1-[5-(trifluoromethyl)pyrimidin-2-yl]cinnoline-3-carboxylate (compound 2) [ka] To a solution of methyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate (0.500 g, 1.77 mmol) in dimethylformamide (5 mL) was added 2-chloro-5-(trifluoromethyl)pyrimidine (0.645 g, 3.53 mmol) and potassium carbonate (0.731 g, 5.30 mmol). The reaction mixture was heated at 120° C. for 1 h under microwave irradiation. The reaction mixture was filtered through diatomaceous earth and then partitioned into water (50 mL) and dichloromethane (50 mL). The phases were separated and the aqueous phase was extracted into dichloromethane (2×50 mL). The combined organic extracts were washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-50% ethyl acetate in hexanes as eluent to give the desired product as a bright yellow solid. 1 H NMR(400MHz,DMSO-d6)δ=9.57(s,2H),7.88-7.85(m,2H),7.63(t,1H),3.87(s,3H).

[0131] Example 3: Synthesis of ethyl 5-bromo-1-(2-chloro-4-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 3) Step 1: Synthesis of ethyl 3-(2-bromo-6-fluoro-phenyl)-3-oxo-propanoate [ka] 2-Bromo-6-fluoro-benzoic acid (0.500 g, 2.3 mmol) was dissolved in tetrahydrofuran (4.6 mL) and stirred under nitrogen atmosphere while cooling with an ice bath. Di(imidazol-1-yl)methanone (0.48 g, 3.0 mmol) was added and the reaction mixture was heated at 65° C. for 0.5 h. Meanwhile, potassium; 3-ethoxy-3-oxo-propanoic acid (1.30 g, 7.6 mmol) and magnesium chloride (0.37 g, 3.9 mmol) were added in tetrahydrofuran (6.9 mL) and stirred at room temperature as a suspension. Triethylamine (0.77 g, 7.6 mmol) was added and the reaction mixture was heated at 65° C. for 3 h, after which the solution prepared above was added dropwise. Once the addition was complete, the reaction mixture was heated at 50° C. for 18 h. The cooled reaction mixture was partitioned into aqueous hydrogen chloride (2 M) and ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-100% ethyl acetate in cyclohexane as eluent to give the desired product (mixture of tautomers). 1 H NMR (400 MHz, chloroform) δ = 12.29 (s, 1H) enol, 7.45-7.39 (m, 1H), 7.32-7.23 (m, 1H), 7.14-7.07 (m, 1H), 5.28 (s, 1H) enol, 4.29 (q, 1H) enol, 4.19 (q, 1H) keto, 3.91 (d, 1H) keto, 1.34 (t, 1H) enol, 1.24 (t, 2H) keto.

[0132] Step 2: Synthesis of ethyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-hydrazinylidene-3-oxo-propanoate [ka] Preparation was carried out similarly to methyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate from ethyl 3-(2-bromo-6-fluoro-phenyl)-3-oxo-propanoate (1.0 g, 3.5 mmol) to give ethyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-hydrazinylidene-3-oxo-propanoate. 1 H NMR (400 MHz, chloroform) δ ppm 7.34 (d, 1H), 7.20 (td, 1H), 7.03 (t, 1H), 4.39 (q, 2H), 1.40 (t, 3H).

[0133] Step 3: Synthesis of ethyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate [ka] Similar to methyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate, the preparation was carried out using ethyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-hydrazinylidene-3-oxo-propanoate (2.1 g, 6.6 mmol) in bis(2-methoxyethyl)ether (1.5 mL) at 150° C. to give ethyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate. 1 H NMR (400 MHz, chloroform) δ ppm 7.77 (d, 1H), 7.67 (d, 1H), 7.56-7.49 (m, 1H), 4.52 (q, 2H), 1.44 (t, 3H).

[0134] Step 4: Synthesis of ethyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate (compound 3) [ka] To ethyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate (0.500 g, 1.7 mmol) in acetonitrile (20 mL) was added (2-chloro-4-pyridyl)boronic acid (0.55 g, 3.5 mmol) and copper(II) acetate (0.36 g, 2.0 mmol). The reaction mixture was heated at 50° C. for 6 h. The cooled reaction mixture was poured into aqueous hydrogen chloride (2 M) and extracted into dichloromethane. The organic extracts were washed with saturated aqueous sodium bicarbonate and then evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on reversed-phase C-18 silica gel using a gradient of 20-85% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to give the desired product as a pale yellow liquid. 1 H NMR (400 MHz, chloroform) δ ppm = 8.65 (d, 1H), 7.76 (dd, 1H), 7.57 (d, 1H), 7.50-7.41 (m, 2H), 7.28 (dd, 1H), 4.46 (q, 2H), 1.42 (t, 3H).

[0135] Example 4: Synthesis of ethyl 5-bromo-1-(6-methoxy-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 4) [ka] To a suspension of ethyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate (0.750 g, 2.52 mmol) in acetonitrile (50 mL) was added copper(II) acetate monohydrate (0.555 g, 1.78 mmol), N,N-diethylethanamine (1.02 g, 10.1 mmol) and 4 Å molecular sieves (0.061 g). Compressed air was bubbled through the reaction mixture, followed by the addition of 6-methoxy-3-pyridyl)boronic acid (0.811 g, 5.30 mmol) in several portions at room temperature. The reaction mixture was heated under a stream of compressed air at 60° C. for 0.5 h and then at 60° C. for 18 h. The cooled reaction mixture was poured into aqueous hydrogen chloride (2 M) and extracted into ethyl acetate (3 times). The combined organic extracts were washed sequentially with saturated aqueous sodium bicarbonate, then brine, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on reverse-phase C-18 silica gel using a gradient of 40-70% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to give the desired product as a brown solid. 1 H NMR (400 MHz, chloroform) δ = 8.31 (d, 1H), 7.72-7.66 (m, 2H), 7.39 (dd, 1H), 7.11 (dd, 1H), 6.96 (d, 1H), 4.44 (q, 2H), 4.02 (s, 3H), 1.40 (t, 3H).

[0136] Example 5: Synthesis of ethyl 5-cyano-1-(6-methoxy-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 16) Step 1: Synthesis of ethyl 5-cyano-4-oxo-1H-cinnoline-3-carboxylate [ka] A solution of ethyl 5-bromo-4-oxo-1H-cinnoline-3-carboxylate (0.500 g, 1.7 mmol) in N,N-dimethylformamide (10 mL) was added with zinc cyanide (0.400 g, 3.4 mmol) and tetrakis(triphenyl-λ 5-phosphanyl)palladium (0.200 g, 0.17 mmol) was added. The reaction mixture was heated at 160° C. under microwave irradiation for 45 min. The reaction mixture was partitioned between water and dichloromethane, filtered, and the phases separated. The organic phase was evaporated to dryness under reduced pressure, and the crude residue was purified by flash chromatography on reverse phase C-18 silica gel using a gradient of 10-50% acetonitrile (+0.1% formic acid) in water (+0.1% formic acid) as eluent to give the desired product as a light tan solid. 1 H NMR(DMSO-d6,400MHz)δ=8.02-7.92(m,1H),7.88-7.74(m,2H),4.43(q,2H),1.42(t,3H).

[0137] Step 2: Synthesis of ethyl 5-cyano-1-(6-methoxy-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (compound 16) [ka] A solution of ethyl 5-cyano-1-(6-methoxy-5-methyl-3-pyridyl)-4-oxo-cinnoline-3-carboxylate (0.200 g, 0.83 mmol) in acetonitrile (6 mL) was added to (6-methoxy-5-methyl-3-pyridyl)boronic acid) followed by acetonitrile (0.34 g, 3.32 mmol) and copper acetate (0.17 g, 0.91 mmol). The reaction mixture was heated at 60° C. for 16 h under a continuous flow of compressed air. Ethyl acetate (5 mL) and water (5 mL) were added to cool the reaction mixture and the phases were separated. The aqueous phase was extracted into ethyl acetate (2 times). The combined organic extracts were evaporated to dryness under reduced pressure. The crude residue was purified by mass-directed reverse phase HPLC to give the desired product. 1 H NMR (500 MHz, chloroform) δ = 8.14 (d, 1H), 7.86 (d, 1H), 7.70 (dd, 1H), 7.50 (d, 1H), 7.43 (d, 1H), 4.47 (q, 2H), 4.06 (s, 3H), 2.29 (s, 3H), 1.41 (t, 3H).

[0138] Example 6: Synthesis of ethyl 5-bromo-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 38) Step 1: Synthesis of ethyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-[[2-(difluoromethoxy)-4-pyridyl]hydrazono]-3-oxo-propanoate [ka] To a stirred solution of 2-(difluoromethoxy)pyridin-4-amine (0.117 g, 0.73 mmol) in dilute aqueous hydrogen chloride (2 M, 0.5 mL, 0.62 mmol) was added dropwise a solution of sodium nitrite (0.024 g, 0.34 mmol) in water (2 mL) at 0° C. The resulting reaction mixture was stirred at 0° C. for 2 hours, after which it was added to a stirred solution of ethyl 3-(2-bromo-6-fluoro-phenyl)-3-oxo-propanoate (100 mg, 0.31 mmol) and potassium acetate (0.153 g, 1.56 mmol) at 0° C. The reaction mixture was stirred at 0° C. for 2 hours, after which it was diluted with cold water and extracted into ethyl acetate (2 times). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure to give ethyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-[[2-(difluoromethoxy)-4-pyridyl]hydrazono]-3-oxo-propanoate as a crude solid, which was used directly in the next step without purification.

[0139] Step 2: Synthesis of ethyl 5-bromo-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 38) [ka] To a stirred solution of ethyl (2Z)-3-(2-bromo-6-fluoro-phenyl)-2-[[2-(difluoromethoxy)-4-pyridyl]hydrazono]-3-oxo-propanoate (200 mg, 0.39 mmol) in N,N-dimethylformamide (4 mL) was added potassium carbonate (0.108 g, 0.78 mmol) at room temperature. The resulting reaction mixture was heated at 100° C. for 4 h. The cooled reaction mixture was diluted with cold water (50 mL) and extracted into ethyl acetate (2 times). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography on silica gel using 20% ​​ethyl acetate in hexane as eluent to give ethyl 5-bromo-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate as an off-white solid. 1 H NMR(400MHz,DMSO-d6)δ=8.57(d,1H),7.78(t,1H),7.81(d,1H,)7.64-7.62(m,1. 5H),7.61-7.58(dd,0.5H),7.52(d,1H),7.35(dd,1H),4.35(q,2H),1.29(t,3H).

[0140] Example 7: Synthesis of ethyl 5-acetyl-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (compound 40) [ka] To a stirred solution of ethyl 5-bromo-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (120 mg, 0.26 mmol) in toluene (20 mL) at room temperature was added tributyl(1-ethoxyvinyl)stannane (187 mg, 0.52 mmol). The resulting reaction mixture was purged with argon for 5 minutes, after which dichloropalladium; ethylene; triphenylphosphine (19 mg, 0.026 mmol) were added. The resulting reaction mixture was heated in a sealed tube at 110° C. for 4 hours. After this time, 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 hexanes as eluent to give ethyl 5-acetyl-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate as an off-white solid. 1 H NMR(400MHz,DMSO-d6)δ=8.60(d,1H),7.86-7.65(m,3H),7.56(d,1H),7.45(dd,2H),4.35(q,2H),2.46(s,3H),1.30(t,3H).

[0141] Example 8: Synthesis of ethyl 1-[2-(difluoromethoxy)-4-pyridyl]-5-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-cinnoline-3-carboxylate (compound 41) [ka] To a stirred solution of ethyl 5-acetyl-1-[2-(difluoromethoxy)-4-pyridyl]-4-oxo-cinnoline-3-carboxylate (50 mg, 0.12 mmol) in a mixture of methanol (3 mL) and water (1 mL) at 0° C. was added sodium acetate (0.015 g, 0.19 mmol) and O-methylhydroxylamine hydrochloride (0.010 g, 0.12 mmol). The resulting reaction mixture was stirred for 5 minutes and then heated at 80° C. for 6 hours. The cooled reaction mixture was poured into ice water and neutralized by the addition of aqueous hydrogen chloride (2 M). The mixture was filtered and the filtrate was evaporated under reduced pressure. The crude residue was purified by flash chromatography on reverse-phase C-18 silica gel using a gradient of 0-100% acetonitrile in water to give ethyl 1-[2-(difluoromethoxy)-4-pyridyl]-5-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-oxo-cinnoline-3-carboxylate as an off-white solid. 1 H NMR(400MHz,DMSO-d6)δ=8.58(d,1H),8.00(s,0.5H),7.82-7.76(m,1.5H),7.66-7.63(m,1H), 7.55(d,1H),7.45(dd,1H),7.34(dd,1H),4.34(q,2H),3.86(s,3H),2.07(s,3H),1.28(t,3H).

[0142] [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4] [Table 5-5] [Table 5-6]

Table 5-7

Table 5-8

Table 5-9

Table 5-10

Table 5-11

Table 5-12

Table 5-13

Table 5-14

[0143] examples of biology Seeds of the various test species are sown in standard soil in pots (Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Amaranthus palmeri (AMAPA), Setaria faberi (SETFA), Zea mays (ZEAMX), Ipomoea hederacea (IPOHE)). After 8 days of cultivation in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with an aqueous spray solution obtained from a combination of the technical active ingredients in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Unless otherwise stated, the compounds are applied at 1000 g / h. The test plants are then grown in a greenhouse under controlled greenhouse conditions (24°C / 16°C, day / night; 14 hours of light; 65% humidity) with watering twice a day. After 13 days, the tests are evaluated for the percentage of damage caused to 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=10-20%; 0=0%; -=not tested).

[0144] [Table 6]

[0145] [Table 7]

Claims

1. Compounds of formula (I) 【Chemistry 1】 (In the formula, X is O, NR 7 or S; R 1 is heteroaryl, said heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1, 2, or 3 heteroatoms independently selected from N, O, and S, and said heteroaryl moiety being R 8 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 2 is halogen, cyano, cyano C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkylcarbonyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkoxy C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkenyloxy C 1 ~C 6 Alkyl, -CR 11 =N-OR 10 , Nitro, S(O) n C 1 ~C 6 Alkyl, S(O) n C 1 ~C 6 Haloalkyl or S(O) n C 3 ~C 6 is cycloalkyl; R 3 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Cycloalkyl C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, phenyl or phenyl C 1 ~C 3 alkyl, and the phenyl moiety is R 12 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by R 4 , R 5 and R 6 are hydrogen, halogen, cyano, and C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylsulfanyl, C 1 ~C 6 Alkylsulfinyl and C 1 ~C 6 independently selected from alkylsulfonyl; R 7 is hydrogen, C 1 ~C 3 Alkyl or C 1 ~C 3 is alkoxy; R 8 is halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 6 Alkylsulfanyl or C 1 ~C 6 alkylsulfonyl; or Any two adjacent R 8 The groups may be taken together with the carbon atoms to which they are attached to form a 6-membered aryl ring, or any two adjacent R 8 Groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 8 Groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the aryl, heterocyclyl or heteroaryl ring may be selected from R 9 and optionally substituted with 1, 2, 3 or 4 groups, which may be the same or different, represented by n is 0, 1 or 2; R 9 is a halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl or C 1 ~C 3 is alkoxy; R 10 and R 11 are hydrogen and C 1 ~C 3 independently selected from alkyl; R 12 is halogen, cyano, C 1 ~C 3 Alkyl or C 1 ~C 3 alkoxy) or a salt or N-oxide thereof.

2. R 1 is heteroaryl, said heteroaryl moiety being a 5- or 6-membered aromatic ring containing 1 or 2 heteroatoms independently selected from N and S, and said heteroaryl moiety being R 8 2. The compound of claim 1, optionally substituted with one or two groups, which may be the same or different, represented by:

3. R 1 is heteroaryl, the heteroaryl moiety being a 6-membered aromatic ring containing one or two nitrogen heteroatoms, and the heteroaryl moiety being R 8 2. The compound of claim 1, optionally substituted with one or two groups, which may be the same or different, represented by:

4. R 2 is halogen, cyano, acetyl or N-methoxy-C-methyl-carbonimidoyl.

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

6. R 4 , R 5 and R 6 The compound of claim 1 , wherein all of are hydrogen.

7. R 8 is halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkylsulfanyl or C 1 ~C 3 alkylsulfonyl; or Any two adjacent R 8 Groups may be taken together with the carbon atoms to which they are attached to form a 6-membered aryl ring, or any two adjacent R 8 Groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing 1 or 2 heteroatoms selected from O and N, or any two adjacent R 8 Groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heteroaryl ring containing 1 or 2 heteroatoms selected from O and N, and the heterocyclyl or heteroaryl ring may be selected from R 9 2. The compound of claim 1, optionally substituted with one, two or three groups, which may be the same or different, represented by:

8. R 8 is a halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy or C 1 ~C 3 haloalkyl; or Any two adjacent R 8 Groups may be taken together with the carbon atoms to which they are attached to form a 5- or 6-membered heterocyclyl ring containing one or two oxygen atoms, and the heterocyclyl ring may be R 9 2. The compound of claim 1, optionally substituted with one or two groups, which may be the same or different, represented by:

9. R 9 The compound of claim 1 , wherein is a halogen.

10. 2. The compound of claim 1, wherein X is O.

11. A herbicidal composition comprising the 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 undesired plant growth, comprising the step of applying to the undesired plants or their habitat a compound of formula (I) as defined in any one of claims 1 to 10.

15. A method for controlling the growth of undesirable plants, comprising the step of applying to the undesirable plants or their habitat the herbicidal composition of claim 11.

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

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