Herbicide derivatives

Abstract

A compound having formula (I), wherein the substituents are as defined in claim 1. The invention further relates to herbicidal compositions comprising a compound having formula (I) and the use of a compound having formula (I) for controlling weeds, particularly in crops with useful plants.

Description

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

[0002] EP 0239391, EP 0127313, EP 0040082 and GB 2182931 describe pyridinone derivatives as herbicides.

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

[0004]

[0005] in

[0006] X is O, NR 6 、 or S;

[0007] R 1 It is a C1-C6 alkyl group;

[0008] R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, 3, or 4 heteroatoms that may be the same or different from R. 7 The group to be represented is substituted;

[0009] R 3 It is hydrogen, C1-C6 alkyl, N,N-di(C1-C3 alkyl)amino, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, or phenylC1-C3 alkyl, wherein the phenyl moiety may optionally be composed of 1, 2, 3, or 4 identical or different R 8 The group to be represented is substituted;

[0010] R 4 It is cyano, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C2-C6 alkenyl, C2-C6 alkenoxy-C1-C6 alkyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl;

[0011] R 5 It is a halogen, a C1-C4 alkyl, a C1-C4 alkoxy, a C1-C4 haloalkyl, or a C1-C4 alkoxy-C1-C4 alkyl;

[0012] R 6 It is hydrogen, C1-C3 alkyl, or C1-C3 alkoxy;

[0013] R 7 It is a halogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group;

[0014] R 8 It is a halogen, cyano, C1-C3 alkyl, or C1-C3 alkoxy group;

[0015] Or its salts or N-oxides.

[0016] Surprisingly, it has been found that the new compound with formula (I) has a very favorable level of herbicidal activity for practical purposes.

[0017] According to a second aspect of the invention, an agricultural chemical composition is provided comprising a herbicidally effective amount of the compound of formula (I) according to the invention. This agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0018] According to a third aspect of the invention, a method for controlling weeds at a site is provided, the method comprising applying to the site a composition comprising a compound having formula (I) to control the amount of weeds.

[0019] According to a fourth aspect of the invention, the use of a compound having formula (I) as a herbicide is provided.

[0020] When substituents are indicated as "optionally substituted," this means that they may or may not have one or more identical or different substituents, such as one, two, or three R. 7 Substituents. For example, C1-C6 alkyl groups substituted with 1, 2, or 3 halogens may include, but are not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3 groups. As another example, C1-C6 alkoxy groups substituted with 1, 2, or 3 halogens may include, but are not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups.

[0021] As used in this article, the term "cyano" refers to the -CN group.

[0022] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo).

[0023] As used in this article, the term "hydroxyl group" refers to the -OH group.

[0024] As used herein, the term "acetyl" refers to the -C(O)CH3 group.

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

[0026] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted with one or more identical or different halogen atoms. The terms "C1-C4 haloalkyl" and "C1-C3 haloalkyl" should be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, trifluoromethyl.

[0027] As used herein, the term "C1-C6 alkoxy" refers to an alkoxy group having the formula -OR a The group, wherein R a It is a C1-C6 alkyl group as generally defined above. The terms "C1-C4 alkoxy" and "C1-C3 alkoxy" should be interpreted accordingly. Examples of C1-C6 alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

[0028] As used herein, the term "C2-C6 alkenyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one double bond that may have an (E)- or (Z)- configuration, having two to six carbon atoms attached to the remainder of the molecule by single bonds. The term "C2-C3 alkenyl" should be interpreted accordingly. Examples of C2-C6 alkenyl include, but are not limited to, ethenyl, propyl-1-alkenyl, propyl-2-alkenyl, and butyl-1-alkenyl.

[0029] As used herein, the term "C2-C6 ynyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one triple bond, having two to six carbon atoms, and attached to the rest of the molecule by single bonds. The term "C2-C3 ynyl" should be interpreted accordingly. Examples of C2-C6 ynyl groups include, but are not limited to, ethynyl, propynyl, and butynyl.

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

[0031] As used herein, the term "C3-C6 cycloalkyl" refers to a monocyclic saturated ring system containing 3 to 6 carbon atoms. The terms "C3-C5 cycloalkyl" and "C3-C4 cycloalkyl" should be interpreted accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0032] As used herein, the term “C3-C6 cycloalkyl C1-C6 alkyl” refers to a C3-C6 cycloalkyl ring attached to the remainder of the molecule via a C1-C6 alkylene linker as defined above.

[0033] As used herein, the term "C1-C6 alkoxy-C2-C6 alkenyl" refers to a compound having the formula R b OR a - groups, where R b It is a C1-C6 alkyl group as generally defined above, and R a It is a C1-C6 alkenyl group as generally defined above.

[0034] As used herein, the term "C2-C6 olefinic C1-C6 alkyl" refers to a compound having the formula R b OR a - groups, where R b It is a C2-C6 alkenyl group as generally defined above, and R a It is a C1-C6 alkylene group as generally defined above.

[0035] As used herein, the term "phenyl C1-C3 alkyl" refers to a phenyl ring attached to the remainder of the molecule via a C1-C3 alkylene linker as defined above.

[0036] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group comprising 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl groups include, but are not limited to, furanyl, pyrroleyl, thiopheneyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridinyl.

[0037] As used herein, the term "C1-C6 alkyl carbonyl" refers to an alkyl group having the formula -C(O)R a The group, wherein R a It is a C1-C6 alkyl group as generally defined above.

[0038] As used herein, the terms "hydroxycarbonyl" or "carboxyl" refer to a group having the formula -C(O)OH.

[0039] As used herein, the term "N,N-di(C1-C3 alkyl)amino" refers to an amino group having the formula -N(R a (R) b ) groups, wherein R a and R b Each is individually a C1-C3 alkyl group as generally defined above.

[0040] The presence of one or more possible stereoisomers in a compound having formula (I) means that the compound can exist in optical isomeric form (i.e., enantiomers or diastereomers). As a result of restricted rotation around the single bond, transisomers may also exist. Formula (I) is intended to include all such possible isomeric forms and mixtures thereof. This invention includes all such possible isomeric forms of compounds having formula (I) and mixtures thereof. Similarly, formula (I) is intended to include all possible tautomers. This invention includes all possible tautomeric forms of compounds having formula (I).

[0041] In each case, the compound having formula (I) according to the invention is in free form, oxidized form (such as N-oxide), or salt form (e.g., an agronomically available salt form). Preferably, the compound having formula (I) can form a salt with: amines, including primary, secondary, and tertiary amines (e.g., ammonia, dimethylamine, and triethylamine), alkali metal bases and alkaline earth metal bases, transition metal bases, or quaternary ammonium bases.

[0042] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. For example, they are described by A. Albini and S. Pietra in their book "Heterocyclic N-oxides" published by CRC Press, Boca Raton (1991).

[0043] For compounds having formula (I), the following list provides information on substituents X, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 The definitions, including preferred definitions, are provided below. For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0044] X is O, NR 6 Or S. In one set of embodiments, X is O. In another set of embodiments, X is NR. 6 In another set of embodiments, X is S.

[0045] R 1 It is a C1-C6 alkyl group. Preferably, R 1 It is a C1-C4 alkyl group. More preferably, R 1 It is a C1-C3 alkyl group. More preferably, R 1 It is methyl, ethyl, n-propyl, or isopropyl. Even more preferably, R... 1 It is methyl or ethyl. Most preferably, R 1 It is an ethyl group.

[0046] R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, 3, or 4 heteroatoms that may be the same or different from R. 7 The group substitution is indicated.

[0047] Preferably, R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, or 3 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, or 3 heteroatoms that may be the same or different from R. 7 The group substitution is indicated.

[0048] More preferably, R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising one or two individual heteroatoms selected from N and O, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by one, two, or three atoms that may be the same or different from R. 7 The group substitution is indicated.

[0049] Even more preferably, R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising one or two individual heteroatoms selected from N and O, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by one or two atoms that may be the same or different from R. 7 The group substitution is indicated.

[0050] Even more preferably, R 2 It is optional to be one or two that can be the same or different by R 7 The group representing the substituted phenyl group. In one set of examples, R 2 It is 3,4-dichlorophenyl.

[0051] R 3 It is hydrogen, C1-C6 alkyl, N,N-di(C1-C3 alkyl)amino, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, or phenylC1-C3 alkyl, wherein the phenyl moiety may optionally be composed of 1, 2, 3, or 4 identical or different R 8 The group substitution is indicated.

[0052] Preferably, R 3 It is hydrogen, C1-C6 alkyl, N,N-di(C1-C3 alkyl)amino, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl, or phenylC1-C2 alkyl, wherein the phenyl moiety may optionally be composed of 1, 2, or 3 identical or different R 8 The group substitution is indicated.

[0053] More preferably, R 3 It is hydrogen, C1-C6 alkyl, N,N-di(C1-C3 alkyl)amino, C1-C3 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C2 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, phenyl, or phenylC1-C2 alkyl, wherein the phenyl moiety may optionally be composed of 1, 2, or 3 identical or different R 8 The group substitution is indicated.

[0054] Even more preferably, R 3It is hydrogen, C1-C6 alkyl, or N,N-di(C1-C3 alkyl)amino, C1-C3 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C1-C4 alkoxyC1-C2 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, phenyl, or phenylC1-C2 alkyl, wherein the phenyl moiety may optionally be composed of 1, 2, or 3 identical or different R 8 The group substitution is indicated.

[0055] In one set of embodiments, R 3 It is hydrogen, C1-C4 alkyl, or N,N-di(C1-C3 alkyl)amino. Preferably, R 3 It is hydrogen, C1-C4 alkyl, or N,N-di(methyl)amino, more preferably hydrogen or C1-C3 alkyl. Even more preferably, R 3 It is hydrogen, methyl, or ethyl. More preferably, R 3 It is either hydrogen or methyl.

[0056] R 4 It is cyano, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C2-C6 alkenyl, C2-C6 alkenoxy-C1-C6 alkyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl.

[0057] Preferably, R 4 It is cyano, C2-C6 alkenyl, C2-C6 alkynyl, C1-C4 alkoxy C2-C3 alkenyl, C2-C4 alkenoxy C1-C3 alkyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl.

[0058] More preferably, R 4 It is a C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl. More preferably, R 4 It is a C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkyl carbonyl, or hydroxy carbonyl. Even more preferably, R 4 It is a C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkyl carbonyl, or hydroxycarbonyl. In one set of embodiments, R 4 It is vinyl, acetyl, acetyl, or hydroxycarbonyl.

[0059] R 5 It is a halogen, a C1-C4 alkyl, a C1-C4 alkoxy, a C1-C4 haloalkyl, or a C1-C4 alkoxy-C1-C4 alkyl. Preferably, R 5 It is a C1-C4 alkyl, C1-C3 alkoxy, or C1-C3 alkoxy-C1-C2 alkyl. More preferably, R 5 It is a C1-C4 alkyl group. More preferably, R 5It is a C1-C3 alkyl group. In one set of examples, R 5 It is a methyl group.

[0060] R 6 It is hydrogen, C1-C3 alkyl, or C1-C3 alkoxy. Preferably, R 6 It is hydrogen or a C1-C3 alkyl group. More preferably, R 6 It is hydrogen, methyl, or ethyl. More preferably, R 6 It is a methyl group.

[0061] R 7 It is a halogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group. Preferably, R 7 It is halogen, methyl, ethyl, methoxy, or ethoxy. Even more preferably, R 7 It is a halogen, methyl, or methoxy group. More preferably, R... 7 It's halogen. Even more preferably, R... 7 It is chlorine.

[0062] R 8 It is a halogen, cyano, C1-C3 alkyl, or C1-C3 alkoxy group. Preferably, R 8 It is a halogen, cyano, methyl, ethyl, methoxy, or ethoxy group. More preferably, R 8 It is chlorine, bromine, fluorine, methyl, or methoxy.

[0063] In the compound having formula (I) according to the invention, preferably:

[0064] X is O;

[0065] R 1 It is a C1-C4 alkyl group;

[0066] R 2 It is a phenyl or heteroaryl group, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, or 3 heteroatoms individually selected from N, O, and S, and wherein each phenyl and heteroaryl moiety may optionally be surrounded by 1, 2, or 3 heteroatoms that may be the same or different from R. 7 The group to be represented is substituted;

[0067] R 3 It is hydrogen, C1-C4 alkyl, or N,N-di(C1-C3 alkyl)amino;

[0068] R 4 It is a C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl;

[0069] R 5 It is a C1-C4 alkyl group; and

[0070] R7 It is halogen.

[0071] In another set of embodiments, X is O;

[0072] R 1 It is a C1-C3 alkyl group;

[0073] R 2 It is optional to be one or two that can be the same or different by R 7 The group represents a phenyl group that has been substituted.

[0074] R 3 It is hydrogen, C1-C4 alkyl, or N,N-di(C1-C3 alkyl)amino;

[0075] R 4 It is cyano, C2-C6 alkenyl, C2-C6 alkynyl, C1-C4 alkoxy C2-C3 alkenyl, C2-C4 alkenoxy C1-C3 alkyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl;

[0076] R 5 It is a C1-C3 alkyl group; and

[0077] R 7 It is halogen.

[0078] The compounds of the present invention can be prepared as shown in the following embodiments, wherein, unless otherwise stated, each variable is defined as above for compounds having formula (I). A general method for producing compounds having formula (I) is described below. Unless otherwise stated herein, R 1 R 2 R 3 R 4 R 5 X and X are as defined above. Starting materials used to prepare the compounds of the present invention may be purchased from common commercial suppliers or may be prepared by known methods. Starting materials and intermediates may be purified by existing methods (such as chromatography, crystallization, distillation, and filtration) before use in the next step.

[0079] Option 1:

[0080]

[0081] Compounds having formula (I) (where X is NH and R) 3 -N(CH3)2) can be obtained from compounds having formula (I) (where X is O and R is O). 3The compound is prepared by coupling 1,1-dimethylhydrazine (which is hydrogen) with a coupling agent (such as propylphosphonic anhydride, either in pure form or as a solution in ethyl acetate) in a suitable solvent (such as dichloromethane or ethyl acetate) with an optional additive (such as dimethylaminopyridine). This is shown in Scheme 1 above. Compounds having formula (I) can also be prepared by the method described below.

[0082] Option 2:

[0083]

[0084] Compounds having formula (I) (where X is O and R) 3 (where X is O, and R is hydrogen) can be hydrolyzed by using a suitable base (such as sodium hydroxide or lithium hydroxide) or a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) and optionally a cosolvent (such as water) with a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran). 3 Not hydrogen, but any other R as defined above 3 The product is prepared by using a base followed by acidification with a suitable acid (such as hydrochloric acid). In the case of R... 4 In the case of pyridinyl or pyridazinyl groups, the product obtained is an equivalent salt (such as a hydrochloride). This is shown in Scheme 2 above. Compounds having formula (I) can also be prepared by the method described below.

[0085] Option 3:

[0086]

[0087] In another transformation, compounds having formula (I) (where R) 4 (trimethylsilylethynyl) can be converted into a compound having formula (I) by treatment with a base (such as potassium carbonate) in a solvent (such as methanol) (where R) 4 (It is acetylene group). This is shown in scheme 3 above.

[0088] Option 4:

[0089]

[0090] Compounds having formula (I) (where R) 4Alkynes, alkenes, or ketones (such as trimethylsilylethynyl, vinyl, or acetyl) can be additionally prepared from a compound having formula (B) (where Y is Cl, Br, or I) with, for example, an alkynyl, alkenyl, or ethoxyvinyltinane under Stieler reaction conditions in the presence of a catalyst (such as tetrakis(triphenylphosphine)palladium(0) or dichlorobis(triphenylphosphine)palladium(II)) in a suitable solvent (such as toluene) at elevated temperatures (e.g., 60°C, 120°C, or 125°C). This is shown in Scheme 4 above.

[0091] Option 5:

[0092]

[0093] Compounds having formula (I) (where R) 4 (where Y is Br) can be prepared by treating a compound having formula (B) (where Y is Br) in a solvent (such as tetrahydrofuran) with a Grignard reagent (such as a complex of isopropyl magnesium chloride and lithium chloride), followed by reaction with gaseous carbon dioxide at a temperature between -20°C and room temperature. This is shown in Scheme 5 above.

[0094] Option 6:

[0095]

[0096] Compounds having formula (B) (where X is O, R) 3 (where X is hydrogen and Y is Br or I) can be hydrolyzed by using a suitable base (such as sodium hydroxide or lithium hydroxide) or a suitable acid (such as trifluoroacetic acid, hydrochloric acid, formic acid or sulfuric acid) in a suitable solvent (such as methanol, ethanol, dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) and optionally a co-solvent (such as water) with a suitable solvent (such as water) to hydrolyze a compound having formula (B) (where X is O and R is hydrogen). 3 Not hydrogen, but any other R as defined above 3 It is prepared by using (groups). This is shown in Scheme 6 above.

[0097] Option 7:

[0098]

[0099] A compound having formula (B) (where Y is Br or I) can be prepared by treating a compound having formula (C) in a suitable solvent (such as acetonitrile or trifluoroacetic acid) with a suitable halogenating agent (such as N-iodosuccinimide or N-bromosuccinimide). This is shown in Scheme 7 above.

[0100] Option 8:

[0101]

[0102] A compound having formula (C) (where X is O) can be prepared by reacting a compound having formula (D) with a compound having formula (E) in the absence of solvent at an elevated temperature (e.g., 120°C). The compound having formula D is commercially available or can be prepared by methods familiar to those skilled in the art. This is illustrated in Scheme 8 above.

[0103] Option 9:

[0104]

[0105] Compounds having formula (E) can be prepared by reacting β-keto esters having formula (F) with amine salts. The amine salts can be prepared in situ by acidifying an amine having formula (G) with a suitable acid (such as acetic acid). These amine salts can then be reacted with compounds having formula (F) in a suitable solvent (such as toluene) with an acid (such as acetic acid) and a drying agent (such as... The reaction takes place in the presence of a molecular sieve. Compounds having formula (F) are commercially available or can be prepared using the conditions described below. Compounds having formula (G) are commercially available or can be prepared by methods familiar to those skilled in the art. This is shown in scheme 9 above.

[0106] Option 10:

[0107]

[0108] Compounds having formula (F) can be prepared by treating ketones having formula (H) with a base (such as sodium hydride) in the presence of a dialkyl carbonate having formula (i) (such as dimethyl carbonate). Compounds having formulas (H) and (i) are commercially available or can be prepared by methods familiar to those skilled in the art. This is illustrated in scheme 10 above.

[0109] The present invention further provides a method for controlling weeds at a site, the method comprising applying to the site a composition comprising a compound having formula (I) to control the amount of weeds. Furthermore, the present invention can further provide a method for selectively controlling weeds at a site comprising useful (crop) plants and weeds, wherein the method comprises applying to the site a composition according to the present invention to control the amount of weeds. 'Control' means killing, reducing, or delaying growth or preventing or reducing germination. It should be noted that the compounds of the present invention exhibit significantly improved selectivity compared to known structurally similar compounds. Typically, the plant to be controlled is an unwanted plant (weed). 'Site' means an area in which the plant is growing or will grow. Application can be made to the site before and / or after the emergence of the crop plants. Some crop plants can inherently tolerate the herbicidal effects of compounds having formula (I).

[0110] The application rate of compounds having formula (I) can vary within a wide range and depends on soil properties, application method (pre- or post-emergence; seed dressing; application in seed furrows; no-till application, etc.), crop species, one or more weeds to be controlled, prevailing climatic conditions, and other factors governed by the application method, application time, and target crop. Compounds having formula I according to the invention are typically applied at rates from 10 g / ha to 2500 g / ha, particularly from 25 g / ha to 1000 g / ha, and even more particularly from 25 g / ha to 250 g / ha.

[0111] The composition is usually applied by spraying, typically using a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or immersion can also be used.

[0112] The term "useful plants" should be understood to also include useful plants that have developed tolerance to herbicides (like bromuconazole) or herbicide classes (e.g., 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as flusulfuron, fluprosulfuron, and triflusulfone, (5-enol-pyruvyl-shikimate-3-phosphate-synthetase) (EPSPS) inhibitors, glutamine synthase (GS) inhibitors, or protoporphyrinogen oxidase (PPO) inhibitors) through conventional breeding methods or genetic engineering. Examples of crops that have been induced to tolerate imidazolinones (e.g., methoxyfenozide) through conventional breeding methods (mutation) are... Summer rapeseed (Carnora). Examples of crops genetically engineered to be resistant to herbicides or herbicides include glyphosate- and glufosinate-resistant maize varieties, which are... and Trademark names are available for purchase.

[0113] The term "useful plant" should be understood to also include useful plants that have been transformed by the use of recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to come from toxin-producing bacteria, especially those of the genus Bacillus.

[0114] Examples of such plants are: (Corn variety expressing CryIA(b) toxin); YieldGard (A maize variety expressing CryIIIB(b1) toxin); YieldGard (Maize variety expressing CryIA(b) and CryIIIB(b1) toxins); (A maize variety expressing the Cry9(c) toxin); Herculex (A maize variety that expresses the CryIF(a2) toxin and the enzyme phosphatidylcholine N-acetyltransferase (PAT) to acquire tolerance to the herbicide glufosinate-ammonium); NuCOTN (Cotton variety expressing CryIA(c) toxin); Bolgard (Cotton variety expressing CryIA(c) toxin); Bolgard (Cotton varieties expressing CryIA(c) and CryIIA(b) toxins); (Cotton variety, expressing VIP toxin); (Potato variety that expresses CryIIIA toxin); GT Advantage (GA21 glyphosate resistance) CBAdvantage (Bt11 corn borer (CB) traits), RW (corn rootworm trait) and

[0115] Plant crops or their seed material can be both herbicide-resistant and insect-resistant (“cumulative” transgenic events). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0116] Crop plants should also be understood to include those obtained through conventional breeding or genetic engineering methods and that contain so-called exported traits (such as improved storage stability, higher nutritional value, and improved flavor).

[0117] Unwanted plants (collectively referred to as 'weeds') can be controlled using compounds having formula (I) (or compositions containing it). Weeds to be controlled can be monocotyledonous species, such as *Agrostis*, *Alopecurus*, *Avena*, *Brachiaria*, *Bromus*, *Cenchrus*, *Cyperus*, *Digitaria*, *Echinochloa*, *Eleusine*, *Lolium*, *Monochoria*, *Rottboellia*, *Sagittaria*, *Scirpus*, and *Setaria*. ) and the genus Sorghum, which can also be dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola, and Xanthium.

[0118] Compounds having formula (I) can be used in their unmodified form, or preferably with adjuvants conventionally used in the formulation field to provide a herbicidal composition, using formulation adjuvants such as carriers, solvents, and surfactants (SAAs). Therefore, the present invention further provides a herbicidal composition comprising at least one compound having formula (I) and an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art.

[0119] The herbicidal composition generally comprises, by weight, from 0.1% to 99%, particularly from 0.1% to 95% of a compound having Formula I and by weight, from 1% to 99.9% of a formulation adjuvant, which preferably comprises, by weight, from 0 to 25% of a surfactant.

[0120] The composition can be selected from many formulation types. These include emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersants (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), parent drug (TK), dispersible concentrates (DC), soluble powders (SP), wettable powders (WP), and soluble granules (SG). In any case, the type of formulation chosen will depend on the specific intended purpose and the physical, chemical, and biological properties of the compound having formula (I).

[0121] Soluble powders (SPs) can be prepared by mixing a compound having formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate, or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants, or a mixture of said reagents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SGs).

[0122] Wettable powders (WPs) can be prepared by mixing a compound having formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersants, and optionally one or more suspending agents to promote dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WGs).

[0123] Granules (GR) can be formed by granulating a mixture of a compound having formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound having formula (I) (or a solution thereof in a suitable reagent) into a porous particulate material (such as pumice, attapulgite clay, bleaching clay, kieselguhr, diatomaceous earths, or corn cob powder), or by adsorbing a compound having formula (I) (or a solution thereof in a suitable reagent) onto a hard core material (such as sand, silicates, mineral carbonates, sulfates, or phosphates) and, if necessary, drying it to form pre-formed blank granules. Reagents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and binders (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugars, and vegetable oils). One or more other additives (e.g., emulsifiers, wetting agents, or dispersants) may also be included in the granules.

[0124] Dispersible concentrates (DCs) can be prepared by dissolving a compound having formula (I) in water or an organic solvent (such as a ketone, alcohol, or glycol ether). These solutions may contain surfactants (e.g., to improve water dilution or prevent crystallization in spray cans).

[0125] Emulsifiable concentrates (ECs) or oil-in-water emulsions (EWs) can be prepared by dissolving a compound having formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers, or a mixture of said reagents). Suitable organic solvents used in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150, and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone), and alcohols (such as benzyl alcohol, furfuryl alcohol, or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), and dimethylamides of fatty acids (such as C8-C...). 10 (Fatty acid dimethylamide) and chlorinated hydrocarbons. EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow for spray application using appropriate equipment.

[0126] The preparation of an emulsion (EW) involves obtaining a compound of formula (I) as a liquid (or, if not a liquid at room temperature, which can be melted at a reasonable temperature typically below 70°C) or as a solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution under high shear into water containing one or more SAAs to produce an emulsion. Suitable solvents used in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents with low solubility in water.

[0127] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents and one or more SAAs to spontaneously produce a thermodynamically stable, isotropic liquid formulation. The compound having formula (I) is initially present in water or in the solvent / SAA blend. Suitable solvents used in MEs include those described above used in ECs or EWs. MEs can be oil-in-water or water-in-oil systems (whichever system is present can be determined by conductivity measurements) and can be used to mix water-soluble and oil-soluble biocides in the same formulation. MEs are suitable for dilution in water, maintaining as a microemulsion or forming a conventional oil-in-water emulsion.

[0128] Suspension concentrates (SCs) may comprise aqueous or non-aqueous suspensions of finely dispersed insoluble solid particles of a compound having formula (I). SCs can be prepared by ball milling or bead milling of a solid compound having formula (I) with one or more dispersants in a suitable medium to produce a fine-particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the rate of particle settling. Alternatively, a compound having formula (I) may be dry-milled and added to water containing the reagents described above to produce the desired final product.

[0129] Aerosol formulations comprise compounds having formula (I) and suitable propellants (e.g., n-butane). Compounds having formula (I) can also be dissolved or dispersed in a suitable medium (e.g., water or a water-miscible liquid, such as n-propanol) to provide compositions for use in unpressurized, manually operated spray pumps.

[0130] Capsule suspensions (CS) can be prepared in a manner similar to that used in the preparation of EW formulations, but with an additional polymerization stage, resulting in an aqueous dispersion of oil droplets, each droplet encapsulated in a polymer shell and containing a compound of formula (I) and optionally a carrier or diluent for that droplet. The polymer shell can be produced via interfacial polycondensation or via a coagulation process. These compositions can provide controlled release of compounds of formula (I) and can be used for seed treatment. Compounds of formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0131] The composition may contain one or more additives to improve the biocompatibility of the composition, for example by improving wettability, retention, or distribution on a surface; rain resistance on the treated surface; or absorption or flow of compounds having formula (I). Such additives include surfactants (SAAs), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), modified vegetable oils (such as methylated rapeseed oil (MRSO)), and blends of these with other bioenhancing adjuvants (components that can help or modify the effects of compounds having formula (I)).

[0132] The wetting agent, dispersant, and emulsifier can be cationic, anionic, amphoteric, or nonionic SAA.

[0133] Suitable cationic types of SAAs include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

[0134] Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butyl naphthalene sulfonate, and mixtures of sodium di-isopropyl-naphthalene sulfonate and sodium tri-isopropyl-naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (products of the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), such as the reaction between lauryl alcohol and tetraphosphate; these products may also be ethoxylated), sulfosuccinates, paraffin or olefin sulfonates, taurines, lignosulfonates, and phosphate / sulfate salts of tristyrylphenols.

[0135] Suitable amphoteric types of SAAs include betaine, propionate, and glycine salt.

[0136] Suitable nonionic types of SAAs include condensation products of alkyl oxidases (such as ethylene oxide, propylene oxide, butane oxide, or mixtures thereof) with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol, or octylcresol); partial esters derived from long-chain fatty acids or hexyl anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryl dimethylamine oxide); lecithin and sorbitol and their esters, alkyl polyglycosides, and tristyrylphenols.

[0137] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone, or sodium carboxymethyl cellulose) and expansive clays (such as bentonite or attapulgite).

[0138] The compounds of this invention can also be used in combination with one or more other herbicides and / or plant growth regulators. Examples of such other herbicides or plant growth regulators include acetochlor, trifluralin (including trifluralin-sodium), bensulfuron, atrazine, azoxystrobin, chlorpyrifos, chlorpyrifos, atrazine, flubutyrazole-M, quinalazine, bensulfuron-methyl (including bensulfuron-methyl), bentazon, bicyclopyranone, bispyridine, bispyribac-sodium, bixlozone, chlorpyrifos, bromobenzonitrile, butachlor, flupropylaturon, chlorpyrifos (including chlorpyrifos-ethyl), chlorpyrifos-methyl, chlorpyrifos-ethyl, chlorpyrifos, chlorpyrifos, clodinafop-methyl, clodinafop-methyl, chlorpyrifos-ethyl, chlorpyrifos, chlorpyrifos-methyl, clodinafop-methyl, clodinafop-methyl, chlorpyrifos-ethyl, chlorpyrifos ... esters), isoxaflutole, dichloropyridinic acid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, dichlorvos, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diethylene glycolamine, dimethylamine, dimethylammonium, potassium salt and sodium salt), dichlorvos, pyrfluthrin, flupyrazole, metolachlor, fenfluridine, dibromodiflubenzuron, diuron, epyrifenacil, ethylbutyrate, ethoxysulfuron, oxazolidinone (including fenfluridine) The following herbicides are listed: quizalofop-ethyl, fenoxasulfone, fenquinotrione, tetrazolium, pyrimisulfuron, diflubenzuron, florpyrauxifen (including florpyrauxifen-benzyl), quizalofop-P-ethyl (including quizalofop-butyl), flumetsulam (including flumetsulam-sodium), fluthiamethoxam, pyrimisulfuron, propyzamide, fluroxypyr, flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr-meptyl (including fluroxypyr-meptyl), flufenoxuron, formamide-sulfuron, glufosinate (including L-glufosinate and the ammonium salts of both). Glyphosate (including its hydrazine, isopropylammonium, and potassium salts), halauxifen (including halauxifen-methyl), flupyridine (including flupyridine-methyl), cycloazinone, hydantocidin, methoxyfenozide (including R-methoxyfenozide), imidacloprid, metribuzin, imidacloprid, indazon, iofensulfuron (including iofensulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), iodobenzonitrile, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P (2-methyl-4-chloropropionic acid)Mesosulfuron-methyl (including mesosulfuron-methyl), mesosulfuron-methyl, bensulfuron-methyl, pyrazosulfuron, isoxaflutole, methiozolin, metolachlor, sulfadiazine, cyhalofop-p-ethyl, metsulfuron-methyl, nicosulfuron, dapoxuron, oxadiazon, cyclopyrsulfuron, ethoxysulfuron, paraquat dichlorvos, pendimethalin, penflusulfuron-methyl, bensulfuron-methyl, cyclopyr, propyrisulfuron, pendimethalin, bensulfuron-methyl, flusulfuron-methyl, propyrisulfuron, pendimethalin, bensulfuron-methyl, flusulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, flusulfuron-methyl, propyrisulfuron, pendimethalin, bensulfuron-methyl, flusulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl Pyrimisulfan, pyroxasulfone, pyrazosulfuron, quinclorac, chlorpyrifos, quizalofop-P-tefuryl (including quizalofop-ethyl and quizalofop-P-tefuryl), sulfadiazine, pyrimisulfuron, oxadiazine, simazine, metolachlor, mesosulfuron, sulfonylsulfuron, butisulfuron, terbufos, cyclosulfonone, terbutaline, terbutaline, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, bensulfuron-methyl Herbicides, triazolam, triafamone, wild valerate, bensulfuron-methyl, bensulfuron-methyl (including bensulfuron-methyl), chlorpyrifos, trifluridinesulfuron (including trifluridinesulfuron-sodium), trifludimoxazin, trifluralin, flumethrin, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazoline-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazoline-2-one [Fluoromethyl)-2-pyridyl]imidazolin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolin-2-one, 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2 ... [2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl- ... Hexane-1,3-dione, 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]cyclohexane-1,3-dione, 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazin-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid), 3-ethylthioalkyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(isopropylthioalkylmethyl)-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, 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]ethyl acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, 1-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-4,4,4-trifluoro-but-1-one, and 5-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-3-(difluoromethyl)isoxazole.

[0139] Mixtures of compounds having formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition, British Crop Protection Council, 2012. The mixing ratio of compounds having formula (I) to the mixtures is preferably from 1:100 to 1000:1.

[0140] These mixtures can be advantageously used in the formulations mentioned above (in which case "active ingredient" refers to the corresponding mixture of a compound having formula (I) with a mixed formulation).

[0141] The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include cloquintocet (including cloquinoline), cyclopropanesulfonamide, dichloropropeneamine, cloquinoxal (including cloquinoxal-ethyl), cloquinoxaline, flufenoxam, cloquinoxalic acid (including cloquinoxalic acid-ethyl), mefenpyr (including cloquinoxalic acid-diethyl), metcamifen, and cloquinoxalic acid nitrate. Particularly preferred are mixtures of compounds having formula (I) with cyclopropanesulfonamide, cloquinoxalic acid ethyl ester, cloquinoline, and / or metcamifen.

[0142] Safeguards of compounds having formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition (BCPC), 2012. References to antitoxin quinine also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or phosphonium salts (as disclosed in WO 02 / 34048).

[0143] Preferably, the mixing ratio of the compound having formula (I) to the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0144] Compounds having formula (I) are typically used in the form of agricultural chemical compositions and can be applied simultaneously or sequentially to the crop area or plant to be treated. These additional compounds may, for example, be fertilizers or micronutrient donors or other formulations that influence plant growth. They may also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures thereof, and, if desired, with additional carriers, surfactants, or application-promoting adjuvants commonly used in the formulation field.

[0145] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds, and seedlings, along with the established vegetation.

[0146] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0147] The term "plant propagation material" should be understood to refer to the reproductive parts of a plant, such as seeds, which can be used for plant propagation, as well as nutrient materials, such as cuttings or tubers (e.g., potatoes). References may include, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of the plant. References may also include germinating plants and young plants that will be transplanted after germination or emergence. These young plants may be protected before transplanting by complete or partial treatment with maceration. Preferably, "plant propagation material" should be understood to refer to seeds.

[0148] The pesticides mentioned in this article that use their common names are, for example, known from "The Pesticide Manual", 15th edition, British Crop Protection Council 2009.

[0149] Compounds having formula (I) can be used in their unmodified form, or preferably, in conjunction with adjuvants conventionally used in the field of formulations. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and encapsulants, for example, in polymeric substances. The method of application, such as spraying, atomizing, dusting, spreading, smearing, or watering, is selected according to the intended purpose and the prevailing environment for the type of composition. The composition may also contain additional adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders, or thickeners, along with fertilizers, micronutrient donors, or other formulations used to achieve specific effects.

[0150] Suitable carriers and adjuvants, for example for agricultural uses, can be solid or liquid substances useful in formulation techniques, such as natural or recycled minerals, solvents, dispersions, wetting agents, thickeners, binders, or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0151] Compounds having formula (I) are typically used in the form of a composition and can be applied simultaneously or sequentially with other compounds to the crop area or plant to be treated. For example, these other compounds may be fertilizers or micronutrient donors or other formulations that affect plant growth. They may also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these formulations, and, if desired, with other carriers, surfactants, or application-promoting adjuvants commonly used in the formulation field.

[0152] A compound having formula (I) may be the sole active ingredient in a composition, or, where appropriate, it may be mixed with one or more other active ingredients (such as pest control agents, fungicides, synergists, herbicides, or plant growth regulators). In some cases, the additional active ingredients may produce unexpected synergistic activity.

[0153] Typically, formulations comprise from 0.01% to 90% by weight of the active ingredient, from 0% to 20% of an agriculturally acceptable surfactant, and from 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being a compound having at least formula (I) together with components (B) and (C), and optionally other active agents (particularly microbicides, preservatives, or the like). Concentrated forms of the composition typically contain between about 2% and 80% by weight, preferably between about 5% and 70% by weight of the active agent. Application forms of the formulation may, for example, contain from 0.01% to 20% by weight, preferably from 0.01% to 5% by weight of the active agent. However, commercially available products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0154] The following are examples of individual compounds having formula (I) according to the present invention:

[0155]

[0156] Table 1: Individual compounds of formula (I) according to the present invention

[0157] Compound numbering <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> 001 vinyl methyl 002 vinyl Ethyl 003 vinyl Methoxymethyl 004 Acetylene methyl 005 Acetylene Ethyl 006 Acetylene Methoxymethyl 007 Acetyl methyl 008 Acetyl Ethyl 009 Acetyl Methoxymethyl 010 carboxyl methyl 011 carboxyl Ethyl 012 carboxyl Methoxymethyl

[0158] Table A-1 Twelve compounds A-1.001 to A.1.012 having formula (I) are provided, where X is O, R is R. 1 It is methyl, R 2 It is 3,4-dichlorophenyl, R 3 It is hydrogen, and R 4 and R 5 As defined in Table 1.

[0159] Table A-2 Twelve compounds having formula (I) A-2.001 to A.2.012 are provided, where X is O, R is R. 1 It is ethyl, R 2 It is 3,4-dichlorophenyl, R 3 It is hydrogen, and R 4 and R 5 As defined in Table 1.

[0160] Table A-3 Twelve compounds A-3.001 to A.3.012 having formula (I) are provided, wherein X is O, R is R. 1 It is methyl, R 2 It is 3,4-dichlorophenyl, R 3 It is methyl, and R 4 and R 5 As defined in Table 1.

[0161] Table A-4 Twelve compounds having formula (I) A-4.001 to A.4.012 are provided, where X is O, R is R. 1 It is ethyl, R 2 It is 3,4-dichlorophenyl, R 3 It is methyl, and R 4 and R 5 As defined in Table 1.

[0162] Table A-5 Twelve compounds having formula (I) A-5.001 to A.5.012 are provided, wherein X is NH, R 1 It is methyl, R 2 It is 3,4-dichlorophenyl, R 3 It is -N(CH3)2, and R 4 and R 5 As defined in Table 1.

[0163] Table A-6 Twelve compounds having formula (I) A-6.001 to A.6.012 are provided, wherein X is NH, R 1 It is ethyl, R 2 It is 3,4-dichlorophenyl, R 3 It is -N(CH3)2, and R 4 and R 5 As defined in Table 1.

[0164] Examples of preparations

[0165]

[0166] The active ingredient is thoroughly mixed with the excipients and the mixture is thoroughly ground in a suitable grinder to provide a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0167]

[0168] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to provide a powder that can be used directly for seed treatment.

[0169] Emulsifiable concentrate

[0170]

[0171] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0172]

[0173] A ready-to-use powder is obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. This type of powder can also be used for dry seed dressing.

[0174] Extruder granules

[0175]

[0176] The active ingredient and excipients are mixed and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an air stream.

[0177] Coated granules

[0178] Active ingredient [a compound having formula (I)] 8%

[0179] Polyethylene glycol (molecular weight 200) 3%

[0180] 89% Kaolin

[0181] The finely ground active ingredient is evenly applied to kaolin clay moistened with polyethylene glycol in a mixer. This process yields dust-free coated granules.

[0182] suspension concentrate

[0183]

[0184] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants along with their propagation material can be treated and protected against microbial infection by spraying, watering, or immersion.

[0185] Flowable concentrate for seed treatment

[0186]

[0187] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants along with their propagation material can be treated and protected against microbial infection by spraying, watering, or immersion.

[0188] Sustained-release capsule suspension

[0189] A mixture of 28 parts of compounds of formula (I) was mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water was added to this emulsion. The mixture was stirred until polymerization was complete. The resulting capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contained 28% of the active ingredient. The diameter of the medium capsule was 8-15 micrometers. The resulting formulation was applied to seeds as an aqueous suspension in a suitable apparatus for this purpose.

[0190] Example

[0191] The following non-limiting examples provide specific methods for synthesizing representative compounds used in this invention (as mentioned in Table 2 below).

[0192] Abbreviation list

[0193] ℃ = degrees Celsius, d = bimodal, DMSO = dimethyl sulfoxide, HPLC = high performance liquid chromatography, LCMS = liquid chromatography-mass spectrometry, M = molar concentration, m = multiplet, MHz = megahertz, q = quartet, s = singlet, t = triplet, THF = tetrahydrofuran, TMT = 2,4,6-trimethylmercaptotriazine.

[0194] Example 1: Synthesis of methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-vinylpyridine-3-carboxylate (compound 4.001)

[0195] Step 1: Synthesis of methyl 3-(3,4-dichlorophenyl)-3-oxo-propionate

[0196]

[0197] Sodium hydride (3.17 g, 79.5 mmol, 60% by mass) was added in portions to a stirred solution of 1-(3,4-dichlorophenyl)ethyl ketone (5.00 g, 26.5 mmol) and dimethyl carbonate (40 mL, 466 mmol) cooled to 0 °C under nitrogen. The reaction mixture was heated to room temperature and stirred for 16 hours. After overnight, the reaction mixture became an unstirrable solid paste. More dimethyl carbonate (10 mL) was added in an attempt to produce a flowing slurry for quenching. The reaction mixture was cooled to 0 °C under nitrogen and quenched by adding water (25 mL). The reaction mixture was acidified to pH 3 by adding 2 M hydrochloric acid aqueous solution and then extracted with ethyl acetate. The organic extract was dried over magnesium sulfate and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 0-15% ethyl acetate in isohexane as the eluent to give methyl 3-(3,4-dichlorophenyl)-3-oxopropionate (a mixture of tautomers) (5.78 g, 23.5 mmol, 89%) as a colorless liquid.

[0198] Enols: 1 ¹H NMR (400MHz, chloroform) δ = 12.47 (s, 1H), 7.87 (d, 1H), 7.59 (m, 3H), 7.49 (d, 1H), 5.65 (s, 1H), 3.82 (s, 3H)

[0199] ketone: 1 ¹H NMR (400MHz, chloroform) δ=8.03(d,1H),7.77(m,1H),7.58(d,2H),3.97(s,2H),3.76(s,3H).

[0200] Step 2: Synthesis of methyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate

[0201]

[0202] Acetic acid (1.39 mL, 24.3 mmol) was added dropwise to a stirred solution of ethylamine (2 M, in THF) (12.2 mL, 24.34 mmol) at 0 °C. The mixture was heated to room temperature and stirred for 1 hour, then evaporated to dryness under reduced pressure to give ethylammonium acetate (2.55 g, 24.3 mmol). Ethylammonium acetate (2.55 g, 24.3 mmol) was added to a solution of methyl 3-(3,4-dichlorophenyl)-3-oxo-propionate (2.00 g, 8.09 mmol) in toluene (20 mL), followed by the addition of acetic acid (0.46 mL, 8.09 mmol) and powdered... Molecular sieves were used. The reaction mixture was heated under reflux for 18 hours. The cooled reaction mixture was diluted with ethyl acetate, filtered, and washed with a saturated aqueous sodium bicarbonate solution. The phases were separated, and the aqueous phase was extracted with ethyl acetate (x3). The combined organic extracts were washed with brine, dried over magnesium sulfate, and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel chromatography using a gradient of 0-10% ethyl acetate in isohexane as the eluent to give methyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (1.54 g, 5.61 mmol, 69%) as a pale yellow oil.

[0203] 1 ¹H NMR (400MHz, chloroform) δ=8.37(br s,1H),7.48(d,1H),7.46(d,1H),7.20(m,1H),4.55(s,1H),3.68(s,3H),3.07(m,2H),1.13-1.09(m,3H).

[0204] Step 3: Synthesis of methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate

[0205]

[0206] A stirred mixture of (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (1.50 g, 5.5 mmol) and 2,2,6-trimethyl-1,3-dioxin-4-one (0.82 g, 5.5 mmol) under nitrogen atmosphere was heated at 120 °C for 3 hours. The cooled reaction mixture was evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 0-10% methanol in dichloromethane as the eluent to give methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate (0.95 g, 2.78 mmol, 51%) as a grayish-white solid.

[0207] 1 ¹H NMR (400MHz, chloroform) δ = 7.56 (d, 1H), 7.50 (d, 1H), 7.24 (m, 1H), 6.41 (s, 1H), 3.72 (q, 2H), 3.55 (s, 3H), 2.42 (s, 3H), 1.13 (t, 3H).

[0208] Step 4: Synthesis of methyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylate

[0209]

[0210] At room temperature and under nitrogen atmosphere, 1-iodopyrrolidine-2,5-dione (3.70 g, 16.5 mmol) was added to a solution of methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate (5.60 g, 16.5 mmol) in acetonitrile (56.0 mL), followed by the addition of 2,2,2-trifluoroacetic acid (0.564 g, 0.381 mL, 4.94 mmol). The reaction mixture was heated at 80 °C for 36 h and then stirred at room temperature for 48 h. The cooled reaction mixture was quenched by adding 200 mL of saturated sodium bicarbonate solution and extracted with dichloromethane (x3). The combined organic extracts were washed with saturated sodium thiosulfate solution, then washed with brine, dried over magnesium sulfate, filtered, and evaporated under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 0-100% ethyl acetate in cyclohexane as the eluent to give methyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylate (5.33 g, 11.4 mmol, 70%) as a white solid.

[0211] 1 ¹H NMR (400MHz, chloroform) δ = 7.57 (d, 1H), 7.49 (d, 1H), 7.23 (m, 1H), 3.89 (q, 2H), 3.57 (s, 3H), 2.88 (s, 3H), 1.17 (t, 3H).

[0212] Step 5: Synthesis of methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-vinylpyridine-3-carboxylate

[0213]

[0214] Degassed toluene (4 mL) was added to a mixture of methyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylate (0.270 g, 0.58 mmol) and dichlorobis(triphenylphosphine)palladium(II) (0.021 g, 0.029 mmol) under nitrogen atmosphere, followed by the addition of tributyl(vinyl)stanane (0.551 g, 1.74 mmol). The mixture was heated at 140 °C for 0.75 h under microwave irradiation. The reaction mixture was evaporated to dryness under reduced pressure and purified by silica gel rapid chromatography using a gradient of 0-100% ethyl acetate in cyclohexane as the eluent to give methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-vinyl-pyridine-3-carboxylate (0.155 g, 0.423 mmol, 73%).

[0215] 1 ¹H NMR (400MHz, chloroform) δ=7.55(d,1H),7.50(d,1H),7.24(m,1H),6.63(m,1H),5.99(m,1H),5.62(m,1H),3.80(q,2H),3.57(s,3H),2.54(s,3H),1.15(t,3H).

[0216] Example 2: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-ethynyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (compound 2.005)

[0217] Step 1: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylic acid

[0218]

[0219] Methyl 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.329 g, 0.706 mmol) was added to a solution of methanol (4 mL) and water (2 mL) with lithium hydroxide monohydrate (0.059 g, 1.41 mmol). The reaction mixture was heated to 80 °C for 6 hours. The reaction mixture was evaporated under reduced pressure. The residue was diluted with water (15 mL) and extracted with dichloromethane. The aqueous phase was acidified to pH 3 by adding 2 M hydrochloric acid, followed by further extraction with dichloromethane (2 x 10 mL). The organic extract was dried and then evaporated to dryness under reduced pressure to give 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.311 g, 0.69 mmol, 98%) as a white solid.

[0220] 1 ¹H NMR (400MHz, chloroform) δ = 7.60 (d, 1H), 7.34 (d, 1H), 7.10 (m, 1H), 4.01 (q, 2H), 2.99 (s, 3H), 1.23 (t, 3H).

[0221] Step 2: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-(2-trimethylsilylethynyl)pyridine-3-carboxylic acid

[0222]

[0223] Degassed toluene (1 mL) was added to a mixture of 2-(3,4-dichlorophenyl)-1-ethyl-5-iodo-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.150 g, 0.332 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.077 g, 0.066 mmol) at room temperature under nitrogen atmosphere. Tributyltin (0.308 g, 0.796 mmol) was added, and the reaction mixture was heated at 120 °C for 0.5 h under microwave irradiation. The cooled reaction mixture was passed through a TMT column, and the filtrate was evaporated to dryness under reduced pressure. The crude residue was purified by mass-oriented reversed-phase HPLC to obtain 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-(2-trimethylsilylethynyl)pyridine-3-carboxylic acid (0.022 g, 0.052 mmol, 16%) as a yellow solid.

[0224] 1 ¹H NMR (400MHz, chloroform) δ = 7.59(d, 1H), 7.33(d, 1H), 7.09(m, 1H), 3.89(q, 2H), 2.81(s, 3H), 1.21(t, 3H), 0.31(s, 9H).

[0225] Step 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-5-ethynyl-6-methyl-4-oxo-pyridine-3-carboxylic acid

[0226]

[0227] Potassium carbonate (0.016 g, 0.115 mmol) was added to a solution of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-(2-trimethylsilylethynyl)pyridine-3-carboxylic acid (0.022 g, 0.052 mmol) in methanol (0.52 mL) at room temperature. The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was diluted with ethyl acetate (20 mL) and aqueous hydrochloric acid (2 M, 20 mL). The aqueous phase was extracted with ethyl acetate (x2). The combined organic extracts were washed with water, dried over magnesium sulfate, and evaporated to dryness under reduced pressure. The crude residue was purified by mass-directed HPLC to give 2-(3,4-dichlorophenyl)-1-ethyl-5-ethynyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.017 g, 0.048 mmol, 92%) as a white solid.

[0228] 1¹H NMR (400MHz, acetonitrile-d³) δ = 7.69 (d, 1H), 7.51 (d, 1H), 7.27 (m, 1H), 3.99 (s, 1H), 3.89 (q, 2H), 2.80 (s, 3H), 1.12 (t, 3H).

[0229] Example 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-vinylpyridine-3-carboxylic acid (compound 2.001)

[0230] Step 1: Synthesis of methyl 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate

[0231]

[0232] N-bromosuccinimide (0.26 g, 1.47 mmol) was added in portions to a stirred solution of methyl 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate (0.500 g, 1.47 mmol) in acetonitrile (5.0 mL, 95.7 mmol). The reaction mixture was stirred at room temperature until LC-MS showed complete consumption of the starting material. The reaction mixture was quenched by adding saturated sodium bicarbonate aqueous solution (30 mL), and the aqueous phase was extracted with dichloromethane (3 x 15 mL). The combined organic extracts were passed through a phase separator and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 50%-100% ethyl acetate in isohexane as the eluent to give methyl 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate (0.602 g, 1.44 mmol, 98%) as a colorless solid.

[0233] 1 ¹H NMR (400MHz, chloroform) δ = 7.57(d, 1H), 7.49(d, 1H), 7.23(m, 1H), 3.85(q, 2H), 3.57(s, 3H), 2.74(s, 3H), 1.17(t, 3H).

[0234] Step 2: Synthesis of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid

[0235]

[0236] Methyl 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate

[0237] A solution of lithium hydroxide monohydrate (1.00 g, 23.9 mmol) in water (6 mL) was added to a solution of lithium hydroxide monohydrate (2.50 g, 5.97 mmol) in methanol (15 mL). The resulting solution was heated to 80 °C for 2 hours. The cooled reaction mixture was acidified to pH 1–2 by adding concentrated hydrochloric acid. The precipitated solid was collected by filtration, washed with cold water and dried to give 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (1.84 g, 4.54 mmol, 76%) as a white powder.

[0238] 1 ¹H NMR (400MHz, methanol-d⁴) δ = 7.68 (d, 1H), 7.64 (d, 1H), 7.33 (m, 1H), 4.03 (q, 2H), 2.89 (s, 3H), 1.19 (t, 3H).

[0239] Step 3: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-vinylpyridine-3-carboxylic acid

[0240]

[0241] A solution of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.300 g, 0.741 mmol) in toluene (5 mL) was added to dichlorobis(triphenylphosphine)palladium(II) under nitrogen. The mixture was degassed under nitrogen for 5 min, and then tributyl(vinyl)stanane (0.704 g, 2.22 mmol) was added. The reaction mixture was heated at 120 °C for 0.75 h under microwave irradiation. The cooled reaction mixture was filtered through diatomaceous earth and evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 5%–100% ethyl acetate in cyclohexane as the eluent to give 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-5-vinyl-pyridine-3-carboxylic acid (0.099 g, 0.28 mmol, 38%).

[0242] 1 ¹H NMR (400MHz, chloroform) δ=7.63-7.56(m,1H),7.39-7.33(m,1H),7.15-7.07(m,1H),6.73-6.58(m,1H),5.83-5.80(m,1H),5.79-5.71(m,1H),3.95-3.87(m,2H),2.68-2.61(m,3H),1.26-1.15(m,3H).

[0243] Example 4: Synthesis of 5-acetyl-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (compound 2.008)

[0244] Step 1: Synthesis of methyl 5-acetyl-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate

[0245]

[0246] A solution of methyl 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate (0.462 g, 1.10 mmol) in toluene (15 mL) was added to dichlorobis(triphenylphosphine)palladium(II) (0.039 g, 0.055 mmol). Tributyl(1-ethoxyvinyl)stanane (1.194 g, 3.31 mmol) was added, and the reaction mixture was heated to 60 °C for 1.5 h, and then heated at 125 °C for 5 h. More dichlorobis(triphenylphosphine)palladium(II) (0.039 g, 0.055 mmol) and tributyl(1-ethoxyvinyl)stanane (1.194 g, 3.31 mmol) were added, and the reaction mixture was heated for 18 h. The cooled reaction mixture was evaporated to dryness under reduced pressure. The crude residue was purified by silica gel rapid chromatography using a gradient of 5%-100% ethyl acetate in isohexane as the eluent to give methyl 5-acetyl-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylate (0.062 g, 0.16 mmol, 15%).

[0247] 1 ¹H NMR (400MHz, chloroform) δ=7.65-7.64(m,1H),7.58-7.56(m,1H),7.31-7.30(m,1H),4.18-4.06(m,2H),3.60-3.49(m,3H),2.63-2.53(m,3H),2.43-2.37(m,3H),1.29-1.22(m,3H).

[0248] Step 2: Synthesis of 5-acetyl-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid

[0249]

[0250] Prepared as for 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid, using methyl 5-acetyl-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.062 g, 0.16 mmol) and hydrated lithium hydroxide (0.027 g, 0.65 mmol), stirred at room temperature for 1.5 h, followed by heating under reflux for 2 h, to give 5-acetyl-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.034 g, 0.091 mmol, 56%).

[0251] 1 ¹H NMR (400MHz, chloroform) δ=7.64-7.56(m,1H),7.38-7.31(m,1H),7.14-7.06(m,1H),3.94-3.84(m,2H),2.66-2.58(m,3H),2.55-2.42(m,3H),1.29-1.13(m,3H).

[0252] Example 5: Synthesis of 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3,5-dicarboxylic acid (compound 2.010)

[0253]

[0254] Under nitrogen atmosphere and at -20°C, a suspension of 5-bromo-2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3-carboxylic acid (0.100 g, 0.247 mmol) cooled (at -20°C) in anhydrous tetrahydrofuran (0.50 mL) was added dropwise to a solution of isopropyl magnesium chloride-lithium chloride complex (1.3 M, 0.40 mL, 0.518 mmol in THF). The reaction mixture was stirred for 0.25 h, then heated to -10°C and stirred for 0.3 h. The reaction mixture was recooled to -20°C, and the solution of isopropyl magnesium chloride-lithium chloride complex (1.3 M, 0.34 mL, 0.442 mmol in THF) was added. The reaction mixture was stirred at -10°C for 0.5 h. Under stirring, dry ice particles were sublimated into the reaction mixture via a sleeve over 0.5 h, followed by the direct addition of two small dry ice particles to the reaction mixture. The reaction mixture was stirred at room temperature for 0.5 hours. The reaction mixture was cooled to 0°C and quenched by adding saturated ammonium chloride aqueous solution (5 mL). The pH of the aqueous phase was adjusted to pH 3 by adding hydrochloric acid aqueous solution (2 M). The aqueous phase was extracted with dichloromethane (x3). The combined organic extracts were dried and evaporated to dryness under reduced pressure. The crude residue was purified by mass-directed HPLC to give 2-(3,4-dichlorophenyl)-1-ethyl-6-methyl-4-oxo-pyridine-3,5-dicarboxylic acid (0.019 g, 0.050 mmol, 20%) as a white solid.

[0255] 1 H NMR (400MHz, DMSO-d6) δ = 7.84 (d, 1H), 7.82 (d, 1H), 7.48 (m, 1H), 3.88 (q, 2H), 2.74 (s, 3H), 1.10 (t, 3H).

[0256] Table 2: Compounds selected in Table 1 1 H NMR data.

[0257]

[0258]

[0259] Biological examples

[0260] Seeds of several test species were sown in standard soil in pots (Amaranthus retoflexus (AMARE), Solanum nigrum (SOLNI), Setaria faberi (SETFA), Lolium perenne (LOLPE), Echinochloa crus-galli (ECHCG), and 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 were sprayed with an aqueous spray solution derived from a formulation of one or more industrial-grade active ingredients in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Unless otherwise specified, the compound was applied at 1000 g / ha. Test plants were then grown in a greenhouse under controlled conditions (24°C / 16°C, day / night; 14-hour light; 65% humidity) and watered twice daily. After 13 days, the percentage of damage to the plants was evaluated. Biological activity is shown in the table below on a five-point scale (5 = 81%–100%; 4 = 61%–80%; 3 = 41%–60%; 2 = 21%–40%; 1 = 0–20%).

[0261] Table B1: Post-emergence testing

[0262] Compound numbering AMARE SOLNI SETFA LOLPE ECHCG IPOHE 4.001 1 1 4 4 1 2 2.005 5 4 5 5 3 4 2.001 1 1 4 4 2 4 2.008 2 2 3 5 3 2 2.010 2 2 1 1 1 2

[0263] Table B2: Pre-emergence testing

[0264] Compound numbering AMARE SOLNI SETFA LOLPE ECHCG IPOHE 4.001 1 1 1 1 1 1 2.005 1 4 4 1 1 4 2.001 1 1 4 4 3 3 2.008 1 3 5 4 3 3 2.010 1 3 1 2 1 1

Claims

1. A compound having formula (I): (I) in X is O; R 1 It is a C1-C3 alkyl group; R 2 It is optional to be one or two that can be the same or different by R 7 The group represents a phenyl group that has been substituted. R 3 It is hydrogen or C1-C3 alkyl; R 4 It is a C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl carbonyl, or hydroxy carbonyl; R 5 It is a C1-C3 alkyl group; R 7 It is halogen; Or its salt.

2. The compound according to claim 1, wherein R 4 It is a C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkyl carbonyl, or hydroxy carbonyl.

3. The compound according to claim 1 or 2, wherein R 4 It is a C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkyl carbonyl, or hydroxy carbonyl.

4. The compound according to claim 1 or 2, wherein R 4 It is vinyl, ethynyl, acetyl, or hydroxycarbonyl.

5. The compound according to claim 1 or 2, wherein R 1 It is an ethyl group.

6. The compound according to claim 1 or 2, wherein R 3 It is either hydrogen or methyl.

7. The compound according to claim 1 or 2, wherein R 5 It is a methyl group.

8. The compound according to claim 1 or 2, wherein R 7 It is chlorine.

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

10. The herbicidal composition according to claim 9, further comprising at least one additional pest control agent.

11. The herbicidal composition according to claim 10, wherein, The other pest control agent mentioned is a herbicide or a herbicide safener.

12. A method for controlling unwanted plant growth, the method comprising applying a compound having formula (I) as defined in any one of claims 1 to 8 or a herbicidal composition according to any one of claims 9 to 11 to the unwanted plant or its location.

13. Use of the compound having formula (I) according to any one of claims 1 to 8 as a herbicide.

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