Pyridazinone herbicides

Abstract

This invention discloses compounds of Formula 1 (including all its stereoisomers, N-oxides, and salts), agricultural compositions comprising them, and their use as herbicides, wherein R 1 R 2 L, G, and W are as defined in this disclosure, and A is selected from X. 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 X 9 X 10 Y and Y1 are as defined in this disclosure.

Description

Technical Field

[0001] This invention relates to certain pyridazinone herbicides, their N-oxides, salts and compositions, and methods for using them to control unwanted vegetation. Background Technology

[0002] Controlling unwanted vegetation is crucial for achieving high crop efficiency. This is especially true in available crops such as rice, soybeans, sugar beets, corn, potatoes, wheat, barley, tomatoes, and other cultivated crops, where selective control of weed growth is highly desirable. Uncontrolled weed growth in these crops can lead to significant yield reductions, resulting in increased costs for consumers. Controlling unwanted vegetation in non-cultivated areas is also important. Many products are commercially available for these purposes, but there remains a continuous need for new compounds that are more effective, cheaper, less toxic, environmentally safer, or have different sites of action. Summary of the Invention

[0003] This invention relates to compounds of formula 1 (including all their stereoisomers, N-oxides, and salts), agricultural compositions comprising them, and their use as herbicides.

[0004]

[0005] in

[0006] W represents O or S;

[0007] R 1 It is H, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C4-C7 alkylcycloalkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy, benzyl, or phenyl; or a 5- or 6-membered saturated or partially saturated heterocycle containing a ring member selected from carbon and at most one O and one S;

[0008] R 2H, halogen, cyano, formyl, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C2-C4 alkylcarbonyl, C2-C7 alkylcarbonyloxy, C4-C7 alkylcycloalkyl, C3-C7 alkenyl, C3-C7 alkynyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3- C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C1-C5 alkylthio or C2-C3 alkoxycarbonyl; or phenyl optionally substituted with halogen, C1-C4 alkyl or C1-C4 haloalkyl;

[0009] L represents a direct bond, a C1-C4 alkyl diene, or a C2-C4 olefin diene;

[0010] G is H, C(=O)R 5 C(=S)R 5 CO2R 6 C(=O)SR 6 S(O)2R 5 CONR 7 R 8 S(O)2NR 7 R 8 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl; or 5-membered or 6-membered heterocycles;

[0011] A is selected from

[0012]

[0013] X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 X 9 and X 10 Each is independently N or CR 3 The prerequisite is X. 1 X 2 X 3X 4 X 5 X 6 X 7 X 8 X 9 and X 10 N is defined as having no more than 4 of the following.

[0014] Y represents O, S, or NR. 4 ;

[0015] Y 1 For O, S, NR 4 or CR 3a R 3b ;

[0016] Each R 3 Independently, it is H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C5 haloalkyl, C3-C5 haloalkenyl, C3-C5 haloalkynyl, C2-C5 alkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C5 haloalkylthio or C2-C5 alkoxycarbonyl;

[0017] R 3a It can be H, halogen, -CN, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C5 haloalkyl, C3-C5 haloalkenyl, C3-C5 haloalkynyl, C2-C5 alkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C5 haloalkylthio or C2-C5 alkoxycarbonyl;

[0018] R 3b H, halogen, -CN, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C5 haloalkyl, C3-C5 haloalkenyl, C3-C5 haloalkynyl, C2-C5 alkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C5 haloalkylthio or C2-C5 alkoxycarbonyl; or

[0019] R 3a and R 3b As =O combined; or R 3a and R 3bThey combine with the carbon atoms they are bonded to form optionally substituted 3- to 7-membered carbon rings;

[0020] R 4 It is H, C1-C3 alkyl, or C1-C3 haloalkyl;

[0021] R 5 and R 7 Independently, it is H, C1-C7 alkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl or C4-C7 cycloalkylalkyl; or phenyl, benzyl, or 5 to 6-membered heterocycle, each phenyl, benzyl or heterocycle optionally substituted with halogen, C1-C4 alkyl or C1-C4 haloalkyl;

[0022] R 6 It is a C1-C7 alkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C2-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl or C4-C7 cycloalkylalkyl; or phenyl, benzyl, or 5 to 6-membered heterocycle, each phenyl, benzyl or heterocycle optionally substituted with halogen, C1-C4 alkyl or C1-C4 haloalkyl;

[0023] R 8 It can be H, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C7 haloalkyl or C2-C7 alkoxyalkyl;

[0024] R 9 It is a C1-C7 alkyl or C1-C7 alkoxy; and

[0025] R 10 It is a C1-C7 alkyl or C1-C7 alkoxy group.

[0026] More specifically, the present invention relates to compounds of Formula 1 (including all stereoisomers), their N-oxides, or salts. The present invention also relates to a herbicide composition comprising the compound of the present invention (i.e., a herbicidal effective amount) and at least one component selected from surfactants, solid diluents, and liquid diluents. The present invention further relates to a method for controlling unwanted vegetation growth, the method comprising contacting the vegetation or its environment with a herbicidal effective amount of the compound of the present invention (e.g., as described herein).

[0027] The present invention also includes a herbicide mixture comprising (a) a compound selected from Formula 1, its N-oxide and salt, and (b) at least one additional active ingredient selected from (b1) to (b16); and a salt of the compound (b1) to (b16) as described below. Detailed Implementation

[0028] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “contains,” “containing,” “has,” “having,” “characterized by,” or any other variations thereof are intended to cover non-exclusive inclusion, which is subject to any expressly indicated limitations. For example, a composition, mixture, process, or method that includes a list of elements is not necessarily limited to those elements, but may also include other elements not expressly listed or inherent to such compositions, mixtures, processes, or methods.

[0029] The conjunction "composed of..." excludes any unspecified elements, steps, or ingredients. If present in a claim, this would exclude materials other than those typically associated with impurities. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following it, it limits only the elements listed in that clause; other elements as a whole are not excluded from the claim.

[0030] The conjunction "consistently composed of" is used to define a composition or method that includes materials, steps, features, components, or elements other than those literally disclosed, provided that such additional materials, steps, features, components, or elements do not materially affect the essential and novel features of the invention protected by the claims. The term "consistently composed of" falls between "comprising" and "composed of".

[0031] If the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also using the terms “consistently composed of” or “comprises with” to describe the invention.

[0032] Furthermore, unless explicitly stated otherwise, "or" refers to an inclusive "or" and not an exclusive "or". For example, conditions A or B are satisfied by any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0033] Furthermore, the indefinite articles “a” and “an” preceding the elements or components of the present invention are intended to be non-limiting in terms of the number of instances (i.e., occurrences) of the elements or components. Therefore, “a” or “an” should be understood to include one or at least one, and the singular form of an element or component also includes the plural, unless the quantity is obviously singular.

[0034] As mentioned in this article, the term "seedling" used alone or in combination of words refers to a young plant that develops from a seed embryo.

[0035] As mentioned in this article, the term "broadleaf" used alone or in words such as "broadleaf weeds" refers to dicotyledons or the subphylum Dicotyledons, a term used to describe a group of angiosperms characterized by an embryo with two cotyledons.

[0036] As used herein, the term "alkylation" refers to a reaction in which a nucleophile replaces a leaving group, such as a halide or sulfonate ion, from a carbon-containing group. Unless otherwise specified, the term "alkylation" does not limit the carbon-containing group to alkyl groups.

[0037] In the above description, the term "alkyl" as used alone or in compound terms such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, or various butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl, and various butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and various butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include a moiety consisting of multiple triple bonds, such as 2,5-hexadiynyl.

[0038] "Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and various butoxy, pentoxy, and hexoxy isomers. "Alkoxyalkyl" refers to an alkoxy substituent on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2, and CH3CH2OCH2CH2. "Alkoxyalkoxy" refers to an alkoxy substituent on an alkoxy group. "Alkthio" includes branched or straight-chain alkthio groups, such as methylthio, ethylthio, and various propylthio, butylthio, pentthio, and hexthio isomers. "Alkthioalkyl" refers to an alkoxy substituent on an alkyl group. Examples of "alkthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2, and CH3CH2SCH2CH2. "Alkylsulfinyl" includes two enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)-, and various butylsulfinyl, pentylsulfinyl, and hexylsulfinyl isomers. Examples of “alkylsulfonyl” include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2-, and various butylsulfonyl, pentylsulfonyl, and hexylsulfonyl isomers. “Cyanoalkyl” refers to an alkyl group substituted with a cyano group. Examples of “cyanoalkyl” include NCCH2 and NCCH2CH2 (or CH2CH2CN). “Nitroalkyl” refers to an alkyl group substituted with a nitro group. Examples of “nitroalkyl” include O2NCH2 and O2NCH2CH2 (or CH2CH2NO2). “Cyano” refers to NC-, and “formyl” refers to HC(=O)-. “Alkylamino” includes straight-chain or branched alkyl-substituted NH groups. Examples of “alkylamino” include CH3CH2NH, CH3CH2CH2NH, and (CH3)2CHCH2NH. Examples of “dialkylamino” include (CH3)2N, (CH3CH2CH2)2N, and CH3CH2(CH3)N.

[0039] "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkylalkyl" refers to a cycloalkyl substituent on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term "alkylcycloalkyl" refers to an alkyl group bonded to a cycloalkyl moiety.

[0040] The term "halogen" includes fluorine, chlorine, bromine, or iodine, either alone or in compound terms such as "halogenated alkyl" or when used to describe "halogen-substituted alkyl". Additionally, when used in compound terms such as "halogenated alkyl" or when used to describe "halogen-substituted alkyl", the alkyl group may be partially or completely substituted by the same or different halogen atoms. Examples of "halogenated alkyl" or "halogen-substituted alkyl" include F3C, ClCH2, CF3CH2, and CF3CCl2. The terms "halogenated alkoxy", "halogenated alkoxyalkyl", "halogenated alkylthio", "halogenated alkenyl", "halogenated alkynyl", etc., are used as defined similarly to the term "halogenated alkyl". Examples of "halogenated alkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O-, and CF3CH2O-. Examples of “haloalkoxyalkyl” include CF3OCH2-, CCl3CH2OCH2-, HCF2CH2CH2OCH2-, and CF3CH2OCH2-. Examples of “haloalkoxythio” include CCl3S-, CF3S-, CCl3CH2S-, and ClCH2CH2CH2S-. Examples of “haloalkenyl” include (Cl)2C=CHCH2- and CF3CH2CH=CHCH2-. Examples of “haloalkynyl” include HC≡CCHCl-, CF3C≡C-, CCl3C≡C-, and FCH2C≡CCH2-.

[0041] "alkyl carbonyl" refers to a straight-chain or branched alkyl moiety bonded to a C(=O) portion. Examples of "alkyl carbonyl" include CH3C(=O)-, CH3CH2C(=O)-, CH3CH2CH2C(=O)-, (CH3)2CHC(=O)-, and various butoxycarbonyl or pentoxycarbonyl isomers. "alkoxy carbonyl" refers to a straight-chain or branched alkoxy moiety bonded to a C(=O) portion. Examples of "alkoxy carbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)-, and various butoxycarbonyl or pentoxycarbonyl isomers. The term "alkoxycarbonyl alkyl" refers to a straight-chain or branched alkoxy moiety bonded by an alkyl portion. The term "alkyl carbonyl alkyl" refers to a straight-chain or branched alkyl carbonyl moiety bonded by an alkyl portion. The term "alkylcarbonyloxy" includes examples of alkylcarbonyloxy groups representing an alkyl carbonyl moiety bonded by oxygen, including CH3C(=O)O-, CH3CH2C(=O)O-, CH3CH2CH2C(=O)O-, and (CH3)2CHC(=O)-. The terms alkadiyl or alkenadiyl refer to straight-chain or branched alkane or alkene linking chains, respectively. Examples of alkadiyl groups include -CH2-, -CH2CH(CH3)-, or -CH2CH2CH2-. Examples of alkenadiyl groups include -CH=CH-, -CH2C=CH-, or -CH=C(CH3)-. In the context of directing substituents, the term "proximate" means "adjacent" or "closely adjacent."

[0042] The total number of carbon atoms in the substituents is determined by "C i -C j The prefix indicates that i and j are numbers from 1 to 7. For example, C1-C4 alkylsulfonyl groups represent methanesulfonyl to butanesulfonyl groups; C2 alkoxyalkyl groups represent CH3OCH2-; C3 alkoxyalkyl groups represent, for example, CH3CH(OCH3)-, CH3OCH2CH2-, or CH3CH2OCH2-; and C4 alkoxyalkyl groups represent various isomers of alkoxy-substituted alkyl groups containing a total of four carbon atoms, examples of which include CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.

[0043] When a group contains a substituent that can be hydrogen (e.g., R... 2 Or R 4 When the substituent is hydrogen, it is considered equivalent to the group being unsubstituted. When one or more positions on a group are referred to as "unsubstituted" or "unreplaced," a hydrogen atom is attached to occupy any free valence. Unless otherwise specified as optionally substituted, the term "phenyl" means unsubstituted phenyl. Unless otherwise specified as optionally substituted, the term "benzyl" means unsubstituted benzyl.

[0044] Compounds of Formula 1 are believed to be direct bonds (where L is a direct bond and G is H, i.e., the "OLG" substituent of Formula 1 is a hydroxyl moiety) that bind to active sites on plant enzymes or receptors, thereby producing a herbicidal effect on plants. Other compounds of Formula 1 (wherein the substituent LG forms a group that can be converted into the hydroxyl moiety within the plant or environment) provide similar herbicidal effects and are within the scope of this invention. Therefore, LG can be any derivative known in the art that does not eliminate the herbicidal activity of compounds of Formula 1 and is, or can be, hydrolyzed, oxidized, reduced, or otherwise metabolized in plants or soil to provide a carboxylic acid functional group, which is in a dissociated or undissociated form depending on pH. The term "cyclic system" refers to two or more fused rings. The term "bicyclic system" refers to a ring system consisting of two fused rings.

[0045] The compounds of the present invention can exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, trans-isomers, and geometric isomers. Stereoisomers are isomers with the same composition but different spatial arrangements of their atoms, and include enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and trans-isomers. Trans-isomers are caused by restricted rotation around a single bond, wherein the rotational energy barrier is high enough to allow the isomer species to separate. Those skilled in the art will recognize that a stereoisomer may be more active and / or exhibit beneficial effects when enriched relative to other stereoisomers or when separated from other stereoisomers. Furthermore, those skilled in the art know how to separate, enrich, and / or selectively prepare said stereoisomers. The compounds of the present invention can exist as mixtures of stereoisomers, individual stereoisomers, or as optically active forms.

[0046] Compounds of Formula 1 typically exist in more than one form, and therefore Formula 1 encompasses all crystalline and amorphous forms of the compounds they represent. Amorphous forms include embodiments in solid form (such as waxes and gums) and embodiments in liquid form (such as solutions and melts). Crystalline forms include embodiments that substantially represent a single crystal form and embodiments that represent a mixture of polymorphs (i.e., different crystal forms). The term "polymorph" refers to a specific crystalline form of a chemical compound that can crystallize in different crystalline forms, having different molecular arrangements and / or molecular conformations in the crystal lattice. Although polymorphs may have the same chemical composition, they may differ in composition due to the presence or absence of co-crystallization water or other molecules that may be weakly or strongly bound in the crystal lattice. The chemical, physical, and biological properties of polymorphs, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate, and bioavailability, may vary. Those skilled in the art will understand that, relative to another polymorph or mixture of polymorphs of the same compound of Formula 1, one polymorph of a compound of Formula 1 may exhibit beneficial effects (e.g., suitability for the preparation of usable formulations, improved biological properties). The preparation and isolation of specific polymorphs of compounds of Formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using a selected solvent and temperature. For a comprehensive discussion of polymorphism, see R. Hilfiker (ed.), *Polymorphism in the Pharmaceutical Industry*, Wiley-VCH, Weinheim, 2006.

[0047] Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides, as a lone pair of electrons is required to oxidize nitrogen to an oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize tertiary amines that can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, and these methods involve oxidizing heterocycles and tertiary amines with peroxy acids (such as peracetic acid and m-chloroperoxybenzoic acid (MCPBA)), hydrogen peroxide, alkyl hydrogen peroxides (such as tert-butyl hydrogen peroxide), sodium perborate, and peroxide ketones (such as dimethyl peroxide ketone). These methods for preparing N-oxides have been well described and reviewed in the literature, see, for example: T.L. Gilchrist, Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, edited by SV. Ley, Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimemett and B.R. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, edited by A.R. Katritzky, Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and GW.H. Heeseman and E.S. G.W. Gerstiuk, Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, edited by A.R. Katritzky and A.J. Boulton, Academic Press.

[0048] Those skilled in the art recognize that, because salts of compounds exist in equilibrium with their corresponding non-salt forms under environmental and physiological conditions, the salts share the bioavailability of the non-salt forms. Therefore, a wide variety of salts of Formula 1 compounds can be used to control undesirable vegetation (i.e., agriculturally suitable). Salts of Formula 1 compounds include acid addition salts with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. When a compound of Formula 1 contains an acidic moiety (such as an enol functional group) (e.g., when L is a direct bond and G is H), the salt also includes those formed with organic or inorganic bases such as pyridine, triethylamine, or ammonia, or amides, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium, or barium. Therefore, the present invention includes compounds selected from Formula 1, its N-oxides, and agriculturally suitable salts.

[0049] Unless otherwise stated, when R 5 R 6 Or R 7 When it is a 5- or 6-membered nitrogen-containing heterocycle, it can be attached to the remainder of Formula 1 by any available carbon or nitrogen ring atom. As noted above, R 5 R 6 Or R 7 A phenyl group may be (among others) optionally substituted with one or more substituents selected from the group of substituents defined in the invention. An example of a phenyl group optionally substituted with one to five substituents is a ring as shown in U-1 of Example 1, wherein R... v As a substituent, R is located in the context of the invention as defined in the invention. 5 R 6 Or R 7 Above, and r is an integer.

[0050] As pointed out above, R 5 R 6 Or R 7 A 5- or 6-membered heterocycle may be (among others) optionally substituted with one or more substituents selected from the group of substituents defined in the invention, and may be saturated or unsaturated. Examples of 5- or 6-membered unsaturated aromatic heterocycles optionally substituted with one or more substituents include rings U-2 to U-61 shown in Example 1, wherein R v For R 5 R 6 Or R 7Any substituent as defined in the invention (i.e., halogen, C1-C4 alkyl, or C1-C4 haloalkyl), and r is an integer from 0 to 4, limited by the number of available positions on each U group. For example, U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42, and U-43 have only one available position; for these U groups, r is limited to an integer of 0 or 1, and r = 0 means that the U group is unsubstituted and hydrogen is present in (R... v ) r The indicated location.

[0051] Example 1

[0052]

[0053]

[0054] It should be noted that when R 5 R 6 Or R 7 For optional selection as described in the invention content, R 5 R 6 Or R 7 One or more substituents of the group of substituents defined represent a 5- or 6-membered saturated or unsaturated non-aromatic heterocycle, wherein one or both carbocyclic members of the heterocycle may optionally be in the oxidized form of the carbonyl moiety.

[0055] Examples of 5- or 6-membered heterocycles include rings T-1 to T-35 as shown in Example 2, which are saturated or non-aromatic unsaturated heterocycles containing ring members selected from up to two O atoms and up to two S atoms, and optionally substituted for up to five halogen atoms on the carbon ring member. Note that when the linking point on the T group is shown as floating, the T group can be linked to the remainder of Formula 1 by substituting hydrogen atoms via any available carbon or nitrogen atom of the T group. Corresponding to R v Optional substituents can be attached to any available carbon or nitrogen atom by substituting hydrogen atoms. For these T rings, r is typically an integer from 0 to 4, limited by the number of available positions on each T group. The term "optionally substituted" means "substituted or unsubstituted." Note that when T... 2 When the nitrogen atom is N, it can be produced by using H or the atom corresponding to R. 5 R 6 Or R 7 R as defined in the invention description v The valence is perfected by substituting the substituents. R 1 Exemplary values ​​include T-1, T-2, T-7, and T-9 (i.e., when R...). 1When the ring contains a 5- or 6-membered saturated or partially saturated heterocycle selected from carbon and at most one O and one S ring member, etc., and T-28 to T-31, wherein T 2 It can be O or S.

[0056] Example 2

[0057]

[0058] Although R v The groups are shown in structures U-1 to U-61. Note that they are not required, as they are optional substituents. Note the presence of R... v In the case of H, when attached to an atom, it behaves as if the atom were unsubstituted. The nitrogen atom, which needs substitution to fill its valence, is represented by H or R. v Replacement. Note that when (R) v ) r The connection point with the U group is shown as when floating, (R v ) r Any available carbon or nitrogen atom can be attached to the U group. Note that when the attachment point on the U group is shown as floating, the U group can be attached to the remainder of Formula 1 by substituting a hydrogen atom via any available carbon or nitrogen atom of the U group. Note that some U groups can only be attached to fewer than four R atoms. v Group substitution (e.g., U-2 to U-5, U-7 to U-48, and U-52 to U-61).

[0059] A wide variety of synthetic methods are known in the art for allowing the preparation of aromatic and non-aromatic heterocycles and cyclic systems; for a comprehensive review, see the eight-volume *Comprehensive Heterocyclic Chemistry*, edited by A.R. Katritzky and C.W. Rees, Pergamon Press, Oxford, 1984, and the twelve-volume *Comprehensive Heterocyclic Chemistry II*, edited by A.R. Katritzky, C.W. Rees and E.F. V. C. Scriven, Pergamon Press, Oxford, 1996.

[0060] The embodiments of the present invention as described in the summary of the invention include (wherein Formula 1 as used in the following embodiments includes its N-oxide and salt):

[0061] Implementation Scheme 1: A compound of Formula 1, its N-oxide and salt, a composition comprising the thereof, and a method thereof for controlling unwanted vegetation (as described in the summary of the invention).

[0062] Implementation Scheme 2: The compound according to Implementation Scheme 1, wherein R 1 It can be H, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C4-C7 alkylcycloalkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy, benzyl, or phenyl.

[0063] Implementation Scheme 3: The compound according to any one of Implementation Scheme 1 or 2, wherein R 1 It can be H, C1-C7 alkyl, C3-C8 alkoxycarbonyl alkyl, C4-C7 alkylcycloalkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy or benzyl.

[0064] Implementation Scheme 4: The compound according to Implementation Scheme 3, wherein R 1 It is a C1-C4 alkyl, C3-C4 cycloalkyl, C2-C3 cyanoalkyl, C1-C3 haloalkyl or C2-C4 alkoxyalkyl.

[0065] Implementation Scheme 5: The compound according to Implementation Scheme 4, wherein R 1 It is a C1-C3 alkyl, NCCH2CH2-, C1-C2 haloalkyl or 2-methoxyethyl.

[0066] Implementation Scheme 6: The compound according to Implementation Scheme 5, wherein R 1 It can be methyl, ethyl, n-propyl or 2-methoxyethyl.

[0067] Implementation Scheme 7: The compound according to Implementation Scheme 6, wherein R 1 It can be methyl or ethyl.

[0068] Implementation Scheme 8: The compound according to Implementation Scheme 6, wherein R 1 It is a methyl group.

[0069] Implementation Scheme 9: The compound according to Implementation Scheme 1, wherein R 1 Not H.

[0070] Implementation Scheme 10: The compound according to Implementation Scheme 1, wherein R 1 It is not a phenyl group.

[0071] Implementation Scheme 11: The compound according to any one of Implementation Schemes 1 to 10, wherein W is O.

[0072] Implementation Scheme 12: Formula 1 or a compound according to any one of Implementation Schemes 1 to 11, wherein A is selected from A-1, A-4 and A-6.

[0073] Implementation Scheme 13: Formula 1 or the compound according to Implementation Scheme 12, wherein A is A-1.

[0074] Implementation Scheme 14: Formula 1 or the compound according to Implementation Scheme 12, wherein A is A-4.

[0075] Implementation Scheme 15: Formula 1 or the compound according to Implementation Scheme 12, wherein A is A-6.

[0076] Implementation Scheme 16: A compound of Formula 1 or according to Implementation Scheme 12, wherein A is A-1, and X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 and X 9 Each independently for CR 3 .

[0077] Implementation Scheme 17: A compound of Formula 1 or according to Implementation Scheme 12, wherein A is A-1, and X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 and X 9 Each is CH.

[0078] Implementation Scheme 18: The compound according to any one of Implementation Schemes 1 to 17, wherein R 2It can be H, halogen, cyano, formyl, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C2-C4 alkylcarbonyl, C2-C7 alkylcarbonyloxy, C4-C7 alkylcycloalkyl, C3-C7 alkenyl, C3-C7 alkynyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, or C1-C5 alkylthio.

[0079] Implementation Scheme 19: The compound according to Implementation Scheme 18, wherein R 2 It can be H, halogen, cyano, formyl, C1-C7 alkyl, C2-C4 alkyl carbonyl, C2-C7 alkyl carbonyloxy, C4-C7 alkyl cycloalkyl, C1-C4 alkyl sulfinyl, C1-C4 alkyl sulfonyl, C1-C4 alkylamino, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl or C1-C7 alkoxy.

[0080] Implementation Scheme 20: The compound according to Implementation Scheme 19, wherein R 2 It can be H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl or C1-C3 alkoxy.

[0081] Implementation Scheme 21: The compound according to Implementation Scheme 20, wherein R 2 It can be H, halogen, cyano, C1-C3 alkyl, cyclopropyl, C1-C2 haloalkyl, methoxy, or ethoxy.

[0082] Implementation Scheme 22: The compound according to Implementation Scheme 21, wherein R 2 It can be H, Cl, Br, I, cyano, methyl, or methoxy.

[0083] Implementation Scheme 23: The compound according to Implementation Scheme 22, wherein R 2 It can be H, Cl, methyl or methoxy.

[0084] Implementation Scheme 24: The compound according to Implementation Scheme 23, wherein R 2 It is either Cl or methyl.

[0085] Implementation Scheme 25: The compound according to any one of Implementation Schemes 1 to 23, wherein R 2Not H.

[0086] Implementation Scheme 26: The compound according to any one of Implementation Schemes 1 to 17, wherein R 2 It is not a phenyl group.

[0087] Implementation Scheme 27: The compound according to Implementation Scheme 18, wherein R 2 It can be halogen, C1-C7 alkyl, C1-C4 alkylamino, C2-C8 dialkylamino or C3-C7 cycloalkyl.

[0088] Implementation Scheme 28: The compound according to Implementation Scheme 27, wherein R 2 It is a C1-C4 alkylamino or a C2-C8 dialkylamino.

[0089] Implementation Scheme 29: Formula 1 or a compound according to any one of Implementation Schemes 1 to 28, wherein L is a direct bond.

[0090] Scheme 30: A compound of Formula 1 or according to any one of Schemes 1 to 28, wherein L is a direct bond and G is H, C(=O)R. 5 C(=S)R 5 CO2R 6 C(=O)SR 6 CONR 7 R 8 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl.

[0091] Implementation Scheme 31: The compound according to Implementation Scheme 30, wherein G is H, C(=O)R 5 CO2R 6 CONR 7 R 8 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl.

[0092] Implementation Scheme 32: The compound according to Implementation Scheme 31, wherein G is H, C(=O)R 5 CO2R 6 Or P(=O)R 9 R 10Or C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C3-C6 cycloalkyl.

[0093] Implementation Scheme 33: The compound according to Implementation Scheme 32, wherein G is H, C(=O)R 5 or CO2R 6 Or C2-C4 alkoxyalkyl or C3-C6 cycloalkyl.

[0094] Implementation Scheme 34: The compound according to Implementation Scheme 33, wherein G is H.

[0095] Implementation Scheme 35: The compound according to Implementation Scheme 33, wherein G is C(=O)R 5 .

[0096] Implementation Scheme 36: The compound according to Implementation Scheme 33, wherein G is CO2R 6 .

[0097] Implementation Scheme 37: The compound according to Implementation Scheme 33, wherein G is a C2-C4 alkoxyalkyl group.

[0098] Implementation Scheme 38: The compound according to Implementation Scheme 33, wherein G is a C3-C6 cycloalkyl group.

[0099] Implementation Scheme 39: A compound of Formula 1 or according to any one of Implementation Schemes 1 to 28, wherein L is a C1-C2 alkyldiyl or a C2-C3 olefinicdiyl.

[0100] Implementation Scheme 40: The compound according to Implementation Scheme 39, wherein L is a C1-C2 alkyldiyl.

[0101] Implementation Scheme 41: The compound according to Implementation Scheme 39, wherein L is a C2-C3 enediyl group.

[0102] Implementation Scheme 42: The compound according to Implementation Scheme 39, wherein L is -CH2- or -CH=CH-.

[0103] Implementation Scheme 43: The compound according to Implementation Scheme 42, wherein L is -CH2-.

[0104] Implementation Scheme 44: Formula 1 or a compound according to any one of Implementation Schemes 1 to 43, wherein each R 3 It can be independently H, halogen, C1-C3 alkyl, C3-C4 cycloalkyl, C1-C3 haloalkyl or C1-C3 alkoxy.

[0105] Implementation Scheme 45: The compound according to Implementation Scheme 44, wherein each R 3It is independently H, halogen, C1-C2 alkyl, cyclopropyl or C1-C2 haloalkyl.

[0106] Implementation Scheme 46: The compound according to Implementation Scheme 45, wherein each R 3 It can be H, halogen, methyl, ethyl or CF3 independently.

[0107] Implementation Scheme 47: The compound according to Implementation Scheme 46, wherein each R 3 It can be H, F, Cl, Br or methyl independently.

[0108] Implementation Scheme 48: The compound according to Implementation Scheme 47, wherein each R 3 For H.

[0109] The embodiments of the present invention, including embodiments 1-48 above and any other embodiments described herein, can be combined in any way, and the variables in the described embodiments belong not only to compounds of formula 1, but also to starting compounds and intermediate compounds that can be used to prepare compounds of formula 1. Furthermore, the embodiments of the present invention, including embodiments 1-48 above and any other embodiments described herein, and any combination thereof, belong to the compositions and methods of the present invention.

[0110] Implementation Scheme A: A compound of Formula 1, its N-oxide and salt, a composition comprising the thereof, and a method thereof for controlling unwanted vegetation, wherein...

[0111] R 1 It can be H, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C4-C7 alkylcycloalkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy, benzyl, or phenyl;

[0112] W is O;

[0113] A is selected from A-1, A-4 and A-6;

[0114] L stands for direct bond;

[0115] G is H, C(=O)R 5 C(=S)R 5 CO2R 6 C(=O)SR 6 CONR 7 R 8 Or P(=O)R9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl;

[0116] R 2 The following are possible meanings: H, halogen, cyano, formyl, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C2-C4 alkylcarbonyl, C2-C7 alkylcarbonyloxy, C4-C7 alkylcycloalkyl, C3-C7 alkenyl, C3-C7 alkynyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, or C1-C5 alkylthio; and

[0117] Each R 3 It can be independently H, halogen, C1-C3 alkyl, C3-C4 cycloalkyl, C1-C3 haloalkyl or C1-C3 alkoxy.

[0118] Implementation Scheme B: The compound according to Implementation Scheme A, wherein

[0119] R 1 It can be H, C1-C7 alkyl, C3-C8 alkoxycarbonylalkyl, C4-C7 alkylcycloalkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy or benzyl;

[0120] A is A-1;

[0121] G is H, C(=O)R 5 CO2R 6 CONR 7 R 8 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl;

[0122] R 2The following are possible meanings: H, halogen, cyano, formyl, C1-C7 alkyl, C2-C4 alkyl carbonyl, C2-C7 alkyl carbonyloxy, C4-C7 alkyl cycloalkyl, C1-C4 alkyl sulfinyl, C1-C4 alkyl sulfonyl, C1-C4 alkylamino, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, or C1-C7 alkoxy; and

[0123] Each R 3 It is independently H, halogen, C1-C2 alkyl, cyclopropyl or C1-C2 haloalkyl.

[0124] Implementation Scheme C: The compound according to Implementation Scheme B, wherein

[0125] R 1 It is a C1-C4 alkyl, C3-C4 cycloalkyl, C2-C3 cyanoalkyl, C1-C3 haloalkyl or C2-C4 alkoxyalkyl;

[0126] G is H, C(=O)R 5 CO2R 6 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl, or C3-C6 cycloalkyl;

[0127] R 2 It is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, or C1-C3 alkoxy; and

[0128] Each R 3 It can be H, halogen, methyl, ethyl or CF3 independently.

[0129] Implementation Scheme D: The compound according to Implementation Scheme C, wherein

[0130] R 1 It can be methyl, ethyl, n-propyl or 2-methoxyethyl;

[0131] G is H, C(=O)R 5 or CO2R 6 Or C2-C4 alkoxyalkyl or C3-C6 cycloalkyl;

[0132] R 2 It is H, Cl, Br, I, -CN, methyl or methoxy; and

[0133] Each R 3It can be H, F, Cl, Br or methyl independently.

[0134] The specific implementation scheme includes compounds of formula 1, which are selected from:

[0135] 4-(9-anthrayl)-6-chloro-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound 1);

[0136] 6-Chloro-4-(10-Chloro-9-anthrayl)-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound 2); and

[0137] 4-(10-bromo-9-anthrayl)-6-chloro-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound 3).

[0138] The present invention also relates to a method for controlling unwanted vegetation, comprising applying a herbicidally effective amount of the compounds of the present invention (e.g., compositions as described herein) to the site of the vegetation. It is noteworthy that embodiments related to the method of use involve those compounds described above. The compounds of the present invention are particularly useful for selectively controlling weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, rapeseed, and rice, as well as specialty crops such as sugarcane, citrus, fruit, and nut crops.

[0139] As an embodiment of the invention, the herbicide composition of the present invention comprising the compounds described above is also noteworthy.

[0140] The present invention also includes a herbicide mixture comprising (a) a compound selected from Formula 1, its N-oxides and salts, and (b) at least one additional active ingredient selected from: (b1) a photosystem II inhibitor, (b2) an acetylhydroxy acid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimic, (b5) a 5-enol-pyruvate-shikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase (PPO) inhibitor, (b8) a glutamine synthase (GS) inhibitor, (b9) a very long-chain fatty acid (VLCFA) elongation enzyme inhibitor, (b10) an auxin transport inhibitor, and (b11) a phytoene dehydrogenase. Saturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogenate solanyltransferase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides, including mitotic disruptors, organoarsenic compounds, chlorpyrifos, bromobutyroxyfen, cyclohexane, bensulfuron, dazomet, oat thiophanate-methyl, sapuram, ethoxybenzamide, phosmet, phosphonophosphorus, hydantoin, fenproxil fumarate, methyl methazine, oleic acid, oxadiazon, nonanoic acid and barnyardgrass, and (b16) herbicide safeners; and salts of compounds (b1) to (b16).

[0141] "Optical System II inhibitor" (b1) is in Q B - Binds to the D-1 protein at the binding niche and thus hinders electron transfer from Q in the thylakoid membrane of the chloroplast. A Pass to Q B The compound. Electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds, damaging the cell membrane and causing chloroplast swelling, membrane leakage, and ultimately cell destruction. Q B- The binding niche has three different binding sites: binding site A binds triazine such as atrazine, triazine such as cycloazine, and uracil such as chlorpyrifos; binding site B binds phenylurea such as diuron; and binding site C binds benzothiadiazole such as metribuzin, nitrile such as bromoxynil, and phenylpyridazine such as dapoxetine. Examples of photosystem II inhibitors include atrazine, azoxystrobin, atrazine, thiamethoxam, bromophenol oxime, bromosulfuron, chlorobromosulfuron, chlorpyrifos ...

[0142] "AHAS inhibitors" (b2) are compounds that inhibit acetylhydroxy acid synthase (AHAS) (also known as acetyllactic acid synthase (ALS)), and thus kill plants by inhibiting the production of branched-chain aliphatic amino acids such as valine, leucine, and isoleucine, which are essential for protein synthesis and cell growth. Examples of AHAS inhibitors include pyrimisulfuron, tetrazolium-sulfuron, bensulfuron-methyl, bispyribac-sodium, chlorpyrifos-sulfuron, chlorpyrifos-sulfuron, chlorsulfuron-methyl, ethersulfuron, cyprosulfuron-sulfuron, dichlorvos-sulfuron, acesulfuron-sulfuron, pyrimisulfuron-sulfuron, flupyrimisulfuron, flupyrimisulfuron, formamide-sulfuron, chlorpyrifos-sulfuron, imazalil, methoxysulfuron, methylimidazolium, and metsulfuron-methyl. Smoke, metsulfuron, pyrazosulfuron, iodosulfuron (including sodium salt), thiophene sulfone (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mesosulfuron, pyrazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy ... methyl disulfuron, pyrazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-yl)]carbonyl]benzenesulfonamide), pyrazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-yl)]carbonyl]benzenesulfonamide), pyrazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-yl)]carbonyl]benzenesulfonamide), pyrazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[4,6-dimethoxy-2-yl) (pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), sulfadiazine, mesosulfuron, nicosulfuron, cyclosulfuron, penoxsulam, methyl flusulfuron, propanilsulfuron, promethazine-sulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), flusulfuron, pyrimisulfuron, pyrimisulfuron The following are listed: pyrimethanil, cyclopyrimethanil, pyrimethanil, sulfadiazine, methylsulfuron, sulfonylsulfuron, thiamethoxam, thiamethoxam, fluoxetine (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylsulfonamide), etherbenzylsulfuron, benzylsulfuron, trifluridinesulfuron (including sodium salt), flumethanil, and trifluridinesulfuron.

[0143] "ACCase inhibitors" (b3) are compounds that inhibit acetyl-CoA carboxylase, an enzyme responsible for catalyzing early steps in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the resulting lack of lipid production lead to a loss of cell membrane integrity, particularly in actively growing areas such as meristems. Ultimately, bud and rhizome growth ceases, and bud meristems and flagella begin to die. Examples of ACCase inhibitors include quizalofop-P-ethyl, clethodim, clodinafop-propargyl, thiamethoxam, cyhalofop-propargyl, quizalofop-P-ethyl, haloxyfop-P-ethyl, haloxyfop-P-ethyl, clodinafop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, and quizalofop-P-ethyl, including split forms such as quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, and quizalofop-P-ethyl, as well as ester forms such as clodinafop-P-ethyl, cyhalofop-P-ethyl, quizalofop-P-ethyl methyl, and quizalofop-P-ethyl.

[0144] Auxins are plant hormones that regulate the growth of many plant tissues. "Auxin mimics" (b4) are compounds that mimic the plant growth hormone auxin, thus causing uncontrolled and disorganized growth, leading to the death of susceptible species. Examples of auxin mimics include cyclopropylpyrimidine acid (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters, as well as their sodium and potassium salts; chlorpyrifos; ethyl chlorpyrifos; glyphosate; chlorpyrifos; barnyardgrass; dichloropyridine acid; dicamba; 2,4-D; 2,4-DB; propionic acid; clopyralid; and fluorochloropyridine acid (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy)). Methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid, MCPA, MCPB, chloropropionic acid, doxycycline, dichloroquinoline acid, chloroquinoline acid, 2,3,6-TBA, chlorpyrifos, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylic acid.

[0145] "EPSP synthase inhibitors" (b5) are compounds that inhibit the enzyme 5-enol-pyruvate-shikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant leaves and translocated from the phloem to the growing point. Glyphosate is a relatively non-selective post-emergence herbicide belonging to this category. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium), and trimethylsulfonium (or glyphosate).

[0146] "Photosystem I electron diverters" (b6) are compounds that accept electrons from photosystem I and, after several cycles, generate hydroxyl radicals. These groups are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts cell membrane integrity, causing cells and organelles to "leak," leading to rapid leaf wilting and dehydration, ultimately resulting in plant death. Examples of this class II photosynthesis inhibitor include paraquat and chlorpyrifos.

[0147] "PPO inhibitors" (b7) are compounds that inhibit the enzyme protoporphyrinogen oxidase, thereby rapidly leading to the formation of highly reactive compounds in plants that rupture cell membranes, causing leakage of cell sap. Examples of PPO inhibitors include trifluralin, pyrazosulfuron, cyhalofop-P-ethyl, cyhalofop-P-ethyl, flupropargyl, pyrazosulfuron, trifluralin, methoxyfenozide, indole-methyl, isopyrazosulfuron, flupyridaben, fluazinam, propyzoxystrobin, ethoxysulfuron, fluazinam, flusulfanilamide, flufenoxuron, propyzoxystrobin, oxadiazon, ethoxysulfuron, cyclopentoxazin, fluazinam, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, mesotrione, thiamethoxam, trifludimoxazin (dihydro-) -1,5-Dimethyl-6-thio-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazin-2,4(1H,3H)-dione) and tiafenacil (N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alanine methyl ester).

[0148] "GS inhibitors" (b8) are compounds that inhibit the activity of glutamine synthase, an enzyme used in plants to convert ammonia into glutamine. As a result, ammonia accumulates and glutamine levels decrease. Plant damage may occur due to a combination of ammonia toxicity and the lack of amino acids required for other metabolic processes. GS inhibitors include glufosinate and its esters and salts such as glufosinate and other glufosinate derivatives, glufosinate-ammonium ((2S)-2-amino-4-(hydroxymethylphosphono)butyric acid), and dialanylphosphonate.

[0149] "VLCFA elongase inhibitors" (b9) are herbicides with a wide variety of chemical structures that inhibit elongation enzymes. Elongation enzymes are enzymes located in or near chloroplasts that participate in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are major components of hydrophobic polymers that prevent leaf surface dehydration and provide stability for pollen grains. Such herbicides include acetochlor, metolachlor, sphagnum molybdate, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), tetrazolium-methyl, fluthiamethoxam, indicarb, bensulfuron-methyl, pyrazosulfuron, metolachlor, naphthylpropane, diltiazem, diltiazem-M ((2R)-N,N-diethyl-2-(1-naphthoxy)propamide), clethodim, piperazine, pretilachlor, doxycycline, methylpropane, methylpropane, and methoxythiamethoxam, including split forms such as metolachlor and chloroacetamide and oxyacetamide.

[0150] "Auxin transport inhibitors" (b10) are chemicals that inhibit auxin transport in plants, such as by binding to auxin carrier proteins. Examples of auxin transport inhibitors include flupyradifurone, naphthalenesulfonamide (also known as N-(1-naphthyl)-o-carbamoylbenzoic acid and 2-[(1-naphthylamino)carbonyl]benzoic acid).

[0151] "PDS inhibitors" (b11) are compounds that inhibit the carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include flubutyrazole, pyrfluthrin, flupyridaben, flurfluthrin, flurfluthrin, flurfluthrin, flurfluthrin, and flupyrfluthrin.

[0152] HPPD inhibitors (b12) are chemicals that inhibit the biosynthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include benzo[3]bicycloketone, piracetam, flupyrazole (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), and fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxolinyl]carbonyl]- 1,3-Cyclohexanedione), chlorpyrifos, isoxaflutole, mesotrione, sulfonylpyridinium, pyrazosulfuron, benzylpyridinium, sulfonylpyridinium, terfurantoin, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methanesulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carboxylate), benzylpyridinium, 5-chloro-3-[(2-hydroxy-6-oxo- [1-Cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-hydroxyquinoxaline, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-1-yl)carbonyl]-1-(4-methoxyphenyl ...(1H)carbonyl]-2-(4-methoxyphenyl)carbonyl]-2-(4-methoxyphenyl)carbonyl]-2-(4-methoxyphenyl)carbonyl]-2-(4-methoxyphenyl) [-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl-1)-4-(trifluoromethyl)benzamide, and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.

[0153] The “HST inhibitor” (b13) disrupts the plant’s ability to convert homogentisic acid into 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl-4-morpholinocarboxylate), flupyridine, chlorpyrifos, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthidin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyridino[2,3-b]-diazabenzyl-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0154] HST inhibitors also include compounds of formulas A and B.

[0155]

[0156] Where R d1 H, Cl, or CF3; R d2 For H, Cl, or Br; R d3 For H or Cl; R d4 H, Cl, or CF3; R d5 It is CH3, CH2CH3 or CH2CHF2; and R d6 It is OH or -OC(=O)-i-Pr; and R e1 For H, F, Cl, CH3 or CH2CH3; R e2 For H or CF3; R e3 For H, CH3, or CH2CH3; R e4 For H, F, or Br; R e5 It can be Cl, CH3, CF3, OCF3, or CH2CH3; R e6 For H, CH3, CH2CHF2, or C≡CH; R e7 For OH, -OC(=O)Et, -OC(=O)-i-Pr, or -OC(=O)-t-Bu; and A e8 It can be N or CH.

[0157] Cellulose biosynthesis inhibitors (b14) inhibit cellulose biosynthesis in specific plants. They are most effective when applied to young or fast-growing plants before or early after emergence. Examples of cellulose biosynthesis inhibitors include cypermethrin, flumetsulam, and indazon-flumetsulam (N... 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-indene-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaflutole, and triazineflutole.

[0158] "Other herbicides" (b15) includes herbicides that act through a variety of different mechanisms of action, such as mitosis disruptors (e.g., methyl methacrylate and isopropyl methacrylate), organoarsenic compounds (e.g., DSMA and MSMA), 7,8-dihydropteridate synthase inhibitors, chloroplast isoprene synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides include those with unknown mechanisms of action, those not falling into the specific categories listed in (b1) to (b14), or those acting through a combination of the mechanisms of action listed above. Examples of other herbicides include bensulfuron, fensulfuron, chlorpyrifos, bromobutyrazosulfuron, cyclohexane, isoxaflutole, bensulfuron-methyl, chlorpyrifos, ethoxybenzamide, fensulfuron-methyl, chlorpyrifos, phosphonosulfuron, dazomet, sapuram, triazolyl acetamiprid (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazol-4-amide), fenpyroxetine, methyl chlorpyrifos, oleic acid, oxadiazon, nonanoic acid, barnyardgrass, and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxaazole. "Other herbicides" (b15) also includes compounds of formula (b15A).

[0159]

[0160] in

[0161] R 12 It can be H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl;

[0162] R 13 It is H, C1-C6 alkyl or C1-C6 alkoxy;

[0163] Q 1 The ring system is selected from phenyl, thiophene, pyridyl, benzo[m]dioxanepentyl, naphthyl, naphthalene, benzofuranyl, furanyl, benzothiophene, and pyrazolyl, wherein when substituted, the ring system is formed by 1 to 3 R groups. 14 replace;

[0164] Q 2 The ring system is selected from phenyl, pyridinyl, benzo[m]dioxanepentyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, wherein when substituted, the ring system is surrounded by 1 to 3 R groups. 15 replace;

[0165] Each R 14Independently, it is a halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, cyano, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, SF5, NHR 17 ; or optionally by 1 to 3 R 16 Substituted phenyl groups; or optionally with 1 to 3 R groups. 16 Substituted pyrazol group;

[0166] Each R 15 Independently, it is a halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl.

[0167] Each R 16 It is independently a halogen, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;

[0168] R 17 It is a C1-C4 alkoxycarbonyl group.

[0169] In one embodiment of "other herbicides" (b15) which also includes compounds of formula (b15A), R is preferred. 12 It is H or C1-C6 alkyl; more preferably R 12 It is H or methyl. Preferably R 13 H is preferred. Q is preferred. 1 It is a benzene ring or a pyridine ring, each ring being separated by 1 to 3 R... 14 Replace; more preferably Q 1 For 1 to 2 R 14 Substituted benzene ring. Preferably Q 2 1 to 3 R 15 Substituted benzene ring; more preferably Q 2 For 1 to 2 R 15 Substituted benzene ring. Preferably, each R 14 Independently, it is a halogen, a C1-C4 alkyl, a C1-C3 haloalkyl, a C1-C3 alkoxy, or a C1-C3 haloalkoxy; more preferably, each R 14 Independently, it is chlorine, fluorine, bromine, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Preferably, each R 15 Independently, it is a halogen, C1-C4 alkyl, or C1-C3 haloalkoxy; more preferably, each R 15Independently, it is chlorine, fluorine, bromine, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Particularly preferred as “other herbicides” (b15) are any of the following (b15A-1) to (b15A-15):

[0170]

[0171]

[0172]

[0173] "Other herbicides" (b15) also includes compounds of formula (b15B).

[0174]

[0175] in

[0176] R 18 It can be H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl;

[0177] Each R 19 It is independently a halogen, a C1-C6 haloalkyl, or a C1-C6 haloalkoxy.

[0178] p is an integer of 0, 1, 2 or 3;

[0179] Each R 20 Independently, it is a halogen, a C1-C6 haloalkyl, or a C1-C6 haloalkoxy; and

[0180] q is an integer of 0, 1, 2 or 3.

[0181] In one embodiment of "other herbicides" (b15) which also includes compounds of formula (b15B), R is preferred. 18 It is H, methyl, ethyl or propyl; more preferably R 18 It is H or methyl; most preferably R 18 For H. Preferably, each R 19 Independently, it is chlorine, fluorine, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably, each R 19 Independently, it is chlorine, fluorine, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably, each R 20 Independently, it is chlorine, fluorine, C1 haloalkyl, or C1 haloalkoxy; more preferably, each R 20Independently, it is chlorine, fluorine, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Particularly preferred as “other herbicides” (b15) are any of the following (b15B-1) to (b15B-19):

[0182]

[0183]

[0184]

[0185] "Herbicide safeners" (B16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of herbicides on specific crops. These compounds protect crops from herbicides but generally do not prevent the herbicide from controlling unwanted vegetation. Examples of herbicide safeners include, but are not limited to, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, cyclopropanesulfonamide, chlorpyrifos, dichloropropenesulfonamide, dietholate, piperazine, chlorpyrifos, chlorpyrifos, chlorpyrifos, fluroxypyr, chlorpyrifos, pyrazosulfuron, pyrazosulfuron, mephenate, chlorpyrifos, naphthalene anhydride, chlorpyrifos, N-(aminocarbonyl)-2-toluenesulfonylamine and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethyl ketone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.

[0186] In another embodiment of "other herbicides" (b15), compounds of formula (b15C) are also included.

[0187]

[0188] Where R 1 It is Cl, Br, or CN; and R 2 It is C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3 or 3-CHF2-isoxazol-5-yl.

[0189] For better control of undesirable vegetation (e.g., lower utilization rates, such as due to greater than additive effects; a broader spectrum of weeds controlled; or improved crop safety) or for preventing the development of resistant weeds, a mixture of the compounds of the present invention with herbicides selected from: atrazine, tetrazolium-sulfuron, flubutyramide, S-flubutyramide, benzisothiazolinone, triadimefon, chlorpyrifos, chlorsulfuron-methyl, chlorpyrifos, potassium dichloropyridinate, chlorpyrifos-sulfuron, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolone ... [5-Dichlorophenyl)methyl]-4,4-dimethyl-isoxazosone, benzylsulfuron, pyrazosulfuron, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrimisulfuron, methyl methacrylate, flusulfanilamide, imazalil ethionyl, cyclosporine, mesotrione, cyprodinil, mesosulfuron, clethodim, sulfadiazine, sulfosulfuron, quinclorac, sulfosulfuron, sulfadiazine, metolachlor, mesosulfuron, flusulfanilamide, flusulfanilamide, and benzylsulfuron.

[0190] One or more of the methods and variations described in Schemes 1-16 can be used to prepare compounds of Formula 1. Unless otherwise specified, the R group in compounds of Formulas 1-29 1 R 2 The definitions of W, A, L, and G are as defined in the above description of the invention. Formulas 1a, 1b, and 1c are subgroups of compounds of Formula 1, and unless otherwise specified, all substituents of Formulas 1a, 1b, and 1c are as defined above for Formula 1.

[0191] As shown in Scheme 1, the pyridazinone of Formula 1a (a subgroup of compounds of Formula 1, wherein W is O, and L and G are as defined above, but L is not a direct bond and G is not hydrogen) can be obtained by reacting the substituted 5-hydroxy-3(2H)-pyridazinone of Formula 1b (i.e., Formula 1, wherein W is O, L is a direct bond and G is H) with a suitable electrophile of Formula 2 (i.e., Z) in the presence of a base in a suitable solvent. 1 -LG, where Z 1 It is prepared by reaction of a leaving group (or a nucleus-free group, such as a halogen). Representational formula 2 (where Z...) 1 Some examples of reagent classes with Cl and L being direct bonds include acyl chlorides (G being -(C=O)R). 5 ), chloroformate (G is -CO2R) 6 ), carbamoyl chloride (G is -CONR) 7 R 8 ), sulfonyl chloride (G is -S(O)2R) 5 ) and aminosulfonyl chloride (G is -S(O)2NR) 7 R 8Examples of bases suitable for this reaction include, but are not limited to, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, or potassium tert-butoxide. Depending on the specific base used, a suitable solvent may be a protic or aprotic solvent, and anhydrous or an aqueous mixture may be used. Preferred solvents for this reaction include acetonitrile, methanol, ethanol, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, dichloromethane, or N,N-dimethylformamide. The reaction can be carried out in a temperature range typically from 0°C to the solvent reflux temperature.

[0192] Option 1

[0193]

[0194] The substituted 5-hydroxy-3(2H)-pyridazinone of formula 1b can be prepared by cyclizing an acylhydrazine of formula 3 (where Ra is an alkyl group, typically methyl or ethyl) in the presence of a base and a solvent, as outlined in scheme 2. Suitable bases for this reaction include, but are not limited to, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium tert-butoxide, or 1,8-diazabicyclo[5.4.0]undec-7-ene. Depending on the specific base used, a suitable solvent may be a protic or aprotic solvent, and anhydrous or as an aqueous mixture is used. Solvents used for this cyclization include acetonitrile, methanol, ethanol, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, dichloromethane, or N,N-dimethylformamide. The temperature range for this cyclization is typically from 0°C to the solvent reflux temperature. A documented method for cyclizing an acylhydrazine ester intermediate of formula CH3(CO2C2H5)C=NNCH3C(=O)CH2Ar (where Ar is a substituted phenyl group, not the bicyclic system shown in formula 3) to the corresponding 4-aryl-5-hydroxy-pyridazinone is disclosed in U.S. Patents 8,541,414 and 8,470,738. The same conditions reported in these patents are applicable to cyclizing a hydrazone ester of formula 3 to a pyridazinone of formula 1b.

[0195] Option 2

[0196]

[0197] The substituted hydrazone of Formula 3 can be prepared by coupling a hydrazone of Formula 4 (where Ra is an alkyl group, typically methyl or ethyl) with an acyl chloride of Formula 5 in the presence of a base and a solvent, as outlined in Scheme 3. The preferred base for this reaction is typically a tertiary amine, such as triethylamine or a Hunig base, but other bases may also be used, including N,N-dimethylaminopyridine, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, or potassium tert-butoxide. Depending on the specific base used, a suitable solvent may be a protic or aprotic solvent, wherein the reaction occurs under anhydrous conditions or as an aqueous mixture under Shoten-Baumann conditions. Solvents used for this nitrogen-on-acylation include acetonitrile, tetrahydrofuran, diethyl ether, dioxane, toluene, 1,2-dimethoxyethane, dichloromethane, or N,N-dimethylformamide. The temperature range for this reaction can be from 0°C to the solvent reflux temperature. Methods for preparing hydrazide intermediates of the relevant formula CH3(CO2C2H5)C=NNCH3C(=O)Ar (where Ar is a substituted phenyl group) are disclosed in patent literature, see U.S. Patents 8,541,414 and 8,470,738, and U.S. Patent Application Publication 2010 / 0267561. The methods disclosed in these patent publications are directly applicable to the preparation of intermediates that can be used to prepare compounds of the present invention as depicted in Scheme 3.

[0198] Option 3

[0199]

[0200] By using a suitable solvent such as ethanol, methanol, acetonitrile, or dioxane or dichloromethane, at a temperature typically ranging from 0°C to 80°C, formula R... 1 Appropriately substituted hydrazine with formula R 2 (C=O)CO2R a The hydrazone of formula 4 can be readily obtained by reacting a ketone or aldehyde ester (where Ra is usually methyl or ethyl) with the ketone or aldehyde ester. U.S. Patent Application Publication 2007 / 0112038 and 2005 / 0256123 disclose methods for forming hydrazones from methylhydrazine and ketoester CH3(C=O)CO2C2H5.

[0201] As shown in Scheme 4, an acetate of the corresponding formula 6 (where R) can be formed via ester hydrolysis and acyl chloride. bAcetyl chloride of Formula 5 is prepared by (usually methyl or ethyl). Standard methods for this conversion are known in the literature. For example, ester hydrolysis can be achieved by heating an alcoholic solution of an ester of Formula 6 with an aqueous solution of an alkali metal hydroxide, followed by acidification with an inorganic acid. The resulting carboxylic acid of Formula 7 can then be converted to the corresponding acyl chloride of Formula 5 by treatment with oxalyl chloride and a catalytic amount of N,N-dimethylformamide in an inert solvent such as dichloromethane. J. Heterocyclic Chem. 1983, 20(6), 1697-1703; J. Med. Chem. 2007, 50(1), 40-64; and PCT patent publications WO 2005 / 012291, WO 98 / 49141 and WO 98 / 49158 disclose the hydrolysis of benzofuran- and benzothiophene-acetic acid esters to the corresponding acetic acid. Monatshefte für Chemie 1968, 99(2)715-720 and patent publications WO 2004046122, WO 2009 / 038974 and JP09077767 disclose the conversion of benzofuran- and benzothiophene-acetic acid to the corresponding acyl chlorides.

[0202] Option 4

[0203]

[0204] As shown in Scheme 5, heteroarylacetic acid derivatives of Formula 6c can be prepared from appropriately substituted heteroarylamines of Formula 8. According to this method, the amine of Formula 8 is diazotized in the presence of 1,1-dichloroethylene (9) (preferably tert-butyl nitrite in the presence of acetonitrile containing copper chloride) to give the corresponding trichloroethyl heterocycle of Formula 10. The trichloroethyl heterocycle of Formula 10 is then heated together with a suitable alkali metal or alkaline earth metal alkoxide, such as a sodium alkoxide of Formula 11, in a suitable solvent, such as an alcohol of Formula 12, followed by acidification, such as with concentrated sulfuric acid, to provide a heterocyclic acetate of Formula 6c. This method is taught in Pest. Manag. Sci. 2011, 67, 1499-1521 and U.S. Patent 5,376,677.

[0205] Option 5

[0206]

[0207] An alternative method for preparing the heteroaryl acetate of formula 6c is outlined in Scheme 6. As taught by the method in Pest. Manag. Sci. 2011, 67, 1499-1521, the methyl heterocycle of formula 13 can be brominated with N-bromosuccinimide (NBS) in an inert solvent such as dichloromethane, dichloroethane, or tetrachloromethane under radical conditions (e.g., with benzoyl peroxide as a catalyst) to give the heteroarylmethyl bromide of formula 14. The bromine is then replaced by cyanide by reacting the compound of formula 14 with a base or basic cyanide (e.g., potassium cyanide) to give the heteroarylacetonitrile of formula 15, which can then be esterified and hydrolyzed to the acetate of formula 6c by heating in an acidic alcohol (e.g., methanol or ethanol containing HCl) at a solvent reflux temperature. The alcohol RbOH is a lower alkanol.

[0208] Option 6

[0209]

[0210] Hydrolysis of the leaving group at position 5 of the pyridazinone ring can be achieved as shown in Scheme 7. When the X group is a lower alkoxy group, a lower thioether (sulfoxide or sulfone), a halide, or an N-bonded azole, it can be removed by hydrolysis with a basic reagent such as tetrabutylammonium hydroxide in a solvent such as tetrahydrofuran, dimethoxyethane, or dioxane at a temperature of 0°C to 120°C. Other hydroxide reagents used for this hydrolysis include potassium hydroxide, lithium hydroxide, and sodium hydroxide (see, for example, WO 2009 / 086041). When the X group is a lower alkoxy group, hydrolysis of the X group can also be achieved using dealkylating agents such as boron tribromide or morpholine (see, for example, WO2009 / 086041, WO2013 / 160126, and WO2013 / 050421).

[0211] Option 7

[0212]

[0213] The introduction of a halogen at the 6-position of pyridazinones can be achieved by zincate treatment followed by halogenation. For the conditions, reagents, and examples of zincation of pyridazinones, see Verhelst, T., PhD dissertation, University of Antwerp, 2012. Typically, pyridazinones of Formula 17 are treated in tetrahydrofuran with a Zn(TMP)-LiCl or Zn(TMP)2-MgCl2-LiCl solution (i.e., a 2,2,6,6-bis(tetramethylpiperidine)zinc, magnesium chloride, lithium chloride complex, soluble in toluene / tetrahydrofuran) at -20°C to 30°C to form a zinc reagent. The subsequent addition of bromine, N-bromosuccinimide, or iodine provides a compound of Formula 18 (where R2 is Br or I, respectively). Reagents such as trichloroisocyanuric acid or 1,3-dichloro-5,5-dimethylhydantoin give a compound of Formula 18 (where R2 is C1). This method is shown in Scheme 8. For the preparation of various suitable zinc-containing reagents, see Wunderlich, S., doctoral dissertation, University of Munich, 2010 and the references cited therein, as well as WO2008 / 138946 and WO2010 / 092096. Zincification at the 6th position of the pyridazinone ring can be achieved in the presence of an aromatic / heteroaromatic substituent, an alkoxy substituent, or a halogen at the 4th position of the pyridazinone ring, or in the presence of a halogen or alkoxy substituent at the 5th position of the pyridazinone ring.

[0214] Option 8

[0215]

[0216] R of compound of formula 19 2 Substituents (where R) 2 (The group consisting of a halogenated or sulfonate group) can be further converted into other functional groups. As shown in Scheme 9, the compound of Formula 19 can be prepared by subjecting it to a transition metal-catalyzed reaction. 2Compounds that are alkyl, cycloalkyl, or substituted alkyl groups. For reviews of these types of reactions, see: E. Negishi, Handbook of Organicopalladium Chemistry for Organic Synthesis, John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-Coupling Reactions: A Practical Guide, Springer, New York, 2002; HC Brown et al., Organic Synthesis via Boranes, Aldrich Chemical Co., Milwaukee, Vol. 3, 2002; Suzuki et al., Chemical Reviews 1995, 95, 2457-2483; and Molander et al., Accounts of Chemical Research 2007, 40, 275-286. See also Tetrahedron Organic Chemistry Series, Volume 26: Palladium in Heterocyclic Chemistry, 2nd ed., edited by Gribble and Li, Elsevier, Amsterdam, 2007. For a review of Buchwald-Hartwig chemistry, see Yudin and Hartwig, Catalyzed Carbon-Heteroatom Bond Formation, 2010, Wiley, New York.

[0217] Option 9

[0218]

[0219] For R in Equation 21 2Synthetic methods for introducing other functional groups at this position are known in the art. Copper-catalyzed reactions can be used to introduce CF3 groups. For a comprehensive and up-to-date review of the reagents used in this reaction, see Wu, Neumann, and Beller, Chemistry: An Asian Journal, 2012, ASAP, and the references cited therein. For the introduction of sulfur-containing substituents at this position, see the method disclosed in WO 2013 / 160126. For the introduction of cyano groups, see WO 2014 / 031971. For the introduction of nitro groups, see J. Am. Chem. Soc. 2009, 12898. For the introduction of fluorine substituents, see J. Am. Chem. Soc. 2014, 3792.

[0220] As shown in Scheme 10, compounds of Formula 19 can be prepared by reacting an organometallic reagent of Formula 22 with a pyridazinone of Formula 21 having a reactive group at the 4th position. Depending on the leaving group, a transition metal catalyst may be desirable. When the leaving group is a lower alkoxy group, an N-bonded azole (such as a pyrazole or triazole), or a sulfonate group, no catalyst is required, and the reaction can proceed directly with a magnesium or lithium reagent at the 4th position. The reaction can be carried out in a variety of solvents that do not react with organomagnesium reagents. Typical reaction conditions include tetrahydrofuran as a solvent, a reaction temperature from -20°C to 65°C, and an excess of organomagnesium or organolithium reagent. When the reactive group at the 4th position is a halogen, transition metal catalysts and ligands are useful. A variety of different coupling partners can be used, including boron (Suzuki reaction), tin (Stille reaction), and zinc (Negishi reaction); these reactions can be catalyzed by palladium and nickel catalysts with a wide variety of ligands. The conditions used for these reactions are known in the art; see, for example, Palladium-Catalyzed Coupling Reactions: Practical Aspects and Future Development, edited by Arpad Molnar, Wiley, 2013, and the references cited therein. The organomagnesium reagents used in non-catalytic methods can be prepared by: directly inserting magnesium into a carbon-halogen bond (optionally in the presence of lithium halides); by Grignard exchange reaction with isopropyl magnesium halide (optionally in the presence of lithium halides); or by conversion of the organolithium reagent, through reaction with a magnesium salt such as diethyl ether magnesium bromide. In these reactions, various groups inert to the organomagnesium reagent may be present in the R group of the pyridazinone. 2 The compound of Formula 21 can be prepared according to the methods described in Knochel et al., Angew. 2011, 50, 9794-9824 and Heterocycles 2014, 88, 827-844.

[0221] Option 10

[0222]

[0223] Compounds of Formula 21 are known in the art or can be prepared by methods described in Maes and Lemiere, Comprehensive Heterocyclic Chemistry III, Vol. 8, edited by Katritsky, Ramsden, Scriven, and Taylor, and the references cited therein. See also Verhelst, Doctoral Dissertation, University of Antwerp, and the references cited therein. Functional transformations on pyridazinones are also described in Stevenson et al., J. Heterocyclic Chem. 2005, 42, 427; U.S. Patent 6,077,953; WO 2009 / 086041 and the references cited therein; U.S. Patent 2,782,195; WO 2013 / 160126; and WO 2013 / 050421.

[0224] The compound of Formula 1b can also be prepared by hydrolysis of the sulfone of Formula 23 in an alkaline aqueous solution. Suitable bases include sodium hydroxide, potassium hydroxide, or tetrabutylammonium hydroxide. Typical reaction temperatures range from 0°C to 80°C, and typical reaction times are 1–12 hours. This method is shown in Scheme 11.

[0225] Option 11

[0226]

[0227] Compounds of formula 23 can be produced by reacting compounds of formula 24 (where R) with alkyl halides and sulfonates. 1 The solution is prepared by alkylation of H. Typical bases that can be used in this method include potassium carbonate, sodium carbonate, or cesium carbonate. Typical solvents include acetonitrile, tetrahydrofuran, or N,N-dimethylformamide, as shown in Scheme 12.

[0228] Option 12

[0229]

[0230] The compound of Formula 24 can be prepared by cyclizing the compound of Formula 25 with a base. Typical bases that can be used in this method include potassium carbonate, sodium carbonate, or cesium carbonate. Typical solvents include acetonitrile, tetrahydrofuran, or N,N-dimethylformamide, as shown in Scheme 13.

[0231] Option 13

[0232]

[0233] The compound of Formula 25 can be prepared by the method shown in Scheme 14. In this method, the compound of Formula 26 is coupled to the compound of Formula 27 in the presence of a base. Bases that can be used in this method include triethylamine, sodium carbonate or potassium carbonate, pyridine or diisopropylethylamine.

[0234] Option 14

[0235]

[0236] The compounds of Formula 26 can be prepared by methods known in the art.

[0237] Compounds of formula 16 can be prepared by coupling the organometallic pyridazinone coupling partner of formula 28 with the heteroaryl halide and sulfonate of formula 29. The organometallic coupling partner can be, for example, an organozinc, organomagnesium, organotin, or organoboron agent. Palladium catalysts such as palladium tetra(triphenylphosphine) and those generated from other palladium sources such as Pd₂dba₃ and Pd(OAc)₂, as well as phosphine or N-heterocyclic carbene ligands, can be used in the coupling process (Maes et al. J. Org. Chem. 2011, 76, 9648-9659). Palladium precatalysts based on dialkyl diarylphosphine ligands such as X-Phos, S-Phos, and Ru-Phos (Buchwald et al., Angew. Chem. Int. Ed., 2013, 52(2), 615-619) or precatalysts derived from N-heterocyclic carbene ligands such as PEPPSI-i-Pr and PEPPSI-i-Pent (Organ et al., Eur. J. Org. Chem. 2010, 4343-4354) can also influence this coupling. The reaction can be carried out in solvents such as tetrahydrofuran, dimethoxyethane, N-methyl-2-pyrrolidone, and dioxane. The coupling partner can be a heterocyclic halide or sulfonate. Particularly available types of coupling partners for this reaction are those based on the perfluorobutyl sulfonate group (OSO2C4F9) of heteroaromatic compounds. Halogenated heterocyclic coupling partners are commercially available or known in the literature. Other available types of heterocyclic halides and synthetic routes are given in Tetrahedron Organic Chemistry Series, Volume 26: Palladium in Heterocyclic Chemistry, 2nd Edition, edited by Gribble and Li, Elsevier, Amsterdam, 2007.

[0238] Option 15

[0239]

[0240] The zincation at the 4th position of pyridazinone can be achieved using zincation reagents, such as toluene / tetrahydrofuran (i.e., Zn(TMP)-LiCl or Zn(TMP)2-MgCl2-LiCl) containing a complex of 2,2,6,6-bis(tetramethylpiperidine)zinc, magnesium chloride, and lithium chloride.

[0241] Magnesiation at this position can also be achieved by treatment with Mg(TMP)-LiCl. For the metallization of pyridazinones and the conditions for palladium-catalyzed cross-coupling of 4-zinc- and 4-magnesiated pyridazinones, see Verhelst, T., PhD dissertation, University of Antwerp, 2012. The synthesis and cross-coupling conditions of 4-methyltinylpyridazinones are known from Stevenson et al., J. Heterocyclic Chem. 2005, 42, 427.

[0242] As shown in Scheme 16, the pyridazinone of Formula 1a (a subgroup of the compound of Formula 1, wherein W is O) can be sulfided in a suitable solvent (e.g., toluene, tetrahydrofuran, or dioxane) at a temperature typically in the range of 0°C to room temperature, using a sulfiding agent—typically pyridine containing diphosphine pentasulfide or Lawson's agent (2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphatane-2,4-disulfide)—to give the corresponding thionone of Formula 1c (i.e., Formula 1, wherein W is S).

[0243] Option 16

[0244]

[0245] The compound of formula 6c (where A = A-1 and R) can be prepared by reacting diarylacetic acid of formula 30 with ethyl acrylate in tert-amyl alcohol under an oxygen atmosphere in the presence of palladium(II) acetate, benzoquinone, N-acetyl-isoleucine, and potassium carbonate. 31 =Et), which uses Angew.Chem.Int.Ed., 2016, 55, 8652-8655 and the process described in scheme 17.

[0246] Option 17

[0247]

[0248] Those skilled in the art will recognize that various functional groups can be transformed into other functional groups to provide different compounds of Formula 1. For valuable resources illustrating the interconversion of functional groups in a simple and straightforward manner, see Larock, RC, “Comprehensive Organic Transformations: A Guide to Functional Group Preparations,” 2nd edition, Wiley-VCH, New York, 1999. For example, an intermediate used to prepare a compound of Formula 1 may contain an aromatic nitro group, which can be reduced to an amino group and then converted to various halides via reactions known in the art (such as the Sandmeier reaction), thereby providing a compound of Formula 1. These reactions can also be performed in several alternative orders.

[0249] It should be recognized that some of the reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be suitable for certain functional groups present in the intermediates. In these cases, incorporating protecting / deprotecting sequences or interconversions of functional groups into the synthesis will facilitate obtaining the desired product. The use and selection of protecting groups will be apparent to those skilled in the art of chemical synthesis (see, for example, Greene, TW; Wuts, PGM Rotective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). Those skilled in the art will recognize that, in some cases, additional conventional synthetic steps, not described in detail, may be required to complete the synthesis of compounds of Formula 1 after the introduction of a given reagent as described in any individual scheme. Those skilled in the art will also recognize that combinations of the steps shown in the above schemes may need to be performed in a sequence other than the specific order presented to prepare compounds of Formula 1.

[0250] Those skilled in the art will also recognize that the compounds of Formula 1 and the intermediates described herein can undergo a variety of electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0251] Without further detailed explanation, it is believed that those skilled in the art will be able to fully utilize the invention using the foregoing description. The following non-limiting examples are illustrative of the invention. The steps in the following examples illustrate the process of each step in the entire synthetic transformation, and the starting material for each step may not necessarily be prepared by the specific preparation process described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or otherwise specified. Unless otherwise specified, the parts and percentages of chromatographic solvent mixtures are by volume. Unless otherwise specified, all NMR spectra from tetramethylsilane in CDCl3 are reported at low field at 500 MHz, where s represents a singlet, brs represents a broad singlet, d represents a doublet, t represents a triplet, and m represents a multiplet.

[0252] Synthesis Example 1

[0253] Preparation of 4-(9-anthrayl)-6-chloro-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound 1)

[0254] Step A: Preparation of 4-(9-anthrayl)-6-chloro-5-methoxy-2-methyl-3(2H)-pyridazinone

[0255] Using an ice-water cooling bath, at a temperature below 15°C, zinc chloride solution (10 mL of 1.9 M 2-methyltetrahydrofuran solution, 19.0 mmol) was added to a solution of 2,2,6,6-tetramethylpiperidinyl magnesium chloride-lithium chloride complex (1.0 M dissolved in tetrahydrofuran / toluene, 38.0 mL). The resulting solution was stirred at 5°C for 15 min and then at 25°C for 45 min. Subsequently, at -40°C, the resulting solution of bis(2,2,6,6-tetramethylpiperidinyl)zinc, lithium chloride, and magnesium chloride complex was transferred to a feeding funnel and added dropwise to a suspension of 6-chloro-5-methoxy-2-methyl-3(2H)-pyridazinone (3.0 g, 17.2 mmol) and tetrahydrofuran (86 mL). The resulting solution was stirred at -40°C for 15 min, warmed to 5°C, and then stirred at 5°C for 45 min. The solution was successively treated with 9-bromoanthracene (4.2 g, 16.3 mmol) and SPhos precatalyst-G2 (chloro(2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II), 1.2 g, 1.7 mmol). The resulting dark brown solution was heated at solvent reflux temperature for 3 h, cooled to ambient temperature, and concentrated. The residue was partitioned between ethyl acetate and a saturated ammonium chloride aqueous solution, the resulting aqueous layer was extracted with ethyl acetate, and the combined organic layers were successively washed with water and brine, dried over anhydrous MgSO4, filtered, and concentrated to give 8.63 g of a yellow oil. The oil was purified by silica gel (330 g) column chromatography by elution with hexane containing 0% to 100% ethyl acetate gradients to provide 3.35 g of the title compound as an oily solid.

[0256] 1 H NMR δ 8.57 (s, 1H), 8.08-8.03 (m, 2H), 7.69-7.63 (m, 2H), 7.53-7.45 (m, 4H), 3.82 (s, 3H), 3.05 (s, 3H).

[0257] Step B: Preparation of 4-(9-anthrayl)-6-chloro-5-hydroxy-2-methyl-3(2H)-pyridazinone

[0258] A mixture of 2.15 g (6.1 mmol) of the product from step A and morpholine (12 mL) was heated at 100 °C for 2 h. The resulting reaction mixture was concentrated and the residue was ground with diethyl ether. After filtration, the resulting solid was washed with diethyl ether and dried on a sintered glass funnel. The resulting solid was suspended in a 1 N hydrochloric acid aqueous solution (about 30 mL), stirred at ambient temperature for 2 h, and filtered. The solid was washed with water and dried under vacuum to give 1.50 g of the title compound as a pale yellow solid, which is the compound of the present invention.

[0259] 1 H NMR (DMSO-d6) δ 8.70 (s, 1H), 8.15 (d, 2H), 7.68 (d, 2H), 7.52 (t, 2H), 7.45 (t, 2H), 5.75 (s, 1H), 3.67 (s, 3H).

[0260] Synthesis Example 2

[0261] Preparation of 6-chloro-4-(10-chloro-9-anthrayl)-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound 2)

[0262] Step A: Preparation of 6-chloro-4-(10-chloro-9-anthrayl)-5-methoxy-2-methyl-3(2H)-pyridazinone

[0263] A solution of the product obtained from step A of Synthetic Example 1 (143 mg, 0.41 mmol), N-chlorosuccinimide (65 mg, 0.49 mmol), and chloroform (4 mL) was stirred at room temperature for 15 h. The resulting solution was diluted with dichloromethane and washed twice with water. The organic layer was dried over anhydrous MgSO4, filtered, and concentrated to give 160 mg of the title compound as a yellow glassy substance. The crude product was used in the next step without further purification.

[0264] 1 ¹H NMR δ 8.60 (d, 2H), 7.69 (d, 2H), 7.62 (distorted t, 2H), 7.53 (distorted t, 2H), 3.82 (s, 3H), 3.09 (s, 3H).

[0265] Step B: Preparation of 6-chloro-4-(10-chloro-9-anthrayl)-5-hydroxy-2-methyl-3(2H)-pyridazinone

[0266] A suspension of 155 mg of the product from step A and morpholine (1 mL) was heated at 100 °C for 2 h. The resulting mixture was diluted with diethyl ether (5 mL), stirred for 30 min, and the resulting supernatant was decanted from the solid product. The solid product was partitioned between dichloromethane and 1N hydrochloric acid aqueous solution, the organic layer was dried over anhydrous MgSO4, filtered, and concentrated to give 120 mg of the title compound as a yellow solid, which is the compound of the present invention.

[0267] 1 ¹H NMR (DMSO-d6) δ 8.52 (d, 2H), 7.61 (d, 2H), 7.74 (distorted t, 2H), 7.56 (distorted t, 2H), 3.67 (s, 3H).

[0268] The compounds listed in Table 1 below can be prepared up to (960) by the process described herein in conjunction with methods known in the art. The following abbreviations are used in the subsequent tables: t for tert-, s for secondary-, n for normal-, i for iso-, c for cyclo-, Me for methyl, Et for ethyl, Pr for propyl, Bu for butyl, i-Pr for isopropyl, c-Pr for cyclopropyl, t-Bu for tert-butyl, Ph for phenyl, OMe for methoxy, OEt for ethoxy, SMe for methylthio, -CN for cyano, -NO2 for nitro, TMS for trimethylsilyl, SOMe for methylsulfinyl, C2F5 for CF2CF3 and SO2Me for methylsulfonyl.

[0269] Table 1

[0270]

[0271] W = O, R 1 =Me,R 2 =Me, LG=H and the remaining variables are defined below.

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283] This disclosure also includes Tables 2 through 48, wherein the header row phrase in Table 1 (i.e., "W=O, R") 1 =Me,R 2 =Me, LG=H”) are replaced with the heading row phrases listed in the corresponding table, and the remaining variables are defined as in Table 1.

[0284]

[0285]

[0286] Table 49

[0287]

[0288] W = O, R 1 =CH3,R 2 =CH3, LG=H and the remaining variables are defined below.

[0289]

[0290] This disclosure also includes Tables 50 to 56, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 49. For example, in Table 50, the header row phrase is “W=O, R”. 1 =CH3,R 2 =Cl, LG = H, and the remaining variables are defined below.

[0291] surface header row variable 50 <![CDATA[R 2 =Cl]]> 51 <![CDATA[R 2 = OCH3]]> 52 <![CDATA[R 1 =CH2CH3]]> 53 <![CDATA[R 1 =CH2CH3,R 2 =Cl]]> 54 <![CDATA[R 1 =CH2CH3,R 2 =OCH3<!-- 47 --> ]]> 55 <![CDATA[R 1 CH2CH2OCH3]]> 56 <![CDATA[R 1 =CH2CH2OCH3,R 2 =Cl]]>

[0292] Table 57

[0293]

[0294] W = O, R 1 =CH3,R 2 =CH3, LG=H and the remaining variables are defined below.

[0295]

[0296]

[0297] This disclosure also includes Tables 58 to 65, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 57. For example, in Table 58, the header row phrase is “W=O, R”. 1 =CH3,R 2 =Cl, LG = H, and the remaining variables are defined below.

[0298]

[0299] Table 66

[0300]

[0301] W = O, R 1 =CH3,R 2=CH3, Y=O, LG=H and the remaining variables are defined below.

[0302]

[0303]

[0304] This disclosure also includes Tables 67 to 74, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 66. For example, in Table 67, the header row phrase is “W=O, R”. 1 =CH3,R 2 =CH3, Y=S, LG=H and the remaining variables are defined below.

[0305]

[0306] Table 75

[0307]

[0308] W = O, R 1 =CH3,R 2 =CH3, Y=O, LG=H and the remaining variables are defined below.

[0309]

[0310] This disclosure also includes Tables 76 to 83, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 75. For example, in Table 76, the header row phrase is “W=O, R”. 1 =CH3,R 2 =CH3, Y=S, LG=H and the remaining variables are defined below.

[0311]

[0312] Table 84

[0313]

[0314] W = O, R 1 =CH3,R 2 =CH3, Y=O, LG=H and the remaining variables are defined below.

[0315]

[0316]

[0317] This disclosure also includes Tables 85 to 92, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 84. For example, in Table 85, the header row phrase is “W=O, R”. 1 =CH3,R 2 =CH3, Y=S, LG=H and the remaining variables are defined below.

[0318]

[0319] Table 93

[0320]

[0321] W = O, R 1 =CH3,R 2 =CH3, LG=H, Y=O, and the remaining variables are defined below.

[0322]

[0323]

[0324] This disclosure also includes Tables 94 to 101, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 93. For example, in Table 94, the header row phrase is “W=O, R”. 1 =CH3,R 2 =CH3, LG=H, Y=S and the remaining variables are defined below.

[0325] surface header row variable 94 Y = S 95 <![CDATA[Y=NCH3]]> 96 <![CDATA[R 2 =Cl]]> 97 <![CDATA[R 2 =Cl,Y=S]]> 98 <![CDATA[R 2 =Cl,Y=NCH3]]> 99 <![CDATA[R 2 = OCH3]]> 100 <![CDATA[R 2 =OCH3,Y=S]]> 101 <![CDATA[R 2 =OCH3,Y=NCH3]]>

[0326] Table 102

[0327]

[0328] W = O, R 1 =CH3,R 2 =CH3, LG=H, Y=O, and the remaining variables are defined below.

[0329]

[0330] This disclosure also includes Tables 103 to 110, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 102. For example, in Table 103, the header row phrase is “W=O, R”. 1 =CH3,R 2 =CH3, LG=H, Y=S and the remaining variables are defined below.

[0331]

[0332] Table 111

[0333]

[0334] W = O, R 1 =CH3,R 2 =CH3,LG=H,Y 1 =O and the remaining variables are defined below.

[0335]

[0336] This disclosure also includes Tables 112 to 122, wherein the specific variables listed in each table replace the corresponding variables in the header row phrase of Table 111. For example, in Table 112, the header row phrase is “W=O, R”. 1 =CH3,R 2 =CH3,LG=H,Y 1 =S and the remaining variables are defined below.

[0337]

[0338] Table 123

[0339]

[0340] W = O, R 1 =CH3,R 2 =CH3,LG=H,Y 1 =O and the remaining variables are defined below.

[0341]

[0342]

[0343] This disclosure also includes Tables 124 to 134, wherein the specific variables listed in each table replace the corresponding variables in the header row phrases of Table 123. For example, in Table 124, the header row is “W=O, R”. 1 =CH3,R 2 =CH3,LG=H,Y 1 =S and the remaining variables are defined below.

[0344]

[0345] The compounds of the present invention will generally be used as herbicidal active ingredients in compositions, i.e., formulations containing at least one additional component (acting as a carrier) selected from surfactants, solid diluents, and liquid diluents. The formulation or composition components are selected to conform to the physical properties of the active ingredient, application mode, and environmental factors such as soil type, moisture, and temperature.

[0346] Available formulations include liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, suspension concentrates, and / or suspension emulsions), which may optionally be thickened into gels. Common types of aqueous liquid compositions include soluble liquids, suspensions, microcapsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, suspension concentrates, and suspension emulsions. Common types of anhydrous liquid compositions include emulsifiable concentrates, microemulsion concentrates, dispersible liquids, and oil dispersions.

[0347] Common types of solid compositions include powders, granules, pellets, balls, small granules, lozenges, tablets, and filler films (including seed coatings), which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredients can be encapsulated (micro)capsules and further formed into suspensions or solid formulations; alternatively, the entire formulation of the active ingredient can be encapsulated (or “coated”). Encapsulation enables controlled or sustained release of the active ingredient. Emulsifiable granules combine the advantages of emulsifiable concentrates and dry granular formulations. High-concentration compositions are primarily used as intermediates for further formulation.

[0348] Sprayable formulations are typically spread in a suitable medium before spraying. These liquid and solid formulations are formulated to be easily diluted in the spraying medium (usually water), but sometimes in another suitable medium such as aromatic or alkanes or vegetable oils. Spray volumes can range from about one to several thousand liters per hectare, but more commonly from about ten to several hundred liters per hectare. For foliar treatments using air or ground spraying, or for application to the plant growth medium, sprayable formulations can be tank-mixed with water or another suitable medium. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into furrows during planting.

[0349] The formulation typically contains effective amounts of the active ingredient, diluent, and surfactant within the following approximate ranges, totaling 100% by weight.

[0350]

[0351] Solid diluents include, for example, clays such as bentonite, montmorillonite, palygorskite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate, and sodium bicarbonate, as well as sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Dorland Books, Caldwell, New Jersey.

[0352] Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), alkyl phosphate esters (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butyl carbonate, alkanes (e.g., paraffin oil, n-alkanes, isoalkanes), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-hydroxyl ... -Methyl-2-pentanone, acetate esters such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkyl lactates, divalent esters, alkyl benzoates, and aryl benzoates, as well as γ-butyrolactone, and alcohols that can be straight-chain, branched, saturated, or unsaturated, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, n-decanol, isodecanol, isoctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol, and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acid glycerides (typically C6-C6). 22 Liquid diluents include plant seed and fruit oils (e.g., olive, castor, flaxseed, sesame, corn, peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut, and palm kernel oil), animal fats (e.g., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated), which are obtained by hydrolyzing plant and animal-derived glycerides and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0353] The solid and liquid compositions of the present invention typically contain one or more surfactants. When added to a liquid, the surfactant (also known as a "surfactant") typically alters, most commonly by reducing the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant can be used as a wetting agent, dispersant, emulsifier, or defoamer.

[0354] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants that can be used in the compositions of this invention include, but are not limited to: alcohol alkoxylates, such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butane oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean, castor, and rapeseed oils; alkylphenol alkoxylates, such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonylphenol ethoxylates, and dodecylphenol ethoxylates (prepared from phenols and ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide, and trans-block polymers (wherein the terminal block is prepared from propylene oxide); ethoxylates... Alkylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated styrene-phenol (including those prepared from ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters, such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters, and polyethoxylated glycerol fatty acid esters; other dehydrated sorbitol derivatives, such as dehydrated sorbitol esters; polymer surfactants, such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, grafted or comb-type polymers, and star-type polymers; polyethylene glycols (PEG); polyethylene glycol fatty acid esters; organosilicon-based surfactants; and sugar derivatives, such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0355] Available anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurine; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzene; sulfonates of condensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; petroleum-grade sulfonates; sulfosuccinates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

[0356] Available cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines, such as N-alkylpropylenediamine salts, tripropylenetriamine and dipropylenetetraamine, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butyl oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts, such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, such as alkyl dimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0357] Also usable in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants, and their recommended uses, are disclosed in numerous published references, including McCutcheon's Emulsifiers and Detergents, annual U.S. and international editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisley and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, 7th edition, John Wiley and Sons, New York, 1987.

[0358] The compositions of the present invention may also comprise formulation auxiliaries and additives, referred to by those skilled in the art as formulation adjuvants (some of which may also be considered as solid diluents, liquid diluents, or surfactants). Such formulation auxiliaries and additives can control: pH (buffers), foaming during processing (defoamers such as polysiloxanes), precipitation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth within the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), washout (film-forming agents or adhesives), evaporation (anti-evaporation agents), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol copolymers, and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon Volume 2: Functional Materials, Annual International and North American Edition, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03 / 024222.

[0359] Compounds of Formula 1 and any other active ingredients are typically introduced into the compositions of the present invention by dissolving the active ingredient in a solvent or by milling in a liquid or anhydrous diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. If the solvent of a liquid composition intended to be used as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added during dilution with water to emulsify the solvent containing the active substance. A media mill can be used to wet-mill suspensions of active ingredients with a particle size of up to 2,000 μm to obtain particles with an average diameter of less than 3 μm. Aqueous suspensions can be formulated as finished suspensions (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling process, which produces an average particle size in the range of 2 μm to 10 μm. Powders and granules can be prepared by blending and typically by milling (e.g., using a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active substance onto a pre-formed granular carrier or by agglomeration techniques. See Browning, “Agglomeration,” Chemical Engineering, December 4, 1967, pp. 147-48; Perry’s Chemical Engineer’s Handbook, 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 and thereafter; and WO 91 / 13546. Globes may be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules may be prepared as taught in U.S. 4,144,050, U.S. 3,920,442, and DE 3,246,493. Tablets may be prepared as taught in U.S. 5,180,587, U.S. 5,232,701, and U.S. 5,208,030. Films may be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

[0360] For further information on formulation technology, see T.S. Woods, “The Formulator’s Toolbox – Product Forms for Modern Agriculture,” Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR. Roberts, Proceedings of the 9th International Conference on Pesticide Chemistry, Cambridge, Royal Society of Chemistry, 1999, pp. 120–133. See also U.S. 3,235,361, column 6, line 16 to column 7, line 19, and Examples 10-41; U.S. 3,309,192, column 5, line 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. 2,891,855, column 3, line 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th edition, Blackwell Scientific Publications, Oxford, 1989; and Developments informulation technology, PJB Publications, Richmond, UK, 2000.

[0361] In the following examples, all percentages are by weight, and all formulations were prepared in a conventional manner. Compound numbers refer to compounds in Index Table A. Without further detail, it is believed that those skilled in the art will be able to utilize the invention to its fullest extent using the foregoing description. Therefore, the following examples are to be interpreted as merely illustrative and, in any way, not as limiting the scope of this disclosure. Unless otherwise specified, percentages are by weight.

[0362] Example A

[0363] High concentration concentrate

[0364] Compound 1 98.5%

[0365] 0.5% silica aerogel

[0366] Synthetic amorphous fine silica 1.0%

[0367] Example B

[0368] Wetting powder

[0369]

[0370] Example C

[0371] Particles

[0372] Compound 1 10.0%

[0373] Green slope palygorskite particles (low volatile matter, 0.71 / 0.30 mm; US standard 90.0%)

[0374] Specification No. 25-50 sieve)

[0375] Example D

[0376] Extruded pellets

[0377]

[0378] Example E

[0379] emulsifiable concentrate

[0380] Compound 1 10.0%

[0381] Sorbitol polyoxyethylene ether hexaoleate 20.0%

[0382] C6-C 10 Fatty acid methyl esters 70.0%

[0383] Example F

[0384] microemulsion

[0385]

[0386] Example G

[0387] Suspension

[0388]

[0389]

[0390] Example H

[0391] water emulsion

[0392]

[0393] Example I

[0394] oil dispersion

[0395]

[0396] This disclosure also includes the above embodiments A to I, except that “compound 1” is replaced by “compound 2”, “compound 3”, “compound 4”, “compound 5”, “compound 6”, “compound 7”, “compound 8”, “compound 9” or “compound 10”.

[0397] Test results show that the compounds of the present invention are highly active pre-emergence and / or post-emergence herbicides and / or plant growth regulators. The compounds of the present invention generally exhibit the highest activity for post-emergence weed control (i.e., application after weed seedlings have emerged from the soil) and pre-emergence weed control (i.e., application before weed seedlings have emerged from the soil). Many of these compounds are practical for broad-spectrum pre-emergence and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in cinemas, airports, riverbanks, irrigation and other canals, billboards, and around highway and railway structures. Many of the compounds of the present invention can be used for selective control of grasses and broadleaf weeds in crop / weed mixtures due to selective metabolism of crops relative to weeds, or selective activity at physiologically inhibiting sites in crops and weeds, or selective distribution in or within the environment of a crop / weed mixture. Those skilled in the art will recognize that preferred combinations of these selective factors within a compound or class of compounds can be readily determined by performing routine biological and / or biochemical assays. The compounds of this invention can exhibit tolerance to important agronomic crops, including but not limited to alfalfa, barley, cotton, wheat, rapeseed, sugar beets, corn, sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea, and forestry such as eucalyptus and conifers (e.g., slash pine), as well as grasses (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and Bermuda grass). The compounds of this invention can be used on crops that have been genetically modified or bred to introduce herbicide tolerance; express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxins); and / or express other available traits. Those skilled in the art will recognize that not all compounds are equally effective against all weeds. Alternatively, the subject compound can be used to alter plant growth.

[0398] Because the compounds of the present invention possess both pre-emergence and post-emergence herbicidal activity, they can be readily applied by a variety of methods to control unwanted vegetation by killing or damaging it or slowing its growth. This includes applying a herbicidally effective amount of the compound of the present invention, or a composition comprising the compound and at least one of a surfactant, solid diluent, or liquid diluent, to the leaves or other parts of the unwanted vegetation, or to the environment of the unwanted vegetation, such as soil or water in which the unwanted vegetation grows or surrounds seeds or other reproductive buds of the unwanted vegetation. Undesirable vegetation includes at least one selected from grasses and broadleaf weeds. Undesirable vegetation includes annual bluegrass, rice-bag grass, black grass, black nightshade, broadleaf signal grass, Canada thistle, bromegrass, common burdock (Pennsylvanicum), common ragweed, poppy, field violet, millet grass, goosegrass, green foxtail grass, sheep grass, hairy beggarticks, herbicide-resistant blackgrass, fleabane, Italian ryegrass, datura, Johnson grass (false sorghum), red crabgrass, little seed canary grass, morning glory, Pennsylvania nettle, pitted morning glory, pricklysida, sedge, red-rooted amaranth, sugarcane field, shepherd's purse, silky windgrass, sunflower (as a weed in potato fields), wild buckwheat (Polygonum curcuma). Convolvulus, Brassica kaber, wild oats (Avena fatua), wild poinsettia, golden foxtail grass, and esculenta (Cyperus esculentus).

[0399] The herbicidal effective amount of the compounds of this invention is determined by several factors. These factors include: the selected formulation, the application method, the amount and type of vegetation present, and growing conditions. Generally, the herbicidal effective amount of the compounds of this invention is from about 0.001 kg / ha to 20 kg / ha, and preferably from about 0.004 kg / ha to 1 kg / ha. Those skilled in the art can readily determine the herbicidal effective amount required for the desired level of weed control.

[0400] In a common embodiment, the compounds of the invention, typically in the formulated composition, are applied to a site comprising both desired vegetation (e.g., crops) and undesired vegetation (i.e., weeds), both of which can be seeds, seedlings, and / or large plants in contact with a growth medium (e.g., soil). At this site, the composition containing the compounds of the invention can be applied directly to the plant or portions thereof, particularly the undesired vegetation, and / or to the growth medium in contact with the plant.

[0401] While the compounds of the present invention are most generally used to control undesirable vegetation, exposure of desired vegetation to the compounds of the present invention at the site of treatment may result in an additive or enhancing effect on the genetic traits (including traits introduced through genetic modification) in the desired vegetation. For example, resistance to herbivorous pests or plant diseases, tolerance to biotic / abiotic stresses, or storage stability may be greater than the genetic traits expected in the desired vegetation.

[0402] The compounds of the present invention can also be mixed with one or more other biologically active compounds or reagents, including herbicides, herbicide safeners, fungicides, insecticides, nematicides, fungicides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemical sterilizers, chemical pheromones, repellents, attractants, pheromones, feeding stimulants, phytonutrients, other biologically active compounds, or insect pathogenic bacteria, viruses, or fungi, to form multi-component insecticides, thereby providing even broader-spectrum agricultural protection. Mixtures of the compounds of the present invention with other herbicides can broaden the activity spectrum against additional weed species and inhibit the proliferation of any resistant biotypes. Therefore, the present invention also relates to compositions comprising a compound of Formula 1 (herbicidal effective amount) and at least one additional biologically active compound or reagent (biologically effective amount), and may further comprise at least one of a surfactant, a solid diluent, or a liquid diluent. Other biologically active compounds or reagents can be formulated in compositions comprising at least one of a surfactant, a solid or liquid diluent. For the mixtures of the present invention, one or more other bioactive compounds or reagents may be formulated together with the compounds of Formula 1 to form a premix, or one or more other bioactive compounds or reagents may be formulated independently of the compounds of Formula 1 and the formulations may be mixed together (e.g., in a spray can) or alternatively applied sequentially.

[0403] Mixtures of one or more of the following herbicides with the compounds of this invention may be particularly effective for weed control: acetochlor, trifluralin and its sodium salt, bensulfuron, acrolein (2-acrylaldehyde), metolachlor, quizalofop-P-ethyl, atrazine, azoxystrobin, pyrimisulfuron, cyclopropamidic acid and its esters (e.g., methyl ester, ethyl ester) and salts (e.g., sodium, potassium), chlorpyrifos, glyphosate, ammonium aminosulfonate, sphagnum molybdate, cypermethrin, atrazine, tetrazoxystrobin, flubutyroxyfen, glufosinate, ketoxam, bencarbazone, fluroxypyr, furazolidone, bensulfuron-methyl, dimethoate, bentazon, cypermethrin, bispyribac-sodium, bispyribac-sodium and its sodium salt, chlorpyrifos, brobutyroxyfen, chlorpyrifos, brobutyroxyfen, brobutyroxyfen , bromobenzonitrile octanoate, deslane, flupropargyl, chlorpyrifos, terbufos, styraclostrobin, styraclostrobin, styraclostrobin, styraclostrobin, styraclostrobin, styraclostrobin, styraclostrobin, chlorpyrifos, chlorpyrifos, chlorpyrifos, dimethyl chlorpyrifos, styraclostrobin, indole-methyl, cyclohexane, chlorpyrifos, chlorpyrifos, cyclohexane, clopyrifos, clopyrifos, chlorpyrifos, chlorpyrifos, dichloropyridine acid, dichloropyridine acid ethanolamine salt, chlorpyrifos, bensulfuron-methyl, chlorpyrifos, cyclopyrimorate, cyclopyrifos, cyclopyrifos, cyhalofop-butyl, 2,4-D and its butoxy, butyl, isooctyl and isopropyl esters, as well as its dimethylamine, di... Ethanolamine and triethanolamine salts, chlorpyrifos, chlorpyrifos, daraben, dazomet, 2,4-DB and its dimethylamine, potassium and sodium salts, betaine, diquat, dicamba and its diethylene glycolamine, dimethylamine, potassium and sodium salts, diquat, propionic acid, quizalofop-P-ethyl, dichlorvos sulfate, pyrifluquinazon, flupyrazole, oxazolone, piperazine, metolachlor, isoamyl sulfadiazine, dimethoate, thiamethoxam, thiamethoxam, dimethyl arsine and its sodium salt, dichlorvos, terbuprofen, fenproxetine, diquat, flusulfuron, diuron, DNOC, fenproxetine, EPTC, pendimethalin, ethylbutyrate, acesulfame K, flufenoxuron, ethoxysulfuron, fluroxypyr, ethoxysulfuron, ethoxysulfuron, oxazol, quizalofop-P-ethyl, isoxafen daphnetin Fenquizalofop-P-ethyl, tetrazolium-methyl, felflurium-methyl, methyl methacrylate, methyl methacrylate, pyrimisulfuron, quizalofop-P-ethyl, succinyl-methyl, isopyrazosulfuron, flufensulfuron-methyl, flupyrazosulfuron, flupyrazosulfuron, flufensulfuron-methyl, flufensulfuron-methyl, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron and its sodium salt, chlorpyrifos, fluorenyl butyl ester, flupyrazosulfuron, flupyrazosulfuron, furazolidone, methyl methacrylate, flupyrazosulfuron, formamide, phosmet, glufosinate, glufosinate-ammonium, glyphosate and its salts such as ammonium, isopropylamine, potassium, sodium (including sesquisodium) trimethylsulfonium (or glyphosate), fluchloropyridine acid,Halauxifen-methyl, haloxyfop-methyl, flupyridine, methyl haloxyfop-methyl, cyclopyridone, hydantocidin, methyl imidacloprid, methoxyfenozide, methyl imidacloprid, metribuzin, metribuzin ammonium, imidacloprid, imidacloprid ammonium, pyrazosulfuron, indicarb, indicafluazuron, iofensulfuron, iofensulfuron, iofensulfuron, iofensulfuron octanoate, iofensulfuron sodium, triazolyl acetamiprid, isoproturon, isoxaflutole, isoxaflutole, isoxaflutole, chlorpyrifos, quizalofop-p-ethyl, cyclopyridoxine, linuron, methylphenidate, MCPA and its salts (e.g., MCPA-dimethylamine, MCPA-potassium, and MCPA-sodium), esters (e.g., MCPA-2). -Ethylhexyl, MCPA-butoxy) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), Mefenoxam, Chlorpropionic acid, Benzoyl sulfadiazine, Flusulfanilamide, Metsulfuron-methyl, Metsulfuron-methyl, Metsulfuron-methyl, Oxazolidinyl, Benzoyl sulfadiazine, Pyrazosulfuron, Pyrazosulfuron-methyl, Metsulfuron-methyl, Methylammonium methyl, Monoammonium methyl, Monosodium and Disodium salts, Methylsulfuron, Metsulfuron-methyl, S-methyl ... Phosphorus, cyclosulfuron, oxadiazon, ethoxyflufenoxam, paraquat dichlorvos, chlorpyrifos, nonanoic acid, pendimethalin, penflusulfuron, metolachlor, cyclooxadiazon, cypermethrin, clethodim, pethoxyamid, bendiclofen, chlorpyrifos, potassium ampicillin, flupyridine, clodinafop-methyl, piperazine, pretilachlor, methyl flusulfuron, amflurazole, cyclosulfuron, cyclosulfuron Benzoate, propiconazole, propiconazole, chlorpyrifos, propiconazole, propiconazole, propiconazole, acetamiprid, isopropanol, propiconazole, propiconazole, propiconazole, propiconazole, bensulfuron-methyl, flusulfuron-methyl, pyrazosulfuron ... Sodium pyrimisulfonate, sulfadiazine, pyrazosulfuron, quinclorac, chlorpyrifos, quizalofop-P-ethyl, quizalofop-P-ethyl, sulfadiazine, sulfadiazine, pyrazosulfuron, cyproconazole, simazine, cyproconazole, sulfadiazine, mesotrione, sulfadiazine, sulfonylsulfuron, 2,3,6-TBA, TCA, TCA-sodium, methoxysulfuron, butyrazosulfuron, terbufos, cyproconazole, pyrazosulfuron, terbufos, terbufos, terbufos, methoxysulfuron, thiamethoxam, thiamethoxam, thiamethoxam, methyl thiamethoxam, quizalofop-P-ethyl, tiafenacil, tolpyralate, pyrazosulfuron, oxadiazine, pyrazosulfuron, fluazinam, fensulfuron-methyl, triazine fluazinamBenzsulfuron-methyl, chlorpyrifos, triclopyralid butoxyethyl ester, chlorpyrifos-triethylammonium, metribuzin, glyphosate, trifludimoxazin, trifluralin, flusulfanilamide, triflumethoprim, metsulfuron-methyl, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthidium-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexene)] [-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-hydroxyquinoxaline, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridyl)-5-(2,2-difluoroethyl)-8-hydroxypyridino[2,3-b]pyrazin-6(5H)-one, 4-(2,6-diethyl-4-methylphenyl)-5 -hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (formerly methioxolin), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H) ,4H)-diketone, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides include biological herbicides such as *Alternaria destruens* (Simmons), *Colletotrichum gloeosporiodes* (Penz.) Penz. & Sacc., *Drechsiera monoceras* (MTB-951), *Myrothecium verrucaria* (Atbertini & Schweinitz) Ditmar: Fries, *Phytophthora palmivora* (Butl.) Butl., and *Puccinia thlaspeos* Schub.

[0404] For better control of undesirable vegetation (e.g., lower utilization rates, such as due to enhancement effects; broader spectrum of weeds controlled; or improved crop safety) or for preventing the development of resistant weeds, mixtures of the compounds of the present invention with herbicides selected from: atrazine, tetrazolium-sulfuron, S-flumethoprim, benzisothiazolinone, triadimefon, chlorpyrifos, chlorsulfuron-methyl, chlorpyrifos, potassium dichloropyridinate, chlorpyrifos-sulfuron, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolone, 2-[(2,5 ...-3-dimethyl-3-dimethyl-3- [phenyl)methyl]-4,4-dimethyl-3-isoxazosone, benzylsulfuron, pyrazosulfuron, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrimisulfuron, methyl methazine, flusulfanilamide, imazalil ethionyl, cyclosporine, mesotrione, cyprodinil, mesosulfuron, clethodim, sulfadiazine, sulfosulfuron, quinclorac, sulfosulfuron, sulfadiazine, metolachlor, mesosulfuron, flusulfanilamide, flusulfanilamide, and benzylsulfuron.

[0405] The compounds of the present invention can also be used in combination with plant growth regulators such as aminoethoxyvinylglycine, N-(phenylmethyl)-1H-purine-6-amine, propionyl brassinolide, gibberellic acid, gibberellin A4 and A7, hypersensitive protein, mepiperidine, calcium cyclohexanoate, jasmonic acid inducer, sodium nitrophenolate and anti-loosening ester, as well as plant growth regulators such as Bacillus cereus strain BP01.

[0406] General references for agricultural protective agents (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biopesticides) include The Pesticide Manual, 13th edition, edited by CDSTomlin, British Crop Protection Council, Famham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd edition, edited by L.G. Copping, British Crop Protection Council, Famham, Surrey, UK, 2001.

[0407] For embodiments using one or more of these various mixed couples, the mixed couples are typically used in amounts similar to those conventionally used when the mixed couples are used alone. More specifically, in the mixture, the active ingredient is typically applied at an amount between half and the full application amount specified on the product label of the active ingredient used alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixed couples (total) to the compound of Formula 1 is typically from about 1:3000 to about 3000:1. It is noteworthy that the weight ratio is between about 1:300 and about 300:1 (e.g., a ratio between about 1:30 and about 30:1). Those skilled in the art can readily determine, through simple experiments, the bioeffective amount of the active ingredient required for the desired bioactivity spectrum. It is evident that including these additional components extends the spectrum of controlled weeds beyond that of the compound of Formula 1 alone.

[0408] In specific circumstances, the combination of the compounds of the present invention with other bioactive (particularly herbicidal) compounds or agents (i.e., active ingredients) can result in a greater than additive (i.e., enhancing) effect on weeds and / or a less than additive (i.e., safety) effect on crops or other desired plants. It is always desirable to ensure effective pest control while reducing the amount of active ingredient released into the environment. It is also desirable to be able to use larger amounts of active ingredient to provide more effective weed control without excessive crop phytotoxicity. Such combinations can benefit from reducing crop production costs and environmental impact when they produce an enhancing effect on weeds at application rates that provide agronomically satisfactory weed control levels. When they result in the safety of the herbicidal active ingredient on crops, such combinations can benefit from improved crop protection by reducing weed competition.

[0409] It is noteworthy that the compounds of the present invention are combined with at least one other herbicidal active ingredient. Particularly noteworthy are combinations where the other herbicidal active ingredient has a different site of action than the compounds of the present invention. In certain cases, combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly beneficial for resistance management. Therefore, the compositions of the present invention may also contain (an effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.

[0410] The compounds of this invention can also be used in combination with herbicide safeners to improve safety for specific crops, such as dipropionylamine, cyprosulfonamide, cyprosulfuron, bensulfuron, cyprosulfuron-methyl, dichloropropionylamine, dimethoate, dietholate, piperazine, cyprosulfuron-methyl, cyprosulfuron-methyl, fluroxypyr, cyprosulfuron-methyl, pyrazopyr, pyrazopyr, mephenate, cyprosulfuron-methyl, 1,6-chlorophenyl methylcarbamate, cyprosulfuron-methyl, 1,8-naphthalenedicarboxylic acid, cyprosulfuron-methyl, N-(aminocarbonyl)-2-methylbenzenesulfonylamine, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4,5]decane (MON). 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo-1-cyclohexen-1-yl-1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolyl)-ethyl ketone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide. An effective amount of the herbicide safener can be applied simultaneously with the compounds of this invention or during seed treatment. Therefore, one aspect of the invention relates to a herbicide mixture comprising the compound of the invention and an effective amount of a herbicide safener for detoxification. Seed treatment can be particularly useful for selective weed control because it physically limits detoxification of the crop. Therefore, a particularly usable embodiment of the invention is a method for selectively controlling unwanted vegetation growth in crops, comprising contacting the crop site with an effective amount of the compound of the invention, wherein seeds from which the crop grows are treated with an effective amount of a safener for detoxification. The effective amount of the safener for detoxification can be readily determined by those skilled in the art through simple experiments.

[0411] The compounds of the present invention may also be mixed with: (1) polynucleotides, including but not limited to DNA, RNA and / or chemically modified nucleotides, which exhibit a weeding effect by influencing the amount of a specific target through downregulation, interference, inhibition or silencing of genetically derived transcripts; or (2) polynucleotides, including but not limited to DNA, RNA and / or chemically modified nucleotides, which exhibit a safety effect by influencing the amount of a specific target through downregulation, interference, inhibition or silencing of genetically derived transcripts.

[0412] It is noteworthy that a composition comprising the compound of the present invention (an effective amount for weed control), at least one additional active ingredient (an effective amount) selected from other herbicides and herbicide safeners, and at least one component selected from surfactants, solid diluents and liquid diluents.

[0413] For better control of undesirable vegetation (e.g., lower utilization rates, such as due to enhancement effects; broader spectrum of weeds controlled; or improved crop safety) or for preventing the development of resistant weeds, the compounds of the present invention are preferably mixed with herbicides selected from: chlorimuron, nicosulfuron, mesotrione, thiamethoxam, flupyrimisulfuron, bensulfuron, pyrazole herbicides, cyclosulfuron, metoxychloride, methoxysulfuron, and S-metolachlor.

[0414] The following tests demonstrate the efficacy of the compounds of the present invention against specific weeds. However, the weed control obtained by the compounds is not limited to these species. See Index Table A for compound descriptions. The following abbreviations are used in the subsequent index table: “Cmpd.No.” represents “Compound Number,” “Ex.” represents “Example,” and the following number indicates in which example the compound was prepared. Unless otherwise specified, tetramethylsilane in DMSO-d6 solution is reported in ppm low field. 1 HNMR spectrum; "s" indicates a singlet, "d" indicates a doublet, "t" indicates a triplet, and "m" indicates a multiplet.

[0415] Index Table A

[0416]

[0417] W is O

[0418]

[0419]

[0420]

[0421] * 1 See Index Table B for H NMR or MS data.

[0422] Index Table B

[0423]

[0424] a 1 1H NMR data from tetramethylsilane are reported in ppm low field. Couplings are represented as (s)-single, (d)-double, (t)-triple, and (m)-multiplexes.

[0425] Biological Examples of the Invention

[0426] Test A

[0427] Seeds of plant species selected from Echinochloa crus-galli, Kochia scoparia, Ambrosia elatior, Lolium multiflorum, Setaria viridis, and Amaranthus retroflexus were sown in a mixture of loam and sandy soils and pre-emergence treatment was performed by targeted soil spraying with test chemicals formulated in a mixture of non-phytotoxic solvents containing surfactants.

[0428] Simultaneously, plants selected from these weed species, along with wheat (Triticum aestivum), maize (Zea mays), black grass (Alopecurus myosuroides), and cleavers (Galium aparine), were planted in pots containing the same mixture of loam and sand, and treated with the same test chemical formulation after emergence. For post-emergence treatment, plants were 2-10 cm tall and in the single-leaf to two-leaf stage. The treated plants and untreated controls were maintained in a greenhouse for approximately 10 days. After this time, all treated plants were compared to the untreated controls, and damage was visually assessed. The plant response ratings summarized in Table A are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result.

[0429]

[0430]

[0431]

[0432] Test B

[0433] Plant species selected from flooded paddy fields for testing (Oryza sativa), Cyperus difformis, Heteranthera limosa, and Echinochloa crus-galli) were grown to the 2-leaf stage for testing. During treatment, test pots were submerged 3 cm above the soil surface, and the test compound was applied directly to the paddy field water. This water depth was maintained for the duration of the test. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which all species were compared to the control and visually evaluated. Plant response ratings summarized in Table B are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result.

[0434]

Claims

1. A compound of formula 1, wherein N -Oxides and Salts in W represents O or S; R 1 It is H, C1–C7 alkyl, C3–C8 alkylcarbonylalkyl, C3–C8 alkoxycarbonylalkyl, C4–C7 alkylcycloalkyl, C3–C7 cycloalkyl, C4–C7 cycloalkylalkyl, C2–C3 cyanoalkyl, C1–C4 nitroalkyl, C2–C7 haloalkoxyalkyl, C1–C7 haloalkyl, C2–C7 alkoxyalkyl, C3–C7 alkylthioalkyl, C1–C7 alkoxy, benzyl or phenyl; or a 5- or 6-membered saturated or partially saturated heterocycle containing a ring member selected from carbon and at most one O and one S; R 2 It is H, halogen, cyano, formyl, C1–C7 alkyl, C3–C8 alkylcarbonylalkyl, C3–C8 alkoxycarbonylalkyl, C2–C4 alkylcarbonyl, C2–C7 alkylcarbonyloxy, C4–C7 alkylcycloalkyl, C1–C4 alkylsulfinyl, C1–C4 alkylsulfonyl, C1–C4 alkylamino, C2–C8 dialkylamino, C3–C7 cycloalkyl, C4–C7 cycloalkylalkyl, C2–C3 cyanoalkyl, C1–C4 nitroalkyl, C2–C7 haloalkoxyalkyl, C1–C7 haloalkyl, C2–C7 alkoxyalkyl, C1–C7 alkoxyalkyl, C1–C7 alkoxy, C1–C5 alkylthio or C2–C3 alkoxycarbonyl; or optionally substituted with halogen, C1–C4 alkyl or C1–C4 haloalkyl; L stands for direct bond; G is H, C(=O)R 5 C(=S)R 5 Or P(=O)R 9 R 10 Or C1–C4 alkyl, C2–C4 alkenyl, C2–C4 alkynyl, C1–C4 haloalkyl, C2–C4 haloalkenyl, C2–C4 haloalkynyl, C2–C4 alkoxyalkyl, C3–C6 cycloalkyl or C4–C7 cycloalkylalkyl; or 5-membered or 6-membered heterocycles; A is selected from X 1 、 X 2 、 X 3 、 X 4 、 X 5 、 X 6 、 X 7 、 X 8 and X 9 are CR 3 ; Y is either O or S; Each R 3 Independently, it is H, halogen, cyano, nitro, C1–C5 alkyl, C2–C5 alkenyl, C2–C5 alkynyl, C3–C5 cycloalkyl, C4–C5 cycloalkylalkyl, C1–C5 haloalkyl, C3–C5 haloalkenyl, C3–C5 haloalkynyl, C2–C5 alkoxyalkyl, C1–C5 alkoxy, C1–C5 haloalkoxy, C1–C5 alkylthio, C1–C4 alkylsulfinyl, C1–C4 alkylsulfonyl, C1–C5 haloalkylthio or C2–C5 alkoxycarbonyl; R 3a It can be H, halogen, -CN, nitro, C1–C5 alkyl, C2–C5 alkenyl, C2–C5 alkynyl, C3–C5 cycloalkyl, C4–C5 cycloalkylalkyl, C1–C5 haloalkyl, C3–C5 haloalkenyl, C3–C5 haloalkynyl, C2–C5 alkoxyalkyl, C1–C5 alkoxy, C1–C5 haloalkoxy, C1–C5 alkylthio, C1–C4 alkylsulfinyl, C1–C4 alkylsulfonyl, C1–C5 haloalkylthio or C2–C5 alkoxycarbonyl; R 3b H, halogen, -CN, nitro, C1–C5 alkyl, C2–C5 alkenyl, C2–C5 alkynyl, C3–C5 cycloalkyl, C4–C5 cycloalkylalkyl, C1–C5 haloalkyl, C3–C5 haloalkenyl, C3–C5 haloalkynyl, C2–C5 alkoxyalkyl, C1–C5 alkoxy, C1–C5 haloalkoxy, C1–C5 alkylthio, C1–C4 alkylsulfinyl, C1–C4 alkylsulfonyl, C1–C5 haloalkylthio or C2–C5 alkoxycarbonyl; or R 3a and R 3b As =O combined; or R 3a and R 3b They combine with the carbon atoms they are bonded to form optionally substituted 3- to 7-membered carbon rings; R 4 It is H, C1–C3 alkyl, or C1–C3 haloalkyl; R 5 and R 7 Independently, it is H, C1–C7 alkyl, C3–C7 alkenyl, C3–C7 alkynyl, C3–C7 cycloalkyl, C1–C7 haloalkyl, C3–C7 haloalkenyl, C2–C7 alkoxyalkyl or C4–C7 cycloalkylalkyl; or phenyl, benzyl, or 5 to 6-membered heterocycle, each phenyl, benzyl or heterocycle optionally substituted with halogen, C1–C4 alkyl or C1–C4 haloalkyl; R 6 It is a C1–C7 alkyl, C3–C7 alkenyl, C3–C7 alkynyl, C3–C7 cycloalkyl, C2–C7 haloalkyl, C3–C7 haloalkenyl, C2–C7 alkoxyalkyl or C4–C7 cycloalkylalkyl; or phenyl, benzyl, or 5 to 6-membered heterocycle, each phenyl, benzyl or heterocycle optionally substituted with a halogen, C1–C4 alkyl or C1–C4 haloalkyl; R 8 It can be H, C1–C7 alkyl, C2–C7 alkenyl, C2–C7 alkynyl, C3–C7 cycloalkyl, C4–C7 cycloalkylalkyl, C1–C7 haloalkyl or C2–C7 alkoxyalkyl; R 9 It is a C1–C7 alkyl or C1–C7 alkoxy; and R 10 It is a C1–C7 alkyl or C1–C7 alkoxy.

2. The compound according to claim 1, wherein... R 1 It can be H, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C4-C7 alkylcycloalkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy, benzyl, or phenyl; W is O; L stands for direct bond; G is H, C(=O)R 5 C(=S)R 5 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl; R 2 The following are possible meanings: H, halogen, cyano, formyl, C1-C7 alkyl, C3-C8 alkylcarbonylalkyl, C3-C8 alkoxycarbonylalkyl, C2-C4 alkylcarbonyl, C2-C7 alkylcarbonyloxy, C4-C7 alkylcycloalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, or C1-C5 alkylthio; and Each R 3 It can be independently H, halogen, C1-C3 alkyl, C3-C4 cycloalkyl, C1-C3 haloalkyl or C1-C3 alkoxy.

3. The compound according to claim 2, wherein... R 1 It can be H, C1-C7 alkyl, C3-C8 alkoxycarbonylalkyl, C4-C7 alkylcycloalkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy or benzyl; A is A-1; G is H, C(=O)R 5 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 alkoxyalkyl, C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl; R 2 The following are possible meanings: H, halogen, cyano, formyl, C1-C7 alkyl, C2-C4 alkyl carbonyl, C2-C7 alkyl carbonyloxy, C4-C7 alkyl cycloalkyl, C1-C4 alkyl sulfinyl, C1-C4 alkyl sulfonyl, C1-C4 alkylamino, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C4 nitroalkyl, C2-C7 haloalkoxyalkyl, C1-C7 haloalkyl, C2-C7 alkoxyalkyl, or C1-C7 alkoxy; and Each R 3 It is independently H, halogen, C1-C2 alkyl, cyclopropyl or C1-C2 haloalkyl.

4. The compound according to claim 3, wherein R 1 It is a C1-C4 alkyl, C3-C4 cycloalkyl, C2-C3 cyanoalkyl, C1-C3 haloalkyl or C2-C4 alkoxyalkyl; G is H, C(=O)R 5 Or P(=O)R 9 R 10 Or C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl, or C3-C6 cycloalkyl; R 2 It is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, or C1-C3 alkoxy; and Each R 3 It can be H, halogen, methyl, ethyl or CF3 independently.

5. The compound according to claim 4, wherein... R 1 It can be methyl, ethyl, n-propyl or 2-methoxyethyl; G is H or C (=O)R 5 Or C2-C4 alkoxyalkyl or C3-C6 cycloalkyl; R 2 It is H, Cl, Br, I, -CN, methyl or methoxy; and Each R 3 It can be H, F, Cl, Br or methyl independently.

6. The compound according to claim 1, wherein the compound is selected from: 4-(9-Anthracene)-6-chloro-5-hydroxy-2-methyl-3(2H)-pyridazinone; 6-Chloro-4-(10-Chloro-9-anthrayl)-5-hydroxy-2-methyl-3(2H)-pyridazinone; and 4-(10-bromo-9-anthrayl)-6-chloro-5-hydroxy-2-methyl-3(2H)-pyridazinone.

7. The compound according to claim 2, wherein A is A-4.

8. The compound according to claim 2, wherein A is A-6.

9. A herbicide composition comprising the compound according to claim 1 and at least one component selected from surfactants, solid diluents and liquid diluents.

10. A herbicide composition comprising the compound of claim 1, at least one additional active ingredient selected from other herbicides and herbicide safeners, and at least one component selected from surfactants, solid diluents and liquid diluents.

11. A herbicide mixture comprising (a) the compound according to claim 1, and (b) at least one additional active ingredient selected from: (b1) a photosystem II inhibitor, (b2) an acetylhydroxy acid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimic, (b5) an 5-enol-pyruvate-shikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase (PPO) inhibitor, (b8) a glutamine synthase (GS) inhibitor, (b9) a very long-chain fatty acid (VLCFA) elongation enzyme inhibitor, (b10) an auxin transport inhibitor, (b11) a phytopenic lycopene desaturase (PDS) inhibitor, (b12) a 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor, (b13) Urocyanidin solanyltransferase (HST) inhibitor, (b14) cellulose biosynthesis inhibitor, (b15) mitotic disruptor, organoarsenic compound, fenbendazim, bromobutyroxyfen, cyclohexane, bensulfuron, dazomet, oat thiophanate-methyl, sapuram, ethoxybenzamide, styrafosinate, phosphonophosphorus, hydantocidin, fenbendazim, methyl sulfadiazine, oleic acid, oxadiazon, nonanoic acid or barnyardgrass, and (b16) herbicide safener; and salts of compounds (b1) to (b16).

12. A method for controlling unwanted vegetation growth, the method comprising contacting the vegetation or its environment with a herbicidal amount of the compound according to claim 1.

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