Pyridazinone herbicides and pyridazinone intermediates used in the manufacture of herbicides

Abstract

To provide methods for producing pyridazinone compounds useful as herbicides.SOLUTION: The invention provides a method for producing a compound of Formula I-A, where: R1 is C1-C4 alkyl or C3-C6 cycloalkyl; R2 is H, Cl, or the like; R3 is Cl or the like; R5 is H, F, Cl, or CH3; and R6 is H or Cl. The production method comprises: reacting a specific brominated naphthalene compound with Mg to form an intermediate compound; and reacting the intermediate compound with a corresponding pyridazinone compound.SELECTED DRAWING: None

Description

[Background technology]

[0001] Background of the Invention This disclosure provides pyridazinones and methods for producing pyridazinones. The pyridazinones disclosed herein may be used as synthetic intermediates for producing pyridazinone-based herbicides or as pyridazinone herbicides. Patent documents 1 and 2 disclose synthetic intermediates used for producing herbicidal pyridazinones. There is a need for improved methods for producing improved herbicidal pyridazinones. [Prior art documents] [Patent Documents]

[0002] [Patent Document 1] WO 2015 / 168010 [Patent Document 2] WO 2017 / 074988 [Overview of the Initiative] [Means for solving the problem]

[0003] Summary of the Invention In one embodiment, this disclosure relates to Formula I [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl; R 2 is H, Cl, Br, or I; R 3 is Cl or OR 4 and; R 4 is H or C1-C4 alkyl; R 5 is H, F, Cl or CH3; and R 6is H or Cl] provides a compound thereof and its N-oxide or salt.

[0004] In another aspect, the present disclosure relates to formula I-A [Chemical formula] [wherein, R 1 is C1-C4 alkyl or C3-C6 cycloalkyl; R 2 is H or Cl; R 5 is H, F, Cl or CH3; and R 6 is H or Cl] provides a method for producing a compound of formula I-A, the method comprising:

[0005] (1) reacting a compound of formula II [Chemical formula] [wherein, R 5 is H, F, Cl or CH; and R 6 is H or Cl] with magnesium to form an intermediate compound of formula III [Chemical formula] ; and

[0006] (2) reacting the intermediate compound of formula III formed in (1) with a compound of formula IV-A or IV-B [Chemical formula] [wherein, R 1 is C1-C4 alkyl or C3-C6 cycloalkyl; G is C1-C4 alkyl, SO2CF or SO2(4-Me-Ph)] comprising reacting with a compound of formula IV-A or IV-B.

[0007] In another embodiment, this disclosure relates to formula IB [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl; R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] The present invention provides a method for producing a compound of which R in the formula shown above. 2 The process involves reacting a compound of formula IA, in which the parent molecule is H, with a methoxylation agent.

[0008] In another embodiment, this disclosure relates to formula IC [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl; R 2 is Cl, Br, or I; R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] A method for producing the compound is provided, and the method is:

[0009] (1) The compound of formula IB shown above is reacted with tmp-zinc base to obtain formula V [ka] To form zincated intermediate compounds; and (2) React the zincated intermediate compound of formula V formed in (1) with a halogenating agent. Includes.

[0010] In another embodiment, this disclosure relates to formula ID [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl; R 2 is Cl, Br, or I; R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] The present invention provides a method for producing a compound of formula IC shown above, the method comprising reacting the compound of formula IC with a demethylating agent.

[0011] In another embodiment, this disclosure relates to formula IE [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl; R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] This provides further methods for producing compounds;

[0012] The method is, Formula VI [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl, R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] This involves reacting the compound with phosphorus oxychloride.

[0013] In another embodiment, this disclosure relates to formula IE [ka] [In the formula, R 1 These are C1-C4 alkyl or C3-C6 cycloalkyl; R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] This provides further methods for producing compounds;

[0014] The method is: (1) Formula II [ka] [In the formula, R 5 is H, F, Cl or CH3; and R 6 [is H or Cl] The compound is reacted with magnesium to produce formula III [ka] To form an intermediate compound; and

[0015] (2) The intermediate compound of formula III formed in (1) is given formula 7 [ka] [In the formula, R 1 [These are C1-C4 alkyl or C3-C6 cycloalkyl compounds.] This includes reacting it with the compound. [Modes for carrying out the invention]

[0016] Detailed description of the invention As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “have,” “have,” “contain,” “contain,” “characterized by,” or any variation thereof are intended to refer to comprehensive inclusion under any expressly indicated limitation. For example, a process or method that includes a list of elements may include other elements that are not expressly listed or that are specific to such a process or method, but are not necessarily limited to those elements.

[0017] The transitional phrase “consisting of” excludes any unspecified element, process, or component. In the case of claims, the phrase would close the claim to the inclusion of substances other than those described, except for impurities that are usually present. If the phrase “consisting of” appears in a section of the claim rather than immediately following the preface, it limits only the elements described in that section; other elements are not excluded from the claim as a whole.

[0018] The transitional phrase “essentially from” is used to define a process or method that includes materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additional materials, processes, features, components, or elements do not substantially affect the fundamental and novel features of the disclosure. The term “essentially from” lies between “including” and “consisting of.”

[0019] If the applicants define the disclosure or any part thereof using a non-restrictive term such as “including,” that term shall, naturally, be interpreted (unless otherwise stated) as also describing disclosures that use the terms “essentially consisting of” or “consisting of.”

[0020] Furthermore, unless explicitly stated otherwise, "or" refers to a compatible or not an exclusive or. For example, condition A or or B is satisfied by one 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).

[0021] Furthermore, the indefinite articles “a” and “an” preceding any element or component of this disclosure are intended to be non-restrictive with respect to the number of instances (i.e., existences) of that element or component. Thus, “a” or “an” is to be read as including one or at least one, and the singular form of an element or component also includes plurals unless it is explicitly stated that the number is singular.

[0022] As used herein, the term "C1-C6 alkyl" includes linear or branched alkyl groups having 1 to 6 carbon atoms, e.g., methyl, ethyl, n-propyl, i-propyl, or various butyl, pentyl, or hexyl isomers. Similarly, the term "C1-C4 alkyl" includes linear or branched alkyl groups having 1 to 4 carbon atoms, e.g., methyl, ethyl, n-propyl, i-propyl, or various butyl isomers, and the term "C1-C3 alkyl" includes methyl, ethyl, n-propyl, and i-propyl.

[0023] As used herein, the term “halogen” includes fluorine, chlorine, bromine, or iodine. Where G is “SO2(4-Me-Ph)”, this is instead defined as “SO2(p-tolyl)”. The term “reacting” and similar terms refer to adding, contacting, or mixing two or more reagents under appropriate conditions to produce the indicated and / or desired product. Naturally, the reaction producing the indicated and / or desired product does not necessarily have to occur directly from the combination of the two reagents initially added; i.e., one or more intermediates may be present in the mixture that ultimately lead to the formation of the indicated and / or desired product. The reaction may occur in or without a solvent, at temperatures above or below room temperature, under an inert atmosphere, etc.

[0024] As used herein, the term “methoxylating agent” refers to a chemical reagent used to add a methoxy group, i.e., OCH3, to a compound. Examples of non-limiting methoxylating agents include sodium methoxide or potassium methoxide. As used herein, the term “tmp-zinc base” refers to a chemical complex containing zinc and 2,2,6,6-tetramethylpiperidine. Examples of non-limiting zinc bases include (tmp)2Zn·2·MgCl2·2·LiCl, (tmp)2Zn·2·LiCl, and (tmp)2Zn.

[0025] As used herein, the term “halogenating agent” refers to a chemical reagent used to add a halogen atom, such as Cl, Br, or I, to a compound. Examples of non-limiting halogenating agents include iodine, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, trichloroisocyanuric acid, sulfuryl chloride, N-bromosuccinimide, and N-chlorosuccinimide.

[0026] Compounds of formula I typically exist in more than one solid form. Therefore, compounds of formula I encompass all crystalline and amorphous forms of the compounds they represent. Amorphous forms include embodiments that are solids, such as waxes and rubbers, as well as embodiments that are liquids, such as solutions and dissolves. Crystalline forms include embodiments that represent essentially a single crystalline form and embodiments that represent a mixture of polymorphs (i.e., different crystalline forms). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and / or conformations of molecules in the crystal lattice. Polymorphs may have the same chemical composition, but they may also differ in composition due to the presence or absence of co-crystallized water or other molecules, which may be weakly or strongly bonded in the lattice. Polymorphs may differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate, and bioavailability.

[0027] As is obvious to those skilled in the art, polymorphs of compounds of formula I may exhibit beneficial effects (e.g., suitability for the manufacture of useful formulations, improved biological performance) compared to other polymorphs or mixtures of polymorphs of the same compound of formula I. The manufacture and isolation of specific polymorphs of compounds of formula I can be achieved by methods known to those skilled in the art, such as crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphisms, see R. Hilfi. See ke (ed.), Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

[0028] Synthetic methods for producing N-oxides of heterocyclic and tertiary amines are well known to those skilled in the art. Examples of procedures for producing N-oxides include the oxidation of heterocyclic and tertiary amines using peroxy acids, such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides, such as t-butyl hydroperoxide, sodium perborate, and dioxiranes, such as dimethyldioxirane. These methods for producing N-oxides have been widely described and reviewed in the literature, e.g.: TLGilchrist in Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, edited by SVLey, Pergamon See also: Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, edited by AJBoulton and A. McKillop, Pergamon Press; MRGrimmett and BRTKeene in Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, edited by ARKatritzky, Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291, edited by ARKatritzky and AJBoulton, Academic Press; and GWHCheeseman and ESGWerstiuk in Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, edited by ARKatritzky and AJBoulton, Academic Press. Therefore, as is obvious to those skilled in the art, not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires a lone pair of electrons to be available for oxidation to an oxide; those skilled in the art will know which nitrogen-containing heterocycles can form N-oxides.

[0029] Those skilled in the art will understand that salts of chemical compounds, under environmental and physiological conditions, are in equilibrium with their corresponding unsalted forms, and therefore salts share the biological utility of their unsalted forms. Accordingly, a wide variety of salts of compounds of formula I are useful (i.e., agrochemically suitable) for controlling undesirable vegetation. Examples of salts of compounds of formula I 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. Therefore, this disclosure includes compounds selected from formula I, its N-oxides, and agrochemically suitable salts.

[0030] Embodiments of this disclosure (wherein compounds of formula I include compounds of formulas IA, IB, IC, ID, and IE) also include their N-oxides and / or salts):

[0031] A. Compounds of formula I Embodiment A1. A compound of formula I as described in the abstract of the invention, and its N-oxide or salt.

[0032] Embodiment A2.R 1 The compound of Embodiment A1 is a C1-C4 alkyl group.

[0033] Embodiment A3.R 1 A compound in either Embodiment A1 or A2, wherein the compound is CH3.

[0034] Embodiment A3A.R 2 A compound from any one of embodiments A1 to A3, wherein the compound is Cl.

[0035] Embodiment A4.R 2 The compound is Br, one of any one of embodiments A1 to A3.

[0036] Embodiment A5.R 3 A compound from any one of embodiments A1 to A4, wherein the compound is Cl.

[0037] Embodiment A6.R3 is OR 4 And R 4 A compound from any one of embodiments A1 to A4, wherein H is present.

[0038] Embodiment A7.R 3 is OR 4 And R 4 The compound is a C1-C4 alkyl group, one of any one of embodiments A1 to A4.

[0039] Embodiment A8.R 3 is OR 4 And R 4 A compound from any one of embodiments A1 to A4, wherein is CH3.

[0040] Embodiment A9.R 5 A compound is F, which is one of the compounds in any of embodiments A1 to A8.

[0041] Embodiment A10.R 5 A compound from any one of embodiments A1 to A8, wherein the compound is Cl.

[0042] Embodiment A11.R 5 A compound from any one of embodiments A1 to A8, wherein the compound is CH3.

[0043] Embodiment A12.R 5 A compound from any one of embodiments A1 to A8, wherein H is present.

[0044] Embodiment A13.R 6 A compound from any one of embodiments A1 to A12, wherein is H.

[0045] Embodiment A14.R 6 The compound is Cl, one of any one of embodiments A1 to A12.

[0046] Embodiment A15.R 1 It is CH3, and R in formula I 2 , R 3 , R 4 , R 5and R 6 The compound of Embodiment A1, as defined in Table AA.

[0047] [Table 1] [Table 2] [Table 3]

[0048] Embodiment A16. 5-Chloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone; 5-Chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone; 5-Methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone; 4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone; 6-Chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone; and 6-Chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone A compound of embodiment A1 selected from (i.e., a compound of formula I).

[0049] Embodiment A17. The compound of Embodiment A1, however, (a) R 3 is OR 4 And; R 4 H is and R 5 If H, then R 6 is Cl; and (b) R 2 Br is :R 3 is OR 4 And R 4 If H, then R6 H is H.

[0050] B. Method for producing the compound of formula IA Embodiment B1. A method for producing the compound of formula IA as described in the abstract of the invention.

[0051] Embodiment B2.R 1 The method of Embodiment B1, wherein is a C1-C4 alkyl group.

[0052] Embodiment B3.R 1 The method is either embodiment B1 or B2, wherein CH3 is present.

[0053] Embodiment B4.R 2 The method is one of embodiments B1 to B3, wherein is Cl.

[0054] Embodiment B5.R 2 The method is one of the embodiments B1 to B3, wherein Br is Br.

[0055] Embodiment B6.R 5 F is one of the embodiments B1 to B5.

[0056] Embodiment B7.R 5 The method is one of embodiments B1 to B5, wherein is Cl.

[0057] Embodiment B8.R 5 The method is one of the embodiments B1 to B5, wherein CH3 is present.

[0058] Embodiment B9.R 5 H is one of the methods of Embodiments B1 to B5.

[0059] Embodiment B10.R 6 H is one of the methods of Embodiments B1 to B9.

[0060] Embodiment B11.R 6 The method is one of embodiments B1 to B9, wherein is Cl.

[0061] Embodiment B12. The compound of formula I-A is selected from the group consisting of compound numbers 1, 2, 3, 4, 5, 6, 7, 8, 45, 46, 47, 48, 49, 50, 51 and 52 (i.e., as listed in Table BB, R 1 is CH3; R 5 is H, F, Cl or CH3; R 2 is H; R 3 is Cl; and R 6 is H or Cl, a method of Embodiment B_{1}).[[ID=!13]] [[ID=!14]]

[0062] [[ID=!15]] [[ID=!16]] [[ID=!17]][Table 4][[ID=!18]] [[ID=!19]]<00ooo659>[[ID=!20]] [[ID=!21]] [[ID=!22]]

[0063] [[ID=!23]] [[ID=!24]]Embodiment B13. The compound of formula II or III is as described in the gist of the invention, a method of any one of Embodiments B1 to B12.[[ID=!25]] [[ID=!26]]

[0064] [[ID=!27]] [[ID=!28]]Embodiment B14. R[[ID=!29]] 5 [[ID=!30]]is F, a method of Embodiment B13.[[ID=!31]] [[ID=!32]]

[0065] [[ID=!33]] [[ID=!34]]Embodiment B15. R[[ID=!35]] 5 [[ID=!36]]is Cl, a method of Embodiment B13.[[ID=!37]] [[ID=!38]]

[0066] [[ID=!39]] [[ID=!40]]Embodiment B16. R[[ID=!41]] 5 [[ID=!42]]is CH3, a method of Embodiment B13.[[ID=!43]] [[ID=!44]]

[0067] [[ID=!45]] [[ID=!46]]Embodiment B17. R[[ID=!47]] 5 [[ID=!48]]is H, a method of Embodiment B13.[[ID=!49]] [[ID=!50]]

[0068] [[ID=!51]] [[ID=!52]]Embodiment B18. R[[ID=!53]] 6 [[ID=!54]]is H, a method of any one of Embodiments B1 or B13 to B17. [[ID=!l55]] [[ID=!56]]

[0069] [[ID=!57]] [[ID=!58]]Embodiment B19. R[[ID=!59]] 6 [[ID=!60]]is Cl, a method of any one of Embodiments B13 to B17.[[ID=!61]] [[ID=!62]]

[0070] [[ID=!63]] Embodiment B20. The method of any one of Embodiments B13 - B17, wherein the compound of Formula IV - A or IV - B is as defined in the gist of the invention.

[0071] Embodiment B21. R 1 is C1 - C4 alkyl, in the method of Embodiment B20.

[0072] Embodiment B22. R 1 is C3 - C6 cycloalkyl, in the method of Embodiment B20.

[0073] Embodiment B23. R 1 is CH3, in the method of Embodiment B20.

[0074] Embodiment B24. G is C1 - C6 alkyl, in the method of any one of Embodiments B20 - B23.

[0075] Embodiment B25. G is CH3, in the method of Embodiment B24.

[0076] Embodiment B26. The method of any one of Embodiments B1 - B25, further comprising isolating the compound of Formula I - A.

[0077] Embodiment B27. The method of any one of Embodiments B1 - B26, wherein the reaction of the compound of Formula II with magnesium is carried out in a suitable solvent.

[0078] Embodiment B28. The method of Embodiment B27, wherein the reaction of the compound of Formula II with magnesium is carried out in tetrahydrofuran.

[0079] Embodiment B29. The method of any one of Embodiments B1 - B28, wherein the reaction of the compound of Formula II with magnesium is carried out at a temperature higher than 80°C.

[0080] Embodiment B30. The method of any one of Embodiments B1 - B28, wherein the reaction is carried out at a temperature of 0°C or lower.

[0081] Embodiment B31. The reaction is carried out at a temperature of approximately 0°C to approximately 80°C, using any one of the methods of Embodiments B1 to B30.

[0082] C. Method for producing the compound of formula IB Embodiment C1. A method for producing a compound of formula IB as described in the abstract of the invention.

[0083] Embodiment C2.R 1 The method of Embodiment C1, wherein is a C1-C4 alkyl group.

[0084] Embodiment C3.R 1 The method of embodiment C2, wherein CH3.

[0085] Embodiment C4.R 5 F is one of the embodiments C1 to C3.

[0086] Embodiment C5.R 5 The method is one of embodiments C1 to C3, wherein is Cl.

[0087] Embodiment C6.R 5 The method is one of the embodiments C1 to C3, wherein CH3 is present.

[0088] Embodiment C7.R 5 H is one of the methods of embodiments C1 to C3.

[0089] Embodiment C8.R 6 H is one of the methods of embodiments C1 to C7.

[0090] Embodiment C9.R 6 The method is one of embodiments C1 to C7, wherein is Cl.

[0091] Embodiment C10. Compounds of formula IB are compound numbers 29, 30, 31, 32, 73, 74, 75 and 76 (i.e., as listed in Table CC, R 1 is CH3; R 2 H is R 3is OR 4 And; R 4 is CH3; R 5 is H, F, Cl or CH3; and R 6 One of the methods of Embodiments C1 to C9, selected from the group consisting of compounds of formula I, wherein is H or Cl.

[0092] [Table 5]

[0093] Embodiment C11. The reaction is carried out in a suitable solvent, according to any one of Embodiments C1 to C10.

[0094] Embodiment C12. The method of Embodiment C11, wherein the suitable solvent is methanol.

[0095] Embodiment C13. Any one of Embodiments C1 to C12, wherein the reaction is carried out at a temperature of 0°C or below.

[0096] Embodiment C14. Any one of Embodiments C1 to C13, wherein the methoxylation agent is sodium methoxide.

[0097] D. Method for producing compounds of formula IC Embodiment D1. A method for producing a compound of formula IC as described in the abstract of the invention.

[0098] Embodiment D2.R 1 The method of embodiment D1, wherein is a C1-C4 alkyl group.

[0099] Embodiment D3.R 1 The method of embodiment D1, wherein is a C3-C6 cycloalkyl.

[0100] Embodiment D4.R 2 One of the embodiments D1 to D3, wherein is Cl or Br.

[0101] Embodiment D5.R 2The method of embodiment D4, wherein is Cl.

[0102] Embodiment D6.R 5 One of the embodiments D1 to D5, wherein is H or CH3.

[0103] Embodiment D7.R 5 The method of embodiment D6, where H is.

[0104] Embodiment D8.R 5 The method of embodiment D6, wherein CH3 is used.

[0105] Embodiment D9.R 6 H is one of the embodiments D1 to D8.

[0106] Embodiment D10. In the intermediate compound of formula V, R 1 The method of embodiment D1, wherein is a C1-C4 alkyl group.

[0107] Embodiment D11. In the intermediate compound of formula V, R 1 The method of embodiment D1, wherein is a C3-C6 cycloalkyl.

[0108] Embodiment D12. In the intermediate compound of formula V, R 5 The method is one of the embodiments D10 to D11, wherein is H or CH3.

[0109] Embodiment D13.R 5 The method of embodiment D12, where H is.

[0110] Embodiment D14.R 5 The method of embodiment D12, wherein CH3 is used.

[0111] Embodiment D15.R 6 H is one of the methods of embodiments D10 to D14.

[0112] Embodiment D16.R 6 The method is one of embodiments D10 to D14, wherein is Cl.

[0113] Embodiment D17. Any one of Embodiments D1 to D16, further comprising isolating a compound of formula IC.

[0114] Embodiment D18. Compounds of formula IC are compound numbers 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87 and 88 (i.e., as listed in Table DD, R 1 is CH3; R 2 is Cl, Br, or I; R 3 is OR 4 And; R 4 is CH3; R 5 is H, F, Cl or CH3; and R 6 The method of Embodiment D1, selected from the group consisting of compounds of formula I, wherein is H or Cl.

[0115] [Table 6]

[0116] Embodiment D19. The reaction of the compound of formula IB with tmp-zinc base is carried out in a suitable solvent, in any one of the methods of Embodiments D1-D18.

[0117] Embodiment D20. The method of Embodiment D19, wherein the suitable solvent is tetrahydrofuran.

[0118] Embodiment D21. The tmp-zinc base is an organometallic tmp-zinc base, one of the methods of Embodiments D1-D20.

[0119] Embodiment D22. The tmp-zinc base is prepared from zinc chloride and a 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex, according to the method of Embodiment D21.

[0120] Embodiment D23. The method of Embodiment D22, wherein the tmp-zinc base is a bis(2,2,6,6-tetramethylpiperidinyl)zinc, lithium chloride, magnesium chloride complex.

[0121] Embodiment D24. The intermediate is reacted with a halogenating agent in a suitable solvent. or any one of the embodiments D1 to D22.

[0122] Embodiment D25. The method of Embodiment D24, wherein the suitable solvent is tetrahydrofuran.

[0123] Embodiment D26. Any one of Embodiments D1 to D25, wherein the halogenating agent is iodine, N-bromosuccinimide, or isocyanuric acid chloride.

[0124] Embodiment D27. Any one of Embodiments D1 to D26, wherein the halogenating agent is N-bromosuccinimide or isocyanuric acid chloride.

[0125] Embodiment D28. Any one of Embodiments D1 to D27, wherein the halogenating agent is isocyanuric acid chloride.

[0126] Embodiment D29. In a compound of formula IC, R 1 R is a C1-C4 alkyl or C3-C6 cycloalkyl group; 2 is Cl; R 5 is H, F, Cl or CH3; and R 6 A method from any one of embodiments D1 to D28, wherein is H or Cl, and comprises reacting a compound of formula IE with a methoxylation agent.

[0127] Embodiment D30. The method of Embodiment D29, wherein the methoxylation agent is sodium methoxide.

[0128] E. Method for producing the compound of formula ID Embodiment E1. A method for producing the compound of formula ID as described in the abstract of the invention.

[0129] Embodiment E2.R 1 The method of Embodiment E1, wherein it is C1-C4 alkyl.

[0130] Embodiment E3.R 1 The method of Embodiment E1, wherein it is C3-C6 cycloalkyl.

[0131] Embodiment E4.R 1 The method of Embodiment E1 or E2, wherein it is CH3. [[ID=)]]

[0132] Embodiment E5.R 2 The method of any one of Embodiments E1-E4, wherein it is Cl.

[0133] Embodiment E6.R 2 The method of any one of Embodiments E1-E4, wherein it is Br.

[0134] Embodiment E7.R 2 The method of any one of Embodiments E1-E4, wherein it is I.

[0135] Embodiment E8.R 5 The method of any one of Embodiments E1-E7, wherein it is H.

[0136] Embodiment E9.R 5 The method of any one of Embodiments E1-E7, wherein it is F.

[0137] Embodiment E10.R 5 The method of any one of Embodiments E1-E7, wherein it is Cl.

[0138] Embodiment E11.R 5 The method of any one of Embodiments E1-E7, wherein it is CH3.

[0139] Embodiment E12.R 6 The method of any one of Embodiments E1-E11, wherein it is H.

[0140] Embodiment E13.R 6The method is one of embodiments E1 to E11, wherein is Cl.

[0141] Embodiment E14. Compounds of formula IB are compound numbers 20, 21, 22, 23, 24, 25, 26, 27, 28, 65, 66, 67, 68, 69, 70, 71 and 72 (i.e.) As listed in Table EE, R 1 is CH3; R 2 is Cl, Br, or I; R 3 is OR 4 And; R 4 H;R 5 is H, F, Cl or CH3; and R 6 The method of Embodiment E1, selected from the group consisting of compounds of formula I, wherein is H or Cl.

[0142] [Table 7]

[0143] Embodiment E15. The reaction is carried out in a suitable solvent, according to any one of Embodiments E1 to E13.

[0144] Embodiment E16. The method of Embodiment E14, wherein the reaction is carried out in a liquid demethylating agent in the absence of further solvent.

[0145] Embodiment E17. Any one of Embodiments E2 to E15, wherein the reaction is carried out at a temperature higher than 80°C.

[0146] Embodiment E18. Any one of Embodiments E1 to E16, wherein the demethylating agent is morpholine.

[0147] Embodiment E18. Any one of Embodiments E1 to E16, wherein the demethylating agent is other than morpholine.

[0148] F. Method for producing compounds of formula IE Embodiment F1. A method for producing a compound of formula IE as described in the abstract of the invention.

[0149] Embodiment F2.R 1 The method of Embodiment F1, wherein it is C1-C4 alkyl.

[0150] Embodiment F3.R 1 The method of Embodiment F1, wherein it is C3-C6 cycloalkyl.

[0151] Embodiment F4.R 1 The method of Embodiments F1-F2, wherein it is CH3.

[0152] Embodiment F5.R 5 The method of any one of Embodiments F1-F4, wherein it is H.

[0153] Embodiment F6.R 5 The method of any one of Embodiments F1-F4, wherein it is F.

[0154] Embodiment F7.R 5 The method of any one of Embodiments F1-F4, wherein it is Cl.

[0155] Embodiment F8.R 5 The method of any one of Embodiments F1-F4, wherein it is CH3.

[0156] Embodiment F9.R 6 The method of any one of Embodiments F1-F8, wherein it is H.

[0157] Embodiment F10.R 6 The method of any one of Embodiments F1-F8, wherein it is Cl.

[0158] Embodiment F11. The compound of Formula I-E is compounds No. 5, 6, 7 and 8 (i.e., as listed in Table FF, wherein R 1 is CH3; R 2 is Cl; R 3 is Cl; R 4 is absent (i.e., --); R 5 is H, F, Cl or CH3; and R6 The method of Embodiment F1, selected from the group consisting of compounds of formula I, wherein is H or Cl.

[0159] [Table 8]

[0160] Embodiment F12. The reaction is carried out in a suitable solvent, according to any one of Embodiments F1 to F11.

[0161] Embodiment F13. The method of Embodiment F12, wherein the suitable solvent is toluene.

[0162] Alternative methods for producing compounds of formula G. IE Embodiment G1. A method for producing a compound of formula IE as described in the abstract of the invention.

[0163] Embodiment G2.R 1 The method of Embodiment G1, wherein is a C1-C4 alkyl group.

[0164] Embodiment G3.R 1 The method is one of embodiments G1 to G2, wherein CH3 is present.

[0165] Embodiment G4.R 5 F is one of the methods of embodiments G1 to G3.

[0166] Embodiment G5.R 5 The method is one of embodiments G1 to G3, wherein is Cl.

[0167] Embodiment G6.R 5 The method is one of embodiments G1 to G3, wherein CH3 is present.

[0168] Embodiment G7.R 5 H is one of the embodiments G1 to G3.

[0169] Embodiment G8.R 6H is one of the embodiments G1 to G7.

[0170] Embodiment G9.R 6 The method is one of embodiments G1 to G7, wherein is Cl.

[0171] Embodiment G13. Compounds of formula IE are compound numbers 5, 6, 7 and 8 (i.e., as listed in Table FF, where R in the formula). 1 is CH3; R 2 is Cl; R 3 is OR 4 And; R 4 H is R 5 is H, F, Cl or CH3; and R 6 The method of Embodiment G1, selected from the group consisting of compounds of formula I, where is H or Cl.

[0172] Embodiment G14. A method according to any one of Embodiments G1 to G13, wherein the compound of formula II or III is as described in the abstract of the invention.

[0173] Embodiment G15.R 5 The method of embodiment G14, where is F.

[0174] Embodiment G16.R 5 The method of embodiment G14, wherein is Cl.

[0175] Embodiment G17.R 5 The method of embodiment G14, where CH3 is used.

[0176] Embodiment G18.R 5 The method of embodiment G14, where H is.

[0177] Embodiment G19.R 6 H is one of the methods of embodiments G14 to G18.

[0178] Embodiment G20.R 6 The method is one of embodiments G14 to G18, wherein is Cl.

[0179] Embodiment G21. Any one of Embodiments G1 to G20, as defined in the gist of the invention, for a compound of formula 7.

[0180] Embodiment G22.R 1 The method of embodiment G20, wherein is a C1-C4 alkyl group.

[0181] Embodiment G23.R 1 The method of Embodiment G20, wherein is a C3-C6 cycloalkyl.

[0182] Embodiment G24.R 1 The method of embodiment G22, where is CH3.

[0183] Embodiment G25. Any one of Embodiments G1 to G24, further comprising isolating a compound of formula IE.

[0184] Embodiment G26. The reaction of the compound of formula II with magnesium is carried out in a suitable solvent, in any one of the methods of Embodiments G1 to G25.

[0185] Embodiment G27. The reaction of the compound of formula II with magnesium is carried out in tetrahydrofuran, as in Embodiment G26.

[0186] Embodiment G28. The reaction of the compound of formula II with magnesium is carried out at a temperature higher than 80°C, using any one of the methods of Embodiments G1 to G27.

[0187] Embodiment G29. The reaction is carried out at a temperature of 0°C or below, using any one of the methods of Embodiments G1 to G28.

[0188] The present invention also relates to a method for controlling undesirable vegetation, comprising applying an effective amount of the compound of the present invention (for example, as a composition described herein) to the site of vegetation. Embodiments relating to the method of use particularly include the compounds of the embodiments described above. The compounds of the present invention are particularly useful for the selective control of weeds in crops such as wheat, barley, maize, soybeans, sunflowers, cotton, rapeseed, and rice, as well as in specialty crops such as sugarcane, citrus fruits, fruits, and nuts.

[0189] The herbicide composition of the present invention, which includes the compounds of the above embodiments, is also noteworthy as an embodiment.

[0190] The present invention also relates to (a) compounds selected from Formula I, its N-oxide, and salts, and (b) (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimetic compounds, (b5) 5-enoylpyruvirshikimic acid-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthase (GS) inhibitors, (b9) very long-chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) (b16) Herbicides comprising a 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor, (b13) homogentisic acid soranesyltransferase (HST) inhibitor, (b14) Cellulose biosynthesis inhibitor, (b15) Mitotic disruptors, organoarsenic agents, ashram, bromobutide, simmethylline, cumilon, dazomet, difenzoquat, dimuron, etobenzanide, flurenol, hosamine, hosamine-ammonium, hydantocidin, metam, methyl dimuron, oleic acid, oxadiclomefone, pelargonic acid and pyributicarb, as well as (b16) Herbicide phytotoxicity reducers; and herbicide mixtures comprising at least one further active ingredient selected from salts of compounds (b1) to (b16).

[0191] "Photosystem II inhibitors" (b1) are Q B - Binds to the D-1 protein in the binding niche, and as a result Q in the chloroplast thylakoid membrane. A From Q B It is a chemical compound that blocks electron transport to photosystem II. Electrons whose passage through photosystem II is blocked are transferred through a series of reactions to form toxic compounds, which disrupt the cell membrane and lead to chloroplast swelling, membrane leakage, and ultimately cell destruction. BThe binding niche has three distinct binding sites: binding site A binds to triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil; binding site B binds to phenylureas such as diurone; and binding site C binds to benzothiadiazoles such as bentazone, nitriles such as bromoxynil, and phenylpyridazines such as pyridate. Examples of photosystem II inhibitors include ametrine, amicarbazone, atrazine, bentazone, bromacil, bromophenoxime, bromoxynil, chlorbromulone, chloridazone, chlorotolurone, chloroxurone, cumilone, cyanazine, dimuron, desmedifam, desmethrin, dimeflon, dimethametrin, diurone, ethidimulone, fenulon, fluomethron, hexazinone, ioxynil, and isoproturone. Examples include isouron, renacil, linuron, metamitron, metabenzthiazulon, metobromulone, metoxlon, metrivudine, monolinuron, nevron, pentanochlor, fenmedifam, prometon, prometrin, propanil, propazine, pyridafor, pyridate, sidurone, simazine, simetrin, tebuthiurone, terbasil, terbumeton, terbutyrazine, terbutrin, and trietadine.

[0192] "AHAS inhibitors" (b2) are acetolactate synthase (ALS), also known as acetolactate synthase. It is a chemical compound that inhibits tohydroxy acid synthase (AHAS), and therefore kills plants by inhibiting the production of branched-chain aliphatic amino acids such as valine, leucine, and isoleucine, which are necessary for protein synthesis and cell proliferation.Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, bispiribac-sodium, chloransulam-methyl, chlorimulon-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, etamethulfuron-methyl, ethoxysulfuron, flurazasulfuron, florasulam, flucarbazone-sodium, flumethoslam, flupyrsulfuron-methyl, and flupyrsulfuron-na Thorium, horamsulfuron, halosulfuron-methyl, imazametabenz-methyl, imazamox, imazapick, imazapyr, imazakine, imazetapir, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazine-2-yl)amino]carbonyl]benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-Chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), Methoslam, Methosulfuron-methyl, Nicosulfuron, Oxasulfuron, Penoxuslam, Primisulfuron-methyl, Propoxycarbazone-sodium, Propyrisulfuron Examples include (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrifthalide, pyriminovac-methyl, pyrithiovac-sodium, limsulfuron, sulfomethane-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazine-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron, trivenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl, and tritosulfuron.

[0193] "ACCase inhibitors" (b3) are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which catalyzes the initial stages of 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 subsequent loss of lipid production lead to a loss of cell membrane integrity, particularly in areas of active growth such as meristems. Ultimately, shoot and rhizome growth stops, and shoot meristems and rhizome buds begin to wither. Examples of ACCase inhibitors include alloxidim, butroxidim, cretodym, clodinahop, cycloxidim, cyhalofop, diclohop, phenoxaprop, fluazihop, haloxyhop, pinoxadene, propoxoxidim, propaxifop, quizalohop, cethoxidim, tepraloxidim, and tralcoxidim, which include fragmented forms such as phenoxaprop-P, fluazihop-P, haloxyhop-P, and quizalohop-P, as well as ester forms such as clodinahop-propargyl, cyhalofop-butyl, diclohop-methyl, and phenoxaprop-P-ethyl.

[0194] Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimics" (b4) are chemical compounds that mimic the plant growth hormone auxin and therefore cause uncontrolled and disordered growth that leads to plant death in susceptible species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters, as well as its sodium and potassium salts, aminopyralide, benazoline-ethyl, chloramben, crasiphos, clomeprop, clopyralide, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, and harauxifen (4-amino-3-c Examples include lol-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), harauxifen-methyl (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate methyl), MCPA, MCPB, mecoprop, picrolam, quinchlorac, kinmelac, 2,3,6-TBA, triclopyr, and 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate methyl.

[0195] "EPSP synthase inhibitors" (b5) are chemical compounds that inhibit 5-enoylpyruvicishikimic acid-3-phosphate synthase, an enzyme involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant leaves and travel through the phloem to the growing point. Glyphosate is a relatively non-selective post-emergence herbicide belonging to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium), and trimethium (or referred to as sulfosate).

[0196] "Photosystem I electron diverters" (b6) are chemical compounds that accept electrons from Photosystem I and, after several cycles, generate hydroxyl radicals. These radicals are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts cell membrane integrity, resulting in the "leakage" of cells and organelles, rapid wilting and drying of leaves, and ultimately plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

[0197] "PPO inhibitors" (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, which rapidly leads to the formation of highly reactive compounds in plants that rupture cell membranes and cause leakage of cell sap. Examples of PPO inhibitors include asifluorphen-sodium, azaphenidine, benzfenzizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, clomethoxyfen, synidone-ethyl, fluazolate, flufenpyr-ethyl, flumimicrolac-pentyl, flumioxazine, fluoroglycofen-ethyl, fluthiaset-methyl, homesafen, halosaphen, lactofen, oxaziargyl, oxadiazone, oxyflofen, pentoxazone, profluazole, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, tidiadimine, and trifludimoxazine Examples include (dihydro-1,5-dimethyl-6-thioxo-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyne-1-yl)-2H-1,4-benzoxazine-6-yl]-1,3,5-triazine-2,4(1H,3H)-dione) and thiafenacil (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).

[0198] "GS inhibitors" (b8) are chemical compounds that inhibit the activity of glutamine synthase, which plants use to convert ammonia into glutamine. As a result, ammonia accumulates and glutamine levels decrease. Plant damage is likely due to a combination of ammonia toxicity and a deficiency of amino acids required for other metabolic processes. Examples of GS inhibitors include glufosinate and glufosinate-ammonium and other phosphinothricin derivatives, as well as its esters and salts such as glufosinate-P ((2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.

[0199] "VLCFA elongase inhibitors" (b9) are herbicides with a wide variety of chemical structures that inhibit elongase. Elongase is involved in the biosynthesis of VLCFAs in chloroplasts. Alternatively, it is one of the enzymes located near chloroplasts. In plants, very long-chain fatty acids are the main components of hydrophobic polymers that prevent drying on the leaf surface and provide stability to pollen grains. Examples of such herbicides include acetochlor, alachlor, anirophos, butachlor, cafenstrole, dimetachlor, dimethenamide, diphenamide, and phenoxasulfone. Examples include (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanophan, mefenacet, metazachlor, metrachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), petoxamide, piperofos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and tenylchlor, which include divided forms such as S-metrachlor and chloroacetamide and oxyacetamide.

[0200] Auxin transport inhibitors (b10) are chemical substances that inhibit auxin transport in plants, for example, by binding to auxin-transporter proteins. Examples of auxin transport inhibitors include diflufenzopyr and naptalam (also known as N-(1-naphthyl)-phthalamidic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).

[0201] "PDS inhibitors" (b11) are chemical compounds that inhibit the carotenoid biosynthesis pathway at the phytoene desaturation stage. Examples of PDS inhibitors include beflubutamide, diflufenican, flulidone, flurochloridone, flurutamon, norflurzon, and picolinafene.

[0202] HPPD inhibitors (b12) are chemical substances that inhibit the biosynthesis of 4-hydroxyphenylpyruvate dioxygenase. Examples of HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]octa-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlortol, isoxaflutol, mesotrione, pyrasulfol, pyrazolinate, pyrazoxifen, sulcotrione, tefuryltrione, tembotrione, and tolpyrate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazole-5-yl]oxy]ethyl methyl Carbonate), topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 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)- Examples include dione, 5-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazole-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide, and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazole-5-yl)-4-(trifluoromethyl)benzamide.

[0203] "HST inhibitors" (b13) disrupt the plant's ability to convert homogentisic acid to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include cyclopyrimorate (4-morpholinecarboxylic acid 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl), haloxydine, pyriclor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazine-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0204] HST inhibitors also include compounds of formulas A and B. [ka] In the formula, R d1 is H, Cl or CF3; R d2 is H, Cl, or Br; R d3 is H or Cl; R d4 is H, Cl or CF3; R d5 is CH3, CH2CH3 or CH2CHF2; and R d6 is OH, or -OC(=O)-i-Pr; and R e1 R is H, F, Cl, CH3 or CH2CH3; e2 is H or CF3; R e3 is H, CH3, or CH2CH3; R e4 is H, F, or Br; R e5 is Cl, CH3, CF3, OCF3 or CH2CH3; R e6 R is H, CH3, CH2CHF2 or C≡CH; e7 OH, -OC(=O)Et, -OC(=O)-i-Pr or -OC(=O)-t-Bu; and A e8 It is N or CH.

[0205] "Cellulose biosynthesis inhibitors" (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied to young or rapidly growing plants before or early after emergence. Examples of cellulose biosynthesis inhibitors include chlorthiamide, diclobenyl, flupoxam, and indadiphram (N 2 Examples include -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben, and triaziphram.

[0206] "Other herbicides" (b15) include herbicides that act by various different modes of action, such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organoarsenic agents (e.g., DSMA and MSMA), 7,8-dihydropteroic acid synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell wall biosynthesis inhibitors. Other herbicides include herbicides that have an unknown mode of action, or that do not fall into any of the specific categories listed in (b1) to (b14), or that act by a combination of the modes of action listed above. Examples of other herbicides include acronifen, ashram, amitorol, bromobutide, simmethyline, cromazon, cumilon, dymron, diphenzocoat, etobenzanide, fluomethron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-(2 Examples include ,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyl dimuron, oleic acid, oxadiclomefone, pelargonic acid, pyributicarb, and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole. "Other herbicides" (b15) include formula (b15A)

[0207] [ka] [In the formula, R 12 is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl; R 13 is H, C1-C6 alkyl, or C1-C6 alkoxy; Q 1 This is a optionally substituted ring system selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, where, if substituted, the ring system has 1 to 3 R 14 Replaced by; Q 2 This is a optionally substituted ring system selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, where, if substituted, the ring system has 1 to 3 R 15 Replaced by; Each R 14 These are independently halogens, C1-C6 alkyls, C1-C6 haloalkyls, C1-C6 alkoxys, C1-C6 haloalkoxys, C3-C8 cycloalkyls, cyanos, C1-C6 alkylthios, C1-C6 alkylsulfinyls, C1-C6 alkylsulfonyls, SF5, and NHR. 17 ; or 1 to 3 R 16 It is a phenyl compound that may be substituted in some cases; or 1 to 3 R 16 It is a pyrazolyl that may be substituted in some cases; Each R 15 These are independently halogens, C1-C6 alkyls, C1-C6 haloalkyls, C1-C6 alkoxys, C1-C6 haloalkoxys, cyanos, nitros, C1-C6 alkylthios, C1-C6 alkylsulfinyls, and C1-C6 alkylsulfonyls; Each R 16 These are independently halogens, C1-C6 alkyls, or C1-C6 haloalkyls; R 17 [It is a C1-C4 alkoxycarbonyl] It also includes the following compounds.

[0208] In one embodiment, “other herbicides” (b15) also includes compounds of formula (b15A), preferably R 12 is H or C1-C6 alkyl; uFurther R 12 is H or methyl. Preferably, R 13 is H. Preferably Q. 1 The ring is either a phenyl ring or a pyridinyl ring, and each ring has 1 to 3 R rings. 14 Replaced by; more preferably, Q 1 is 1-2 R 14 A phenyl ring substituted with Q. Preferably, Q 2 1 to 3 R 15 A phenyl ring substituted with; more preferably Q 2 is 1-2 R 15 A phenyl ring substituted with R. Preferably each R 14 R is independently a halogen, a C1-C4 alkyl, a C1-C3 haloalkyl, a C1-C3 alkoxy, or a C1-C3 haloalkoxy; more preferably, each R 14 These are independently chloro, fluoro, bromo, and C1-C2 haloalkyl compounds. , C1-C2 haloalkoxy or C1-C2 alkoxy. Preferably, each R 15 R is independently a halogen, a C1-C4 alkyl, or a C1-C3 haloalkoxy; more preferably, each R 15 These are independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Particularly preferred as "other herbicides" (b15) are any one of the following (b15A-1) to (b15A-15):

[0209] [Table 9] [Table 10] [Table 11]

[0210] "Other herbicides" (b15) include formula (b15B) [ka] [In the formula, R 18 is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl; Each R 19 These are independently halogens, C1-C6 haloalkyls, or C1-C6 haloalkoxys; p is an integer, either 0, 1, 2, or 3; Each R 20 These are independently halogens, C1-C6 haloalkyls, or C1-C6 haloalcohydrates. It is C; and q is an integer, either 0, 1, 2, or 3. It also includes the following compounds.

[0211] In one embodiment, "other herbicides" (b15) also includes a compound of formula (b15B), preferably R 18 is H, methyl, ethyl, or propyl; more preferably R 18 is H or methyl; most preferably R 18 is H. Preferably each R 19 R is independently chloro, fluoro, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably each R 19 R is independently chloro, fluoro, C1-fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1-fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably each R 20 R is independently chloro, fluoro, C1-haloalkyl, or C1-haloalkoxy; more preferably each R 20These are independently chloro, fluoro, C1-fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1-fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Particularly preferred "other herbicides" (b15) include any of the following (b15B-1) to (b15B-19):

[0212] [Table 12] [Table 13] [Table 14] [Table 15]

[0213] "Herbicide phytotoxicity reducers" (b16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of herbicides on specific crops. These compounds protect crops from herbicide damage but typically do not interfere with the herbicide's ability to control undesirable vegetation. Examples of herbicide phytotoxicity reducers include, but are not limited to, benoxacol, croquintoset-mexyl, cumylon, siomethrinil, cyprosulfamide, dimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenchlorim, flurazole, fluxofenim, flirazole, isoxadifen-ethyl, mefenpyr-diethyl, and Examples include mephenate, methoxyphenone, naphthalic anhydride, oxavethrinyl, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloro-methyl)-sulfonyl]-benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide.

[0214] "Other herbicides" (b15) are given by formula (b15C), [ka] [In the formula, R 1 is Cl, Br or CN; and R 2Another embodiment also includes compounds of C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3 or 3-CHF2-isoxazol-5-yl. Specific examples include (b15C1) 5-chloro-2-[3-chloro-2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]pyrimidine and (b15C2) 1-[2-chloro-6-[(5-chloro-2-pyrimidine] Examples include compounds of formula (b15C) selected from dinyl)oxy]phenyl]-4,4,4-trifluoro-1-butanone.

[0215] For better control of undesirable vegetation (e.g., lower usage rates from higher efficacy than additive effects, broader weed control, or enhanced crop safety) or for the prevention of weed resistant growth, atrazine, azimusulfuron, beflubutamide, S-beflubutamide, benzoisothiazolinone, carfentrazon-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, chromazon, clopyralid Potassium, Chloranthurum-methyl, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethylisoxazolidinone, 2-[(2,5-dichlorophenyl)methyl]-4,4-dimethylisoxazolidinone, etamethosulfuron-methyl, flumethurum, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)- A mixture of the compound of the present invention with a herbicide selected from the group consisting of dione, flupyrsulfuron-methyl, fluthiaset-methyl, homesaphen, imazetapyr, lenacil, mesotrione, metrivudine, metosulfuron-methyl, petoxamide, picloram, pyroxasulfone, quinchlorac, limsulfuron, S-esmethrachlor, sulfenthrazone, thifensulfuron-methyl, triflusulfuron-methyl, and trivenuron-methyl is preferred.

[0216] Formula I (wherein, R 5Compounds of formula I (where is H, F, Cl or CH3) can be prepared by acidification of the corresponding morpholine salt of formula IM, as shown in Scheme 1. The reaction in Scheme 1 typically involves adding the compound of formula IM to an aqueous acidic solution such as hydrochloric acid or sulfuric acid, either as a solid, slurry, or solution. The solvent used to make the compound of formula IM into a slurry is typically a water-miscible organic solvent such as methanol, ethanol, acetonitrile, tetrahydrofuran, or N,N-dimethylformamide. The free acid form of formula I is typically insoluble in aqueous acidic solutions and can be isolated by filtration. Alternatively, the free acid form of the compound of formula I can be isolated by partitioning the morpholine salt of the compound of formula I between an aqueous acidic solution and a suitable immiscible solvent such as dichloromethane, chloroform, or ethyl acetate.

[0217] [ka]

[0218] As shown in schemes 2 and 3, the compound of formula IM is the compound of formula 2 (wherein R 5 It can be produced in two steps, starting with (where is H, F, Cl or CH3). In Scheme 2, the compound of Formula 2 is reacted with sodium methoxide or potassium methoxide in a solvent such as dioxane, tetrahydrofuran, toluene, N,N-dimethylformamide, or methanol at a temperature ranging from 0°C to the reflux temperature of the solvent. 1-2 moles A small amount of sodium methoxide or potassium methoxide is typically used. The product of Scheme 2 is the compound of Formulas 3 and 4 (wherein R is used in the formulas). 5 It may contain a mixture of (where is H, F, Cl or CH3). This mixture can be used without purification as shown in Scheme 3.

[0219] [ka]

[0220] In Scheme 3, when the mixtures of formulas 3 and 4 are heated in morpholine at reflux temperature, the compound of formula 3 immediately forms the compound of formula IM, but the compound of formula 4 does not react with morpholine. Post-reaction treatment may involve removing excess morpholine by distillation or under vacuum, followed by dilution with an organic solvent such as diethyl ether or ethyl acetate. Compound formula IM is typically insoluble in the solvent and can be isolated by filtration, while unreacted compound 4 remains in solution and can be removed by filtration.

[0221] [ka]

[0222] As shown in Scheme 4, the compound of formula 4 can be formed by heating the compound of formula 2 in phosphorus oxychloride containing pyridine. The conditions for the reaction in Scheme 4 can be found in Polish Journal of Chemistry, 1990, Vol. 64, p. 741. As shown in Schemes 4 and 2, the compound of formula 4 can be converted to the compound of formula 3 by chlorination followed by methoxylation.

[0223] [ka]

[0224] Compound of formula 2 (wherein R 5 The compound (where R is H, F, Cl or CH3) can be prepared by the reaction of the compound of formula 5 with the Grignard reagent of formula 6, as shown in scheme 5. The reaction in scheme 5 is typically carried out in a solvent such as tetrahydrofuran or diethyl ether at temperatures ranging from -78°C to the reflux temperature of the solvent, most typically at -20°C to 25°C. 5 The Grignard reagent in equation 6, where =H, is commercially available, but in the equation R 5The Grignard reagent of formula 6, which is =CH3, can be prepared from 1-bromo-2,7-dimethylnaphthalene using a procedure known to those skilled in the art (see J.Am.Chem.Soc.2008, Vol. 130, p. 6848).

[0225] [ka]

[0226] Compound of formula 2 (wherein R 5 The compound (where is H, F, Cl, or CH3) can also be prepared by the reaction of the compound of formula 7 with the Grignard reagent of formula 6, as shown in scheme 6. The reaction in scheme 6 is typically carried out in a solvent such as tetrahydrofuran or diethyl ether at a temperature ranging from -78°C to the reflux temperature of the solvent, most typically at -20°C to 25°C.

[0227] [ka]

[0228] This disclosure also relates to a method for controlling undesirable vegetation, comprising applying one or more compounds of formula I (for example, as compositions described herein) to the area of ​​undesirable vegetation in a herbicidal amount. Compounds of formula I are particularly useful for the selective control of weeds in crops, which include, but are not limited to, specialty crops such as wheat, barley, maize, soybeans, sunflowers, cotton, rapeseed, rice, and sugarcane, citrus fruits, fruits, and nuts.

[0229] Herbicide compositions of the present disclosure containing the compound of Formula I should also be noted as embodiments.

[0230] The disclosure also includes herbicide mixtures comprising (a) a compound selected from formula I, its N-oxide, and salts, and (b) at least one further active ingredient.

[0231] Without further detail, those skilled in the art can utilize the present disclosure to the fullest extent using the foregoing description. The following non-limiting examples are for illustrative purposes of the present disclosure. The steps in the following examples illustrate the procedure for each step in the overall synthetic transformation, and the starting materials for each step may not necessarily have been prepared by a specific preliminary run described in other examples or steps. Percentages are by mass unless otherwise indicated for chromatographic solvent mixtures. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1 The 1H NMR spectrum is reported in ppm as the low-field shift from tetramethylsilane in CDCl3 unless otherwise indicated; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means double doublet, "dt" means double triplet, and "br s" means broad singlet. The mass spectrum (MS) is reported as the molecular weight of the parent ion (M+1) with the highest isotopic abundance formed by the addition of H+ (molecular weight 1) to the molecule, or (M-1) formed by the loss of H+ (molecular weight 1) from the molecule, and these are observed using either atmospheric pressure chemical ionization (AP+) by liquid chromatography (LCMS) connected to a mass spectrometer, in which case "amu" represents the unified atomic mass unit. [Examples]

[0232] Synthesis Example 1 Preparation of 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone Step A: 5-Chloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2 Preparation of H)-pyridazinone (compound number 1) Under a nitrogen atmosphere, magnesium (5.4 g, 0.22 mol) was introduced into a clean, dry flask. Two to three iodine crystals were added to activate the magnesium. A solution of 1-bromo-2-methylnaphthalene (31.0 mL, 0.20 mol) in tetrahydrofuran (200 mL) was added dropwise to the magnesium. After adding 25 mL of the solution, the addition was stopped and the mixture was allowed to gradually generate heat. When a small amount of bubbles were observed, the addition was continued at a rate that maintained a controlled, active reaction. Towards the end of the addition, the reaction mixture was externally heated to maintain a gentle reflux. The reaction mixture was heated for 1 hour after the addition was complete. Grignard formation was monitored by HPLC of aliquots quenched with 1N hydrochloric acid aqueous solution. The reaction mixture was cooled to -55°C. While maintaining a reaction temperature below -40°C, a solution of 5-chloro-4-methoxy-2-methyl-3(2H)-pyridazinone (34.9 g, 0.20 mol) in tetrahydrofuran (400 mL) was slowly added. After the addition was complete, the cooling bath was removed and the reaction mixture was allowed to rise to room temperature. The reaction mixture was stirred for a further 1 hour and monitored for completion. Once complete, the reaction mixture was cooled to 0°C, quenched with 1N hydrochloric acid aqueous solution (500 mL), and stirred at ambient temperature for 18 hours. The reaction mixture was extracted twice with dichloromethane. The extracts were combined, dried over MgSO4, filtered, and concentrated. The concentrate was triturated with hexane for 18 hours. The resulting mixture was cooled in an ice bath, filtered, washed with cold hexane, and vacuum-dried to obtain a beige-colored solid (50.8 g, yield 88%). 1 H NMR δ 7.90(s, 1H), 7.85(m, 2H), 7.40(m, 3H), 7.30(m, 1H), 3.87(s, 3H), 2.29(s, 3H).

[0233] Step B: Preparation of 5-Methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 29) Sodium methoxide (25% by mass in methanol, 61 mL, 0.27 mol) was added to 5-chloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (i.e., the product obtained in step A, 50.8 g, 0.18 mol) in methanol (180 mL). The reaction mixture was heated to the reflux temperature of the solvent. After 18 hours 1 The reaction was monitored by 1H NMR, which indicated that the starting material had been consumed. The reaction mixture was cooled to 0°C, and then water (500 mL) was added. The resulting mixture was filtered and then vacuum-dried to obtain a beige-colored solid (40.9 g, 81% yield). 1 H NMR δ 7.90(s, 1H), 7.80(m, 2H), 7.40(m, 4H), 3.85(s, 3H), 3.66(s, 3H), 2.28(s, 3H).

[0234] Step C: Preparation of 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 33) Step C-1: A solution of zinc chloride (2.9 M, 28 mL, 0.10 mol in 2-methyltetrahydrofuran) in a dry flask was cooled to 5°C under a nitrogen atmosphere. The 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (1.0 M, 100 mL, 0.10 mol in tetrahydrofuran / toluene) was slowly added at a rate that limited the exothermic temperature to 15°C. The mixture was then heated to room temperature to obtain a clear 0.39 M solution of bis(2,2,6,6-tetramethylpiperidine)zinc, magnesium chloride, and lithium chloride complex for use in the next step.

[0235] Step C-2: The stirred solution of 5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (i.e., the product obtained in Step B above, 14 g, 50 mmol) in dichloromethane (250 mL) was cooled to -20°C. While maintaining the reaction temperature below -15°C, the bis(2,2,6,6-tetramethylpiperidine)zinc, magnesium chloride, lithium chloride complex (0.39 M, 128 mL, 50 mmol) was slowly added, and the mixture was cooled and stirred for 10 minutes. A thin layer of aliquots quenched with I2 was then added. TLC (i.e., electrolytic cell chromatography) showed that zincation was complete. Freshly powdered trichloroisocyanuric acid (17.4 g, 74.9 mmol) was added all at once to the stirred reaction mixture at -20°C. After a gentle exothermic reaction to 0°C, the reaction mixture was cooled back to -20°C and stirred for 30 minutes. TLC analysis showed that the reaction was complete. 1N hydrochloric acid aqueous solution (300 mL) was added to the cold reaction mixture and stirred at room temperature for 20 minutes. This mixture was then converted to Celite (R) The material was passed through a short pad of diatomaceous earth filter aid and filtered with dichloromethane. The filtrate was extracted twice with dichloromethane. The extracts were combined, dried over MgSO4, filtered, and Celite (R) The solution was concentrated on a diatomaceous earth filter aid and purified by elution with 20% ethyl acetate in hexane using medium-pressure liquid chromatography ("MPLC") to obtain the desired product as a light beige solid (14.1 g, yield 89%). 1 H NMR δ 7.85 (d, 2H), 7.45 (m, 4H), 3.79 (s, 3H), 3.25 (s, 3H), 2.33 (s, 3H).

[0236] Step D: Preparation of 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone A mixture of 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (14.1 g, 44.8 mmol) in morpholine (45 mL) was heated under reflux for 1 hour, followed by cooling to room temperature. This mixture was diluted with hexane (45 mL), stirred for 18 hours, and then filtered. The filtered solid was dried over a filtration funnel under a nitrogen stream. The solid was transferred to a flask using 1N hydrochloric acid aqueous solution (200 mL). This mixture was stirred for 3 hours. The solid was filtered and then vacuum-dried to obtain a pale beige solid (10.4 g, yield 77%). 1 H NMR (DMSO-d6) δ 10.89-11.27 (b, 1H), 7.95 (m, 2H), 7.40 (m, 4H), 3.64 (s, 3H), 2.20 (s, 3H).

[0237] Synthesis Example 2 Alternative manufacturing of 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone Step A: Preparation of 5-chloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 1) To a solution of 1-bromo-2-methylnaphthalene (100 g, 452 mmol) in tetrahydrofuran (400 mL), magnesium shavings (21.7 g, 904 mmol) and iodine (20 mg) were added. The reaction mixture was heated at 70°C for 2 hours, during which time the color changed to dark green and vigorous reflux was observed. 5-chloro-4-methoxy-2-methyl-3(2H)-pyridazinone (65 g, 373 mmol) in tetrahydrofuran (400 mL) was placed in a separate round-bottom flask, and the above reaction mixture was added at -100°C. The reaction mixture was then stirred at ambient temperature for 4 hours. TLC analysis with 20% ethyl acetate in petroleum ether indicated completion of the reaction. The reaction mixture was then quenched with saturated NH4Cl solution and extracted twice with ethyl acetate. The combined organic layer was washed with water and brine and dried over Na2SO4. The solvent was evaporated to obtain the crude product. The crude compound was washed with petroleum ether to obtain 84 g (65.3% yield) of the title compound as a grayish-white solid.

[0238] Step B: Preparation of 5-Methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 29) To a solution of 5-chloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (i.e., the compound obtained in step A, 500 g, 1.76 mol) in dioxane (5.0 L), 30% sodium methoxide in methanol (949 mL, 5.26 mol) was added at room temperature, and the reaction mixture was stirred at 110°C for 2 hours. 50% acetate TLC analysis with chill / petroleum ether indicated completion of the reaction. The reaction mixture was poured into ice water, quenched with saturated NH4Cl solution, and extracted twice with dichloromethane. The combined organic layer was washed with water, brine, and dried over Na2SO4. The solvent was evaporated to obtain the crude product, which was washed with petroleum ether to obtain 449 g (91.2% yield) of the title compound as a solid.

[0239] Step C: Preparation of 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 33) ZnCl2 (194 g, 1.42 mol) was placed in a round-bottom flask, and 1 M 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (2378 mL, 2.37 mol) in tetrahydrofuran was added, and the reaction mixture was stirred at ambient temperature for 2 hours. 5-Methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (i.e., the product obtained in step B, 333 g, 1.18 mol) and 1,3-dichloro-5,5-dimethylhydantoin (281 g, 1.42 mol) were added gradually, and the reaction mixture was stirred at room temperature for 16 hours. TLC analysis with 30% ethyl acetate / petroleum ether indicated completion of the reaction. The reaction mixture was poured into ice water, quenched with saturated sodium bicarbonate solution, and extracted twice with dichloromethane. The combined organic layers were washed with water and brine, and dried over Na2SO4. The solvent was evaporated to obtain the crude product. The crude product was washed with diethyl ether / petroleum ether to obtain 205 g (yield 55%) of the title compound as a white solid.

[0240] Step D: Preparation of 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (i.e., the product obtained in step C, 410 g, 1.30 mol) in morpholine (1.2 L) was stirred at 120°C for 2 hours. TLC analysis with 50% ethyl acetate / petroleum ether indicated completion of the reaction. The reaction mixture was then evaporated, acidified with concentrated hydrochloric acid, and stirred at ambient temperature for 1 hour. The reaction mixture was filtered, washed with excess water, and dried under vacuum to obtain 290 g (yield 74.3%) of the title compound as a grayish-white solid.

[0241] Synthesis Example 3 Preparation of 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound number 20): Process A. Preparation of 5-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone (compound number 4): Magnesium shavings (4.22 g, 173 mmol, partially ground with a mortar and pestle before weighing) were placed in a 1 L three-necked round-bottom flask equipped with a dropping funnel, a large magnetic stirrer, and a reflux condenser. The apparatus was heated with a heat gun while slowly stirring the magnesium under a stream of N2. After cooling, a small amount of iodine crystals (80 mg) was added, and the mixture was heated again briefly (reddish-brown vapor was observed), and then only 5 mL of a solution of 1-bromo-2,7-dimethylnaphthalene (35.2 g, 0.15 mol) and tetrahydrofuran (80 mL) was added. The color of the reaction mixture rapidly began to change from reddish-brown to pale blue while foaming. The solution of 1-bromo-2,7-dimethylnaphthalene and tetrahydrofuran was slowly added at a rate that maintained a gentle reflux (total time approximately 30 minutes). The resulting mixture was diluted with 64 mL of tetrahydrofuran, refluxed for 1 hour, and then cooled to -40°C. Next, a solution of 5-chloro-4-methoxy-2-methyl-3(2H)-pyridazinone (21.7 g, 124 mmol) and tetrahydrofuran (80 mL) was added, and the resulting solution was stirred at ambient temperature for 14 hours. The resulting mixture was cooled with ice / water, and then quenched by adding saturated NH4Cl aqueous solution (100 mL) at <15°C. The resulting mixture was then mixed with ethyl acetate (1. The mixture was partitioned between 2 L of saturated NH4Cl aqueous solution (1 L), the aqueous layer was extracted with ethyl acetate (500 mL), and the combined organic layer was washed with saturated NH4Cl and brine, dried over MgSO4, and concentrated to obtain 38.1 g (85%) of crude 5-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone, which was used in the next step without further purification. The crude product contained a small amount of by-products including 2,7-dimethylnaphthalene. Analytical samples were prepared by MPLC on a silica gel column eluted with 0-50% ethyl acetate in hexane. 1 H NMR (500MHz) δ 7.95(s, 1H), 7.79(d, 1H), 7.74(d, 1H), 7.35(d, 1H), approximately 7.26(dd, 1H), 7.03(br s, 1H), 3.88(s, 3H), 2.42(s, 3H), 2.26(s, 3H).

[0242] Process B. Preparation of 4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (compound number 32): A solution of crude 5-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone from step A (i.e., the product obtained in step A, 38.1 g, 12 8 mmol) and dioxane (890 mL) was treated with NaOMe (25% solution in MeOH, 87 mL, 383 mmol). The resulting dark brown mixture was heated under reflux for 16 hours, cooled, and concentrated to remove most of the dioxane. The resulting residue was partitioned between CH2Cl2 and an excess saturated NH4Cl aqueous solution. The aqueous layer (pH approximately 10) was extracted with CH2Cl2, and the combined organic matter was washed with saturated NH4Cl and brine, dried over MgSO4, and concentrated to obtain 57 g of a brown oily slurry. This slurry was triturated with diethyl ether to produce a beige solid, which was isolated by filtration, washed with some diethyl ether, and dried on frit to obtain 4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone as a beige solid (10.6 g, 28%). 1 ¹H NMR analysis showed the desired product with high purity. The filtrate from the above was concentrated to obtain a dark brown oily residue, which was then triturated with ether and hexane to obtain an additional compound (2.2 g, 6%). 1 H NMR (500MHz) δ 7.92(s, 1H), 7.73(d, 1H), 7.71(d, 1H), 7.32(d, 1H), 7.22(dd, 1H), 7.11(br s, 1H), 3.87(s, 3H), 3.70(s, 3H), 2.41(s, 3H), 2.26(s, 3H).

[0243] Process C. Preparation of 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)5-methoxy-2-methyl-3(2H)-pyridazinone (compound number 36): A solution of 4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step B, 27.2 g, 92 mmol) and CH2Cl2 (646 mL) was cooled to -10°C in an ice / acetone bath. A solution of bis(2,2,6,6-tetra-methylpiperidine)zinc, magnesium chloride, and lithium chloride complex in tetrahydrofuran / 2-methyltetrahydrofuran (approximately 0.40 M solution, 231 mL, approximately 92 mmol) was added at <0°C. The resulting mixture was heated to 18°C ​​using a water bath, stirred for 15 minutes, and then cooled to -15°C. 1,3-dichloro-5,5-dimethylhydantoin (21.8 g, 111 mmol) was added gradually while maintaining the temperature at <-10°C. The resulting mixture was heated to ambient temperature and stirred for 7 hours. The resulting mixture was cooled to -10°C, quenched with a solution of sodium metabisulfite (50 g), and water (250 mL) was added at <0°C. The resulting mixture was heated to ambient temperature over 1 hour while being stirred at high speed. The resulting mixture was diluted with CH2Cl2 (600 mL) and water (300 mL), the aqueous layer was extracted with CH2Cl2 (300 mL), the combined organic matter was washed with saturated ammonium chloride aqueous solution (2 x 500 mL) and brine (300 mL), dried over MgSO4, and concentrated to obtain 50 g of a brown oily substance. The crude product was preparatively divided into MPLC. The solution was purified by elution with 20-100% ethyl acetate in hexane using a 750g column. The desired product, 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone, was eluted first (11.2g, 37%, and 3.3g of the desired product, slightly impure, in the first fraction). Further elution recovered unreacted 4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone (10.2g, 38% recovered). 1 H NMR (500 MHz) δ 7.78 (d, 1H), 7.73 (d, 1H), 7.32 (d, 1H), ca.7.25 (dd, 1H), 7.15 (br s, 1H), 3.80(s, 3H), 3.26(s, 3H), 2.45(s, 3H), 2.30(s, 3H).

[0244] Process D. Preparation of 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound number 20) A suspension of 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step C, 6.9 g, 21 mmol) and morpholine (21 mL) was gently refluxed and heated for 1 hour, cooled to room temperature, and then poured into a mixture of concentrated hydrochloric acid (30 mL) and ice (approximately 200 mL). This mixture was extracted with CH2Cl2 (2 x 200 mL), and the combined organic layer was washed with saturated NH4Cl (2 x 100 mL), dried over MgSO4, and concentrated to obtain 6.0 g (91% yield) of the title compound as a bright yellow solid. mp = 232~234°C. 1 H NMR (500MHz) δ 7.83(d, 1H), 7.75(d, 1H), 7.38(d, 1H), 7.29(dd, 1H), 7.13(br s, 1H), 5.55(v br s, 1H), 3.83(s, 3H), 2.44(s, 3H), 2.28(s, 3H).

[0245] Synthesis Example 4 Alternative manufacturing of 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound number 20): Process A: Production of 2,7-dimethylnaphthalene To a solution of 2,7-dibromonaphthalene (250 g, 0.877 mol) in dioxane (4 L), Pd(dppf)Cl2 and 2M dimethylzinc in toluene (2.19 L, 4.38 mol) were added at room temperature. The reaction mixture was stirred at 100°C for 16 hours. TLC analysis with hexane indicated completion of the reaction. The reaction mixture was diluted with ethyl acetate and poured into ice water. The combined organic layer was washed with water and brine and dried over sodium sulfate. The solvent was evaporated to obtain the crude product, which was charged onto a silica gel column. This column was eluted with petroleum ether to obtain 111 g (81% yield) of the title product as a white solid.

[0246] Step B: Production of 1-bromo-2,7-dimethylnaphthalene 2,7-dimethylnaphthalene (i.e., the product obtained in step A, 282 g, 1.8 mol) was dissolved in CH3CN (2.8 L) and N,N-dimethylformamide (200 mL), to which N-bromosuccinimide (321 g, 1.8 mol) was added, and the reaction mixture was stirred at room temperature for 16 hours. TLC analysis with hexane indicated completion of the reaction. The reaction mixture was poured into ice water and extracted three times with petroleum ether. The combined organic layers were washed with water and brine and dried over Na2SO4. The solvent was evaporated to obtain the crude product, which was purified by elution with petroleum ether by silica gel chromatography to obtain 415 g (yield 97%) of the title product as a pale yellow solid.

[0247] Step C: Preparation of 5-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone (compound number 4) 1-Bromo-2,7-dimethylnaphthalene (i.e., the product obtained in step B, 10 To a solution of 0 g, 0.42 mol (500 mL) of tetrahydrofuran, magnesium shavings (20.42 g, 0.851 mol) and iodine (20 mg) were added. The reaction mixture was superheated at 70°C for 2 hours, during which time the color of the reaction mixture changed to dark green (vigorous reflux was observed). The Grignard reagent prepared above was added to a solution of 5-chloro-4-methoxy-2-methyl-3(2H)-pyridazinone (61.1 g, 0.351 mol) in tetrahydrofuran (500 mL), and the reaction mixture was stirred at room temperature for 4 hours. TLC analysis with 20% ethyl acetate / petroleum ether indicated completion of the reaction. The reaction mixture was quenched with saturated NH4Cl solution and extracted twice with ethyl acetate. The combined organic layer was washed with water and brine and dried over Na2SO4. The solvent was evaporated to obtain the crude product. The crude product was washed with petroleum ether to obtain 82 g (64% yield) of the title compound as a white solid.

[0248] Step D: Preparation of 4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (compound number 32) To a solution of 5-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step C, 365 g, 1.2 mol) in dioxane (3.6 L), 30% NaOMe (661 mL, 3.6 mol) in methanol was added at room temperature, and the reaction mixture was stirred at 110 °C for 2 hours. TLC analysis with 50% ethyl acetate / petroleum ether indicated completion of the reaction. The reaction mixture was poured into ice water, quenched with saturated NH4Cl solution, and extracted twice with dichloromethane. The combined organic layer was washed with water and brine and dried over Na2SO4. The solvent was evaporated to obtain the crude product. The crude product was washed with petroleum ether to obtain 355 g (98% yield) of the pure title product as a grayish-white solid.

[0249] Step E: Preparation of 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (compound number 36) In a round-bottom flask, combine ZnCl2 (65g, 0.47mol) and 1M tetrahydrofuran. 2,2,6,6-tetramethylpiperidinyl MgCl2LiCl (952 mL, 0.952 mol) was added, and the reaction mixture was stirred at room temperature for 2 hours. 4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step D, 140 g, 0.476 mol) and 1,3-dichloro-5,5-dimethylhydantoin (112 g, 0.571 mol) were added gradually, and the reaction mixture was stirred at room temperature for 16 hours. TLC analysis with 30% ethyl acetate / petroleum ether indicated completion of the reaction. The reaction mixture was poured into ice water and quenched with saturated sodium bisulfite solution, and extracted twice with dichloromethane. The combined organic layer was washed with water and brine, and dried over Na2SO4. The solvent was evaporated to obtain the crude product. The crude compound was washed with diethyl ether / petroleum ether to obtain 82 g (52% yield) as a grayish-white solid.

[0250] Step F: 6-Chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-hydroxy-2-methyl-3(2H)-pyridazinone (compound number 20) 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step E, 208 g, 0.634 mol) in morpholine (650 mL) was stirred at 120 °C for 2 hours. TLC analysis with 50% ethyl acetate / petroleum ether indicated completion of the reaction. The reaction mixture was evaporated, acidified with concentrated hydrochloric acid, and stirred at room temperature for 1 hour, during which time a solid precipitated. This solid was filtered, washed with excess water, and dried under vacuum to obtain 195 g (98% yield) of the title compound as a grayish-white solid.

[0251] Synthesis Example 5 Preparation of 5-chloro-6-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone Process A: Production of 6-amino-5-chloro-4-methoxy-2-methyl-3(2H)-pyridazinone A solution of sodium methoxide in methanol (4.8 mL, 4.4 M solution, 21.0 mmol) was added to a suspension of 6-amino-4,5-dichloro-2-methyl-3(2H)-pyridazinone (3.70 g, 19.1 mmol) and dioxane (95 mL, anhydrous) while cooling in an ice bath. The resulting suspension was stirred at ambient temperature for 3 hours, poured into a saturated aqueous solution of ammonium chloride (150 mL), and the resulting mixture was extracted with methylene chloride (150 mL). The aqueous layer was extracted with methylene chloride at least twice. The combined organic extract was dried over anhydrous MgSO4, filtered, and concentrated to obtain 3.45 g of the title compound as a yellow semi-solid. 1 H NMR (500MHz) δ 4.34(brs, 2H), 4.29(s, 3H), 3.60(s, 3H).

[0252] Step B: Preparation of 5,6-dichloro-4-methoxy-2-methyl-3(2H)-pyridazinone To a solution of 6-amino-5-chloro-4-methoxy-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step A, 529 mg, 2.8 mmol), copper(II) chloride (618 mg, 4.6 mmol), and acetonitrile (8 mL, anhydrous), tert-butyl nitrite (0.48 mL, 90% by mass, 3.6 mmol) was added while cooling in an ice bath. The resulting mixture was stirred at ambient temperature for 1 hour, and then partitioned between ethyl acetate and saturated ammonium chloride aqueous solution. The organic layer was washed with saturated ammonium chloride aqueous solution, dried over anhydrous MgSO4, filtered, and concentrated to obtain 0.51 g of the title compound as a yellow semi-solid. 1 H NMR (500MHz) δ 4.33(s, 3H), 3.74(s, 3H).

[0253] Step C: Preparation of 5,6-dichloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 5) 5,6-Dichloro-4-methoxy-2-methyl-3(2H)-pyridazinone (i.e., the product obtained in step B, 0.41 g, 1.9 mmol) was added to 2-methyl-1-naphthalenyl-magnesium bromide (9.0 mL, 0.25 M solution in tetrahydrofuran, 2.3 mmol) at -20°C. The resulting mixture was stirred at ambient temperature for 30 minutes, at which point the reaction mixture was cooled to 5°C and quenched with saturated ammonium chloride aqueous solution (3 mL). The resulting mixture was partitioned between ethyl acetate and saturated ammonium chloride aqueous solution, the resulting organic layer was washed with saturated ammonium chloride aqueous solution, dried over anhydrous MgSO4, filtered, and concentrated to obtain 0.69 g of the title compound in crude form, which was used in subsequent steps without further purification. The analytical sample was prepared by elution with 0% to 100% ethyl acetate in hexane by MPLC on a silica column. 1 H NMR (500MHz) δ 7.87-7.85 (m, 2H), 7.47-7.40 (m, 3H), 7.30-7.27 (m, 1H), 3.86 (s, 3H), 2.29 (s, 3H).

[0254] Process D. Preparation of 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (compound number 33) Solid potassium methoxide (0.29 g, 3.4 mmol) was added at ambient temperature to a solution of 5,6-dichloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone (i.e., the product obtained in step C, crude product 0.69 g, about 1.7 mmol) and toluene (17 mL). The resulting mixture was stirred at ambient temperature for 3 days, cooled in an ice bath, and quenched with saturated ammonium chloride aqueous solution (10 mL). The resulting mixture was partitioned between ethyl acetate and saturated ammonium chloride aqueous solution. The organic layer was then converted to anhydrous MgS The compound was dried over O4, filtered, and concentrated to obtain 0.60 g of the title compound in crude form, which was used in subsequent processes without further purification. 1 ¹H NMR analysis revealed a mixture of the desired product, 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone, the isomer, 5-chloro-6-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone, and unreacted 5,6-dichloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone, in a ratio of 3.0:1.0:2.8. The analytical sample was obtained by MPLC in silica using a gradient of 0% to 100% ethyl acetate in hexane. 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone: 1 ¹H NMR (500 MHz) δ 7.84 (distorted d, 2H), 7.47-7.38 (m, 4H), 3.80 (s, 3H), 3.26 (s, 3H), 2.33 (s, 3H). 5-Chloro-6-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone: 1 H NMR (500MHz) δ 7.86-7.83(m, 2H), 7.45-7.37(m, 3H), 7.33-7.30(m, 1H), 4.01(s, 3H), 3.77(s, 3H), 2.29(s, 3H).

[0255] Synthesis Example 6 Process A. Production of 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone A solution of the crude product (0.60 g) from Synthesis Example 5, Step D, containing morpholine (2 mL) and a mixture of 6-chloro-5-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone, 5-chloro-6-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone, and 5,6-dichloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone, was heated at 110°C for 2 hours. The resulting mixture was concentrated, and the residue was triturated with diethyl ether. The resulting solid was filtered, washed with diethyl ether, and dried on frit to obtain the morpholine salt of 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone. The filtrate contained unreacted 5-chloro-6-methoxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone and 5,6-dichloro-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone. The solid 6-chloro-5-hydroxy-2-methyl-4-(2-methyl-1-naphthalenyl)-3(2H)-pyridazinone morpholine salt was partially dissolved in a minimum amount of tetrahydrofuran, and the resulting mixture was gradually added to 10 mL of 1N hydrochloric acid aqueous solution with stirring. The resulting solid was isolated by filtration, washed with 1N hydrochloric acid aqueous solution, and dried on frit to obtain 200 mg of the title product as a grayish-white solid. 1 H NMR (500MHz) δ 7.92-7.86 (m, 2H), 7.48-7.40 (m, 6H), 3.83 (s, 3H), 2.33 (s, 3H).

[0256] Compounds of formula I are generally used in compositions, i.e., formulations, as herbicidal active ingredients, together with at least one further component selected from the group consisting of surfactants, solid diluents, and liquid diluents. In certain embodiments, the further component may act as a carrier. The components of the formulation or composition are selected to be in harmony with the physical properties of the active ingredient, the method of application, and environmental factors such as soil type, humidity, and temperature.

[0257] Useful formulations include both liquid and solid compositions containing the compound of formula I. Examples of liquid compositions include liquid formulations (including emulsions), suspensions, and emulsions (including microemulsions, oil-in-water emulsions, flowable formulations, and / or suspend emulsions). These can be made into gels by increasing their viscosity in some cases. Common types of aqueous liquid compositions include liquids, SC agents (suspension concentrates), CS agents (capsule suspensions), concentrated emulsions, microemulsions, oil-in-water emulsions, flowables, and suspension emulsions. Common types of non-aqueous liquid compositions include emulsions, microemulsifiable concentrates, DC agents (dispersible concentrates), and OD agents (oil dispersions).

[0258] Common types of solid compositions include powders, granules, pellets, prills, aromatic tablets, tablets, and filled films (including seed coatings), which may be water-dispersible ("hydrated") or water-soluble. Films and coatings formed from film-forming solutions or fluid suspensions are particularly useful for seed treatment. Active ingredients can be (micro)encapsulated to form further suspensions or solid dosage forms; or the entire formulation of the active ingredient can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsion and dry granule formulations. High-strength compositions are mainly used as intermediates for further formulation.

[0259] Sprayable formulations are typically spread in a suitable medium before spraying. Such liquid and solid formulations are formulated to be easily diluted in a spray medium, usually water, but may also be another suitable medium such as aromatic or paraffinic hydrocarbons or vegetable oils. Spray rates can range from approximately 1 liter to several thousand liters per hectare, but more typically from approximately 10 liters to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment by aerial or ground spraying, or for application to the plant's growth medium. Liquid and dry formulations may be measured and added directly into drip irrigation systems or measured and added between rows during sowing.

[0260] The formulation typically contains effective amounts of an active ingredient, diluent, and surfactant within a suitable range, totaling 100% by mass.

[0261] [Table 16]

[0262] Examples of solid diluents include clays such as bentonite, montmorillonite, attapulgite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, and Examples include chistrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described by Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd edition, Dorland Books, Caldwell, New Jersey.

[0263] Examples of liquid diluents include water, N,N-dimethylalkaneamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), alkyl phosphate (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, linear paraffin, isoparaffin), alkylbenzene, alkylnaphthalene, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic hydrocarbons, alkylbenzenes, alkylnaphthalene, ketones, such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-pentane. Non-acetates, such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactic acid esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols which may be linear or branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents may also include saturated and unsaturated fatty acids (typically C6-C6). 22Liquid diluents also include glycerol esters of, for example, plant seed and fruit oils (e.g., olive, castor bean, linseed, sesame, maize, peanut, sunflower, grape seed, safflower, cottonseed, soybean, rapeseed, coconut, and palm kernel oils), 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, and butylated), where fatty acids can be obtained by hydrolysis of plant and animal glycerol esters and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd edition, Interscience, New York, 1950.

[0264] The solid and liquid compositions of this disclosure often contain one or more surfactants. When added to a liquid, surfactants (also known as “surfactants”) generally modify, and most frequently reduce, the surface tension of the liquid. Depending on the hydrophilic and lipophilic nature of their groups, surfactants may be useful as wetting agents, dispersants, emulsifiers, or defoamers.

[0265] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alkoxylated alcohols, e.g., alkoxylated alcohols based on natural and synthetic alcohols (which may be branched or linear) and produced from alcohols with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; ethoxylated amines, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, e.g., ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates, e.g., octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (phenol and ethylene oxide) Polyethoxylated polymers produced from propylene oxide, butylene oxide, or mixtures thereof; block polymers produced from ethylene oxide or propylene oxide and reverse block polymers in which the terminal blocks are produced from propylene oxide; ethoxylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those produced from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters, e.g., polyethoxylated esters Examples include toxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives, such as sorbitan esters; polymer surfactants, such as random copolymers, block copolymers, alkydopeg (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives, such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0266] Useful 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, e.g., lignosulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, e.g., phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol Examples include 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 taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzene; sulfonates of condensed naphthalenes; sulfonates of naphthalenes and alkylnaphthalenes; sulfonates of fractionally distilled petroleum; sulfosucciniamidates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

[0267] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, trippropylenetriamines and dipropylenetetramines, as well as ethoxylated amines, ethoxylated diamines and propoxylated amines (made from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, e.g., amine acetate and diamine salts; quaternary ammonium salts, e.g., quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, e.g., alkyldimethylamine oxide and bis-(2-hydroxyethyl)-alkylamine oxide.

[0268] A mixture of nonionic and anionic surfactants or a mixture of nonionic and cationic surfactants is also useful in the compositions of the present invention. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in various published references, including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. Davidson and B. Milwidsky, Synthetic Detergents. One example is Seventh Edition, John Wiley and Sons, New York, 1987.

[0269] The compositions of this disclosure may also contain formulation aids known to those skilled in the art (some of which may also be considered to function as solid diluents, liquid diluents, or surfactants). Such formulation aids and additives can control: pH (buffering agents), foaming during processing (antifoaming agents such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobial agents), product freezing (antifreeze agents), color (pigment / dye dispersion), washability (film-forming agents or stickers), evaporation (evaporation retarders), and other formulation attributes. Examples of film-forming agents include polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives are listed in McCutcheon's Volume 2: Functional Materials, annual international and North American editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co., as well as in PCT publication WO 03 / 024222.

[0270] Compounds of formula I and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredients in a solvent or by grinding them in a liquid or dry diluent. Liquid formulations containing emulsions can be prepared simply by mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsion is water-immiscible, an emulsifier is typically added to emulsify the solvent containing the active ingredients when diluted with water. Slurries of active ingredients having particle sizes up to 2,000 μm can be wet-ground using a medium mill to obtain particles with an average diameter of less than 3 μm. Aqueous slurries can be made into finished SC formulations (see, for example, US3,060,084) or further processed by spray drying to form hydrated granules. Dry formulations typically require a dry grinding process, which results in an average particle size in the range of 2 to 10 μm. Powders and powders can be prepared by mixing and usually grinding (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 flocculation 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 below, as well as WO91 / 13546. Pellets may be manufactured as described in US4,172,714. Hydrated and water-soluble granules may be manufactured as taught in US4,144,050, US3,920,442 and DE3,246,493. Tablets may be manufactured as taught in US5,180,587, US5,232,701 and US5,208,030. Films may be manufactured as taught in GB2,095,558 and US3,299,566.

[0271] For further information on formulation technology, see Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society. See TSWoods, "The Formulator's Toolbox - Product Forms for Modern Agriculture," in *of Chemistry*, Cambridge, 1999, pp. 120-133. US3,235,361, column 6, line 16-7, column 7, line 19 and Example 10- See also 41; US3,309,192, column 5, lines 43-7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US2,891,855, column 3, lines 66-5, 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 in formulation technology, PJB Publications, Richmond, UK, 2000.

[0272] In the following examples, all percentages are mass percentages, and all formulations were prepared by conventional methods. Compound number, i.e., "Cpd. No.", refers to the compound in Table 1. Without further ado, those skilled in the art will be able to utilize the present disclosure to its fullest extent using the preceding description. Therefore, the following examples should be interpreted as being for illustrative purposes only and not limiting the present disclosure in any way. Unless otherwise indicated, percentages are mass percentages.

[0273] Example A High Strength Concentrate Compound number 22 98.5% Silica aerogel 0.5% Synthetic amorphous fine silica 1.0%

[0274] Example B Wettable powder Compound number 22 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignin sulfonate 4.0% Sodium aluminosilicate 6.0% Montmorillonite (calcined) 23.0%

[0275] Example C (i) Granules Compound number 22 10.0% Attapulgite granules (low volatility, 0.71 / 0.30 mm; USS No. 25-50 sieve) 90.0%

[0276] Example D Extruded pellets Compound number 22 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignin sulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0277] Example E emulsion Compound number 22 10.0% Polyoxyethylene sorbitol hexaoleate 20.0% C6-C 10 Fatty acid methyl ester 70.0%

[0278] Example F Microemulsion Compound number 22 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0279] Example G SC agent Compound number 22 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Slylen acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based defoaming agent 0.1% 1,2-Benzisothiazolin-3-one 0.1% Water 53.7%

[0280] Example H EW agent (Emulsion in Water) Compound number 22 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based defoaming agent 0.1% 1,2-Benzisothiazolin-3-one 0.1% Aromatic petroleum hydrocarbons 20.0 Water 58.7%

[0281] Example I OD agent (Oil Dispersion) Compound number 22 25% Hexaoleic acid, polyoxyethylene sorbitol 15% Organically modified bentonite clay 2.5% Fatty acid methyl ester 57.5%

[0282] Examples A to I described above are also disclosed, in which compound number 22 is replaced with compound number 20, compound number 21, or compound number 65.

[0283] The test results showed that certain compounds of formula I are active pre-emergence and / or post-emergence herbicides and / or plant growth regulators. Compounds of formula I generally showed the highest activity for post-emergence weed control (i.e., applied after weed seedlings emerge from the soil) and pre-emergence weed control (i.e., used before weed seedlings emerge from the soil). Many of these compounds are practical for widespread pre- and post-emergence weed control in areas where complete control of all vegetation is desirable, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, airports, riverbanks, irrigation and other waterways, around billboards, and main roads and railway structures. Many of the compounds of this disclosure are useful for selective control of grasses and broadleaf weeds in crop / weed mixes by selective metabolism of weeds in crops, or by selective activity at sites of physiological inhibition in crops and weeds, or by selective placement on or within mixed crop and weed environments. Those skilled in the art will see that preferred combinations of these selective factors within a compound or group of compounds can be readily determined by performing conventional biological and / or biochemical assays.

[0284] Compounds of formula I may exhibit resistance to important agricultural crops, including, but are not limited to, perpetually cultivated crops such as alfalfa, barley, cotton, wheat, rapeseed, sugar beet, maize, sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, coffee, cocoa, oil palm, rubber, sugarcane, citrus fruits, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, and tea, as well as forests such as eucalyptus and conifers (e.g., pine), and turfgrass species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and Bermuda grass). The compounds of this disclosure may be used in or on crops that have been genetically transformed or cultivated to incorporate resistance to herbicides, to express toxic proteins against invertebrate pests (e.g., Bacillus thuringiensis toxin), and / or to express other useful traits. As will be obvious to those skilled in the art, not all compounds are equally effective against all weeds. Alternatively, the compounds of the subject matter may be useful for modifying plant growth.

[0285] Since the compounds of this disclosure have activity for controlling undesirable vegetation by killing or damaging vegetation or reducing its growth (both pre- and post-emergence herbicides), the compounds can be usefully applied by various methods, including bringing a herbicidally effective amount of the compounds of this disclosure, or a composition comprising the compounds and at least one surfactant, solid diluent, or liquid diluent, into contact with the leaves or other parts of the undesirable vegetation, or with the environment of the undesirable vegetation, such as the soil or water surrounding the growing or seeds or other bulbils of the undesirable vegetation.

[0286] The effective amount of compound I in herbicides is determined by several factors. These factors include: Examples include the selected formulation, application method, amount and type of vegetation present, and growth conditions. Generally, the effective herbicidal dose of the compounds disclosed herein is about 0.001 to 20 kg / ha, with a preferred range of about 0.004 to 1 kg / ha. Those skilled in the art can easily determine the effective herbicidal dose required for a desired level of weed control.

[0287] In one general embodiment, the compound of formula I is typically applied in a formulated composition to a location containing both desirable vegetation (e.g., crops) and undesirable vegetation (i.e., weeds) in contact with a growth medium (e.g., soil), where both vegetation may be seeds, seedlings, and / or larger plants. In this location, the composition containing the compound of the present disclosure may be applied directly to the plants of the particularly undesirable vegetation or to a portion thereof, and / or to the growth medium in contact with the plants.

[0288] Fine varieties and cultivars of plants of a desired vegetation in a site treated with the compounds of this disclosure can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a different gene (introduced gene) is stably incorporated into the plant genome. Depending on its specific location in the plant genome The introduction of a specified gene is called a transformation or transgenic event.

[0289] Most typically, the compounds of this disclosure are applied to control undesirable vegetation, but contact of the compounds of this disclosure with the desired vegetation at the treated site may produce additive or synergistic effects with the genetic traits of the desired vegetation, including traits incorporated through genetic modification. For example, resistance to herbivorous insect pests or plant diseases, tolerance to biotic / abiotic stress, or storage stability may be higher than what would be expected from the genetic traits of the desired vegetation.

[0290] The compounds of this disclosure can also be mixed with one or more other biologically active compounds or agents to form multicomponent pesticides that provide a broader range of agricultural protection, such as herbicides, herbicide phytotoxicity reducers, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, such as insect molting inhibitors and rooting stimulants, chemical sterilizers, signaling substances, repellents, attractants, pheromones, contact irritants, plant nutrients, other biologically active compounds, or entomopathogenic bacteria, viruses, or fungi. Mixtures of the compounds of this disclosure with other herbicides can broaden the range of activity against further weed species and suppress the growth of any resistant biotypes. Accordingly, this disclosure also relates to a composition comprising a compound of formula I (in a herbicidally effective amount) and at least one further biologically active compound or agent (in a biologically effective amount), which may further comprise at least one surfactant, solid diluent, or liquid diluent. Other biologically active compounds or agents may be formulated into compositions comprising at least one surfactant, solid, or liquid diluent. The mixtures of the present disclosure may include one or more other biologically active compounds or agents formulated together with the compound of formula I to form a premix, or one or more other biologically active compounds or agents may be formulated separately from the compound of formula I, and these formulations may be mixed before application (e.g., in a spray tank) or applied sequentially.

[0291] For general references on agricultural protective agents (i.e., herbicides, herbicide phytotoxicity reducers, insecticides, fungicides, nematicides, acaricides, and biological agents), see The Pesticide Manual, 13th edition, CDSTomlin, Ed., British Crop References include the Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd edition, LGCopping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0292] In embodiments in which one or more of these various mixing partners are used, the mixing partners are typically used in amounts similar to the usual amounts used when the mixing partner is used alone. More specifically, in the mixture, the active ingredient is often applied at a dosage between half and the full dosage specified on the product label for use of the active ingredient alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The mass ratios of these various mixing partners (in total) to the compound of Formula I are typically between about 1:3000 and about 3000:1. In particular, mass ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). Those skilled in the art can easily determine the biologically effective amount of the active ingredient required for the desired range of biological activity by simple experiments. It will be apparent that including these additional components can broaden the range of weeds controlled beyond the range controlled by the compound of Formula I alone.

[0293] Of particular note is that the compound of the present invention (in an effective amount for herbicidal control), other herbicides, and herbicide phytotoxicity reducers... The composition comprises at least one further active ingredient (in an effective amount) selected from the group, and at least one component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0294] Table A1 lists specific combinations of component (a) and component (b) that are useful in describing the mixtures, compositions, and methods of the present invention. Compound number 1 in the component (a) column (i.e., "Cpd. No." represents "compound number") is identified in Table AA. The second column of Table A1 lists specific compounds of component (b) (e.g., "2,4-D" in the first row). The third, fourth, and fifth columns of Table A1 list the range of mass ratios of the amount of compound (a) typically applied to outdoor crops to component (b) (i.e., (a):(b)). Thus, for example, the first row of Table A1 specifically discloses that the combination of component (a) (i.e., compound number 1 in Table AA) with 2,4-D is typically applied in a mass ratio between 1:192 and 6:1. The remaining rows of Table A1 should be interpreted similarly.

[0295] [Table 17] [Table 18] [Table 19] [Table 20] [Table 21] [Table 22]

[0296] Table A2 shows that the items under the column heading "Component (a)" represent each of the components (a) shown below. Except for the substitution of items in the column, it is interpreted as being the same as Table A1 above. Compound number 2 in the Component (a) column is identified in Table AA. Therefore, for example in Table A2, all items under the heading of the "Component (a)" column should list compound number 2 (i.e., compound number 2 identified in Table AA), and the first row under the heading of the column in Table A2 specifically discloses a mixture of compound number 2 and 2,4-D.

[0297] [Table 23]

[0298] In certain cases, combinations of the compounds of this disclosure with other biologically active (particularly herbicidal) compounds or agents (i.e., active ingredients) may produce a more-than-additive (i.e., synergistic) effect on weeds and / or a less-than-additive effect (i.e., phytotoxicity reduction) on crops or other desired plants. It is always desirable to reduce the amount of active ingredients released into the environment while ensuring effective pest control. The ability to provide more effective weed control using a larger amount of active ingredients without excessive crop damage is also desirable. When a synergistic effect of herbicidal active ingredients occurs on weeds at application rates that produce an agronomically sufficient level of weed control, such combinations may be advantageous in reducing crop production costs and decreasing environmental impact. When phytotoxicity reduction of herbicidal active ingredients occurs on crops, such combinations may be advantageous in increasing crop protection by reducing weed competition.

[0299] Of particular note are combinations of the compounds of this disclosure with at least one other herbicidal active ingredient. Of particular note are combinations in which the other herbicidal active ingredient has a different site of action than the compounds of this disclosure. In certain examples, combinations with at least one other herbicidal active ingredient having a similar control range but a different site of action are particularly useful for resistance management. It would be beneficial. Therefore, the compositions of the present disclosure may further contain (in an effective herbicidal amount) at least one additional herbicidal active ingredient having a similar control range but a different site of action.

[0300] The compounds disclosed herein also include alidocrol, benoxacol, croquintoset-mexyl, cumylon, cyometrinil, cyprosulfonamide, dimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenchlorim, flurazole, fluxofenim, flirazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride (1,8-naphthalic anhydride), oxavethrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, and 1-bromo-4-[(chloro-methyl)-sulfonyl]-benzene. (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG191) can be used in combination with herbicide reducers such as ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidine carboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide to increase safety for certain crops. A detoxifying amount of the herbicide reducer may be applied simultaneously with the compounds of this disclosure or as a seed treatment. Accordingly, one aspect of the present disclosure relates to a herbicide mixture comprising the compounds of the present disclosure and an effective amount of herbicide phytotoxicity reducer. Seed treatment is particularly useful for selective weed control because it physically limits detoxification to crop plants.Therefore, a particularly useful embodiment of the present disclosure is a method for selectively controlling the growth of undesirable vegetation on a crop, comprising contacting the crop site with a herbicidally effective amount of the compound of the present disclosure, where the crop and the seeds from which it grows are treated with a detoxifyingly effective amount of the phytotoxicity reducer. Those skilled in the art can readily determine the detoxifyingly effective amount of the phytotoxicity reducer by simple experiments.

[0301] The compounds of this disclosure may also be mixed with: (1) polynucleotides including, but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the amount of a particular target by downregulating, interfering with, repressing or silencing genetically induced transcripts to confer a herbicidal effect; or (2) polynucleotides including, but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the amount of a particular target by downregulating, interfering with, repressing or silencing genetically induced transcripts to confer a phytotoxicity-reducing effect.

[0302] The following tests A-M demonstrate the control efficacy of representative compounds of this disclosure against typical weeds, but the weed control provided by these compounds is not limited to these species. See Index Table 1 for a description of the compounds. The mass spectra were observed using atmospheric pressure chemical ionization (AP+) to which H2 was directed onto the molecules. + The molecular weight of the parent ion (M+1) with the highest isotopic abundance formed by the addition of (molecular weight 1) is reported with an estimation accuracy of within ±0.5 Da.

[0303] [Table 24]

[0304] Test A Barnyard grass (Echinochloa crus-galli), Kochia scoparia, common ragweed (Ambrosia) Seeds of plant species selected from elatior, ryegrass (Lolium multiflorum), foxtail grass (Setaria faberii), foxtail grass (Setaria viridis), and pigweed (Amaranthus retroflexus) were planted in a blend of loam and sand, and pre-treated using a directed soil spray with a test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0305] Simultaneously, these weed species, as well as plants selected from wheat (Triticum aestivum), maize (Zea mays), blackgrass (Alopecurus myosuroides), and catchweed bedstraw (Galium aparine), were planted in pots containing the same blend of loam and sand and treated with post-emergence application of the test chemicals formulated in the same manner. For post-emergence treatment, the plants ranged in height from 2 to 10 cm and were at the 1-2 leaf stage. Treated plants and untreated controls were maintained in a greenhouse for approximately 10 days, after which all treated plants were compared to untreated controls and visually assessed for damage. The plant response ratings summarized in Table A are based on a scale from 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) indicates no test result.

[0306] [Table 25]

[0307] Test B In the paddy field experiment, plant species selected from rice (Oryza sativa), small-flower umbrella sedge (Cyperus difformis), American barnyard grass (Heteranthera limosa), and barnyard grass (Echinochloa crus-galli) were grown to the two-leaf stage for the experiment. At the time of treatment, the test pots were submerged in water up to 3 cm above the soil surface, and the test compound was applied directly to the paddy field water. This water depth was then maintained throughout the experiment. The treated plants and controls were kept in a greenhouse for 13–15 days, after which all species were compared to the controls and visually evaluated. The plant response ratings summarized in Table B are based on a scale of 0 to 100, where 0 represents no effect and 100 represents a perfect control. A dash (-) indicates no result in the experiment.

[0308] Table B Compounds 250g ai / ha 20 21 22 65 flooding Barnyard grass 25 80 40 40 American weed 100 90 90 80 Rice 15 35 60 20 Cyperus rotundus 90 90 85 90

[0309] Test C Alopecurus myosuroides, Lolium multiflorum, Triticum aestivum, Galium aparine, Zea mays, Digitaria sanguinalis, Setaria faberii, Sorghum halepense, Chenopodium album, Ipomoea coccinea, Cyperus esculentus, Amaranthus retroflexus, Ambrosia elatior, Glycine max, Echinochloa crus-galli, Brassica napus Seeds of plant species selected from napus, water hemp (common water hemp, Amaranthus rudis), Amaranthus palmeri, Kochia scoparia, Avena fatua, Brachiaria decumbens (surinam grass), Apera spica-venti (windgrass), poinsettia (wild) (Euphorbia heterophylla), and Abutilon theophrasti were planted in siltromous soil and pre-treated with test chemicals formulated in a mixture of non-phytotoxic solvents containing surfactants.

[0310] At the same time, plants selected from these crop and weed species, as well as common chickweed (Stellaria media), buckwheat vine (Polygonum convolvulus), wild mustard (Sinapis arvensis), poppy (Papaver rhoeas), Viola arvensis, black nightflower (Solanum ptycanthum), bird's-eye speedwell (Veronica persica), Conyza canadensis, Geranium dissectum, and cirsium arvense, are also included in Redi-Earth, which contains spaghnum peat moss, vermiculite, wetting agents, and initiating nutrients. (R) Plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and treated with the same method-formulated test chemical as a post-emergence treatment. For post-emergence treatment, the plants ranged in height from 2 to 18 cm (1 to 4 leaf stage). Treated plants and controls were kept in a greenhouse for 13 to 21 days, after which all species were compared to controls and visually evaluated. The plant response ratings summarized in Tables C-1 (post-emergence treatment) and C-2 (pre-emergence treatment) are based on a scale of 0 to 100, where 0 is no effect and 100 is a perfect control. A dash (-) indicates no test result.

[0311] The plant species used in the paddy field experiment were rice (transplanted and direct-seeded in flooded fields, Oryza sativa) grown to the two-leaf stage for the experiment, Cyperus difformis, Heteranthera limosa, and Scirpus juncoides. The test consisted of *Pus juncoides* and barnyard grass (Echinochloa crus-galli). At the time of treatment, the test pots were immersed in water up to 3 cm above the soil surface, and the test compound was applied directly to the paddy field water. The plants were then maintained at that water depth for the duration of the test. The treated plants and controls were kept in a greenhouse for 13–15 days, after which all species were compared to the controls and visually evaluated. The plant response ratings summarized in Table C are based on a scale of 0 to 100, where 0 represents no effect and 100 represents a perfect control. A dash (-) indicates no test result.

[0312] [Table 26]

[0313] [Table 27]

[0314] [Table 28]

[0315] [Table 29]

[0316] [Table 30]

[0317] [Table 31]

[0318] Test D Seeds of plant species selected from Alopecurus myosuroides, Galium aparine, Kochia scoparia, Brassica napus, Hordeum vulgare, Triticum aestivum, Avena fatua, and Hordeum vulgare and Triticum aestivum were planted in siltromous soil and pre-treated with test chemicals formulated with a mixture of non-phytotoxic solvents containing surfactants.

[0319] At the same time, plants selected from these crop species and weed species, as well as bluegrass (Poa annua), canary grass (Phalaris minor), chickweed (Stellaria media), downy bromegrass (Bromus tectorum), poppy (Papaver rhoeas), violet (Viola arvensis), foxtail grass (Setaria viridis), henbit deadnettle (Lamium amplexicaule), ryegrass (Lolium multiflorum), white goosefoot (Chenopodium album), blue amaranth (Amaranthus retroflexus), chamomile (Matricaria inodora), and thorny seaweed (Russian seaweed). Thistle (Salsola kali), speedwell (Veronica persica), buckwheat vine (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild radish (Raphanus raphanistrum), corn stalk (Apera spica-venti), geranium cutleaf (Geranium dissectum), and thorny thistle (Cirsium arvense) are also included in Redi-Earth, which contains sphagnum peat moss, vermiculite, wetting agent and initial nutrient. (R)Plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and treated with the same method-formulated test chemicals via post-growth application. Plants ranged in height from 2 to 18 cm (1 to 4 leaf stage). Treated plants and controls were maintained in a controlled growth environment for 14 to 21 days. After this period, all species were compared to controls and visually evaluated. The plant response ratings summarized in Table D are based on a scale of 0 to 100, where 0 represents no effect and 100 represents a perfect control. A dash (-) indicates no test result.

[0320] [Table 32]

[0321] [Table 33]

[0322] [Table 34]

[0323] [Table 35]

[0324] Test E Corn (Zea mays), soybeans (Glycine max), yew (Abutilon theophrasti), white goosefoot (Chenopodium album), false red sedge (Euphorbia heterophylla), long-horned blue amaranth (Amaranthus palmeri), water hemp (common water hemp, Amaranthus rudis), Suriname grass (Brachiaria decumbens), giant crabgrass (Digitaria sanguinea). sanguinalis), crabgrass, Brazilian mulberry (Digitaria horizontalis), large brown millet (Panicum dichotomiflorum), autumn foxtail grass (Setaria faberii), foxtail grass (Setaria viridis), goosegrass (Eleusine indica), halepense (Sorghum halepense), ragweed (Ambrosia elatior), barnyard grass (Echinochloa crus-galli), sandbur (southern sandbur, Cenchrus echinatus), golden sedge (Sida rhombifolia), ryegrass (Lolium multiflorum), Virginia dayflower (Virginia (VA) dayflower, Commelina virginica), morning glory (Convolvulus arvensis), cornflower (Ipomoea Seeds of plant species selected from coccinea, Conyza canadensis, Kochia scoparia, Cyperus esculentus, and Bidens pilosa were planted in siltromous soil and pre-treated with test chemicals formulated in a mixture of non-phytotoxic solvents containing surfactants.

[0325] At the same time, plants selected from these crops and weed species, as well as waterhemp_RES1 (ALS and triazine-resistant common water hemp, Amaranthus rudis) and waterhemp_RES2 (ALS and HPPD-resistant common water hemp, Amaranthus rudis), are also included in Redi-Earth, which contains sphagnum peat moss, vermiculite, wetting agents and initiating nutrients. (R)The plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and then treated with a test chemical compound formulated in the same manner as a post-growth treatment. For the post-growth treatment, the plants were raised to a certain height. The treatment ranged from 2 to 18 cm (1 to 4 leaf stage). Treated plants and controls were kept in a greenhouse for 14 to 21 days, after which all species were compared to controls and visually evaluated. The plant response ratings summarized in Table E are based on a scale of 0 to 100, where 0 indicates no effect and 100 indicates a perfect control. A dash (-) indicates no test result.

[0326] [Table 36]

[0327] [Table 37]

[0328] [Table 38]

[0329] [Table 39]

[0330] Test F Three plastic pots (approximately 16 cm in diameter) per assessment were partially filled with sterilized Tama siltromous soil containing sand, silt, and clay in a ratio of 35:50:15, along with 2.6% organic matter. Separate sowing for each of the three pots was as follows: Seeds of Monochoria vaginalis, Cyperus difformis, and purple redstem (Ammannia coccinea) from the United States were planted in one 16 cm pot for each assessment. Seeds from the United States of Cyperus iria, bearded sprangletop (Leptochloa fascicularis), 9 or 10 flooded direct-sown rice seedlings per bundle (rice, WSJap, Oryza sativa cv. "Japonica-M202" or rice, WSInd, "Indica"), and 3 or 4 transplanted rice seedlings per bundle (Oryza sativa cv. "Japonica-M202") were planted in one 16 cm pot for each assessment. Barnyard grass (Echinochloa crus-galli) and Chinese barnyard grass (Echino) Seeds of Chloa oryzicola from the United States were planted in one 16cm pot for each grade.

[0331] At the time of treatment, crop species and weed species were planted sequentially so that they were at the 2.0 to 2.5 leaf stage.

[0332] Potted plants were grown in a greenhouse with a daytime / nighttime temperature setting of 30 / 27°C, and supplemental balanced lighting was provided to maintain a 16-hour light period. The test pots were kept in the greenhouse until the end of the experiment.

[0333] At the time of treatment, the test pots were immersed in water up to 3 cm above the soil surface, and the test compound was applied directly to the paddy field water. This water depth was then maintained throughout the experiment. After 21 days, the effect of the treatment on rice and weeds was visually evaluated by comparing it to an untreated control. The plant response ratings summarized in Table F are based on a scale of 0 to 100, where 0 represents no effect and 100 represents a perfect control. A dash (-) indicates no result from the experiment.

[0334] [Table 40]

[0335] [Table 41]

[0336] Test G This study evaluated the effects of a mixture of compound number 20 and (b15C1) on several plant species. Seeds of plants selected from corn (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybean (GLXMA; Glycine max, cv. Pioneer 35T58), foxtail grass (SETFA; Setaria faberi), barnyard grass (ECHCG; Echinochloa crus-galli), crabgrass (DIGSA; Digitaria sanguinalis), amapa (AMAPA; Amaranthus palmeri), common water hemp (AMATU; Amaranthus rudis), and ragweed (AMBEL; Ambrosia artemisiifolia) were planted in pots containing Tama siltrom soil and pre-treated using directed soil spray with test chemicals formulated in a non-phytotoxic solvent mixture containing surfactants.

[0337] Treated plants and untreated controls were maintained in a greenhouse for approximately 21 days. Afterward, all treated plants were compared to the untreated controls, and damage was visually assessed. The plant response ratings, summarized in Table G, are based on a scale of 0 to 100, where 0 represents no effect and 100 represents perfect control. A dash (-) indicates no test result. Test results are shown as the average of four repeats.

[0338] [Table 42]

[0339] [Table 43]

[0340] Test H This study evaluated the effects of a mixture of compound number 20 with atrazine or glyphosate on several plant species. Corn (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybeans (GLXMA; Glycine max, cv. Pioneer 35T58), foxtail grass (SETFA; Setaria faberi), Suriname grass (BRADC; Brachiaria decumbens), large millet (PANDI; Panicum dichotomiflorum), Japanese yew (ABUTH; Abutilon threophrasti), mare's tail (ERICA; Conyza canadensis), barnyard grass (ECHCG; Echinochloa crus-galli), giant crabgrass (DIGSA; Digitaria sanguinalis), large blue amaranth (AMAPA; Amaranthus palmeri), common water hemp (AMATU; Amaranthus Seeds of plant species selected from rudis, American nightshade (Solanum ptycanthum), and ragweed (Ambrosia artemisiifolia) are grown in Redi-Earth(R) growing medium containing sphagnum peat moss, vermiculite, wetting agent, and initiating nutrient (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio). Plants were planted in pots containing (43041) and then post-emergence treatment with the test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant. For post-emergence treatment, the plants ranged in height from 2 to 10 cm and were at the 1-2 leaf stage. Treated plants and untreated controls were kept in a greenhouse for approximately 14 days. After this period, all plants were compared to the untreated controls and visually assessed for damage. The plant response ratings summarized in Tables H1 and H2 are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) indicates no test result. Test results are shown as the average of four repeats.

[0341] [Table 44]

[0342] [Table 45]

[0343] [Table 46]

[0344] [Table 47]

[0345] [Table 48]

[0346] [Table 49]

[0347] Test I This study evaluated the effects of a mixture of compound number 20 with saflufenacil or pyroxasulfone on several plant species: corn (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybean (GLXMA; Glycine max, cv. Pioneer 35T58), foxtail grass (SETFA; Setaria faberi), and blue amaranth (AMAPA; Amaranthus Seeds of selected plant species from palmeri, common water hemp (AMATU; Amaranthus rudis), dwarf coneflower (ERICA; Conyza canadensis), and ragweed (AMBEL; Ambrosia artemisiifolia) were planted in pots containing Tama siltrom soil, and directed soil spray was applied using a test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant. Pre-processing was performed using -.

[0348] At the same time, plants from these crop and weed species are grown using Redi-Earth, which includes sphagnum peat moss, vermiculite, wetting agents, and initiating nutrients. (R) Plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and then post-emergence treatment with the same preparation of the test chemical. For post-emergence treatment, the plants ranged in height from 2 to 10 cm and were at the 1-2 leaf stage. Treated plants and untreated controls were maintained in a greenhouse for approximately 14-21 days, after which all treated plants were compared to untreated controls and visually assessed for damage. Plant response ratings, summarized in Tables I1-I4, are based on a scale of 0-100, where 0 represents no effect and 100 represents perfect control. A dash (-) indicates no test result. Test results are presented as the average of four repeats.

[0349] [Table 50]

[0350] [Table 51]

[0351] [Table 52]

[0352] [Table 53]

[0353] [Table 54]

[0354] [Table 55]

[0355] [Table 56]

[0356] [Table 57]

[0357] Test J This study evaluated the effects of a mixture of compound number 20 and (b15C2) on several plant species. Seeds of plant species selected from maize (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybean (GLXMA; Glycine max, cv. Pioneer 35T58), foxtail grass (SETFA; Setaria faberi), amapa; Amaranthus palmeri, common water hemp (AMATU; Amaranthus rudis), dwarf confectioner (ERICA; Conyza canadensis), and ragweed (AMBEL; Ambrosia artemisiifolia) were planted in pots containing Tama siltrom soil and pre-treated using a directed soil spray with the test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0358] At the same time, plants from these crop and weed species are grown using Redi-Earth, which includes sphagnum peat moss, vermiculite, wetting agents, and initiating nutrients. (R) Plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and then post-emergence treatment with the same preparation of the test chemical. For post-emergence treatment, the plants ranged in height from 2 to 10 cm and were at the 1-2 leaf stage. Treated plants and untreated controls were maintained in a greenhouse for approximately 14-21 days, after which all treated plants were compared to untreated controls and visually assessed for damage. Plant response ratings summarized in Tables J1 and J2 are based on a scale of 0 to 100, where 0 represents no effect and 100 represents perfect control. A dash (-) indicates no test result. Test results are shown as the average of four repeats.

[0359] [Table 58]

[0360] [Table 59]

[0361] [Table 60]

[0362] [Table 61]

[0363] Test K This study evaluated the effects of a mixture of compound number 20 with metrivudine or limsulfuron on several plant species: corn (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybean (GLXMA; Glycine max, cv. Pioneer 35T58), and foxtail grass (SETFA; Setaria). Seeds of plant species selected from Amaranthus palmeri, Amaranthus rudis, Conyza canadensis, and Ambrosia artemisiifolia were planted in pots containing Tama siltrom soil and pre-treated using a directed soil spray with a test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0364] At the same time, plants selected from these crop and weed species are treated with Redi-Earth, which includes sphagnum peat moss, vermiculite, wetting agents, and initiating nutrients. (R) The plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and then post-emergence treatment with a test chemical compound formulated in the same manner. For post-emergence treatment, the plants were raised to a height of 2-1 The treatment ranged from 0 cm to the 1-2 leaf stage. Treated plants and untreated controls were maintained in a greenhouse for approximately 14-21 days. After that, all treated plants were compared to untreated controls, and damage was visually assessed. The plant response ratings summarized in Tables K1-K4 are based on a scale of 0-100, where 0 represents no effect and 100 represents perfect control. A dash (-) indicates no test result. Test results are shown as the average of four repeats.

[0365] [Table 62]

[0366] [Table 63]

[0367] [Table 64]

[0368] [Table 65]

[0369] [Table 66]

[0370] [Table 67]

[0371] [Table 68]

[0372] [Table 69]

[0373] Test L This study evaluated the effects of compound number 20 and mixtures with benoxacol, isooxadifen-ethyl, or croquintoset-mexyl on several plant species: corn (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybean (GLXMA; Glycine max, cv. Pioneer 35T58), autumn-sown wheat (TRZAW; Triticum aetivum, cv. Arezzo), and Seeds of plant species selected from Oryza sativa (cv. M202) and Setaria faberi (SETFA) are grown in Redi-Earth, which contains sphagnum peat moss, vermiculite, a wetting agent, and an initiating nutrient solution. (R) Plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and then post-emergence treatment with a test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant. For post-emergence treatment, the plants ranged in height from 7 to 10 cm and were at the 1-2 leaf stage. Treated plants and untreated controls were maintained in a greenhouse for approximately 14 days. After this period, all plants were compared to the untreated controls and visually assessed for damage. The plant response ratings summarized in Tables L1-L3 are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) indicates no test result. Test results are shown as the average of four repeats.

[0374] [Table 70]

[0375] [Table 71]

[0376] [Table 72]

[0377] Test M This study evaluated the effects of mixtures of compound number 20 with isooxadifen-ethyl, croquintoset-mexyl, or mefenpyr-diethyl on several plant species. Seeds of plant species selected from maize (ZEAMD; Zea mays, cv. "Pioneer 1184"), soybean (GLXMA; Glycine max, cv. Pioneer 35T58), autumn-sown wheat (TRZAW; Triticum aetivum, cv. Arezzo), autumn-sown barley (HORVW; Hordeum vulgare, cv. Boone), rice (ORYSS; Oryza sativa, cv. M202), and autumn foxtail grass (SETFA; Setaria faberi) were used in a Redi-Earth environment containing sphagnum peat moss, vermiculite, a wetting agent, and an initiating nutrient solution. (R) Plants were planted in pots containing a growing medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) and then post-emergence treatment with a test chemical formulated in a non-phytotoxic solvent mixture containing a surfactant. For post-emergence treatment, the plants ranged in height from 7 to 10 cm and were at the 1-2 leaf stage. Treated plants and untreated controls were maintained in a greenhouse for approximately 14 days. After this period, all plants were compared to the untreated controls and visually assessed for damage. The plant response ratings summarized in Tables M1-M3 are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) indicates no test result. Test results are shown as the average of three repeats.

[0378] [Table 73]

[0379] [Table 74]

[0380] [Table 75]

Claims

[Claim 1] Formula I-A 【Chemistry 1】 [In the formula, R 1 is C 1 -C 4 Alkyl or C 3 -C 6 It is a cycloalkyl; R 2 is Cl; R 5 is F, Cl or CH 3 and R 6 is H; ] A method for producing the compound, The method is: (1) Formula II 【Chemistry 2】 [In the formula, R 5 is F, Cl or CH 3 and R 6 H is;] The compound is reacted with magnesium to form formula III 【Transformation 3】 To form an intermediate compound; and (2) The intermediate compound of formula III formed in (1) is IV-B 【Chemistry 4】 [In the formula, R 1 is C 1 -C 4 Alkyl or C 3 -C 6 It is a cycloalkyl; G is C 1 -C 4 Alkyl, SO 2 CF 3 or SO 2 (4-Me-Ph) To make it react, The above method, including.

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