fungicidal pyridone

Abstract

Disclosed is the formula 1 [Formula 1] TIFF2024514589000036.tif42170 (including all geometric and stereoisomers, N-oxides, and salts thereof), wherein W, R 1 , R 2 , R 3 , Q 1 , and Q 2 is as defined in the present disclosure. Also disclosed are compositions comprising the compounds of formula 1, as well as methods for controlling plant diseases caused by fungal pathogens, comprising applying an effective amount of a compound or composition of the invention.

Description

[Technical Field]

[0001] The present invention relates to certain pyridones, their N-oxides, salts, and compositions, as well as methods for using them as fungicides. [Background technology]

[0002] Controlling plant diseases caused by fungal plant pathogens is crucial for achieving high crop efficiency. Damage from plant diseases to ornamental plants, vegetables, fields, grains, and fruit crops can significantly reduce productivity, potentially increasing costs for consumers. While many products are commercially available for these purposes, there is a continuing need for novel compounds that are more effective, less expensive, less toxic, safer for the environment, or have different sites of action.

[0003] International Publication No. 2018 / 195155 discloses pyridone derivatives and their use in pharmaceutical compositions.

[0004] International Publication No. 2009158257 and International Publication No. 2010 / 093595 disclose fungicides such as 2-pyridone and pyridine derivatives. [Overview of the project] [Means for solving the problem]

[0005] The present invention is based on formula 1 [ka] Compounds (including all stereoisomers), their N-oxides and salts, compositions containing these, and the use of these as fungicides, During the ceremony W is either O or S; Q 1 and Q 2 However, each is independent of R 4A phenyl ring optionally substituted with up to 5 substituents independently selected from; or a 5-6 membered heteroaromatic ring, each ring comprising a carbon atom and 1-4 heteroatoms independently selected from up to 2 oxygen atoms, up to 2 sulfur atoms, and up to 4 nitrogen atoms, each ring comprising R 4 Optionally substituted with up to 5 substituents independently selected from; or a 3-6 member non-aromatic heterocycle, each ring comprising a ring member selected from a carbon atom and 1-4 heteroatoms independently selected from up to 2 oxygen atoms, up to 2 sulfur atoms, and up to 4 nitrogen atoms, with up to 2 ring members independently selected from C(=O), C(=S), S(=O), and S(=O)2, each ring comprising R 4 It may be substituted with up to five substituents independently selected from; R 1 However, amino, cyano, hydroxy, NH2C(=O)H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C2-C6 cyanoalkoxy, C1-C6 alkylamino, C1-C6 haloal It is a methylamino, C2-C6 dialkylamino, C4-C8 alkylcarbonylamino, C2-C6 alkoxyalkylamino, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, or C2-C6 haloalkoxycarbonyl; or a C3-C6 cycloalkyl or C4-C6 cycloalkylalkyl, each optionally substituted with up to three substituents independently selected from halogens, cyanos, and C1-C3 alkyls; R 2is H, halogen, cyano, hydroxy, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyalkoxy, or C2-C6 haloalkoxyalkoxy; or C3-C6 cycloalkyl or C4-C6 cycloalkylalkyl, each optionally substituted with up to 3 substituents independently selected from halogen, cyano, and C1-C3 alkyl; R 3 is H, halogen, amino, cyano, hydroxy, nitro, C(=O)H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, or C2-C6 alkoxycarbonyl; or a 3- to 6-membered non-aromatic ring containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms, and up to 4 N atoms, with up to 2 carbon atom ring members independently selected from C(=O) and C(=S), and each ring optionally substituted with up to 5 substituents independently selected from 5 R; each R 4However, independently, halogen, cyano, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C6 alkylcycloalkyl, C4-C6 cycloalkylalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C3-C6 cycloalkoxy , C2-C4 alkylcarbonyloxy, C2-C4 haloalkylcarbonyloxy, C1-C6 alkylsulfonyloxy, C1-C6 haloalkylsulfonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C6 dialkylamino, or -UVT; Each R 5 However, these are independently halogen, cyano, hydroxy, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkylcarbonyl, or C2-C4 alkylcarbonyloxy; Each U can be directly joined to O, S (=O) independently. m , or NR 6 and; Each V is independently a C1-C6 alkylene, C2-C6 alkenylene, C3-C6 alkylylene, C3-C6 cycloalkylene, or C3-C6 cycloalkenylene, with up to two carbon atoms being (C=O), each possibly substituted with up to five substituents independently selected from halogens, cyano, nitro, hydroxy, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 haloalkoxy; Each T independently produces cyano, NR 7a R 7b, OR 8 , or S(=O) m R 9 and; Each R 6 However, independently, these are H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 (alkylthio)carbonyl, or C2-C6 alkoxy(thiocarbonyl); Each R 7a and R 7b However, independently, H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, or C2-C6 alkoxycarbonyl; or R 7a and R 7b However, together with the nitrogen atom to which they are bonded, they form a 3-6 member heterocycle, and this ring can, in some cases, R 10 It is substituted with up to three substituents independently selected from; Each R 8 and R 9 However, independently, these are H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, or C2-C6 alkoxycarbonyl; Each R 10 However, independently, these are halogens, C1-C3 alkyls, C1-C3 haloalkyls, C1-C3 alkoxys, or C1-C3 haloalkoxys; Each m is independently 0, 1, or 2; however, (a)Q 1 However, in some cases, if it is a substituted phenyl ring, Q 2 This is, in some cases, a ring other than a substituted 1H-pyrazole-4-yl ring; (b) The compound of formula 1, 3,6-Dichloro-1-methyl-4,5-diphenyl-2(1H)-pyridinone; 1-Methyl-4,5-diphenyl-2(1H)-pyridinone; 1-[5-[1-(cyclopropylmethyl)-1H-pyrazole-4-yl]-1,2-dihydro-1-methyl-2-oxo-4-pyridinyl]-1H-pyrrole-3-carboxylic acid; 1-[1,2-dihydro-1-methyl-5-(1-methyl-1H-pyrazole-4-yl)-2-oxo-4-pyridinyl]-1H-pyrrole-3-carboxylic acid; 1-Methyl-5-(1-methyl-1H-pyrazole-4-yl)-4-(1H-pyrrole-1-yl)-2(1H)-pyridinone; 1-amino-3,6-dimethyl-4,5-diphenyl-2(1H)-pyridinone; Methyl(3,6-dimethyl-2-oxo-4,5-diphenyl-1(2H)-pyridinyl)carbamate; or Ethyl (3,6-dimethyl-2-oxo-4,5-diphenyl-1(2H)-pyridinyl)carbamate isn't it, The compound (including all stereoisomers), its N-oxide, and salts, compositions containing these, and their use as fungicides are intended.

[0006] More specifically, the present invention relates to the compound of formula 1 (including all stereoisomers), its N-oxide, or salt.

[0007] The present invention also relates to a fungicidal composition comprising (a) the compound of the present invention (i.e., the compound of the present invention in a fungicidally effective amount) and (b) at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0008] The present invention also relates to a fungicidal composition comprising (a) the compound of the present invention and (b) at least one other fungicidal agent (for example, at least one other fungicidal agent with a different site of action).

[0009] The present invention further relates to a method for controlling plant diseases caused by fungal plant pathogens, comprising applying a fungicidal effective amount of the compound of the present invention (for example, as a composition described herein) to a plant or a part thereof, or to a plant seed.

[0010] The present invention also relates to a composition comprising a compound of formula 1, its N-oxide, or a salt, and at least one invertebrate pest control compound or agent. [Modes for carrying out the invention]

[0011] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by,” or any other variation thereof, are intended to cover non-exclusive inclusion, subject to any expressly indicated limitations. For example, a composition, mixture, process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, and may include other elements not expressly listed or that are specific to such composition, mixture, process, method, article, or apparatus.

[0012] The transitional phrase "consisting of" excludes any elements, processes, or materials not explicitly stated. In the context of patent claims, such exclusion excludes the inclusion of materials other than those enumerated, excluding impurities typically associated with them. If the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the preamble, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0013] The transitional phrase "consisting essentially of" is used to define a composition, method, or apparatus 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 characteristics of the claimed invention. The term "consisting essentially of" occupies an intermediate area between "comprising" and "consisting of."

[0014] If applicants define an invention or part thereof using open-ended terms such as “comprising,” it should be readily apparent that (unless otherwise specified) this description should also be interpreted as describing such invention using terms such as “essentially consisting of” or “consisting of.”

[0015] Furthermore, unless explicitly stated otherwise, "or" means an inclusive "or" and not an exclusive "or". For example, condition A 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).

[0016] Furthermore, the indefinite articles "a" and "an" preceding the elements or components of the present invention are intended to be non-restrictive with respect to the number of elements or components (i.e., occurrences). Therefore, "a" or "an" should be read as including one or at least one, and the singular form of an element or component also includes the plural form unless it is specifically intended that the number is singular.

[0017] The term "agricultural" refers to the production of crops for food and fiber, and includes the cultivation of maize or corn, soybeans and other legumes, rice, grains (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage and other cruciferous crops), fruiting vegetables (e.g., tomatoes, peppers, eggplants, cruciferous plants and cucurbits), potatoes, sweet potatoes, grapes, cotton, fruit trees (e.g., pears, drupes and citrus fruits), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflowers and olives).

[0018] The term "non-agricultural" refers to agricultural products other than horticultural crops (e.g., greenhouse plants, nursery plants, or ornamental plants that cannot be grown in fields), residential, agricultural, commercial, and industrial structures, turf (e.g., turf farms, pastures, golf courses, turf soil, sports fields, etc.), wood products, storage products, agroforestry and plant management, and public health (i.e., human) and animal health (e.g., domesticated animals, e.g., pets, livestock, and poultry, etc., and undomesticated animals, e.g., wildlife, etc.).

[0019] The term "crop growth rate" refers to the rate of crop growth or biomass accumulation. "Increased growth rate" refers to an increase in crop growth or biomass accumulation compared to an untreated control crop. The term "crop yield" refers to the crop material return obtained after harvest, in terms of both quantity and quality. "Increased crop yield" refers to an increase in crop yield compared to an untreated control crop.

[0020] The term "biologically effective amount" refers to the amount of a biologically active compound (e.g., the compound of Formula 1, or a mixture with at least one other fungicidal compound) that is sufficient to produce the desired biological effect when applied (i.e., in contact) to the fungus to be controlled or its environment, or to the plant, the seeds on which the plant grows, or the location of the plant (e.g., the growing medium), in order to protect the plant from damage caused by fungal diseases or for other desired effects (e.g., increased plant growth).

[0021] Where referred to in this disclosure and claims, “plant” includes members of the Plantae kingdom of all life cycles, in particular seed plants (Spermatopsida), including, for example, young plants (e.g., germinating seeds growing into seedlings) and mature reproductive stages (e.g., plants producing flowers and seeds). Parts of a plant typically include geotropic members that grow below the surface of the growing medium (e.g., soil) (e.g., roots, tubers, bulbs, and corms) and members that grow above the growing medium (e.g., leaves (including stems and leaves), flowers, fruits, and seeds).

[0022] Where used herein, the term “seedling,” either alone or in combination with other words, refers to a young plant developing from a seed embryo.

[0023] Where used herein, the term “broadleaf” either alone or in a word (e.g., broadleaf crops) means dicotyledon, a group of angiosperms characterized by embryos having two cotyledons.

[0024] Where used in this disclosure, the terms “fungal pathogen” and “fungal plant pathogen” include pathogens of the Ascomycota, Basidiomycota, and Zygomycota phyla, as well as Oomycota, which are pathogens of a wide range of economically important plant diseases affecting ornamental plants, turf, vegetables, fields, grains, and fruit crops. In the context of this disclosure, “protecting plants from disease” or “controlling plant diseases” includes prophylactic action (disruption of the fungal cycle of infection, colonization, symptom development, and spore production) and / or curative action (inhibition of colonization of plant host tissues).

[0025] As used herein, the term “mode of action” (MOA) is as defined by the Fungicide Resistance Action Committee (FRAC) and is used to distinguish fungicides according to their biochemical mode of action and resistance risk in the biosynthetic pathway of plant pathogens. Modes of action as defined by the FRAC include: (A) nucleic acid metabolism, (B) cytoskeleton and motility proteins, (C) respiration, (D) amino acid and protein synthesis, (E) signaling, (F) lipid synthesis or transport, and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell walls, (P) induction of host plant defense, (U) unknown mode of action, (M) multisite active chemicals, and (BM) biological substances with multiple modes of action. Each mode of action (i.e., letters A-BM) includes one or more subgroups based on individual effective target sites of action or, if the exact target site is unknown, based on cross-resistance profiles within the group or in relation to other groups (e.g., A includes subgroups A1, A2, A3, and A4). Each of these subgroups (e.g., A1, A2, A3, and A4) is assigned a FRAC code, which is a number and / or letter. For example, the FRAC code for subgroup A1 is 4. Further information regarding target sites and FRAC codes can be obtained, for example, from publicly available databases maintained by FRAC.

[0026] As used herein, the term "cross-resistance" refers to the phenomenon in which a pathogen develops resistance to one fungicide and simultaneously becomes resistant to one or more other fungicides. These other fungicides are typically, though not always, of the same chemical class, have the same target site of action, or can be detoxified by the same mechanism.

[0027] As used herein, the term “alkylating agent” refers to a compound in which a carbon-containing radical is bonded via a carbon atom to a leaving group (e.g., a halide or sulfonate) that can be substituted by a nucleophile bonding to the carbon atom. Unless otherwise specified, the term “alkylating agent” is not limited to alkyl carbon-containing radicals; for example, R 2 Various carbon bond substituent radicals defined in relation to this include:

[0028] Generally, when a molecular fragment (i.e., a radical) is represented by a set of atomic symbols (e.g., C, H, N, O, and S), any unexpressed single or multiple bonding points will be readily apparent to those skilled in the art. In some cases herein, such single or multiple bonding points may also be explicitly indicated by a hyphen ("-"), particularly where other bonding points are possible.

[0029] In the above description, the term "alkyl," whether used alone or in compound terms such as "haloalkyl," includes linear and branched alkyls, e.g., methyl, ethyl, n-propyl, and i-propyl. "Alkenyl" includes linear and branched alkenes, e.g., ethenyl, 1-propenyl, 2-propenyl, and various butenyl and pentenyl isomers. "Alkenyl" also includes polyenes, e.g., 1,2-propadienyl and 2,4-pentadienyl. "Alkynyl" includes linear and branched alkynes, e.g., ethynyl, 1-propynyl, 2-propynyl, and various butynyl and pentynyl isomers. "Alkynyl" may also include moieties composed of multiple triple bonds (e.g., 2,5-pentadienyl). "Alkylene" refers to linear or branched alkanediyls. Examples of "alkylenes" include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and various butylene isomers, pentylene isomers, or hexylene isomers. "Alkenylenes" refer to linear or branched alkenediyls containing one olefin bond. Examples of "alkenylenes" include CH=CH, CH2CH=CH, and CH=C(CH3). "Alkynylenes" refer to linear or branched alkyndiyls containing one triple bond. Examples of "alkynylenes" include CH2C≡C, C≡CCH2, and various butynylene isomers, pentynylene isomers, or hexynylene isomers.

[0030] "Alkylthio" includes branched or linear alkylthio moieties (e.g., methylthio, ethylthio, and various propylthio isomers). "Alkylsulfinyl" includes both enantiomers of the alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(=O), CH3CH2S(=O), CH3CH2CH2S(=O), and (CH3)2CHS(=O). Examples of "alkylsulfonyl" include CH3S(=O)2, CH3CH2S(=O)2, CH3CH2CH2S(=O)2, and (CH3)2CHS(=O)2.

[0031] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, i-propyloxy, and various butoxy isomers. "Alkenyloxy" includes linear or branched alkenyls bonded to and linked via an oxygen atom. Examples of "alkenyloxy" include H2C=CHCH2O and CH3CH=CHCH2O. "Alkynyloxy" includes linear or branched alkynyls bonded to and linked via an oxygen atom. Examples of "alkynyloxy" include HC≡CCH2O and CH3C≡CCH2O. The term "alkylsulfonyloxy" refers to alkylsulfonyls bonded to and linked via an oxygen atom. Examples of "alkylsulfonyloxy" include CH3S(=O)2O, CH3CH2S(=O)2O, CH3CH2CH2S(=O)2O, and (CH3)2CHS(=O)2O. "Alkoxyalkyl" refers to an alkoxy substituent on an alkyl group. Examples of "alkoxyalkyl" groups include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2, and CH3CH2CH2OCH2CH2. "Alkoxyalkyl" also refers to an alkoxy substituent on another alkoxy moiety. Examples of "alkoxyalkyl" groups include CH3OCH2O, CH3OCH2CH2CH2O, and CH3CH2OCH2O.

[0032] "Alkylcarbonyl" refers to a linear or branched alkyl group bonded to the C(=O) moiety. Examples of "alkylcarbonyl" include CH3C(=O), CH3CH2CH2C(=O), and (CH3)2CHC(=O). Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O), and various pentoxycarbonyl or hexoxycarbonyl isomers. The term "alkylcarbonyloxy" refers to a linear or branched alkyl group bonded to the C(=O)O moiety. Examples of "alkylcarbonyloxy" include CH3CH2C(=O)O and (CH3)2CHC(=O)O. "(Alkylthio)carbonyl" refers to a linear or branched alkylthio group bonded to the C(=O) moiety. Examples of "(alkylthio)carbonyl" include CH3SC(=O), CH3CH2CH2SC(=O), and (CH3)2CHSC(=O). "Alkoxy(thiocarbonyl)" refers to a linear or branched alkoxy group bonded to the C(=S) moiety. Examples of "Alkoxy(thiocarbonyl)" include CH3OC(=S), CH3CH2CH2OC(=S), and (CH3)2CHOC(=S).

[0033] "Alkylamino" refers to an NH radical substituted with a linear or branched alkyl group. Examples of "alkylamino" include CH3CH2NH, CH3CH2CH2NH, and (CH3)2CHNH. Examples of "dialkylamino" include (CH3)2N, (CH3CH2)2N, and CH3CH2(CH3)N. The term "alkylcarbonylamino" refers to an alkyl group bonded to the C(=O)NH moiety. Examples of "alkylcarbonylamino" include CH3C(=O)NH and CH3CH2C(=O)NH.

[0034] The term "cycloalkyl" refers to a saturated carbon ring consisting of 3 to 6 carbon atoms linked to each other by single bonds. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkylalkyl" refers to a cycloalkyl substitution on an alkyl group. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to linear or branched alkyl groups. "Alkylcycloalkyl" refers to an alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl. The term "cycloalkoxy" refers to a cycloalkyl group bonded to an oxygen atom and linked via this oxygen atom (e.g., cyclopentyloxy and cyclohexyloxy). The term "cycloalkenylene" refers to a cycloalkendiyl ring containing one olefin bond. Examples of "cycloalkenylene" include cyclopropenylene and cyclopentenylene.

[0035] The term "halogen," either alone or in compound terms such as "halomethyl" or "haloalkyl," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound terms such as "haloalkyl," the alkyl may be partially or completely substituted with the same or different halogen atoms. Examples of "haloalkyl" include F3C, ClCH2, CF3CH2, and CF3CCl2. The terms "haloalkenyl," "haloalkoxy," "haloalkylthio," "haloalkylsulfinyl," "haloalkylsulfonyl," "halocycloalkyl," and similar terms are defined in the same way as the term "haloalkyl." Examples of "haloalkenyl" include Cl2C=CHCH2 and CF3CH2=CH. Examples of "haloalkoxy" include CF3O, CCl3CH2O, F2CHCH2CH2O, and CF3CH2O. Examples of "haloalkylthio" include CCl3S, CF3S, CCl3CH2S, and ClCH2CH2CH2S. Examples of "haloalkylsulfinyl" include CF3S(=O), CCl3S(=O), CF3CH2S(=O), and CF3CF2S(=O). Examples of "haloalkylsulfonyl" include CF3S(=O)2, CCl3S(=O)2, CF3CH2S(=O)2, and CF3CF2S(=O)2. Examples of "halocycloalkyl" include chlorocyclopropyl, fluorocyclobutyl, and chlorocyclohexyl.

[0036] "Cyanoalkyl" refers to an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2, and CH3CH(CN)CH2. The term "cyanoalkoxy" is defined similarly to the term "cyanoalkyl."

[0037] The total number of carbon atoms in the substituent is "C i ~C jThese are indicated by the prefix ", where i and j are numbers from 1 to 6. For example, C1-C3 alkyl represents from methyl to propyl; C2 alkoxyalkyl represents CH3OCH2; C3 alkoxyalkyl represents, for example, CH3CH(OCH3), CH3OCH2CH2, or CH3CH2OCH2; and C4 alkoxyalkyl represents various isomers of alkyl groups substituted with alkoxy groups containing a total of four carbon atoms (including, for example, CH3CH2CH2OCH2 and CH3CH2OCH2CH2).

[0038] In relation to ring-like groups, the term “unsubstituted” means a group that has no substituents on one or more bonds with respect to the remainder of Formula 1. The term “possibly substituted” means that the number of substituents may be zero. Unless otherwise specified, a potentially substituted group may be substituted with as many arbitrary substituents as possible, as long as it is possible to replace hydrogen atoms on various available carbon or nitrogen atoms with non-hydrogen substituents. Generally, the number of arbitrary substituents (if present) is in the range of 1 to 3. As used herein, the term “possibly substituted” is interchangeable with the phrases “substituted or unsubstituted” or “(un)substituted.”

[0039] The number of substituents may be limited by the expressed limits. For example, "In some cases, R 4 The phrase "substituted with up to three substituents independently selected from " means that there can be 0, 1, 2, or 3 substituents (if the number of possible bond sites allows).

[0040] The specified range for the number of substituents (for example, in Appendix A, n is an integer from 0 to 4) is the number of available positions for substituents on the ring (for example, in Appendix A, on A-6 (R 4 ) n If the number of available locations exceeds two, the actual upper limit of this range is recognized as the number of available locations.

[0041] The nomenclature of substituents in this disclosure uses recognized terminology that provides conciseness for accurately conveying the chemical structure to those skilled in the art. For the sake of brevity, locant descriptors may be omitted.

[0042] The term "ring member" refers to an atom (e.g., C, O, N, or S) or other part (e.g., C(=O), C(=S), S(=O), and S(=O)2) that forms the framework of a ring or ring system. The term "aromatic" indicates that each ring atom is essentially coplanar and has a p orbital perpendicular to the ring plane, and that the arrangement of (4n+2)π electrons (where n is a positive integer) is related to the ring in order to obey Hückel's rule.

[0043] The term "carbocyclic ring" refers to a ring in which the atoms forming the ring's framework are selected from carbon atoms only. Unless otherwise specified, a carbocyclic ring can be saturated, partially unsaturated, or completely unsaturated. If a completely unsaturated carbocyclic ring satisfies Hückel's rule, the ring is also called an "aromatic ring." A "saturated carbocyclic ring" refers to a ring having a framework of carbon atoms linked to one another by single bonds, where, unless otherwise specified, the remaining carbon atoms are occupied by hydrogen atoms.

[0044] As used herein, the terms “partially unsaturated ring” or “partially unsaturated heterocycle” refer to a ring that contains an unsaturated ring atom and one or more double bonds but is not aromatic.

[0045] The term "heterocyclic ring" or "heterocycle" refers to a ring in which at least one of the atoms forming the ring's framework is not carbon. Unless otherwise specified, a heterocyclic ring can be saturated, partially unsaturated, or completely unsaturated. If a completely unsaturated heterocyclic ring satisfies Hückel's rule, the ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring." A "saturated heterocyclic ring" refers to a heterocyclic ring that contains only single bonds between its ring members.

[0046] Unless otherwise indicated, heterocycles are bonded to the remainder of Formula 1 via any available carbon or nitrogen atom, by substitution of hydrogen atoms on said carbon or nitrogen atom.

[0047] The compounds of the present invention may have one or more stereoisomers. Stereoiomers are isomers that have the same composition but differ in the spatial arrangement of their atoms, and include enantiomers, diastereomers, cis- and trans-isomers (also called geometric isomers), and atropisomers. Atropisomers arise from binding rotations around single bonds, and because the barrier to these rotations is high, it is possible to isolate these isomer species. As those skilled in the art will understand, one stereoisomer may be more reactive and / or exhibit a more advantageous effect when concentrated in a higher concentration than other stereoisomers or when separated from other stereoisomers. In addition, those skilled in the art will know methods for separating, enriching, and / or selectively preparing such stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see: Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0048] The present invention includes all stereoisomers, conformational isomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.

[0049] As those skilled in the art will recognize, not all nitrogen-containing heterocycles can form N-oxides, because the nitrogen requires an available lone pair of electrons to be oxidized to an oxide. Those nitrogen-containing heterocycles capable of forming N-oxides will be well known to those skilled in the art. It will also be well known to those skilled in the art that tertiary amines can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines, including oxidizing heterocycles and tertiary amines with peroxy acids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide and sodium perborate, and dioxiranes such as dimethyldioxiran, are very well known to those skilled in the art.These methods for preparing N-oxides are widely described in the literature, and review articles have been written about them. For example, please refer to the following: TLGilchrist, Comprehensive Organic Synthesis, vol.7, pp.748-750 (SVLey, Ed., Pergamon Press); M.Tisler and B.Stanovnik, Comprehensive Heterocyclic Chemistry, vol.3, pp.18-20 (AJBoulton and A.McKillop, Eds., Pergamon Press); MRGrimmett and BRTKeene, Advances in Hetrocyclic Chemistry, vol.43, pp.149-161 (ARKatritzky, Ed., Academic Press); M.Tisler and B.Stanovnik, Advances in Hetrocyclic Chemistry, vol.9, pp.285-291 (ARKatritzky and AJBoulton, Eds., Academic Press) Press); and GWHCheeseman and ESGWerstiuk, Advances in Hetrocyclic Chemistry, vol. 22, pp. 390-392 (ARKatritzky and AJ Boulton, Eds., Academic Press).

[0050] As those skilled in the art recognize, under environmental and physiological conditions, salts of compounds are in equilibrium with their corresponding unsalted forms, and therefore salts share biological utility with their unsalted forms. For this reason, a wide variety of salts of the compounds of formula 1 are useful (i.e., agriculturally suitable) for controlling plant diseases caused by fungal plant pathogens. Examples of salts of the compounds of formula 1 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, propic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. If the compound of formula 1 contains an acidic residue such as a carboxylic acid, the salt may further include those formed using organic or inorganic bases such as: pyridine, triethylamine, or ammonia, or hydroxides or carbonates of amides, hydrides, sodium, potassium, lithium, calcium, magnesium, or barium. Therefore, the present invention includes compounds selected from Formula 1, their N-oxides, and agriculturally suitable salts and solvates.

[0051] Compounds selected from Formula 1, their stereoisomers, tautomers, N-oxides, and salts typically exist in two or more forms; therefore, Formula 1 encompasses all crystalline and amorphous forms of the compounds represented by Formula 1. Amorphous forms include solid embodiments such as waxes and rubbers, as well as liquid embodiments such as solutions and melts. Crystalline forms include embodiments that substantially represent single-crystal types, and embodiments that represent mixtures of polymorphs (i.e., multiple crystalline types). The term "polymorph" refers to a particular crystalline form of a compound that can crystallize in various crystalline forms, and these forms have various arrangements and / or conformations of molecules in the crystal lattice. Multiple polymorphs may have the same chemical composition, but they may also differ in composition depending on the presence or absence of co-crystallized water or other molecules that can be weakly or strongly bonded in their lattice. Polymorphs can differ in terms of chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension properties, dissolution rate, and biological availability. As those skilled in the art will acknowledge, polymorphs of compounds represented by Formula 1 can exhibit advantageous effects (e.g., suitability for preparing useful formulations, improved biological performance) compared to other polymorphs of the same compound represented by Formula 1, or mixtures of multiple polymorphs. The preparation and isolation of specific polymorphs of compounds represented by Formula 1 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 polymorphism, see: R. Hilfiker Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

[0052] Embodiments of the present invention, as described in [Means for Solving the Problems], include those described below. In the following embodiments, Formula 1 includes their stereoisomers, N-oxides, and salts, and the term "compound of Formula 1" includes the definitions of substituents specified in [Means for Solving the Problems], unless further defined in the embodiments.

[0053] [Embodiment 1] The compound of formula 1, where W is O.

[0054] [Embodiment 2] The compound of formula 1, where W is S.

[0055] [Embodiment 3] Q 1 and Q 2 However, each is independent, as shown in Appendix A. [ka] [ka] Select from A-1 to A-47 shown, In the formula, a floating bond is connected to Equation 1 via any available carbon or nitrogen atom of the ring being depicted, where n is independently 0, 1, 2, 3, or 4. A compound according to Formula 1 or Embodiment 1 or 2.

[0056] [Embodiment 4] The compound according to Embodiment 3, wherein each n is independently 0, 1, 2, or 3.

[0057] [Embodiment 5] The compound according to Embodiment 4, wherein each n is independently 1, 2, or 3.

[0058] [Embodiment 6] The compound according to Embodiment 5, wherein each n is independently 2 or 3.

[0059] [Embodiment 7] Q 1 and Q 2 However, each is independently selected from A-1 to A-13, A-19, A-20, A-21, A-23, A-24, A-25, and A-26, and is a compound according to Formula 1 or any one of Embodiments 1 to 6.

[0060] [Embodiment 8] Q 1 and Q 2 The compounds according to Embodiment 7, each independently selected from A-1, A-2, A-3, A-4, A-5, A-6, A-7, and A-19.

[0061] [Embodiment 9] Q 1 and Q 2 However, each compound is independently selected from A-1, A-4, A-5, and A-19, as described in Embodiment 9.

[0062] [Embodiment 10] Q 1 and Q 2 However, each compound is independently selected from A-1 and A-4, as described in Embodiment 9.

[0063] [Embodiment 11] Q 1 and Q 2 However, each of these is the compound described in Embodiment 10, which is 1-A.

[0064] [Embodiment 12] Q 1 However, R 4 A-1 is substituted at the 2nd and 4th positions (i.e., ortho and para positions) with substituents independently selected from; or Q 1 However, R 4 A-1 is substituted at the 2nd and 6th positions (i.e., the ortho position) with substituents independently selected from; or Q 1 However, R4 A-1 is a compound according to Formula 1 or any one of Embodiments 1 to 11, wherein A-1 is substituted at the 2nd, 4th, and 6th positions (i.e., the para and ortho positions) with substituents independently selected from A.

[0065] [Embodiment 13] Q 1 However, R 4 A-1 is substituted at the 2nd and 4th positions (i.e., ortho and para positions) with substituents independently selected from; or Q 1 However, R 4 The compound according to Embodiment 12, wherein A-1 is substituted at the 2nd and 6th positions (i.e., the ortho position) with substituents independently selected from A.

[0066] [Embodiment 14] Q 1 However, R 4 The compound according to Embodiment 13, which is A-1 substituted at the 2nd and 4th positions with substituents independently selected from the original compound.

[0067] [Embodiment 15] Q 1 However, R 4 The compound according to Embodiment 13, wherein A-1 is substituted at the 2nd and 6th positions (i.e., the ortho position) with substituents independently selected from A.

[0068] [Embodiment 16] Q 2 However, R 4 A-1 is substituted at the 3rd and 5th positions (i.e., the meta position) with substituents independently selected from; or Q 2 However, R 4 A-1 is substituted at the 2nd and 4th positions (i.e., ortho and para positions) with substituents independently selected from; or Q 2 However, R 4 A-1 is substituted at the 2nd and 5th positions (i.e., the para and meta positions) with substituents independently selected from; or Q 2 However, R 4A-1 is a compound according to Formula 1 or any one of Embodiments 1 to 15, wherein A-1 is substituted at the 2nd, 3rd, and 5th positions (i.e., the ortho and meta positions) with substituents independently selected from A.

[0069] [Embodiment 17] Q 2 However, R 4 A-1 is substituted at the 3rd and 5th positions (i.e., the meta position) with substituents independently selected from; or Q 2 However, R 4 A-1 is substituted at positions 2 and 5 (i.e., ortho and para) with substituents independently selected from; or Q 2 However, R 4 The compound according to Embodiment 16, wherein A-1 is substituted at the 2nd, 3rd, and 5th positions (i.e., the ortho and meta positions) with substituents independently selected from A.

[0070] [Embodiment 18] Q 2 However, R 4 A-1 is substituted at the 3rd and 5th positions (i.e., the meta position) with substituents independently selected from; or Q 2 However, R 4 The compound according to Embodiment 17, wherein A-1 is substituted at the 2nd and 5th positions (i.e., the ortho and para positions) with substituents independently selected from A.

[0071] [Embodiment 19] Q 1 However, R 4 A-1 is substituted with substituents independently selected from Q at positions 2 and 4 or 2 and 6, and Q 2 However, R 4 A-1 is a compound according to Formula 1 or any one of Embodiments 1 to 18, wherein A-1 is substituted at the 3rd and 5th positions, at the 2nd and 5th positions, or at the 2nd, 3rd, and 5th positions with substituents independently selected from A.

[0072] [Embodiment 20] R 1The compound according to Formula 1 or any one of Embodiments 1 to 19, wherein the compound is a cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, or C2-C3 cyanoalkoxy; or a cyclopropyl optionally substituted with up to three substituents independently selected from halogens and methyl.

[0073] [Embodiment 20a] R 1 The compound according to Embodiment 20, wherein the compound is an amino, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, C1-C3 alkylamino, C2-C4 dialkylamino, C4-C5 alkylcarbonylamino, C2-C4 alkoxyalkylamino, or C2-C3 cyanoalkoxy; or a cyclopropyl optionally substituted with up to three substituents independently selected from halogens and methyl.

[0074] [Embodiment 21] R 1 The compound according to Embodiment 20, wherein the compound is cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, or C2-C3 cyanoalkoxy.

[0075] [Embodiment 21a] R 1The compound according to Embodiment 21, wherein it is amino, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, C1-C3 alkylamino, C2-C4 dialkylamino, C2-C4 alkoxyalkylamino, or C2-C3 cyanalkoxy.

[0076] [Embodiment 22] R 1 The compound according to Embodiment 21, wherein it is cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, or C2-C3 cyanalkoxy.

[0077] [Embodiment 22a] R 1 The compound according to Embodiment 22, wherein it is amino, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, C1-C3 alkylamino, C2-C4 dialkylamino, or C2-C3 cyanalkoxy.

[0078] [Embodiment 23] R 1 The compound according to Embodiment 22, wherein it is C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy.

[0079] [Embodiment 23a] R 1 The compound according to Embodiment 23, wherein it is amino, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, or C1-C3 alkylamino.

[0080] [Embodiment 24] R 1The compound according to Embodiment 23, wherein it is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy.

[0081] [Embodiment 24a] R 1 The compound according to Embodiment 24, wherein it is amino, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, or C1-C2 alkylamino.

[0082] [Embodiment 25] R 1 The compound according to Embodiment 24, wherein it is C1-C2 alkyl or C1-C2 alkoxy.

[0083] [Embodiment 25a] R 1 The compound according to Embodiment 25, wherein it is amino, C1-C2 alkyl, or C1-C2 alkoxy.

[0084] [Embodiment 26] R 1 The compound according to Embodiment 25, wherein it is methyl.

[0085] [Embodiment 27] R 2 The compound according to Formula 1 or any one of Embodiments 1-26, wherein it is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl, C2-C3 haloalkynyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; or cyclopropyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, and methyl.

[0086] [Embodiment 28] R 2The compound according to Embodiment 27, wherein the compound is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy.

[0087] [Embodiment 29] R 2 The compound according to Embodiment 28, wherein the compound is H, halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C2-C3 cyanoalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy.

[0088] [Embodiment 30] R 2 The compound according to Embodiment 29, wherein the compound is H, halogen, cyano, C1-C2 alkyl, or C1-C2 haloalkyl.

[0089] [Embodiment 31] R 2 The compound according to Embodiment 30, wherein the compound is H, halogen, cyano, or C1-C2 alkyl.

[0090] [Embodiment 32] R 2 The compound according to Embodiment 31, wherein the compound is halogen, cyano, methyl, or ethyl.

[0091] [Embodiment 33] R 2 The compound according to Embodiment 32, wherein the compound is halogen, methyl, or ethyl.

[0092] [Embodiment 33a] R 2 The compound according to Embodiment 33, wherein the compound is a halogen or methyl.

[0093] [Embodiment 33b] R 2 However, the compound described in Embodiment 33a is a halogen.

[0094] [Embodiment 34] R 2 The compound according to embodiment 33b, wherein the compound is Br or Cl.

[0095] [Embodiment 35] R 2 However, the compound described in Embodiment 34 is Cl.

[0096] [Embodiment 36] R 3 The ring is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; or a 3-6 membered non-aromatic ring comprising a carbon atom and, optionally, a ring member selected independently from up to 2 oxygen atoms, up to 2 sulfur atoms, and up to 4 heteroatoms independently selected from up to 4 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and each ring may optionally be R 5 A compound according to Formula 1 or any one of Embodiments 1 to 35, substituted with up to three substituents independently selected from the original compound.

[0097] [Embodiment 37] R 3 The compound according to Embodiment 36, wherein the compound is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy.

[0098] [Embodiment 38] R 3 The compound according to Embodiment 37, wherein the compound is H, a halogen, a C1-C2 alkyl, or a C1-C2 haloalkyl.

[0099] [Embodiment 39] R 3 The compound according to Embodiment 38, wherein the compound is H, a halogen, or a C1-C2 alkyl group.

[0100] [Embodiment 40] R 3The compound according to Embodiment 39, wherein the element is H, Br, Cl, or methyl.

[0101] [Embodiment 41] R 3 The compound according to Embodiment 40, wherein H is present.

[0102] [Embodiment 42] Each R 4 The compound according to Formula 1 or any one of Embodiments 1 to 41, wherein each of the following is independently a halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 alkynyloxy, C2-C4 haloalkynyloxy, C2-C4 alkylcarbonyloxy, C2-C4 haloalkylcarbonyloxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, or -UVT.

[0103] [Embodiment 43] Each R 4 The compound according to Embodiment 42, wherein independently, it is a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, or -UVT.

[0104] [Embodiment 44] Each R 4 The compound according to Embodiment 43, wherein the compound is independently a halogen, a C1-C3 alkyl, a C1-C3 haloalkyl, a C2-C3 alkenyl, a C2-C3 haloalkenyl, a C1-C3 alkoxy, or a C1-C3 haloalkoxy.

[0105] [Embodiment 45] Each R 4 The compound according to Embodiment 44, wherein the compound is independently a halogen, a C1-C3 alkyl, a C1-C3 haloalkyl, a C1-C3 alkoxy, or a C1-C3 haloalkoxy.

[0106] [Embodiment 46] Each R 4 The compound according to Embodiment 45, wherein the compound is independently a halogen, a C1-C2 alkyl, a C1-C2 haloalkyl, a C1-C2 alkoxy, or a C1-C2 haloalkoxy.

[0107] [Embodiment 47] Each R 4 The compound according to Embodiment 46, wherein independently, it is Br, Cl, F, methyl, C1-C2 alkoxy, or C1-C2 haloalkoxy.

[0108] [Embodiment 48] Each R 4 The compound according to Embodiment 47, wherein the compound is independently Br, Cl, F, methyl, methoxy, or ethoxy.

[0109] [Embodiment 49] Each R 4 The compound according to Embodiment 48, wherein the compound is independently Br, Cl, F, or methoxy.

[0110] [Embodiment 50] Each R 5 The compound according to Formula 1 or any one of Embodiments 1 to 49, wherein the compound is independently a halogen, cyano, methyl, halomethyl, or methoxy.

[0111] [Embodiment 51] Each U can be independently directly bonded, O, or NR. 6 A compound according to Formula 1 or any one of Embodiments 1 to 50.

[0112] [Embodiment 52] The compound according to Embodiment 51, wherein each U is independently a directly bonded O or NH.

[0113] [Embodiment 53] The compound according to Embodiment 52, wherein each U is directly bonded.

[0114] [Embodiment 54] The compound according to Formula 1 or any one of Embodiments 1 to 53, wherein each V is independently a C1-C3 alkylene, up to two carbon atoms are C(=O), and optionally substituted with up to three substituents independently selected from halogens, C1-C2 alkyls, C1-C2 haloalkyls, C1-C2 alkoxys, and C1-C2 haloalkoxys.

[0115] [Embodiment 55] The compound according to Embodiment 54, wherein each V is independently a C1-C3 alkylene, where up to one carbon atom is C(=O) and optionally substituted with up to two substituents independently selected from halogens, methyl, halomethyl, and methoxy.

[0116] [Embodiment 56] The compound according to Embodiment 55, wherein each V is independently CH2 or CH2CH2.

[0117] [Embodiment 57] The compound according to Embodiment 56, wherein each V is CH2.

[0118] [Embodiment 58] Each T is independent of NR 7a R 7b OR 8 A compound according to Formula 1 or any one of Embodiments 1 to 57.

[0119] [Embodiment 59] Each R 6The compound according to Formula 1 or any one of Embodiments 1 to 58, wherein each of the following is independently H, C1-C3 alkyl, C1-C3 haloalkyl, or C2-C4 alkylcarbonyl.

[0120] [Embodiment 60] Each R 6 The compound according to Embodiment 59, wherein the compound is independently H or methyl.

[0121] [Embodiment 61] R 7a and R 7b However, if they are separate (i.e., do not form a ring together), then each R 7a and R 7b The compound according to Formula 1 or any one of Embodiments 1 to 60, wherein each of the following is independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, C2-C3 alkylcarbonyl, or C2-C3 alkoxycarbonyl.

[0122] [Embodiment 62] Each R 7a and R 7b The compound according to Embodiment 61, wherein the member is independently H, C1-C2 alkyl, C1-C2 haloalkyl, or cyclopropyl.

[0123] [Embodiment 63] Each R 7a and R 7b The compound according to Embodiment 62, wherein the compound is independently H, methyl, or halomethyl.

[0124] [Embodiment 64] R 7a and R 7b However, if they form a ring together (i.e., are not separated), each R 7a and R 7b However, together with the nitrogen atom to which they are bonded, they form a 3-6 member heterocycle, and this ring can, in some cases, R 10A compound according to Formula 1 or any one of Embodiments 1 to 63, substituted with up to two substituents independently selected from the compound.

[0125] [Embodiment 65] Each R 7a and R 7b However, the compound according to embodiment 64, wherein these atoms, together with the nitrogen atoms to which they are bonded, form a 3- to 6-membered heterocycle.

[0126] [Embodiment 66] Each R 8 and R 9 The compound according to Formula 1 or any one of Embodiments 1 to 65, wherein the compound is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, or cyclopropyl.

[0127] [Embodiment 67] Each R 8 and R 9 The compound according to Embodiment 66, wherein each component is independently H, C1-C2 alkyl, or C1-C2 haloalkyl.

[0128] [Embodiment 68] Each R 8 and R 9 The compound according to Embodiment 67, wherein the compound is independently methyl or ethyl.

[0129] [Embodiment 69] Each R 10 The compound according to Formula 1 or any one of Embodiments 1 to 68, wherein the compound is independently a halogen, methyl, halomethyl, or methoxy.

[0130] [Embodiment 70] A compound according to Formula 1 or any one of Embodiments 1 to 69, wherein each m is 0 or 2.

[0131] The embodiments of the present invention, including Embodiments 1 to 70 described above, as well as various other embodiments described herein, may be combined in any way, and the various descriptions in those embodiments relate not only to the compound of Formula 1, but also to the starting compound and intermediate compounds useful for preparing the compound of Formula 1. In addition, the embodiments of the present invention, including Embodiments 1 to 70 described above, as well as various other embodiments described herein, and various combinations thereof, also relate to the composition and method of the present invention.

[0132] The combinations of Embodiments 1 to 70 are shown below. [Embodiment A] W is O; Q 1 and Q 2 However, each is independent, A-1 to A-47 [ka] [ka] Selected from, In the formula, the floating bond is connected to formula 1 via any available carbon or nitrogen atom of the ring being depicted, where n is independently 0, 1, 2, 3, or 4; R 1 However, it is a cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, or C2-C3 cyanoalkoxy; or it is a cyclopropyl optionally substituted with up to three substituents independently selected from halogens and methyl; R 2is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl, C2-C3 haloalkynyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; or is a cyclopropyl optionally substituted with up to three substituents independently selected from halogen, cyano, and methyl; R 3 The ring is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; or a 3-6 membered non-aromatic ring comprising a carbon atom and, optionally, a ring member selected independently from up to 2 oxygen atoms, up to 2 sulfur atoms, and up to 4 heteroatoms independently selected from up to 4 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and each ring may optionally be R 5 It is substituted with up to three substituents independently selected from; Each R 4 However, independently, these are halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 alkynyloxy, C2-C4 haloalkynyloxy, C2-C4 alkylcarbonyloxy, C2-C4 haloalkylcarbonyloxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, or -UVT; Each R 5 However, these are independently halogen, cyano, methyl, halomethyl, or methoxy; Each U can be independently directly bonded, O, or NR. 6 and; Each V is independently a C1-C3 alkylene, with up to one carbon atom being C(=O), and possibly substituted with up to two substituents independently selected from halogens, methyl, halomethyl, and methoxy; Each T is independent of NR 7a R 7b OR 8 and; Each R 6 However, these are independently H, C1-C3 alkyl, C1-C3 haloalkyl, or C2-C4 alkylcarbonyl; Each R 7a and R 7b However, these are independently H, C1-C2 alkyl, C1-C2 haloalkyl, or cyclopropyl; Each R 8 However, independently, they are H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, or cyclopropyl. The compound of formula 1.

[0133] [Embodiment B] Q 1 and Q 2 However, each is independently selected from A-1, A-2, A-3, A-4, A-5, A-6, A-7, and A-19; R 1 However, it is cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, or C2-C3 cyanoalkoxy; R 2 However, it is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 3 However, it is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; Each R 4 is independently halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, or -U-V-T; Each U is independently a direct bond, O, or NH; Each V is independently CH2 or CH2CH2; Each R 7a and R 7b are independently H, methyl, or halomethyl; Each R 8 is independently H, C1-C2 alkyl, or C1-C2 haloalkyl, The compound according to Embodiment A.

[0134] [Embodiment C] Q 1 and Q 2 are each independently selected from A-1, A-4, A-5, and A-19; Each n is independently 1, 2, or 3; R 1 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy; R 2 is H, halogen, cyano, or C1-C2 alkyl; R 3 is H, halogen, or C1-C2 alkyl; Each R 4 is independently halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy, The compound according to Embodiment B.

[0135] [Embodiment D] Q 1 and Q 2 are each 1-A; Each n is independently either 2 or 3; R 1 However, it is a C1-C2 alkyl or C1-C2 alkoxy; R 2 However, it is halogen, cyano, methyl, or ethyl; R 3 However, it is H, Br, Cl, or methyl; Each R 4 However, independently, they are halogens, C1-C2 alkyls, C1-C2 haloalkyls, C1-C2 alkoxys, or C1-C2 haloalkoxys. The compound described in Embodiment C.

[0136] [Embodiment E] Q 1 However, R 4 A-1 is substituted at the 2nd and 4th positions with substituents independently selected from; or Q 1 However, R 4 A-1 is substituted at the 2nd and 6th positions with substituents independently selected from; or Q 1 However, R 4 A-1 is a substituent independently selected from the original A-1 at positions 2, 4, and 6; R 1 However, it is methyl; Each R 4 However, independently, they are Br, Cl, F, methyl, C1-C2 alkoxy, or C1-C2 haloalkoxy. The compound described in Embodiment D.

[0137] [Embodiment F] Q 1 However, R 4 A-1 is substituted at positions 2 and 4 or 2 and 6 with substituents independently selected from; R 2 However, it is a halogen, methyl, or ethyl; R 3 However, H is; Each R 4 However, independently, they are Br, Cl, F, methyl, methoxy, or ethoxy. The compound described in Embodiment E.

[0138] [Embodiment G] W is O; Q 1 and Q 2 However, each is independently selected from A-1, A-4, A-5, and A-19; Each n is independently 1, 2, or 3; R 1 However, it is amino, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 cyanoalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, C1-C3 alkylamino, C2-C4 dialkylamino, C2-C4 alkoxyalkylamino, or C2-C3 cyanoalkoxy; R 2 However, it is H, halogen, cyano, or C1-C2 alkyl; R 3 However, it is H, a halogen, or a C1-C2 alkyl; Each R 4 However, independently, they are halogens, C1-C3 alkyls, C1-C3 haloalkyls, C1-C3 alkoxys, or C1-C3 haloalkoxys. The compound of formula 1.

[0139] [Embodiment H] Q 1 and Q 2 However, each of them is 1-A; Each n is independently either 2 or 3; R 1 However, these are amino, C1-C2 alkyl, C1-C2 alkoxy, C1-C2 alkylamino, or C2-C4 dialkylamino; R 2 However, it is halogen, cyano, methyl, or ethyl; R 3 However, it is H, Br, Cl, or methyl; Each R 4is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy, The compound according to Embodiment G.

[0140] [Embodiment I] Q 1 is R 4 Is A-1 substituted at the 2- and 4-positions with substituents independently selected from R 4 Is A-1 substituted at the 2- and 6-positions with substituents independently selected from R 1 is R 4 Is A-1 substituted at the 2-, 4-, and 6-positions with substituents independently selected from R; R 1 is amino, methyl, or methylamino; Each R 4 is independently Br, Cl, F, methyl, C1-C2 alkoxy, or C1-C2 haloalkoxy, The compound according to Embodiment H.

[0141] Specific embodiments are as follows: 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone (Compound 4); 5-(2-bromo-3,5-dimethoxyphenyl)-3-chloro-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone (Compound 9); 5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-2(1H)-pyridinone (Compound 13); 5-(2-bromo-5-methoxyphenyl)-3-chloro-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone (Compound 20); 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone (Compound 29); 3-Chloro-5-(2-chloro-5-methoxyphenyl)-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone (compound 30); 3-Chloro-4-(2-chloro-4-fluorophenyl)-5-(2-chloro-5-methoxyphenyl)-1-methyl-2(1H)-pyridinone (compound 32); 3-Bromo-4-(2-chloro-4-fluorophenyl)-5-(2-chloro-5-methoxyphenyl)-1-methyl-2(1H)-pyridinone (compound 33); 4-(2-chloro-4-fluorophenyl)-5-(2-chloro-5-methoxyphenyl)-1,3-dimethyl-2(1H)-pyridinone (compound 43); 3-Chloro-4-(2,4-difluorophenyl)-5-(2-fluoro-3,5-dimethoxyphenyl)-1-methyl-2(1H)-pyridinone (compound 51); 5-(2-chloro-5-methoxyphenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-2(1H)-pyridinone; and 5-(2-bromo-5-methoxyphenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-2(1H)-pyridinone It includes a compound of formula 1 selected from the group consisting of the following:

[0142] In addition to the embodiments described above, the present invention also provides fungicidal compositions comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) and at least one other fungicide. Of particular note as embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above.

[0143] The present invention also provides fungicidal compositions comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) (i.e., a fungicidally effective amount of the compound of Formula 1) and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents. Of particular note as embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above.

[0144] The present invention provides a method for controlling plant diseases caused by fungal plant pathogens, comprising applying a fungicidal effective amount of a compound of formula 1 (including all stereoisomers, N-oxides, and salts thereof) to a plant, a part thereof, or a plant seed. Of particular note as an embodiment of such a method is a method comprising applying a fungicidal effective amount of a compound corresponding to any of the compound embodiments described above. Of particular note is an embodiment in which this compound is applied as a composition of the present invention.

[0145] The compounds of formula 1 can be prepared using one or more of the following methods and modifications described in schemes 1 to 12. W and Q in the compounds of formulas 1 to 18 below. 1 Q 2 , R 1 , R 2 , and R 3 The definition of is as defined above in the summary of the present invention, unless otherwise specified. The compounds of formula 1a are various subsets of the compounds of formula 1, and all substituents of formula 1a are as defined above with respect to formula 1, unless otherwise specified.

[0146] As shown in Scheme 1, the compound of formula 1a (i.e., formula 1 where W is O) is converted to formula 3 (wherein Lg is a leaving group such as a halogen, (halo)alkyl sulfonate, or nonafluorobutanesulfonate (e.g., Cl, Br, I, p-toluenesulfonate, methanesulfonate, or trifluoromethanesulfonate), and R 1 However, it can be prepared by alkylation of the compound of formula 2 with a compound of alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like. Where used herein, the terms “alkylation” and “alkylating agent” are used in reference to R 1The alkyl group is not limited to being an alkyl group. Particularly useful alkylating agents include, but are not limited to, alkyl halides and similar compounds (e.g., iodoethane, allyl bromide, propargyl chloride, cyanide bromide), and alkyl sulfates (e.g., dimethyl sulfate). This reaction is often carried out in the presence of a base (e.g., sodium hydride, potassium tert-butoxide, sodium ethoxide, or potassium carbonate) and in a solvent compatible with the base (e.g., dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, or ethanol). This reaction can be carried out at temperatures in the range of about 0 to 100°C. Alternatively, the alkyl group can be transferred as an alkyl carbocation, free radical, carbanion, or carbene. For example, formula 1 (wherein R 1 However, the preparation of the haloalkyl (e.g., CHF2 or CHCl2) compound can be achieved under difluorocarbene-mediated conditions by contacting the compound of formula 2 with 2-chloro-2,2-difluoroacetic acid or 2,2-difluoro-2-(fluorosulfonyl)acetic acid in a solvent such as acetonitrile and in the presence of a base such as sodium bicarbonate. General procedures for the N-alkylation of 2-pyridone are well described in the chemical literature; see, for example, Journal of Medicinal Chemistry 1980, 23(12), 1398-1405; Organic Biomolecular Chemistry 2008, 16, 4151-4158; and Royal Society of Chemistry 2020, 10, 29829-29832. It will be apparent to those skilled in the art that regioselective N-alkylation versus O-alkylation depends on various factors (e.g., the structure of the alkylating agent, the substituents on the 2-pyridone ring of formula 2, the solvent, and the temperature). The conversion and regioselectivity of these alkylations can be improved by changing the reaction conditions. For references discussing regioselective N-alkylation conditions, see Organic Letters 2015, 17, 3382-3385; and Tetrahedron Letters 2013, 54(30), 3926-3928.

[0147] Carbene reagents (e.g., difluorocarbenes) can be produced by several methods under various reaction conditions (e.g., phase-transfer conditions). The most common phase-transfer conditions involve chloroform, hydrated sodium hydroxide or potassium hydroxide, and a phase-transfer reagent (e.g., benzyltriethylammonium chloride (TEBA), 2-benzyridine-N,N,N,N,N,N-hexaethylpropane-1,2-diammonium dibromide (Diqua), and 18-crown-6). For an overview of this type of reaction, see Organic Synthesis, Fourth Edition, 2017, Pages 917-980.

[0148] Formula 1 (wherein, R 1 Compounds of formula 2 (wherein R) can be prepared from compounds of formula 2 by N-amination using reagents such as O-(diphenylphosphoryl)hydroxylamine, O-(2,4-dinitrophenyl)hydroxylamine, or O-(mesitylsulfonyl)hydroxylamine, in the presence of a base (e.g., potassium carbonate, cesium carbonate, or sodium hydroxide) in a polar solvent (e.g., N,N-dimethylformamide or N-methylpyrrolidinone) at a temperature in the range of air ~100°C. The N-amino group can be further modified by methods known to those skilled in the art to obtain compounds of formula 1 (wherein R) 1 However, compounds of alkylamino, dialkylamino, and similar types can be obtained. [ka]

[0149] As shown in Scheme 2, Q 2However, a compound of formula 1a (i.e., formula 1 where W is O), which is a carbon-linked ring, can be prepared by the reaction of an organometallic compound of formula 5 with a compound of formula 4 (wherein Lg is a leaving group such as a halogen or (halo)alkyl sulfonate (e.g., Cl, Br, I, p-toluenesulfonate, methanesulfonate, or trifluoromethanesulfonate)) under transition metal-catalyzed cross-coupling reaction conditions in the presence of a suitable palladium catalyst, copper catalyst, or nickel catalyst. In this method, the compound of formula 5 is an organoboronic acid (e.g., M is B(OH)2), an organoboronic acid ester (e.g., M is B(-OC(CH2)3O-), an organotrifluoroborate (e.g., M is BF3K), an organotin reagent (e.g., M is Sn(n-Bu)3, Sn(Me)3), a Grignard reagent (e.g., M is MgBr or MgCl), or an organozinc reagent (e.g., M is ZnBr or ZnCl). Suitable metal catalysts include, but are not limited to, palladium(II) acetate, palladium(II) chloride, tetrakis(triphenylphosphine)palladium(O), bis(triphenylphosphine)palladium(II) dichloride, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II), bis( (Liphenylphosphine) dichloronickel(II) and copper(I) salts (e.g., copper(I) iodide, copper(I) bromide, copper(I) chloride, copper(I) cyanide, or copper(I) triflate). The optimal conditions will depend, as will be understood by those skilled in the art, on the catalyst used and the counterion (i.e., M) bonded to the compound of formula 5. In some cases, the addition of a ligand (e.g., substituted phosphine or substituted bisphosphine noalkane) will enhance the reactivity. Also, some reactions involving the organoboron reagents of formula 5 may require the presence of a base (e.g., alkali carbonate, tertiary amine, or alkali fluoride). This reaction is typically carried out at temperatures in the range of about air to the boiling point of the solvent. This reaction can also be carried out at temperatures above the boiling point of the solvent by using a pressurized vessel (e.g., microwave reactor or Fischer-Porter tube).For an overview of this type of reaction, please refer to E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis, John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-Coupling Reactions: A Practical Guide, Springer, New York, 2002; H. Brown et al., Organic Synthesis via Boranes, Vol.3, Aldrich Chemical Co., Milwaukee, WI, 2002; Suzuki et al., Chemical Review 1995, 95, 2457-2483; and Molander et al., Accounts of Chemical Research 2007, 40, 275-286. Furthermore, Example 1 (Step C), Example 2 (Step B), and Example 4 (Step E) also demonstrate the method of Scheme 2 (where Q2 is a substituted phenyl ring).

[0150] The presence of certain functional groups on the compound of formula 4 may make the reaction conditions in the method of scheme 2 unsuitable, and in such cases, the use of protecting groups may be desirable to obtain the desired product with improved yield and / or purity. For example, R 1 However, in the case of a hydroxyl group, the incorporation of a hydroxyl protecting group may be advantageous in obtaining the desired product. A variety of protecting groups are suitable for use in the method of Scheme 2 (see, for example, TW Greene and PGMWuts, Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991), and the selection of an appropriate protecting group will be obvious to those skilled in chemical synthesis. Example 6 (Step C) is a product of formula 4 (wherein R 1 However, we will show the Scheme 2 method, which starts with a compound (which is a hydroxybenzyl protecting group). [ka]

[0151] As shown in Scheme 3, Q 2 However, compounds of formula 1a (i.e., formula 1 where W is O), which are heterocycles with linked nitrogen atoms, can be prepared by metal-catalyzed coupling reactions of compounds of formula 4 with heterocycles of formula 6 (wherein the formula is a heterocycle bonded to a hydrogen atom (e.g., 1H-pyrazole and 1H-imidazole)). This reaction is typically carried out in a solvent (e.g., dimethyl sulfoxide, NN-dimethylformamide, toluene, acetonitrile, or 1,4-dioxane) in the presence of a catalyst, such as a copper salt (e.g., copper(I) iodide, copper(I) bromide, copper(I) cyanide, copper(I) oxide, or copper(II) acetate) and a base (e.g., NaO-t-Bu, K2CO3, K3PO4, or Cs2CO3). In some cases, this reaction may be carried out in the presence of a ligand or solubilizer, which is generally carried out with an amine. For example, ligand catalyst systems such as CuI, N,N'-dimethylethylenediamine, N,N'-dimethyl-trans-1,2-cyclohexanediamine, proline, or bipyridyl. Typical reaction temperatures range from approximately 50°C to the boiling point of the solvent. For key references, see, for example, Nature Protocols 2007, 2(10), 2474-2479 and Journal of Organic Chemistry 2007, 72(16), 6190-6199. [ka]

[0152] As shown in Scheme 4, the compounds of formula 4 can be prepared by reacting pyridine of formula 7 (preferably 2-chloropyridine) with an alkylating agent of formula 3 (wherein Lg is Cl, Br, I, or a leaving group such as p-toluenesulfonate, methanesulfonate, or trifluoromethanesulfonate). This alkylating agent is generally present in excess, typically in the range of about 1.1 to 20 molar equivalents relative to the pyridine of formula 7. This reaction is often carried out in a solvent (e.g., tetrahydrofuran, acetonitrile, chloroform, dichloromethane, N,N-dimethylformamide, and alcohol (e.g., methanol, ethanol)) at a temperature of about 0 to 100°C. Preferably, this reaction is carried out using a solvent in which the pyridine of formula 7 is completely or at least substantially dissolved and the pyridinium salt of formula 8 typically has low solubility at air temperature (e.g., about 15 to 40°C). The subsequent conversion of the pyridinium salt of formula 8 to the compound of formula 4 can be achieved under either acidic or basic conditions. For example, treatment with an acid (e.g., acetic acid or trifluoroacetic acid), a base (e.g., triethylamine or sodium hydroxide), or a mixture thereof, often involving the addition of a second solvent (e.g., ethanol, methanol, or water) and heating of the mixture typically at a temperature below the boiling point of the solvent or solvent system. For typical procedures, see Biochemical Journal 1948, 43, 423-426; and Canadian Journal of Chemistry 2011, 89(6), 617-622. Also, in Example 1 (Step B), dimethyl sulfate is used as the alkylating agent for formula 4 (wherein R 1 Scheme 4 shows the method for obtaining a compound (where is methyl). [ka]

[0153] Formula 4 (wherein, R 1 However, compounds of a haloalkyl group (such as difluoromethyl) can be prepared using difluorocarbene-mediated conditions similar to those described in Scheme 1.

[0154] As shown in Scheme 5, Equation 4 (wherein R 2 A compound of the form of a halogen or alkyl group is given the corresponding compound of formula 4 (wherein R 2 It can be prepared from a compound of formula 4 (where R is H). Typically, halogenation can be achieved using various halogenating agents known in the art, such as elemental halogens (e.g., Cl2, Br2, I2), sulfuryl chloride, iodine monochloride, or N-halosuccinimide (e.g., NBS, NCS, NIS), in a suitable solvent such as N,N-dimethylformamide, carbon tetrachloride, acetonitrile, dichloromethane, or acetic acid. Alkylation can be achieved using formula 4 (where R is H). 2 However, the compound (which is H) is reacted with a metallizing agent, and then formula R 2 This is achieved by reacting -Lg (wherein Lg is a leaving group (e.g., Cl, Br, I, or a sulfonate (e.g., p-toluenesulfonate, methanesulfonate, or trifluoromethanesulfonate))) with an alkylating agent. Suitable metalling agents include, for example, n-butyllithium (n-BuLi), lithium diisopropylamide (LDA), or sodium hydride (NaH). As used herein, the terms "alkylation" and "alkylating agent" are used interchangeably with R 2 The group is not limited to an alkyl group, but includes groups such as haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like, in addition to alkyl. Example 2 (Step A), Example 4 (Step D), and Example 6 (Step B) use formula 4 (wherein R 2 Scheme 5 shows a method using N-chlorosuccinimide as a halogenating agent to provide a compound (which is chloro). [ka]

[0155] As shown in Scheme 6, Equation 4 (wherein R 1Compounds of alkoxy, haloalkoxy, and the like can be prepared by oxidation of pyridine of formula 7, followed by hydroxylation and then alkylation. Various oxidizing agents can be used in the method of scheme 6, for example, peracids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, sodium perborate, and magnesium monoperphthalate. The solvent is selected depending on the oxidizing agent used, for example, dichloromethane is generally preferred with MCPBA. A wide variety of oxidation conditions for preparing pyridine N-oxides that can be easily adapted to the preparation of the compounds of the present invention are described in the synthetic literature; see, for example, Bioorganic & Medicinal Chemistry 2009, 17(16), 6106-6122. For oxidation conditions using trifluoroacetic anhydride and hydrogen peroxide-urea complex, see Tetrahedron Letters 2000, 41, 2299-2302. The resulting pyridine N-oxide of formula 9 can be hydrolyzed to the corresponding hydroxypyridine of formula 9a. This reaction is typically carried out in an aqueous solution containing an inorganic base (e.g., lithium, sodium, or potassium hydroxide) at a temperature in the range of about 70–100°C. Subsequently, the compound of formula 9a is converted to formula R 1 -Lg (wherein Lg is a leaving group such as a halogen (e.g., Cl, Br, or I)) is reacted with an alkylating agent to produce formula 4 (wherein R 1 Compounds of this type (alkoxy, haloalkoxy, and the like) can be obtained. This reaction is preferably carried out in the presence of a base (e.g., potassium carbonate, potassium hydroxide, or triethylamine) and in a solvent (e.g., N,N-dimethylformamide, tetrahydrofuran, toluene, or water). General procedures for this type of alkylation are known in the art and can be readily adapted to the preparation of the compounds of the present invention. Similarly, steps A-C of this Example 4 illustrate the method of Scheme 6. [ka]

[0156] As shown in Scheme 7, Equation 4 (wherein R1 However, the compounds (which are alkyl) can also be prepared by alkylation of the compounds of formula 10, similar to the method in scheme 1. [ka]

[0157] As shown in Scheme 8, the compound of formula 7 can be prepared in a manner similar to the methods of Schemes 2 and 3. In this method, the compound of formula 12 is identical to the organometallic compound described for formula 5, and the compound of formula 13 is the same heterocycle as described for the compound of formula 6 in Scheme 3. This reaction is carried out in the same manner as shown in Schemes 2 and 3. 1 X bonded to the compound of formula 11 so that the group is first substituted to obtain the desired compound of formula 7. 1 Those skilled in the art will understand that the group should be selected considering the relative reactivity of other functional groups (e.g., Lg group) present on formula 7. Optimal selectivity (i.e., X 1 For the preferential substitution of the Lg group, under cross-coupling conditions, X 1 It must be less reactive than the other, and therefore it is possible to distinguish between the two reaction centers. For example, in equation 11 (where X 1 However, by using a compound (where I is and Lg is Br or Cl), Q at the 4-position of the pyridine ring 1 Selective introduction of rings is often possible. This embodiment 1 (step A) is given by formula 11 (wherein Lg is Br and X 1 Starting from a compound of I, we arrive at equation 7 (where Q 1 The method of Scheme 7, in which a compound (which is a substituted phenyl ring) is obtained, is explained. The method of Scheme 7 is explained by the Lg functional group and X bonded to the compound of formula 11. 1 The functional groups are reversed, therefore Q 1 Q instead of ring 2 Those skilled in the art will also recognize that this can be done if it is possible to introduce a ring. [ka]

[0158] As shown in Scheme 9, Q is obtained to obtain the compound of formula 1a. 2 Those skilled in the art will recognize that if the substituent is attached to a pyridine ring, a reaction similar to that shown in Scheme 4 may also be used. [ka]

[0159] As shown in Scheme 10, Equation 14 (wherein X 1 , R 2 , and R 3 The compound (which is Cl) can be prepared by treating the compound of formula 15 with a chlorinating agent (e.g., thionyl chloride, phosphorus oxychloride, or phosphorus pentachloride) in a solvent (e.g., dichloromethane). For typical reaction conditions, see, for example, Australian Journal of Chemistry 1968, 21(2) 467-76; and Bioorganic & Medicinal Chemistry Letters 2011, 21(10), 2958-2961. [ka]

[0160] As shown in Scheme 11, the compound of formula 15 can be prepared from the compound of formula 16 by treatment with a strong acid such as sulfuric acid, as described in Australian Journal of Chemistry 1968, 21(2) 467-76; and Monatshefte fuer Chemie 1987, 118(8-9), 987-91. Alternatively, the ester group can be initially hydrolyzed by treatment with, for example, aqueous sodium hydroxide (in a cosolvent such as methanol or tetrahydrofuran), followed by treatment with an acid (e.g., sulfuric acid or hydrochloric acid) in a solvent (e.g., water or acetic acid). See Journal of Organic Chemistry 2007, 72(16), 6091-6096 for reference. [ka]

[0161] As shown in Scheme 12, the compound of formula 16 can be prepared by reacting the compounds of formulas 17 and 18 in the presence of a base (e.g., potassium tert-butoxide) and in a solvent (e.g., 2-methyl-2-propanol or tetrahydrofuran). For reaction conditions, see Monatshefte fuer Chemie 1987, 118(8-9), 987-91. The compounds of formulas 17 and 18 are commercially available and can be prepared by methods known in the art. [ka]

[0162] The compound of formula 1 and the intermediate described above (wherein W is O) can be converted to the corresponding thiolate (wherein W is S) using various standard thiating reagents such as phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosfetan-2,4-disulfide (Lawson's reagent). This type of reaction is publicly known; see, for example, Heterocycles 1995, 40, 271-278; Journal of Medicinal Chemistry 2008, 51, 8124-8134; Journal of Medicinal Chemistry 1990, 33, 2697-706; Synthesis 1989, (5), 396-3977; J. Chem. Soc., Perkin Trans. 1, 1988, 1663-1668; Tetrahedron 1988 44, 3025-3036; and Journal of Organic Chemistry 1988 53(6), 1323-1326.

[0163] Those skilled in the art will recognize that the compounds of formula 1 can be subjected to a number of other electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to provide other functionalized compounds of formula 1. The compounds of formula 1, or intermediates for preparing them, may contain aromatic nitro groups, which can be reduced to amino groups and then converted to various halides via reactions well known to those skilled in the art (e.g., the Sandmeyer reaction). By similar known reactions, aromatic halides such as bromides or iodides prepared by the Sandmeyer reaction can be reacted with alcohols under copper-catalyzed conditions, such as the Ullmann reaction or known modifications thereof, to obtain compounds of formula 1 containing alkoxy substituents. Furthermore, it is also possible to substitute several halogen groups, such as fluorine or chlorine, with alcohols under basic conditions to obtain compounds of formula 1 containing corresponding alkoxy substituents. The compounds of formula 1, or their precursors containing halides, preferably bromides or iodides, are particularly useful as intermediates for cross-coupling reactions using transition metal catalysts for preparing compounds of formula 1. These types of reactions are extensively documented in the literature; see, for example, the following: Tsuji, "Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis," John Wiley and Sons, Chichester, 2002; Tsuji, "Palladium in Organic Synthesis," Springer, 2005; and Miyaura and Buchwald, "Cross Coupling Reactions: A Practical Guide, 2002"; and the references cited therein.

[0164] It is acknowledged that some of the reagents and reaction conditions described above for preparing the compounds of Formula 1 may be incompatible with certain functional groups present in the intermediate. In these cases, the incorporation of protection / deprotection sequences or the interconversion of functional groups in the synthesis may help in obtaining the desired product. The use and selection of protecting groups will be obvious to those skilled in chemical synthesis (see, for example, Greene, TW; Wuts, PGMP Rotective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). Those skilled in the art will recognize that, in some cases, additional periodic synthetic steps not described in detail may be required to complete the synthesis of the compounds of Formula 1 after the introduction of the reagents depicted in the individual schemes. Those skilled in the art will also recognize that, in order to prepare the compounds of Formula 1, it may be necessary to perform combinations of the steps described in the above schemes in an order other than that implied by the specific order presented.

[0165] Without further careful consideration, those skilled in the art using prior art will be able to utilize the present invention to the maximum extent. The following examples are therefore illustrative and should be construed as not limiting the present disclosure in any way. The steps in the following examples illustrate the procedure of each step in a total synthetic transformation, and the starting materials for each step may not necessarily have been produced by the specific manufacturing experiments described in other examples or steps. Ambient temperature or room temperature is defined as about 20–25°C. Percentages are by weight unless otherwise specified for chromatographic solvent mixtures. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise specified. HPLC refers to high-pressure liquid chromatography using silica gel. 1The 1H NMR spectrum is reported in ppm from tetramethylsilane to low field; "s" indicates singlet, "br s" indicates broad singlet, "d" indicates doublet, "dd" indicates doublet of doublet, "t" indicates triplet, and "m" indicates multiplet. The mass spectrum is reported under atmospheric pressure chemical ionization (AP). + ) or electrospray ionization (ESI + The H2N1 molecule was observed by using liquid chromatography in conjunction with a mass spectrometer (LCMS) that uses one of the following methods: + The molecular weight of the parent ion (M+1) with the highest isotopic abundance formed by the addition of (molecular weight 1), or the amount of H from the molecule. + This is reported as the molecular weight of (M-1) formed by the loss of (molecular weight 1). [Examples]

[0166] Example 1 Preparation of 4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methyl-2(1H)-pyridinone (compound 53) Step A: Preparation of 5-bromo-2-chloro-4-(2-chloro-4-fluorophenyl)pyridine A mixture of 1,4-dioxane (20 mL), 5-bromo-2-chloro-4-iodopyridine (1.51 g, 4.75 mmol, prepared as in Tetrahedron 2004 60(51), 11869-11874), 2-chloro-4-fluorophenylboronic acid (0.827 g, 5.72 mmol), and potassium carbonate (1.31 g, 9.49 mmol) in water (2 mL) was purged with nitrogen for 15 minutes, and then a [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex containing dichloromethane (0.19 g, 0.24 mmol) was added. The reaction mixture was heated at 100 °C for 16 hours, then cooled to ambient temperature, filtered through a Celite® bed, and rinsed with ethyl acetate (50 mL). The filtrate was poured into water (50 mL) and extracted with ethyl acetate (twice × 50 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure to obtain an oily substance (purple). The obtained oily substance was purified by CombiFlash™ chromatography (elution with petroleum ether) to obtain the title compound as an oily substance (1.2 g). 1 H NMR(CDCl3):δ 8.61(s,1H),7.30-7.25(m,2H),7.20(m,1H),7.11(m,1H). LCMS:m / z:322[M+H] +

[0167] Step B: Preparation of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone To a mixture of 5-bromo-2-chloro-4-(2-chloro-4-fluorophenyl)pyridine (i.e., the product of step A) (1.21 g, 3.77 mmol) in chloroform (30 mL), dimethyl sulfate (2.8 g, 22 mmol) was added at 0°C. This reaction mixture was heated at 80°C for 20 hours, cooled to 0°C, and then triethylamine (4.8 mL), acetic acid (ice, 3 mL), and ethanol (3 mL) were added sequentially. This reaction mixture was heated under reflux for 2 hours, cooled to ambient temperature, and then water (50 mL) was added. The resulting mixture was extracted with ethyl acetate (2 times × 40 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was purified by silica gel column chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the title compound as an off-white solid (0.60 g). 1 H NMR(CDCl3):δ 7.57(s,1H),7.28-7.14(m,2H),7.06(m,1H),6.52(s,1H),3.60(s,3H). LCMS m / z:318[M+H] +

[0168] Step C: Preparation of 4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethylphenyl)-1-methyl-2(1H)-pyridinone A mixture of 1,4-dioxane (5 mL) and water (0.5 mL) containing 5-bromo-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone (i.e., the product of step B) (100 mg, 0.317 mmol), 3,5-dimethoxyphenylboronic acid (58 mg, 0.32 mmol), and cesium carbonate (310 mg, 0.95 mmol, 3.0 eq) was purged with nitrogen for 15 minutes, and then [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex containing dichloromethane (18 mg, 0.022 mmol) was added. The reaction mixture was heated at 100°C for 2 hours, then cooled to air temperature, filtered through a Celite® bed, and rinsed with ethyl acetate (30 mL). The filtrate was poured into ice-cold water (40 mL) and extracted with ethyl acetate (30 mL twice). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure to obtain a solid (purple). The obtained solid was purified by CombiFlash™ chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the compound of the present invention, the title compound, as an off-white solid (20 mg). 1 H NMR(CDCl3):δ 7.38(s,1H),7.12-7.05(m,2H),6.93(m,1H),6.55(s,1H),6.30(m,1H),6.13(m,2H),3.65(s,3H),3.63(s,6H). LCMS m / z:374[M+H] +

[0169] Example 2 Preparation of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methyl-2(1H)-pyridinone (compound 3) Step A: Preparation of 5-bromo-3-chloro-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone To a solution of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone (i.e., the product of Step B, Example 1) (1.00 g, 3.17 mmol) in N,N-dimethylformamide (10 mL), N-chlorosuccinimide (508 mg, 3.81 mmol) was added in small amounts at 0°C. The reaction mixture was heated at 60°C for 16 hours, cooled to ambient temperature, and then poured into ice-cold water (50 mL). The resulting solid precipitate was collected by filtration, washed with water (80 mL), and dried under reduced pressure to obtain the title compound as an off-white solid (0.60 g). 1 H NMR(CDCl3):δ 8.10(s,1H),7.42(m,1H),7.30-7.22(m,2H),3.68(s,3H). LCMS:m / z:352[M+H] +

[0170] Step B: Preparation of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methyl-2(1H)-pyridinone A mixture of 1,4-dioxane (8 mL) and water (1 mL) containing 5-bromo-3-chloro-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone (i.e., the product of step A) (0.50 g, 1.43 mmol), 3,5-dimethoxyphenylboronic acid (0.26 g, 1.43 mmol), and cesium carbonate (1.41 g, 4.30 mmol) was purged with nitrogen for 15 minutes, and then [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex containing dichloromethane (82 mg, 0.10 mmol) was added. The reaction mixture was heated at 100°C for 2 hours, cooled to ambient temperature, filtered through a Celite® bed, and rinsed with ethyl acetate (30 mL). The filtrate was poured into ice-cold water (40 mL) and extracted with ethyl acetate (twice × 40 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure to obtain a solid (purple). The obtained solid was purified by CombiFlash™ chromatography (elution with 80% ethyl acetate in petroleum ether) to obtain the compound of the present invention, the title compound, as an off-white solid (320 mg). 1 H NMR (DMSO-d6): δ 7.95(s,1H),7.54(m,1H),7.30-7.23(m,2H),6.32(m,1H),6.21(m,1H),3.63(s,3H),3.60(s,6H). LCMS m / z:408[M+H] +

[0171] Example 3 3-Chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone (compound 4) and Preparation of 3-chloro-5-(4-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone (compound 5) To a mixture of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methyl-2(1H)-pyridinone (i.e., the product of Example 2) (0.25 g, 0.61 mmol) in dimethylformamide (5 mL), N-chlorosuccinimide (82 mg, 0.61 mmol) was added in small amounts at 0°C. This reaction mixture was heated at 60°C for 16 hours, then poured into ice-cold water (30 mL), and extracted with ethyl acetate (twice in 30 mL increments). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone, the compound of the present invention, as an off-white solid (150 mg). 1 H NMR (DMSO-d6): δ 7.91(s,1H),7.52-7.40(m,3H),6.60-6.35(m,2H),3.77-3.76(2s,3H),3.65(s,3H),3.63(s,3H). LCMS:m / z:444[M+H] +

[0172] Further elution of the chromatographic column with 50% ethyl acetate in petroleum ether yielded 3-chloro-5-(4-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone, the compound of the present invention, as an off-white solid (20 mg) that melted at 186-190°C.

[0173] Example 4 Preparation of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methoxy-2(1H)-pyridinone (compound 19) Step A: Preparation of 5-bromo-2-chloro-4-(2-chloro-4-fluorophenyl)pyridine 1-oxide To a mixture of 5-bromo-2-chloro-4-(2-chloro-4-fluorophenyl)pyridine (i.e., the product of Example 1, Step A) (6.0 g, 18.8 mmol) in dichloromethane (60 mL), 3-chloroperoxybenzoic acid (6.49 g, 37.6 mmol) was added at 0°C. The reaction mixture was stirred for 48 hours and then concentrated under reduced pressure. The resulting substance was diluted with water (500 mL) and extracted with ethyl acetate (2 sets of 200 mL). The collected organic extract was washed with saturated aqueous sodium chloride solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 70% ethyl acetate in petroleum ether) to obtain the title compound as a yellow solid (3 g). 1 H NMR (DMSO-d6): δ 9.02(s,1H),7.99(s,1H),7.68-7.65(m,1H),7.53-7.49(m,1H),7.42-7.37(m,1H). LCMS:m / z:338[M+H] +

[0174] Step B: Preparation of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone 5-Bromo-2-chloro-4-(2-chloro-4-fluorophenyl)pyridine 1-oxide (i.e., the product of step A) (2.50 g, 7.40 mmol) was mixed with sodium hydroxide (10% aqueous solution, 25 mL). The reaction mixture was heated at 100°C for 6 hours, cooled to room temperature, and then hydrochloric acid (2N aqueous solution, 10 mL) was added. The resulting precipitate was collected on a frit funnel by vacuum filtration, washed with water (50 mL), and dried under reduced pressure to obtain the title compound as a white solid (1 g). 1 H NMR (DMSO-d6): δ 8.46(s,1H),7.62-7.60(m,1H),7.42-7.34(m,2H),6.55(s,1H). LCMS m / z:318[M+H] +

[0175] Step C: Preparation of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-methoxy-2(1H)-pyridinone To a mixture of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone (i.e., the product of step B) (1.00 g, 3.16 mmol) in N,N-dimethylformamide (10 mL), potassium carbonate (870 mg, 6.32 mmol) was added at 0°C, followed by methyl iodide (0.40 mL, 6.32 mmol). The reaction mixture was stirred for 2 hours, then diluted with water (20 mL) and extracted with ethyl acetate (2 sets of 50 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the title compound as a white solid (400 mg). 1 H NMR(CDCl3):δ 7.81(s,1H),7.24-7.22(m,1H),7.18-7.15(m,1H),7.09-7.05(m,1H),6.62(s,1H),4.15(s,3H). LCMS m / z:332[M+H] +

[0176] Step D: Preparation of 5-bromo-3-chloro-4-(2-chloro-4-fluorophenyl)-1-methoxy-2(1H)-pyridinone To a mixture of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-methoxy-2(1H)-pyridinone (i.e., the product of step C) (400 mg, 1.20 mmol) in N,N-dimethylformamide (4 mL), N-chlorosuccinimide (193 mg, 1.44 mmol) was added at 0°C. The reaction mixture was heated at 70°C for 1 hour, cooled to room temperature, and then diluted with water (20 mL). The resulting mixture was extracted with ethyl acetate (2 times × 50 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 10% ethyl acetate in petroleum ether) to obtain the title compound as a white solid (300 mg). 1 H NMR(CDCl3):δ 7.84(s,1H),7.29(s,1H),7.13-7.12(m,2H),4.19(s,3H). LCMS m / z:367[M+H] +

[0177] Step E: Preparation of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methoxy-2(1H)-pyridinone To a mixture of 1,4-dioxane (6 mL) and 5-bromo-3-chloro-4-(2-chloro-4-fluorophenyl)-1-methoxy-2(1H)-pyridinone (i.e., the product of step D) (600 mg, 1.64 mmol) in water (1.20 mL), 3,5-dimethoxyphenylboronic acid (299 mg, 1.64 mmol) was added, followed by the addition of cesium carbonate (1.07 g, 3.28 mmol). The reaction mixture was purged with argon gas for 10 minutes, and then [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (120 mg, 0.164 mmol) was added. The reaction mixture was heated at 80°C for 3 hours, cooled to room temperature, filtered through a Celite® bed, and rinsed with ethyl acetate (20 mL). The filtrate was diluted with water (50 mL) and extracted with ethyl acetate (twice × 50 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the compound of the present invention, the title compound, as a white solid (500 mg). 1 H NMR (DMSO-d6): δ 8.27(s,1H),7.54-7.52(m,1H),7.34-7.31(m,1H),7.26-7.22(m,1H),6.33(t,1H),6.24(d,2H),4.10(s,3H),3.60(s,6H). LCMS m / z:424[M+H] +

[0178] Example 5 Preparation of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(2-chloro-3,5-dimethoxyphenyl)-1-methoxy-2(1H)-pyridinone (compound 22) To a mixture of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-methoxy-2(1H)-pyridinone (i.e., the product of Example 4) (500 mg, 1.18 mmol) in N,N-dimethylformamide (10 mL), N-chlorosuccinimide (189 mg, 1.42 mmol) was added at 0°C. This reaction mixture was heated at 60°C for 3 hours, diluted with water (20 mL), and then extracted with ethyl acetate (2 times × 50 mL). The collected organic extract was washed with saturated aqueous sodium chloride solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 20% ethyl acetate in petroleum ether) to obtain the title compound, which is the compound of the present invention, as a white solid (300 mg). 1 H NMR (DMSO-d6): δ 8.27(d,1H),7.52-7.50(m,1H),7.21-7.15(m,2H),6.58-6.36(m,2H),4.07(s,3H),3.77(s,3H),3.65(s,3H). LCMS m / z:458[M+H] +

[0179] Example 6 Preparation of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone (compound 39) Step A: Preparation of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-(phenylmethoxy)-2(1H)-pyridinone To a mixture of 5-bromo-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone (i.e., the product of Example 4, Step B) (3.60 g, 11.30 mmol) in N,N-dimethylformamide (36 mL), potassium carbonate (3.13 g, 22.70 mmol) was added at 0°C. After 10 minutes, benzyl bromide (1.61 mL, 13.6 mmol) was added to this reaction mixture. After 2 hours, the reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (2 times × 100 mL). The collected organic extract was washed with water and saturated aqueous sodium chloride solution, then dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 40% ethyl acetate in petroleum ether) to obtain the title compound as a white solid (3.5 g). 1 H NMR (DMSO-d6): δ 8.45(s,1H),7.63-7.602(dd,8.8Hz,1H),7.55(m,2H),7.44-7.33(m,5H),6.63(s,1H),5.26(s,2H). LCMS:m / z:408[M+H] +

[0180] Step B: Preparation of 5-bromo-3-chloro-4-(2-chloro-4-fluorophenyl)-1-(phenylmethoxy)-2(1H)-pyridinone 5-bromo-4-(2-chloro-4-fluorophenyl)-1-(phenylmethoxy)-2(1H)-pyridinone (i.e., the product of step A) (3.50 g, 8.56 mmol) in N,N-dimethylformamide (35 mL) was mixed with N-chlorosuccinimide (1.15 g, 8.61 mmol) at 0°C. The reaction mixture was heated at 70°C for 1 hour, cooled to room temperature, diluted with water (50 mL), and extracted with ethyl acetate (2 sets of 100 mL). The combined organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the title compound as a white solid (3.1 g). 1 H NMR(CDCl3):δ 7.45-7.42(m,6H),7.27(s,1H),7.12(d,2H),5.39-5.37(m,2H). LCMS m / z:442[M+H] +

[0181] Step C: Preparation of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-(phenylmethoxy)-2(1H)-pyridinone To a mixture of 1,4-dioxane (31 mL) and 5-bromo-3-chloro-4-(2-chloro-4-fluorophenyl)-1-(phenylmethoxy)-2(1H)-pyridinone (i.e., the product of step B) (3.10 g, 7.03 mmol) in water (6.2 mL), (3,5-dimethoxyphenyl)boronic acid (1.53 g, 8.43 mmol) was added, followed by the addition of cesium carbonate (6.87 g, 21.1 mmol). This reaction mixture was purged with argon gas for 20 minutes, and then [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (514 mg, 0.702 mmol) was added. This reaction mixture was heated at 80°C for 3 hours, cooled to room temperature, diluted with water (30 mL), and extracted with ethyl acetate (twice × 100 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 40% ethyl acetate in petroleum ether) to obtain the title compound as a white solid (2.56 g). 1 H NMR(DMSO-d6):δ 8.00(s,1H),7.56-7.51(m,3H),7.45-7.44(m,3H),7.34-7.31(m,1H), 7.24-7.21(m,1H),6.30(t,1H),6.09(d,2H).5.35(d,2H),3.58(s,6H). LCMS m / z:500[M+H] +

[0182] Step D: Preparation of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-(phenylmethoxy)-2(1H)-pyridinone To a mixture of 3-chloro-4-(2-chloro-4-fluorophenyl)-5-(3,5-dimethoxyphenyl)-1-(phenylmethoxy)-2(1H)-pyridinone (i.e., the product of step C) (2.50 g, 5.12 mmol) in N,N-dimethylformamide (25 mL), N-chlorosuccinimide (684 mg, 5.12 mmol) was added at 0°C. The reaction mixture was heated at 70°C for 1 hour, cooled to room temperature, diluted with water (50 mL), and extracted with ethyl acetate (twice × 100 mL). The collected organic extract was washed with saturated sodium chloride aqueous solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 40% ethyl acetate in petroleum ether) to obtain the title compound as a white solid (2.1 g). 1 H NMR(CDCl3):δ 7.43-7.40(m,5H),7.07-7.00(m,3H),6.85(s,1H),6.31(br s,1H),6.10(s,1H),5.43(s,2H),3.77(s,3H),3.62(s,3H). LCMS m / z:534[M+H] +

[0183] Step E: Preparation of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone To a mixture of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-(phenylmethoxy)-2(1H)-pyridinone (i.e., the product of step D) (2.1 g, 3.9 mmol) in ethanol (11 mL), palladium (10% on carbon, 1.0 g, 10 mol) was added. The reaction mixture was stirred under a hydrogen balloon for 1 hour, then filtered through a Celite® pad and rinsed with ethyl acetate (50 mL). The filtrate was concentrated to dryness under reduced pressure to obtain the title compound, which is the compound of the present invention, as an off-white solid (1.3 g). LCMS m / z:444[M+H]+

[0184] Example 7 Preparation of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-(difluoromethoxy)-2(1H)-pyridinone (compound 38) To a mixture of acetonitrile (1 mL) and water (1 mL) containing 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone (i.e., the product of Example 6) (200 mg, 0.449 mmol), potassium hydroxide (302 mg, 5.38 mmol) was added at -78°C, followed by the addition of diethyl (bromodifluoromethyl)phosphonate (468 mg, 1.75 mmol). The reaction mixture was heated to room temperature and stirred for 16 hours, then diluted with water (20 mL), followed by dilution with hydrochloric acid (1 N aqueous solution, 1 mL). The resulting mixture was extracted with ethyl acetate (2 times × 50 mL). The collected organic extract was washed with ice-cold water (50 mL) and saturated sodium chloride aqueous solution, then dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by preparative HPLC to obtain the compound of the present invention, the title compound, as a white solid (40 mg). 1 H NMR (CDCl3): δ 7.51(s,1H),7.13-6.77(m,4H),6.37(d,1H),6.31(d,1H),3.81(s,3H),3.66(s,3H). LCMS m / z:494[M+H] +

[0185] Example 8 Preparation of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-(2-propynyloxy)-2(1H)-pyridinone (compound 36) To a mixture of 3-chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-hydroxy-2(1H)-pyridinone (i.e., the product of Example 6) (300 mg, 0.677 mmol) in N,N-dimethylformamide (3 mL), potassium carbonate (187 mg, 1.33 mmol) was added at 0°C, followed by the addition of 3-bromo-1-propyne (96.0 mg, 0.79 mmol). After 6 hours, the reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (twice in 50 mL increments). The collected organic extract was washed with saturated aqueous sodium chloride solution, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by preparative HPLC to obtain the title compound, which is the compound of the present invention, as a white solid (82 mg). 1 H NMR(CDCl3):δ 7.60(s,1H),7.08-7.05(m,2H),6.89-6.87(m,1H),6.37-6.31(m,2H),5.22(d,1H),5.01(d,1H),3.82(s,3H),3.66(s,3H).2.66(t,1H). LCMS m / z:482[M+H] +

[0186] Formulation / Usefulness A compound of Formula 1 of the present invention (including its N-oxide and salt), or a mixture (i.e., a composition) comprising this compound and at least one additional fungicidal compound as described in the outline of the present invention, is generally used as a fungicidal active ingredient in a composition (i.e., a preparation) together with at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents, which functions as a carrier. The preparation or composition components are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.

[0187] The compound of Formula 1 or a mixture thereof can be prepared in various ways, including the following: (i) The compound of Formula 1 and, if applicable, one or more other biologically active compounds or reagents may be prepared separately and applied separately, or (for example, as a tank mix) may be applied simultaneously in an appropriate weight ratio; or (ii) The compound of formula 1 may be compounded together with one or more other biologically active compounds or agents in an appropriate weight ratio.

[0188] Useful formulations include liquid and solid compositions. Liquid compositions include solutions (including emulsifying concentrates), suspensions, and emulsions (including microemulsions, oil-in-water emulsions, fluid concentrates, and / or suspendemulsions), which can sometimes be thickened to form gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, fluid concentrates, and suspendemulsions. Common types of non-aqueous liquid compositions are emulsifying concentrates, microemulsifying concentrates, dispersible concentrates, and oil dispersions.

[0189] Common types of solid compositions include fine powders, powders, granules, pellets, granules, aromatic tablets, tablets, and filler-filled films (including seed coatings), which may be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or fluid suspensions are particularly useful for seed treatment. Active ingredients may be (micro)encapsulated and further formed into suspensions or solid formulations; or the entire formulation of the active ingredient may be encapsulated (or "coated"). Encapsulation can control or slow the release of the active ingredient. Emulsified granules combine the advantages of both emulsified concentrate formulations and dry granular formulations. High-strength compositions are primarily used as intermediates for further formulations.

[0190] Sprayable formulations are typically diluted in a suitable medium before spraying. Such liquid and solid formulations are readily diluted with a spray medium, usually water, but sometimes with other suitable mediums such as aromatic or paraffinic hydrocarbons or vegetable oils. Spray rates can range from about 1 to several thousand liters per hectare, but more typically from about 10 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 growing medium of plants. Liquid and dry formulations can be metered and supplied directly to a flow irrigation system or metered and supplied between rows during planting. Liquid and solid formulations can be applied to the seeds of crops and other desirable vegetation as a pre-planting seed treatment to protect growing roots and other underground plant parts and / or foliage by osmotic absorption.

[0191] The formulation will typically contain an effective amount of the active ingredient, along with diluents and surfactants, within the following approximate ranges, up to 100% by weight.

[0192] [Table 1]

[0193] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, saccharose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

[0194] Liquid diluents include, for example, 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, paraffin (e.g., white mineral oil, normal paraffin, isoparaffin), alkylbenzene, alkylnaphthalene, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomaticated aliphatic compounds, alkylbenzene, alkylnaphthalene, cyclohexanone, 2-heptanone, isophorone, and ketones such as 4-hydroxy-4-methyl-2-pentanone, isoamyl This includes acetates such as acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate; other esters such as alkylated lactic acid esters, dibasic acid esters, alkyl and aryl benzoates; and γ-butyrolactone, as well as alcohols, which may be linear, 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) such as vegetable and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. 22The liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, or they may be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

[0195] The solid and liquid compositions of the present invention often contain one or more surfactants. When added to a liquid, surfactants (also known as surface-active agents) generally modify, and in most cases reduce, the surface tension of the liquid. Depending on the hydrophilic and lipophilic properties of the surfactant molecules, surfactants can be useful as wetting agents, dispersants, emulsifiers, or defoamers.

[0196] Surfactants can be classified as nonionic, anionic, or cationic surfactants. Nonionic surfactants useful in this composition include: alcohol alkoxylates such as alcohol alkoxylates, which are based on natural and synthetic alcohols (which may be branched or linear) and are produced from alcohol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (produced from phenols and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers produced from ethylene oxide or propylene oxide and reverse block polymers in which the terminal block is prepared from propylene oxide; ethoxylate This includes, but is not limited to, xylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those produced from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); polyethoxylate esters such as fatty acid SLs, glycerol esters, lanolin-based derivatives, polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; high molecular weight surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as saccharose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0197] Useful anionic surfactants include alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignosulfonate derivatives; maleic acid or succinic acid or their acid anhydrides; olefin sulfonates; phosphate esters such as alcohol alkoxylate phosphates, alkylphenol alkoxylate phosphate phosphates, and styrylphenol ethoxylate phosphate phosphate esters; protein-based surfactants; sarcosine derivatives; and styrylphenol ether sulfate. This includes, but is not limited to, sulfonates 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 fractionated petroleum; sulfosuccinates; and sulfosuccinates such as dialkyl sulfosuccinate salts and their derivatives.

[0198] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, trippropylenetriamines and dipropylenetetraamines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (made from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts and diamine salts such as amine acetates; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxide and bis-(2-hydroxyethyl)-alkylamine oxide.

[0199] Mixtures of nonionic surfactants and anionic surfactants, or mixtures of nonionic surfactants and cationic surfactants, are also useful in this composition. 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, Seventh Edition, John Wiley and Sons, New York, 1987.

[0200] The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as formulation aids (some of which may also 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 (dye / pigment dispersions), washing off (film-forming agents or stickers), evaporation (evaporation inhibitors), and other formulation attributes. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of compounding 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., and in PCT Public Publication No. 03 / 024222.

[0201] The compounds of Formula 1 and any other active ingredients are typically incorporated into the composition by dissolving the active ingredients in a solvent or by grinding them in a liquid or dry diluent. Solutions, such as emulsifiable concentrates, can be prepared simply by mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-miscible, an emulsifier is typically added to emulsify the active ingredient-containing solvent when diluted with water. Active ingredient slurries with particle sizes of 2,000 μm or less can be wet-milled using a medium mill to obtain particles with an average diameter of less than 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. Patent No. 3,060,084) or further processed by spray-drying to form water-dispersible granules. Dry preparations typically require dry milling to produce an average particle size in the range of 2 to 10 μm. Fine powders and fine powders can be prepared by blending and grinding, typically (using a hammer mill or fluid energy mill, for example). Granules and pellets can be prepared by spraying an active material onto a pre-formed granular carrier or by agglomeration techniques. See Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp. 8-57 and subsequent articles, and International Publication No. 91 / 13546. Pellets can be prepared as described in U.S. Patent No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Patent No. 4,144,050, U.S. Patent No. 3,920,442, and German Patent No. 3,246,493. The tablets may be prepared as taught in U.S. Patent Nos. 5,180,587, 5,232,701 and 5,208,030.The film can be prepared as taught in British Patent No. 2,095,558 and U.S. Patent No. 3,299,566.

[0202] One embodiment of the present invention is a method for controlling fungal pathogens, comprising diluting a fungicidal composition of the present invention (a compound of Formula 1 prepared with a surfactant, a solid diluent, and a liquid diluent, or a mixture of a compound of Formula 1 and at least one other fungicidal agent) with water, optionally adding an auxiliary agent to form a diluted composition, and contacting a fungal pathogen or its environment with an effective amount of the diluted composition.

[0203] A spray composition formed by diluting a sufficiently concentrated fungicidal composition with water may provide sufficient efficacy in controlling fungal pathogens, but separately formulated auxiliary products may also be added to the spray tank mixture. These additional auxiliary products are generally known as “spray auxiliary products” or “tank mix auxiliary products” and include any substances mixed in the spray tank to improve the performance of the pesticide or to modify the physical properties of the spray mixture. Auxiliaries may be anionic or nonionic surfactants, emulsifiers, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners, or defoamers. Auxiliaries are used to enhance efficacy (e.g., bioavailability, adhesion, penetration, uniformity of coverage, and durability of protection) or to minimize or eliminate spray application problems related to incompatibility, foaming, drift, evaporation, vaporization, and decomposition. To obtain optimal performance, auxiliary products are selected with respect to the properties of the active ingredient, formulation, and target (e.g., crop, pest).

[0204] The amount of auxiliaries added to the spray mixture is generally in the range of approximately 0.1 to 2.5 volume percent. The application rate of auxiliaries added to the spray mixture is typically about 1 to 5 liters per hectare. Representative examples of spray auxiliaries include: Adigor® (Syngenta), which is 47% methylated rapeseed oil in liquid hydrocarbons; Silwet® (Helena Chemical Company), which is polyalkylene oxide-modified heptamethyltrisiloxane; and Assist® (BASF), which is a 17% surfactant blend in 83% paraffin-based mineral oil.

[0205] One method of seed treatment involves spraying or dusting the seeds with the compound of the present invention (i.e., the compound as a formulated composition) before sowing. The composition formulated for seed treatment generally includes a film-forming agent or adhesive. Therefore, typically, the seed coating composition of the present invention comprises a biologically effective amount of the compound of Formula 1 and a film-forming agent or adhesive. Seeds may be coated by directly spraying a fluid suspension concentrate into a seed rolling bed and then drying the seeds. Alternatively, other types of formulations (e.g., wet powders, solutions, suspension emulsions, emulsifiable concentrates, and emulsions in water) may be sprayed onto the seeds. This process is particularly useful when applying a film coating to the seeds. Various coating machines and processes are available to those skilled in the art. Preferred processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994, BCPC Monograph No. 57, and the references listed therein.

[0206] For further information on the technical aspects of formulations, see T.Swoods, "The Formulator's Toolbox—Product Forms for Modern Agriculture," in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and TR. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120–133. Also, U.S. Patent No. 3,235,361, columns 6, rows 16-7, row 19 and Examples 10-41; U.S. Patent No. 3,309,192, columns 5, rows 43-7, row 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Patent No. 2,891,855, columns 3, rows 66-5, row 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 Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB See Publications, Richmond, UK, 2000.

[0207] In the following examples, all percentages are by weight, and all preparations are prepared by conventional methods. Active ingredients refer to the compounds in Traction Table A disclosed herein. Without further detail, those skilled in the art will be able to make the most of the present invention using the foregoing description. Therefore, the following examples are provided for illustrative purposes only and do not limit the present disclosure in any way.

[0208] Example A high strength concentrate Compound 1 98.5% Silica Aerogel 0.5% Synthetic amorphous silica powder 1.0%

[0209] Example B Wettable powder Compound 2 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignin sulfonate 4.0% Sodium silicate 6.0% Montmorillonite (calcined product) 23.0%

[0210] Example C granules Compound 3 10.0% Attapulgite granules (low volatility, 0.71 / 0.30 mm; USS No. 25-50 sieve) 90.0%

[0211] Example D Extruded pellets Compound 4 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignin sulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0212] Example E emulsifiable concentrate Compound 5 10.0% Polyoxyethylene sorbitol hexoleate 20.0% C6~C 10 Fatty acid methyl ester 70.0%

[0213] Example F Microemulsion Compound 13 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0214] Example G Seed treatment agent Compound 22 20.00% Polyvinylpyrrolidone-vinyl acetate copolymer 5.00% Montane wax 5.00% Calcium lignin sulfonate 1.00% Polyoxyethylene / polyoxypropylene block copolymer 1.00% Stearyl alcohol (POE 20) 2.00% Polyorganosilane 0.20% Coloring agent: Red dye 0.05% Water 65.75%

[0215] Example H stick fertilizer Compound 25 2.50% Pyrrolidone-styrene copolymer 4.80% Tristyrylphenyl 16-ethoxylate 2.30% Talc 0.80% Cornstarch 5.00% Time-release fertilizer 36.00% Kaolin 38.00% Water 10.60%

[0216] Example I Suspension concentrate Compound 30 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan rubber 0.1% Propylene glycol 5.0% Silicone-based defoamer 0.1% 1,2-Benzisothiazolin-3-one 0.1% Water 53.7%

[0217] Example J Underwater emulsion Compound 32 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan rubber 0.1% Propylene glycol 5.0% Silicone-based defoamer 0.1% 1,2-Benzisothiazolin-3-one 0.1% Aromatic petroleum-based hydrocarbons 20.0 Water 58.7%

[0218] Example K oil dispersion Compound 33 25% Polyoxyethylene sorbitol hexaoleate 15% Organically modified bentonite clay 2.5% Fatty acid methyl ester 57.5%

[0219] Example L Suspension emulsion Compound 51 10.0% Imidaclopride 5.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan rubber 0.1% Propylene glycol 5.0% Silicone-based defoamer 0.1% 1,2-Benzisothiazolin-3-one 0.1% Aromatic petroleum-based hydrocarbons 20.0% Water 53.7%

[0220] Water-soluble and water-dispersible formulations are typically diluted with water to form aqueous compositions before application. Aqueous compositions for direct application to plants or parts thereof (e.g., spray tank compositions) typically contain at least about 1 ppm (e.g., 1 ppm to 100 ppm) of the compound of the present invention.

[0221] Seeds are typically treated at a rate of approximately 0.001 g (more typically about 0.1 g) to 10 g per kilogram of seed (i.e., approximately 0.0001 to 1% by weight of the seed before treatment). The fluid suspension prepared for seed treatment typically contains approximately 0.5 to 70% active ingredient, approximately 0.5 to 30% film-forming adhesive, approximately 0.5 to 20% dispersant, 0 to 5% thickener, 0 to 5% pigment and / or dye, 0 to 2% defoamer, 0 to 1% preservative, and 0 to 75% volatile liquid diluent.

[0222] The compounds of the present invention are useful as plant disease control agents. Accordingly, the present invention further comprises a method for controlling plant diseases caused by fungal plant pathogens, comprising applying an effective amount of the compound of the present invention, or a fungicidal composition containing the compound, to a plant to be protected, a part thereof, or the seeds of a plant to be protected. The compounds and / or compositions of the present invention provide control of diseases caused by a wide range of fungal plant pathogens of the Ascomycota, Basidiomycota, Zygomycota, and Oomycota classes. This is effective in controlling a wide range of plant diseases, and is particularly effective in controlling pathogens of the leaves of ornamental plants, turf, vegetables, fields, grains, and fruit crops. Examples of these pathogens are, but are not limited to, those listed in Table 1-1. In the case of Ascomycota and Basidiomycota, both the names of the sexual / sexual / perfect stage and the asexual / asexual / imperfect stage (in parentheses) are listed if known. Synonyms for pathogens are indicated by an equals sign. For example, the name of the sexual / sexual / perfect stage, Phaeosphaeria nodorum, is followed by the name of the corresponding asexual / asexual / imperfect stage, Stagnospora nodorum, and the older, synonymous name, Septoria nodorum.

[0223] [Table 2]

[0224] [Table 3]

[0225] In addition to its fungicidal activity, this composition or combination also possesses activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species. By controlling harmful microorganisms, the compounds of the present invention are useful in improving (i.e., increasing) the ratio of beneficial microorganisms to harmful microorganisms in contact with crop plants or their vegetative propagates (e.g., seeds, corms, bulbs, tubers, scions) or the agricultural environment of crop plants or their vegetative propagates.

[0226] The compounds of the present invention are useful in the treatment of whole plants, parts of plants, and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods, or by genetic engineering methods. Genetically modified plants or seeds (transformed plants or seeds) are those in which a different gene (introduced gene) is stably incorporated into the genome of the plant or seed. An introduced gene, defined by a specific location in the plant genome, is called a transformation or gene transfer event.

[0227] Examples of genetically modified plant cultivars that can be treated according to the present invention include those exhibiting resistance to one or more biological stresses (e.g., nematodes, insects, mites, fungi, etc.) or abiotic stresses (e.g., drought, low temperatures, soil salinity, etc.), or those containing other desired characteristics. Plants can be genetically modified to exhibit characteristics such as herbicide resistance, insect resistance, modified oil profiles, or drought resistance.

[0228] Treatment of genetically modified plants and seeds with the compounds of the present invention can yield superadditive or enhanced effects. For example, reduced application rates, broader activity spectra, increased resistance to biotic / abiotic stress, or enhanced storage stability may be greater than those expected from the mere additive effects of applying the compounds of the present invention to genetically modified plants and seeds.

[0229] The compounds of the present invention are useful in seed treatments for protecting seeds from plant diseases. In the context of this disclosure and claims, seed treatment means bringing the seeds into contact with a biologically effective amount of the compounds of the present invention (typically formulated as a composition of the present invention). This seed treatment protects the seeds from soilborne pathogens and may also protect the roots and other plant parts in contact with the soil of seedlings growing from germinated seeds. This plant treatment may also protect the leaves by translocation of the compounds of the present invention or by other active ingredients within the growing plant. Seed treatments can be applied to all types of seeds (e.g., those from which genetically transformed plants grow to express specialized characteristics). Representative examples include: those expressing proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis toxin) or those expressing herbicide resistance (e.g., glyphosate acetyltransferase that confers resistance to glyphosate). Seed treatments with the compounds of the present invention may also increase the growth potential of plants growing from seeds.

[0230] The compounds and compositions of the present invention are particularly useful for the seed treatment of crops, both alone and in combination with other fungicides, nematodeicides, and insecticides, including, but not limited to, the following crops: maize or corn, soybeans, cotton, grains (e.g., wheat, oats, barley, rye, and rice), potatoes, vegetables, and rapeseed.

[0231] Furthermore, the compounds of the present invention are useful for treating post-harvest diseases of fruits and vegetables caused by fungi, oomycetes, and bacteria. These infections can occur before, during, and after harvest. For example, an infection may occur before harvest and then remain dormant until a point during maturation (e.g., when the host begins tissue changes that allow the infection to progress, or when conditions promote the onset of the disease); similarly, an infection may occur from a surface wound caused by mechanical or insect damage. In this regard, the compounds of the present invention can reduce losses (i.e., losses in quantity and quality) resulting from post-harvest diseases that may occur at any point between harvest and consumption. Treatment of post-harvest diseases with the compounds of the present invention allows perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) to be stored refrigerated or unrefrigerated after harvest, maintaining their edibility and extending the period during which they are free from significant or harmful decomposition or contamination by fungi or other microorganisms. Treatment of edible plant parts with the compounds of the present invention before or after harvesting can also reduce the formation of toxic metabolites of fungi or other microorganisms (e.g., mycotoxins such as aflatoxins).

[0232] Control of plant diseases can usually be achieved by applying an effective amount of the compound of the present invention to the part of the plant to be protected, such as roots, stems, leaves, fruits, seeds, tubers, or bulbs, or to the growing medium (soil or sand) in which the plant is growing, either before or after infection. The compound can also be applied to seeds to protect the seeds and the seedlings grown from them. The compound can also be applied to treat plants via irrigation water. Control of post-harvest pathogens that infect crops before harvest is typically achieved by field application of the compound of the present invention, and if infection occurs after harvest, the compound can be applied to the harvested crop as a dip agent, spray agent, fumigant, treatment wrap, and box liner.

[0233] The compound may also be applied by using an unmanned aerial vehicle (UAV) to spray the composition disclosed herein across an entire planting area. In some embodiments, this planting area is a crop-containing area. In some embodiments, the crop is selected from monocots or dicots. In some embodiments, the crop is selected from rice, maize, barley, soybeans, wheat, vegetables, tobacco, tea plants, fruit trees, and sugarcane. In some embodiments, the composition disclosed herein is formulated for spraying at very low volumes. Products applied by drones may use water or oil as a spray carrier. Typical spray volumes (including the product) used for drone applications are globally between 5.0 liters / ha and 100 liters / ha (approximately 0.5 to 10 gpa). This includes the range from very low spray volumes (ULV) to low spray volumes (LV). Less common, however, there may be situations where even lower spray volumes of as low as 1.0 liter / ha (0.1 gpa) may be used.

[0234] The preferred application ratio (i.e., mycogenic effective amount) of the compounds of the present invention may be influenced by factors such as the plant disease to be controlled, the plant species to be protected, the population structure of the pathogen to be controlled, ambient humidity and temperature, and should be determined under actual usage conditions. Those skilled in the art can easily determine the mycogenic effective amount required for the desired level of control of plant diseases through simple experiments. Leaves can be protected by treatment with the activator at a rate of typically less than about 1 g / ha to about 5,000 g / ha. Seeds and seedlings can be protected by treatment with the activator at a rate of typically about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed. Those skilled in the art can easily determine the application ratio of the compounds and compositions of the present invention necessary to provide the desired spectrum of plant protection, as well as control of plant diseases and, optionally, other plant pests, through simple experiments.

[0235] The compounds of the present invention may also be useful in enhancing the growth potential of crops. The method comprises the step of contacting a crop (e.g., foliage, flowers, fruits, or roots) or the seeds from which the crop grows with a compound of Formula 1 in an amount sufficient to achieve the desired plant growth potential effect (i.e., a biologically effective amount). Typically, the compound of Formula 1 is applied in a formulation. While the compound of Formula 1 is often applied directly to the crop or its seeds, it is also applied to the location of the crop, i.e., the environment of the crop, particularly a part of the environment that is close enough to transfer the compound of Formula 1 to the crop. Suitable locations for the method most commonly include a growing medium (i.e., a medium that provides nutrients to plants), typically the soil in which the plants grow. The treatment of a crop to enhance its growth potential therefore comprises the step of contacting the crop, the seeds from which the crop grows, or the location of the crop with a biologically effective amount of the compound of Formula 1.

[0236] Enhanced crop growth can result in one or more of the following observed effects: (a) an optimal crop system as demonstrated by superior seed germination, crop emergence and crop gregariousness; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of suckers (e.g., for rice), root tubers and the total dry weight of the crop mass; (c) improved crop yield as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e., yield) and / or marketability of the fruit or grain grade of the agricultural product (i.e., harvest quality); (d) an enhanced ability of the crop to withstand or prevent plant disease infection and the spread of arthropod, nematode or mollusk pests; and (e) an enhanced ability of the crop to withstand environmental stresses such as extreme heat, suboptimal humidity or exposure to phytotoxic chemicals.

[0237] The compounds of the present invention can increase the growth potential of treated plants compared to untreated plants by preventing and / or curing plant diseases caused by fungal plant pathogens in the plant environment. In the absence of such control of plant diseases, these diseases reduce the growth potential of plants by consuming plant tissue or sap, or by transmitting plant pathogens such as viruses. Even in the absence of fungal plant pathogens, the compounds of the present invention can increase the growth potential of plants by altering their metabolism. Generally, the growth potential of crop plants will increase most significantly by treating them with the compounds of the present invention when the plants are growing in a non-ideal environment (i.e., an environment that includes one or more aspects unfavorable to plants achieving the maximum genetic potential that would be exhibited in an ideal environment).

[0238] Of particular note are methods for increasing the growth potential of crop plants when they are grown in an environment containing plant diseases caused by fungal plant pathogens. Similarly, of note are methods for increasing the growth potential of crop plants when they are grown in an environment free from plant diseases caused by fungal plant pathogens. Similarly, of note are methods for increasing the growth potential of crop plants when they are grown in an environment with less moisture than ideal for supporting their growth.

[0239] The compounds of the present invention may also be mixed with one or more biologically active compounds or agents, including: fungicides, insecticides, anthelmintics, fungicides, acaricides, herbicides, herbicide detoxifiers, growth regulators, such as insect molting inhibitors, and rooting stimulants, sterilizers, signaling substances, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or entomopathogenic bacteria, and viruses or fungi to form multi-component pesticides that provide a wide range of agricultural protections. Therefore, the present invention also relates to compositions comprising (a fungicidal amount) of the compound of Formula 1 and (a biologically effective amount) at least one additional biologically active compound or agent, and further comprising at least one of surfactants, solid diluents, or liquid diluents. Other biologically active compounds or agents may be formulated into compositions comprising at least one of surfactants, solid diluents, or liquid diluents. In the case of the mixture of the present invention, one or more other biologically active compounds or agents can be compounded together with the compound of Formula 1 to form a premix, or one or more other biologically active compounds or agents can be compounded separately from the compound of Formula 1, and these formulations can be combined and then applied (for example, in a spray tank) or applied sequentially.

[0240] As described in the summary of the invention, one aspect of the present invention is a fungicidal composition (i.e., a mixture or combination) comprising a compound of formula 1, its N-oxide or salt (i.e., component a) and at least one other fungicidal agent (i.e., component b). Of note is the combination such that the other fungicidal active ingredient has a different site of action than the compound of formula 1. In certain particular cases, a combination with at least one other fungicidal active ingredient having a similar control spectrum but a different site of action would be particularly advantageous for resistance control. Therefore, the composition of the present invention may further contain a fungicidal effective amount of at least one additional fungicidal active ingredient having a similar control spectrum but a different site of action.

[0241] Of particular note is a composition comprising, in addition to the compound of formula 1 as component (a), at least one fungicidal compound selected from the group consisting of the following as component (b): a mode of action (MOA) class as defined by FRAC (e.g., (A) nucleic acid metabolism, (B) cytoskeleton and motor proteins, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport, and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell walls, (P) induction of host plant defense, (U) unknown modes of action, (M) multisite active chemicals, and (BM) biological agents having multiple modes of action).

[0242] Along with the FRAC target site codes belonging to the above MOA class, the target sites recognized or proposed by FRAC are as follows: (A1) RNA polymerase I, (A2) adenosine deaminase, (A3) DNA / RNA synthesis (proposed), (A4) Type II DNA topoisomerase (gyrase), (B1)-(B3) β-tubulin construction in mitosis, (B4) cell division (unknown site), (B5) delocalization of spectrin-like proteins, (B6) function of actin / myosin / fimbrin, (C1) complex I(C2) Complex II: NADH oxide reductase, (C3) Complex III: Cytochrome bc1 at the Qo site (ubiquinol oxidase), (C4) Complex III: Cytochrome bc1 at the Qi site (ubiquinone reductase), (C5) Uncoupling agent for oxidative phosphorylation, (C6) Inhibitor of oxidative phosphorylation, ATP synthase, (C7) ATP production (proposed), (C8) Complex III: Cytochrome bc1 at the Qo site, which is a stigmatyl binding subsite. Tochrome bc1 (ubiquinone reductase), (D1) Methionine biosynthesis (proposed), (D2) Protein synthesis (ribosome, termination stage), (D3) Protein synthesis (ribosome, initiation stage), (D4) Protein synthesis (ribosome, initiation stage), (D5) Protein synthesis (ribosome, elongation stage), (E1) Signal transduction (mechanism unknown), (E2)-(E3) MAP / histidine kinase in osmotic signal transduction, (F2) Phospholipid biosynthesis, methyltransferase, (F3) Cellular peroxidation (proposed), (F4) Cell membrane permeability, fatty acids (proposed), (F6) Microbial disruption agent of pathogen cell membrane, (F7) Cell membrane disruption, (F8) Ergosterol binding, (F9) Lipid homeostasis and transport / storage, (G1) C14-demethylase in sterol biosynthesis, (G2) Δ14-reductase and Δ8→Δ7-isomerase in sterol biosynthesis, (G3) 3-ketereductase, C4-demethylation, (G4) Squalene epoxy in sterol biosynthesis (H4) Chitin synthase, (H5) Cellulose synthase, (I1) Reductase in melanin biosynthesis, (I2) Dehydratase in melanin biosynthesis, (I3) Polyketide synthase in melanin biosynthesis, (P1)~(P3) Salicylate-related substances, (P4) Polysaccharide inducers, (P5) Anthraquinone inducers, (P6) Microbial inducers, (P7) Phosphonates, (BM01) Plant extracts, and (BM02) Microorganisms, living microorganisms, or extracts and metabolites.

[0243] Of particular note is the composition comprising, in addition to the compound of formula 1 as component (a), at least one fungicidal compound selected from the group consisting of the following classes as component (b): (b1) methylbenzimidazole carbamate (MBC) fungicide; (b2) dicarboxamide fungicide; (b3) demethylation inhibitor (DMI) fungicide; (b4) phenylamide (PA) fungicide; (b5) amine / morpholine fungicide; (b6) phospholipid biosynthesis inhibitor fungicide; (b7) succinate dehydrogenase inhibitor (SDHI) fungicide; (b8) hyphenamide (b10) Droxy(2-amino-)pyrimidine fungicides; (b11) Anilinopyrimidine (AP) fungicides; (b12) N-phenylcarbamate fungicides; (b13) Quinone external inhibitor (QoI) fungicides; (b14) Phenylpyrrole (PP) fungicides; (b15) Azananaphthalene fungicides; (b16a) Cell peroxidation inhibitor fungicides; (b16b) Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides; (b16a) Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides; (b16b) Melanin biosynthesis inhibitor-polyketide Synthase (MBI-P) fungicides; (b17) Ketoreductase inhibitors (KRI) fungicides; (b18) Squalene epoxidase inhibitor fungicides; (b19) Polyoxin fungicides; (b20) Phenylurea fungicides; (b21) Quinone internal inhibitors (QiI) fungicides; (b22) Benzamide and thiazole carboxamide fungicides; (b23) Enopyranuronic acid antibiotic fungicides; (b24) Hexopyranosyl antibiotic fungicides; (b25) Glucopyranosyl antibiotics: protein synthesis fungicides; (b26) Glucopyran (b) Nosyl antibiotic fungicides; (b) Cyanoacetamidooxime fungicides; (b) Carbamate fungicides; (b) Oxidative phosphorylation uncoupling fungicides; (b) Organotin fungicides; (b) Carboxylic acid fungicides; (b) Heterocyclic aromatic fungicides; (b) Phosphonate fungicides; (b) Phthalamidic acid fungicides; (b) Benzotriazine fungicides; (b) Benzene sulfonamide fungicides; (b) Pyridazinone fungicides; (b) Thiophene carboxamide fungicides; (b) Complex I NADH oxidoreductase inhibitor fungicides; (b) Carboxylic acid amide (CAA) fungicides;(b41) Tetracycline antibiotic fungicides; (b42) Thiocarbamate fungicides; (b43) Benzamide fungicides; (b44) Microbial fungicides; (b45) Quinone external inhibitors, stigmatelin-conjugated (QoSI) fungicides; (b46) Plant extract fungicides; (b47) Cyanoacrylate fungicides; (b48) Polyene fungicides; (b49) Oxysterol-binding protein inhibitor (OSBPI) fungicides; (b50) Aryl-phenyl-ketone fungicides; (b51) Host plant defense-inducing fungicides; (b52) Multisite active fungicides; (b53) Biological preparations with multiple modes of action; (b54) Fungicides other than those of component (a) and components (b1) to (b53); and salts of compounds of (b1) to (b54).

[0244] Equally noteworthy is an embodiment in which component (b) comprises at least one fungicidal compound from each of two different groups selected from (b1) to (b54).

[0245] Further explanations for groups (b1) to (b54) are as follows.

[0246] (b1) Methylbenzimidazole carbamate (MBC) fungicides (FRAC code 1) inhibit mitosis by binding to β-tubulin during microtubule construction. This inhibition of microtubule construction may impair cell division, intracellular transport, and cellular structure. Examples of methylbenzimidazole carbamate fungicides include benzimidazole fungicides and thiophanate fungicides. Examples of benzimidazole include benomyl, carbendazim, fuberidazole, and thiabendazole. Examples of thiophanate include thiophanate and thiophanate-methyl.

[0247] (b2) Dicarboxamide fungicides (FRAC code 2) inhibit mitogen-activated protein (MAP) / histidine kinase in osmotic signaling. Examples include clozolinate, dimethacrone, iprodione, procymidone, and vinclozoline.

[0248] (b3) Demethylation inhibitor (DMI) fungicides (FRAC code 3) (sterol biosynthesis inhibitors (SBI): class I) inhibit C14-demethylase, which plays a role in sterol production. Sterols such as ergosterol are necessary for membrane structure and function, and are essential for the development of functional cell walls. Therefore, exposure to these fungicides leads to the abnormal growth and eventual death of susceptible fungi. DMI fungicides are divided into several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles, and triazolinthions. Triforine is an example of a piperazine. Examples of pyridines include: butiobate, pyrifenox, pyrisoxazole, and (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol. Examples of pyrimidines include phenalimol, nualimol, and trialimol. Examples of imidazoles include econazole, imazalil, oxpoconazole, pefurazoate, prochloraz, and triflumizole.Examples of triazoles include: azaconazole, vitertanol, bromconazole, cyproconazole, difenoconazole, diniconazole (e.g., diniconazole-M), epoxyconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafole, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimephon, triadimenol, triticonazole, uniconazole, uniconazole-P, α-(1-chloro Cyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-5-(2-propene-1-ylthio)-1H-1,2,4-triazole. Prothioconazole is an example of a triazolinthion. Biochemical studies have shown that all of the above-mentioned fungicides are DMI fungicides as described in KHKuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

[0249] (b4) Phenylamide fungicides (FRAC code 4) are specific inhibitors of RNA polymerase in oomycetes. Susceptible fungi exposed to these fungicides show a reduced ability to incorporate uridine into rRNA. Growth and development of susceptible fungi are inhibited by exposure to this class of fungicides. Examples of phenylamide fungicides include acylalanine fungicides, oxazolidinone fungicides, and butyrolactone fungicides. Examples of acylalanine include venalaxyl, venalaxyl-M (also known as quilaraxyl), flaxyl, metalaxyl, and metalaxyl-M (also known as mephenoxam). An example of oxazolidinone is oxadixyl. An example of butyrolactone is oflas.

[0250] (b5) "Amine / morpholine fungicides" (FRAC code 5) (SBI: class II) target the following two sites in the sterol biosynthesis pathway: Δ 8 →Δ 7 isomerase and Δ 14 They inhibit reductase. Sterols such as ergosterol are necessary for membrane structure and function, and are essential for the development of functional cell walls. Therefore, exposure to these fungicides leads to abnormal growth and eventual death of susceptible fungi. Examples of amine / morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine fungicides, piperidine fungicides, and spirochetal-amine fungicides. Examples of morpholines include algimorph, dodemorph, fenpropimorph, toridemorph, and trimorphamide. Examples of piperidines include fenpropidine and piperaline. Examples of spirochetal-amines include spiroxamine.

[0251] (b6) "Phospholipid biosynthesis inhibitor fungicides" (RFAC code 6) inhibit fungal growth by affecting phospholipid biosynthesis. Examples of phospholipid biosynthesis fungicides include phosphorothioate fungicides and dithiolane fungicides. Examples of phosphorothioates include edifenfos, iprobenfos, and pyrazofos. An example of a dithiolane is isoprothiolane.

[0252] (b7) Succinate dehydrogenase inhibitors (SDHI) fungicides (FRAC code 7) inhibit the respiration of Complex II fungi by disrupting the major enzyme in the Krebs cycle (TCA cycle) called succinate dehydrogenase. This inhibition of respiration prevents the fungi from producing TAP, thus inhibiting their growth and reproduction. Examples of SDHI fungicides include: phenylbenzamide, phenyloxoethylthiophenamide, pyridinylethylbenzamide, furacarboxamide, oxathiincarboxamide, thiazolecarboxamide, pyrazole-4-carboxamide, N-cyclopropyl-N-benzylpyrazolecarboxamide, N-methoxy-(phenyl-ethyl)-pyrazolecarboxamide, pyridinecarboxamide, and pyrazinecarboxamide fungicides. Examples of phenylbenzamide include benodanil, flutolanil, and mepronil. Examples of phenyloxoethylthiophenamides include isofetamide. Examples of pyridinylethylbenzamides include fluoropyram. Examples of furancarboxamides include fenflam. Examples of oxatiincarboxamides include carboxyne and oxycarboxyne. Examples of thiazolecarboxamides include tifluzamide. Examples of pyrazole-4-carboxamides include: benzovindiflupir, bixafen, flubeneteram (provisional generic name, registration number 1676101-39-5), fluindapir, fraxapyroxad, flametopyr, impilfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne (provisional generic name, registration number 1803108-03-3), sedaxane, and N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. An example of an N-cyclopropyl-N-benzylpyrazolecarboxamide is isoflucipram. Examples of N-methoxy-(phenyl-ethyl)-pyrazolecarboxamides include pidflumetofen. Examples of pyridinecarboxamides include boscalid. Examples of pyrazinecarboxamides include pyraziflumid.

[0253] (b8) Hydroxy-(2-amino-)pyrimidine fungicides (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethylmol, and ethylmol.

[0254] (b9) Anilinopyrimidine fungicides (FRAC code 9) have been proposed to inhibit the biosynthesis of the amino acid methionine and impair the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim, and pyrimethanil.

[0255] (b10) N-phenylcarbamate fungicides (FRAC code 10) inhibit mitosis by binding to β-tubulin and disrupting microtubule formation. This inhibition of microtubule formation can potentially disrupt cell division, intracellular transport, and cellular structure. Dietofencarb is an example of such an agent.

[0256] (b11) "Quinone external inhibitor (QoI) mycicides" (FRAC code 11) inhibit fungal complex III mitochondrial respiration by affecting ubiquinol oxidase. Oxidation of ubiquinol affects cytochrome b located in the inner mitochondrial membrane of fungi. c1 The "quinone outer" of the complex (Q oBlocked at the ) site. Inhibition of mitochondrial respiration hinders the normal growth and development of fungi. Examples of quinone external inhibitory fungicides include: methoxyacrylate fungicides, methoxyacetamide fungicides, methoxycarbamate fungicides, oxyminoacetate fungicides, oxyminoacetamide fungicides, and dihydrodioxazine fungicides (collectively known as strobilurin fungicides), as well as oxazolidinedione fungicides, imidazolinone fungicides, and benzylcarbamate fungicides. Examples of methoxyacrylates include: azoxystrobin, chemoxystrobin, enoxastrobin (also known as enestrobrin), fluphenoxystrobin, picoxystrobin, and pyraoxystrobin. An example of methoxyacetamide is mandestrobin. Examples of methoxycarbamates include pyraclostrobin, pyrametostrobin, and triclopyricarb. Examples of oxyminoacetates include kresoxime-methyl and trifloxystrobin. Examples of oxyminoacetamides include dimoxystrobin, phenaminestrobin, metminostrobin, and orysastrobin. Examples of dihydrodioxazines include fluoxastrobin. Examples of oxazolidinediones include famoxadone. Examples of imidazolinones include phenamidone. Examples of benzylcarbamates include pyribencarb.

[0257] (b12) Phenylpyrrole fungicides (FRAC code 12) inhibit MAP / histidine kinases involved in fungal osmotic signaling. Fenpiclonil and fludioxonil are examples of this class of fungicides.

[0258] (b13) Azanafthane fungicides (FRAC code 13) have been proposed to inhibit signal transduction through an unknown mechanism. These fungicides are known to interfere with the germination and / or appressorium formation of fungi that cause powdery mildew. Examples of azanafthane fungicides include aryloxyquinolines and quinazolinones. An example of an aryloxyquinoline is quinoxyfen. An example of a quinazolinone is proquinazide.

[0259] (b14) Lipid peroxidation inhibitors (FRAC code 14) are proposed to inhibit lipid peroxidation, which affects fungal membrane synthesis. Members of this class, such as etridiazoles, may also affect other biological processes such as respiration and melanin biosynthesis. Examples of cell peroxidizing fungicides include aromatic hydrocarbon fungicides and 1,2,4-thiadiazole fungicides. Examples of aromatic hydrocarbon fungicides include biphenyl, chloreneb, dichlorane, quintozen, technazen, and tolclophos-methyl. An example of a 1,2,4-thiadiazole is etridiazole.

[0260] (b15) "Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides" (FRAC code 16.1) inhibit the naphthalene reduction step in melanin biosynthesis. Melanin is required for host plant infection by several fungi. Examples of melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone fungicides, pyrroloquinolinone fungicides, and triazolobenzothiazole fungicides. Phthalide is an example of isobenzofuranone. Pyrroquilon is an example of pyrroloquinolinone. Tricyclazole is an example of triazolobenzothiazole.

[0261] (b16a) "Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides" (RFAC code 16.2) inhibit citalone dehydratase in melanin biosynthesis. Melanin is required for host plant infection by several fungi. Examples of melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropanecarboxamide fungicides, carboxamide fungicides, and propionamide fungicides. Examples of cyclopropanecarboxamide include carpropamide. Examples of carboxamide include diclocimet. Examples of propionamide include phenoxanil.

[0262] (b16b) "Melanin biosynthesis inhibitors - polyketide synthase (MBI-P) fungicides" (FRAC code 16.3) inhibit polyketide synthase in melanin biosynthesis. Melanin is required for host plant infection by several fungi. Examples of melanin biosynthesis inhibitors - polyketide synthase fungicides include trifluoroethyl carbamate fungicides. An example of a trifluoroethyl carbamate is tolprocarb.

[0263] (b17) "Sterol biosynthesis inhibitors (SBI): Class III fungicides" (FRAC code 17) inhibit 3-keteductase during C4 demethylation in sterol production. Examples of keteductase inhibitor fungicides (also known as sterol biosynthesis inhibitors (SBI): Class III) include hydroxyanilides and aminopyrazolinones. Fenhexamide is an example of a hydroxyanilide. Fenpyrazamine is an example of an aminopyrazolinone. Quinofumelin (provisional generic name, registration number 861647-84-9) and ipflufenoquin (provisional generic name, registration number 1314008-27-9) are also considered to be keteductase inhibitor fungicides.

[0264] (b18) Squalene epoxidase inhibitors (FRAC code 18) (SBI: class IV) inhibit squalene epoxidase in the sterol biosynthesis pathway. Sterols such as ergosterol are necessary for membrane structure and function, and are essential for the development of functional cell walls. Therefore, exposure to these fungicides leads to abnormal growth and eventual death of susceptible fungi. Examples of squalene epoxidase inhibitors include thiocarbamate fungicides and allylamine fungicides. Examples of thiocarbamates include pyributicarb. Examples of allylamines include naphthifine and terbinafine.

[0265] (b19) "Polyoxin fungicides" (FRAC code 19) inhibit chitin synthesis. Polyoxins are an example.

[0266] (b20) Phenylurea fungicides (FRAC code 20) have been suggested to affect cell division. Pencyclon is an example.

[0267] (b21) "Quinone internal inhibitor (QiI) mycicides" (FRAC code 21) inhibit fungal complex III mitochondrial respiration by affecting ubiquinone reductase. Ubiquinone reduction is associated with cytochrome b located in the inner mitochondrial membrane of fungi. c1 The "quinone interior" of the complex (Q i Blocked at the ) site. Inhibition of mitochondrial respiration hinders the normal growth and development of fungi. Examples of quinone internal inhibitor fungicides include cyanoidazole fungicides, sulfamoyltriazole fungicides, and picolineamide fungicides. An example of a cyanoidazole is cyazofamide. An example of a sulfamoyltriazole is amisulfrom. An example of a picolineamide is fenpicoxamide (registration number 517875-34-2).

[0268] (b22) "Benzamide and thiazole carboxamide fungicides" (FRAC code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule construction. This inhibition of microtubule construction may disrupt cell division, intracellular transport, and cellular structure. Examples of benzamides include toluamides such as zoxamide. Examples of thiazole carboxamides include ethylaminothiazole carboxamides such as etaboxam.

[0269] (b23) Enopyranuronic acid antibiotic fungicides (FRAC code 23) inhibit fungal growth by affecting protein biosynthesis. Blastocydin-S is an example.

[0270] (b24) Hexopyranosyl antibiotic fungicides (FRAC code 24) inhibit fungal growth by affecting protein biosynthesis. Kasugamycin is an example.

[0271] (b25) "Glucopyranosyl antibiotics: protein synthesis fungicides" (FRAC code 25) inhibit fungal growth by affecting protein biosynthesis. Streptomycin is an example.

[0272] (b26) "Glucopyranosyl antibiotic fungicides" (FRAC code U18, formerly FRAC code 26, which was reclassified as U18) have been proposed to inhibit the biosynthesis of trehalase and inositol. Validamycin is an example.

[0273] (b27) Cymoxanil is an example of a "cyanoacetamidooxime fungicide" (FRAC code 27).

[0274] (b28) Carbamate fungicides (FRAC code 28) are considered multisite inhibitors of fungal growth. These fungicides are proposed to interfere with fatty acid synthesis in the cell membrane, and subsequently disrupt cell membrane permeability. Iodocarb, propamacarb, and prothiocarb are examples of this class of fungicides.

[0275] (b29) Oxidative phosphorylation uncoupling fungicides (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. This inhibition of respiration hinders normal fungal growth and development. Examples of this class include 2,6-dinitroaniline (e.g., fluazinam) and dinitrophenyl crotonates (e.g., dinocap, meptyldinocap, and binapacril).

[0276] (b30) "Organotin fungicides" (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in the oxidative phosphorylation pathway. Examples include triphenyltin acetate, triphenyltin chloride, and triphenyltin hydroxide.

[0277] (b31) Carboxylic acid fungicides (FRAC code 31) inhibit fungal growth by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Oxolinic acid is an example.

[0278] (b32) "Heterocyclic aromatic fungicides" (FRAC code 32) have been proposed to affect DNA / ribonucleic acid (RNA) synthesis. Examples of heterocyclic aromatic fungicides include isoxazole and isothiazolone. Himexazole is an example of isoxazole, and octylinone is an example of isothiazolone.

[0279] (b33) Examples of "phosphonate fungicides" (FRAC code P07, formerly FRAC code 33, which was reclassified as P07) include phosphite and its various salts (e.g., fosetyl-aluminum).

[0280] (b34) Tecrophthalam is an example of a "phthalamido acid fungicide" (FRAC code 34).

[0281] (b35) Triazoxide is an example of a "benzotriazine fungicide" (FRAC code 35).

[0282] (b36) Fursulfamide is listed as a "benzene-sulfonamide fungicide" (FRAC code 36).

[0283] (b37) Diclomezin is an example of a "pyridazinone fungicide" (FRAC code 37).

[0284] (b38) Thiophene-carboxamide fungicides (FRAC code 38) have been suggested to affect ATP production. Silthiofam is an example.

[0285] (b39) "Complex I NADH oxidoreductase inhibitor fungicides" (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidineamines such as diflumetrim, pyrazole-5-carboxamides such as tolfenpyrad, and quinazolines such as phenazaquin.

[0286] (b40) Carboxylic acid amide (CAA) fungicides (FRAC code 40) inhibit cellulose synthesis, thereby preventing the growth of target fungi and killing them. Examples of carboxylic acid amide fungicides include cinnamic acid amide fungicides, valine amide carbamate fungicides, and mandelic acid amide fungicides. Examples of cinnamic acid amides include dimethomorph, fulmorph, and pyrimorph. Examples of valine amide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprofalicarb, tolprocarb, and valifenalate (also known as valifenal). Examples of mandelic acid amides include: mandipropamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, and N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

[0287] (b41) Tetracycline antibiotic fungicides (FRAC code 41) inhibit fungal growth by affecting protein synthesis. Oxytetracycline is an example.

[0288] (b42) Metasulfocarb is an example of a "thiocarbamate fungicide" (FRAC code M12, previously reclassified as M12 under FRAC code 42).

[0289] (b43) Benzamide fungicides (FRAC code 43) inhibit fungal growth by delocalizing spectrin-like proteins. Examples include pyridinyl methylbenzamides such as fluopicolide and fluopimomide.

[0290] (b44) "Microbial fungicides" (FRAC code BM02, formerly FRAC code 44, which was reclassified as BM02) disrupt the cell membrane of fungal pathogens. Examples of microbial fungicides include: Bacillus species such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB1600, D747, TJ100 (also known as strain 1 BE; known from European Patent No. 2962568), and the fungicidal lipopeptides they produce.

[0291] (b45) "Quinone external inhibitors, stigmatellin-binding (QoSI) mycicides" (FRAC code 45) inhibit fungal complex III mitochondrial respiration by affecting ubiquinone reductase at the stigmatellin-binding subsite of the "quinone external" (Qo) site of the cytochrome bc1 complex. Inhibition of mitochondrial respiration hinders normal fungal growth and development. Examples of QoSI mycicides include triazolopyrimidylamines such as ametoctrazine.

[0292] (b46) "Plant extract fungicides" (FRAC code 46) cause cell membrane disruption. Examples of plant extract fungicides include terpene hydrocarbons, terpene alcohols, and terpene phenols (e.g., extracts from Melaleuca alternifolia (tea tree)), as well as vegetable oils (mixtures, e.g., eugenol, geraniol, and thymol).

[0293] (b47) "Cyanoacrylate fungicides" (FRAC code 47) bind to the myosin motor domain and affect motor activity and actin aggregates. Examples of cyanoacrylates include fungicides such as phenamacryl.

[0294] (b48) "Polyene fungicides" (FRAC code 48) cause the destruction of fungal cell membranes by binding to ergosterol, the major sterol of the membrane. An example is natamycin (pimaricin).

[0295] (b49) Oxysterol-binding protein inhibitors (OSBPIs) (FRAC code 49) bind to the oxysterol-binding protein of oomycetes, causing inhibition of zoospore release, zoospore motility, and sporangia germination. Examples of oxysterol-binding fungicides include piperdinylthiazole isoxazolines such as oxathiapiproline and fluoxapiproline.

[0296] (b50) "Aryl-phenyl-ketone fungicides" (FRAC code 50, formerly FRAC code U8, which was reclassified as 50) inhibit the growth of fungal hyphae. Examples of aryl-phenyl-ketone fungicides include benzophenones such as metraphenone and benzoylpyridines such as pyriophenone.

[0297] (b51) "Host plant defense-inducing mycicides" induce host plant defense mechanisms. Examples of host plant defense-inducing mycicides include: benzothiadiazole mycicides (FRAC code P01), benzisothiazole mycicides (FRAC code P02), thiadiazole carboxamide mycicides (FRAC code P03), polysaccharide mycicides (FRAC code P04), plant extract mycicides (FRAC code P05), microbial mycicides (FRAC code P06), and phosphonate mycicides (FRAC code P07, see (b33) above). Examples of benzothiadiazoles include acibenzoral-S-methyl. Examples of benzisothiazole include probenazole. Examples of thiadiazole carboxamides include thiadianil and isothianil. Examples of polysaccharides include laminarin. Examples of plant extracts include those derived from Reynoutria sachalinensis (Japanese knotweed). Examples of microorganisms include the cell walls of Bacillus mycoides isolate J and Saccharomyces cerevisiae strain LAS117.

[0298] (b52) A "multisite active fungicide" inhibits fungal growth through multiple sites of action and also has contact / preventive activity. Examples of multi-site active fungicides include: copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfamide fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code M11), and thiocarbamate fungicides (FRAC code M12; see (b42) above). Copper fungicides are typically inorganic compounds containing copper in a copper(II) oxidized state, such as copper oxychloride, copper sulfate, and copper hydroxide (e.g., compositions such as Bordeaux mixture (tribasic copper sulfate)). Sulfur fungicides are inorganic chemical substances containing a ring or chain of sulfur atoms, such as elemental sulfur. Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety, such as felbam, mancozeb, maneb, methylam, propineb, thyram, zinc thiazole, zineb, and ziram. Phthalimide fungicides contain a phthalimide molecular moiety, such as holpet, captan, and captahole. Chloronitrile fungicides contain aromatic rings substituted with chloro and cyano, such as chlorothalonil. Sulfamide fungicides include diclofluanide and trifluanide. Examples of multi-site contact guanidine fungicides include guazatine, iminoctadine albesylate, and iminoctadine triacetate. An example of a triazine fungicide is anilazine. An example of a quinone fungicide is dithianone. An example of a quinoxaline fungicide is quinomethionate (also known as chinomethionate). An example of a maleimide fungicide is fluoroimide.

[0299] (b53) "Biological preparations with multiple modes of action" include preparations of biological origin that exhibit multiple mechanisms of action for which there is no evidence of a dominant mode of action. Examples of fungicides in this class include polypeptide (lectin) fungicides, phenolic fungicides, sesquiterpene fungicides, tritepenoid fungicides, and coumarin fungicides (FRAC code BM01), for example, extracts from the cotyledons of the lupine plant. This class also includes single microbial fungicides (FRAC code BM02, see (b44) above).

[0300] (b54) "Fungicides other than those of component (a) and components (b1) to (b53)" include certain fungicides whose mode of action may be unknown. These include: (b54.1) "Phenylacetamide fungicide" (FRAC code U06), (b54.2) "Guanidine fungicide" (FRAC code U12), (b54.3) "Thiazolidine fungicide" (FRAC code U13), (b54.4) "Pyrimidinone hydrazone fungicide" (FRAC code U14), (b54.5) "4-Quinolyl acetate fungicide" (FRAC code U16), (54.6) "Tetrazoyl oxime fungicide" (FRAC code U17), and "Glucopyranosyl antibiotic fungicide" (FRAC code U18, see (b26) above). Cyflufenamide is an example of phenylacetamide. Dozin is an example of quanidine. Fluthianil is an example of thiazolidinedione. Felimzon is an example of pyrimidinone hydrazone. Tebufloxin is an example of 4-quinolyl acetate. Picarbtrazox is an example of tetrazoyl oxime.

[0301] The (b54) class also includes: bethoxazine, diclobentiazox (provisional generic name, registration number 957144-77-3), dipymetitrone (provisional generic name, registration number 16114-35-5), flomethquin, neo-asodine (ferric methanearsone), pyrrolnitrin, torniphanide (registration number 304911-98-6), N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanymidamide, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine, and 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate.

[0302] Further "fungicides other than those of class (b1) to (b54)" whose mode of action may be unknown or which have not yet been classified include fungicidal compounds selected from components (b54.7) to (b54.12), as shown below.

[0303] The component (54.7) is (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional generic name florylpicoxamid, registration number 1961312-55-9), which is considered to be a quinone internal inhibitor (QiI) mycicide (FRAC code 21) that inhibits mitochondrial respiration of fungal complex III.

[0304] The component (54.8) is thought to be a quinone external inhibitor (QoI) mycicide (FRAC code 45) that inhibits mitochondrial respiration of fungal complex III and is effective against QoI-resistant strains, specifically 1-[2-[[[1-(4-chlorophenyl)-1H-pyrazole-3-yl]oxy]methyl]-3-methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazole-5-one (tentative generic name: methyltetrapyrrole, registration number 1472649-01-6).

[0305] Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional generic name pyridaclomethyl, registration number 1358061-55-8), which is thought to promote tubulin polymerization and, as a result, produce antifungal activity against fungal species belonging to the Ascomycota and Basidiomycota phyla.

[0306] Component (54.10) relates to (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (provisional generic name aminopyrifen, registration number 1531626-08-0), which is thought to inhibit the GWT-1 protein in the glycosylphosphatidylinositol-anchor biosynthesis of Neurospora crassa.

[0307] The component (b54.11) is given by formula b54.11 [ka] Regarding the compound, During the ceremony, R b1 and R b3 Each of them is a halogen; R b2 These are H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, or C3-C6 cycloalkyl.

[0308] Examples of compounds of formula b54.11 include: (b54.11a) methyl N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11b) methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11c) methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11d) methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11e)methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate, and (b54.11f)methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate. The compound of formula b54.11, its use as a fungicide, and its preparation methods are generally known; see, for example, International Publication Nos. 2008 / 124092, 2014 / 066120, and 2020 / 097012.

[0309] The component (b54.12) is given by formula b54.12 [ka] Regarding the compound, During the ceremony, R b4 teeth, [ka] and; R b6These are C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl; L is CH2 or CH2O, where the right-hand atom is bonded to the phenyl ring in formula b54.12; R b5 teeth, [ka] and; R b7 The compounds are C1-C3 alkyl groups, and the wavy bond in the formula indicates that adjacent double bonds are either (Z) configuration, (E) configuration, or a mixture thereof.

[0310] Examples of compounds of formula b54.12 include: (b54.12a) N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]-4-oxazolecarboxamide, (b54.12b) ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, (b54.12c) ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, and (b54.12d) ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]1H-pyrazole-4-carboxylate. The compound of formula b54.12, its use as a fungicide, and methods of preparation are generally known; see, for example, International Publication Nos. 2008 / 187553 and 2020 / 056090.

[0311] Therefore, of particular note are mixtures (i.e., compositions) comprising the compound of Formula 1 and at least one fungicidal compound selected from the group consisting of classes (b1) to (b54) (including (b54.7) to (b54.12)). Also of particular note are compositions comprising the mixture (in a fungicidal effective amount) and further comprising at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents. Of particular note are mixtures (i.e., compositions) comprising the compound of Formula 1 and at least one fungicidal compound selected from the group consisting of specific compounds enumerated above in relation to classes (b1) to (b54). Also of particular note are compositions comprising the mixture (in a fungicidal effective amount) and further comprising at least one additional surfactant selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0312] Examples of fungicides in component (b) include: acibenzolar-S-methyl, algimorph, ametoctrazine, amisulbrom, anilazine, azaconazole, azoxystrobin, venalaxyl (e.g., venalaxyl-M), benodanil, benomyl, bentheavalicarb (e.g., bentheavalicarb-isopropyl), benzovindiflupir, betoxazine, binapacril, biphenyl, vitertanol, bixafen, blasticidine-S, boscalid, bromconazole, bupirimate, butthiovate, captahol, captan, and carbene. Dadimon, Carboxyne, Carpropamide, Chloroneb, Chlorthalonil, Clozolinate, Clotrimazole, Copper Hydroxide, Copper Oxychloride, Copper Sulfate, Cormoxystrobin, Cyazofamide, Cyflufenamid, Cymoxanil, Cyproconazole, Cyprodinil, Diclofluanide, Diclocimeth, Diclomazine, Dichloran, Dietofencarb, Difenoconazole, Diflumetrim, Dimethyrimol, Dimethomorph, Dimoxystrobin, Diniconasol (e.g., Diniconasol-M), Dinocup, Dithianone, Dithiolan, Dodemorph, Dodi Dipimethitron, Econazole, Edifenphos, Enoxastrobin (also known as Enestrobrin), Epoxyconazole, Etaconazole, Etaboxam, Ethyrimol, Etridiazole, Famoxadone, Phenamidon, Phenarimol, Phenaminestrobin, Fenbuconazole, Fenflam, Fenhexamide, Phenoxanil, Fenpiclonil, Fenpropidine, Fenpropimorph, Fenpyrazamine, Triphenyltin acetate, Triphenyltin chloride, Triphenyltin hydroxide, Ferubam, Ferimzon, Flo Metquin, Florylpicoxamide, Fluazinam, Fludioxonil, Flufenoxystrobin, Fluindapir, Flumorph, Fluopicolid, Fluopimomid, Fluopyram, Fluoroimide, Fluoxastrobin, Fluquinconazole, Flusilazole, Flusulfamide, Fluthianil, Flutolanil, Flutriafor, Fluxapiroxad, Holpet, Phthalide, Fuberidazole, Flalaxil, Flametpir, Guazatin, Hexaconazole, Himexazole, Imazalil, Imibenconazole, Iminooctadine albesylate,Iminoctadine triacetate, iodocarb, ipconazole, ipuphentrifluconazole, iprobenphos, iprodione, iprovalicarb, isoconazole, isofetamide, isoprothiolane, isoflucipram, isopyrazam, isothianil, kasugamycin, kresoxim-methyl, mancozeb, mandepropamide, mandestrobin, maneb, mepanipyrim, mepronil, meptildinocap, metalaxyl (e.g., metalaxyl-M / mephenoxam), mefentrifluconazole, metconazole, metasulfocarb, me Thyramine, metminostrobin, metraphenone, micronazole, mycrobutanil, naphthifine, neo-asodine, nualimol, octylinone, ofurase, orysastrobin, oxadixyl, oxatiapiproline, oxolinic acid, oxpoconazole, oxycarboxyne, oxytetracycline, pefurazoate, penconazole, pencyclon, penflufen, penthiopyrad, phosphates (including their salts, e.g., fosetyl-aluminum), picarbutrazox, picoxystrobin, piperarin, polyoxin, probenazole, p Lochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazide, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyroxystrobin, pyrazofos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriophenone, pyrisoxazole, pyrroquinone, pyrrolnitrin, quinconazole, quinofumerine (registration number 861647-84-9), quinomethionate, quinoxyfen, quintozen, sedaxane, silthiofame, simeconazole, spiroxamine, strep Tomycin, sulfur, tebuconazole, tebufloquine, tecrophthalam, technazene, terbinafine, tetraconazole, thiabendazole, tifluzamide, thiophanate, thiophanate-methyl, thyram, thiadinyl, tolcrophos-methyl, tolniphanide, tolprocarb, trifluanide, triadimefone, triadimenol, trialimol, triticonazole, triazoxide, tribasic copper sulfate, tricyclazole, triclopyricarb, tridemorph, trifloxystrobin, triflumisole, triforine, trimorphamide,Uniconazole, Uniconazole-P, Validamycin, Valifenarate (also known as Valifenal), Vinclozoline, Zineb, Ziram, Zoxamide, N-[2-(1S,2R)-[1,1'-Bicyclopropyl]-2-ylphenyl]-3-(Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)-ethyl]-1H-1,2,4-triazole-1-ethanol, (αS)-[3-(4-chloro-2-fluorophenyl)-5- (2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-diflu Olophenyl)-2-oxyranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole, N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)-amino]butanamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide, N'-[4-[4-chloro-3-(trif [(Oromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanymidamide, N-[[(Cyclopropylmethoxy)amino][6-(Difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-(3',4'-difluoro[1,1'-biphenyl]-2-yl)-3-(trifluoromethyl)-2-pyrazinecarboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-quinazolinamine, 1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]ethanone, 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine, α(methoxyimino)-N-methyl-2-[[[1-[[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, and [[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl-2 methylpropanoate. Therefore, what is noteworthy is a fungicidal composition comprising the compound of formula 1 (or its N-oxide or salt) as component (a), and at least one fungicide selected from the aforementioned list as component (b).

[0313] Of particular note are the combinations of the compound of Formula 1 (or its N-oxide or salt) (i.e., component (a) in the composition) with the following (i.e., as component (b) in the composition): aminopyriphen (registration number 1531626-08-0), azoxystrobin, benzovindiflupyr, bixafen, captan, carpropamide, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, diclobentiazox (registration number 957144-77-3), diethofencarb, Difenoconazole, dimethomorph, dipimethitrone, epoxyconazole, etaboxam, phenalimol, fenhexamide, fluazinam, fludioxonil, fluindapir, fluopyram, flusilazole, fluthianil, flutriafole, fluxapyroxad, folpet, ipuflufenoquin (registration number 1314008-27-9), iprodione, isofetamide, isoflucipram, isopyrazam, kresoxim-methyl, mancozeb, mandestrobin, meptyldinocap, metalaxyl (e.g., meta Laxil-M / mefenoxam), mefentrifluconazole, metconazole, metraphenone, methyltetrapyrrole (registration number 1472649-01-6), mycrobutanil, oxathiapiproline, penflufen, penthiopyrad, phosphate (including their salts, e.g., focetyl-aluminum), picoxystrobin, propiconazole, proquinazide, prothioconazole, pyridaclomethyl (registration number 1358061-55-8), pyraclostrobin, pyrapropoin (registration number 1803108-03-3) ), pyrimethanil, sedaxane, spiloxamine, sulfur, tebuconazole, thiophanate-methyl, trifloxystrobin, zoxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)-ethyl]-1H-1,2,4-triazole-1-ethanol, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-Trimethyl-1H-Indene-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]-ethanone, 1,1-dimethylethyl N-[6-[[[[(1-methyl-1H-tetrazole-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl) -2-oxyranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-5-(2-propene-1-ylthio)-1H-1,2,4-triazole.

[0314] Generally, for better control of plant diseases caused by fungal plant pathogens (e.g., lower usage rates or a broader spectrum of controlled plant pathogens), or for resistance management, preferred are mixtures of the compound of Formula 1, its N-oxide or salt, and a fungicidal compound selected from the following group: amisulbrom, azoxystrobin, boscalid, carbendazim, carboxyne, cymoxanil, cyproconazole, difenoconazole, dimethomorph, dimoxystrobin, fenpropimorph, florylpicoxamide, fluazinam, fludioxonil, fluphenoxystrobin, fluindapyr, and fluquinconazole. , fluopicolide, fluoxastrobin, flutriafole, fluxapiroxad, ipconazole, ipufentrifluconazole, iprodione, kresoxim-methyl, metalaxyl, mefenoxam, mefentrifluconazole, metconazole, metminostrobin, mycrobutanil, paclobutrazol, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, pyrametostrobin, pyroxystrobin, pyriophenone, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, cyram, trifloxystrobin, and triticonazole.

[0315] Examples of other bioactive compounds or agents that can be formulated with the compounds of the present invention are invertebrate pest control compounds or agents, for example: abamectin, acephate, acetamiprid, acrinatrin, afidopiropene ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a, 12b-Decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), amidoflumet (S-1955), ivermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, cal Bofran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyantraniliprole (3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), cyclanili Prol(3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide), cycloxapride((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine), cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiurone, diazinon, dierudrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, phenothiocarb, phenoxycarb, fenpropathrin, fenvalerate, fipronil, flubendiamide, flucitrinate, flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate), flufen Sulfone (5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole), Flupiprol (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitride), Flupyradiflon (4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), Tau-fluvalinate, Fluphenelim (UR-50701), Flufenoxuron, Phonofos, Halophenozide, Heptafluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), hexaflumurone, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, meperfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyphenozide, metofluthrin, milbemycin oxime, monfluotrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-3-(2-cyano-1-propen-1-yl)-2,2-Dimethylcyclopropanecarboxylate), monoclotophos, nicotine, nitenpyram, nithiazine, novalon, nobiflumulon (XDE-007), oxamyl, piflubumid (1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide), parathion, parathion-methyl, permethrin, phorate, phosalon, phos Met, phosphamidone, pyrimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridaryl, pyrifluquinazone, pyriminostrobin (methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzene acetate), pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramato, sulfoxaflor, sulprophos, tebufenozide, teflubenzuron, tefluthrin, tarbuphos, tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, and triflumulon; and biological agents, such as entomopathogenic bacteria, such as Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, and Bacillus thuringiensis Encapsulated delta-endotoxins of *Tricholoma thuringiensis* (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi, e.g., *Tricholoma rhodopsum*; and entomopathogenic viruses, e.g., baculoviruses, nuclear polyhedron virus (NPV), e.g., HzNPV, AfNPV; and granulosis viruses (GV), e.g., CpGV.

[0316] Examples of biological agents to be mixed with the compounds of this disclosure include: entomopathogenic bacteria such as Bacillus thuringiensis, and encapsulated delta-endotoxin of Bacillus thuringiensis (e.g., MVP® and MVPII® bioinsecticides prepared by the CellCap® process) (CellCap®, MVP®, and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi, e.g., green muscardine fungus; and entomopathogenic viruses (both naturally occurring and genetically modified), e.g., baculoviruses, polyhedrosis viruses (NPVs), e.g., Helicoverpa zea polyhedrosis virus (HzNPV), Anagrapha farfera falcifera) nuclear polyhedron disease virus (AfNPV); and granulosis viruses (GV), such as codlinga (Cydia pomonella) granulosis virus (CpGV).

[0317] General references for these agricultural protective agents (i.e., insecticides, fungicides, anthelmintics, acaricides, herbicides, and biological agents) include The Pesticide Manual, 13th Edition, CDSTomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd Edition, LGCopping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0318] In embodiments using one or more of these various mixing partners, the weight ratio of these various mixing partners (total) to the compound of Formula 1 is typically about 1:3000 to about 3000:1, and more typically about 1:500 to about 500:1. Of particular note are compositions in which the weight ratio of component (a) to component (b) is about 125:1 to about 1:125. Due to the many fungicidal compounds of component (b), these compositions are particularly effective in controlling plant diseases caused by fungal plant pathogens. Of particular note are compositions in which the weight ratio of component (a) to component (b) is about 25:1 to about 1:25 or about 5:1 to about 1:5. Those skilled in the art can easily determine the weight ratio and application amount of the fungicidal compound required for the desired spectrum of fungicidal protection and control by simple experiments. It will be clear that by including further fungicidal compounds in component (b), the spectrum of plant diseases controlled can be expanded beyond the spectrum controlled by component (a) alone.

[0319] In certain cases, combinations of the compounds of the present invention with other biologically active (particularly fungicidal) compounds or agents (i.e., active ingredients) may produce additive (i.e., synergistic) effects. It is always desirable to reduce the amount of active ingredients released into the environment while ensuring effective pest control. When the synergistic effect of fungicidal active ingredients manifests at a spray rate that provides an agriculturally satisfactory level of fungal control, such combinations may be advantageous in reducing crop production costs and lowering environmental impact.

[0320] Furthermore, in certain cases, combinations of the compounds of the present invention with other biologically active compounds or agents may produce a non-additive (i.e., safer) effect on organisms beneficial to the agricultural environment. For example, the compounds of the present invention may make herbicides safer on crop plants or protect beneficial insect species (e.g., insect predators, pollinators such as bees) from insecticides.

[0321] Notable fungicides that, when compounded with the compounds of Formula 1, yield mixtures useful for seed treatment include, but are not limited to, amisulbrom, azoxystrobin, boscalid, carbendazim, carboxyne, cymoxanil, cyproconazole, difenoconazole, dimethomorph, florylpicoxamide, fluazinam, fludioxonil, fluphenoxystrobin, fluquinconazole, fluopicolid, fluoxastrobin, flutriafole, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, mefentrifluconazole, metconazole, mycrobutanil, paclobutrazol, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, cyram, trifloxystrobin, and triticonazole.

[0322] The following are, but are not limited to, invertebrate pest control compounds or agents that can be compounded with the compounds of Formula 1 to obtain a mixture useful for seed treatment: abamectin, acetamiprid, acrinatrin, afidopyropene, amitraz, evermectin, azadirachtin, bensultap, bifenthrin, buprofezin, kazusafos, carbaryl, carbofuran, cartap, chloranthraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, and cyanoacrylate. Anthraniliprole, cyclaniliprol, cyfluthrin, beta-cyfluthrin, cyhalotrin, gamma-cyhalotrin, lambda-cyhalotrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dierdrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, phenothiocarb, phenoxycarb, fenvalerate, phi Pronil, flonicamide, flubendiamide, fluensulfone, flufenoxuron, fluhyprol, flupyradiflon, fluvalinate, formethanate, fostiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, monofluorothrin, nitenpyram, nithiazine, novaron, oxamyl, piflu Bumid, pymetrozine, pyrethrin, pyridaben, pyriminostrobin, pyridaryl, pyriproxyfen, ryanodine, spinetram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumulon, Bacillus thuringiensis delta-endotoxin, strains of Bacillus thuringiensis, and strains of the nuclear polyhedron virus.

[0323] Compositions containing the compound of Formula 1 that are useful for seed treatment can further include bacteria and fungi that have the ability to protect against harmful effects from plant pathogenic fungi or bacteria and / or soil animals such as nematodes. Examples of nematode-killing bacteria include, but are not limited to, Bacillus firmus, Bacillus cereus, Bacillus subtiliis, and Pasteuria penetrans. A suitable Bacillus firmus strain is strain CNCM I-1582 (GB-126), which is used in BioNem TM It is commercially available as such. A preferred Bacillus cereus strain is strain NCMM I-1592. All Bacillus strains are disclosed in U.S. Patent No. 6,406,690. Other preferred bacteria exhibiting nematicidal activity are B. amyloliquefaciens IN937a and B. subtilis strain GB03. A bacterium exhibiting fungicidal activity is, but is not limited to, B. pumilus strain GB34. Examples of fungal species that exhibit nematodic activity include Myrotheciium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum, but are not limited to these.

[0324] Seed treatment may also include one or more naturally occurring nematicides, such as an inducing factor protein called harpin, isolated from certain bacterial plant pathogens like Erwinia amylovora. An example is N-Hibit. TM This is Harpin-N-Tek seed treatment technology available as Gold CST.

[0325] Seed treatment may also include one or more species of leguminous root-nosing bacteria, such as the microsymbiotic nitrogen-fixing bacterium Bradyrhizobium japonicum. These inoculants may optionally contain one or more lipochito-oligosaccharides (LCOs), which are nodule-forming (Nod) factors produced by Rhizobia bacteria during the initiation of nodule formation on the roots of leguminous plants. For example, the Optimize® brand seed treatment technology combines LCOs with LCO Promoter Technology in combination with the inoculant. TM It incorporates this.

[0326] Seed treatment may also contain one or more isoflavones that can enhance the level of root establishment by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by increasing root uptake of nutrients such as water, sulfates, nitrates, phosphates, and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin, and platencein. Formononetin is available as an active ingredient in mycorrhizal inoculation materials such as PHC Colonize® AG.

[0327] Seed treatment may also include one or more plant activators that induce systemic acquired resistance in plants after contact with pathogens. An example of a plant activator that induces such protective mechanisms is acibenzolar-S-methyl.

[0328] The following tests demonstrate the control efficacy of the compound of the present invention against specific pathogens. However, the pathogen control and protection provided by this compound is not limited to these species. For a description of the compound, please refer to Table A below. The abbreviation "Cmpd." represents the "compound," and the abbreviation "Ex." represents the "example," followed by a number indicating which example of the compound was prepared. The values ​​reported in the "MS" column indicate the molecule with the highest isotopic abundance. + The molecular weight (M+1) of the positively charged parent ion with the highest isotopic abundance, formed by adding (molecular weight 1), or H + This is the molecular weight (M-1) of the negatively charged ion with the highest isotopic abundance, formed by the decrease in (molecular weight 1). It refers to one or more isotopes with higher atomic weights that are present in lower abundances (e.g., 37 Cl, 81 The presence of molecular ions containing Br) has not been reported. The reported MS peaks were observed by mass spectrometry using electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI).

[0329] [Table 4]

[0330] [Table 5]

[0331] [Table 6]

[0332] Biological embodiments of the present invention A schematic protocol for preparing the test suspensions for tests A-F was as follows: First, the test compound was dissolved in an amount of acetone equal to 3% of the final volume, and then suspended at the desired concentration (ppm) in purified water (50 / 50 mix by volume) containing acetone and 250 ppm of the surfactant PEG400 (polyhydric alcohol ester). The resulting test suspension was then used in tests A-F.

[0333] Test A The test solution was sprayed onto wheat seedlings until it ran off. The following day, these seedlings were inoculated with a spore suspension of Zymoseptoria tritici (the pathogen of wheat leaf blight), incubated at 24°C in a saturated atmosphere for 48 hours, then transferred to a cultivation chamber at 20°C for 17 days, and subsequently, disease progression was evaluated over time.

[0334] Test B The test solution was sprayed onto wheat seedlings until it ran off. The following day, these seedlings were inoculated with a spore suspension of Puccinia recondita f.sp. tritici (the pathogen of wheat leaf rust), incubated at 20°C in a saturated atmosphere for 24 hours, then transferred to a cultivation chamber at 20°C for 7 days, and subsequently visual disease assessment over time.

[0335] Test C The test suspension was sprayed onto wheat seedlings until it ran off. The following day, these seedlings were inoculated with spore dust of Blumeria graminis f.sp. tritici (the pathogen of wheat powdery mildew, also known as Erysiphe graminis f.sp. tritici), incubated at 20°C in a cultivation chamber for 8 days, and then visual disease assessment was performed over time.

[0336] Test D The test solution was sprayed onto soybean seedlings until it ran off. The following day, these seedlings were inoculated with a spore suspension of Phakopsora pachyrhizi (the pathogen of soybean rust disease), incubated at 22°C in a saturated atmosphere for 24 hours, then transferred to a cultivation chamber at 22°C for 8 days, and subsequently visual disease assessment was performed over time.

[0337] Test E The test suspension was sprayed onto tomato seedlings until it ran off. The following day, these seedlings were inoculated with a spore suspension of Botrytis cinerea (the pathogen of tomato botrytis disease), incubated at 20°C in a saturated atmosphere for 48 hours, then transferred to a cultivation chamber at 24°C for 3 days, and subsequently visual disease assessment over time.

[0338] Test F The test suspension was sprayed onto tomato seedlings until it ran off. The following day, these seedlings were inoculated with a spore suspension of Alternaria solani (the pathogen of tomato leaf blight), incubated at 27°C in a saturated atmosphere for 48 hours, then transferred to a cultivation chamber at 20°C for 3 days, and subsequently, disease progression was evaluated over time.

[0339] The results of tests A through F are shown in Table A below. A rating of 100 indicates 100% disease control, and a rating of 0 indicates no disease control (compared to the control). A dash (-) indicates that the compound was not tested.

[0340] [Table 7]

[0341] [Table 8]

[0342] [Table 9]

[0343] Table 10

Claims

1. Formula 1 【Chemistry 1】 Compounds selected from, their tautomers, N-oxides, and salts, During the ceremony W is O; Q1 and Q2 are, independently, A-1 【Chemistry 2】 Selected from, During the ceremony, A floating bond is connected to formula 1 via any available carbon atom; n is 1, 2, or 3; R 1 is cyano, C 1 to C 3 alkyl, C2 - C 3 alkenyl, C2 - C 3 cyanoalkyl, C 1 to C 3 alkoxy, C 1 to C 3 haloalkoxy, C2 - C 3 haloalkenyloxy, C 2 to C 3 alkynyloxy, or C 2 to C 3 cyanoalkoxy; R 2 However, H, halogen, cyano, or C 1 ~C 3 It is alkyl; R 3 However, H, halogen, or C 1 ~C 3 It is alkyl; Each R 4 However, independently, halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 It is an alkoxy. Compounds, their tautomers, N-oxides, and salts.

2. R1 is cyano, C 1 ~C 3 Alkyl, C2-C 3 Cyanoalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkoxy, C2-C 3 Haloalkenyloxy, C 2 ~C 3 Alkynyloxy, or C 2 ~C 3 It is a cyanoalkoxy; Each R 4 However, independently, halogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, or C1-C 3 It is an alkoxy. The compound according to claim 1.

3. R1 is C 1 ~C 2 Alkyl, C1-C 2 Alkoxy, or C 1 ~C 2 It is a haloalkoxy; R 2 However, H, halogen, cyano, or C 1 ~C 2 It is alkyl; R 3 However, H, halogen, or C 1 ~C 2 It is alkyl; Each R 4 However, independently, halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, or C 1 ~C 3 It is an alkoxy. The compound according to claim 2.

4. Each n is independently 2 or 3; R 1 However, C 1 ~C 2 Alkyl or C 1 ~C 2 It is an alkoxy; R 2 However, it is halogen, cyano, methyl, or ethyl; R 3 However, it is H, Br, Cl, or methyl; Each R 4 However, independently, halogen, C 1 ~C 2 Alkyl, C 1 ~C 2 Haloalkyl, or C 1 ~C 2 It is an alkoxy. The compound according to claim 3.

5. Q 1 However, R 4 A-1 is substituted at the 2nd and 4th positions with substituents independently selected from; or Q 1 However, R 4 A-1 is substituted at the 2nd and 6th positions with substituents independently selected from; or Q 1 However, R 4 A-1 is substituted at positions 2, 4, and 6 with substituents independently selected from; R 1 However, it is methyl; Each R 4 However, independently, Br, Cl, F, methyl, or C 1 ~C 2 It is an alkoxy. The compound according to claim 4.

6. Q 1 However, R 4 A-1 is substituted at the 2nd and 4th positions or at the 2nd and 6th positions with substituents independently selected from; R 2 is halogen, methyl, or ethyl; R 3 However, it is H, Each R 4 However, independently, they are Br, Cl, F, methyl, methoxy, or ethoxy. The compound according to claim 5.

7. The following groups: 3-Chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1-methyl-2(1H)-pyridinone; 5-(2-bromo-3,5-dimethoxyphenyl)-3-chloro-4-(2,4-dimethophenyl) Luorophenyl)-1-methyl-2(1H)-pyridinone; 5-(2-chloro-3,5-dimethoxyphenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-2(1H)-pyridinone; 5-(2-bromo-5-methoxyphenyl)-3-chloro-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone; 3-Chloro-5-(2-chloro-3,5-dimethoxyphenyl)-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone; 3-Chloro-5-(2-Chloro-5-methoxyphenyl)-4-(2,4-difluorophenyl)-1-methyl-2(1H)-pyridinone; 3-Chloro-4-(2-chloro-4-fluorophenyl)-5-(2-chloro-5-methoxyphenyl)-1-methyl-2(1H)-pyridinone; 3-bromo-4-(2-chloro-4-fluorophenyl)-5-(2-chloro-5-methoxyphenyl)-1-methyl-2(1H)-pyridinone; 4-(2-chloro-4-fluorophenyl)-5-(2-chloro-5-methoxyphenyl)-1,3-dimethyl-2(1H)-pyridinone; 3-Chloro-4-(2,4-difluorophenyl)-5-(2-fluoro-3,5-dimethoxyphenyl)-1-methyl-2(1H)-pyridinone; 5-(2-chloro-5-methoxyphenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-2(1H)-pyridinone; and 5-(2-bromo-5-methoxyphenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-2(1H)-pyridinone Selected from, The compound according to claim 1.

8. (a) a compound according to claim 1, and (b) an additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

9. A method for controlling plant diseases caused by fungal plant pathogens, comprising applying a fungicidal effective amount of the compound described in claim 1 to a plant or a part thereof, or to a plant seed.

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