Substituted 5,6-diphenyl-3(2H)-pyridazinones for use as fungicides

Abstract

What is disclosed is the formula (1) [Formula 1] TIFF2023513239000040.tif45170, including all geometric and stereoisomers, N-oxides, and salts thereof, wherein W, R 1 , R 2 , R 3 , R 4 , R 5 , m, n, and p are as defined in this disclosure. Also disclosed are compositions comprising the compounds of formula (1), and 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 pyridazinones, their N-oxides, salts, and compositions, and methods for their use as fungicides. [Background technology]

[0002] Control of plant diseases caused by fungal plant pathogens is of great importance in achieving high crop efficiency. Damage caused by plant diseases to ornamental, vegetable, field, cereal, and fruit crops can significantly reduce productivity, thereby increasing costs to consumers. Many products are commercially available for these purposes, but there is a continuing need for new compounds that are more effective, less costly, less toxic, environmentally safer, or have a different site of action.

[0003] US Patent No. 5,949,999 discloses diphenylpyridazinones and their use as herbicides and plant growth regulators.

[0004] US Patent No. 5,929,999 discloses fungicidal dihydropyridazinones and pyridazinones and their use in agriculture.

[0005] US Pat. No. 5,629,999 discloses pyridazin-3-ones and their use as medicines.

[0006] US Pat. No. 5,629,999 discloses pyridazine derivatives and their use as medicines.

[0007] Patent Document 5 discloses a method for inhibiting the production of osteopontin, which comprises administering a pyridazine derivative. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 1982 / 00402 Pamphlet [Patent Document 2] European Patent Application Publication No. 478195(A1) [Patent Document 3] U.S. Patent No. 6,680,316 [Patent Document 4] US Patent Application Publication No. 2002 / 0123496 [Patent Document 5] US Patent Application Publication No. 2007 / 0021418 Summary of the Invention [Means for solving the problem]

[0009] The present invention relates to a compound of formula 1 [ka] (including all stereoisomers), N-oxides and salts thereof, compositions containing them, and their use as fungicides, During the ceremony, W is O or S; R 1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C6 cyanoalkyl, or C2-C6 alkoxyalkyl, each of which is optionally substituted with up to three substituents independently selected from halogen; R 2 H, halogen, cyano, hydroxy, nitro, C(=O)NR 7a R 7b, C(=O)OH, 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 cyanoalkyl, C1-C6 hydroxyalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C2-C6 alkylcabonyl carbonyloxy, C2-C6 haloalkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 haloalkoxycarbonyl, C1-C6 alkylamino, C1-C6 haloalkylamino, or C2-C6 dialkylamino; p is 0 or 1; The dotted line in Formula 1 represents an optional bond, provided that this optional bond is present when p is 0 and this optional bond is absent when p is 1; R 3 is H or C1-C3 alkyl; Each R 4 and R 5 are independently cyano, nitro, halogen, or hydroxy; or are C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 cyanoalkyl, C1-C6 hydroxyalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C2-C6 cyanoalkoxy, or C1-C6 alkylthio, each optionally substituted with up to three substituents independently selected from halogen and C1-C3 alkyl; or -UVT: Each U is independently a direct bond, O, C(=O), or NR6 and; each V is independently C1-C6 alkylene, C2-C6 alkenylene, or C3-C6 alkynylene, where up to two carbon atoms are C(=O), each optionally substituted with up to three substituents independently selected from halogen, cyano, nitro, hydroxy, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 haloalkoxy; Each T is independently NR 7a R 7b , OR 8 , or S(=O) q R 9 and; Each R 6 are independently 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 are 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, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkylcarbonyl, or C2-C6 alkoxycarbonyl; or R 7a and R 7b together with the nitrogen atom to which they are attached form a 3- to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the nitrogen atom to which they are attached, ring members selected from carbon atoms and up to two heteroatoms independently selected from up to two O atoms, up to two S atoms, and up to two N atoms, and each ring optionally contains R 10 and is substituted with up to three substituents independently selected from: Each R 8 and R 9are independently 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 are independently halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; m and n are each independently 0 to 5; each q is independently 0, 1, or 2; provided that the compound of formula 1 is 2-Methyl-5,6-diphenyl-3(2H)-pyridazinone; 2-Ethyl-5,6-diphenyl-3(2H)-pyridazinone; 2-(Methoxymethyl)-5,6-diphenyl-3(2H)-pyridazinone; 2-(2-Methoxyethyl)-5,6-diphenyl-3(2H)-pyridazinone; 2-(2-Methoxyethyl)-5,6-diphenyl-3(2H)-pyridazinethione; 2,3-Dihydro-2-methyl-3-oxo-5,6-diphenyl-4-pyridazinecarbonitrile; 2,3-Dihydro-3-oxo-5,6-diphenyl-2-propyl-4-pyridazinecarbonitrile; 2,3-Dihydro-2-(1-methylethyl)-3-oxo-5,6-diphenyl-4-pyridazinecarbonitrile; 5-cyano-6-oxo-3,4-diphenyl-1(6H)-pyridazinepropanenitrile; 2,3-Dihydro-3-oxo-2-(2-pentyn-1-yl)-5,6-diphenyl-4-pyridazinecarbonitrile; 5,6-bis(4-chlorophenyl)-2-methyl-3(2H)-pyridazinone; 2-(Methoxymethyl)-5-(4-methylphenyl)-6-phenyl-3(2H)-pyridazinone; 5-(4-chlorophenyl)-2-(methoxymethyl)-6-phenyl-3(2H)-pyridazinone; 2-(2-chloroethyl)-5,6-bis(4-chlorophenyl)-2,3-dihydro-3-oxo-4-pyridazinecarbonitrile; 5,6-bis(4-methoxyphenyl)-2-methyl-3(2H)-pyridazinone; 2-Ethyl-5,6-bis(4-methoxyphenyl)-3(2H)-pyridazinone; 5,6-bis(4-methoxyphenyl)-2-(1-methylethyl)-3(2H)-pyridazinone; 2-Cyclopropyl-5,6-bis(4-methoxyphenyl)-3(2H)-pyridazinone; 2-(2-chloroethyl)-5,6-bis(4-methoxyphenyl)-3(2H)-pyridazinone; 5,6-bis(4-methoxyphenyl)-2-(2-propen-1-yl)-3(2H)-pyridazinone; 2-Cyclopentyl-5,6-bis(4-methoxyphenyl)-3(2H)-pyridazinone; 2-Ethyl-2,3-dihydro-5,6-bis(4-methoxyphenyl)-3-oxo-4-pyridazinecarbonitrile; 2,3-Dihydro-5,6-bis(4-methoxyphenyl)-3-oxo-2-propyl-4-pyridazinecarbonitrile; 2,3-Dihydro-5,6-bis(4-methoxyphenyl)-2-(1-methylethyl)-3-oxo-4-pyridazinecarbonitrile; 2-Ethyl-6-(3-fluoro-4-methoxyphenyl)-5-(4-methoxyphenyl)-3(2H)-pyridazinone; 2-Ethyl-5-(3-fluoro-4-methoxyphenyl)-6-(4-methoxyphenyl)-3(2H)-pyridazinone; 2-Ethyl-5,6-bis(3-fluoro-4-methoxyphenyl)-3(2H)-pyridazinone; 2-Ethyl-5,6-bis(3-fluoro-4-methoxyphenyl)-4,5-dihydro-3(2H)-pyridazinone; 6-(4-Methoxyphenyl)-2-methyl-5-(3,4,5-trimethoxyphenyl)-3(2H)-pyridazinone; 2-methyl-4-nitro-5,6-diphenyl-3(2H)-pyridazinone; 2-methyl-4-(methylthio)-5,6-diphenyl-3(2H)-pyridazinone; and 4-(Ethylthio)-2-methyl-5,6-diphenyl-3(2H)-pyridazinone isn't it, The compounds (including all stereoisomers), their N-oxides and salts, compositions containing them, and their use as fungicides are directed to the compounds (including all stereoisomers), their N-oxides and salts, compositions containing them, and their use as fungicides.

[0010] More specifically, the present invention relates to compounds of Formula 1 (including all stereoisomers), an N-oxide, or a salt thereof:

[0011] The present invention also relates to fungicidal compositions comprising (a) a compound of the present invention (i.e., a compound of the present invention in a fungicidally effective amount), and (b) at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent.

[0012] The present invention also relates to fungicidal compositions comprising (a) a compound of the present invention and (b) at least one other fungicide (eg, at least one other fungicide with a different site of action).

[0013] The present invention further relates to a method for controlling plant diseases caused by fungal plant pathogens, comprising applying to a plant or part thereof, or to a plant seed, a fungicidally effective amount of a compound of the present invention (e.g., as a composition described herein).

[0014] The present invention also relates to compositions comprising a compound of Formula 1, an N-oxide, or a salt thereof, and at least one invertebrate pest control compound or agent. DETAILED DESCRIPTION OF THE INVENTION

[0015] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitations expressly stated. For example, a composition, mixture, process, method, article, or device that includes a list of elements is not necessarily limited to only those elements and may include other elements that are not expressly listed or inherent in such composition, mixture, process, method, article, or device.

[0016] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. In the context of a claim, such excludes the inclusion of materials other than those recited, except for impurities normally associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim, rather than immediately following a preamble, it limits only the elements recited in that clause; other elements are not excluded from the claim as a whole.

[0017] The transitional phrase "consisting essentially of" is used to define a composition, method, or apparatus that includes materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additional materials, steps, features, ingredients, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of."

[0018] Where applicants have defined an invention or portion thereof using open-ended language such as "comprising," it should be readily understood that (unless otherwise expressly stated) this description should be construed as also describing such invention using the terms "consisting essentially of" or "consisting of."

[0019] Furthermore, unless expressly stated to the contrary, "or" means an inclusive "or" and not an exclusive "or." For example, a condition A or B is satisfied by any 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).

[0020] Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be open-ended regarding the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural, unless the number is specifically intended to be singular.

[0021] The term "agronomic" refers to the production of agricultural crops, such as for food and fiber, and includes the growing of corn or maize, 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, eggplant, crucifers, and cucurbits), potatoes, sweet potatoes, grapes, cotton, fruit trees (e.g., pome fruits, stone fruits, and citrus fruits), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflowers, and olives).

[0022] The term "non-agronomic" refers to uses such as, for example, crops other than horticultural crops (e.g., greenhouse plants, nursery plants, or ornamental plants not grown in fields), residential, agricultural, commercial, and industrial structures, turf (e.g., turf farms, ranches, golf courses, turf, sports fields, etc.), wood products, storage products, forestry and plant care, public health (i.e., humans) and animal health (e.g., domesticated animals, such as pets, livestock, and poultry, and non-domesticated animals, such as wildlife) uses.

[0023] The term "crop vigor" refers to the rate of growth or biomass accumulation of a crop. "Increased vigor" refers to an increase in crop growth or biomass accumulation relative to an untreated control crop. The term "crop yield" refers to the return of crop material, both in terms of quantity and quality, obtained after harvesting the crop. "Increased crop yield" refers to an increase in crop yield relative to an untreated control crop.

[0024] The term "biologically effective amount" refers to an amount of a biologically active compound (e.g., a compound of Formula 1) sufficient to produce a desired biological effect when applied to (i.e., contacted with) the fungus to be controlled or its environment, or to a plant, a seed on which the plant grows, or the locus of the plant (e.g., a growth medium), either to protect the plant from damage caused by a fungal disease or for other desired effect (e.g., increased plant vigor).

[0025] As referred to in this disclosure and claims, "plants" include members of the Plantae kingdom (especially seed plants (Spermatopsida)) in all life cycles, including, for example, young plants (e.g., germinating seeds developing into seedlings) and mature reproductive stages (e.g., plants that produce flowers and seeds). Plant parts include geotropic members that typically grow below the surface of the growing medium (e.g., soil) (e.g., roots, tubers, bulbs, and corms), as well as members that grow above the growing medium (e.g., leaves (including stems and leaves), flowers, fruits, and seeds).

[0026] As referred to herein, the term "seedling" used alone or in combination with words means a young plant developing from the embryo of a seed.

[0027] As referred to herein, the term "broadleaf" used alone or in words (e.g., broadleaf crops) refers to dicotyledons or dicotyledons, terms used to describe a group of angiosperms characterized by an embryo with two cotyledons.

[0028] As used herein, the term "alkylating agent" refers to a compound in which a carbon-containing radical is bonded through a carbon atom to a leaving group (e.g., a halide or sulfonate) that is displaceable by attachment of a nucleophile to said carbon atom. Unless otherwise specified, the term "alkylating agent" does not limit the carbon-containing radical to alkyl; examples of carbon-containing radicals in alkylating agents include, for example, R 1 Illustrative examples include a variety of carbon-bonded substituent radicals defined in terms of:

[0029] As referred to in this disclosure, the terms "fungal pathogen" and "fungal plant pathogen" include pathogens of the phyla Ascomycota, Basidiomycota, and Zygomycota, as well as fungus-like Oomycota, which are causative agents of a wide range of economically important plant diseases affecting ornamental, turf, vegetable, field, grain, and fruit crops. In the context of this disclosure, "protecting plants from disease" or "controlling plant diseases" includes preventative effects (interruption of the fungal cycle of infection, colonization, symptom development, and spore production) and / or curative effects (inhibition of colonization of plant host tissue).

[0030] 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 FRAC include: (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell walls, (P) induction of host plant defenses, (U) unknown mode of action, (NC) not classified, (M) chemicals with multisite contact activity, and (BM) biological agents with multiple modes of action. Each mode of action (i.e., letters A-BM) contains one or more subgroups based on individual effective target sites of action or, if the exact target site is unknown, on cross-resistance profiles within the group or in relation to other groups (e.g., A contains subgroups A1, A2, A3, and A4). Each of these subgroups (e.g., A1, A2, A3, and A4) is assigned a FRAC code (numbers and / or letters). 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.

[0031] As used herein, the term "cross-resistance" refers to the phenomenon that occurs when a pathogen develops resistance to one fungicide and simultaneously becomes resistant to one or more other fungicides, which are typically, but not always, in the same chemical class, have the same target site of action, or can be detoxified by the same mechanism.

[0032] Generally, when a molecular fragment (i.e., radical) is represented by a series of atomic symbols (e.g., C, H, N, O, and S), the implicit point or points of attachment will be readily apparent to one of ordinary skill in the art. In some instances herein, the point or points of attachment may also be explicitly indicated by a hyphen ("-"), particularly when alternative points of attachment are possible. Dotted lines in rings depicted herein (e.g., the ring in Formula 1) indicate that the indicated bond may be a single or double bond.

[0033] In the above description, the term "alkyl," whether used alone or in compound words such as "haloalkyl," includes straight-chain and branched alkyls, such as methyl, ethyl, n-propyl, and i-propyl. "Alkenyl" includes straight-chain and branched alkenes, such as ethenyl, 1-propenyl, 2-propenyl, and the various butenyl and pentenyl isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-pentadienyl. "Alkynyl" includes straight-chain and branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and the various butynyl and pentynyl isomers. "Alkynyl" can also include moieties composed of multiple triple bonds (e.g., 2,5-pentadiynyl).

[0034] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, i-propyloxy, and the different butoxy isomers. "Alkenyloxy" includes straight-chain and branched alkenyls bonded to and linked through an oxygen atom. Examples of "alkenyloxy" include HC=CHCHO and CHCH=CHCHO. "Alkynyloxy" includes straight-chain and branched alkynyls bonded to and linked through an oxygen atom. Examples of "alkynyloxy" include HC≡CCHO and CHC≡CCHO.

[0035] "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CHOCH2, CH3CH2CH2OCH2, and CH3CH2CH2OCH2CH2. "Alkoxyalkoxy" denotes alkoxy substitution on another alkoxy moiety. Examples of "alkoxyalkoxy" include CH3OCHO, CH3OCH2CH2CH2O, and CH3CHOCH2OCH2O.

[0036] The term "cycloalkyl" refers to a saturated carbocyclic ring of 3 to 5 carbon atoms joined together by single bonds. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, and cyclopentyl.

[0037] The term "halogen," whether used alone or in compound words such as "haloalkyl," or in descriptions such as "alkyl substituted with halogen," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound words such as "haloalkyl" or in descriptions such as "alkyl substituted with halogen," the alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include CF, ClCH, CFCHCH, and CFCC1.

[0038] "Cyanoalkyl" refers to an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH, NCCHCH, and CHCH(CN)CH. The term "cyanoalkoxy" is defined analogously to the term "cyanoalkyl."

[0039] The total number of carbon atoms in the substituent is "C i ~C j" prefix notation, where i and j are numbers from 1 to 5. For example, C1-C3 alkyl refers to methyl through propyl; C2 alkoxyalkyl refers to CHOCH2; C3 alkoxyalkyl refers to, for example, CH3CH(OCH3), CHOCH2CH2, or CH3CHOCH2; and C4 alkoxyalkyl refers to the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms (including, for example, CH3CH2CH2OCH2 and CH3CHOCH2CH2).

[0040] The term "unsubstituted" in connection with a group such as a ring means that the group does not have any substituents at one or more bonds to the remainder of Formula 1. The term "optionally substituted" means that the number of substituents can be zero. Unless otherwise specified, an optionally substituted group may be substituted with as many optional substituents as possible, so long as the non-hydrogen substituents replace hydrogen atoms on various available carbon or nitrogen atoms. Generally, the number of optional substituents (if present) ranges from 1 to 3. As used herein, the term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or the term "(un)substituted."

[0041] The number of optional substituents may be limited by expressed limits. For example, the phrase "optionally substituted with up to three substituents independently selected from halogen" means that there can be 0, 1, 2, or 3 substituents (if the number of available points of attachment permits).

[0042] The compounds may have a variable number of substituents (e.g., (R 4 ) m When substituted with any of the above substituents having a subscript indicating m (where m is 0 to 5), unless otherwise specified, the substituents are independently selected from the defined group of substituents. Various groups may optionally be present at certain positions (e.g., (R 4 ) m(where m can be 0), a hydrogen may be present at this position even if not recited in the definition of the various groups.

[0043] The naming of substituents in this disclosure uses accepted terminology that provides simplicity in accurately conveying chemical structures to those of skill in the art. For the sake of simplicity, descriptors indicating positions within structural formulas may be omitted.

[0044] The term "carbocycle" refers to a ring in which the atoms forming the backbone of the ring are selected only from carbon. Unless otherwise specified, a carbocycle can be saturated, partially unsaturated, or fully unsaturated. If a fully unsaturated carbocycle satisfies Hückel's rule, the ring is also referred to as an "aromatic ring." A "saturated carbocycle" refers to a ring having a backbone made of carbon atoms connected to each other by single bonds, and unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.

[0045] As used herein, the term "partially unsaturated ring" or "partially unsaturated heterocycle" refers to a ring that contains unsaturated ring atoms and one or more double bonds, but is not aromatic.

[0046] The term "heterocyclic ring" or "heterocycle" refers to a ring in which at least one of the atoms forming the backbone of the ring is other than carbon. Unless otherwise specified, a heterocycle can be saturated, partially unsaturated, or fully unsaturated. If a fully unsaturated heterocycle satisfies Hückel's rule, the ring is also referred to as a "heteroaromatic ring" or "aromatic heterocyclic ring." A "saturated heterocycle" refers to a heterocycle containing only single bonds between ring members.

[0047] The compounds of the present invention can exist as one or more stereoisomers. Stereoisomers are isomers that have identical constitution but differ in the spatial arrangement of their atoms, and include enantiomers, diastereomers, cis- and trans-isomers (also called geometric isomers), and atropisomers. Atropisomers result from restricted rotation around a single bond, and the high barrier to rotation makes it possible to isolate these isomeric species. As will be appreciated by those skilled in the art, one stereoisomer may be more reactive and / or exhibit advantageous effects when enriched or separated from other stereoisomers. In addition, those skilled in the art 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 invention includes all stereoisomers, conformations 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 the oxide. Those nitrogen-containing heterocycles capable of forming N-oxides will be familiar to those skilled in the art. Those skilled in the art will also be familiar with the ability of tertiary amines to form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are very familiar to those skilled in the art, including the oxidation of heterocycles and tertiary amines using peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.These methods for preparing N-oxides have been widely described and reviewed in the literature, see, for example, T. L. Gilchrist, Comprehensive Organic Synthesis, vol. 7, pp. 748-750 (S.V. Ley, Ed., Pergamon Press); M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, vol. 3, pp. 18-20 (A.J. Boulton and A. McKillop, Eds., Pergamon Press); M.R. Grimmett and B.R.T. Keene, Advances in Hetrocyclic Chemistry, vol. 43, pp. 149-161 (A.R. Katrittzky, Ed., Academic Press); M. Tisler and B. Stanovnik, Advances in Hetrocyclic Chemistry, vol. 9, pp. 285-291 (A.R. Katrittzky and A.J. Boulton, 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] Those skilled in the art will recognize that salts of compounds share biological utility with their corresponding non-salt forms because, under environmental and physiological conditions, salts are in equilibrium with their corresponding non-salt forms. Therefore, a wide variety of salts of compounds of Formula 1 are useful (i.e., agronomically suitable) for controlling plant diseases caused by fungal plant pathogens. Salts of 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, propynoic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. When compounds of Formula 1 contain an acidic residue, such as a carboxylic acid, salts also include those formed with organic or inorganic bases, such as pyridine, triethylamine, or ammonia, or amides, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium, or barium. Thus, 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 more than one form; therefore, Formula 1 includes 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 exhibit a substantially single crystal type and embodiments that exhibit a mixture 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, which have different molecular arrangements and / or conformations within the crystal lattice. Polymorphs can have the same chemical composition, but they can also differ in composition due to the presence or absence of co-crystallized water or other molecules that can be weakly or strongly bound in the lattice. Polymorphs may differ in chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and biological availability. As will be appreciated by those skilled in the art, polymorphs of the compound of Formula 1 may exhibit advantageous effects (e.g., compatibility in preparing useful formulations, improved biological performance) compared to other polymorphs of the same compound of Formula 1 or mixtures of multiple polymorphs. Preparation and isolation of specific polymorphs of the compound of 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 invention as described in the Summary of the Invention include those described below. In the following embodiments, Formula 1 includes stereoisomers, N-oxides, and salts thereof, and references to "compounds of Formula 1" include the definitions of the substituents specified in the Summary of the Invention, unless further defined in the embodiments.

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

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

[0055] [Embodiment 3] R 1 The compound of Formula 1 or Embodiments 1-2, wherein is C1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C2-C4 cyanoalkyl, or C2-C5 alkoxyalkyl.

[0056] [Embodiment 4] R 1 is C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C4 cycloalkyl, C2-C3 cyanoalkyl, or C2-C3 alkoxyalkyl.

[0057] [Embodiment 5] R 1 is C1-C2 alkyl, C3-C4 cycloalkyl, or C2-C3 cyanoalkyl.

[0058] [Embodiment 6] R 1 The compound of embodiment 5, wherein is methyl, ethyl, cyclopropyl, or —CH 2 C≡N.

[0059] [Embodiment 7] R 1is methyl, ethyl, or cyclopropyl.

[0060] [Embodiment 8] R 1 is methyl or ethyl.

[0061] [Embodiment 9] R 1 is methyl.

[0062] [Embodiment 10] R 1 is ethyl.

[0063] [Embodiment 11] R 1 is methyl, ethyl, or cyclopropyl, each optionally substituted with up to three substituents independently selected from halogen.

[0064] [Embodiment 12] R 1 is methyl or halomethyl.

[0065] [Embodiment 13] R 2 H, halogen, cyano, C(=O)NR 7a R 7b , C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl, C2-C3 haloalkynyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, C2-C3 haloalkenyloxy, C2-C3 alkynyloxy, C2-C3 haloalkynyloxy, C3-C5 cycloalkoxy, C1-C3 alkylamino, or C2-C3 dialkylamino.

[0066] [Embodiment 14] R 2 is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, halocyclopropyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, or C2-C3 haloalkenyloxy.

[0067] [Embodiment 15] R 2 The compound of embodiment 14, wherein is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, C1-C3 alkoxy, or C1-C3 haloalkoxy.

[0068] [Embodiment 16] R 2 Compounds according to embodiment 15, wherein is H, halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy.

[0069] [Embodiment 17] R 2 The compound of embodiment 16, wherein is H, halogen, C1-C2 alkyl, haloalkyl, or methoxy.

[0070] [Embodiment 18] R 2 The compound of embodiment 17, wherein is H, halogen, C1-C2 alkyl, or methoxy.

[0071] [Embodiment 19] R 2 The compound of embodiment 18, wherein is Br, Cl, methyl, ethyl, or methoxy.

[0072] [Embodiment 19a] R 2 The compound of embodiment 19, wherein is Cl, methyl, ethyl, or methoxy.

[0073] [Embodiment 19b] R 2 Compounds according to embodiment 19a, wherein is Cl or methyl.

[0074] [Embodiment 20] R 2 is methyl.

[0075] [Embodiment 21] R 2 The compound of embodiment 13, wherein is H, halogen, cyano, methyl, ethyl, C1-C2 haloalkyl, or cyclopropyl.

[0076] [Embodiment 22] R 2 22. The compound of embodiment 21, wherein is H, halogen, cyano, methyl, ethyl, halomethyl, or cyclopropyl.

[0077] [Embodiment 23] R 2 23. The compound of embodiment 22, wherein is H, halogen, cyano, methyl, ethyl, or cyclopropyl.

[0078] [Embodiment 24] R 2 The compound of embodiment 23, wherein is H, Br, Cl, cyano, or methyl.

[0079] [Embodiment 25] R 2 The compound of embodiment 24, wherein is H, Br, Cl, methyl, or ethyl.

[0080] [Embodiment 26] R 2 The compound of embodiment 25, wherein is H, Br, Cl, or methyl.

[0081] [Embodiment 27] The compound of formula 1 or any one of embodiments 1-26, wherein p is 0 (ie, any bond in formula 1 is present).

[0082] [Embodiment 28] The compound of formula 1 or any one of embodiments 1-26, wherein p is 1 (ie, any bond in formula 1 is absent).

[0083] [Embodiment 29] R 3 The compound of Formula 1 or any one of Embodiments 1-28, wherein is H, methyl, or ethyl.

[0084] [Embodiment 30] R 3 is H or methyl.

[0085] [Embodiment 31] R 3 is H.

[0086] [Embodiment 32] R 3 is methyl.

[0087] [Embodiment 33] Each R 4 and R 5 are independently cyano, nitro, or halogen; or C1-C3 alkyl, C2-C3 alkenyl, C2-C4 cyanoalkyl, C1-C3 alkoxy, C2-C4 alkenyloxy, or C2-C4 cyanoalkoxy, each optionally substituted with up to three substituents independently selected from halogen; or -UVT.

[0088] [Embodiment 34] Each R 4 and R 5is independently cyano or halogen; or C1-C2 alkyl, C2-C3 cyanoalkyl, C1-C2 alkoxy, C2-C3 alkenyloxy, or C2-C3 cyanoalkoxy, each optionally substituted with up to 3 substituents independently selected from halogen; or -UVT.

[0089] [Embodiment 35] Each R 4 and R 5 is independently cyano or halogen; or C1-C2 alkyl or C1-C2 alkoxy, each optionally substituted with up to 3 substituents independently selected from halogen; or -UVT.

[0090] [Embodiment 36] Each R 4 and R 5 is independently halogen or methoxy.

[0091] [Embodiment 36a] Each R 4 and R 5 is independently Br, Cl, F, or methoxy.

[0092] [Embodiment 37] Each R 4 and R 5 are independently cyano, nitro, or halogen; or are C1-C2 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C3 alkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, or C2-C4 cyanoalkoxy, each optionally substituted with up to three substituents independently selected from halogen.

[0093] [Embodiment 38] Each R 4 and R 5 is independently cyano, nitro, halogen, C1-C2 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 alkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, or C2-C3 cyanoalkoxy.

[0094] [Embodiment 39] Each R 4 and R 5 is independently cyano, nitro, halogen, C1-C2 alkyl, C2-C3 alkenyl, C1-C2 alkoxy, C2-C3 alkenyloxy, or C2-C3 cyanoalkoxy.

[0095] [Embodiment 40] Each R 4 and R 5 is independently cyano, nitro, halogen, C1-C2 alkyl, C1-C2 alkoxy, C2-C3 alkenyloxy, or C2-C3 cyanoalkoxy.

[0096] [Embodiment 41] Each R 4 and R 5 is independently cyano, nitro, halogen, C1-C2 alkyl, C1-C2 alkoxy, or C2-C3 cyanoalkoxy.

[0097] [Embodiment 42] Each R 4 and R 5 is independently cyano, nitro, Br, Cl, F, C1-C2 alkyl, C1-C2 alkoxy, or C2-C3 cyanoalkoxy.

[0098] [Embodiment 43] Each R 4 and R 5is independently cyano, nitro, Br, Cl, F, methyl, or methoxy.

[0099] [Embodiment 44] Each R 4 and R 5 is independently nitro, Br, Cl, F, or methoxy.

[0100] [Embodiment 45] Each R 4 is independently Cl, F, or methoxy.

[0101] [Example 46] Each R 4 is independently Cl or F.

[0102] [Embodiment 47] Each R 4 is F.

[0103] [Embodiment 48] Each R 5 is independently Br, Cl, F, or methoxy.

[0104] [Embodiment 49] Each R 5 is independently Cl, F, or methoxy.

[0105] [Embodiment 50] Each R 5 The compound of embodiment 49, wherein is Cl or methoxy.

[0106] [Embodiment 51] A compound of Formula 1 or any one of Embodiments 1-50, wherein each U is independently a direct bond, O, C(=O), or NH.

[0107] [Embodiment 52] Compounds according to embodiment 51, wherein each U is independently a direct bond, O, or NH.

[0108] [Embodiment 53] Compounds according to embodiment 52, wherein each U is independently a direct bond or O.

[0109] [Embodiment 54] The compound of embodiment 53, wherein each U is independently a direct bond.

[0110] [Embodiment 55] The compound of embodiment 53, wherein each U is independently O.

[0111] [Embodiment 56] The compound of Formula 1 or any one of Embodiments 1-55, wherein each V is independently C1-C3 alkylene, where up to two carbon atoms are C(=O), each optionally substituted with up to three substituents independently selected from halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0112] [Embodiment 57] Compounds according to embodiment 56, wherein each V is independently C1-C3 alkylene, where up to one carbon atom is C(=O), each optionally substituted with up to two substituents independently selected from halogen, methyl, halomethyl, and methoxy.

[0113] [Embodiment 58] Compounds according to embodiment 57, wherein each V is independently CH2, CH2CH2, or C(=O).

[0114] [Embodiment 59] The compound of embodiment 58, wherein each V is CH2.

[0115] [Embodiment 60] Each T is independently NR 7a R 7b OR 8 The compound of Formula 1 or any one of Embodiments 1-59, wherein:

[0116] [Embodiment 61] R 7a and R 7b are separate (i.e., do not form a ring together), each R 7a and R 7b is independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, C2-C3 alkylcarbonyl, or C2-C3 alkoxycarbonyl.

[0117] [Embodiment 62] Each R 7a and R 7b is independently H, C1-C2 alkyl, C1-C2 haloalkyl, or cyclopropyl.

[0118] [Embodiment 63] Each R 7a and R 7b is independently H, methyl, or halomethyl.

[0119] [Embodiment 64] Each R 8 and R 9 is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, or cyclopropyl.

[0120] [Embodiment 65] Each R 8 and R 9 is independently H, C1-C2 alkyl, or C1-C2 haloalkyl.

[0121] [Embodiment 66] Each R 8 and R 9 is independently methyl or ethyl.

[0122] [Embodiment 67] Each R 10 A compound of Formula 1 or any one of Embodiments 1-66, wherein is independently halogen, methyl, halomethyl, or methoxy.

[0123] [Embodiment 68] The compound of formula 1 or any one of embodiments 1-67, wherein each q is 0 or 2.

[0124] [Embodiment 69] The compound of Formula 1 or any one of Embodiments 1-68, wherein m and n are each independently 1-5.

[0125] [Embodiment 70] The compound of embodiment 69, wherein m and n are each independently 1 to 4.

[0126] [Embodiment 71] The compound of embodiment 70, wherein m and n are each independently 1 to 3.

[0127] [Embodiment 72] The compound of embodiment 71, wherein m is 2 or 3.

[0128] [Embodiment 73] The compound of embodiment 72, wherein m is 2.

[0129] [Embodiment 74] The compound of embodiment 72, wherein m is 3.

[0130] [Embodiment 75] The compound of formula 1 or any one of embodiments 1-76, wherein n is 1-4.

[0131] [Embodiment 76] The compound of embodiment 70, wherein n is 2-4.

[0132] [Embodiment 77] The compound of embodiment 76, wherein n is 2 or 3.

[0133] [Embodiment 78] The compound of embodiment 77, wherein n is 2.

[0134] [Embodiment 79] The compound of embodiment 77, wherein n is 3.

[0135] [Embodiment 80] The compound of formula 1 or any one of embodiments 1-79, wherein m is 2 and n is 2 or 3.

[0136] [Embodiment 81] m is 2 and R 4 is attached at the 2- and 6-positions (i.e., ortho positions); or m is 2 and R 4 is attached at the 2- and 4-positions (i.e., the ortho and para positions); or m is 2 and R 4 are attached at the 3- and 5-positions (i.e., meta positions), all relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0137] [Embodiment 82] m is 2 and R 4 is attached at the 2- and 6-positions (i.e., ortho positions); or m is 2 and R 4 is attached at the 2- and 4-positions (i.e., ortho and para positions).

[0138] [Embodiment 83] m is 2 and R 4is attached at the 2- and 6-positions (i.e., ortho positions).

[0139] [Embodiment 83a] m is 2 and R 4 is attached at the 2- and 4-positions (i.e., ortho positions).

[0140] [Embodiment 84] n is 2 and R 5 is attached at the 3- and 5-positions (i.e., meta positions); or n is 2 and R 5 is attached at the 2- and 4-positions (i.e., the ortho and para positions); or n is 2 and R 5 is attached at the 2- and 6-positions (i.e., ortho positions); or n is 3 and R 5 is attached at the 2-, 3-, and 5-positions (ie, ortho and meta positions).

[0141] [Embodiment 85] n is 2 and R 5 is attached at the 3- and 5-positions (i.e., meta positions); or n is 3 and R 5 is attached at the 2-, 3-, and 5-positions (i.e., ortho and meta positions).

[0142] [Embodiment 86] n is 2 and R 5 is attached at the 3- and 5-positions (i.e., meta positions).

[0143] [Embodiment 87] n is 3 and R 5 is attached at the 2-, 3-, and 5-positions (i.e., ortho and meta positions).

[0144] [Embodiment 88] The compound of formula 1 or any one of embodiments 1-87, wherein at least one of m or n is other than 0.

[0145] [Embodiment 89] A compound of formula 1 or any one of embodiments 1-88, wherein when p is 0, then at least one of m or n is other than 0.

[0146] [Embodiment 90] At least one of m or n is other than 0, and R 4 or R 5 The compound of Formula 1 or any one of Embodiments 1-89, wherein at least one of is in the ortho position.

[0147] [Embodiment 91] When p is 0, at least one of m or n is other than 0, and R 4 or R 5 The compound of Formula 1 or any one of Embodiments 1-90, wherein at least one of is in the ortho position.

[0148] The embodiments of the present invention, including the above-described embodiments 1-91, as well as various other embodiments described herein, may be combined in any combination, and the various statements within those embodiments relate not only to compounds of Formula 1, but also to starting compounds and intermediate compounds useful for preparing compounds of Formula 1. In addition, the embodiments of the present invention, including the above-described embodiments 1-91, as well as various other embodiments described herein, and various combinations thereof, also relate to the compositions and methods of the present invention.

[0149] Combinations of embodiments 1 to 91 are described below.

[0150] [Embodiment A] W is O; R 1 is C1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C2-C4 cyanoalkyl, or C2-C5 alkoxyalkyl; R 2is H, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, halocyclopropyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkenyloxy, or C2-C3 haloalkenyloxy; R 3 is H, methyl, or ethyl; Each R 4 and R 5 are independently cyano, nitro, or halogen; or are C1-C3 alkyl, C2-C3 alkenyl, C2-C4 cyanoalkyl, C1-C3 alkoxy, C2-C4 alkenyloxy, or C2-C4 cyanoalkoxy, each optionally substituted with up to 3 substituents independently selected from halogen; or -UVT; each U is independently a direct bond, O, C(=O), or NH; each V is independently a C1-C3 alkylene, where up to one carbon atom is C(=O), each optionally substituted with up to two substituents independently selected from halogen, methyl, halomethyl, and methoxy; Each T is independently NR 7a R 7b OR 8 and; Each R 7a and R 7b are independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, C2-C3 alkylcarbonyl, or C2-C3 alkoxycarbonyl; m and n are each independently 1 to 4; A compound of formula 1.

[0151] [Embodiment B] R 1 is C1-C2 alkyl, C3-C4 cycloalkyl, or C2-C3 cyanoalkyl; R 2is H, halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy; R 3 is H or methyl; Each R 4 and R 5 is independently cyano or halogen; or is C1-C2 alkyl or C1-C2 alkoxy, each optionally substituted with up to 3 substituents independently selected from halogen; or is -UVT; each U is independently a direct bond, O, or NH; each V is independently CH2, CH2CH2, or C(=O); Each R 7a and R 7b is independently H, C1-C2 alkyl, C1-C2 haloalkyl, or cyclopropyl; m and n are each independently 1 to 3; A compound according to embodiment A.

[0152] [Embodiment C] R 1 is methyl, ethyl, cyclopropyl, or —CHC≡N; R 2 is H, halogen, C1-C2 alkyl, or methoxy; p is 0; Each R 4 and R 5 is independently halogen or methoxy; A compound according to embodiment B.

[0153] [Embodiment D] R 1 is methyl; R 2 is Br, Cl, methyl, ethyl, or methoxy; Each R 4 and R 5 is independently Br, Cl, F, or methoxy; m is 2 and R 4 the substituents are attached at the 2- and 6-positions; or m is 2 and R 4 the substituents are attached at the 2- and 4-positions; or m is 2 and R 4 the substituents are attached at the 3- and 5-positions; n is 2 and R 5 the substituents are attached at the 3- and 5-positions; or n is 2 and R 5 the substituents are attached at the 2- and 4-positions; or n is 2 and R 5 the substituents are attached at the 2- and 5-positions; or n is 2 and R 5 the substituents are attached at the 2- and 6-positions; or n is 3 and R 5 The substituents are attached at the 2-, 3-, and 5-positions; A compound according to embodiment C.

[0154] [Embodiment E] R 2 is Cl, methyl, ethyl, or methoxy; Each R 4 is independently Cl or F; Each R 5 is independently Br, Cl, F, or methoxy; A compound according to embodiment D.

[0155] [Embodiment F] R 2 is Cl or methyl; Each R 5 is independently Cl, F, or methoxy; A compound according to embodiment E.

[0156] [Embodiment G] m is 2, n is 2 or 3; A compound according to any one of embodiments AF.

[0157] Specific embodiments include compounds of Formula 1 selected from the group consisting of: 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 25); 4-chloro-6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 35); 5,6-bis(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 44); 4-chloro-6-(2-chloro-5-methoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 57); 4-chloro-6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 58); 6-(2-bromo-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 64); 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 66); 6-(2-chloro-5-methoxyphenyl)-5-(2,6-difluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 68); 6-(2-bromo-3,5-dimethoxyphenyl)-4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 77); 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-4-methoxy-2-methyl-3(2H)-pyridazinone (compound 80); 4-chloro-5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methoxyphenyl)-2-methyl-3(2H)-pyridazinone (compound 83); 5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methoxyphenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 102); 5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methoxyphenyl)-4-ethyl-2-methyl-3(2H)-pyridazinone (compound 134); 6-(2-chloro-5-methoxyphenyl)-5-(2,6-difluorophenyl)-4-ethyl-2-methyl-3(2H)-pyridazinone (compound 179); and 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 194).

[0158] The embodiments of the present invention also include the following embodiments AA to FF.

[0159] [Embodiment AA] W is O or S; R 1 is C1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C2-C4 cyanoalkyl, or C2-C5 alkoxyalkyl, each of which is optionally substituted with up to three substituents independently selected from halogen; R 2 is H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, or C3-C5 cycloalkyl; The dotted lines in Formula 1 represent optional bonds; p is 0 or 1, provided that if any bond is present then p is 0, and if any bond is not present then p is 1; R 3 is H or C1-C3 alkyl; Each R 4 and R 5are independently cyano, nitro, or halogen; or are C1-C3 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 alkoxyalkoxy, C2-C4 alkoxyalkyl, or C2-C4 cyanoalkoxy, each optionally substituted with up to three substituents independently selected from halogen and C1-C3 alkyl; m and n are each independently 0 to 5; A compound of formula 1.

[0160] [Embodiment BB] W is O; R 1 is C1-C3 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C2-C4 cyanoalkyl, or C2-C5 alkoxyalkyl; R 2 is H, cyano, halogen, methyl, ethyl, halomethyl, or cyclopropyl; R 3 is H, methyl, or ethyl; Each R 4 and R 5 are independently cyano, nitro, halogen, C1-C2 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 alkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, C2-C3 alkoxyalkoxy, C2-C3 alkoxyalkyl, or C2-C3 cyanoalkoxy; m and n are each independently 1 to 4; A compound according to embodiment AA.

[0161] [Embodiment CC] R 1 is C1-C2 alkyl, C3-C4 cycloalkyl, or C2-C3 cyanoalkyl; R 2 is H, cyano, halogen, methyl, ethyl, or cyclopropyl; R3 is H or methyl; Each R 4 and R 5 are independently cyano, nitro, halogen, C1-C2 alkyl, C1-C2 alkoxy, or C2-C3 cyanoalkoxy; m and n are each independently 1 to 3; The compound of embodiment BB.

[0162] [Embodiment DD] R 1 is methyl, ethyl, cyclopropyl, or —CHC≡N; R 2 is H, cyano, Br, Cl, methyl, or ethyl; p is 0; Each R 4 and R 5 are independently cyano, nitro, Br, Cl, F, C1-C2 alkyl, C1-C2 alkoxy, or C2-C3 cyanoalkoxy; The compound described in embodiment CC.

[0163] [Embodiment EE] R 1 is methyl, ethyl, or cyclopropyl; R 2 is H, cyano, Br, Cl, or methyl; Each R 4 and R 5 is independently cyano, nitro, Br, Cl, F, methyl, or methoxy; m is 2; n is 2 or 3; The compound of embodiment DD.

[0164] [Embodiment FF] R 1 is methyl or ethyl; R 2 is H, Br, Cl, or methyl; Each R 4 is independently Cl or F; Each R 5 is independently nitro, Br, Cl, F, or methoxy; The compound of embodiment EE.

[0165] 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. Notable embodiments of such compositions are those comprising a compound corresponding to any of the compound embodiments described above.

[0166] 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 a compound of Formula 1) and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents. Notable embodiments of such compositions are those comprising a compound corresponding to any of the compound embodiments described above.

[0167] The present invention provides a method for controlling plant diseases caused by fungal plant pathogens, comprising applying to a plant or part thereof, or to plant seeds, a fungicidally effective amount of a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof). Of note are embodiments of such methods that comprise applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments described above. Of particular note are embodiments in which the compound is applied as a composition of the invention.

[0168] Compounds of Formula 1 may be prepared using one or more of the following methods and variations illustrated in Schemes 1-10. 1 , R 2 , R 3 , R 4 , R 5The definitions of m, n, and p are as defined above in the Summary of the Invention unless otherwise specified. The compounds of Formulas 1a, 1b, 1c, 1d, and 1e are various subsets of the compounds of Formula 1, and all substituents of Formulas 1a, 1b, 1c, 1d, and 1e are as defined above for Formula 1 unless otherwise specified.

[0169] As shown in Scheme 1, a compound of formula 1 can be reacted with a compound of formula R 1 The compound of formula 2 can be prepared by alkylation of a compound of formula 2 with a compound of formula -Lg, where Lg is a leaving group such as a halogen (e.g., Cl, Br) or a sulfonate (e.g., methanesulfonate). Particularly useful alkylating agents include, but are not limited to, alkyl halides and the like (e.g., iodoethane, allyl bromide, propargyl chloride), and alkyl sulfates (e.g., dimethyl sulfate). Typically, this reaction is 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 a temperature ranging from about 0 to 100°C. For reaction conditions, see Journal of Medicinal Chemistry 1980, 23(12), 1398-1405. Similarly, this Example 14, Step E, illustrates the method of Scheme 1. [ka]

[0170] As shown in Scheme 2, a compound of Formula 1a (i.e., Formula 1 in which the dotted line represents a bond and p is 0) can be prepared by oxidative dehydrogenation of the corresponding compound of Formula 1b (i.e., Formula 1 in which the dotted line is absent and p is 1). A wide range of oxidizing agents and reaction conditions are suitable for the method of Scheme 2. For example, oxygen can be used as an oxidizing agent in the presence of a copper(II) salt such as copper(II) chloride and a solvent such as acetonitrile (see, e.g., Synthetic Communications 2000, 30(1), 1-7). Copper(II) acetate can also be used in the presence of a base such as sodium carbonate and a solvent such as toluene at temperatures from about ambient temperature to the boiling point of the solvent (see, e.g., European Journal of Organic Chemistry 2013, 2013(27), 6130-6136). Compounds of Formula 1b can also be treated with elemental halogens (e.g., Cl, Br, I) in a solvent such as acetic acid or dimethyl sulfoxide to give compounds of Formula 1a. For relevant references using dihalides, see, for example, Arzneimittel Forschung 2005, 55(6), 318-325 and Chinese Chemical Letters 2011, 22(12), 1435-1438. Alternatively, activated manganese dioxide can be used as an oxidizing agent in a solvent (e.g., dichloromethane, dichloroethane, toluene, or chlorobenzene) at temperatures from about ambient temperature to the boiling point of the solvent. This reaction can also be carried out at temperatures above the boiling point of the solvent using a pressurized vessel (optionally in conjunction with a microwave reactor). The method of Scheme 2 using manganese dioxide is described in this Example 2. [ka]

[0171] One skilled in the art can prepare intermediate compounds of formula 2 where the dotted line represents a bond and p is 0 by analogy with the oxidation method described in Scheme 2 above (where R 1 will recognize that the 'H' has been replaced by 'H'.

[0172] As shown in Scheme 3, compounds of Formula 1b, where W is O, can be prepared by cyclization of an α-keto acid or ester of Formula 3 with an appropriately substituted hydrazine of Formula 4. This reaction can be carried out in a variety of solvents, such as ethanol, 1-butanol, tetrahydrofuran, 1,4-dioxane, heptane, or toluene. Optionally, an acid or base catalyst can be added to the reaction mixture to facilitate the removal of water. Particularly useful catalysts include bases such as pyridine, sodium acetate, or triethylamine; or acids such as acetic acid, oxalic acid, or hydrochloric acid. Alternatively, an acid salt of the hydrazine of Formula 4 can be used in combination with a base such as an alkali metal hydroxide or carbonate (preferably sodium acetate). In some cases, it may be advantageous to carry out the initial condensation of Formulas 3 and 4 in an alcoholic solvent (e.g., ethanol), concentrate the reaction mixture, and then add a solvent such as toluene or chlorobenzene, followed by heating under azeotropic conditions, optionally in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. This type of cyclization reaction is well described in the chemical literature; see, for example, Archives of Pharmaceutical Research 2010, 33(1), 25-46; Journal of Medicinal Chemistry 2001, 44(16), 2511-2522; Monatshefte für Chemie 2004, 135(12), 1519-1527; and Indo Global Journal of Pharmaceutical Sciences 2016, 6(2), 65-71. This Example 1, Step D, involves the reaction of R 1 Scheme 3 illustrates a method for preparing compounds of formula 1b where is methyl, using methylhydrazine. [ka]

[0173] Intermediate compounds of formula 2 where the dotted line is absent and p is 1 can be prepared similarly to the method described in Scheme 3, using hydrazine or hydrazine hydrate in place of compounds of formula 4.

[0174] As shown in Scheme 4, R a α-Ketoesters of formula 3, where Lg is alkyl, can be prepared by alkylation of diaryl ketones of formula 5 with compounds of formula 6, where Lg is a leaving group such as a halogen (e.g., Cl, Br) or a sulfonate (e.g., methanesulfonate) in the presence of a base (e.g., sodium hydride, sodium acetate, potassium tert-butoxide, lithium diisopropylamide, or lithium bis(trimethylsilyl)amide). This reaction is typically carried out in a suitable solvent (e.g., dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 2-methyl-2-propanol, or toluene) selected for its compatibility with the base. The use and selection of an appropriate solvent will be apparent to those skilled in the art of chemical synthesis. For a representative procedure for the alkylation method of Scheme 4 using lithium diisopropylamide in tetrahydrofuran, see Journal of Medicinal Chemistry 2006, 49(2), 456-458. Similarly, the method of Scheme 4 using sodium hydride in a mixture of dimethylsulfoxide and tetrahydrofuran is described in Example 1, Step B. [ka]

[0175] R a is hydrogen, by means known to those skilled in the art, to form a carboxylic acid of formula 3, a This Example 1, Step C illustrates the hydrolysis of the ethyl ester of formula 3 to the corresponding carboxylic acid.

[0176] Alternatively, as shown in Scheme 5, R 3Compounds of formula 3, wherein is H, can be prepared by reacting compounds of formula 7 with benzaldehydes of formula 8 in the presence of a cyanide salt such as sodium cyanide. For reaction conditions, see, for example, Chemische Berichte 1976, 109(2), 541-545.

[0177] Compounds of formula 7 and 8 are commercially available and can be prepared by methods described in the chemical literature. [ka]

[0178] General methods useful for preparing diaryl ketones of Formula 5 are known in the art; see, for example, Chemical Research in Toxicology 2011, 24(11), 1853-1861; and Royal Society of Chemistry 2017, 7, 11367-11372; and references therein. Of particular note is the method illustrated in Scheme 6 below, which involves the reaction of a phenylacetic acid of Formula 9 with a benzoic acid ester of Formula 10. Typically, this reaction is carried out with the aid of a base and in the presence of an inert organic solvent, such as sodium hydride, lithium diisopropylamide, or lithium bis(trimethylsilyl)amide (LiHMDS) in a solvent such as benzene, toluene, N,N-dimethylformamide, or tetrahydrofuran. The product can be isolated by adjusting the pH to about 1-7, followed by filtration or extraction, optionally after removal of the organic solvent. This Example 1, Step A, illustrates the method of Scheme 6. [ka]

[0179] Formula 1c (i.e., the dotted line represents a bond, p is 0, and R 2Compounds of formula 1 (wherein R is cyano and W is O) can be synthesized as outlined in Scheme 7. In a first step, compounds of formula 12 are prepared by the reaction of compounds of formula 11 with hydrazine or hydrazine hydrate. This reaction is typically carried out in a solvent such as ethanol or methanol, following general procedures known in the art. Reaction of compounds of formula 12 with cyanoacetate salts of formula 13 in the presence of a base (e.g., sodium hydride or potassium tert-butoxide) and a solvent (e.g., ethanol) gives compounds of formula 2a (i.e., where the dotted line represents a bond, p is 0, and R is O). 2 Compounds of formula 2) where OH is cyano and W is O are obtained. The intermediate of formula 2a can be alkylated to give compounds of formula 1c, similar to the method of Scheme 1. For references, see, for example, Journal of Medicinal Chemistry 1980, 23(12), 1398-1405. Similarly, the method of Scheme 7 is illustrated in this Example 14, Steps C, D, and E. [ka]

[0180] Compounds of formula 11 are commercially available and can be prepared according to common methods known to those skilled in the art. For example, as shown in Scheme 8, catalytic oxidation of compounds of formula 14 can be achieved with oxygen as an oxidant in the presence of a catalyst such as copper(II) oxide and iodine, or 1,4-diazabicyclo[2.2.2]octane (DABCO). This reaction is typically carried out in a solvent such as dimethyl sulfoxide. For reaction conditions, see, for example, Synthesis 2011, 3, 387-396; Synthesis 2013, 45(12), 1701-1707; and Journal of the American Chemical Society 2016, 138(3), 810-813. Similarly, this Example 14, Step B, illustrates the method of Scheme 8. [ka]

[0181] Those skilled in the art will recognize that for some compounds of formula 1, the substituent R attached to the phenyl ring 4 and / or R 5 It will be appreciated that R may be more conveniently incorporated after formation of the central pyridazinone ring to which it is attached. For example, as shown in Scheme 9, compounds of Formula 1 may be aromatically nitrated to form R 4 or R 5 is nitro. Nitration can be accomplished according to known methods, for example, by treating a compound of Formula 1 with nitric acid (or a derivative thereof) or a mixture of nitric acid and an acid catalyst (e.g., sulfuric acid or acetic anhydride). Those skilled in the art will recognize certain functional groups (i.e., other R attached to the phenyl ring) that may be present in a compound of Formula 1. 4 and / or R 5 It will be recognized that the substituents (such as methyl, ... 5 The method of Scheme 9 for adding a nitro group is illustrated. [ka]

[0182] Similar to the method of Scheme 9, compounds of formula 1 can be treated with a halogenating agent to afford R 4 and / or R 5Compounds of Formula 1 can be obtained in which at least one of the groups is a halogen. Various halogenating agents known in the art can be used, such as N-halosuccinimides (e.g., NBS, NCS, NIS), elemental halogens (e.g., Cl, Br, I), and sulfuryl chloride. Typically, this reaction is carried out in a suitable solvent, such as N,N-dimethylformamide, acetonitrile, dichloromethane, benzene, chlorobenzene, or tetrahydrofuran. Optionally, an organic base, such as triethylamine, pyridine, or N,N-dimethylaniline, can be added. Typical reaction temperatures range from about room temperature to 150°C. See Examples 6 and 7 for specific reaction conditions.

[0183] R 2 Compounds of formula 1, etc., where R is halogen or alkyl can be prepared by converting R 2 For example, as shown in Scheme 10, first prepare a compound of formula 1d (i.e., where the dotted line represents a bond, p is 0, and R 2 Compounds of formula 1) where R is H can be treated with an organometallic agent, such as an alkyllithium base (e.g., n-butyllithium, s-butyllithium, lithium diisopropylamide, or lithium tetramethylpiperidide), or a Grignard reagent (e.g., tetramethylpiperidinyl magnesium chloride), in a solvent such as toluene, ethyl ether, tetrahydrofuran, or dimethoxymethane at a temperature ranging from about −78° C. to ambient temperature. Subsequent treatment with a halogenating or alkylating agent affords the formation of R 2 is halogen or alkyl to obtain a compound of formula 1e. For alkylation reaction conditions, see, for example, Journal of Medicinal Chemistry 1980, 23(12), 1398-1405. For halogenation reaction conditions, see Examples 4, 8, and 11. [ka]

[0184] The methods of Schemes 9 and 10 are just two examples of techniques for adding or modifying existing substituents in compounds of Formula 1. Those skilled in the art will recognize that compounds of Formula 1 can also be subjected to numerous other electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to provide other functionalized compounds of Formula 1. For example, as illustrated in this Example 12, R 2 Using a compound of formula 1 where R is a halogen, 2 Compounds of Formula 1 in which is alkyl can be prepared. 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). Similar known reactions allow aromatic halides, such as bromides or iodides, prepared by the Sandmeyer reaction to be reacted with alcohols under copper-catalyzed conditions, such as the Ullmann reaction or known modifications thereof, to give compounds of Formula 1 containing alkoxy substituents. Furthermore, some halogen groups, such as fluorine or chlorine, can be displaced with alcohols under basic conditions to give compounds of Formula 1 containing the corresponding alkoxy substituents. Compounds of Formula 1, or their precursors containing halides, preferably bromides or iodides, are particularly useful as intermediates for transition-metal-catalyzed cross-coupling reactions to prepare compounds of Formula 1. These types of reactions are well described in the literature, see, for example, 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 references cited therein.

[0185] Compounds of Formula 1 where W is O and the intermediates described in the methods above can be converted to the corresponding thiolates where W is S using a variety of standard thiating reagents, such as phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawson's reagent). Reactions of this type are 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. See also, for example, for pyridazinones, Journal of Heterocyclic Chemistry 1988, 25(6), 1719-23; and Phosphorus, Sulfur and Silicon and the Related Elements 2000, 156, 213-223.

[0186] It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may be incompatible with certain functional groups present in the intermediates. In these cases, the incorporation of protection / deprotection sequences or functional group interconversions into the synthesis may be helpful to obtain the desired products. The use and selection of protecting groups will be apparent to those skilled in chemical synthesis (see, for example, Greene, TW; Wuts, PGM Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). Those skilled in the art will recognize that, in some cases, after the introduction of the reagents depicted in the individual schemes, additional routine synthetic steps not described in detail may be required to complete the synthesis of compounds of Formula 1. Those skilled in the art will also recognize that, to prepare 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.

[0187] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following examples are therefore merely illustrative and should not be construed as limiting the present disclosure in any way. The steps in the following examples illustrate the procedure for each step in a total synthetic transformation, and the starting materials for each step may not necessarily have been prepared by the specific preparative experiment whose procedure is described in another example or step. Ambient or room temperature is defined as approximately 20-25°C. Percentages are by weight unless otherwise specified. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise specified. MPLC refers to medium pressure liquid chromatography on silica gel. 1 H NMR spectra are reported in ppm downfield from tetramethylsilane; "s" means singlet, "t" means triplet, "m" means multiplet, "t" means triplet, and "br s" means broad singlet. 19F NMR spectra are reported in ppm using trichlorofluoromethane as the reference. Mass spectra were analyzed by atmospheric pressure chemical ionization (APCI). + ) or electrospray ionization (ESI + ) or ) using liquid chromatography coupled with a mass spectrometer (LCMS), + The parent ion (M+1) of highest isotopically abundant formed by addition of (Molecular Weight 1) or H from the molecule + It is reported as the molecular weight of (M-1) formed by the loss of (molecular weight 1). [Example]

[0188] Example 1 Preparation of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-4,5-dihydro-2-methyl-3(2H)-pyridazinone (compound 39) Step A: Preparation of 2-(2,6-difluorophenyl)-1-(3,5-dimethoxyphenyl)ethanone To a solution of 2,6-difluorophenylacetic acid (12 g, 69.8 mmol) in tetrahydrofuran (200 mL) was added lithium bis(trimethylsilyl)amide (1.0 M in tetrahydrofuran, 209.3 mL, 209.3 mmol) dropwise at −78° C. The reaction mixture was stirred for 1 hour at −78° C., and then methyl 3,5-dimethoxybenzoate (13.7 g, 69.8 mmol) in tetrahydrofuran (100 mL) was added dropwise. The reaction mixture was stirred for 16 hours at ambient temperature and then acidified with hydrochloric acid (1 N aqueous solution) to a pH of approximately 6. The resulting mixture was extracted with ethyl acetate (2×200 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride solution (2×150 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (elution with 5% ethyl acetate in petroleum ether) to give the title compound as an off-white solid (13 g) melting at 88-92°C. 1H NMR(DMSO-d6)δ 7.40(m,1H),7.20(m,2H),7.12(m,2H),6.80(m,1H),4.50(s,2H),3.80(s,6H). LCMS: m / z: 293 [M+H] +

[0189] Step B: Preparation of ethyl β-(2,6-difluorophenyl)-3,5-dimethoxy-γ-oxobenzene-butanoate To a mixture of sodium hydride (60% in mineral oil, 1.36 g, 34.25 mmol) in dimethyl sulfoxide (76 mL) was added dropwise a solution of 2-(2,6-difluorophenyl)-1-(3,5-dimethoxyphenyl)ethanone (i.e., the product of Step A) (10 g, 34.25 mmol) in tetrahydrofuran (66 mL) at 5° C. After 1 hour, ethyl bromide (5.71 g, 34.25 mmol) was added dropwise to the reaction mixture. The reaction mixture was allowed to warm to room temperature, stirred for 16 hours, and then poured into ice-water (200 mL). The resulting mixture was extracted with ethyl acetate (2×200 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride (2×150 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (elution with 10% ethyl acetate in petroleum ether) to give the title compound as an off-white solid (8.0 g) melting at 100-104°C. 1 H NMR(DMSO-d6)δ 7.36(m,1H),7.10(m,2H),6.90(m,2H),6.70(m,1H),5.20(m,1H),4.07(q,2H),3.70(s,6H),3.15(m,1H),2.75(m,1H),1.13(t,3H). LCMS m / z: 379 [M+H] +

[0190] Step C: Preparation of β-(2,6-difluorophenyl)-3,5-dimethoxy-γ-oxobenzenebutanoic acid To a mixture of ethyl β-(2,6-difluorophenyl)-3,5-dimethoxy-γ-oxobenzenebutanoate (i.e., the product of Step B) (8.0 g, 21.2 mmol) in tetrahydrofuran / ethanol (200 mL, 1:1) was added a solution of sodium hydroxide (1.69 g, 42.3 mmol) in water (53 mL). The reaction mixture was stirred for 16 hours and then extracted with petroleum ether (2×150 mL). The combined organic extracts were further extracted with water (100 mL). The combined aqueous extracts were acidified with hydrochloric acid (1 N aqueous solution) to a pH of approximately 4-5. The resulting solid precipitate was collected by filtration, washed with water (2×100 mL), and dried under reduced pressure to give the title compound as a white solid (5.5 g). 1 H NMR(DMSO-d6)δ 12.4(br s,1H),7.36(m,1H),7.10(m,2H),6.90(m,2H),6.70(m,1H),5.15(m,1H),3.73(s,6H),3.15(m,1H),2.64(m,1H). LCMS m / z: 351 [M+H] +

[0191] Step D: Preparation of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-4,5-dihydro-2-methyl-3(2H)-pyridazinone To a mixture of β-(2,6-difluorophenyl)-3,5-dimethoxy-γ-oxobenzenebutanoic acid (i.e., the product of Step C) (2.0 g, 5.7 mmol) in ethanol (20 mL) was added methylhydrazine (85% aqueous solution, 0.611 g, 11.4 mmol). The reaction mixture was heated in a sealed tube at 100°C in a microwave reactor for 3 hours and then poured into ice water (150 mL). The resulting solid precipitate was collected by filtration, washed with water (2 x 20 mL), and dried under reduced pressure. The solid was then triturated with diethyl ether (2 x 10 mL), filtered, and dried to give the title compound, a compound of the present invention, as an off-white solid (1.5 g) melting at 139-142°C. 1H NMR(DMSO-d6)δ 7.35(m,1H),7.10(m,2H),6.73(m,2H),6.48(m,1H),5.03(m,1H),3.70(s,6H),3.40(s,3H),3.15(m,1H),2.54(m,1H). LCMS m / z: 361 [M+H] +

[0192] Example 2 Preparation of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (compound 38) To a mixture of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-4,5-dihydro-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 1) (500 mg, 1.39 mmol) in chlorobenzene (15 mL) was added manganese dioxide (1.79 g, 20.8 mmol). The reaction mixture was heated in a sealed tube at 100° C. for 16 hours, cooled to room temperature, and filtered through Celite® diatomaceous earth filter aid, rinsing with ethyl acetate (2×50 mL). The filtrate was concentrated under reduced pressure, and the resulting material was purified by MPLC (eluting with 20% ethyl acetate in petroleum ether) to afford the title compound, a compound of the present invention, as an off-white solid (0.30 g) melting at 132-136° C. 1 H NMR(DMSO-d6)δ 7.34(m,1H),7.00(s,1H),6.90(m,2H),6.40-6.35(m,3H),3.92(s,3H),3.64(s,6H). LCMS: m / z: 359 [M+H] +

[0193] Example 3 Preparation of 4-chloro-5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (compound 36) To a mixture of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 2) (1.5 g, 4.19 mmol) in tetrahydrofuran (12 mL) at −20° C. was added 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (1 M solution in tetrahydrofuran, 5.0 mL, 5.0 mmol). The reaction mixture was stirred at −20° C. for 1 hour, and then benzenesulfonyl chloride (0.76 g, 4.3 mmol) was added. The reaction mixture was warmed to 0° C., stirred for 2 hours, and then poured into ice water (100 mL). The resulting mixture was extracted with ethyl acetate (2×100 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride (2×150 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (elution with 20% ethyl acetate in petroleum ether) to give the title compound, a compound of this invention, as a solid (0.40 g) melting at 150-154°C. 1 H NMR(DMSO-d6)δ 7.35(m,1H),6.90(m,2H),6.40-6.35(m,3H),3.97(s,3H),3.65(s,6H). LCMS: m / z: 393 [M+H] +

[0194] Example 4 Preparation of 4-chloro-5-(2,6-difluorophenyl)-6-(3,5-dimethoxy-2-nitrophenyl)-2-methyl-3(2H)-pyridazinone (compound 37) To a mixture of 4-chloro-5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 3) (200 mg, 0.51 mmol) in acetic anhydride (0.6 mL) was added concentrated nitric acid (0.06 mL) at −40° C. After 10 minutes at −40° C., the reaction mixture was poured into ice water (50 mL). The resulting solid precipitate was collected by filtration, washed with water (2×10 mL), and dried under reduced pressure. The solid was then triturated with n-pentane (20 mL), filtered, and dried to give the title compound, a compound of the present invention, as an off-white solid (104 mg) that melted at 223-227° C. 1 H NMR (DMSO-d6): δ 7.35(m,1H),7.10(m,2H),6.73(m,2H),6.48(m,1H),5.03(m,1H),3.70(s,6H),3.40(s,3H),3.15(m,1H),2.54(m,1H). LCMS: m / z: 438 [M+H] +

[0195] Example 5 Preparation of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxy-2-nitrophenyl)-2-methyl-3(2H)-pyridazinone (compound 13) To a mixture of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 2) (500 mg, 1.40 mmol) in acetic anhydride (1.5 mL) was added concentrated nitric acid (0.15 mL) at −40° C. After 10 minutes at −40° C., the reaction mixture was poured into ice-water (50 mL). The resulting solid precipitate was collected by filtration, rinsed with water (2×10 mL), and dried under reduced pressure. The solid was purified by MPLC (eluting with 25% ethyl acetate in petroleum ether) to afford the title compound, a compound of the present invention, as an off-white solid (280 mg) melting at 174-178° C. 1H NMR(CDCl3)δ 7.35(m,1H),7.00(s,1H),6.90(m,2H),6.48(m,1H),6.23(m,1H),3.85(s,6H),3.67(s,3H). LCMS: m / z: 404 [M+H] +

[0196] Example 6 Preparation of 4-chloro-6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 35) To a mixture of 4-chloro-5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 3) (600 mg, 1.53 mmol) in acetonitrile (10 mL) was added N-chlorosuccinimide (224 mg, 1.68 mmol). The reaction mixture was heated at 80°C for 16 hours, cooled, and then poured into ice-water (100 mL). The resulting mixture was extracted with ethyl acetate (2 x 150 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride (2 x 50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 30% ethyl acetate in petroleum ether) to afford the title compound, a compound of this invention, as an off-white solid (290 mg) melting at 192-196°C. 1 H NMR(CDCl3)δ 7.30(m,1H),6.88-6.80(br s,2H),6.46-6.43(m,2H),3.96(s,3H),3.79(s,3H),3.74(s,3H). LCMS: m / z: 427 [M+H] +

[0197] Example 7 Preparation of 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (Compound 12) and 6-(4-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (Compound 14) To a mixture of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 2) (600 mg, 1.68 mmol) in acetonitrile (10 mL) was added N-chlorosuccinimide (226 mg, 1.68 mmol). The reaction mixture was heated at 80° C. for 16 hours, cooled to room temperature, and poured into ice water (100 mL). The resulting mixture was extracted with ethyl acetate (2×150 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride solution (2×50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by supercritical fluid chromatography to give the compound of the present invention, 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone, as an off-white solid (280 mg) melting at 172-176°C. 1 H NMR(CDCl3)δ 7.25(m,1H),7.00(s,1H),6.80(br s,2H),6.51(m,1H),6.45(m,1H),3.90(s,3H),3.78(s,3H),3.76(s,3H). LCMS: m / z: 393 [M+H] +

[0198] Also isolated was the compound of the present invention, 6-(4-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone, as a white solid (40 mg) melting at 221-225°C. 1H NMR(CDCl3)δ 7.35(m,1H),7.02(s,1H),6.90(m,2H),6.46(s,2H),3.93(s,3H),3.70(s,6H). LCMS: m / z: 393 [M+H] +

[0199] Example 8 Preparation of 4-bromo-5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (compound 34) To a mixture of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 2) (300 mg, 0.84 mmol) in tetrahydrofuran (2.5 mL) was added 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (1 M in tetrahydrofuran, 1.25 mL, 1.25 mmol) at −20° C. The reaction mixture was stirred for 1 hour at −20° C., and then 1,3-dibromo-5,5-dimethyl-2,4-imidazolidinedione (251 mg, 0.88 mmol) in tetrahydrofuran (1 mL) was added dropwise. After stirring for an additional 2 hours at 0° C., the reaction mixture was poured into ice water (10 mL) and extracted with ethyl acetate (2×50 mL). The combined organic extracts were washed with saturated aqueous sodium chloride (2 x 20 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 20% ethyl acetate in petroleum ether) to afford the title compound, a compound of this invention, as an off-white solid (70 mg) melting at 153-157 °C. 1 H NMR(CDCl3)δ 7.35(m,1H),6.90(m,2H),6.35-6.30(m,3H),3.97(s,3H),3.66(s,6H). LCMS: m / z: 437 [M+H] +

[0200] Example 9 Preparation of 5,6-bis(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 5) Step A: Preparation of 5,6-dichloro-2-methyl-3(2H)-pyridazinone To a mixture of 5,6-dichloro-3(2H)-pyridazinone (5.3 g, 32.1 mmol) in N,N-dimethylformamide (65 mL) was added cesium carbonate (12.5 g, 37.8 mmol) and iodomethane (2.6 mL, 41.5 mmol). The reaction mixture was stirred for 16 hours and then partitioned between ethyl acetate (300 mL) and water (150 mL). The layers were separated, and the organic layer was washed with water (5 x 100 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the title compound as a white solid (4.6 g). 1 H NMR(CDCl3)δ 7.10(s,1H),3.80(s,3H). LCMS: m / z: 179 [M+H] +

[0201] Step B: Preparation of 5,6-bis(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone (compound 5) To a mixture of 2-bromo-1,3-difluorobenzene (2.5 g, 12.9 mmol) in tetrahydrofuran (17 mL) was added n-butyllithium (1.6 M in hexane, 9.0 mL, 14.2 mmol) dropwise at −78° C. The reaction mixture was stirred at −78° C. for 1 h, then zinc chloride (1.9 M in 2-methyltetrahydrofuran, 8.2 mL, 15.5 mmol) was added dropwise and the mixture was allowed to warm gradually to room temperature. After 1 hour, 5,6-dichloro-2-methyl-3(2H)-pyridazinone (i.e., the product of Step A) (1.0 g, 5.6 mmol), dicyclohexyl[2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine (53.0 mg, 0.11 mmol), and (2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (93.0 mg, 0.11 mmol) were added to the reaction mixture. After 16 hours, the reaction mixture was diluted with water (20 mL) and ethyl acetate (50 mL), and the organic layer was separated, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0-100% ethyl acetate in hexane) to afford the title compound, a compound of this invention, as a white solid (949 mg). 1 H NMR(CDCl3)δ 7.30(m,2H),7.10(s,1H),6.80(m,4H),3.90(s,3H).

[0202] Example 10 Preparation of 6-(2,6-difluorophenyl)-5-(3,5-dimethoxyphenyl)-2-ethyl-3(2H)-pyridazinone (compound 4) Step A: Preparation of 5,6-dichloro-2-ethyl-3(2H)-pyridazinone To a mixture of 5,6-dichloro-3(2H)-pyridazinone (15 g, 91 mmol) in N,N-dimethylformamide (182 mL) was added cesium carbonate (36 g, 109 mmol) and iodoethane (9.5 mL, 118 mmol). After 16 h, the reaction mixture was partitioned between ethyl acetate (500 mL) and water (200 mL), the layers were separated, and the organic layer was washed with water (5 x 100 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the title compound as a white solid (14.9 g). 1 H NMR(CDCl3)δ 7.07(s,1H),4.17(q,2H),1.38(t,3H).

[0203] Step B: Preparation of 6-chloro-5-(3,5-dimethoxyphenyl)-2-ethyl-3(2H)-pyridazinone A mixture of 5,6-dichloro-2-ethyl-3(2H)-pyridazinone (i.e., the product of Step A) (1.0 g, 5.2 mmol), 3,5-dimethoxyphenylboronic acid (1.0 g, 5.7 mmol), tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol), and sodium carbonate (1.1 g, 10.4 mmol) in a solution of toluene (20 mL), ethanol (5 mL), and water (5 mL) was stirred under a stream of nitrogen gas for 1 hour and then heated at 90° C. for 16 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (150 mL) and water (50 mL). The organic layer was separated, washed with saturated aqueous sodium chloride solution (50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0-100% ethyl acetate in hexanes) to afford the title compound as a white solid (576 mg). 1 H NMR(CDCl3)δ 6.90(s,1H),6.54(s,3H),4.22(q,2H),3.81(s,6H),1.43(t,3H). LCMS m / z: 295 [M+H] +

[0204] Step C: Preparation of 6-(2,6-difluorophenyl)-5-(3,5-dimethoxyphenyl)-2-ethyl-3(2H)-pyridazinone To a mixture of 2-bromo-1,3-difluorobenzene (448 mg, 2.32 mmol) in tetrahydrofuran (3 mL) was added n-butyllithium (2.5 M in hexane, 1.0 mL, 2.56 mmol) dropwise at −78° C. The reaction mixture was stirred at −78° C. for 1 h, zinc chloride (1.9 M in 2-methyltetrahydrofuran, 1.5 mL, 2.8 mmol) was added dropwise, and the mixture was allowed to warm gradually to room temperature. After 1 hour, 6-chloro-5-(3,5-dimethoxyphenyl)-2-ethyl-3(2H)-pyridazinone (i.e., the product of Step B) (0.3 g, 1.0 mmol), dicyclohexyl[2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine (24.1 mg, 0.05 mmol), and (2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (43.2 mg, 0.05 mmol) were added to the reaction mixture. After 16 hours, the reaction mixture was diluted with water (20 mL) and ethyl acetate (50 mL), and the organic layer was separated, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0-100% ethyl acetate in hexane) to afford the title compound, a compound of this invention, as a white solid (313 mg). 1 H NMR(CDCl3)δ 7.32(m,1H),6.97(s,1H),6.87(m,2H),6.37(m,1H),6.26(m,2H),4.33(q,2H),3.62(s,6H),1.45(t,3H). 19 F NMR(CDCl3)δ -112.08. LCMS m / z: 373 [M+H] +

[0205] Example 11 Preparation of 4-chloro-6-(2,6-difluorophenyl)-5-(3,5-dimethoxyphenyl)-2-ethyl-3(2H)-pyridazinone (compound 10) To a mixture of 6-(2,6-difluorophenyl)-5-(3,5-dimethoxyphenyl)-2-ethyl-3(2H)-pyridazinone (i.e., the product of Example 10) (154.0 mg, 0.4 mmol) in tetrahydrofuran (0.2 mL) was added 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (1.0 M solution in tetrahydrofuran / toluene, 0.6 mL, 0.6 mmol) at −20° C. The reaction mixture was stirred at −20° C. for 30 minutes, then benzenesulfonyl chloride (63 μL, 0.5 mmol) was added, and the mixture was allowed to warm gradually to room temperature. After 4 hours, the reaction mixture was cooled to 0° C., and additional 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (1.0 M solution in tetrahydrofuran / toluene, 0.6 mL, 0.6 mmol) was added. After stirring at 0°C for 1 hour, additional benzenesulfonyl chloride (63 µL, 0.5 mmol) was added to the reaction mixture, and the mixture was allowed to warm gradually to room temperature. After 16 hours, water (15 mL) and ethyl acetate (50 mL) were added to the reaction mixture, and the organic layer was separated, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0 to 100% ethyl acetate in hexane) to afford the title compound, a compound of the present invention, as a white solid (26.6 mg). 1 H NMR(CDCl3)δ 7.28(m,1H),6.83(m,2H),6.36(m,1H),6.29(m,2H),4.39(q,2H),3.69(s,6H),1.49(t,3H). 19 F NMR(CDCl3)δ -111.07. LCMS m / z: 408 [M+H] +

[0206] Example 12 Preparation of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2,4-dimethyl-3(2H)-pyridazinone (compound 21) To a mixture of 4-bromo-5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Example 8) (90 mg, 0.20 mmol) in 1,4-dioxane (1 mL) was added water (2 drops), dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane complex (17 mg, 0.020 mmol), cesium carbonate (130 mg, 0.40 mmol), and 2,4,6-trimethylboroxine (147 μL, 1.05 mmol). The reaction mixture was heated at 100° C. for 4 hours, cooled to room temperature, and filtered through Celite® diatomaceous earth filter aid, rinsing with ethyl acetate. The filtrate was concentrated under reduced pressure and the resulting material was purified by silica gel column chromatography (eluting with a gradient of 5 to 100% ethyl acetate in hexanes) to afford the title compound, a compound of this invention, as a white solid (73 mg). 1 H NMR(DMSO-d6)δ 7.50(m,1H),7.20(m,2H),6.42(s,1H),6.25(s,2H),3.79(s,3H),3.60(s,6H),1.95(s,3H). LCMS m / z: 373 [M+H] +

[0207] Example 13 Preparation of 5-(2,6-difluorophenyl)-6-(3,5-dimethoxyphenyl)-4,5-dihydro-2-ethyl-3(2H)-pyridazinone (compound 33) To a mixture of β-(2,6-difluorophenyl)-3,5-dimethoxy-γ-oxobenzenebutanoic acid (i.e., the product of Example 1, Step C) (5.0 g, 14.3 mmol) in pyridine (35 mL) was added ethylhydrazine hydrochloride (2.74 g, 28.6 mmol). The reaction mixture was heated at 100°C for 3 days, poured into ice water (200 mL), and extracted with ethyl acetate (2 x 200 mL). The combined organic extracts were washed with saturated aqueous sodium chloride (2 x 150 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (eluting with 30% ethyl acetate in hexane) to afford the title compound, a compound of this invention, as an off-white solid (1.6 g) melting at 119-122°C. 1 H NMR(CDCl3)δ 7.18(m,1H),6.84(m,2H),6.77(s,2H),6.40(m,1H),4.82(m,1H),4.08( m,1H),3.88(m,1H),3.74(s,6H),2.98(m,1H),2.74(m,1H),1.33(t,3H). LCMS: m / z: 375 [M+H] +

[0208] Example 14 Preparation of 5,6-bis(2-chloro-4-fluorophenyl)-2,3-dihydro-2-methyl-3-oxo-4-pyridazinecarbonitrile (compound 6) Step A: Preparation of 1,2-bis(2-chloro-4-fluorophenyl)ethanone To a solution of 2-chloro-4-fluorobenzeneacetic acid (5.0 g, 26.5 mmol) in tetrahydrofuran (100 mL) was added lithium bis(trimethylsilyl)amide (1.0 M in tetrahydrofuran, 80 mL, 80 mmol) dropwise at −78° C. The reaction mixture was stirred at −78° C. for 1 hour, then methyl 2-chloro-4-fluorobenzoate (5.0 g, 26.5 mmol) in tetrahydrofuran (50 mL) was added dropwise, and the mixture was allowed to warm to room temperature. The reaction mixture was stirred at room temperature for 16 hours and then acidified with hydrochloric acid (1 N aqueous solution) to a pH of approximately 6. The resulting mixture was extracted with ethyl acetate (2×200 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride solution (2×150 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 5% ethyl acetate in petroleum ether) to give the title compound as an oil (5 g). 1 H NMR(CDCl3)δ 7.80(m,1H),7.25(m,1H),7.20-7.10(m,2H),7.10-7.00(m,1H),7.00(m,1H),4.38(s,2H).

[0209] Step B: Preparation of 1,2-bis(2-chloro-4-fluorophenyl)-1,2-ethanedione To a solution of 1,2-bis(2-chloro-4-fluorophenyl)ethanone (i.e., the product of Step A) (5.00 g, 16.7 mmol) in dimethyl sulfoxide (80 mL) at 5° C., copper(II) oxide (1.32 g, 16.7 mmol) and iodine (4.62 g, 36.66 mmol) were added. The reaction mixture was heated at 100° C. under an oxygen atmosphere for 6 hours, then cooled to room temperature and treated with saturated aqueous sodium thiosulfate (100 mL). The resulting mixture was extracted with ethyl acetate (2×200 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride (2×50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 20% ethyl acetate in petroleum ether) to give the title compound as a yellow solid (4.0 g).

[0210] Step C: Preparation of 1,2-bis(2-chloro-4-fluorophenyl)-1,2-ethanedione 1-hydrazone To a solution of 1,2-bis(2-chloro-4-fluorophenyl)-1,2-ethanedione (i.e., the product of Step B) (300 mg, 0.955 mmol) in methanol (5 mL) was added hydrazine hydrate (0.071 mL, 1.4 mmol). The reaction mixture was heated at reflux for 15 minutes and then cooled to ambient temperature. The resulting solid precipitate was collected by filtration and dried under reduced pressure to give the title compound as a white solid (0.25 g).

[0211] Step D: Preparation of 5,6-bis(2-chloro-4-fluorophenyl)-2,3-dihydro-3-oxo-4-pyridazinecarbonitrile To a mixture of sodium metal (0.22 g, 9.4 mmol) in ethanol (30 mL) cooled in an ice bath was added ethyl cyanoacetate (1.0 mL, 9.4 mmol). The reaction mixture was stirred for 30 minutes, allowed to warm to room temperature, and then 1,2-bis(2-chloro-4-fluorophenyl)-1,2-ethanedione 1-hydrazone (i.e., the product of Step C) (2.8 g, 8.5 mmol) was added. The reaction mixture was heated at reflux for 6 hours, cooled to room temperature, and then acidified with hydrochloric acid (1 N aqueous solution) to a pH of approximately 4-5. The resulting mixture was extracted with ethyl acetate (2 x 100 mL), and the combined organic extracts were washed with saturated aqueous sodium chloride (2 x 50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 30% ethyl acetate in petroleum ether) to give the title compound as an off-white solid (0.91 g).

[0212] Step E: Preparation of 5,6-bis(2-chloro-4-fluorophenyl)-2,3-dihydro-2-methyl-3-oxo-4-pyridazinecarbonitrile To a mixture of 5,6-bis(2-chloro-4-fluorophenyl)-2,3-dihydro-3-oxo-4-pyridazinecarbonitrile (i.e., the product of Step D) (750 mg, 1.99 mmol) in N,N-dimethylformamide (5 mL) was added potassium carbonate (549 mg, 3.98 mmol) and iodomethane (0.185 mL, 2.98 mmol). After 2 h, the reaction mixture was poured into ice-water (50 mL) and extracted with ethyl acetate (2 x 100 mL). The combined organic extracts were washed with saturated aqueous sodium chloride (2 x 50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 20% ethyl acetate in petroleum ether) to afford the title compound, a compound of this invention, as an off-white solid (238 mg) melting at 137-140 °C. 1 H NMR(DMSO-d6)δ 7.60(m,1H),7.55(m,1H),7.49-7.42(m,2H),7.34(m,1H),7.25(m,1H),3.87(s,3H),3.32(s,6H). LCMS: m / z: 392 [M+H] +

[0213] Example 15 Preparation of 5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methylphenyl)-2,4-dimethyl-3(2H)-pyridazinone (Compound 136) Step A: Preparation of 6-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone A mixture of 5,6-dichloro-2-methyl-3(2H)-pyridazinone (2.0 g, 11.2 mmol), 2-chloro-4-fluorophenylboronic acid (2.1 g, 11.7 mmol), sodium carbonate (4.9 mL, 2.0 M solution in water), and bis(triphenylphosphine)palladium(II) dichloride (1.57 g, 2.24 mmol) in dioxane (78.1 mL) was heated at 100 °C for 16 hours. After cooling to room temperature, the mixture was diluted with water and ethyl acetate. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organics were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0 to 40% ethyl acetate in hexanes) to afford the title compound as a solid (1.68 g). 1 H NMR(CDCl3)δ 7.28-7.21(m,2H),7.13-7.09(m,1H),6.87(s,1H),3.82(s,3H).

[0214] Step B: Preparation of 6-chloro-5-(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone To a mixture of 6-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Step A) (5.0 g, 18.3 mmol) in tetrahydrofuran (183 mL) at −20° C. was added methylmagnesium bromide (21.5 mL, a 3.4 M solution in tetrahydrofuran). The reaction mixture was stirred for 10 minutes, and then bromine (3.8 mL, 73.2 mmol) was added. The reaction mixture was gradually warmed to room temperature, and additional tetrahydrofuran (30 mL) was added to facilitate stirring. After 3 hours, the reaction mixture was poured into sodium thiosulfate solution. The resulting mixture was extracted with ethyl acetate, and the combined organic extracts were washed with water, dried, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (eluting with a gradient of 0–40% ethyl acetate in hexane) to afford the title compound as a solid (4.57 g). 1H NMR(CDCl3)δ 7.30-7.28(m,1H),7.16-7.11(m,2H),3.83(s,3H),1.99(s,3H).

[0215] Step C: Preparation of 5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methylphenyl)-2,4-dimethyl-3(2H)-pyridazinone A mixture of 6-chloro-5-(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone (i.e., the product of Step B) (0.3 g, 1.05 mmol), 2-chloro-5-methylphenylboronic acid (0.19 g, 1.1 mmol), sodium carbonate (0.46 mL, 2.0 M solution in water), and bis(triphenylphosphine)palladium(II) dichloride (0.15 g, 0.21 mmol) in dioxane (7.3 mL) was heated at 100° C. for 16 hours. The reaction mixture was cooled to room temperature and then partitioned between ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organics were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0-100% ethyl acetate in hexane) to afford the title compound, a compound of this invention, as an oil (75 mg). 1 H NMR(CDCl3)δ 7.12(m,2H),7.07-7.04(m,2H),7.00-6.98(m,1H),6.89-6.86(m,1H),3.91(s,3H),2.23(s,3H),2.01(s,3H).

[0216] Example 16 Preparation of 4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-6-phenyl-3(2H)-pyridazinone (Compound 141) Step A: Preparation of 4-chloro-5-iodo-2-methyl-3(2H)-pyridazinone To a mixture of 4,5-dichloro-2-methyl-3(2H)-pyridazinone (7.32 g, 40.9 mmol) in N,N-dimethylformamide (68 mL) was added sodium iodide (24.5 g, 163 mmol). The reaction mixture was heated at 150° C. for 16 hours, after which additional sodium iodide (6.13 g, 40.9 mmol) was added to the reaction mixture. After stirring at 150° C. for an additional 6 hours, additional sodium iodide (6.13 g, 40.9 mmol) was added to the reaction mixture, and stirring at 150° C. was continued for an additional 20 hours. After cooling to room temperature, the reaction mixture was partitioned between ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organics were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting solid (7.8 g) was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.77(s,1H),3.82(s,3H).

[0217] Step B: Preparation of 4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone A mixture of 4-chloro-5-iodo-2-methyl-3(2H)-pyridazinone (i.e., the product of Step A) (5.0 g, 18.5 mmol), 2-chloro-4-fluorophenylboronic acid (3.55 g, 20.3 mmol), bis(triphenylphosphine)palladium(II) dichloride (2.6 g, 3.7 mmol), and sodium carbonate (8.14 mL, 2 M solution in water) in dioxane (129 mL, 0.14 M) was heated at 100 °C for 16 h. After cooling to room temperature, the reaction mixture was partitioned between ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organics were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0 to 60% ethyl acetate in hexanes) to afford the title compound as a solid (3.5 g). 1H NMR(CDCl3)δ 7.64(s,1H),7.31-7.28(2H,m),7.15-7.12(1H,m),3.9(s,3H).

[0218] Step C: Preparation of 4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-6-phenyl-3(2H)-pyridazinone To 4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone (i.e., the product of Step B) (0.25 g, 0.93 mmol) in tetrahydrofuran (1.86 mL) was added zinc chloro 2,2,6,6-tetramethylpiperidide lithium chloride complex (2.42 mL, 0.7 M in tetrahydrofuran). After 5 minutes, the reaction mixture was added via syringe to a mixture of tris(dibenzylideneacetone)dipalladium(0) (0.17 g, 0.19 mmol), tri(2-furyl)phosphine (0.09 g, 0.37 mmol), and iodobenzene (0.38 g, 1.86 mmol) in tetrahydrofuran (1.5 mL). After stirring for 16 hours, the reaction mixture was partitioned between ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organics were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (gradient elution with 0-40% ethyl acetate in hexanes) to afford the title compound, a compound of this invention, as a solid (0.26 g). 1 H NMR(CDCl3)δ 7.3-7.26(m,1H),7.24-7.21(m,2H),7.17-7.13(m,3H),7.06-7.03(m,1H),6.99-6.95(m,1H),3.98(s,3H).

[0219] Example 17 Preparation of 5-(2-chloro-4-fluorophenyl)-4-methoxy-2-methyl-6-phenyl-3(2H)-pyridazinone (compound 142) To a mixture of 4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-6-phenyl-3(2H)-pyridazinone (i.e., the product of Example 16) (0.2 g, 0.57 mmol) in toluene (5.7 mL) was added sodium methoxide (1.38 mL, a 0.5 M solution in methanol). After 3 hours, additional sodium methoxide (1.38 mL, a 0.5 M solution in methanol) was added to the reaction mixture, and stirring was continued for an additional 2 hours. The reaction mixture was concentrated under reduced pressure, and the resulting material was purified by silica gel column chromatography (gradient elution with 10-60% ethyl acetate in hexane) to afford the title compound, a compound of the present invention, as a solid (90 mg). 1 H NMR(CDCl3)δ 7.25-7.18(m,3H),7.15-7.10(m,3H),6.98-6.95(m,1H),6.91-6.87(m,1H),4.13(s,3H),3.91(s,3H).

[0220] Compounding / Usefulness The compounds of formula 1 of the present invention (including their N-oxides and salts) may be used as fungicidal active ingredients in compositions (i.e., formulations), generally with at least one additional ingredient selected from the group consisting of surfactants, solid diluents, and liquid diluents, which functions as a carrier. The formulation or composition ingredients 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.

[0221] Useful formulations include liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspoemulsions), which can optionally 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, flowable concentrates, and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0222] Common types of solid compositions are dusts, powders, granules, pellets, pellets, pastilles, tablets, filled films (including seed coatings), etc., which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatments. Active ingredients can be (micro)encapsulated and further formed into suspensions or solid formulations; alternatively, whole formulations of active ingredients can be encapsulated (or "overcoated"). Encapsulation can control or slow the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate and dry granular formulations. High-strength compositions are primarily used as intermediates for further formulations.

[0223] Sprayable formulations are typically diluted in a suitable vehicle before spraying. Such liquid and solid formulations are formulated and readily diluted in a spray vehicle, usually water, but sometimes another suitable vehicle such as an aromatic or paraffinic hydrocarbon or vegetable oil. Application rates can range from about one to several thousand liters per hectare, but are more typically in the range of about 10 to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable vehicle for foliar treatment by aerial or ground application, or for application to the plant's growing medium. Liquid and dry formulations can be metered directly into drip irrigation systems or into furrows during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as pre-plant seed treatments to protect developing roots and other underground plant parts and / or foliage by systemic absorption.

[0224] The formulations will typically contain effective amounts of the active ingredient, diluent and surfactant within the approximate ranges set forth below, which add up to 100 weight percent.

[0225] [Table 1]

[0226] 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.

[0227] Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, normal paraffin, isoparaffin), alkylbenzenes, alkylnaphthalenes, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, cyclohexanone, 2-heptanone, isophorone, and ketones such as 4-hydroxy-4-methyl-2-pentanone, isoamyl alcohol, and the like. Other esters such as acetates such as acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, alkylated lactate esters, dibasic acid esters, alkyl and aryl benzoates, and gamma-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 also include saturated and unsaturated fatty acids (typically C6-C8), such as vegetable seed oils and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn (maize) oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), fats of animal origin (e.g., beef tallow, pork fat, lard, cod liver oil, fish oil), and mixtures thereof. 22) glycerol esters. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which may be obtained by hydrolysis of glycerol esters from plant and animal sources, or which can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

[0228] 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 lower, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be useful as wetting agents, dispersing agents, emulsifying agents, or antifoaming agents.

[0229] Surfactants can be classified as nonionic, anionic, or cationic surfactants. Nonionic surfactants useful in the present compositions include alcohol alkoxylates, such as those based on natural and synthetic alcohols (which may be branched or linear) and those prepared from alcohols 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 (prepared from phenols and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers in which the end blocks are prepared from propylene oxide; ethoxylated triglycerides, such as ethoxylated soybean oil, castor oil, and rapeseed oil; ... ethoxylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those made from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric 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 sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0230] Useful anionic surfactants include alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acid or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates 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 tridecyl benzene; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalenes; sulfonates of fractionated petroleum; sulfosuccinates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.

[0231] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, tripropylenetriamines, 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 diquaternized salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0232] Mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants are also useful in the present compositions. 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.S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

[0233] 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 may control pH (buffers), foaming during processing (antifoaming agents such as polyorganosiloxanes), active ingredient settling (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), leaching (film formers or stickers), evaporation (evaporation inhibitors), and other formulation attributes. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those 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 PCT Publication No. WO 03 / 024222.

[0234] The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredients in a solvent or by grinding in a liquid or dry diluent. Solutions, such as emulsifiable concentrates, can be prepared by simply 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-containing solvent upon dilution with water. Active ingredient slurries with particle sizes of 2,000 μm or less can be wet-milled using a media mill to obtain particles with an average diameter below 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, e.g., U.S. Pat. No. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling, which produces an average particle size in the 2-10 μm range. Fines and powders can be prepared by blending and grinding, usually (such as with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto a preformed 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 publications; and WO 91 / 13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, and German Patent No. 3,246,493. Tablets can be prepared as taught in US Pat. Nos. 5,180,587, 5,232,701, and 5,208,030.Films can be prepared as taught in British Patent No. 2,095,558 and US Pat. No. 3,299,566.

[0235] One embodiment of the present invention relates to a method for controlling fungal pathogens, comprising diluting a fungicidal composition of the present invention (a compound of Formula 1 formulated with a surfactant, a solid diluent, and a liquid diluent, or a formulated mixture of a compound of Formula 1 and at least one other fungicide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of the diluted composition.

[0236] Although a spray composition formed by diluting a sufficient concentration of the fungicidal composition with water may provide sufficient efficacy for the control of fungal pathogens, separately formulated adjuvant products may also be added to the spray tank mixture. These additional adjuvants, commonly known as "spray adjuvants" or "tank-mix adjuvants," include any substance mixed in the spray tank to improve pesticide performance or modify the physical properties of the spray mixture. Adjuvants may be anionic or nonionic surfactants, emulsifiers, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners, or antifoaming agents. Adjuvants 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 associated with incompatibility, foaming, drift, evaporation, vaporization, and decomposition. To achieve optimal performance, adjuvants are selected with respect to the characteristics of the active ingredient, formulation, and target (e.g., crop, pest).

[0237] The amount of adjuvant added to the spray mixture generally ranges from about 0.1 to 2.5% by volume. The application rate of adjuvant added to the spray mixture is typically about 1 to 5 L per hectare. Representative examples of spray adjuvants include: Adigor® (Syngenta), a 47% methylated rapeseed oil in a liquid hydrocarbon; Silwet® (Helena Chemical Company), a polyalkylene oxide-modified heptamethyltrisiloxane; and Assist® (BASF), a 17% surfactant blend in 83% paraffin-based mineral oil.

[0238] One method of seed treatment involves spraying or dusting the seeds with a compound of the present invention (i.e., the compound as a formulated composition) before sowing. Compositions formulated for seed treatment generally contain a film former or adhesive. Thus, a seed coating composition of the present invention typically contains a biologically effective amount of a compound of Formula 1 and a film former or adhesive. Seeds can be coated by spraying a flowable suspension concentrate directly into a rolling bed of seeds and then allowing the seeds to dry. Alternatively, other types of formulations (e.g., wet powders, solutions, suspoemulsions, emulsifiable concentrates, and emulsions in water) can be sprayed onto the seeds. This process is particularly useful when applying a film coating onto the seeds. A variety of coating machines and processes are available to those skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994, BCPC Monograph No. 57, and the references cited therein.

[0239] For further information regarding the technical field 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 T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, column 6, row 16-7, row 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, row 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. Pat. No. 2,891,855, column 3, row 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 Publications, Richmond, UK, 2000.

[0240] In the following examples, all percentages are by weight, and all formulations are prepared by conventional methods. The active ingredients refer to the compounds in Tables A-L disclosed herein. Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples are intended to be merely illustrative and are not intended to limit the present disclosure in any way.

[0241] Example A high strength concentrate Compound 25 98.5% Silica aerogel 0.5% Synthetic amorphous fine silica 1.0%

[0242] Example B Wettable powder Compound 35 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignosulfonate 4.0% Sodium silicoaluminate 6.0% Montmorillonite (calcined) 23.0%

[0243] Example C granules Compound 44 10.0% Attapulgite Granules (Low Volatile Content, 0.71 / 0.30 mm; USS No. 25-50 Sieve) 90.0%

[0244] Example D Extruded pellets Compound 35 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignosulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0245] Example E emulsifiable concentrate Compound 57 10.0% Polyoxyethylene sorbitol hexoleate 20.0% C6~C 10 Fatty acid methyl ester 70.0%

[0246] Example F Microemulsion Compound 58 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0247] Example G seed treatment agents Compound 64 20.00% Polyvinylpyrrolidone-vinyl acetate copolymer 5.00% Montan Acid Wax 5.00% Calcium lignosulfonate 1.00% Polyoxyethylene / Polyoxypropylene Block Copolymer 1.00% Stearyl alcohol (POE 20) 2.00% Polyorganosilane 0.20% Colorant: Red dye 0.05% Water 65.75%

[0248] Example H stick fertilizer Compound 66 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%

[0249] Example I Suspension concentrate Compound 68 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Water 53.7%

[0250] Example J Emulsion in water Compound 77 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Aromatic Petroleum-Based Hydrocarbons 20.0 Water 58.7%

[0251] Example K Oil dispersion Compound 80 25% Polyoxyethylene sorbitol hexaoleate 15% Organically modified bentonite clay 2.5% Fatty acid methyl esters 57.5%

[0252] Example L Suspo Emulsion Compound 83 10.0% Imidacloprid 5.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Aromatic Petroleum-Based Hydrocarbons 20.0% Water 53.7%

[0253] Water-soluble and water-dispersible formulations are typically applied after dilution with water to form an aqueous composition. Aqueous compositions for direct application to plants or parts thereof (e.g., spray tank compositions) typically contain at least about 1 ppm or more (e.g., 1 ppm to 100 ppm) of a compound of the invention.

[0254] Seeds are typically treated at a rate of about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed (i.e., about 0.0001 to 1% by weight of the seed before treatment). Flowable suspensions formulated for seed treatment typically contain about 0.5 to about 70% active ingredient, about 0.5 to about 30% film-forming adhesive, about 0.5 to about 20% dispersant, 0 to about 5% thickener, 0 to 5% pigment and / or dye, 0 to about 2% antifoaming agent, 0 to about 1% preservative, and 0 to about 75% volatile liquid diluent.

[0255] The compounds of the present invention are useful as plant disease control agents. Accordingly, the present invention further includes a method for controlling plant diseases caused by fungal plant pathogens, comprising applying an effective amount of a compound of the present invention or a fungicidal composition containing the compound to a plant or part thereof, or to a plant seed 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 in the phyla Ascomycota, Basidiomycota, Zygomycota, and Oomycota. This is effective in controlling a wide range of plant diseases, particularly foliar pathogens of ornamental plants, turf, vegetables, field, cereal, and fruit crops. These pathogens include, but are not limited to, those listed in Table 1-1. In the case of Ascomycota and Basidiomycota, both the sexual / telomorph / telomorph names and the asexual / asexual / deuteromorph names (in parentheses) are listed when known. Synonymous names of pathogens are indicated with an equal sign. For example, the sexual / telomorph / deuteromorph name Phaeosphaeria nodorum is followed by the corresponding asexual / asexual / deuteromorph name Stagnospora nodorum and the synonymous, older name Septoria nodorum.

[0256] [Table 2]

[0257] [Table 3]

[0258] [Table 4]

[0259] In addition to fungicidal activity, the compositions or combinations also have 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 for improving (i.e., increasing) the ratio of beneficial to harmful microorganisms in contact with crop plants or their vegetative propagules (e.g., seeds, corms, bulbs, tubers, cuttings) or the agronomic environment of crop plants or their vegetative propagules.

[0260] The compounds of the present invention are useful in treating whole plants, plant parts, and seeds. Plant and seed varieties and cultivars can be obtained by conventional breeding and propagation methods, or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the genome of the plant or seed. A transgene defined by a specific location in the plant genome is called a transformation or transgenic event.

[0261] Genetically modified plant cultivars that can be treated according to the present invention include those that exhibit tolerance to one or more biotic stresses (pests, such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperatures, soil salinity, etc.), or that contain other desirable traits. Plants can be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, modified oil profile, or drought tolerance.

[0262] Treatment of genetically modified plants and seeds with the compounds of the invention can result in superadditive or enhanced effects, such as reduced application rates, broadened spectrum of activity, increased tolerance to biotic / abiotic stresses, or enhanced storage stability, relative to what would be expected from the merely additive effects of applying the compounds of the invention to genetically modified plants and seeds.

[0263] The compounds of the present invention are useful in seed treatments to protect seeds from plant diseases. In the context of this disclosure and claims, treating seeds means contacting the seeds with a biologically effective amount of a compound of the present invention (typically formulated as a composition of the present invention). This seed treatment protects the seeds from soil-borne disease pathogens and may also generally protect the roots and other plant parts of the seedlings that grow from the germinating seeds and are in contact with the soil. This plant treatment may also protect the leaves through translocation of the compound of the present invention or through the release of another active ingredient within the growing plant. Seed treatments can be applied to all types of seeds (e.g., those from which plants genetically transformed to express specialized traits are grown). Representative examples include those that express proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis toxins) or those that express herbicide resistance (e.g., glyphosate acetyltransferase, which confers tolerance to glyphosate). Seed treatments with the compounds of the present invention may also increase the vigor of plants growing from the seeds.

[0264] The compounds of the present invention and compositions thereof, both alone and in combination with other fungicides, nematicides, and insecticides, are particularly useful in seed treatment of crops including, but not limited to, maize or corn, soybeans, cotton, cereals (e.g., wheat, oats, barley, rye, and rice), potatoes, vegetables, and oilseed rape.

[0265] Furthermore, the compounds of the present invention are useful for treating postharvest diseases of fruits and vegetables caused by fungi, oomycetes, and bacteria. This infection can occur before, during, and after harvest. For example, infection can occur before harvest and then remain dormant until some point during ripening (e.g., when the host begins tissue changes that allow infection to progress or conditions that favor disease development); similarly, infection can occur through surface wounds 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) due to postharvest diseases that can occur at any time from harvest to consumption. Treatment of postharvest diseases with the compounds of the present invention can allow perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) to be stored refrigerated or unrefrigerated after harvest, maintain their edibility, and extend the period without significant or harmful decomposition or contamination by fungi or other microorganisms. Pre- or post-harvest treatment of edible plant parts with the compounds of the invention may also reduce the formation of toxic metabolites of fungi or other microorganisms (eg, mycotoxins such as aflatoxins).

[0266] 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 the roots, stems, leaves, fruits, seeds, tubers, or bulbs, or to the medium (soil or sand) in which the plant to be protected is growing, either before or after infection. The compound can also be applied to seeds to protect the seeds and the seedlings that grow from the seeds. The compound can also be applied via irrigation water to treat plants. Control of post-harvest pathogens that infect agricultural products before harvest is typically achieved by field application of the compound of the present invention; when infection occurs after harvest, the compound can be applied to the harvested crop as a dip, spray, fumigant, treatment wrap, and box liner.

[0267] The compounds may also be applied using unmanned aerial vehicles (UAVs) to spray the compositions disclosed herein over a cropped area. In some embodiments, the cropped area is a crop-containing area. In some embodiments, the crop is selected from monocotyledonous or dicotyledonous plants. In some embodiments, the crop is selected from rice, corn, barley, soybean, wheat, vegetables, tobacco, tea plants, fruit trees, and sugarcane. In some embodiments, the compositions disclosed herein are formulated for spraying at ultra-low volumes. Products applied by drones may use water or oil as the spray carrier. Typical spray volumes (including product) used for drone application worldwide are 5.0 liters / ha to 100 liters / ha (approximately 0.5 to 10 gpa). This includes the ultra-low spray volume (ULV) to low spray volume (LV) range. Although not common, there may be situations where spray volumes as low as 1.0 liter / ha (0.1 gpa) may be used.

[0268] The application rate of the compound (i.e., a fungicidally effective amount) may be affected 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 use conditions. Those skilled in the art can easily determine, through simple experimentation, the fungicidally effective amount required for the desired level of plant disease control. Foliage can usually be protected when treated at rates of less than about 1 g / ha to about 5,000 g / ha of active agent. Seeds and seedlings can usually be protected when treated at rates of about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed.

[0269] The compounds of the present invention may also be useful for enhancing the vigor of crops. The method involves contacting a crop (e.g., foliage, flowers, fruits, or roots) or a seed from which the crop grows with a compound of Formula 1 in an amount sufficient to achieve the desired plant vigor effect (i.e., a biologically effective amount). Typically, the compound of Formula 1 is applied in a formulated composition. While the compound of Formula 1 is often applied directly to the crop or its seeds, it can also be applied to the locus of the crop, i.e., to the crop's environment, particularly to a portion of the environment sufficiently close to the crop to allow the compound of Formula 1 to migrate thereto. A suitable locus for the method most commonly includes the growth medium (i.e., the medium that provides nutrients to the plant), typically the soil in which the plant grows. Treating a crop to enhance crop vigor therefore involves contacting the crop, the seed from which the crop grows, or the locus of the crop with a biologically effective amount of a compound of Formula 1.

[0270] Increased crop vigor can result in one or more of the following observed effects: (a) optimal cropping system as evidenced by superior seed germination, crop emergence, and crop stand; (b) increased crop growth as evidenced by fast and robust leaf growth (e.g., as measured by leaf area index), plant height, number of shoots (e.g., for rice), root mass, and total dry weight of the plant mass of the crop; (c) improved crop yield as evidenced by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e., yield), and / or marketability of the fruit or grain quality of the produce (i.e., harvest quality); (d) increased ability of the crop to withstand or prevent plant disease infection and arthropod, nematode, or mollusk pest infestation; and (e) increased ability of the crop to withstand environmental stresses, such as extreme heat, suboptimal moisture, or exposure to phytotoxic chemicals.

[0271] The compounds of the present invention can increase the vigor of treated plants compared to untreated plants by preventing and / or curing plant diseases caused by fungal plant pathogens in the plant's environment. In the absence of such control of plant diseases, the disease reduces plant vigor by consuming plant tissues 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 plant vigor by modifying plant metabolism. Generally, the vigor of crop plants will be most significantly increased by treating the plants with the compounds of the present invention when the plants are grown in a non-ideal environment (i.e., an environment that contains one or more aspects unfavorable to the plant achieving its maximum genetic potential, which would be indicative of an ideal environment).

[0272] Of note is a method for increasing the vigor of a crop plant when the plant is grown in an environment that includes a plant disease caused by a fungal plant pathogen. Also of note is a method for increasing the vigor of a crop plant when the plant is grown in an environment that does not include a plant disease caused by a fungal plant pathogen. Also of note is a method for increasing the vigor of a crop plant when the plant is grown in an environment that is less watery than ideal for supporting the growth of the crop plant.

[0273] The compounds of the present invention can also be mixed with one or more biologically active compounds or agents, including fungicides, insecticides, nematicides, bactericides, acaricides, herbicides, herbicide antidotes, growth regulators, such as insect molting inhibitors, and root stimulators, sterilizers, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or insect pathogenic bacteria, viruses, or fungi to form multi-component pesticides that provide broad-spectrum agricultural protection. Therefore, the present invention also relates to compositions comprising a fungicidally effective amount of a compound of Formula 1 and a biologically effective amount of at least one additional biologically active compound or agent, which may further comprise at least one surfactant, solid diluent, or liquid diluent. Other biologically active compounds or agents can be formulated in compositions that include at least one surfactant, solid diluent, or liquid diluent. In the case of the mixtures of the present invention, one or more other biologically active compounds or agents may be formulated together with the compound of Formula 1 to form a premix, or one or more other biologically active compounds or agents may be formulated separately from the compound of Formula 1 and the formulations may be combined together before application (e.g., in a spray tank) or applied sequentially.

[0274] As noted 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 fungicide (i.e., component b). Of note are combinations in which the other fungicidally active ingredient has a different site of action than the compound of Formula 1. In certain cases, combinations with at least one other fungicidally active ingredient having a similar spectrum of control but a different site of action may be particularly advantageous for resistance management. As such, the compositions of the present invention may further comprise a fungicidally effective amount of at least one additional fungicidally active ingredient having a similar spectrum of control but a different site of action.

[0275] Of note are compositions comprising, in addition to component (a) a compound of Formula 1, as component (b), at least one fungicidal compound selected from the group consisting of the following Mode of Action (MOA) classes defined by FRAC: (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis in membranes, (I) melanin synthesis in cell walls, (P) induction of host plant defense, (M) chemicals with multi-site activity, (U) unknown mode of action, and (BM) biologicals with multiple modes of action.

[0276] The target sites of action recognized or proposed by FARC along with the FRAC target site codes belonging to the above MOA classes are: (A1) RNA polymerase I, (A2) adenosine deaminase, (A3) DNA / RNA synthesis (proposed), (A4) DNA topoisomerase, (B1-B3) β-tubulin assembly in mitosis, (B4) cell division (proposed), (B5) delocalization of spectrin-like proteins, (B6) function of actin / myosin / fimbrin, (C1) complex I. NADH oxidoreductase, (C2) Complex II: succinate dehydrogenase, (C3) Complex III: cytochrome bc1 (ubiquinol oxidase) at the Qo site, (C4) Complex III: cytochrome bc1 (ubiquinone reductase) at the Qi site, (C5) uncoupler of oxidative phosphorylation, (C6) inhibitor of oxidative phosphorylation, ATP synthase, (C7) ATP production (proposed), (C8) Complex III: cytochrome bc1 (ubiquinone reductase) at the Qx site (unknown), (D1) methionine biosynthesis (proposed), (D2-D5) protein synthesis, (E1) signal transduction (mechanism unknown), (E2-E3) MAP / histidine kinase in osmotic signal transduction, (F2) phospholipid biosynthesis, methyltransferase, (F3) lipid peroxidation (proposed). , (F4) Cell membrane permeability, fatty acids (proposed), (F6) microbial disruptors of pathogen cell membranes, (F7) cell membrane disruption (proposed), (G1) C14-demethylase in sterol biosynthesis, (G2) Δ14-reductase and Δ8→Δ7-isomerase in sterol biosynthesis, (G3) 3-ketoreductase, C4-demethylation, (G4) squalene epoxidase in sterol biosynthesis, (H3) trehalase and inositol biosynthesis, (H4) chitin synthase, (H5) cellulose synthase, (I1) reductase in melanin biosynthesis, and (I2) dehydratase in melanin biosynthesis, (I3) polyketide synthase in melanin biosynthesis, (BM01) plant extract, and (BM02) microorganism, living microorganism, or extract, metabolite.

[0277] Of particular note are compositions comprising, in addition to component (a) a compound of formula 1, as component (b), at least one fungicidal component selected from the group consisting of the following classes: (b1) methyl benzimidazole carbamate (MBC) fungicides; (b2) dicarboxamide fungicides; (b3) demethylation inhibitor (DMI) fungicides; (b4) phenylamide fungicides; (b5) amine / morpholine fungicides; (b6) phospholipid biosynthesis inhibitor fungicides; (b7) succinate dehydrogenase inhibitor fungicides; (b8) hydroxybenzoates; (b9) Anilinopyrimidine fungicides; (b10) N-phenylcarbamate fungicides; (b11) Quinone external inhibitor (QoI) fungicides; (b12) Phenylpyrrole fungicides; (b13) Azanaphthalene fungicides; (b14) Lipid peroxidation inhibitor fungicides; (b15) Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides; (b16) Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides; (b17) Sterol biosynthesis inhibitors (SBI); (b18) Squalene-epoxidase inhibitor fungicides; (b19) Polyoxin fungicides; (b20) Phenylurea fungicides; (b21) Quinone internal inhibitor (QiI) fungicides; (b22) Benzamide and thiazolecarboxamide fungicides; (b23) Enopyranuronic acid antibiotic fungicides; (b24) Hexopyranosyl antibiotic fungicides; (b25) Glucopyranosyl antibiotic: protein synthesis fungicides; (b26) Glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides Fungicides; (b27) cyanoacetamide oxime fungicides; (b28) cargamete fungicides; (b29) oxidative phosphorylation uncoupler fungicides; (b30) organotin fungicides; (b31) carboxylic acid fungicides; (b32) heterocyclic aromatic fungicides; (b33) phosphonate fungicides; (b34) phthalamic acid fungicides; (b35) benzotriazine fungicides; (b36) benzene-sulfonamide fungicides; (b37) pyridazinone fungicides; (b38) thiophene-carboxamide fungicides; (b39) complex I NADH oxidoreductase inhibitor fungicides; (b40) carboxylic acid amide (CAA) fungicides; (b41) tetracycline antibiotic fungicides;(b42) Thiocarbamate fungicides; (b43) Benzamide fungicides; (b44) Microbial fungicides; (b45) Q; x I Fungicides; (b46) plant extract fungicides; (b47) host plant defense induction fungicides; (b48) multi-site contact active fungicides; (b49) fungicides other than those of classes (b1) to (b48); and salts of compounds of classes (b1) to (b48).

[0278] Further description of these classes of fungicidal compounds is provided below.

[0279] (b1) "Methyl benzimidazole carbamate (MBC) fungicides" (FARC code 1) inhibit mitosis by binding to beta-tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, intracellular transport, and cellular structure. Methyl benzimidazole carbamate fungicides include benzimidazole fungicides and thiophanate fungicides. Benzimidazoles include benomyl, carbendazim, fuberidazole, and thiabendazole. Thiophanates include thiophanate and thiophanate-methyl.

[0280] (b2) "Dicarboxamide fungicides" (FRAC code 2) inhibit MAP / histidine kinases in osmotic signaling. Examples include chlozolinate, iprodione, procymidone, and vinclozolin.

[0281] (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, which are essential for the development of a functional cell wall. Therefore, exposure to these fungicides results in the abnormal growth and eventual death of susceptible fungi. DMI fungicides are divided into several chemical classes: azoles (e.g., triazoles and imidazoles), pyrimidines, piperazines, pyridines, and triazolinethiones. Triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (e.g., diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, and α-(1-chlorocyclopropyl) -α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, rel-1-[[(2R,3S)-3-(2-chloro-phenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chloro-phenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole. Imidazoles include econazole, imazalil, oxpoconazole, prochloraz, pefurazoate, and triflumizole.Pyrimidines include fenarimol, nuarimol, and triarimol. Piperazines include triforine. Pyridines include buthiobate, pyrifenox, pyrisoxazole (3-[(3R)-5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine, a mixture of the 3R,5R-isomer and the 3R,5S-isomer), and (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridine-methanol. Triazolinethiones include prothioconazole and 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione. Biochemical investigations have shown that all of the above-mentioned fungicides are DMI fungicides as described by KH Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

[0282] (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 is hindered by exposure to this class of fungicide. Phenylamide fungicides include acylalanine fungicides, oxazolidinone fungicides, and butyrolactone fungicides. Acylalanines include benalaxyl, benalaxyl-M (also known as chiralaxyl), furalaxyl, metalaxyl, and metalaxyl-M (also known as mefenoxam). Oxazolidinones include oxadixyl. Butyrolactones include ofuras.

[0283] (b5) "Amine / morpholine fungicides" (FRAC code 5) (SBI: class II) target two sites in the sterol biosynthetic 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 results in the abnormal growth and eventual death of susceptible fungi. Amine / morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine fungicides, piperidine fungicides, and spiroketal-amine fungicides. Morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph, and trimorphamide. Piperidines include fenpropidin and piperaline. Spiroketal-amines include spiroxamine.

[0284] (b6) "Phospholipid biosynthesis inhibitor fungicides" (RFAC code 6) inhibit the growth of fungi by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phosphorothioate fungicides and dithiolane fungicides. Phosphorothiolates include edifenphos, iprobenfos, and pyrazophos. Dithiolanes include isoprothiolane.

[0285] (b7) "Succinate dehydrogenase inhibitor (SDHI) fungicides" (FAC Code 7) inhibit Complex II fungal respiration by disrupting a key enzyme in the Krebs cycle (TCA cycle) called succinate dehydrogenase. Inhibition of respiration prevents fungi from producing TAP, thereby inhibiting growth and reproduction. SDHI fungicides include: phenylbenzamide, furancarboxamide, oxathiincarboxamide, thiazolecarboxamide, pyrazole-4-carboxamide, pyridinecarboxamide, phenyloxoethylthiophenamide, and pyridinylethylbenzamide. Benzamides include benodanil, flutolanil, and mepronil. Furancarboxamides include fenfuram. Oxathiincarboxamides include carboxin and oxycarboxin. Thiazolecarboxamides include thifluzamide.Pyrazole-4-carboxamides include: benzovindiflupyr (N-[9-(dichloro-methylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide), bixafen, fluindapyr, fluxapyroxad (3-(difluoromethyl)-1-methyl-N-(3',4',5'-trifluoro[1,1'-biphenyl] ]-2-yl)-1H-pyrazole-4-carboxamide), furametpyr, isopyrazam (3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methano-naphthalen-5-yl]-1H-pyrazole-4-carboxamide), penflufen (N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide), pen Thiopyrad, pydiflumetofen, sedaxane (N-[2-[1,1'-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide), N-[2-(1S,2R)-[1,1'-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethylphenyl)- Methyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, and N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide. Pyridinecarboxamides include boscalid. Phenyloxoethylthiophenamides include isofetamide (N-[1,1-dimethyl-2-[2-methyl-4-(1-methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide). Pyridinylethylbenzamides include fluoropyram.

[0286] (b8) "Hydroxy-(2-amino-)pyrimidine fungicides" (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol, and ethirimol.

[0287] (b9) "Anilinopyrimidine fungicides" (FRAC code 9) are proposed to inhibit the biosynthesis of the amino acid methionine, disrupting the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim, and pyrimethanil.

[0288] (b10) "N-phenylcarbamate fungicides" (FRAC code 10) inhibit mitosis by binding to beta-tubulin and disrupting microtubule assembly. Disruption of microtubule assembly can disrupt cell division, intracellular transport, and cellular structure. An example is diethofencarb.

[0289] (b11) "Quinone external inhibitor (QoI) fungicides" (FRAC code 11) inhibit fungal complex III mitochondrial respiration by affecting ubiquinol oxidase. The oxidation of ubiquinol occurs via cytochrome b, which is located in the inner mitochondrial membrane of fungi. c1 The "quinone outer" (Q o) site. Inhibition of mitochondrial respiration prevents normal fungal growth and development. Quinone external inhibitor fungicides include: methoxyacrylate fungicides, methoxycarbamate fungicides, oximinoacetate fungicides, oximinoacetamide fungicides, and dihydrodioxazine fungicides (collectively known as strobilurin fungicides), and oxazolidinedione fungicides, imidazolinone fungicides, and benzyl carbamate fungicides. Methoxyacrylates include azoxystrobin, cumoxystrobin (methyl(αE)-2-[[(3-butyl-4-methyl-2-oxo-2H-1-benzopyran-7-yl)oxy]methyl]-α-(methoxy-methylene)-benzeneacetate), enoxastrobin (methyl(αE)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxymethylene (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)-phenoxy]methyl]-α-(methoxymethylene)-benzeneacetate) (also known as enestrobin), flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)-phenoxy]methyl]-α-(methoxymethylene)-benzeneacetate), picoxystrobin, and pyraoxystrobin (methyl(αE)-2-[[[3-(4-chlorophenyl)-1-methyl-1H-pyrazol-5-yl]oxy]methyl]-α-(methoxy-methylene)-benzeneacetate). Methoxycarbamates include pyraclostrobin, pyrametostrobin (methyl N-[2-[[(1,4-dimethyl-3-phenyl-1H-pyrazol-5-yl)oxy]methyl]phenyl]-N-methoxy-carbamate), and triclopyricarb (methyl N-methoxy-N-[2-[[(3,5,6-trichloro-2-pyridinyl)oxy]methyl]phenyl]carbamate). Oximinoacetates include kresoxim-methyl and trifloxystrobin.Oximinoacetamides include dimoxystrobin, phenaminestrobin ((αE)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methyl-benzeneacetamide), metominostrobin, orysastrobin, and α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide. Dihydrodioxazines include fluoxastrobin. Oxazolidinediones include famoxadone. Imidazolinones include fenamidone. Benzyl carbamates include pyribencarb. Class (b11) also includes mandestrobin (2-[(2,5-dimethylphenoxy)methyl]-α-methoxy-N-benzeneacetamide).

[0290] (b12) "Phenylpyrrole fungicides" (FRAC code 12) inhibit MAP / histidine kinases involved in osmotic signaling in fungi. Fenpiclonil and fludioxonil are examples of this fungicide class.

[0291] (b13) "Azanaphthalene fungicides" (FRAC code 13) are proposed to inhibit signal transduction by an unknown mechanism. The fungicides have been shown to interfere with germination and / or appressorium formation of powdery mildew-causing fungi. Azanaphthalene fungicides include aryloxyquinolines and quinazolinones. Aryloxyquinolines include quinoxyfen. Quinazolinones include proquinazide.

[0292] (b14) "Lipid peroxidation inhibitor fungicides" (FRAC code 14) are proposed to inhibit lipid peroxidation, which affects fungal membrane synthesis. Members of this class, such as etridiazole, may also affect other biological processes, such as respiration and melanin biosynthesis. Lipid peroxidation fungicides include aromatic hydrocarbon fungicides and 1,2,4-thiadiazole fungicides. Aromatic hydrocarbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene, and tolclofos-methyl. 1,2,4-thiadiazoles include etridiazole.

[0293] (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 some fungi. Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone fungicides, pyrroloquinolinone fungicides, and triazolobenzothiazole fungicides. Isobenzofuranones include phthalides. Pyrroloquinolinones include pyroquilon. Triazolobenzothiazoles include tricyclazole.

[0294] (b16) "Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides" (RFAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropanecarboxamide fungicides, carboxamide fungicides, and propionamide fungicides. Cyclopropanecarboxamides include carpropamid. Carboxamides include diclocymet. Propionamides include fenoxanil.

[0295] (b17) "Sterol biosynthesis inhibitors (SBI): Class III fungicides" (FRAC code 17) inhibit 3-ketoreductase during C4 demethylation in sterol production. SBI: Class III inhibitors include hydroxyanilide fungicides and amino-pyrazolinone fungicides. Hydroxyanilides include fenhexamid. Amino-pyrazolinones include fenpyrazamine (S-2-propen-1-yl 5-amino-2,3-dihydro-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-1H-pyrazole-1-carbothioate).

[0296] (b18) "Squalene epoxidase inhibitor fungicides" (FRAC code 18) (SBI: Class IV) inhibit squalene epoxidase in the sterol biosynthetic pathway. Sterols, such as ergosterol, are required for membrane structure and function, which are essential for the development of a functional cell wall. Therefore, exposure to these fungicides results in the abnormal growth and eventual death of susceptible fungi. Squalene epoxidase inhibitor fungicides include thiocarbamate fungicides and allylamine fungicides. Thiocarbamates include pyributicarb. Allylamines include naftifine and terbinafine.

[0297] (b19) "Polyoxin fungicides" (FRAC code 19) inhibit chitin synthesis. Examples include polyoxins.

[0298] (b20) "Phenylurea fungicides" (FRAC code 20) are proposed to affect cell division. An example is pencycuron.

[0299] (b21) "Quinone internal inhibitor (QiI) fungicides" (FRAC code 21) inhibit fungal complex III mitochondrial respiration by affecting ubiquinone reductase. The reduction of ubiquinone is mediated by cytochrome b, which is located in the inner mitochondrial membrane of fungi. c1 The "quinone interior" (Qi ) site. Inhibition of mitochondrial respiration prevents normal fungal growth and development. Quinone internal inhibitor fungicides include cyanoimidazole fungicides and sulfamoyltriazole fungicides. Cyanoimidazoles include cyazofamid. Sulfamoyltriazoles include amisulbrom.

[0300] (b22) "Benzamide and thiazolecarboxamide fungicides" (FRAC code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, intracellular transport, and cellular structure. Benzamides include zoxamide. Thiazolecarboxamides include ethaboxam.

[0301] (b23) "Enopyranuronic acid antibiotic fungicides" (FRAC code 23) inhibit fungal growth by affecting protein biosynthesis. An example is blasticidin-S.

[0302] (b24) "Hexopyranosyl antibiotic fungicides" (FRAC code 24) inhibit fungal growth by affecting protein biosynthesis. Examples include kasugamycin.

[0303] (b25) "Glucopyranosyl antibiotics: protein synthesis fungicides" (FRAC code 25) inhibit fungal growth by affecting protein biosynthesis. Examples include streptomycin.

[0304] (b26) "Glucopyranosyl antibiotics: trehalase and inositol biosynthesis fungicides" (FRAC code 26) inhibit the biosynthesis of trehalose and inositol. Examples include validamycin.

[0305] (b27) "Cyanoacetamide oxime fungicides" (FRAC code 27) include cymoxanil.

[0306] (b28) "Cargamete fungicides" (FRAC code 28) are considered to be multisite inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in the cell membrane, which then disrupts the permeability of the cell membrane. Propamacarb, iodocarb, and prothiocarb are examples of this fungicide class.

[0307] (b29) "Oxidative phosphorylation uncoupling fungicides" (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibition of respiration prevents normal fungal growth and development. This class includes 2,6-dinitroanilines (e.g., fluazinam) and dinitrophenylcrotonates (e.g., dinocap, meptyldinocap, and binapacryl).

[0308] (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.

[0309] (b31) "Carboxylic acid fungicides" (FRAC code 31) inhibit fungal growth by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). An example is oxolinic acid.

[0310] (b32) "Heteroaromatic fungicides" (Fungicide Resistance Action Committee (FRAC) code 32) are proposed to affect DNA / ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. Isoxazoles include hymexazole, and isothiazolones include octhilinone.

[0311] (b33) "Phosphonate fungicides" (FRAC code 33) include phosphorous acid and its various salts (for example fosetyl-aluminum).

[0312] (b34) "Phthalamic acid fungicides" (FRAC code 34) include tecloftalam.

[0313] (b35) "Benzotriazine fungicides" (FRAD code 35) include triazoxide.

[0314] (b36) "Benzene-sulfonamide fungicides" (FRAC code 36) include flusulfamide.

[0315] (b37) "Pyridazinone fungicides" (FRAC code 37) include diclomedine.

[0316] (b38) "Thiophene-carboxamide fungicides" (FRAC code 38) have been proposed to affect ATP production. An example is silthiofam.

[0317] (b39) "Complex I NADH oxidoreductase inhibitor fungicides" (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidinamines such as diflumetrim and pyrazole-5-carboxamides such as tolfenpyrad.

[0318] (b40) "Carboxylic acid amide (CAA) fungicides" (FRAC code 40) inhibit cellulose synthesis, thereby preventing the growth and killing of target fungi. Carboxylic acid amide fungicides include cinnamic acid amide fungicides, valinamide fungicides, and other carbamate fungicides, as well as mandelamide fungicides. Cinnamic acid amides include dimethomorph, flumorph, and pyrimorph (3-(2-chloro-4-pyridinyl)-3-[4-(1,1-dimethylethyl)phenyl]-1-(4-morpholinyl)-2-propen-1-one). Valinamides and other carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb (2,2,2-trifluoroethyl N-[(1S)-2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate), and valifenalate (methyl N-[(1-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)-β-alaninate) (also known as valifenal). Mandelic acid amides include: mandipropamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, and N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

[0319] (b41) "Tetracycline antibiotic fungicides" (RFAC code 41) inhibit fungal growth by affecting protein synthesis. Examples include oxytetracycline.

[0320] (b42) "Thiocarbamate fungicides" (FRAC code 42) include metasulfocarb.

[0321] (b43) "Benzamide fungicides" (FRAC code 43) inhibit fungal growth by delocalizing spectrin-like proteins. Examples include pyridinylmethylbenzamide fungicides such as fluopicolide (now FRAC code 7, pyridinylethylbenzamide).

[0322] (b44) "Microbial fungicides" (FRAC code 44) disrupt the cell membrane of fungal pathogens. Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains QST 713, FZB24, MB1600, and D747, and the fungicidal lipopeptides they produce.

[0323] (b45) "Q x "Fungicide" (FRAC code 45) is a fungicide that inhibits cytochrome b c1 Complex unknown (Q x Q inhibits fungal complex III mitochondrial respiration by affecting ubiquinone reductase at the mitochondrial respiration site. Inhibition of mitochondrial respiration prevents normal fungal growth and development. x Fungicides include triazolopyrimidylamines such as ametoctrazine (5-ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine).

[0324] (b46) "Plant extract fungicides" are proposed to act by disrupting cell membranes. Plant extract fungicides include terpene hydrocarbons and terpene alcohols (e.g., extracts from Melaleuca alternifolia (tea tree)).

[0325] (b47) "Host plant defense induction fungicides" (FRAC code P) induce host plant defense mechanisms. Host plant defense induction fungicides include benzothiadiazole fungicides, benzisothiazole fungicides, and thiadiazole-carboxamide fungicides. Benzothiadiazoles include acibenzolar-S-methyl. Benzisothiazoles include probenazole. Thiadiazole-carboxamides include thiadianils and isotianils.

[0326] (b48) "Multi-site contact-active fungicides" inhibit fungal growth through multiple sites of action and have contact / preventive activity. This class of fungicides includes: (b48.1) "copper fungicides" (FRAC code M1), (b48.2) "sulfur fungicides" (FRAC code M2), (b48.3) "dithiocarbamate fungicides" (FRAC code M3), (b48.4) "phthalimide fungicides" (FRAC code M4), (b48.5) "chloronitrile fungicides" (FRAC code M5), (b48.6) " "Sulfamide fungicides" (FRAC code M6), (b48.7) multi-site contact "guanidine fungicides" (FRAC code M7), (b48.8) "triazine fungicides" (FRAC code M8), (b48.9) "quinone fungicides" (FRAC code M9), (b48.10) "quinoxaline fungicides" (FRAC code M10), and (b48.11) "maleimide fungicides" (FRAC code M11). "Copper fungicides" are inorganic compounds containing copper, typically in the copper(II) oxidation state, examples of which include copper oxychloride, copper sulfate, and copper hydroxide (e.g., compositions such as Bordeaux's mixture (tribasic copper sulfate)). "Sulfur fungicides" are inorganic chemicals containing a ring or chain of sulfur atoms, examples of which include elemental sulfur. "Dithiocarbamate fungicides" contain a dithiocarbamate molecular moiety, and examples include mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb, and ziram. "Phthalimide fungicides" contain a phthalimide molecular moiety, and examples include folpet, captan, and captafol. "Chloronitrile fungicides" contain chloro- and cyano-substituted aromatic rings, and examples include chlorothalonil. "Sulfamide fungicides" include dichlofluanid and trifluanid. Multi-site contact "guanidine fungicides" include guazatine, iminoctadine arbesylate, and iminoctadine triacetate. "Triazine fungicides" include anilazine. "Quinone fungicides" include dithianon. "Quinoxaline fungicides" include quinomethionate (also known as chinomethionate)."Maleimide fungicides" include fluoroimides.

[0327] (b49) "Fungicides other than those of classes (b1) to (b48)" include certain fungicides whose mode of action may be unknown, such as (b49.1) "phenyl-acetamide fungicides" (FRAC code U6), (b49.2) "aryl-phenyl-ketone fungicides" (FRAC code U8), (b49.3) "guanidine fungicides" (FRAC code U12), (b49.4) "thiazolidine fungicides" (FRAC code U13), (b49.5) "pyrimidinone-hydrazone fungicides" (FRAC code U14), and (b49.6) compounds that bind to oxysterol-binding proteins, as described in WO 2013 / 009971. Phenylacetamides include cyflufenamid and N-[[(cyclopropylmethoxy)-amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide. Arylphenylketones include benzophenones such as metrafenone and benzoylpyridines such as pyriophenone (5-chloro-2-methoxy-4-methyl-3-pyridinyl) (2,3,4-trimethoxy-6-methylphenyl)methanone. Quanidines include dodine. Thiazolidines include fluthianil ((2Z)-2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile). Pyrimidinonehydrazones include ferimzone. The (b49.6) class includes: oxathiapiproline (1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone), and its R-enantiomer 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-Dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (Registration No. 1003319-79-6). The (b49) class also includes: bethoxadin, flometoquin (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), fluoroimide, neo-asodine (ferric methanearsonate), picarbutrazox (1,1-dimethylethyl N-[6-[[[[((Z)-1-methyl-1H-tetrazol-5-yl)phenylmethylene]-amino]oxy]-methyl]-2-pyridinyl]carbamate), pyrrolnitrin, quinomethionate, tebufloquine (6-(1,1-dimethylethyl)-8-fluoro-2,3-dimethyl-4-quinolinyl acetate), tolnifanide (N-(4-chloro-2-)nitro-phenyl)-N-ethyl-4-methylbenzenesulfonamide), 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-yl, N-[6-[[[[(1-methyl-1H-tetrazole- 5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide), N'-[4-[4-chloro-3-(trifluoromethyl)-phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimid-amide, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']-dipyrrole-1,3,5,7(2H,6H)-Tetrone, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-fluoro-phenyl)methoxy]-4-pyrimidinamine, and 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, pentyl N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenyl-methylene]amino]oxy]methyl]-2-pyridinyl]carbamate, pentyl N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)-phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate, and pentyl N-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate. The (b46) class further includes fungicides that inhibit mitosis and cell division, in addition to those in the specific classes above (e.g., (b1), (b10), and (b22)).

[0328] Further "fungicides other than those of classes (1) to (46)", whose mode of action may be unknown or cannot yet be classified, include fungicide compounds selected from components (b49.7) to (b49.13), as shown below.

[0329] Component (b49.7) is the formula b49.7 [ka] [In the formula, R b1 but, [ka] is] The present invention relates to the compound

[0330] Examples of compounds of formula b49.7 include: (b49.7a) (2-chloro-6-fluorophenyl)-methyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate (Registry No. 1299409-40-7), and (b49.7b) (1R)-1,2,3,4-tetrahydro-1-naphthalenyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate (Registry No. 1299409-42-9). Methods for preparing compounds of formula b46.2 are described in WO 2009 / 132785 and WO 2011 / 051243.

[0331] Component (b49.8) is given by formula 49.8 [ka] [In the formula, R b2 is CH3, CF3, or CHF2; R b3 is CH3, CF3, or CHF2; R b4 is halogen or cyano; and n is 0, 1, 2, or 3. The present invention relates to the compound

[0332] Examples of compounds of formula b49.8 include (b49.8a) 1-[4-[4-[5-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone. Methods for preparing compounds of formula b49.8 are described in PCT Patent Application No. PCT / US11 / 64324.

[0333] The component (b4799) is the formula b49.9 [ka] [In the formula, R b5 is -CH2OC(O)CH(CH3)2, -C(O)CH3, -CH2OC(O)CH3, -C(O)OCH2CH(CH3)2, or [ka] is] The present invention relates to the compound

[0334] Examples of compounds of formula b49.9 include: (b49.9a) [[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 (Registration No. 517875-34-2; generic name fenpicoxamid), (b49.9b) (3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-Methylpropanoate (Registry No. 234112-93-7), (b49.9c) (3S,6S,7R,8R)-3-[[[3-[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-Methylpropanoate (Registry No. 517875-31-9), (b49.9d) (3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methyl-propoxy)carbonyl]oxy]-2-pyridinyl]carbonyl]amino]6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-Methyl-propanoate (Registry No. 328256-72-0), and (b49.9e) N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)L-arabinonoyl]-L-serine, (1→4')-lactone (Registry No. 1285706-70-8). Methods for preparing compounds of formula b49.9 are described in WO 99 / 40081, WO 2001 / 014339, WO 2003 / 035617, and WO 2011044213.

[0335] Component (b.49.10) is given by formula b49.10 [ka] [In the formula, R b6 is H or F, and R b7 is -CF2CHFCF3 or -CF2CF2H]

[0049] Examples of compounds of formula b49.10 are (b49.10a) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoro-propoxy)-phenyl]-1-methyl-1H-pyrazole-4-carboxamide (registry number 1172611-40-3) and (b49.10b) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide (registry number 923953-98-4). Compounds of formula 49.10 can be prepared by the methods described in WO 2007 / 017450.

[0336] Component b49.11 is the formula b49.11 [ka] [In the formula, R b8 is halogen, C1-C4 alkoxy, or C2-C4 alkynyl; R b9 is H, halogen, or C1-C4 alkyl; R b10 However, C1~C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Alkoxy, C2-C 12 Alkoxyalkyl, C2-C 12 Alkenyl, C2-C 12 Alkynyl, C4-C 12 Alkoxyalkenyl, C4-C 12 Alkoxyalkynyl, C1-C 12 Alkylthio or C2-C 12 is alkylthioalkyl; R b11 is methyl or -Yb13 -R b12 and; R b12 is C1-C2 alkyl; Y b13 is CH2, O, or S] The present invention relates to the compound

[0337] Examples of compounds of formula b49.11 include: (b49.11a) 2-[(3-bromo-6-quinolinyl)-oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide, (b49.11b) 2[(3-ethynyl-6-quinolinyl)oxy]-N-[1(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide, (b49.11c) N-(1, 1-Dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide, (b49.11d) 2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2-(methylthio)acetamide, and (b49.11e) 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butanamide. Compounds of formula b49.11, their use as fungicides, and methods for preparation are generally known, see, for example, WO 2004 / 047538, WO 2004 / 108663, WO 2006 / 058699, WO 2006 / 058700, WO 2008 / 110355, WO 2009 / 030469, WO 2009 / 049716, and WO 2009 / 087098.

[0338] Component 49.12 is related to N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, which is thought to inhibit C24-methyltransferase involved in sterol biosynthesis.

[0339] Ingredient 49.13 relates to (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (registration number 1961312-55-9, generic name florylpicoxamide), which is believed to be a quinone internal inhibitor (QiI) fungicide (FRAC code 21) that inhibits fungal complex III mitochondrial respiration.

[0340] Accordingly, of note are mixtures (i.e., compositions) comprising a compound of Formula 1 and at least one fungicidal compound selected from the group consisting of classes (1) to (49) described above. Also of note are compositions comprising the mixtures (in a fungicidally 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 a compound of Formula 1 and at least one fungicidal compound selected from the group of specific compounds listed above in connection with classes (1) to (49). Also of particular note are compositions comprising the mixtures (in a fungicidally effective amount) and further comprising at least one additional surfactant selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0341] Examples of component (b) fungicides include acibenzolar-S-methyl, aldimorph, ametoctrazine, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (e.g., benalaxyl-M), benodanil, benomyl, benthiavalicarb (e.g., benthiavalicarb-isopropyl), benzovindiflupyr, bethoxadin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captan, carbendazim, and carboxymethyl. Cin, carpropamid, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper hydroxide, copper oxychloride, copper sulfate, comoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomedine, dicloran, diethofencarb, difenoconazole, diflumetrim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole (e.g. diniconazole-M), dinocap, dithianon, dithiolane, dodemorph, dodine, econazole , edifenphos, enoxastrobin (also known as enestrobrin), epoxiconazole, etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, phenaminestrobin, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, ferbam, ferimzone, flometoquin, florylpicoxamide, Fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, flumorph, fluopicolide, fluopyram, fluorimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, phthalide, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hymexazole, imazalil, imibenconazole, iminooctadine albesilate, iminooctadine triacetate, iodocarb,Ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isofetamide, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandepropamide, mandestrobin, maneb, mepanipyrim, mepronil, meptyldinocap, metalaxyl (e.g., metalaxyl-M / mefenoxam), mefentrifluconazole, metconazole, methasulfocarb, metiram, metominostrobin, metrafenone, miclobutanil, naftifi Neo-Asozin, Nuarimol, Octilinone, Ofurace, Orysastrobin, Oxadixyl, Oxathiapiprolin, Oxolinic Acid, Oxpoconazole, Oxycarboxin, Oxytetracycline, Pefurazoate, Penconazole, Pencycuron, Penflufen, Penthiopyrad, Phosphorous Acid (including its salts, e.g., Fosetyl-aluminum), Picarbtrazox, Picoxystrobin, Piperalin, Polyoxin, Probenazole, Prochloraz, Procymidone, Propamocarb, Propiconazole, Propineb, Proximidine Nadid, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriophenone, pyrisoxazole, pyroquinone, pyrrolnitrin, quinconazole, quinmethionate, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquine, tecloftalam, tecnazene, terbinafine, tetraconazole, thiazolinone, Bendazole, thifluzamide, thiophanate, thiophanate-methyl, thyram, tiadinil, tolclofos-methyl, tolnifanide, tolprocarb, trifluanid, triadimefon, triadimenol, triarimol, triticonazole, triazoxide, tribasic copper sulfate, tricyclazole, triclopiricarb, tridemorph, trifloxystrobin, triflumizole, triforine, trimorphamide, uniconazole, uniconazole-P, validamycin, valifenalate (also known as valifenal), Vinclozolin, zineb, ziram, zoxamide, (3S,6S,7R,8R)-3-[[[3-[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-methyl-propanoate, (3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-Methylpropanoate, N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)-L-arabinonoyl]-L-serine, (1→4')-lactone, N-[2-(1S,2R)-[1,1'-bicyclopropyl]-2-yl phenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)-butanamide, 2-[(3-bromo-8-methyl-6-quinolin linyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2(methylthio)acetamide, 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-yl N-[6-[[[[(1-methyl-1H-tetra-zol-5-yl)-phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)-ethyl]-1H-1,2,4-triazole-1-ethanol, 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, (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-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydr r-3H-1,2,4-triazole-3-thione, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole, 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine, (2-chloro-6-fluorophenyl)methyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-triazolecarboxylate, N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[( N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluoro-phenyl]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, 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3 ,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, 5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-quinazolinamine, 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1 H-pyrazole-4-carboxamide, 1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinol) 2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide, 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine, (3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-Dioxonan-7-yl-2-methylpropanoate, α(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, [[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, pentyl N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, pentyl N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate, and pentyl N-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, and (1R)-1,2,3,4-tetrahydro-1-naphthalenyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate. Of note, therefore, is a fungicidal composition comprising a compound of formula 1 (or its N-oxide or salt) as component (a) and at least one fungicide selected from the foregoing list as component (b).

[0342] Of particular note are combinations of a compound of formula 1 (or an N-oxide or salt thereof) (i.e., component (a) in the composition) with the following (i.e., as component (b) in the organism): azoxystrobin, benzovindiflupyr, bixafen, captan, carpropamid, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, diethofencarb, difenoconazole, dimethomorph, epoxiconazole, ethaboxam, fenarimol, fenhexamid, Fluazinam, fludioxonil, fluindapir, fluopyram, flusilazole, flutianil, flutriafol, fluxapyroxad, folpet, iprodione, isofetamide, isopyrazam, kresoxim-methyl, mancozeb, mandestrobin, meptyldinocap, metalaxyl (e.g., metalaxyl-M / mefenoxam), mefentrifluconazole, metconazole, metrafenone, myclobutanil, oxathiapiprolin, penflufen, penthiopyrad, phosphorous acid (those salts, e.g., fosetyl-aluminum), picoxystrobin, propiconazole, proquinazide, prothioconazole, pyraclostrobin, pyrimethanil, sedaxane, spiroxamine, sulfur, tebuconazole, thiophanate-methyl, trifloxystrobin, zoxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)-ethyl]-1H-1,2,4-triazole-1-ethanol, 2-[2-(1-chlorocyclopropyl)-4-(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-inden-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-pyrazol-1-yl]-ethanone, 1,1-dimethylethyl N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemeth ol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole.

[0343] Examples of other biologically active compounds or agents that may be formulated with the compounds of the present invention are invertebrate pest control compounds or agents, such as abamectin, acephate, acetamiprid, acrinathrin, afidopyropen ([(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]methyl cyclopropanecarboxylate), Amidoflumet (S-1955), Avermectin, Azadirachtin, Azinphos-methyl, Bifenthrin, Bifenazate, Buprofezin, Cal Bofuran, 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 proline (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, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flubendiamide, flucythrinate, 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), flupiprole (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), flupyradifurone (4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonofos, halofenozide, heptafluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, meperfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, milbemycin oxime, monfluothrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate), monocrotophos, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron (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, phosalone, phos Met, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrins, pyridalyl, pyrifluquinazone, pyriminostrobin (methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate), pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulfoxaflor, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, and triflumuron; and biological agents, such as entomopathogenic bacteria, for example, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, and Bacillus Encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); insect pathogenic fungi, such as Mycoplasma nigra; and insect pathogenic viruses, such as baculoviruses, nuclear polyhedrosis viruses (NPVs), such as HzNPV and AfNPV; and granulosis viruses (GVs), such as CpGV.

[0344] The compounds and compositions of the present invention can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis delta-endotoxin). The effects of exogenously applied fungicidal compounds of the present invention can be synergized by the expressed toxin protein.

[0345] General references on agricultural protection agents (i.e., insecticides, fungicides, nematicides, acaricides, herbicides, and biological agents) include The Pesticide Manual, 13th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003 and The BioPesticide Manual, 2004. nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0346] In embodiments employing one or more of these various mixing partners, the weight ratio of these various mixing partners (combined) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). Those skilled in the art can easily determine by simple experimentation the biologically effective amount of active ingredient required to achieve the desired spectrum of biological activity. It will be apparent that the inclusion of these additional components can broaden the spectrum of disease control beyond that achieved by the compound of Formula 1 alone.

[0347] In certain cases, the combination of the compound of the present invention with other biologically active (especially fungicidal) compounds or agents (i.e., active ingredients) can produce a superadditive (i.e., synergistic) effect.It is always desirable to reduce the amount of active ingredient released into the environment while ensuring effective pest control.When the synergistic effect of fungicidal active ingredients is manifested at an application rate that provides an agriculturally satisfactory level of fungal control, such a combination can be advantageous for reducing crop production costs and reducing environmental burdens.

[0348] Also, in certain cases, combinations of the compounds of the present invention with other biologically active compounds or agents may result in less-than-additive (i.e., safer) effects on beneficial organisms in agricultural environments. 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 pesticides.

[0349] Notable fungicides that can be formulated with the compounds of Formula 1 to provide mixtures useful in seed treatment include, but are not limited to, amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, florylpicoxamide, fluazinam, fludioxonil, flufenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, mefentrifluconazole, metconazole, myclobutanil, paclobutrazol, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thyram, trifloxystrobin, and triticonazole.

[0350] Invertebrate pest control compounds or agents that can be formulated with the compounds of Formula 1 to produce mixtures useful in seed treatments include, but are not limited to, abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cinnamyl benzoate ... Antraniliprole, cyclaniprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fi Pronil, flonicamid, flubendiamide, fluensulfone, flufenoxuron, fluhyprol, flupyradifuron, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, monofluorothrin, nitenpyram, nithiazine, novaluron, oxamyl, pifur bumide, pymetrozine, pyrethrins, pyridaben, pyriminostrobin, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis delta-endotoxin, strains of Bacillus thuringiensis, and strains of Nucleopolyhydrosis virus.

[0351] Compositions containing a compound of Formula 1 useful for seed treatment may further include bacteria and fungi capable of protecting against the harmful effects of plant pathogenic fungi or bacteria and / or soil-borne animals, such as nematodes. Bacteria that exhibit nematicidal properties include, but are not limited to, Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria penetrans. Suitable Bacillus firmus strains include strain CNCM I-1582 (GB-126), available from BioNem. TM It is commercially available as a Bacillus cereus strain. A suitable Bacillus cereus strain is strain NCMM I-1592. Both Bacillus strains are disclosed in U.S. Patent No. 6,406,690. Other suitable bacteria that exhibit nematicidal activity are B. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteria that exhibit fungicidal properties include, but are not limited to, B. pumilus strain GB34. Fungal species that exhibit nematicidal properties include, but are not limited to, Myrotheciium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum.

[0352] Seed treatments may also include one or more nematicides of natural origin, such as an inducer protein called a harpin, which is isolated from certain bacterial plant pathogens, such as Erwinia amylovora. Examples include N-Hibit TM and Harpin-N-Tek seed treatment technology available as Gold CST.

[0353] Seed treatments can also include one or more species of legume-root nodulating bacteria, such as the microsymbiotic nitrogen-fixing bacterium Bradyrhizobium japonicum. These inoculants can optionally include one or more lipochitooligosaccharides (LCOs), which are nodulation (Nod) factors produced by Rhizobia bacteria during the initiation of nodulation on legume roots. For example, Optimize® brand seed treatment technology uses LCO Promoter Technology in combination with an inoculant. TM It incorporates the following.

[0354] Seed treatments can also include one or more isoflavones, which can increase the level of root colonization by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by increasing root uptake of nutrients such as water, sulfate, nitrate, phosphate, and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin, and pratensein. Formononetin is available as an active ingredient in mycorrhizal inoculant products such as PHC Colonize® AG.

[0355] The seed treatment may also include one or more plant activators that induce systemic acquired resistance in the plant after contact with the pathogen. An example of a plant activator that induces such a protective mechanism is acibenzolar-S-methyl.

[0356] The following tests demonstrate the control efficacy of the compounds of the present invention against specific pathogens. However, the pathogen control protection provided by the compounds is not limited to these species. See Tables A and B below for compound descriptions. The abbreviation "Cmpd." stands for "Compound," and the abbreviation "Ex." stands for "Example," followed by a number indicating which example compound was prepared. The number reported in the "MS" column indicates the H in the molecule with the highest isotopic abundance. + is the molecular weight (M+1) of the highest isotopically abundant positively charged parent ion formed by adding H + The molecular weight (M-1) of the negatively charged ion of highest isotopically abundant formed by the reduction of one or more higher atomic mass isotopes (e.g., 37 Cl, 81 The presence of molecular ions containing Br) is not reported. The reported MS peaks were observed by mass spectrometry using electrospray ionization (ESI) or atmospheric pressure chemical ionization (PCI).

[0357] [Table 5]

[0358] [Table 6]

[0359] [Table 7]

[0360] [Table 8]

[0361] [Table 9]

[0362] [Table 10]

[0363] [Table 11]

[0364] [Table 12]

[0365] Biological Examples of the Invention General protocol for preparing test suspensions for Tests A-F: Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume, then suspended at the desired concentration (ppm) in acetone and purified water containing 250 ppm of the surfactant PEG400 (polyhydric alcohol ester) (50 / 50 mix by volume). The resulting test suspensions were then used in Tests A-F.

[0366] Test A The test solution was sprayed onto wheat seedlings until runoff. The next day, the seedlings were inoculated with a spore suspension of Zymoseptoria tritici (the causative agent of wheat leaf blight) and incubated for 48 hours at 24°C in a saturated atmosphere, then transferred to a growth chamber at 20°C for 17 days, after which time-course disease assessments were performed.

[0367] Test B The test solution was sprayed onto wheat seedlings until runoff. The next day, the seedlings were inoculated with a spore suspension of Puccinia recondita f.sp. tritici (cause of wheat leaf rust) and incubated for 24 hours at 20°C in a saturated atmosphere, then transferred to a growth chamber at 20°C for 7 days, after which time-course disease assessments were performed.

[0368] Test C The test suspension was sprayed onto wheat seedlings until runoff. The next day, the 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) and incubated in a growth chamber at 20°C for 8 days, after which time-dependent visual disease assessments were made.

[0369] Test D The test solution was sprayed onto soybean seedlings until runoff. The next day, the seedlings were inoculated with a spore suspension of Phakopsora pachyrhizi (the causal agent of soybean rust) and incubated for 24 hours at 22°C in a saturated atmosphere, then transferred to a growth chamber at 22°C for 8 days, after which time-dependent visual disease assessments were made.

[0370] Test E The test suspension was sprayed onto tomato seedlings until runoff. The next day, the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of tomato botrytis disease) and incubated for 48 hours at 20°C in a saturated atmosphere, then transferred to a growth chamber at 24°C for 3 days, after which time-dependent visual disease assessments were made.

[0371] Test F The test suspension was sprayed onto tomato seedlings until runoff. The next day, the seedlings were inoculated with a spore suspension of Alternaria solani (the causal agent of tomato leaf blight) and incubated for 48 hours at 27°C in a saturated atmosphere, then transferred to a growth chamber at 20°C for 3 days, after which time-course disease assessments were performed.

[0372] The results of tests A-F are shown in Table A below. A rating of 100 indicates 100% disease control, a rating of 0 indicates no disease control (compared to the control). A dash (-) indicates that the compound was not tested.

[0373] [Table 13]

[0374] [Table 14]

[0375] [Table 15]

[0376] [Table 16]

[0377] [Table 17]

[0378] [Table 18]

[0379] [Table 19]

Claims

1. Formula 1 【Chemical 1】 and tautomers, N-oxides, and salts thereof selected from During the ceremony, W is O; R 1 But C 1 ~C2 alkyl, C 3 to C4 cycloalkyl, or C 2 -C3 cyanoalkyl; R 2 H, halogen, cyano, C 1 ~C2 alkyl, C 1 ~C2 haloalkyl, C 1 to C2 alkoxy, or C 1 -C haloalkoxy; p is 0 or 1; The dotted lines in Formula 1 represent optional bonds, provided that said optional bond is present when p is 0 and said optional bond is absent when p is 1; R 3 is H, methyl, or ethyl; Each R 4 and R 5 are independently cyano, nitro, or halogen; or C 1 ~C 3 Alkyl, C 2 ~C 3 Alkenyl, C 2 ~C 4 Cyanoalkyl, C 1 ~C 3 Alkoxy, C 2 ~C 4 Alkenyloxy or C 2 ~C 4 cyanoalkoxy, each optionally substituted with up to three substituents independently selected from halogen; or -UVT: each U is independently a direct bond, O, or NH; each V is independently CH2, CH2CH2, or C(=O); Each T is independently NR 7a R 7b OR 8 and Each R 7a and R 7b However, independently, H, C 1 ~C2 alkyl, C 1 -C haloalkyl, or cyclopropyl; each R 8 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 haloalkylcarbonyl, or C 2 -C 6 alkoxycarbonyl; m and n are each independently 1 to 3; At least one of R 4 or R 5 is in the ortho position; The compounds, their tautomers, N-oxides, and salts.

2. R3 is H or methyl; Each R 4 and R 5 is independently cyano or halogen; or C 1 ~C 2 Alkyl or C 1 ~C 2 2. The compound of claim 1, wherein the aryl group is -C, -D, or -E.

3. The compound of claim 1, wherein the aryl group is -C, -D, or -E.

3. R 1 is methyl, ethyl, cyclopropyl, or —CH 2 C≡N; R 2 H, halogen, C 1 ~C 2 alkyl, or methoxy; p is 0, Each R 4 and R 5 is independently halogen or methoxy; The compound of claim 2.

4. R 1 is methyl; R 2 is Br, Cl, methyl, ethyl, or methoxy; Each R 4 and R 5 is independently Br, Cl, F, or methoxy; m is 2, and R 4 The substituents are attached at the 2- and 6-positions; or m is 2 and R 4 the substituents are attached at the 2- and 4-positions; n is 2, and R 5 The substituents are attached at the 2- and 4-positions; or n is 2 and R 5 The substituents are attached at the 2- and 5-positions; or n is 2 and R 5 The substituents are attached at the 2- and 6-positions; or n is 3 and R 5 the substituents are attached at the 2-, 3-, and 5-positions; The compound of claim 3.

5. R 2 is Cl, methyl, ethyl, or methoxy; Each R 4 is independently Cl or F; Each R 5 is independently Br, Cl, F, or methoxy; The compound of claim 4.

6. R 2 is Cl or methyl; Each R 5 is independently Cl, F, or methoxy; The compound of claim 5.

7. The following groups: 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone; 4-chloro-6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl) (fluorophenyl)-2-methyl-3(2H)-pyridazinone; 5,6-bis(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone; 4-chloro-6-(2-chloro-5-methoxyphenyl)-5-(2,6-difluorophenyl)-2-methyl-3(2H)-pyridazinone; 4-chloro-6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone; 6-(2-bromo-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone; 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone; 6-(2-chloro-5-methoxyphenyl)-5-(2,6-difluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone; 6-(2-bromo-3,5-dimethoxyphenyl)-4-chloro-5-(2-chloro-4-fluorophenyl)-2-methyl-3(2H)-pyridazinone; 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2-chloro-4-fluorophenyl)-4-methoxy-2-methyl-3(2H)-pyridazinone; 4-chloro-5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methoxyphenyl)-2-methyl-3(2H)-pyridazinone; 5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methoxyphenyl)-2,4-dimethyl-3(2H)-pyridazinone; 5-(2-chloro-4-fluorophenyl)-6-(2-chloro-5-methoxyphenyl)-4-ethyl-2-methyl-3(2H)-pyridazinone; 6-(2-chloro-5-methoxyphenyl)-5-(2,6-difluorophenyl)-4-ethyl-2-methyl-3(2H)-pyridazinone; and 6-(2-chloro-3,5-dimethoxyphenyl)-5-(2,6-difluorophenyl)-2,4-dimethyl-3(2H)-pyridazinone 2. The compound of claim 1 selected from:

8. 10. A fungicidal composition comprising: (a) a compound of claim 1; and (b) at least one other fungicide.

9. 10. A fungicidal composition comprising: (a) a compound of claim 1; and (b) at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent.

10. 10. A method for controlling plant diseases caused by fungal plant pathogens, comprising applying to a plant or part thereof, or to a plant seed, a fungicidally effective amount of a compound of claim 1.

11. The compound according to claim 1, wherein R 1 is methyl; R2 is Br, Cl, cyano, methyl, or ethyl; p is 0; each R 4 is independently Cl, F, or methoxy; each R5 is independently Br, Cl, F, or methoxy; The compound of claim 1.

12. A compound of the following group: 【Chemistry 2】 Selected from: The compound of claim 1.

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