Fungicidal mixtures containing pyrazole derivatives

Abstract

Disclosed is a fungicidal composition comprising: (a) at least one compound selected from the group consisting of compounds of Formula 1, including all geometric and stereoisomers, tautomers, N-oxides, and salts thereof, (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , m and n are as defined in the disclosure, and (b) at least one additional fungicidal compound. Also disclosed is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or plant seed, a fungicidally effective amount of a compound of Formula 1, N-oxide, or salt thereof (e.g., as a component in the above composition). Also disclosed is a composition comprising: (a) at least one compound selected from the group consisting of the above-mentioned compounds of Formula 1, N-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.

Description

TECHNICAL FIELD

[0001] The present invention relates to certain pyrazoles, N-oxides, salts thereof, and to mixtures and compositions comprising such halomethyl ketone and hydrate derivatives and methods of using such halomethyl ketone and hydrate derivatives and mixtures and compositions thereof as fungicides. BACKGROUND

[0002] Controlling plant diseases caused by fungal plant pathogens is of utmost importance to achieve high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant yield loss and thus result in increased costs to the consumer. In addition to often being highly destructive, plant diseases can be difficult to control and can develop resistance to commercial fungicides. Many products are commercially available for these purposes, but there is a continuing need for new fungicidal compounds that are more effective, less costly, less toxic, more environmentally safe, or have different sites of action. In addition to the introduction of new fungicides, combinations of fungicides are often used to promote disease control, expand the spectrum of control, and delay the development of resistance. Furthermore, certain rare fungicide combinations exhibit more than additive (i.e., synergistic) action to provide commercially important levels of plant disease control. The advantages of particular fungicide combinations are recognized in the art to be different, depending on factors such as the particular plant species and plant disease to be treated, and whether the plant is treated before or after infection by the fungal plant pathogen. Thus, there is a need for new advantageous combinations to provide various options to best meet the particular plant disease control needs. Such combinations have now been discovered.

[0003] PCT Patent Publications WO 2018 / 052838, WO 2013 / 192126, WO 2012 / 031061, and WO 2010 / 101973 disclose fungicidal pyrazoles and their use in agriculture. PCT Patent Publication WO 2019 / 020981 discloses pyrazole, isothiazole, and isoxazole derivatives and their use in agriculture. SUMMARY

[0004] The present invention relates to a fungicidal composition (i.e., combination) comprising: (a) at least one compound selected from the group consisting of compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof:

[0005]

[0006] wherein

[0007] R 1 is C1-C2 alkyl;

[0008] R 2is cyano, halogen, C1-C2alkyl or C1-C2haloalkyl;

[0009] R 3 is halogen or methyl;

[0010] each R 4 is independently halogen, cyano, nitro, C1-C3alkyl, C1-C3alkoxy, C1-C3haloalkoxy, C2-C6alkenyloxy, C2-C6alkynyloxy, C2-C6cyanoalkoxy, C2-C6alkoxyalkyl or C2-C6alkoxyalkoxy;

[0011] each R 5 is independently halogen, C1-C3alkyl, C2-C6alkoxyalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C2-C6alkenyloxy, C2-C6alkynyloxy, C2-C6cyanoalkoxy or C2-C6alkoxyalkoxy;

[0012] m and n are each independently 0, 1, 2 or 3;

[0013] R 6 is H; or C1-C3alkyl or C1-C3haloalkyl, each optionally substituted with up to 2 substituents independently selected from R 6a ; or amino, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl, CH(=O), S(=O)2OM, S(=O) u R 7 , (C=W)R 8 or OR 9 ;

[0014] each R 6a is independently cyano, C3-C6cycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl or C1-C3alkylsulfonyl;

[0015] M is K or Na;

[0016] u is 0, 1 or 2;

[0017] R 7 is C1-C3alkyl or C1-C3haloalkyl;

[0018] W is O or S;

[0019] R 8 is C1-C3alkyl, C2-C4alkoxyalkyl, C2-C4alkylaminoalkyl, C3-C6dialkylaminoalkyl, C1-C3alkoxy, C1-C3alkylthio or C2-C4alkylthioalkyl;

[0020] R9 H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to two substituents independently selected from R 9a 10

[0021] each R 9a is independently cyano, C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, or C1-C3 alkylsulfonyl; and

[0022] R 10 is C1-C3 alkyl, C2-C4 alkoxyalkyl, C2-C4 alkylaminoalkyl, C3-C6 dialkylaminoalkyl, C1-C3 alkoxy, C1-C3 alkylthio, or C2-C4 alkylthioalkyl; and

[0023] (b) at least one additional fungicidal compound;

[0024] provided that the compound of Formula 1 is not:

[0025] 4-(2,6-difluoro-4-methoxyphenyl)-N-(2,4-difluoro-6-nitrophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0026] 4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-N-(2-nitrophenyl)-1 H-pyrazol-5-amine;

[0027] 4-(2-chloro-4-fluorophenyl)-N-(2,4-difluoro-6-nitrophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0028] 4-(2-chloro-4-fluorophenyl)-3-ethyl-1 -methyl-N-(2-nitrophenyl)-1 H-pyrazol-5- amine;

[0029] 4-(2-chloro-4-fluorophenyl)-1 -methyl-N-(2-nitrophenyl)-3-(trifluoromethyl)- 1 H-pyrazol-5-amine;

[0030] 4-(2,6-difluoro-4-methoxyphenyl)-N-(2-methoxy-6-nitrophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0031] 4-(2-chloro-4-fluorophenyl)-N-(2-methoxy-6-nitrophenyl)-1,3-dimethyl-1 H- pyrazol-5-amine;

[0032] ​​N-(2-chloro-6-nitrophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0033] N-(2-chloro-3-fluoro-6-nitrophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3- dimethyl-1 H-pyrazol-5-amine;

[0034] 4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-N-(2-methyl-6-nitrophenyl)-1 H- pyrazol-5-amine;

[0035] N-(2-bromo-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0036] 4-(2-chloro-4-fluorophenyl)-N-(4-methoxy-2-nitrophenyl)-1,3-dimethyl-1 H- pyrazol-5-amine;

[0037] 4-(2,6-difluoro-4-methoxyphenyl)-N-(4-fluoro-2-nitrophenyl)-1,3-dimethyl-1 H- pyrazol-5-amine;

[0038] 4-(2,6-difluoro-4-methoxyphenyl)-N-(4-methoxy-2-nitrophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0039] N-(4-chloro-2-nitrophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0040] 4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-[2-nitro-4-(2-propyn-1 - yloxy)phenyl]-1 H-pyrazol-5-amine;

[0041] 4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-[2-nitro-4-(2-propen-1 - yloxy)phenyl]-1 H-pyrazol-5-amine;

[0042] N-(4-bromo-2-nitrophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine;

[0043] N-(4-chloro-2-fluoro-6-nitrophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3- dimethyl-1 H-pyrazol-5-amine;

[0044] 3-chloro-4-(2-chloro-4-fluorophenyl)-N-(2,4-difluoro-6-nitrophenyl)-1-methyl-1H- pyrazol-5-amine;

[0045] 4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-[4-methyl-2-nitrophenyl]-1 H- pyrazol-5-amine;

[0046] 4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-N-(4-methyl-2-nitrophenyl)-1 H-pyrazol-5- amine; and

[0047] N-(4-bromo-2-fluoro-6-nitrophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine.

[0048] The present application also relates to a composition comprising: (a) at least one compound selected from the compounds of Formula 1, N-oxides, and salts thereof, described above; and at least one additional compound or agent that controls invertebrate pests.

[0049] The present application also relates to a composition comprising one of the above compositions comprising component (a) and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0050] The present application also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or plant seed, a fungicidally effective amount of one of the above compositions.

[0051] The above method can also be described as a method for protecting a plant or plant seed from disease caused by a fungal pathogen comprising applying to the plant (or portion thereof) or plant seed a fungicidally effective amount of one of the above compositions (directly or through the environment of the plant or plant seed (e.g., the growth medium)).

[0052] The present application also relates to a compound of Formula 1, or an N-oxide or salt thereof, described above. DETAILED DESCRIPTION

[0053] 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 limitation explicitly indicated. For example, a composition, a mixture, a process, a method, an article, or an apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

[0054] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. If used in the claims, this phrase shall cover only those elements as are recited. The transitional phrase "consisting essentially of" shall cover the elements as are recited and such other elements that do not materially affect the basic and novel characteristics of the invention.

[0055] The transitional phrase "consisting essentially of" is used to define compositions, methods or apparatuses that include materials, steps, features, components, or elements in addition to those literally disclosed, so long as these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the invention. The term "consisting essentially of" is intermediate in meaning between "comprising" and "consisting of."

[0056] When the application or a portion thereof is defined by open-ended terms such as "comprising," it should be readily understood (unless otherwise indicated) that the description is to be interpreted to also describe the invention using the terms "consisting essentially of" or "consisting of."

[0057] In addition, unless explicitly stated otherwise, "or" means an inclusive or and not an exclusive or. For example: A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0058] Also, the indefinite articles "a" and "an," as used herein in the specification, unless clearly indicated to the contrary, should be understood to mean "at least one." The singular form "a" or "an" includes plural references unless the numeric quantity clearly dictates otherwise. Thus, for example, reference to "a" or "an" element is a reference to one or more elements.

[0059] The term "agronomy" refers to the production of field crops such as those used for food and fiber, and includes the growth of maize or corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone, and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflower, and olives).

[0060] The term "non-agronomy" refers to applications other than field crops, such as horticultural crops (e.g., greenhouse, nursery, or ornamental plants not grown in a field), residential, agricultural, commercial, and industrial structures, turf (e.g., sod farms, pastures, golf courses, lawns, athletic fields, and the like), wood products, stored products, forestry and vegetation management, public health (i.e., human) and animal health (e.g., domestic animals such as pets, livestock, and poultry, and non-domestic animals such as wildlife).

[0061] The term "crop vigor" refers to the rate of growth or biomass accumulation of a crop plant. An "increase in vigor" refers to an increase in growth or biomass accumulation of a crop plant relative to an untreated control crop plant. The term "crop yield" refers to the return in quantity and quality of crop material obtained after harvesting a crop plant. An "increase in crop yield" refers to an increase in crop yield relative to an untreated control crop plant.

[0062] The term "biologically effective amount" refers to the amount of a biologically active compound (e.g., a compound of Formula 1) that is sufficient to produce a desired biological effect when applied to (i.e., contacted with) a fungus to be controlled or its environment, or a plant, a seed from which the plant grows, or a locus of the plant (e.g., a growth medium) to protect the plant from damage by a fungal disease or for other desired effects (e.g., increasing plant vigor).

[0063] As referred to in the present disclosure and claims, "plants" include members of the plant kingdom at all life stages, particularly Spermatopsida, at all life stages including young plants (e.g., developing seedlings from germinated seeds) and mature, reproductive stages (e.g., flowering and seed-producing plants). Parts of plants include both geotropic members that typically grow below the surface of a growth medium (e.g., soil), such as roots, tubers, bulbs, and corms, and also members that grow above the growth medium, such as leaves (including stems and foliage), flowers, fruits, and seeds.

[0064] As referred to herein, the term "seedling" used alone or in combination with the word "broadleaf" refers to a young plant that develops from the embryo of a seed.

[0065] As referred to herein, the term "broadleaf" used alone or in combination with a word such as "broadleaf crop" refers to a dicotyledon or dicotyledonous plant, a term used to describe a group of angiosperms characterized by embryos with two cotyledons.

[0066] As referred to in the present disclosure, the terms "fungal pathogen" and "fungal plant pathogen" include pathogens in the phyla Ascomycota, Basidiomycota, and Zygomycota, as well as the fungal-like phylum Oomycota, which are causative agents of a broad spectrum of economically important plant diseases affecting ornamental, turf, vegetable, field, cereal, and fruit crops. In the context of the present disclosure, "protecting a plant from disease" or "controlling a plant disease" includes prophylactic action (interrupting the cycle of infection, colonization, symptom development, and spore production of the fungus) and / or therapeutic action (inhibiting colonization of plant host tissues).

[0067] 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 in the biosynthetic pathway of the plant pathogen and their resistance risk. The modes of action defined by FRAC include (A) nucleic acid metabolism, (B) cytoskeletal and motor proteins, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell walls, (P) host plant defense induction, (U) unknown mode of action, (M) chemicals with multiple site activity, and (BM) biological agents with multiple modes of action. Each mode of action (i.e., the letters A through BM) contains one or more subgroups (e.g., A includes subgroups Al, A2, A3, and A4) that are based on individually validated target sites of action, or in cases where the precise target site is unknown, based on cross-resistance characteristics within or with other groups. Each of these subgroups (e.g., Al, A2, A3, and A4) is assigned a FRAC code (number and / or letter). For example, the FRAC code for subgroup Al is 4. Additional information on target sites and FRAC codes can be obtained from, for example, a publicly available database maintained by FRAC.

[0068] As used herein, the term "cross-resistance" refers to the phenomenon that occurs when a pathogen becomes resistant to one fungicide and at the same time becomes resistant to one or more other fungicides. These other fungicides are typically, but not always, of the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.

[0069] Generally, when a molecular fragment (i.e., a radical) is represented by a series of atomic symbols (e.g., C, H, N, O, and S), one or more points of attachment will be readily identified by one of skill in the art. In some instances herein, particularly where an alternative point of attachment is possible, one or more points of attachment can be represented by a hyphen (“-”). For example, “-NCS” indicates that the point of attachment is a nitrogen atom (i.e., isothiocyanato, rather than thiocyanato).

[0070] As used herein, the term “alkylating agent” refers to a compound in which a carbon- containing group is bonded to a leaving group such as a halide or sulfonate ester through a carbon atom, which can be displaced by the bonding of a nucleophile to the carbon atom. Unless otherwise indicated, the term “alkylation” does not limit the carbon-containing group to an alkyl group; carbon-containing groups in alkylating agents include, for example, for R 5 The various carbon-bonded substituent groups designated.

[0071] In the above detailed description, the term “alkyl,” used alone or in compound words such as “alkylthio” or “haloalkyl,” includes straight-chain or branched-chain alkyl groups such as methyl, ethyl, n-propyl, and i-propyl, or the different butyl, pentyl, or hexyl isomers. “Alkenyl” includes straight-chain or branched-chain alkenes such as ethenyl, 1- propenyl, 2-propenyl, and the different butenyl, pentenyl, and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched-chain alkynes such as 1-propynyl, 2-propynyl, and the different butynyl, pentynyl, and hexynyl isomers. “Alkynyl” can also include moieties composed of multiple triple bonds such as 2,5-hexadiynyl.

[0072] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and the various butyloxy, pentyloxy, and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2, and CH3CH2OCH2CH2. "Alkenyloxy" includes straight- or branched-chain alkenyl groups attached to and linked by an oxygen atom. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, CH3CH=CHCH2O, CH3CH=C(CH3)CH2O, and CH2=CHCH2CH2O. "Alkynyloxy" includes straight- or branched-chain alkynyl groups attached to and linked by an oxygen atom. Examples of "alkynyloxy" include HC≡CCH2O, CH3C≡CCH2O, and CH3C≡CCH2CH2O. "Alkoxyalkoxy" denotes alkoxy substitution on another alkoxy moiety. Examples of "alkoxyalkoxy" include CH3OCH2O, CH3OCH2O, and CH3CH2OCH2O.

[0073] "Alkylthio" includes branched- or straight-chain alkylthio moieties, such as methylthio, ethylthio, and the various propylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on an alkyl group. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, and CH3CH2SCH2CH2. "Alkylsulfinyl" includes both enantiomers of alkylsulfinyl. Examples of "alkylsulfinyl" include CH3S(=0), CH3CH2S(=0), CH3CH2CH2S(=0), and (CH3)2CHS(=0). Examples of "alkylsulfonyl" include CH3S(=0)2, CH3CH2S(=0)2, CH3CH2CH2S(=0)2, and (CH3)2CHS(=0)2.

[0074] "Alkylaminoalkyl" denotes alkylamino substitution on an alkyl group. Examples of "alkylaminoalkyl" include CH3NHCH2, CH3NHCH2CH2, CH3CH2NHCH2, CH3CH2CH2CH2NHCH2, and CH3CH2NHCH2CH2. Examples of "dialkylaminoalkyl" include (CH3)2NCH2, (CH3CH2)2NCH2CH2, and CH3CH2(CH3)NCH2CH2.

[0075] The term "cycloalkyl" denotes a saturated carbocyclic ring consisting of between 3 and 6 carbon atoms connected to each other by single bonds. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl group. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight chain or branched alkyl groups.

[0076] The term "halogen", alone or in compound, such as "haloalkyl", or when used in describing substituents such as "alkyl substituted by halogen", includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound, such as "haloalkyl", or when used in describing substituents such as "alkyl substituted by halogen", the alkyl group can be partially or fully substituted by halogen atoms, which can be the same or different. Examples of "haloalkyl" or "alkyl substituted by halogen" include F3C, CICH2, CF3CH2, and CF3CCl2. The term "haloalkoxy" and the like are defined similarly to the term "haloalkyl". Examples of "haloalkoxy" include CF3O, CCl3CH2O, F2CHCH2CH2O, and CF3CH2O.

[0077] "Cyanoalkoxy" denotes an alkoxy group substituted by one cyano group. Examples of "cyanoalkoxy" include NCCH2O, NCCH2CH2O, and CH3CH(CN)CH2O.

[0078] The total number of carbon atoms in a substituent group is designated by the prefix "C i -C j " prefix, wherein i and j are numbers from 1 to 6. For example, C1-C3 alkylsulfonyl denotes methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl denotes CH3OCH2; C3 alkoxyalkyl denotes, for example, CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl denotes the various isomers of an alkyl group substituted by an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2.

[0079] The term "unsubstituted" in relation to a group such as a ring means that the group has no substituents other than its one or more points of attachment to the remainder of Formula 1. The term "optionally substituted" means that the number of substituents can be zero. Unless otherwise indicated, an optionally substituted group can be substituted with as many optional substituents as the available carbon or nitrogen atoms will allow, by replacing a hydrogen atom with a non-hydrogen substituent. Typically, the number of optional substituents, when present, is in the range of from 1 to 3. As used herein, the term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted".

[0080] The number of optional substituents can be subject to explicit limitations. For example, the phrase “optionally substituted with up to 2 substituents independently selected from R 6a

[0081] Unless otherwise indicated, when a compound is substituted with a substituent bearing a subscript that indicates that the number of said substituents can vary (e.g., (R 4 ) m wherein m is 0 to 3), then said substituents are independently selected from the group of substituents defined. When a variable group is shown as optionally attached to a position (e.g., (R 4 ) m wherein m can be 0), then hydrogen can be at that position even though not mentioned in the definition of the variable group.

[0082] The nomenclature of substituents in this disclosure uses accepted terminology to convey chemical structures accurately to those skilled in the art with concision. Position descriptors can be omitted for brevity. In some instances herein, the point(s) of attachment of a substituent (e.g., R 4 and R 5 ) are indicated with position numbers, which can differ from the Chemical Abstracts Service nomenclature system if the difference does not affect the meaning.

[0083] The compounds of the present application can exist as one or more stereoisomers. Stereoisomers are isomers that have the same constitutional (connective) formula, but differ in the arrangement of atoms or groups in space. The present application includes all possible stereoisomers of the compounds of the present application, including but not limited to, enantiomers, diastereomers, cis- and trans-isomers (also known as E- and Z-isomers), and atropisomers. Atropisomers are stereoisomers that arise from hindered rotation about a single bond, where the energy barrier to rotation is high enough to allow separation of the isomers. It will be understood by those skilled in the art that a stereoisomer can be more active and / or can exhibit a beneficial effect when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. Additionally, those skilled in the art know how to isolate, enrich and / or selectively prepare the stereoisomers. For a comprehensive discussion of stereoisomerism see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0084] ​The compounds of the present application can exist as one or more conformational isomers due to restricted rotation about the amide bond (e.g., C(=0)-N) in Formula 1. The present application includes mixtures of conformational isomers. In addition, the present application includes compounds enriched for one conformational isomer relative to other conformational isomers.

[0085] The present application includes all stereoisomers, conformational isomers, and mixtures thereof in all proportions, and isotopic forms such as deuterated compounds.

[0086] Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, as the nitrogen requires an available lone pair to oxidize to an oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are very well known to those skilled in the art, including the use of peroxy acids such as peroxyacetic acid and meta-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and diepoxides such as dimethyldiepoxyethane to oxidize the heterocycle or tertiary amine. These methods for preparing N-oxides have been widely described and reviewed in the literature, see for example: T. L. Gilchrist, Comprehensive Organic Synthesis, Volume 7, pages 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Volume 3, pages 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene, Advances in Heterocyclic Chemistry, Volume 43, pages 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, Volume 9, pages 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk, Advances in Heterocyclic Chemistry, Volume 22, pages 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

[0087] Those skilled in the art recognize that, because the salt of compound is in balance with their corresponding non-salt form in the environment and under physiological conditions, salt shares the biological effectiveness of non-salt form.Therefore, the salt of a variety of compounds with Formula 1 can be used to control the plant diseases (i.e., suitable in agriculture) caused by fungal plant pathogens.The salt with the compound of Formula 1 includes the acid addition salt formed with inorganic acid or organic acid, these acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid.When the compound with Formula 1 contains acidic moieties such as carboxylic acid, salt also includes those formed with organic bases or inorganic bases, these alkalis such as pyridine, triethylamine or ammonia or sodium, potassium, lithium, calcium, magnesium or barium amide, hydride, hydroxide or carbonate.Therefore, the present invention includes compounds selected from Formula 1, its N-oxides and suitable salts in agriculture.

[0088] The compounds selected from Formula 1, their stereoisomers, N-oxides and salts typically exist in more than one form, and thus Formula 1 includes all crystalline and non-crystalline forms of the compounds represented by Formula 1. Non-crystalline forms include solid embodiments such as waxes and gums, and liquid embodiments such as solutions and melts. Crystalline forms include embodiments representing substantially single crystal types and embodiments representing mixtures of polymorphs (i.e., different crystalline types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystalline forms, which have different molecular arrangements and / or conformations in the crystal lattice. Although polymorphs may have the same chemical composition, they may also differ in composition due to the presence or absence of co-crystallized water or other molecules, which may be weakly or strongly bound to the crystal lattice. Polymorphs may differ in such chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. Those skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 may exhibit beneficial effects (e.g., suitability for preparing useful formulations, improved biological properties) relative to another polymorph or mixture of polymorphs of the same compound represented by Formula 1. The preparation and isolation of a specific polymorph of a compound represented by Formula 1 may be achieved by methods known to those skilled in the art, including, for example, crystallization using a selected solvent and temperature.

[0089] As described in the Summary of the Invention, aspects of the present invention relate to a composition comprising: (a) at least one compound selected from Formula 1, its N-oxides and salts, and (b) at least one additional fungicidal compound. More particularly, component (b) is selected from the group consisting of

[0090] (b1) methyl benzimidazole carbamate (MBC) fungicides;

[0091] (b2) dicarboximide fungicides;

[0092] (b3) demethylation inhibitor (DMI) fungicides;

[0093] (b4) phenylamide (PA) fungicides;

[0094] (b5) amine / morpholine fungicides;

[0095] (b6) phospholipid biosynthesis inhibitor fungicides;

[0096] (b7) succinate dehydrogenase inhibitor (SDHI) fungicides;

[0097] (b8) hydroxy(2-amino-)pyrimidine fungicides;

[0098] (b9) anilinopyrimidine (AP) fungicides;

[0099] (b10) N-phenylcarbamate fungicides;

[0100] (b11) quinone outside inhibitor (QoI) fungicides;

[0101] (b12) phenylpyrrole (PP) fungicides;

[0102] (b13) naphthylamine fungicides;

[0103] (b14) cell permeability inhibitor fungicides;

[0104] (b15) melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;

[0105] (b16a) melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides;

[0106] (b16b) melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides;

[0107] (b17) ketolide reductase inhibitor (KRI) fungicides;

[0108] (b18) squalene-epoxidase inhibitor fungicides;

[0109] (b19) polyoxin fungicides;

[0110] (b20) phenylurea fungicides;

[0111] (b21) quinone inside inhibitor (QiI) fungicides;

[0112] (b22) benzamide and thiazolecarboxamide fungicides;

[0113] (b23) enopyranuronic acid antibiotic fungicides;

[0114] (b25) pyranoglucosyl antibiotic: protein synthesis fungicides;

[0115] (b26) pyranoglucosyl antibiotic fungicides;

[0116] (b27) cyanoacetamide oxime fungicides;

[0117] (b28) carbamate fungicides;

[0118] (b29) oxidative phosphorylation uncoupling fungicides;

[0119] (b30) organotin fungicides;

[0120] (b31) carboxylic acid fungicides;

[0121] (b32) heteroaromatic fungicides;

[0122] (b33) phosphonate fungicides;

[0123] (b34) anthranilic acid fungicides;

[0124] (b35) benzotriazine fungicides;

[0125] (b36) benzene-sulfonamide fungicides;

[0126] (b37) pyridazinone fungicides;

[0127] (b38) thiophene-carboxamide fungicides;

[0128] (b39) complex I NADH oxidoreductase inhibitor fungicides;

[0129] (b40) carboxylic acid amide (CAA) fungicides;

[0130] (b41) tetracycline antibiotic fungicides;

[0131] (b42) thiocarbamic acid fungicides;

[0132] (b43) benzamide fungicides;

[0133] (b44) microbial fungicides;

[0134] (b45) quinone outside inhibitors, stilbene binding (QoSI) fungicides;

[0135] (b46) plant extract fungicides;

[0136] (b47) cyanoacrylate fungicides;

[0137] (b48) polyene fungicides;

[0138] (b49) oxysteryl binding protein inhibitor (OSBPI) fungicides;

[0139] (b50) aryl-phenyl-ketone fungicides;

[0140] (b51) host plant defense inducing fungicides;

[0141] (b52) multi-site activity fungicides;

[0142] (b53) biologicals with multiple modes of action;

[0143] (b54) fungicides other than fungicides of component (a) and components (bl) to (b53); and

[0144] (b1) to (b54) of the compounds.

[0145] Of note are embodiments in which component (b) comprises at least one fungicidal compound from each of two different groups selected from (bl) to (b54).

[0146] “benzimidazole methylcarbamate (MBC) fungicides (bl)” (FRAC code 1) inhibit mitosis by binding to beta-tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within cells, and cellular structure. Benzimidazole methylcarbamate fungicides include benzimidazoles and thiophanate fungicides. Benzimidazoles include benomyl, carbendazim, furan-based benzimidazoles, and thiabendazole. Thiophanate fungicides include thiophanate and thiophanate-methyl.

[0147] “dicarboximide fungicides (b2)” (FRAC code 2) inhibit mitogen-activated protein (MAP) / histidine kinase in osmotic signal transduction. Examples include iprodione, procymidone, iphencarbandazole, procymidone, and vinclozolin.

[0148] “Demethylation Inhibitor (DMI) fungicides (b3)” (FRAC code 3) (Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit the C14-demethylase, which plays a role in sterol production. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of a functional cell wall. Thus, exposure to these fungicides results in abnormal growth and eventual death of susceptible fungi. DMI fungicides are divided into several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles, and triazole thione. Piperazines include carpropamid. Pyridines include benthiavalicarb, dimoxystrobin, fenamidophrth and (aS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4- isoxazolyl]-3-pyridinemethanol. Pyrimidines include chlorphenospiracarb, fluazinam, and myclobutanil. Imidazoles include azaconazole, climbazole, iminoctad, iprobenfos, prochloraz, and triflumizole. Triazoles include bitertanol, bifenzthiazole, bromocryptone, cyroconazole, cyprodinil, diniconazole (including diniconazole-M), fluquinconazole, etaconazole, fenbuconazole, fenhexamid, fenpiclonil, ferbam, flutriafol, hexaconazole, ipconazole, ipfenphos triflumizole, metconazole, myclobutanil, pefurazoate, propiconazole, quinconazole, silthiofam, tebuconazole, tetraconazole, triadimefon, triadimenol, tricyclazole, uniconazole, zeta-picox, alpha-(1-chlorocyclopropyl)-alpha-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, rac-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rac-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rac-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole. Triazole thione includes prothioconazole. Biochemical studies have shown that all of the above fungicides are DMI fungicides, as described by K.H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

[0149] “Phenylamide (PA) fungicides (b4)” (FRAC code 4) are specific inhibitors of RNA polymerase in fungi of the class Oomycetes. Susceptible fungi exposed to these fungicides show a reduced ability to incorporate uridine into rRNA. Growth and development of susceptible fungi is prevented by exposure to fungicides of this class. Phenylamide fungicides include acylalanine, oxazolidine, and butyrolactone fungicides. Acylalanines include benodanil, benodanil-M (also known as precise), furalaxyl, metalaxyl, and metalaxyl-M (also known as precise metalaxyl). Oxazolidines include oxadixyl. Butyrolactones include ofurace.

[0150] “Amines / morpholines fungicides (b5)” (FRAC code 5) (SBI: class II) inhibit two target sites within the sterol biosynthetic pathway, Δ 8 → Δ 7 isomerase and Δ 14 reductase. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for development of a functional cell wall. Exposure to these fungicides thus results in abnormal growth and eventual death of susceptible fungi. Amines / morpholines fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholines, piperidines, and spiro-lactone-amine fungicides. Morpholines include aldimorph, cycladiamorph, fenpropimorph, tridiamorph, and trimorphamide. Piperidines include fenpropidine and pyunicarb. Spiro-lactone-amine includes spiroxamine.

[0151] “Phospholipid biosynthesis inhibitor fungicides (b6)” (FRAC code 6) inhibit the growth of fungi by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phosphorothiolates and dithiolane fungicides. Phosphorothiolates include phosphorous acid, iprobenfos, and pyrazolynate. Dithiolanes include anilazin.

[0152] “Succinate dehydrogenase inhibitor (SDHI) fungicides (b7)” (FRAC code 7) inhibit complex II fungal respiration by destroying a key enzyme in the Krebs cycle (TCA cycle) called succinate dehydrogenase. Inhibiting respiration prevents the fungus from producing ATP, and thus inhibits growth and reproduction. SDHI fungicides include phenylbenzamides, phenyloxylethylthiopheneamides, pyridylethylbenzamides, furancarboxamides, oxathiapiprolinamides, thiazolecarboxamides, pyrazole-4-carboxamides, N-cyclopropyl-N-benzyl-pyrazolecarboxamides, N-methoxy-(phenyl-ethyl)-pyrazolecarboxamides, pyridinecarboxamides, and pyrazinecarboxamide fungicides. Phenylbenzamides include carboxin, flutolanil, and fenhexamid. Phenyloxylethylthiopheneamides include ethaboxam. Pyridylethylbenzamides include fluopyram. Furancarboxamides include fenfuram. Oxathiapiprolinamides include furalaxyl and oxycarboxin. Thiazolecarboxamides include ethaboxam. Pyrazole-4-carboxamides include benzovindiflucy, bixafen, fluopimide (provisional common name, Reg. No. 1676101-39-5), fluindapyr, fluopyram, fenpyrazamine, inpyrfluxam, pyracolpyrun, pyrametostrobin, pyribencarb, pyrapropoyne (provisional common name, Reg. No. 1803108-03-3), sedaxane, and N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. N-cyclopropyl-N-benzyl-pyrazolecarboxamides include isoflucypram. N-methoxy-(phenyl-ethyl)-pyrazolecarboxamides include fluazinam. Pyridinecarboxamides include carpropamid. Pyrazinecarboxamides include bixafen.

[0153] “Hydroxy-(2-amino-)pyrimidine fungicides (b8)” (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol, and ethirimol.

[0154] “Anilinopyrimidine (AP) fungicides (b9)” (FRAC code 9) are proposed to inhibit the biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, pyrimethanil, and pyrimethanil.

[0155] “N-phenylcarbamate fungicides (b10)” (FRAC code 10) inhibit mitosis by binding to beta-tubulin and disrupting microtubule assembly. Inhibiting microtubule assembly can disrupt cell division, transport within cells, and cell structure. An example includes diethofencarb.

[0156] “Quinone outside inhibitors (Qol) fungicides (bl l)” (FRAC code 11) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the “quinone outside” (Qo) site of the cytochrome bcl complex located in the inner membrane of the mitochondria of fungi. Inhibition of mitochondrial respiration prevents normal fungal growth and development. Quinone outside inhibitor fungicides include the strobilurin fungicides (collectively known as the azoles fungicides) and the oxazolidinedione, imidazolinone, and benzylcarbamate fungicides. The strobilurin fungicides include azoxystrobin, coumoxystrobin, enoxastrobin (also known as enstroburin), fluoxastrobin, picoxystrobin, and pyraclostrobin. The oxazolidinedione fungicide includes pyraclostrobin. The imidazolinone fungicide includes iminoctad. The benzylcarbamate fungicide includes metyltetraprole.

[0157] “Phenylpyrrole (PP) fungicides (b12)” (FRAC code 12) inhibit MAP / histidine kinases associated with osmotic signal transduction in fungi. Fenpiclonil and fludioxonil are examples of this class of fungicides.

[0158] “Phenylpyrrole (PP) fungicides (b12)” (FRAC code 12) inhibit MAP / histidine kinases associated with osmotic signal transduction in fungi. Fenpiclonil and fludioxonil are examples of this class of fungicides.

[0159] “Cellular respiration inhibitors fungicides (bl 4)” (FRAC code 14) are proposed to inhibit lipid peroxidation affecting membrane synthesis in fungi. Members of this class, such as etridiazole, can also affect other biological processes such as respiration and melanin biosynthesis. Cellular respiration fungicides include the arene and 1,2,4-thiadiazole fungicides. The arene fungicides include biphenyl, chloroneb, dicofol, quintozene, tecnazene, and toclofos-methyl. The 1,2,4-thiadiazole fungicide includes etridiazole.

[0160] “Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides (b15)” (FRAC code 16.1) inhibit the naphthoquinone reductase step in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranones, pyrroloquinolinones, and triazolobenzothiazole fungicides. Isobenzofuranones include tetrachlorophthalide. Pyrroloquinolinones include pyroquilon. Triazolobenzothiazoles include tricyclazole.

[0161] “Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides (b16a)” (FRAC code 16.2) inhibit the scytalone dehydratase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropane carboxamides, formamidines, and propionamides. Cyclopropane carboxamides include carpropamid. Formamidines include dichlofluanid. Propionamides include iprodione.

[0162] “Melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides (b16b)” (FRAC code 16.3) inhibit the polyketide synthase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-polyketide synthase fungicides include trifluoroethyl carbamates. Trifluoroethyl carbamates include toprocarb.

[0163] “Keto reductase inhibitor (KRI) fungicides (b17)” (FRAC code 17) inhibit the 3-keto reductase during C4-demethylation in sterol production. Keto reductase inhibitor fungicides (also known as sterol biosynthesis inhibitors (SBI): class III) include hydroxyanilides and amino-pyrazolones. Hydroxyanilides include fenhexamid. Amino-pyrazolones include metrafenone. Quinofumelin (provisional common name, Reg. No. 861647-84-9) and ipflufenoquin (provisional common name, Reg. No. 1314008-27-9) are also considered keto reductase inhibitor fungicides.

[0164] “Squalene-epoxidase inhibitor fungicides (b18)” (FRAC code 18) (SBI: class IV) inhibit squalene-epoxidase in the sterol biosynthesis pathway. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of a functional cell wall. Thus, exposure to these fungicides results in abnormal growth and eventual death of sensitive fungi. Squalene-epoxidase inhibitor fungicides include thio- carbamates and allylamine fungicides. Thio-carbamates include clomazone. Allylamines include naftifine and terbinafine.

[0165] “Polyoxin fungicides (b19)” (FRAC code 19) inhibit chitin synthase. Examples include polyoxins.

[0166] “Phenylurea fungicides (b20)” (FRAC code 20) are proposed to affect cell division. Examples include pencycuron.

[0167] “Quinone inside inhibitors (QiI) fungicides (b21)” (FRAC code 21) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Reduction of ubiquinone is blocked at the “quinone inside” (Qi) site of the cytochrome bcl complex located in the inner membrane of the mitochondria of fungi. Inhibition of mitochondrial respiration prevents normal fungal growth and development. Quinone inside inhibitor fungicides include cyanoguanidine, sulfonamide triazole, and pyridine amide fungicides. Cyanoguanidines include cyprodinil. Sulfonamide triazoles include iminoctadine. Pyridine amides include fenpicoxamid (Registry number 517875-34-2).

[0168] “Benzamide and thiazolecarboxamide fungicides (b22)” (FRAC code 22) inhibit mitosis by binding to beta-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, intracellular transport, and cell structure. Benzamides include toluylenes such as carpropamid. Thiazolecarboxamides include ethylaminothiazolecarboxamides such as thiazolylalanine.

[0169] “Enolpyranosidic acid antibiotic fungicides (b23)” (FRAC code 23) inhibit fungal growth by affecting protein biosynthesis. Examples include blasticidin-S.

[0170] “Hexopyranosyl antibiotic fungicides (b24)” (FRAC code 24) inhibit the growth of fungi by affecting protein biosynthesis. Examples include springomycin.

[0171] “Glucopyranosyl antibiotic: protein synthesis fungicides (b25)” (FRAC code 25) inhibit the growth of fungi by affecting protein biosynthesis. Examples include streptomycin.

[0172] “Glucopyranosyl antibiotic fungicides (b26)” (FRAC code U18, formerly FRAC code 26 reclassified as U18) are proposed to inhibit trehalase and inositol biosynthesis. Examples include validamycin.

[0173] “Cyanoacetamide oxime fungicides (b27)” (FRAC code 27) include cymoxanil.

[0174] “Carbamate fungicides (b28)” (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in the cell membrane, which then disrupts cell membrane permeability. Iodocarb, Propamocarb, and Proquinazid are examples of this class of fungicides.

[0175] “Oxidative phosphorylation uncouplers (b29)” (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development. This class includes dinitrophenyl crotonates such as Binapacryl, Dinobuton, and Dinocap, and 2,6-dinitroanilines such as Fluazinam.

[0176] “Organotin fungicides (b30)” (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in the oxidative phosphorylation pathway. Examples include fentin acetate, fentin chloride, and fentin hydroxide.

[0177] “Carboxylic acid fungicides (b31)” (FRAC code 31) inhibit fungal growth by affecting DNA topoisomerase type II (gyrase). An example includes Oxolinic acid.

[0178] “Heteroaromatic fungicides (b32)” (FRAC code 32) are proposed to affect DNA / RNA synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. Isoxazoles include Hymexazol, and isothiazolones include Octhiozole.

[0179] “Phosphonate fungicides (b33)” (FRAC code P07, formerly FRAC code 33 reclassified as P07) include phosphorous acid and its various salts, including fosetyl-aluminum.

[0180] “Anthranilic diamide fungicides (b34)” (FRAC code 34) include iprodione.

[0181] “Benzotriazine fungicides (b35)” (FRAC code 35) include triforine.

[0182] “Benzene-sulfonamide fungicides (b36)” (FRAC code 36) include flusulfamide.

[0183] “Pyridazinone fungicides (b37)” (FRAC code 37) include diclomezine.

[0184] “Thiophene-carboxamide fungicides (b38)” (FRAC code 38) are proposed to affect ATP production. An example includes silthiofam.

[0185] “Complex I NADH oxidoreductase inhibitor fungicides (b39)” (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidine amines such as fluazinam, pyrazole-5-carboxamides such as pyridaben, and quinazolines such as chinomethionat.

[0186] “Carboxamide (CAA) fungicides (b40)” (FRAC code 40) inhibit cellulose synthase, which prevents target fungi from growing and causes target fungi to die. Carboxamide fungicides include cinnamic acid amides, valinamide carbamates, and mandelic acid amide fungicides. Cinnamic acid amides include dimoxystrobin, fluoxastrobin, and pyramoxystrobin. Valinamide carbamates include fenhexamid, fenhexamid-isopropyl, iphinstrobin, and valifenalate (also known as flufenoxystrobin). Mandelic acid amides include dual fungicide, 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.

[0187] “Tetracycline antibiotic fungicides (b41)” (FRAC code 41) inhibit the growth of fungi by affecting protein synthesis. Examples include oxytetracycline.

[0188] “Thioaminocarbamate fungicides (b42)” (FRAC code M12, formerly FRAC code 42 reclassified as M12) include ethaboxam.

[0189] “Benzamide fungicides (b43)” (FRAC code 43) inhibit fungal growth by delocalization of hemopexin-like proteins. Examples include pyridylmethyl benzamides such as fluopicolide and fluopimide.

[0190] “Microbial fungicides (b44)” (FRAC code BM02, formerly FRAC code 44 reclassified as BM02) destroy fungal pathogen cell membranes. Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB1600, D747, TJ100 (also known as strain 1BE; known from EP 2962568), and the fungicidal lipopeptides they produce.

[0191] “Quinone outside inhibitors, stilbines binding (QoSI) fungicides (b45)” (FRAC code 45) inhibit complex III mitochondrial respiration in fungi by affecting the ubiquinol reductase at the “quinone outside” (Qo) site, stilbines binding sub-site of the cytochrome bcl complex. Inhibition of mitochondrial respiration prevents normal fungal growth and development. QoSI fungicides include triazolopyrimidine amine such as ametoctradin.

[0192] “Plant extract fungicides (b46)” (FRAC code 46) cause cell membrane disruption. Plant extract fungicides include terpene hydrocarbons, terpene alcohols and terpene phenols such as extracts from Melaleuca alternifolia (tea tree) and plant oils (mixtures) such as eugenol, geraniol and thymol.

[0193] “Cyanoacrylate fungicides (b47)” (FRAC code 47) bind to the myosin motor domain and affect motility activity and actin assembly. Cyanoacrylates include fungicides such as cyenopyrafen.

[0194] “Polyene fungicides (b48)” (FRAC code 48) cause disruption of fungal cell membranes by binding to the major sterol ergosterol in the membrane. Examples include pimaricin (pimaricin).

[0195] “Oxidative sterol binding protein inhibitor (OSBPI) fungicides (b49)” (FRAC code 49) bind to the oxidative sterol binding protein in oomycetes, causing inhibition of zoospore release, zoospore motility and sporangium germination. Oxidative sterol binding fungicides include piperidinyl thiazole isoxazoline such as oxathiapiprolin and fluoxapiprolin.

[0196] “Aryl-phenyl-ketone fungicides (b50)” (FRAC code 50, previously FRAC code U8 reclassified as 50) inhibit growth of mycelium in fungi. Aryl-phenyl ketone fungicides include benzophenones such as metrafenone, and benzoylpyridines such as pyridaben.

[0197] “Host plant defense inducing fungicides (b51)” induce host plant defense mechanisms. Host plant defense inducing fungicides include benzothiadiazoles (FRAC code P01), benzoisothiazoles (FRAC code P02), thiazolidines (FRAC code P03), polysaccharides (FRAC code P04), plant extracts (FRAC code P05), microorganisms (FRAC code P06), and phosphonate fungicides (FRAC code P07, see (b33) above). Benzothiadiazoles include acibenzolar-S-methyl. Benzoisothiazoles include probenazole. Thiazolidines include tiadinil and isotianil. Polysaccharides include laminarin. Plant extracts include extracts from Reynoutria sachalinensis ( giant knotweed). Microorganisms include cells walls of Bacillus mycoides strain J and Saccharomyces cerevisiae strain LAS117.

[0198] "Multi-site active fungicides (b52)" inhibit fungal growth by multiple sites of action and have contact / preventive activity. Multi-site active fungicides include copper fungicides (FRAC code M01), sulphur fungicides (FRAC code M02), dithio carbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulphonylurea fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code M11) and thiocarbamate (FRAC code M12, see (b42) above) fungicides. Copper fungicides are inorganic compounds containing copper, typically in the copper (II) oxidation state; examples include copper oxychloride, copper sulphate and copper hydroxide (e.g. including compositions such as Bordeaux mixture (ternary copper sulphate)). Sulphur fungicides are inorganic chemicals containing rings or chains of sulphur atoms; examples include elemental sulphur. Dithio carbamate fungicides contain a dithio carbamate molecular moiety; examples include ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram and zolezimate. Phthalimide fungicides contain a phthalimide molecular moiety; examples include captan, folpet and diclomezine. Chloronitrile fungicides contain an aromatic ring substituted by chlorine and cyano groups; an example includes chlorothalonil. Sulphonylurea fungicides include dichlofluanid and tolylfluanid. Multi-site contact guanidine fungicides include guanidine salts, iminoctadine albesilate and iminoctadine tris(albesilate). Triazine fungicides include anilazine. Quinone fungicides include dithianon. Quinoxaline fungicides include quinomethionate (also known as chinomethionat). Maleimide fungicides include fluoroimide.

[0199] "Biologicals with multiple modes of action (b53)" include agents from biological sources that show multiple mechanisms of action without evidence of a primary mode of action. Fungicides in this category include polypeptides (lectins), phenols, sesquiterpenes, triterpenes and coumarin fungicides (FRAC code BM01) such as extracts from Lupin seedlings. This category also includes microbial fungicides (FRAC code BM02, see (b44) above).

[0200] "Fungicides other than fungicides of component (a) and components (b1) to (b53); (b54)" include certain fungicides whose mode of action can not be known. These include: (b54.1) "phenyl-acetamide fungicides" (FRAC code U06), (b54.2) "guanidine fungicides" (FRAC code U12), (b54.3) "thiazolidine fungicides" (FRAC code U13), (b54.4) "pyrimidinone-hydrazone fungicides" (FRAC code U14), (b54.5) "4-quinolinyl acetate fungicides" (FRAC code U16), (54.6) "tetrazole oxime fungicides" (FRAC code U17) and "glucopeptide antibiotic fungicides" (FRAC code U18, see (b26) above). Phenyl-acetamides include cyflufenamid. Guanidines include dodine. Thiazolidines include flutianil. Pyrimidinone hydrazones include metrafenone. 4-Quinolinyl acetates include tebufloquin. Tetrazole oximes include picarbutrazox.

[0201] The (b54) class also includes bethoxazin, dichlobentiazox (provisional common name, Reg. No. 957144-77-3), dipymetitrone (provisional common name, Reg. No. 16114-35-5), flometoquin, fentin (fentin acetate), nitrapyrin, silthiame (Reg. No. 304911-98-6), N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine and N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamic acid 4-fluorophenyl ester.

[0202] Additional "fungicides other than fungicides of classes (1) to (54)" whose mode of action can not be known or can not yet be classified include fungicidal compounds selected from components (b54.7) to (b54.12) as described below.

[0203] Component (54.7) relates to (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name pydiflumetofen, Reg. No. 1961312-55-9) which is considered to be a quinone inside inhibitor (QiI) fungicide (FRAC code 21) that inhibits complex III mitochondrial respiration in fungi.

[0204] Component (54.8) relates to 1-[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]-3- methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazol-5-one (interim common name mety ltetraprole, Reg. No. 1472649-01-6), which is believed to be a quinone outside inhibitor (QoI) fungicide (FRAC code 45) that inhibits complex III mitochondrial respiration in fungi, and is effective against QoI resistant strains.

[0205] Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5- phenylpyridazine (interim common name pyridachlometyl, Reg. No. 1358061-55-8), which is believed to be a promoter of microtubule polymerization, resulting in antifungal activity against fungal species belonging to the phyla Ascomycota and Basidiomycota.

[0206] Component (54.10) relates to 2-amino-6-methyl-pyridine-3-carboxylic acid (4- phenoxyphenyl)methyl ester (interim common name aminopyrifen, Reg. No. 1531626-08-0), which is believed to inhibit the GWT-1 protein in the glycosylphosphatidylinositol-anchor biosynthesis in Neurospora crassa.

[0207] Component (b54.11) relates to a compound of Formula b54.11

[0208]

[0209] wherein

[0210] R b1 and R b3 are each independently halogen; and

[0211] R b2 is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, or C3-C6 cycloalkyl.

[0212] Examples of compounds of formula b54.11 include (b54.11a) methyl N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11b) methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11c) methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11d) methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11e) methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, and (b54.11f) methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate. Compounds of formula b54.11, their use as fungicides, and methods of preparation are generally known; see, for example, PCT Patent Publications WO 2008 / 124092, WO 2014 / 066120, and WO 2020 / 097012.

[0213] methyl

[0214] Component (b54.12) relates to compounds of formula b54.12

[0215]

[0216] wherein

[0217] R b4 is

[0218]

[0219] R b6 is C2-C4alkoxycarbonyl or C2-C4haloalkylaminocarbonyl;

[0220] L is CH2or CH2O, wherein the atom on the right is attached to the phenyl ring in formula b54.12;

[0221] R b5 is

[0222] and R b7 is C1-C3alkyl, wherein the wavy bond indicates that the adjacent double bond is in the (Z)- or (E)-configuration, or a mixture thereof.

[0223] Examples of compounds of Formula b54.12 include (b54.12a) N-(2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide, (b54.12b) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenoxy]methyl]-1H-pyrazole-4-carboxylic acid ethyl ester, (b54.12c) 1-[[4- [[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4- carboxylic acid ethyl ester, and (b54.12d) 1-[[4-[[2-(trifluoromethyl)-1,3- dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylic acid ethyl ester. Compounds of Formula b54.12, their use as fungicides, and methods of preparation are generally known; see, e.g., PCT Patent Publications WO 2008 / 187553 and WO 2020 / 056090.

[0224] The embodiments of the present application as described in the SUMMARY include those described below. In the following examples, Formula 1 includes its stereoisomers, N-oxides, and salts, and reference to “a compound of Formula 1” includes the definitions of the substituents specified in the SUMMARY, unless further defined in the example.

[0225] Example 1. The composition comprising components (a) and (b) as described in the SUMMARY, wherein in Formula 1, wherein R 1 is methyl.

[0226] Example 2. The composition comprising components (a) and (b) as described in the SUMMARY, wherein in Formula 1, wherein R 1 is ethyl.

[0227] Example 3. The composition comprising components (a) and (b) as described in the SUMMARY of Examples 1 or 2, wherein in Formula 1, wherein R 2 is cyano, halo, or C1-C2alkyl.

[0228] Example 4. The composition comprising components (a) and (b) as described in the SUMMARY of Examples 1 or 2, wherein in Formula 1, wherein R 2 is cyano, Br, Cl, F, C1-C2alkyl, or C1-C2haloalkyl.

[0229] Example 5. The composition of Example 4, wherein R 2 is cyano, Br, Cl, F, C1-C2alkyl, or halomethyl.

[0230] Example 6. The composition of Example 5, wherein R 2 is cyano, Br, CI, F, C1-C2 alkyl, or CF3.

[0231] Example 7. The composition of Example 6, wherein R 2 is cyano, Br, CI, F, or C1-C2 alkyl.

[0232] Example 8. The composition of Example 7, wherein R 2 is cyano or C1-C2 alkyl.

[0233] Example 9. The composition of Example 8, wherein R 2 is C1-C2 alkyl.

[0234] Example 10. The composition of Example 8, wherein R 2 is cyano or methyl.

[0235] Example 11. The composition of Example 10, wherein R 2 is methyl.

[0236] Example 12. The composition of Example 7, wherein R 2 is Br, CI, or methyl.

[0237] Example 13. The composition comprising components (a) and (b) recited in the Summary of the Invention of any one of Examples 1 to 12, wherein in Formula 1, wherein R 3 is halogen or methyl.

[0238] Example 13a. The composition of Example 13, wherein R 3 is halogen.

[0239] Example 13b. The composition of Example 13, wherein R 3 is Br, CI, F, or methyl.

[0240] Example 14. The composition of Example 13, wherein R 3 is Br, CI, or F.

[0241] Example 15. The composition of Example 14, wherein R 3 is CI or F.

[0242] Example 16. The composition of Example 15, wherein R 3 is CI.

[0243] Example 17. The composition of Example 15, wherein R 3 is F.

[0244] Example 18. The composition of Example 13, wherein R 3 is Cl, F, or methyl.

[0245] Example 19. The composition of Example 18, wherein R 3 is Cl or methyl.

[0246] Example 20. The composition of Example 19, wherein R 3 is methyl.

[0247] Example 21. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Examples 1 to 20, wherein in Formula 1, wherein each R 4 is independently halogen, cyano, C1-C2 alkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 cyanoalkoxy, C2-C4 alkoxyalkyl, or C2-C4 alkoxyalkoxy.

[0248] Example 22. The composition of Example 21, wherein each R 4 is independently halogen, cyano, methyl, methoxy, halomethoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 cyanoalkoxy, C2-C4 alkoxyalkyl, or C2-C4 alkoxyalkoxy.

[0249] Example 23. The composition of Example 22, wherein each R 4 is independently halogen, cyano, methyl, methoxy, halomethoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, or C2-C4 cyanoalkoxy.

[0250] Example 24. The composition of Example 23, wherein each R 4 is independently halogen, cyano, methyl, methoxy, halomethoxy, or C2-C4 cyanoalkoxy.

[0251] Example 25. The composition of Example 24, wherein each R 4 is independently halogen, cyano, methyl, or methoxy.

[0252] Example 25a. The composition of Example 25, wherein each R 4 is independently halogen, cyano, or methoxy.

[0253] Example 25b. The composition of Example 25, wherein each R 4 is independently halogen, cyano, or methyl.

[0254] Example 26. The composition of Example 25, wherein each R 4 is independently Br, CI, F, cyano, methyl, or methoxy.

[0255] Example 27. The composition of Example 26, wherein each R 4 is independently Br, CI, F, cyano, or methoxy.

[0256] Example 28. The composition of Example 27, wherein each R 4 is independently CI, F, cyano, or methoxy.

[0257] Example 29. The composition of Example 27, wherein each R 4 is independently Br, CI, or F.

[0258] Example 30. The composition of Example 29, wherein each R 4 is independently CI, or F.

[0259] Example 31. The composition of Example 30, wherein each R 4 is CI.

[0260] Example 32. The composition of Example 30, wherein each R 4 is F.

[0261] Example 33. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Examples 1 to 32, wherein in Formula 1, wherein each R 4 is independently halogen, cyano, or C1-C2alkoxy.

[0262] Example 34. The composition of Example 33, wherein each R 4 is independently halogen.

[0263] Example 35. The composition of Example 33, wherein each R 4 is independently Br, CI, or F or cyano.

[0264] Example 36. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Examples 1 to 35, wherein in Formula 1, wherein m is 0, 1, or 2.

[0265] Example 37. The composition of Example 36, wherein m is 1 or 2.

[0266] Example 38. The composition of Example 37, wherein m is 1.

[0267] Example 39. The composition of Example 38, wherein m is 2.

[0268] Example 40. The composition comprising components (a) and (b) recited in the Summary of the Invention of any one of Examples 1 to 39, wherein in Formula 1, wherein each R 5 is independently halogen, C1-C2 alkyl, C2-C4 alkoxyalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 cyanoalkoxy, or C2-C4 alkoxyalkoxy.

[0269] Example 41. The composition of Example 40, wherein each R 5 is independently halogen, methyl, methoxy, halo methoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, or C2-C4 cyanoalkoxy.

[0270] Example 42. The composition of Example 41, wherein each R 5 is independently halogen, methyl, methoxy, halo methoxy, C2-C4 alkenyloxy, or C2-C4 cyanoalkoxy.

[0271] Example 43. The composition of Example 42, wherein each R 5 is independently halogen, methyl, methoxy, halo methoxy, or C2-C4 cyanoalkoxy.

[0272] Example 44. The composition of Example 43, wherein each R 5 is independently halogen, methyl, or methoxy.

[0273] Example 45. The composition of Example 44, wherein each R 5 is independently Br, Cl, F, methyl, or methoxy.

[0274] Example 46. The composition of Example 45, wherein each R 5 is independently Br, Cl, F, or methoxy.

[0275] Example 46a. The composition of Example 46, wherein each R 5 is independently Br, Cl, or F.

[0276] Example 47. The composition of Example 46, wherein each R 5 is independently Cl, F, or methoxy.

[0277] Example 48. The composition of Example 47, wherein each R 5 is independently Cl or F.

[0278] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein each R is independently H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 5 is independently Br, Cl, F, or methyl.

[0279] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein each R is independently H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 5 is independently F or methyl.

[0280] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein each R is independently H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 5 is F.

[0281] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein n is 0, 1, or 2.

[0282] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein n is 1 or 2.

[0283] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein n is 1.

[0284] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein n is 2.

[0285] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein each R is independently H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6a is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R u is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 7 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 8 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 9 .

[0286] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein each R is independently H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6a is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R u is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 7 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 8 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 9 .

[0287] In some embodiments, the composition of the application comprises a compound of Formula 1, wherein each R is independently H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6asubstituted with up to 6 substituents independently selected from the group consisting of R u R 7 or OR 9 .

[0288] Embodiment 59. The composition of embodiment 58, wherein R 6 is H; or C1-C2 alkyl or C1-C2 haloalkyl, each optionally substituted with up to 1 substituent selected from R 6a .

[0289] Embodiment 60. The composition of embodiment 59, wherein R 6 is H, C1-C2 alkyl or C1-C2 haloalkyl.

[0290] Embodiment 61. The composition of embodiment 60, wherein R 6 is H, methyl or halomethyl.

[0291] Embodiment 62. The composition of embodiment 61, wherein R 6 is H, methyl or trifluoromethyl.

[0292] Embodiment 63. The composition of embodiment 62, wherein R 6 is H or methyl.

[0293] Embodiment 64. The composition of embodiment 63, wherein R 6 is H.

[0294] Embodiment 65. The composition of formula 1 of any one of embodiments 1 to 64, wherein each R 6a is independently cyano, C3-C6 cycloalkyl or C1-C3 alkoxy.

[0295] Embodiment 66. The composition of embodiment 65, wherein each R 6a is independently cyano, cyclopropyl or methoxy.

[0296] Embodiment 67. The composition of embodiment 66, wherein each R 6a is independently cyano or cyclopropyl.

[0297] Embodiment 68. The composition comprising components (a) and (b) recited in the Summary of the Invention of any one of embodiments 1 to 58, wherein in formula 1, wherein u is 0.

[0298] Embodiment 69. The composition comprising components (a) and (b) recited in the Summary of the Invention of any one of embodiments 1 to 58, wherein in formula 1, wherein R 7 is methyl or halomethyl.

[0299] Example 70. The composition comprising components (a) and (b) as described in the summary of the application in any of embodiments 1 to 57, wherein in Formula 1, wherein W is O.

[0300] Example 71. The composition comprising components (a) and (b) as described in the summary of the application in any of embodiments 1 to 57, wherein in Formula 1, wherein R 8 is C1-C3 alkyl, C1-C3 alkoxy, or C1-C3 alkylthio.

[0301] Example 72. The composition of Example 71, wherein R 8 is methyl, ethyl, methoxy, ethoxy, methylthio, or ethylthio.

[0302] Example 73. The composition of Example 72, wherein R 8 is methyl, methoxy, or methylthio.

[0303] Example 74. The composition comprising components (a) and (b) as described in the summary of the application in any of embodiments 1 to 58, wherein in Formula 1, wherein R 9 is H; or C1-C3 alkyl or C1-C3 haloalkyl, each optionally substituted with up to 1 substituent selected from R 9a ; or CH(=0), cyclopropyl, S(=0)2OM, or (C=W)R 10 .

[0304] Example 75. The composition of Example 74, wherein R 9 is H; or C1-C2 alkyl or C1-C2 haloalkyl, each optionally substituted with up to 1 substituent selected from R 9a .

[0305] Example 76. The composition comprising components (a) and (b) as described in the summary of the application in any of embodiments 1 to 75, wherein in Formula 1, wherein each R 9a is independently cyano, C3-C6 cycloalkyl, or C1-C3 alkoxy.

[0306] Example 77. The composition of Example 76, wherein each R 9a is independently cyano, cyclopropyl, or methoxy.

[0307] Example 78. The composition of Example 77, wherein each R 9a is independently cyano or cyclopropyl.

[0308] Example 79. The composition comprising components (a) and (b) as described in the summary of the application in any of embodiments 1 to 78, wherein in Formula 1, wherein R10 is C1-C3 alkyl, C1-C3 alkoxy, or C1-C3 alkylthio.

[0309] Embodiment 80. The composition of Embodiment 79, wherein R 10 is methyl, ethyl, methoxy, ethoxy, methylthio, or ethylthio.

[0310] Embodiment 81. The composition of Embodiment 80, wherein R 10 is methyl, methoxy, or methylthio.

[0311] Embodiment 82. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Embodiments 1 to 81, wherein in Formula 1, wherein m is 1 and R 4 is located at the 4-position (or para position) relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0312] Embodiment 83. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Embodiments 1 to 81, wherein in Formula 1, wherein m is 1 and R 4 is located at the 6-position (or ortho position) relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0313] Embodiment 84. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Embodiments 1 to 81, wherein in Formula 1, wherein m is 1 and R 4 is located at the 4-position (or para position); or m is 1 and R 4 is located at the 6-position (or ortho position) relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0314] Embodiment 85. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Embodiments 1 to 81, wherein in Formula 1, wherein m is 2 and one R 4 is located at the 4-position (or para position) and the other is located at the 6-position (or ortho position) relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0315] Embodiment 86. The composition comprising components (a) and (b) as recited in the Summary of the Invention of any one of Embodiments 1 to 81, wherein in Formula 1, wherein m is 1 and R 4 is located at the 4-position (or para position); or m is 1 and R 4 is located at the 6-position (or ortho position); or m is 2 and one R 4 is located at the 4-position (or para position) and the other is located at the 6-position (or ortho position) relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0316] Embodiment 86a. The composition of Embodiment 86, wherein m is 1 and R4 in the 4-position (or para position); or m is 2 and one R 4 in the 4-position (or para position) and the other in the 6-position (or ortho position) relative to the attachment of the phenyl ring to the remainder of Formula 1.

[0317] Example 87. A composition comprising components (a) and (b) as described in the summary of the application in any of examples 1 to 86a, wherein in Formula 1, wherein n is 1 and R 5 in the 4-position (or para position) relative to the attachment of the nitroaniline ring to the remainder of Formula 1.

[0318] Example 88. A composition comprising components (a) and (b) as described in the summary of the application in any of examples 1 to 86a, wherein in Formula 1, wherein n is 1 and R 5 in the 6-position (or ortho position) relative to the attachment of the nitroaniline ring to the remainder of Formula 1.

[0319] Example 89. A composition comprising components (a) and (b) as described in the summary of the application in any of examples 1 to 86a, wherein in Formula 1, wherein n is 2 and one R 5 in the 4-position (or para position) and the other in the 6-position (or ortho position) relative to the attachment of the nitroaniline ring to the remainder of Formula 1.

[0320] Example 90. A composition comprising components (a) and (b) as described in the summary of the application in any of examples 1 to 86a, wherein in Formula 1, wherein n is 1 and R 5 in the 4-position (or para position); or

[0321] n is 1 and R 5 in the 6-position (or ortho position); or

[0322] n is 2 and one R 5 in the 4-position (or para position) and the other in the 6-position (or ortho position) relative to the attachment of the nitroaniline ring to the remainder of Formula 1.

[0323] Example 91. A composition comprising components (a) and (b) as described in the summary of the application in any of examples 1 to 90, wherein in Formula 1, wherein m and n are each 1 and R 4 in the 4-position (or para position) and R 5 in the 6-position (or ortho position); or m is 1 and R 4 in the 4-position (or para position) and n is 2 and one R 5 in the 4-position (or para position) and the other in the 6-position (or ortho position); or m and n are each 1 and R 4at the 4-position (or para); or m is 2 and one R 5 at the 4-position (or para); or m is 2 and one R 4 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R 5 at the 6-position (or ortho), relative to the attachment of the phenyl ring and the nitroaniline ring to the rest of Formula 1.

[0324] Embodiment 92. The composition of Embodiment 91, wherein m and n are each 1 and R 4 at the 4-position (or para); or m is 2 and one R 5 at the 6-position (or ortho); or m is 1 and R 4 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R 5 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R 4 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R 5 at the 6-position (or ortho), relative to the attachment of the phenyl ring and the nitroaniline ring to the rest of Formula 1.

[0325] Embodiment 93. The composition of Embodiment 92, wherein m and n are each 1 and R 4 at the 4-position (or para); or m is 2 and one R 5 at the 6-position (or ortho); or m is 1 and R 4 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R 5 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R

[0326] Embodiment 94. The composition of Embodiment 93, wherein m and n are each 1 and R 4 at the 4-position (or para); or m is 2 and one R 5 at the 6-position (or ortho).

[0327] Embodiment 95. The composition of Embodiment 93, wherein m is 1 and R 4 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R 5 at the 4-position (or para) and the other at the 6-position (or ortho), and n is 1 and R

[0328] Embodiment 96. The composition comprising components (a) and (b) recited in the Summary of the Invention of any one of Embodiments 1 to 95, wherein component (a) does not comprise N-oxides of the compound having Formula 1.

[0329] Embodiment 97. The composition comprising components (a) and (b) as described in the Summary of the Invention in any of embodiments 1 to 95, wherein component (a) comprises a compound selected from the group consisting of

[0330] 4-(2-bromo-4,6-difluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 1),

[0331] 3-chloro-4-[5-[(2-chloro-4-fluoro-6-nitrophenyl)amino]-1,3-dimethyl- 1 H-pyrazol-4-yl]benzonitrile (Compound 18),

[0332] N-(2-chloro-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-methoxyphenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 73),

[0333] 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 93),

[0334] 4-(2-chloro-4-fluorophenyl)-N-(4-fluoro-2-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 1 1 1),

[0335] 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 93),

[0336] 4-(2-chloro-4-fluorophenyl)-N-(4-fluoro-2-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 1 1 1),

[0337] 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 93),

[0338] 4-(2-chloro-4-fluorophenyl)-N-(4-fluoro-2-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 1 1 1),

[0339] 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 93),

[0340] 4-(2-chloro-4-fluorophenyl)-N-(4-fluoro-2-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 1 1 1),

[0341] 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1 H- pyrazol-5-amine (Compound 112),

[0342] 4-(2,4-difluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1 H-pyrazol-5- amine (Compound 118),

[0343] N-(4-chloro-2-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine (Compound 121), and

[0344] 3-chloro-4-[5-[(2-fluoro-4-methyl-6-nitrophenyl)amino]-1,3-dimethyl-1 H- pyrazol-4-yl]benzonitrile (Compound 127).

[0345] Embodiment 98. The composition of Embodiment 97, wherein component (a) comprises a compound selected from the group consisting of Compound 1, 19, 57, 60, 68, 72, 93, 112, 121, and 127.

[0346] Embodiment 99. The composition of Embodiment 98, wherein component (a) comprises a compound selected from the group consisting of Compound 68, 72, and 112.

[0347] Embodiment 100. The composition of Embodiment 99, wherein component (a) comprises Compound 68.

[0348] Embodiment 101. The composition of Embodiment 99, wherein component (a) comprises Compound 72.

[0349] Embodiment 102. The composition of Embodiment 99, wherein component (a) comprises Compound 112.

[0350] Embodiment 103. The composition comprising components (a) and (b) as described in the Summary of the Invention of any one of Embodiments 1 to 99, wherein component (a) is 4-(2-chloro-4,6-difluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl- 1 H-pyrazol-5-amine.

[0351] Embodiment 104. The composition comprising components (a) and (b) as described in the Summary of the Invention of any one of Embodiments 1 to 99, wherein component (a) is 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-3-ethyl-1 -methyl- 1 H-pyrazol-5-amine.

[0352] Example 105. The composition comprising components (a) and (b) as described in the Summary of the Invention in any of Examples 1 to 99, wherein component (a) is 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1 H- pyrazol-5-amine.

[0353] Example 106. The composition of Examples 1 to 105, wherein component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of these fungicidal compounds is cyproconazole, difenoconazole, epoxiconazole, flusilazole, metconazole, prothioconazole, or tebuconazole, then the other fungicidal compound is not azoxystrobin, benzovindiflucy, bixafen, boscalid, fluopimide, furametpyr, fluazinam, isopyrazam, dimethomorph, penthiopyrad, picoxystrobin, pyrifluquinazon, pyraclostrobin, pyrimicarbacin, or trifloxystrobin.

[0354] Example 107. The composition of Example 106, wherein component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of these fungicidal compounds is cyproconazole, difenoconazole, epoxiconazole, flusilazole, prothioconazole, or tebuconazole, then the other fungicidal compound is not azoxystrobin, bixafen, fluopimide, fluazinam, isopyrazam, picoxystrobin, pyraclostrobin, or trifloxystrobin.

[0355] Example 108. The composition of Example 107, wherein (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of these fungicidal compounds is cyproconazole, difenoconazole, epoxiconazole, flusilazole, prothioconazole, or tebuconazole, then the other fungicidal compound is not azoxystrobin, bixafen, fluopimide, fluazinam, picoxystrobin, pyraclostrobin, or trifloxystrobin.

[0356] Embodiments of the present application, including embodiments 1-108 above as well as any other embodiments described herein, can be combined in any manner and the description of variables in the embodiments is not only directed to compositions comprising a compound of Formula 1 in combination with at least one other fungicidal compound, but also to compositions comprising a compound of Formula 1 in combination with at least one invertebrate pest control compound or agent, and also to compounds of Formula 1 and compositions thereof, and also to starting and intermediate compounds useful for making compounds of Formula 1. Furthermore, embodiments of the present application, including embodiments 1-108 above as well as any other embodiments described herein, and any combinations thereof, are directed to the methods of the present application. Thus, as another embodiment, of note is a composition disclosed above comprising: (a) at least one compound selected from the group consisting of compounds of Formula 1, N-oxides, and salts thereof described above; and at least one invertebrate pest control compound or agent.

[0357] The combinations of embodiments 1-108 are shown below:

[0358] Embodiment A. A composition comprising components (a) and (b) as described in the SUMMARY, wherein component (a) comprises a compound of Formula 1, or a salt thereof, wherein in Formula 1,

[0359] R 1 is methyl;

[0360] R 2 is cyano, halo, or C1-C2alkyl;

[0361] R 3 is halo;

[0362] each R 4 is independently halo, cyano, methyl, methoxy, halomethoxy, C2-C4alkenyloxy, C2-C4alkynyloxy, or C2-C4cyanoalkoxy;

[0363] each R 5 is independently halo, methyl, methoxy, halomethoxy, C2-C4alkenyloxy, C2-C4alkynyloxy, or C2-C4cyanoalkoxy;

[0364] R 6 is H; or C1-C2alkyl or C1-C2haloalkyl, each optionally substituted with up to 1 substituent selected from R 6a ; or S(=O) u R 7 or OR 9 ;

[0365] R 6a is cyano, C3-C6cycloalkyl, or C1-C3alkoxy;

[0366] R 7 is methyl or halomethyl;

[0367] R 9 is H; or C1-C2 alkyl or C1-C2 haloalkyl, each optionally substituted with up to 1 substituent selected from R 9a ; and

[0368] R 9a is cyano, C3-C6 cycloalkyl or C1-C3 alkoxy.

[0369] Embodiment B. The composition of Embodiment B, wherein in Formula 1,

[0370] R 2 is methyl or ethyl;

[0371] R 3 is Br, Cl or F;

[0372] each R 4 is independently halogen, cyano, methyl or methoxy;

[0373] m is 1 and R 4 is located at the 4-position (or para position); or m is 1 and R 4 is located at the 6-position (or ortho position); or m is 2 and one R 4 is located at the 4-position (or para position) and the other is located at the 6-position (or ortho position);

[0374] each R 5 is independently halogen, methyl or methoxy;

[0375] n is 1 and R 5 is located at the 4-position (or para position); or n is 1 and R 5 is located at the 6-position (or ortho position); or n is 2 and one R 5 is located at the 4-position (or para position) and the other is located at the 6-position (or ortho position); and

[0376] R 6 is H or methyl.

[0377] Embodiment C. The composition of Embodiment B, wherein in Formula 1,

[0378] R 2 is methyl;

[0379] each R 4 is independently Br, Cl, F, cyano or methoxy;

[0380] each R 5 is independently Br, Cl, F, methyl or methoxy; and

[0381] R 6 is H.

[0382] Example D. The composition of Example C, wherein in Formula 1,

[0383] each R 4 is independently Br, CI, or F;

[0384] each R 5 is independently Br, CI, F, or methoxy; and

[0385] m and n are each 1 and R 4 is at the 4-position (or para position) and R 5 is at the 6-position (or ortho position); or m is 1 and R 4 is at the 4-position (or para position), and n is 2 and one R 5 is at the 4-position (or para position), and the other is at the 6-position (or ortho position); or m is 2 and one R 4 is at the 4-position (or para position), and the other is at the 6-position (or ortho position), and n is 1 and R 5 is at the 6-position (or ortho position).

[0386] Example E. The composition of Example D, wherein in Formula 1,

[0387] R 4 is CI or F;

[0388] each R 5 is independently CI, F, or methoxy; and

[0389] m and n are each 1 and R 4 is at the 4-position (or para position) and R 5 is at the 6-position (or ortho position); or m is 1 and R 4 is at the 4-position (or para position), and n is 2 and one R 5 is at the 4-position (or para position), and the other is at the 6-position (or ortho position).

[0390] Example F. The composition comprising components (a) and (b) recited in the Summary, wherein component (a) comprises a compound having Formula 1 or a salt thereof, wherein in Formula 1,

[0391] R 1 is C1-C2 alkyl;

[0392] R 2 is cyano, halo, C1-C2 alkyl, or C1-C2 haloalkyl;

[0393] R 3 is halo or methyl;

[0394] each R 4 independently halogen, cyano, nitro, C1-C3alkyl, C1-C3haloalkoxy, C2-C6alkenyloxy, C2-C6alkynyloxy, C2-C6cyanoalkoxy, C2-C6alkoxyalkyl, or C2-C6alkoxyalkoxy;

[0395] each R 5 independently halogen, C1-C3alkyl, C2-C6alkoxyalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C2-C6alkenyloxy, C2-C6alkynyloxy, C2-C6cyanoalkoxy, or C2-C6alkoxyalkoxy; provided that at least one R 5 is selected from halogen;

[0396] m and n are each independently 1, 2, or 3;

[0397] R 6 is H; or C1-C3alkyl or C1-C3haloalkyl, each optionally substituted with up to 2 substituents independently selected from R 6a ; or amino, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl, CH(=0), S(=0)2OM, S(=0) u R 7 , (C=W)R 8 , or OR 9 ;

[0398] each R 6a is independently cyano, C3-C6cycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, or C1-C3alkylsulfonyl;

[0399] M is K or Na;

[0400] u is 0, 1, or 2;

[0401] R 7 is C1-C3alkyl or C1-C3haloalkyl;

[0402] W is O or S;

[0403] R 8 is C1-C3alkyl, C2-C4alkoxyalkyl, C2-C4alkylaminoalkyl, C3-C6dialkylaminoalkyl, C1-C3alkoxy, C1-C3alkylthio, or C2-C4alkylthioalkyl;

[0404] R 9 is H; or C1-C3alkyl or C1-C3haloalkyl; 9asubstituted with 1 to 3 substituents independently selected from the group consisting of halogen, cyano, C1-C2alkyl, C1-C2alkoxy, C1-C2haloalkyl, C1-C2haloalkoxy, C1-C2alkylthio, C1-C2alkylsulfinyl, C1-C2alkylsulfonyl, C3-C6cycloalkyl, S(=O)2OM, and (C=W)R; 10 ; and

[0405] each R 9a is independently cyano, C3-C6cycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, or C1-C3alkylsulfonyl; and

[0406] R 10 is C1-C3alkyl, C2-C4alkoxyalkyl, C2-C4alkylaminoalkyl, C3-C6dialkylaminoalkyl, C1-C3alkoxy, C1-C3alkylthio, or C2-C4alkylthioalkyl;

[0407] with the proviso that the compound of Formula 1 is not:

[0408] N-(2-bromo-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H- pyrazol-5-amine; or

[0409] 3-chloro-4-(2-chloro-4-fluorophenyl)-N-(2,4-difluoro-6-nitrophenyl)-1-methyl-1H- pyrazol-5-amine;

[0410] In one embodiment, the compound of Formula 1 is:

[0411] R 1 is methyl;

[0412] R 2 is cyano, halogen, or C1-C2alkyl;

[0413] R 3 is halogen;

[0414] each R 4 is independently halogen, cyano, methyl, C1-C2alkoxy, or C1-C2haloalkoxy;

[0415] m is 1 and R 4 is located at the 4-position (or para position); or m is 1 and R 4 is located at the 6-position (or ortho position); or m is 2 and one R 4 is located at the 4-position (or para position) and the other is located at the 6-position (or ortho position);

[0416] each R 5 is independently halogen, methyl, methoxy, halomethyl, C2-C4alkenyloxy, or C2-C4cyanoalkoxy;

[0417] n is 1 and R 5is located at the 4-position (or para position); or n is 1 and R 5 is located at the 6-position (or ortho position); or n is 2 and one R 5 is located at the 4-position (or para position) and the other is located at the 6-position (or ortho position); and

[0418] R 6 is H or methyl.

[0419] Example H. The composition of Example G, wherein in Formula 1,

[0420] R 2 is methyl;

[0421] each R 4 is independently Br, Cl, F, cyano, or methoxy;

[0422] each R 5 is independently Br, Cl, F, methyl, or methoxy; and

[0423] R 6 is H.

[0424] Example I. The composition of Example H, wherein in Formula 1,

[0425] R 4 is Br, Cl, or F;

[0426] each R 5 is independently Br, Cl, F, or methoxy; and

[0427] m and n are each 1 and R 4 is located at the 4-position and R 5 is located at the 6-position; or m is 1 and R 4 is located at the 4-position, and n is 2 and one R 5 is located at the 4-position and the other is located at the 6-position.

[0428] Example J. The composition of Example I, wherein

[0429] R 4 is Cl or F; and

[0430] each R 5 is independently Cl, F, or methoxy.

[0431] Example K. The composition of any one of Examples A to J, wherein component (a) comprises a compound selected from the group consisting of Compound 1, Compound 18, Compound 19, Compound 23, Compound 57, Compound 60, Compound 68, Compound 72, Compound 73, Compound 93, Compound 111, Compound 112, Compound 121, and Compound 127.

[0432] Example L. The composition of Example K, wherein component (a) comprises a compound selected from the group consisting of: Compound 68, Compound 72, and Compound 112.

[0433] Example M. The composition of Example L, wherein component (a) comprises Compound 112.

[0434] Example B1. The composition recited in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (bl) a benzimidazole methylcarbamate fungicide such as benomyl, carbendazim, furanil, thiabendazole, and thiophanate-methyl.

[0435] Example B2. The composition recited in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b2) a dicarboximide fungicide such as acrobel, dimethirimol, iprodione, procymidone, and vinclozolin.

[0436] Example B3. The composition recited in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b3) a demethylation inhibitor fungicide such as azaconazole, benthival, bixpyr-acetate, bixpyr-ethanol, bromocyclen, cyprodinil, dichlobenil, difenzoquat, dimetnamine, fluquinconazole, ipconazole, metconazole, myclobutanil, naftalide, nuarimol, pefurazoate, penconazole, picoxystrobin, prothioconazole, pyracarbolid, pyrametostrobin, pyramoxystrobin, pyricarbolid, pyrifenox, pyrimethanil, pyrimixostrobin, quinconazole, silthioconazole, simeconazole, spicinazole, tebufloquinconazole, tebuconazole, tetraconazole, triflumizole, triforine, uniconazole, uniconazole-P, and zeta-cyprodinil.

[0437] Example B4. The composition recited in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b4) a phenylamide fungicide such as metalaxyl, metalaxyl-M, mefenoxam, ofurace, ofuracarb, and oxadixyl.

[0438] Example B5. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b5) amine / morpholine fungicides such as 4-dodecyl-2,6-dimethylmorpholine, dodecylguanidine, fenpropimorph, tridemorph, zoxamide, fenpropidine, piperalin, and spiroxamine.

[0439] Example B6. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b6) phospholipid biosynthesis inhibitor fungicides such as edifenphos, isinotofen, pyrazophos, and anilazin.

[0440] Example B7. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b7) succinate dehydrogenase inhibitor fungicides such as benodanil, flutolanil, fenfuram, ethaboxam, fluopimide, carboxin, oxycarboxin, thifluzamide, fenhexamid, bixafen, pyridabene, isotianil, fluindapyr, sedafoxam, pyracolpyrun, isopyrazam, fluopyram, penthiopyrad, fenpyrazamine, fluoroimide, fluoxasulfam, boscalid, and benzene- pyrazine fungicides.

[0441] Example B8. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b8) hydroxy(2-amino-)pyrimidine fungicides such as bupirimate, fenarimol, and nitotrimo.

[0442] Example B9. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b9) anilinopyrimidine fungicides such as cyprodinil, pyrimethanil, and pyrimicarb.

[0443] Example B10. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b10) N-phenylcarbanilate fungicides such as diethofencarb.

[0444] Example B11. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b11) a fungicidal quinone outside inhibitor fungicide such as azoxystrobin, coumoxystrobin, enoxastrobin, fluoxastrobin, picoxystrobin, pyraclostrobin, ravid, pyrametostrobin, pyramoxystrobin, spicloram, kresoxim-methyl, trifloxystrobin, enestrobin, dimoxystrobin, fenaminstrobin, pyrametostrobin, famoxadone, fenamidone, and anilazodine.

[0445] Example B12. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b12) a phenylpyrrole fungicide compound such as fenpicolnil and fludioxonil.

[0446] Example B13. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b13) an anilinoazoles fungicide such as fenoxanil and proquinazid.

[0447] Example B14. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b14) a cell peroxidation inhibitor fungicide such as benthival, chloroneb, dicofol, endothal, tetrachloroendothal, toclofos-methyl, and hymexazol.

[0448] Example B15. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b15) a melanin biosynthesis inhibitor-reductase fungicide such as phthalide, pyroquilon, and tricyclazole.

[0449] Example B16a. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b16a) a melanin biosynthesis inhibitor-dehydratase fungicide such as carpropamid, diclocymet, and iprodione.

[0450] Example B16b. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b16b) a melanin biosynthesis inhibitor-polyketide synthase fungicide such as tolylfluanid.

[0451] Example B17. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b17) ketoreductase inhibitor fungicides such as fenhexamid, mandipropamid, quinoxyfen, and fluazinam.

[0452] Example B18. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b18) squalene- epoxidase inhibitor fungicides such as pyridinitr, naftifine, and terbinafine.

[0453] Example B19. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b19) polyoxin fungicides such as polyoxin.

[0454] Example B20. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b20) phenylurea fungicides such as pencycuron.

[0455] Example B21. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b21) quinone inside inhibitor fungicides such as cyanodiamide, indaziflam, and fenpiclonil (CAS Reg. No. 517875-34-2).

[0456] Example B22. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b22) benzamide and thiazolecarboxamide fungicides such as benomyl and thiabendazole.

[0457] Example B23. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b23) enolpyranosyl uronic acid antibiotic fungicides such as blasticidin-S.

[0458] Example B24. A composition as described in the Summary of the Invention (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b24) hexopyranosyl antibiotic fungicides such as springymycin.

[0459] Example B25. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b25) glucopyranosyl antibiotic: protein synthesis fungicide such as streptomycin.

[0460] Example B26. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicide such as validamycin.

[0461] Example B27. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b27) cyanoacetamide oxime fungicide such as cymoxanil.

[0462] Example B28. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b28) carbamate fungicide such as propamocarb, fenoxycarb and iodocarb.

[0463] Example B29. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b29) oxidative phosphorylation uncoupling fungicide such as fluazinam, binapacryl, dinocap and dinobuton.

[0464] Example B30. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b30) organotin fungicide such as fentin acetate, fentin chloride and fentin hydroxide.

[0465] Example B31. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b31) carboxylic acid fungicide such as oxolinic acid.

[0466] Example B32. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b32) heteroaromatic fungicide such as hymexazol and octhilinone.

[0467] Example B33. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b33) phosphonate fungicides such as phosphorous acid and various salts thereof, including fosetyl-aluminum.

[0468] Example B34. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b34) anthranilic acid fungicides such as tecloftalam.

[0469] Example B35. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b35) benzotriazine fungicides such as zoxamide.

[0470] Example B36. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b36) benzenesulfonamide fungicides such as fluopsinamide.

[0471] Example B37. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b37) pyridinyl ketone fungicides such as pyridachlor.

[0472] Example B38. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b38) thiophene carboxamide fungicides such as silthiofam.

[0473] Example B39. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b39) complex I NADH oxidoreductase inhibitor fungicides such as fluvoxolin, amidoflumet, and chinomethionat.

[0474] Example B40. A composition described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b40) carboxylic acid amide fungicides such as dimoxystrobin, fenhexamid, fenhexamid-isopropyl, iminoctadine, iprovalicarb, mandipropamid, flumetover, and piperazine.

[0475] Example B41. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b41) a tetracycline antibiotic fungicide such as oxytetracycline.

[0476] Example B42. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b42) a thiocarbamate fungicide such as ethaboxam.

[0477] Example B43. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b43) a benzamide fungicide such as fluopicolide and fluopimide.

[0478] Example B44. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b44) a microbial fungicide such as Bacillus amyloliquefaciens strains QST713, FZB24, MB1600, D747, F727, TJ100 (also known as strain 1BE; known from EP2962568) and the fungicidal lipopeptides they produce.

[0479] Example B45. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b45) a quinone outside inhibitor, a fungicide such as fampronil.

[0480] Example B46. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b46) a plant extract fungicide such as Melaleuca alternifolia, eugenol, geraniol and thymol.

[0481] Example B47. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b47) a cyanoacrylate fungicide such as acypetacs.

[0482] Example B48. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b48) a polyene fungicide such as natamycin.

[0483] Example B49. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b49) an oxysterol binding protein inhibitor fungicide such as flutriafol and epoxiconazole.

[0484] Example B50. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b50) an aryl-phenyl-ketone fungicide such as metrafenone and pydiflumetofen.

[0485] Example B51. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b51) a host plant defense inducer fungicide such as acibenzolar-S-methyl, thiabendazole, thiadicarbamide, isotianil, laminarin, extract from giant knotweed, and cell walls of Bacillus mycoides strain J and Saccharomyces cerevisiae strain LAS117.

[0486] Example B52. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b52) a multisite activity fungicide such as copper oxychloride, copper sulfate, copper hydroxide, Bordeaux mixture (tribasic copper sulfate), elemental sulfur, ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram, fometozone, folpet, chloroneb, dichlofluanid, tolylfluanid, a bisguanide, a bisguazidium, a bisguazidium triacetate, anilazin, dithianon, milneb, and flutolanil.

[0487] Example B53. A composition as described in the Summary (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b53) a biological agent fungicide with multiple modes of action such as extract from Lupinus luteus subsp. albus.

[0488] Example B54. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b54) a fungicide other than the fungicides of component (a) and components (bl) to (b53), such as cyrodanil, bethoxazine, tianan, nitrapyrin, tebufloquin, dodine, fluazinam, fenamidone, tetraconazole, dichlofluanid (Registry number 957144-77-3), dipyrithione (Registry number 16114-35-5), flumetover, fenhexamid (Registry number 304911-98-6), N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine, and N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamic acid 4-fluorophenyl ester (XR-539).

[0489] Example B55. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises (b55) N-[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alanine (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl ester (tentative common name pyridinylidene).

[0490] Example B56. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises (b56) 1-[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]-3-methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazol-5-one (tentative common name methyltetrazolin).

[0491] Example B57. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises (b57) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (tentative common name pyridylchloromethyl).

[0492] Example B58. A composition as described in the Summary herein (including but not limited to a composition as described in any one of Examples 1 to 108 and A to M), wherein component (b) comprises (b58) 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (tentative common name aminopyrine).

[0493] Example B59. The composition described in the Summary, including but not limited to the composition of any one of Examples 1 to 108 and A to M, wherein component (b) comprises at least one compound selected from (b54.11) (i.e., of formula b54.11)

[0494] Component (b54.11) pertains to compounds of formula b54.11

[0495]

[0496] wherein

[0497] R b1 and R b3 are each independently halogen; and

[0498] R b2 is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, or C3-C6 cycloalkyl.

[0499] Example B60. The composition of Example B59, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of methyl N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, and methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate.

[0500] Example B60b. The composition of Example B60, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of methyl N-[[5-[1-(4- cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2- methylphenyl]methyl]carbamate, and methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate.

[0501] Example B61. The composition described in the Summary (including but not limited to the composition of any one of Examples 1 to 108 and A to M), wherein component (b) comprises at least one compound selected from (b54.12) (i.e., of formula b54.12)

[0502] Component (b54.12) relates to compounds of formula b54.12

[0503]

[0504] wherein

[0505] R b4 is

[0506]

[0507] R b6 is C2-C4alkoxycarbonyl or C2-C4haloalkylaminocarbonyl;

[0508] L is CH2or CH2O, wherein the atom to the right is attached to the phenyl ring in formula b54.12;

[0509] R b5 is

[0510] and R b7 is C1-C3alkyl, wherein the wavy bond indicates that the adjacent double bond is in the (Z)- or (E)-configuration, or a mixture thereof.

[0511] Example B62. The composition of Example B61, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of N-(2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]- 1H-pyrazole-4-carboxylic acid ethyl ester, 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1- propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylic acid ethyl ester, and 1-[[4- [[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4- carboxylic acid ethyl ester.

[0512] Example B62b. The composition of Example B62, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of N-(2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide and 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl] methyl]-1H-pyrazole-4-carboxylic acid ethyl ester.

[0513] Example B63. The composition described in the Summary, including but not limited to the composition of any one of Examples 1 to 108 and A to M, wherein component (b) comprises at least one fungicidal compound (fungicide) selected from the group consisting of azoxystrobin, benzovindiflucarb, boscalid, bifenazate, bromocryptone, carbendazim, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, fluquinconazole, famoxadone, fenbuconazole, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluoxapyroxasde, hexaconazole, ipconazole, mefenoxam, metiram, metconazole, milneb, pencycuron, penthiopyrad, picoxystrobin, prochloraz, propiconazole, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, spicinonazole quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2- methylphenyl]methyl]carbamate, methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3- yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H- pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl) phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, N-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolcarboxamide, and ethyl 1-[[4-[[(1Z)-2- ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate.

[0514] Example B64. The composition of Example B63, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflucy, bifenathi, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenpropidine, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, kresoxim-methyl, mancozeb, metconazole, mefenoxam, metrafenone, myclobutanil, penthiopyrad, picoxystrobin, propiconazole, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyramutostrobin, spicin, triforine, quinoxyfen, tebuconazole, triflumizole, triticonazole, methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2- methylphenyl]methyl]carbamate, methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3- yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H- pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4- (trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, N-(2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, and ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4- carboxylate.

[0515] Example B65. The composition of Example B64, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflucarb, bifenathi, chlorothalonil, copper hydroxide, cyproconazole, difenacozide, difenacozon, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluoxymetofen, flutriafol, metiram, phosethyl-Al, propineb, spicin, silthiofam, triclopyr, prothioconazole, pyraclostrobin, triflumizole, and N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2- methylphenyl]methyl]carbamic acid methyl ester, N-[[5-[1-(4-chloro-2,6-difluorophenyl)- 1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamic acid methyl ester, N-[[5-[1-[2,6-difluoro-4- (1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamic acid methyl ester, N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl] carbamic acid methyl ester, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]-4-oxazolecarboxamide, and 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1- propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylic acid ethyl ester.

[0516] Example B66. The composition of Example B65, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflucarb, bifenathi, chlorothalonil, copper hydroxide, cyproconazole, difenacozide, difenacozon, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluoxymetofen, flutriafol, metiram, phosethyl-Al, propineb, spicin, silthiofam, triclopyr, and pyraclostrobin.

[0517] It is noted that the composition of any of the embodiments described herein, including any of Examples 1-108, A-M, and B1-B66, wherein reference to Formula 1 includes salts thereof, but not N-oxides thereof; thus, the phrase "a compound having Formula 1" can be replaced with the phrase "a compound having Formula 1 or a salt thereof." In this noted composition, component (a) comprises a compound having Formula 1 or a salt thereof.

[0518] Also noted as an embodiment is a fungicidal composition of the present application comprising a fungicidally effective amount of the composition of Examples 1-108, A-M, and B1-B66, and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0519] Embodiments of the invention further include methods for controlling plant diseases caused by fungal plant pathogens, the method comprising applying to a plant or part thereof, or a plant seed or seedling, a fungicidally effective amount of a composition as described in any one of embodiments 1 to 108, A to M, and B1 to B66 (e.g., as a composition comprising the formulation ingredients as described herein). Embodiments of the invention also include methods for protecting a plant or plant seed from disease caused by a fungal pathogen, the method comprising applying to the plant or plant seed a fungicidally effective amount of a composition as described in any one of embodiments 1 to 108, A to M, and B1 to B66.

[0520] Some embodiments of the invention relate to controlling or protecting against plant diseases that primarily affect plant foliage or applying the compositions of the invention to plant foliage (i.e., to the plant and not the seed). Preferred methods of use include those involving the above preferred compositions; and diseases that are particularly effectively controlled include plant diseases caused by fungal plant pathogens. The combination of fungicides used according to the invention can facilitate disease control and delay the development of resistance.

[0521] Method embodiments further include:

[0522] Embodiment C1. A method for protecting a plant from a disease selected from the group consisting of rust diseases, powdery mildew, and Corynespora diseases, the method comprising applying to the plant a fungicidally effective amount of a composition comprising components (a) and (b) as described in the Summary of the Invention of any one of embodiments 1 to 108.

[0523] Embodiment C2. The method of embodiment C1, wherein the disease is a rust disease and component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of (b3) demethylation inhibitor (DMI) fungicides, (b5) amine / morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b11) quinone outside inhibitor (QoI) fungicides, (b13) benzimidazole carbamate fungicides, and (b52) multi-site activity fungicides.

[0524] Embodiment C3. The method of embodiment C2, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides, and (b11) quinone outside inhibitor (QoI) fungicides.

[0525] Embodiment C4. The method of embodiment C3, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides, and (b11) quinone outside inhibitor (QoI).

[0526] Example C5. The method of any one of Examples CI to C4, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, benzovindiflucy, bixafen, cyprodinil, difenoconazole, fluquinconazole, fenpropimorph, pyridinylamide, fluindapyr, flutriafol, fluazinam, ipfentrifluconazole, iprovalicarb, metrafenone, pyraclostrobin, prothioconazole, trifloxystrobin, and uniconazole.

[0527] Example C6. The method of Example C5, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, benzovindiflucy, cyprodinil, fluquinconazole, fluindapyr, fluazinam, metrafenone, pyraclostrobin, prothioconazole, trifloxystrobin, uniconazole, and trifloxystrobin.

[0528] Example C7. The method of any one of Examples C2 to C6, wherein the disease is Asian Soybean Rust caused by Phakopsora pachyrhizi.

[0529] Example C8. The method of any one of Examples C2 to C6, wherein the disease is wheat leaf rust caused by Puccinia recondita.

[0530] Example C9. The method of Example CI, wherein the disease is powdery mildew and component (b) of the composition comprises at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (bll) quinone outside inhibitor (QoI) fungicides, (bl3) naphthylamine fungicides, and (b52) multi-site active fungicides.

[0531] Example C10. The method of Example C9, wherein component (b) of the composition comprises at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (bll) quinone outside inhibitor (QoI) fungicides, and (b52) multi-site active fungicides.

[0532] Example C11. The method of Examples C9 and C10, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, chlorothalonil, copper sulfate, cyprodinil, difenoconazole, fluquinconazole, fenpropimorph, pyridinylamide, flutriafol, mancozeb, metrafenone, pyraclostrobin, prothioconazole, trifloxystrobin, uniconazole, and trifloxystrobin.

[0533] Example C12. The method of Example C11, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of cyprodinil, difenoconazole, fluquinconazole, prothioconazole, and tebuconazole.

[0534] Example C13. The method of Example C10, wherein component (b) of the composition comprises at least one fungicidal compound selected from (b3) DMI fungicides.

[0535] Example C14. The method of Example C13, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of cyprodinil, difenoconazole, and prothioconazole.

[0536] Example C15. The method of Example C10, wherein component (b) of the composition comprises at least one fungicidal compound selected from (b11) QoI fungicides.

[0537] Example C16. The method of Example C15, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, picoxystrobin, and pyraclostrobin.

[0538] Example C17. The method of any one of Examples C9-C16, wherein the disease is wheat powdery mildew caused by Erysiphe graminis.

[0539] Example C18. The method of Example C1, wherein the disease is a Sphaeropsis disease and component (b) of the composition comprises at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides and (b11) quinone outside inhibitor (QoI) fungicides.

[0540] Example C19. The method of Example C18, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, cyprodinil, difenoconazole, fluquinconazole, fenpropimorph, pyridinitril, flutriafol, metconazole, benclothiazol, picoxystrobin, prothioconazole, pyraclostrobin, tebuconazole, and trifloxystrobin.

[0541] Example C20. The method of Example C19, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of fluquinconazole and fenpropimorph.

[0542] Example C21. The method of any one of Examples C18-C20, wherein the disease is wheat brown leaf spot caused by Zymoseptoria tritici.

[0543] Example C22. The method of Example C1, wherein the disease is an Uncinula disease and component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of (b11) a quinone outside inhibitor (QoI) fungicide and (b52) a multisite activity fungicide.

[0544] Example C23. The method of Example C22, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, chlorothalonil, pyridinylamide, mancozeb, bifenoxycarb, picoxystrobin, pyraclostrobin, and trifloxystrobin.

[0545] Example C24. The method of Example C23, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin and chlorothalonil.

[0546] Example C25. The method of any one of Examples C1-C24, wherein components (a) and (b) are applied in a synergistically effective amount (and in a synergistically effective ratio relative to one another).

[0547] Of note are embodiments corresponding to Examples C1-C25 that relate to a method for controlling a plant disease caused by a fungal plant pathogen, the method comprising applying to the plant or portion thereof a fungicidally effective amount of a fungicidal composition of the present application.

[0548] As noted in the SUMMARY, the present application also relates to a compound of Formula 1, or an N-oxide or salt thereof. It is also noted that embodiments of the present application, including Examples 1-108, also relate to a compound of Formula 1.

[0549] The present application provides a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) and at least one other fungicide. Of note are embodiments of such compositions that comprise a compound corresponding to any of the compound embodiments described above.

[0550] The present application provides a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) (i.e., in a fungicidally effective amount) and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent. Of note are embodiments of such compositions that comprise a compound corresponding to any of the compound embodiments described above.

[0551] The present application provides a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or plant seed, 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 comprising 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 present application.

[0552] Of note are compounds of Formula 1 (which are compounds of Formula 1A) (including all geometric and stereoisomers), N-oxides, hydrates, and salts thereof, and agricultural compositions containing them and their use as fungicides:

[0553]

[0554] wherein

[0555] R 2 is cyano, halogen, or C1-C2 alkyl;

[0556] R 3 is halogen;

[0557] R 4a and R 4b are each independently H or halogen, provided that at least one is halogen; and

[0558] R 5a and R 5b are each independently H, halogen, methyl, or methoxy, provided that at least one is halogen;

[0559] provided that when R 3 is Cl, R 4a is F and R 4b is H, then R 5a is H, Br, Cl, I, methyl, or methoxy.

[0560] Embodiment A1. A compound of Formula 1A, wherein

[0561] R 2 is methyl or ethyl;

[0562] R 3 is Br, Cl, or F;

[0563] R 4a and R 4b are each independently H, Br, Cl, or F; and

[0564] R 5a and R 5beach independently is H, Br, CI, F, or methyl.

[0565] Embodiment B1. The compound of Embodiment A1, wherein,

[0566] R 2 is methyl;

[0567] R 4a is CI or F;

[0568] R 4b is H, CI, or F; and

[0569] R 5a is H, CI, F, or methyl; and

[0570] R 5b is H or F.

[0571] Also of note is a fungicidal composition comprising a fungicidally effective amount of a compound of Formula 1A (including all geometric and stereoisomers, N-oxides, and salts thereof) as described in any of the corresponding embodiments (which are embodiments corresponding to Embodiments 1-107 and Embodiments A-M) and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents. In addition, of note is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or plant seed, a fungicidally effective amount of a compound of Formula 1A (including all geometric and stereoisomers, N-oxides, and salts thereof) as described in any of the described corresponding embodiments. Of particular note are embodiments wherein the compound of Formula 1A is applied as a composition of the present application.

[0572] One or more of the following methods and variations as described in Schemes 1-12 can be used to prepare compounds of Formula 1. Unless otherwise indicated, the definitions of R 1 , R 2 , R 3 , R 4 , R 5 , m, n, and R 6 in the following compounds of Formulae 1-21 are as defined in the Summary above. Formulae 1a and 1b are subsets of Formula 1. Unless otherwise indicated, the substituents of the subset formulae are as defined for their parent formula.

[0573] As shown in Scheme 1, compounds of Formula 1 can be prepared by reacting a 5- aminopyrazole of Formula 2 with a compound of Formula 3, optionally in the presence of a metal catalyst, and typically in the presence of a base such as potassium tert-butoxide, triethylamine, or potassium carbonate and a solvent such as tetrahydrofuran, N,N- dimethylformamide, 1,4-dioxane, toluene, ethanol, methanol, or dimethyl sulfoxide. 1nitrophenyl compound of Formula 3 that is a leaving group such as a halogen (e.g., F, CI, Br, I) or a sulfonate (e.g., methanesulfonate, trifluoromethanesulfonate, or p-toluenesulfonate). In certain cases, the use of a metal catalyst in amounts ranging from catalytic to superstoichiometric can facilitate the desired reaction. Typical reaction conditions include, for example, reacting in the presence of a metal catalyst such as a copper salt complex (e.g., Cul with N,N'-dimethylethylenediamine, proline, or bipyridine), a palladium complex (e.g., tris(dibenzylideneacetone)dipalladium(0)) or a palladium salt (e.g., palladium acetate) with a ligand such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, or 2,2'- bis(diphenylphosphino)1,1 '-binaphthalene, a base such as potassium carbonate, cesium carbonate, potassium phosphate, sodium phenoxide, or sodium tert-butoxide, and a solvent such as N,N-dimethylformamide, 1,2-dimethoxyethane, dimethyl sulfoxide, 1,4-dioxane, or toluene (optionally containing an alcohol such as ethanol). For related references, see PCT Patent Publication WO 2013 / 126283, Synthesis Example 1, Step C; and WO 2010 / 020363, Example 2A. In addition, the method of Scheme 1 is illustrated in Inventive Example 1, Step C; Example 5, Step C; and Example 3. Compounds of Formula 3 are commercially available or their preparation is known in the art.

[0574] Scheme 1

[0575]

[0576] General methods that can be used to prepare 5-aminopyrazoles of Formula 2 are well known in the art; see, for example, Journal für Praktische Chemie [Journal of Practical Chemistry] (Leipzig) 1911, 83, 171 and J. Am. Chem. Soc. [Journal of the American Chemical Society] 1954, 76, 501. One such method is illustrated in Scheme 2 below, wherein a 5-aminopyrazole of Formula 2 is prepared by condensing a compound of Formula 4 with a hydrazine of Formula 5 (e.g., methylhydrazine or ethylhydrazine) in a solvent such as ethanol or methanol and optionally in the presence of an acid such as acetic acid according to general procedures known in the art; see, for example, PCT Patent Publication WO 2012 / 031061 Synthesis Example 1, Step A; and Synthesis Example 2, Step C. In addition, the method of Scheme 2 is illustrated in Inventive Example 1, Step B.

[0577] Scheme 2

[0578]

[0579] Alternatively, as shown in Scheme 3, 5-aminopyrazoles of formula 2 can also be prepared by reacting 4-bromo or 4-iodopyrazoles of formula 6 with boronic acid compounds of formula 7 using well-known transition metal catalyzed cross-coupling reaction conditions.

[0580] Scheme 3

[0581]

[0582] Methods useful for preparing compounds of formula 6 are known in the art.

[0583] Compounds of formula 1a (i.e., formula 1 where R 6 1) can be prepared as shown in Scheme 4. In this method, compounds of formula 8 are condensed with hydrazines of formula 5 (e.g., methylhydrazine or ethylhydrazine) according to general procedures known in the art in solvents such as ethanol or methanol and optionally in the presence of an acid or base catalyst such as acetic acid, piperidine, or sodium methoxide. For reaction conditions, see PCT Patent Publication WO 2013 / 116251, Synthesis Example 1, Step C and Example 2, Step B. In addition, the method of Scheme 4 using a compound of formula 8 where R a is methyl is illustrated in Example 2, Step C of the present application.

[0584] Scheme 4

[0585]

[0586] Compounds of formula 8 can be prepared as shown in Scheme 5 by reacting enone dithioacetal derivatives of formula 9 with compounds of formula 10, optionally in the presence of a base such as sodium hydride or ethylmagnesium chloride, in solvents such as toluene, tetrahydrofuran, or dimethoxy methane, at temperatures ranging from about -10 °C to the boiling point of the solvent. For related references, see, for example, J. Heterocycl. Chem. 1975, 12(1), 139. Methods useful for preparing compounds of formula 9 are known in the art.

[0587] Scheme 5

[0588]

[0589] In addition, as shown in Scheme 6, compounds of formula 8 (where R a is lower alkyl) (e.g., methyl, ethyl, n-propyl) and formula 8a (i.e., when R aCompounds of Formula 8 (when R is H) can be prepared by condensation of an isothiocyanate compound having Formula 11 with a carbonyl compound having Formula 12 to give an intermediate compound having Formula 13, which is a salt of a thioamide having Formula 8a. The intermediate compound having Formula 13 can be used in situ (as illustrated in WO 2013 / 116251, Synthesis Example 1, Step C; and Example 2, Step C of the present application) or isolated (as illustrated in WO 2013 / 116251, Example 2, Step A). Bases useful for preparing compounds having Formula 13 include sodium or potassium hydride, alkoxide, hydroxide, or carbonate, such as sodium hydride, potassium tert-butoxide, sodium ethoxide, potassium hydroxide, sodium hydroxide, or potassium carbonate. Amine bases (e.g., triethylamine or N,N-diisopropylethylamine) can also be used to effect condensation of compounds having Formula 11 and 12 with Formula 13. Various solvents are useful, such as tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, an alcohol (e.g., ethanol), an ester (e.g., ethyl acetate or isopropyl acetate), or mixtures thereof. The solvent is selected to be compatible with the base, as understood by one skilled in the art. The reaction temperature can range from -78 °C to the boiling point of the solvent. One useful combination of base and solvent is potassium tert-butoxide or potassium tert-pentoxide in tetrahydrofuran to which a solution of the isothiocyanate having Formula 11 and the carbonyl compound having Formula 12 can be added, either as a solution that is combined into one solution, or added separately, preferably the carbonyl compound is added followed by the isothiocyanate. Typically, this reaction is carried out at -70 °C to 0 °C. The salt having Formula 13 can be acidified to form the ketothioamide compound having Formula 8a or treated with a reagent that displaces the leaving group R a is lower alkyl (e.g., methyl, ethyl, n-propyl) and X 1 is a leaving group (i.e., a nucleophilic reaction leaving group such as Br, I, OS(O)2CH3) of R a X 1 alkylation to form the corresponding compound of Formula 8. This general method is known in the chemical literature; see, for example, Zhurnal Organicheskoi Khimii [Journal of Organic Chemistry] 1982, 18(12), 2501. The preparation of compounds of Formula 8 where R a The method of Scheme 6 for the preparation of compounds of Formula 8 where R

[0590] Scheme 6

[0591]

[0592] Ketone thioamides of Formula 8a can also be prepared by allowing the corresponding ketone amide to react with a sulfurizing agent such as Lawesson's reagent or P2S5; see, for example, Helv. Chirn. Act. [Swiss Chemical Journal] 1998, 81(7), 1207.

[0593] As shown in Scheme 7, compounds of Formula 1 can also be prepared by reacting a 1H-pyrazole compound of Formula 15 with a compound of Formula 16, wherein R 1 is methyl or ethyl and L 2 is a leaving group such as a halogen (e.g., CI, Br, I), sulfonate (e.g., mesylate, triflate, or tosylate), or phosphate (e.g., dimethyl phosphate), preferably in the presence of a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene, potassium carbonate, or potassium hydroxide, and a solvent such as N,N-dimethylformamide, tetrahydrofuran, toluene, or water. General procedures for this type of methylation are well known in the art and can be readily adapted to prepare compounds of the present application. Using general procedures known in the art, such as those described in Canada Journal of Chemistry [Can. J. Chem.] 1986, 64, 2211-2219 and Heterocycles [Heterocycles] 2000, 53(12), 2775-2780, particularly useful methylation agents include diazomethane and iodomethane. 1 -L 2 A general procedure for this type of methylation is well known in the art and can be readily adapted to prepare compounds of the present application. Using general procedures known in the art, such as those described in Canada Journal of Chemistry [Can. J. Chem.] 1986, 64, 2211-2219 and Heterocycles [Heterocycles] 2000, 53(12), 2775-2780, particularly useful methylation agents include diazomethane and iodomethane.

[0594] Scheme 7

[0595]

[0596] Compounds of Formula 15 can be prepared by condensing a compound of Formula 8 with hydrazine in a manner analogous to the method of Scheme 4. This method is described in Chemistry of Heterocyclic Compounds [Chem. Heterocycl. Compd.] 2005, 41(1), 105-110.

[0597] In an alternative method, as shown in Scheme 8, compounds of Formula 1 can be prepared by reacting a 4-bromo or 4-iodopyrazole of Formula 16 with an organometallic compound of Formula 17 under transition metal catalyzed cross-coupling reaction conditions in the presence of a suitable palladium, copper, or nickel catalyst. In this method, compounds of Formula 17 are organoboronic acids (e.g., M 1 is B(OH)2), organoboronates (e.g., M 1 is B(-OC(CH2)3O-)), organotrifluoroborates (e.g., M 1BF3K), organotin reagents (e.g., M 1 Sn(n-Bu)3, Sn(Me)3), Grignard reagents (e.g., M 1 MgBr or MgCl) or organozinc reagents (e.g., M 1 ZnBr or ZnCl). Suitable metal catalysts include, but are not limited to, palladium(II) acetate, palladium(II) chloride, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) dichloride, dichloro[l,l'-bis(diphenylphosphino)ferrocene]palladium(II), bis(triphenylphosphine)nickel(II) dichloride, and copper(I) salts (e.g., copper(I) iodide, copper(I) bromide, copper(I) chloride, copper(I) cyanide, or copper(I) triflate). As will be appreciated by those skilled in the art, the optimal conditions will depend on the catalyst used and the counterion (i.e., M 1 ) attached to the coupling reagent. In some cases, the addition of a ligand such as a substituted phosphine or substituted bisphosphinoalkane facilitates the reaction. In addition, the presence of a base such as an alkali metal carbonate, a tertiary amine, or an alkali metal fluoride can be necessary for some reactions involving organoboron reagents of Formula 17. For a review of this type of reaction, see: E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis, John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-Coupling Reactions: A Practical Guide, Springer, New York, 2002; H. C. Brown et al., Organic Synthesis via Boranes, Vol. 3, Aldrich Chemical Co., Milwaukee, WI, 2002; Suzuki et al., Chemical Review 1995, 95, 2457-2483 and Molander et al., Accounts of Chemical Research 2007, 40, 275-286. In addition, the methods of Scheme 8 are illustrated in PCT Patent Publications WO 2010 / 101973 and WO 2012 / 031061.

[0598] Scheme 8

[0599]

[0600] As shown in Scheme 9, pyrazole intermediates of Formula 16 are readily prepared from the corresponding pyrazoles of Formula 18 by treatment with a halogenating agent. Suitable halogenating agents for this process include N-bromosuccinimide (NBS), N- iodosuccinimide (NIS), bromine, sodium bromite, thionyl chloride, oxalyl chloride, phosphorus oxychloride, or phosgene. Particularly useful are N-bromosuccinimide (NBS) and N- iodosuccinimide (NIS). Suitable solvents for this reaction include, for example, N,N- dimethylformamide, N,N-dimethylacetamide, dichloromethane, chloroform, chlorobutane, benzene, xylene, chlorobenzene, tetrahydrofuran, p-dioxane, acetonitrile, and the like. Optionally, an organic base such as triethylamine, pyridine, N,N- dimethylaniline, and the like can be added. Typical reaction temperatures range from about ambient temperature to 200 °C. For representative procedures, see Synthesis 2006, 17, 2855-2864; Journal of Medicinal Chemistry 2005, 48, 6843-6854; Journal of Medicinal Chemistry 2007, 50, 3086-3100, and Journal of Medicinal Chemistry 2005, 48, 4420-4431.

[0601] Scheme 9

[0602]

[0603] As shown in Scheme 10, compounds of Formula 18 can be prepared from the corresponding compounds of Formula 19 by procedures analogous to those used in Scheme 1. Compounds of Formula 19 are either commercially available or can be prepared by methods known in the art.

[0604] Scheme 10

[0605]

[0606] The compounds of Formula 1 described herein, and intermediates thereto, can undergo a variety of electrophilic, nucleophilic, organometallic, oxidative, and reductive reactions to add substituents or modify existing substituents, and thus provide other functionalized compounds of Formula 1. For example, as shown in Scheme 11, compounds of Formula lb (i.e., where (R 5 ) nThe compound of formula 1) wherein CH3 can be prepared by reacting L in the presence of a catalyst such as [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride dichloromethane adduct, preferably in the presence of a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene, cesium carbonate or potassium hydroxide and in a solvent such as N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, ethanol, toluene or water. 3 The compound of formula 20 having a leaving group such as a halogen (e.g., Br, I) or a sulfonate (e.g., methanesulfonate, trifluoromethanesulfonate, or p-toluenesulfonate) is prepared by reacting with a reagent such as 2,4,6-trimethylboroxane or tetramethylstannane. The method of Scheme 11 is described in Example 4, Step A of PCT Patent Publication WO2013 / 192126 and Example 4, Step B of the present invention.

[0607] Compounds of formula 20 can be prepared by methods described in PCT patent publications WO 2010 / 101973 and WO 2012 / 031061. Those skilled in the art will recognize that, in some cases, preparing an N-protected compound of formula 20 prior to functional group interconversion will aid in obtaining the desired product. The selection and use of suitable N-protecting groups will be readily apparent to those skilled in the art; for representative examples, see TW Greene and PGM Wuts, Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991. In addition, step A of Example 4 of the present invention illustrates the preparation of an N-Boc protected compound of formula 20.

[0608] Scheme 11

[0609]

[0610] Analogously to the method of Scheme 11, compounds of formula 20 can be treated with potassium (trifluoromethyl)trimethoxyborate to provide trifluoromethyl analogs of formula 1b.

[0611] In another embodiment, as shown in Scheme 12, wherein R 6 Compounds of formula 1 other than H may be prepared by the corresponding 6 The compound of formula 1 is H by reacting with R 6 Typically, the reaction is carried out in the presence of a base such as sodium hydride and a polar solvent such as N,N-dimethylformamide. In this context, the expression "comprising R 6 "Electrophile" means an electrophile capable of 6to a nucleophile (i.e., when R 6 is H, the nitrogen atom in Formula 1). Typically, the electrophile comprising R 6 has the formula R 6 X 2 where X 2 is a leaving group (i.e., a leaving group in a nucleophilic reaction). Typical leaving groups include halides (e.g., Br, CI, I) or sulfonates (e.g., mesylate, triflate, tosylate). However, some electrophiles comprising R 6 do not comprise a leaving group; an example is sulfur trioxide (SO3), which, when R 6 is H, can bond to the nitrogen atom in Formula 1 upon deprotonation of the nitrogen atom (such as by a base having the formula M + H - where M + is a cation) as an -SO3M substituent.

[0612] Scheme 12

[0613]

[0614] It will be recognized that certain reagents and reaction conditions described above for preparing compounds having Formula 1 can not be compatible with certain functional groups present in intermediates. In these instances, the incorporation of protection / deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired product. The use and choice of the protecting groups will be apparent to a person skilled in the art of chemical synthesis (see, e.g., T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nded.; Wiley: New York, 1991). It will be recognized by one skilled in the art that, in some cases, after the introduction of a given reagent as depicted in any individual scheme, it can be necessary to carry out additional routine synthetic steps not described in detail to complete the synthesis of a compound of Formula 1. It will also be recognized by one skilled in the art that it can be necessary to carry out combinations of the steps shown in the above schemes in a different order than the specific sequences presented for preparing compounds having Formula 1.

[0615] It will also be recognized by one skilled in the art that the compounds of Formula 1 and intermediates described herein can be subjected to a variety of electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0616] Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present application to its fullest extent. The following Examples are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. The steps in the following examples show the procedure for each step in the overall synthetic transformation, and the starting material used for each step does not necessarily have to be prepared from the specific preparative experiment whose procedure is described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages of chromatographic solvent mixtures are by volume, unless otherwise indicated. 1 H NMR spectra are reported in ppm from the low field of tetramethylsilane;“s” means singlet,“d” means doublet,“t” means triplet,“m” means multiplet,“br s” means broad singlet and“dd” means doublet of doublets.

[0617] Example 1

[0618] Preparation of 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl- 1H-pyrazol-5-amine (Compound 112)

[0619] Step A: Preparation of a-acetyl-2-chloro-4-fluorophenylacetonitrile

[0620] A mixture of sodium methoxide solution (30% in methanol, 85 mL, 0.47 mol) in toluene (400 mL) was heated to 120 °C using a Dean-Stark trap to azeotropically remove methanol. After cooling to 90 °C, 2-chloro-4-fluorophenylacetonitrile (40.0 g, 0.24 mol) in ethyl acetate (200 mL) was added dropwise to the reaction mixture. The reaction mixture was stirred at 90 °C for 1 h, and then hydrochloric acid (1 N, 30 mL) was added. The resulting mixture was extracted with ethyl acetate (3 x 250 mL) and the combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography eluting with 3:7 ethyl acetate-petroleum ether to provide the title compound as a white solid (35 g).

[0621] 1 H NMR (CDCI3): δ 7.49 (dd, 1 H), 7.24 (dd, 1 H), 7.14-7.09 (m, 1 H), 5.13 (s, 1 H), 2.36 (s, 3 H).

[0622] Step B: Preparation of 4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine

[0623] To a mixture of a-acetyl-2-chloro-4-fluorobenzeneacetonitrile (i.e. the product of Step A) (28 g, 0.13 mol) in ethanol (400 mL) was added methylhydrazine sulfate (28.6 g, 0.20 mol) and sodium acetate (21.7 g, 0.27 mol). The reaction mixture was heated at 120 °C for 12 h, and then concentrated under reduced pressure to remove the solvent. The resulting mixture was poured into ice water (500 mL) and the white solid was collected by filtration. The solid was rinsed with water and pentane, then dried to provide the title compound as an off-white solid (24 g).

[0624] 1 H NMR (CDCI3): δ 7.45 (dd, 1 H), 7.27 (t, 1 H), 7.23-7.12 (m, 1 H), 4.89 (s, 2 H), 3.49 (s, 3 H).

[0625] Step C: Preparation of 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-amine

[0626] To a mixture of 4-(2-chloro-4-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine (i.e. the product of Step B) (1.2 g, 5.0 mmol) in tetrahydrofuran (40 mL) at 0 °C was added potassium tert-butoxide (1 M in THF, 10 mL, 10 mmol) in portions. The reaction mixture was stirred at 0 °C for 1 h, and then 1,2-difluoro-3-nitrobenzene (0.85 g, 5.3 mmol) was added dropwise. After 30 min at 0 °C, saturated aqueous ammonium chloride solution was added to the reaction mixture, and the resulting mixture was extracted with ethyl acetate (100 mL). The aqueous layer was further extracted with ethyl acetate (2 x 40 mL), and the combined organic extracts were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (eluting with 40% ethyl acetate in petroleum ether) to provide the title compound (a compound of the invention) as a yellow solid (1.1 g).

[0627] 1 H NMR (CDCI3): δ 8.59 (s, 1 H), 7.59 (d, 1 H), 7.31 (d, 1 H), 7.2 (d, 1 H), 7.09 (t, 1 H), 7.04-7.01 (m, 1 H), 6.82-6.86 (m, 1 H), 3.74 (s, 3 H), 1.97 (s, 3 H).

[0628] Example 2

[0629] 3-Chloro-4-[5-[(2-fluoro-6-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]benzonitrile (Compound 113)

[0630] Step A: Preparation of 3-chloro-4-(2-oxopropyl)benzonitrile

[0631] To a mixture of 4-amino-3-chlorobenzonitrile (50.0 g, 0.33 mol) in diethyl ether (500 mL) at -10 °C was added boron trifluoride diethyl etherate (61 mL, 0.50 mol). The reaction mixture was stirred at -10 °C for 10 min and then tert-butylnitrite (48 mL, 0.4 mol) was added. After 20 min at -10 °C, the reaction mixture was allowed to warm to room temperature, stirred for 2 h and then the white solid was collected by filtration. The white solid was triturated with diethyl ether and pentane (1 : 1, 300 mL), filtered and dried to provide intermediate compound 2-chloro-4-cyanophenyl diazonium tetrafluoroborate as an off-white solid (72 g).

[0632] To a mixture of 2-chloro-4-cyanophenyl diazonium tetrafluoroborate (72 g, 0.33 mol) in dimethylformamide (500 mL) at -10 °C was added isopropenyl acetate (354 mL, 3.2 mol). The reaction mixture was stirred at -10 °C for 20 min and then 4-aminomorpholine (1.0 mL) in dimethylsulfoxide (40 mL) was added. After 1 h, ice cold water (1000 mL) was added and the resulting mixture was extracted with ethyl acetate (3 x 250 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography eluting with 1 :4 ethyl acetate-petroleum ether to provide the title compound as a solid (52 g).

[0633] 1 H NMR (CDCI3): δ 7.69 (s, 1 H), 7.53 (d, 1 H), 7.32 (d, 1 H), 3.93 (s, 2 H), 2.28 (s, 3 H).

[0634] Step B: Preparation of 1-fluoro-2-isothiocyanato-3-nitrobenzene

[0635] To a mixture of 2-fluoro-6-nitroaniline (1.0 g, 6.4 mmol) in 1,2-dichlorobenzene (10 mL) at 0 °C was added 2 drops of dimethylformamide followed by thionyl chloride (1.46 mL, 19 mmol). The reaction mixture was heated at 160 °C for 1 h, cooled to room temperature and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography eluting with 1 :9 ethyl acetate-petroleum ether to provide the title compound as an oil (0.91 g).

[0636] 1 H NMR (CDCI3) δ 7.88 (d, 1 H), 7.46 (t, 1 H), 7.36 (m, 1 H).

[0637] Step C: Preparation of 3-chloro-4-[5-[(2-fluoro-6-nitrophenyl)amino]-1,3-dimethyl- 1 H-pyrazol-4-yl]benzonitrile

[0638] To a mixture of 3-chloro-4-(2-oxopropyl)benzonitrile (the product of Step A) (1.0 g, 5.2 mmol) in tetrahydrofuran (20 mL) at -10 °C was added potassium tert-butoxide (0.7 g, 6.2 mmol). After 30 minutes at -10 °C, 1 -fluoro-2-isothiocyanato-3-nitrobenzene (the product of Step B) (0.99 g, 5.0 mmol) in tetrafluoro furan (10 mL) was added to the reaction mixture and stirring was continued for about 15 minutes to provide a reaction mixture containing the intermediate compound 4-[1 - [[(2-chloro-6-nitrophenyl)amino]mercaptomethyl]-2-oxopropyl]-3-chloro-benzonitrile potassium salt which is the potassium salt of alpha-acetyl-N-(2-chloro-6-nitrophenyl)-2-chloro-4-cyano- phenylacetamidine. Methyl iodide (1.2 mL, 19 mmol) was added to the reaction mixture. After 20 minutes at -10 °C, the reaction temperature was allowed to reach 0 °C and acetic acid (5.0 mL) and methylhydrazine (85% in water, 0.5 g, 10 mmol) were added. The reaction mixture was allowed to warm to room temperature, heated under reflux for 2 h and then poured into ice-cold water (30 mL) and ethyl acetate (20 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2 x 10 mL). The combined organic extracts were washed with saturated sodium chloride solution (20 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography eluting with 2:3 ethyl acetate-petroleum ether to provide the title compound (a compound of the invention) as a light yellow solid (0.850 g).

[0639] 1 H NMR (CDCI3) δ 8.71 (d, 1 H), 7.85 (d, 1 H), 7.64-7.58 (m, 2H), 7.34-7.25 (m, 2H), 6.87-6.81 (m, 1 H), 3.75 (s, 3H), 1.99 (s, 3H).

[0640] Example 3

[0641] Preparation of N-(4-bromo-2-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3- dimethyl-1 H-pyrazol-5-amine (Compound 61 )

[0642] To a mixture of 4-(2-chloro-4-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine (i.e. the product from Example 1, Step B) (0.5 g, 2.1 mmol) in tetrahydrofuran (30 mL) at 0 °C was added potassium tert-butoxide (1 M in THF, 4.2 mL, 4.2 mmol) in portions. The reaction mixture was stirred at 0 °C for 1 h and then 5-bromo-l,2-difluoro-3-nitrobenzene (0.54 g, 2.3 mmol) was added dropwise. After 30 min at 0 °C, saturated aqueous ammonium chloride solution was added to the reaction mixture and the resulting mixture was extracted with ethyl acetate (100 mL). The aqueous layer was further extracted with ethyl acetate (2 x 40 mL) and the combined organic extracts were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography eluting with 40% ethyl acetate in petroleum ether to afford the title compound (compound of the invention) as a yellow solid (0.45 g).

[0643] 1 H NMR (CDCI3): δ 8.69 (br s, 1H), 7.77 (t, 1H), 7.66 (dd, 1H), 7.27 (dd, 2.0 Hz, 1H), 7.09-7.06 (m, 2H), 3.73 (s, 3H), 1.97 (s, 3H).

[0644] Example 4

[0645] Preparation of 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)- 1,3-dimethyl-lH-pyrazol-5-amine (Compound 93)

[0646] Step A: Preparation of l,l-dimethylethyl N-(4-bromo-2-fluoro-6-nitrophenyl)-N-[4- (2-chloro-4-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-yl]carbamate

[0647] To a mixture of N-(4-bromo-2-fluoro-6-nitrophenyl)-4-(2-chloro-4- fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine (i.e. the product of Example 3) (1 g, 2.2 mmol) and triethylamine (1.24 mL, 8.9 mmol) in dichloromethane (20 mL) at 0 °C was added di-tert-butyl dicarbonate (1.46 g, 6.7 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight, and then diluted with water (20 mL) and extracted with dichloromethane (2 x 20 mL). The combined organic extracts were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by column chromatography on silica gel, eluting with 40% ethyl acetate in petroleum ether, to provide the title compound as a yellow solid (750 mg).

[0648] 1 H NMR (CDCI3): δ 7.85 (s, 1H), 7.78 (s, 1H), 7.52-7.47 (m, 1H), 7.17-7.19 (m, 1H), 6.97-6.88 (m, 1H), 3.8 (s, 3H), 1.96 (s, 3H), 1.49 (s, 9H).

[0649] Step B: Preparation of 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6- nitrophenyl)-l,3-dimethyl-lH-pyrazol-5-amine

[0650] A mixture of N-(4-bromo-2-fluoro-6-nitrophenyl)-N-[4-(2-chloro-4-fluorophenyl)- 1,3-dimethyl- 1 H-pyrazol-5-yl]carbamic acid 1,1 -dimethylethyl ester (i.e. the product of Step A) (600 mg, 1.07 mmol), potassium carbonate (372 mg, 2.7 mmol), dichloro[1,1 '- bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane complex (1 :1 ) (40 mg, 0.05 mmol) and trimethylboroxine (0.54 mL, 3.9 mmol) in 1,4-dioxane (20 mL) was heated at reflux for 3 h. The reaction mixture was diluted with water (15 mL) and extracted with ethyl acetate (2 x 10 mL). The combined organic extracts were washed with saturated aqueous sodium chloride solution (3 x 5 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was dissolved in dichloromethane and trifluoroacetic acid (3:1 ; 4 mL) and stirred at room temperature for 16 h. The reaction mixture was concentrated under reduced pressure and the resulting material was dissolved in dichloromethane (5 mL) and washed with saturated aqueous sodium bicarbonate solution (2 mL). The aqueous layer was further extracted with dichloromethane (3 x 10 mL). The combined organic extracts were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by column chromatography on silica gel eluting with 40% ethyl acetate in petroleum ether to afford the title compound (a compound of the invention) as a yellow solid (210 mg).

[0651] 1 H NMR (CDCI3) δ 8.41 (s, 1 H), 7.45 (s, 1 H), 7.24-7.15 (m, 2H), 7.1 -7.01 (m, 2H), 3.72 (s, 3H), 2.15 (s, 3H), 1.95 (s, 3H).

[0652] Example 5

[0653] Alternative preparation of 3-chloro-4-[5-[(2-fluoro-6-nitrophenyl)amino]-1,3- dimethyl- 1 H-pyrazol-4-yl]benzonitrile (Compound 113)

[0654] Step A: Preparation of 1 -methyl-hydrazinecarbonitrile

[0655] A solution of cyanogen bromide (13.5 g, 127.5 mmol) and dichloromethane (250 mL) was cooled to 0 °C and then a mixture of methylhydrazine (85% aqueous solution, 6.0 g, 127.5 mmol), sodium carbonate (7.5 g, 63.9 mmol) and water (60 mL) was added dropwise with vigorous stirring. After visible signs of gas evolution had ceased, the aqueous layer was separated and extracted with dichloromethane (3x). The combined organic layers were dried over magnesium sulfate, filtered and the filtrate concentrated under reduced pressure to afford the title compound as an oil (6.0 g).

[0656] Step B: Preparation of 4-(5-amino-l,3-dimethyl-lH-pyrazol-4-yl)-3-chlorobenzonitrile

[0657] A mixture of 3-chloro-4-(2-oxopropyl)benzonitrile (13.7 g, 71.4 mmol) and l-methylhydrazine cyanohydrate (i.e. the product of Step A) (6.0 g, 86 mmol) was heated at 60 °C with stirring. After 48 h, the reaction mixture was dissolved in dichloromethane (100 mL) and water (100 mL), the layers were separated and the aqueous layer was extracted with dichloromethane (3x). The combined organic layers were dried over magnesium sulfate, filtered and the filtrate concentrated under reduced pressure. The resulting material was purified by column chromatography on silica gel eluting with 60% ethyl acetate in petroleum ether to afford the title compound as a light yellow solid (8.1 g).

[0658] LCMS: 247 (M+1)

[0659] Step C: Preparation of 3-chloro-4-[5-[(2-fluoro-6-nitrophenyl)amino]-l,3-dimethyl- lH-pyrazol-4-yl]benzonitrile

[0660] To a mixture of 4-(5-amino-l,3-dimethyl-lH-pyrazol-4-yl)-3-chlorobenzonitrile (i.e. the product of Step B) (1.2 g, 4.8 mol) in tetrahydrofuran (40 mL) at 0 °C was added dropwise potassium tert-butoxide (9.7 mL, 1M in tetrahydrofuran). The reaction mixture was stirred at 0 °C for 1 h and then 1,2-difluoro-3-nitrobenzene (0.85 g, 5.3 mmol) was added dropwise and stirring was continued at 0 °C for a further 30 minutes. The reaction mixture was diluted with saturated aqueous ammonium chloride and ethyl acetate (100 mL) and the layers were separated. The aqueous layer was extracted with ethyl acetate (40 mL x 2) and the combined organic extracts were washed with saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and the filtrate concentrated under reduced pressure. The resulting material was purified by column chromatography on silica gel eluting with 40% ethyl acetate in petroleum ether to afford a yellow solid. This yellow solid was crystallized from ethanol to afford the title compound (a compound of the invention) as a light yellow solid (560 mg).

[0661] 1 H NMR (CDC13) δ 8.71 (d, 1H), 7.85 (d, 1H), 7.63-7.58 (m, 2H), 7.33-7.25 (m, 2H), 6.86-6.82 (m, 1H), 3.75 (s, 3H), 1.99 (s, 3H).

[0662] LCMS: 386 (M+1).

[0663] The compounds disclosed in the following table can be prepared by the procedures described herein and methods known in the art. The following abbreviations are used in the subsequent table: Me means methyl, MeO means methoxy, EtO means ethoxy, and CN means cyano.

[0664] Table 1

[0665]

[0666]

[0667]

[0668] The disclosure also includes Tables 1A through 46A, each of which is of identical construction to Table 1 above, except that the row headings (i.e., “R 2 is CH3, R 3 is Cl and (R 4 ) m is 4-F”) are replaced by the corresponding row headings shown below.

[0669]

[0670]

[0671] Table 2

[0672]

[0673]

[0674]

[0675] Formulation / Utility

[0676] The compounds of the formula 1 (including N-oxides and salts thereof) of the present application or mixtures (i.e. compositions) comprising the compounds with at least one additional fungicidal compound as described in the Summary will generally be used as the fungicidal active ingredient in a composition (i.e. formulation) wherein at least one additional component is selected from the group consisting of surfactants, solid diluents and liquid diluents, serving as a carrier. The formulation or composition components are selected to be consistent with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, moisture and temperature.

[0677] Mixtures of component (a) (i.e. at least one compound of formula 1, N-oxides or salts thereof) with component (b) (e.g. selected from (b1) to (b54) as described above and salts thereof) and / or one or more other biologically active compounds or agents (i.e. insecticides, other fungicides, nematicides, acaricides, herbicides and other biological agents) can be formulated in various ways, including:

[0678] (i) Component (a), component (b) and / or one or more other biologically active compounds or agents can be formulated and applied separately or simultaneously, e.g. as a tank mix, in the appropriate weight ratios; or

[0679] (ii) Component (a), component (b) and / or one or more other biologically active compounds or agents can be formulated together in the appropriate weight ratios.

[0680] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water, flowable concentrates and / or suspoemulsions) optionally which can be gelled, and the like. General types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates and suspoemulsions. General types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

[0681] General types of solid compositions are dusts, powders, granules, pellets, prills, tablets, filled films (including seed coatings) and the like, 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. The active ingredient can be (micro)encapsulated and further formed into suspensions or solid formulations; alternatively, the entire formulation of the active ingredient can be encapsulated (or "coated"). Encapsulation can control or delay release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular formulations. High-strength compositions are primarily used as intermediates for further formulation.

[0682] Of note are composition embodiments in which particles of a solid composition comprising a compound of Formula 1 (or an N-oxide or salt thereof) are mixed with particles of a solid composition comprising component (b). These mixtures can be further mixed with particles comprising additional agricultural protectants. Alternatively, two or more agricultural protectants (e.g., a compound of Formula 1 of component (a), a compound of component (b), an agricultural protectant different from component (a) or (b)) can be combined in a solid composition of one set of particles, which is then mixed with particles of one or more sets of solid compositions comprising one or more additional agricultural protectants. These particle mixtures can be according to the general particle mixture disclosure of PCT Patent Publication WO 94 / 24861, or more preferably the uniform particle mixture teachings of U.S. Patent 6,022,552.

[0683] Sprayable formulations are typically dispersed in a suitable medium prior to spraying. Such liquid and solid formulations are prepared to be readily dilutable in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or a vegetable oil. The volume of spray can range from about one liter to several thousand liters per hectare, but more typically is in the range of from about ten to several hundred liters per hectare. The sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by air or ground application, or for application into the growth medium of the plant. Liquid and dry formulations can be metered directly into a drip irrigation system, or metered into a furrow during planting. Liquid and solid formulations can be applied as seed treatments to the seeds of crops and other desired vegetation prior to planting to protect developing roots and other below-ground plant parts and / or foliage by systemic uptake.

[0684] Formulations will typically contain up to 100 weight percent of an active ingredient, diluent, and surfactant in effective amounts in the approximate ranges below.

[0685]

[0686] 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, sucrose), silica, talc, mica, kieselguhr, urea, calcium carbonate, sodium and sodium 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.

[0687] Liquid diluents include, for example, water, N,N-dimethylalkaneamides (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 oils, n-paraffins, iso-paraffins), alkylbenzenes, alkylnaphthalenes, glycerols, glycerol triacetates, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone The present invention also includes 4-hydroxy-4-methyl-2-pentanone, acetic acid esters such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactates, dibasic esters, alkyl and aryl benzoates and gamma-butyrolactone, and alcohols which may be linear, branched, saturated or unsaturated such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, 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-C 22 ) glycerides of plant seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (maize oil), peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., tallow, lard, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which can be obtained by hydrolysis of glycerides from plant and animal sources and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd ed., Interscience, New York, 1950.

[0688] The solid and liquid compositions of the present invention typically contain one or more surfactants. When added to a liquid, surfactants (also known as "surface active agents") typically alter, and most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can act as wetting agents, dispersants, emulsifiers, or defoaming agents.

[0689] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present application include, but are not limited to: alcohol alkoxylates, such as alcohol alkoxylates based on natural and synthetic alcohols, which can be branched or straight chain, and 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; alkyl phenol alkoxylates, such as octyl phenol ethoxylate, nonyl phenol ethoxylate, dinonyl phenol ethoxylate, and dodecyl phenol ethoxylate (prepared from phenol 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 terminal block is prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyryl phenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated 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, alkyl peg (polyethylene glycol) resins, grafted 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.

[0690] Useful anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and their salts; carboxylated alcohols or alkyl phenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, alkyl phenol alkoxylates, and styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkyl phenols; 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 benzenes; sulfonates of condensed polynaphthalenes; sulfonates of naphthalene and alkyl naphthalenes; sulfonates of petroleum fractions; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinates.

[0691] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropylenediamines, tripropylenetriamine, and dipropylenetetraamine, and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as ammonium acetate and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides such as alkyl dimethyl amine oxides and bis-(2-hydroxyethyl)-alkyl amine oxides.

[0692] Mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants, can also be used in the compositions of the present application. Nonionic, anionic, and cationic surfactants and their recommended uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, McCutcheon Division of The Manufacturing Confectioner Publishing Co., annual American and International Editions; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, 7th Edition, John Wiley and Sons, New York, 1987.

[0693] The compositions of the present application can also contain formulation aids and additives known to those skilled in the art as formulation aids and additives. Such formulation aids and additives can control: pH (buffers), foaming during processing (antifoams such as polyorganosiloxanes (e.g., 416)), settling of active ingredients (suspending agents), viscosity (thixotropic thickening agents), microbial growth in the container (antimicrobial agents), product freeze (antifreeze agents), color (dye / pigment dispersions (e.g., Colorant Red)), elution (film-forming agent or tackifier), evaporation (evaporation retarder), and other formulation attributes. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymer, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer, and wax. 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 Division of Manufacturing Confectioner Publishing Company; and PCT Publication WO 03 / 024222.

[0694] The compounds of Formula 1 and any additional active ingredients are incorporated into the compositions of the present application typically by dissolving the active ingredients in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of the liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifying agent is typically added to emulsify the solvent containing the active ingredient upon dilution with water. Active ingredient slurries having a particle size of up to 2,000 μm can be wet milled using a media mill to obtain particles having a mean particle size of less than 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations generally require a dry milling process, resulting in a mean particle size in the range of 2 to 10 μm. Dusts and powders can be prepared by blending and, usually, by grinding (for example, 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 et seq., and WO 91 / 13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442, and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701, and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

[0695] One embodiment of the present application relates to a method for controlling a fungal pathogen comprising diluting a fungicidal composition of the present application (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.

[0696] The spray composition that forms by the fungicidal composition of the present invention of diluting enough concentration with water can provide the effect of fully controlling fungal pathogens, the adjuvant product of separate preparation also can be added in the spray bucket mixture.These extra adjuvants are commonly referred to as " spray adjuvant " or " bucket mix adjuvant ", and are included in any material that mixes in the spray bucket to improve the performance of pesticide or change the physical property of spray mixture.Adjuvant can be anionic or nonionic surfactant, emulsifier, petroleum-based crop oil, seed oil derived from crop, acidulant, buffer, thickener or defoamer.Adjuvant is used to enhance effect (for example, bioavailability, adhesion, permeability, coverage uniformity and protection durability), or minimizes or eliminates the spraying application problem associated with incompatibility, foaming, drift, evaporation, volatilization and degradation.In order to obtain optimal performance, according to the characteristic, preparation and target (for example, crop, insect pest) of active ingredient, select adjuvant.

[0697] The amount of adjuvant added to the spray mixture is generally in the range of about 2.5% to 0.1% by volume. The application rate of the adjuvant added to the spray mixture is typically between about 1 and 5 L per hectare. Representative examples of spray adjuvants include: 47% methylated rapeseed oil in liquid hydrocarbons (Syngenta), (Helena Chemical Company) polyether-modified heptamethyltrisiloxane and (BASF) 17% surfactant blend in 83% paraffinic mineral oil.

[0698] One method of seed treatment is to spray or dust the seeds with the compound of the present invention (i.e., as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally include a film former or adhesive. Therefore, typically, the seed coating composition of the present invention includes a biologically effective amount of a compound of Formula 1 and a film former or adhesive. Seed coating can be achieved by spraying a flowable suspending agent directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wet powders, solutions, suspoemulsions, emulsifiable concentrates, and emulsions in water can be sprayed on the seeds. This method is particularly useful for applying film coatings to seeds. Various coating machines and methods can be used by those skilled in the art. Suitable methods include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects [seed treatment: progress and prospects], 1994 BCPC monograph No. 57 and the references listed therein.

[0699] For further information on the field of formulation, see T.S. Woods, "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. 3,235,361, col. 6, line 16 to col. 7, line 19 and Examples 10-41; U.S. 3,309,192, col. 5, line 43 to col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, col. 3, line 66 to col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0700] In the following examples, all percentages are by weight, and all formulations are prepared in the conventional manner. Compound numbers refer to the compounds in Index Tables A-B. Without further elaboration, we believe that one of skill in the art can, using the preceding description, utilize the present application to its fullest extent. Therefore, the following examples are to be construed as merely illustrative, and not limitative of the disclosure in any way whatsoever.

[0701] Example A

[0702] High strength concentrate

[0703]

[0704] Example B

[0705] Wettable powder

[0706]

[0707] Example C

[0708] Granule

[0709] Compound 72 10.0% attapulgite granules (low volatile, 0.71 / 0.30 mm; 90.0% compound 72

[0710] U.S.S. No. 25-50 mesh

[0711] Example D

[0712] Extruded pellet

[0713]

[0714] Example E

[0715] Emulsifiable concentrate

[0716] Compound 112 10.0% polyoxyethylene sorbitol hexaoleate 20.0%

[0717] C6-C 10 fatty acid methyl ester 70.0%

[0718] Example F microemulsion

[0719]

[0720] Example G seed treatment

[0721]

[0722] Example H fertilizer stick

[0723]

[0724]

[0725] Example I suspension

[0726]

[0727] Example J emulsion in water

[0728]

[0729]

[0730] Example K

[0731] Oil dispersion

[0732]

[0733] Example L

[0734] Suspoemulsion

[0735]

[0736] Water-soluble and water-dispersible formulations are typically diluted with water prior to application to form an aqueous composition. Aqueous compositions (e.g., spray tank compositions) that are applied directly to a plant or portion thereof typically contain at least about 1 ppm or more (e.g., from 1 ppm to 100 ppm) of one or more compounds of the present application.

[0737] Seeds are typically treated at a rate from about 0.001 g (more typically about 0.1 g) to about 10 g per kg of seed (i.e., from about 0.0001% to 1% by weight of the seed prior to treatment). Flowable suspensions formulated for seed treatment typically comprise from about 0.5% to about 70% active ingredient, from about 0.5% to about 30% film-forming binder, from about 0.5% to about 20% dispersing agent, from 0% to about 5% thickening agent, from 0% to about 5% pigment and / or dye, from 0% to about 2% antifoam agent, from 0% to about 1% preservative, and from 0% to about 75% volatile liquid diluent.

[0738] The compounds of the present application are useful as plant disease control agents. Accordingly, the present application further includes a method for controlling plant diseases caused by fungal plant pathogens, comprising applying to the plant or portion thereof to be protected, or to the seed of the plant to be protected, an effective amount of a compound of the present application or a fungicidal composition containing said compound. The compounds and / or compositions of the present application provide control of diseases caused by a broad spectrum of fungal plant pathogens in the phyla Ascomycota, Basidiomycota, Zygomycota phyla, and the class of fungal-like Oomycata. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops. These pathogens include, but are not limited to, those listed in Table 1-1. For Ascomycetes and Basidiomycetes, the name of the teleomorph / anamorph / sexual stage is listed, where known, along with the name of the asexual / anamorph / sexual stage (in parentheses). Synonyms for the pathogen are indicated by an equal sign. For example, the teleomorph / anamorph / sexual stage name Phaeosphaeria nodorum is followed by the corresponding asexual / anamorph / sexual stage name Stagnospora nodorum and the synonymous older name Septoria nodorum.

[0739] Table 1-1

[0740]

[0741]

[0742]

[0743]

[0744] In addition to their fungicidal activity, the compositions or combinations 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 application can be used to increase (i.e., increase) the ratio of beneficial microorganisms to harmful microorganisms in contact with or in the agronomic environment of a crop plant or propagule thereof (e.g., seed, corm, bulb, tuber, cutting).

[0745] The compounds of the present application can be used to treat all plants, plant parts, and seeds. Plant and seed varieties and cultivars can be obtained by conventional methods of breeding and selection 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 plant or seed genome. A transgene is defined by its specific location in the plant genome and is referred to as a transformation or transgenic event.

[0746] Genetically modified plant cultivars which can be treated according to the application include all plants which have been modified by the use of genetic engineering methods, including but not limited to corn, soybean, cotton, canola, and other crops. Genetically modified plants that have been modified to be herbicide-tolerant, i.e., tolerant to herbicides that are active on photosynthesis or on the growth of plants, are for example glyphosate-tolerant, glufosinate-ammonium-tolerant, 2,4-dichlorophenoxyacetic acid-tolerant, or dicamba-tolerant plants. Further genetically modified plants are insect- resistant plants, i.e., plants made tolerant to attack by insects or other pests by genetic modification. Examples of such plants are plants that are resistant to attack by European corn borer or by cotton boll weevil. Further examples of genetically modified plants are plants that are tolerant to herbicides or other biotic stresses.

[0747] The treatment of genetically modified plants and seeds with the compounds of the present application can result in over-additive or synergistic effects. For example, the reduction of the application rate, the broadening of the activity spectrum, the increase of the tolerance to biotic / non-biotic stress or the enhancement of the storage stability can be greater than expected from the simply additive effects of applying the compounds of the present application on genetically modified plants and seeds.

[0748] The compounds and compositions of the present application can be used in seed treatments to protect the seed from plant diseases. In the context of the present disclosure and claims, treating seed means contacting the seed with a biologically effective amount of the compounds of the present application, typically formulated into a composition of the present application. The seed treatment protects the seed from soil-borne disease pathogens and can also generally protect the roots and other plant parts of the seedling that develops from the germinating seed from soil-borne pathogens. The seed treatment can also provide protection to the foliage by translocation of the compounds of the present application or second active ingredients into the developing plant. Seed treatments can be applied to all types of seeds, including those that germinate to form plants that are genetically transformed to express particular traits, such as those that express proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxins, or those that express herbicide resistance, such as phosphinothricin acetyl transferase that provides glyphosate resistance. Seed treatments using the compounds of the present application can also increase the vigor of the plant that grows from the seed.

[0749] The compounds of the present application and their compositions, both alone and in combination with other fungicides, nematicides, and insecticides, are particularly useful for seed treatment of crops including, but not limited to, maize or corn, soybean, cotton, cereals (for example, wheat, oats, barley, rye, and rice), potato, vegetables, and rape.

[0750] In addition, the compounds of the present application can be used to treat postharvest diseases of fruits and vegetables caused by fungi and bacteria. These infections 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., the host begins to change organization in a way that infection can progress); infection can also be caused by surface wounding resulting from mechanical or insect damage. In this regard, the compounds of the present application can reduce losses (i.e., losses resulting from 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 application can increase the time period during which perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) can be stored after harvest, either refrigerated or unrefrigerated, and remain edible and free from significant or deleterious degradation or contamination by fungi or other microorganisms. Treatment of edible plant parts before or after harvest with the compounds of the present application can also reduce the formation of toxic metabolites of fungi or other microorganisms, for example, mycotoxins such as aflatoxins.

[0751] Plant disease control is generally achieved by applying an effective amount of a compound of the present application to the parts 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 compounds can also be applied to the seed to protect the seed and the seedling that develops from the seed. The compounds can also be applied through irrigating water to treat the plant. Control of postharvest pathogens that infect preharvest produce is typically achieved by applying a compound of the present application in situ, and in cases where infection occurs after harvest, the compounds can be applied to the harvested crop as a dip, spray, fumigant, treatment wrap, and box liner.

[0752] The compounds can also be applied using unmanned aerial vehicles (UAV) to disperse the compositions disclosed herein over a planted area. In some embodiments, the planted area is an area containing a crop. In some embodiments, the crop is selected from a monocot or a dicot. In some embodiments, the crop is selected from rice, corn, barley, soybean, wheat, vegetables, tobacco, tea, fruit trees, and sugar cane. In some embodiments, the compositions disclosed herein are formulated for application as an ultra-low volume spray. Products applied by drone can use water or oil as the spray carrier. Typical spray volumes (including product) for global drone applications. 5.0 liters / acre - 100 liters / acre (approximately 0.5 gpa - 10 gpa). This includes a range from ultra-low volume (ULV) to low volume (LV). While not common, there can be instances where even lower spray volumes as low as 1.0 liter / acre (0.1 gpa) or even lower can be used.

[0753] Suitable application rates (e.g., fungicidally effective amounts) of component (a) (i.e., at least one compound selected from the group consisting of compounds of Formula 1, N-oxides, and salts thereof) and suitable application rates (e.g., biologically effective amounts, fungicidally effective amounts, or insecticidally effective amounts) of mixtures and compositions comprising component (a) according to the present application can be influenced by factors such as the plant disease to be controlled, the plant species to be protected, the population structure of the pathogen to be controlled, environmental humidity and temperature, and the like and should be determined under practical use conditions. One of ordinary skill in the art can readily determine the fungicidally effective amount necessary to achieve the desired level of plant disease control through simple experimentation. Leaves can generally be protected when treated at a rate of from less than about 1 g / ha to about 5,000 g / ha of active ingredient. Seeds and seedlings can generally be protected when treated at a rate of from about 0.001 g (more typically about 0.1 g) to about 10 g per kg of seed. One of ordinary skill in the art can readily determine application rates of component (a) and mixtures and compositions thereof, containing the particular combination of active ingredients according to the present application necessary to provide the spectrum of desired plant protection and control of plant diseases and, optionally, other plant pests, through simple experimentation.

[0754] The compounds and compositions of the present application can also be used to increase the vigor of a crop plant. This method comprises contacting a crop plant (e.g., a leaf, flower, fruit, or root) or a seed from which a crop plant grows with an amount (i.e., a biologically effective amount) of a composition comprising a compound of Formula 1 sufficient to achieve the desired plant vigor effect. Typically, the compound of Formula 1 is applied in a formulated composition. Although the compound of Formula 1 is typically applied directly to the crop plant or to a seed thereof, the compounds can also be applied to the locus of the crop plant, i.e., the environment of the crop plant, particularly in sufficient proximity to allow the compound of Formula 1 to migrate to the environment portion of the crop plant. The locus associated with this method most typically includes the growth medium (i.e., the medium that provides nutrients to the plant), typically soil in which the plant is growing. Thus, treatment of a crop plant to increase the vigor of the crop plant comprises contacting the crop plant, a seed from which the crop plant grows, or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.

[0755] Increasing the vigor of a crop plant can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by superior seed germination, crop emergence, and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., as measured by leaf area index), plant height, tiller number (e.g., for rice), root mass, and total dry weight of the vegetative mass of the crop; (c) improved crop yield as demonstrated by flowering time, flowering duration, number of flowers, total biomass accumulation (i.e., yield), and / or fruit or grain product quality marketability (i.e., yield quality); (d) enhanced ability of the crop to tolerate or prevent infection by plant disease pathogens and arthropod, nematode, or mollusk pests; and (e) increased ability of the crop to tolerate environmental stress such as exposure to extreme heat, suboptimal moisture, or phytochemicals.

[0756] The compounds and compositions of the present application can increase the vigor of a treated plant by preventing and / or curing plant disease caused by fungal plant pathogens in the plant's environment, as compared to an untreated plant. In the absence of such control of plant disease, the disease reduces the vigor of the plant by consuming plant tissue or sap, or by spreading plant pathogens such as viruses. Even in the absence of fungal plant pathogens, the compounds of the present application can increase the vigor of a plant by altering the plant's metabolism. Generally, the vigor of a crop plant will be most significantly increased by treating the plant with the compounds of the present application if the plant is growing in a non-ideal environment, i.e., an environment that includes one or more aspects that are not conducive to the plant realizing its full genetic potential as it would perform in an ideal environment.

[0757] Of note are methods for increasing the vigor of a crop plant, wherein the crop plant is growing in an environment that includes plant disease caused by a fungal plant pathogen. Also of note are methods for increasing the vigor of a crop plant, wherein the crop plant is growing in an environment that does not include plant disease caused by a fungal plant pathogen. Also of note are methods for increasing the vigor of a crop plant, wherein the crop plant is growing in an environment that includes an amount of water that is less than an ideal amount of water to support the growth of the crop plant.

[0758] The compounds and compositions of the present application can also be mixed with one or more other biologically active compounds or agents to form a multi-component pesticidal agent to impart an even broader spectrum of agricultural protection, including fungicides, insecticides, nematicides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect ecdysis inhibitors and root growth stimulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi. Accordingly, the present application is also directed to compositions comprising a compound of Formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount), and the composition can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compound or agent can be formulated into a composition comprising at least one of a surfactant, a solid or liquid diluent. For the mixtures of the present application, one or more other biologically active compounds or agents can be formulated together with the compound of Formula 1 to form a pre-mix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1 and the formulations combined together (e.g., in a spray tank) prior to application, or alternatively, applied sequentially.

[0759] As mentioned in the SUMMARY, one aspect of the present application is a fungicidal composition comprising a compound of Formula 1, N-oxide, or salt thereof (i.e., component a) and at least one other fungicide (i.e., component b) (i.e., a mixture or combination thereof). Of note are such combinations wherein the other fungicidally active ingredient has a different site of action than the compound of Formula 1. In certain instances, combinations with at least one other fungicidally active ingredient having a similar control spectrum but a different site of action would be particularly advantageous for resistance management. Accordingly, the compositions of the present application can further comprise a fungicidally effective amount of at least one additional fungicidally active ingredient having a similar control spectrum but a different site of action.

[0760] Examples of component (b) fungicides include acibenzolar-S-methyl, 4-dodecyl-2,6-dimethylmorpholine, ametoctradin, azaconazole, anilazine, azoxystrobin, benlate (including benlate-M), benodanil, benomyl, benothiadin (including benothiadin-isopropyl), benzovindiflucy, bethoxazin, binapacryl, bixafen, bithionol, carpropamid, carvyl, chlorothalonil, chlozolinate, climbazole, copper hydroxide, copper oxychloride, copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, dicarboximide, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclomezni, diclAcibenzolar-S-methyl, Ametoctradin, Bacillus subtillis, Bacillus subtillis var. tropicus, Bacillus subtillis var. amyloliquefaciens, Bacillus subtillis var. lentimorbus, Bacillus subtillis var. tiopeae, Bacillus subtillis var. indicus, Bacillus subtillis var. koreensis, Bacillus subtillis var. chungangensis, Bacillus subtillis var. mycoides, Bacillus subtillis var. subtilis, Bacillus subtillis var. subtilis natto, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtilis var. subtilis, Bacillus subtillis var. subtil3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1 H-inden-4-yl)-1 -methyl-1 H- pyrazole-4-carboxamide, 5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2- pyridyl]oxy]phenyl]ethyl]-4-quinazolinamine, 1 -[4-[4-[5R-[(2,6-difluorophenoxy)methyl]- 4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)- 1 H-pyrazol-1 -yl]ethanone, 4-fluorophenyl 4-fluorophenyl N-[1 -[[[1 -(4- cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)methoxy]- 4-pyrimidinamine, alpha-(methoxyimino)-N-methyl-2-[[[1 -[3-(trifluoromethyl)phenyl]ethoxy] imino]methyl]benzeneacetamide, and [[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2- methyl-1 -oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]- 3-pyridyl]oxy]methyl 2-methylpropanoate. Thus, of interest are fungicidal compositions comprising as component (a) a compound of Formula 1 (or an N-oxide or salt thereof) and as component (b) at least one fungicide selected from the preceding list.

[0761] Of particular note are compounds of Formula 1 (or N-oxides or salts thereof) (i.e., component (a) in the composition) in combination with a component (b) compound selected from the group consisting of aminophenazole (Reg. No. 1531626-08-0), azoxystrobin, benzovindiflucarb, bifenazate, captan, carpropamid, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, dichlorophenyl-dichloro hydrazine (Reg. No. 957144-77-3), diethofencarb, difenacozole, dimoxystrobin, fluquinconazole, ethaboxam, chlozolinate, fenarimol, fluazinam, fludioxonil, fluindapyr, fluopicolide, flusilazole, flutianil, flutriafol, fluazinam, folpet, fluquinconazole, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, flutriafol, fl4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazol-3-thione and meso-1 -[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1 - ylsulfanyl)-1 H-1,2,4-triazole (i.e. as component (b) in the composition).

[0762] Of particular note are compounds of Formula 1 (or N-oxides or salts thereof) (i.e., component (a) in the composition) in combination with a component (b) compound selected from the group consisting of aminophenylarsonic acid (Registry No. 1531626-08-0), azoxystrobin, benzovindiflucarb, bifenazate, captan, carpropamid, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, dichlorophenyl-dichloroazene (Registry No. 957144-77-3), diethofencarb, difenacozole, dimoxystrobin, dipyridyone, epoxiconazole, ethaboxam, fenbuconazole, fenpiclonil, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, fluopyram, flusilazole, flutianil, flutriafol, fluxapyroxad, folpet, fluquinconazole (Registry No. 1314008-27-9), iprodione, iprovalicarb, isoflucypram, isopyrazam, kresoxim-methyl, mancozeb, mandaraquin, meptyldinocap, metalaxyl (including metalaxyl-M / precis), metconazole, metrafenone, methyltetrahydropyridine (Registry No. 1472649-01-6), myclobutanil, nu-2-dihydro-3H-1,2,4-triazole-3-thione and meso-1 -[[(2R,3S)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1 - ylthio)-1 H-1,2,4-triazole (i.e., as component (b) in the composition).

[0763] It is generally preferred to use the compounds of Formula 1, N-oxides, and salts thereof for better

[0764] It is generally preferred to use the compounds of Formula 1, N-oxides, and salts thereof for better

[0765] In the fungicidal compositions of the present application, component (a) (i.e., at least one compound selected from the group consisting of the compounds of Formula 1, N-oxides, and salts thereof) and component (b) are present in fungicidally effective amounts. The weight ratio of component (b) (i.e., one or more additional fungicidal compounds) to component (a) is generally between about 1 :3000 to about 3000:1, and more typically between about 1 :500 and about 500:1. Of note are compositions wherein the weight ratio of component (a) to component (b) is from about 125:1 to about 1 :125. Of particular note are compositions wherein the weight ratio of component (a) to component (b) is from about 25:1 to about 1 :25, or from about 5:1 to about 1 :5. One of skill in the art can determine by simple experimentation the weight ratio and application rate of fungicidal compounds needed to achieve the desired spectrum of fungicidal protection and control. It will be apparent that the inclusion of additional fungicidal compounds in component (b) can extend the spectrum of plant diseases controlled beyond that controlled by component (a) alone. In addition, exemplary weight ratios for combinations of the fungicidal compounds of the present application are provided below in Tables A1-A15 and C1-C15. Table B1 below lists the typical, more typical, and most typical ratio ranges for the specific fungicidal compounds involved in component (b).

[0766] Table Al discloses specific mixtures of a compound of component (a) with a compound of component (b). The compound of component (a) is identified by its compound number, and the compound description is found in the Index Tables A-B. The entries under the heading "Illustrative Ratios" disclose three specific weight ratios of component (a) to component (b) for the disclosed mixtures. For example, the first row of Table Al discloses a mixture of Compound 1 of the present application with Alantoin-S-methyl, where the weight ratio of Compound 1 to Alantoin-S-methyl is 1 : 1, 1 : 4, or 1 : 18.

[0767]

[0768]

[0769]

[0770]

[0771]

[0772]

[0773]

[0774]

[0775]

[0776]

[0777] (*) Weight ratio of component (b) to component (a).

[0778] Tables A2 through A15 are each constructed identically to Table Al above, except that the entries under the heading "Component (a)" are replaced by the corresponding component (a) column entries shown below. Thus, for example, in Table A2, the entries under the heading "Component (a)" all recite "Compound 18". Thus, the first entry in Table A2 specifically discloses a mixture of Compound 18 with Alantoin-S-methyl. Tables A3 through A15 are similarly constructed.

[0779]

[0780] Table B1 lists combinations of component (b) compounds with component (a) compounds illustrating the mixtures, compositions, and methods of the present application. The first column of Table B1 lists a particular component (b) compound (e.g., "acibenzolar-S-methyl" is the first entry). The second, third, and fourth columns of Table B1 list ranges of weight ratios relative to the rate at which component (a) compounds are typically applied to field grown crops. Thus, for example, the first row of Table B1 discloses that combinations of component (a) compounds with acibenzolar-S-methyl are typically applied at a weight ratio of component (a) to component (b) between 2: 1 and 1 : 180, more typically between 1 : 1 and 1 : 60, and most typically between 1 : 1 and 1 : 18. The remaining rows of Table B1 will be similarly constructed. Of particular note are compositions comprising mixtures of any one of the compounds listed in Example 97 as component (a) with the compounds listed in the component (b) column of Table B1. Table B1 thus supplements the particular ratios disclosed in Tables A1-A15 with ranges of ratios for these combinations.

[0781] Table B1

[0782]

[0783]

[0784]

[0785]

[0786]

[0787]

[0788]

[0789]

[0790]

[0791]

[0792]

[0793]

[0794] As already indicated, the present application includes embodiments in which in the composition comprising components (a) and (b), component (b) comprises at least one fungicidal compound from each of two groups selected from (bl) to (b54). Table Cl lists specific mixtures to illustrate embodiments in which component (b) comprises at least one fungicidal compound from each of two groups selected from (bl) to (b54). Table Cl discloses mixtures of Compound 1 with at least two component (b) compounds. The entries under the heading "Illustrative Ratios" disclose three specific weight ratios of component (a) to each component (b) compound. For example, the first row discloses mixtures of Compound 1 with cyproconazole and azoxystrobin and lists weight ratios of Compound 1 to cyproconazole to azoxystrobin of 1 : 1 : 1, 2: 1 : 1, or 3: 1 : 1.

[0795] Table C1

[0796]

[0797]

[0798]

[0799]

[0800]

[0801]

[0802] (*) The weight ratio of component (a) to component (b) in order.

[0803] Tables C2 to C15 are each of identical construction to Table Cl above, except that the entries under the heading "Component (a)" are replaced by the corresponding entries for component (a) shown below. Thus, for example, in Table C2, the entries under the heading "Component (a)" all recite "Compound 18". Thus, the first entry in Table C2 specifically discloses a mixture of Compound 18 with cyproconazole and azoxystrobin, with illustrative weight ratios of Compound 18 to cyproconazole to azoxystrobin of 1 : 1 : 1, 2: 1 : 1, and 3: 1 : 1. Tables C3 to C15 are similarly constructed.

[0804]

[0805] Of note are compositions of the present application which comprise a compound of Formula 1 (or an N-oxide or salt thereof) in combination with at least one other fungicidal compound having a different site of action than the compound of Formula 1. In certain instances, combinations with at least one other fungicidal compound having a similar control spectrum but a different site of action would be particularly advantageous for resistance management. Thus, the compositions of the present application can advantageously comprise at least one fungicidally active compound selected from the group consisting of (b1) to (b54) as described above which have a similar control spectrum but a different site of action.

[0806] Component (a), or the combination of component (a) and component (b), can be further mixed with one or more other biologically active compounds or agents, including insecticides, nematicides, fungicides, acaricides, herbicides, herbicide safeners, growth regulators such as insect ecdysis inhibitors and root growth stimulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi, to form a multi-component pest control agent, to impart an even broader spectrum of agricultural protection. Thus, the present application is also directed to a composition comprising a fungicidally effective amount of component (a), or a mixture of component (a) and component (b), and a biologically effective amount of at least one additional biologically active compound or agent, and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can also be formulated separately into a composition comprising at least one of a surfactant, a solid or liquid diluent. For the compositions of the present application, one or more other biologically active compounds or agents can be formulated together with either or both of components (a) and (b) to form a pre-mix, or one or more other biologically active compounds or agents can be formulated separately from components (a) and (b) and the formulations combined together (e.g., in a spray tank) prior to application, or alternatively, applied sequentially.

[0807] Examples of such biologically active compounds or agents that can be formulated with component (a), or the combination of component (a) and component (b), are: insecticides such as abamectin, acephate, acifluorfen, acetamiprid, acrinathrin, acynonapyr, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, benzoylpyrimoxan, bifenthrin, kappa-bifenthrin, bifenazate, bistrifluron, borax, broflanilide, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlordimeform, chlorfenapyr, chlorfluazuron, chloroprallethrin, chlorpyrifos, chlorpyrifos-e, chlorpyrifos-methyl, chromafenozide, clofentezine, cis-chloroprallethrin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyclometrin, cyanofenpham, cyanofenpham, cyflumetofen, cyhalothrin, beta-cyhalothrin, chlorfenapyr, chlorfenapyr, cyflumetofen, cyflumetofen, cyhalothrin, cis-cyhalothrin, zeta-cyhalothrin, cyromazine, cyromazine, diafenthiuron, diazinon, dicloromesotiaz, dieldrin, diflubenzuron, dimefluthrin, dimethoate, ethiprole, ethiprole, etofenprox, fenoxycarb, fenoxycarb, fenpyroximate, fipronil, flonicamid, flonicamid, flubendiamide, flubrocythrinate, flucythrinate, flumethrin, flumite, flumite, flumioxazin, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumite, flumitePyrethrin, pyridabenz, pyridalyl, pyrimethamine, pyraclostrobin, pyriproxyfen, rotenone, ryanodine, silafluanid, spinosad, spinosad, spirodiclofen, spiromesifen, spiropidion, spirotetramat, sulfoxaflor, tebufenozide, tebufenpyrad, tefluthrin, κ-tefluthrin, terbufos, tetracycline, cypermethrin, tetrafluthrin, tetracycline, thiacloprid, thiamethoxam, thiodicarb, dimethoate, thiazolin, tolfenpyrad, tralomethrin, trichlorfon, triflumuron, tyclopyrazoflor, ζ-cypermethrin, Bacillus thuringiensis delta-endotoxin, entomopathogenic bacteria, entomopathogenic viruses, or entomopathogenic fungi.

[0808] General references to these agricultural protectants (i.e., insecticides, fungicides, nematicides, acaricides, herbicides and bioagents) include The Pesticide Manual, 13th edition, ed. CDS Tomlin, British Crop Protection Council, Farnham, Surrey, UK, 2003 and The Biopesticide Manual, 2nd edition, ed. L.G. Copping, British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0809] For embodiments in which one or more of these different mixing partners are used, the weight ratio of these different mixing partners (total amount) to component (a), or the mixture of component (a) and component (b), is generally between about 1:3000 and about 3000: 1. Of note are weight ratios between about 1:100 and about 3000: 1, or between about 1:30 and about 300: 1 (e.g., ratios between about 1: 1 and about 30: 1). It will be apparent that the inclusion of these additional components can expand the spectrum of diseases controlled beyond that controlled by component (a), or the mixture of component (a) and component (b).

[0810] The compound of component (a) and / or its combination with the compound of component (b) and / or one or more other biologically active compounds or agents can be applied to plants that have been genetically transformed to express a protein toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxin). The action of the exogenously applied component (a) of the present invention, alone or in combination with component (b), can act synergistically with the expressed toxin protein.

[0811] Of note are combinations or compositions comprising component (a) or components (a) and (b) as described in the SUMMARY, which further comprise at least one invertebrate pest control compound or agent (e.g., an insecticide, acaricide). Of particular note are compositions comprising component (a) and at least one (i.e., one or more) invertebrate pest control compound or agent, which can then be subsequently combined with component (b) to provide a composition comprising components (a) and (b) and one or more invertebrate pest control compound or agent. Alternatively, without first being mixed with component (b), a biologically effective amount of a composition comprising component (a) with at least one invertebrate pest control agent can be applied to a plant or plant seed (directly or through the environment of the plant or plant seed) to protect the plant or plant seed from disease caused by a fungal pathogen and injury caused by an invertebrate pest.

[0812] Notably, compositions of the present application comprise, in addition to the compound of component (a) (alone or in combination with component (b)), at least one unsegmented pest control compound or agent selected from the group consisting of abamectin, acetamiprid, acrinathrin, afidopyropen, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, chlorfenapyr, chloethocarb, chlorfluazuron, clothianidin, cyantraniliprol, cyclaniliprol, cycloprothrin, cyfluthrin, beta-cyfluthrin, gamma-cyfluthrin, lambda-cyfluthrin, zeta-cyfluthrin, diacloden, dicrotophos, dinotefuran, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fipronil, flometoquin, flonicamid, flubendiamide, flufensulfone, flufenoxuron, flufenoxystrobin, fluindapyr, fluoroimid, fluoroxydime, fluvalinate, fosthiazate, furathiocarb, hexythidene, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, kappa-cyfluthrin, lambda-cyfluthrin, methoxychlor, methomyl, methoprene, methoxyfenozide, metofluthrin, monoflurothrin, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyrrolidono, rannate, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tefluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap, tralomethrin, triazamate, triflumuron, triflumuroxystrobin, triflumuron, tritrophenyltriazine, typhus, bacillus thuringiensis delta-endotoxin, all strains and biotypes of bacillus thuringiensis, and all strains of nucleopolyhedrovirus.

[0813] In certain instances, combinations of the compound of component (a) (alone or in admixture with component (b)) of the present application with other biologically active, particularly fungicidal, compounds or agents (i.e., active ingredients) can result in an effect greater than additive (i.e., synergistic). It is always desirable to reduce the amount of active ingredient released into the environment while ensuring effective pest control. Such combinations can be advantageously used to reduce crop production costs and to reduce environmental load when the fungicidal active ingredient produces an enhanced effect at an application rate to achieve an agronomically satisfactory level of fungal control.

[0814] Table D1 lists specific combinations of an invertebrate pest control agent and Compound 1 (the compound number refers to the compound in Index Tables A-B) as the compound of Component (a), illustrating mixtures and compositions comprising these active ingredients and methods of using them in accordance with the application. The second column of Table D1 lists the specific invertebrate pest control agent (e.g., "abamectin" in the first row). The third column of Table D1 lists the mode of action (if known) or chemical class of the invertebrate pest control agent. The fourth column of Table D1 lists one or more embodiments of a range of weight ratios at which the invertebrate pest control agent is typically applied relative to Compound 1 alone or in combination with Component (b) (e.g., abamectin to Compound 1 is "50: 1 to 1 :50" by weight). Thus, for example, the first row of Table D1 specifically discloses a combination of Compound 1 and abamectin is typically applied in a weight ratio between 50: 1 and 1 :50. The remaining rows of Table D1 will be similarly constructed.

[0815] Table D1

[0816]

[0817]

[0818]

[0819]

[0820] Tables D2 through D15 are each similarly constructed as Table D1 above, except that the entries under the heading "Component (a)" are replaced by the corresponding Component (a) column entries shown below. Thus, for example, in Table D2, the entries under the heading "Component (a)" all recite "Compound 18", and the first row under the column headings in Table D2 specifically discloses a mixture of Compound 18 and abamectin. Tables D3 through D15 are similarly constructed.

[0821]

[0822] Compositions comprising a compound of Formula 1 that can be used in seed treatment agents can further comprise bacteria and fungi that have the ability to provide protection from the harmful effects of plant pathogenic fungi or bacteria and / or soil dwelling animals such as nematodes. Bacteria that exhibit nematicidal properties can include, but are not limited to, Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria penetrans. A suitable strain of B. firmus is sold as BioNem TMCommercially available strain CNCM 1-1582 (GB-126). A suitable Bacillus cereus strain is strain NCMM 1-1592. Both Bacillus strains are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are Bacillus amyloliquefaciens IN937a and Bacillus subtilis strain GB03. Bacteria exhibiting fungicidal properties may include, but are not limited to, Bacillus pumilus strain GB34. Fungal species exhibiting nematicidal properties may include, but are not limited to, Myrothecium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum.

[0823] Seed treatments may also contain one or more nematicides of natural origin, such as elicitor proteins known as harpins, which are isolated from certain bacterial plant pathogens such as Erwinia amylovora. Examples are N-Hibit TM Gold CST available Harpin-N-Tek seed treatment technology.

[0824] Seed treatments may also include one or more species of legume root-nodulating bacteria, such as the microsymbiotic nitrogen-fixing bacterium Bradyrhizobium japonicum. These inoculants may optionally include one or more lipid chitosan oligosaccharides (LCOs), which are nodulation (Nod) factors produced by Rhizobium bacteria during the initiation of nodule formation on the roots of legumes. For example, Branded seed treatment technology combines LCO promoter technology with inoculants TM .

[0825] Seed treatments may also contain one or more isoflavones, which may increase the level of root colonization by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing root uptake of nutrients such as water, sulfates, nitrates, phosphates, and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin, and tricholin. Formononetin is used as a mycorrhizal inoculant in products such as The active ingredient in AG is available.

[0826] The seed treatment may also contain one or more plant activators that induce systemic acquired resistance in the plant after exposure to the pathogen. An example of a plant activator that induces such a protective mechanism is acibenzolar-S-methyl.

[0827] In the fungicidal compositions of the present application, the compound of formula 1 of component (a) can act synergistically with the additional fungicidal compound of component (b) to provide such beneficial results as an expanded spectrum of plant diseases controlled, an extended duration of preventive and curative protection, and inhibition of the proliferation of resistant fungal pathogens. In particular embodiments, compositions are provided according to the present application comprising component (a) and component (b) in proportions useful, inter alia, for the control of specific fungal diseases such as Alternaria solani, Erysiphe graminis, Botrytis cinerea, Puccinia recondita, Rhizoctonia solani, Ascochyta tritici, Septoria tritici.

[0828] Mixtures of fungicides can also provide better disease control than might be expected based on the activities of the individual components. Such synergism has been described as "the cooperative action of two components of a mixture so that the total effect is greater than, or more than the sum of the individual effects" (see P. M. L. Tames, Neth. J. Plant Pathology 1964, 70, 73-80). In a method of providing plant disease control, wherein synergism is exhibited from a combination of active ingredients (e.g., fungicidal compounds) applied to a plant or seed, the active ingredients are applied in synergistic weight ratios and in synergistic (i.e., synergistically effective) amounts. The measure of disease control, inhibition, and prevention cannot exceed 100%. Thus, the expression of substantial synergism typically requires the use of application rates of active ingredients, wherein the active ingredients alone provide far less than 100% of the effect, such that their additive effect is substantially less than 100%, to allow the possibility of increased effect due to synergism. On the other hand, application rates of active ingredients that are too low can show little activity in the mixture even with the benefit of synergism. One skilled in the art can readily determine and optimize the weight ratios and application rates (i.e., amounts) of fungicidal compounds that provide synergism through simple experimentation.

[0829] The presence of a synergistic effect between two active ingredients is determined by means of the Colby formula (see Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds, (1967), 15, 20-22):

[0830]

[0831] The presence of a synergistic interaction between two active ingredients is determined using the Colby method by first calculating the expected activity p of a mixture based on the activities of the two components applied separately. Synergy occurs if p is lower than the experimentally determined effect. In the above formula, A is the percent controlled fungicidal activity of one component applied alone at rate x. Term B is the percent controlled fungicidal activity of the second component applied at rate y. The formula estimates p, the expected fungicidal activity of a mixture of A at rate x and B at rate y, if their effects are strictly additive and no interaction occurs.

[0832] The seed treatment agent can also comprise one or more plant activators that elicit systemic acquired resistance in the plant upon contact with a pathogen. An example of a plant activator that elicits such protective mechanisms is acibenzolar-S-methyl.

[0833] 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. Compound descriptions are referenced in the following index tables A-B. In index table A the following abbreviations are used: Me means methyl, i-Pr means isopropyl, MeO means methoxy and -NO2 means nitro. The abbreviation "Cmpd." stands for "Compound" and the abbreviation "Ex." stands for "Example" and is followed by a number that indicates in which example the compound was prepared. In index table A, for the substituent R 4 and R 5 the listed position numbers are shown in the structure above the table. The order in which the substituents R 4 and R 5 are listed can differ from the Chemical Abstracts nomenclature system if the difference does not affect the meaning. For example, compound 1 in index table A lists the substituent R 5 in position 6 (i.e., 6-F), whereas the CAS name for compound 1 is 4-(2-bromo-4,6-difluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1 H-pyrazol-5-amine. In the "AP + (M+1)" column the values reported are the molecular weights of the observed molecular ions formed by adding H + (molecular weight 1) to the molecule with the greatest isotopic abundance (i.e., M); in the "AP - (M-1)" column the values reported are the molecular weights of the observed molecular ions formed by losing H + (molecular weight 1) from the molecule with the greatest isotopic abundance (i.e., M). Values are not reported for the presence of one or more of the higher atomic weight isotopes of higher abundance (e.g., 37 Cl、 81The presence of molecular ions of formula (Br) was observed by mass spectrometry using electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) to observe the reported M+1 and M-1 peaks.

[0834] Index Table A

[0835]

[0836] R 5 A dash "-" in a column means that R is not present 5 substituents and the remaining carbon valencies are occupied by hydrogen atoms.

[0837]

[0838]

[0839]

[0840]

[0841]

[0842]

[0843]

[0844]

[0845] Index Table B

[0846]

[0847] Biological Examples of the Invention

[0848] General protocol for preparing test suspensions for testing A-F: The test compound was first dissolved in acetone in an amount equal to 3% of the final volume and then suspended in acetone and purified water containing 250 ppm of the surfactant PEG400 (polyol ester) (50 / 50 mix by volume) at the desired concentration (in ppm). The resulting test suspensions were then used for testing A-F.

[0849] Test A

[0850] The test solutions were sprayed to runoff point on wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (the causal agent of wheat leaf blotch) and incubated for 48 h in a saturated atmosphere at 24°C and then moved to a growth chamber at 20°C for 17 days, after which disease rating was performed.

[0851] Test B

[0852] Test solutions were sprayed to run-off on wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici (the causal agent of wheat leaf rust) and incubated for 24 h in a saturated atmosphere at 20°C and then moved to a growth chamber at 20°C for 7 days after which visual disease ratings were performed.

[0853] Test C

[0854] Test solutions were sprayed to run-off on wheat seedlings. The next day, the seedlings were inoculated with a spore dusting of Blumeria graminis f. sp. tritici (also known as Erysiphe graminis f. sp. tritici), the causal agent of wheat powdery mildew, and incubated for 8 days in a growth chamber at 20°C after which visual disease ratings were performed.

[0855] Test D

[0856] Test solutions were sprayed to run-off on soybean seedlings. The next day, the seedlings were inoculated with a spore suspension of Phakopsora pachyrhizi (the causal agent of Asian soybean rust) and incubated for 24 h in a saturated atmosphere at 22°C and then moved to a growth chamber at 22°C for 8 days after which visual disease ratings were performed.

[0857] Test E

[0858] Test solutions were sprayed to run-off on tomato seedlings. The next day, the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of tomato gray mold) and incubated for 48 h in a saturated atmosphere at 20°C and then moved to a growth chamber at 24°C for 3 days after which visual disease ratings were performed.

[0859] Test F

[0860] Test solutions were sprayed to run-off on tomato seedlings. The next day, the seedlings were inoculated with a spore suspension of Alternaria solani (the causal agent of tomato early blight) and incubated for 48 h in a saturated atmosphere at 27°C and then moved to a growth chamber at 20°C for 3 days after which visual disease ratings were performed.

[0861] The results of the tests A-F are given in the following Table A. The rating 100 indicates 100% disease control and the rating 0 indicates no disease control (relative to the control). A dash (-) means that the compound was not tested.

[0862] Table A

[0863]

[0864]

[0865]

[0866]

[0867]

[0868]

[0869]

[0870]

[0871]

[0872]

[0873] The test results presented in the above Table A for the compounds of formula 1 illustrate the fungicidal activity of component (a) which contributes to the plant disease control utility of the compositions comprising component (a) in combination with component (b) and optionally at least one additional fungicidal compound according to the present application.

[0874] Biological Comparative Examples

[0875] General protocol for the preparation of the test suspensions for tests A1-F1 : The test compound was first dissolved in acetone in an amount equal to 3% of the final volume and then suspended in acetone and purified water (50 / 50 mix by volume) containing 250 ppm of the surfactant PEG400 (polyol ester) at the desired concentration (in ppm). The resulting test suspensions were then used for tests A1-F1.

[0876] Test A1

[0877] Test solutions were sprayed to run-off on wheat seedlings. The following day, the seedlings were inoculated with a spore suspension of Septoria tritici (causal agent of wheat leaf blotch) and incubated for 48 h at 20°C under saturated atmosphere and then moved to a growth chamber at 20°C for 17 days after which disease rating was performed.

[0878] Test B1

[0879] Test solutions were sprayed to run-off on wheat seedlings. The following day, the seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici (causal agent of wheat leaf rust) and incubated for 24 h at 20°C under saturated atmosphere and then moved to a growth chamber at 20°C for 7 days after which disease rating was performed.

[0880] Test C1

[0881] Test solutions were sprayed to run-off on wheat seedlings. The following day, the seedlings were inoculated with a spore dusting of Blumeria graminis f. sp. tritici (also known as Erysiphe graminis f. sp. tritici, causal agent of wheat powdery mildew) and incubated for 8 days at 20°C in a growth chamber after which visual disease rating was performed.

[0882] Test E1

[0883] Test solutions were sprayed to run-off on tomato seedlings. The following day, the seedlings were inoculated with a spore suspension of Botrytis cinerea (causal agent of tomato gray mold) and incubated for 48 h at 20°C under saturated atmosphere and then moved to a growth chamber at 24°C for 3 days after which visual disease rating was performed.

[0884] Test F1

[0885] Test solutions were sprayed to run-off on tomato seedlings. The following day, the seedlings were inoculated with a spore suspension of Alternaria solani (causal agent of tomato early blight) and incubated for 48 h at 27°C under saturated atmosphere and then moved to a growth chamber at 20°C for 3 days after which visual disease rating was performed.

[0886] Results for Test A1-F1 are given in Table B below. Rating 100 indicates 100% disease control and rating 0 indicates no disease control (relative to control). Data is presented for the following compounds:

[0887]

[0888] Table B

[0889]

Claims

1. A fungicidal composition comprising: (a) a compound having Formula 1 and salts thereof, which is: and (b) at least one additional fungicidal compound selected from the group consisting of: (b3) demethylation inhibitor fungicides selected from the group consisting of: anilazin, bithionol, bixpyrilinate, bixafen, carpropamid, fenhexamid, fenoxanil, hymexazol, iminoctad, imazalil, imazapic, iprobenfos, prochloraz, triflumizole, triticonazole, bitertanol, bromocyclen, cyproconazole, diclobutrazol, difenacozide, difenacozon, fluquinconazole, etaconazole, fenbuconazole, fluquinconazole, hexaconazole, metconazole, pefurazoate, triclozole, uniconazole, propiconazole, prothioconazole, ipfenpyrazol, quinazamyl, simeconazole, uniconazole-P, silthioconazole, tetraconazole, triflumizole, triforine, uniconazole, myclobutanil, uniconazole-P, and uniconazole-P; (b5) amine / morpholine fungicides selected from the group consisting of: 4-dodecyl-2,6-dimethylmorpholine, dodemorph acetate, fenpropimorph, tridemorph, spiroxamine, fenpropidine, fenpiclonil, and spirocyclic lactone; (b7) succinate dehydrogenase inhibitor fungicides selected from the group consisting of: benodanil, flutolanil, fenfuram, ethaboxam, fluopimomide, ofurace, carboxin, oxycarboxin, thifluzamide, zoxamide, bifenalaxy-hub, fluindapyr, fluazinam, pyracarbolid, pyribencarb, pyridaben, pyrisoxazole, pyraclostrobin, pyribencarb, pyridinitr, pyrifenox, pyrimidinyl, pyrimidinyl, pyrimidinyl, and pyrimidinyl; (b9) anilide pyrimidine fungicides selected from the group consisting of: azaconazole, cyprodinil, and pyrimethanil; (b11) quinone outside inhibitor fungicides selected from the group consisting of: azoxystrobin, coumoxystrobin, enoxastrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, datura stramonium, pyraclostrobin, pyramoconazole, pyramoconazole, chlorfenazole, chlorothalonil, trifloxystrobin, dimoxystrobin, enoxystrobin, famoxadone, fenamidone, fluoxystrobin, pyraclostrobin, pyramoconazole, and pyraclostrobin; (b12) phenylpyrrole fungicides selected from the group consisting of: fenpropidin and fludioxonil; (b13) naphthylamine fungicides selected from the group consisting of: pyroxychlor and pyroxyfur; (b16b) melanin biosynthesis inhibitor-polyketide synthase fungicides selected from the group consisting of: tolylfluanid; (b17) ketoreductase inhibitor fungicides selected from the group consisting of: spicamadin, metrafenone, quinofumelin, and fluquinconazole; (b21) quinone inside inhibitor fungicides selected from the group consisting of: cyazofamid, indaziflam, and fenpicolil; (b52) multi-site activity fungicides selected from the group consisting of: copper oxychloride, copper sulfate, copper hydroxide, Bordeaux mixture, elemental sulfur, ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram, fentin acetate, captan, chloroneb, dichlofluanid, guazatine, iminoctadine albesilate, iminoctadine tris(albesilate), iminoctadine triacetate, guazatine, dithianon, binamite, and flutolanil; and (b54) other fungicides selected from the group consisting of pyridinylamide, methyltetrahydropyrimidine, pyridine chloromethyl, aminophenylol, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate and N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolcarboxamide.

2. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound selected from (b3).

3. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound selected from (b7).

4. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound selected from (b21).

5. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound from each of two different groups selected from (b3), (b5), (b7), (b9), (b11), (b12), (b13), (b16b), (b17), (b21), (b52) and (b54).

6. The composition of claim 1, wherein, Component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflucarb, bifenathi, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidine, fenpropimorph, fluindapyr, flutriafol, fluoxastrobin, mancozeb, metominostrobin, orysastrobin, prothioconazole, pyraclostrobin, tebuconazole and trifloxystrobin.

7. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, benzovindiflucarb, bifenathi, chlorothalonil, copper hydroxide, cyproconazole, cyprodinil, dimoxystrobin, epoxiconazole, fampek, fenpropidine, fenpropimorph, flutriafol, fluoxastrobin, fluquinconazole, flusilazole, metominostrobin, myclobutanil, orysastrobin, pyraclostrobin, prothioconazole, pyrametostrobin, pyrametostrobin, pyrametostrobin, quinoxylenol, tebuconazole, trifloxystrobin, triticonazole, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate and N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolcarboxamide.

8. The composition of claim 7, wherein, Component (b) comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, benzovindiflucy, bifenathi, chlorothalonil, copper hydroxide, cyproconazole, difenacozide, etaconazole, fenpropidine, fenpropimorph, fluindapyr, flutriafol, ipconazole, mefenoxam, mancozeb, pyridinitr, picoxystrobin, prothioconazole, pyridinylcarboxamide, pyraclostrobin, tebuconazole, trifloxystrobin, N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamic acid methyl ester and N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolcarboxamide.

9. The composition of claim 8, wherein, Component (b) comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, benzovindiflucy, bifenathi, chlorothalonil, copper hydroxide, cyproconazole, difenacozide, etaconazole, flutriafol, ipconazole, mefenoxam, pyraclostrobin, tebuconazole and trifloxystrobin.

10. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound selected from the group consisting of pyridinylcarboxamide, methyltetrahydropyridine, pyridinylchloromethyl and aminophenazone.

11. The composition of claim 1, wherein, Component (b) comprises at least one fungicidal compound selected from the group consisting of pyridinylcarboxamide, methyltetrahydropyridine, pyridinylchloromethyl and aminophenazone.

12. The composition of any one of claims 1 to 11, wherein, The weight ratio of the component (a) to component (b) is from 125:1 to 1:

125.

13. The composition of claim 12, wherein, The weight ratio of the component (a) to component (b) is from 25:1 to 1:

25.

14. The composition of claim 13, wherein, The weight ratio of the component (b) to component (a) is from 5:1 to 1:

5.

15. A composition comprising the composition of claim 1 and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent.

16. A method for protecting a plant or plant seed from a disease caused by a fungal pathogen, the method comprising applying to the plant or plant seed a fungicidally effective amount of the composition of any one of claims 1 to 14.

17. The method of claim 16, wherein, The fungal pathogen is selected from the group consisting of Alternaria solani, Erysiphe graminis, Botrytis cinerea, Puccinia recondita, Rhizoctonia solani, Leptosphaeria needans and Septoria tritici.

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