Substitution tollyl as a disinfectant

Abstract

To provide substituted tolyl as fungicides for controlling plant diseases caused by a fungal pathogen.SOLUTION: The present invention provides a compound selected from the compound of formula 12 and salts thereof [where A is a group having a pyrazole ring, the bond extending to the right being attached to the ring containing Q, and the bond extending to the left being attached to the phenyl ring; n is 0; Q is CR6; R1 and R2 are each F; R6 is C1-C6 hydroxyalkyl, C1-C6 alkenyl, or -ZC(=O)V; Z is a direct bond; V is R9; and R9 is methyl].SELECTED DRAWING: None

Description

[Technical Field]

[0001] Field of Invention The present invention relates to specific tolyl fungicides, their N-oxides, salts, and compositions, as well as methods for using them as fungicides. [Background technology]

[0002] Background of the Invention Controlling plant diseases caused by fungal plant pathogens is crucial for achieving high yield efficiency. Plant diseases that damage ornamental plants, vegetables, crops, grains, and fruit crops can cause significant reductions in productivity, resulting in increased costs for consumers. While many products are commercially available for these purposes, there is a persistent need for novel compounds that are more efficient, less expensive, less toxic, more environmentally safe, or have different sites of action.

[0003] Patent documents 1, 2, 3, and 4 disclose toll fungicides and their use in agriculture. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] PCT International Public Gazette WO2015157005 [Patent Document 2] PCT International Public Gazette WO2014066120 [Patent Document 3] PCT International Public Gazette WO2011059619 [Patent Document 4] PCT International Public Gazette WO2008124092 [Overview of the project] [Means for solving the problem]

[0005] Summary of the Invention The present invention relates to formula 1: [Chemical formula] [In the formula, A is [Chemical formula] a radical selected from the group consisting of here, the bond extending to the right is bonded to the ring containing Q, and the bond extending to the left is Y-N(R 3 )C(=W)R 4 bonded to a phenyl ring having a substituent; Q is CR 6 or N; Y is CR 7a R 7b , O or NR 8 ; W is O or S; R 1 and R 2 are each independently halogen, cyano, hydroxy, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 cyanoalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C2-C6 cyanoalkoxy, C3-C6 cycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; R 3These are H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C4 alkoxycarbonyl, or C2-C4 haloalkoxycarbonyl; R 4 These are C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylamino, or C2-C4 dialkylamino; Each R 5 These are independently halogens, cyanos, C1-C3 alkyls, C1-C3 haloalkyls, C1-C3 alkoxys, or C1-C3 haloalkoxys; n is 0, 1, or 2; R 6 H, halogen, cyano, hydroxy, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 cyanoalkyl, C1-C6 hydroxyalkyl, C2-C6 alkoxyalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 halo Alkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C2-C6 cyanoalkoxy, C2-C6 alkoxyalkoxy, C1-C6 alkylamino, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, -ZC(=O)V, CR 10a =NOR 10b , ON=CR 11a R 11b , CR 12a =NNR 12b R 12c or -LJ; R 7a These are H, hydroxyl, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylsulfinyl, or C1-C3 alkylsulfonyl; R7b is H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 8 is H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkylcarbonyl, or C2-C3 haloalkylcarbonyl; Z is a CH2 which is optionally substituted with a direct bond, O, S, or NH; or up to two substituents independently selected from halogens, methyl, or methoxy; V is R 9 OR 9 and; R 9 , R 10b , R 11a and R 12c These are, respectively, H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, or C4-C8 cycloalkylalkyl; R 10a , R 11b , R 12a and R 12b Each of these is independent of H, C1-C3. It is either a C1-C3 haloalkyl or a C1-C3 haloalkyl; L is a direct bond, CH2, O, S, NR 13 , OCH2, CH2O, C(=O), S(=O), or S(=O)2; J is a 3-6 member non-aromatic carbocyclic ring, where up to three carbon atom ring members are independently selected from C(=O) and C(=S), and each ring is R 14 Optionally substituted with up to four substituents independently selected from; or J is a 3-6 member heterocyclic ring, where each ring contains ring members selected from carbon atoms and 1-4 heteroatoms independently selected from up to 2 oxygen atoms, up to 2 sulfur atoms, and up to 4 nitrogen atoms, where up to 3 carbon atom ring members are independently selected from C(=O) and C(=S), and each ring is R 14Optionally substituted with up to four substituents independently selected from; R 13 is H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkylcarbonyl, or C2-C3 haloalkylcarbonyl; Each R 14 These are independently halogen, hydroxy, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy or C(=O)OR 15 and Each R 15 [These are independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, or C3-C6 halocycloalkyl] This invention relates to compounds (including all stereoisomers), their N-oxides, and salts, agricultural compositions containing them, and their use as fungicides.

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

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

[0008] The present invention also relates to a bactericidal composition comprising (a) the compound of the present invention; and (b) at least one other bactericidal agent (e.g., at least one other bactericidal agent having a different site of action).

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

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

[0011] Details of the invention As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “have,” “contains,” “contains,” “characterized by,” or any variation thereof are intended to cover comprehensive inclusion under any expressly indicated limitation. For example, a composition, mixture, process, method, article, or apparatus containing a list of elements may contain other elements not expressly listed or that are inherent to such composition, mixture, process, method, article, or apparatus, but is not necessarily limited to those elements alone.

[0012] The transitional phrase “consisting of” excludes any unspecified element, process, or component. In the case of claims, the phrase would close the claim to the inclusion of substances other than those described, except for impurities that are usually present. If the phrase “consisting of” appears in a section of the claim rather than immediately following the preface, it limits only the elements described in that section; other elements are not excluded from the claim as a whole.

[0013] The transitional phrase “essentially from” is used to define a composition, method, or apparatus that includes materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additional materials, processes, features, components, or elements do not substantially affect the fundamental and novel features of the claimed invention. The term “essentially from” lies between “including” and “consisting of.”

[0014] If the applicants define the present invention or a part thereof using non-limiting terms such as “including,” then, naturally, (unless otherwise stated) such description shall also be interpreted as describing an invention that is essentially made from or consists of the terms “essentially made from.” Furthermore, unless explicitly stated otherwise, "or" refers to a compatible or not an exclusive or. For example, condition A or B is satisfied by one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0015] Furthermore, the indefinite articles "a" and "an" preceding the elements or components of the present invention are intended to be non-limiting with respect to the number of instances (i.e., existences) of that element or component. Thus, "a" or "an" is to be read as including one or at least one, and the singular form of an element or component also includes plurals unless it is explicitly stated that the number is singular.

[0016] As used in this disclosure and claims, “plant” includes members of the Plant Kingdom at all life stages, including young plants (e.g., budding seeds developing into seedlings) and mature reproductive stages (e.g., plants producing flowers and seeds), in particular seed plants (Spermatopsida). Parts of a plant include geotropic members that typically grow below the surface of a growth medium (e.g., soil), such as roots, tubers, bulbs and corms, as well as members that grow above the growth medium, such as branches and leaves (including stems and leaves), flowers, fruits and seeds.

[0017] As used herein, the term “seedling,” used alone or in combination with other words, refers to a young plant that develops from the embryo of a seed.

[0018] As referred to herein, the term “broadleaf,” used alone or in any phrase such as “broadleaf crops,” means dicotyledonous plants or dicotyledons, which is a term used to describe a group of angiosperms characterized by embryos having two cotyledons.

[0019] As used herein, the terms “fungal pathogen” and “fungal plant pathogen” include pathogens in the Ascomycota, Basidiomycota, and Zygomycota, as well as fungal-like Oomycetes, that are the causative agents of a wide range of economically important plant diseases affecting ornamental plants, turfgrasses, vegetables, sports fields, cereals, and fruit crops. In the context of this disclosure, “protecting plants from disease” or “controlling plant diseases” includes prophylactic effects (disruption of the fungal cycle of infection, colonization, symptom development, and spore production) and / or therapeutic effects (inhibition of colonization of plant host tissues).

[0020] As used herein, the term “Mechanism of Action” (MOA) is defined by the Fungicide Resistance Action Committee. As defined by (FRAC), fungicides are used to identify fungicides according to their biochemical mechanisms of action in the biosynthetic pathways of plant pathogens, as well as their resistance risk. Mechanisms of action as defined by FRAC include (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signaling, (F) lipid synthesis and cell membrane integrity, (G) cell membrane sterol biosynthesis, (H) cell wall biosynthesis, (I) cell wall melanin synthesis, (P) host plant defense induction, (U) unknown mechanism of action, (NC) unclassified, (M) multi-site contact activity, and (BM) biologics with multiple mechanisms of action. Each mechanism of action (i.e., letters A-BM) contains one or more subgroups (e.g., A is subgroups A1, A2, A3, and A4) based on any of the individual effective target sites of action, or, if the exact target site is unknown, based on cross-resistance profiles within the group or in relation to other groups. Each of these subgroups (e.g., A1, A2, A3, and A4) is assigned a FRAC code (number and / or letter). For example, the FRAC code for subgroup A1 is 4. Further information regarding target sites and FRAC codes can be obtained from publicly available databases maintained by FRAC, for example.

[0021] As used herein, the term “cross-resistance” refers to the phenomenon that occurs when a pathogen develops resistance to one fungicide and simultaneously develops resistance to one or more other fungicides. These other fungicides are typically, but not always, of the same chemical class, have the same target site of action, or can be detoxified by the same mechanism.

[0022] In general, when a molecular fragment (i.e., a radical) is represented by a set of atomic symbols (e.g., C, H, N, O, and S), the potential bonding sites or bonding sites are readily recognizable to those skilled in the art. In some examples herein, particularly where alternative bonding sites are possible, the bonding sites may be explicitly indicated by a hyphen ("-"). For example, "-NCS" indicates that the bonding site is a nitrogen atom (i.e., isothiocyanate rather than thiocyanate).

[0023] As used herein, the term “alkylating agent” refers to a chemical compound in which a carbon-containing radical is bonded via a carbon atom to a leaving group such as a halide or sulfonate, and this leaving group can be substituted by the bonding of a nucleophile to the carbon atom. Unless otherwise indicated, the term “alkylation” does not limit the carbon-containing radical to alkyl; the carbon-containing radical in an alkylating agent is, for example, R 1 and R 2 This includes various carbon bond substituent radicals identified in relation to this.

[0024] In the above description, the term "alkyl," used alone or in compound terms such as "alkylthio" or "haloalkyl," includes linear or branched alkyls, e.g., methyl, ethyl, n-propyl, and i-propyl, or various butyl, pentyl, or hexyl isomers. "Alkenyl" includes linear or branched alkenes, e.g., ethenyl, 1-propenyl, 2-propenyl, and various butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes linear or branched alkynes, e.g., ethynyl, 1-propynyl, 2-propynyl, and various butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include moieties composed of multiple triple bonds, such as 2,5-hexadienyl.

[0025] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, i-propyloxy, and various butoxy, pentoxy, and hexyloxy isomers. "Alkoxyalkyl" indicates alkoxy substitution on an alkyl group. Examples of "Alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, and CH3CH2C Examples include H2CH2OCH2 and CH3CH2OCH2CH2. "Alkenyloxy" includes linear or branched alkenyls bonded to an oxygen atom and linked via the oxygen atom. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, CH3CH=CHCH2O, CH3CH=C(CH3)CH2O, and CH2=CHCH2CH2O. "Alkynyloxy" includes linear or branched alkynyls bonded to an oxygen atom and linked via the oxygen atom. Examples of "alkkynoxy" include HC≡CCH2O, CH3C≡CCH2O, and CH3C≡CCH2CH2O. "Alkoxyalkoxy" refers to an alkoxy substituent on another alkoxy moiety. Examples of "alkoxyalkoxy" include CH3OCH2O, CH3OCH2O, and CH3CH2OCH2O.

[0026] "Alkylthio" includes branched or linear alkylthio moieties, such as methylthio, ethylthio, and various propyl, butyl, pentyl, and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of the alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(=O), CH3CH2S(=O), CH3CH2CH2S(=O), (CH3)2CHS(=O), and various butylsulfinyl, pentylsulfinyl, and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(=O)2, CH3CH2S(=O)2, CH3CH2CH2S(=O)2, (CH3)2CHS(=O)2, and various butylsulfonyl, pentylsulfonyl, and hexylsulfonyl isomers.

[0027] "Alkylamino" includes NH radicals substituted with linear or branched alkyl groups. Examples of "alkylamino" include CH3NH, CH3CH2NH, CH3CH2CH2NH, and (CH3)2CHNH. Examples of "dialkylamino" include (CH3)2N, (CH3CH2)2N, and CH3CH2(CH3)N.

[0028] The term "cycloalkyl" refers to a saturated carbocyclic ring consisting of 3 to 6 carbon atoms linked to each other by single bonds. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkylalkyl" refers to a cycloalkyl substitution on an alkyl group. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyls bonded to a linear or branched alkyl group. The term "cycloalkoxy" refers to a cycloalkyl group bonded to and linked via an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. "Cycloalkylalkoxy" refers to a cycloalkyl substitution on an alkoxy group. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to a linear or branched alkoxy group.

[0029] "Alkylcarbonyl" refers to a linear or branched alkyl group bonded to the C(=O) portion. Examples of "alkylcarbonyl" include CH3C(=O), CH3CH2CH2C(=O), and (CH3)2CHC(=O). Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), and (CH3)2CHOC(=O).

[0030] The term "halogen" includes fluorine, chlorine, bromine, or iodine when used alone, in any compound word such as "haloalkyl," or in a description such as "halogen-substituted alkyl." Furthermore, when used in a compound word such as "haloalkyl" or in a description such as "halogen-substituted alkyl," the alkyl may be partially or completely substituted with the same or different halogen atoms. Examples of "haloalkoxy" include F3C, ClCH2, CF3CH2, and CF3CCl2. The term "haloalkoxy" is defined in the same way as "haloalkyl." Examples of "haloalkoxy" include CF3O, CCl3CH2O, F2CHCH2CH2O, and CF3CH2O.

[0031] "Cyanoalkyl" refers to an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" groups include NCCH2, NCCH2CH2, and CH3CH(CN)CH2. The term "cyanoalkoxy" refers to an alkyloxy group substituted with one cyano group. Examples of "cyanoalkoxy" groups include NCCH2O, NCCH2CH2O, and CH3CH(CN)CH2O. "Hydroxyalkyl" refers to an alkyl group substituted with one hydroxyl group. Examples of "hydroxyalkyl" groups include HOCH2CH2, CH3CH2(OH)CH, and HOCH2CH2CH2CH2.

[0032] The total number of carbon atoms in the substituent is "C i -C jThese are indicated by the prefix, where i and j are numbers from 1 to 6. For example, C1-C3 alkylsulfonyls specify methylsulfonyl to propylsulfonyl; C2 alkoxyalkyls specify CH3OCH2; C3 alkoxyalkyls specify, for example, CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyls specify various isomers of alkyl groups substituted with alkoxy groups containing a total of four carbon atoms, examples of which include CH3CH2CH2OCH2 and CH3CH2OCH2CH2.

[0033] The term “unsubstituted” in relation to a ring-like group means that the group has no substituents other than one or more of its bonds to the rest of Formula 1. The term “optionally substituted” means that the number of substituents may be zero. Unless otherwise indicated, an optionally substituted group may be substituted with many arbitrary substituents to the extent that this can be adapted by replacing the hydrogen atoms with non-hydrogen substituents on any available carbon or nitrogen atoms. In general, the number of arbitrary substituents (if any) ranges from 1 to 3. As used herein, the term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or the term “(un)substituted”.

[0034] The number of substituents may be limited by the given constraints. For example, the clause "R 14 "Optionally substituted with up to four substituents independently selected from " may have 0, 1, 2, 3, or 4 substituents.

[0035] When a compound is substituted with a substituent that has a subscript indicating that the number of substituents can vary (for example, in formula 1 where n is 0 to 2, (R 5 ) n ), the substituent is selected independently from the defined group of substituents unless otherwise indicated. If it is indicated that a variable group may optionally be substituted at a certain position, for example n may be 0 (R 5 ) nHydrogen can be present in a variable group even if it is not listed in the definition of a variable group.

[0036] The nomenclature of substituents in this disclosure uses recognized terminology that provides conciseness in accurately conveying their chemical structure to those skilled in the art. For the sake of brevity, locant descriptors may be omitted.

[0037] Unless otherwise indicated, the “ring” (e.g., J) as a component of Equation 1 is a carbocyclic or heterocyclic structure. The term “ring member” refers to the atoms (e.g., C, O, N, or S) or other parts (e.g., C(=O) and C(=S)) that form the framework of a ring or relation. The term “aromatic” indicates that the ring atoms are each essentially in the same plane, the p orbitals are perpendicular to the ring plane, and (4n+2) π electrons [where n is a positive integer] are attached to the ring in such a way that they satisfy Hückel’s rule.

[0038] The term "carbocyclic ring" refers to a ring in which the atoms forming the ring skeleton are selected solely from carbon atoms. Unless otherwise specified, a carbocyclic ring may be saturated, partially unsaturated, or completely unsaturated. A completely unsaturated carbocyclic ring that satisfies Hückel's rule is also called an "aromatic ring." A "saturated carbocyclic ring" refers to a ring having a skeleton of carbon atoms linked to each other by single bonds; unless otherwise specified, the remaining carbon atoms are occupied by hydrogen atoms.

[0039] As used herein, the terms “partially unsaturated ring” or “partially unsaturated heterocycle” refer to a ring that contains an unsaturated ring atom and one or more double bonds but is not aromatic.

[0040] The term "heterocyclic ring" or "heterocyclic ring" refers to a ring in which at least one of the atoms forming the ring skeleton is not carbon. Unless otherwise specified, a heterocyclic ring may be saturated, partially unsaturated, or completely unsaturated. A completely unsaturated heterocyclic ring that satisfies Hückel's rule is also called a "heteroaromatic ring" or aromatic heterocyclic ring. A "saturated heterocyclic ring" refers to a heterocyclic ring that contains only single bonds between its members.

[0041] Unless otherwise indicated, the heterocyclic ring is bonded to the rest of formula 1 by replacing a hydrogen atom on any of the available carbon or nitrogen atoms.

[0042] The compounds of the present invention may exist as one or more stereoisomers. Stereoiomers are isomers that have the same composition but differ in the spatial arrangement of their atoms, and these include enantiomers, diastereomers, cis- and trans-isomers (also known as geometric isomers), and atropisomers. Atropisomers arise as a result of restricted rotation around a single bond when the rotational barrier is high enough to allow the isolation of the isomer species. As is obvious to those skilled in the art, one stereoisomer may be more active and / or exhibit beneficial effects when concentrated compared to or separated from other stereoisomers. Furthermore, methods for separating, concentrating, and / or selectively producing the above stereoisomers are known to those skilled in the art. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0043] The compounds of the present invention may exist as one or more conformational isomers due to restricted rotation around the amide bond (e.g., C(=O)-N) in Formula 1. The present invention includes mixtures of conformational isomers. Furthermore, the present invention includes compounds in which one conformational isomer is concentrated compared to the other.

[0044] The present invention includes all stereoisomers, conformational isomers, mixtures of all their proportions, and even isotopic forms such as deuterated compounds.

[0045] As is obvious to those skilled in the art, not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires a lone pair of electrons available for oxidation to an oxide; those skilled in the art will know which nitrogen-containing heterocycles can form N-oxides. Those skilled in the art will also know that tertiary amines can form N-oxides. Synthetic methods for producing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, and these include heterocycles and dioxiranes using peroxy acids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. Examples include the oxidation of tertiary amines. These methods for the production of N-oxides have been extensively described and re-examined in the literature, for example: TL. Gilchrist, Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, SV. Ley (ed.), Pergamon Press; M. Tisler and See B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, edited by A. J Boulton and A. McKillop, Pergamon Press; M. Grimmett and B. T. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, edited by A. Katritzky, Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291, edited by A. Katritzky and A. J Boulton, Academic Press; and G. W. Cheeseman and E. S.g. Werstiuk in Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, edited by A. Katritzky and A. J Boulton, Academic Press.

[0046] Those skilled in the art will recognize that, under environmental and physiological conditions, salts of chemical compounds exist in equilibrium with their corresponding unsalted forms, and therefore salts share the biological utility of their unsalted forms. Accordingly, a wide variety of salts of the compounds of Formula 1 are useful (i.e., agriculturally suitable) for controlling plant diseases caused by fungal plant pathogens. Examples of salts of the compounds of Formula 1 include acid addition salts with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. If the compound of Formula 1 contains an acidic moiety such as a carboxylic acid, the salt may also include those formed with organic or inorganic bases such as pyridine, triethylamine, or ammonia, or amides, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium, or barium. Therefore, the present invention includes compounds selected from Formula 1, their N-oxides, and agriculturally suitable salts.

[0047] Compounds selected from Formula 1, their stereoisomers, N-oxides, and salts typically exist in more than one form, and therefore Formula 1 encompasses all crystalline and amorphous forms of the compound represented by Formula 1. Amorphous forms include embodiments that are solids, such as waxes and rubbers, and even embodiments that are liquids, such as solutions and dissolutions. Crystalline forms include embodiments that represent essentially a single crystalline form and embodiments that represent a mixture of polymorphs (i.e., different crystalline forms). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and / or conformations of molecules in the crystal lattice. Polymorphs may have the same chemical composition, but they may also differ in composition due to the presence or absence of co-crystallized water or other molecules, which may be weakly or strongly bonded in the lattice. Polymorphs may differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate, and bioavailability. As is obvious to those skilled in the art, polymorphs of compounds represented by formula I may exhibit beneficial effects (e.g., suitability for the manufacture of useful formulations, improved biological performance) compared to other polymorphs or mixtures of polymorphs of the same compound represented by formula I. The manufacture and isolation of specific polymorphs of compounds represented by formula I can be achieved by methods known to those skilled in the art, such as crystallization using selected solvents and temperatures.

[0048] The embodiments of the present invention described in the abstract of the invention include those described below. In the following embodiments, formula 1 comprises its stereoisomer, N-oxide and salt, and References to the "compound of Formula 1" include the definitions of substituents specified in the abstract of the invention, unless further defined in the embodiments.

[0049] Embodiment 1. A compound of formula 1, wherein A is A-1, A-3, or A-4.

[0050] Embodiment 1a. The compound of Embodiment 1, wherein A is A-1 or A-3.

[0051] Embodiment 2. The compound of Embodiment 1, wherein A is A-1.

[0052] Embodiment 3. The compound of Embodiment 1, wherein A is A-3.

[0053] Embodiment 4. The compound of Embodiment 1, wherein A is A-4.

[0054] Embodiment 5. A compound of formula 1, where A is A-2.

[0055] Embodiment 6. Q is CR 6 A compound that is either Formula 1 or one of Embodiments 1 to 5.

[0056] Embodiment 7. A compound of formula 1 or any one of embodiments 1 to 5, wherein Q is N.

[0057] Embodiment 8. Y is CR 7a R 7b A compound that is either O or one of the compounds of formula 1 or embodiments 1 to 7.

[0058] Embodiment 9. Y is CR 7a R 7b or NR 8 A compound that is either Formula 1 or one of Embodiments 1 to 7.

[0059] Embodiment 10. Y is CR 7a R 7b The compound of Embodiment 8 or 9.

[0060] Embodiment 11. The compound of Embodiment 8, where Y is O.

[0061] Embodiment 12. Y is NR 8 The compound of Embodiment 9.

[0062] Embodiment 13. A compound of formula 1 or any one of embodiments 1 to 12, wherein W is O.

[0063] Embodiment 14. A compound of formula 1 or any one of embodiments 1 to 12, wherein W is S.

[0064] Embodiment 15. R 1 and R 2 Each of these is independently halogen, cyano, hydroxy, nitro, amino, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C2-C4 cyanoalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 halo A compound of formula 1 or any one of embodiments 1 to 14, which is an alkenyloxy, C2-C4 alkynyloxy, C2-C4 haloalkynyloxy, C2-C4 cyanoalkoxy, C3-C6 cycloalkoxy, C4-C6 cycloalkylalkoxy, C2-C4 alkoxyalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 haloalkylsulfinyl, C1-C3 alkylsulfonyl, or C1-C3 haloalkylsulfonyl.

[0065] Embodiment 16. R 1 and R 2 Each of these is independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, The compound of Embodiment 15 is a C2-C4 cyanoalkyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 cyanoalkoxy, C2-C4 alkoxyalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 haloalkylsulfinyl, C1-C3 alkylsulfonyl, or C1-C3 haloalkylsulfonyl.

[0066] Embodiment 17. R 1 and R2 The compound of Embodiment 16, wherein each is independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 alkoxyalkoxy, or C1-C3 alkylthio.

[0067] Embodiment 18. R 1 and R 2 The compound of Embodiment 17, wherein each of the elements is independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, or C1-C3 alkylthio.

[0068] Embodiment 19. R 1 and R 2 The compound of Embodiment 18, wherein each is independently a halogen, cyano, methyl, halomethyl, methoxy, or halomethoxy.

[0069] Embodiment 20. R 1 and R 2 The compound of Embodiment 19, wherein each of the elements is independently Br, Cl, F, methyl, trifluoromethyl, methoxy, or trifluoromethoxy.

[0070] Embodiment 21. R 1 and R 2 The compound of Embodiment 20, wherein each is independently Cl, F, or methyl.

[0071] Embodiment 22. R 1 and R 2 The compound of Embodiment 21, wherein each is independently Cl or F.

[0072] Embodiment 23. R 1 and R 2 The compounds of Embodiment 22, where each is F.

[0073] Embodiment 24. R 3The compound is one of the compounds of formula 1 or embodiments 1 to 23, wherein is H, C1-C3 alkyl, C2-C4 alkylcarbonyl, or C2-C4 alkoxycarbonyl.

[0074] Embodiment 25. R 3 The compound of Embodiment 24, wherein H is methyl, methylcarbonyl, or methoxycarbonyl.

[0075] Embodiment 26. R 3 The compound of Embodiment 25, wherein is H or methyl.

[0076] Embodiment 27. R 3 The compound of embodiment 26, wherein is H.

[0077] Embodiment 28. R 4 The compound is methyl, methoxy, ethoxy, methylamino, or dimethylamino, and is one of the compounds of Formula 1 or Embodiments 1 to 27.

[0078] Embodiment 29. R 4 The compound of Embodiment 28 is methyl, methoxy, or ethoxy.

[0079] Embodiment 30. R 4 The compound of embodiment 29 is methoxy.

[0080] Embodiment 31. Each R 5 The compound is independently a halogen, cyano, methyl, or methoxy compound of formula 1 or any one of embodiments 1 to 30.

[0081] Embodiment 32. Each R 5 The compound of Embodiment 31, wherein is independently a halogen or methyl.

[0082] Embodiment 33. Each R 5 The compound of embodiment 32, wherein is methyl.

[0083] Embodiment 34. A compound of formula 1 or any one of embodiments 1 to 33, where n is 0 or 1.

[0084] Embodiment 35. The compound of Embodiment 34, wherein n is 0.

[0085] Embodiment 36. R 6 is H, halogen, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C2-C6 alkoxyalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, -ZC(=O)V, CR 10a =NOR 10b 、ON=CR 11a R 11b 、CR 12a =NNR 12b R 12c or -L-J, a compound of Formula 1 or any one of Embodiments 1 to 35.

[0086] Embodiment 37. R 6 is H, halogen, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C2-C6 alkoxyalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, -ZC(=O)V, CR 10a =NOR 10b 、CR 12a =NNR 12b R 12c or -L-J, the compound of Embodiment 36.

[0087] Embodiment 38. R 6 H, halogen, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, CR 10a =NOR 10b The compound of Embodiment 37, which is -LJ.

[0088] Embodiment 39. R 6 H, halogen, amino, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, CR 10a =NOR 10b The compound of Embodiment 38, which is -LJ.

[0089] Embodiment 40. R 6 H, halogen, amino, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CR 10a =NOR 10b The compound of embodiment 39, which is -LJ.

[0090] Embodiment 40a. R 6 The compound of Embodiment 40 is H, Br, Cl, I, amino, methyl, i-propyl, trifluoromethyl, CH2F, CHF2, methoxy, ethoxy, i-propyloxy, trifluoromethoxy, CH2FO, CHF2O, CH=NOCH3, CH=NOCH2CH3.

[0091] Embodiment 41. R 6The compound of Embodiment 40a is H, Br, Cl, I, amino, methyl, i-propyl, trifluoromethyl, CHF2, methoxy, ethoxy, i-propyloxy, trifluoromethoxy, CHF2O, CH=NOCH3, CH=NOCH2CH3, C(CH3)=NOCH3, or -LJ.

[0092] Embodiment 41a. R 6 The compound of Embodiment 41, wherein is H, Br, Cl, I, amino, methoxy, ethoxy, i-propyloxy, trifluoromethoxy, CHF2O, C(CH3)=NOCH3, or -LJ.

[0093] Embodiment 42. R 6 The compound of Embodiment 41, wherein is H, Br, Cl, I, amino, methoxy, ethoxy, i-propyloxy, trifluoromethoxy, C(CH3)=NOCH3, or -LJ.

[0094] Embodiment 43. R 6 The compound of Embodiment 42, wherein is H, Br, Cl, amino, methoxy, ethoxy, or i-propyloxy.

[0095] Embodiment 44. R 6 The compound of Embodiment 43, wherein is H, Br, Cl, amino, or methoxy.

[0096] Embodiment 45. R 7a The compound is one of the compounds of Formula 1 or Embodiments 1 to 44, wherein is H, hydroxy, halogen, cyano, methyl, halomethyl, methoxy, or halomethoxy.

[0097] Embodiment 46. R 7a The compound of Embodiment 45, wherein is H, halogen, methyl, or methoxy.

[0098] Embodiment 47. R 7a The compound of Embodiment 46, wherein is H or methyl.

[0099] Embodiment 48. R 7aThe compound of Embodiment 47, wherein is H.

[0100] Embodiment 49. R 7b The compound is one of the compounds of Formula 1 or Embodiments 1 to 48, wherein is H, methyl, halomethyl, methoxy, or halomethoxy.

[0101] Embodiment 50. R 7b The compound of Embodiment 49, wherein is H, methyl, or methoxy.

[0102] Embodiment 51. R 7b The compound of Embodiment 50, wherein is H or methyl.

[0103] Embodiment 52. R 7b The compound of embodiment 51, wherein is H.

[0104] Embodiment 53. R 8 The compound is one of the compounds of formula 1 or embodiments 1 to 44, wherein H is methyl, halomethyl, or methylcarbonyl.

[0105] Embodiment 54. R 8 The compound of Embodiment 53, wherein is H or methyl.

[0106] Embodiment 55. R 8 The compound of embodiment 54, wherein is H.

[0107] Embodiment 56. A compound of any one of the embodiments of Formula 1 or Embodiments 1 to 55, where Z is a direct bond, O, NH, CH2, or CH(OCH3).

[0108] Embodiment 57. The compound of Embodiment 56, wherein Z is directly bonded, O, or CH2.

[0109] Embodiment 58. The compound of Embodiment 57, wherein Z is a direct bond.

[0110] Embodiment 59. The compound of Embodiment 57, wherein Z is O.

[0111] Embodiment 59a. The compound of Embodiment 57, wherein Z is CH2.

[0112] Embodiment 60. R 9 , R 10b , R 11a and R 12c Each of the following compounds is a compound from formula 1 or any one of embodiments 1 to 59a, wherein each of the following is H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, or C2-C4 alkynyl.

[0113] Embodiment 61. R 9 , R 10b , R 11a and R 12c The compound of Embodiment 60, wherein each of the elements is H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, or C2-C4 haloalkenyl.

[0114] Embodiment 62. R 9 , R 10b , R 11a and R 12c The compound of Embodiment 61, wherein each of the elements is H, methyl, ethyl, or a C2-C4 alkenyl.

[0115] Embodiment 63. R 9 , R 10b , R 11a and R 12c The compound of Embodiment 62, wherein each is H or methyl.

[0116] Embodiment 64. R 9 , R 10b , R 11a and R 12c The compound of embodiment 63, wherein each of the elements is H.

[0117] Embodiment 65. R 9 , R 10b , R 11a and R 12c The compound of Embodiment 63, wherein each of the elements is methyl.

[0118] Embodiment 66. R 10a , R 11b , R 12a and R 12b Each of the compounds is independently H, methyl, or halomethyl, and is one of the compounds of formula 1 or embodiments 1 to 65.

[0119] Embodiment 67. R 10a , R 11b , R 12a and R 12b The compound of Embodiment 66, wherein each is independently H or methyl.

[0120] Embodiment 68. R 10a , R 11b , R 12a and R 12b The compound of embodiment 67, wherein each of the elements is H.

[0121] Embodiment 69. R 10a , R 11b , R 12a and R 12b The compound of Embodiment 68, wherein each of the elements is methyl.

[0122] Embodiment 70. L is directly bonded, CH2, O, S, NR 13 A compound of any one of the following forms: OCH2, CH2O, or C(=O): Formula 1 or Embodiments 1 to 69.

[0123] Embodiment 71. The compound of Embodiment 70, wherein L is directly bonded, CH2, O, OCH2, CH2O, or C(=O).

[0124] Embodiment 72. The compound of Embodiment 71, wherein L is directly bonded, CH2, O, OCH2, or CH2O.

[0125] Embodiment 73. The compound of Embodiment 72, wherein L is directly bonded, O, or OCH2.

[0126] Embodiment 74. The compound of Embodiment 72, where L is directly bonded.

[0127] Embodiment 75. The compound of Embodiment 72, wherein L is CH2.

[0128] Embodiment 76. The compound of Embodiment 72, wherein L is O.

[0129] Embodiment 77. The compound of Embodiment 72, wherein L is OCH2 or CH2O.

[0130] Embodiment 78. J is one compound of Formula 1 or Embodiments 1 to 797, selected from J-1 to J-71 shown in Appendix A.

[0131] Appendix A [ka] [ka] [ka] [ka] Here, the floating bond is connected to L via any available carbon or nitrogen atom of the indicated ring; and x is 0, 1, 2, or 3.

[0132] Embodiment 79. The compound of Embodiment 78, wherein J is J-4, J-5, J-6, J-7, J-8, J-9, J-18, J-19, J-20, J-21, J-22, J-23, J-24, J-25, J-26, J-27, J-34, J-35, J-36, J-37, J-38, J-56, J-57, J-58, J-59, J-60, J-61, J-63, J-64, J-65, J-66, J-67, J-69, or J-70.

[0133] Embodiment 80. The compound of Embodiment 79, wherein J is J-4, J-5, J-6, J-22, J-23, J-24, J-35, J-36, J-37, J-38, J-57, J-58, J-63, J-64, J-65, J-66, J-67, J-69, or J-70.

[0134] Embodiment 81. The compound of Embodiment 80, wherein J is J-6, J-22, J-35, J-37, J-58, J-64, J-65, J-66, J-67, J-69, or J-70.

[0135] Embodiment 82. The compound of Embodiment 81, where J is J-35.

[0136] Embodiment 83. The compound of Embodiment 81, where J is J-58.

[0137] Embodiment 84. The compound of Embodiment 81, where J is J-66.

[0138] Embodiment 85. The compound of Embodiment 81, where J is J-67.

[0139] Embodiment 86. The compound of Embodiment 81, where J is J-69.

[0140] Embodiment 87. The compound of Embodiment 81, where J is J-70.

[0141] Embodiment 88. The compound of Embodiment 81, wherein J is J-65, J-66, or J-67.

[0142] Embodiment 88a. The compound of Embodiment 88, wherein J is J-66 or J-67.

[0143] Embodiment 89. A compound from any one of Embodiments 78 to 88a, where x is 0, 1, or 2.

[0144] Embodiment 89a. The compound of Embodiment 89, wherein x is 0 or 1.

[0145] Embodiment 90. A compound from either Embodiment 89 or 89a, where x is 0.

[0146] Embodiment 91. Each R 14These are independently halogens, cyanos, C1-C4 alkyls, C1-C4 haloalkyls, C1-C4 alkoxys, C1-C4 haloalkoxys, or C(=O)OR 15 A compound that is either Formula 1 or one of Embodiments 1 to 89.

[0147] Embodiment 92. Each R 14 These are independently halogen, cyano, methyl, halomethyl, methoxy, halomethoxy or C(=O)OR 15 The compound of Embodiment 91.

[0148] Embodiment 93. Each R 14 These are independently halogen, methyl, methoxy, or C(=O)OR 15 The compound of embodiment 92.

[0149] Embodiment 94. Each R 14 These are independently halogens, methyl or C(=O)OR 15 The compound of embodiment 93.

[0150] Embodiment 95. Each R 14 The compound of Embodiment 94, wherein is independently a halogen or methyl.

[0151] Embodiment 95a. Each R 14 The compound of Embodiment 95, wherein is independently Br, Cl, F, or methyl.

[0152] Embodiment 96. Each R 15 The compound is independently a C1-C3 alkyl, a C1-C3 haloalkyl, or a cyclopropyl, and is one of the compounds of formula 1 or any one of embodiments 1 to 94.

[0153] Embodiment 97. Each R 15 The compound of Embodiment 96, wherein is independently a C1-C3 alkyl or a C1-C3 haloalkyl.

[0154] Embodiment 98. Each R 15 The compound of Embodiment 97, wherein is independently methyl or ethyl.

[0155] Embodiment 99. Each R 15 is methyl, the compound of Embodiment 98.

[0156] In addition to the above Embodiments 1 to 99, embodiments of the present invention including any other embodiments described herein can be combined in any way, and the description of variables in the embodiments is related not only to the compounds of Formula 1 but also to starting compounds and intermediate compounds useful for producing the compounds of Formula 1. Further, embodiments of the present invention including any other embodiments described herein in addition to the above Embodiments 1 to 99, and any combinations thereof, are related to the compositions and methods of the present invention.

[0157] Combinations of Embodiments 1 to 99 are exemplified as follows: Embodiment A. In the formula, A is A-1, A-3 or A-4; Q is CR 6 ; Y is CR 7a CR 7b ; W is O; R 1 and R 2 are each independently halogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C2-C4 alkoxyalkoxy or C1-C3 alkylthio; R 3 is H, methyl, methylcarbonyl or methoxycarbonyl; R 4 is methyl, methoxy, ethoxy, methylamino or dimethylamino; Each R 5 is independently halogen or methyl; R 6H, halogen, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkynyloxy, C2-C6 haloalkynyloxy, C2-C6 alkoxyalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, -ZC(=O)V, CR 10a =NOR 10b , CR 12a =NNR 12b R 12c or -LJ; R 7a is H, halogen, methyl, or methoxy; R 7b is either H or methyl; Z is a direct bond, O, NH, CH2, or CH(OCH3); R 9 , R 10b and R 12c Each of these is H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, or C2-C4 haloalkenyl; R 10a , R 12a and R 12b Each of these is independently H, methyl, or halomethyl; L is a direct bond, CH2, O, OCH2, or CH2O;

[0158] J represents J-1 to J-71 [ka] [ka] [ka] Selected from, Here, the floating bond is connected to L via any available carbon or nitrogen atom of the indicated ring; and x is 0, 1, 2, or 3; Each R 14 These are independently halogen, methyl, methoxy, or C(=O)OR 15 and Each R 15 These are independently C1-C3 alkyl, C1-C3 haloalkyl, or cyclopropyl. The compound of formula 1.

[0159] Embodiment B. In the formula, A is A-1; R 1 and R 2 Each of these is independently Br, Cl, F, methyl, trifluoromethyl, methoxy, or trifluoromethoxy; R 3 is H or methyl; R 4 These are methyl, methoxy, or ethoxy; Each R 5 It is methyl; R 6 H, halogen, amino, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, CR 10a =NOR 10b or -LJ; R 7a is H or methyl; R 7b is H or methyl; R 10b is H, methyl, C2-C4 alkenyl, or C2-C4 haloalkenyl; R 10a is H or methyl; L is a direct bond, O, or OCH2; J is J-6, J-22, J-35, J-37, J-58, J-64, J-65, J-66, J-67, J-69 or J-70; and Each R 14 These are independently halogens or methyl compounds. Compound of Embodiment A

[0160] Embodiment C. Wherein R 1 and R 2 are each independently Cl, F or methyl; R 3 is H; R 4 is methoxy; n is 0; R 6 is H, Br, Cl, I, amino, methyl, i - propyl, trifluoromethyl, CH2F, CHF2, methoxy, ethoxy, i - propyloxy, trifluoromethoxy, CH2FO, CHF2O, CH = NOCH3, CH = NOCH2CH3, C(CH3)=NOCH3 or -L-J; R 7a is H; R 7b is H; and J is J - 65, J - 66 or J - 67, Compound of Embodiment B

[0161] Embodiment D. Wherein R 1 and R 2 are each independently Cl or F; R 6 is H, Br, Cl, I, amino, methoxy, ethoxy, i - propyloxy, trifluoromethoxy, CHF2O, C(CH3)=NOCH3 or -L-J; J is J - 66 or J - 67; x is 0, 1 or 2; and R 14 is Br, Cl, F or methyl, Compound of Embodiment C

[0162] Embodiment E. Wherein R 1 and R 2 are each F; and R 6is H, Br, Cl, amino, methoxy, ethoxy, or i-propyloxy. Compound of Embodiment D.

[0163] Specific embodiments include: N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 1); N-[[5-[1-(2,6-difluoro-4-methoxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 3); N-[[5-[1-(2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 4); N-[[5-[1-(4-amino-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 5); N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 6); N-[[5-[1-(4-bromo-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 7); N-[[5-[1-(2,6-difluoro-4-iodophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (compound 8); N-[[5-[1-(2,6-difluoro-4-hydroxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 10); N-[[5-[1-(4-ethoxy-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 11); N-[[5-[1-[4-(cyclobutyloxy)-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 13); N-[[5-[1-[2,6-difluoro-4-(1-methylethoxy)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 14); N-[[5-[1-[4-(difluoromethoxy)-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 15); N-[[5-[1-[2,6-difluoro-4-(2-propyne-1-yloxy)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 30); N-[[5-[1-(2,6-difluoro-4-methoxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 33); N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 41); N-[[5-[1-[4-[(1,1-dimethylethyl)thio]-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 42); N-[[5-[1-[4-[(difluoromethyl)thio]-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 43); N-[[5-[1-(4-ethynyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 53); N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 63); N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 64); N-[[5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 65); N-[[5-[1-[4-(cyclopropyloxy)-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 66); N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 67); N-[[5-[1-(4-acetyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]methyl carbamate (compound 68); 3,5-Difluoro-4-[3-[3-[[(methoxycarbonyl)amino]methyl]-4-methylphenyl]-1H-pyrazole-1-yl]methyl benzoate (compound 70); N-[[5-[1-[2,6-difluoro-4-(hydroxymethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 71); N-[[5-[1-[2,6-difluoro-4-(trifluoromethoxy)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 78); N-[[5-[1-[2,6-difluoro-4-[1-(methoxyimino)ethyl]phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 83); N-[[5-[1-[4-(difluoromethyl)-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 87); N-[[5-[2-[2,6-difluoro-4-(1-methylethyl)phenyl]-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methylcarbamate (compound 108); N-[[5-[2-(4-amino-2,6-difluorophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 115); N-[[5-[2-(4-chloro-2,6-difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 117); N-[[5-[2-(2,6-difluoro-4-nitrophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 118); N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 121); N-[[5-[1-(4-amino-2,6-difluorophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 131); and N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 132) A compound of formula 1 selected from the group consisting of the following is an example.

[0164] The present invention provides a bactericidal composition comprising the compound of Formula 1 (including all stereoisomers thereof, N-oxides, and salts) and at least one other bactericidal agent. Embodiments of this composition and Of particular note is the composition containing a compound corresponding to any of the above-described compound embodiments.

[0165] The present invention provides a bactericidal composition comprising the compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) (i.e., in a bactericidally effective amount), and at least one further component selected from the group consisting of surfactants, solid diluents, and liquid diluents. Of particular note as embodiments of this composition are compositions comprising the compound corresponding to any of the above compound embodiments.

[0166] The present invention provides a method for controlling plant diseases caused by fungal plant pathogens, comprising applying a fungicidal amount of the compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) to a plant or part thereof, or to the seeds of a plant. Of particular note as an embodiment of this method is a method comprising applying a fungicidal amount of the compound corresponding to any of the above compound embodiments. Of particular note is an embodiment in which the compound is applied as a composition of the present invention.

[0167] Compounds of formula 1 can be prepared using the following methods and one or more of the variations described in schemes 1 to 12. A, Q, R in the following compounds of formulas 1 to 16 1 , R 2 , R 3 , R 4 , R 5 The definitions of W, Y, and n are as defined above in the abstract of the invention, unless otherwise shown. The compounds of formulas 1a to 1e are a subset of formula 1, and all substituents for formulas 1a to 1e are as defined above for formula 1, unless otherwise shown.

[0168] As shown in Scheme 1, the compound of Formula 1 can be prepared by reacting the compound of Formula 2 with the compound of Formula 3 under copper or palladium-catalyzed cross-coupling conditions. For the compound of Formula 3 where X is a halogen or triflate, Ullmann or Buchwald-Hartwig conditions can be used. For relevant references, see, for example, Chemical Reviews 2002, 102(5), 1359-1470; Angew. Chem. Int. Ed. Engl. 2008, 47(34), 6338-6361; and Chem. Sci. 2010, 1(1), 13-31; and PCT International Publication WO2014 / 066120. This Example 1 also illustrates the method of Scheme 1. These reactions typically require the presence of a base, such as a metal carbonate like potassium carbonate, and a suitable catalyst and ligand, such as copper(I) iodide and a ligand like trans-1,2-diamino-N,N'-dimethylcyclohexane. The reaction is generally carried out in an aprotic solvent such as dioxane or toluene at a temperature between the ambient temperature and the boiling point of the solvent. The compound in Equation 3 has an electron-withdrawing substituent (e.g., R 1 , R 2 and / or R 6 Direct nucleophilic substitution of X by the compound of formula 2 can be achieved when X contains (where is nitro, cyano, or ester) and X is a halogen. These reactions are carried out in solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, or acetonitrile at a temperature between ambient temperature and 130°C in the presence of a base such as an alkali metal carbonate, hydride, alkoxide, or trialkylamine. For reaction conditions, see Bioorganic & Medicinal Chemistry Letters 2014, 24(24), 5805-5813; Bioorganic & Medicinal See Chemistry Letters 2010, 20(15), 4521-4525; and Journal of Materials Chemistry A: Materials for Energy and Sustainability 2014, 2(21), 7917-7926; and PCT International Publication WO2016 / 187667. Also, Examples 2, 7, 11 and 17 (Step A) illustrate the preparation of the compound of Formula 1 by direct nucleophilic substitution. For the compound of Formula 3 where X is a boronic acid, see Cha N-Ram conditions can be used. These reactions are carried out in the presence of a suitable base such as pyridine or triethylamine and a catalyst such as copper(II) acetate. Typically, the reactions are carried out in an aprotic solvent such as dichloromethane or chloroform, at a temperature approximately between the ambient temperature and the boiling point of the solvent, and in the presence of oxygen. For key references, see, for example, Tetrahedron 2018, 74(5), 606-617; and Tetrahedron Lett. 1998, 39(19), 2933-2936.

[0169] Scheme 1 [ka]

[0170] The compound of Formula 3 is widely available from commercial sources and can be readily prepared using commercially available precursors and known methods (see, for example, US2013 / 0158004 and WO2018 / 011094).

[0171] In some cases, the method of Scheme 1 yields two positional isomers. For example, as shown in Scheme 2, the reaction of the compound of formula 2a (i.e., formula 2 where A is A-3) with the compound of formula 3 typically yields a mixture of isomers of the compound of formula 1a (i.e., formula 1 where A is A-3) and the compound of formula 1b (i.e., formula 1 where A is A-4). Purification of the positional isomers can be achieved using standard techniques such as column chromatography. For relevant references, see, for example, PCT International Publication WO2009 / 013211. The method of Scheme 2 is also illustrated in Example 18, step F.

[0172] Scheme 2 [ka]

[0173] As shown in Scheme 3, the compounds of formula 2a can be prepared by reacting the alkyne of formula 4 with a suitable source of azide ions in the presence of a copper(I) salt. Suitable azide sources include, for example, trimethylsilyl azide and sodium azide. Suitable copper(I) salts include copper(I) iodide, copper(I) bromide, and copper(I) chloride. Alternatively, a copper(II) salt can be used in combination with a mild reducing agent, for example, copper(II) sulfate with sodium ascorbate. The reaction is typically carried out at a temperature of about 25–100°C in solvents such as N,N-dimethylformamide, tetrahydrofuran, methanol, tert-butanol, and dimethyl sulfoxide (sometimes including water). In some cases, the use of low-boiling point solvents may require increasing the pressure to facilitate the reaction at temperatures higher than the normal boiling point of the solvent. For the main references, see, for example, Organic Letters 2009, 11(23), 5490-5493; European J. Organic Chem. 2004, (18), 3789-3791; Synlett 2005, (19), 2941-2947; and Tetrahedron Letters 2006, 47(18), 3035-3038; and PCT International Publication WO2004 / 072243. The method of Scheme 3 is also illustrated in Example 18, Step E.

[0174] Scheme 3 [ka]

[0175] As shown in Scheme 4, Method A below, the compound of Formula 4 can be prepared from the compound of Formula 5 and the alkyne of Formula 6 using Sonogashira coupling conditions. Sonogashira coupling is well known in the literature. For example, Molecules 2010, 15, 9157-9173; Sonogashira, K. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E., Ed.; Wiley-Interscience: New See York, 2002, pp 493-529; Palladium in Heterocyclic Chemistry, A Guide for the Synthetic Chemist, Li, J.; Gribble, G., Eds. in Tetrahedron Organic Series, Volume 20; Pergamon Press: New York, 2000.

[0176] As shown in Scheme 4, Method B, the compound of Formula 4 can be produced by reacting the compound of Formula 5 with ethynyltrimethylsilane (Formula 7) in the presence of a suitable palladium catalyst (e.g., tetrakis(triphenylphosphine)palladium or dichlorobis(triphenylphosphine)palladium(II)) and a suitable copper catalyst (copper(I) iodide). This reaction is preferably carried out in the presence of an amine base, such as triethylamine, N,N-diisopropylethylamine, diethylamine, or piperidine. The reaction is typically carried out in the presence of tetrahydrofuran, toluene, or N,N-dimethylformamine. The reaction is carried out in solvents such as ethanol; however, in some cases, the reaction may be carried out without any solvent other than the compound of formula 5, ethynyltrimethylsilane, and amine base. The removal of the trimethylsilane group to obtain the compound of formula 4 can be carried out using well-known conditions, such as treatment in methanol or ethanol with alkali metal hydroxides or alkali metal carbonates, such as potassium hydroxide, sodium hydroxide, or potassium carbonate. The reaction is preferably carried out in a suitable organic solvent. Typically, this method is carried out most satisfactorily at temperatures ranging from about 0°C to the reflux temperature of the solvent. For typical procedures, see JACS 2003, 125(38), 11545-11552 and Bioorganic & Medicinal Chemistry 2009, 17(24), 8149-8160; and Example 18, steps A and B.

[0177] Scheme 4 [ka]

[0178] As shown in Scheme 5, the compound of formula 2 can be produced by Suzuki coupling of the compound of formula 5 with the boron intermediate of formula 8 [wherein A (i.e., A-1, A-2, A-3 or A-4) is bonded to boron via carbon atom ring members and is unsubstituted on the N atom ring member (i.e., A is a five-membered heteroaromatic ring containing the ring members -(NH)- and -(CB(OH)2)-)]. This reaction is carried out in the presence of a Pd(0) or Pd(II) salt, a suitable ligand, and a base. Suitable bases for this conversion are potassium carbonate or cesium carbonate, but Pd(II) salts such as Pd(OAc)2 or PdCl2 are used in combination with ligands such as triphenylphosphine or 1,1'-bis(diphenylphosphin)ferrocene (dppf). The conditions for Suzuki coupling are well documented in the literature; see, for example, Angewandte Chemie International Edition 2006, 45(21), 3484-3488 and Tetrahedron Letters 2002, 43(16), 2885-2888. The boron intermediate of formula 8 is commercially available and can be prepared from the corresponding halide or trifluorosulfonate by methods known in the literature; see, for example, PCT International Publication WO2007 / 043278; U.S. Patent No. 8080566; Organic Letters 2011, 13(6), 1366-1369; European Journal of Medicinal Chemistry 2014, 87, 529-539 and Organic Letters 2012, 14(2), 600-603.

[0179] Other coupling procedures offer numerous alternatives to the introduction of the heterocyclic A ring on Equation 5, including the coupling methods published by Heck, Stille, and Kumada. Also, for example, Zificsak et al., Tetrahedron See also 2004, 60, 8991-9016.

[0180] Scheme 5 [ka]

[0181] As shown in Scheme 6, the compound of Formula 5 can be produced by reacting the amine of Formula 9 with the acid chloride of Formula 10 in the presence of a base such as potassium carbonate, triethylamine, or pyridine. This reaction can be carried out without solvents other than Formulas 9, 10, and the base, or in solvents such as acetonitrile, dichloromethane, chloroform, diethyl ether, or tetrahydrofuran, at a temperature ranging from about 0 to 50°C. For reaction conditions, see, for example, PCT International Publication WO2004 / 037770 and European Patent No. EP1586552. The method of Scheme 6 is also illustrated in Example 18, Step D.

[0182] For the synthesis of the compound of formula 10, see Advanced Organic Synthesis, 4th edition, Wiley & Sons 1992, 437, and its cited references. The compound of formula 9 is commercially available and can be readily synthesized by general methods known to those skilled in the art.

[0183] Scheme 6 [ka]

[0184] As shown in Scheme 7, the compound of Formula 1 can be produced from the compound of Formula 11 by reaction with the acid chloride of Formula 10, similar to the method in Scheme 6. The method in Scheme 7 is illustrated in Example 17, Step F of this specification.

[0185] Scheme 7 [ka]

[0186] As shown in Scheme 8, the compounds of Formula 11 can be prepared from the nitrile of Formula 12 by using a suitable reducing agent such as lithium aluminum hydride, a borane / tetrahydrofuran complex, or tris(pentafluorophenyl)borane in an aprotic solvent such as tetrahydrofuran at a temperature between the ambient temperature and the boiling point of the solvent. For relevant examples, see the procedures and references contained in PCT International Publications WO2011 / 079102 and WO2011 / 073444. The method of Scheme 8 is also illustrated in Example 17, Step E of this specification.

[0187] The nitrile of formula 12 can also be converted to the amine of formula 11 by catalytic hydrogenation. These reactions are traditionally carried out in a lower alcohol solvent such as methanol or ethanol at a temperature between ambient temperature and 100°C under a hydrogen gas atmosphere and at a pressure between 1 and 7500 kPa in the presence of a transition metal such as carbon-supported palladium(O), Raney nickel, or platinum oxide. For relevant examples, see the procedures and references contained in PCT patent application publications WO2009 / 152868 and WO2010 / 023161.

[0188] Scheme 8 [ka]

[0189] As shown in Scheme 9, the compound of Formula 12 can be produced by coupling the compound of Formula 13 [wherein A (i.e., A-1, A-2, A-3, or A-4) is unsubstituted on the N atomic ring member (i.e., A is a five-membered heteroaromatic ring containing a ring member -(NH)-)] with the compound of Formula 3 using a method similar to that in Scheme 1. Example 17, Step A of this specification illustrates the method of Scheme 9.

[0190] Scheme 9 [ka]

[0191] As shown in Scheme 10, the compound of Formula 13 can be prepared from the compound of Formula 14. In a typical procedure, the compound of Formula 14 is brought into contact with a cyanide salt such as copper(I) cyanide or zinc(II) cyanide in a polar aprotic solvent such as N,N-dimethylformamide or dimethyl sulfoxide at a temperature between approximately 50 and 150°C in the presence of a suitable transition metal catalyst such as copper(I) iodide or tetrakis(triphenylphosphine)palladium(O). For the relevant procedure, see the references contained in PCT patent application publications WO2012 / 032528 and WO2011 / 133882.

[0192] Scheme 10 [ka]

[0193] As shown in Scheme 11, the compound of formula 14 can be produced by first reacting the compound of formula 15 with N,N-dimethylformamide dimethylacetal (DMF-DMA) in a solvent such as toluene or benzene at a temperature between approximately 40 and 100°C to obtain the intermediate compound of formula 16. In a subsequent step, the compound of formula 16 is reacted with hydrazine or a hydrazine salt in a lower alcohol solvent such as methanol or ethanol to obtain the compound of formula 14.

[0194] Scheme 11 [ka]

[0195] The compounds of Formula 1 and their intermediates described herein can be subjected to various electrophilic, nucleophilic, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents, thereby yielding other functionalized compounds of Formula 1. For example, as shown in Scheme 13, compounds of Formula 1c (i.e., where Q is CR) 6 And R 6 Formula 1) where Q is NH2 is expressed by using Fe, Zn, or SnCl2 in an acidic aqueous solution at temperatures ranging from ambient temperature to reflux temperature to produce the corresponding nitro compound of Formula 1e (i.e., where Q is CR). 6 And R 6 It can be produced by reducing formula 1) in which is NO2. Alcohol cosolvents such as methanol, ethanol, and i-propanol may be used. In the subsequent reaction, the amino compound of formula 1c is converted to a halogen under diazotization conditions in the presence of a halogen source to produce formula 1d (i.e., where Q is CR). 6 And R 6 A halogen (formula 1) can be obtained. Various halogen sources can be used in the method of scheme 12. The presence of a Lewis acid, such as titanium(IV) isopropoxide, may also be advantageous. For example, tert-butylnitrile is added to a solution of the amino compound of formula 1c in a solvent such as acetonitrile in the presence of CuBr2 to obtain the corresponding bromide compound of formula 1d. Similarly, the amino compound of formula 1c is converted to a diazonium salt by a general procedure well known to those skilled in the art, and then dissolved in a mineral acid (e.g., I, R) typically containing the same halide atom in a solvent such as water, acetic acid, or trifluoroacetic acid. 6The compounds can be converted to the corresponding compounds of formula 1d by treatment with sodium nitrite in the presence of an aqueous solution of HI, followed by treatment with the corresponding copper(I) or copper(II) salt. Many known reduction, diazotization, and halogenation methods can be readily adapted to produce the compounds of formulas 1c and 1d; see, for example, the procedures and references contained in U.S. Patent Applications US2017 / 0121300, US2017 / 069105, and US2017 / 038909, and PCT Patent Application Publication WO2017 / 036357. The method of scheme 12 is also illustrated in Examples 3 and 4 of this specification.

[0196] Scheme 12 [ka]

[0197] It should be recognized that some of the reagents and reaction conditions described above for preparing the compounds of Formula 1 may not be suitable for certain functional groups present in the intermediate. In these examples, incorporating protection / deprotection sequences or functional group interconversions into the synthesis can help obtain the desired product. The use and selection of protecting groups will be obvious to those skilled in chemical synthesis (see, for example, TW Greene and PGMWuts, Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). In some cases, those skilled in the art will be able to complete the synthesis of the compounds of Formula 1 after introducing the specified reagents shown in the individual schemes. To complete the process, it may be necessary to perform additional conventional synthesis steps not described in detail. Those skilled in the art will also understand that it may be necessary to perform combinations of steps described in the above scheme in an order other than that shown by the specific order presented for producing the compound of Formula 1.

[0198] Those skilled in the art will also understand that the compounds and intermediates of Formula 1 described herein can be subjected to a variety of electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0199] Without further ado, those skilled in the art can utilize the present invention to its fullest extent using the preceding description. Therefore, the following examples are for illustrative purposes only and should not be construed as limiting the present disclosure in any way. The steps in the following examples illustrate the procedure for each step in the overall synthetic transformation, and the starting materials for each step may not have been produced by the specific manufacturing process described in other examples or steps. Percentages are by mass unless otherwise indicated for chromatographic solvent mixtures or other materials. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1 The H NMR spectrum is reported in ppm with a low field shift from tetramethylsilane; "s" means singlet, "d" means doublet, "t" means triplet, "m" means multiplet, "br s" means broad singlet, and "dd" means double doublet. The mass spectrum is H + The molecular weight of the parent ion (M+1) with the highest isotopic abundance formed by the addition of (molecular weight 1) to the molecule is reported, and these are chemically ionized at atmospheric pressure (AP) by liquid chromatography (LCMS) connected to a mass spectrometer. + ) or electrospray ionization (ESI + Observed using one of the following methods.

[0200] Example 1 Preparation of N-[[5-[1-(2,6-difluoro-4-methoxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 3) Methyl N-[[2-methyl-5-(1H-pyrazole-3-yl)phenyl]methyl]carbamate (1.12 g, 4.57 mmol) (see PCT International Publication WO2008124092 for preparation method), copper(I) iodide (0.17 g, 0.914 mmol), and 2-bromo-1,3-difluoro-5-methoxybenzene (1.32 g, 5.94 mmol) were mixed with potassium carbonate (11.4 mmol), followed by N,N-dimethylformamide (8 mL). The reaction mixture was bubbling with nitrogen gas for 30 minutes, and then trans-N,N'-dimethylcyclohexane-1,2-diamine (0.26 g, 1.83 mmol) was added. The reaction mixture was heated overnight at 80°C, cooled to room temperature, and then diluted with ethyl acetate. The resulting mixture was washed with saturated sodium chloride aqueous solution (4x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with a gradient of 20-80% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as a colorless oil (0.43 g). 1 H NMR (CDCl3): δ 7.74(d, 1H), 7.67(dd, 1H), 7.59(d, 1H), 7.22(d, 1H), 6.74(d, 1H), 6.61(d, 2H), 4.87(br s, 1H), 4.41(d, 2H), 3.84(s, 3H), 3.69(s, 3H), 2.36(s, 3H). LCMS: m / z: 388 [M+H] +

[0201] Example 2 N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-pyrazole- Preparation of 3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 1) To a stirred solution of methyl N-[[2-methyl-5-(1H-pyrazole-3-yl)phenyl]methyl]carbamate (0.45 g, 1.84 mmol) (see PCT International Publication WO2008124092 for preparation method) in dimethyl sulfoxide (5 mL), potassium carbonate (762 mg, 5.52 mmol) and 1,2,3-trifluoro-5-nitrobenzene (0.235 mL, 2.02 mmol) were added. The reaction mixture was stirred overnight at room temperature and then diluted with ethyl acetate. The resulting mixture was washed with saturated aqueous sodium chloride (4x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by column chromatography (elution with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a yellow solid (0.44 g). 1 H NMR (CDCl3): δ 8.02(d, 2H), 7.79(dd, 1H), 7.75(d, 1H), 7.69(dd, 1H), 7.25(d, 1H), 6.85(d, 1H), 4.86(br s, 1H), 4.44(d, 2H), 3.71(s, 3H), 2.38(s, 3H).

[0202] Example 3 Preparation of N-[[5-[1-(4-amino-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 5) Methyl N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 2) (0.4 g, 0.995 mmol) and ammonium chloride (32 mg, 0.597 mmol) were mixed in ethanol / water (9:1, 20 mL) and iron powder (555 mg, 9.95 mmol) was added little by little. The reaction mixture was heated under reflux for 1.5 hours, then cooled to room temperature, filtered through a Celite® pad (diatomaceous earth filter aid), and rinsed with ethyl acetate. The filtrate was washed with saturated aqueous sodium chloride (4x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with a gradient of 30-100% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a bright yellow solid (0.3 g). 1 H NMR (CDCl3): δ 7.75(d, 1H), 7.66(dd, 1H), 7.56(d, 1H), 7.21(d, 1H), 6.72(d, 1H), 6.31(d, 2H), 4.82(br s, 1H), 4.41(d, 2H), 4.04(br s, 2H), 3.69(s, 3H), 2.36(s, 3H).

[0203] Example 4 Preparation of N-[[5-[1-(4-bromo-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 7) To a mixture of N-[[5-[1-(4-amino-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 3) (90 mg, 0.242 mmol) in acetonitrile (2 mL), copper(II) bromide (65 mg, 0.290 mmol) was added. The reaction mixture was cooled to approximately 0°C, and then n-butyl nitrite (0.043 mL, 0.363 mmol) was added. The reaction mixture was stirred overnight at room temperature, and then quenched with hydrochloric acid (1N aqueous solution). The resulting mixture was extracted with ethyl acetate (2x), and the combined extract was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with a gradient of 10-40% ethyl acetate in hexane). The obtained substance was further purified by column chromatography (elution with a gradient of 0-10% ethyl acetate in dichloromethane) to obtain the title compound, which is the compound of the present invention, as a yellow oily substance. 1 H NMR (CDCl3): δ 7.74(d, 1H), 7.67-7.65 ( m, 2H), 7.29(d, 2H), 7.23(d, 1H), 6.78(d, 1H), 4.83(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.37(s, 3H). LCMS: m / z: 436 [M+H] +

[0204] Example 5 Preparation of N-[[5-[1-(2,6-difluoro-4-hydroxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 10) To a mixture of N-[[5-[1-(2,6-difluoro-4-methoxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 1) (1.20 g, 3.10 mmol) in dichloromethane (30 mL), boron tribromide (1 M solution in dichloromethane, 9.40 mL, 9.30 mmol) was added dropwise at 0°C. The reaction mixture was heated to room temperature and stirred overnight. The reaction mixture was slowly quenched with water (35 mL), followed by the dropwise addition of methanol (35 mL), and then stirred at room temperature for 1 hour. The layers were separated, and the aqueous layer was extracted with dichloromethane (2x). The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was eluted by silica gel column chromatography (elution with a gradient of 20-70% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as a white solid (0.87 g). 1 H NMR (CDCl3): δ 7.74(br s, 1H), 7.63(dd, 1H), 7.60(d, 1H), 7.24(d, 1H), 6.75(d, 1H), 6.46(d, 2H), 4.95(br s, 1H), 4.42(d, 2H), 3.69(s, 3H), 2.37(s, 3H).

[0205] Example 6 Preparation of N-[[5-[1-[2,6-difluoro-4-(1-methylethoxy)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 14) To a mixture of methyl N-[[5-[1-(2,6-difluoro-4-hydroxyphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 5) (87 mg) in tetrahydrofuran (3 mL), triphenylphosphine (122 mg, 0.46 mmol), followed by 2-propanol (0.035 mL, 0.46 mmol) and diethyl azodicarboxylate (0.073 mL, 0.46 mmol) were added. The reaction mixture was stirred at room temperature for 48 hours and then concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluting with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as a white solid (85 mg). 1 H NMR (CDCl3): δ 7.75(d, 1H), 7.67(dd, 1H), 7.59(d, 1H), 7.22(d, 1H), 6.74(d, 1H), 6.58(d, 2H), 4.54 (m, 1H), 4.83(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.36(s, 3H), 1.37(d, 6H). LCMS: m / z: 416 [M+H] +

[0206] Example 7 Preparation of 3,5-difluoro-4-[3-[3-[[(methoxycarbonyl)amino]methyl]-4-methylphenyl]-1H-pyrazole-1-yl]methyl benzoate (compound 70) N-[[2-methyl-5-(1H-pyrazole-3-yl)phenyl]methyl]carbamate methyl (2.58g, 10.5 mmol) (For manufacturing methods, see PCT International Publicly Available Publication) (See report WO2008124092) and a mixture of methyl 3,4,5-trifluorobenzoate (2.41 g, 12.6 mmol) in dimethyl sulfoxide (10 mL) were mixed with potassium carbonate (4.35 g, 31.5 mmol). The reaction mixture was stirred at room temperature for 48 hours and then diluted with ethyl acetate. The resulting mixture was washed with saturated aqueous ammonium chloride (4x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by column chromatography (elution with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as a pale red solid (3.55 g). 1 H NMR(CDCl3): δ 7.76(d, 2H), 7.74(m, 2H), 7.68(d, 1H), 7.24(d, 1H), 6.80(d, 1H), 4.87(br s, 1H), 4.42(d, 2H), 3.97(s, 3H), 3.70(s, 3H), 2.37(s, 3H).

[0207] Example 8 Preparation of N-[[5-[1-[2,6-difluoro-4-(hydroxymethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 71) To a mixture of 3,5-difluoro-4-[3-[3-[[(methoxycarbonyl)amino]methyl]-4-methylphenyl]-1H-pyrazole-1-yl]methyl benzoate (i.e., the product of Example 7) (3.55 g, 8.55 mmol) in methanol (45 mL), sodium borohydride (1.94 g, 51.3 mmol) was gradually added. The reaction mixture was stirred overnight at room temperature, then quenched with hydrochloric acid (1 N aqueous solution), and filtered. The filtrate was extracted with ethyl acetate (3x), and the combined extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluting with a gradient of 20-100% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a white solid (2.52 g). 1 H NMR(DMSO-d6,): δ 8.11(d, 1H), 7.73(d, 1H), 7.65(t, 1H), 7.62(dd, 1H), 7.29(d, 1H), 7.22(d, 1H) , 6.94(d, 1H), 5.59(t, 1H), 4.60(d, 2H), 4.21(d, 2H), 3.55(s, 3H), 2.30(s, 3H).

[0208] Example 9 Preparation of N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 67) To a mixture of N-[[5-[1-[2,6-difluoro-4-(hydroxymethyl)phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 8) (2.30 g, 5.94 mmol) in tetrahydrofuran (70 mL), des-martin periodinane (2.52 g, 5.94 mmol) was gradually added. The reaction mixture was stirred overnight at room temperature, then quenched with aqueous sodium carbonate solution, and extracted with ethyl acetate (2x). The combined extract was filtered and rinsed with ethyl acetate. The filtrate was washed with saturated aqueous sodium bicarbonate solution (3x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluting with a gradient of 20-60% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a white solid (1.78 g). 1 H NMR (CDCl3): δ 9.98(t, 1H), 7.76 (m, 2H), 7.69(dd, 1H), 7.62(d, 2H), 7.24(d, 1H), 6.83(d, 1H), 4.86(br s, 1H), 4.43(d, 2H), 3.71(s, 3H), 2.38(s, 3H).

[0209] Example 10 Preparation of N-[[5-[1-[4-(difluoromethyl)-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 87) To a mixture of N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 9) (0.25 g, 0.65 mmol) in dichloromethane (10 mL), Deoxo-Fluor® (0.36 mL, 1.95 mmol) was added dropwise at approximately 0°C, followed by the addition of ethanol (1 drop). The reaction mixture was stirred overnight at room temperature and then slowly poured into saturated sodium carbonate aqueous solution (200 mL). After 30 minutes, the layers were separated, and the aqueous layer was extracted with dichloromethane (1x). The combined organic matter was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a colorless oil (0.23 g). 1 H NMR(CDCl3): δ 7.75(d, 1H), 7.71-7.68 (m, 2H), 7.27(d, 2H), 7.23(d, 1H), 6.80(d, 1H), 6.78-6.55(t, 1H), 4.85(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.37(s, 3H). LCMS: m / z:408 [M+H] +

[0210] Example 11 Preparation of N-[[5-[1-(4-acetyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 68) To a mixture of methyl N-[[2-methyl-5-(1H-pyrazole-3-yl)phenyl]methyl]carbamate (2.0 g, 8.16 mmol) (see PCT International Publication WO2008124092 for preparation method) and 1-(3,4,5-trifluorophenyl)ethanone (2.0 g, 11.4 mmol) in dimethyl sulfoxide (9 mL), potassium carbonate (3.38 g, 24.5 mmol) was added. The reaction mixture was stirred overnight at room temperature and then diluted with ethyl acetate. The resulting mixture was washed with saturated aqueous ammonium chloride (4x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with a gradient of 10-70% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a pale orange solid (2.10 g). 1 H NMR (CDCl3): δ 7.75 (m, 2H), 7.69 (dd, 1H), 7.67 (d, 2H), 7.24 (d, 1H), 6.81 (d, 1H), 4.87 (br s, 1H), 4.43(d, 2H), 3.70(s, 3H), 2.64(s, 3H), 2.37(s, 3H).

[0211] Example 12 Preparation of N-[[5-[1-[2,6-difluoro-4-[1-(methoxyimino)ethyl]phenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 83) Methyl N-[[5-[1-(4-acetyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 11) (0.24 g, 0.602 mmol), O-methylhydroxylamine hydrochloride (60.3 mg, 0.722 mmol), and sodium acetate (59.2 mg, 0.722 mmol) were mixed in ethanol and heated overnight under reflux. The reaction mixture was cooled to room temperature and diluted with water. The resulting mixture was extracted with ethyl acetate (2x), and the combined extract was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain the title compound, which is the compound of the present invention, as an amber solid (239 mg). 1 H NMR(CDCl3): δ 7.75(d, 1H), 7.68(m, 2H), 7 .41(d, 2H), 7.23(d, 1H), 6.78(d, 1H), 4.85(br s, 1H), 4.42(d, 2H), 4.04(s, 3H), 3.70(s, 3H), 2.37(s, 3H), 2.21(s, 3H). LCMS:m / z: 429 [M+H] +

[0212] Example 13 Preparation of N-[[5-[1-(2,6-difluoro-4-iodophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 8) To a mixture of N-[[5-[1-(4-amino-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 3) (2.38 g, 6.40 mmol) in acetonitrile (50 mL), diiodomethane (2.1 mL, 25.6 mmol) was added. The reaction mixture was cooled to approximately 0°C, and then tert-butyl nitrite (0.84 mL, 7.04 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 5 hours, and then diiodomethane (12 mL, 150 mmol) was added. After stirring overnight, the reaction mixture was diluted with ethyl acetate and washed with saturated sodium metabisulfite (3x), saturated sodium chloride solution (2x), and hydrochloric acid (1N aqueous solution). The mixture was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with a gradient of 0-10% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as a grayish-white solid (1.0 g). 1 H NMR (CDCl3): δ 7.73(d, 1H), 7.66-7.64 (m, 2H), 7.47(d, 2H), 7.22(d, 1H), 6.77(d, 1H), 4.86(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.36(s, 3H).

[0213] Example 14 Preparation of N-[[5-[1-(4-ethynyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 53) Process A: Preparation of N-[[5-[1-(2,6-difluorophenyl-4-(2-(trimethylsilyl)ethynyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate Methyl N-[[5-[1-(2,6-difluoro-4-iodophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 13) (0.2 g, 0.414 mmol), copper(I) iodide (8 mg, 0.041 mmol), N,N-dimethylformamide (4 mL), ethinyltrimethylsilane (0.088 mL, 0.621 mmol), and dichlorobis(triphenylphosphine)palladium (29 mg, 0.041 mmol) were mixed with triethylamine (0.063 mL, 0.455 mmol). The reaction mixture was stirred overnight at room temperature, then diluted with ethyl acetate, washed with saturated sodium chloride solution (4x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with a gradient of 5-40% ethyl acetate in hexane) to obtain the title compound as a light brown oily substance (0.17 g). 1 H NMR (CDCl3): δ 7.74(d, 1H), 7.67 (m, 2H), 7.23(d, 1H), 7.16(d, 2H), 6.77(d, 1H), 4.84(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.37(s, 3H), 0.27(s, 9H).

[0214] Step B: Preparation of N-[[5-[1-(4-ethynyl-2,6-difluorophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (compound 53) To a mixture of N-[[5-[1-(2,6-difluorophenyl-4-(2-(trimethylsilyl)ethynyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of step A) (0.12 g, 0.265 mmol) in methanol (6 mL), potassium carbonate (44 mg, 0.318 mmol) was added. The reaction mixture was stirred at room temperature for 1.5 hours, then diluted with ethyl acetate and water, and left to stand overnight at room temperature. The resulting mixture was washed with saturated sodium chloride solution (2x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluting with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as an amber-colored oil (0.109 g). 1 H NMR (CDCl3): δ 7.75(d, 1H), 7.68-7.66(m, 2H), 7.23(d, 1H), 7.20(d, 2H), 6.78(d, 1H), 4.84(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 3.24(s, 1H), 2.37(s, 3H). LCMS m / z:382[M+H] +

[0215] Example 15 Preparation of N-[[5-[1-[4-[(1,1-dimethylethyl)thio]-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 42) A mixture of methyl N-[[5-[1-(2,6-difluoro-4-iodophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 13) (0.217 g, 0.450 mmol) and N,N-dimethylformamide (2 mL) was purged under a nitrogen stream for 10-15 minutes, then tetrakis(triphenylphosphine)palladium (52 ​​mg, 0.045 mmol) was added, followed by 2-methyl-2-propanthol (0.100 mL, 0.900 mmol) and triethylamine (0.20 mL, 1.35 mmol). The reaction mixture was heated at 70°C for 1 hour, then cooled to room temperature, and diluted with ethyl acetate. The resulting mixture was washed with saturated sodium chloride solution (3x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel column chromatography (elution with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as an orange oily substance (0.189 g). 1 H NMR (CDCl3): δ 7.75(d, 1H), 7.69-7.67(m, 2H), 7.27(d, 2H), 7.23(d, 1H), 6.79(d, 1H), 4.84(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.37(s, 3H), 1.37(s, 9H).

[0216] Example 16 Preparation of N-[[5-[1-[4-[(difluoromethyl)thio]-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 43) Process A: Preparation of N-[[5-[1-(2,6-difluoro-4-mercaptophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate To a mixture of N-[[5-[1-[4-[(1,1-dimethylethyl)thio]-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 15) (0.16 g, 0.360 mmol) in dichloromethane (5 mL), boron tribromide (1 M solution in dichloromethane, 1.10 mL, 1.08 mmol) was added dropwise at approximately 0°C. The reaction mixture was stirred overnight at room temperature and then quenched with water (6 mL) and methanol (6 mL). After stirring for 2 hours, the layers were separated, and the aqueous layer was extracted with dichloromethane (2x). The combined organic matter was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was subjected to silica gel column chromatography. The title compound was purified by elution using a gradient of 20-100% ethyl acetate in hexane to obtain a solid (77 mg). 1 H NMR (CDCl3): δ 7.74 (d, 1H), 7.67 (dd, 1H), 7.62 (m, 1H), 7.22 (d, 1H), 6.98 (d, 2H), 6.75 (d, 1H), 4.83 (br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.36(s, 3H).

[0217] Step B: Preparation of N-[[5-[1-[4-[(difluoromethyl)thio]-2,6-difluorophenyl]-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate To a mixture of methyl N-[[5-[1-(2,6-difluoro-4-mercaptophenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of step A) (77 mg, 0.198 mmol) in acetonitrile and water (1:1, 2 mL), potassium hydroxide (222 mg, 3.96 mmol) was added, followed by diethyl phosphonate (bromodifluoromethyl) (0.070 mL, 0.396 mmol). The reaction mixture was stirred at room temperature for 1.5 hours and then diluted with ethyl acetate. The resulting mixture was washed with saturated sodium chloride solution (2x), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluting with a gradient of 10-50% ethyl acetate in hexane) to obtain the title compound, the compound of the present invention, as a grayish-white solid (64 mg). 1 H NMR (CDCl3): δ 7.75(d, 1H), 7.70-7.68(m, 2H), 7.34(d, 2H), 7.24(d, 1H), 7.02-6.80(t, 1H), 6.80(d, 1H), 4.84(br s, 1H), 4.42(d, 2H), 3.70(s, 3H), 2.37(s, 3H). LCMS m / z:440[M+H] +

[0218] Example 17 Preparation of N-[[5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate methyl (compound 65) Process A: Production of 5-[1-(2,6-dichloro-4-nitrophenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile A mixture of 2-methyl-5-(1H-pyrazole-3-yl)benzonitrile (3.0 g, 16.4 mmol) (see PCT International Publication WO2014066120 for preparation method), 1,3-dichloro-2-fluoro-5-nitrobenzene (4.12 g, 19.6 mmol), and potassium carbonate (2.72 g, 19.6 mmol) in N,N-dimethylformamide (51 mL) was heated at 80°C for 4 hours, then stirred overnight at room temperature. The reaction mixture was diluted with water, and the resulting precipitate was collected by filtration and rinsed with water. The solid precipitate was triturated with a hexane / 1-chlorobutane mixture, filtered, and air-dried to obtain the title compound (3.59 g). 1 H NMR (CDCl3): δ 8.37(s, 2H), 8.11(s, 1H), 7.96(d, 1H), 7.64(s, 1H), 7.38(d, 1H), 6.87(s, 1H), 2.60(s, 3H).

[0219] Step B: Production of 5-[1-(4-amino-2,6-dichlorophenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile A mixture of tin(II) chloride dihydrate (12.82 g, 56.82 mmol), acetic acid (51.78 mL), and concentrated hydrochloric acid (34.57 mL) was mixed while maintaining the reaction temperature at approximately 25°C, and 5-[1-(2,6-dichloro-4-nitrophenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile (i.e., the product of step A) (6.07 g, 16.26 mL) was added. (ol) was added little by little. The reaction mixture was stirred overnight, and then slowly poured into a mixture of potassium hydroxide (200 g), water (200 g), and ice (400 g). The resulting solid precipitate was collected by filtration and dried to obtain the title product (6.8 g). 1 H NMR (CDCl3): δ 8.22(s, 1H), 7.98(d, 1H), 7.55(s, 1H), 7.35(d, 1H), 6.76(s, 1H), 6.71(s, 2H), 4.06(s, 2H), 2.57(s, 3H).

[0220] Process C: Preparation of 5-[1-(4-bromo-2,6-dichlorophenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile A mixture of 5-[1-(4-amino-2,6-dichlorophenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile (i.e., the product of step B) (6.75 g, 18.67 mmol) and n-butyl nitrite (27.38 mL, 233.7 mmol) was heated under reflux overnight, then cooled to room temperature and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluted with 20% ethyl acetate in hexane) to obtain the title compound (4.3 g). 1 H NMR (CDCl3): δ 8.22(s, 1H), 7.96(d, 1H), 7.66(s, 2H), 7.58(s, 1H), 7.36(d, 1H), 6.80(s, 1H), 2.57(s, 3H).

[0221] Step D: Preparation of 5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile A mixture of 5-[1-(4-bromo-2,6-dichlorophenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile (i.e., the product of step C) (2.19 g, 5.37 mmol), cyclopropylboronic acid (0.53 g, 6.31 mmol), sodium carbonate (1.99 g, 18.75 mmol), and bis(triphenylphosphine)palladium(II) dichloride (0.46 g, 0.66 mmol) in 1,2-dimethoxyethane (43.7 mL) and water (10.03 mL) was heated overnight at 85 °C. The reaction mixture was cooled to room temperature and then partitioned between water and ethyl acetate. The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (0-10% ethyl acetate in hexane) to obtain the title compound (0.90 g). 1 H NMR(CDCl3):δ 8.13(s, 1H), 7.97(d, 1H), 7.55(s, 1H), 7.34(d, 1H), 7.15(s, 2H), 6.78(s, 1H), 2.57(s, 3H), 1.98-1.90(m, 1H), 1.14-1.08(m, 2H), 0.81-0.75(m, 2H).

[0222] Step E: Preparation of 5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylbenzenemethaneamine hydrochloride To a mixture of 5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylbenzonitrile (i.e., the product of step D (0.88 g, 2.39 mmol)) in dichloromethane (5 mL), tris(2,3,4,5,6-pentafluorophenyl)borane (0.01 g, 0.07 mmol), followed by diethylsilane (0.53 g, 5.97 mmol) was added. The reaction mixture was stirred overnight at room temperature and cooled to approximately 0-5°C, after which hydrochloric acid (4N solution in dioxane, 2.02 mL) was added dropwise. The resulting precipitate was collected by filtration and air-dried to obtain the title compound as a solid (0.82 g). 1 H NMR(CDCl3):δ 8.30(br s, 3H), 8.03(s, 1H), 7.95(s, 1H), 7.77(d, 1H), 7.43(s, 2H), 7.32(d, 1H), 6.97(s, 1H), 3.57(s, 2H), 2.36(s, 3H), 2.13-2.05(m, 1H), 1.14-1.05(m, 2H), 0.91-0.85( m, 2H).

[0223] Step F: Preparation of N-[[5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylphenyl]methyl]carbamate 5-[1-(2,6-dichloro-4-cyclopropylphenyl)-1H-pyrazole-3-yl]-2-methylbenzenemethaneamine hydrochloride (i.e., the product of step E) (0.82 g, 2.01 mmol) and potassium carbonate (0.83 g, 6.02 mmol) were mixed in acetonitrile (10 mL) and methyl chloroformate (0.21 g, 2.21 mmol) at approximately 0-5°C. The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluting with 0%-100% ethyl acetate in hexane) to obtain the title compound, which is the compound of the present invention, as a solid (0.87 g). 1H NMR (CDCl3): δ 7.78(s, 1H), 7.70(d, 1H), 7.63(s, 1H), 7.22(d, 1H), 7.15(s, 2H), 6.76(s, 1H), 4.82(br s, 1H), 4.41(br s, 2H), 3.70(s, 3H), 2.37(s, 3H), 1.95-1.88(m, 1H), 1.12-1.08(m, 2H), 0.80-0.72(m, 2H). LCMS: m / z 430[M+H] +

[0224] Example 18 Preparation of N-[[5-[2-(2,6-difluoro-4-nitrophenyl)-2H-1,2,3-triazol-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 118) and N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-1,2,3-triazol-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 132) Process A: Production of 2-methyl-5-[2-(trimethylsilyl)ethynyl]benzonitrile To a mixture of 2-amino-5-bromobenzonitrile (50 g, 255 mmol) and ethinyltrimethylsilane (181 mL, 1275 mmol) in tetrahydrofuran (600 mL), bis(triphenylphosphine)palladium(II) dichloride (26 g, 38 mmol), copper(I) iodide (14.5 g, 76.5 mmol), triphenylphosphine (20 g, 76.5 mmol), and triethylamine (600 mL) were added. The reaction mixture was stirred at room temperature for 24 hours and then concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (elution with 5% ethyl acetate in petroleum ether) to obtain the title compound as a solid (45 g). 1 H NMR (CDCl3): δ 7.68 (d, J=1.6Hz, 1H), 7.63 (dd, J=8.0, 1.6 Hz, 1H), 7.24 (s, 1H), 2.53 (s, 3H), 0.24 (s, 9H).

[0225] Process B: Production of 5-ethynyl-2-methylbenzonitrile Potassium hydroxide (67 mL, 1% in methanol) was added to a mixture of 2-methyl-5-[2-(trimethylsilyl)ethynyl]benzonitrile (i.e., the product of step A) (40 g, 187.7 mmol) in methanol (800 mL). The reaction mixture was stirred at room temperature for 16 hours, and then the methanol was removed by distillation. The resulting mixture was diluted with water (200 mL) and extracted with ethyl acetate. The combined organic extract was washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluted with 12% ethyl acetate in petroleum ether) to obtain the title compound as a solid (15 g). 1 H NMR(CDCl3): δ 7.70(d, J=1.2Hz, 1H), 7.57( dd, J=8.4, 2.0 Hz, 1H), 7.28(d, J=7.6 Hz, 1H), 3.12(s, 1H), 2.55(s, 3H).

[0226] Process C: Production of 5-ethynyl-2-methylbenzenemethaneamine hydrochloride To a mixture of diphenylsilane (81 mL, 443 mmol) in chloroform (250 mL), tris(2,3,4,5,6-pentafluorophenyl)borane (2.7 g, 5.3 mmol), followed by 5-ethynyl-2-methylbenzonitrile (i.e., the product of step B) (25 g, 177.3 mmol) in chloroform was added. The reaction mixture was stirred at room temperature for 16 hours and then concentrated under reduced pressure. Hydrochloric acid (2N solution in diethyl ether) was added to the resulting substance, and the mixture was stirred for 1 hour. The resulting solid precipitate was collected by filtration and dried to obtain the title compound as a solid (30 g). 1 H NMR (DMSO-d6): δ 8.26 (br s, 3H), 7.53 (s, 1H), 7.37-7.39 (m, 1H), 7.27-7.25 (m, 1H), 4.19 (s, 1H), 4.01 (s, 2H), 2.35 (s, 3H).

[0227] Process D: Production of methyl [(5-ethynyl-2-methylphenyl)methyl]carbamate 5-Ethynyl-2-methylbenzenemethaneamine hydrochloride (i.e., the product of step C) (30 g, 165.7 mmol) and potassium carbonate (68.5 g, 497 mmol) were mixed in acetonitrile (330 mL) and methyl chloroformate (23.3 g, 248.6 mmol) was added dropwise over 20 minutes at 0°C. The reaction mixture was stirred at room temperature for 16 hours, then diluted with water (200 mL) and extracted with ethyl acetate. The combined organic extract was washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by column chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the title compound as a solid (25 g). 1 H NMR(CDCl3): δ 7.38(br s, 1H), 7.33-7.31(m, 1H), 7.13-7.11 (m, 1H), 4.83 (brs, 1H) 4.34 (d, J=5.6Hz, 2H), 3.71 (s, 3H), 3.04 (s, 1H), 2.32 (s, 3H).

[0228] Step E: Preparation of N-[[5-(1H-1,2,3-triazol-4-yl)-2-methylphenyl]methyl]carbamate methyl To a mixture of methyl [(5-ethynyl-2-methylphenyl)methyl]carbamate (i.e., the product of step D) (30 g, 165.7 mmol) in N,N-dimethylformamide (117 mL), methanol (12 mL), trimethylsilyl azide (11.7 mL, 88.6 mmol) and copper(I) iodide (0.56 g, 2.9 mmol) were added. The reaction mixture was heated at 100 °C for 16 hours, then diluted with saturated ammonium chloride solution and extracted with ethyl acetate. The combined organic extract was washed with water and saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel column chromatography (eluted with 20% ethyl acetate in petroleum ether) to obtain the title compound as a solid (4 g). 1H NMR (CDCl3): δ 11.8(br s, 1H), 7.94(s, 1H), 7.71(s, 1H), 7.64-7.61(m, 1H), 7.24(s, 1H), 4.93(br s, 1H), 4.43(d, J=6.0Hz, 2H), 3.71(s, 3H), 2.37(s, 3H).

[0229] Step F: N-[[5-[2-(2,6-difluoro-4-nitrophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 118) and N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate Preparation of methyl rubamate (compound 132) To a mixture of methyl N-[[5-(1H-1,2,3-triazole-4-yl)-2-methylphenyl]methyl]carbamate (i.e., the product of step E) (4 g, 16.2 mmol) in dimethyl sulfoxide (40 mL), potassium carbonate (6.7 g, 48.6 mmol) was added, followed by 1,2,3-trifluoro-5-nitrobenzene (3.1 g, 17.8 mmol). The reaction mixture was stirred at room temperature for 16 hours, then diluted with water (30 mL) and extracted with ethyl acetate. The combined organic extracts were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel chromatography (elution with 20% ethyl acetate in petroleum ether) to obtain N-[[5-[2-(2,6-difluoro-4-nitrophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 118), which is the compound of the present invention, as a solid (2g). 1 H NMR (DMSO-d6): δ 8.77 (s, 1H), 8.45 (dd, J=9.2, 2 Hz, 2H), 7.80(s, 1H), 7.76-7.74(m, 1H), 7.69-7.66(m, 1H), 7.32(d, J=8.0Hz, 1H), 4.24(d, J=5.6 Hz, 2H), 3.55(s, 3H), 2.33(s, 3H). LCMS: m / z: 404 [M+H] + .

[0230] A solid containing a mixture of N-[[5-[2-(2,6-difluoro-4-nitrophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 118) and N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 132) was also obtained. This solid was further purified by silica gel chromatography to obtain N-[[5-[1-(2,6-difluoro-4-nitrophenyl)-1H-1,2,300-triazole-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 132), the compound of the present invention, as a solid (800 mg). 1 H NMR (DMSO-d6): δ 9.08 (s, 1H), 8.50 (d, J=7.6 Hz, 2H), 7.83-7.82(m, 2H), 7.71-7.67(m, 2H), 7.29(d, 8.4Hz, 1H), 4.24(d, J=6.4Hz, 2H), 3.57(s, 3H), 2.32(s, 3H). LCMS: m / z:404[M+H] + .

[0231] Example 19 Preparation of N-[[5-[2-(4-amino-2,6-difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 115) To a mixture of N-[[5-[2-(2,6-difluoro-4-nitrophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate (i.e., product of Example 18, step F, compound 118) (2 g, 4.9 mmol) in ethanol (18 mL) and water (2 mL), iron powder (2.7 g, 49.6 mmol) and ammonium chloride (0.16 g, 2.9 mmol) were added. The reaction mixture was heated under reflux for 1.5 hours, stirred at room temperature for 16 hours, then filtered through a Celite® (diatomaceous earth filter aid) pad and rinsed with ethyl acetate (30 mL). The filtrate was diluted with water and extracted with ethyl acetate. The combined organic matter was washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained substance was purified by silica gel chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the title compound, which is the compound of the present invention, as a solid (1.6 g). 1 H NMR (CDCl3): δ 8.08(s, 1H), 7.74-7.73(m, 1H), 7.67-7.65(m, 1H), 7.24(s, 1H), 6.33-6.30( m, 2H), 4.89(br s, 1H), 4.42(d, J=5.2Hz, 2H), 4.13(s, 2H), 3.70(s, 3H), 2.37(s, 3H) LCMS: m / z:374[M+H] + .

[0232] The following compounds were prepared in the same manner as in Example 19: N-[[5-[1-(4-amino-2,6-difluorophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 131). 1 H NMR(CDCl3):δ 7.91(s, 1H), 7.81(s, 1H), 7.70(d, 1H), 7.25(s, 1H), 6.35(d, 2H), 4.93(brs, 1H), 4.45(s, 2H), 4.19(brs, 2H), 3.71(s, 3H), 2.39(s, 3H).

[0233] Example 20 Preparation of N-[[5-[2-(4-chloro-2,6-difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-methylphenyl]methyl]carbamate methyl (compound 117) To a mixture of methyl N-[[5-[2-(4-amino-2,6-difluorophenyl)-2H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]carbamate (i.e., the product of Example 19) (1 g, 2.68 mmol) in carbon tetrachloride (125 mL), n-butyl nitrite (3.3 g, 32.17 mmol) was added. The reaction mixture was heated under reflux for 16 hours, then filtered through a Celite® (diatomaceous earth filter aid) pad and rinsed with ethyl acetate (20 mL). The filtrate was diluted with water (60 mL) and extracted with ethyl acetate. The combined organic matter was washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (elution with 30% ethyl acetate in petroleum ether) to obtain the title compound, the compound of the present invention, as a solid (0.12 g). 1 H NMR (CDCl3): δ 8.13(s, 1H), 7.74-7.73 (m, 1H), 7.66(dd, J=8.0, 1.6 Hz, 1H), 7.28(s, 1H), 7.19-7.15 (m, 2H), 4.90 (brs, 1H), 4.43(d, J=5.6 Hz, 2H), 4.71(s, 3H), 2.38(s, 3H). LCMS:m / z:393[M+H] + .

[0234] The following compounds were prepared in the same manner as in Example 20: N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-1,2,3-triazole-4-yl]-2-methylphenyl]methyl]methyl carbamate (compound 121). 1 H NMR (CDCl3): δ 7.98(s, 1H), 7.79(brs, 1H), 7.70(d, J=6.4 Hz, 1H), 7.27-7.20(m, 3H), 4.91(br s, 1H), 4.44-4.43(m, 2H), 3.71(s, 3H), 2.38(s, 3H). LCMS:m / z:393[M+H] + .

[0235] The following compounds listed in Tables 1A to 33D can be prepared by the procedures described herein, in conjunction with methods known in the art. The following abbreviations are used in the table below: n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, MeO means methoxy, EOt means ethoxy, MeS means methylthio, EtS means ethylthio, -CN means cyano, and -NO2 means nitro.

[0236] [Table 1]

[0237] This disclosure also includes Tables 2A to 33A, which correspond to the column headings of Table 1A (i.e., "R 1 and R 2 The structure is the same as Table 1A above, except that "is F" is replaced by the column headings shown below. For example, in Table 2A, the column heading is "R 1 and R 2 "is Cl", and R 6 This is defined in Table 1A above.

[0238] [Table 2]

[0239] Table 1B Table 1B is the same as Table 1A except that the chemical structures in Table 1A are replaced with the following structures: [ka]

[0240] Tables 2B~33B Tables 2B to 33B are constructed in the same manner as Tables 2A to 33A.

[0241] Table 1C Table 1C is the same as Table 1A except that the chemical structures in Table 1A are replaced with the following structures: [ka]

[0242] Tables 2C~33C Tables 2C to 33C are constructed in the same manner as Tables 2A to 33A.

[0243] Table 1D Table 1D is identical to Table 1A except that the chemical structures in Table 1A are replaced with the following structures: [ka]

[0244] Tables 2D~33D Tables 2D to 33D are constructed in the same manner as Tables 2A to 33A.

[0245] Formulation / Practicality The compounds of Formula 1 of the present invention (including their N-oxides, hydrates, and salts) are generally used as bactericidal active ingredients in compositions, i.e., formulations, together with at least one further component that functions as a carrier, selected from the group consisting of surfactants, solid diluents, and liquid diluents. The components of the formulation or composition are selected to be in harmony with the physical properties of the active ingredient, the method of application, and environmental factors such as soil type, humidity, and temperature.

[0246] Useful formulations include both liquid and solid compositions. Liquid compositions include liquid formulations (emulsified). Examples include liquids, suspensions, and emulsions (including microemulsions and / or suspendemulsions), which can be made into gels by increasing their viscosity if necessary. Common types of aqueous liquid compositions include liquids, suspension concentrates (SCs), capsule suspensions (CSs), concentrated emulsions, microemulsions, and suspendemulsions. Common types of non-aqueous liquid compositions include emulsions, microemulsifiable concentrates, dispersible concentrates (DCs), and oil dispersions (ODs).

[0247] Common types of solid compositions include powders, granules, pellets, pills, aromatic tablets, tablets, and filled films (including seed coatings), which may be water-dispersible ("hydrated") or water-soluble. Films and coatings formed from film-forming solutions or fluid suspensions are particularly useful for seed treatment. Active ingredients can be (micro)encapsulated to form further suspensions or solid dosage forms; or the entire formulation of the active ingredient can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsion and dry granule formulations. High-strength compositions are mainly used as intermediates for further formulation.

[0248] Sprayable formulations are typically spread in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily dilutable in a spray medium, usually water, but may also be another suitable medium such as aromatic or paraffinic hydrocarbons or vegetable oils. Spray rates can range from approximately 1 liter to several thousand liters per hectare, but more typically from approximately 10 liters to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment by aerial or ground spraying, or for application to the plant's growth medium. Liquid and dry formulations may be measured and added directly into drip irrigation systems, or measured and added between rows during sowing. Liquid and solid formulations may also be applied to the seeds of crops and desired vegetation as a seed treatment before sowing to protect the developing roots and other subterranean plant parts and / or leaves by systemic ingestion.

[0249] The formulation typically contains effective amounts of an active ingredient, diluent, and surfactant within a suitable range, totaling 100% by mass.

[0250] [Table 3]

[0251] Examples of solid diluents include clays such as bentonite, montmorillonite, attapulgite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate, and sodium bicarbonate, as well as sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd edition, Dorland Books, Caldwell, New Jersey.

[0252] Examples of liquid diluents include water, N,N-dimethylalkaneamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), alkyl phosphate (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, linear paraffin, isoparaffin), alkylbenzene, alkylnaphthalene, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic hydrocarbons, alkylbenzenes, alkylnaphthalene, ketones, such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-pentane. Non-acetates, such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactic acid esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols which may be linear or branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents may also include saturated and unsaturated fatty acids (typically C6-C6). 22 Glycerol esters of ) for example, plant seed and fruit oils (e.g., olive, castor bean, linseed, sesame, maize, peanut, sunflower, grape seed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel oil), This also includes plant-derived fats (e.g., beef tallow, lard, cod liver oil, fish oil) and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated), where the fatty acids can be obtained by hydrolysis of glycerol esters of plant and animal origin and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, Second Edition, Interscience, New York, 1950.

[0253] The solid and liquid compositions of the present invention often contain one or more surfactants. When added to a liquid, surfactants (also known as "surfactants") generally modify, and most frequently reduce, the surface tension of the liquid. Depending on the hydrophilic and lipophilic properties of the surfactant molecules, surfactants may be useful as wetting agents, dispersants, emulsifiers, or defoamers.

[0254] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alkoxylated alcohols, e.g., based on natural and synthetic alcohols (which may be branched or linear), and produced from alcohols with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; ethoxylated amines, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, e.g., ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates, e.g., octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (produced from phenols with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers produced from ethylene oxide or propylene oxide, and reverse block polymers in which the terminal blocks are produced from propylene oxide; Examples include ethoxylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those made from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters, e.g., polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives, e.g., sorbitan esters; polymer surfactants, e.g., random copolymers, block copolymers, alkyl PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives, e.g., sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0255] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, e.g., lignosulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, e.g., phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarco Syn derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, e.g., N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzene; sulfonates of condensed naphthalenes; sulfonates of naphthalenes and alkylnaphthalenes; sulfonates of fractionally distilled petroleum; sulfosucciniamidates; and sulfosuccinates and their derivatives Examples include dialkyl sulfosuccinates.

[0256] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, trippropylenetriamines and dipropylenetetramines, as well as ethoxylated amines, ethoxylated diamines and propoxylated amines (made from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, e.g., amine acetate and diamine salts; quaternary ammonium salts, e.g., quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, e.g., alkyldimethylamine oxide and bis-(2-hydroxyethyl)-alkylamine oxide.

[0257] Mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants are also useful in the compositions of the present invention. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in various published references, including McCutcheon's Emulsifiers and Detergents, annual international and North American editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and AS Davidson and B. Milwidsky, Synthetic Detergents, 7th edition, John Wiley and Sons, New York, 1987.

[0258] The compositions of this disclosure may also contain formulation aids and additives known to those skilled in the art as formulation aids. Such formulation aids and additives can control: pH (buffering agents), foaming during processing (antifoaming agents such as polyorganosiloxanes (e.g., Rhodorsil® 416)), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobial agents), product freezing (antifreeze agents), color (pigment / dye dispersion (e.g., Pro-lzed® Colorant Red)), washability (film-forming agents or stickers)), evaporation (evaporation retarders), and other formulation attributes. Examples of film-forming agents include polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives are listed in McCutcheon's Volume 2: Functional Materials, annual international and North American editions, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co., and in PCT International Publication No. WO03 / 024222.

[0259] Compounds of formula I and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredients in a solvent or by grinding them in a liquid or dry diluent. Liquid formulations containing emulsions can be prepared simply by mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsion is water-immiscible, an emulsifier is typically added to emulsify the active ingredient-containing solvent when diluting with water. Active ingredient slurries having particle sizes up to 2,000 μm can be wet-ground using a medium mill to obtain particles with an average diameter of less than 3 μm. The aqueous slurry can be made into a finished SC formulation (see, for example, US3,060,084) or further processed by spray-drying to form hydrated granules. Dry formulations usually require a dry grinding process, which results in an average particle size in the range of 2 to 10 μm. Powders and powders are mixed and usually It can be manufactured by grinding (e.g., using a hammer mill or a fluid energy mill). Granules and pellets can be manufactured by spraying the active substance onto a pre-formed granular carrier or by agglomeration techniques. See Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147–48; Perry's Chemical Engineer's Handbook, 4th edition, McGraw-Hill, New York, 1963, pp. 8–57 and below, as well as WO91 / 13546. Pellets can be manufactured as described in US4,172,714. Hydrated and water-soluble granules can be manufactured as taught in US4,144,050, US3,920,442 and DE3,246,493. Tablets can be manufactured as taught in US5,180,587, US5,232,701 and US5,208,030. The film may be manufactured as taught in gB2,095,558 and US3,299,566.

[0260] One embodiment of the present invention relates to a method for controlling a fungal pathogen, comprising diluting a bactericidal composition of the present invention (a compound of Formula 1 formulated together with a surfactant, a solid diluent and a liquid diluent, or a formulation mixture of a compound of Formula 1 and at least one other fungicide) with water, optionally adding an adjuvant to form a diluted composition, and contacting a fungal pathogen or its environment with an effective amount of the diluted composition.

[0261] A spray composition formed by diluting a sufficiently concentrated bactericidal composition of the present invention with water may provide sufficient efficacy to control fungal pathogens, but separately formulated adjuvant products may be added to the spray tank mixture. These additional adjuvants are commonly known as “spray adjuvants” or “tank mix adjuvants,” and include any substances mixed in a spray tank to improve the performance of the insecticide or to alter the physical properties of the spray mixture. Adjuvants may be anionic or nonionic surfactants, emulsifiers, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners, or defoamers. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, penetration, uniformity of coverage, and persistence of disease control), or to minimize or eliminate problems associated with spray application related to incompatibility, foaming, drift, evaporation, volatilization, and decomposition. To obtain optimal performance, adjuvants are selected with respect to the properties, formulation, and target of the active ingredient (e.g., crops, harmful insects).

[0262] The amount of adjuvant added to the spray mixture is generally in the range of approximately 2.5% to 0.1% by volume. The application rate of adjuvant added to the spray mixture is typically about 1 to 5 liters per hectare. Representative examples of spray adjuvants include: Adigor® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkylene oxide-modified heptamethyltrisiloxane, and Assist® (BASF) 17% surfactant blend in 83% paraffinic mineral oil.

[0263] One method of seed treatment involves spraying or applying the compound of the present invention (i.e., as a formulated composition) to the seeds before sowing. Formulated compositions for seed treatment generally contain a film-forming agent or adhesive. Therefore, typically, a seed coating composition of the present invention contains a biologically effective amount of the compound of Formula 1 and a film-forming agent or adhesive. Seeds can be coated by spraying a flowable formulation directly onto a rotating seed bed and then drying the seeds. Alternatively, other formulations such as wettable powders, liquids, saspoemulsions, emulsions, and aqueous emulsions may be sprayed onto the seeds. This process is particularly useful for forming a coating on the seeds. Various coating machines and coating processes are available to those skilled in the art. A suitable process is described in P. Kosters et al., Seed Treatment: Progress and Prospects, 19. This includes the references listed in 94 BCPC Mongraph No. 57 and the bibliography listed therein.

[0264] For further information on formulation technology, see Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR. Roberts, Proceedings of the 9th International Congress. TS Woods, "The Formulator's Toolbox - on Pesticide Chemistry," The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See "Product Forms for Modern Agriculture." US3,235,361, column 6, line 16-7, line 19 and Examples 10-41; US3,309,192, column 5, line 43-7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US2,891,855, column 3, line 66-5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments See also *In Formulation Technology*, PJB Publications, Richmond, UK, 2000.

[0265] In the following examples, all percentages are by mass, and all formulations are manufactured by conventional methods. Compound numbers refer to compounds in index tables A-G. It is assumed that those skilled in the art can utilize the present invention to its fullest extent by using the prior description without further ado. Therefore, the following examples are for illustrative purposes only and should be construed as not limiting the present disclosure in any way.

[0266] Example A high strength concentrate Compound 1 98.5% Silica aerosol 0.5% Synthetic amorphous fine silica 1.0%

[0267] Example B Wettable powder Compound 3 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignin sulfonate 4.0% Sodium aluminosilicate 6.0% Montmorillonite (calcined) 23.0%

[0268] Example C Granules Compound 4 10.0% Attapulgite granules (low volatility, 0.71 / 0.30 mm; USS No. 25-50 sieve) 90.0%

[0269] Example D Extruded pellets Compound 5 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignin sulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0270] Example E emulsion Compound 6 10.0% Polyoxyethylene sorbitol hexaoleate 20.0% C6-C 10 Fatty acid methyl ester 70.0%

[0271] Example F Microemulsion Compound 7 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0272] Example G Seed treatment Compound 8 20.00% Polyvinylpyrrolidone-vinyl acetate copolymer 5.00% Montane wax 5.00% Calcium lignin sulfonate 1.00% Polyoxyethylene / polyoxypropylene block copolymer 1.00% Stearyl alcohol (POE2O) 2.00% Polyorganosilane 0.20% Red pigment 0.05% Water 65.75%

[0273] Example H Fertilizer sticks Compound 10 2.50% Pyrrolidone-styrene copolymer 4.80% Tristyrylphenyl 16-ethoxylate 2.30% Talc 0.80% Cornstarch 5.00% Sustained-release fertilizer 36.00% Kaolin 38.00% Water 10.60%

[0274] Example I SC agent Compound 33 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based defoaming agent 0.1% 1,2-Benzisothiazolin-3-one 0.1% Water 53.7%

[0275] Example J EW agent (Emulsion in Water) Compound 41 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based defoaming agent 0.1% 1,2-Benzisothiazolin-3-one 0.1% Aromatic petroleum hydrocarbons 20.0 Water 58.7%

[0276] Example K OD agent (Oil Dispersion) Compound 68 25% Hexaoleic acid, polyoxyethylene sorbitol 15% Organically modified bentonite clay 2.5% Fatty acid methyl ester 57.5%

[0277] Example L Suspension emulsion Compound 115 10.0% Imidaclopride 5.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based defoaming agent 0.1% 1,2-Benzisothiazolin-3-one 0.1% Aromatic petroleum hydrocarbons 20.0% Water 53.7%

[0278] Water-soluble and hydrated formulations are typically diluted with water before application to form aqueous compositions. Aqueous compositions for direct application to plants or parts thereof (e.g., spray tank compositions) typically contain at least about 1 ppm or more (e.g., 1 ppm to 100 ppm) of the compound of the present invention.

[0279] Seeds are typically treated with an amount of approximately 0.001 g (more typically about 0.1 g) to 10 g per kilogram of seed (i.e., about 0.0001 to 1 mass% of the seed weight before treatment). Flowable formulations prepared for seed treatment typically contain approximately 0.5 to 70% active ingredient, approximately 0.5 to 30% film-forming adhesive, approximately 0.5 to 20% dispersant, 0 to 5% thickener, 0 to 5% pigment and / or dye, 0 to 2% defoamer, approximately 1% preservative, and volatile liquids. Contains 0-75% diluent.

[0280] The compounds of the present invention are useful as plant disease control agents. Therefore, the present invention further includes a method for controlling plant diseases caused by fungal plant pathogens, comprising applying an effective amount of the compound of the present invention or a fungicidal composition containing the compound to a plant or part thereof to be protected, or to plant seeds to be protected. The compounds and / or compositions of the present invention provide control of diseases caused by a wide range of fungal plant pathogens in the Ascomycota, Basidiomycota, Zygomycota, and fungal-like Oomycota. These are effective in controlling a wide range of plant diseases, particularly leaf diseases, in ornamental plants, turfgrasses, vegetables, grounds, grains, and fruit crops. Examples of these pathogens, but not limited to those listed in Table 1-1, are included. For Ascomycota and Basidiomycota, the list includes both the names for the sexual / sexual / perfect stage and the asexual / asexual / imperfect stage (in parentheses) if known. Synonyms for pathogens are indicated by an equals sign. For example, the name Phaeosphaeria nodorum, which refers to the sexual / sexual / perfect stage, is followed by the corresponding name Stagnospora nodorum, which refers to the asexual / asexual / imperfect stage, and the older, synonymous name Septoria nodorum.

[0281] [Table 4]

[0282] [Table 5]

[0283] In addition to their fungicidal activity, the composition or combination is effective against burn blight bacteria (Erwinia). amylovora), Xanthomonas campestris, Pseudomonas syringae, and It also has activity against other related species of bacteria. By controlling harmful microorganisms, the compounds of the present invention are useful for improving (i.e., increasing) the ratio of beneficial microorganisms to harmful microorganisms in contact with crop plants or their bulbils (e.g., seeds, corms, bulbs, tubers, cuttings) or in the agricultural environment of crops or their bulbils.

[0284] The compounds of the present invention are useful in the treatment of all plants, plant parts, and seeds. Varieties and cultivars of plants and seeds can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which heterologous genes (introduced genes) are stably incorporated into the genome of the plant or seed. Introduced genes, defined by their specific location in the plant genome, are referred to as formal transformations or transgenic events.

[0285] Genetically modified plant varieties that can be treated according to the present invention include those that are resistant to one or more biological stresses (such as nematodes, insects, mites, and fungi) or abiotic stresses (such as drought, low temperatures, and soil salinity), or that possess other desirable characteristics. Plants can be genetically modified to exhibit, for example, herbicide resistance, insect resistance, an improved oil profile, or drought tolerance.

[0286] Treatment of genetically modified plants and seeds with the compounds of the present invention may produce additive or enhanced effects. For example, reduced application rates, expanded activity range, increased tolerance to biotic and abiotic stress, or enhanced storage stability may be greater than what would be expected from the mere additive effects of applying the compounds of the present invention to genetically modified plants and seeds.

[0287] The compounds of the present invention are useful in seed treatments for protecting seeds from plant diseases. In the context of this disclosure and claims, seed treatment means bringing seeds into contact with a biologically effective amount of the compounds of the present invention, which are typically formulated as compositions of the present invention. This seed treatment protects seeds from pathogens of soilborne diseases and, generally, also protects the roots and other plant parts in contact with the soil of seedlings developing from germinating seeds. Seed treatment may also provide leaf protection by translocation of the compounds of the present invention or a second active ingredient within the developing plant. Seed treatments can be applied to all types of seeds, including those from which genetically transformed plants will germinate, expressing specialized traits. Typical examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin, or those expressing herbicide resistance, such as glyphosate acetyltransferase, which provides resistance to glyphosate. Seed treatment using the compounds of the present invention can also increase the vitality of plants growing from those seeds.

[0288] The compounds and compositions of the present invention, both alone and in combination with other fungicides, nematicides, and insecticides, are particularly useful in seed treatment for crops, including, but not limited to, maize or corn, soybeans, cottonseed, cereals (e.g., wheat, oats, barley, rye, and rice), potatoes, vegetables, and rapeseed.

[0289] Furthermore, the compounds of the present invention are useful in treating post-harvest diseases of fruits and vegetables caused by fungi and bacteria. These infections can occur before, during, and after harvest. For example, infection may occur before harvest and remain dormant until some point during maturation (e.g., the host initiates tissue changes in a way that allows the infection to progress); or infection may arise from surface wounds caused by mechanical or insect damage. In this regard, the compounds of the present invention are useful in treating damage caused by post-harvest diseases that may occur at any point between harvest and consumption. The damage (i.e., damage resulting from quantity and quality) can be reduced. Treatment of post-harvest diseases with the compounds of the present invention can increase the period during which perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) can be stored refrigerated or unrefrigerated after harvest and remain edible and free from noticeable or harmful degradation or contamination by fungi or other microorganisms. Treatment of edible plant parts before or after harvest with the compounds of the present invention can also reduce the formation of toxic metabolites of fungi or other microorganisms, such as mycotoxins such as aflatoxins.

[0290] Plant disease control is usually achieved by applying an effective amount of the compound of the present invention to the part of the plant to be protected, such as roots, stems, leaves, fruits, seeds, tubers, or bulbs, either before or after infection, or to the medium (soil or sand) in which the plant to be protected grows. The compound may also be applied to protect seeds and seedlings that develop from seeds. The compound may also be applied via irrigation water to treat plants. Pre-harvest control of post-harvest pathogens that infect crops is typically achieved by applying the compound of the present invention to fields, and if infection occurs after harvest, the compound may be applied to harvested crops as a dip, spray, fumigant, treated packaging material, and box lining.

[0291] The application rate (i.e., effective fungicidal dose) for these compounds may be influenced by factors such as the plant disease to be controlled, the plant species to be protected, ambient humidity, and temperature, and should be determined under actual usage conditions. Those skilled in the art can easily determine the effective fungicidal dose required for the desired level of plant disease control through simple experiments. Leaves can usually be protected when treated with amounts ranging from less than about 1 g / ha to about 5,000 g / ha of the active ingredient. Seeds and seedlings can usually be protected when treated with amounts ranging from about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed.

[0292] The compounds of this disclosure can also be mixed with one or more other biologically active compounds or agents to form multicomponent pesticides that provide a broader range of agricultural protection, such as fungicides, insecticides, nematicides, bactericides, acaricides, herbicides, herbicide phytotoxicity reducers, growth regulators, such as insect molting inhibitors and rooting stimulants, chemical sterilizers, signaling substances, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or entomopathogenic bacteria, viruses, or fungi. Accordingly, this disclosure also relates to a composition comprising a compound of formula I (in a bactericidal amount) and at least one further biologically active compound or agent (in a biologically effective amount), which may further comprise at least one surfactant, solid diluent, or liquid diluent. Other biologically active compounds or agents can be formulated into a composition comprising at least one surfactant, solid, or liquid diluent. The mixtures of the present disclosure may include one or more other biologically active compounds or agents which may be formulated together with the compound of formula I to form a premix, or one or more other biologically active compounds or agents which may be formulated separately from the compound of formula I, and these formulations may be mixed before application (e.g., in a spray tank) or applied sequentially.

[0293] As described in the summary of the present invention, one aspect of the present invention is a bactericidal composition comprising (i.e., a mixture or combination of) a compound of formula 1, its N-oxide, or salt (i.e., component a), and at least one other fungicide (i.e., component b). Of note is the combination such that the other bactericidal active ingredient has a different site of action from the compound of formula 1. In certain particular examples, a combination with at least one other bactericidal active ingredient having a similar control range but a different site of action is particularly advantageous for resistance control. Accordingly, the composition of the present invention may further contain at least one additional bactericidal active ingredient in a bactericidal effective amount having a similar control range but a different site of action.

[0294] Of particular note is that, in addition to the compound of formula 1 in component (a), component (b) includes at least one bactericidal compound selected from the group consisting of the following mechanisms of action (MOA) classes as defined by FRAC: (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and cell membrane integrity, (G) cell membrane sterol biosynthesis, (H) cell wall biosynthesis in the membrane, (I) melanin synthesis in the cell wall, (P) induction of host plant defense, multi-point contact activity, and unknown mechanisms of action.

[0295] The target sites recognized or proposed in FRAC, along with their FRAC target site codes belonging to the above MOA class, are: (A1) RNA polymerase I, (A2) adenosine deaminase, (A3) DNA / RN biosynthesis (proposed), (A4) DNA topoisomerase, (B1-B3) β-tubulin polymerization in mitosis, (B4) cell division (proposed), (B5) delocalization of spectrin-like proteins, and (C1) complex I. (C2) Complex II: succinate dehydrogenase, (C3) Complex III: cytochrome bc1 (ubiquinol oxidase) Qo site, (C4) Complex III: cytochrome bc1 (ubiquinone reductase) Qi site, (C5) uncoupling of oxidative phosphorylation, (C6) oxidative phosphorylation, inhibitor of ATP synthase, (C7) ATP production (proposed), (C8) Complex III: cytochrome bc1 (ubiquinone reductase) Qx (unknown) site, (D1) methionine biosynthesis (proposed), (D2-D5) protein biosynthesis, (E1) signal transduction (mechanism of action unknown), (E2-E3) histidine kinase in MAP / osmotic signal transduction, (F2 (F3) Phospholipid biosynthesis, methyltransferase, (F4) Lipid peroxidation (proposed), (F6) Cell membrane permeability, fatty acids (proposed), (F7) Microbial disruption of pathogenic cell membranes, (G1) C14-demethylase in sterol biosynthesis, (G2) Δ14-reductase and Δ8→Δ7-isomerase in sterol biosynthesis, (G3) 3-keto reductase, C4-demethylation, (G4) Squalene epoxidase in sterol biosynthesis, (H3) Trehalase and inositol biosynthesis, (H4) Chitin synthase, (H5) Cellulose synthase, (I1) Reductase in melanin biosynthesis, and (I2) Dehydrase in melanin biosynthesis.

[0296] Of particular note are the compounds of formula 1 in component (a), as well as component (b), class (b1) benzimidazole carbamate methyl (MBC) bactericides; (b2) dicarboximide bactericides; (b3) demethylation inhibitor (DMI) bactericides; (b4) phenylamide bactericides; (b5) amine / morpholine bactericides; (b6) phospholipid biosynthesis inhibitor bactericides; (b7) succinate dehydrogenase inhibitor bactericides; (b8) hydroxy(2-amino-)pyrimidine bactericides; (b9) anilinopyrimidine bactericides; (b10) N-phenylcarbamate bactericides; (b11) quinone external inhibitor (QoI) bactericides; (b12) phenyl (b13) Lupyrrole disinfectant; (b14) Azanaphthalene disinfectant; (b15) Lipid peroxidation inhibitor disinfectant; (b16) Melanin biosynthesis inhibitor-reductase (MBI-R) disinfectant; (b17) Melanin biosynthesis inhibitor-dehydrase (MBI-D) disinfectant; (b18) Sterol biosynthesis inhibitor (SBI): Class III disinfectant; (b19) Squalene-epoxidase inhibitor disinfectant; (b20) Polyoxin disinfectant; (b21) Phenylurea disinfectant; (b22) Quinone internal inhibitor (QiI) disinfectant; (b23) Benzamide and thiazole carboxamide disinfectant; (b24) Enopyranuronic acid (b24) Antibiotic bactericides; (b25) Hexopyranosyl antibiotic bactericides; (b26) Glucopyranosyl antibiotics: Protein synthesis bactericides; (b27) Glucopyranosyl antibiotics: Trehalase and inositol biosynthesis bactericides; (b28) Cyanoacetamidooxime bactericides; (b29) Carbamic acid bactericides; (b20) Oxidative phosphorylation uncoupling bactericides; (b30) Organotin bactericides; (b31) Carboxylic acid bactericides; (b32) Heteroaromatic bactericides; (b33) Phosphonate bactericides; (b34) Phthalamic acid bactericides; (b35) Benzotriazine bactericides; (b36) Benzene sulfonamide bactericides; (b37) Pyridazinone bactericides; (b38) Thiofen-carbohydrate bactericides Ruboxamide fungicide; (b39) Complex I NADH oxidoreductase inhibitor fungicide; (b40) Carboxylate amide (CAA) fungicide; (b41) Tetracycline antibiotic fungicide; (b42) Thiocarbamate fungicide; (b43) Benzamide fungicide; (b44) Microbial fungicide; (b45) Q x(b) a fungicide; (b) a plant extract fungicide; (b) a host plant defense-inducing fungicide; (b) a multi-point contact active fungicide; (b) a fungicide other than those of classes (b) to (b)8; and at least one fungicide selected from the group consisting of salts of compounds of classes (b) to (b)8.

[0297] A further description of this class of bactericidal compounds is provided below.

[0298] (b1) Benzimidazole methyl carbamate (MBC) bactericide (FRAC code 1) inhibits mitosis by binding to β-tubulin during microtubule polymerization. Inhibition of microtubule polymerization can disrupt cell division, intracellular transport, and cellular structure. Benzimidazole methyl carbamate bactericides include benzimidazole and thiophanate bactericides. Benzimidazoles include benomyl, carbendazim, fuberidazole, and thiabendazole. Thiophanates include thiophanate and thiophanate-methyl.

[0299] (b2) Dicarboximide fungicides (FRAC code 2) inhibit MAP / histidine kinases in osmotic signaling. Examples include clozolinates, iprodione, procymidone, and vinclozoline.

[0300] (b3) Demethylation inhibitor (DMI) fungicides (FRAC code 3) (sterol biosynthesis inhibitors (SBI): class I) inhibit C14-demethylase, which plays a role in sterol production. Sterols such as ergosterol are necessary for membrane structure and function and are essential for the development of functional cell walls. Therefore, exposure to these fungicides can lead to abnormal growth and even death of susceptible fungi. DMI fungicides are divided into several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines, pyridines, and triazolinthions. Triazoles include azaconazole, vitertanol, bromconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxyconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, and Niconazole, Uniconazole-P, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3 Examples include -(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-5-(2-propene-1-ylthio)-1H-1,2,4-triazole.Examples of imidazoles include econazole, imazalil, oxpoconazole, prochloraz, pefurazoate, and triflumizole. Examples of pyrimidines include phenalimol, nualimol, and triarimol. Examples of piperazines include trifo. Phosphorus is one example. Pyridines include butthiobate, pyrifenox, pyrisoxazole (a mixture of 3-[(3R)-5-(4-chlorophenyl)-2,3-dimethyl3-isoxazolidinyl]pyridine, 3R,5R- and 3R,5S-isomers), and (αS)-[3-(4-chloro-2-fluorophenyl)5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol. Triazolinthions include prothioconazole and 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thion. Biochemical studies have shown that all of the aforementioned fungicides are DMI fungicides as described by KHKuck et al. in Modern Selective Fungicides-Properties, Applications and Mechanisms of Action, H. Lyr (ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

[0301] (b4) Phenylamide fungicides (FRAC code 4) are specific inhibitors of RNA polymerase in oomycetes. Susceptible fungi exposed to these fungicides show a reduced ability to incorporate uridine into rRNA. Growth and development in susceptible fungi are prevented by exposure to this class of fungicides. Examples of phenylamide fungicides include acylalanine, oxazolidinone, and butyrolactone fungicides. Examples of acylalanine include venalaxyl, venalaxyl-M (also known as kiralaxyl), flaxyl, metalaxyl, and metalaxyl-M (also known as mefenoxam). An example of oxazolidinone is oxadixyl. An example of butyrolactone is ofurace.

[0302] (b5) "Amine / morpholine fungicides" (FRAC code 5) (SBI: class II) target two sites in the sterol biosynthesis pathway, Δ 8 →Δ 7 isomerase and Δ 14 They inhibit reductase. Sterols such as ergosterol are necessary for membrane structure and function and are essential for the development of functional cell walls. Therefore, exposure to these fungicides can lead to abnormal growth and even death of susceptible fungi. Amine / morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine, piperidine, and spiroketal-amine fungicides. Morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph, and trimorphamide. Piperidines include fenpropidine and piperaline. Spiroketal-amines include spiroxamine.

[0303] (b6) Phospholipid biosynthesis inhibitor fungicides (FRAC code 6) inhibit fungal growth by affecting phospholipid biosynthesis. Examples of phospholipid biosynthesis fungicides include phosphorothiolates and dithiolanes. Examples of phosphorothiolates include edifenphos, ipropenphos, and pyrazophos. An example of a dithiolane isoprothiolane.

[0304] (b7) Succinate dehydrogenase inhibitor (SDHI) fungicides (FRAC code 7) inhibit complex II fungal respiration by disrupting succinate dehydrogenase, a key enzyme in the Krebs cycle (TCA cycle). Inhibition of respiration prevents fungi from producing ATP, thus inhibiting growth and reproduction. Examples of SDHI fungicides include phenylbenzamide, furacarboxamide, oxathiincarboxamide, thiazolecarboxamide, pyrazole-4-carboxamide, pyridinecarboxamide, and phenyloxoethyl Examples include thiophenamides and pyridinylethylbenzamides. Examples of benzamides include benodanil, flutolanil, and mepronil. An example of francarboxamide is fenflam. Examples of oxatiincarboxamides include carboxyne and oxycarboxyne. An example of thiazolecarboxamide is tifluzamide.Examples of pyrazole-4-carboxamides include benzovindiflupyr (N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide), bixafen, fluindapyr, fluxapyroxad (3-(difluoromethyl)-1-methyl-N-(3',4',5'-trifluoro[1,1'-biphenyl]-2-yl)-1H-pyrazole-4-carboxamide), flametopyr, isoflucypram, and isopyrazam. (3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalene-5-yl]-1H-pyrazole-4-carboxamide), Penflufen (N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide), Penthiopyrad, Pidiflumetofen, Sedaxane (N-[2-[1,1'-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide), N-[2-(1S,2R)-[1,1'-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-indene- Examples include 4-yl)-1-methyl-1H-pyrazole-4-carboxamide, N-[2-(2,4-dichlorophenyl)2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, and N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide. Boscalid is an example of pyridinecarboxamides. Isophetamide (N-[1,1-dimethyl-2-[2-methyl-4-(1-methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide) is an example of phenyloxoethylthiophenamides.Examples of pyridinyl ethylbenzamides include fluopyram.

[0305] (b8) Hydroxy-(2-amino-)pyrimidine fungicides (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, methylmol, and ethylmol.

[0306] (b9) "Anilidopyrimidine fungicides" (FRAC code 9) are proposed to inhibit the biosynthesis of the amino acid methionine and disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim, and pyrimethanil.

[0307] (b10) "N-phenylcarbamate bactericide" (FRAC code 10) inhibits mitosis by binding to β-tubulin and disrupting microtubule polymerization. Inhibition of microtubule polymerization can disrupt cell division, intracellular transport, and cellular structure. An example is diethofencarb.

[0308] (b11) "Quinone external inhibitor (QoI) fungicides" (FRAC code 11) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol inhibits "Quinone external (QoI)" cytochrome bc1 complex located in the internal mitochondrial membrane of fungi. o It is blocked at the site. Inhibition of mitochondrial respiration interferes with the normal growth and development of fungi. As a quinone external inhibitor fungicide, Examples include methoxyacrylates, methoxycarbamates, oxyiminoacetates, oxyiminoacetamides, and dihydrodioxazine fungicides (collectively known as strobilurin fungicides), as well as oxazolidinediones, imidazolinones, and benzylcarbamate fungicides. Methoxyacrylates include azoxystrobin and coumoxystrobin. ((αE)-2-[[(3-butyl-4-methyl-2-oxo-2H-1-benzopyran-7-yl)oxy]methyl]-α-(methoxymethylene)benzene acetate methyl), enoxastrobin ((αE)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-1-methyl-2-propene-1-ylidene]amino]oxy]methyl]-α-(methoxymethylene)benzene acetate methyl) (also known as enestroburin), flufenoxystrobin ((αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzene acetate methyl), picoxystrobin, and pyraoxystrobin Examples of methyl methyl phosphates include ((αE)-2-[[[3-(4-chlorophenyl)-1-methyl-1H-pyrazole-5-yl]oxy]methyl]-α-(methoxymethylene)benzene acetate methyl). Examples of methoxycarbamates include pyraclostrobin, pyrametostrobin (N-[2-[[(1,4-dimethyl-3-phenyl-1H-pyrazole-5-yl)oxy]methyl]phenyl]-N-methoxycarbamate methyl), and triclopyricarb (N-methoxy-N-[2-[[(3,5,6-trichloro-2-pyridinyl)oxy]methyl]phenyl]carbamate methyl). Examples of oxyiminoacetates include kresoxime-methyl and trifloxystrobin.Examples of oxyiminoacetamides include dimoxystrobin, fenaminstrobin ((αE)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)-1-methyl-2-propene-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide), metminostrobin, orysastrobin, and α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide. Examples of dihydrodioxazines include fluoxastrobin. Examples of oxazolidinediones include famoxadone. Examples of imidazolinones include fenamidone. Examples of benzylcarbamates include pyribencarb. Class (b11) also includes mandestrobin (2-[(2,5-dimethylphenoxy)methyl]-α-methoxy-N-benzeneacetamide).

[0309] (b12) Phenylpyrrole fungicides (FRAC code 12) inhibit MAP / histidine kinases involved in osmotic signaling in fungi. Fenpiclonil and fludioxonil are examples of this class of fungicides.

[0310] (b13) Azanafthene fungicides (FRAC code 13) are proposed to inhibit signal transduction by a mechanism that is still unknown. They have been shown to interfere with germination and / or appressorium formation in fungi that cause powdery mildew. Examples of azanafthene fungicides include aryloxyquinolines and quinazolinones. Examples of aryloxyquinolines include quinoxyfen. Examples of quinazolinones include proquinazide.

[0311] (b14) Lipid peroxidation inhibitors (FRAC code 14) are proposed to inhibit lipid peroxidation that affects membrane synthesis in fungi. Members of this class, such as etridiazoles, may also affect other biological processes such as respiration and melanin biosynthesis. Lipid peroxidation inhibitors include aromatic hydrocarbons and Examples of 1,2,4-thiadiazole fungicides include biphenyl, chloreneb, dichlorane, quintozen, technazen, and tolclophos-methyl. Examples of 1,2,4-thiadiazoles include etridiazole.

[0312] (b15) "Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides" (FRAC code 16.1) inhibit the naphthal reduction process in melanin biosynthesis. Melanin is required for host plant infection by several fungi. Examples of melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranones, pyrroloquinolinones, and triazolobenzothiazole fungicides. Examples of isobenzofuranones include phthalides. Examples of pyrroloquinolinones include pyrroquilons. Examples of triazolobenzothiazoles include tricyclazoles.

[0313] (b16) "Melanin biosynthesis inhibitors-dehydrating enzyme (MBI-D) fungicides" (FRAC code 16.2) inhibit citalone dehydratase in melanin biosynthesis. Melanin is necessary for host plant infection by several fungi. Examples of melanin biosynthesis inhibitors-dehydrating enzyme fungicides include cyclopropanecarboxamide, carboxamide, and propionamide fungicides. Examples of cyclopropanecarboxamides include carpropamide. Examples of carboxamides include diclocimet. Examples of propionamides include phenoxanil.

[0314] (b17) Sterol biosynthesis inhibitors (SBIs): Class III fungicides (FRAC code 17) inhibit 3-ketoreductase during C4-demethylation in sterol production. Examples of SBIs: Class III fungicides include hydroxyanilide fungicides and aminopyrazolinone fungicides. Examples of hydroxyanilides include fenhexamide. Examples of aminopyrazolinones include fenpyrazamine (S-2-propen-1-yl 5-amino-2,3-dihydro-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-1H-pyrazole-1-carbocioate).

[0315] (b18) Squalene epoxidase inhibitors (FRAC code 18) (SBI: class IV) inhibit squalene epoxidase in the sterol biosynthesis pathway. Sterols such as ergosterol are necessary for membrane structure and function and are essential for the development of functional cell walls. Therefore, exposure to these fungicides can lead to abnormal growth and even death of susceptible fungi. Examples of squalene epoxidase inhibitors include thiocarbamates and allylamine fungicides. Examples of thiocarbamates include pyributicarb. Examples of allylamines include naphthifine and terbinafine.

[0316] (b19) "Polyoxin disinfectants" (FRAC code 19) inhibit chitin synthase. Polyoxins are an example.

[0317] (b20) Phenylurea disinfectants (FRAC code 20) are suggested to affect cell division. An example is Pencyclon.

[0318] (b21) "Quinone internal inhibitor (QiI) fungicides" (FRAC code 21) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Ubiquinone reduction is performed by "Quinone internal (QiI)" cytochrome bc1 complex. iIt is blocked at the site, which is located in the internal mitochondrial membrane of fungi. By inhibiting mitochondrial respiration, normal fungal growth and development are disrupted. Examples of quinone internal inhibitor fungicides include cyanoidazole and sulfamoyltriazole fungicides. An example of a cyanoidazole is cyazofamide. Sulfamoyltriazoles and Amisulblom is one example.

[0319] (b22) "Benzamide and thiazole carboxamide fungicides" (FRAC code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule polymerization. Inhibition of microtubule polymerization can disrupt cell division, intracellular transport, and cellular structure. Examples of benzamides include zoxamide. Examples of thiazole carboxamides include etaboxam.

[0320] (b23) Enopyran uronic acid antibiotic fungicides (FRAC code 23) inhibit fungal growth by affecting protein biosynthesis. An example is blastocydin-S.

[0321] (b24) Hexopyranosyl antibiotic fungicides (FRAC code 24) inhibit fungal growth by affecting protein biosynthesis. An example is kasugamycin.

[0322] (b25) "Glucopyranosyl antibiotics: protein synthesis fungicides" (FRAC code 25) inhibit fungal growth by affecting protein biosynthesis. An example is streptomycin.

[0323] (b26) "Glucopyranosyl antibiotics: trehalase and inositol biosynthesis fungicides" (FRAC code 26) inhibit trehalase and inositol biosynthesis. Validamycin is an example.

[0324] (b27) "Cymoxanil is an example of a cyanoacetamidooxime fungicide (FRAC code 27)."

[0325] (b28) Carbamic acid fungicides (FRAC code 28) are considered to be multi-site inhibitors of fungal growth. They are proposed to interfere with fatty acid synthesis in the cell membrane and subsequently disrupt nuclear permeability. Propamacarb, iodocarb, and prothiocarb are examples of this class of fungicides.

[0326] (b29) "Oxidative phosphorylation uncoupling fungicides" (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. By inhibiting respiration, normal fungal growth and development are disrupted. This class includes 2,6-dinitroanilines such as fluazinam, and dinitrophenyl crotates such as dinocap, meptyldinocap, and binapacril.

[0327] (b30) "Organotin fungicides" (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in the oxidative phosphorylation pathway. Examples include fentin acetate, fentin chloride, and fentin hydroxide.

[0328] (b31) Carboxylic acid fungicides (FRAC code 31) inhibit fungal growth by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). An example is oxolinic acid.

[0329] (b32) "Heteroaromatic fungicides" (Fungicide Resistance Control Committee (FRAC) Code 32) It has been suggested that these substances affect DNA / ribonucleic acid (RNA) synthesis. Examples of heteroaromatic fungicides include isoxazoles and isothiazolones. Hymexazole is an example of an isoxazole, and octylinone is an example of an isothiazolone.

[0330] (b33) Examples of "phosphonate fungicides" (FRAC code 33) include phosphorous acid and its various salts, such as fosetyl aluminum.

[0331] (b34) Teclofthalam is an example of a "phthalamic acid fungicide" (FRAC code 34).

[0332] (b35) Triazoxide is an example of a "benzotriazine fungicide" (FRAC code 35).

[0333] (b36) Fursulfamide is an example of a "benzene-sulfonamide fungicide" (FRAC code 36).

[0334] (b37) Diclomezin is an example of a "pyridazinone fungicide" (FRAC code 37).

[0335] (b38) Thiophen-carboxamide fungicides (FRAC code 38) have been suggested to affect ATP production. Silthiofam is an example.

[0336] (b39) "Complex I NADH oxidoreductase inhibitor bactericides" (FRAC code 39) inhibit electron transport in mitochondria, and these include pyrimidineamines such as diflumetrim and pyrazole-5-carboxamides such as tolfenpyrad.

[0337] (b40) Carboxylic acid amide (CAA) fungicides (FRAC code 40) inhibit cellulose synthase, which hinders the growth of target fungi and leads to their death. Examples of carboxylic acid amide fungicides include percutaneous acid amides, valine amides, other carbamates, and mandelic acid amide fungicides. Examples of percutaneous acid amides include dimethomorph, flumorph, and pyrimorph (3-(2-chloro-4-pyridinyl)-3-[4-(1,1-dimethylethyl)phenyl]-1-(4-morpholinyl)-2-propen-1-one). Examples of valinamides and other carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprofalicarb, tolprocarb (2,2,2-trifluoroethyl N-[(1S)-2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamic acid) and valifenalate (methyl N-[(1-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)-β-alaninate) (also known as valiphenal). Examples of mandelic acid amides include mandipropamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, and N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

[0338] (b41) Tetracycline antibiotic fungicides (FRAC code 41) inhibit fungal growth by affecting protein synthesis. An example is oxytetracycline Phosphorus is one example.

[0339] (b42) Metasulfocarb is an example of a "thiocarbamate disinfectant" (FRAC code 42).

[0340] (b43) Benzamide fungicides (FRAC code 43) inhibit fungal growth by delocalizing spectrin-like proteins. Examples include pyridinylmethylbenzamide fungicides such as fluopicolide (currently FRAC code 7, pyridinylethylbenzamides).

[0341] (b44) "Microbial fungicides" (FRAC code 44) disrupt the cell membrane of fungal pathogens. Examples of microbial fungicides include Bacillus species such as Bacillus amyloricephasiens strains QST 713, FZB24, MB1600, and D747, and the fungicidal lipopeptides they produce.

[0342] (b45) "Q x I Bactericide (FRAC code 45) is an unknown (Q) cytochrome bc1 complex. x It inhibits mitochondrial respiration of complex III in fungi by affecting ubiquinone reductase at the ) site. Inhibition of mitochondrial respiration interferes with the normal growth and development of fungi. Q x Examples of disinfectants include triazolopyrimidylamines such as ametoctrazine (5-ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidine-7-amine).

[0343] (b46) It has been proposed that "plant extract fungicides" act by disrupting cell membranes. Examples of plant extract fungicides include terpene hydrocarbons and terpene alcohols such as extracts from Melaleuca alternifolia (tea tree).

[0344] (b47) "Host plant defense-inducing fungicides" (FRAC code P) induce the defense mechanisms of host plants. Examples of host plant defense-inducing fungicides include benzothiadiazoles, benzoisothiazols, and thiadiazole-carboxamide fungicides. Examples of benzothiadiazoles include acibenzoral-S-methyl. Examples of benzoisothiazols include probenazole. Examples of thiadiazole-carboxamides include thiadinyl and isothianil.

[0345] (b48) A "multi-point contact active fungicide" inhibits fungal growth through multiple points of action and has a contact / preventive effect. Examples of fungicides in this class include: (b48.1) copper fungicides (FRAC code M1), (b48.2) sulfur fungicides (FRAC code M2), (b48.3) dithiocarbamate fungicides (FRAC code M3), (b48.4) phthalimide fungicides (FRAC code M4), (b48.5) chloronitrile fungicides (FRAC code M5), (b48.6) sulfamide fungicides (FRAC code M6), (b48.7) multi-point contact guanidine fungicides (FRAC code M7), (b48.8) triazine fungicides (FRAC code M8), (b48.9) quinone fungicides (FRAC code M9), (b48.10) quinoxaline fungicides (FRAC code M10), and (b48.11) maleimide fungicides (FRAC code M11). "Copper fungicides" are typically inorganic compounds containing copper in the copper(II) oxide state; examples include copper oxychloride, copper sulfate, and copper hydroxide, and compositions such as Bordeaux mixture (tribasic copper sulfate). "Sulfur fungicides" are inorganic chemical substances containing a ring or chain of sulfur atoms; an example is elemental sulfur. "Dithiocarbamate fungicides" contain a dithiocarbamate molecular part; examples include mancozeb, methylam, propineb, ferbam, maneb, thiram, zineb, and ziram. "Phthal "Imide fungicides" contain the phthalimide molecular portion; examples include folpet, captan, and captafol. "Chloronitrile fungicides" contain aromatic rings substituted with chloro and cyano; an example is chlorothalonil. "Sulfamide fungicides" include diclofluanide and tolyfluanid. "Guanidine fungicides" with multiple contact points include guazatine, iminoctadine albesilate, and iminoctadine triacetate. "Triadine fungicides" include anilazine. "Quinone fungicides" include dithianone. "Quinoxaline fungicides" include quinomethionate (also known as chinomethionate). "Maleimide fungicides" include fluorimide.

[0346] (b49) “Fungicides other than those of classes (b1) to (b48)” include certain fungicides whose mode of action is unknown. These include: (b49.1) “Phenyl-acetamide fungicides” (FRAC code U6), (b49.2) “Aryl-phenyl-ketone fungicides” (FRAC code U8), (b49.3) “Guanidine fungicides” (FRAC code U12), (b49.4) “Thiazolidine fungicides” (FRAC code U13), (b49.5) “Pyrimidine-hydrazone fungicides” (FRAC code U14), and (b49.6) compounds that bind to oxysterol-binding proteins as described in PCT International Publication WO2013 / 009971. Examples of phenyl-acetamides include cyflufenamide and N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide. Examples of aryl-phenyl ketones include benzophenones such as metraphenone, and benzoylpyridines such as pyriophenone (5-chloro-2-methoxy-4-methyl-3-pyridinyl)(2,3,4-trimethoxy-6-methylphenyl)methanone). Examples of quanidines include dodine. Examples of thiazolidinedions include fluthianil ((2Z)-2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile). Examples of pyrimidinone hydrazones include ferrimzone. The (b49.6) class is oxathiapiproline. This includes (1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]ethanone) and its R-enantiomer, 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]ethanone (registration number 1003319-79-6).(b49) class includes bethoxazin, flomethquine carbonate (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinyl methyl), fluorimide, neo-asozin (ferric methanearsonate), picarbutrazox (N-[6-[[[[((Z)1-methyl-1H-tetrazole-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate 1,1-dimethylethyl), pyrrolnitrin, quinomethionate, tebufloxin (6-(1,1-dimethylethyl)-8-fluoro-2,3-dimethyl-4-quinolinyl acetate), and tolnifanide. (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide), 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-buty-1-yl, N-[6-[[[[(1-methyl-1H-tetrazole-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide), N'-[4-[4-chloro-3-(trifluoromethyl. )phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethaneimamide, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetron, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidineamine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine and N-[1-[[[1-(4-shea The (b46) class also includes 4-fluorophenyl nophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, N-[6-[[[[(1-methyl-1H-tetrazole-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate pentyl, N-[4-[[[[(1-methyl-1H-tetrazole-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate pentyl, and N-[6-[[[[(Z)-(1-methyl-1H-tetrazole-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate pentyl. The (b46) class further includes mitotic and cell division inhibitory bactericides in addition to the specific classes described above (e.g., (b1), (b10), and (b22)).

[0347] Further "bactericides other than those in Class (1) to (46)" whose mechanisms of action are unknown or have not yet been classified include bactericidal compounds selected from the following components (b49.7) to (b49.12).

[0348] The component (b49.7) is given by formula 49.7 [ka] [In the formula, R b1 teeth [ka] Regarding the compound of [this].

[0349] Examples of compounds of formula b49.7 include (b49.7a) 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylic acid (2-chloro-6-fluorophenyl)methyl (registration number 1299409-40-7) and (b49.7b) 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylic acid (1R)-1,2,3,4-tetrahydro-1-naphthalenyl (registration number 1299409-42-9). Methods for producing compounds of formula b46.2 are described in PCT International Publication WO2009 / 132785 and WO2011 / 0 It is listed in issue 51243.

[0350] The component (b49.8) is given by formula b49.8 [ka] [In the formula, R b2 is CH3, CF3, or CHF2; R b3 is CH3, CF3, or CHF2; R b4 The compound is a halogen or cyano; and n is 0, 1, 2, or 3.

[0351] An example of a compound of formula b49.8 is (b49.8a) 1-[4-[4-[5-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]ethanone. A method for producing a compound of formula b49.8 is described in PCT International Patent Application No. PCT / US11 / 64324.

[0352] Component (b4799) is given by formula b49.9 [ka] [In the formula, R b5is -CH2OC(O)CH(CH3)2, -C(O)CH3, -CH2OC(O)CH3, -C(O)OCH2CH(CH3)2 or [ka] Regarding the compound of [this].

[0353] Examples of compounds of formula b49.9 include (b49.9a) 2-methylpropanoic acid [[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl (registration number 517875-34-2), and (b49.9b) 2-methylpropanoic acid (3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl [Bonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl (Registration No. 234112-93-7), (b49.9c) 2-methylpropanoic acid (3S,6S,7R,8R)-3[[[3[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl (Registration No. 517875-31-9), (b49.9d) Examples include 2-methylpropanoic acid (3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]carbonyl]amino]6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl (registration number 328256-72-0), and (b49.9e) N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)L-arabinonoyl]-L-serine, (1→4')-lactone (registration number 1285706-70-8). Methods for producing the compound of formula b49.9 are described in PCT International Publications WO99 / 40081, WO2001 / 014339, WO2003 / 035617 and WO2011044213.

[0354] Component (b49.10) is formula 49.10 [ka] [In the formula, R b6 is H or F, and R b7 This relates to compounds of formula b49.10, which is -CF2CHFCF3 or -CF2CF2H. An example of a compound of formula b49.10 is (b49.10a) These are 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide (registration number 1172611-40-3) and (b49.10b) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide (registration number 923953-98-4). The compound of formula 49.10 can be prepared by the method described in PCT International Publication WO2007 / 017450.

[0355] Component b49.11 is given by formula b49.11 [ka] [In the formula, R b8 These are halogens, C1-C4 alkoxys, or C2-C4 alkynyls; R b9 is H, halogen, or C1-C4 alkyl; R b10 C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Arco Kishi, C2-C 12 Alkoxyalkyl, C2-C 12 Alkenyl, C2-C 12 Alkinyl, C4-C 12 Alkoxyalkenyl, C4-C 12 Alkoxyalkynyl, C1-C 12 Alkylthio or C2-C 12 It is alkylthioalkyl; R b11 is methyl or -Y b13 -R b12 and; R b12 It is a C1-C2 alkyl group; and Y b13 [is CH2, O, or S] Regarding the compounds.

[0356] Examples of compounds of formula b49.11 include (b49.11a) 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyne-1-yl)-2-(methylthio)acetamide, (b49.11b) 2[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyne-1-yl]-2-(methylthio)acetamide, (b49.11c) N-(1,1-dimethyl-2-butyne-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide, (b49.11d) Examples include 2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyne-1-yl)-2-(methylthio)acetamide and (b49.11e) 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butanamide. The compounds of formula b49.11, their use as bactericides and methods of preparation are generally known; see, for example, PCT International Publications WO2004 / 047538, WO2004 / 108663, WO2006 / 058699, WO2006 / 058700, WO2008 / 110355, WO2009 / 030469, WO2009 / 049716 and WO2009 / 087098.

[0357] Component 49.12 is N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazole-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidoamide, which is thought to inhibit C24-methyltransferase, an enzyme involved in the biosynthesis of sterols.

[0358] Therefore, of particular note are mixtures (i.e., compositions) comprising the compound of Formula 1 and at least one bactericidal compound selected from the group consisting of classes (1) to (49) described above. Also of particular note are compositions comprising the above mixture (in a bactericidal effective amount) and further comprising at least one further component selected from the group consisting of surfactants, solid diluents and liquid diluents. Of particular note are mixtures (i.e., compositions) comprising the compound of Formula 1 and at least one bactericidal compound selected from the group consisting of specific compounds listed above relating to classes (1) to (49). Also of particular note are compositions comprising the above mixture (in a bactericidal effective amount) and further comprising at least one further surfactant selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0359] Examples of ingredients (b) bactericides include acibenzoral-S-methyl, algimorph, ametoctrazine, amisulbrom, anilazine, azaconazole, azoxystrobin, venalaxyl (including venalaxyl-M), benodanil, benomyl, bentheavalicarb (including bentheavalicarb-isopropyl), benzovindiflupir, betoxazine, binapacril, biphenyl, vitertanol, bixafen, blastosidine-S, boscalid, bromconazole, bupirimate, b Thiobate, Captahol, Captan, Carbendazim, Carboxone, Carpropamide, Chloroneb, Chlorthalonil, Clozolinate, Clotrimazole, Copper hydroxide, Copper oxychloride, Copper sulfate, Comoxystrobin, Cyazofamide, Cyflufenamid, Cymoxanil, Cyproconazole, Cyprodinil, Diclofluanid, Diclosimet, Diclomazine, Dichloran, Dietofencarb, Difenoconazole, Diflumetrim, Dimethyrimol, Dimethomorph, Dimoxystrobin Diniconazole (including diniconazole-M), dinocap, dithianone, dithiolanes, dodemorph, dozin, econazole, edifenphos, enoxastrobin (also known as enestrobrin), epoxyconazole, etaconazole, etaboxam, etirimol, etridiazole, famoxadone, fenamidon, phenalimol, phenaminestrobin, fenbuconazole, fenflam, fenhexamide, phenoxanil, fenpiclonil, fenpropidine, fenpropimorph, fenpyrazamine, phentin Cete, fentin chloride, fentin hydroxide, Ferbam, Felimzon, Frometkin, florylpicoxamide, fluazinam, fludioxonil, fluphenoxystrobin, fluindapir, flumorph, fluopicolide, fluopyram, flouroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthianil, flutolanil, flutriafole, fluxapyroxad, Holpet, Fusalide, fuberidazole, flalac Sil, Flamethopir, Guazatin, Hexaconazole, Himexazole, Imazalil, Imibenconazole, Iminoctadine albesilate, Iminoctadine triacetate, Iodocarb, Ipconazole, Iprobenphos, Iprodione, Iprovalicarb, Isoconazole, Isofetamide, Isoprothiolane, Isoflucipram, Isopyrazam, Isothianil, Kasugamycin, Kresoxim-methyl, Mancozeb, Mandepropamide, Mandestrobin, Maneb, Mepanipyrim, Mepronil, Meptildinocap, Metalaxyl (including Metalaxyl-M / mefenoxam), mefentrifluconazole, metconazole, metasulfocarb, methylam, metminostrobin, metraphenone, miconazole, mycrobutanil, naphthifine, neo-azosine, nualimol, octylinone, ofrace, orysastrobin, oxadixyl, oxatiapiproline, oxolinic acid, oxpoconazole, oxycarboxyne, oxytetracycline, pefurazoate, penconazole, pencyclon, penflufen, penthiopyrad, phosphate (and its salts, e.g.,(Containing fosetyl-aluminum), picarbtrazox, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamacarb, propiconazole, propineb, proquinazide, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyroxystrobin, pyrazofos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriophenone, pyrisoxazole, pyrroquilon, pyrrolnitrin, quinconazole, quinomethionate, quinoxyfen, quintozen, sedaxane, silthiofame, simeconazole, spiroxamine, s Treptomycin, sulfur, tebuconazole, tebufloquine, tecrophthalam, technazene, terbinafine, tetraconazole, thiabendazole, tifluzamide, thiophanate, thiophanate-methyl, thyram, thiadinyl, tolclophos-methyl, tolniphanide, tolprocarb, trifluanide, riadimefon, triadimenol, trialimol, triticonazole, triazoxide, tribasic copper sulfate, tricyclazole, triclopyricarb, tridemorph, trifloxystrobin, triflumizole, triforine, trimorphamide, uniconazole, uniconazole-P, validamycin, valifenalate (Also known as Valifenal), Vinclozoline, Zineb, Ziram, Zoxamide, 2-Methylpropanoic acid (3S,6S,7R,8R)-3-[[[3-[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl, 2-Methylpropanoic acid (3S,6S,7R,8R)-3-[[[3-(acetyloxy)- 4-Methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl, N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)-L-arabinonoyl]-L-serine, (1→4')-lactone,N-[2-(1S,2R)-[1,1'-bicyclopropyl]-2-ylphenyl]-3-, (Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyne-1-yl)-2-(methylthio)acetamide, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butanamide, 2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyne-1-yl)-2-(methylthio)acetamide, 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran -4-one, N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate 3-buty-1-yl, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, (αS)-[3-(4 -chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thion, rel-1-[[(2R,3S) -3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-5-(2-propene-1-ylthio)-1H-1,2,4-triazole, 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine, 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylic acid (2-chloro-6-fluorophenyl)methyl, N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazole-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyne-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide , N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidoamide, N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, N-[2-(2,4-dichloro [phenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-(3',4'-difluoro[1,1'-biphenyl]-2-yl)-3-(trifluoromethyl)-2-pyrazinecarboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2, 3,3,3-Hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, 5,8-Difluoro-N-[2-[3-Methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-Quinazolinamine, 3-(Difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, 1-[4-[4-[5R-[(2,6-Difluorophenoxy)methyl]-4,5-Dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]ethanone, N-(1,1-dimethyl-2-butyne-1-, Il)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetron, 2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyne-1-yl]-2-(methylthio)acetamide, N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate 4-fluorophenyl, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidineamine, (3S,6S,7R,8R)-3-[[[4-Methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl-2-methylpropanoate, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, 2-methylpropanoate[[4-Methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl, Examples include N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]pentyl carbamate, N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]pentyl carbamate, and N-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]pentyl carbamate and 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylic acid (1R)-1,2,3,4-tetrahydro-1-naphthalenyl. Therefore, of note is a bactericidal composition comprising, as component (a), a compound of formula 1 (or its N-oxide or salt), and as component (b), at least one bactericide selected from the previous list.

[0360] Of particular note are the compounds of Formula 1 (or their N-oxides or salts) (i.e., component (a) in the composition) and azoxystrobin, benzovin, diflupyr, bixafen, captan, carpropamide, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, dietofencarb, difenoconazole, dimethomorph, epoxyconazole, etaboxam, phenalimol, fenhexamide, fluazinam, fludioxonil, fluindapyr, fluopyram, flusilazole, fluthianil, lutriahol, and flux Sapyroxad, Holpet, Iprodione, Isofetamide, Isoflucipram, Isopyrazam, Kresoxim-methyl, Mancozeb, Mandestrobin, Meptildinocap, Metalaxyl (including Metalaxyl-M / Mephenoxam), Mefentrifluconazole, Metoconazole, Metraphenone, Mycrobutanil, Oxatiapiproline, Penflufen, Penthiopyrad, Phosphite (including its salts, e.g., Fosetyl-aluminum), Picoxystrobin, Propiconazole, Proquinazide, Prothioconazole, Pyraclostrobin, Pyrimethanil, Sedaxane Spiroxamine, sulfur, tebuconazole, thiophanate-methyl, trifloxystrobin, zoxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3 H-1,2,4-triazole-3-thione, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 1-[4-[4- [5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]ethanone, N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate 1,1-dimethylethyl, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetron, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidineamine, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidineamine, (αS)-[3 -(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxyranyl]methyl]-5-(2-propene-1-ylthio)-1H-1,2,4-triazole (That is, a combination with component (b) in the composition.)

[0361] Examples of other biologically active compounds or drugs that can be formulated together with the compounds of the present invention include: Compounds or agents for the control of harmful invertebrates, such as abamectin, acephate, acetamiprid, acrinatrin, afidopyropen (cyclopropanecarboxylic acid [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl), amidoflumet (S-1955), avermectin, azadirachtin, azinfos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyantraniliprole (3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), cyclanilipol (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide), cycloxaprid ((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine), cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiurone, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, phenothiocarb, phenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamide, flubendiamide, flucitrinate, fluphenoxystrobin ((αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate methyl), fluensulfone (5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole), flupiprole (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propene, -1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitride), flupyradiflon (4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), tau-fluvalinate, fluphenelim (UR-50701), flufenoxlon, fonophos, halofenozide, heptafluthrin (2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl), hexaflumurone, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, mepafluthrin ((1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl), metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyphenozide, metofluthrin, milbemycin oxime, momfluorothrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate), monocrotophos, nicotine, nitenpyram, nithiazine, novalon, nobiflumulon (XDE-007), oxamyl, piflubumido (1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-Trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide), parathion, parathion-methyl, permethrin, phorate, fosalon, fosmet, phosphamidone, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridaryl, pyrifluquinazone, pyriminostrobin ((αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate methyl), pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramato, sulfoxaflor, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon and triflumulon; and biological preparations containing entomopathogenic bacteria, e.g., Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, and encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); and entomopathogenic fungi, e.g., green muscardine fungus; and entomopathogenic viruses including baculoviruses, nuclear polyhedron virus (NPV) such as HzNPV and AfNPV; as well as granulomatous virus (GV) such as CpGV.

[0362] The compounds and compositions of the present invention can be applied to plants genetically transformed to express proteins toxic to harmful invertebrates (e.g., Bacillus thuringiensis delta-endotoxin). The effects of the exogenously applied fungicidal compounds of the present invention may be enhanced together with the expressed toxic proteins.

[0363] General references on agricultural protective agents (i.e., insecticides, fungicides, nematicides, acaricides, herbicides, and biological agents) include The Pesticide Manual, 13th Edition, CDSTomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd Edition, L. g. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0364] For embodiments in which one or more of these various mixed partners are used, the mass ratio of these various mixed partners (in total) to the compound of Formula 1 is typically between approximately 1:3000 and approximately 3000:1. Of particular note are mass ratios between approximately 1:300 and approximately 300:1 (e.g., between approximately 1:30 and approximately 30:1). Those skilled in the art can easily determine, through simple experiments, the biologically effective amount of the active ingredient required for the desired range of biological activity. It will be apparent that by including these additional components, the range of diseases controlled can be expanded beyond that controlled by the compound of Formula 1 alone.

[0365] In certain cases, combinations of the compounds of the present invention with other biologically active (particularly fungicidal) compounds or agents (i.e., active ingredients) may produce a greater-than-additive (i.e., enhanced) effect. It is always desirable to reduce the amount of active ingredients released into the environment while ensuring effective pest control. When an enhanced effect of a fungicidal active ingredient occurs at application rates that produce an agriculturally satisfactory level of fungal control, such combinations may be advantageous in reducing crop production costs and environmental impact.

[0366] Furthermore, in certain cases, combinations of the compounds of the present invention with other biologically active compounds or agents may produce a less-than-additive (i.e., phytotoxicity reduction) effect on organisms beneficial to the agricultural environment. For example, the compounds of the present invention may reduce the phytotoxicity of herbicides on crop plants or protect beneficial insect species (e.g., insect predators, pollinators such as honeybees) from insecticides.

[0367] Notable fungicides for formulation with the compounds of Formula 1 to provide a useful mixture in seed treatment include, but are not limited to, amisulbrom, azoxystrobin, boscalid, carbendazim, carboxyne, cymoxanil, cyproconazole, difenoconazole, dimethomorph, florylpicoxamide, fluazinam, fludioxonil, fluphenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin, flutriafole, Examples include fluxapiroxad, ipconazole, iprodione, metalaxyl, mefenoxam, mefentrifluconazole, metconazole, mycrobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofamm, tebuconazole, thiabendazole, thiophanate-methyl, thyram, trifloxystrobin, and triticonazole.

[0368] Compounds or agents for controlling harmful invertebrates that can be formulated together with the compound of Formula 1 to provide a useful mixture in seed treatment include, but are not limited to, abamectin, acetamiprid, acrinatrin, afidopyropen, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, kazusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, and cyflutri. Beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, phenothiocarb, phenoxycarb, fenvalerate, fipronil, flonicamide, flubendiamide, fluensulfone, flufenoxuron, flufiprole, flupyradifuron, fluvalinate, formethanate, fostiazate, heptafluthrin, hexaflumuron, hydramethylnon, i Examples include midacloprid, indoxacarb, lufenuron, mepafluthrin, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, monfluorothrin, nitenpyram, nithiazine, novaron, oxamyl, piflubmid, pymetrozine, pyrethrin, pyridaben, pyriminostrobin, pyridaryl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumulon, Bacillus thuringiensis delta-endotoxin, Bacillus thuringiensis virus strains, and nucleo polyhedron virus strains.

[0369] A composition containing a compound of formula 1 useful for seed treatment may further contain bacteria and fungi having the ability to provide protection from the harmful effects of plant pathogenic fungi or bacteria and / or soil-born animals such as nematodes. Examples of bacteria exhibiting nematode properties include, but are not limited to, Bacillus firmus, Bacillus cereus, Bacillius subtiliis, and Pasteuria penetrans. A suitable Bacillus firmus strain is CNCM I-1582 (GB-126), which is BioNem TM It is commercially available as such. A suitable Bacillus cereus strain is NCMM I-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 include, but are not limited to, Bacillus pumilus strain gB34. Fungal species exhibiting nematicidal properties include, but are not limited to, Myrothecium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum.

[0370] Seed treatments, also known as harpins, may also include one or more naturally occurring nematicides, such as elicitor proteins isolated from certain bacterial plant pathogens like the burn blight bacterium (Erwinia amylovora). One example is N-Hibit. TM This is the Harpin-N-Tek seed treatment technology available as Gold CST.

[0371] Seed treatment may also include one or more species of leguminous rhizobia, such as the microsymbiotic nitrogen-fixing bacterium Bradyrhizobium japonicum. These inocculants may contain one or more lipo-chitooligosaccharides (LCOs), which are nodule-forming (Nod) factors produced by rhizobia during the initiation of nodule formation on the roots of leguminous plants. For example, the seed treatment technology traded as Optimize® combines LCOs with the inoculated strain. Technology TM Incorporate it.

[0372] Seed treatment may also include one or more isoflavones that can increase the level of root establishment 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, naringeni, and platencein. Formononetin is available as an active ingredient in mycorrhizal inoculant products such as PHC Colonize® AG.

[0373] Seed treatment may also include one or more plant activators that induce systemic acquired resistance in plants after contact with the pathogen. An example of a plant activator that induces such a protective mechanism is acibenzol-S-methyl.

[0374] The following tests demonstrate the control efficacy of the compounds of this invention against specific pathogens. However, the pathogen control protection provided by the compounds is not limited to these species. See Index Tables A-E below for a description of the compounds. The following abbreviations are used in Index Tables A-E: :Me means methyl, i-Pr means isopropyl, c-Pr means cyclopropyl, i-Bu means isobutyl, c-Bu means cyclobutyl, t-Bu means tert-butyl, and NO2 means nitro. The abbreviation "Cmpd." represents "compound," and the abbreviation "Ex." represents "example," followed by a number indicating the compound produced in that example. The abbreviation "mp" represents melting point. "AP + The value reported in the "(M+1)" column represents the H to the molecule with the highest isotopic abundance (i.e., M). + This is the molecular weight of the observed molecular ion formed by the addition of (molecular weight 1). One or more isotopes with lower abundance and larger atomic weights (e.g., 37 Cl, 81 The presence of molecular ions containing Br) was not reported. The reported MS peaks were observed by mass spectrometry using electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI).

[0375] [Table 6]

[0376] [Table 7]

[0377] [Table 8]

[0378] [Table 9]

[0379] [Table 10]

[0380] [Table 11]

[0381] [Table 12]

[0382] [Table 13]

[0383] [Table 14]

[0384] Biological embodiments of the present invention Overall protocol for preparing test suspensions for tests A-F: The test compound was first dissolved in acetone in an amount equal to 3% of the final volume, and then suspended at the desired concentration (ppm) in a mixture of acetone and purified water (50 / 50 (vol)) containing 250 ppm of the surfactant PEG400 (polyhydric alcohol ester). The resulting suspension was then used in tests A-F.

[0385] Test A The test solution was sprayed onto the run-off points of wheat seedlings. The following day, the seedlings were sowed with a spore suspension of Zymoseptoria tritici (the pathogen of wheat leaf blight), incubated at 24°C for 48 hours under a saturated atmosphere, then transferred to a growth chamber at 20°C for 17 days, after which disease assessment was performed.

[0386] Test B The test solution was sprayed onto the outflow points of wheat seedlings. The next day, Puscinia recondita was applied to the seedlings. A spore suspension of Puccinia recondita f.sp. tritici (the pathogen of wheat rust disease) was sown and incubated at 20°C for 24 hours under a saturated atmosphere, then moved to a growth chamber at 20°C for 7 days, after which disease assessment was performed.

[0387] Test C The test suspension was sprayed onto the outflow points of wheat seedlings. The following day, the seedlings were sowed with a spore powder of Blumeria graminis f.sp. tritici (also known as Erysiphe graminis f.sp. tritici, the pathogen of wheat powdery mildew), and incubated in a 20°C growth chamber for 8 days. After that period, a visual disease assessment was performed.

[0388] Test D The test solution was sprayed onto the outflow points of soybean seedlings. The following day, a spore suspension of Phakopsora pachyrhizi (the pathogen of Asian soybean rust) was sown onto the seedlings, and they were incubated at 22°C for 24 hours under a saturated atmosphere, then moved to a growth chamber at 22°C for 8 days, after which a visual disease assessment was performed.

[0389] Test E The test suspension was sprayed onto the outflow points of tomato seedlings. The following day, the seedlings were inoculated with a spore suspension of Botrytis cinerea (the pathogen of tomato gray mold), incubated at 20°C for 48 hours under a saturated atmosphere, then moved to a growth chamber at 24°C for 3 days, after which a visual disease assessment was performed.

[0390] Test F The test suspension was sprayed onto the outflow points of tomato seedlings. The following day, the seedlings were sowed with a spore suspension of Alternaria solani (the pathogen of tomato summer blight), incubated at 27°C for 48 hours under a saturated atmosphere, then moved to a 20°C growth chamber for 3 days, after which a visual disease assessment was performed.

[0391] The results for tests A through F are shown in Table A below. A score of 100 indicates 100% disease control, and a score of 0 indicates no disease control (compared to the control). A dash (-) indicates that the compound... This indicates that the test was not performed.

[0392] [Table 15]

[0393] [Table 16]

[0394] [Table 17]

[0395] [Table 18]

[0396] [Table 19]

Claims

[Claim 1] Compounds selected from formula 12 【Chemistry 1】 [In the formula, Q is CR 6 And; R 1 and R 2 These are F, respectively; R 6 C 1 -C 6 Hydroxyalkyl, C2-C 6 It is an alkenyl or -ZC(=O)V; Z is a direct bond; V is R 9 And; R 9 is methyl, A is a substructure of formula A-1. 【Chemistry 2】 (In the formula, The bond extending to the right is bonded to the ring containing Q in formula 12, and the bond extending to the left is bonded to the phenyl ring in formula 12; n is 0) [is] or its salt.

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