Fungicidal aryl amidines

Abstract

The present disclosure provides a compound of formula I [Formula 1] TIFF2022533267000333.tif49170 and their use as fungicides. One embodiment of the present disclosure is the use of a compound of formula I for the protection of plants against attack by or treatment of plants infested by plant pathogenic organisms, comprising applying a compound of formula I or a composition comprising the compound to the soil, the plant, plant parts, leaves and / or roots.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This disclosure claims the benefit of U.S. Provisional Patent Application No. 62 / 852,074, filed May 23, 2019, which is expressly incorporated herein by reference. [Background technology]

[0002] Fungicides are compounds of natural or synthetic origin that act to protect and / or treat plants against damage caused by agriculturally relevant fungi. Generally, there is no single fungicide that is useful in all situations. Therefore, research is ongoing to produce fungicides that may have good performance, are easy to use, and are less costly. Summary of the Invention [Means for solving the problem]

[0003] The present disclosure relates to aryl amidines and their use as fungicides. The compounds of the present disclosure may provide protection against Ascomycota, Basidiomycota, Deuteromycota and Oomycota.

[0004] One embodiment of the present disclosure is a compound of formula I: [ka] (In the formula, R 1 is hydrogen, C 1 ~C 8 Alkyl, C 1 ~C 8 Substituted alkyl, C 2 ~C 8 Alkenyl, C 2 ~C 8 Substituted alkenyl, C 2 ~C 8 Alkynyl, C 2 ~C 8 Substituted Alkynyl, C 3 ~C 8 Cycloalkyl, C3 ~C 8 Substituted cycloalkyl, C 3 ~C 8 Heterocycloalkyl, C 3 ~C 8 Substituted Heterocycloalkyl, C 5 ~C 7 Heteroaryl, C 5 ~C 7 Selected from the group consisting of substituted heteroaryl, phenyl, substituted phenyl, benzyl, and substituted benzyl; Each R 2 , R 3 , R 4 and R 5 are independently hydrogen, halogen, cyano, nitro, C 1 ~C 8 Alkyl, C 1 ~C 8 Substituted alkyl, C 2 ~C 8 Alkenyl, C 2 ~C 8 Substituted alkenyl, C 2 ~C 8 Alkynyl, C 2 ~C 8 Substituted Alkynyl, C 1 ~C 8 Alkoxy and C 1 ~C 8 substituted alkoxy; R 6 is hydrogen, C 1 ~C 8 Alkyl, C 1 ~C 8 Substituted alkyl, C 2 ~C 8 Alkenyl, C 2 ~C 8 Substituted alkenyl, C 2 ~C 8 Alkynyl, C 1 ~C 8 Substituted Alkynyl, C 1 ~C 8 Alkoxy, C 1 ~C 8 is selected from the group consisting of substituted alkoxy, thiol, alkylthio, and substituted alkylthio; or R6 and R 7 are covalently bonded together and are saturated or unsaturated C 3 ~C 8 Heterocycloalkyl or C 3 ~C 8 It may form a substituted heterocycloalkyl group; Each R 7 and R 8 are independently hydrogen, C 1 ~C 8 Alkyl, C 1 ~C 8 Substituted alkyl, C 2 ~C 8 Alkenyl, C 2 ~C 8 Substituted alkenyl, C 2 ~C 8 Alkynyl, C 2 ~C 8 Substituted Alkynyl, C 3 ~C 8 Cycloalkyl, C 3 ~C 8 is selected from the group consisting of substituted cycloalkyl, phenyl, substituted phenyl, benzyl, and substituted benzyl; or R 7 and R 8 are covalently bonded together and are saturated or unsaturated C 3 ~C 8 Heterocycloalkyl or C 3 ~C 8 It may form a substituted heterocycloalkyl group; Any heterocyclic ring may contain up to three heteroatoms selected from the group consisting of O, N and S. or a tautomer or salt thereof.

[0005] Another embodiment of the present disclosure may include a fungicidal composition for controlling or preventing fungal attack, comprising the above-described compound and a phytologically acceptable carrier material.

[0006] Yet another embodiment of the present disclosure may include a method for controlling or preventing fungal attack on a plant comprising applying a fungicidally effective amount of one or more compounds described above to at least one fungus, a seed, a plant, and an area adjacent to the plant.

[0007] It will be understood by one of ordinary skill in the art that the following terms may include generic "R" groups within their definitions, for example, the term "alkoxy" refers to an -OR substituent. It is also understood that within the definitions for the following terms, these "R" groups are included for illustrative purposes and should not be construed as limiting or being limited by substitutions on Formula I.

[0008] The term "alkyl" refers to a branched, unbranched or saturated acyclic substituent composed of carbon and hydrogen atoms, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, and the like.

[0009] The term "alkenyl" refers to an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched substituent composed of carbon and hydrogen, including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, and the like.

[0010] The term "alkynyl" refers to an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched substituent composed of carbon and hydrogen, such as ethynyl, propargyl, butynyl, and pentynyl.

[0011] The term "cycloalkenyl" refers to a mono- or polycyclic unsaturated (at least one carbon-carbon double bond) substituent composed of carbon and hydrogen, such as cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.

[0012] The term "cycloalkyl" refers to a mono- or polycyclic saturated substituent composed of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.

[0013] The term "cycloalkoxy" further refers to a cycloalkyl consisting of a carbon-oxygen single bond, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and bicyclo[2.2.2]octyloxy.

[0014] The terms "aryl" and "Ar" refer to any aromatic monocyclic or bicyclic ring containing zero heteroatoms, such as phenyl and naphthyl.

[0015] The term "heteroaryl" refers to any aromatic monocyclic or bicyclic ring containing one or more heteroatoms, such as pyridinyl, piperazinyl, and thiophenyl.

[0016] The term "heterocycloalkyl" refers to any non-aromatic monocyclic or bicyclic ring containing carbon and hydrogen atoms and one or more heteroatoms.

[0017] The term "alkoxy" refers to an --OR substituent.

[0018] The term "cyano" refers to a -C≡N substituent.

[0019] The term "amino" refers to -N(R) 2 Refers to a substituent.

[0020] The terms "halogen" or "halo" refer to one or more halogen atoms defined as F, Cl, Br, and I.

[0021] The term "nitro" refers to -NO 2 Refers to a substituent.

[0022] The term "thiol" refers to a --SH substituent.

[0023] The term "alkylthio" refers to an --SR substituent.

[0024] The term "benzyl" refers to -CH 2 -refers to a phenyl substituent.

[0025] Throughout this disclosure, reference to a compound of formula I is to be read as including all its stereoisomers, such as diastereomers, enantiomers and mixtures thereof.In another embodiment, formula (I) is to be read as including its salts and hydrates.Exemplary salts include, but are not limited to, hydrochloride, hydrobromide, hydroiodide, trifluoroacetate and trifluoromethanesulfonate.

[0026] It will also be understood by those skilled in the art that further substitutions may be tolerated unless otherwise indicated, so long as the laws of chemical bonding and strain energies are satisfied and the product still exhibits fungicidal activity.

[0027] Another embodiment of the present disclosure is the use of a compound of formula I for the protection of plants against attack by phytopathogenic organisms or the treatment of plants infested by phytopathogenic organisms, comprising applying a compound of formula I or a composition comprising the compound to the soil, the plant, the plant parts, the leaves and / or the roots.

[0028] Additionally, another embodiment of the present disclosure is a composition useful for protecting plants against attack by phytopathogenic organisms and / or treating plants infested by phytopathogenic organisms, comprising a compound of formula I and a phytologically acceptable carrier material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The compounds of the present disclosure can be applied by any of a variety of known techniques as compounds or formulations containing compounds.For example, the compounds can be applied to the roots or leaves of plants to control a variety of fungi without damaging the commercial value of the plants.The materials can be applied in any of the commonly used formulation forms, such as liquid, dust, wettable powder, flowable or emulsifiable concentrate.

[0030] Preferably, the compound of the present disclosure is applied in the form of a formulation that comprises one or more compounds of formula I together with a phytologically acceptable carrier.Concentrated formulations can be dispersed in water or other liquids for application, or formulations can be dust or granules, which can then be applied without further processing.Formulations can be prepared according to the procedures conventional in agrochemical technology.

[0031] The present disclosure contemplates all vehicles in which one or more compounds can be formulated to be delivered and used as fungicides. Typically, the formulation is applied as an aqueous suspension or emulsion. Such suspension or emulsion can be made from a water-soluble, water-suspendable or emulsifiable formulation, which is a solid, usually known as a wettable powder; or from a liquid, usually known as an emulsifiable concentrate, an aqueous suspension or suspension. As can be easily understood, any material to which these compounds can be added can be used, so long as it produces the desired utility without significantly interfering with the activity of these compounds as antifungal agents.

[0032] A wettable powder, which can be compressed to form a wettable granule, comprises an intimate mixture of one or more compounds of formula I, an inert carrier, and a surfactant. The concentration of the compound in the wettable powder can be from about 10 weight percent to about 90 weight percent, more preferably from about 25 weight percent to about 75 weight percent, based on the total weight of the wettable powder. In preparing wettable powder formulations, the compound can be combined with any finely divided solid, such as prophyllite, talc, chalk, gypsum, fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clay, diatomaceous earth, refined silicates, and the like. In such operations, finely divided carriers and surfactants are typically blended with the compound and milled.

[0033] Emulsions of compounds of formula I may contain any convenient concentration of compound in a suitable liquid, such as from about 1 weight percent to about 50 weight percent based on the total weight of the emulsion. The compound may be dissolved in an inert carrier, which may be either a water-miscible solvent or a mixture of a water-immiscible organic solvent and an emulsifier. The emulsion may be diluted with water and oil to form a dispersal mixture in the form of an oil-in-water emulsion. Useful organic solvents include aromatics, particularly the high boiling naphthalene and olefinic portions of petroleum, such as heavy aromatic naphtha. Other organic solvents may also be used, such as terpene solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and alcohol complexes such as 2-ethoxyethanol.

[0034] Emulsifiers that can be advantageously used herein can be easily determined by those skilled in the art and include a variety of nonionic, anionic, cationic and amphoteric emulsifiers or blends of two or more emulsifiers. Examples of nonionic emulsifiers useful for preparing emulsions include polyalkylene glycol ethers, alkyl and aryl phenols, condensates of aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxide such as ethoxylated alkylphenols, and carboxylic acid esters solubilized with polyols or polyoxyalkylenes. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or suitable salts of sulfated polyglycol ethers and phosphated polyglycol ethers.

[0035] Representative organic liquids that can be used to prepare emulsions of the compounds of the present disclosure include aromatic liquids such as xylene, propylbenzene fractions; or substituted aromatic organic liquids such as mixed naphthalene fractions, mineral oil, dioctyl phthalate, kerosene; dialkylamides of various fatty acids, such as n-butyl ether, ethyl ether or methyl ether of diethylene glycol, methyl ether of triethylene glycol, especially dimethylamides of fatty glycols and glycol derivatives, mineral oil, aromatic solvents, paraffin oil, and other petroleum fractions or hydrocarbons; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, and other vegetable oils; esters of the above vegetable oils, and the like. A mixture of two or more organic liquids can be used to prepare emulsions. Organic liquids include xylene and propylbenzene fractions, with xylene being the most preferred in some cases. Surface active dispersants are typically used in liquid formulations in amounts of 0.1 to 20 weight percent based on the combined weight of the dispersant and one or more compounds. The formulations may also contain other compatible additives, such as plant growth regulators and other biologically active compounds used in agriculture.

[0036] Aqueous suspensions comprise one or more water-insoluble compounds of formula I dispersed in an aqueous vehicle at a concentration ranging from about 1 to about 50 weight percent based on the total weight of the aqueous suspension. The suspensions are prepared by finely grinding the one or more compounds and vigorously mixing the ground material with a vehicle composed of water and surfactants selected from the same classes as discussed above. Other ingredients such as inorganic salts and synthetic or natural gums may also be added to increase the density and viscosity of the aqueous vehicle.

[0037] The compounds of formula I can also be applied as granular formulations, which are particularly useful for application to soil. Granular formulations generally contain about 0.5 to about 10 weight percent of the compound, based on the total weight of the granular formulation, dispersed in an inert carrier composed entirely or predominantly of coarsely divided inert materials such as attapulgite, bentonite, diatomaceous earth, clay, or similar inexpensive materials. Such formulations are usually prepared by dissolving the compound in a suitable solvent and applying to a granular carrier preformed to an appropriate particle size in the range of about 0.5 to about 3 mm. A suitable solvent is one in which the compound is substantially or completely soluble. Such formulations can also be prepared by making a dough or paste of the carrier, compound, and solvent, crushing, and drying to obtain the desired granular particles.

[0038] Dusts containing a compound of formula I can be prepared by intimately mixing one or more compounds in powder form with a suitable powdered agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, etc. Dusts can suitably contain from about 1 to about 10 weight percent of the compound, based on the total weight of the dust.

[0039] The formulation may additionally contain co-surfactants to enhance the adhesion, wetting and penetration of the compound into target crops and organisms. These co-surfactants can be optionally used as components of the formulation or as tank mixes. The amount of co-surfactant typically varies from 0.01 to 1.0 volume percent, preferably 0.05 to 0.5 volume percent, based on the application rate of water. Suitable co-surfactants include ethoxylated nonylphenols, ethoxylated synthetic or natural alcohols, salts of esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylates; benzylcoalkyldimethyl quaternary ammonium salts; blends of petroleum hydrocarbons, alkyl esters, organic acids and anionic surfactants; C 9 ~C 11 Alkyl polyglycosides; Phosphorylated alcohol ethoxylates; Natural primary alcohols (C 12 ~C 16 ) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15EO); PEG (400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Publication No. 11 / 495,228, the disclosure of which is expressly incorporated herein by reference.

[0040] The formulation may optionally include a combination containing other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematicides, acaricides, arthropodicides, bactericides, or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application and do not antagonize the activity of the compounds of the present invention. Thus, in such an embodiment, the other pesticidal compounds are used as supplementary poisons in the same or different pesticidal applications. The compound of formula I and the pesticidal compounds in the combination can generally be present in a weight ratio of 1:100 to 100:1.

[0041] The compounds of the present disclosure may be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied with one or more other fungicides to control a variety of undesirable diseases. When used with other fungicides, the compounds claimed herein may be formulated with the other fungicides, tank mixed with the other fungicides, or applied sequentially to the other fungicides. Such other fungicides include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, amethoctrazine, aminopyrifen, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, Bacillus subtilis, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benzalbarricarb isopropyl, benzobindiflupyr, benzylaminobenzenesulfonic acid (BABS) salt, bicarbonate, biphenyl, bismerthiazole, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, buprimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, capropamide, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans minitans), copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylene bis(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomedine, dicloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetrim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestrobulin, epoxiconazole,Ethaboxam, Ethoxyquin, Etridiazole, Famoxadone, Fenamidon, Fenarimol, Fenbuconazole, Fenfuram, Fenhexamid, Fenoxanil, Fenpiclonil, Fenpropidin, Fenpropimorph, Fenpyrazamine, Fentin, Fentin Acetate, Fentin Hydroxide, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluindapyr, Flumorph, Fluopicolide, Fluopyram, Fluorimide, Fluoxapiproline, Fluoxastrobin, Fluquinconazole, Flusilazole, Flu Sulfamide, Flutianil, Flutolanil, Flutriafol, Fluxapyroxad, Folpet, Formaldehyde, Fosetyl, Fosetylaluminum, Fuberidazole, Furalaxyl, Furametpyr, Guazatine, Guazatine acetate, GY-81, Hexachlorobenzene, Hexaconazole, Hymexazole, Imazalil, Imazalil sulfate, Imibenconazole, Iminoctadine, Iminoctadine triacetate, Iminoctadine tris(albesilate), Impilfluxam, Iodocarb, Ipconazole, Ipfenpyrazo lon (ipfenpyrazolone), iprobenfos, iprodione, iprovalicarb, isofetamide, isoflucipram, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim methyl, laminarin, mancopper, mancozeb, mandipropamide, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercuric chloride, metalaxyl, metalaxyl-M, metam, metam ammonium, metam potassium, metam sodium, metam Toconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrotar isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acid), orysastrobin, oxadixyl, oxathiapiproline, oxine copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenol laurate, penthiopyrad,Phenylmercuric acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxin, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pydiflumetofen, pyrametostrobin, pyroxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriophenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sakarinensis (Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oil, tebuconazole, tebufloquine, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate methyl, thiram, thiadinil, tolclofos methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valifenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum oxysporum, Gliocladium species, Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma species, (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-Dihydro-5-phenyl-1,4-dithi-in 1,1,4,4-tetraoxide, 2-methoxyethylmercuric acetate, 2-methoxyethylmercuric chloride, 2-methoxyethylmercuric silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanate, ampropylphos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacryl; benzamacryl isobutyl, benzamorph, binapacryl, bis(methylmercuric) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, clobentiazone, chloraniformethane, chlorphenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cumoxistorrobin, kufuraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramide, cypendazole, cyproflam, decaphentin, diclobentiazox, dicloron , diclozolin, diclobutrazol, dimethirimol, dinoctone, dinosulfone, dinotervone, dipimethitron, dipyrithione, ditalinphos, dodysin, drazoxolone, EBP, enoxastrobin, ESBP, etaconazole, etem, ethirim, phenaminestrobin, fenaminosulf, fenapanil, fenitropan, fenpicoxamide, flurylpicoxamide, flufenoxystrobin, fluopimomide, fluorotrimazole, flucarbanil, fluconazole, fluconazole-cis, flumecyclox, furofanate, gliodin, griseofulvin, halacrinate, Hercules 3944, hexylthiophos, ICIA0858, ipfentrifluconazole, ipflufenoquin, isopamphos, isovaledion, mandestrobin, mebenil, mecarbinzide, mefentrifluconazole, metazoxolone, metofloxam, methylmercuric dicyandiamide, metsulfovax, methyltetraprole, milneb, mucochloric anhydride, mycozolin, N-3,5-dichlorophenyl-succinimide,N-3-Nitrophenylitaconimide, Natamycin, N-Ethylmercurio-4-toluenesulfonanilide, Nickel bis(dimethyldithiocarbamate), OCH, Phenylmercuric dimethyldithiocarbamate, Phenylmercuric nitrate, Phosdifen, Prothiocarb; Prothiocarb hydrochloride, Pyracarbollide, Pyrapropoin, Pyridaclomethyl, Pyridinitrile, Pyrisoxazole, Pyroxchlor, Pyroxyflur, Quinaceto; Quinaceto sulfur These may include benzoyl peroxide, quinazamide, quinconazole, quinofumelin, rabenzazole, salicylanilide, SSF-109, sultropene, techoram, thiadifluor, thiophene, thiochlorfenfim, thiophanate, thioquinox, tioximide, triamiphos, triarimol, triazbutyl, triclamide, triclopyricarb, triflumezopyrim, urbacid, zaliramide, and any combination thereof.

[0042] In addition, the compounds described herein can be combined with other pesticides, including insecticides, nematicides, acaricides, arthropodicides, bactericides, or combinations thereof, which are compatible with the compounds of the present disclosure in the medium selected for application and do not antagonize the activity of the compounds of the present invention, to form pesticidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure can be applied with one or more other pesticides to control a variety of undesirable pests.When used with other pesticides, the compounds claimed herein can be formulated with the other pesticides, tank-mixed with the other pesticides, or applied sequentially to the other pesticides. Typical insecticides include 1,2-dichloropropane, abamectin, acephate, acetamiprid, acetion, acetoprole, acrinathrin, acrylonitrile, acinonapyr, aphidopyropen, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, alixycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithione, aminocarb, amiton, amiton oxalate, amitraz, anabasine, atidathion, azadirachtin, azamethiphos, azinphos ethyl, azinphos methyl, azotoate, barium hexafluorosilicate, bartholin, bendiocarb, benfuracarb, bensultap, benzpyrimoxane, beta-cyfluthrin, beta-cypermethrin, Bifenthrin, bioalentrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, brofuranilide, bromfenvinphos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiophos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, chlorinated camphenes, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothione, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chloroethoxyphos, chlorfenapyr, chlorfenvinphos,Chlorfluazuron, chlormephos, chloroform, chloropicrin, chloroprallethrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, cumitoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanotoate, cyantraniliprole, Cyclaniliprole, ciclethrin, cycloprothrin, cyfluthrin, cyhalodiamide, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demefion, demefion-O, demefion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfone, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapton, diclofenthion, dichlorvos, dichloromethiaz, dichlormethiazol, dichlormethiazol Resyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilol, dimefluthrin, dimefox, dimethane, dimethoate, dimethrine, dimethylvinphos, dimethiran, ginex, ginex-diclexin, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzophos, dioxacarb, dioxathion, disulfoton, dicyclophos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate , EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, epsilon-metofluthrin, epsilon-monfluorothrin, esdeparethrin, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimphos, EXD, famfur, fenamiphos, fenazaflor, fenchlorphos,Fenetacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpyrithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flometoquin, flonicamid, fluazaindolizine, flubendiamide, flucofuron, flucycloxuron, flucythrinate, fluensulfone, flufenerim, flufenoxuron, flufenprox, flufiprole, fluhexafon, flupyradifurone, flupirimine, fluba linate, fluxamethamide, fonophos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmetilan, fospirate, fostietan, furathiocarb, fretrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptafluthrin, heptenephos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hikincarb, imidacloprid, imiprothrin, indoxacarb, yo Domethane, IPSP, isazofos, isobenzane, isocarbophos, isocycloceram, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kappa-bifenthrin, kappa-tefluthrin, kereban, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lilimphos, lufenuron, ritidathion, malathione On, Malonoben, Magidox, Mecarbam, Mecarfone, Menazone, Meperfluthrin, Mephosphoran, Mercurous chloride, Mesulfenphos, Metaflumizone, Methacrifos, Methamidophos, Methidathion, Methiocarb, Metoclotophos, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Methyl bromide, Methyl isothiocyanate, Methyl chloroform, Methylene chloride, Metofluthrin, Metolcarb, Methoxadiazone, Mevinphos, Mexacarbate, Milbemectin, Milbemycin oxime, Mipafox, Mirex,molosultap, momfluorotrin, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naphthalophos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxazosulfil, oxydemeton-methyl, oxydeprophos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, fencapton, fen Enthrin, phenthoate, phorate, phosalone, phospholane, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pyrimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluthrin, promacyl, promecarb, propafos, propetamphos, propoxur, protidathion, prothiofos, protoate, protrifen Buto, Piflubumid, Pyraclofos, Pyrafluprole, Pyrazophos, Pyresmethrin, Pyrethrin I, Pyrethrin II, Pyrethrin, Pyridaben, Pyridalyl, Pyradaphenthion, Pyrifluquinazon, Pyrimidifen, Pyriminostrobin, Pirimitate, Pyriprole, Pyriproxyfen, Cassia, Quinalphos, Quinalphos-methyl, Quinothione, Lafoxanide, Resmethrin, Rotenone, Riania, Sabadilla, Schraderdan, Selamectin, Silafluofen, Silica gel, Sodium arsenite, Sodium fluoride, Sodium hexafluorosilicate um, sodium thiocyanate, sofamid, spinetoram, spinosad, spiromesifen, spiropydione, spirotetramat, sulcofuron, sulcofuron-sodium, sulfuramide, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, thazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, teralethrin, terbufos, tetrachlorantraniliprole, tetrachloroethane, tetrachlorvinphos, tetramethrin,These include, but are not limited to, tetramethylfluthrin, tetraniliprole, theta-cypermethrin, thiacloprid, thiamethoxam, cyclophos, thiocarboxim, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, thioxazaphen, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarasene, triazamate, triazophos, trichlorfon, trichlormethaphos-3, trichloronate, tripenophos, triflumezopyrim, triflumuron, trimethacarb, triplen, cyclopyrazoflor, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprophos, and any combination thereof.

[0043] In addition, the compounds described herein can be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application and do not antagonize the activity of the compounds of the present invention to form pesticidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure can be applied together with one or more other herbicides to control a variety of undesirable plants.When used together with herbicides, the compounds claimed herein can be formulated with the herbicide, tank-mixed with the herbicide, or applied consecutively to the herbicide. Typical herbicides include 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, aridochlor, alloxydim, allyl alcohol, arorac, ametridione, ametryn, and ametrine. Mivudine, Amicarbazone, Amidosulfuron, Aminocyclopyrachlor, Aminopyralid, Amiprophos-methyl, Amitrole, Ammonium sulfamate, Anilofos, Anisrone, Ashlam, Atraton, Atrazine, Azafenidine, Azimsulfuron, Aziprothrin, Burban, BCPC, Beflubutamid, Beflubutamid-M, Benazolin, Bencarbazone, Benfluralin, Benfuresate, Bensulf ron, bensulide, bentazon, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, viranaphos, bispyribac, bixlozone, borax, bromacil, bromobonyl, bromobutide, bromofenoxime, bromoxynil, brompyrazone, butachlor, butafenacil, butamiphos, butenachlor, butidazole, buthiuron, butralin, butroxydim, buturon, butyrate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlormethoxyfen, chloramben, chloranocryl, chlorradifop, chlorazine, chlorbromuron,Chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon ethyl, cinmethylin, cinosulfuron, cisanilide, clasifos, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam Methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatrin, cyanazine, cycloate, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyclouron, cyhalofop, cypercort, cyprazine, cyprazole, cypromid, dymron, dalapon, dazomet, delacorl, desmedipham, desmetrin, diallate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, dietham Cort, diethathyl, diphenopentene, difenoxuron, difenzocort, diflufenican, diflufenzopyr, dimefron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinophenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamide, dipropetrine, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinadin, endothal, epronaz, EPTC, ervon, esprocarb, etaluf Luralin, ethametsulfuron, etidimuron, ethiolate, ethofumesate, ethoxyfene, ethoxysulfuron, ethinofen, ethonipromide, etobenzanide, EXD, fenashulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenquinotrion, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, florpyrauxifen, fluazifop, fluazifop-P, fluazolate,Flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropine, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, fluroxyfene, glufon Glufosinate, Glufosinate-P, Glyphosate, Haloxifene, Halosafen, Halosulfuron, Haloxyzin, Haloxyfop, Haloxyfop-P, Hexachloroacetone, Hexaflurate, Hexazinone, Imazamethabenz, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Indanofan, Indaziflam, Iodobonyl, Iodomethane, Iodosulfuron, Iofensulfuron, Ioxynil, Ipazine, Ipfencarbazone, Iprimidam, Isocarbamide, Isosil, Isomethiozine , isonoruron, isopolynate, isoproparin, isoproturon, isouron, isoxaben, isoxachlorthor, isoxaflutole, isoxapyrifop, carbutilate, ketospiradox, lancotrione, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metoflurane Zon, methabenzthiazuron, methaproparin, methazole, methiobencarb, methiozoline, methiuron, methometon, metoprothrin, methyl bromide, methyl isothiocyanate, methyldimethron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morphamcort, MSMA, naproanilide, napropamide, napropamide-M, naptalam, nebulon, nicosulfuron, nipiraclofen,Nitraline, Nitrofen, Nitrofluorfen, Norflurazon, Norlon, OCH, Orbencarb, Ortho-Dichlorobenzene, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxapyrazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Parafluron, Paraquat, Pebulate, Pelargonic Acid, Pendimethalin, Penoxsulam, Pentachlorophenol, Pentanochlor, Pentoxazone, Perfluidone, Petoxamide, Phenisofam, Phenmedipham, Phenmedipham-ethyl , Fenobenzuron, Phenylmercuric acetate, Picloram, Picolinafen, Pinoxaden, Piperophos, Potassium arsenite, Potassium azide, Potassium cyanate, Pretilachlor, Primisulfuron, Procyazin, Prodiamine, Profluazole, Profluralin, Profoxydim, Proglinadin, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Propyrisulfuron, Propyzamide, Prosulfarin, Prosulfocarb, Prosulfuron, Proxil San, prinachlor, pidanone, pyraclonil, pyraflufen, pyrasulfotole, pyrazolinate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyrichlor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quinonamide, quizalofop, quizalofop-P, rodetanil, rimsulfuron, saflufenacil, S-metolachlor, sebutylazine, secbumeton, sethoxydim, cyde uron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfurate, sulfentrazone, sulfometuron, sulfosulfuron, sulfate, sulglicapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiadimine, thidiazuron, thiencarbazone methyl,These include, but are not limited to, thifensulfuron, thiobencarb, thiaphenacyl, thiocarbazil, thioclorim, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, trisulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphan, trietazine, trifloxysulfuron, trifludimoxazine, trifluralin, triflusulfuron, triphop, trifopsim, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

[0044] In another embodiment of the invention, Formula 1 may be used in combination with one or more active ingredients such as those listed above (eg, in a compositional mixture or in simultaneous or sequential application).

[0045] In another embodiment of the invention, Formula 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential application) with one or more active ingredients each having the same, similar or preferably different mechanism of action (MoA) as the MoA of Formula 1.

[0046] In another embodiment, Formula 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential application) with one or more molecules having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal and / or virucidal properties.

[0047] In another embodiment, Formula 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential application) with one or more molecules that are antifeedants, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammalian repellents, mating disruptants, plant activators, plant growth regulators, plant health stimulants or promoters, nitrification inhibitors, and / or synergists.

[0048] In another embodiment, Formula 1 can be used in combination with one or more biopesticides (e.g., in a compositional mixture or in sequential or simultaneous applications).

[0049] In another embodiment, the combination of Formula 1 and the active ingredient in the biocidal composition can be used in a variety of weight ratios. For example, in a two-component mixture, the weight ratios in TABLE 1 can be used as the weight ratio of Formula 1 to the active ingredient. However, generally, the weight ratio is preferably from about 10:1 to less than about 1:10.

[0050]

Table 1A

[0051] The weight ratio of the molecule of Formula 1 to the active ingredient can also be expressed as X:Y, where X is the part by weight of Formula 1 and Y is the part by weight of the active ingredient. The numerical range of the part by weight of X is 0 < X ≤ 100, and the part by weight of Y is 0 < Y ≤ 100, which is shown in a chart in TABLE 2. By way of non-limiting example, the weight ratio of Formula 1 to the active ingredient can be 20:1.

[0052]

Table 1B

[0053] The range of the weight ratio of Formula I to the active ingredient is X 1 :Y 1 ~X 2 :Y 2 and can be expressed as, where X and Y are defined above.

[0054] In one embodiment, the range of the weight ratio is X 1 :Y 1 ~X 2 :Y 2 and can be, where X 1 >Y 1 and X 2 <Y 2By way of non-limiting example, the weight ratio of Formula 1 to active ingredient may range from 3:1 to 1:3, inclusive.

[0055] In another embodiment, the weight ratio range is X 1 :Y 1 ~X 2 :Y 2 where X 1 >Y 1 and X 2 >Y 2 By way of non-limiting example, the weight ratio of Formula 1 to active ingredient may range from 15:1 to 3:1, inclusive.

[0056] In another embodiment, the weight ratio range is X 1 :Y 1 ~X 2 :Y 2 where X 1 <Y 1 and X 2 <Y 2 By way of non-limiting example, the weight ratio of Formula 1 to the active ingredient may range from about 1:3 to about 1:20, inclusive.

[0057] Another embodiment of the present disclosure is a method for controlling or preventing fungal attack.The method comprises applying a fungicidal amount of one or more compounds of formula I to soil, plants, roots, leaves or the location where fungi are present or where the occurrence is to be prevented (e.g., to crops or vines).The compounds are suitable for treating a variety of plants at fungicidal levels while exhibiting low phytotoxicity.The compounds can be useful in both protectant and / or eradicator modes.

[0058] The compounds have been found to have significant fungicidal activity, particularly in agricultural applications, and many of the compounds are particularly effective for use on agricultural crops and horticultural plants.

[0059] It will be appreciated by those skilled in the art that the efficacy of a compound against the aforementioned fungi establishes the general utility of the compound as a fungicide.

[0060] The compounds have a broad spectrum of activity against fungal pathogens. Exemplary pathogens include wheat leaf blight (Zymoseptoria tritici), wheat leaf rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), apple scab (Venturia inaequalis), grape powdery mildew (Uncinula necator), barley scald (Rhynchosporium commune), rice blast (Magnaporthe grisea), soybean rust (Phakopsora pachyrhizi), and others. pachyrhizi), wheat gall blight (Parastagonospora nodorum), powdery mildew of wheat (Blumeria graminis f.sp. tritici), powdery mildew of barley (Blumeria graminis f.sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of turnip (Cercospora beticola), late blight of tomato (Alternaria solani), solani), barley spot disease (Cochliobolus sativus), and barley net blotch (Pyrenophora teres). The exact amount of active material applied will depend not only on the particular active material being applied, but also on the particular effect desired, the species of fungus and its developmental stage to be controlled and the part of the plant or other produce with which the compound is contacted.Thus, all compounds and formulations containing them may not be equally effective at similar concentrations or against the same fungal species.

[0061] The compounds are effective for application to plants in disease-suppressing and botanically acceptable amounts. The term "disease-suppressing and botanically acceptable amount" refers to an amount of compound that will kill or suppress the plant disease which it is desired to control, but which is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required will vary with the fungal disease being controlled, the type of formulation used, the method of application, the particular plant species, climatic conditions, and the like. Suitable application rates are typically from about 0.10 to about 4 pounds per acre (about 0.01 to 0.45 grams per square meter, g / m2). 2 ) range.

[0062] Any ranges or desired values ​​presented herein can be expanded or modified without losing the effect sought, as would be apparent to one of ordinary skill in the art upon understanding the teachings herein.

[0063] Compounds of formula I can be made using well-known chemical procedures. Intermediates not specifically described in this disclosure are either commercially available, can be made by routes disclosed in the chemical literature, or can be readily synthesized from commercially available starting materials using standard procedures.

[0064] General Scheme The following schemes illustrate methods for producing aryl amidine compounds of formula (I): The following descriptions and examples are offered for illustrative purposes and should not be construed as limiting with respect to substituents or substitution patterns.

[0065] A compound of formula 1.4, where R 2 , R 3 , R 4 and R 5Compounds of formula 1.2, where R is as defined initially, can be prepared by the methods shown in Scheme 1, steps a-c. 2 , R 4 and R 5 Compounds of formula 1.1, where R is as defined initially, can be prepared by the method shown in Scheme 1, step a. 2 , R 4 and R 5 is defined as the first step) in a solvent such as N,N-dimethylformamide (DMF) with iodine (I 2 ) at a temperature of about 23° C. to 50° C. to give a compound of formula 1.2, as shown in a, 2 , R 4 and R 5 is as defined initially. Compounds of formula 1.3, where R 2 , R 3 , R 4 and R 5 Compounds of formula 1.2, where R is as defined initially, can be prepared by the method shown in Scheme 1, step b. 2 , R 4 and R 5 is defined as the first step, and then cesium carbonate (Cs 2 CO 3 ) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex (PdCl) at temperatures between about 23°C and 120°C under microwave irradiation. 2 (dppf)DCM) and other catalysts and B 3 O 3 R 3 3 (In the formula, R 3 is as originally defined) to give compounds of formula 1.3, 2 , R 3 , R 4 and R 5is as defined initially. Compounds of formula 1.4, where R 2 , R 3 , R 4 and R 5 Compounds of formula 1.3, where R is as defined initially, can be prepared by the method shown in Scheme 1, step c. 2 , R 3 , R 4 and R 5 is as originally defined) in 3:2:1 tetrahydrofuran (THF):methanol (MeOH):water (H 2 2H, to give compounds of formula 1.4, where R 2 , R 3 , R 4 and R 5 is defined as first. Scheme 1 [ka]

[0066] Alternatively, a compound of formula 1.4, where R 2 , R 3 , R 4 and R 5 Compounds of formula 2.2, where R is as defined initially, can be prepared by the methods shown in Scheme 2, steps d-f. 2 , R 4 and R 5 Compounds of formula 2.1, where R is as defined initially, can be prepared by the method shown in Scheme 2, step d. 2 , R 4 and R 5 is as originally defined) with a halogenating agent such as N-bromosuccinimide (NBS) in a solvent such as N,N-dimethylformamide (DMF) at a temperature between about 0° C. and 23° C., as shown in d, to give a compound of formula 2.2, 2 , R4 and R 5 is as defined initially. Compounds of formula 2.3, where R 2 , R 3 , R 4 and R 5 Compounds of formula 2.2, where R is as defined initially, can be prepared by the method shown in Scheme 2, step e. 2 , R 4 and R 5 is as defined initially) in a solvent mixture such as 10:1 1,4-dioxane:water at a temperature of about 23° C. to 100° C., as shown in e. 3 PO 4 ) in the presence of a base such as (2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (XPhos-Pd-G3) and B 3 O 3 R 3 3 (In the formula, R 3 is as originally defined) to give compounds of formula 2.3, 2 , R 3 , R 4 and R 5 is as defined initially. Compounds of formula 1.4, where R 2 , R 3 , R 4 and R 5 Compounds of formula 2.3, where R is as defined initially, can be prepared by the method shown in Scheme 2, step f. 2 , R 3 , R 4 and R 5 is as originally defined) with a base such as potassium hydroxide (KOH) in a solvent such as water at a temperature of about 23° C. to 60° C., as shown in f, to give a compound of formula 1.4, where R 2 , R 3 , R 4 and R5 is defined as first. Scheme 2 [ka]

[0067] Alternatively, a compound of formula 1.4, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.2, where R is as defined initially, can be prepared by the methods shown in Scheme 3, steps g-n. 2 , R 3 , R 4 and R 5 Compounds of formula 3.1, where R is as defined initially, can be prepared by the method shown in Scheme 3, step g. 2 , R 3 , R 4 and R 5 is as defined initially) in a solvent such as acetic acid at a temperature of about 23° C. to 85° C., as shown in g. 2 ) to give compounds of formula 3.2, 2 , R 3 , R 4 and R 5 is as defined initially. Compounds of formula 3.3, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.2, where R is as defined initially, can be prepared by the method shown in Scheme 3, step h. 2 , R 3 , R 4 and R 5 is as defined initially) in a 1:1 ethanol (EtOH):H 2 Ammonium chloride (NH 4In the presence of ammonium salts such as iron (FeCl), 0 ) to give compounds of formula 3.3, 2 , R 3 , R 4 and R 5 Alternatively, a compound of formula 3.3, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.4, where R is as defined initially, can be prepared by the method shown in Scheme 3, step i. 2 , R 3 , R 4 and R 5 is as defined initially), as shown in i, is treated with a halogenating agent such as N-bromosuccinimide (NBS) in a solvent such as N,N-dimethylformamide (DMF) at a temperature between about 0° C. and 23° C. to give a compound of formula 3.3, where R 2 , R 3 , R 4 and R 5 is as defined initially. Compounds of formula 3.5, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.3, where R is as defined initially, can be prepared by the method shown in Scheme 3, step j. 2 , R 3 , R 4 and R 5 is as defined initially) is treated with a metal cyanide such as CuCN in a solvent such as N-methyl-2-pyrrolidone (NMP) at a temperature of about 23° C. to 180° C. under microwave irradiation as shown in j to give a compound of formula 3.5, where R 2 , R 3 , R 4 and R 5 Alternatively, a compound of formula 3.5, where R 2 , R 3 , R4 and R 5 Compounds of formula 3.3, where R is as defined initially, can be prepared by the method shown in Scheme 3, step k. 2 , R 3 , R 4 and R 5 is as defined initially) in a solvent such as DMF at a temperature of about 23° C. to 120° C. to give tetrakis(triphenylphosphine)-palladium(0) (Pd(PPh 3 ) 4 In the presence of a metal catalyst such as zinc(II) cyanide (Zn(CN) 2 ) to give compounds of formula 3.4, 2 , R 3 , R 4 and R 5 is as defined initially. Compounds of formula 1.4, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.5, where R is as defined initially, can be prepared by the method shown in Scheme 3, step l. 2 , R 3 , R 4 and R 5 is as defined initially) at a temperature of about 23 to 120° C., as shown in l. 2 2H, to give a compound of formula 1.4, 2 , R 3 , R 4 and R 5 Alternatively, a compound of formula 3.6, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.3, where R is as defined initially, can be prepared by the method shown in Scheme 3, step m. 2 , R 3 , R 4 and R5 is as defined initially) is treated with carbon monoxide (CO) gas in the presence of a ligand such as 1,4-bis(diphenylphosphanyl)butane with a base such as triethylamine (TEA) in a solvent such as methanol at a pressure of about 400 psi and a temperature of about 23° C. to 125° C. to give a compound of formula 3.6, where R 2 , R 3 , R 4 and R 5 is as defined initially. Compounds of formula 1.4, where R 2 , R 3 , R 4 and R 5 Compounds of formula 3.6, where R is as defined initially, can be prepared by the method shown in Scheme 3, step n. 2 , R 3 , R 4 and R 5 is as defined initially), as shown in n, is treated with a base such as lithium hydroxide (LiOH) in a solvent mixture such as 3:2:1 THF:MeOH:water at a temperature between about 23° C. and 125° C. to give a compound of formula 1.4, where R 2 , R 3 , R 4 and R 5 is defined as first. Scheme 3 [ka]

[0068] A compound of formula 4.1, where R 1 , R 2 , R 3 , R 4 and R 5 Compounds of formula 1.4, where R is as defined initially, can be prepared by the method shown in Scheme 4, step o. 2 , R 3 , R 4 and R 5is as initially defined) in the presence of a peptide coupling reagent such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDCI), N,N'-dicyclohexylcarbodiimide (DCC) or benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) and a catalyst such as dimethylaminopyridine (DMAP) or N-ethyl-N-isopropylpropan-2-amine (DIPEA) in a solvent such as dichloromethane (DCM) at a temperature between about 0°C and ambient temperature, as shown in o. 1 -OH(in the formula, R 1 is as defined initially) to give a compound of formula 4.1, 1 , R 2 , R 3 , R 4 and R 5 Alternatively, a compound of formula 4.1, where R 1 , R 2 , R 3 , R 4 and R 5 Compounds of formula 1.4, where R is as defined initially, can be prepared by the method shown in Scheme 4, step p. 2 , R 3 , R 4 and R 5 is as defined initially) in a solvent such as DMF at a temperature of about 23° C., as shown in p. 2 CO 3 ) in the presence of a base such as R 1 -Br(wherein, R 1 is as defined initially) to give compounds of formula 4.1, 1 , R 2 , R 3 , R 4 and R 5 is defined as first. Scheme 4 [ka]

[0069] A compound of formula 5.2, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 4.1, where R is as defined initially, can be prepared by the method shown in Scheme 5, step q. 1 , R 2 , R 3 , R 4 and R 5 is as defined initially) in a solvent such as toluene at a temperature of about 23° C. to 90° C. to give a compound of formula 5.1, 7 and R 8 is as defined initially) to give compounds of formula 5.2, 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 is defined as first. Scheme 5 [ka]

[0070] Alternatively, a compound of formula 5.2, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 6.1, where R is as defined initially, can be prepared by the methods shown in Scheme 6, steps r-s. 1 , R 2 , R 3 , R 4 and R 5Compounds of formula 4.1, where R is as originally defined and Z is an alkyl group, can be prepared by the method shown in Scheme 6, step r. 1 , R 2 , R 3 , R 4 and R 5 is as defined initially) is reacted with p-toluenesulfonic acid monohydrate (pTsOH-H) at a temperature of about reflux (about 100° C. or about 140° C., respectively) as shown in r. 2 In the presence of an acid catalyst such as trialkyl orthoformate (CH(OZ) 3 ) (wherein Z is an alkyl group) to give compounds of formula 6.1 (wherein R 1 , R 2 , R 3 , R 4 and R 5 is as defined initially and Z is an alkyl group. 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 6.1, where R is as initially defined, can be prepared by the method shown in Scheme 6, step s. 1 , R 2 , R 3 , R 4 and R 5 is as defined initially and Z is an alkyl group) in a solvent such as DCM at a temperature of about 23° C. to 40° C. to form a compound of formula 6.2, where R 7 and R 8 is as defined initially) to give compounds of formula 5.2, 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8is defined as first. Scheme 6 [ka]

[0071] A compound of formula 7.2, where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Compounds of formula 4.1, where R is as defined initially, can be prepared by the method shown in Scheme 7, step t. 1 , R 2 , R 3 , R 4 and R 5 is as defined above) in a solvent such as toluene at a temperature of about 23 °C to reflux (about 110 °C), as shown in t. 3 ) to give a compound of formula 7.1, 6 , R 7 and R 8 is as defined initially) to give compounds of formula 7.2, 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is defined as first. Scheme 7 [ka]

[0072] A compound of formula 8.2, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R8 Compounds of formula 8.1, where R is as defined initially, can be prepared by the methods shown in Scheme 8, steps u-v. 1 , R 2 , R 3 , R 4 and R 5 Compounds of formula 4.1, where R is as previously defined, can be prepared by the method shown in Scheme 8, step u. 1 , R 2 , R 3 , R 4 and R 5 is as previously defined) in 1:1 DCM:H at a temperature of about 23° C., as shown in u. 2 Sodium bicarbonate (NaHCO 3 ) to give compounds of formula 8.1, 1 , R 2 , R 3 , R 4 and R 5 is as previously defined). Compounds of formula 8.2, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 8.1, where R is as previously defined, can be prepared by the method shown in Scheme 8, step v. 1 , R 2 , R 3 , R 4 and R 5 is as previously defined) in a solvent such as DCM at a temperature of about 23° C. to give a compound of formula 6.2, where R 7 and R 8 is as defined initially) to give compounds of formula 8.2, 1 , R 2 , R 3 , R 4 , R 5 , R 7and R 8 is defined as first. Scheme 8 [ka]

[0073] Alternatively, a compound of formula 9.3, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 9.1, where R is as defined initially, can be prepared by the methods shown in Scheme 9, steps w to x. 1 , R 2 , R 3 , R 4 and R 5 Compounds of formula 4.1, where R is as originally defined, can be prepared by the method shown in Scheme 9, step w. 1 , R 2 , R 3 , R 4 and R 5 is as defined initially) is reacted with p-toluenesulfonic acid monohydrate (pTsOH-H 2 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 1 , R 2 , R 3 , R 4 and R 5 is as defined initially. Compounds of formula 9.3, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 9.1, where R is as originally defined, can be prepared by the method shown in Scheme 9, step x. 1 , R 2, R 3 , R 4 and R 5 is as defined initially) in the presence of a base such as triethylamine in a solvent mixture such as 1:1 methanol:1,4-dioxane at a temperature between about 23° C. and reflux (about 80° C.), as shown in x, to give a compound of formula 9.2, where R 7 and R 8 is as defined initially) to give compounds of formula 9.3, 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 is defined as first. Scheme 9 [ka]

[0074] A compound of formula 10.2, where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Compounds of formula 10.1, where R is as defined initially, can be prepared by the method shown in Scheme 10, step y. 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is as originally defined), as shown in y, is treated with a base such as sodium hydroxide (NaOH) in a solvent such as MeOH at a temperature between about 23° C. and 60° C. to give a compound of formula 10.2, where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8is defined as first. Scheme 10 [ka]

[0075] A compound of formula 11.1, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 Compounds of formula 8.2, where R is as defined initially, can be prepared by the method shown in Scheme 11, step z. 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 is as defined initially) in a solvent such as acetone at a temperature of about 23° C., as shown in z. 2 CO 3 ) to give compounds of formula 11.1, 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 is defined as first. Scheme 11 [ka]

[0076] A compound of formula 12.1, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8Compounds of formula 5.2, where R is as defined initially, can be prepared by the method shown in Scheme 12, step aa. 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 is as originally defined) with a protic acid (HX) such as hydrochloric acid (HCl), hydrobromic acid (HBr), acetic acid (HOAc), trifluoroacetic acid, para-toluenesulfonic acid (pTsOH) or citric acid in a solvent such as heptane or ethyl acetate at a temperature of about 23° C., as shown in aa, to give a compound of formula 12.1, where R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 is defined as first. Scheme 12 [ka] EXAMPLES

[0077] Example 1A: Preparation of methyl 4-amino-5-iodo-methylbenzoate [ka] A solution of methyl 4-amino-2-methylbenzoate (0.29 g, 1.76 mmol) in DMF (1.5 mL) was diluted with sodium periodate (0.14 g, 0.70 mmol) and I 2 (74 mg, 1.41 mmol) was added. The reaction mixture was stirred at 50° C. for 3 h. The reaction mixture was diluted with saturated sodium thiosulfate solution (5 mL). The solid was then filtered and dried. The crude product was triturated with EtOHc (1 mL) and pentane (9 mL) to give the title compound (0.22 g, 43% yield) as a pink solid. 1 H NMR (400 MHz, CDCl3 )δ 8.27(s,1H),6.54(s,1H),4.38(brs,2H),3.84(s,3H),2.50(s,3H);ESIMS m / z 292([M+H] + ).

[0078] Example 1B: Preparation of methyl 4-acetamido-5-bromo-2-methoxybenzoate [ka] To a solution of methyl 4-acetamido-2-methoxybenzoate (4.04 g, 18.1 mmol) in DMF (80 mL) was added N-bromosuccinimide (3.22 g, 18.1 mmol) at 0° C. The mixture was stirred at 0° C. and allowed to slowly warm to room temperature with stirring overnight. The mixture was then diluted with water and a precipitate formed. The precipitate was filtered off and washed with additional water. The precipitate was dried under vacuum to give an impure product. The crude product was purified by flash column chromatography (silica gel (SiO 2 ), 0→100% ethyl acetate in hexanes) to give the title compound (3.89 g, 12.9 mmol, 71% yield) as a white solid. 1 H NMR (400 MHz, CDCl 3 )δ 8.32(s,1H),8.04(s,1H),7.76(s,1H),3.93(s,3H),3.87(s,3H),2.28(s,3H); 13 C NMR (101 MHz, CDCl 3 )δ 166.28,162.47,157.58,137.80,132.74,113.36,102.13,99.53,54.06,49.79,22.92;ESIMS m / z 304[(M+H) + ].

[0079] Example 1C: Preparation of 4-bromo-5-methyl-2-(trifluoromethyl)aniline [ka] In a 25 mL vial, a solution of 5-methyl-2-(trifluoromethyl)aniline (1.00 g, 5.71 mmol) was prepared in DMF (18 mL). The reaction was cooled to 0 °C in an ice-water bath. N-bromosuccinimide (1.02 g, 5.71 mmol) was then added in one portion. The reaction was stirred overnight and allowed to warm slowly to ambient temperature so that the ice melted. After 18 h, the reaction was quenched with water (50 mL) and diluted with EtOAc (50 mL). The layers were separated and the aqueous layer was extracted with EtOAc (3 x 50 mL). The combined organic layers were then washed with brine (3 x 100 mL) and MgSO 4 Drying at rt, filtering and concentrating afforded the title compound (1.31 g, 5.16 mmol, 90% yield) as a dark yellow oil which was used without further purification. 1 H NMR (400 MHz, CDCl 3 )δ 7.54(s,1H),6.63(s,1H),4.09(s,2H),2.32(s,3H); 19 F NMR (376 MHz, CDCl 3 ) δ -62.58; HRMS-ESI(m / z)[M+H] + C 8 H 8 BrF 3 Calculated value for N: 253.9787; measured value: 253.9778.

[0080] Example 2A: Preparation of methyl 4-amino-2,5-dimethylbenzoate [ka] Cesium carbonate (0.98 g, 3.02 mmol) was added to a solution of methyl 4-amino-5-iodo-2-methylbenzoate (0.22 g, 0.75 mmol) in 1,4-dioxane (5 mL), which was degassed for 5 min. Then, PdCl 2(dppf)DCM (0.061 g, 0.07 mmol) and trimethylboroxine (0.23 g, 1.88 mmol) were added and the reaction mixture was heated to 120° C. under microwave irradiation for 1 h. The reaction mixture was diluted with water (15 mL) and extracted with EtOAc (2×40 mL). The combined organic layers were washed with anhydrous Na 2 SO 4 The crude product was purified by flash column chromatography (silica gel (SiO 2 ), 20→25% ethyl acetate in hexanes) to give the title compound (0.11 g, 84% yield) as a brown solid. ESIMS m / z 180 ([M+H] + ).

[0081] Example 2B: Preparation of methyl 4-acetamido-2-methoxy-5-methylbenzoate [ka] Methyl 4-acetamido-5-bromo-2-methoxybenzoate (2.00 g, 6.62 mmol), methylboronic acid (0.594 g, 9.93 mmol), XPhosPd G3 (0.112 g, 0.132 mmol) and tripotassium phosphate (2.81 g, 13.2 mmol) were dissolved / suspended in 1,4-dioxane (30.1 mL) / water (3.01 mL) and heated to 100 °C. The mixture was stirred at 100 °C for 4 h. The mixture was cooled to room temperature (UPLC shows about 50% conversion) and diluted with DCM and water. The mixture was then passed through a phase separator and the product was extracted with DCM. The crude product was purified by flash column chromatography (silica gel (SiO 2 ), 0→100% ethyl acetate in hexanes) to afford the title compound (658 mg, 2.77 mmol, 42% yield) as a white solid and 866 mg (43%) of recovered starting material. 1 H NMR (400 MHz, CDCl 3 )δ 8.01(s,1H),7.70-7.63(m,1H),7.11(s,1H),3.90(s,3H),3.87(s,3H),2.25(s,3H),2.22(s,3H);13 C NMR (101 MHz, CDCl 3 )δ 167.27,165.10,157.74,139.71,132.51,131.72,115.99,103.58,55.11,50.80,23.93,15.45;ESIMS m / z 236[(MH) - ].

[0082] Example 3A: Preparation of 4-amino-2,5-dimethylbenzoic acid [ka] THF:MeOH:H 2 To a solution of methyl 4-amino-2,5-dimethylbenzoate (0.11 g, 0.69 mmol) in O (3:2:1) (2 mL) was added LiOH (0.073 mg, 3.07 mmol) and the reaction mixture was stirred at 70° C. for 16 h. The reaction mixture was then acidified with acetic acid (0.5 mL). The precipitated solid was filtered and dried to give the title compound (0.062 g, 68% yield) as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3 )δ 7.82(s,1H),6.48(s,1H),3.97(brs,2H),2.54(s,3H),2.14(s,3H);ESIMS m / z 166([M+H] + ).

[0083] Example 3B: Preparation of 4-amino-2-methoxy-5-methylbenzoic acid [ka] In a 50 mL round bottom flask, methyl 4-acetamido-2-methoxy-5-methylbenzoate (0.658 g, 2.77 mmol) was dissolved / suspended in 6 M aqueous KOH. To the suspension was added MeOH (5 mL) at room temperature. The mixture was then heated to 60° C. and stirred overnight. The reaction was cooled to room temperature, diluted with water, and carefully acidified to pH approx. 4-5 with 6 N HCl (dropwise). The product was extracted with EtOAc (3×). The combined organic layers were then washed with Na2 SO 4 Dry at rt, filter and concentrate to give the title compound (437 mg, 2.41 mmol, 87% yield) as an off-white solid. 1 H NMR (500 MHz, CDCl 3 )δ 7.84(s,1H),6.25(s,1H),4.19(s,3H),3.98(s,3H),2.11(s,3H); 13 C NMR (126 MHz, CDCl 3 )δ 165.97,158.27,151.07,135.66,115.42,106.65,96.62,56.49,16.15;ESIMS m / z 182[(M+H) + ].

[0084] Example 4: Preparation of 1-bromo-5-chloro-2-methyl-4-nitrobenzene [ka] To a solution of 5-chloro-2-methyl-4-nitroaniline (5.3 g, 28.49 mmol) in acetic acid (53 mL) was added aqueous HBr (7.7 mL) at room temperature. 2 (1.96 g, 28.49 mmol) was added over 45 min. The reaction mixture was stirred at 85° C. for 2 h. After 2 h, the reaction mixture was cooled to room temperature and poured into ice water (100 mL). The resulting solid was filtered, washed with water (100 mL), and dried to give the title compound (5.5 g, 74% yield) as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3 )δ 7.79(s,1H),7.52(s,1H),2.45(s,3H).

[0085] Example 5: Preparation of 4-bromo-2-chloro-5-methylaniline [ka] Fe 0 Powder (12.1 g, 220.8 mmol) and NH 4Cl (11.7g, 220.8mmol) in EtOH:H 2 The mixture was added to a solution of 1-bromo-5-chloro-2-methyl-4-nitrobenzene (5.5 g, 22.08 mmol) in 2H2O (55 mL, 1:1) at room temperature. The reaction mixture was stirred at 70° C. for 30 min. Then, the reaction mixture was cooled to room temperature and the solvent was concentrated under reduced pressure. The crude material was diluted with water (30 mL), filtered, and the solid was washed with EtOAc (30 mL). The aqueous layer was extracted with EtOAc (2×30 mL). The combined organic layers were washed with anhydrous Na 2 SO 4 The crude product was purified by flash column chromatography (silica gel (SiO 2 ), 3→5% ethyl acetate in petroleum ether) to give the title compound (2.8 g, 58% yield) as an off-white solid. 1 H NMR (400MHz, DMSO-d 6 )δ 7.38(s,1H),6.65(s,1H),3.96(brs,2H),2.27(s,1H);ESIMS m / z 220([M+H] + ).

[0086] Example 6A: Preparation of 4-amino-2,5-dichlorobenzonitrile [ka] To a solution of 4-bromo-2,5-dichloroaniline (2 g, 8.33 mmol) in NMP (20 mL) was added CuCN (2.2 g, 24.99 mmol) and the reaction mixture was heated to 180° C. under microwave irradiation for 1.5 h. The reaction mixture was poured into ice-cold water (30 mL) and extracted with EtOAc (3×60 mL). The organic layer was washed with anhydrous Na 2 SO 4 The crude product was purified by column chromatography (silica gel (SiO 2 ), 15→20% ethyl acetate in petroleum ether) to afford the title compound (1 g, 64% yield) as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3)δ 7.83(s,1H),6.92(s,1H),6.73(brs,2H);ESIMS m / z 187([M+H] + ).

[0087] Example 6B: Preparation of 4-amino-2,5-dimethylbenzonitrile [ka] 4-Bromo-2,5-dimethylaniline (15 g, 75.00 mmol) and Zn(CN) in DMF (150 mL) 2 A solution of (9.6 g, 82.50 mmol) was degassed for 10 min. Then, tetrakis(triphenylphosphine)-palladium(0) (12.9 g, 11.25 mmol) was added and the reaction mixture was heated to 120° C. in a sealed tube for 2 days. After 2 days, the reaction mixture was poured into ice-cold water (400 mL) and extracted with EtAOc (3×600 mL). The combined organic layers were washed with anhydrous Na 2 SO 4 The crude product was purified by column chromatography (silica gel (SiO 2 ), 15→20% ethyl acetate in petroleum ether) to give the title compound (5.7 g, 52% yield) as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3 )δ 7.25(s,1H),6.50(s,1H),3.98(brs,2H),2.40(s,3H),2.11(s,3H);ESIMS m / z 147([M+H] + ).

[0088] Example 6C: Preparation of methyl 4-amino-5-methoxy-2-methylbenzoate [ka] A solution of 4-bromo-2-methoxy-5-methylaniline (2.0 g, 9.3 mmol), palladium(II) acetate (0.302 g, 1.345 mmol), 1,4-bis(diphenylphosphanyl)butane (1.19 g, 2.79 mmol) and triethylamine (2.6 mL, 19 mmol) was prepared in MeOH (20 mL) in a 45 mL Parr reactor. The reactor was sealed and purged with CO (3 cycles from 50 to 100 psi). The reactor was then charged with CO to 400 psi, placed in a heat block and heated to 130 °C for 24 h. The crude material was concentrated and the crude residue was dissolved in water (10 mL) and EtOAc (40 mL) and filtered through Celite. The aqueous layer was extracted with EtOAc (3 x 20 mL). The combined organic layers were washed with brine (10 mL) and MgSO 4 The crude product was purified by column chromatography (silica gel (SiO 2 ), 0→40% ethyl acetate in petroleum ether) to afford the title compound (363 mg, 20% yield) as a rose-red solid. 1 H NMR (400 MHz, CDCl 3 )δ 7.42(s,1H),6.50(s,1H),4.12(s,2H),3.87(s,3H),3.84(s,3H),2.49(s,3H);ESIMS m / z 196([M+H] + ).

[0089] Example 7A: Preparation of 4-amino-2,5-dichlorobenzoic acid [ka] To a solution of 4-amino-2,5-dichlorobenzonitrile (1 g, 5.37 mmol) in water (10 mL) was added KOH (6.0 g, 107.52 mmol) at room temperature and the reaction mixture was heated to 120° C. in a sealed tube for 2 days. After 2 days, the reaction mixture was extracted with EtOAc (2×25 mL). The aqueous layer was acidified with acetic acid (12 mL) and extracted with 10% MeOH in DCM (2×75 mL). The combined organic layers were washed with anhydrous Na 2 SO 4Drying at rt, filtration and concentration under reduced pressure afforded the title compound (0.7 g, 63% yield) as a pale yellow solid which was used in the next step without further purification. 1 H NMR (400 MHz, CDCl 3 )δ 7.61(s,1H),6.77(s,1H),5.89(brs,2H);ESIMS m / z 206([M+H] + ).

[0090] Example 7B: Preparation of 4-amino-5-methoxy-2-methylbenzoic acid [ka] A solution of methyl 4-amino-5-methoxy-2-methylbenzoate (155 mg, 0.794 mmol) and lithium hydroxide (86 mg, 3.6 mmol) was prepared in 3:2:1 THF:MeOH:water (2.4 mL). The resulting dark purple reaction was stirred at 70 °C overnight. 1 M HCl was then carefully added to acidify the reaction to approximately pH = 4, precipitating a solid. The aqueous layer was extracted with EtOAc (3 x 30 mL). The combined organic layers were washed with anhydrous MgSO 4 Drying at rt, filtering and concentrating under reduced pressure afforded the title compound (92 mg, 64% yield) as a dark green solid which was used in the next step without further purification. 1 H NMR (400MHz, DMSO-d 6 )δ 11.95(s,1H),7.29(s,1H),6.44(s,1H),5.40(s,2H),3.75(s,3H),2.37(s,3H); 13 C NMR (126 MHz, DMSO-d 6 )δ 168.71,143.69,142.34,134.93,116.12,115.89,113.25,55.76,21.98;IR (thin film)3 500,3396,2935,2836,1669,1608,1529,1451,1364,1258,1217,1081,1022,867cm -1 ;HRMS-ESI(m / z)[M+H] + C 9 H12 NO 3 Calculated value: 182.0812; measured value: 182.0812.

[0091] Example 8A: Preparation of 1-(p-tolyl)propan-1-ol [ka] In a 250 mL flask, a solution of 4-methylbenzaldehyde (0.736 mL, 6.24 mmol) was prepared in diethyl ether (31.2 mL) and cooled to 0° C. in an ice bath. To this clear solution was added ethylmagnesium bromide (1 M in THF, 7.49 mL, 7.49 mmol) dropwise over 5 min, and the resulting solution was stirred overnight, slowly warming to room temperature as the ice bath melted. After 18 h, TLC indicated consumption of starting material and conversion to more polar products. The reaction was purified with NH 4 The mixture was quenched with saturated aqueous Cl (50 mL) and extracted with diethyl ether (3×50 mL). The combined organic layers were passed through a phase separator and concentrated to a clear oil. The crude material was purified by flash column chromatography (silica gel (SiO 2 ), 0→50% ethyl acetate in hexanes) to give the title compound (476 mg, 1.89 mmol, 51% yield) as a clear, colorless oil. 1 H NMR (500 MHz, CDCl 3 )δ 7.24-7.20(m,2H),7.15(d,J=7.9Hz,2H),4.54(ddd,J=7.0,4.7,1.6Hz,1H),2.34(s,3H),1.88-1.68(m,3H),0.90(t,J=7.4Hz,3H); 13 C NMR (126 MHz, CDCl 3 )δ 141.64,137.15,129.08,125.93,75.89,31.80,21.11,10.20;IR(thin film)3340,2962,2926,1454,1097,1039,1012,815cm -1 .

[0092] Example 8B: Preparation of (R)-1-(p-tolyl)ethan-1-ol [ka] In a 100 mL flask, a solution of 1-(p-tolyl)ethan-1-one (0.747 mL, 5.59 mmol) and (S)-1-methyl-3,3-diphenyltetrahydro-1H,3H-pyrrolo[1,2-c][1,3,2]oxaborole ((S)-CBS catalyst, 1 M in toluene, 1.118 mL, 1.118 mmol) was prepared in toluene (37.3 mL) and cooled to 0 °C in an ice / water bath. Then, BH 3 -DMS (2M in THF, 3.49 mL, 6.99 mmol) was added via syringe over 2 min and the ice bath was removed. The reaction was stirred at room temperature. After 1 h, TLC indicated consumption of starting material. Methanol (2.27 mL, 55.9 mmol) was added slowly and the reaction was concentrated to give a clear, colorless oil. The crude material was purified by flash column chromatography (silica gel (SiO 2 ), 0→50% ethyl acetate in hexanes) to give the title compound (784 mg, 5.76 mmol, quantitative yield) as a clear, colorless oil. 1 H NMR (500 MHz, CDCl 3 )δ 7.26(d,J=8.0Hz,2H),7.16(d,J=7.9Hz,2H),4.86(qd,J=6.4,2.7Hz,1H),2.34(s,3H),1.78(d,J=3.1Hz,1H),1.48(d,J=6.5Hz,3H); 13 C NMR (126 MHz, CDCl 3 )δ 142.88,137.16,129.17,125.35,70.26,25.08,21.09;IR(thin film)3341,2971,1513,1071,1009,897,816cm -1 .

[0093] Example 9A: Preparation of 4-methylbenzyl 4-amino-2,5-dimethylbenzoate [ka] In a 20 mL vial, p-tolylmethanol (222 mg, 1.82 mmol), 4-amino-2,5-dimethylbenzoic acid (150 mg, 0.908 mmol) and DMAP (11.1 mg, 0.091 mmol) were dissolved in DCM (4.45 mL) and cooled to 0° C. in an ice / water bath. After approximately 5 min, EDC (211 mg, 1.36 mmol) was added in one portion and the resulting pale yellow reaction was stirred overnight, slowly warming to room temperature as the ice melted. After 18 h, TLC indicated consumption of starting material. The reaction was concentrated to give an oil. The crude material was purified by flash column chromatography (C18 reverse phase, 50→100% acetonitrile in water) to give the title compound (192 mg, 0.712 mmol, 78% yield) as an off-white semi-solid. 1 H NMR (400 MHz, CDCl 3 )δ 7.74(s,1H),7.36-7.29(m,2H),7.18(d,J=7.8Hz,2H),6.46(s,1H),5.25(s,2H),3.88(s,2H),2.52(s,3H),2.36(s,3H),2.12(s,3H); 13 C NMR (101 MHz, CDCl 3 )δ HRMS-ESI(m / z)[M+H] + C 17 H 20 NO 2 Calculated value: 270.1489; measured value: 270.1477.

[0094] Example 9B: Preparation of 2-methylbenzyl 4-amino-2,5-dimethylbenzoate [ka] A solution of 4-amino-2,5-dimethylbenzoic acid (4.2 g, 25.45 mmol) in DMF (40 mL) was diluted with 1-(bromomethyl)-2-methylbenzene (3.5 mL, 25.45 mmol) and K 2 CO 3 (3.8 g, 27.99 mmol) was added. The reaction mixture was stirred at room temperature for 3 h. The reaction mixture was then poured into ice-cold water (100 mL) and extracted with EtOAc (2×200 mL). The combined organic layers were washed with anhydrous Na 2 SO 4 The crude product was purified by flash column chromatography (silica gel (SiO 2 ), 10→15% ethyl acetate in hexanes) to give the title compound (3.8 g, 55% yield) as an off-white solid. 1 H NMR (400 MHz, CDCl 3 )δ 7.74(s,1H),7.40(d,1H),7.20(m,3H),6.47(s,1H),5.29(s,2H),3.89(brs,2H),2.52(s,3H),2.40(s,3H),2.11(s,3H);ESIMS m / z 270([M+H] + ).

[0095] Example 9C: Preparation of 1-(p-tolyl)propyl 4-amino-2,5-dimethylbenzoate [ka] To a 20 mL vial containing 4-amino-2,5-dimethylbenzoic acid (200 mg, 1.21 mmol) was added 2-(p-tolyl)propan-2-ol (364 mg, 2.42 mmol) and PyBOP (945 mg, 1.82 mmol). DCM (12.1 mL) was added followed by N-ethyl-N-isopropylpropan-2-amine (844 μl, 4.84 mmol) dropwise over 45 seconds. After 10 min, most of the solids had solubilized and the resulting pale pink reaction was stirred at room temperature overnight. After 18 h, the reaction was filtered and concentrated to a brown oil. The crude material was purified by flash column chromatography (C18 reverse phase, 50→100% acetonitrile in water) to give the title compound (107 mg, 0.36 mmol, 30% yield) as an orange oil. 1 H NMR (500 MHz, CDCl 3 )δ 7.77(s,1H),7.33 7.27(m,2H),7.18 7.10(m,2H),6.44(s,1H),5.82(t,J=6.8Hz,1H),3.87(s,2H),2.51(s,3H),2.32(s,3H),2.1 4(s,3H),2.03(dt,J=13.7,7.5Hz,1H),1.90(tt,J=13.7,7.4Hz,1H),0.94(t,J=7.4Hz,3H); 13 C NMR (126 MHz, CDCl 3 )δ 166.70,148.20,140.65,138.30,137.17,133.76,129.02,126.50,118.97,118.60,117.06,76.92,2 9.66,22.08,21.14,16.70,10.17;IR (thin film)3376,2967,2927,1689,1624,1562,1253,1156,1053,814cm -1; HRMS-ESI(m / z)[M+H] + C 19 H 24 NO 2 Calculated value: 298.1802; measured value: 298.1801.

[0096] Example 10A: Preparation of (E)-4-(((ethyl(methyl)amino)methylene)amino)-2,5-dimethylbenzoate 4-Methylbenzyl [ka] In a 100 mL round bottom flask, a solution of 4-methylbenzyl 4-amino-2,5-dimethylbenzoate (359 mg, 1.33 mmol) was prepared in toluene (26.6 mL). N-(dimethoxymethyl)-N-methylethanamine (532 mg, 4.00 mmol) was then added and the resulting solution was attached to a reflux condenser, heated to 80° C., and stirred for 48 h. After 48 h, the solution was concentrated to an oil. The crude material was purified by flash column chromatography (C18 reverse phase, 30→100% acetonitrile in water) to give the title compound (333 mg, 0.98 mmol, 74% yield) as a brown oil. 1 H NMR (400 MHz, CDCl 3 )δ 7.79(s,1H),7.45(s,1H),7.33(d,J=7.9Hz,2H),7.17(d,J=7.8Hz,2H),6.56(s,1H),5.26(s,2H),3 .39(bd,J=67.1Hz,2H),2.99(s,3H),2.55(s,3H),2.35(s,3H),2.22(s,3H),1.20(t,J=7.1Hz,3H); 13 C NMR (101 MHz, CDCl 3 )δ 167.49,154.64,151.69,139.49,137.70,133.73,132.81,129.17,128.79,12 8.27,122.55,121.90,65.92,47.85,32.02,21.80,21.18,17.41,14.37;ESIMS m / z 339[(M+H) + ].

[0097] Example 10B: Preparation of (E)-4-(((diethylamino)methylene)amino)-2,5-dimethylbenzoate 4-Methylbenzyl [ka] In a 20 mL vial, 4-methylbenzyl 4-amino-2,5-dimethylbenzoate (100 mg, 0.37 mmol) was dissolved in triethyl orthoformate (2 mL, 12.00 mmol) followed by the addition of p-toluenesulfonic acid monohydrate (7.06 mg, 0.03 mmol). The reaction was heated to reflux (140° C.) and stirred for 3 h. After 3 h, TLC showed nearly complete conversion of the starting material. The reaction was purified with NaHCO 3 The reaction was quenched with saturated aqueous solution (10 mL) and extracted with DCM (3×10 mL). The combined organic phase was passed through a phase separator and concentrated to a pale yellow oil. The residue was redissolved in DCM (0.371 mL) and diethylamine (0.058 mL, 0.55 mmol) was added dropwise via syringe. The solution was heated to 40° C. and stirred for 3 h. The reaction was quenched with water (10 mL) and extracted with DCM (3×10 mL). The combined organic phase was passed through a phase separator and concentrated. The crude material was purified by flash column chromatography (C18 reverse phase, 30→100% acetonitrile in water) to give the title compound (75.8 mg, 0.21 mmol, 58% yield) as a brown oil. 1 H NMR (500 MHz, CDCl 3 )δ 7.79(t,J=1.4Hz,1H),7.42(s,1H),7.38 7.30(m,2H),7.18(dt,J=6.6,1.7Hz,2H),6.55(s,1H),5.26(s,2H),3.40(d,J=94.6Hz,4H),2.55(s,3H),2.36( s,3H),2.22(s,3H),1.22(t,J=7.1Hz,6H);IR(thin film)2970,2927,1707,1629,1592,1549,1371,1250,1110,1047cm -1 ;HRMS-ESI(m / z)[M+H] + C 22 H 29 N 2 O 2 Calculated value: 353.2224; measured value: 353.2227.

[0098] Example 10C: Preparation of (E)-4-methylbenzyl 2,5-dimethyl-4-(piperidin-2-ylideneamino)benzoate [ka] In a 20 mL vial, a solution of piperidin-2-one (0.103 mL, 1.11 mmol) was dissolved in N 2 The crude reaction was stirred overnight. The layers were separated and the aqueous layer was washed with ethyl acetate (3×20 mL). The combined organic layers were washed with brine and diluted with toluene (2×20 mL). The aqueous layer was washed with ethyl acetate (2×20 mL). The combined organic layers were washed with brine and diluted with toluene (2×20 mL). The crude reaction was stirred overnight. The layers were separated and the ... crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. The crude reaction was stirred overnight. 2 SO 4 The crude material was purified using an SCX column (equilibrated with DCM, DMF, MeOH). The material was loaded in DCM and the column was flushed with DCM and MeOH to elute the undesired components. 7N NH in MeOH 3 The SCX column was run at rt to give the title compound (95.0 mg, 0.27 mmol, 49% yield) as a yellow oil. 1 H NMR (600MHz, CDCl 3 )δ 7.79(s,1H),7.34(d,J=7.8Hz,2H),7.19(d,J=7.8Hz,2H),6.63(s,1H),5.27(s,2H),4.39(s,1H),3.22(d,J=1 00.6Hz,2H),2.59(d,J=31.6Hz,2H),2.52(s,3H),2.36(s,3H),2.07(s,3H),1.76(dh,J=8.3,4.0,3.3Hz,4H); 13 C NMR (151 MHz, CDCl 3)δ 167.43,155.09,152.08,139.70,137.84,133.52,133.42,129.21,128.35,127.2 9,125.05,123.33,66.08,42.55,30.85,23.06,21.70,21.22,21.14,17.02;ESIMS m / z 351[(M+H) + ].

[0099] Example 10D: Preparation of 4-methylbenzyl 4-(3,3-diethylthioureido)-2,5-dimethylbenzoate [ka] In a 20 mL vial, a solution of 4-methylbenzyl 4-amino-2,5-dimethylbenzoate (100 mg, 0.37 mmol) and sodium bicarbonate (312 mg, 3.71 mmol) was prepared in DCM (1.24 mL) and water (1.24 mL). To this solution was added thiophosgene (31.3 μL, 0.40 mmol) dropwise via syringe. The resulting orange biphasic mixture was stirred vigorously at room temperature for 2 h. After 2 h, TLC indicated complete consumption of starting material. The biphasic mixture was diluted with water (5 mL) and DCM (5 mL), passed through a phase separator, and concentrated to give a pale yellow oil. The crude material was redissolved in DCM (1.24 mL) followed by the addition of diethylamine (77 μL, 0.74 mmol) in one portion via syringe. The resulting solution was stirred at room temperature for 1 h. After 1 h, the solution was concentrated to an oil. The crude material was purified by flash column chromatography (silica gel (SiO 2 ), 0→50% ethyl acetate in hexanes) to afford the title compound (140.0 mg, 0.36 mmol, 98% yield) as a white semi-solid. 1 H NMR (400 MHz, CDCl 3)δ 7.81(s,1H),7.36-7.28(m,2H),7.23-7.15(m,3H),6.75(s,1H),5.27(s,2H),3.7 6(q,J=7.1Hz,4H),2.54(s,3H),2.36(s,3H),2.23(s,3H),1.31(t,J=7.1Hz,6H); 13 C NMR (101 MHz, CDCl 3 )δ 180.90,167.00,141.68,138.92,138.00,133.26,133.19,130.80,129.63,129.26,128.37,127.11,6 6.42,45.82,21.54,21.21,17.59,12.70;IR (thin film) 3240,2974,1713,1516,1258,1141,1055,806,728cm -1 ;HRMS-ESI(m / z)[M+H] + C 22 H 29 N 2 O 2 Calculated value for S: 385.1944; measured value: 385.1950.

[0100] Example 10E: Preparation of (Z)-2-methylbenzyl 4-((methoxy(methylamino)methylene)amino)-2,5-dimethylbenzoate [ka] A solution of 2-methylbenzyl 4-amino-2,5-dimethylbenzoate (0.22 g, 0.81 mmol) in trimethyl orthoformate (6 mL) was refluxed at 120° C. for 16 hours. The reaction mixture was then concentrated under reduced pressure to give 0.22 g of crude 2-methylbenzyl 4-((methoxymethylene)amino)-2,5-dimethylbenzoate as a pale yellow gummy liquid. The crude material was then dissolved in 1,4-dioxane (3 mL) and methanol (3 mL). To this solution was added N,O-dimethylhydroxylamine hydrochloride (0.97 g, 0.71 mmol) and triethylamine (0.09 mL, 0.71 mmol). The reaction mixture was then stirred at 80° C. in a sealed tube for 16 hours. The reaction mixture was concentrated under reduced pressure to give the crude material. The material was purified by preparative HPLC to give the title compound (12 mg, 4% yield) as an off-white solid. mp 90~92℃; 1 H NMR (400MHz, DMSO-d 6 )δ 7.67(s,1H),7.38(d,J=6.8Hz,1H),7.27-7.20(m,3H),6.62(s,1H),5.59-5.51(m,1H),5.2 8(s,2H),3.73(s,3H),2.54(d,J=4.8Hz,3H),2.43(s,3H),2.35(s,3H),2.01(s,3H);ESIMS m / z 341([M+H] + ).

[0101] Example 11: Preparation of (E)-4-(((ethyl(methyl)amino)methylene)amino)-2,5-dimethylbenzoic acid [ka] In a 25 mL vial, a solution of (E)-4-(((ethyl(methyl)amino)methylene)amino)-2,5-dimethylbenzoate (1.20 g, 4.83 mmol) was prepared in methanol (9.66 mL). Aqueous NaOH (1 M, 4.83 mL, 4.83 mmol) was then added and the reaction was heated to 60° C. and stirred overnight. After 18 h, the reaction was cooled to room temperature and concentrated to dryness. The reaction was redissolved in water (20 mL) and diluted with Et2 HCl (20 mL). The aqueous layer was acidified with dilute 1N HCl and extracted with DCM (3×20 mL). No material was observed in the organic layer, so the aqueous layer was concentrated to give the crude material. The material was purified by flash column chromatography (C18 reverse phase, 10→90% acetonitrile in water) to give the title compound (443 mg, 1.89 mmol, 39% yield) as a tan solid. 1 H NMR (400MHz, DMSO-d 6 )δ 12.94(s,1H),11.20(s,1H),8.40(d,J=56.6Hz,1H),7.76(s,1H),7.31(d,J=10.6Hz,1H),3.70(dq,J=46.9,7.1Hz,2H) ,3.30(d,J=2.6Hz,3H),2.50(dd,J=3.7,1.9Hz,2H),2.36(d,J=2.5Hz,3H),1.26(dt,J=9.7,7.1Hz,3H);mp>250℃;ESIMS m / z 335[(M+H) + ].

[0102] Example 12: Preparation of (Z)-3-(trifluoromethyl)benzyl 4-(((ethyl(methyl)amino)(methylthio)methylene)amino)-2,5-dimethylbenzoate [ka] A solution of 3-(trifluoromethyl)benzyl 4-(3-ethyl-3-methylthioureido)-2,5-dimethylbenzoate (0.050 g, 0.118 mmol) was prepared in acetone (1.18 mL). 2 CO 3 (0.033 g, 0.24 mmol) and iodomethane (10 μL, 0.16 mmol) were added. The mixture was then stirred at ambient temperature for 18 h. The reaction was then diluted with ethyl acetate (50 mL), filtered through Celite, and concentrated to an oil. The crude material was purified by flash column chromatography (silica gel (SiO 2 ), 0→70% ethyl acetate in hexanes) to give the title compound (49 mg, 0.11 mmol, 95% yield) as a clear oil.1 H NMR (500 MHz, CDCl 3 )δ 7.82-7.78(m,1H),7.71(d,J=1.8Hz,1H),7.64(d,J=7.6Hz,1H),7.59(d,J=7.8Hz,1H),7.51(t,J=7.7Hz,1H),6.68(s ,1H),5.35(s,2H),3.57(q,J=7.1Hz,2H),3.08(s,3H),2.54(s,3H),2.14(s,3H),1.94(s,3H),1.20(t,J=7.0Hz,3H); 19 F NMR (471MHz, CDCl 3 )δ -62.60;ESIMS m / z 439[(M+H) + ].

[0103] Example 13: Preparation of 3-(trifluoromethyl)benzyl 4-(((ethyl(methyl)amino)methylene)amino)-2,3-dimethylbenzoate hydrochloride [ka] (E)-3-(trifluoromethyl)benzyl 4-(((ethyl(methyl)amino)methylene)amino)-2,3-dimethylbenzoate was dissolved in heptane and transferred to a separatory funnel. 2N HCl was added and the resulting layers were separated. The heptane layer was discarded and the aqueous layer was extracted with ethyl acetate. The organic layer was concentrated to give 3-(trifluoromethyl)benzyl 4-(((ethyl(methyl)amino)methylene)amino)-2,3-dimethylbenzoate hydrochloride (237 mg, 0.553 mmol) as a light brown solid and a ca. 2:1 mixture of E:Z isomers. 1 H NMR (500 MHz, CDCl 3)δ 12.64-12.53(m,1H),7.95-7.86(m,1H),7.70-7.65(m,1H),7.65-7.57(m,3H),7.56-7.49(m,1H),7.28-7.22(m,0.6H),5.37(s ,2H),4.00(q,J=7.2Hz,0.6H),3.64(q,J=7.2Hz,1.4H),3.50(s,2H),3.33(s,1H),2.44(s,3H),2.38(s,3H),1.36-1.28(m,3H); 19 F NMR (471MHz, CDCl 3 ) δ -62.64; HRMS-ESI(m / z)[M+H] + C 21 H 23 F 3 N 2 O 2 Calculated value: 393.1784, measured value: 393.1793; mp 172-176℃.

[0104] Overall biological experiment details Example A: Evaluation of fungicidal activity: Wheat leaf spot (Zymoseptoria tritici; Bayer code SEPTTR): Technical grade material was dissolved in acetone, which was then diluted with 9 volumes of water containing 110 ppm Triton X-100 (H 2 The fungicide solutions were mixed with 100% ethanol (O). The fungicide solutions were applied to wheat seedlings until runoff using an automatic spray applicator. All sprayed plants were allowed to air dry before further handling. Unless otherwise stated, all fungicides were evaluated for their activity against all target diseases using the methods described above.

[0105] Wheat plants (variety "Yuma") were grown in a greenhouse with 7-10 seedlings per pot until the first leaf was fully emerged from the seed in soilless potting medium. The plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici either 3 days before fungicide treatment (3-day treatment; 3DC) or 1 day after fungicide treatment (1-day protectant; 1DP). After inoculation, the plants were kept at 100% relative humidity for 3 days to allow the spores to germinate and infect the leaves. The plants were then transferred to the greenhouse for disease to develop. When disease symptoms were fully expressed on the first leaf of untreated plants, the infection level was assessed on a disease severity scale of 0 to 100 percent. The percent disease control was calculated using the ratio of disease severity between treated and untreated plants.

[0106] Example B: Evaluation of fungicidal activity: Wheat leaf rust (Puccinia triticina; synonym: Puccinia recondita f.sp. tritici; Bayer code PUCCRT): Wheat plants (variety "Yuma") were grown in a greenhouse with 7-10 seedlings per pot until the first leaf was fully emerged from the seed in soilless potting medium. The plants were inoculated with an aqueous spore suspension of Puccinia triticina after fungicide treatment. After inoculation, the plants were kept overnight in a dark fog chamber at 100% relative humidity to allow the spores to germinate and infect the leaves. The plants were then transferred to the greenhouse for disease development. Fungicide formulations, applications and disease evaluation followed the procedures described in Example A.

[0107] Example C: Evaluation of fungicidal activity: Asian soybean rust (Phakopsora pachyrhizi; Bayer code PHAKPA): Technical grade material was dissolved in acetone, which was then diluted with 9 volumes of H2O containing 0.011% Tween 20. 2The fungicide solutions were applied to soybean seedlings until runoff using an automatic spray applicator. All sprayed plants were allowed to air dry before further handling.

[0108] Soybean plants (variety "Williams 82") were grown one plant per pot in soilless potting medium. Ten-day-old seedlings were used for the test. Plants were inoculated as described in Example A. Plants were incubated in a dark fog room at 100% relative humidity for 24 hours and then transferred to a growth room for disease development. Fungicide formulations and applications were made as described in Example A. When disease symptoms were fully developed, disease severity was assessed on the sprayed leaves on a scale of 0 to 100 percent. Percentage of disease control was calculated using the ratio of disease severity on treated and untreated plants.

[0109] Example D: Evaluation of fungicidal activity: Barley leaf spot (Rhynchosporium secalis; Bayer code RHYNSE): Barley plants (variety "Harrington") were grown in the greenhouse with 7-10 seedlings per pot until the first leaf was fully emerged from the seed in soilless potting medium. The plants were inoculated with an aqueous spore suspension of Rhynchosporium secalis after fungicide treatment. After inoculation, the plants were kept in a dark fog chamber at 100% relative humidity for 2 days to allow the spores to germinate and infect the leaves. The plants were then transferred to the greenhouse for disease development. Fungicide formulations and applications were made as described in Example A. Disease evaluations were performed as described in Example A.

[0110] Example E: Evaluation of fungicidal activity: Spot blotch of barley (Cochliobolus sativus; Bayer code COCHSA): Barley seedlings (variety Harrington) were propagated in soilless potting medium with pots containing 8-12 plants each and used for testing when the first leaf was fully emerged. Test plants were inoculated with a spore suspension of Cochliobolus sativus 24 hours after fungicide treatment. After inoculation, plants were kept at 100% relative humidity for 2 days to allow the spores to germinate and infect the leaves. Plants were then transferred to a greenhouse for disease development. Fungicide formulation, application and disease evaluation followed the procedures described in Example A.

[0111] [Table 1C-1]

[0112] [Table 1C-1]

[0113] [Table 1C-2]

[0114] [Table 1C-3]

[0115] [Table 1C-4]

[0116] [Table 1C-5]

[0117] [Table 1C-6]

[0118] [Table 1C-7]

[0119]

Table 1C-8

[0120]

Table 1C-9

[0121]

Table 1C-10

[0122]

Table 1C-11

[0123]

Table 1C-12

[0124]

Table 1C-13

[0125]

Table 1C-14

[0126]

Table 1C-15

[0127]

Table 1C-16

[0128]

Table 1C-17

[0129]

Table 1C-18

[0130]

Table 1C-19

[0131]

Table 1C-20

[0132]

Table 1C-21

[0133]

Table 1C-22

[0134]

Table 1C-23

[0135]

Table 1C-24

[0136]

Table 1C-25

[0137]

Table 1C-26

[0138]

Table 1C-27

[0139]

Table 1C-28

[0140]

Table 1C-29

[0141]

Table 1C-30

[0142]

Table 1C-31

[0143]

Table 1C-32

[0144]

Table 1C-33

[0145]

Table 1C-34

[0146]

Table 1C-35

[0147]

Table 1C-36

[0148]

Table 1C-37

[0149]

Table 1C-38

[0150]

Table 1C-39

[0151]

Table 1C-40

[0152]

Table 1C-41

[0153]

Table 1C-42

[0154]

Table 1C-43

[0155]

Table 1C-44

[0156]

Table 1C-45

[0157]

Table 1C-46

[0158]

Table 1C-47

[0159]

Table 1C-48

[0160]

Table 1C-49

[0161]

Table 1C-50

[0162]

Table 1C-51

[0163]

Table 1C-52

[0164]

Table 1C-53

[0165]

Table 1C-54

[0166]

Table 1C-55

[0167]

Table 1C-56

[0168]

Table 1C-57

[0169]

Table 1C-58

[0170]

Table 1C-59

[0171]

Table 1C-60

[0172]

Table 1C-61

[0173]

Table 1C-62

[0174]

Table 1C-63

[0175]

Table 1C-64

[0176]

Table 1C-65

[0177]

Table 1C-66

[0178]

Table 1C-67

[0179]

Table 1C-68

[0180]

Table 1C-69

[0181]

Table 1C-70

[0182]

Table 1C-71

[0183]

Table 1C-72

[0184]

Table 1C-73

[0185]

Table 1C-74

[0186]

Table 1C-75

[0187]

Table 1C-76

[0188]

Table 1C-77

[0189]

Table 1C-78

[0190]

Table 1C-79

[0191]

Table 1C-80

[0192]

Table 1C-81

[0193]

Table 1C-82

[0194]

Table 1C-83

[0195]

Table 1C-84

[0196]

Table 1C-85

[0197]

Table 1C-86

[0198]

Table 1C-87

[0199]

Table 1C-88

[0200]

Table 1C-89

[0201]

Table 1C-90

[0202]

Table 1C-91

[0203]

Table 1C-92

[0204]

Table 1C-93

[0205]

Table 1C-94

[0206]

Table 1C-95

[0207]

Table 1C-96

[0208]

Table 1C-97

[0209]

Table 2-1

[0210]

Table 2-2

[0211]

Table 2-3

[0212]

Table 2-4

[0213]

Table 2-5

[0214]

Table 2-6

[0215]

Table 2-7

[0216]

Table 2-8

[0217]

Table 2-9

[0218]

Table 2-10

[0219]

Table 2-11

[0220]

Table 2-12

[0221]

Table 2-13

[0222]

Table 2-14

[0223]

Table 2-15

[0224]

Table 2-16

[0225]

Table 2-17

[0226]

Table 2-18

[0227]

Table 2-19

[0228]

Table 2-20

[0229]

Table 2-21

[0230]

Table 2-22

[0231]

Table 2-23

[0232]

Table 2-24

[0233]

Table 2-25

[0234]

Table 2-26

[0235]

Table 2-27

[0236]

Table 2-28

[0237]

Table 2-29

[0238]

Table 2-30

[0239]

Table 2-31

[0240]

Table 2-32

[0241]

Table 2-33

[0242]

Table 2-34

[0243]

Table 2-35

[0244]

Table 2-36

[0245]

Table 2-37

[0246]

Table 2-38

[0247]

Table 2-39

[0248]

Table 2-40

[0249]

Table 2-41

[0250]

Table 2-42

[0251]

Table 2-43

[0252]

Table 2-44

[0253]

Table 2-45

[0254]

Table 2-46

[0255]

Table 2-47

[0256]

Table 2-48

[0257]

Table 2-49

[0258]

Table 2-50

[0259]

Table 2-51

[0260]

Table 2-52

[0261]

Table 2-53

[0262]

Table 2-54

[0263]

Table 2-55

[0264]

Table 2-56

[0265]

Table 2-57

[0266]

Table 2-58

[0267]

Table 2-59

[0268]

Table 2-60

[0269]

Table 2-61

[0270]

Table 2-62

[0271]

Table 2-63

[0272]

Table 2-64

[0273]

Table 2-65

[0274]

Table 2-66

[0275]

Table 2-67

[0276]

Table 2-68

[0277]

Table 2-69

[0278]

Table 2-70

[0279]

Table 2-71

[0280]

Table 2-72

[0281]

Table 2-73

[0282]

Table 2-74

[0283]

Table 2-75

[0284]

Table 2-76

[0285]

Table 2-77

[0286]

Table 2-78

[0287]

Table 2-79

[0288]

Table 2-80

[0289]

Table 2-81

[0290]

Table 2-82

[0291]

Table 2-83

[0292]

Table 2-84

[0293]

Table 2-85

[0294]

Table 2-86

[0295]

Table 2-87

[0296]

Table 2-88

[0297]

Table 2-89

[0298]

Table 2-90

[0299]

Table 2-91

[0300]

Table 2-92

[0301]

Table 2-93

[0302]

Table 2-94

[0303]

Table 2-95

[0304]

Table 2-96

[0305]

Table 2-97

[0306]

Table 2-98

[0307]

Table 2-99

[0308]

Table 2-100

[0309]

Table 2-101

[0310]

Table 2-102

[0311]

Table 2-103

[0312]

Table 2-104

[0313]

Table 2-105

[0314]

Table 2-106

[0315]

Table 2-107

[0316]

Table 2-108

[0317]

Table 2-109

[0318]

Table 2-110

[0319]

Table 2-111

[0320]

Table 2-112

[0321]

Table 2-113

[0322]

Table 2-114

[0323]

Table 2-115

[0324]

Table 2-116

[0325]

Table 2-117

[0326]

Table 2-118

[0327]

Table 2-119

[0328]

Table 2-120

[0329]

Table 2-121

[0330]

Table 2-122

[0331]

Table 2-123

[0332]

Table 2-124

[0333]

Table 2-125

[0334]

Table 2-126

[0335]

Table 2-127

[0336]

Table 2-128

[0337]

Table 2-129

[0338]

Table 2-130

[0339]

Table 2-131

[0340]

Table 2-132

[0341]

Table 2-133

[0342]

Table 2-134

[0343]

Table 2-135

[0344]

Table 2-136

[0345]

Table 2-137

[0346]

Table 2-138

[0347]

Table 2-139

[0348]

Table 2-140

[0349]

Table 2-141

[0350]

Table 2-142

[0351]

Table 2-143

[0352]

Table 2-144

[0353]

Table 2-145

[0354]

Table 2-146

[0355]

Table 2-147

[0356]

Table 2-148

[0357]

Table 2-149

[0358]

Table 2-150

[0359]

Table 2-151

[0360]

Table 2-152

[0361]

Table 2-153

[0362]

Table 2-154

[0363]

Table 2-155

[0364]

Table 2-156

[0365]

Table 2-157

[0366]

Table 2-158

[0367]

Table 2-159

[0368]

Table 2-160

[0369]

Table 2-161

[0370]

Table 2-162

[0371]

Table 2-163

[0372]

Table 2-164

[0373]

Table 2-165

[0374]

Table 2-166

[0375]

Table 2-167

[0376]

Table 2-168

[0377]

Table 2-169

[0378]

Table 2-170

[0379]

Table 2-171

[0380]

Table 2-172

[0381]

Table 3

[0382]

Table 4-1

[0383]

Table 4-2

[0384]

Table 4-3

[0385]

Table 4-4

[0386]

Table 4-5

[0387]

Table 4-6

[0388]

Table 4-7

[0389]

Table 4-8

[0390]

Table 4-9

[0391]

Table 4-10

[0392]

Table 4-11

[0393]

Table 4-12

[0394]

Table 4-13

[0395]

Table 4-14

[0396]

Table 4-15

[0397]

Table 4-16

[0398]

Table 4-17

Claims

1. Formula I: 【Chemistry 1】 (In the formula, R １ is C １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl, C ２ ~C ８ Alkynyl, C ２ ~C ８ Substituted alkynyl, C ３ ~C ８ Cycloalkyl, C ３ ~C ８ selected from the group consisting of substituted cycloalkyl, phenyl, substituted phenyl, benzyl, and substituted benzyl; Each R ２ , R ３ , R ４ and R ５ are independently hydrogen, halogen, cyano, nitro, C １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl, C ２ ~C ８ Alkenyl, C ２ ~C ８ Substituted alkenyl, C ２ ~C ８ Alkynyl, C ２ ~C ８ Substituted alkynyl, C １ ~C ８ Alkoxy and C １ ~C ８ substituted alkoxy; R ６ is hydrogen, C １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl, C ２ ~C ８ Alkenyl, C ２ ~C ８ Substituted alkenyl, C ２ ~C ８ Alkynyl, C １ ~C ８ Substituted alkynyl, C １ ~C ８ Alkoxy, C １ ~C ８ is selected from the group consisting of substituted alkoxy, thiol, alkylthio, and substituted alkylthio; or R ６ and R ７ are covalently bonded together and are saturated or non-aromatic unsaturated C ３ ~C ８ Heterocycloalkyl or C ３ ~C ８ It may form a substituted heterocycloalkyl group; Each R ７ and R ８ is independently １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl, C ２ ~C ８ Alkenyl, C ２ ~C ８ Substituted alkenyl, C ２ ~C ８ Alkynyl, C ２ ~C ８ Substituted alkynyl, C ３ ~C ８ Cycloalkyl, C ３ ~C ８ is selected from the group consisting of substituted cycloalkyl, benzyl and substituted benzyl; or R ７ and R ８ are covalently bonded together and are saturated or unsaturated C ３ ~C ８ Heterocycloalkyl or C ３ ~C ８ It may form a substituted heterocycloalkyl group; Any heterocyclic ring may contain up to three heteroatoms selected from the group consisting of O, N and S. or a tautomer or salt thereof, provided that said compound is is not ethyl 4-(dimethylaminomethylideneamino)benzoate, butyl 4-(dimethylaminomethylideneamino)benzoate, 2-(dimethylamino)ethyl 4-(dimethylaminomethylideneamino)benzoate, methyl 4-(dimethylaminomethylideneamino)benzoate, 1-(diethylamino)ethyl 4-(dimethylaminomethylideneamino)benzoate, 1-(diethylamino)ethyl 4-(dimethylaminomethylideneamino)benzoate dihydrochloride, ethyl 4-(((dimethylamino)methylene)amino)-3,5-dimethylbenzoate hydrochloride, or methyl 3-bromo-4-[(E)-dimethylaminomethylideneamino]benzoate.

2. R １ The compound of claim 1 , wherein is selected from the group consisting of benzyl and substituted benzyl.

3. R ２ and R ５ The compound according to claim 1 or 2, wherein both are hydrogen.

4. R ３ and R ４ are independently halogen, C １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl and C １ ~C ８ The compound of claim 3, wherein the compound is selected from the group consisting of alkoxy.

5. R ３ and R ４ Both are CH ３ 5. The compound of claim 4,

6. R ４ and R ５ The compound according to claim 1 or 2, wherein both are hydrogen.

7. R ２ and R ３ are independently halogen, C １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl and C １ ~C ８ 7. The compound of claim 6, selected from the group consisting of alkoxy.

8. R ２ and R ３ Both are CH ３ 8. The compound of claim 7,

9. Each R ７ and R ８ are independently hydrogen, C １ ~C ８ Alkyl, C １ ~C ８ Substituted alkyl, C ２ ~C ８ Alkenyl, C ３ ~C ８ and / or R is selected from the group consisting of cycloalkyl, benzyl and substituted benzyl. ６ is hydrogen, C １ ~C ８ Alkyl, C １ ~C ８ The compound of any one of claims 1 to 8, which is selected from the group consisting of substituted alkyl, thiol, alkylthio and substituted alkylthio.

10. The following table: Any one of the compounds of the above formula (I).

11. A fungicidal composition comprising a phytologically acceptable amount of a compound according to any one of formula I or any one of claims 1 to 10 and a carrier.

12. 12. The composition of claim 11, wherein the carrier is one or more of a thickener, an emulsifier, a rheological agent, a dispersant, and a polymer.

13. A method of controlling fungal attack on a plant, the method comprising contacting an area adjacent to the plant, soil adapted to support the growth of the plant, the roots of the plant and the leaves of the plant with a botanically tolerated amount of a compound according to any one of formula I or any one of claims 1 to 10 or a composition according to claim 11 or 12.

14. An antifungal agent comprising a compound according to any one of formula I or any one of claims 1 to 10 for use in controlling fungal pathogens.

15. The fungal pathogens include Zymoseptoria tritici, Cochliobolus sativus, Puccinia triticina, Puccinia striiformis, Venturia inaequalis, Ustilago maydis, Uncinula necator, Rhynchosporium commune, Magnaporthe grisea, and the like. grisea), Phakopsora pachyrhizi, Parastagonospora nodorum, Glomerella lagenarium, Cercospora beticola, Alternaria solani, Pyrenophora teres, Blumeria graminis f.sp. tritici, Blumeria graminis f.sp. tritici, Blumeria graminis f.sp. hordei f. sp. hordei, Erysiphe cichoracearum, Fusarium virguliforme, Rhizoctonia solani, Pythium ultimum and Botrytis cinerea, or the control of said fungal pathogens is selected from the group consisting of wheat leaf spot (Zymoseptoria tritici), barley leaf spot (Cochliobolus sativus), and sativus), wheat leaf rust (Puccinia triticina), yellow rust (Puccinia striiformis)striiformis), apple scab (Venturia inaequalis), corn blister (Ustilago maydis), grape powdery mildew (Uncinula necator), barley leaf spot (Rhynchosporium commune), rice blast (Magnaporthe grisea), Asian soybean rust (Phakopsora pachyrhizi), pachyrhizi), wheat burr blight (Parastagonospora nodorum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of turnip (Cercospora beticola), summer blight of tomato (Alternaria solani), net blotch of barley (Pyrenophora teres), powdery mildew of wheat (Blumeria graminis tritici differentiated), f. sp. tritici), powdery mildew of barley (Blumeria graminis f.sp.hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), sudden death syndrome of soybean (Fusarium virguliforme), neck rot or damping off of seedlings (Rhizoctonia solani), root rot (Pythium ultimum), grey mold (Botrytis cinerea), The antifungal agent of claim 14, comprising treating one of the following:

16. A composition for use in controlling fungal pathogens comprising a phytologically acceptable amount of a compound according to any one of formula I or any one of claims 1 to 10 and a carrier.

17. The fungal pathogens include Zymoseptoria tritici, Cochliobolus sativus, Puccinia triticina, Puccinia striiformis, Venturia inaequalis, Ustilago maydis, Uncinula necator, Rhynchosporium commune, Magnaporthe grisea, and the like. grisea), Phakopsora pachyrhizi, Parastagonospora nodorum, Glomerella lagenarium, Cercospora beticola, Alternaria solani, Pyrenophora teres, Blumeria graminis f.sp. tritici, Blumeria graminis f.sp. tritici, Blumeria graminis f.sp. hordei f. sp. hordei, Erysiphe cichoracearum, Fusarium virguliforme, Rhizoctonia solani, Pythium ultimum and Botrytis cinerea, or the composition is selected from the group consisting of the following diseases caused by the fungal pathogens: wheat leaf spot (Zymoseptoria tritici), barley leaf spot (Cochliobolus sativus), wheat staghorn foxtail (Cochliobolus satibus ... sativus), wheat leaf rust (Puccinia triticina), yellow rust (Puccinia striiformis)striiformis), apple scab (Venturia inaequalis), corn blister (Ustilago maydis), grape powdery mildew (Uncinula necator), barley leaf spot (Rhynchosporium commune), rice blast (Magnaporthe grisea), Asian soybean rust (Phakopsora pachyrhizi), pachyrhizi), wheat burr blight (Parastagonospora nodorum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of turnip (Cercospora beticola), summer blight of tomato (Alternaria solani), net blotch of barley (Pyrenophora teres), powdery mildew of wheat (Blumeria graminis tritici differentiated), f. sp. tritici), powdery mildew of barley (Blumeria graminis f.sp.hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), sudden death syndrome of soybean (Fusarium virguliforme), neck rot or damping off of seedlings (Rhizoctonia solani), root rot (Pythium ultimum), grey mold (Botrytis cinerea), 17. The composition of claim 16, wherein the disease is one of wheat leaf blight, barley leaf spot, wheat leaf rust, and Asian soybean rust.

18. Seeds treated with a phytologically acceptable amount of a compound according to any one of formula I or any one of claims 1 to 10.

Images