BR102017018526A2 - THYPICOLINAMIDE COMPOUNDS WITH FUNGICIDE ACTIVITY - Google Patents

Abstract

The present invention relates to thiopicolinamides of formula I and their use as fungicides.

Description

(54) Title: COMPOUNDS OF

THIOPICOLINAMIDE WITH FUNGICIDE ACTIVITY (51) Int. Cl .: C07D 211/04; C07D 213/02; A01N 33/10; A01N 43/40; A01P 3/00 (52) CPC: C07D 211/04, C07D 213/02, A01N 33/10, A01N 43/40 (30) Unionist Priority: 08/30/2016 US 62 / 381,268 (73) Holder (s) : DOW AGROSCIENCES LLC (72) Inventor (s): KYLE DEKORVER; KEVIN MEYER; CHENGLIN YAO; KARLA BRAVO ALTAMIRANO; RONALD HEEMSTRA (74) Attorney (s): DANNEMANN, SIEMSEN, BIGLER & IPANEMA MOREIRA (57) Abstract: The present invention relates to Formula I thiopicolinamides and their use as fungicides.

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Invention Patent Descriptive Report for THIOPICOLINAMIDE COMPOUNDS WITH FUNGICIDE ACTIVITY. BACKGROUND & SUMMARY [0001] Fungicides are compounds, of natural or synthetic origin, that act to protect and / or cure plants against damage caused by agriculturally relevant fungi. Generally, no fungicide alone is useful in all situations. As a result, research is underway to produce fungicides that can perform better, are easier to use and are cheaper. [0002] The present description refers to thiopicolinamides and their use as fungicides. The compounds of the present description can offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

[0003] One embodiment of the present description can include compounds of Formula I:

on what:

R ₁ is hydrogen or C 1 - C ₅ alkyl, substituted by 0, 1 or multiple R ₆ ;

R ₂ is hydrogen, C 1 - C ₅ alkyl or cycloalkyl, each optionally substituted by 0, 1 or multiple R ₆ ;

R ₃ is chosen from alkyl, cycloalkyl, alkenyl, aryl or heteroaryl, each optionally substituted by 0, 1 or multiple

King

R ₄ is chosen from alkyl, cycloalkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, each optionally substituted 870170072950, from 28/09/2017, p. 8/110

2/97 with O, 1 or multiple R ₆ ;

R ₅ is chosen from hydrogen, - C (O) R ₇ , or -CH ₂ OC (O) Ry

R ₆ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclyl, each optionally substituted by 0, 1 or multiple R ₈ ;

R ₇ is chosen from alkyl, alkoxy or aryl, each replaced by O, 1 or multiple R ₆ ;

R ₈ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy or heterocyclyl.

[0004] Another embodiment of the present description may include a fungicidal composition for the control or prevention of fungal attacks that comprises the compounds described above and a phytologically acceptable carrier material.

[0005] Yet another embodiment of the present description may include a method for controlling or preventing a fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more compounds described above to at least one among fungus, plant and an area adjacent to the plant.

[0006] It will be understood by those skilled in the art that the following terms may include generic R groups within their definitions, for example, the term alkoxy refers to a -OR substituent. It is also understood that, within the definitions for the following terms, these R groups are included for purposes of illustration and should not be construed as limiting or being limited by substitutions over Formula I.

[0007] The term alkyl refers to a branched, unbranched or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl,

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3/97 hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0008] The term alkenyl refers to a cyclic, branched or unbranched carbon chain containing one or more double bonds, including, but not limited to, ethylene, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cycle -hexenil and the like.

[0009] The term alkynyl refers to a branched or unbranched carbon chain containing one or more triple bonds, including, but not limited to, propynyl, butynyl and the like.

[0010] The terms aryl and Ar refer to any aromatic ring, mono- or bicyclic, containing 0 heteroatom.

[0011] The term heterocyclyl refers to any aromatic or non-aromatic ring, mono- or bicyclic, containing one or more heteroatoms. [0012] The term alkoxy refers to a substituent -OR.

[0013] The term acyloxy refers to a substituent -OC (O) R.

[0014] The term cyan refers to a substituent -C ^ N.

[0015] The term hydroxyl refers to a substituent -OH.

[0016] The term amino refers to a substituent -N (R) ₂ .

[0017] The term arylalkoxy refers to -O (CH ₂ ) „Ar where n is an integer selected from the list of 1,2, 3, 4, 5 or 6.

[0018] The term haloalkoxy refers to a substituent -OR-X, where X is Cl, F, Br, or I, or any combination thereof.

[0019] The term haloalkyl refers to an alkyl that is replaced by Cl, F, I or Br or any combination of these.

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

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

[0022] The term thioalkyl refers to a substituent -SR.

[0023] Throughout the description, the reference to the compounds of Formula I will be read as also including all stereoisomers, for example

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4/97 example, diastereomers, enantiomers and mixtures thereof. In another embodiment, Formula I is read as also including its salts or hydrates. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, hydroiodide, trifluoroacetate and trifluoromethane sulfonate.

[0024] It is also understood by those skilled in the art that additional substitution is permitted, unless otherwise noted, provided that the chemical bonding and voltage energy rules are satisfied and the product still exhibits fungicidal activity.

[0025] Another modality of the present description is the use of a compound of Formula I to protect a plant from being affected by a phytopathogenic organism or to treat a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I , or a composition comprising applying the compound to the soil, a plant, a part of the plant, foliage and / or roots.

[0026] In addition, another embodiment of the present description is a composition useful for protecting a plant from being affected by a phytopathogenic organism and / or for treating a plant infested by a phytopathogenic organism comprising a compound of Formula I and a suitable carrier material. . DETAILED DESCRIPTION [0027] The compounds of the present description can be applied by any of the varieties of known techniques, as well as the compounds or formulations comprising the compounds. For example, the compounds can be applied to the roots or foliage of plants to control various fungi, without damaging the commercial value of the plants. The materials can be applied in the form of any of the types of formulation generally used, for example, as solutions, powders, soluble powders, dispersible concentrates or conPetition 870170072950, of 28/09/2017, pg. 11/110

5/97 centered emulsifiable.

[0028] Preferably, the compounds of the present description are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations can be dispersed in water or other liquids for application, or formulations can be similar to powders or granules, which can then be applied without further treatment. The formulations can be prepared according to the procedures that are conventional in the agricultural chemistry technique.

[0029] This description covers all vehicles by which one or more of the compounds can be formulated for distribution and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions can be produced from water-soluble, water-suspended or emulsifiable formulations that are solid, generally known as soluble powders; or liquids generally known as emulsifiable concentrates, aqueous suspensions or suspension concentrates. As will be readily appreciated, any material to which these compounds can be added can be used, as long as it results in the desired utility without significant interference in the activity of these compounds as antifungal agents.

[0030] Soluble powders that can be compacted to form water-dispersible granules comprise an integral mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the soluble powder can be from about 10 percent to about 90 percent by weight based on the total weight of the soluble powder, more preferably, about 25 percent by weight to about 75 percent by weight . In the preparation of soluble powder formulations, the compounds can be combined with any solid

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6/97 finely divided, such as profilite, talc, chalk, plaster, Fuller's earth, bentonite, atapulgite, starch, casein, gluten, montmorillonite clay, diatomaceous earth, purified silicates or similar. In these operations, the finely divided vehicle and surfactants are typically mixed with the compound (s) and ground.

[0031] Emulsifiable concentrates of the compounds of Formula I can comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds can be dissolved in an inert vehicle that is a water-miscible solvent or a mixture of water-immiscible organic solvents and emulsifiers. The concentrates can be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high boiling naphthalene and olefinic portions of oil, such as heavy aromatic naphtha. Other organic solvents can also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone and complex alcohols, such as 2-ethoxyethanol.

[0032] Emulsifiers that can be used advantageously in this document can be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers or a mixture of two or more emulsifiers. Examples of non-ionic emulsifiers useful in the preparation of emulsifiable concentrates include polyalkylene glycol ethers and alkyl condensation products and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as alkyl phenols ethoxylated and carboxylic esters solubilized with polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. EmulsiPetição 870170072950, of 09/28/2017, p. 1/13

Anionic solids include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphate polyglycol ether. [0033] Representative organic liquids that can be used in the preparation of the emulsifiable concentrates of the compounds of the present description are aromatic liquids, such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids, such as dioctyl phthalate; kerosene; dialkyl amides of several fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives, such as n-butyl ether, ethyl ether or diethylene glycol methyl ether, triethylene glycol methyl ether, oil fractions or hydrocarbons, such such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, flaxseed oil, palm oil , peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids can also be used in the preparation of the emulsifiable concentrate. Organic liquids include xylene and propylene benzene fractions with xylene being the most preferred in some cases. Surface active dispersing agents are typically used in liquid formulations and in an amount of 0.1 to 20 weight percent based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.

[0034] Aqueous suspensions comprise suspensions of one or more water insoluble compounds of Formula I dispersed in a

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8/97 aqueous vehicle in a concentration in the range of about 1 to about 50 weight percent based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds and vigorously mixing the background material in a vehicle composed of water and surfactants chosen from the same types discussed above. Other compounds such as inorganic salts and synthetic or natural gums can also be added to increase the density and viscosity of the aqueous vehicle.

[0035] The compounds of Formula I can also be applied as granular formulations that are particularly useful for soil applications. Granular formulations generally contain from about 0.5 to about 10 weight percent based on the total weight of the granular formulation of the compound (s) dispersed in an inert vehicle that consists entirely or largely of divided inert material roughly as atapulgite, bentonite, diatomite, clay or a similar cheap substance. These formulations are generally prepared by dissolving the compounds in a suitable solvent and applying them in a granular vehicle that has been preformed to the appropriate particle size in the range of about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. These formulations can also be prepared by creating a mass or paste of the vehicle and the compound and solvent and grinding and drying to obtain the desired granular particle. [0036] The powders containing the compounds of Formula I can be prepared by thoroughly mixing one or more of the compounds in powder form with a suitable powdered agricultural carrier, such as, for example, kaolin clay, ground volcanic rock and the like . Powders may suitably contain from about 1 to about 10 weight percent of the compounds based on the total weight of the powder.

[0037] Formulations may additionally contain surfactants

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9/97 adjuvants to intensify the deposition, wetting and penetration of compounds in the target crop or organism. These adjuvant surfactants can optionally be used as a component of the formulation or as a tank mixture. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 volume percent based on the volume of water spray, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to, ethoxylated nonyl phenols, ethoxylated natural or synthetic alcohols, salts of sulfosuccinic esters or acids, ethoxylated organosilicon, ethoxylated fatty amines, mixtures of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); ethoxylated nonylphenol; benzylcocoalkylldimethyl quaternary ammonium salt; mixture of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C ₉ - Cn alkyl polyglycoside; phosphate alcohol ethoxylate; natural primary alcohol ethoxylate (C ₁₂ - C ₁₆ ); block copolymer of di-secbutylphenol EO-PO; polysiloxane-methyl cap; ethoxylated nonylphenol + urea and ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); ethoxylated tallow amine (15 EO); dioleate-99 of PEG (400). The formulations may also include oil-in-water emulsions such as those disclosed in US Patent Application Serial No. 11 / 495,228, the description of which is expressly incorporated by reference in this document.

[0038] Formulations may optionally include combinations that contain other pesticidal compounds. These additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present description in the medium selected for application, and not antagonistic to the activity of the present compounds. Consequently, in such modalities, ouPetição 870170072950, of 09/28/2017, p. 1/16

10/97 pesticide compound is used as an additional toxic product for the same pesticide or for a different pesticide use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of 1: 100 to 100: 1.

[0039] The compounds of the present description can also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present description are generally applied in conjunction with one or more other fungicides to control a wider range of undesirable diseases. When used in conjunction with other fungicide (s), the compounds currently claimed can be formulated with the other fungicide (s), mixed in the tank with the other pesticide (s) or applied sequentially with the other pesticide (s). These other fungicides may include 2- (thiocyanatomethylthio) -benzothiazole,

2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradine, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxistrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomile, bentiavalicarbenzylbenzyl, bicarbonate, bicarbonate biphenyl, bismertiazole, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalide, bromuconazole, bupyrimide, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamide, carvone, clazafenone, chloronitone, chloronebot, chloronebot , copper hydroxide, copper octanoate, copper oxychloride, copper sulphate, copper sulphate (tribasic), coumoxystrobin, cuprous oxide, cyazofamide, cyflufenamide, cymoxanil, cyproconazole, cyprodinyl, dazomet, debacarb, diamone (ethyl) carbamide). diclofluanide, dichlorophene, diclocimet, diclomezine, dichloran, dietofencarb, diphenoconazole, difenzoquat ion, diflumetorim, dimetomorfo, dimoxistro bina, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, diphymetitrone dithianon, dodemorfo, dodemorfo acetate, dodine, base

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11/97 dodine-free, edifenfos, enestrobin, enestroburin, enoxastrobin, epoxiconazole, etaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, phenaminostrobin, fenarimol, fenbuconazole, fenfuram, phenoxyphenate, phenoxyphenide, phenoxamine, phenoxamine, phenoxamine of fentin, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumorfo, fluopicolide, fluopiram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianyl, flutolanyl, fluorohydride, fluorohydride, fluorohydride , fuberidazole, furalaxil, furametpir, guazatin, guazatin acetates, GY-81, hexachlorobenzene, hexaconazole, himexazole, imazalil, imazalyl sulfate, imibenconazole, iminoctadine, iminoctadine, iminoctazol, trifacetone, iminoctazol, trinacethazine; , iprodione, iprovalicarb, isofetamid, isoprothiolane, isopirazam, isothianyl, casugamycin, hydrochloride of hydrated casugamycin, cresoxim-methyl, laminarin, mancobre, mancozeb, mandestrobin, mandipropamide, maneb, mefenoxam, mepanipyrim, mepronila, meptil-dinocap, mercuric chloride, mercuric oxide, mercury chloride, metalaxyl, methaxyl, metalaxyl, metalaxyl, metalaxyl, metalaxyl, , metam-potassium, metam-sodium, metconazole, metasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrotal-isopropyl, nuarimol, octilinone, offurace, oleic acids (oleic acids) orisastrobin, oxadixyl, oxatiapiproline, oxin-copper, oxpoconazole fumarate, oxycarboxine, pefurazoate, penconazole, pencicuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, pentiopirad, phenylmercury acetate, phosphoroxyoxyoxyoxyoxide, phaoxyoxyoxyoxide , potassium bicarbonate, hydroxyquinoline potassium sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propic onazole, propineb, proquinazid, protioconazole, pyraclostrobin, pirametostrobin, piraoxystrobin, pyraziflumid, pyrazophos,

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12/97 piribencarb, pyributicarb, pirifenox, pyrimethanil, pyriophenone, pyrisoxazole, pyroquilone, quinoclamine, quinoxifene, quintozene, Reynoutria sachalinensis extract, silkxane, siltiofam, simeconazole, sodium 2-phenyloxyphenoxide, sodium bicarbonate, sodium chloride sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, tifluzamide, thiophanate-methyl, extract, thiadinyl, tolclofos-methyl, tolprocarb, tolylfluanid, triadimide, triadimide, triadimide trifloxystrobin, triflumizole, triforin, triticonazole, validamycin, valifenalate, valifenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomypis (RS. , 5-dichlorophenyl) -2- (methoxymethyl) -succinimide, 1,2-dichloropropane, 1,3dichloro-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-dithinine 1,1,4,4-tetraoxide, 2-acetate -methoxyethylmercury, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3- (4-chlorophenyl) -5-methylrodanine, 4- (2-nitroprop-1-enyl) phenyl thiocyanate, ampropylphos, anilazine, azithiram, bile polysulfide , Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacryl-isobutyl, benzamorf, binapacryl, bis (methylmercury) sulfate, bis (tributyltin) oxide, butiobate, calcium copper and zinc cadmium chromate sulphate, carbamorph, ECSC, clobentiazone, chloramphoromethane, chlorfenazole, chlorine, bis Copper 3-phenylsalicylate), copper and zinc chromate, cufraneb, cupric hydrazinium sulphate, cuprobam, ciclafuramid, cipendazole, ciprofuram, decafentin, diclone, diclozoline, diclobutrazol, dimethyrimol, dinocton, dinosulfon, dinosulfon, dinosulfon, dinosulfon, dinosulfonate drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanila, fenitropano, fluotrimazol, furcarbanila, furconazol, furconazol-cis, furmeciclox, furofanato, gliodina, griseofulvina, halacrinato, 717, Hercules of 28/09/2017, p. 1/1910

13/97 ona, mebenyl, mecarbinzide, metazoxolon, metfuroxam, methylmercury diciandiamide, metsulfovax, milneb, mucochloric anhydride, miclozolin, A / -3,5-dichlorophenyl succinimide, / V-3-nitrophenylitaconimide, etamic, natamic -toluenesulfonanilide, nickel bis (dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, protiocarb; protiocarb hydrochloride, piracarbolid, pyridinitrile, pyroxychlor, pyroxifur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropene, weave, thiadifluoride, thiocyanin, thioclorphenphen, thiophanate, thioquinox, thioximide, triamiphos, triarimol, triazide, triazide, triazide, triazide, tridazide

[0040] Additionally, the compounds described in this document can be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present description in the medium selected for application, and not antagonistic to activity of the present compounds to form mixtures of pesticides and synergistic mixtures thereof. The fungicidal compounds of the present description can be applied in conjunction with one or more other pesticides to control a wider range of undesirable pests. When used in conjunction with other pesticides, the compounds currently claimed can be formulated with other pesticide (s), mixed in tank with other pesticide (s) or applied sequentially with other pesticide (s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acetion, acetoprol, acrinatrine, acrylonitrile, aphidopyropene, alanicarb, aldicarb, aldoxicarb, aldrin, aletrine, alosamidine, alipericarb, alpha-methetrone, alpha-methetrone, alpha-methetrone, alpha-methrone, alpha-methrim, alpha-metric-alpha , alpha-endosulfan, amidition, aminocarb, amiton, amiton oxalate, amitraz, anabasine, atidation, azadiraquitina, azametifos, azinfos-ethyl, azinfos-methyl, azotoato, hexafluorossiliPetição 870170072950, of 28/09/2017, p. 1/20

14/97 barium cato, bartrin, bendiocarb, benfuracarb, bensultap, betaciflutrin, beta-cypermethrin, bifenthrin, bioalethrin, bioethanometrine, biopermethrin, bistrifluron, borax, boric acid, broflanilide, bromofenviruses, bromocyclines, bromocyclines, bromocycles, bromocyclines, bromocyclines, bromocyclines, bromocyclines, bromocyclines, bromocyclines, bromocyclines ethyl, bufencarb, buprofezin, butacarb, butatiofos, butocarboxim, butonate, butoxicarboxim, cadusafos, calcium arsenate, calcium polysulfide, campheclor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbofenocarbon, carbofenox cartap, clorantraniliprol, clorbiciclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyphos, chlorfenapyr, chlorfenvinfos, chlorfluazuron, clormefos, chloroform, chloropicrin, chlorfoxin, chlorprazofos, chlorprazofos, chlorprazofos, chlorpyriformes, chlorprazofos, chlorprazofos cinerins, schismetrine, clacifos, cloetocarb, closantel, clothianidin, copper acetoarsenia, copper arsenate, naphth copper enate, copper oleate, coumafos, coumitoate, crotamiton, crotoxifos, crufomato, cryolite, cyanophenphos, cyanophos, cyantoate, cyantraniliprol, cyclaniliprol, cyclethrin, cycloprotrin, cyfluthrin, cytothyrin, cytothyrin, cyperothyrin, cyperothyrin, cyperothyrin, cyperothyrin, cyperothyrin, cyperothyrin, cyperothyrine deltamethrin, demefion, demefion-O, demefion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfon, diafentiuron, dialiphos, land of diatoms, diazinon, dicapton, diclofention, dichlorvos, dichloromezothiaz, dicresila, dicrotofos, dicyclanyl, dieldrin, diflubenzuron, dilor, dimeflutrina, dimefox, dimetan, dimetho, dimethine, dimethyl dine, dine, dinetine, dine, dine, dinetine diofenolan, dioxabenzofos, dioxacarb, dioxation, disulfoton, dichrophos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOCsodium, doramectin, ecdisterone, emamectin, emamectin benzoate, EMPC, endentine, endosulfan, endosulfan, endosulfan, endosulfan, endosulfan EPN, epophenonane, eprinomectin, sdepalethrin, sphenoperine, etafos, etiofencarb, etion, etiprol, etoate-methyl, etoprofos, ethyl formate, ethyl-DDD,

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15/97 ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimphos, EXD, famfur, fenamiphos, fenazaflor, fenclorfos, fenetacarb, fenflutrina, fenitrotion, fenobucarb, fenoxacrim, fenoxicarb, féntrin, féntrin, féntrin, fénatrin -ethyl, fenvalerate, fipronil, flometoquine, flonicamide, flubendiamide, flucofuron, flucicloxuron, flucitrinate, flufenerin, flufenoxuron, flufenprox, flufiprol, fluhexafon, flupiradurate, fluvirate, formofanhydrate, formulanate, formofanhydrate, formofanate , phospirate, fostietane, furatiocarb, furetrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptaflutrin, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroxy, hydroprene, hydroprene , indoxacarb, iodomethane, IPSP, isazophos, isobenzan, isocarbophos, isodrine, isofenphos, isofenfos-methyl, isoprocarb, isoprothiolane, isothioa to, isoxation, ivermectin, jasmine I, jasmine II, jodfenfos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kappa-bifentrine, kappa-teflutrin, quelevan, quinoprene, lambda-cyhalotine, lead arsenate, lepimectin, lepimectin, lepimectin, lepimectin lindane, lirimphos, lufenuron, litidation, malation, malonoben, mazidox, mecarbam, mecarfon, menazon, mefosfolan, mercury chloride, mesulfenphos, metaflumizone, metacrifos, metamidophos, metidene, metiocarb, methoxymetho, methoxymethoxy , methyl isothiocyanate, methylchloroform, methylene chloride, metoflutrin, metolcarb, methoxyzone, mevinfos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monfluorothrin, monocrotofos, nymphide, monome, monome nicotine, nifluridide, nitenpiram, nitiazine, nitrilacarb, novaluron, noviflumuron, ometoate, oxamyl, oxidemeton-methyl, oxideprofos, oxidisulfoton, para-dic lorobenzene, paration, paration-methyl, penfluron, pentachlorophenol, permethrin, fencapton, phenothrin, phentoate, phorate, fosalone, phospholane, fosmet, fosniPetition 870170072950, of 28/09/2017, pg. 22/110

16/97 chlor, phosphamidon, phosphine, foxim, foxim-methyl, pyrimetafos, pirimicarb, pyrimiphos-ethyl, pyrimiphos-methyl, potassium arsenate, potassium thiocyanate, ρρ'-DDT, praline, precocene I, precocene II, precocene III , primidofos, profenofos, profluralin, promacila, promecarb, propaphos, propetamphos, propoxur, protidation, prothiofos, prothoate, protrifenbute, piflubumide, pyraclofos, pirafluprol, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrin, pyridaben, piridalila, piridafention, pirifluquinazon , pyrimidifene, pyriminostrobin, pyrimitate, pyriprol, pyriproxifene, quassia, quinalfos, quinalfos-methyl, quinotion, rafoxanide, resmetrine, rotenone, riania, sabadila, scradan, selamectin, silica fluoride, silica gel, arsenic fluoride, arsenic, fluoride sodium, sodium thiocyanate, sofamide, spinetoram, spinosad, spiromesifene, spirotetramat, sulcofurone, sulcofurone-sodium, sulfluramide, sulfotep, sulfoxaflor, sulfuryl fluoride, su lprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpirade, tebupirimphos, teflubenzurone, teflutrin, temefos, TEPP, teralethrin, terbufos, tetrachloroethane, tetracetamethyl, tetramethyl, tetramethyl, tetramethyl, tetramethyl, tetramethyl tiocyclam, tiocyclam oxalate, thiodicarb, tiofanox, tiometon, tiosultap, tiosultap-disodium, tiosultap-monosodium, thuringiensin, thioxazafene, tolfenpirade, tralometrine, transflutrin, transpermetrin, triaratene, triazamate, trichlorohydrate, trichlorohydrate triflumezopyrim, triflumuron, trimetacarb, triprene, vamidotion, vaniliprol, XMC, xylilcarb, zetacipermethrin, zolaprofos, and any combinations thereof.

[0041] Additionally, the compounds described in this document can be combined with herbicides that are compatible with the compounds of the present description in the medium selected for application, and not antagonistic to the activity of the present compounds to form mixtures of pesticides and synergistic mixtures thereof. The fungicidal compounds of the present description can be applied together

Petition 870170072950, of September 28, 2017, p. 1/23

17/97 with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the compounds currently claimed can be formulated with the herbicide (s), mixed in tank with the herbicide (s) or applied sequentially with the herbicide (s). Typical herbicides include, but are not limited to: 4-CPA, 4-CPB, 4-CPP, 2,4-D, 3,4-DA, 2,4-DB, 3,4-DB, 2,4DEB, 2,4 -DEP, 3,4-DP, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, acetochlor, acifluorfen, aclonifen, alachlor, alidochlor, aloxidim, alorac, ametridione, ametrin , amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralide, amiprofos-methyl, amitrol, ammonium sulfamate, anilophos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotin, benflamine, benflamine, , bensulfuron-methyl, bensulide, bentiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoilprop, benztiazuron, bialafos, bicyclopyrone, biphenox, bilanafos, bispyrobromine, byribromine, byribromine, byribromine, bromobromine, bromibromine, bromibromine , bromoxynil, brompirazon, butachlor, butafenacil, butamiphos, butenachlor, butidazole, butiuron, butralin, butroxidim, buturon, butylate, cacodylic acid, cafenstrol, c chlorate calcium, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone-ethyl, CDEA, CEPC, clomethoxyfen, chloramben, chloranocrila, chlorazifop, chlorazine, chlorobromuron, chlorinamide, chloreturon, chlorphenyl, chlorphenol chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorprofam, clorsulfuron, chlortal, chlortiamid, cinidon-ethyl, cinmetilin, cinosulfuron, cisanilide, cletodim, cliodinate, clodinafop-propion, clodinafop- methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumiluron, cyanatrin, cyanazine, cyclopyrimorate, cyclosulfamuron, cycloxidine, cycluron, cihalofop-butyl, cyperquat, cyprazine, cyprazol, cypromide, dalap, dalap, dalap

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18/97 dazomet, delaclor, desmedifam, desmetrin, di-alate, dicamba, dichlobenyl, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop-methyl, diclosulam, dietamquat, diethyl, difenopenten, difenoxuron, difenoxuron, difenoxuron, difenoxuron, difenoxuron, difenoxuron, difenoxuron , dimetachlor, dimetametrin, dimetenamide, dimetenamide-P, dimexane, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamide, dipropetrin, diquat, disul, dithiopir, diuron, DMPA, DNOC, DSMA, EBEP, DSMA and EBEP, ; , fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, flucloralin, flufenacet, flufenican, flufenpir, flumetsulam, flumezi n, flumiclorac, flumioxazin, flumipropin, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluotiuron, flupoxam, flupropacil, flupropanate, flupirsulfuron, fluridone, flurochloridone, fluoroxen, fluoroxen, fluoroxen, fluroxyl, fluoroxen P, glyphosate, halauxifene, halauxifene, halosafen, halosulfuron, haloxidine, haloxifop, haloxifop-P, hexachloroacetone, hexaflurate, hexazinone, imazametabenz, imazamox, imazapic, imazapir, imaapon, imaaphon, imazapan, imamaquin, imazapan iofensulfuron, ioxinil, ipazin, ipfencarbazone, iprimidam, isocarbamide, isocyl, isometiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxaclortol, isoxaflutyl, isoxapyropyl, loxoxypropyl, isoxapyrate, isoxapyrate MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrion a, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, metabenztiazuron, metalpropalin, metazol, mePetition 870170072950, of 28/09/2017, p. 25/110

19/97 thiobencarb, metiozolin, metiuron, metometon, methoprotrin, methyl bromide, methyl isothiocyanate, methyldimron, metobenzuron, metobromuron, metolachlor, metosulam, methoxyuron, metribuzin, metsulfuron, moninuron, monolin, monolinide, monolinide, monolin morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, orfo-dichloronurine, oxorizonur, oxide oxazyclomefone, oxifluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimetalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, petoxamide, fenisofam, fenmedifam, phenmedifam-ethyl, pyrobenzene, phenobenzuron, penholamine potassium, potassium azide, potassium cyanide, pretilachlor, primisulfuron-methyl, prociazine, prodiamine, proflua zol, profluralin, profoxidim, proglinazine, prometon, prometrin, propachlor, propanyl, propaquizafop, propazine, profam, propisochlor, propoxycarbazone, propyrisulfuron, propizamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prinachlor, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine pirazosulfuron, pirazoxifen, piribenzoxim, piributicarb, piriclor, pyridafol, pyridate, pyriftalide, piriminobac, pirimisulfan, piritiobac, pyroxassulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamide, quizalofurac, rizalopyr, quizalofac, rizal, pyridine sebutilazine, secbumeton, setoxidim, siduron, simazine, simeton, simetrin, SMA, sodium arsenate, sodium azide, sodium chlorate, sulcotrione, sulfalate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglicapin, swep, TCA, teburam, tebutam, teb , tefuriltrione, tembotrione, tepraloxidim, terbacil, terbucarb, terbuclor, terbumeton, terbutilazine, terbutrin, tetrafluron, teni lclor, tiazafluron, tiazopir, tidiazimin, tidiazuron, tiencarbazonamethyl, tifensulfuron, thiobencarb, thiafenacil, tiocarbazil, thioclorin, tolpiPetition 870170072950, of 28/09/2017, p. 26/110

20/97 rate, topramezone, tralcoxidim, triafamone, tri-alate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridifan, trietazine, trifloxisulfuron, trifludimoxazin, trifluralin, trifluridone, triflhittron, triflhtrifluorhin , vernolate and xylachlor. [0042] Another modality of the present description is a method of controlling or preventing an attack by fungi. This method includes application to the soil, plant, roots, foliage, or the fungus site, or to a location where infestation is to be prevented (for example, application to grains or vines), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for the treatment of various plants at the fungicide level, while having low phytotoxicity. The compounds can be useful both in a protective and / or eradicating manner.

[0043] The compounds were found to have a significant fungicidal effect on for agricultural use. Many compounds are particularly effective for use with agricultural crops and horticultural plants. [0044] It will be understood by those skilled in the art that the effectiveness of the compound for the previously exposed fungi establishes the general utility of the compounds as fungicides.

[0045] The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, the causative agent of Wheat Leaf Stain (Zymoseptoria tritici), Brown Wheat Rust (Puccinia triticina), Cool Wheat Rust (Puccinia striiformis), Apple Scab (Venturia inaequalis), Oídio Vine (Uncinula necator), Barley Scald (Rhynchosporium secalis), Rice Blast (Pyricularia oryzae), Soybean Rust (Phakopsora pachyrhizi), Wheat Glaze (Leptosphaeria nodorum), Wheat Oid (Blumeria grumamin. . tritici), Barium Powder (Blumeria graminis f. sp. hordei), Powder Powder Powder, 870170072950, of 28/09/2017, p. 27/110

21/97 curbitáceas (Erysiphe cichoracearurri), Cucurbit anthracnose (Glomerella lagenarium), Beet leaf spot (Cercospora beticola), Tomato black spot (Alternaria solani) and Brown barley spot (Cochliobolus sativus). The exact amount of active material to be applied depends not only on the specific active material being applied, but also on the specific action desired, the species of fungi to be controlled and the stage of their growth, as well as the part of the plant or of another product that should come into contact with the compound. Thus, all compounds and formulations containing the same, may not be equally effective at similar concentrations or against the same species of fungi. [0046] The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term disease-inhibiting and phytologically acceptable amount refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but which is not significantly toxic to the plant. This amount will generally be about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of the required compound varies with the fungal disease to be controlled, the type of formulation used, the method of application, the specific plant species, the climatic conditions and the like. An appropriate application rate typically ranges from about 0.01 to 0.45 grams per square meter, g / m ² (0.10 to about 4 pounds / acre).

[0047] Any desired range or value mentioned in this document can be extended or changed without losing the intended effects, as is evident to those skilled in the art to understand the teachings contained in this document.

[0048] The compounds of Formula I can be made using well-known chemical procedures. Intermediaries do not mention Petition 870170072950, of 28/09/2017, p. 1/28

22/97 of those specifically in this description are commercially available, can be made by the routes disclosed in the chemical literature, or can be easily synthesized from commercial raw materials, using standard procedures.

GENERAL SCHEMES [0049] The following schemes illustrate approaches for generating Formula I thiopicolinamide compounds. The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.

[0050] The compounds of Formula I, in which R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as originally defined, can be prepared according to the methods outlined in Scheme 1, steps a and b. The compounds of Formula 1.0, where R ₁ , R ₂ , R ₃ and R ₄ are as originally defined, can be prepared as described by the procedures outlined in US patent applications WO 2016/109289, WO 2016/109300, WO 2016 / 109257, WO 2016/109302 and WO 2016/109304. The compounds of Formula 1.0 can be treated with a thionation reagent, such as phosphorus pentasulfide, an additive, such as hexamethyldisiloxane, optionally in a polar aprotic solvent, such as acetonitrile (CH ₃ CN), at a temperature of about 0 Ό to 80 Ό to generate the compounds of Formula 1.1, wherein R ;, R ₂ , R ₃ and R ₄ are as originally defined, as shown in a. It will be understood by those skilled in the art that compounds, such as those of Formula 1.1, can also be prepared using other thioning agents, including, but not limited to: sulfur, sulfuric acid, sodium sulfide, sodium hydrosulfide, boron trisulfide , bis (diethylaluminum) sulfide, ammonium sulfide, Lawesson's reagent, Ο dithiophosphate, Ο'-diethyl ammonium, rhodanine, or a polymer supported thioning reagent. Additives may include, but are not limited to, Petition 870170072950, of 28/09/2017, p. 1/29

23/97 of a, aluminum oxide (AI ₂ O ₃ ); inorganic bases, such as potassium carbonate and sodium bicarbonate; organic bases, such as triethylamine, diethylaniline, pyridine and morpholine. Optional solvents may include, but are not limited to, aliphatic, alicyclic or aromatic hydrocarbons, such as hexane, cyclohexane or toluene; halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane and chlorobenzene; ethers, such as diethyl ether, 1,4-dioxane, THF and 1,2-dimethoxyethane; and other polar aprotic solvents, such as pyridine and hexamethylphosphoramide (HMPA). In step b, the treatment of the compounds of Formula 1.1, wherein R ₁ , R ₂ , R ₃ and R ₄ are as originally defined, with an appropriate aikyl halide with or without reagent, such as sodium iodide (Nal) and an alkali carbonate base, such as sodium carbonate (Na ₂ CO ₃ ) or potassium carbonate (K ₂ CO ₃ ), in a solvent such as acetone at a temperature of about 55 Ό, or by treatment with a halide or anhydride of acyl in the presence of an amine base, such as pyridine, triethylamine (Et ₃ N), DMAP, or mixtures thereof, in an optional aprotic solvent, such as DCM, at a temperature of about 23 Ό, to generate the compounds of Formula I, wherein R ₄ , R ₂ , R ₃ , R ₄ and R ₅ are as originally defined.

EXAMPLES

[0051] Example 1: Preparation of (1R, 2S) -1- (2-chlorophenoxy) -1-phenylpropan-2ila (3-hydroxy-4-methoxypyridine-2carbonothioyl) -L-alaninate. Compound 22.

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24/97

[0052] To a (1R, 2S) -1- (2-chlorophenoxy) -1-phenylpropan-2-yl (3-hydroxy-4-methoxypolycolinoyl) -L-alaninate (WO 2016/109304) (0,100 g, 0.206 mmol) in acetonitrile (1 ml), phosphorus pentasulfide (0.092 g, 0.412 mmol) and 1,1,1,3,3,3-hexamethyldisiloxane (0.220 ml, 1.031 mmol) were added. The mixture was heated to 45 ° C for 30 min. The mixture was diluted with EtOAc (10 ml) and the reaction was stopped with NaHCO ₃ (10 ml). The organic phase was stirred and separated and the products extracted with EtOAc (2x10 ml). The combined organic products were passed through a phase separator and concentrated under reduced pressure. The crude residue was purified by flash chromatography (4 g silica column) using a mixture of 5-60% acetone / hexanes as the eluent to provide the title compound (83 mg, 0.166 mmol, 80% yield) like a yellow foam. ¹ H NMR (400 MHz, CDCI ₃ ) δ 12.83 (s, 1H), 10.62 (d, J = 7.5 Hz, 1H), 7.95 (d, J = 5.1 Hz, 1H ), 7.45 - 7.38 (m, 2H), 7.37 - 7.28 (m, 4H), 6.99 (ddd, J = 8.3, 7.5, 1.7 Hz, 1H ), 6.86 (d, J = 5.1 Hz, 1H), 6.81 (td, J = 7.7, 1.4 Hz, 1H), 6.65 (dd, J = 8.4, 1.5 Hz, 1H), 5.42 - 5.35 (m, 1H), 5.29 (d, J = 4.8 Hz, 1H), 5.03 (p, J = 7.2 Hz, 1H), 3.95 (d, J = 2.8 Hz, 3H), 1.46 (d, J = 6.4 Hz, 3H), 1.42 (d, J = 7.2 Hz, 3H) . IR (thin film) 2937, 1735, 1512, 1481, 1274, 1245, 1201, 1059, 728 cm ^-1 . HRMS-ESI (m / z) ([M + H] +) calculated for C25H26CIN2O5S, 501.1245; found, 501.1272.

[0053] Example 2: Preparation of (1R, 2S) -1- (2-chlorophenoxy) -1-phenylpropan (2-acetoxy-4-methoxypyridine-2carbonothioyl) -L-alaninate. Compound 57.

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25/97

[0054] To a stirred solution of (1R, 2S) -1- (2-chlorophenoxy) -1-phenylpropan-2ila (3-hydroxy-4-methoxypyridine-2carbonothioyl) -L-alaninate (Compound 22) (0.066 g , 0.132 mmol) in pyridine (0.5 mL, 6.21 mmol) acetic anhydride (0.5 mL, 5.30 mmol) was added. The mixture was stirred at room temperature for 30 min. The mixture was then concentrated under reduced pressure. The residue was purified by flash chromatography (4 g of silica column) using a mixture of 560% acetone / hexanes as the eluent to provide the title compound (54 mg; 75%) as a yellow foam. ¹ H NMR (400 MHz, CDCb) δ 9.86 (d, J = 7.2 Hz, 1H), 8.28 (dd, J = 5.4, 0.9 Hz, 1H), 7.45 7 , 37 (m, 2H), 7.36 - 7.27 (m, 4H), 7.02 - 6.93 (m, 2H), 6.81 (td, J = 7.6, 1.4 Hz , 1H), 6.67 (dd, J = 8.3, 1.4 Hz, 1H), 5.41 - 5.32 (m, 1H), 5.28 (d, J = 4.8 Hz, 1H), 5.13 (p, J = 7.1 Hz, 1H), 3.89 (s, 3H), 2.34 (s, 3H), 1.46 (d, J = 6.4 Hz, 3H), 1.35 (d, J = 7.2 Hz, 3H). IR (thin film) 2983, 1768, 1739, 1481, 1192, 1175, 731 cm ^-1 . HRMS-ESI (m / z) ([M + H] +) calculated for C ₂ 7H28CIN ₂ O ₆ S, 543.1351; found, 543.1382.

[0055] The compounds of the present description, their method of preparation, and appearance are shown below in Table 1. The analytical data for the compounds shown in Table 1 are shown in Table 2 below.

[0056] Example A: Fungicidal Activity Evaluation: Wheat leaf spot (Zymoseptoria tritici; Bayer SEPTTR code):

[0057] The technical grades of the materials were dissolved in acetone, and were then mixed with nine volumes of water (H ₂ O) containing 110 ppm of Triton X-100. Fungicide solutions

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26/97 were applied to wheat seedlings using a cabin sprayer to cover superficially. All sprayed plants were allowed to dry in the open air for later handling. All fungicides were evaluated using the method mentioned above for their activity vs. all target diseases, unless otherwise specified. The activity of leaf spot and brown rust of wheat were also evaluated using spray applications in trails, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.

[0058] Wheat plants (variety Yuma) were grown from seeds in a greenhouse in a Metro mixture 50% mineral soil / 50% without soil until the first leaf emerged completely, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici before or after fungicide treatments. After inoculation, the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a dew chamber lit at 20 ° C) to allow the spores to germinate and infect the leaf. The plants were then transferred to a 20Ό greenhouse for the disease to develop. When the symptoms of the disease were fully expressed in the 1 ^to leaves of untreated plants, the levels of infection were assessed on a scale of 0 to 100 percent severity of the disease. The percentage of disease control was calculated using the ratio of disease severity in treated plants to untreated plants. The results of the assessment are shown below in Table 4.

[0059] Example B: Evaluation of Fungicidal Activity: Brown wheat rust (Puccinia triticina ', synonym: Puccinia recondita f. Sp. Tritici', Bayer PUCCRT code):

[0060] Wheat plants (variety Yuma) were grown from

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27/97 seeds in a greenhouse in a Metro mixture 50% mineral soil / 50% without soil until the first leaf emerges completely, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia trithycin before or after fungicide treatments. After inoculation, the plants were kept in a dark dew environment at 22 ° C with 100% relative humidity overnight to allow the spores to germinate and infect the leaf. The plants were then transferred to a 24Ό greenhouse for the disease to develop e. Fungicide formulation, application and evaluation of the disease followed by the procedures as described in Example A. The results of the evaluation are shown below in Table 4.

[0061] Example C: Fungicidal Activity Assessment: Asian soybean rust (Phakopsora pachyrhizr, Bayer PHAKPA code):

[0062] The technical grades of the materials were dissolved in acetone, and were then mixed with nine volumes of water H ₂ O containing 0.011% Tween 20. The fungicide solutions were applied to soybean seedlings using a cabin spray to cover superficially . All sprayed plants were allowed to dry in the open air for later handling.

[0063] Soy plants (variety Williams 82) were grown in a Metro mix without soil, with one plant per pot. Two-week seedlings were used for testing. The plants were inoculated 3 days before or 1 day after fungicide treatments. The plants were incubated for 24 hours in a dark environment with dew at 22 Ό and 10% relative humidity and then transferred to a growth environment at 23 Ό for the disease to develop. The severity of the disease was assessed in the sprayed leaves. The results of the assessment are shown below in Table 5.

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Table 1. Compound Structure, Preparation Method and Appearance

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Compound # - compound number

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Table 2. Analytical data

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Table 3. Biological Test Classification Scale

Classification table for fungal pathogens % of control Classification > 80 THE <80 B Not tested Ç No activity observed in the Reported Trial D

Table 4. Biological activity - PUCCRT and SEPTTR disease control in high and low volume applications

HV activity at 100 ppm LV activity at 121.5 g / H PUCCRT * SEPTTR * PUCCRT * SEPTTR * Compound No. 1DP * 3DC * 1DP * 3DC * 1DP * 3DC * 1DP * 3DC * 1 THE THE B B Ç Ç Ç Ç 2 THE D THE THE Ç Ç Ç Ç 3 THE D THE THE Ç Ç Ç ç 4 THE D THE THE Ç Ç Ç ç 5 THE D THE THE Ç Ç Ç ç 6 THE B THE THE Ç Ç Ç ç 7 B D B D Ç Ç Ç ç 8 THE D B B Ç Ç ç ç 9 THE D THE THE Ç Ç ç ç 10 B D D D Ç Ç ç ç 11 THE THE THE B Ç Ç ç ç 12 THE B THE B Ç ç ç ç 13 THE B THE THE Ç ç ç ç 14 THE B THE THE Ç ç ç ç 15 D D THE D Ç ç ç ç 16 THE THE THE B Ç ç ç ç 17 THE D B D Ç ç ç ç 18 THE THE THE THE Ç ç ç ç 19 THE THE THE D Ç ç ç ç 20 THE B THE THE Ç ç ç ç

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HV activity at 100 ppm LV activity at 121.5 g / H PUCCRT * SEPTTR * PUCCRT * SEPTTR * Compound No. 1DP * 3DC * 1DP * 3DC * 1DP * 3DC * 1DP * 3DC * 21 D D B B Ç Ç Ç Ç 22 THE B THE B Ç Ç Ç Ç 23 THE B THE THE Ç Ç Ç Ç 24 THE B THE THE Ç Ç Ç Ç 25 B D D D Ç Ç Ç Ç 26 THE B THE THE Ç Ç Ç Ç 27 B D D B Ç Ç Ç Ç 28 D D D D Ç Ç Ç Ç 29 THE THE THE THE Ç Ç Ç Ç 30 THE B THE THE Ç Ç Ç Ç 31 THE B THE THE Ç Ç Ç Ç 32 B B B THE Ç Ç Ç Ç 33 THE THE THE B Ç Ç Ç Ç 34 D D B D Ç Ç Ç Ç 35 THE B THE THE Ç Ç Ç Ç 36 THE THE THE B Ç Ç Ç Ç 37 THE THE B D Ç Ç Ç Ç 38 THE THE THE B Ç Ç Ç Ç 39 B B THE THE Ç Ç Ç Ç 40 Ç Ç Ç Ç D B D D 41 Ç Ç Ç Ç THE THE THE THE 42 Ç Ç Ç Ç B B B D 43 Ç Ç Ç Ç THE THE THE B 44 Ç Ç Ç Ç THE B THE THE 45 Ç Ç Ç Ç THE THE THE THE 46 Ç Ç Ç Ç THE THE THE THE 47 Ç Ç Ç Ç THE B THE THE 48 Ç Ç Ç Ç THE D THE THE 49 Ç Ç Ç Ç B D B D 50 Ç Ç Ç Ç THE THE THE THE 51 Ç Ç Ç Ç THE B THE THE 52 Ç Ç Ç Ç THE B THE THE

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HV activity at 100 ppm LV activity at 121.5 g / H PUCCRT * SEPTTR * PUCCRT * SEPTTR * Compound No. 1DP * 3DC * 1DP * 3DC * 1DP * 3DC * 1DP * 3DC * 53 Ç Ç Ç ç THE B THE THE 54 Ç Ç ç ç THE D THE THE 55 Ç Ç ç ç D D B D 56 Ç Ç ç ç THE THE B B 57 Ç Ç ç ç THE B THE THE 58 Ç Ç ç ç THE THE THE THE 59 Ç Ç ç ç B B THE D 60 Ç ç ç ç THE THE B B 61 Ç ç ç ç THE THE B THE 62 Ç ç ç ç THE THE B D 63 Ç ç ç ç THE B THE THE 64 Ç ç ç ç THE B THE THE 65 Ç ç ç ç THE THE THE THE 66 Ç ç ç ç B B D D 67 Ç ç ç ç THE B THE THE 68 Ç ç ç ç D B B D 69 Ç ç ç ç B B D B 70 Ç ç ç ç THE THE THE THE 71 Ç ç ç ç THE THE THE B 72 Ç ç ç ç THE THE THE THE 73 Ç ç ç ç THE THE THE THE 74 ç ç ç ç THE B THE THE 75 ç ç ç ç THE B THE THE 76 ç ç ç ç D D D D 77 ç ç ç ç THE THE B THE 78 ç ç ç ç THE B THE THE

‘Compound No. - Compound number‘ PUCCRT - Brown Rust of Wheat (Puccinia triticina) ‘SEPTTR - Wheat Leaf Stain (Zymoseptoria tritici)

Ί DP - 1 Day Protection ‘3DC - 3 Day Healing

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Table 5. Biological activity - Disease control at 25 ppm

PHAKPA * Compound No. 1DP * 3DC * 40 B D 61 THE THE 62 B B 63 THE B 64 THE THE 65 THE B 66 B B 67 THE B 68 B D 69 B D 70 THE B 71 B D 72 THE THE 73 THE THE 74 B B 75 B B 76 B D 77 THE B 78 B D

‘Compound # - compound number‘ PHAKPA - Asian Rust from So] a (Phakopsora pachyrhizi) Ί DP - 1 Day Protection ‘3DC - 3 Day Healing

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Claims (17)

1. Composition for the control of a fungal pathogen, characterized by the fact that it includes mixtures of at least one of the compounds of Formula I, in which: R ₁ is hydrogen or C ₁ - C ₅ alkyl, substituted by 0, 1 or multiple R ₆ ; R ₂ is hydrogen, C ₁ - C ₅ alkyl or cycloalkyl, each optionally substituted by 0, 1 or multiple R ₆ ; R ₃ is alkyl, cycloalkyl, alkenyl, aryl or heteroaryl, each optionally substituted by 0, 1 or multiple R ₆ ; R ₄ is alkyl, cycloalkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, each optionally substituted by 0, 1 or multiple R ₆ ; R ₅ is hydrogen, - C (O) R ₇ , or -CH ₂ OC (O); R ₆ is hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclyl, each optionally substituted by 0, 1 or multiple R ₈ ; R ₇ is among alkyl, alkoxy, or aryl, each replaced by 0, 1 or multiple R ₆ ; R ₈ is hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; and a phytologically acceptable carrier material. 2. Composition according to claim 1, characterized by the fact that R ₅ is hydrogen. Petition 870170072950, of September 28, 2017, p. 105/110 2/5 Composition according to claim 2, characterized by the fact that R ₁ is methyl, R ₂ is C ₁ - C ₅ alkyl, R ₃ and R ₄ are independently aryl, each optionally substituted by 0, 1, or multiple R ₆ . 4. Composition, according to claim 1, characterized by the fact that R ₅ is chosen from - C (O) R ₇ or CH ₂ OC (O) R ₇ . 5. Composition according to claim 4, characterized by the fact that R ₇ is alkyl optionally substituted by 0, 1, or multiple R ₆ . 6. Composition according to claim 5, characterized by the fact that R ₁ is methyl, R ₂ is C ₁ - C ₅ alkyl, R ₃ and R ₄ are independently aryl, each optionally substituted by 0, 1, or multiple R ₆ . 7. Compound according to claim 6, characterized by the fact that R _g is chosen from -CH ₃ , -CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -cyclopropyl. 8. Composition, according to claim 1, characterized by the fact that the fungal pathogen is one among Wheat Leaf Spot (Zymoseptoria tritici), Brown Rust Wheat (Puccinia triticina), Striated Rust (Puccinia striiformis), Scabies of the Apple Tree (Venturia inaequalis), Common Corn Coal (Ustilago maydis), Powdery Mildew (Uncinula necator), Barley Scald (Rhynchosporium secalis), Rice Blast (Pyricularia oryzae), Soybean Rust (Phakopsora pachyrhizi), Manuma da Pachyrhizi) Wheat (Leptosphaeria nodorum), Wheat Mildew (Blumeria graminis f. Sp. Tritici), Barley Mildew (Blumeria graminis f. Sp. Hordei), Cucurbit Mildew (Erysiphe cichoracearum), Cucurbitaceae Anthracnose (Colletotrichum) Beet (Cercospora beticola), Pinta Preta do Tomate (Alternaria solani) and Reticular Spot Petition 870170072950, of September 28, 2017, p. 106/110 3/5 Barley (Pyrenophora teres). 9. Composition, according to claim 3, characterized by the fact that the fungal pathogen is one of the Wheat Leaf Spot (Zymoseptoria tritici), Brown Rust Wheat (Puccinia triticina), Apple Scab (Venturia inaequalis), Scald of the Barley (Rhynchosporium secai is), Rice Blast (Pyricularia oryzae), Soybean Rust (Phakopsora pachyrhizi), Wheat Glaze (Leptosphaeria nodorum), Cucurbit Anthracnose (Colletotrichum lagenarium) and Mancha Foliar Pinta Preta do Tomate (Alternaria solani). 10. Composition according to claim 4, characterized by the fact that the fungal pathogen is one of the Wheat Leaf Spot (Zymoseptoria tritici), Brown Rust Wheat (Puccinia triticina), Apple Scab (Venturia inaequalis), Scald of the Barley (Rhynchosporium secai is), Rice Blast (Pyricularia oryzae), Soybean Rust (Phakopsora pachyrhizi), Wheat Glaze (Leptosphaeria nodorum), Cucurbit Anthracnose (Colletotrichum lagenarium) and Mancha Foliar Pinta Preta do Tomate (Alternaria solani). 11. Composition, according to claim 6, characterized by the fact that the fungal pathogen is one among Wheat Leaf Spot (Zymoseptoria tritici), Brown Rust Wheat (Puccinia triticina), Apple Scab (Venturia inaequalis), Scald of the Barley (Rhynchosporium secai is), Rice Blast (Pyricularia oryzae), Soybean Rust (Phakopsora pachyrhizi), Wheat Glaze (Leptosphaeria nodorum), Cucurbit Anthracnose (Colletotrichum lagenarium) and Mancha Foliar Pinta Preta do Tomate (Alternaria solani). 12. Composition, according to claim 7, characterized by the fact that the fungal pathogen is one among Leaf Spot Petition 870170072950, of September 28, 2017, p. 107/110 4/5 Wheat (Zymoseptoria tritici), Brown Wheat Rust (Puccinia triticina), Apple Scab (Venturia inaequalis), Barley Scald (Rhynchosporium secai is), Rice Brusone (Pyricularia oryzae), Soybean Rust (Phakhops) ), Wheat Glume Spot (Leptosphaeria nodorum), Cucurbit Anthracnose (Colletotrichum lagenarium), Beet Leaf Spot (Cercospora beticola) and Pinta Preta do Tomate (Alternaria solani). 13. Method for controlling and preventing a fungal attack in a plant, characterized by the fact that the method includes the step of: applying a fungicidally effective amount of at least one of the compositions, as defined in claim 3, to at least one of the plant, an area adjacent to the plant, the soil adapted to support the growth of the plant, the root of the plant, and the foliage of the plant. 14. Method for controlling and preventing a fungal attack in a plant, characterized by the fact that the method includes the step of: applying a fungicidally effective amount of at least one of the compositions, as defined in claim 6, to at least one of the plant, an area adjacent to the plant, the soil adapted to support the growth of the plant, the root of the plant, and the foliage of the plant. 15. Method for controlling and preventing a fungal attack in a plant, characterized by the fact that the method includes the step of: applying a fungicidally effective amount of at least one of the compositions, as defined in claim 7, to at least one of the plant, an area adjacent to the plant, the soil adapted to support the growth of the plant, the root of the plant, and the foliage gives Petition 870170072950, of September 28, 2017, p. 108/110 5/5 plant. 16. Method for controlling and preventing a fungal attack in a plant, characterized by the fact that the method includes the step of: applying a fungicidally effective amount of at least one of the compositions, as defined in claim 8, to at least one of the plant, an area adjacent to the plant, the soil adapted to support the growth of the plant, the root of the plant, and the foliage of the plant. 17. Method for control and prevention of fungal attack in a plant, characterized by the fact that the method includes the step of: applying a fungicidally effective amount of at least one of the compositions, as defined in claim 12, to at least one of the plant, an area adjacent to the plant, the soil adapted to support the growth of the plant, the root of the plant, and the foliage of the plant. Petition 870170072950, of September 28, 2017, p. 109/110 1/1