PICOLINAMIDES AS FUNGICIDES

Abstract

Claim 1: A compound of formula (1) wherein: Q is a compound of the group of formulas (2); X is hydrogen or C(O)R⁴; Y is hydrogen or C(O)R⁴; Z is N or N⁺®O⁻ and W is O or S; R¹ is hydrogen or alkyl, substituted with 0, 1 or multiple R⁷; R² is methyl; R³ is alkyl, aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R⁷; R⁴ is alkoxy or benzyloxy, each optionally substituted with 0, 1 or multiple R⁷; R⁵ is hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple R⁷; R⁶ is hydrogen, -C(O)R⁸, or -CH₂OC(O)R⁸; R⁷ is hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy cyano, or heterocyclyl, each optionally substituted with 0, 1, or multiple R⁹; R⁸ is alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple R⁷; R⁹ is hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; and R⁹⁰ is hydrogen or alkyl, each substituted with 0, 1, or multiple R⁷.

Description

PICOLINAMIDES AS FUNGICIDES;\ * Background and Summary. \S -

[0001] Fungicides are compounds of natural or synthetic origin, which act to protect and / or cure plants against damage caused by fungi relevant from an agricultural point of view. Generally, no single fungicide is useful in all situations. Therefore, research is ongoing to produce fungicides that perform better, are easier to use and have a lower cost.

[0002] The present description refers to picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

[0003] An embodiment of the present description may include compounds of Formula I: Or R2H Q___A„A\ / R3 A ° Γ-Η R1 Rw CH3 I in which: Q is R5 Re )R4; Y is hydrogen or C(O)R4i Z is N or N+—>O‘and W is O or S; «k. 1. . .4 * r5 O 1 IF-2019-52232722-APN-ANP#INPI Page 1 of 408 or IF-2019-52232722-APN-ANP#INPI ráuiiki 2 ÜL 400 o Ri is hydrogen or alkyl, substituted with 0.1 or multiple R7; . t Rz is methyl; >1- Λ’ λ _ .·-'* í ' *¿* R3 is selected from alkyl, aryl or heteroaryl, each optional merit* *- · *i f? replaced with 0.1 or multiple R7; R4 is selected from alkoxy or benzyloxy, each optionally substituted with 0.1, or multiple R7; Λ ' / *ή;; ;f?·· .:' Rs is selected from hydrogen, alkoxy, or halo, each optionally \ substituted with 0.1, or multiple R7; Re is selected from hydrogen, -C(O)R8, or -CH2OC(O)R8; R7 is selected from hydrogen, alkyl, aryl, acyl, halo, alkenyl, t*alkynyl, alkoxy, cyane, or heterocyclyl, each optionally substituted with 0.7 1, or multiple R^ R8 is selected from alkyl, alkoxy, or aryl, each optionally substituted with 0.1, or multiple R7; R9 is selected from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; and Rio is selected from hydrogen or alkyl, each substituted with 0.1 or multiple R7.

[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 carrier material acceptable from a phytological point of view.: I

[0005] Even another embodiment of the present description may include a method for controlling or preventing fungal attacks on a plant, method I / IF-2Q19-5223^^2eA¿¿ ANP#INPI Page 3 of 408 IF-2019-52232722-APN-ANP#INPI or which includes the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one mushroom, the plant, and an area adjacent to the plant.

[0006] Those skilled in the art will understand that the following terms • / 1 ” *. > · may include generic R groups within their definitions / ' by . For example, the term alkoxy refers to an -OR substituent. Also, it is understood that'inside. - .♦ of the definitions for the following terms, these R groups are included for illustrative purposes and should not be construed as limiting or limited by substitutions in 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, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0008] The term alkenyl refers to a branched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. ' '1'eí“10'

[0009] The terms aryl and “Ar” refer to any aromatic ring; monocyclic or bicyclic, containing 0 heteroatom.

[0010] The term heterocyclyl refers to any aromatic or non-aromatic ring, monocyclic or bicyclic, containing one or more heteroatoms.1,<L eí:'n

[0011] The term alkoxy refers to an OR-substituent:

[0012] The term acyloxy refers to a -OC(O)R substituent.

[0013] The term "cyano" refers to a C=N substituent.

[0014] The term hydroxyl refers to a substituent -OH.'' “cn f”. i :¡ >Ui 3 IF-2019-52232722-APN-ANP#INPI Ϊ Page 5 of 408 or IF-2019-52232722-APN-ANP#INPI

[0015] The term "amino" refers to a -N(R)2 substituent. :Yo:

[0016] The term arylalkoxy refers to -O(CH2)nAr, where n is an integer selected from the list 1,2,3,4,5, or 6. I ' * * · *· ’ ’

[0017] The term "haloalkoxy" refers to a substituent -OR-X, where X is ·1 Cl, F, Br, or I, or any combination of them. ; ’ \.i-í ’· ; * / Zñ - *v’ ’ V' ' í-4'· < ->.k

[0018] The term haloalkyl refers to an alkyl, which is substituted with Cl, F, I, or Br or any combination thereof.1\ _ * * *'*·♦-r A ♦ η f

[0019] The term halogen or halo refers to one or more halogen atoms, defined as F, Cl, Br, and I. <. *t

[0020] The term nitro refers to a -NO2 substituent.

[0021] The term thioalkyl refers to an -SR substituent.

[0022] Throughout the description, reference to compounds of Formula Ί is also read as inclusive of all stereoisomers, for example diastereomers, enantiomers and mixtures thereof. In another embodiment, Formula (I) is also read as inclusive of its salts and hydrates. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, iohydrate, trifluoroacetate, and trifluoromethane sulfonate. .· 4

[0023] Those skilled in the art also understand that additional substitution may be permitted unless otherwise indicated, provided that chemical binding and strain energy standards are met and the product still exhibits fungal activity.

[0024] Another embodiment of the present description is a use of a compound of Formula I for the protection of a plant against attack by a phytopathogenic organism or for the treatment of a plant infested by a phytopathogenic organism, which comprises the application of a composed of Formula'I?ó*'una: IF-2019-52232722-APN-ANP#INPI Page 7 of 408 or IF-2019-52232722-APN-ANP#INPI Page 8 do 108 o composition that includes the compound in the soil, in a plant, in a part of a plant, in the foliage and / or in the roots.

[0025] Additionally, another embodiment of the present description is a * · * » ’ * ' composition useful for protecting a plant against attack by an organism. · phytopathogenic and / or for the treatment of a plant infested by a / :. / !· / <· phytopathogenic organism that comprises a compound of Formula I and a philologically acceptable carrier material. . * * *1 Detailed description

[0026] The compounds of the present description can be applied by any of various known techniques, either in the form of the compounds or formulations comprising such compounds. For example, the compounds can be applied to the roots or foliage of vegetables to control various fungi, without harming the commercial value of the vegetables. The materials can be applied in the form of any of the generally used formulation types, for example, in the form of solutions, powders, wettable powders, flowable concentrates, or emulsifiable concentrates. ” 'VuJ cíí;

[0027] 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 philologically acceptable carrier. Can concentrated formulations be dispersed in water or other liquids for application? Or the formulations can be of powder or granular type, which can then be applied without additional treatment. The formulations can be prepared according to conventional procedures in the agricultural chemical art.

[0028] The present invention contemplates all vehicles through the I which one or more of the compounds can be formulated for administration^1 IF-2019-52232722-AP^-ANP#INPI1i dPage 9 of 408 o IF-2019-52232722-APN-ANP#INPI Pígini Ifl do 10^ o use as fungicides. Generally, the formulations are applied in the form of aqueous suspensions or emulsions. These suspensions or emulsions can be produced from water-soluble, water-suspendable, or emulsifying formulations that are solid, generally known as wettable powders; or liquids, generally known as emulsifiable concentrates, aqueous suspensions or suspension concentrates. As will be easily appreciated, any material to which these can be added can be used. · · • * >' ; <1. ? i •'-τ^ i. -1compounds, provided that it provides the desired utility without significant interference with the activity of these compounds as antifungal agents.

[0029] Wettable powders, which can be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 percent by weight to about 75 percent by weight. In the preparation of wettable powder formulations, the compounds can be compounded with any finely divided solid, such as, for example, pyrophyllite, talc, chalk, gypsum, derFülÍér earth, bentonite, attapulgite, starch, casein, gluten, clays of montmorillonite, diatomaceous earth, purified silicates or similar. In such operations, the finely divided carrier and surfactants are generally mixed with the compounds and ground. '' '1

[0030] Emulsifiable concentrates of Formularl compounds may comprise a convenient concentration such as, for example, «. IF-2Q19r52232|^:^^-ANP#INPI _ Page 11 of 408 or IF-2019-52232722-APN-ANP#INPI ' rríc ‘dr ” / · 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, which is a*” · water-miscible solvent or a mixture of water-immiscible organic solvents,1*7 · * - ? 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 high-boiling naphthalene and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpene solvents, including rosin derivatives, aliphatic ketones, such as, for example, cyclohexanone, and complex alcohols, for example, 2-ethoxyethanol. * ':‘

[0031] Emulsifiers that may be used advantageously* herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a combination of two or more emulsifiers. Examples of nonionic emulsifiers useful in the preparation of polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as, for example, ethoxylated alkylphenols and esters carboxylic acids solubilized with polyoxyalkylene polyol b. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts (e.g., calcium) of alkylarylsulfonic acids, oil-soluble salts or sulfated polyglycol ethers, and suitable phosphate polyglycol ether salts.

[0032] Representative organic liquids that can be used in the preparation of emulsifiable concentrates of the compounds of the present IF-2019-52232722- ApJ-ANP#INPI Page 13 of 408 IF-2019-52232722-APN-ANP#INPI Pigini 11 o'clock description are aromatic liquids such as xylene, fractions^ Ηβ propylbenzene; or mixed fractions of naphthalene, mineral oils, liquids - , f - ,4 ¿ * * *¿4»*^*' ·» *φ· C substituted aromatic organics such as, for example, dioctyl phthalate; kerosene;,· dialkylamides of various fatty acids, particularly the dimethylamides of fatty glycols and glycol derivatives such as, for example, n-butyl ether, ethyl ether or · methyl ether of diethylene glycol, the methyl ether of triethylene glycol, fractions of. oil? or . ..^5 '-· * ’·'·? ··’:‘ ''' * < .. < ·,·,, .1 -· >' hydrocarbons such as, for example, mineral oil, aromatic solvents, 'oils', paraffinic and similar; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, > ΐ linseed, palm oil, peanut oil, sunflower oil, sesame oil, tung oil and the like; esters of the aforementioned 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 propylbenzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are generally used in liquid formulations and in an amount of 0.1 to 20 percent by weight based on the! combined weight of the dispersing agent with one or more of the compounds. The formulations may also contain other 'compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.?' *or

[0033] Aqueous suspensions comprise suspensions of water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range of about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. . The suspensions ·. or . . CHr|aOéIT IF-2019-5223W3rtW’ANP#INPI Page 15 of 408 or IF-2019-52232722-APN-ANP#INPI Page 16 of 4OS or They are prepared by finely grinding one or more of the compounds and vigorously mixing the ground material in a compound vehicle-pornwater^and~ surfactants selected from the same types described above. Other components, such as inorganic salts and synthetic or natural rubbers, can also be added to increase the density and viscosity of the vehicle; • - v. ,' watery. - '· . '

[0034] The compounds of Formula I can also be applied in the form of granular formulations, which are particularly useful for application to soil. Granular formulations generally contain from about 0.5 to about 10 percent, based on the total weight of the granular formulation of the compound or compounds, dispersed in an inert carrier consisting entirely or largely of an inert material divided into coarse form such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. These formulations are generally prepared by dissolving the compounds in a suitable solvent and applying them to a granular carrier 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 mass or paste formation of the carrier and the compound and solvent, and their grinding and drying to obtain the desired granular particle.1· 'crk

[0035] Powders containing compounds of Formula I can be prepared by intimately mixing one or more of the compounds in powder form with a suitable powdery agricultural vehicle such as, for example, kaolin clay, crushed volcanic rock, and the like. The powders may adequately contain descie IF-2019-52232722-AP^-ANP#INPI Page 17 of 408 or IF-2019-52232722-APN-ANP#INPI Page IV gives or about 1 to about 10 weight percent of the compounds, based on! total weight of powder. . -,. ___ .

[0036] The formulations may additionally contain adjuvant surfactants to improve the discharge, wetting and penetration of the compounds on the target crop and organism. These adjuvant surfactants are . They can optionally be used as components of the formulation or as * tank mix. The amount of adjuvant surfactant will generally range from 0.01 to 1.0 volume percent, based on a volume of spray water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to, ethoxylated nonylphenols, ethoxylated synthetic or natural alcohols, salts of sulfosuccinic acids or esters, ethoxylated organosilicones, ethoxylated fatty amines, combinations of surfactants with mineral or vegetable oils, crop oil concentrate# -t r L·' (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; combination of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9Cu alkylpolyglycoside; phosphate alcohol ethoxylate; natural primary alcohol ethoxylate (C12 - Cw); di-sec-butylphenol EO-PO block copolymer; polysiloxanemethyl cap; nonylphenol ethoxylate + urea-ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol ethoxylate (synthetic) (8EO); tallowamine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as, for example, those described in US Patent Application Act No. 11 / 495,228, the description of which is expressly incorporated herein by reference. . ¡jees .-tk) Ci10 IF-2019-52232722-APN-ANP#INPI , . . . Yo Page 19 of 408 or IF-2019-52232722-APN-ANP#INPI Page 20 gives 10¾ or

[0037] The formulations may optionally include combinations containing other pesticidal compounds. These additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or their combinations that are compatible; with the Af compounds of the present description in the medium selected for the application, ' * *' and not antagonistic to the activity of the compounds of the present. According to the above, in said modalities, the other pesticide compound is used as a complementary toxicant for the same pesticide use or for a different pesticide use. The compounds of Formula I and the pesticidal compound in the combination may generally be present in a weight ratio of 1:100 to100:1. 'Λ

[0038] The compounds of the present description can be combined * - ir , I *: · also with other fungicides to form fungicidal mixtures and their synergistic mixtures. The fungicidal compounds of the present disclosure are frequently applied in conjunction with one or more other fungicides for the purposes of controlling a greater variety of undesirable diseases. When used in conjunction with one or more other fungicides, the compounds claimed herein can be formulated with one or more of the other fungicides, tank mixed with one or more of the other fungicides, or applied sequentially with one or more of the other fungicides. the other fungicides. Such other fungicides may include 2-{thiocyanatomethylthio)-benzothiazole, í2phenylphenol, 8-hydroxyquinoline sulfate, ametoctradine, aminopyrifen, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, bentiavalicarb-isopropyl , benzovindffflupir. benzylaminobenzenesulfonate salt (BABS), bicarbonates, biphenyl, bismerthiazole, bitertahoí, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, IF-2019-52232722xAPN-ANP#INPI . . i c miiA Page 21 of 408 or IF-2019-52232722-APN-ANP#INPI Page 22 of 408 or id. Ji •i * calcium polysulfide, Captafol, Captan, Carbendazim, Carboxin, Carpropamid, Carvone, Clazafenone, Cloroneb, Chlorothalonil, Clozolinate, Coniothynum minitans, Copper hydroxide, Copper octanoate, Copper oxychloride, Copper sulfate, Copper sulfate ( tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, -.cyproconazole,·. ciprodinil, dazomet, debacarb, ethylenebis-diammonium (dithiocarbamate), diclofluanid,.,' 4 > » i dichlorofen, diclocimet, diclomezine, dichloran, dietofencarb, difenoconazole, ion·difenzoquat, diflumetorim, dimetomorph, dimoxystrobin, diniconazole, diniconazol-M , dinobuton, dinocap, diphenylamine, ditianon, dodemorf, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, etaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpirayarnin, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluindapir, flumorf, fluopicolide, fluopyram, fluoroimide, fluoxapiprolin, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, il, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminum, fuberidazole, furalaxil, furametpir, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, himexazole, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesylate), inpirfluxam, iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamide, isoflucipram, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, bre, 'mancozeb, mandipropamid, maneb, mefenoxam, mepanipirim, mepronil, meptil-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M,'metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, metasulfocarb',* 'methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrapheny, , IF-2019-52232J22- -ANP#INPI r . _ Page 23 of 408 mildiomycin, myclobutanil, nabam, nitrotal-isopropyl, nuarimol, octylinone, ofurace, oleic acid (fatty acids), orisastrobin, oxadixil, oxathiapiprolin, oxin-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencicuron. penfkrfen / / - / L pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyioxin B, polyoxins, polioxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone , propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, -.· prothioconazole, pidiflumetofen, pirametostrobin, pyraoxyestrobin, pyraclostrobin, pyraziflumid, pyrazophos, piribencarb, piributicarb, pirifenox, pyrimethanil, pyriofenone, piroquilon, quinoclamine, quincecene, Reynoutria sachalinensis extract, sedaxane, siltiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-ZÓ48, tar oils, tebuconazole, tebufloquin, technazene, tetraconazole, thiabendazole, tifluzamide, thiophanate -methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin,' ' triflumizole, 'triforin, triticonazole, validamycin, valifenalate, valifenal, vinclozolin, zineb, ziram, zoxamida, Candida oleophila , Fusaríum oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseovirídis, Tríchoderma spp., (RS)- / V-(3,5-dichlorophenyl)-2(methoxymethyl)-succinimide, 1,2-dichloropropane, hydrate of 1, 3-dichloro-1,113;3tetrafluoroacetone, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropary?' -2,3-dihydro-5-phenyl-1,4-dithiyne tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-thiocyanatem -(2-nftroprop1-enyl)phenyl, ampropylphos, anylazine, azitiram, barium polysulfide, Bayer* 32394, benodanil, benquinox, bentaluron, benzamacryl; benzamacryl-isobutyl, benzamorph,tIF-2Q19-522327^,-AW-ANP#INPI Page 25 of 408 or IF-2019-52232722-APN-ANP#INPI Page· 26 do 108 '· '.sN ·:·· ΛΊ o binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, butiobate,I - ·?I cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, clobenthiazoria..I - - ,. * chloraniformetan, chlorfenazol, chlorquinox, climbazo!, bis(3-phenylosalicylate) of copper / ? / 1 copper zinc chromate, cumoxystrobin, cufraneb, hydrazinium cupric sulfate, cuprobam, I cyclafuramid, cipendazole, ciprofuram, decafentin, diclobenthiazox, diclone, diclozoline, I d cío but razo 1, dimetirimol, dinocton, dinosulfon, dínoterbon, dipimethitrone, dipyrithione, . I ditalimfos, dodicin, drazoxolon, EBP, enoxastrobin, ESBP, etaconazole, etirirn ' - / ¾ | . l.- :I phenaminstrobin, fenaminosulf, fenapanil, fenitropan, fenpicoxamid, florilpicoxamid, I flufenoxystrobin, fluopimomide, fluotrimazole, furcarbanil, furconazole, furconazole-cis, I furmecyclox, furofanate, gliodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, I ' ICIA0858, ipfentrifluconazole, ipflufenoquin, isopanphos, sovaledione, mandestrobiri, ·'1 mebenil, mecarbínzid, mefentrifluconazole, metazoxolon, metfuroxam, methylmercury dicyandiamida I, metsulfovax, methyltetraprol, milneb, mucochloric anhydride, I myclozolin, dichlorophen ¡l-succinimide, / V-3-nitropheníIitaconimide, natamycin,I • ethylmercury-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate)1?0OCH, « | phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosphodrphene,| prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyrapropoin, pyridaclomethyl,I pyridinitrile, pyrisoxazole, piroxiclor, piroxifur, quinacetol; kyriacetol sulfate,[ * quinazamid, quinconazole, quinofumelin, rabenzazole, salicylahilide, ' SSF-lb9,| sultropen, tecoram, tiadifluor, ticiofen, tioclorfenfim, tiophanate, tioquinox, tioximid, I triamiphos, triarimol, triazbutil, trida mida, triclopiricarb, triflumezopyrim, urbacid, I zarilamid, and any combination of them. *' I, '

[0039] Additionally, the compounds described herein can* | combine with other pesticides, including insecticides, nematocides, acaricides,| arthropodicides, bactericides or their combinations that are compatible with the I *I IF-2019-522327^2i|^-ANP#INPI [ Page 27 of 408 or IF-2019-52232722-APN-ANP#INPI Pygim 7¾ gives 10¾ or in. i Hi*. I compounds of the present description in the medium selected for the application I and not antagonistic to the activity of the compounds herein to form pesticidal mixtures and their synergistic mixtures. The fungicidal compounds of Ja1'* · G. ¡ present description can be applied together with one or more other pesticides to control a greater diversity of undesirable pests. When used in conjunction with other pesticides, the compounds claimed herein may be formulated with one or more other pesticides, tank mixed with one or more of the other pesticides, or applied sequentially with one or more of the other pesticides. other pesticides. Typical insecticides include, but are not limited to: 1,2dichloropropane, abamectin, acephate, acetamiprid, acetion, acetoprol, acrinathrin, acrylonitrile, acinonapyr, afidopyropen, alanicarb, aldicarb, aldoxicarb, aldrin, aletrina, alosamidin, alixicarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, atidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, YO . bendiocarb, benfuracarb, bensultap, benzpirimoxan, beta-cyfluthrin,'*!betaI cypermethrin, bifenthrin, bioalethrin, bioethanemethrin, biopermethrin, bistrifluron, borax, boric acid, broflanilide, bromphenvinphos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb , buprofezin, butacarb, butatiofos, butocarboxym, bütonate, tbutoxycarboxym, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbofenothion, carbosulfan, cartap, cartap hydrochloride, chlorantranlliprole, chlorbicyclen, chlordan, chlordecone, chlordimeform, chlordimeform hydrochloride, tchlorethoxifos, chlorfenapyr, chlorfenvinfos, chlorfluazuron,' chlormefos, chlorofomium, chlorpicrin, chlorpraletrin, chlorfoxim, chlorprazophos, chlorpyrifos, chlorplrifos-methyl, Ichlorthiofos, chromafenozide, cinerin 1, cinerin II, cinerins, cismethrin, cloetocarb, A.,:, o,, ,.IF-2Q19r5?23^fe^-ANP#INPI * ' _ Page 29 of 408 o IF-2019-52232722-APN-ANP#INPI Page 30 of closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, cumitoate, crotamiton, crotoxiphos, - crufomate^ryolite,____ i * cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclaniliprol, cycletrin , cycloprothrin, ·· '· ' * ! cyfluthrin, cyhalodiamide, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cithioate, DDT, decarbofuran, deltamethrin, demefion, demefion-O, demefion-S, demeton,:demeton-metüo, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, ;(* . ¿ * í * it· * t * demeton-S-methylsulfone, diafenthiuron, dialiphos, diatomaceous earth, diazihóri,' .-.λ'- ' ' dicapton, diclofenthion, dichlorvos, dichloromezothiaz, dicresyl, dicrotofos, dicyclanii, dieldrin, diflubenzuron, dilor , dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimethylan, dinex, dinex-diclexin, dinoprop, dinosam, dínotefuran, diofenolan, dioxabenzophos, dioxacarb, dioxation, disulfoton, dithicrophos, d-limorienó, μi DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empentrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, epsilon-metofluthrin, epsilon' momfluorothrin, esdepalléthrine, esfenvalerate, etafos, etiofencarb , ethiprole, ethoate-methyl, etrimfos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, fanfur, fenamiphos, fenazaflor, fenchlorphos, fenetacarb, fenfluthrin, fenitrothion , fenobucarb, fenoxacrim, fehbxicarb, fenpythrin, fenpropatrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, Tpronil, flomethoquin, flonicamid, fluazaindolizine, flubendiamide, flucofuron, flucicloxuron, flucitrinate, fluensulfone, flufenerim, flufenoxuron, flufiprole, fluhexafon, Iflupyradifurone , flupyrimin, fluvalinate, fluxametamide, fonofos, formetahate, formethanate hydrochloride, formothion, formparanate, formparanal hydrochloride, fosmethylan, fospirate, fostietan, furatiocarb, furethrin, gamma-cyalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor , heptafluthrin, heptenofos, • I i ! ; , IF-2Q19-52232nU>^^-ANP#INPI Page 31 of 408 or IF-2019-52232722-APN-ANP#INPI du 400 or heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide,· hydroprene,--—' hiquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazophos, isobenzan, isocarbofos, isocycloseram, isodrin, isofenphos, isofenphos-methyl, t. isoprocarb, isoprothiolane, isothioate, isoxathione, ivermectin, jasmolin I, jasmolinll, jodfenfos, youth hormone I, youth hormone II, youth hormone III, kappa-bifenthrin, J * / *->, <· kappa-tefluthrin, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, r< lepimectin, leptophos, lindane, lirimphos, lufenuron, litidathion, malathion, malonoben, mazidox, mecarbam, mecarfon, menazon, meperfluthrin, mefosfolan, mercurous chloride, mesulfenios, metaflumizone, metacryfos, methamidophos, methidathion , Metiocarb, Metocrotophos, Metomil, Metoprene, Metoxiclor, Metoxycezide, Methyl Bromide, Methyl, MethylCloroform, Methylene Chloride, Metoflutrine, * Metolcarb, Metoxadiazone, Mevinfos, Mexacarbita, Milbemectin, Milbemicinoxima, Milexima , Molosultap, Momfluorotrina, Monochrotophos, monomehypo, I monosultop, morphotion, moxidectin, naphthafos, naled, naphthalene, nicotine, nifluridide, nitenpiram, n'rtiazine, nitrilacarb, novaluron, noviflumuron, ometarata, oxamil, oxázosulfil, oxidemeton-methyl, oxid Foton, Para-Decllorobencene , parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, fenkápton, phenothrin, fentoate, phorate, fosalone, fosfolan, fosmet, fosniclor, phosphamidon, festino, foxim, foxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl , potassium arsenite I, potassium thiocyanate, pp'-DDT, praletrin, precocene I, precocene'll, precocene III, pidophos, profenofos, profluralin, promacil, promecarb,' prbpafos, I propetamfos, propoxur, protidathion, prothiofos, protoate , protriphenbuto, p'rflubumi'da, I pyraclophos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, I pyridaben, pyridalyl, pyridafenthion, pyrifluquinazon, pyrimidifen, pyriminostrobin, I pyrimitate, pyriprole, piriprox'rfen, quasia, quinaffos, quinalfos-methyl, quíóntion,I IF-2019-52232722-ApKaNP#INPI I Page 33 of 408 | either IF-2019-52232722-APN-ANP#INPI rafoxanide, resmetharin, rotenone, riania, sabadilla, scradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sofamide, spinetoram , spinosad, spiromesifen, < spiropidion, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid^ súffotép,' . • ' * · . ’ ‘ ‘tsulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE,í~ .. ';í tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, temefos, TEPP, teraletrin, terbufos, tetrachlorantraniliprole, tetrachloroethane, . tetrachlorvinphos,.' tetramethrin, tetramethylfluthrin, tetraniliprol, theta-cypermethrin, thiacloprid, thiamethoxam, ticrofos, thiocarboxyme, thiocyclam, thiocyclam oxalate, thiodicarb, tiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, thioxazafen, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triaratene, triazophos triazamate, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumezopyrim, triflumuron, trimetacarb, triprene, ticlopyrazoflor, vamidothion, vaniliprol, XMC, xylylcarb, zeta-cypermetnna, zolaprofos, and any combination thereof .

[0040] Additionally, the compounds described herein can be combined with herbicides compatible with the compounds of the present disclosure in the medium selected for the application, and that are not antagonistic to the activity of the compounds herein to form pesticidal mixtures. and synergistic mixtures thereof. The fungicidal compounds of the present description can be applied together with one or more herbicides for the control of a wide diversity of undesirable plants. When used in conjunction with herbicides, the compounds claimed herein may be formulated with one or more herbicides, tank mixed with one or more of the herbicides, or applied sequentially with one or more of the herbicides. 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% IF-2019-52232722- A^-ANP#INPI i . : ; Page 35 of 408 or IF-2019-52232722-APN-ANP#INPI Page S6 gives 10¾ DEB; 2,4-DEP; 3,4-DP; 2t3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolelna, alachlor, alidoclor, aloxidim, allyl alcohol, alorac, ametridione, ametrine, amibuzin, arnica rbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprophos-methyl, amitrol, ammonium sulfamate, anilophos, anisuron, asulam, atraton, . ?. * atrazine, azafenidin, azimsulfuron, aziprothrin, barban, BCPC, beflubutamld, beflubutamid-M, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzphendizone, benzipram, benzobicyclone, benzofenap, benzofluor, zoilprop, benzthiazuron, bicyclopyrone , bifenox, bilanafos, bispiribac, bixlozone, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompirazon, butaclor, butafenacil, butamifos, butenaclor, butidazole, butiuron, butralin, butroxidim, buturon, butylate, cacodylic acid, cafenstrol, chlorate calcium, calcium cyanamide, cambendichlor, carbasulam, carbetamide, chlorprocarb carboxazole, carfentrazone, CDEA, CEPC, clomethoxyfen, chloramben, chloranocrile, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, clomitrofen CMA copper sulfate, CPMF, CPPC, credazine, cresol, cumiluron, cyanathrin, cia nabina, cycloate, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxidim, cicluron, cyhalofop, cyperquat, ciprazine, ciprazole, cipromid, daimuron, dalapon, dazomet, delachlor, desmedifam , desmethrin, di-alate, dicamba, diclobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, dietmcuat, diettil, diphenopenten, difenoxuron, dienzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimetacfor, dimetamethrin, dimetenamid, dimetenamid -P, dimexane, dimidazon, dinitramine, . IF-2019-52232722-A^§-ANP#INPI ' - ’ file it fp ______________ Page 37 of 408 o 4Viginti 3 IF-2019-52232722-APN-ANP#INPI or dinofenate, dinoprop, dinosam, dinoseb, dinoterb, difenamid, dipropetrin, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endotal, epronaz, EPTC, erbon, esprocarb, etalfluralin, etametsulfuron, etidimuron, · etiolated, ' · .. -a? * * · *'.· '7v'' * \ ''Ά* ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid / EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, phenquinotrione, phenteracol, fentiaprop, fentrazamide , fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, florpirauxifen, fluazifop, fluaz'rfop-P, fluazolatp,t. ;5 ··»,,,*«* / -'ir flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpir, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropin, fluometuron, fluorodifen, fluoroglycophen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam , flupropacil, flupropanate, flupirsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furiloxifen, glufosinate, glufosinate-P, glyphosate, halauxifen, halosafen, halosulfuron, haloxidine, haloxifop-P, , hexachloroacetone, hexaflurate , hexazinone, imazametabenz, imazamox, Imazapic, imazapyr, imazaquin, imazetapyr, imazosulfuron, indanofan, índaziflam, iodobonil, iodomethane, iodosulfuron, iofensulfuron, ¡oxynil, ipazine, ipfencarbazone, iprimidam, isocarbamid, isocil, isomethiozin, sonoruron, is opolinate, isopropalin , isoproturon, isouron, isoxaben, isoxachlortol, isoxaflutol, isoxapyrifop, karbutylate, ketospiradox, lancotrione, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, rMCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine , mesosulfuron, mesotrione, metam, metamifop, metamitron, metala dor, metazosulfuron, metflurazon, methabenzthiazuron, metalpropalin, metazole, methiobencarb, methiozolin, methiuron, metometon, metoprothrin, methiium bromide, methyl isothiocyanate, methyldimron, metobenzuron, metobromuron, metolachlor , metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, ¡ . I ·, 41 · ' IF-2019-5223^7gft-^^-ANP#INPI__ Page 39 of 408 or IF-2019-52232722-APN-ANP#INPI Page or monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipíraclofen, - ' nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho- '1dichlorobenzene, orthosulfamuron , orizalin, oxadiargil, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefona, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazoña, perfluidone, petoxamid, fenisofam, fenmedifam, fenmedifam-ethyl, satchel, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profiuralin, profoxidim, proglinazine, promisen, promethrin, p ropaclo r, propanil, propaquizafop, propazine, profam, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prinaclor, pidanon, pyraclonil, pyraflufen, pyrasulfotol, pyrazolinate, pyrazosulfuron, pyrazoxifen, piribenzoxim, piributicarb, piriclor, pyridafol, pi ridatd, piriftalid, pyríminobac, pyrímisulfan, pyrithiobac, pyroxasulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rodetanil, rimsulfuron, saflufenacil, S-metolachlor, sebutylazine, secbumeton, setoxydim / siduron, simazine, simeton, simethrin, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfalate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglicapin, swep, TCA, tebutam, tebutiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbutylazine , terbutrin, tetrafluron, tenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, tiencarbazone-methio, tifensulfuron, thiobencarb, thiaphenacil, thiocarbazil, thioclorim, tolpyralate, topramezone, tralkoxidim, triafamone, tri-alato, triasulfuron, triaziflam, tribenuron, tricamba, lopir , tridifan, trietazine, trifloxisulfuron, trifludimoxazin, trifluralin, triflusulfuron; tripop, IF-2019-52232722-A^-ANP#INPI Page 41 of 408 or IF-2019-52232722-APN-ANP#INPI Page or triphopsim, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vemolate, and xylchlor. :'<> , \··

[0041] Another embodiment of the present description is a method for the control or prevention of fungal attacks. This method includes applying to the soil, plant, roots or place where the fungus is located or in a place where the fungus must be avoided. infestation (for example, applying to cereals or grapevines), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for the treatment of various vegetables at fungicidal levels, while presenting low phytotoxicity. The compounds can be useful both as protectors and / or eradicators.

[0042] The compounds were found to have a significant fungicidal effect, particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural vegetables:'

[0043] Those skilled in the art will understand that the effectiveness of the compound for the fungi mentioned above establishes the general usefulness of the compounds as fungicides.

[0044] The compounds have wide ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, the causative agent of wheat glume spot (Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia stríiformis), apple leaf spot (Venturia inaequalis). ), vine powdery mildew (Uncinula riecatoij, barley scald (Rhynchosporíum secalis), rice blast (Magnápórthe grísea), soybean rust (Phakopsora pachyrhizi), wheat glume spot (Parastagonospora nodorum), powdery mildew of wheat (Blumería graminis f sp. trítici), powdery mildew of barley (Blumería graminis f. sp. hordei), downy mildew IF-2019-52232722-AI^-ANP#INPI Page 43 of 408 or IF-2019-52232722-APN-ANP#INPI or cucurbit powdery mildew (Erysiphe cichoracearum), cucurbit anthracnose (Glomerella lagenarium), beet leaf spot (Cercospora baticola), tomato early blight (Alternaria sotaní), and barley spot (Cochllobolus sativa). The exact amount of active material to be applied depends not only on the specific active material being applied, but also on the particular desired action, the fungal species to be controlled and their growth stage as well as the part of the vegetable or other product that will come into contact with the compound. Thus, all compounds and formulations containing them may not be equally effective at similar concentrations or against the same fungal species.

[0045] The compounds are effective for use with vegetables in an amount. I philologically acceptable and disease inhibiting. The term philologically acceptable and disease-inhibiting amount ► refers to an amountΐ of a compound that kills or inhibits the disease of the plant for which control is desired but that is not significantly toxic to the plant. This amount > will generally be about 0.1 to about 1000 ppm (parts per million), preferably 1 to 500 ppm. The exact required concentration of the compound varies with the fungal disease to be controlled, the type of formulation used, the application method, the particular plant species / climatic conditions, and the like. An adequate application rate is generally in the range of about 0.10 to about 4 pounds / acre (about 0.01 to 0.45 grams per square meter, g / m2).

[0046] Any desired range or value indicated herein may be extended or altered without loss of intended effects as evident to the skilled person. an understanding of the teachings of the present.j1<r ti1..Jh1 IF-2019-52232¡Z|22?í^|§-ANP#INPI? Page 45 of 408 IF-2019-52232722-APN-ANP#INPI Póginti 16 gives 108 — or

[0047] The compounds of Formula I can be prepared by well-known chemical procedures. Intermediates not specifically mentioned in this description are commercially available, can be prepared by routes described in the chemical literature, or can be easily synthesized from starting materials with the use of standard procedures. ·:,«· General Schemes

[0048] The following schemes illustrate approaches for generating picolinamide compounds of Formula (I). The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.

[0049] Racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5-Rac, 1.6Rac, in which R3 is as defined above, can be prepared by u # the method shown in Scheme 1, step a. Subjecting the racemic epoxide mixtures of Formulas 1.0-Rac and 1.4-Rac to a reaction with an organometallic nucleophile, such as, for example, an arylmagnesium halide, in the presence of a metal halide, for example copper iodide, in a polar, aprotic solvent, such as, for example, tetrahydrofuran (THF) or diethyl ether (Et20), at a temperature of approximately -78°C to 55°C, provides racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5- Rac, 1.6-Rac, where R3 is as defined above, and as shown in step a. Scheme 1 ' 1 g u >·' U’ I / : fir IF-2019-52232722- AP^ANP#INPI i . Yo I Page 47 of 408 or Yo II II l IF-2019-52232722-APN-ANP#INPI Pigim 18 of 108 I or either .Ο-Rac EITHER 1.4-Rac „ ^R3 BrMg31.1 BrMg^3 1.1

[0050] Racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5-Rac, 1.6Rac, where R3 is as defined above, can be separated into individual enantiomers with the use of a lipase-catalyzed kinetic redissolution described by Akita (Tetrahedron: Asymmetry 2009, 20, 1286-1294) and outlined in Scheme 2, steps a and b. Subjecting racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5-Rac, 1.6-Rac, where R3 is as defined above, to Candida antarctica lipase B (CAL-B) in an acetylating solvent, such as, For example, vinyl acetate, at a temperature of about 25°C to about 60°C, provides the unreacted secondary alcohols of Formulas 1.2-Abs and 1.5-Abs, where R3 is as originally defined and the acetylated compounds of Formulas 2.1-Abs and 2.3-Abs, where R3 is as originally defined. The mixtures can be purified by silica gel chromatography with the use of a hexane-ethyl acetate mixture as the mobile phase, resulting in resolved secondary alcohols and acetates of Formulas 1.2-Abs, 1.5-Abs, 2.1-Abs and 2.3-Abs, where R3 is as originally defined, and in a high enantiomeric excess. Lipase recognition of the secondary alcohol of 1.2-Rac, 1.3-Rac, 1.5-Rac and 1.6-Rac, where R3 is how it was originally defined, was similar to the empirical standard for kinetic resolution IF-2019-52232722-Af^-ANP#INPI J 4 f < I f ______ ______________________ Page 49 of 408 o IF-2019-52232722-APN-ANP#INPI Page 50 do or of secondary alcohols (Bomscheuer and Kazlauskus, Hidratases in Organic Synthesis; Wiley-VCH, 2006). The treatment of acetates of Formulas 2.1-Abs and 2.3Abstwhere R3 is as originally defined, with a carbonate base, such as, . for example, potassium carbonate, in an alcoholic solvent, such as . Methanol, at a temperature of about 25°C to about 60°C, provides the resolved secondary alcohols of Formulas 2.2-Abs and 2.4-Abs, where R3 is as originally defined. Scheme 2 h3 122-Abs IJ-Rac 13-Rac CH3 2.1-Abs 2.2-Abs CH3 2.3-Abs Or CH3 H3C^O^Y^R3¿h3 23-Abs 2.4-Abs

[0051] Compounds of Formula 3.2, where R1, R2, Rs, and R10 are as originally defined, can be prepared according to the method outlined in Scheme 3, step a. Alcohols of Formula 3.0, where R2 and R3 are as originally defined, can be treated with compounds of Formula 3.1, IF-2019-52232722-AI??-ANP#INPI Page 51 of 408 or i IF-2019-52232722-APN-ANP#INPI Page where Ri and Rio are as originally defined, a pairing reagent, such as, for example, 3-(ethyliminomethyleneamino)-W, / V-dimethylpropan-1amine hydrochloride (EDC) or a polymer-supported carbodiimide (PS- CDI), and a ' * ' A**hó · t' catalyst, for example, / V,A / -dimethylpyridine-4-amine (DMAP), in an aprotic, polar or halogenated solvent, such as, for example, (CH2CI2) or THF, to provide compounds of Formula 3.2, where Ri, R2, R3, and R10 are as originally defined, as shown in step a. ? ·??:*- .?X. • . * fl* *T Scheme 3

[0052] Compounds of Formula 4.5, where R1(R21R3, R5, and R10 are as originally defined, can be prepared according to the methods outlined in Scheme 4, steps a — cf. Compounds of Formula 3.2, where - . '-'."(YO Ri. R2. R3. and R10 are as originally defined, they can be treated with an acid, such as a 4 Normal (N) solution of hydrogen chloride (HCl) in dioxane, in a halogenated solvent such as ChkCfe, to provide compounds of Formula 4.1, where Ri, R2, R3, and R10 as shown in step a. Compounds of Formula 4.2, where RbR2, R3, and Rw are as originally defined, can be prepared by treating the compounds of Formula 3.2, where Ri, R2, R3, and R10 are as originally defined, with an acid, such as, for example, 2,2,2-trifluoroacetic acid, in a halogenated solvent such as, for example, CH2CI2, as shown in step c. Compounds of Formulas 4.1 and 4.2, where R1fR2, R3, and R10 are as originally defined, can be treated with compounds of Formula 4.3, where IF-2019-52232722-A^?-ANP#INPI Page 53 of 408 or IF-2019-52232722-APN-ANP#INPI Page Rg is as originally defined, in the presence of a base, such as, for example, disopropylethylamine, and a peptide pairing reagent, such as, for example, ... hexafluorophosphate hexafluorophosphate in a benzotriazol-1-yl-oxytripyrrolidinephosphonium solvent (PyBOP); 7 p, of O-ÍT-azabenzo-triazol-l-ylJ-W. / VA^'-tetramethyluronium (HATU), halogenated as, for example, CH2CI2, to provide compounds of Formula 4.5, where Ri, R2, R3, R5 and Riq are as originally defined1•, as shown in steps b and d. < -. < r * Scheme 4 3.2 H HR2 / HrI h Ri R10CH 4.5

[0053] Compounds of Formula 5.1, where R1tR2, R3, R5 and R10 are as originally defined, can be prepared according to the outlined method IF-2019-52232722-APN-ANP#INPI Page 55 of 408 or IF-2019-52232722-APN-ANP#INPI Page 56 do in Scheme 5, steps a or b. Compounds of Formula 4.5, where Ru R2, R3,_ Rs and R10 are as originally defined, can be treated with a suitable alkyl halide, with or without a reagent such as sodium iodide (Nal) and a carbonate alkali base, such as sodium carbonate (Na2CO3) or . potassium carbonate (K2CO3), in a solvent such as acetone, at a temperature of about 25°C to about 50°C, as shown in step a. Or, alternatively, by treatment with an acyl halide or anhydride in the presence of an amine base, such as pyridine, triethylamine (NETa), DMAP, or mixtures thereof, in an aprotic solvent, such as CH2CI2 , to provide compounds of Formula 5.1, where R1(R2, R3, R5, Re, and Rio are as originally defined, as shown in step b. Scheme 5

[0054] Compounds of Formula 6.1 and 6.2, where R1, R2, R3, R5, Re, and Rw are as originally defined, can be prepared according to the method outlined in Scheme 6, steps a and b. Compounds of Formula 4.5, where Ri, R2, R3, R5, and R10 are as originally defined, can be treated with a thionation reagent such as phosphorus pentasulfide, an additive such as hexamethyldisiloxane, optionally in a polar aprotic solvent such as, for example, acetonitrile (CH3CN), at a temperature of about 0°C to 80°C to provide compounds of Formula 6.1, where Ri, R2, R3, Rs and R10 are as originally defined, and as shown in the IF-2019-52232722-AI??-ANP#INPI Page 57 of 408 or IF-2019-52232722-APN-ANP#INPI Pygim 58 of 108 or step to. Those skilled in the art will understand that compounds such as, for example, Formula 6.1 can also be prepared with the use of other phonation agents including, but not limited to: sulfur, hydrogen sulfide, sodium sulfide, sodium hydrosulfide, boron trisulfide, bis(diethylaluminum) sulfide, ammonium sulfide, Lawesson's reagent, O,O*-diefl ammonium dithiophosphate, rhodanine, or a polymer-supported phonation reagent. Additives may include, but are not limited to, aluminum oxide (AI2O3); inorganic bases, such as, for example, 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, for example, 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 compounds of Formula 6.1, in which R1fR2, R3, R5 and R10 are as originally defined, with a suitable alkyl halide with or without a reagent such as, for example, sodium iodide (Nal) and an acali carbonate base, like? for example, sodium carbonate (Na2CO3) or potassium carbonate (K2CO3) / in a polar aprotic solvent, such as acetone, at a temperature of about 55°C, or by treatment with a de1acyl halide or anhydride in The presence of an amine base, such as pyridine, DMAP, or mixtures thereof, in an optional aprotic solvent, such as CH2Cl2, at a temperature of about 23°C, can provide compounds of Formula 6.2 in which R1, R2, R3, R5, Re, and R10 are as originally defined. Scheme 6 m IF-2019-52232722-AÍ^-ANP#INPI Page 59 of 408 IF-2019-52232722-APN-ANP#INPI Pflginti 60 do lOfr o 6.2

[0055] Compounds of Formula 7.1, in which RbR2, R3|R5 and R10, are as originally defined, can be prepared according to the method outlined in Scheme 7, step a. Compounds of Formula 4.5, where R1tR2, R3·R5 and R10 are as originally defined, can be treated with an oxidizing reagent such as m-chloroperbenzoic acid (mCPBA) in a polar solvent such as CH2CI2, at a temperature of about 0eC to 50°C, to provide compounds of Formula 7.1, wherein Ri, R2, Ra, R5 and Rio are as defined above, and as shown in a. Those skilled in the art will understand that compounds of Formula 7.1, in which Rt, R2, R3, R5 and R10 are as originally defined, can also be prepared with the use of other oxidizing agents including, but not limited to, hydrogen peroxides, hydrogen peroxide-urea complex, magnesium monoperoxyphthalate hexahydrate (MMPP), peroxyacetic acid, oxone, sodium perchlorate or dimethyldioxirane. Scheme 7. il. IF-2019-52232722-Af^-ANP#INPI Page 61 of 408 or IF-2019-52232722-APN-ANP#INPI 4'57.1

[0056] Compounds of Formula 8.1, in which R1(R2|R3, R5 and R10 are as originally defined, can be prepared according to the method outlined in Scheme 8, step a. Compounds of Formula 4.5, in While Ri, R2, R3, Rs and R10 are as originally defined, they can be treated with a diactivated carbonyl reagent such as triphosphene, with a base such as pyridine, and in a polar solvent such as , for example, CH2CI2, at a temperature of about 0°C to 50°C, to provide compounds of Formula 8.1, wherein Ri, R2, R3, R5 and R10, are as originally defined, as illustrated in a. Scheme 8 R5 R5 4.5 8.1 Examples...

[0057] Example 1A: Preparation of racemic freo-3-(2,4-dimethylphenyl)butan-2-ol. IF-2019-52232722-AI??-ANP#INPI Page 63 of 408 IF-2019-52232722-APN-ANP#INPI Póginti 61 gives 108 racemic Racemic '

[0058] To a suspension of freshly activated magnesium metal filings (1.14 g, 46.80 mmol) in anhydrous Et2O (20 mL) was added dropwise 1-bromo-2,4dimethylbenzene (8 g, 43 .20 mmol). The mixture was gently heated to slight reflux. (36°C) for 5 hours (hr). The resulting dark brown solution was added via syringe to a flask containing copper(I) iodide (4.12 g, 21.61 mmol) suspended in Et2O (50 mL) at -20°C. The dark yellow suspension was stirred for 15 minutes (min) at -20°C and subsequently cooled to -50eC. Racemic frans-butene epoxide (1.3 g, 18.01 mmol) was slowly added dropwise followed by warming the reaction to room temperature and stirred overnight. The mixture was then cooled to 0°C and slowly quenched with the addition of a saturated aqueous solution of ammonium chloride (NH4Cl). The mixture was filtered through a Celite pad and the pad was rinsed completely with ethyl acetate. The organic solution was washed with saturated NH4Cl solution and brine. The solution was dried (magnesium sulfate (MgSO4)), filtered and concentrated under reduced pressure. The residue was purified by automated flash column chromatography (SiO2, 0-40% ethyl acetate / hexanes gradient) to provide racemic freo-3-(2,4-dimethylphenyl)butan-2-oI, ♦ - I J in yellow oil form (813 mg, 25%): Ή NMR (500 MHz, CDCI3) δ 7.06 (d, J = 8.5 Hz, 1H), 7.01 - 6.97 (m, 2H), 3.94 - 3.82 (m, 1H), 2.97 (p,' J = 6.9 Hz, 1H), 2.29 (d, J = 7.7 Hz, 6H), 1.50 ( d, J = 3.9 Hz, 1H). 1.28 (d, J = 7.0 Hz, 3H), f i114U IF-2019-52232722-4P^?-ANP#INPI Page 65 of 408 IF-2019-52232722-APN-ANP#INPI Page 66 of 108 — 1.11 (d, J = 6.3 Hz, 3H);13C NMR (126 MHz, CDCI3) δ 139.99, 135.49, 135.38, 131,31,126,81,126,18,71,92,41,42,21,25, 20,87,19,85,16,06; EIMSrtó.178_____

[0059] Example 1B: Preparation of racemic enfro-3-(o-tolyl)butan-2-ol. \η3 racemic HO ch3ch3Racemic

[0060] To a -20°C suspension of copper (I) iodide (4.15 g, 21.60 mmol). In anhydrous EtzO (40 mL), 2-methylphenylmagnesium bromide (2.0 M in Et2O, 22.5 mL, 43.20 mmol) was added slowly dropwise. After stirring for 30 min, the orange suspension was cooled to −78°C and racemic c / s-butene epoxide (1.3 g, 18.01 mmol) was slowly added. The dry ice bath was removed, the mixture was allowed to warm slowly to room temperature and stirred overnight. The mixture was cooled with an ice bath to 0°C and slowly quenched by dropwise addition of a saturated aqueous NH4Cl solution. The mixture was warmed to room temperature and filtered through Celite, then the pad was rinsed with ethyl acetate (EtOAc). The resulting filtrate was washed with a saturated aqueous solution of NH4Cl and brine. The solution was then dried (MgSO4) and concentrated under reduced pressure. The residue was purified by automated flash column chromatography (SiO2030% ethyl acetate / hexanes gradient) to provide racemic enfro-3-(otolyl)butan-2-ol (2.05 g, 69%) as yellow oil:1H NMR (500 MHz, CDCI3) δ 7.34-7.01 (m, 4H), 3.92 (p, 6.3 Hz, 1H), 3.01 (p, J= 7.1 Hz, 1H), 2.36 (s, 3H), 1.47 (s, 1H), 1.28 (d, J= 6.1 Hz, 3H), 1.19 (d, J = 7.0 Hz, 3H); 13C NMR (126 MHz, CDCI3) δ 142.14, 136.84, 130.61, 126.49, 125.81, 72.33, 42.62, 20.47, 19.93,17.88; ElMS / n£ 164. IF-2019-52232722-AT^-ANP#INPI Page 67 of 408 IF-2019-52232722-APN-ANP#INPI Pnginn 6? gives 10¾ — or

[0061] Example 1C: Preparation of freo-3-phenylobutan-2-o! racemic. ouch Η3Ο'^ΟΗ3' n x ·CH Racemic Racemic4

[0062] To a suspension of copper (I) iodide (1.86 g, 9.76 mmol) in ethyl ether (18.0 mL) phenyllithium (1.9 M in butyl ether, 10.3 mL, 19.53 mmol) at 0°C under a nitrogen atmosphere. After stirring at 0°C for 1 hr, racemic frans-2,3-dimethyloxirane (0.64 g, 8.88 mmol) was added dropwise followed by an ice bath and then warmed to room temperature with stirring. for 2 hr. The reaction mixture was quenched with water (20 mL), filtered through a Celite pad and extracted with ethyl ether (3x20 mL). The organics were passed through a phase separator and concentrated in vacuo. The crude residue was purified by automated flash column chromatography (SiO2, 0 - 25% acetone / hexanes gradient) to provide freo-3-phenylobutan-2-ol (1.33 g, 8.85 mmol, 99% ) as an orange oil: *Η NMR (400 MHz, CDCI3) 07.38-7.12 (m, 5H), 3.91 -3.84 (m, 1H), 2.80-2.68 ( m, 1H), 1.43 (s, 1H), 1.33 (d, J = 7.1 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). The spectral data were consistent with those reported in the literature: Tetrahedron 1981, 37, 709 713.

[0063] Example 2: Preparation of (2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol' and (2R,3R)-3-(2,4-dimethylphenyl)butan-2 -ol. I(Λ“ίΟΓ

[0064] Step 1: Preparation of (2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol and (2R,3R)-3-(2,4-dÍmethylphenyl)butan-2-acetate ilo. IF-2019-52232722- -ANP#INPI Page 69 of 408 „ Yo Item 1' I1t II Yo IF-2019-52232722-APN-ANP#INPI Page 70 do ch3ch3óh3ch3 Racemic h3ch3ch3ch3

[0065] A flask containing a solution of frans-3-(2,4-dimet¡lfeniÍ)butan-. Racemic 2-ol (800 mg, 4.49 mmol) dissolved in vinyl acetate (15 mL) was loaded ·.'·. with doses of Novozym 435 Lipase (CAL-B, 1.6 g, 4.49 mmol). The flask was placed on an orbital shaker, shaken at 200 rpm, and heated at 55°C for 7.5 hrs. The reaction was cooled and filtered through a frit disk with an EtOAc rinse. The levigant was concentrated under reduced pressure to provide 906 mg of a yellow crude oil. The residue was purified by flash column chromatography (SiO2, gradient 0-20% ethyl acetate / hexanes) to provide (2 / ?,3 / 7)-3-(2,4-dimethylphenyl)butane acetate. 2-yl (clear oil, 466 mg, 47%) followed by (2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol (clear yellow oil, 357 mg, 43%). Acetate: 'H NMR (500 MHz, CDCb) δ 7.07 (d, J = 7.7 Hz, 1H), 7.01-6.97 (m, 2H), 5.08 (dq, J = 8 .5, 6.3 Hz, 1H), 3.16-3.05 (m, 1H), 2.30 (s, 3H), 2.28 (s, 3H), 2.06 (s, 3H) , 1.21 (d, J = 6.9 Hz, 3H), 1.06 (d, J = 6.3 Hz, 3H);nC NMR (126 MHz, CDCb) δ 170.80, 138.92, 135.56, 135.42, 131.22, 126.93, 126.33, 75.09, 39.48, 21.34, 20.89, 19.88, 18.34,17.96; EIMS m / z 220. Alcohol:1H NMR (500 MHz, CDCb) δ 7.06 (d, J = 8.5 Hz, 1H), 7.01 - 6.97 (m, 2H), 3.88 ( tt, J = 9.2, 4.7 Hz, 1H), 2.97 (p, J = 6.9 Hz, 1H), 2.30 (s, 3H), 2.28 (s, 3H), 1.49 (d; J = 3.5 Hz, 1H), 1.28 (d, J = 7.0 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H);13C NMR (126'MHz, CDCb) δ 140.00, 135.49, 135.38, 131.31, 126.82, 126.18, 71.92, 41.43, 21.25, 20.87.19, 85,16,07; EIMS mfz 178. The enantiomeric ratio of (2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol was determined to be 96:4 by enantiomeric HPLC separation analysis (wavelength 21 Onm ).|H' ·,ι;: IF-2019-52232722- -ANP#INPI Page 71 of 408 or IF-2019-52232722-APN-ANP#INPI Page or

[0066] Step 2: Preparation of (2R,3R)-3-(2,4-dimethylphenyl)butan-2-ol. CH3ch3

[0067] To a solution that CH3ch3 contained (2R,3R)-3-(2,4 dimethylphenyl)butan-2-yl acetate prepared above (458 mg, 2.08 mmol) dissolved in I I methane! (4.2 mL) potassium carbonate (431 mg, 3.12 mmol) was added. The mixture I was stirred at room temperature for 1.5 hr, then heated to 50°C for I hr. The reaction was cooled and concentrated under reduced pressure. The residue was diluted with acetone and passed through a small plug of silica gel, washing the pad well with acetone. The solvent was concentrated in vacuo to provide (2R,3R)-3-(2,4-dimethylphenyl)butan-2-o! (332 mg, 90%) as yellow oil: NMR (500 MHz, CDCfe) δ 7.06 (d, J = 8.5 Hz, 1H), 7.01 - 6.97 (m, 2H), 3.88 (p, J = 6.3 Hz, 1H), 2.97 (p, J = 6.9 Hz, 1H). 2.30 (s, 3H), 2.28 (s, 3H), 1.49 (s, 1H), 1.28 (d, J = 7.0 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H);13C NMR (126 MHz, CDCI3) δ 140.00, 135.49, 135.38, 131.31, 126.82, 126.18, 71.92, 41.43, 21.26, 20.87, 19.85, 16.07; EIMS m / z 178. The enantiomeric ratio of the alcohol was determined to be 7:93 by enantiomeric HPLC analysis.

[0068] Example 3: Preparation of (2S.3S)3-phenylbutan-2-ol (fer-butoxycarbonylJ-L-alaninate.

[0069] To a solution of (2S,3S)-3-phenylbutan-2-o! (0.23 g, 1.53 mmol) dissolved in methylene chloride (7.7 mL) Λ / -βίΠ-ΛΓ-(3IF-2019-52232722-AI?7-ANP#INPI) hydrochloride was added Page 73 of 408 or IF-2019-52232722-APN-ANP#INPI Pygim 71 íIb 10? or dimethylaminopropyl)carbodiimide (0.59 g, 3.06 mmol) and N,A / -dimethylpyridine-4-amine (19 mg, 0.15 mmol). The reaction mixture was purged with nitrogen, stirred for 16 hr, followed by concentration in vacuo. The crude residue was purified by automated flash column chromatography (SiO2, gradient 0-20% ethyl acetate / hexanes) to provide ((2S,3S)-3- tert-butoxycarbonylJ-L-alaninate phenylbutan-2-yl (0.43 g, 1.34 mmol, yield 83%) as oil Colorless: 1H NMR (400 MHz, CDCfe) 67.35-7.25 (m, 2H), 7, 27-7.15 (m, 3H), 5.12·:: , - 5.01 (m, 2H), 4.35 - 4.26 (m, 1H), 2.95 - 2.83 (m , 1H), 1.45 (s, 9H), 1.37 (d, J = 7.2 Hz, 3H), 1.29 (d, J = 7.1 Hz, 3H), 1.09 (d , J = 6.3 Hz, 3H);13C NMR (126 MHz, CDCh) 6 172.9,155.0, 143.0,128.5,127.8, 126.7, 79.7, 76.1, 49.5, 45.1, 28.3,18.9, 18.3, 17.5; IR (thin film) 3355, 2978, 2934, 1711, 1495, 1452, 1366, 1161, 1087,1065,701 cm·1. ''

[0070] Example 4: Preparation of (2S,3S)-3-phenylbutan-2-yl (S-hydroxM-methoxypicolinoiH-alaninate.

[0071] Step 1: Preparation of (2S,3S)-3-phenylbutan-2-yl-L·alaninate hydrochloride. · . cr ch3. oh3* I ·

[0072] To pure (2S,3S)-3-phenylbutan-2-ol (tert-butoxycarbonyl)-L-alaninate (0.42 g, 1.31 mmol) a solution of HCl dissolved in dioxane was added dropwise. (4 M, 3.3 mL, 13.07 mmol) under nitrogen. Upon stirring for 16 hr, the reaction mixture was concentrated in vacuo to provide crude (2S,3S)-3-phenylbutan-2-yl-L·alaninate-hydrogen chloride as a white solid, which was taken directly to the next step: HRMS-ESI (m / z) [M+H]+ calculated for C^H^NO^ 222.1489; found 222.1485. IF-2019-52232722-A^-ANP#INPI Page 75 of 408 IF-2019-52232722-APN-ANP#INPI Pigini 76 gives 108

[0073] Step 2: Preparation of (2S,3S)-3-phenylbutan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate.

[0074] To a solution of (2S,3S)-3-phenylobutan-2-yl-L-alaninate-chloride. hydrogen, 3-hydroxy-4-methoxypicolinic acid (0.24 g, 1.44 mmol), and (benzotriazol-1-yloxy)tripyrrolidinephosphonium hexafluorophosphate (0.75 g, 1.44 mmol) dissolved in methylene chloride (6.5 mL) Λ / ,ΛΛdiisopropylethylamine (0.75 mL, 4.31 mmol) was added dropwise under nitrogen. After stirring for 16 hr, the reaction mixture was concentrated in vacuo. The crude residue was purified by automated flash column chromatography (SiO2, 045% acetone / hexanes gradient) to provide (2S,3S)-3-phenylbutane (3-hydroxy-4-methoxypicolinoyl)-L·alaninate. 2-yl (0.46 g, 1.173 mmol, 90% yield) as colorless oil: 1H NMR (500 MHz, CDCI3) δ 12.16 (s, 1H), 8.50 (d, J = 8 .0 Hz, 1H), 8.01 (d, J = 5.2 Hz, 1H), 7.32 - 7.27 (m, 2H), 7.24 - 7.16 (m, 3H), 6 .88 (d, J= 5.2 Hz, 1H), 5.11 (dq, J = 7.7, 6.3 Hz, 1H), 4.77 - 4.67 (m, 1H), 3, 95 (s, 3H), 2.97 - 2.87 (m, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.31 (d, J = 7.0 Hz, 3H ), 1.13 (d, J = 6.3 Hz, 3H): IR (thin film) 2978,2937,1733,1647,1527,1451,1262,1147,701 cm'1; HRMS-ESI (m / z) [M+H]+ calculated for C2qH25N2O5, 373.1758; found, 373.1752.

[0075] Example 5A: Preparation of (2S,3S)-3-phenylbutan-2-yl (3-acetoxy-4-methoxypicolinoyl)-L-allannate. {Item. IF-2019-52232722-A^-ANP#INPI Page 77 of 408 or IF-2019-52232722-APN-ANP#INPI Piigino 7? da 108

[0076] To a solution containing (2S,3S)-3-phenylbutan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (84 mg, 0.23 mmol) dissolved in pyridine (1, 0 mL) is . added acetic anhydride (0.25 mL, 2.65 mmol) dropwise under nitrogen. Upon stirring for 30 min, the reaction mixture was concentrated in vacuo, followed by azeotropization with toluene (10 mL). The crude residue was purified by automated flash column chromatography (SIO2, 0-40% acetone / hexanes gradient) to provide (3-acetoxy-4-methoxypicolinoyl)-(2S)-alaninate. 3S)-3-phenylbutan-2-yl (90 mg, 0.21 mmol, 91% yield) as colorless oil: 1H NMR (500 MHz, CDCI3) δ 8.56 (s, 1H), 8, 34 (d, 5.5 Hz, 1H), 7.32 - 7.27 (m, 2H), 7.24 - 7.16 (m, 3H), 7.01 (d, J = 5.5 Hz, 1H), 5.09 (dq, J = 7.7, 6.3 Hz, 1H), 4.77 - 4.67 (m, 1H), 3.91 (s, 3H), 2.96 - 2.86 (m, 1H), 2.41 (s, 3H); 1.49 (d, J = 7.2 Hz, 3H), 1.30 (d, J = 7.0 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H); IR (thin film) 3377, 2980, 2938, 1770, 1732, 1674, 1507, 1310, 1198, 1174, 702 cm'1; HRMS-ESI (m / z) [M+H]+ calculated for C^H^hfeOe, 415.1864; found, 415,1859.

[0077] Example 5B: Preparation of (2S,3R)-3-(o-tolyl)butan-2-yl (3-(acetoxymethoxy)-4-methoxypicolino¡I>!alaninate.

[0078] To a solution containing (2S,3R)-3-(o-tolyl)butan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate dissolved in 0.7 mL of acetone was added IF-2019-5223272-A^?-ANP#INPI Page 79 of 408 Yo IF-2019-52232722-APN-ANP#INPI Pigim 80 gives 1O& Potassium carbonate (39 mg, 0.279 mmol) followed by bromomethyl acetate (27 pL, 0.279 mmol). The solution was heated at 50°C for 1.5 hr. The reaction mixture was cooled and concentrated in vacuo. The crude residue was purified by automated flash column chromatography (SiO2, 0-80% acetone / hexanes gradient) to provide (2S,3R)-(3-(acetoxymethoxy)-4-methoxypicolinoyl)-L·alaninate. 3-(o-tolÍI)butan-2-yl (63 mg, 93% yield) as thick oil:1H NMR (500 MHz, CDCI3) δ 8.26 (d, J= 5.4 Hz, 1H ), 8.22 (t, J= 7.4 Hz, 1H), 7.22-7.03 (m, 4H), 6.93 (d, 5.4 Hz, 1H), 5.73 (dd, J = 5,6,1.8Hz, 2H), 5.16 (dq, J= 8.1, 6.3 Hz, 1H), 4.58-4.51 (m, 1H), 3.90 (s, 3H), 3.31-3.22 ( m, 1H), 2.37 (s, 3H), 2.06 (s, 3H), 1.31 (d, J = 6.2 Hz, 3H), 1.24 (d, J= 7.0 Hz, 3H), 1.03 (d, J = 7.2 Hz, 3H);13C NMR (126 MHz, CDCI3) δ 172.26, 170.26, 162.87, 160.25, 145.68, 143.94, 142.57, 141.57, 136.03, 130.21, 126.16, 125.94, 109.49, 89.57, 75.57, 56.16, 48.08, 39, 48, 20.87, 19.84, 17.92, 17.77, 17.05; HRMS-ES! (m / z) [M+H]* calculated for C^H^NaCh, 459.2126; found 459.2121. ': Zt

[0079] Example 5C: Preparation of 4-methoxy-2-(((S)-1-oxo-1(((2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl) isobutyrate )ox¡)propan-2-yl)carbamoyl)pyridin-3-iIo. o ch3n ΊΓ i0o ch3¿h3cf3o ch3n Π \0o ch3¿h3cf3

[0080] A solution containing (2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaniriate (283.9 mg, 0.645 mmol ) y¿ / V, / Vdimethylpyridin-4-amine (15.75 mg, 0.129 mmol) was prepared in CH2CI2 (2 mL). To this solution, triethylamine (0.180 mL, 1.289 mmol) was added followed by isobutyryl chloride (0.102 mL, 0.967 mmol). The resulting clear reaction was stirred at IF-2019-52232722-AI^-ANP#INPI Page 81 of 408 or IF-2019-52232722-APN-ANP#INPI or room temperature overnight. The reaction was concentrated under reduced pressure to give an orange oil under a stream of N2-_. The crude residue was purified by automated flash column chromatography (SiO2, 0 - 100% ethyl acetate / hexanes gradient) to provide 4-methoxy-2-(((5)-1-oxo-1-(((2S,35)-3^(2-:(trifluoromethyl)phenyl)butan-2-yl)oxy)propane isobutyrate 2-yl)carbamoyl)pyridin-3-yl (252.3 mg, 0.494 mmol, 77% yield) as yellow oil:1H NMR (400 MHz, CDCl3) δ 8.50 (d, J = 7, 4 Hz, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.64 (dd, J = 8.0, 1.3 Hz, 1H), 7.54 - 7t47 (m, 1H), 7.44 (d, J = 7.8 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 6.99 (d, J = 5.4 Hz, 1H) , 5.26 - 5.11 (m, 1H), 4.76 (p, J = 7.3 Hz, 1H), 3.89 (s, 3H), 3.34 (p, J = 6.6 Hz, 1H), 2.96 (hept, J = 7.0 Hz, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.36 (dd, J = 7.0, 1 .3 Hz, 6H), 1.28 (d, J = 6.8 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H);19F NMR (376 MHz, CDCb) δ -58 .25; IR (thin film) 3383, 2981, 1737, 1679, 1505, 1310, 1114, 1045, 732 cm'1; HRMS-ESI (m / z) [M+Hf calculated for C25H3oF3N206, 511.2050; found, 511.2048.

[0081] Example 6: Preparation of (3-acetoxy-4-methoxypyridin-2-carbonothioyl)-Lalaninatode(2S,35)-3-(2,4-dimethylphenyl)butan-2-yl. ¡

[0082] Step 1: Preparation of (25,35)-3-(2-(trifluoromethyl)phenyl)butan-2-yl (3-hydroxy-4-methoxypyridin-2-carbonothioII)-alaninate.

[0083] To a solution containing (2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl (3-hydroxy-4-methoxypicol¡no¡l)-L-alaninate (120, 1 mg, 0.273 mmol) dissolved in acetonitrile (2.73 mL), phosphorus pentasulfide (121 mg, 0.545 mmol) was added IF-2019-52232722-Al4?-ANP#INPI ______________________ Page 83 of 408 or IF-2019-52232722-APN-ANP#INPI or followed by 1,1,1,3,3,3-hexamethyldisiloxane (291 pL, 1.363 mmol) added in one portion. The reaction was heated to 45°C for 30 min. The reaction was cooled, diluted with CH2CI2 (10 mL) and quenched with the addition of saturated aqueous NaHCO3 (10 mL). The layers were separated and the aqueous layer was extracted with CH2CI2 (3 x 10 mL). The combined organic layers were passed through a phase separator and concentrated to a yellow oil. The crude material was purified by automated flash column chromatography (SiOz, gradient 0 - 50% acetone / hexanes) to provide (3-hydroxy-4methoxypyridin-2-carbonothioyl)-L-alaninate (2S, 3S)-3-(2-(trifluoromethyl)phenyl)butan-2yl (104.7 mg, 0.229 mmol, 84% yield) as a yellow semisolid; 'H NMR (400 MHz, CDCI3) δ 12.93 (s, 1H), 10.74 (d, J = 7.6 Hz, 1H), 8.00 (d, J = 5.1 ' Hz, 1H ), 7.73-7.59 (m, 1H),7.51 (t, J=7.7Hz, 1H), 7.43 (d, J= 7.8 Hz, 1H), 7.33 ( t, J = 7.5 Hz, 1H), 6.89 (d, J = 5.1 Hz, 1H), 5.30 - 5.18 (m, 1H), 5.14 (p, J = 7 .2 Hz, 1H), 3.96 (s, 3H), 3.37 (p, J= 6.8 Hz, 1H), 1.69 (dd, J = 7.2, 3.2 Hz, 3H ), 1.30 (d, J = 6.8 Hz, 3H), 1.14 (d, J = 6.3 Hz, 3H);,9F NMR (376 MHz, CDCI3) δ -58.23; IR (thin film) 3087,2984,1737,1513,1484,1311,1151,1118, 800, 771 cm'1; HRMS-ESI (m / z) [M+Hf calculated for CjiHmFjNjC^S, 457.1403; found, 457.1399. --.-1.1

[0084] Step 2: Preparation of (3-acetoxy-4-methoxypyridin-2-carbonothioyl)-(2S,3S)-3-(2-(trifluoromet¡l)phen¡!)butan-2-yl lalaninate.

[0085] To a solution containing (3-hydroxy-4-methoxypyridin-2-carbonothioyl)-(2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl lalaninate (53.9 mg , 0.118 mmol) and IF-2019-52232722-APN-ANP#INPI Page 85 of 408 or c 108 IF-2019-52232722-APN-ANP#INPI or To / ,AZ-dimethylpyridin-4-amine (2.89 mg, 0.024 mmol) dissolved in CH2CI2 (2 mL)' triethylamine (0.041 mL, 0.295 mmol) was added followed by acetyl chloride (9.23 pL, 0.130 mmol ). The resulting light orange reaction was stirred at room temperature for 18 hr. The reaction was concentrated under reduced pressure; A to provide an orange oil under a current of N2. The crude residue was purified by automated flash column chromatography (SIO2, r' ' * gradient 0 - 50% acetone / hexanes) to provide (3-acetoxMmethoxypyridin-2-carbonothioyl)-L-alaninate ( 2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2yl (51.7 mg, 0.104 mmol, 88% yield) as yellow oil: 'H NMR (400 MHz, CDCIj) δ 9, 96 (d, J = 7.3 Hz, 1H), 8.34 (d, J= 5.5 Hz, 1H), 7.71 -7.59 (m, 1H), 7.59 - 7.47 (m, 1H), 7.44 (d, J = 7.8 Hz, 1H), 7.39 - 7.28 (m, 1H), 7.00 (d, J = 5.5 Hz, 1H) , 5.28-5.15 (m, 2H), 3.91 (s, 3H), 3.42-3.29 (m, 1H), 2.37 (s, 3H), 1.64 (d , J= 7.2 Hz, 3H), 1.30 (d, J = 6.8 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H);19F NMR (376 MHz, CDCIj ) δ -58.23; HRMS-ESI (m / z) [M+H]+calculated for C23H26F3N2O5S, 499.1509; found, 499.1508. ' '

[0086] Example 7: Preparation of 3-hydroxy-4-methoxy-2-(((S)-Í-oxo1-(((2S,3S)-3-phenylbutan-2-yl)oxy) 1-oxide propan-2-yl)carbamoyl)pyridine.

[0087] To a solution containing (2S,3S)-3-phenylbutan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (54 mg, 0.15 mmol) dissolved in methylene chloride ( 1.0 mL) m-CPBA (50 mg, 0.29 mmol) was added. After stirring for 30 min at room temperature, the reaction mixture was concentrated in vacuo. The crude residue was purified by automated flash column chromatography (SÍO2, IF-2019-52232722-APÍ?-ANP#INPI Page 87 of 408 or IF-2019-52232722-APN-ANP#INPI Figinti or •J.líi (MÍJ;. gradient 0 - 50% acetone / hexanes) to provide 3-hydroxy-4methoxy-2-(((S)-1-oxo-1-(((2S,3S)-3-phenylbutan-2- yl)oxy)propan-2-yl)carbamoyl)pyridine · — - —f —* —·— * (51 mg, 0.13 mmol, 86% yield) as a pale yellow, viscous oil: 'H NMR (500 MHz, CDCI3) δ 14.39 (s, 1H), 12.82 (d, J = 6.9 Hz, 1H), 7.89 (<f 'J = 7.2· .. ·. Hz, 1H), 7.32 - 7.25 (m, 2H), 7.25 - 7.15 (m, 3H), 6.78 (d, J = 7.2 Hz, 1H), 5.10 (dq, 4= 8.1,6.3 Hz, 1H), 4.75 - 4.64 (m, 1H), 3.97 (s, 3H), 2.96-2.86 (m, 1H ), 1.56 (d, J = 7.2 Hz, 3H), 1.30 (d, J= 6.9 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H); IR (thin film) 2978, 2937, 1735, 1643, 1569,1479,1452, 1211,1154, 729, 702 cm''; HRMS-ESI (m / z) [M+H]+ calculated for C20H25N2O6,389.1707; found 389.1703.

[0088] Example 8: Preparation of (S)-2-(8-methoxy¡-2,4-dioxo-2H-pyrido[2,3e][1,3]oxazin-3(4H)-yl) (2S,3S)-3-phenylbutan-2-yl propanoate. ''

[0089] To a solution containing (3-hydroxy-4-methoxypicolinoyl)-Z.-alaninate of 1' - (2S,3S)-3-phenylbutan-2-yl (54 mg, 0.15 mmol) and triphosgene (86 mg, 0.29 mmol) dissolved in methylene chloride (1.0 mL), pyridine (0.1 mL, 1.24 mmol) was added. After stirring for 45 min, the reaction mixture was quenched with saturated sodium bicarbonate solution (5 mL) and extracted with methylene chloride (3 5____...... ' > 11. ·. > yes.. mL). The organics were passed through a phase separator and concentrated in vacuo. The crude residue was purified by automated flash column chromatography (SiO2, gradient 0 - 40% acetone / hexanes) to provide (S)-2-(8-methoxy-2,4-dioxo-2H-pyrido[ (2S,3S)-3-phenylbutan-2-yl 2,3-e][1,3]oxazin3(4H)-iI)propanoate (41 mg, 0.10 mmol, 67% yield) as whitish foam:1H NMR (500 MHz, CDCI3) δ 8.61 (d, J IF-2019-52232722-AI^-ANP#INPI .., .: j i Page 89 of 408 o an λ.· / ing IF-2019-52232722-APN-ANP#INPI J / . I V'«, or = 5.3 Hz, 1H), 7.24-7.17 (m,2H), 7.17-7.06 (m, 4H), 5.61 (q, J = 7.1 Hz, 1H) , 5.16 * — · * ' * * * * * * * - * I —w- Μ φ, - 5.06 (m, 1H), 4.06 (s, 3H), 2.93 - 2.83 (m, 1H), 1.70 (d, J = 7.1 Hz, 3H), 1, 27 (d, J = 7.1 Hz, 3H), 1.04 (d, J = 6.3 Hz, 3H); IR (thin film) 2978, 2942; 1769,\ '. F 1712, 1602, 1501, 1371, 1242, 1081, 702 cm'1; HRMS-ES1 (m / z) [M+H]+ calculated for C21H23N2O6,399,1551; found 399.1549.

[0090] Example A: Evaluation of fungicidal activity: Wheat leaf spot (Zymoseptoria tritici; Bayer code SEPTTR): ' >.

[0091] Technical grades of materials were dissolved in acetone, which was then mixed with nine volumes of water containing 110 ppm Triton X-100. The fungicide solutions were applied to wheat seedlings with the use of an automated booth sprayer for slip runoff. All sprayed seedlings were allowed to air dry before further handling. All fungicides were evaluated by the method mentioned above for activity with respect to all target diseases, unless otherwise stated. Wheat leaf spot and wheat brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941. in spray solutions. 'ς 0i

[0092] Wheat plants (Yuma variety) were grown from seed in a greenhouse in a Metro 50% mineral soil / 50% soilless mixture until the first leaf fully emerged, with 7-10 seedlings per well? These plants were inoculated with an aqueous suspension of Zymoseptoria tntici spores either before or after fungicide treatments. After inoculation, the plants were maintained with 100% relative humidity (one day in a chamber Yo IF-2019-522327r2^-A?^ANP#INPI í Page 91 of 408 or IF-2019-52232722-APN-ANP#INPI Page or dark dew chamber followed by two to three days in an illuminated dew chamber at , 20°C) to allow spore germination and leaf infection. The plants were then transferred to a greenhouse set at 20°C for disease development. When disease symptoms were fully expressed in the first leaves of untreated plants, infection levels were evaluated based 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 on treated plants to untreated plants. *

[0093] Example B: Evaluation of fungicidal activity: brown rust of wheat (Puccinia triticina; synonym: Puccinia recondita f. sp. tritici; Bayer code PUCCRT):

[0094] Wheat plants (Yuma variety) were grown from seeds in a I 'greenhouse in a mixture Metro 50% mineral soil / 50% soilless until the first leaf fully sprouted, with 7-10 seedlings per pot. These plants were inoculated with an aqueous suspension of Puccinia triticina spores either I before or after fungicide treatments. After inoculation, the plants were kept in a dark dew room at 22°C with 100% Relative Humidity overnight to allow the spores to germinate and infect the leaves. The plants were then transferred to a greenhouse set at 24°C. Ifor the disease to develop. The fungicide formulation, fungicide application and disease evaluation followed the procedures as described in Example A.

[0095] Example C: Evaluation of fungicidal activity: Asian soybean rust (Phakopsorapachyrhizi; Bayer code PHAKPA):,bí IF-2019-52232722-APN-ANP#INPI Page 93 of 408 or IF-2019-52232722-APN-ANP#INPI Page 91 gives 108 or ,

[0096] Technical grades of materials were dissolved in acetone and then ? : mixed with nine volumes of water containing 0011% Tween 20. The fungicide solutions were applied to soybean seedlings with the use of an automated booth sprayer until runoff. All plants atomized... , were allowed to air dry before further handling. · / - t · ·’ / '?< >

[0097] Soybean plants (Williams 82 variety) were grown in a soilless Metro mix, with one plant per pot. Two-week-old seedlings were used for the test. The plants were inoculated either 3 days before or 2 days after the fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22°C and 100% relative humidity and then transferred to a growth room at 23°C for disease development. The severity of the disease was evaluated on the sprayed leaves.' ,

[0098] Example D: Evaluation of fungicidal activity: early burn of tomato (Alternaria solani; Bayer code ALTESO):

[0099] Tomato plants (Outdoor Giri variety) were propagated in a soilless Metro mix, with one plant per pot, and used when they reached 12 to 14 days of age. The test plants were inoculated with an aqueous suspension* of Alternaria solani spores 24 hours after the fungicide treatments. After inoculation, plants were maintained at 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber* at 20°C) to allow spores to germinate and infect. The leaves' plants were then transferred to a growth room at 22°C for disease development. The fungicide formulation, application and evaluation of the disease on the sprayed leaves followed the procedures described in Example A.11. IF-2019-52232722-APN-ANP#INPI __ _ Page 95 of 408 or IF-2019-52232722-APN-ANP#INPI Page

[00100] Example E: Evaluation of Fungicidal Activity: Leaf spot ·, - \ of sugar beets {Cercospora b etico la; Bayer code CERCBE):

[00101] Sugar beet plants (variety HH88) were grown in soilless Metro mix and pruned regularly to maintain uniform plant size / size prior to testing. The plants were inoculated with a '* ' · ' spore suspension 24 hours after the fungicide treatments. The inoculated plants were kept in a dew chamber at 22°C for 48 hr, then incubated in a greenhouse at 24°C under a transparent plastic hood with ventilation at the bottom until disease symptoms were fully expressed. . The fungicide formulation, application and evaluation of the disease on the sprayed leaves followed the procedures described in Example A.

[00102] Example F: Evaluation of fungicidal activity: Cucumber anthracnose (Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer code COLLLA):

[00103] Cucumber seedlings (Bush Pickle variety) were propagated in a soilless Metro mix, with one plant per pot, and used in the test when they reached 12 to 14 days of age. The test plants were inoculated with an aqueous suspension of Colletotrichum lagenarium spores 24 hr after the fungicide treatments. After inoculation, the plants were kept in a dew room at 22°C with 100% relative humidity for 48 hr to allow the spores to germinate and infect the leaves. The plants were then transferred to a growth room set at 22°C for disease development. The fungicide formulation, application and evaluationLde -la IF-2019-52232722-APN-ANP#INPI Page 97 of 408 O il I IF-2019-52232722-APN-ANP#INPI or disease on sprayed leaves followed the procedures described in Example A.

[00104] Example G: Evaluation of fungicidal activity: Wheat glume spot (Parastagonospora nodorum; Bayer code LEPTNO):

[00105] Wheat plants (Yuma variety) were grown from seed in a greenhouse in a Metro 50% mineral soil / 50% soilless mixture until the first leaf fully emerged, with 7-10 seedlings per pot. These plants. · ; They were inoculated with an aqueous suspension of Parastagonospora nodorum spores 24 hr after the fungicide treatments. After inoculation, plants were maintained at 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20°C) to allow spores to germinate and infect. to the leaves. The plants were then transferred to a greenhouse set at 20°C for disease development. The fungicide formulation, application and disease evaluation followed the procedures described in Example A. I

[00106] Example H: Evaluation of fungicidal activity: cucumber powdery mildew (Pseudoperonospora cubensis; Bayer code PSPECU):ur:í;r

[00107] Cucumber seedlings (Bush Pickle variety) were grown in soilless Metro mix, with one plant per pot, and used in the test when they reached 12 to 14 days of age. The plants were inoculated with a spore suspension 24 hours after the fungicide treatments. The test plants were inoculated with an aqueous suspension of Pseudoperonospora cubensis spores 24 hours after the fungicide treatments. After inoculation, plants were kept in a dew room at 22°C with 100% relative humidity for 24 hr to allow spores to germinate. IF-2019-52232722-APN-ANP#INPI . ,<1 í l . Hey» Page 99 of 408 IF-2019-52232722-APN-ANP#INPI and infect the leaves. Plants were transferred to a greenhouse set at 20°C until the disease was fully expressed. The fungicide formulation, application and disease evaluation on the sprayed leaves followed ' * =. the procedures described in Example A. ’1 / · ‘ .

[00108] Example I: Evaluation of fungicidal activity: rice blast (Magnaporthe grísea; anamorph: Piricularía oryzae; Bayer code PIRIOR):

[00109] Rice seedlings (Japonica variety) were propagated in a soilless λ Metro mixture, with 8 to 14 plants per pot, and used in the test when they reached 12 to 14 days of age. The test plants were inoculated with an aqueous suspension of Piricularía oryzae spores 24 hr after the fungicide treatments. After inoculation, the plants were kept in a dew room at 22°C, with 100% relative humidity for 48 hr to allow the spores to germinate and infect the leaves. The plants were then transferred to a greenhouse set at 24°C for disease development. The fungicide formulation, application and evaluation of the disease on the sprayed leaves followed the procedures described in Example A.

[00110] Example J: Evaluation of fungicidal activity: scald of barley (Rhyncosporíum secalis; Bayer code RHYNSE):.....'A

[00111] Barley seedlings (variety Harrington) were propagated in soilless Metro mix, with 8 to 12 plants per pot, and used in the test when the first leaf fully emerged. The test plants were inoculated with an aqueous suspension of Rhyncosporíum secalis spores 24 tir after the fungicide treatments. After inoculation, plants were kept in a dew room at 20eC with 100% relative humidity for 48 hr. The * * - * 51 IF-2019-52232722-APN-ANP#INPI . T’ h Page 101 of 408 IF-2019-52232722-APN-ANP#INPI Page : Plants were then transferred to a greenhouse established at 20°C for the disease to develop, the fungicide formulation, application and evaluation of the disease on the sprayed leaves followed the procedures Rescribed____ in Example A. . . , -v '

[00112] Example K: Evaluation of fungicide activity: powdery mildew of grapes (Uncinula necator, Bayer code UNCINE):

[00113] Grape seedlings (Carignane variety) were grown in a mixture meter without soil, with one plant per pot, and were used in the test when they reached approximately 1 month of age. Plants were inoculated 24 hours after fungicide treatment by shaking spores from infected leaves on the test plants. The plants were kept in a greenhouse established at 20°C until the disease fully developed. The fungicide formulation, application and evaluation of the disease on the sprayed leaves followed the procedures described in Example A. Table 1. Structure of the compound, appearance and preparation method Cmpd. No. Structure According to preparation according to f .4 Appearance 1 or ch3 η II ! h3c. >^ch3 HaC-q Π 0 I CH3 O H3C^^k F Example 1A Example 2 Example 3 Oil . _ * 1.7 ι-t IF-2019-52232722-APN-ANP#INPI .. i Page 103 of 408 or IF-2019-52232722-APN-ANP#INPI Page or Cmpd. No. ch3o structure h3c or H ° N H ye? fk Jl u 9H3C^°^n, J¡ HaC-T V ÍcV°yw'CH3 O CH3H3C ° CH3H3C ch3 CH, CH3ch3 HaC^CHf ch3 ch3 ch3ch3o CH3 ,»\CH3 CHi,.cCH3 According to the Preparation <faith according to Appearance Example 1A I Example 2 r Oil Examples' Example 1A j Example 2 I Oil Example 3 Example 1A j Example 2 I Oil Example 3 I Example 1A í Example 2 j Oil Example 3 I Example 1A Example 2 I Oil Example 3 I Page 105 of 408 IF-2019-52232722-APN-ANP#INTI or IF-2019-52232722-APN-ANP#INPI Page 106 of 408 Cmpd. No. Structure HΠ jl H ° NCH3 or ch3h3c ch3O either According to the [ —--Preparation^ according ¡AP¡appearance with I ch3ó l u p ch3 ,*xCH3ch3 CH, „.ΧΗ3.g'CH3 H3c Example 1A Example 2 Example'3 Example 1A Example 2 Example 3 Example 1B Example 2 Example 3 *· Oil Oil Oil CH3o h3c o or h3c CH, ch3CH3 or CH· Example 1B Example 2 Example 3 ch3 oil ,^ch3 Example 1B Example 2 Example 3 Oil IF-2019-52232722-APN-ANP#! Page 107 of 408 or IF-2019-52232722-APN-ANP#INPI Page 108 of 408 or Cmpd. No. Structure According to l preparationAgree I Appearance with nH° rV oCHs or ch3h3c ch3 ,.^ch3 Example 1B Example 2 Ί Oil Example3 h H ff N Jí O CH3o ch3 ch3 Example 1B Example 2 Example 3 oil or H3c O. Nh3C7 JT CH3o Or ch3ch3 ch3 Example 1B Example 2 Example 3 OilH3Cx^°^J. JtΗ3θ·Π Π ΥΌ ch3ch3ch3o HaC CH3 F Example 1B Example 2 Example 3 Oil H ° NO CH3 H3C. rrΗ3°-ητ > CH3o ch3 ch3 Example 1B Example 2 Example 3 Oil Page 109 of 408 IF-2019-52232722-APN-ANP#INPl or IF-2019-52232722-APN-ANP#INPI Page 110 of 408 or Cmpd. No. Structure According to Preparation according to •Appearance ch3o H ye? N Jl o h3c ch3h3c° or ch7 ch3h3c-° Example 1B Example 2 Example 3 I π Γ o CH3O 1H cch3 ch3 Example 1B Example 2 Example 3 h3c^°nΗ ° CH3rV oCHs or ch3h3c ch3h3c^° Example 1B Example 2 Example 3 Example 1B Example 2 Example 3 Oil Oil Oil Page 111 of 408 IF-2019-52232722-APN-ANP#! either IF-2019-52232722-APN-ANP#INPI Page 112 of 408 or h3c ch3h3c oil Oil H3c CH3h3c ch3__ oil .ch ch3 oil CH H3C Oil h N h N h N h N,, ch ch3.cCH3 No. or ch3h3c or h3c Preparation according to I Appearance with ch. ch3h3c h3c ch3h3c h3c ’3 Cmpd. Structure According to ,.»'CH3,aCH ,»xCH3 Example 1A Example 2 Example 3 Example 1A Example 2 Example 3 Example 1A Example 2 Example 3 Example 1A Example 2 Example 3 Example 1A Example 2 Example 3 Page 113 of 408 IF-2019-52232722-APN-ANP#INII or IF-2019-52232722-APN-ANP#INPI Page 114 of 40. either Page 115 of 408 IF-2019-52232722-APN-ANP#! either IF-2019-52232722-APN-ANP#INPI Page 116 of 408 « 59 Page 117 of 408 IF-2019-52232722-APN-ANP#! either IF-2019-52232722-APN-ANP#INPI Page 118 of 408 Page 119 of 408 IF-2019-52232722-APN-ANP#INP or IF-2019-52232722-APN-ANP#INPI Page 120 of 408 or Page 121 of 408 it·. IF-2019-52232722-APN-ANP#! either IF-2019-52232722-APN-ANP#INPI Page 122 of 408 Cmpd. No. Structure According to l -----PreparationAgree IAPar¡ance with τ ’ ·H3CN / °-s, h3c / T lí ch3o Example 1A Ί Example 2 Example 3 I 'Yellow oil HaC-T J[CH3 O CH3 H3C h3c or H HaC'T |fCH3 O ch3ch3ch3h3c ch3ch3 Example 1A Example 3. Oil . colorless, transparent Example 1A Example 3 Pale yellow oil I - ·λΊ·. . Yo Example 1A Example 2 Example 3 CH3O Ah i3 υ CH3 ch3ch3 Colorless, transparent h3c oil. H3C' ch3O •áWch3 ch3¿h3 Σ jíc η30< IT ch3o ch3 ch3ch3h3c H3C‘CH3 or CH3 ch3ch3h3c H3C' H 5? either. JL Jl Ί ί] T ° OH, OR CH3 ch3CL ch3 Example 1A í Oil I Example 2 1 yellow I Example 3 1 pale I Example 1A 1 Oil I Example 2 1 colorless, Example 3 ' transparent Example 1A I Oil Example 2 colorless, Example 3 I transparent Example 1B 1 I* > - p: · - 1 Example 2 Colorless j oil 1 Example 3 1 IF-20192232722-APN*#ΙΝΡ1 Page 123 of 408 IF-2019-52232722-APN-ANP#INPI Page 124 of 408 or ch3 CH3 CH3 CH3 CH CH3 CH3ch3ch3 CH ch3o residue Oil CH ch3h2N Oil Oil CH3ch No. Colorless oil h3c h3c ch3h3c h3c ch3h3c h3c ch with ch3 N CH3ch3o or HN Cmpd. Structure According to Preparation of agreement IAParfencla ch3ch3 CH3CH Example 1C Example 2. Example 3 Example 1B Example 2 Example 3 Example 1B Example 2 Example 3 Example 1B Example 2 Example 3 Example 4 Step 1 Example 4 Step 1 Example 4 Step 1 yellow oil colorless oil IF-2019-52232722-APN-ANP#! Page 125 of 408 or IF-2019-52232722-APN-ANP#INPI Page 126 of 41 Cmpd. No. Structure According to preparation according to Appearance 61 H2Nx o ch3 ij^<F ch3 Example 4. Step 1 • » ♦ · * Oil 62 or xr ?Ha rr%H3 ch3 ch3 Example'4 · . Step 1 . ; Oil 63 h2nx 0 9h3 ch3 ch3 Example 4 Step 1 Oil 64 0 Η2ΝΧ^Λ( ?H3 Í^VF ch3 ch3 Example 4 Step 1 Oil 65 H2Nx 0 QH3 ch3 ch3 Example 4 Step 1 Oil 66 H2N\x 0 χ·χχ' ch3 Example 4 Step 1 Oil 67 or H2N^X^> ?H3 ch3 ch3 Example 4 Step 1 Oil 68 ch3 ch3 ch3 Example 4 Step 1 Oil IF-2019-52232722-APN-ANP#INPI Page 127 of 408 IF-2019-52232722-APN-ANP#INPI Page 128 of 408 Page 129 of 408 IF-2019-52232722-APN-ANP#INP] IF-2019-52232722-APN-ANP#INPI Page 130 of 408 or ί li .66 Page 131 of 408 IF-2019-52232722-APN-ANP#INP] or IF-2019-52232722-APN-ANP#INPI Page 132 of 408 or Page 133 of 408 IF-2019-52232722-APN-ANP#! either IF-2019-52232722-APN-ANP#INPI Page 134 of 4! ch3h2n ch3h2n oil ch3h2n oil ch3ch3ch oil H2N Oil CH3ch3ch H2n Oil ch3ch3ch h2n ch3ch3h2n,. ch3 Step 1 Step 1 Step 1 Step 1 Step 1 Step 1 Step 1 ch3ch3ch3ch3ch3ch3ch3ch3 Cmpd. No. Structure According to preparation according to----Appearance h2n ch3ch3 Example 4 Step 1 Example 4 Example 4 Example 4 Example 4 Example 4 Example 4 Example 4 Oil Oil dark yellow oil IF-2019-52232722-APN-ANP#INPI Page 135 of 408 or IF-2019-52232722-APN-ANP#INPI Page 136 of 408 or Cmpd. No. Structure According to the preparation V v, according to Appearance with . 100 101 102 103 104 h2n„. CH3ch3ch3ch3h2n ch3 CH ch3 CH ch3h2n,„ ch3ch3 CH ° ch3h2n,„ ° ch3 H2N„, ch3 CH CH3 Example 4 · 'Step 1 ·vOil' yellow. - dark' Example 4 Step 1 Example 4 Step 1 Semisolid • brown Light brown semisolid Example 1A Example 2 Example 3 Example 4 1 Step 1 Pale yellow oil I Example 4 Step 1 I - ’ ' I Orange semisolid Example 4 1 Step 1 i < f I j S t Orange semisolid IF-2019-52232722-APN-ANP#INPI Page 137 of 408 or IF-2019-52232722-APN-ANP#INPI Page 138 of 408 105 106 107 108 109 110 Cmpd. No. Structure0ch3 CH3h3c H2N,, ch3CH3ch3h3c H2N„, ch3ch3ch3ch3 ch3ch3 H3c H2N,, -AVa' CH3r»|J Jttj4^Π3CH3 ch3ch3ch3 H2N,, ch3ch3ch3 According to the I Preparation according to lAParfencla with Example 1A Examples lo' 7 ‘ ' I Semisolid Example 3 I white Example 4 I Step 1 I. Example 4 · I;SemisolidPas°1white Example 4 Step 1 Example 4 Step 1 Pale yellow oil A rí 'i ' White semisolid Example 4 Step 1 Example 4 Step 1 Example 4 Step 1 I Glass I I colorless, transparent I Oil I colorless, transparent Colorless oil, transparent — IF-2019-52232722-APN-ANP#! Page 139 of 408 or IF-2019-52232722-APN-ANP#INPI Page 140 of 40_ or ch3 structure 112 ch3 113 h2n ch3 CH3ch3 114 H2N ch3ch3 115 ch3h3c ch3 116 CH3ch3ch h3c ch3ch3ch3ch .'Oil' • colorless No. colorless Oil Step 2 Step 1 thick oil or ch3ch3ch3ch3 Appearance Oil Step 2 Cmpd. According to preparation according to Example 4. Step 1 Example 4 ch3ch3 Step 1 Example 4 Step 1 Example 4 Example 4 Example 4 Solid J' white yellow Transparent Thick Clear Oil IF-2019-52232722-APN-ANP#INPI Page 141 of 408* • i . p. . either IF-2019-52232722-APN-ANP#INPI Page 142 of 408 or f72 Page 143 of 408 or IF-2019-52232722-APN-ANP#INPI Page 144 of 408 Cmpd. No. Structure According to preparation according to Appearance 124 u. / / A CO / / x V Ό—O \ co \ X co )··πθ X / o IZ §j=o o-M / \ / o \= / <*1 1* f •4 *J * 125 / / A co / / \\ X \ / -° \ CO \ x co )'Ü x / O“( o °i xz X \ o / =° O— / \ / o \= / CO X Example 4 Step 2 5 ΐ ·· : Thick oil 126 LL \ co \ = / ch3 ch3 Example 4 Step 2 - - White solid ______j_________ IF-2019-52232722-APN-ANP#INPI -473 Page 145 of 408 IF-2019-52232722-APN-ANP#INPI Page 146 of 408 Structure h3c appearance 129 CH3h3c 130 ch3ch3ch h3c 131 ch3h3c 132 CH3ch3ch3ch h3c 133 ch3ch thick oil Example 4 Step 2 Example 4 Step 2, Oil • thickened; white solid thick oil Step 2 thick oil thick oil No. Step 2 Step 2 preparation according to ch3ch3 Cmpd. h3cxo 134 According to Example 4 Step 2 or ch3o ch3ch3ch3CH Example 4 Example 4 Example 4 IF-2019-52232722- APN#INPI Page 147 of 408 IF-2019-52232722-APN-ANP#INPI Page 148 of 408 Structure h3c appearance 135 ch3h3c 136 CH3ch3h3c 137 CH3ch3h3c 138 h3c 139 CH3 Example 4 Step 2 Step 2 thick oil thick oil Step 2 Step 2 Step 2 thick oil No. Solid white ch3ch3ch3ch3h3c ch3h3c ch3 Cmpd. CH3 According to preparation according to Example 4 Example 4 Example 4 Example 4 thick oil' IF-2019-52232722-APN-ANP#INPI Page 149 of 408 or IF-2019-52232722-APN-ANP#INPI Page 150 of 408 According to preparation according to Example 4 Step 2 Example 4 Step 2 Example 4 Step 2 Example 4 Step 2 Example 4 Step 2 Appearance / Thick oil white solid thick oil thick oil thick oil IF-2019-52232722-APN-ANP#INPI Page 151 of $40 - p · IF-2019-52232722-APN-ANP#INPI Page 152 of 408 or 146 147 Structure h3c h3c h3c ch3ch3h3c 148 CH3h3c 149 CH3 Step 2 thick oil Step 2 Step 2 Step 2 Step 2 thick oil thick oil thick oil Thick oil ch3ch3ch3ch3h3c ch3h3c ch3ch3h3c ch3con , Cmpd. No. According to the preparation. agree Appearance 145 Example 4 Example 4 Example 4 Example 4 Example 4 IF-2019-52232722-APN-ANP#INPI Page 153 of 4Q§ pz, IF-2019-52232722-APN-ANP#INPI Page 154 of 408 'íj Structure Cmpd. No. i According to the agreement preparation—Appearance IF-2019-522327^APN-ANP#INP> 378 f Page 155 of 408 or IF-2019-52232722-APN-ANP#INPI Page 156 of 408 IF-2019-52232722-APN-ANP#INPI Page 157 of 408 or IF-2019-52232722-APN-ANP#INPI Page 158 of 408 IF-2019-52232722-APN-ANP#INPI Page 159 of 408 IF-2019-52232722-APN-ANP#INPI Page 160 of 408 or h3c structure 165 CH3 166 CH3ch3ch3h3c 167 CH3ch3ch3h3c 168 CH3h3c 169 CH3 No. Step 2 Step 2 Oil yellow oil yellow oil Step 2 Step 2 Step 2 according to ch3ch3ch3ch3ch3ch3 Cmpd. According to the preparation Appearance Example 4 orange Example 4 Example 4 Example 4 Example 4 Colorless, transparent oil colorless, transparent IF-2019-52232722-VPN-ANP#INPI Page 161 of 408 IF-2019-52232722-APN-ANP#INPI Page 162 of 408 IF-2019-52232722-APN-ANP#INPI Page 163 of 4Ó 8 I o IF-2019-52232722-APN-ANP#INPI Page 164 of 408 or IF-2019-52232722-APN-ANP#INPI - í 83 . Page 165 of 408 or IF-2019-52232722-APN-ANP#INPI Page 166 of 408 ch3 structure HiC CH3 180 CH3ch3h3c ch3 181 ch3ch3ch3h,c ch3 182 CH3h3c ch3 183 ch3 184 IF-2019-52232722-APN-ANP#INPI thick oil thick oil Thick oil. No. thick oil Thick oil according to ch3ch3ch3ch3h3c ch3h3c or ch3o ch3o ch3 Cmpd. According to the preparation Example 5C Example 5A Example 5A Example 5A Example 5A Appearance . 84 *w*. Page 167 of 408JG or IF-2019-52232722-APN-ANP#INPI Page 168 of 408 or Cmpd. No. Structure 189 185 186 187 188 Example 5A Example 5A Example 5A As prepared in accordance* with Example 5A Example 5A Appearance Oil: thick thick oil thick oil thick oil thick oil IF-2019-52232722-APN-ANP#INP] •ut85. Page 169 of,40$« or IF-2019-52232722-APN-ANP#INPI Page 170 of 408 or IF-2019-52232722-APN-ANP#INPI Page 171 of 40 8 or ι'Ι h I L lii I f li I t I I I1¡i i l· í Yo Ί l· I l I i¡ |l¡ V I I11i¡ 1' I |i lí I1' I l¡ li I'1 YO' IF-2019-52232722-APN-ANP#INPI I Page 172 of 408 or IF-2019-52232722-APN-ANP#INPI Page 173 of 408 or IF-2019-52232722-APN-ANP#INPI Page 174 of 408 Page 175 of 408 or IF-2019-52232722-APN-ANP#INPI Page 176 of 408 IF-2019-52232722-APN-ANP#INPIf Page 177 of 408 I or IF-2019-52232722-APN-ANP#INPI Page 178 of 408 IF-2019-52232722-APN-ANP#INPI Page 179 of 408 or IF-2019-52232722-APN-ANP#INPI Page 180 of 408 Structure - According to the preparation according to Appearance Example 5C ' / .Oil ··. thick Example 5C Thick oil Example 5C Thick oil Example 5C Thick oil F* IF-2019-52232722-APN-ANP#INPI Page 181 of 408 IF-2019-52232722-APN-ANP#INPI Page 182 of 408 or Page 183 of 408 IF-2019-52232722-APN-ANP#! IF-2019-52232722-APN-ANP#INPI Page 184 of 408 Page 185 of 408 or IF-2019-52232722-APN-ANP#INPI Page 186 of 408 Structure Appearance ch3h3c ch3 227 ch3ch3ch3ch3h3c ch3 228 CH3ch3ch3 229 ch3ch3ch3h3c ch3 230 CH3ch3h3c 231 Example 5B ch3ch3ch3 thick oil 4Γ 2019 52132722-ΛΡΝ· No. thick oil Thick oil ch3ch3ch3ch3 thick oil Cmpd. According to preparation according to ch3Example 5C Example 5C thick oil Example 5C Example 5C ch3 Page 187 of 408 IF-2019-52232722-APN-ANP#INPI Page 188 of 408 or |ι IF-2019-52232722-APN-ANP#INPI Page 189 of 408 IF-2019-52232722-APN-ANP#INPI Page 190 of 408 IF-2019-52232722-APN-ANP#INPI Page 191 of 408 or |l I Ll Ιι i Ιι E |ί IF-2019-52232722-APN-ANP#INPI I Page 192 of 408 IF-2019-52232722-APN-ANP#INPI Page 193 of 408 IF-2019-52232722-APN-ANP#INPI Page 194 of 408 or Cmpd. No. Structure According to preparation according to Appearance 244 ch3 h3cx ck o ch3 o ch3 ch3 ch3 Example 5C Oil - colorless, transparent ** * 4 ¡*- 245 X « )—O X / ° \ o o= / - \ x n ? --O X c O IZ ^“o\ )=° o / =( o V—y « xz b°\ b° o / \ °~VZ o v—y (O X Example 5C Pale yellow oil 247 X O—< “ x \ ω ^=o o / x O—í w Example 5C Colorless, transparent oil 248 X o--< « IF-2019-52232722-APN-ANP#INPI Page 195 of 408 or IF-2019-52232722-APN-ANP#INPI Page 196 of 408 μ Cmpd. No. Structure 'According to preparation according to Appearance 249 H3C< °<^ch3 / vXQ·' or ch3 ch3 ch3 Example 5C , Oil'' •colorless, transparent 250 H3% °<^CH3 O CH3 CH, F F F , f Example 5C Colorless, transparent oil 251 H3C^o °<YCH3 QaM#· 0 CH3ch^ / \fr F Example 50 Colorless, transparent oil 252 h3c^o °^xch3 o ch3 ch3 Example 50 Colorless, transparent oil 253 H3C^o °^j / CH3 / vvX1 or ch3 ch3 ch3 Example 50 Colorless, transparent oil IF-2019-52232722-APN-ANP#INPI Page 197 of 408 or IF-2019-52232722-APN-ANP#INPI Page 198 of 408 Cmpd. No. Structure According to the preparation according to Appearance 254 H3C^ 0<ψχ0Η3 or ch3 ch3 ch3 Example 5C Oil. '•^colorless', transparent 255 Η3<^ο °<y^CH3 or ch3 ch3 ch3 Example 5C Colorless oil, transparent 256 H3C^o °^XCH3 or ch3 ch3 ch3 Example 5C Colorless oil, transparent 257 h3c^ h3c^o O όζ-νΛ-Ρ o ch3 ch3 cl ch3 Example 5A Colorless oil 258 co X co f— U X / O\ o θ^Χ -£? >-s O xz y—© \=o o >= / r> / \ Xo—7 J VJ' «*> X Example 5A Colorless oil IF-2019-52232722-APN-ANP#INPI 100 Page 199 of 408 IF-2019-52232722-APN-ANP#INPI Page 200 of 408 or Cmpd. No. Structure According to the 1st preparation. . . 1 agree APar'®ncia with h3c^ h3cl o 1 o CH3 οςοχΰ 0 CH3 ch3 Γ HjCxjHsC^O 260 1 II h ÍI ?H’ rY ° ch3 CH3 0 _________| ch3 Oil Example 5A pale yellow Example 5A Colorless oil .______ ll >__ v C*1 / \ \ x <\ Λ z=\ ° Vi / / / \ f H £ w~° in j--O \ <? 1 X / \ □z VJ' O-Z z f Vi / / r o V—y <n 101 IF-2019-52232722-APN-ANP#INPI Page 201 of 408 IF-2019-52232722-APN-ANP#INPI Page dr 10? -·—““““ IF-2O19-52232721?ÍPN-ANP#INPI Page 203 of 408 IF-2019-52232722-APN-ANP#INPI or IF-2O19-522327221-^N-ANP#INPI Page 205 of 408 or IF-2019-52232722-APN-ANP#INPI Cmpd No. Structure According to the preparer in accordance with 1 A. . Appearance 1 h3c^ 0 274 ​​ύ O- ^0H 0 y-A o ch3 ch3 f Example 7 Pale yellow oil η3οχ o 275 VM CH3 r χο^η· Example 7 Pale yellow oil O' o ch3 ch3 H3CX o 276 o <° 0 v ¥ ch3 f •OA..A |1 Example 7 Pale yellow oil O' o ch3 ch3 h3c^ 0 277 1 O' O=( o Λ 1 O.. / ° 2=0 o CH3 ch3 ox ^F jj ch3 Example 7 Pale yellow oil ch3 ----------------------------------1 1 H3C·^ O —--- — - -=. i - — 278 \ Ϊ zO fl A TJÍ Example 5C White solid Sr γ Ά 1-------— or ch3 ch3 ch3 IF-2O19-522327221-^N-ANP#INPI Page 207 of 408 or IF-2019-52232722-APN-ANP#INPI or Cmpd. No. Structure According to the preparation according to Appearance 279 ^ch3 H3C^ o o ch3 ch3 ch3 Example 5C White solid 280 ch3 H3C^o ά>ΑΑ9 o ch3 ch3 ch3 Example 5C Yellow oil 281 h3c.o CK / Δ o ch3 ch3 ch3 Example 5C Transparent oil 282 H3Cx CK JL J 0 \í^ cXsvy? or ch3 ch3 ch3 Example 5C White solid ΙΡ-2019-52232722-ΑΡ^-ΑΝΡ#ΙΝΡΙ Page 209 of 408 or IF-2019-52232722-APN-ANP#INPI Page 210 of 408 or Cmpd. No. Structure According to preparation according to Appearance 284 ch3 (k Λ y ch3 h3c^q or ch3 ch3 ch3 Example 5C Thick yellow oil 285 H3% [¿γ°γ°ο ch3 or ch3 ch3 ch3 Example 5C Glassy solid *Cmpd. No. - Compound number Table 2. Analytical data Cmpd, No. Melting point (°C) IR (cm'1) NMR mass spectrum 1 ESIMS 362.3 ([M+Na]+) 2 ESIMS m / z 354.3 ([M+Hf) 3 ESIMS m / z 382.3 ([M+Hf) 106 IF-2019-52232722-APN-ANP#INPI Page 211 of 408 or hl IF-2019-52232722-APN-ANP#INPI Page 212 of 408 or 4 ESIMS m / k 376.3 ([M+Na]*) 5 ESIMS m / z 362.3 ([M+Na]*) 6 ESIMS m / z 354.3 ([M+HD 7 ESIMS m / z 382.3 ([M+HD 8 ESIMS m / z 354.3 ([M+HD 9 ESIMS m / z 344.3 ([M+Na]*)) 10 ESIMS m / z 336.5 ([M+HD 11 ESIMS m / z 364.3 ([M+HD 12 ESIMS m / i 336.2 ([M+HD 13 ESIMS m / z 348.2 ([M+Na]*)) 14 ESIMS m / z 340.5 ([M+HD 15 ESIMS / n£ 390.3 ([M+Na]*) 107 IF-2019-52232722-APN-ANP#INPI Page 213 of 408 or IF-2019-52232722-APN-ANP#INPI Page 214 of 408 16 ESIMS m / z 340.2 ([M+H]j 17 ESIMS m / z 374.3 ([M+Na]j 18 ESIMS m / z 366.3 ([M+H]j 19 ESIMS m / z 394.3 ([M+H]j 20 ESIMS m / z 366.3 ([M+HD 21 ESIMS 362.3 ([M+Na]*) 22 ESIMS mA 376.3 ([M+Na]j 23 ESIMS m / z 382.3 ([M+Hf) 24 ESIMS m / z 354.3 ([M+H]j 25 ESIMS m / z 362.3 ([M+Na]*) 26 ESIMS m / z 376 .3 ([M+Na]*) 27 ESIMS m / z 382.3 ([M+H]j IF-2019-52232722-^N-ANP#INPI Page 215 of 408 or IF-2019-52232722-APN-ANP#INPI Page 216 of 408 28 ESlMSm£ 376.3 ([M+Na]+) 29 ESIMS 344.3 ([M+Na]+) 30 ESIMS m / z 336.2 ([M+HD 31 ESIMS m / z 364.3 ([ M+HD 32 ESIMS m / z 336.3 ([M+HD 33 ESIMS m / z 348.2 ([M+Na]*) 34 ESIMS m / z 340.3 ([M+HD 35 ESIMS m / z 368.3 ([M+HD 36 ESIMS m / z 340.3 ([M+HD 37 — ESIMS m / z 374.3 ([M+Na]+)) - -- - 38 ESIMS m / z 366.3 ([M+HD 39 ESIMS m / z 394.4 ([M+HD 109 IF-2019-52232722-APN-ANP#INPI Page 217 of 408 or IF-2019-52232722-APN-ANP#INPI 40 ESIMS m / z 366.3 ([M+Hf) 41 ESlMSmfc 372.3 ([M+Na]*) 42 ESlMSmZ? 372.3 ([M+Na]*) 43 IR (thin film) 3355.2981, 1711.1310, 1150, 1116, 1046, 770 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for Ci9H26F3NNaO4, 412.1706; found, 412.1698 1H NMR (400 MHz, CDCI3) δ 7.64 (dd, J = 7.8,1.4 Hz, 1H), 7.52 (td, J= 7.6,1.3 Hz , 1H), 7.43 (d, J = 7.9 Hz, 1H), 7,357.28 (m, 1H), 5.25-5.13 (m, 1H), 5.08 (d, J= 7.9 Hz, 1H), 4.42 - 4.28 (m, 1H), 3.41 - 3.27 (m, 1H), 1.46 (s, 9H), 1.43 (d, J = 7.2 Hz, 3H), 1.27 (d, J=6.8 Hz, 3H), 1.07 (d,J = 6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.25. 44 IR (thin film) 3362, 2982, 1711.1499, 1314.1154, 1121.1046, 909, 879 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for Ci9H25F4NNaO4, 430.1612; found, 430.1607 1H NMR (400 MHz, CDCI3) δ 7.42 (dd,J=8.8, 5.4 Hz, 1H), 7.35 (dd, J=9.2, 2.8 Hz , 1H), 7.23 (td, J=8.2, 2.8 Hz, 1H), 5.18-5.09 (m, 1H), 5.07 (d, J = 7.6 Hz, 1H), 4.41 -4.27 (m, 1H), 3.36-3.24 (m, 1H), 1.46 (s, 9H), 1.42 (d, J=7.3 Hz , 3H), 1.26 (d, J=6.8 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.81.-114.05. 110 IF-2019-52232722-APN-ANP#INPI Page 219 of 408 or IF-2019-52232722-APN-ANP#INPI 45 IR (thin film) 3364.2981, 1712, 1310, 1150, 1116, 1046.770 cm'1 HRMS-ESI (m / z) [M+Na]+ calculated for CigHaeFsNNaOí, 412.1706; found, 412.1699 1H NMR (400 MHz, CDCI3) δ 7.64 (dd, J= 8.0, 1.3 Hz, 1H), 7.52 (td, J = 7.6,1.3 Hz , 1 HOUR). 7.43 (d, J=7.8 Hz, 1H), 7.32 (t, J=7.6 Hz, 1H), 5.25-5.13 (m, 1H), 5.04 (d , J=7.8 Hz, 1H), 4.42 - 4.26 (m, 1H), 3.40 - 3.26 (m, 1H), 1.46 (s, 9H), 1.41 ( d, J = 7.3 Hz, 3H),1.29 (d,J=6.7 Hz, 3H), 1.05 (d, J = 6.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.25. 46 IR (thin film) 2981.1711, 1498.1314, 1154, 1120, 1045, 909, 879, 739 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for Ci9H25F4NNaO4t 430.1612; found, 430.1603 1H NMR (400 MHz, CDCI3) δ 7.42 (dd, J=8.8, 5.3 Hz, 1H), 7.35 (dd, J= 9.2, 2.8 Hz , 1H), 7t23 (td,J=8.3, 2.9 Hz, 1H), 5.20 - 5.09 (m, 1H), 5.02 (d, J = 7.8 Hz, 1H) , 4.42 - 4.23 (m, 1H), 3.29 (tt, J=7.6, 6.0 Hz, 1H), 1.46 (s, 9H), 1.40 (d, J = 7.2 Hz, 3H), 1.28 (d, J=6.8 Hz, 3H), 1.07 (d, J=6.4 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.78, -58.80, -114.19. 47 IR (thin film) 3357, 2977, 1713.1500, 1452, 1365, 1162.1055, 1006, 769 cm'1 HRMS-ESI (m / z) [M+NH4]+ calculated for C2oH35N204, 367.2587; found, 367.2587 1H NMR (400 MHz, CDCI3) δ 7.05-6.91 (m, 3H), 5.58 (ddq, J = 10.5, 8.3, 6.2 Hz, 1H) , 5.11 (s, 1H), 4.42 - 4.28 (m, 1H), 3.49 3.33 (m, 1H), 2.44-2.33 (m. 6H), 1, 46 (d, J=1.1 Hz, 9H), 1.45-1.39 (m, 3H), 1.27 (dd, J = 7.1,3.5 Hz, 3H), 1.02 (dd, J = 7.7, 6.2 Hz, 3H). 48 IR (thin film) 3357, 2978, 1712.1366, 1162.1057, 1023.1006, 857 cm'' HRMS-ESI (m / z) M+Na]+ calculated for C2oH3oFNNa04, 390.2051; found, 390.2048 1H NMR (400 MHz, CDCI3) δ 6.70 (ddd, J= 16.1.9.4, 2.9 Hz, 2H), 5.53 (ddq, J= 10.5, 8.6, 6.2 Hz, 1H), 5.11 (s, 1H), 4.414.26 (m, 1H), 3.44-3.27 (m, 1H), 2.40 (d, J =1.7 Hz, 3H), 2.35 (s, 3H), 1.46 (s, 9H), 1.451.38 (m,3H), 1.25 (dd, J=7.2, 3, 8 Hz, 3H), 1.01 (dd, J = 7.6, 6.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 118.37,-118.44. 111 IF-2019-52232722-APN-ANP#INPI Page 221 of 408 or ill IVigiiij IF-2019-52232722-APN-ANP#INPI or 49 IR (thin film) 3361.2977, 1713.1365, 1162.1056, 1006, 769 cm-1 HRMS-ESI (mZzr) [M+Na]* calculated for C2oH3iNNa04, 372.2145; found. 372.2144 1H NMR (400 MHz, CDCI3) δ 7.04 - 6.93 (m, 3H), 5.58 (ddq, J = 10.4, 8.3, 6.2 Hz, 1H), 5 .10 (d, J = 7.3 Hz, 1H), 4.43 - 4.27 (m, 1H), 3.48-3.29 (m, 1H), 2.41 (d, J=1 .6 Hz, 3H), 2.37 (s, 3H), 1.46 (d,J= 1.1 Hz, 9H), 1.451.39 (m, 3H), 1.27 (dd, J= 7 ,1, 3.5 Hz, 3H), 1.02 (dd, J = 7.7, 6.2 Hz, 3H). 50 IR (thin film) 3359, 2978, 1712.1450, 1366.1163, 1057.1023, 1006, 858, 732 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for C20H30FNNaO4, 390, 2051; found, 390.2050 1H NMR (400 MHz, CDCI3) δ 6.70 (ddd, J= 16.2, 9.4, 2.9 Hz, 2H), 5.53 (ddq, J= 10.5, 8.6, 6.2 Hz, 1H), 5.09 (s, 1H), 4.434.28 (m, 1H), 3.34 (dp, J= 10.3, 6.9 Hz, 1H), 2.40 (d,J= 1.7 Hz, 3H), 2.35 (s, 3H), 1.46 (s, 9H), 1.45-1.36 (m, 3H), 1.26 (d, J = 3.8 Hz, 3H), 1.01 (dd, J=7.6, 6.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 118.40, -118.46. 51 IR (thin film) 3356, 2977, 1713.1500, 1452.1163, 1056.769 cnrT1 HRMS-ESI (m / z) M+Na]* calculated for C20H3iNNaO4, 372.2145; found, 372.2137 1H NMR (400 MHz, CDCI3) δ 7.03 - 6.94 (m, 3H), 5.58 (ddq, J = 10.5, 8.3, 6.2 Hz, 1H) , 5.10 (d, J = 7.1 Hz, 1H), 4.43-4.27 (m, 1H), 3.50 - 3.34 (m, 1H), 2.41 (d, J =1.6 Hz, 3H), 2.37 (s, 3H), 1.46 (d, J = 1.1 Hz, 9H), 1.451.36 (m, 3H), 1.27 (dd, J = 7.2, 3.5 Hz, 3H), 1.02 (dd, J = 7.7, 6.2 Hz, 3H). 52 IR (thin film) 3358, 2978, 1712, 1366, 1163.1058, 1023.1006, 858, 733 cm'1 HRMS-ESI (m / z) M+Na]* calculated for C20H30FNNaO4, 390.2051; found, 390.2051 1H NMR (400 MHz, CDCI3) δ 6.70 (ddd, J= 16.0, 9.4, 2.9 Hz, 2H), 5.53 (ddq, J= 10.5, 8.5, 6.2 Hz, 1H), 5.11 (s, 1H), 4.33 (q, J = 7.3 Hz, 1H), 3.35 (ddq, J = 13.0,10 .4, 7.1, 6.5 Hz, 1H), 2.40 (d, J=1.8 Hz, 3H), 2.35 (s, 3H), 1.46 (s, 9H), 1 .45-1.39 (m, 3H), 1.25 (dd, J = 7.2, 3.8 Hz, 3H), 1.01 (dd, J = 7.6, 6.2 Hz, 3H ). 19F NMR (376 MHz, CDCI3) δ 118.39, -118.45. 112 IF-2019-52232722-APN-ANP#INPI Page 223 of 408 IF-2019-52232722-APN-ANP#INPI 53 IR (thin film) 3357, 2977, 2936, 2837, 1711, 1493, 1241.1161, 1052.752 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for CigH^NOsNa, 374, 1938; found, 374.1944 'H NMR (400 MHz, CDCI3) δ 7.23 - 7.12 (m, 2H), 6.96 - 6.79 (m, 2H), 5.24 (dq, J = 7 ,7,6.3 Hz, 1H), 5.00 (d, J = 6.6 Hz, 1H), 4.19-4.10 (m, 1H), 3.81 (s, 3H), 3 .43 (p, J = 7.3 Hz, 1H), 1.42 (s, 9H), 1.25-1.20 (m, 6H), 0.99 (d, J= 7.1 Hz, 3H). 54 IR (thin film) 3355, 2978, 2934,1711, 1495, 1452, 1366, 1161, 1087, 1065. 701 cm'1 1H NMR (400 MHz, CDCI3) δ 7.35 - 7.25 (m, 2H ), 7.27 - 7.15 (m, 3H), 5.12-5.01 (m, 2H), 4.35-4.26 (m, 1H), 2.95 - 2.83 (m , 1H), 1.45 (s, 9H), 1.37 (d. J = 7.2 Hz, 3H), 1.29 (d,J = 7.1 Hz, 3H), 1.09 (d , J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 172.9,155.0.143.0.128.5, 127.8,126.7,79,7,76.1,49.5, 45.1,28.3,18.9,18.3 ,17,5. 55 IR (thin film) 3365, 2977, 2933, 1712, 1500.1449, 1365.1161, 1065, 796 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for Ci7H27NO4SNa, 364.1553; found, 364.1551 Ή NMR (400 MHz, CDCI3) δ 6.64 - 6.53 (m. 2H), 5.11 - 5.05 (m, 1H), 5.06-4.95 (m, 1H) , 4.35 - 4.26 (m, 1H). 3.20 - 3.08 (m, 1H), 2.43 (d, J = 1.2 Hz, 3H), 1.45 (s. 9H). 1.38 (d, J= 7.2 Hz, 3H), 1.31 (d,J= 7.1 Hz,3H), 1.16 (d, J= 6.3 Hz, 3H). 56 IR (thin film) 3365, 2978, 2937, 1708, 1601, 1502, 1163, 1035, 952, 834 cm'1 HRMS-ESI (m / z) [M+Na]* calculated for C19H23FNO5Na, 392.1844; found, 392.1839 'H NMR (500 MHz, CDCI3) δ 7.08 (dd, J=8.5, 6.7 Hz, 1H), 6.65 - 6.53 (m, 2H), 5, 16 - 5.07 (m, 1H), 5.05 (d, J=7.6 Hz, 1H), 4.30-4.23 (m, 1H), 3.80 (s, 3H), 3 .38-3.29 (m, 1H), 1.45 (s, 9H), 1.35 (d, J = 7.2 Hz, 3H), 1.23 (d, J=7.1 Hz, 3H), 1.10 (d, ______J=6.3 Hz, 3H). 113 IF-2019-52232722-APN-ANP#INPI Page 225 of 408 or -í 1 t F IF-2019-52232722-APN-ANP#INPI Page 226 of 400 57 1H NMR (300 MHz, CDCI3) δ 7.13 - 6.95 (m, 2H), 6.77 - 6.52 (m, 2H), 5.11 (d, J = 7.8 Hz, 1H ), 5.00 (dq, 4=8.2, 6.2 Hz, 1H), 4.31 (t, 4=7.4 Hz, 1H), 2.92 (s, 6H), 1.45 (s, 9H), 1.39 (d, 4 = 7.2 Hz, 3H), 1.31 -1.17 (m,4H), 1.08 (d, 4 = 6.3 Hz, 3H) . 13C NMR (75 MHz, CDCI3) δ 172.95, 171.16, 155.04, 149.48, 130.86, 128.41, 112.69, 60.40, 49.51.44,14.40 ,70,28,35, 18.93, 18.27, 17.82,14,21. 58 ESIMS m / z 240.2 ([M+H]*) 59 ESIMS m / z 240.2 ([M+H]*) 60 ESIMS m / z 222.2 ([M+H]*) 61 ESIMS m / z 248.9 ([M+Na]*) 62 ESIMS m / z 252.2 ([M+H]*) 63 - - - ESIMS m / z 240.2 ([M+H]*) 64 ESIMS m / z 240.2 ([M+H]*) 65 ESIMS m / z 222.2 ([M+H]*) 114 IF-2019-52232722-APN-ANP#INPI Page 227 of 408 IF-2019-52232722-APN-ANP#INPI or 66 ESIMS / 716 226.2 «M+HD 67 ESIMS / 716 252.2 «M+HD 68 ESIMS / 716 254.2 ÜM+Hf) 69 ESIMS m6 254.2 «M+HD 70 ESIMS / 716 236.2 ([M+HD 71 ESIMS 7716 240.2 ([M+HD 72 ESIMS / 716 266.3 75 ESIMS / 116 236.2 "M+HD 76 ESIMS / 716 240.2 "M+HD 77 ESIMS / 716 266.3 "M+HD 115 IF-2019-52232722-APN-ANP#INPI Page 229 of 408 or IF-2019-52232722-APN-ANP#INPI or 78 ESIMS m / ϊ 282.3 ([M+HD 79 ESIMS ntó 282.2 ([M+HD 80 ESIMS m / ϊ 264.3 .3 «M+HD 83 ESIMS 282.2 «M+HD 84 ESIMS m / 2 282.2 «M+HD 85 ESIMS 264.3 ([M+HD 86 ESIMS m / z 268.2 ([M+HD 87 ESIMS rafe 294.3 ([M+HD 88 ESIMS mfz 254.2 ([M+HD 89 ESIMS m / z 254.2 «M+HD 116 IF-2019-52232722-APN-ANP#INPI Page 231 of 408 or IF-2019-52232722-APN-ANP#INPI or 90 ESIMS m / z 236.2 ([M+HD 91 ESIMS m / z 240.2 ([M+HD 92 ESIMS m / z 266.3 ([M+HD 93 ESIMS / 716254.2 ([M+HD 94 ESIMS m / z 254.2 ([M+HD 95 ESIMS m / z 236.2 ([M+HD 96 ESIMS m / z 240.2 ([M+Hf) 97 ESIMS m / z 266.3 ([ M+HD 98 ESIMS m / z 250.3 ([M+HD 99 ESIMS / 716250.3 ([M+HD . —— 100 ESIMS / 716290.2 ([M+HD 101 ESIMS / 716 308.1 ([ M+HD 117 IF-2019-52232722-APN-ANP#INPI or IF-2019-52232722-APN-ANP#INPI Page 234 iL 102 ESIMS mA 214.2 ([M+HD 103 ESIMS m / z 290.2 ([M+HD 104 ESIMS mA 308.1 ([M+HD 105 ESIMS m / z 214.2 ([M+HD 106 ESIMS mA 250.2 ([M+HD 107 ESIMS mA 268.2 ([M+HD 108 ESIMS mA 250.2 ([M+HD 109 ESIMS mA 268.2 ([M+HD 110 ESIMS mA 250.2 ([ M+HD 111 ESIMS mA 268.2 ([M+HD 112 HRMS-ESI (m / z) [M+H]* calculated for C14H22NO3, 252.1600; found, 252.1443 118 IF-2019-52232722-APN-ANP#INPI Page 235 of 408 IF-2019-52232722-APN-ANP#INPI 23ΰ ill 4ί» or 113 HRMS-ESI (m / z) [M+H]+ calculated for C13H20NO2, 222.1489; found, 222.1485 114 IR (thin film) 2854.1740, 1233.1203, 1118.1078, 872, 796 cm-1 115 HRMS-ESI (m / z) [M+H]+ calculated for C14H2iFNO3. 270.1500; found, 270.1501 116 HRMS-ESI (m / z) [M+H]+ calculated for C22H29N2O5, 401.2071; found, 401.2067 1H NMR (500 MHz, CDCI3) δ 12.16 (s, 1H), 8.52 (d, J = 7.8 Hz, 1H), 8.00 (d, J=5.2 Hz, 1H), 7.09 - 7.03 (m, 1H), 7.00 - 6.94 (m,2H), 6.88 (d, J=5.1 Hz, 1H), 5.13 (dq, J = 8.4, 6.2 Hz, 1H), 4.79-4.67 (m, 1H), 3.95 (s, 3H), 3.16 (dq, J = 8.9 , 7.0 Hz, 1H), 2.31 (s, 3H), 2.28 (s, 3H), 1.57 (d, J = 7.2 Hz, 3H), 1.24 (d, J =6.9 Hz,3H), 1.14 (d, J = 6.2 Hz, 3H). 13C RMN (126 MHz, CDCI3) Δ 171,86,168,68,155,38,148,77, 140,50,138,63, 135,76,135,33, 131,31,130,52, 126,97,126,26, 109,44, 56.08, 56.08, 56.08 ,48.18, 39.45, 20.89,19.87,18.48,18.46, 17.56. 119 IF-2019-52232722-APN-ANP#INPI Page 237 of 408 or IF-2019-52232722-APN-ANP#INPI Page 2‘30 illus 403 or 117 HRMS-ESI (m / z) [M+H]* calculated for C22H29N2O5, 401.2071; found, 401.2064 1H NMR (500 MHz. CDCI3) δ 12.17 (d, J= 0.6 Hz, 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.01 ( d, J = 5.2 Hz, 1H), 7.10-7.02 (m, 1H), 6.97 (d, J= 6.9 Hz, 2H), 6.88 (d, J = 5 .2 Hz, 1H), 5.16 (dq, J = 8.4, 6.2 Hz, 1H), 4.77 - 4.68 (m, 1H), 3.95 (s, 3H), 3 .19-3.09 (m, 1H), 2.31 (s, 3H), 2.27 (s, 3H), 1.54 (d, J=7.2Hz, 3H), 1.23 (d , J = 6.9 Hz, 3H), 1.12 (d, J= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.87,168.72,155.38,148.76, 140.50,138.60,135.72, 135.36, 131.29,130.53,127.00,126.28, 109.44, 47 .99, 39.42, 20.87,19.88,18,31,18.26, 17.65. 118 HRMS-ESI (mZ?) [M+H]* calculated for C2oH23FN20g, 391.1664; found, 391.1662 'H NMR (500 MHz, CDCI3) δ 12.04 (s, 1H), 8.46 (t, J= 5.8 Hz, 1H), 8.01 (d, J= 5, 2 Hz, 1H), 7.18 - 7.06 (m, 1H), 6.93 - 6.79 (m, 3H), 5.15 (dq, J = 8.0,6.3 Hz, 1H ), 4.21 (dd, J=5.7, 3.2 Hz, 2H), 3.95 (s, 3H), 3.15 (p, J = 7.1 Hz, 1H), 2.33 (s. 3H). 1.24 (d. J = 6.9 Hz, 3H), 1.15 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.32,168.74,161.97,160.03, 155.39,148.70,140.61,137.91, 137.20,130.40,127.85, 117.11, 112.90,109.54 , 76,40,56,10,41,03,39,10, 20,00,18,22,17,42. - 120 IF-2019-52232722-APN-ANP#INPI Page 239 of 408 or IF-2019-52232722-APN-ANP#INPI Page 2 or 119 HRMS-ESl (m / z) [M+H]+ calculated for C20H23FN2O5, 391.1664; found, 391.1660 'H NMR (500 MHz, CDCI3) δ 12.01 (s, 1H), 8.34 (t, J= 5.8 Hz, 1H), 7.99 (d, J= 5, 2 Hz, 1H), 7.15 (dd,J= 9.5, 5.8 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.85 6.75 (m , 2H), 5.24 - 5.10 (m, 1H), 4.23 - 3.92 (m, 5H), 3.23 (p, J = 7.1 Hz, 1H), 2.33 ( s, 3H), 1.25 (m. 6H). 13C NMR (126 MHz, CDCI3) δ 169.19,168.38,161.97,160.02, 155.38,148.68,140.55,138.37, 136.63,130.36,127.68,116.81, 12,70,109,52, 75 .82, 56.09,40.88,38.65, 19.86,17,20,16.64. 120 HRMS-ESl (m / z) [M+H]+ calculated for C20H24N2O5, 373.1758; found, 373.1754 'H NMR (500 MHz, CDCI3) δ 12.03 (s, 1H), 8.34 (t, J-5.8 Hz, 1H), 7.99 (d, J = 5, 2 Hz, 1H), 7.20 (dd, J = 7.6,1.3 Hz, 1H), 7.16-7.06 (m, 3H), 6.87 (d, J = 5.2 Hz, 1H), 5.24-5.17 (m, 1H), 4.16-3.89 (m, 2H), 3.95 (s, 3H), 3.29 (p,J= 7, 1 Hz, 1H), 2.35 (s, 3H), 1.27 (m, 6H). 13C NMR (126 MHz, CDCI3) δ 169.15,168,40,155,35,148.66, 140.97,140.52,136,10,130.41, 130.27,126.30, 126.20,126.14, 109.48, 56 ,08,40,85, 39,18,19,79, 17,18,16,37. 121 IF-2019-52232722-APN-ANP#INPI Page 241 of 408 or IF-2019-52232722-APN-ANP#INPI 121 HRMS-ESI (m / z) [M+H]* calculated for C19H21FN2O5, 377.1507; found, 377.1504 1H NMR (500 MHz, CDCI3) δ 12.04 (s, 1H), 8.46 (t, J= 5.8 Hz, 1H), 8.01 (d, J =5.2 Hz, 1H), 7.15 (dd, 3=8.6, 5.5 Hz, 2H), 7.01-6.94 (m, 2H), 6.89 (d, J = 5.2 Hz , 1H), 5.16-5.05 (m, 1H), 4.21 (dd, J =5.8, 2.1 Hz, 2H), 3.95 (s, 3H), 2.92 ( p, 3= 7.1 Hz, 1H), 1.28 (d, 3=7.0 Hz, 3H), 1.12 (d, 3 = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.33,168.65,162.66,160.72, 155.40,148.71,140,61,138.35, 130.40, 129.27, 129.21, 115.36, 115.19, 109 .55, 76.35, 56.10, 44,12,41,06,17,83,17,27. 122 HRMS-ESI (m / z) [M+H]+ calculated for C21H26N2O6, 403.1864; found, 403.1835 1H NMR (500 MHz, CDCI3) δ 12.06 (s, 1H), 8.47 (t,3=5.8 Hz. 1H), 8.01 (d,3=5.2 Hz, 1H), 7.08 (d, 3= 8.4 Hz, 1H), 6.88 (d, 3 = 5.2 Hz, 1H), 6.77 - 6.66 (m, 2H), 5.15 (dq, 3= 8.2, 6.3 Hz, 1H), 4.22 (dd, 3 =5.7, 2.0 Hz, 2H), 3.95 (s, 3H), 3 .77 (s, 3H), 3.18-3.07 (m, 1H), 2.32 (s, 3H), 1.23 (d,3 = 6.9 Hz, 3H), 1.14 ( d, 3= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.30, 168.80, 157.71,155.38, 148.69,140.60,136.96,133.70, 130.44,127,36,115.97,111.49, 109.52,76.84 , 56.09,55.12, 41.05, 39.03, 20.17, 18.27, 17.59. 122 IF-2019-52232722-APN-ANP#INPI Page 243 of 408 or i I ,i IF-2019-52232722-APN-ANP#INPI ffl!T 244 llu 408 o 123 HRMS-ESl (m / z) [M+HJ* calculated for C20H23EN2O5, 391.1664; found, 391.1662 1H NMR (500 MHz, CDCI3) δ 12.04 (s,1H), 8.46 (t,J= 5.8 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.20 - 7.08 (m, 1H), 6.93 - 6.80 (m, 3H), 5.15 (dq, J = 7.9, 6.3 Hz, 1H) , 4.21 (dd, J=5.7, 3.2 Hz, 2H), 3.95 (s, 3H), 3.15 (p, J = 7.1 Hz, 1H), 2.33 ( s, 3H), 1.24 (d,J = 6.9 Hz, 3H), 1.15 (d, J = 6.3 Hz, 3H). ”C NMR (126 MHz, CDCI3) δ 169.32, 168.75, 161.97, 160.03, 155.39, 148.70, 140.61, 137.91, 137.85, 137.20, 137.17, 130.40, 127.85, 127.78, 117.11, 116.95, 113.06, 112.90, 109.54,76.40, 56.10,41.03, 39, 10,19,99, 18,22,17,42. 124 HRMS-ESl (m / z) [M+H]* calculated for C20H23FN2O5, 391.1664; found, 391.1661 1H NMR (500 MHz, CDCI3) δ 12.01 (d, J= 0.6 Hz, 1H), 8.34 (t, J=5.8 Hz, 1H), 7.99 ( d,J= 5.2 Hz, 1H), 7.15 (dd,J= 9.5, 5.8 Hz, 1H), 6.88 (d, J= 5.2 Hz, 1H), 6, 85 - 6.77 (m, 2H), 5.21 - 5.11 (m, 1H), 4.20-3.91 (m, 2H), 3.95 (s, 3H), 3.23 ( p, J = 7.1 Hz, 1H), 2.33 (s, 3H), 1.30-1.20 (m, 6H). 13C NMR (126 MHz, CDCb) δ 169.19, 168.38, 161.97, 160.02, 155.38, 148.68, 140.55, 138.43, 136.66, 130.36, 127 .75, 127.68, 116.81, 116.65, 112.86, 112.70, 109.52, 75.82, 56.09, 40.88, 38.65, 19.85, 17.20 ,16,64. 123 IF-2019-52232722-APN-ANP#INPI Page 245 of 408 IF-2019-52232722-APN-ANP#INPI or 125 HRMS-ESI (m / z) [M+H]* calculated for C20H24N2O5, 373.1758; found, 373.1755 'H NMR (500 MHz, CDCI3) δ 12.03 (d, J= 0.6 Hz, 1H), 8.34 (t, J= 5.8 Hz, 1H), 7.99 (d, J= 5.2 Hz, 1H), 7.20 (dd, J = 7.7,1.3 Hz, 1H), 7.17-7.04 (m, 3H), 6.87 ( d, J= 5.2 Hz, 1H), 5.255.16 (m, 1H), 4.12 (dd, J= 18.2, 5.9 Hz, 1H), 3.95 (s, 3H), 3.98 3.89 (m, 1H), 3.29 (p, J= 7.1 Hz, 1H), 2.35 (s, 3H), 1.27 (m, 6H). 13C NMR (126 MHz, CDCI3) δ 169,15,168,41,155,35,148,66, 140,97,140,52,136,10,130,41, 130,27,126,30,126,14,109,48, 75,92, .85 , 39,18, 19,79,17,18,16,37. 126 HRMS-ESI (m / z) [M+H]+ calculated for C19H21FN2O5, 377.1507; found, 377.1507 'H NMR (500 MHz, CDCI3) δ 12.04 (s, 1H), 8.46 (t, J= 5.9 Hz, 1H), 8.01 (d, J= 5, 2 Hz, 1H), 7.22 - 7.08 (m, 2H), 6.98 (t, J = 8.7 Hz, 2H), 6.89 (d, J = 5.2 Hz, 1H) , 5.16 - 5.01 (m, 1H), 4.29 4.14 (m, 2H), 3.95 (s, 3H), 2.92 (p, J = 7.1 Hz, 1H) , 1.28 (d, J = 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.33,168.65, 162.67,160.72, 155.41,148.71,140.61,138.37, 130.40,129,27,129.21,115.36, 76.36 , 56,10, 44,12,41,06,17,83,17,27. 124 IF-2019-52232722-APN-ANP#INPI Page 247 of 408 IF-2019-52232722-APN-ANP#INPI or 127 HRMS-ESI (m / z) [M+H]* calculated for CziH^NzOe, 403.1864; found, 403.1853 'H NMR (500 MHz, CDCI3) δ 12.06 (s, 1H), 8.47 (t, J= 5.7 Hz, 1H), 8.01 (d, J=5, 2Hz, 1H). 7.08 (d, J= 8.4 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.82 - 6.66 (m, 2H), 5.15 (dq , J = 8,1,6.3 Hz, 1H), 4.29-4.15 (m, 2H), 3.95 (s, 3H), 3.77 (s, 3H), 3.17 - 3.08 (m, 1H), 2.32 (s, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.14 (d,J = 6.3 Hz, 3H). ,3C NMR (126 MHz, CDCI3) δ 169.30,168.80,157.71,155.38, 148.69,140.60,136.96,133.70, 130.44,127.36,115.97,111.49, 109.52,76.84, 5 6, 09, 55.12, 41.05, 39.03, 20.17,18.27, 17.59. 128 HRMS-ESI (m / z) [M+H]* calculated for C21H25FN2O5, 405.1820; found, 405.1819 1H NMR (500 MHz, CDCI3) δ 12.14 (d, J= 0.6 Hz, 1H), 8.49 (d,J = 7.9Hz, 1H), 8.00 (d ,J = 5.2 Hz, 1H), 7.18-7.05 (m, 1H), 6.93-6.79 (m, 3H), 5.11 (dq, J = 8.0.6 .3 Hz, 1H), 4.78 - 4.64 (m, 1H), 3.95 (s, 3H), 3.233.09 (m, 1H), 2.33 (s, 3H), 1.55 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.9 Hz, 3H), 1.14 (d. J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.79,168.69, 161.97,160.03, 155.39,148.77,140.51, 137.87, 137.81,137,33,137.30,130.47, , 117 ,10,116,94, 113,02,112,85,109,47,76,32, 56,09,48,13, 39,16, 20,00, 18,42,18,36,17,33. 125 IF-2019-52232722-APN-ANP#INPI Page 249 of 408 IF-2019-52232722-APN-ANP#INPI 129 HRMS-ESI (m£) [M+H]* calculated for C21H25FN2O5, 405.1820; found, 405.1820 1H NMR (500 MHz, CDCI3) δ 12.09 (s, 1H), 8.35 (d, 4 = 7.9 Hz, 1H), 7.98 (dd, 4 =5.2 ,3.6 Hz, 1H), 7.13 (dd, 4 =8.4, 5.8 Hz, 1H), 6.94 - 6.73 (m, 3H), 5.21 - 5.08 ( m, 1H), 4.63 - 4.46 (m, 1H), 3.94 (s, 2H), 3.273.15 (m,1H). 13C NMR (126 MHz, CDCI3) δ 171.55,168.59,161.91,159.97, 155.37,148.73,140.44, 138.30, 137.15,130.43,127.47, 116.73, ,112,73,109 .43, 75.74, 56.07,47.87,38.98, 19.90,17.79,17.32. 130 HRMS-ESI (m / z) [M+H]* calculated for C21H26N2O5, 387.1914; found, 387.1911 1H NMR (500 MHz, CDCI3) δ 12.11 (s, 1H), 8.36 (d, 4= 8.0 Hz. 1H), 7.97 (d, 4 = 5.2 Hz, 1H), 7.24 - 7.01 (m, 4H), 6.86 (d, 4 = 5.2 Hz, 1H), 5.27-5.12 (m, 1H), 4.59 - 4.47 (m, 1H), 3.94 (s, 2H), 3.33 - 3.20 (m, 1H), 2.36 (s, 3H), 1.32 (d, 4 = 6 .3 Hz, 3H), 1.24 (d, 4 = 7.1 Hz, 3H), 1.08 (d, 4 = 7.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.58,168.54,155,33,148.71, 141.47,140.41,135.95,130.49, 130.22,126.20, 125.88, 109.39, 75.87, 56.06 .47.85, 39.52, 19.83,17.83,17.74,17.14. 126 IF-2019-52232722-APN-ANP#INPI Page 251 of 408 or IF-2019-52232722-APN-ANP#INPI Page 2^^y4^ 131 HRMS-ESI (m¿) (M+Hf calculated for C20H23FN2O5, 391.1664; found, 391.1662 'H NMR (500 MHz, CDCI3) δ 12.14 (s, 1H), 8.47 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.15 (dd, J = 8.6, 5.4 Hz, 2H), 6.97 ( t.J = 8.7 Hz, 2H). .3 Hz, 1H), 3.95 (s, 3H), 2.92 (p, 7= 7.1 Hz, 1H), 1.53 (d, J = 7.2 Hz, 3H), 1, 29 (d, J = 7.1 Hz, 3H), 1.12 (d, J =6.3 Hz, 3H). ”C NMR (126 MHz, CDCI3) δ 171.67,168.69, 162.64.160, 70, 155.40,148.78,140.51,138.48, 130.46,129.26,129,19,115.32, 115.16,109.48, 76.31, 56.09, 48.12.44,11,18,38.17, 95, 17.16. 132 HRMS-ESI (m / z) [M+Hf calculated for C22H28N2O6, 417.2020; found, 417.2007 'H NMR (500 MHz, CDCI3) δ 12.16 (s, 1H) , 8.51 (d, 7=7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.11 -7.05 (m, 1H), 6.88 ( d, 7= 5.2 Hz, 1H), 6.70 (d, J= 6.7 Hz, 2H), 5.11 (dq, J = 8.3, 6.3 Hz, 1H), 4, 72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.77 (s, 3H), 3.18 3.06 (m, 1H), 2.32 (s, 3H), 1.56 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.14 (d, J= 6.3 Hz, 3H) . 13C NMR (126 MHz, CDCI3) δ 171.85,168.67,157.70,155.38, 148.77,140.50,136.91,133.86, 130.52,127.36, 115.95,111.48, 109.45, 55 ,13,48,17, 39,11,20,18,18,46,17,57, 16,10. 127 IF-2019-52232722-APN-ANP#INPI Page 253 of 408 or IF-2019-52232722-APN-ANP#INPI 133 HRMS-ESI (m / z) [M+H]+ calculated for C2lH25FN2O5, 405.1820; found, 405.1819 1H NMR (500 MHz, CDCI3) δ 12.14 (s,1H), 8.47 (d, J =8.0 Hz, 1H), 8.01 (d, J =5.2 Hz, 1H), 7.13 (dd, J =9.4, 5.8 Hz, 1H), 6.91-6.81 (m, 3H), 5.12 (dq, J = 8.1, 6.3 Hz, 1H), 4.72 (p, J = 7.2 Hz, 1H), 3.95 (s, 3H), 3.203.10 (m, 1H), 2.33 (s, 3H) , 1.54 (d, J = 7.1 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.81,168.74,161.95,160.01, 155.40,148.78,140.51, 137.89, 137.83, 137.29, 137.26, 130.48, 127.87.127 .81,117.08,116.91, 113.06, 112.90, 109.48, 76.19, 56.09,47.96, 39.12, 20.02, 18.24,18.12,17.47 . 134 HRMS-ESI (m / z) [M+H]* calculated for C2iH25FN2O5, 405.1820; found, 405.1818 'H NMR (500 MHz. CDCI3) δ 12.12 (s, 1H), 8.28 (d, J =8.0 Hz, 1H), 7.99 (d, J = 5, 2 Hz, 1H), 7.18-7.12 (m. 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.78 (t, J= 8.2 Hz, 2H) , 5.17 - 5.06 (m, 1H), 4.64 4.51 (m, 1H), 3.95 (s, 3H), 3.23 (p, J = 7.1 Hz, 1H) , 2.33 (s, 3H), 1.38 (d, J- 7.1 Hz, 3H), 1.26 1.20 (m, 6H). 13C NMR (126 MHz, CDCb) δ 171.29,168.55,161.93,159.99, 155.38,148.74,140.44, 138.41, 138.35,136.73,136.71,130.43, 16,77,116,61 , 112.81,112.64,109.45, 75.62, - 56.09,47.82, 38.64,19.89, 19.88,18,06,17,22,16.84. 128 IF-2019-52232722-APN-ANP#INPI Page 255 of 408 or IF-2019-52232722-APN-ANP#INPI ráuiiu ilu 403 135 HRMS-ESI (zn4) [M+H]* calculated for CziHaeNzOs, 387.1914; found, 387.1915 1H NMR (500 MHz, CDCI3) δ 12.15 (s,1H), 8.30 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.21 (dd, J =7.8,1.4 Hz, 1H), 7.15 - 7.00 (m, 3H), 6.87 (d, J = 5.2 Hz , 1H), 5.20 - 5.12 (m, 1H), 4.59-4.50 (m,1H), 3.95 (s, 3H), 3.29 (p, J = 7.1 Hz, 1H), 2.36 (s, 3H), 1.35 (d, J =7.2 Hz, 3H), 1.29-1.22 (m, 6H). 13C NMR (126 MHz, CDCI3) δ 171.30,168.54,155.35,148.73, 141.04,140.40, 136.09,130.51, 130.26,126.23,126.11,109.40, 75.73, 7 .88, 39.15, 19.83,18,11,17,16,16,53. 136 HRMS-ESI (m / z) [M+H]* calculated for C20H23FN2O5, 391.1664; found, 391.1658 1H NMR (500 MHz, CDCI3) δ 12.14 (s, 1H), 8.46 (d, J = 7.7 Hz, 1H), 8.00 (dd, J= 5.2 ,2.2 Hz, 1H), 7.15 (ddd, J= 9.9,6.1, 3.4 Hz, 2H), 6.97 (td, J= 8.8, 2.6 Hz, 2H), 6.88 (dd, J =5.4.1.5 Hz, 1H), 5.12-5.01 (m, 1H), 4.77-4.64 (m, 1H), 3 .95 (s, 3H), 2.92 (p, J= 7.1 Hz, 1H), 1.53 (d, J = 7.2 Hz, 3H), 1.28 (d, J = 7, 0 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171,72,168,76,162,65,160,70, 155,41,148,78,140,51,138,43, 138,40,130,47,129,29,129,23, 09,48,76,12 , 56,09,47,98,44,09,18,20, 17,69,17,30. 129 IF-2019-52232722-APN-ANP#INPI Page 257 of 408 or IF-2019-52232722-APN-ANP#INPI 2ΰ0ιΕ 400 or 137 HRMS-ESI (m / z) [M+H]+ calculated for C22H28N2O6, 417.2020; found, 417.2010 'H NMR (500 MHz, CDCI3)Ó 12.17 (s, 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.01 (d, J=5, 2 Hz, 1H), 7.09 (d,J = 8.4 Hz, 1H), 6.88 (d, J=5.2 Hz, 1H), 6.76-6.67 (m, 2H) , 5.13 (dq, J= 8.3, 6.3 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.76 ( s, 3H), 3,183.07 (m, 1H), 2.32 (s, 3H), 1.54 (d, J=7.2 Hz, 3H), 1.23 (d,J = 6.9 Hz, 3H), 1.12 (d,J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.86,168.72, 157.68,155.38, 148.76, 140.50, 136.94,133.82, 130.53,127,37,115.97,111.47, 109.45.76 .65, 56.08, 55.11, 47.99, 39.06,20.19, 18.31, 18.20, 17.68. 138 HRMS-ESI (m / z) [M+H]* calculated for C23H29FN2O5, 433.2133; found, 433.2130 1H NMR (500 MHz, CDCl3) δ 12.16 (s, 1H), 8.50 (d, J=9.4 Hz, 1H), 8.01 (d, J- 5.2 Hz, 1H), 7.11 (dd, J=8.6, 5.8 Hz, 1H), 6.89 (d, J=5.2 Hz, 1H), 6.876.77 (m,2H), 5.08 (dq, J=8.0, 6.2 Hz, 1H), 4.65 (dd, J=9.4, 4.8 Hz, 1H), 3.95 (s, 3H), 3 .15 (p, J=7.1 Hz, 1H), 2.32 (s, 4H), 1.24 (d, J=6.9 Hz, 3H), 1.14 (d, J=6, 2 Hz, 3H), 1.05 (d,J = 6.8 Hz, 3H), 0.96 (d, J= 6.8 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.73,169.06, 161.95,160.01, 155.42,148.75, 140.52,137.83, 137.77,137.36, 130.51,127.84, 7 , 116.91,113.01, 112.85,109.47, 76.43, 57.26, 56.09,39.06, 31.35,19.99, 19.48,18.45,17.38. 130 IF-2019-52232722-APN-ANP#INPI Page 259 of 408___ or IF-2019-52232722-APN-ANP#INPI Pá uBFa 2Ú0 iL 400 o 139 HRMS-ESI (m / k) [M+Hf calculated for C23H29FN2O5, 433.2133; found, 433.213 1H NMR (500 MHz, CDCI3) δ 12.12 (s, 1H), 8.38 (d, J=9.3 Hz, 1H), 7.99 (t, 7=5.1 Hz, 1H), 7.14 (dd, J = 8.5, 5.9 Hz, 1H), 6.88 (dd, J = 7.6, 5.1 Hz, 1H), 6.84-6.72 (m, 3H), 5.13 (dq, J = 8.4.6.3 Hz, 1H), 4.49 (td, J = 9.4.4.9 Hz, 1H), 3.94 ( s, 3H), 3.20 (p, 7= 7.4 Hz, 1H), 2.33 (s, 3H), 1.94 (pd, 7=6.9,4.6 Hz, 1H), 1.29 (d, 7=6.3 Hz, 3H), 1.21 (d, 7=7.1 Hz,3H), 0.85 (d, 1 / = 6.9 Hz, 3H), 0 .68 (d,7 = 6.8 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.52, 168.98, 161.96, 160.02, 155.39,148.70,140.45,138.31, 138.25,137,28,137.25,130.49, 0 , 116.75,116.59, 112.92, 112.76, 109.42, 75.86, 56.97, 56.08, 38.86, 31.12, 19.89,19.12,17.79 ,17.34, 17.02. 140 HRMS-ESI (m / z) [M+H]* calculated for C23H30N2O5, 415.2227; found, 415.2222 'H NMR (500 MHz, CDCI3) δ 8.38 (d, J= 9.4 Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.20 (d, J = 7.7 Hz, 1H), 7.16-7.08 (m, 1H), 7.08-7.03 (m, 2H), 6.86 (d, J = 5.2 Hz, 1H), 5.25 - 5.11 (m, 1H), 4.49 (dd, J= 9.4,4.5 Hz, 1H), 3.94 (s, 3H), 3.37 —3.18 (m, 1H), 2.34 (s, 3H), 1.91 (pd, J = 6.9,4.5 Hz, 1H), 1.31 (d, J = 6.2 Hz, 3H), 1.23 (d, J = 7.1 Hz, 3H), 0.82 (d, J= 6.8 Hz, 3H), 0.64 (d, J = 6.8Hz,3H ). 5 6 .07, 39.37, 31.11,19.82,19.14, 17.78, 17.11,16.98. 131 IF-2019-52232722-APN-ANP#INPI Page 261 of 408 or IF-2019-52232722-APN-ANP#INPI Page 2Ú2 ilu 400 or 141 HRMS-ESI (m / z) [M+H]* calculated for C22H27FN2O5, 419.1977; found, 419.1973 1H NMR (500 MHz, CDCI3) δ 12.16 (s.1H), 8.48 (d, 4= 9.4 Hz, 1H), 8.01 (d, 4=5.2 Hz, 1H), 7.19-7.10 (m,2H), 6.94 (t, 4 = 8.7 Hz, 2H), 6.89 (d, 4 =5.2 Hz, 1H), 5.11-4.98 (m, 1H), 4.64 (dd, 4 =9.4, 4.8 Hz, 1H), 3.95 (s, 3H), 2.92 (p, 4 = 7.1 Hz, 1H), 2.31 (pd, 4 =6.9, 4.8 Hz, 1H), 1.29 (d, 4 = 7.0 Hz, 3H), 1.12 (d, 4=6.3 Hz, 3H), 1.03 (d, 4=6.8 Hz, 3H), 0.95 (d, 4 = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCI3)6 170.57, 169.05, 162.62,160.67, 155.43, 148.76, 140.52,138.50, 130.50, 129.23, 129.16,115.29 , 115,13,109,47,77,27, 76,39, 57,25, 56,10,43,96,31,33, 19,41,18,04,17,40,17,07. 142 HRMS-ESI (m / z) [M+H]+ calculated for C24H32N2O6, 445.2333; found, 445.2314 1H NMR (500 MHz, CDCl3) δ 12.18 (s, 1H), 8.52 (d, J=9.4 Hz, 1H), 8.02 (d, J = 5.2 Hz, 1H), 7.06 (d, J= 8.4 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.75-6.63 (m, 2H), 5.08 (dq, J= 8.3, 6.2 Hz, 1H), 4.66 (dd, J= 9.4,4.8 Hz, 1H), 3.95 (s, 3H), 3 .76 (s, 3H), 3.19-3.06 (m, 1H), 2.41 -2.33 (m, 1H), 2.31 (s, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.13 (d,J= 6.2 Hz, 3H), 1.05 (d, J=6.9 Hz, 3H), 0.98 (d, J=6 .9Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.79,169.06, 157.68,155.40, 148.74,140.51, 136.87, 133.93, 130.56,127,33,115.96,111.46, 109.44.76 .90, 57.29, 56.08, 55.12, 39.01,31.37, 20.17, 19.50,18.52,17.65,17.40. 132 IF-2019-52232722-APN-ANP#INPI Page 263 of 408 or IF-2019-52232722-APN-ANP#INPI Page 264 du 400 or 143 HRMS-ESI (m / z) [M+HJ* calculated for C23H29FN2O5, 433.2133; found, 433.2142 *H NMR (500 MHz, CDCI3) δ 12.18 (s, 1H), 8.50 (d, J=9.2 Hz, 1H), 8.02 (d, J=5, 2 Hz, 1H), 7.13 (dd, J= 9.5, 5.7 Hz, 1H), 6.89 (d,J=5.2 Hz, 1H), 6.876.82 (m,2H) , 5.12 (dq, J= 8.0, 6.3 Hz, 1H), 4.63 (dd, J=9.3, 5.1 Hz, 1H), 3.95 (s, 3H), 3.15 (p, J = 7.1 Hz, 1H), 2.41-2.25 (m, 4H), 1.24 (d, J = 6.9 Hz, 3H), 1.13 (d ,J = 6.3 Hz, 3H), 1.03 (d, J=6.9 Hz, 3H), 0.99 (d, J=6.9 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.87,169.06, 161.95, 160.01, 155.41,148.74, 140.53, 137.86, 137.80, 137.31, 137.28, 130 .54, 127.91,117.05,116.89,113.06, 112.89,109.46.76.09, 57.04, 56.09, 39.11,31.39, 20.00, 19.12, 18.25 , 17.80, 17.41. 144 - - - - - HRMS-ESI (m / z) [M+H]* calculated for C23H29FN2O5, 433.2133; found, 433.2139 1H NMR (500 MHz, CDCI3) δ 12.16 (s, 1H), 8.32 (d, 7=9.2 Hz, 1H), 8.00 (d, 7= 5.2 Hz, 1H), 7.16 (dd, 7 = 8.4, 5.8 Hz, 1H), 6.89 (d, 7= 5.2 Hz, 1H), 6.78 (ddd, 7= 9 ,8, 7,0,4,1 Hz, 2H). 5.17-5.05 (m, 1H), 4.48 (dd, J = 9.3, 5.3 Hz, 1H), 3.96 (s, 3H), 3.22 (p, 7= 7.2 Hz, 1H), 2.33 (s, 3H), 2.18 (pd, 7 = 6.9, 5.2 Hz, 1H), 1.28- 1.19 (m, 6H), 0.92 (d, 7 = 6.8 Hz, 3H), 0.86 (d, 7 = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCI3)6 170.29, 168.86, 161.96, 160.02,155.40, 148.71, 140.46, 138.45, 138.39,136.79, 136.76, 130 .49, 127.77,127.70,116.77,116.61, 112.79, 112.63, 109.43, 75.66, 57.06, 56.09, 38.58,31.26, 19.91, 18 .94, 17.61,17.30, 16.84. 133 IF-2019-52232722-APN-ANP#INPI Page 265 of 408 or IF-2019-52232722-APN-ANP#INPI Page 2ΰΰ du 4081o 145 HRMS-ESI (m / z) [M+H]+ calculated for C23H30N2O5, 415.2227,* found, 415.2224 'H NMR (500 MHz, CDCI3) δ 12.19 (s, 1H), 8, 34 (d, J = 9.3 Hz, 1H), 8.00 (d, J= 5.2 Hz, 1H), 7.21 (dd, J= 7.6,1.7 Hz, 1H), 7.14 - 7.05 (m, 2H), 7.02 (td, J = 7.2,1.4 Hz, 1H). 6.88 (d, J = 5.2 Hz, 1H), 5.20 - 5.12 (m, 1H), 4.48 (dd, J= 9.3, 5.1 Hz, 1H), 3 .95 (s, 3H), 3.28 (p, J = 7.1 Hz, 1H), 2.36 (s, 3H), 2.17 (pd, J = 6.9, 5.1 Hz, 1H), 1.29-1.22 (m, 6H). 0.90 (d, J = 6.8 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.28,168,84,155,36,148.69, 141.08,140.42,136,11,130.59, 130.28,126.23, 126.11,109.39, 75.76, 57.06, 56 .08, 39.06, 31.33,19.83,18.93,17.59, 17.20,16.50. 146 HRMS-ESI (m / z) [M+H]+ calculated for C22H27FN2O5, 419.1977; found, 419.1974 1H NMR (500 MHz, CDCI3) δ 12.17 (s,1H), 8.50 (d, J = 8.9 Hz. 1H), 8.02 (d, J= 5.2 Hz, 1H), 7.19-7.10 (m, 3H), 7.00-6.93 (m, 2H), 6.89 (d, J = 5.2 Hz, 1H), 5.11 - 5.02 (m, 1H), 4.67 - 4.58 (m, 1H), 3.95 (s, 4H), 2.92 (p, J = 7.1 Hz, 1H), 2, 31 (pd, J= 6.9, 5.0 Hz, 1H), 1.28 (d, J = 7.0 Hz, 3H), 1.10 (d, J= 6.2 Hz, 3H), 1.02 (d, J= 6.9 Hz, 3H), 0.99 (d, J= 6.9 Hz, 3H). 3C NMR (126 MHz, CDCI3) 76, 11, 57.07, 56,09,44,09,31,35,19,09, 17,87,17,82,17,23. 134 IF-2019-52232722-APN-ANP#INPI Page 267 of 408 IF-2019-52232722-APN-ANP#INPI Page 260 ill 40 O' o 147 HRMS-ESI (m / z) [M+H]* calculated for C24H32N20g, 445.2333; found, 445.2334 'H NMR (500 MHz, CDCI3) δ 12.20 (s, 1H), 8.53 (d, J = 9.2 Hz, 1H), 8.02 (d, J = 5, 2 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.75 - 6.64 (m, 2H) , 5.12 (dq, J = 8.2, 6.3 Hz, 1H), 4.65 (dd, J = 9.2, 5.0 Hz, 1H), 3.95 (s, 3H), 3.75 (s, 3H), 3.20-3.06 (m, 1H), 2.32 (s, 4H), 1.23 (d,J= 6.9 Hz, 3H), 1.13 (d, J= 6.2 Hz, 3H), 1.03 (d, J=6.9 Hz, 3H), 1.00 (d,J= 6.9 Hz, 3H). ”C NMR (126 MHz, CDCI3) δ 170.92, 169.04, 157.67, 155.39, 148.73,140.52,136.92,133.85, 130.59,127.40, 116.00, 111.44, 109.43, 76.56, 57.04, 56.08, 55.10, 39.05,31.44, 20.18, 19.13, 18.32,17.80, 17.65. 148 HRMS-ESI (m / z) [M+H]+ calculated for C2iH25FN2O5, 405.1820; found, 405.1820 1H NMR (500 MHz, CDCI3) δ 12.14 (s, 1H), 8.47 (d, J = 7.9 Hz, 1H), 8.01 (d, J=5.2 Hz, 1H), 7.13 (dd, J= 9.5, 5.8 Hz, 1H), 6.91-6.80 (m, 3H), 5.12 (dq, J = 8.1, 6.3 Hz, 1H),4.72(p, J = 7.3 Hz, 1H), 3.95 (s,3H), 3.213.10 (m, 1H), 2.33 (s, 3H) , 1.54 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.12 (d,J= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.81, 168.74, 161.95, 160.01, 155.40,148.78, 140.51,137.89, 137.83, 137.29, 137.26, 130 .48, 127.87,127.81, 117.07, 116.91, 113.06, 112.90, 109.48.76.19, 56.09.47.96,39.12, 20.01, 18 ,24,18,13,17,48. 135 IF-2019-52232722-APN-ANP#INPI Page 269 of 408 or IF-2019-52232722-APN-ANP#INPI 149 HRMS-ESI (m / z) [M+H]* calculated for C21H25FN2O5, 405.1820; found, 405.1820 1H NMR (500 MHz, CDCI3) δ 12.12 (s,1H), 8.28 (d, 7= 8.0 Hz, 1H), 7.99 (d, 7 = 5.2 Hz, 1H), 7.22-7.09 (m, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.83 - 6.74 (m, 2H), 5.19 - 5.06 (m, 1H), 4.62 - 4.50 (m, 1H), 3.95 (s, 3H), 3,313.17 (m, 1H), 2.33 (s, 3H), 1.38 (d, 7=7.2 Hz, 3H), 1.27-1.18 (m, 6H), ”C NMR (126 MHz, CDCI3) δ 171.29,168.55, 161.93, 159 .99, 155.38, 148.74, 140.44, 138.41, 138.35, 136.73, 136.71, 130.43, 127.71,127.64, 116.77, 116.61, 112 .80, 112.64, 109.45, 75.62, 56.09,47.82, 38.64, 18.06, 17.22, 16.84. 150 HRMS-ESI (m / z) [M+H]* calculated for C2iH26N2O5, 387.1914; found, 387.1913 1H NMR (500 MHz, CDCI3) δ 12.15 (s, 1H), 8.30 (d, 7 = 7.9 Hz, 1H), 7.99 (d, 7 = 5.2 Hz, 1H), 7.21 (dd, 7=7.8,1.4 Hz, 1H), 7.15-7.01 (m,4H), 6.87 (d, 7 = 5.2 Hz , 1H), 5.23-5.08 (m, 1H), 4.58-4.49 (m, 1H), 3.95 (s, 3H), 3.28 (h, 7 = 7.3 Hz, 1H), 2.36 (s, 3H), 1.35 (d, 7 = 7.2 Hz, 3H), 1.28-1.22 (m, 6H). 13C NMR (126 MHz, CDCI3) δ 171.29,168.54, 155.35, 148.73, 141.04,140.40, 136.09, 130.51, 130.26, 126.23, 126.11, 109 .40, 75.73, 56.08,47.88, 39.15, 19.83, 18.11, 17.16, 16.53. 136 IF-2019-52232722-APN-ANP#INPI Page 271 of 408 or IF-2019-52232722-APN-ANP#INPI Page 272 di 400 or 151 • HRMS-ESI (m / ¿) [M+H]+ calculated for C20H23FN2O5, 391.1664; found, 391.1658 1H NMR (500 MHz, CDCI3) δ 12.14 (d, J=0.6 Hz, 1H), 8.46 (d, J = 7.9 Hz, 1H), 8.01 ( d, J = 5.2 Hz, 1H), 7.16 (dd, J= 8.7, 5.4 Hz, 2H), 6.97 (t, J=8.7 Hz, 2H), 6, 88 (d, J=5.2 Hz, 1H), 5.07 (dq, J=7.4, 6.3 Hz, 1H), 4.79-4.64 (m, 1H), 3.95 (s, 3H), 2.92 (p, J=7.1 Hz, 1H), 1.53 (d, J=7.2 Hz, 3H), 1.28 (d, J = 7.1 Hz , 3H), 1.09 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.72,168.76,162.65,160.70, 155.40,148.78,140.51,138.43, 130.47,129.29,129.23,115.33, 115.16,109.48, 76,12,56 .09, 47.98,44.09, 18.19, 17.69, 17.30. 152 HRMS-ESI (m / ¿) [M+H]* calculated for C22H28N2O6, 417.2020; found, 417.2007 1H NMR (500 MHz, CDCI3) δ 12.17 (s,1H), 8.50 (d, J = 7.9 Hz, 1H), 8.01 (d,J=5.2 Hz, 1H), 7.09 (d,J=8.3 Hz, 1H), 6.88 (d, J=5.2 Hz, 1H), 6.78-6.64 (m, 2H), 5.13 (dq, J= 8.4, 6.3 Hz, 1H), 4.73 (p, J=7.3 Hz, 1H), 3.95 (s, 3H), 3.76 (s , 3H), 3.18 3.06 (m, 1H), 2.32 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6 .9 Hz, 3H), 1.12 (d,J= 6.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.86,168.72,157.68,155.38, 148.76,140.50,136.94,133.81, 130.53,127.37,115.97,111.47, 109.45, 76.65, 56.08 , 55,11,— 47,99,39,06,20,19,18,30, 18,19,17,68. 137 IF-2019-52232722-APN-ANP#INPI Page 273 of 408 or IF-2019-52232722-APN-ANP#INPI Page or 153 HRMS-ESI (m¿) [M+H]* calculated for C21H25FN2O5, 405.1820; found, 405.1818 1H NMR (500 MHz, CDCI3) δ 12.14 (s,1H), 8.49 (d,7 = 8.0 Hz, 1H), 8.00 (d,7 = 5.2 Hz, 1H), 7.17-7.08 (m, 1H), 6.91-6.81 (m,4H), 5.11 (dq, 7 =8.1, 6.3 Hz, 1H) , 4.72 (p, 7 = 7.3 Hz, 1H), 3.95 (s, 3H), 3.20-3.10 (m, 1H), 2.33 (s, 3H), 1, 55 (d, 7= 7.2 Hz, 3H), 1.24 (d, 7 = 6.9 Hz, 3H), 1.14 (d, 7=6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3)6 171.80, 168.69, 161.97, 160.03, 155.39, 148.77, 140.51, 137.87, 137.81,137,33,137.30, 130 .47, 127.86, 127.79, 117.10, 116.94, 113.02,112.86, 109.47, 76.33, 56.09,48.13, 39.16,20.00, 18 ,41,18,36,17,33. 154 HRMS-ESI (m / z) [M+H]* calculated for C21H25FN2O5, 405.1820; found, 405.1816 1H NMR (500 MHz, CDCI3) δ 12.09 (s, 1H), 8.35 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.13 (dd, 7 =8.4, 5.8 Hz, 1H), 6.86 (d, 7 =5.2 Hz, 1H), 6.80 (ddd, 7= 9 .5, 7.0, 4.1 Hz, 2H), 5.14 (dq, 7=8.2, 6.2 Hz, 1H), 4.60-4.49 (m, 1H), 3, 94 (s, 3H), 3.27 - 3.16 (m, 1H), 2.34 (s, 3H), 1.30 (d, 7 =6.3 Hz, 3H), 1.22 (d , 7 = 7.1 Hz, 3H), 1.14 (d, 7=7.2Hz, 3H). 13C NMR (126 MHz, CDCh) δ 171.55, 168.59, 161.91, 159.97, 155.37, 148.74, 140.44, 138.30, 138.24, 137.15, 137 .13, 130.43, 127.46, 127.40, 116.74, 116.57, 112.90,112.73, 109.43, 75.74, 56.08.47.87, 38.98.19 .90, 19.89,17.79, 17.32. 138 IF-2019-52232722-APN-ANP#INPI Page 275 of 408 ¡I Ί Yo IF-2019-52232722-APN-ANP#INPI I 155 HRMS-ESI (m£) [M+H]* calculated for Cjl^e^Os, 387.1914; found, 387.1912 'H NMR (500 MHz, CDCI3) δ 12.11 (d, J =0.6 Hz, 1H), 8.36 (d, J =8.0 Hz, 1H), 7.97 (d,J = 5.2 Hz, 1H), 7.19 (dd, J = 7.5, 1.2 Hz, 1H), 7.12 (td, 7.8, 7.0, 2.4 Hz, 1H), 7.09 - 7.02 (m, 2H), 6.86 (d, J =5.2 Hz, 1H), 5.19 (dq, J =8.3. 6.2 Hz. 1H ). 4.60-4.45 (m, 1H), 3.94 (s, 3H), 3.33-3.20 (m, 1H), 2.36 (s, 3H), 1.32 (d, J= 6.2 Hz, 3H), 1.24 (d, J =7.0 Hz. 3H), 1.08 (d, J = 7.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171,58,168,54,155,33,148,71, 141,47,140,41,135,95,130,49, 130,22,126,20,125,88,109,39, 75,87, .85 , 39,52, 19,83,17,83,17,74,17,14. 156 HRMS-ESI (m / z) [M+H]* calculated for C20H23FN2O5, 391.1664; found, 391.1661 1H NMR (500 MHz, CDCI3) δ 12.14 (s, 1H), 8.47 (d,J = 7.7 Hz, 1H), 8.00 (d. J =5.2 Hz, 1H), 7.21-7.10 (m, 3H), 6.97 (td, J = 8.8,2.6 Hz, 2H), 6.88 (dd, J = 5.3, 1.7 Hz, 1H), 5.12-5.01 (m, 1H), 4.77 — 4.66 (m, 1H), 3.95 (d, J =1.6 Hz, 4H), 2.92 (p, J = 7.1 Hz, 1H), 1.53 (d, J =7.2 Hz, 4H), 1.29 (d, J =7.0 Hz, 3H), 1, 12 (d, J= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.67, 168.69, 162.64, 160.70, 155.40, 148.78,140.51,138.45, 130.46,129,26,115.32,115.16, 109.48 , 76,31,56,09,48,12, 44.11,18,38,17,95,17,16. 139 IF-2019-52232722-APN-ANP#INPI Page 277 of 408 or IF-2019-52232722-APN-ANP#INPI Page 279 say 400 or 157 HRMS-ESI (m / z) [M+H]+ calculated for C22H28N2O6, 417.2020; found, 417.2006 1H NMR (500 MHz, CDCI3) δ 12.16 (s, 1H), 8.51 (d, J = 7.9 Hz, 1H), 8.00 (d, J= 5.2 Hz, 1H), 7.12-7.06 (m, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.76 - 6.67 (m, 2H), 5.11 (dq, J=8.3, 6.3 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.77 (s, 3H) , 3.19-3.07 (m, 1H), 2.32 (s, 3H), 1.611.51 (m, 4H), 1.23 (d, J = 6.9 Hz, 3H), 1, 14 (d,J= 6.3 Hz, 3H). ”C NMR (126 MHz, CDCI3) δ 171.86, 168.68, 157.70, 155.38, 148.77, 140.50, 136.91, 133.86, 130.51, 127.36, 115.95, 111.48, 109.45, 56.08, 55.13,48.17, 39.11,20.18, 18.46,17.57. 158 1 IR (thin film) 3369, 2983, 1736, 1649, 1528.1310, 1148.1115, 770, 731 cm'1 HRMS-ESI (m / z) [M+H]* calculated for θ2ΐΗ24Ε3Ν2θ5, 441.1632 ; found, 441.1627 1H NMR (400 MHz, CDCI3) δ 12.13 (s, 1H), 8.58-8.47 (m, 1H), 8.01 (d, J= 5.2 Hz, 1H ), 7.68-7.61 (m, 1H), 7.51 (td, J = 7.7,1.2 Hz, 1H), 7.43 (d,J= 7.7 Hz, 1H) , 7.38-7.29 (m, 1H), 6.88 (d, J = 5.2 Hz, 1H), 5.295.15 (m, 1H), 4.82-4.71 (m, 1H ), 3.95 (s, 3H), 3.42-3.29 (m, 1H), 1.60 (d, J = 7.2 Hz, 3H), 1.29 (d, J = 6, 8Hz, 3H), 1.12 (d, J=6.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.24. 140 IF-2019-52232722-APN-ANP#INPI Page 279 of 408 IF-2019-52232722-APN-ANP#INPI or 159 IR (thin film) 3370, 2984, 1737.1528, 1313.1151, 1118, 1045, 908, 799, 738 απ'1 HRMS-ESl (m / z) [M+H]* calculated for C21H23F4N2O5, 459, 1538; found, 459.1535 1H NMR (400 MHz, CDCI3) δ 12.11 (s, 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.01 (d, J=5.2 Hz, 1H), 7.42 (dd, J=8.8, 5.3 Hz, 1H), 7.35 (dd, J=9.2, 2.8 Hz, 1H), 7.21 (td , J= 8.2, 2.8 Hz, 1H), 6.89 (d, J=5.2 Hz, 1H), 5.245.09 (m, 1H), 4.82-4.67 (m, 1H), 3.95 (s, 3H), 3.41-3.26 (m, 1H), 1.59 (d, J = 7.2 Hz,3H), 1.27 (d, J = 6 .8 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.78.-113.91. 160 IR (thin film) 3369, 2944, 1732, 1648, 1526, 1438, 1280,1263, 1216,1149, 1057, 800 cm'1 HRMS-ESl (m / z) [M+H]* calculated for C19H29N2O5, 365,2071; found, 365.2067 1H NMR (400 MHz, CDCI3) δ 12.17 (s, 1H), 8.53 (d, J=7.8 Hz, 1H), 7.99 (d, J=5.2 Hz, 1H), 6.87 (d, J=5.2 Hz, 1H), 5.11 (qd, J = 6.4, 3.1 Hz, 1H), 4.764.64 (m, 1H), 3.95 (s, 3H), 1.76 (dddd, J= 13.2,10.4, 8.0, 6.4 Hz, 2H), 1.69-1.52 (m, 6H), 1.52-1.43 (m, 1H), 1.43-1.35 (m, 1H), 1.24 (d,J = 6.4 Hz, 3H), 1.19- 0.98 ( m, 3H), 0.98 - 0.89 (m, 3H). 13C NMR (101 MHz, CDCI3) δ 171.76,168.71, 155.39, 148.78, 140.46,130.58, 109.43, 74.81, 56.08.48,23.43,31.43 .13, 31.22, 30.74, 25.15, 24.98, 18.51, 17.78, 12.50. 141 IF-2019-52232722-APN-ANP#INPI Page 281 of 408 or IF-2019-52232722-APN-ANP#INPI Page 202 iL 400 or 161 HRMS-ESI (m / z) [M+H]* calculated for C21H24F3N2O5, 441.1632; found, 441.1624 'H NMR (400 MHz, CDCI3) δ 12.15 (s, 1H), 8.48 (d,J= 8.0 Hz, 1H), 8.01 (d, J=5, 2 Hz, 1H), 7.64 (dd, J = 7.9,1.3 Hz, 1H), 7.56 - 7.47 (m, 1H), 7.44 (d, J = 7.8 Hz, 1H), 7.31 (t, J=7.5 Hz, 1H). 6.88 (d, J=5.2 Hz, 1H), 5.27 - 5.17 (m, 1H), 4.83 - 4.68 (m, 1H), 3.95 (s, 3H) , 3,423.28 (m, 1H), 1.58 (d, J = 7.2 Hz, 3H), 1.30 (d, J=6.8 Hz, 3H), 1.10 (d, J= 6.2Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.24. 162 IR (thin film) 2983.1738, 1649.1528, 1313.1152, 1119.1045, 909, 800, 732 cm’1 HRMS-ESI (m / z) [M+H]* calculated for C21H23F4N2O5, 459.1538; found, 459.1530 1H NMR (400 MHz, CDCI3) δ 12.12 (s, 1H), 8.46 (d, J = 7.9 Hz, 1H), 8.01 (d, J= 5.2 Hz, 1H), 7.43 (dd,J= 8.8, 5.3 Hz, 1H), 7.34 (dd, J = 9.2, 2.8 Hz, 1H), 7.21 (td , J=8.2, 2.8 Hz, 1H), 6.89 (d, J= 5.2 Hz, 1H), 5.18 (p, J = 6.6 Hz, 1H), 4.79 - 4.69 (m, 1H), 3.95 (s, 3H), 3.31 (p, J = 7.1 Hz, 1H), 1.57 (d, J = 7.2 Hz, 3H) , 1.29 (d, J = 6.9 Hz, 3H), 1.12 (d, J=6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.78.-114.01. 163 IR (thin film) 3370, 2944, 1732.1649, 1526.1438, 1263.1216, 1150, 1058, 954, 800, 731 cm-1 HRMS-ESI (m / z) [M+H]* calculated for C19H29N2O5, 365.2071; found, 365.2068 1H NMR (400 MHz, CDCI3) δ 12.18 (s, 1H), 8.52 (d, J = 7.8 Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 6.87 (d, J = 5.2 Hz, 1H), 5.10 (qd, J=6.4, 3.0 Hz, 1H), 4.744.64 (m, 1H), 3.95 (s, 3H), 1.83 -1.65 (m, 3H), 1.65-1.52 (m, 6H), 1.52-1.34 (m, 2H), 1, 23 (d, J=6.4Hz, 3H), 1.18-1.03 (m, 2H), 0.94 (d, J = 6.9 Hz, 3H). 13C NMR (101 MHz, CDCI3)6 171.75,168,76,155,39,148.79, 140.46,130.62, 109.44, 74.90, 56.08,48.04,43,11,42.95, 31 .26, 30.67, 25.14,25.00, 18.33, 17.49, 12.53. 142 IF-2019-52232722-APN-ANP#INPI Page 283 of 408 or du 403 IF-2019-52232722-APN-ANP#INPI or 164 IR (thin film) 3369t 2971, 1733, 1648, 1527, 1438, 1263, 1149, 1057, 801, 770,730 cm'1 HRMS-ESI (m / z) [M+H]* calculated for C^HjgNjOs, 401 .2071; found, 401.2072 1H NMR (400 MHz, CDCI3) δ 12.17 (S,1H), 8.58 (t, J=7.7 Hz, 1H), 7.99 (d, J=5.2 Hz, 1H), 7.14 - 6.90 (m, 3H), 6.87 (d, J = 5.3 Hz, 1H), 5.72-5.58 (m, 1H), 4.86 -4.71 (m, 1H), 3.93 (s, 3H), 3.44 (dp, U= 10.5, 7.1 Hz, 1H), 2.42 (d, J=1.7 Hz, 3H), 2.38 (s, 3H), 1.61 (dd, J= 14.3, 7.2 Hz, 3H), 1.29 (dd, J=7.1, 2.7 Hz , 3H), 1.10 - 0.95 (m, 3H). 165 IR (thin film) 3370, 2975, 1734, 1649, 1527, 1480, 1262, 1148, 849, 799, 728 cm'1 HRMS-ESI (m / z) [M+H]+ calculated for C22H28FN2O5, 419, 1977; found, 419.1975 1H NMR (400 MHz, CDCI3) δ 12.15 (s. 1H), 8.69-8.42 (m, 1H), 8.00 (d, 7 = 5.2 Hz, 1H ), 6.88 (d, 7 = 5.2 Hz, 1H), 6.70 (ddd, 7=14.6, 8.1, 2.5 Hz, 2H), 5.59 (ddq, J= 12.4,10.7, 6.2 Hz, 1H), 4.76 (p, 7=7.2 Hz, 1H), 3.94 (d, 7 =1.9 Hz, 3H), 3, 38 (dp, 7=10.5, 7.0 Hz, 1H), 2.41 (d, 7=1.9 Hz, 3H), 2.36 (s, 3H), 1.61 (dd, 7 =13.6, 7.2 Hz, 3H), 1.27 (dd, 7= 7.1, 3.1 Hz, 3H), 1.04 (dt, 7= 11.6, 6.2 Hz, 3H). 19F RMN (376 MHz, CDCI3) δ 118.25, -118.31 166 IR (thin film) 3369, 2971, 1733, 1648, 1527, 1438, 1280, 1263, 1149, 1056, 801,770, 730 cm'1 HRMS -ESI (m / z) [M+H]+ calculated for C^HsgNaOs, 401.2071; found, 401.2066 1H NMR (400 MHz, CDCI3) δ 12.16 (d, 7= 3.9 Hz, 1H), 8.56 (t, 7=7.7Hz, 1H), 8.00 (d .7=5.2 Hz, 1H), 7.07-6.90 (m, 3H), 6.88 (d, 7 = 5.2 Hz, 1H), 5.735.53 (m, 1H), 4 .76 (pd, 7= 7.2, 1.1 Hz, 1H), 3.95 (s, 3H), 3.43 (dp, 7= 10.5,7.2 Hz, 1H), 2, 42 (d, 7= 1.9 Hz, 3H), 2.38 (s, 3H), 1.61 (dd, 7= 14.3,7.2 Hz, 3H), 1.29 (dd, 7 = 7.2, 2.3 Hz, 3H), 1.06 (t, 7 =6.0 Hz, 3H). 143 IF-2019-52232722-APN-ANP#INPI Page 285 of 408 or IF-2019-52232722-APN-ANP#INPI Page JHérteH'W o 167 IR (thin film) 3370, 2976, 1734.1649, 1527, 1480, 1263.1149, 849, 800, 730 cm-1 HRMS-ESI (m / z) [M+H]* calculated for C22H28FN2O5, 419, 1977; found, 419.1971 1H NMR (400 MHz, CDCI3) δ 12.15 (d, 7 = 3.3 Hz, 1H), 8.55 (t, 7 = 7.9 Hz, 1H), 8.00 ( d,7=5.2 Hz, 1H),6.88 (d,7=5.2 Hz, 1H), 6.70 (ddd, < / =15,1,9,4,2.6 Hz, 2H), 5.59 (ddq, 7 = 12.4,10.5, 6.2 Hz, 1H), 4.76 (p,7=7.3 Hz, 1H), 3.95 (s, 3H ), 3.38 (dp,7 = 10.5, 7.0 Hz, 1H), 2.41 (d, J = 1.9 Hz, 3H), 2.36 (s, 3H), 1.61 (dd,7 = 13.6, 7.2 Hz, 3H), 1.27 (dd, 7 = 7.2,2.9 Hz, 3H), 1.05 (t, 7=5.9 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 118.26,-118.27,-118.33. 168 IR (thin film) 3370, 2971, 1734, 1649, 1527, 1451, 1263.1150, 801.770, 730 cm’1 HRMS-ESI (m / z) [M+H]+ calculated for 022Η29Ν2θ5, 401.2071; found, 401.2070 'H NMR (400 MHz, CDCI3) δ 12.16 (d, 7= 3.8 Hz, 1H), 8.56 (t, 7 = 7.6 Hz, 1H), 8.01 (d,7=5.2 Hz, 1H), 7.05-6.91 (m, 3H), 6.88 (d,7=5.2 Hz, 1H), 5.705.57 (m, 1H) , 4.76 (pd,7 = 7.1, 1.1 Hz, 1H), 3.95 (s, 3H), 3.43 (dp, 7=10.5, 7t2 Hz, 1H), 2, 42 (d, 7=2.0 Hz, 3H), 2.38 (s, 3H), 1.61 (dd, 7 =14.3, 7.2 Hz, 3H), 1.29 (dd, 7 = 7.2, 2.1 Hz, 3H), 1.06 (t, 7 = 6.0 Hz, 3H). 169 IR (thin film) 3371.2976, 1734, 1649, 1527.1480, 1280.1262, 1157, 849, 800, 731 cm'1 HRMS-ESI (m / z) [M+Hf calculated for C22H28FN2O5, 419, 1977; found, 419.1971 1H NMR (400 MHz, CDCI3) δ 12.15 (d, 7= 3.3 Hz, 1H), 8.55 (t, 7 = 7.8 Hz, 1H), 8.00 ( d,7=5.2 Hz, 1H), 6.88 (d, 7= 5.2 Hz, 1H), 6.70 (ddd, 7= 17.0, 9.4, 2.8 Hz, 2H ), 5.59 (ddq, 7 =12.2,10.8, 6.2 Hz, 1H), 4.76 (p, 7 = 7.3 Hz, 1H), 3.95 (s, 3H) , 3.38 (dp,7 = 10.4, 7.0 Hz, 1H), 2.41 (d,7=2.2 Hz, 3H), 2.36 (s, 3H), 1.61 ( dd, 7 =13.6, 7.2 Hz, 3H), 1.27 (dd, 7 = 7.2, 2.8 Hz, 3H), 1.05 (t, 7=5.9 Hz, 3H ). 19F NMR (376 MHz, CDCI3) δ 118.29,-118.36. 144 IF-2019-52232722-APN-ANP#INPI Page 287 of 408 IF-2019-52232722-APN-ANP#INPI Page 170 HRMS-ESI (m / z) [M+H]+ calculated for C21H27N2O6, 403.1864; found, 403.1827 'H NMR (400 MHz, CDCI3) δ 12.16 (s, 1H), 8.41 (d, J=7.9 Hz, 1H), 7.97 (d, J=5, 2 Hz, 1H), 7.23-7.10 (m, 2H), 6.92-6.78 (m, 3H), 5.31 (dq, J = 7.8, 6.3 Hz, 1H ), 4.63-4.49 (m, 1H), 3.93 (s, 3H), 3.81 (s, 3H), 3.493.39 (m, 1H), 1.26 (d,J= 6.3 Hz, 3H), 1.23 (d,J = 7.2 Hz, 3H), 1.16 (d, J = 7.2 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 171.5, 168.6, 157.2,155.3, 148.7,140.4, 131.1,130.6, 128.1,127.4,120.5,110.5, 109.4, 75 ,1,56,0, 55,4,48,0, 37,6, 17,9, 17,8, 16,6. 171 IR (thin film) 2978, 2937, 1733, 1647, 1527.1451, 1262.1147, 701 cm'1 HRMS-ESI (m / z) [M+H]* calculated for C2oH25N205, 373.1758; found, 373.1752 1H NMR (500 MHz, CDCfe) δ 12.16 (s,1H), 8.50 (d, J = 8.0 Hz, 1H), 8.01 (d, J= 5.2 Hz, 1H), 7.32 - 7.27 (m, 2H). 7.24 - 7.16 (m, 3H), 6.88 (d, J = 5.2 Hz, 1H), 5.11 (dq, J = 7.7, 6.3 Hz, 1H), 4 .77 - 4.67 (m,1H), 3.95 (s, 3H), 2.97 - 2.87 (m, 1H), 1.54 (d, J= 7.2 Hz, 3H), 1.31 (d, J = 7.0 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.8,168.7,155.3,148.7, 142.9,140.5,130.4,128.5, 127.8,126.8,109.4.76.5, 56.1, 48.1.44 ,9,18,4,18,2,17,2. 145 IF-2019-52232722-APN-ANP#INPI Page 289 of 408 or IF-2019-52232722-APN-ANP#INPI Page 290 di 400 or 172 IR (thin film) 3368, 2978, 1937, 1734, 1648, 1527, 1480, 1438, 1262, 797, 730 cm'1 HRMS-ESI (m / z) [M+Hf calculated for C19H25N2O5S, 393.1479; found, 393.1473 1H NMR (500 MHz, CDCI3) δ 12.16 (s, 1H), 8.50 (d,7=7.9 Hz, 1H), 8.00 (d,7=5.2 Hz, 1H), 6.88 (d, 7=5.2 Hz, 1H), 6.61 (d, J=3.5 Hz, 1H), 6.55 (dq, J = 3.5.1 ,1 Hz, 1H), 5.10-5.01 (m, 1H), 4.77-4.67 (m, 1H), 3.95 (s, 3H), 3.22-3.12 ( m, 1H), 2.42 (d, 1 / =1.1 Hz, 3H), 1.55 (d, 1 / =7.1 Hz, 3H), 1.33 (d,i / =7, 0 Hz, 3H), 1.20 (d, 7= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 171.6,168.7,155.3,148.7, 143.3,140.5,138.0.130.5, 124.5,124.1,109.4, 76.1.56.1, 48.1.40 ,1,18,4,17,8,17,2, 15,3. 173 IR (thin film) 3369, 2977, 2939, 1733, 1649.1528, 1450.1278, 1262.1149, 952 cm'1 HRMS-ESI (m / z) [M+H]+ calculated for C2iH26FN2O6, 421, 1769; found, 421.1770 1H NMR (500 MHz. CDCl3) δ 12.19 (s, 1H), 8.49 (d,i / =7.9 Hz, 1H), 8.01 (d, 7=5, 2 Hz,1H), 7.13-7.06 (m, 1H), 6.88 (d, 7 = 5.3 Hz. 1H), 6.62-6.54 (m, 2H), 5, 21 -5.12 (m, 1H), 4.73-4.63 (m, 1H), 3.95 (s, 3H), 3.79 (s, 3H), 3.42-3.32 ( m, 1H), 1.51 (d, 7 = 7.2 Hz, 3H), 1.24 (d, 7=7.0 Hz, 3H), 1.14 (d, 7=6.3 Hz, 3H). 19F NMR (471 MHz, CDCI3) δ 113.8--113.9 (m). 146 IF-2019-52232722-APN-ANP#INPI Page 291 of 408 or IF-2019-52232722-APN-ANP#INPI Page 292 iL 400 174 ESIMS m / z 387.3 [(M+H)+J 1HRMN (400 MHz, CDCI3) δ 12.16 (d, J = 4.9 Hz, 1H), 8.50 (d, J = 7.8 Hz , 1H), 8.01 (dd, J = 5.2,2.7 Hz, 1H), 7.21-7.01 (m, 4H), 6.88 (dd, J = 5.3.1 .9 Hz, 1H), 5.18 (dq, J = 8.3, 6.3 Hz, 1H), 4.73 (p, J = 7.3 Hz, 1H), 3.95 (d, J = 1 .6 Hz, 3H), 3.19 (dq, J = 9.0, 6.9 Hz, 1H), 2.35 (s, 3H), 1.55 (d, J = 7.0 Hz, 3H ), 1.26 (dd, J = 6.9, 3.8 Hz, 3H), 1.13 (dd, J = 9.0, 6.2 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 171.85,168.74,155,41,148.80, 141.65,140.49,135.53, 130.54, 126.37,126,31,126.29,109.46, 56.07, 8 .00, 39.74, 19.94,18,28,18,27,17,52,0.01. 175 1H NMR (400 MHz, CDCI3) δ 12.16 (d, J = 0.6 Hz, 1H), 8.51 (d, J =7.9 Hz, 1H), 8.00 (d,J = 5.2 Hz, 1H), 7.22-7.02 (m, 5H), 6.88 (d, J =5.2 Hz, 1H), 5.16 (dq. J =8.3, 6 .2 Hz, 1H), 4,784.65 (m, 1H), 3.95 (s, 3H), 3.20 (dq, J = 8.3, 6.9 Hz, 1H), 2.35 (s, 3H ), 1.56 (d, J = 7.2 Hz, 3H), 1.26 (d, J =6.9 Hz, 3H), 1.15 (d. J = 6.3 Hz, 3H). 176 ESIMS m / z 416 ([M+Hf) 1H NMR (300 MHz, CDCI3) δ 12.18 (s, 1H), 8.52 (d, J = 7.9 Hz, 1H). 8.00 (d, J= 5.2 Hz, 1H), 7.13 - 7.01 (m, 2H), 6.88 (d, J = 5.2 Hz, 1H), 6.67 (d , J =8.5 Hz, 2H), 5.12-4.98 (m, 1H), 4.72 (p, J =7.3 Hz, 1H), 3.95 (s, 3H), 2.92 (s, 6H), 2.88-2.75 (m, 1H), 1.57 (s, 3H), 1.26 (dd, J = 7.1,4.0 Hz, 3H), 1, 11 (d, J = 6.2 Hz, 3H). 13C NMR (75 MHz, CDCI3) δ 148.75, 140.49, 130.54, 128.42, 112.68,109,42,40,70,18.33 (d, J =22.8 Hz), 0 .01. 147 IF-2019-52232722-APN-ANP#INPI Page 293 of 408 or IF-2019-52232722-APN-ANP#INPI Page 294 ilu 400 or 177 HRMS-ESI (m / z) [M+H]* calculated for C24H30N2O6, 443.2177; found, 443.2170 1H NMR (500 MHz, CDCI3) δ 8.57 (s, 1H), 8.34 (d, 5.4 Hz, 1H), 7.07 (d, J=8.6 Hz, 1H), 7.01 (d,J= 5.5 Hz, 1H), 6.97 (d, J = 6.7 Hz, 2H), 5.12 (dq, J = 8.5, 6.3 Hz, 1H), 4.78 - 4.67 (m, 1H), 3.91 (s, 3H), 3.19-3.09 (m, 1H), 2.41 (s, 3H), 2 .31 (s, 3H), 2.28 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.23 (d, 6.9 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 172.41,168.96,162,36,159.42, 146.70,141.53,138.75,137.46, 135.67,135.33,131.26,126.95, 6.48, 56 .29, 48.16, 39.45, 20.89, 20.78, 19.90,18.76,18.48,17.67. 178 HRMS-ESI (m / z) [M+H]* calculated for C24H30N2O6, 443.2177; found, 443.2172 1H NMR (500 MHz, CDCI3) δ 8.57 (s, 1H), 8.35 (d, J=5.5 Hz, 1H), 7.07 (d,J=7.7 Hz, 1H), 7.01 (d, J= 5.5 Hz, 1H), 6.98 (d, J = 7.4 Hz, 2H), 5.12 (dq, J = 8.5, 6 .2 Hzt1H), 4.72 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 3.183.09 (m, 1H), 2.41 (s, 3H), 2, 31 (s, 3H), 2.27 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H), 1.22 (d, J=6.9 Hz, 3H), 1, 10 (d, J = 6.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 172.41,168.97,162.40,159.43, 146.70, 141.52, 138.72,137.46, 135.64,135,37,131.24,126.98, .76 .37, 56.29, 48.04, 39.38, 20.88, 20.78, —19.92,18.59,18.24,17.73.-- 148 IF-2019-52232722-APN-ANP#INPI ► Page 295 of 408 or IF-2019-52232722-APN-ANP#INPI I I H11' du 400 179 HRMS-ESI (m / z) [M+H]+ calculated for C26H34N2O6, 471.2490; found, 471.2484 'H NMR (500 MHz, CDCI3) δ 8.51 (s, 1H), 8.33 (d, J= 5.4 Hz, 1H), 7.09 - 7.04 (m, 1H), 7.02 6.94 (m, 3H), 5.11 (dq, 7=8.5, 6.2 Hz, 1H), 4.73 (p, 7= 7.2 Hz, 1H) , 3.89 (s, 3H), 3.19-3.09 (m, 1H), 2.96 (p, 7 = 7.0 Hz, 1H), 2.31 (s, 3H), 2, 28 (s, 3H), 1.51 (d, 7= 7.2 Hz, 3H), 1.36 (dd, 7 = 7.0,1.4 Hz, 5H), 1.23 (d, 7 = 6.9 Hz, 3H), 1.11 (d, 7= 6.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.73,172.50,162,34,159.40, 146.59,141.90,138.78,137.63, 135.66,135.33,131.25,126.95, 6,41, 56 .29, 48.13, 39.45, 33.94,20.89, 19.90,18.80,18.48,17.66. 180 HRMS-ESI (m / z) [M+H]+ calculated for C26H34N2O6, 471.2490; found, 471.2490 1H NMR (500 MHz, CDCI3) δ 8.50 (s, 1H), 8.34 (d, 7= 5.4 Hz, 1H), 7.07 (d, 7= 7.8 Hz, 1H), 7.03-6.93 (m, 3H), 5.12 (dq, 7 = 8.5, 6.2 Hz, 1H). 4.72 (p, 7 = 7.1 Hz, 1H), 3.89 (s, 3H), 3.203.09 (m, 1H), 2.96 (p, 7 = 7.0 Hz, 1H), 2.31 (s, 3H), 2.27 (s, 3H). 1.49 (d, 7 =7.1 Hz, 3H), 1.37 (dd. 7 = 6.9.2.0 Hz. 6H), 1.22 (d, 7 = 6.9 Hz, 3H), 1, 09 (d, 7= 6.2 Hz, 3H). 3C NMR (126 MHz, CDCI3) 76, 29, 56.29, 48.03, 39.40, 33.94, 20.88, “ 19.91,18.81,18.59,18.25, 17.74. 149 IF-2019-52232722-APN-ANP#INPI Page 297 of 408 IF-2019-52232722-APN-ANP#INPI ráuiiu 298 du 403 181 HRMS-ESI (m¿) [M+H]+ calculated for C23H27FN2O6, 447.1926; found, 447.1923 1H NMR (500 MHz, CDCI3) δ 8.37 (s, 1H), 8.33 (d, J= 5.4 Hz, 1H), 7.17 (dd,J= 8.4 , 5.9 Hz, 1H), 7.01 (d, J= 5.4 Hz, 1H), 6.84 - 6.75 (m, 2H), 5.10 (p, J = 6.4 Hz , 1H), 4.57 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 3.22 (p, J= 7.0 Hz, 1H), 2.40 (s , 2H), 2.33 (s, 3H), 1.34 (d, J= 7.1 Hz,2H), 1.27-1.18 (m, 6H). 3C NMR (126 MHz, CDCI3) 12,79,112,62, 109,75,75,32,56,29,47,87, 38,50,20,76,19,89,18,40, 17,06,16,72. 182 HRMS-ESI (m / z) [M+H]+ calculated for C22H25FN2O6, 433.1769; found, 433.1767 1H NMR (500 MHz, CDCI3) δ 8.53 (s, 1H), 8.35 (d, J= 5.5 Hz, 1H), 7.22-7.13 (m, 2H ), 7,056.93 (m, 3H), 5.05 (h, J= 6.5 Hz, 1H), 4.71 (ddt, J=14.7,10.3, 5.3 Hz, 1H) , 3.91 (s, 3H), 2.91 (p, J= 6.8 Hz, 1H), 2.41 (s, 3H), 1.48 (d, J= 7.2 Hz, 3H) , 1.27 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.34,167.06,160.68,160.54, 158.74,157.59,144.78,139.51, 136.64,136.61,135.58,127.40, 13,21,107,93, 73 ,96,54,42,46,14,42,14, 18,85,16,52,15,76,15,38. 150 IF-2019-52232722-APN-ANP#INPI Page 299 of 408 IF-2019-52232722-APN-ANP#INPI Page 183 HRMS-ESI (m / z) [M+H]* calculated for C24H30N2O7, 459.2126; found, 459.2096 1H NMR (500 MHz, CDCI3) δ 8.56 (s, 1H), 8.35 (d, J =5.4 Hz, 1H), 7.09 (d, J =8.4 Hz, 1H), 7.02 (d, J =5.5 Hz, 1H), 6.756.66 (m,2H), 5.15-5.05 (m, 1H), 4.72 (pd, 7 = 7,3,1.5 Hz, 1H), 3.92 (s, 3H), 3.76 (s, 3H). 3.16-3.07 (m, 1H), 2.41 (s, 3H), 2.32 (s, 3H), 1.50 (d, 7 = 7.2 Hz, 3H), 1.22 (d, 7 = 6.8 Hz, 3H), 1.10 (d, 7 = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.45, 167.03, 160.47, 157.55, 155.65, 144.76, 139.57, 135.54, 135.02,132.00,125.43, 113 .97, 109.50,107.85,74.52, 54.38, 53.17,46.15, 37.09,18.83, 18.29,16,63,16,24,15.80. 184 HRMS-ESI (m / z) [M+H]* calculated for C25H31FN2O6, 475.2239; found, 475.2238 1H NMR (500 MHz, CDCI3) δ 8.52 (s, 1H), 8.36 (d, J= 5.5 Hz, 1H), 7.11 (ddd, J = 7.5 , 5.9,1.5 Hz, 1H), 7.02 (d, J =5.5 Hz, 1H), 6.83 (t, J = 8.1 Hz, 2H), 5.06 {dq , J = 8.1, 6.3 Hz, 1H), 4.66 (dd, J = 9.4,4.7 Hz, 1H), 3.92 (s, 3H), 3.20-3, 08 (m, 1H), 2.40 (s, 3H), 2.32 (d, J = 2.3 Hz, 3H). 2.29 (td, J= 6.9,4.8 Hz, 1H), 1.23 (d, J = 6.9 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H), 1.01 (d, J = 6.8 Hz, 3H), 0.93 (d, J = 6.9 Hz, 3H). ”C NMR (126 MHz, CDCI3) δ 171.24,168.92,162.74,161.89, 159.95, 159.47,146.68,141.59, 137.81,137.76,137.49,127.86, 127.79,117.00.11 6.83, 113.00, 112.83,109.75, 76.14, 57.17, 56.31,39.04, 31.46,20.79, 20.00,19.38,18.45,17.47, 17.44. 151 IF-2019-52232722-APN-ANP#INPI Page 301 of 408 or IF-2019-52232722-APN-ANP#INPI Page 302 illu 400 185 HRMS-ESI (m / z) [M+H]* calculated for CzsHaiF^Oe, 475.2239; found, 475.2236 1H NMR (500 MHz, CDCI3) δ 8.41 (s, 1H), 8.33 (d, J =5.4 Hz, 1H), 7.16 (dd, J =9.0 , 5.9 Hz, 1H), 7.01 (d,J=5.4 Hz, 1H), 6.81 (t, J =8.0 Hz, 2H), 5.155.07 (m, 1H), 4.53 (dd, J =9.5, 4.5 Hz, 1H), 3.90 (s, 3H), 3.243.16 (m, 1H), 2.38 (s, 3H), 2.34 (s, 3H), 1.88 (td, J= 6.9, 4.5 Hz, 1H), 1.26 (d,J=6.2 Hz, 3H), 1.21 (d, J = 6.9 Hz, 3H), 0.81 (d, J =6.8 Hz, 3H), 0.63 (d, J =6.8 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.14,167.00, 160.78,160.02, 158.08, 157.53, 144.77, 139.62, 136.49,135.51,135.45,125.64, 125.57.114 ,82,114,66,110,95, 110,79,107,84, 73,69, 54,92, 54,40, 36,84, 29,39,18,86, 17,99,17,09,15,75,15 .30, 15.12. 186 HRMS-ESI (m / z) [M+H]* calculated for C25H32N2O6, 457.2333; found, 457.2330 1H NMR (500 MHz, CDCI3) δ 8.43 (s, 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.24 — 7.19 (m, 1H ), 7.09 (dddd, J =29.3,14,6.7.2, 2.9 Hz, 3H), 7.00 (d, J = 5.5 Hz, 1H), 5.14 ( dq, J = 8.2, 6.2 Hz, 1H), 4.53 (dd, J =9.4, 4.3 Hz, 1H), 3.90 (s, 3H), 3.26 (q , J = 7.4 Hz, 1H), 2.38 (s, 3H), 2.36 (s, 3H), 1.91-1.78 (m, 1H), 1.27 (d, J = 6.2 Hz, 3H), 1.25 - 1.20 (m, 3H), 0.78 (d, J =6.9 Hz, 3H), 0.58 (d, J = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.16, 166.97, 160.75, 157.48, 144.73,139.69,135.46,134.11, 128.31,124,26,124.06,107.75, 73.76, 54 .85, 54.36, 37.31, 29.36,18,84,17.91,17.07, 15.67,15.06,15.00. 152 IF-2019-52232722-APN-ANP#INPI Page 303 of 408 or IF-2019-52232722-APN-ANP#INPI Page 304 iL 404* 187 HRMS-ESI (m£) (M+HJ* calculated for C24H29FN2O6, 461.2082; found, 461.2082 1H NMR (500 MHz, CDCl3) δ 8.50 (d,J=9.8 Hz, 1H) , 8.35 (d, J =5.4 Hz, 1H), 7.14 (dd, J = 8.6, 5.5 Hz, 2H), 7.03 (d, J = 5.5 Hz, 1H), 6.94 (t, J =8.7 Hz, 2H), 5.07-4.99 (m, 1H),4.65 (dd, J = 9.4,4.7 Hz, 1H ), 3.92 (s, 3H), 2.93-2.86 (m, 1H), 2.40 (s, 3H), 2.26 (pd, J =6.8, 4.7 Hz, 1H), 1.28 (d, J = 7.0 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.9 Hz, 3H) , 0.92 (d, J = 6.9 Hz, 3H). 136.70,136.67, 135.57, 127.33, 127.27,113,31,113,14,107.86, 74.15, 55.24, 54.40, 42.02, 29.52,18,86.17, 37.16.09, 15.54, 15.21. 188 - HRMS-ESI (m / z) [M+H]+ calculated for C26H34N2O7, 487.2439; found, 487.2427 1H NMR (500 MHz, CDCI3) ) δ 8.53 (d, J = 9.3 Hz, 1H), 8.36 (d, J = 5.5 Hz, 1H), 7.07 (d, J =9.5 Hz, 1H), 7, 02 (d, J =5.5 Hz, 1H), 6.72 - 6.66 (m, 2H), 5.06 (dq, J = 8.5, 6.3 Hz, 1H), 4.67 (dd, J = 9.4,4.6 Hz, 1H), 3.91 (s, 3H), 3.76 (s, 3H), 3.15-3.06 (m, 1H), 2, 40 (s, 3H), 2.31 (m, 4H), 1.23 (d, J = 6.9 Hz, 3H), 1.10 (d, J =6.2 Hz, 3H), 1, 02 (d, J = 6.8 Hz, 3H), 0.94 (d, J = 6.9 Hz, 3H). 13C RMN (126 MHz, CDCI3) δ 169,38,167.00, 160.80, 157.51, 155,65,144,76,139,71, 135.53, 134,94,132,15,125,41,109,107,80, 74,70 , 55.25, 54.37, 53.18, 37.08,29.56,18.86, 18.27.17,47,16.60,15.86, 15.53. 153 IF-2019-52232722-APN-ANP#INPI Page 305 of 408 or IF-2019-52232722-APN-ANP#INPI Page 300 di 40» 189 HRMS-ESI (m / z) [M+H]* calculated for C25H31FN2O6, 475.2239; found, 475.2238 1H NMR (500 MHz, CDCI3) δ 8.61-8.47 (m, 1H), 8.36 (d, 4 = 5.4 Hz, 1H), 7.13 (dd, 4 = 9.6, 5.7 Hz, 1H), 7.02 (d, 4= 5.5 Hz, 1H), 6.88-6.79 (m, 2H), 5.09 (dq, 4 = 8.0, 6.3 Hz, 1H), 4.64 (dd, 4= 9.1, 5.0 Hz, 1H), 3.92 (s, 3H), 3.13 (p, 4= 7 .1 Hz, 1H), 2.41 (s, 3H), 2.33 (s, 3H), 2.29 (qd, 4 = 7.0, 5.2 Hz, 1H), 1.23 (d , 4 = 7.0 Hz, 3H), 1.12 (d, 4= 6.3 Hz, 3H), 0.99 (d, 4 = 6.8 Hz, 3H), 0.96 (d, 4 = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCI3)5 169.44,167.00, 160.79,159.96, 158.02,157.53,144.78,139.68, 135.91,135.53,135.50,125.99, 4,89,111,11 , 110.95,107.83, 73.93, 55.11, 54.38, 37.14, 29.57, 18.86, 18.10, 17.03, 16.32, 16.00, 15.50 . 190 HRMS-ESI (mZ?) [M+H]* calculated for C25H3iFN2O6, 475.2239; found, 475.2235 _ 'H NMR (500 MHz, CDCI3) δ 8.40 (s,1H), 8.34 (d, 4 =5.4 Hz, 1H), 7.18 (dd, 4 =9 .5, 5.8 Hz, 1H), 7.02 (d, 4 =5.5 Hz, 1H), 6.84 - 6.75 (m, 2H), 5.10 (p, 4 = 6, 4 Hz, 1H), 4.51 (dd,4=9.2, 5.1 Hz, 1H), 3.92 (s,3H), 3.22 (p, 4=7.1 Hz, 1H) , 2.40 (s, 3H), 2.33 (s, 3H), 2.15 (pd, 4= 6.9, 5.0 Hz, 1H), 1.23 (d, 4=7.1 Hz, 3H), 1.21 (d, 4=6.3 Hz, 3H), 0.88 (d, 4 = 6.9 Hz, 3H), 0.84 (d, 4 =6.9 Hz, 3H). ,3C NMR (126 MHz, CDCI3) δ 170.81,168.93, 162.52, 161.93, 159.99, 159.45, 146.63, 141.52, 138.48, 138.42, 137, 46,136.82, 136.79, 127.88, 127.82, 116.75, 116.59,112.77,112.61,109.71, 75.30, 57.02, 56.30, 38.43, 31.44, 20.78,19.90,18.78, 17.72, 17.08,16.67. 154 IF-2019-52232722-APN-ANP#INPI Page 307 of 408 IF-2019-52232722-APN-ANP#INPI Page 300 du 400 or 191 HRMS-ESI (m / z) [M+Hp calculated for C25H32N2O6, 457.2333; found, 457.2331 'H NMR (500 MHz, CDCI3) δ 8.42 (s, 1H), 8.35 (d, J= 5.4 Hz, 1H), 7.23 (dd, J = 7, 8.1.4 Hz, 1H), 7.15 - 7.03 (m, 3H), 7.02 (d,J= 5.4 Hz, 1H), 5.13 (p,J = 6.4 Hz, 1H), 4.53 (dd, J= 9.2, 4.9 Hz, 1H), 3.91 (s, 3H), 3.28 (p, J = 7.1 Hz, 1H), 2.40 (s, 3H), 2.36 (s, 3H), 2.14 (pd, J= 6.9, 4.9 Hz, 1H), 1.26 (d, J = 7.2 Hz , 3H), 1.22 (d.J= 6.3 Hz,3H), 0.86 (d, J= 6.9 Hz, 3H), 0.81 (d, J = 6.9Hz,3H). 3C NMR (126 MHz, CDCI3) 75, 37, 57.02, 56.29, 38.88, 31.51,20.79, 19.83,18.77,17.70,16.91, 16.26. 192 HRMS-ESI (m / z) [M+Hp calculated for C24H29FN2O6, 457.2333; found, 457.2331 1H NMR (500 MHz, CDCI3) δ 8.58 - 8.45 (m, 1H), 8.36 (d, J = 5.5 Hz. 1H). 7.16 (ddd, J= 10.8. 6.6, 3.7 Hz, 2H), 7.02 (d. J = 5.5 Hz, 1H), 7.01-6.94 (m, 2H). 5.10 - 4.99 (m, 1H), 4.63 (dd, J = 9.2, 5.0 Hz, 1H). 3.92 (s. 3H), 2.90 (p, J = 7.1 Hz, 1H), 2.40 (d, J= 2.1 Hz, 3H), 2.31-2.21 (m , 1H), 1.28 (d, J = 7.0 Hz, 3H). 1.09 (d, J = 6.4 Hz, 3H), 1.00 0.97 (m. 3H). 0.96 (d. J = 6.9 Hz. 3H). 3C NMR (126 MHz, CDCI3) 15,11,109,76, 75.84, 57.06,56,31.44.06, 31.47,20.79,18.93,17.96, 17.84,17.26. 155 IF-2019-52232722-APN-ANP#INPI Page 309 of 408 IF-2019-52232722-APN-ANP#INPI iL 48» or 193 HRMS-ESI (m / z) [M+H]* calculated for C26H34N2O / , 487.2439; found, 487.2434 1H NMR (500 MHz, CDCI3) δ 8.62 - 8.50 (m, 1H), 8.36 (d, J = 5.4 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 7.02 (d, J=5.5 Hz, 1H), 6.75 - 6.67 (m, 2H), 5.09 (dq, J = 8.4, 6.3 Hz, 1H), 4.65 (dd, J = 9.1,4.9 Hz, 1H), 3.91 (s, 3H), 3.75 (s, 3H), 3.17 — 3.06 (m, 1H), 2.40 (s,3H), 2.32 (m,4H), 1.22 (d, J=6.9 Hz, 3H), 1.11 (d, J =6.2 Hz, 3H), 0.99 (d, J = 6.8 Hz, 3H), 0.97 (d, J = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 169.50,167.02,160.80,157.52, 155.67, 144.82,139.74,135.53, 135.01, 132.08, 125.49, 114.01, 109.51.107 .84, 74.46, 55.12, 54.40, 53.18, 37.11,29.65. 18,89,18,31,17,06,16.41, 16,02,15,83. 194 HRMS-ESI (m¿) [M+H]* calculated for C23H28N2O6, 429.2020; found, 429.2021 1H NMR (500 MHz, CDCI3) δ 8.45-8.36 (m, 1H), 8.33 (d, J = 5.5 Hz, 1H), 7.25 —7.17 (m , 1H), 7.17-7.03 (m, 3H), 7.01 (d, J = 5.5 Hz, 1H), 5.18-5.09 (m, 1H), 4.61- 4.48 (m,1H), 3.91 (s, 3H), 3.28 (p, J = 7.3 Hz, 1H), 2.39 (d, J= 5.8 Hz, 3H), 2.36 (s, 3H), 1.32 (d, J=7.2 Hz, 3H), 1.26 (d, J= 7.0 Hz, 3H), 1.23 (d, J=6 ,3Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 169.93, 167.04, 160.36, 157.55, 144.72, 139.53, 139.14, 135.53, 134.21,128.32,124.37,124.31 , Ί07.85, 73.52, 54.40,46.07, 37.09, 18.84, 17t93, 16.51, 15.05, 14.45. 156 IF-2019-52232722-APN-ANP#INPI Page 311 of 408 or fl IF-2019-52232722-APN-ANP#INPI Púgiiki 312 du 400 195 HRMS-ESI (m / z) [M+H]+ calculated for C23H27FN2O6, 447.1926; found, 447.1922 1H NMR (500 MHz, CDCI3) δ 8.54 (d, J = 7.4 Hz, 1H), 8.34 (d, J =5.4 Hz, 1H), 7.13 ( dd, J = 9.5, 5.8 Hz, 1H), 7.02 (d, J =5.5 Hz, 1H), 6.88-6.81 (m,2H), 5.09 (dq , J =8.2, 6.3 Hz, 1H), 4.72 (p, J =7.3 Hz, 1H), 3.91 (s, 3H), 3.20-3.09 (m, 1H),2.41 (s, 3H), 2.33 (s, 3H), 1.50 (d, J = 7.1 Hz, 3H), 1.23 (d, J =6.8 Hz. 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 170.39, 167.02, 160.44, 159.98, 158.04,157.54,144.76, 139.53, 135.94,135.88,135.55,135.49, 125.94,125 ,88,115,11,114,94, 111,06,110,90,107,87,74,14, 54,38,46,21,37,21,18,84, 18,08,16,77,16,43,15,46 . 196 HRMS-ESI (m / z) [M+H]+ calculated for C24H2gFN2O6, 461.2082; found, 461.2082 1H NMR (500 MHz, CDCI3) δ 8.44 (s, 1H), 8.34 (d, J= 5.4 Hz, 1H), 7.12 (ddd, J = 9.3 , 4.5, 2.0 Hz. 1H), 7.00 (d, J =5.5 Hz, 1H), 6.86 (dd. J =9.0, 6.7 Hz, 2H), 5 .12 (dq, J = 7.9, 6.3 Hz, 1H), 4.18 (dd, J= 5.7, 2.8 Hz, 2H), 3.90 (s, 3H), 3, 14 (p, J= 7.1 Hz, 1H), 2.95 (p, J =7.0 Hz, 1H), 2.32 (s, 3H), 1.37 (d, J= 7.0 Hz, 6H), 1.22 (d, J =7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.71,169.37,163.02,161.95, 160.00,159.48, 146.62, 141.68, 137.91,137.73,137.35,137.32, .117.05 , 116.89, 113.04,112.87,109.72, 76.09, 56.31,41.38, 39.11,33.98, 20.01,18,81,18,22,17.42. 157 IF-2019-52232722-APN-ANP#INPI Page 313 of 408 or Yo Yo IF-2019-52232722-APN-ANP#INPI 197 HRMS-ESI (m / z) [M+HJ* calculated for C24H29FN2O6, 461.2082; found, 461.2082 1H NMR (500 MHz, CDCI3) δ 8.34 (d,J = 5.0 Hz, 1H), 8.32 (d, J = 5.4 Hz, 1H), 7.21 - 7.10 (m, 1H), 6.99 (d, J=5.4 Hz, 1H), 6.84-6.76 (m, 2H), 5.13 (p,J = 6.4 Hz , 1H), 4.17 - 3.92 (m, 2H), 3.90-3.88 (s, 3H), 3.22 (p,J = 7.1 Hz, 1H), 2.94 ( p, J =7.0 Hz, 1H), 2.33 (s, 3H), 1.36 (d, J = 7.0 Hz, 6H), 1.23 (dd, J = 6.7.1 ,3Hz, 6H). 13C NMR (126 MHz, CDCI3) δ 174.69, 169.03, 162.91, 161.95, 160.01,159.46,146.58,141.61, 138.48,137.71, 136.72, 136.69, 127 ,84,127,77,116,78,116,62, 112,83,112,67,109,70, 75,49, 56,30,41,22, 38,58,33,96, 19,87, 19,86, 18,80, 17 .11, 16.56. 198 HRMS-ESI (m / z) [M+H]* calculated for C24H30N2O6, 443.2177; found, 443.2174 1H NMR (500 MHz, CDCI3) δ 8.33 (m, 2H), 7.21 (dd, J =7.6, 1.5 Hz, 1H), 7.10 (ttd,J = 14.3, 7.8,7,3,1.8 Hz, 3H), 6.98 (d, J = 5.5 Hz, 1H), 5.17 (h. J = 6.5 Hz, 1H), 4.14-3.90 (m, 2H), 3.89 (s, 3H), 3.33-3.23 (m, 1H), 2.94 (p, J = 7.0 Hz , 1H), 2.35 (s, 3H), 1.36 (d, J =7.0 Hz, 6H), 1.28 - 1.19 (m, 6H). 13C NMR (126 MHz, CDCI3) δ 174.69, 169.05, 162.90, 159.44, 146.58,141.67,141.02,137.68, 136.17, 130.25, 126.30, 126.27 , 126.11,109.66, 75.58, 56.29, -41.22, 39.10, 33.97,19.80, — 18.80,18.75,17,05.16.24. 158 IF-2019-52232722-APN-ANP#INPI Page 315 of 408 or IF-2019-52232722-APN-ANP#INPI Page 3 lú iL 400 o 199 HRMS-ESI (m / z) [M+H]* calculated for C23H27FN2O6, 447.1926; found, 447.1926 1H NMR (500 MHz, CDCI3) δ 8.44 (t, J=5.5 Hz, 1H), 8.33 (d, J=5.4 Hz, 1H), 7.18- 7.11 (m, 2H), 7.02 - 6.92 (m, 3H), 5.14 5.02 (m, 1H), 4.22-4.13 (m, 2H), 3.90 (s, 3H), 3.02-2.84 (m, 2H), 1.37 (d, J = 7.0 Hz, 6H), 1.30-1.23 (m, 3H), 1, 09 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.71,169.27, 163.03,162.63, 160.69, 159.48, 146.62,141.66, 138.52,137.74,129.30,129.23, 4,109 .73, 76.02, 56.31,44,12,41,41,33.98, 18.81,17,81,17,26. 200 HRMS-ESI (m / z) (M+HJ* calculated for C25H32N2O7, 473.2282; found, 473.2275 1H NMR (500 MHz, CDCI3) δ 8.45 (t, J= 5.4 Hz, 1H ), 8.33 (d.J=5.4 Hz, 1H), 7.08 (d,J = 8.4 Hz, 1H), 7.00 (d, J= 5.5 Hz, 1H), 6.77-6.67 (m, 2H), 5.12 (dq, J = 8.1,6.2 Hz, 1H), 4.25-4.14 (m, 2H), 3.89 ( s, 3H), 3.77 (s, 3H), 3.16-3.05 (m, 1H), 2.96 (p, J = 7.0 Hz, 1H), 2.31 (s, 3H) ), 1.37 (d, J= 7.0 Hz, 6H), 1.22 (d, J=7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.71,169.43, 163.02, 159.46, 157.66,146.63,141.71,137.71, 136.96,133.86, 127.39,115.94, 0 .76.54, 56.30, 55.11,41.41,39.04, 33.98, 20.18, 18.81, 18.27, 17.62. *ft 159 IF-2019-52232722-APN-ANP#INPI Page 317 of 408 or IF-2019-52232722-APN-ANP#INPI ÜL 400 201 HRMS-ESI (mA) [M+H]* calculated for C25H3iFN2O61 475.2239; found, 475.2234 1H NMR (500 MHz, CDCI3) δ 8.36 (s, 1H), 8.31 (d, J= 5.4 Hz, 1H), 7.16 (ddd, J = 13.0 , 8.8,6.0 Hz, 1H), 6.97 (d, J = 5.4 Hz, 1H), 6.81 (t, J = 7.8 Hz, 2H), 5.11 (dq , J = 8.3,6.4 Hz, 1H), 4.56 (p, J = 7.3 Hz, 1H). 3.88 (s, 3H), 3.26 3.16 (m, 1H), 2.99-2.90 (m, 1H), 2.34 (s, 3H), 1.35 (d, J = 6.9 Hz, 6H), 1.27 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 7.1 Hz, 3H), 1.08 (d, . / = 7.1Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.68,172,20,162,29,161.91, 159.97,159.42, 146.55,141.88, 138.36,138,30,137.64,137.22, 127,50,116 .70, 116.54,112.85,112.68,109.58, 75.44, 56.28,47.83, 38.90, 33.93,19.91,18.80, 18.20, 17.70.17 ,22. 202 HRMS-ESI (m / z) M+H]* calculated for C25H32N2O6, 457.2333; found, 457.2331 1H NMR (500 MHz, CDCI3) δ 8.35 (dd, J = 8.2, 5.5 Hz, 1H), 8.31 (d, J= 5.4 Hz, 1H), 7.19 (dd, J =7.7,1.4 Hz, 1H), 7.09 (ttd, J= 14.5, 7.2,1.7 Hz, 3H), 6.97 (d, J =5.4 Hz, 1H), 5.15 (dq, J = 7.7,6.1 Hz, 1H), 4.60 4.45 (m, 1H), 3.88 (s, 3H) , 3.26 (dp, J= 14.7, 7.2 Hz, 1H), 2.93 (p, J = 7.1 Hz, 1H), 2.36 (s, 3H), 1.35 ( d. J= 7.0 Hz, 6H), 1.28 (d, J= 6.3 Hz, 3H), 1.24 (d. J= 7.2 Hz, 3H), 1.01 (d, J = 7.2Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.68,172.25,162.27, 159.39, 146.55,141.96, 141.54,137.60, 136.03,130,21,126.16,125.98, 109.53,77.28 ,75.56, 56.27, 47.84,39.44, 33.93,19.84, 18.81,18,14,17.71,17.01. 160 IF-2019-52232722-APN-ANP#INPI Page 319 of 408 IF-2019-52232722-APN-ANP#INPI 203 HRMS-ESl (mA) [M+H]* calculated for CjiHjgFNzOe, 461.2082; found, 461.2082 1H NMR (500 MHz, CDCb) δ 8.46 (s, 1H), 8.33 (d, J =5.4 Hz, 1H), 7.15 (dd,J= 8.6 , 5.5 Hz, 2H), 7.01 - 6.92 (m, 3H), 5.09 5.00 (m, 1H), 4.71 (p, J = 7.3 Hz, 1H), 3.89 (s, 3H), 3.00-2.86 (m,2H), 1.47 (d, J = 7.1 Hz, 3H), 1.36 (dd, J =7.0, 1.3 Hz, 6H), 1.27 (d, J =7.0 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). ”C NMR (126 MHz, CDCI3) δ 174.71,172,30,162,61,162.36, 160.67, 159.46, 146.57, 141.90, 138.63,137.71,129.29,129.23, 115.27, 115.10, 109.62, 75.96, 56.30,48,10,44.13, 33.96, 18.81, 18.72, 17.93, 17.20. 204 HRMS-ESl (mA) [M+H]* calculated for C26H34N2O7, 487.2439; found, 487.2431 1H NMR (500 MHz, CDCI3) δ 8.50 (d, J= 9.7 Hz, 1H), 8.33 (d, J =5.4 Hz, 1H), 7.09 ( d, J= 8.3 Hz, 1H), 6.99 (d, J= 5.5 Hz, 1H), 6.76 - 6.66 (m, 2H), 5.08 (dq, J = 8 .3, 6.2 Hz, 1H), 4.73 (p, J = 7.3 Hz, 1H), 3.89 (s, 3H), 3.77 (s, 3H), 3.18-3 .05 (m, 1H), 2.95 (p, J= 7.0 Hz, 1H), 2.32 (s, 3H), 1.50 (d,J= 7.2 Hz, 3H), 1 .36 (dd, J = 7.0,1.5 Hz, 6H), 1.22 (d, J =6.8 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H) . 13C NMR (126 MHz, CDCI3) δ 174.70, 172.48, 162.36, 159.43, 157.65, 146.58, 141.96, 137.67, 136.91,134.03, 127.40 , 115.92, 111.45, 109.59,76.46, 56.29, 55.12,48.15, 39.14, 33.95, 20.19, 18.81, 18.43, 17 .63. 161 IF-2019-52232722-APN-ANP#INPI Page 321 of 408 or IF-2019-52232722-APN-ANP#INPI or 'H NMR (500 MHz, CDCI3) δ 8.51 - 8.39 (m, 1H), 8.34 (d, J= 5.3 Hz, 1H), 7.13 (dd, J= 9.4 , 5.8 Hz, 1H), 6.99 (d, J= 5.4 Hz, 205 HRMS-ESI (m / z) [M+HJ* calculated for C25H31FN2O6, 475.2239; found, 475.2239 1H ), 6.87-6.81 (m, 2H), 5.09 (dq, J = 7.9, 6.2 Hz, 1H). 4.71 (p, J=7.3Hz, 1H), 3.89 (s, 3H), 3.13 (p, J= 7.1 Hz, 1H), 2.95 (p, J = 7, 0Hz, 1H), 2.33 (s, 3H), 1.48 (d,J = 7.1 Hz, 3H), 1.39 — 1.33 (m, 6H), 1.22 (d, J = 6.9 Hz, 3H), 1.10 (d,J= 6.3 Hz,3H). 13C NMR (126 MHz, CDCI3) δ 174.71,172.43,162,41,161.91, 159.97, 159.46,146.57,141.90, 137.88,137.82,137.47,127.91, 116.84,113.03 , 112.87,109,63,75.88, 56.30, 48.01, 39.13, 33.96,20.02, 18.81,18,50,18,12,17.48. 206 HRMS-ESI (m / z) [M+H]+ calculated for C25H32N2O6, 457.2333; found, 457.2332 1H NMR (500 MHz, CDCI3) δ 8.35 - 8.27 (m, 2H), 7.22 (dd, J = 7.7,1.4 Hz, 1H), 7.17 -7.03 ¿m, 3H), 6.98 (d, J= 5.4 Hz, 1H), 5.14 (p, J= 6.5 Hz, 1H), 4.56 (p, J= 7.2 Hz, 1H), 3.89 (s, 3H), 3.28 (p, J= 7.0 Hz, 1H), 2.94 (p, J = 7.0Hz,1H), 2, 35 (s, 3H), 1.39-1.34 (m, 6H), 1.31 (d, J= 7.2 Hz, 3H), 1.25 (d, J = 7.1 Hz, 3H ), 1.22 (d, J = 6.4 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.70,171.97,162,25,159.43, 146.50,141.92, 141.08,137.66, 136.14,130,23,126.33,126.21, 75.33 , 56.29, 47.95, 39.03, 33.95,19.82, 18.81,18.47,16.96,16.35. 162 IF-2019-52232722-APN-ANP#INPI Page 323 of 408 Yo II 'i ιί f ¡ I Ιι i k In Yo II 1' li li I I II li II IF-2019-52232722-APN-ANP#INPI I II ¡I 207 1H NMR (500 MHz, CDCI3) δ 8.45 (s, 1H), 8.33 (d, 7= 5.4 Hz, 1H), 7.20-7.12 (m, 2H), 7.026, 94 (m, 3H), 5.10-4.99 (m, 1H), 4.70 (p, 7 =7.3 Hz, 1H), 3.89 (s, 3H), 2.94 (ddt , 7 = 15.3, HRMS-ESI (m / z) 14.2, 7.1 Hz, 2H), 1.47 (d, 7 = [M+Hf calculated 7.1 Hz, 3H), 1, 38-1.34 (m, 6H), for 1.27 (d, 7 = 6.9 Hz, 3H), 1.07 (d, C24H29FN2O6, 7 = 6.3 Hz, 3H). 461,2082; found, 461.2082 13C NMR (126 MHz, CDCI3) δ 174.72, 172.36, 162.62, 162.44, 160.67, 159.46, 146.57, 141.88, 138.58.137, 70.129.33,129.26, 115.28, 115.11, 109.63, 75.77, 56.30,48.03, 44.07, 33.96, ___________ 18.81, 18.46, 17.65 , 17.30. 208 I 1H NMR (500 MHz, CDCI3) δ 8.49 (d, 7 =5.7 Hz, 1H),8.34(d, 7 = 5.5 Hz, 1H), 7.09 (d, 7 = 8.3 Hz, 1H), 6.99 (d, 7= 5.4 Hz, 1H), 6.75 - 6.67 (m, 2H), 5.09 (dq, 7 = 8.2, 6.2 Hz, 1H), 4.72 (p, 7 = 7.2 Hz, 1H), 3.89 (s, 3H), 3.76 (s, 3H), 3.15-3.05 ( m, 1H), HRMS-ESI (m / z) I2'9®.(pj ^7,'°,Hz'1H)· 2·32 <s· [M+Hf calculated . t'l9 Η2· 3H)> for 02βΗ34Ν20τ H<39-1.34 (m, 6H), 1.21 (d,7 = 487.2439; found, 6·9 Ηζ· 3H>·1·09 «U = W Hz, 487.2432 3H)· 13C NMR (126 MHz, CDCI3) δ 174.71,172.49,162.41,159.44, 157.62,146.58,141.96,137.67, 136.95, 134.00, 127.40 , 115.94, 111.45, 109.60, 76.36, 56.29, _ _ 55.10,48,06,39.08,33.96, 20.21, 18.82, 18.58 , 18.19, 17.74. 163 IF-2019-52232722-APN-ANP#INPI Page 325 of 408 or IF-2019-52232722-APN-ANP#INPI 1H NMR (500 MHz, CDCIj) δ 18.44 (d, J =9.0 Hz, 1H), 8.34 (d, 7 =5.4 Hz, 1H), 7.16-7.08 (m , 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.82 (t, J = 7.9 Hz, 2H), 5.06 (dq, 7 = 8.0, 6, 2 Hz, 1H), 4.66 (dd, J = 9.4, 4.8 Hz, 1H), 3.89 (s, 3H), 3.20 - 3.09 (m, 1H), 2, 95 (p, J = 7.0 Hz, 1H), 2.32 (s, 3H), 2.28 HRMS-ESI (m / z) (qd, J = 7.0,4.9 Hz, 1H), 1.39 — [ Calculated M+Hf 1.32 (m, 6H), 1.23 (d, J= 6.9 Hz for 3H), 1.11 (d, J= 6.2 Hz, 3H), C27H35FN2O6, 1.01 (d, J= 6.8 Hz, 3H), 0.92 (d, 503,2552; found, 7 = 6.8Hz3H) 503.254713C NMR (126 MHz, CDCI3) δ 174.67, 171.34, 162.74, 161.92, 159.98, 159.45, 146.56, 142.09, 137.82,137.67, 137 .55, 127.90, 127.83,117.00, 116.83, 113.00, 112.84,109,59.76,07.57.14, 56.29,39.10,33.94,31.48 , 19,99,19,38,18,82,18,47, 17.46. 'H NMR (500 MHz, CDCI3) δ 8.32 (m,2H), 7.16 (dd, J =9.5, 5.7 Hz, 1H), 6.98 (d, J = 5.5 Hz, 1H), 6.83-6.76 (m,2H), 5.10 (dq, J =8.0, 6.3 Hz, 1H), 4.54 (dd, 7= 9.4, 4.5 Hz, 1H), 3.88 (s, 3H), 3.19 (p, J =7.2 Hz. 1H), 2.93 (p. J = 7.0 Hz, 1H), 2 .34 (s, HRMS-ESI (m / z) ^H), 1.88 (pd, J= 6.9, 4.5 Hz, [M+Hf calculated .= 7.8^Z' θ^) · for 1.25 (d, 7= 6.3 Hz, 3H), 1.21 (d, C27H35FN2O77.1 Hz·3H)·0.81(d·6·9 503,2552; found,Hz'3H^’ °'63(d. J = 6.9 Hz. 3H). 503.2554nc NMR(126CDCIj)δ 174.66, 171.16, 162.69, 161.96, 160.03, 159.41. 146.55. 142.06. 138.40,138.34,137.62, 137.32, 127.61, 116.73, 116.57, 112.86, 112.70,109.54,75,49,56.79, 56,28,38,77.33,92,31,34, 19,89,19,01.18.82,17,63, 17,17. 17.05. 164 IF-2019-52232722-APN-ANP#INPI Page 327 of 408 or IF-2019-52232722-APN-ANP#INPI Page ’H NMR (500 MHz, CDCI3) δ 211 HRMS-ESI (m / z) [M+H]+ calculated for ¿25H36N2O6, 485.2646; found 485.2642 8.38 - 8.27 (m, 2H), 7.21 (dd, J = 7.8.1.3 Hz, 1H), 7.09 (dddd, J = 23.7.14 ,5,7,3,1.6 Hz, 3H), 6.97 (d, J = 5.5 Hz, 1H), 5.14 (dq, J = 6.8, 5.8, 5.3 Hz, 1H), 4.54 (dd, J= 9.5,4.4 Hz, 1H), 3.88 (s, 3H), 3.26 (dp, J= 14.6, 7.1 Hz , 1H), 2.93 (p, J= 6.9 Hz. 1H), 2.36 (d, J= 3.7 Hz, 3H), 1.85 (pd, J = 6.9,4.4 Hz. 1H ). I 1.34 (d, J = 7.0 Hz, 6H), 1.27 (d, J= 6.3 Hz, 3H), 1.23 (d, J = 7.1 Hz, 3H). 0.78 (d, J = 6.9 Hz, 3H), 0.58 (d, J = 6.9 Hz, 3H). NMR 56 .75, 56.29, 39.27,33.92,31,33,19.82, 19.02,18.81,17.57,17.02, 16.89. | 212 I I HRMS-ESI (znZ>) [M+H]* calculated for C26H33FN2O6, 489.2395; found, 489.2391 ’H NMR (500 MHz. CDCI3) δ I 8.42 (d, J = 9.0 Hz. 1H). 8.34 (d, J = 5.5 Hz. 1H). 7.14 (dd, J= 8.6, 5.5 Hz, 2H), 7.00 (d, J= 5.5 Hz, 1H), 6.97 - 6.89 (m, 2H), 5 .03 (p, J = 6.4 Hz. 1H). 4.65 (dd. J = 9.4,4.7 Hz. 1H). 3.89 (s. 3H), 3.00-2.85 (m,2H), 2.25 (Pd. J = 6.9,4.7 Hz, 1H), 1.38 1.31 (m, 6H), 1.28 (d, J= 7.0 Hz, 3H), 1.09 (d. J = 6.3 Hz, 3H), 0.99 (d, J = 6.9 Hz, 3H), 0, 91 (d, J= 6.9 Hz. 3H). ,3C NMR (126 MHz. CDCI3) δ 174.68,171.17, 162.73, 162.59, 160.64,159.46, 146.56,142.06, 138.69,137.69. 129.27,129.21, 115.23,115.07,109.60, 76.00, 57.13, 56.30,43.99, 33.94, 31.47,19.30, 18.81,18.02, 17.49, 17,14. 165 IF-2019-52232722-APN-ANP#INPI Page 329 of 408 IF-2019-52232722-APN-ANP#INPI or 'H NMR (500 MHz, CDCI3) δ 8.45 (d, J= 8.6 Hz, 1H), 8.34 (d, 7= 5.5 Hz, 1H), 7.07 (d, 7= 9.4 Hz, 1H), 6.99 (d, 7 = 5.5 Hz, 1H), 6.72 - 6.65 (m, 2H), 5.06 (dq, 7 = 8.3.6 .2 Hz, 1H), 4.67 (dd, 7= 9.3,4.7 Hz, 1H), 3.89 (s, 3H), 213 3.76 (s,3H), 3.16 - 3.05 (m, 1H), 2.95 (p, 7= 7.0 Hz, 1H), HRMS-ESI (m / z) L2 35 ~ 2 25 (m 3H) 1 40 - 1.30 [M+H]* calculated <m-6”>-1·23 <d· J = 6-s Ηζ· 3H). for C28HMN,O, H .10 (d, 7 = 6.3 Hz. 3H), 1.01 (d. 515.2752; frail, Ηζ· 3H>· °·93 θ·9 | 515.2737 Hz. 3H). 13C NMR (126 MHz, CDCI3) δ 174.67,171.40,162.75, 159.43, 157.63,146.57, 142.14,137.65, 136.86,134,14,127.37,115.93, .76 ,57,60,39, 57,17, 56,29, 55,12, 39,07, 33,94,31,51,20,18,19,40, 18,82,18,54,17,77, 17 .48, I 14.20. | 214 I HRMS-ESI (m / z) [M+HJ* calculated for C27H35FN2O6, 503.2552; found, 503.2549 I 1H NMR (500 MHz, CDCI3) δ I 8.44 (d, 7= 9.1 Hz, 1H), 8.35 (d, 7=5.4Hz, 1H), 7.13 (dd. 7 = 9.6. 5.8 Hz, 1H), 7.00 (d, 7 = 5.4 Hz, 1H), 6.88 - 6.78 (m. 2H), 5.09 (dq. 7 = 8.1, 6, 3 Hz, 1H), 4.63 (dd, 7= 9.1, 5.2 Hz, 1H), 3.89 (s. 3H), 3.13 (p. 7= 7.1 Hz. 1H). 2.95 (p, 7 = 7.0 Hz. 1H), 2.32 (s.3H), 2.26 (pd. 7=6.8, 4.9 Hz, 1H), 1.41 -1.31 (m , 6H), 1.23 (d, 7= 6.9 Hz, 3H), 1.11 (d, 7=6.3Hz, 3H), 0.99 (d, 7 =7.0 _ Hz, 3H ), 0.96 (d, 7= 6.9 Hz, 3H). ,3C NMR (126 MHz, CDCI3) δ 174.68,171.48,162.75, 161.91, 159.97, 159.44,146.59,142.11, 137.84,137.64,137.49,127.88, ,113, 04, 112.88, 109.58, 75.80, 57.04, 56.29, 39.14,33.95,31.48,20.01, 19.00,18.81,18.26, 17.94, 17.46. 166 IF-2019-52232722-APN-ANP#INPI Page 331 of 408 IF-2019-52232722-APN-ANP#INPI 215 'H NMR (500 MHz, CDCI3) δ 8.38 - 8.28 (m, 2H), 7.25 - 7.20 (m, 1H), 7.16-7.02 (m, 3H), 6.99 (d, J= 5.4 Hz, 1H), 5.13 (p, J =6.4 Hz, 1H), 4.53 (dd, J = 9.1.4.9 Hz, 1H), 3.89 (s, 3H), 3.28 (p, J = 7.1 Hz. 1H). 2.94 (h. J=7.0Hz.1H).2.35(s. 3H), HRMS-ESI (mfc) 2-21-2.09 (m, 1H), 1.35 (dd, J (M +Hf calculated ~ ·2 Hz, 6H), 1.26 (d, J = for CzyHjeN.Oe ?«1 ^z' 1.21 (d, j = 6.2 Hz, 485.2646; found. 3H). 0.86 (d. J=6.9 Hz. 3H). 485.2643 0.81 (d, J = 6.9 Hz, 3H). , 146,51,142,10,141,12,137,63, 136,16,130.26,126,41,126,19 126,09,109,52,75,28,57,01, 56,29,38,91,33,94,31,50, 19.81,18.81,17.71,16.90, I | 16.26 Ή NMR (500 MHz, CDCI3) δ 8.48 - 8.39 (m, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.19-7.11 (m, 2H), 7.03 - 6.90 (m, 3H), 5.05 (m, 1H). , J= 9.1, 5.1 Hz. 1H). 3.89 (s. 3H). m / z) 6.9,·4.2 Hz· 1H)· 1.38 - 1.32 (m, [M+Hf calculated . = 7.1 Hz. 3H), for 1.°8(d. J = 6, 2Hz,3H),0.98(d, CieHssFNjOe, P ~ 6.9 Hz, 3H), 0.95 (d, J = 6.9 489.2395; found, Ηζ· 3H)· 489.2391 13C NMR (126 MHz, CDCI3) δ 174.68,171.37,162.76, 162.61, _ 160.67,159.44.146.59,142.08, 138.67,137.64,129.32, 129.26, 115.27,115.10, ,59, 75.75, 57.06.56,30,44,10,33.95, 31.45,18.97,18.81,17.97, | | | 17,84,17,27. 167 IF-2019-52232722-APN-ANP#INPI Page 333 of 408 or IF-2019-52232722-APN-ANP#INPI J¿ínim 331 rlra 1Γί& either 'H NMR (500 MHz, CDCI3) δ 8.46 (d, J = 9.0 Hz, 1H), 8.35 (d, 4 = 5.4 Hz, 1H), 7.09 (d, 4 = 8.4 Hz, 1H), 6.99 (d, J = 5.5 Hz, 1H), 6.75 - 6.66 (m, 2H), 5.09 (dq, 4=8.3, 6 .2 Hz, 1H), 4.65 (dd, 4 = 9.1, 5.0 Hz, 1H), 3.89 (s, 3H), 3.75 (s, 3H), 3.16 -3 .04 (m, I 1H), 2.95 (p, 4 = 7.0 Hz, 1H), HRMS-ESI (m / z) 2.31 (s, 3H), 2.27 (qd, 4= 6.9, [M+H] calculated 5.0 Hz, 1H), 1.39 - 1.32 (m, 6H), for CzeHjeNzO / , 1.22 (d, 4 = 6.9 Hz, 3H) , 1.10 (d, 515.2752; found, 4 = 6.3 Hz, 3H), 0.99 (d, 4 = 6.8 515.2741 Hz, 3H), 0.96 (d, 4 = 6.9Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.68, 171.52, 162.73, 159.42, 157.61, 146.60, 142.18, 137.62, 136.92, 134.06, 127 .42, 115.96, 111.44,109.55.76,31.57.04, 56.29.55,10,39.09,33.94, 31.54.20.20,19.00.18 .82, J__I 18.33, 17.94, 17.77.1H NMR (500 MHz, CDCI3) δ 8.37 - 8.28 (m, 2H), 7.22 - 7.12 (m, 1H) , 6.99 (d, 4 =5.5 Hz, 1H), 6.85 - 6.75 (m, 2H), 5.16 - 5.05 (m, 1H), 4.57 (h, 4 = 7.4 Hz, 1H), 3.89 (s, 3H), 3.22 (pd, 4= 7.3, 4.6 Hz, 1H), 3.00 - 2.89 (m, 1H) , HRMS-ESI (m / z) 2.33 (s, 3H), 1.39-1.30 (m [M+H] calculated 9H), 1.22 (dd, 4= 9.8 6 7 Hz For6H). C25H31FN2O6, 475.2239; found,13C NMR (126 MHz, CDCI3) δ 475.2236 174.70, 171.98, 162.25, 161.93, 159.99, 159.45, 146.51, 141.82, 138.46, 137.69, 136.79, 136.76, 127.85,127.79,116.74,116.58, 112.79,112.62,109.59, 75.24, 56.30, 47.88, 38.53, 33.95, 19.88,18.80,18.41,17.05, 16.71. 168 IF-2019-52232722-APN-ANP#INPI Page 335 of 408 IF-2019-52232722-APN-ANP#INPI Pigini 33(j do o 2191H NMR (500 MHz, CDCI3) δ 8.48 (d, J = 6.9 Hz, 1H), 8.33 (d, J = 5.3 Hz, 1H), 7.13 (dd,7 = 9 .4, 5.8 Hz, 1H), 6.99 (d, J = 5.5 Hz, 1H), 6.88-6.81 (m,2H), 5.09 (dp, 7=8, 1,6.5 Hz, 1H), 4.72 (p, 7 = 7.2 Hz, 1H), 3.89 (s, 3H), 3.14 (p, 7=7.1 Hz, 1H) , HRMS-ESI <m / z}2;θ5 (p, 7 = 7.0 Hz, 1H), 2.33 (d, [M+H]+calculated2'^, !^z'3H)·1, 49U, 7.1 for Hz, 3H), 1.38 - 1.33 (m, 6H), CzsHjiFNjOe, p'23 (d, 7= 6.9 Hz, 3H), 1.11 (d, 1475, 2239; found, > / = 6.3 Hz, 3H). 475.223813C NMR (126 MHz, CDCI3) δ 174.71,172.42, 162.36, 161.94, 159.99,159.45,146.58,141.91, 137.86, 137.80, 137.69, 137.46 , 127.91, 127.84, 117.04, 116.87, 113.00,112.83,109.62, 75.99, 56.30.48.11, 39.18, 33.96 20.00.19, 99,18,85,18,81, 18.36, 17.37. Ή NMR (500 MHz, CDCI3) δ 8.56 (s, 1H), 8.35 (d, 7 = 5.4 Hz, 1H), 7.09 (d, 7=8.4 Hz, 1H), 7.02 (d, 7= 5.5 Hz, 1H), 6.776.67 (m, 2H), 5.10 (dq, 7 = 8.3 6.3 Hz, 1H), 4.72 (tt, 7= 8.8, 6.2 Hz, 1H), 3.91 (s, 3H), 3.76 (s ».Ru,®'ESI ( / n / $ 3H). 3'15 - 3·06 (m ·1H). 22 (d, 7 = 6 9 Hz 459.2126; found, 3H), 1.10 (d, 7= 6.3 Hz 3H) 459.2103 ' 13C NMR (126 MHz, CDCI3) δ 170.46, 167 .04, 160.48, 157.55, _ 155.66, 144.77, 139.57, 135.54, 135.03, 132.01, 125.44, 113.97, 109.50,107.87, 74,52,54,39, 53,17,46,15,37,09,18,84, 18,30,16,63,16,25,15,80. 169 IF-2019-52232722-APN-ANP#INPI Page 337 of 408 IF-2019-52232722-APN-ANP#INPI or 221 HRMS-ESI (m / z) [M+H]* calculated for C24H29FN2O6, 461.2082; found, 461.2080 'H NMR (500 MHz, CDCI3) δ 8.44 (t, J= 5.4 Hz, 1H), 8.34 (d, < / =5.4 Hz, 1H), 7, 12 (ddd, J= 10.1, 6.2, 3.4 Hz. 1H), 7.00 (d, J = 5.5 Hz, 1H), 6.90 - 6.80 (m, 3H) , 5.12 (dq, J= 7.7, 6.2 Hz, 1H), 4.18 (dd, J= 5.4,2.8 Hz, 2H), 3.90 (s, 3H), 3.14 (p,J = 7.1 Hz, 1H), 2.95 (p, J= 7.0 Hz, 1H), 2.32 (s, 3H), 1.37 (d, J= 7 .0 Hz, 6H), 1.22 (d, J = 6.9 Hz, 3H), 1.12 (d. J= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.71,169.37,163.02,161.95, 160.00, 159.48, 146.63, 141.67, 137.91,137.85, 137.73,137.32, 127.89.127 ,82,117,05,116,89, 113,04,112,87,109,72, 76,09, 56,31,41,38,39,11,33,98, 20,00,18,81,18,71,18,22 , 17.42. 222 I Λ HRMS-ESI (m / z) [M+H]* calculated based on C24H3oN206, 143.2177; found, 443.2176 1H NMR (500 MHz, CDCI3) δ 8.36 - 8.27 (m, 2H), 7.21 (dd, J = 7.7,1.4 Hz, 1H), 7.16 -7.05 (m, 3H), 6.98 (d, J = 5.5 Hz, 1H), 5.17 (h, J= 6.6 Hz, 1H), 4,133.89 (m, 2H), 3 .89 (s, 3H), 3.28 (p, J= 7.1 Hz, 1H), 2.94 (p, J = 7.0 Hz, 1H), 2.35 (s, 3H), 1 .36 (d, J = 7.0 Hz, 6H), 1.28 -1.22 (m, 6H). 13C NMR (126 MHz, CDCI3) δ 174.69,169.05,162.90,159.44, 146.58,141.67,141.02,137.68, 136.17,130.25,126.29,126.27, 5.58, 56 .29, 41.22, 39.09, 33.97,19.80, 18.81,17.05,16.23. 170 IF-2019-52232722-APN-ANP#INPI Page 339 of 408 IF-2019-52232722-APN-ANP#INPI iPigini 310 do 108· o 223 ’H NMR (500 MHz, CDCI3) δ 8.44 (t, J= 5.5 Hz. 1H). 8.33 (d, J = 5.4 Hz, 1H), 7.18-7.11 (m, 2H), 7.03 - 6.92 (m, 3H), 5.14 5.01 (m, 1H), 4.17 (d, J-5.4 Hz, HRMS-ESI (m / z) I. 2^' 3.90 (s, 3H), 3.00 — 2.86 I [M+H]*calculated I'377.0 Hz, 6H). for 1127 <d·J = 7·° Ηζ· 3H), 1.09 (d, C23Hz7FN2O6, J = 6.3Hz, 3H). 447.1926; found, i3_ 447 1923 C NMR (126 MHz, CDCI3) δ 174.72,169.28, 163.04,162.64, 160.69,159.48, 146.62,141.66, 138.52,137.74, 129.30,129.24, 115, 31,115,14,109,73.76,02, 56,31,44,12.41,41,33,98, | 18,81.17.81.17.26. | 224 ’H NMR (500 MHz. CDCI3) δ 8.45 (t. J= 5.4 Hz. 1H). 8.33 (d, I J = 5.4 Hz, 1H), 7.08 (d, J = 8.5 Hz. 1H), 7.00 (d, J= 5.5 Hz. 1H). 6.76 - 6.67 (m, 2H). 5.12 (dq. J = 8.3, 6.3 Hz. 1H), 4.24-4.14 (m, 2H), 3.89 (s, 3H), 3.77 (s, HRMS- ESI (m / z) 3Hf 3·16 - 3.05 (m, 1H), 2.96 [M+H]* calculated 1^127,^'? ^Z' ^).2'3^ ís· for C25H32N2O7, 1.'37 / d'2 ~ 7.0 Hz·6H)·1·22 (d· 473.2282; found, J= 6.9 Hz> 3H>· 1·12 (d, J = 6 .2 473.2282 Hz-3H)· 13C NMR (126 MHz, CDCI3) δ 174.71,169.43, 163.01,159.46, 157.66,146.63, 141.71,137.71, 136.96,133.86, 127 ,39,115,94, 111,46,109,70,76,54,56,30, 55,11,41,41,39,04,33.98, __ 20,18,18,81,18,27,17,62. 171 IF-2019-52232722-APN-ANP#INPI Page 341 of 408 Ptiginn 3 IF-2019-52232722-APN-ANP#INPI 225 HRMS-ESl (m / z) [M+H]* calculated for C25H32N2O6, 457.2333; found, 457.2327 1H NMR (500 MHz, CDCI3) δ 8.39 - 8.28 (m, 2H), 7.24 - 7.17 (m, 1H), 7.16-7.02 (m, 3H), 6.98 (d, J= 5.5 Hz, 1H), 5.14 (p, J =6.6 Hz, 1H), 4.55 (dt, J = 10.4, 7.4 Hz, 1H), 3.89 (s, 3H), 3.28 (p, J =7.1 Hz, 1H), 2.94 (p, J =6.9 Hz, 1H), 2.36 ( d, J = 4.9 Hz, 3H), 1.36 (dd, J= 7.0,1.6 Hz, 6H), 1.31 (d, J= 7.1 Hz, 3H), 1, 25 (d, J= 7.2 Hz, 3H), 1.22 (d, J =6.4 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.70,171.96,162.25, 159.42, 146.50, 141.92, 141.08, 137.65, 136.14, 130.23, 126.33, 126 .21, 126.09, 109.55, 75.32, 56.29, 47.95, 39.03, 33.95, 19.82, 18.80, 18.47, 16.95, 16.35 . 226 HRMS-ESl (m / z) [M+H]* calculated | for 1H NMR (500 MHz, CDCI3) δ 8.44 (s, 1H), 8.33 (d, J- 5.4 Hz, 1H), 7.20 - 7.12 (m, 2H), 7, 02 6.93 (m, 3H), 5.07-4.97 (m, 1H), 4.70 (p, J =7.2 Hz, 1H), 3.90 (s, 3H), 3, 01-2.86 (m, 2H), 1.47 (d, J =7.1 Hz, 3H), 1.39 - 1.34 (m, 6H), 1.27 (d, J = 7, 0 Hz, 3H), 1.07 (d, J= 6.3 Hz, C24H29FN2O6, 3H). 461,2082; found, 461.2078 13C NMR (126 MHz, CDCI3) δ 174.72, 172.36, 162.62, 162.44, 160.67, 159.46, 146.57, 141.88, 138.56.137, 70,129.33, 129.26, 115.28, 115.11, 109.63,75.77, 56.30, 48.03,44.07, 33.96, 18.81, 18.46, 17, 65, 17.30. 172 IF-2019-52232722-APN-ANP#INPI Page 343 of 408 or 227 1H NMR (500 MHz, CDCI3) δ 8.49 (d, J = 8.6 Hz, 1H), 8.34 (d, I J = 5.4 Hz, 1H), 7.09 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 5.4 Hz, 1H), 6.75 - 6.64 (m, 2H), 5.09 (dq, J = 8.3, 6 .2 Hz, 1H), 4.72 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.76 (s, 3H), 3.16-3.05 (m ,1H), HRMS-ESI (m£) 2'®θ (pJ ^Z'°,Hz' 1H)' 2'32 <s[M+H]+ calculated . 2! ' 1'49 ^d· ~ 7Ί Hz, 3H), for C26H34N2O7, 1'ο®υ-1.34 (m' 6H)'1.21 = I 487.2439; found, 6.8 Ηζ· 3H). 1·09 (d· J= 6·3 Hz, 487.2425 3H)- 13C NMR (126 MHz, CDCI3) δ 174.71, 172.49, 162.41, 159.44, 157.62, 146, 58, 141.97, 137.67, 136.95,134,01,127,40,115.94, 111,45,109,59,76,36,56,29, 55,11,48,06,39,08,33,96, 20.21, 18.82, 18.58, 18.19, I 17.74. I 228 I 'H NMR (500 MHz, CDCI3) δ 8.40 - 8.33 (m, 1H), 8.31 (d, J= 5.4 Hz, 1H), 7.22 - 7.15 ( m, 1H), 7.15-7.03 (m, 3H), 6.97 (d, J = 5.4 Hz, 1H), 5.15 (dq, J =8.0, 6.2 Hz , 1H), 4.61-4.47 (m, 1H), 3.88 (s, 3H), 3.25 (p, J= 7.3 Hz, HRMS-ESI (m / z) „ 1H) , 2·93 <P· J = 7·° Hz, 1H), [M+H]+ calculated 2.'38Jd' ~ 3.8 Hz> 3H), 1.35 (d, for C25HWN2O6 d = 7, 9 Hz, 6H), 1.28 (d, J= 6.3 457.2333; found, Hz' 3H_\1.'24 <d- J = 7·° Hz. 3H), 457.2329 1.01 (d , J= 7.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 174.68,172.25, 162.26, 159.39.1 146.54,141.96, 141.54, 137.60, 136.03,130.21,126,16.125.98, 109, 53,75,56,56,27,47,84, 39,43,33,93,19,84,18,80 _____________17.71, 17.01. 173 IF-2019-52232722-APN-ANP#INPI Page 345 of 408 either 'H NMR (500 MHz, CDCI3) δ 8.46 (d, J = 8.6 Hz, 1H), 8.33 (d, J=5.4Hz, 1H), 7.18-7.10 (m , 2H),7.01-6.89(m, 3H), 5,095.00 (m, 1H), 4.71 (p, J = 7.3 Hz, 1H), 3.89 (d, J= 1.2 Hz, 3H), HRMS-ESI (m / z)3.81“2.86<m·2H)·1·47(dd. J [M+H]+calculated ~7'1.34( m, 6H), 1.27 (dd,J= 7.1,1.6 C24H29FN2O6,Ηζ· 3H).|4β14™2“ C NMR (126). MHt COCW 6 ' 174,71,172,29,162,61, 162,36, 160,66,159,46,146,57,141,89, 138,63,137,70, 129,33, 129,29, 129,26,115,27,115,10,109,63, 75,95,56,30,48,10,44,13, 33,96,18,81,18,71,17,93, 17,20. 1H NMR (500 MHz, CDCI3) δ 8.50 (d. J = 8.7 Hz, 1H), 8.33 (d, « / = 5.4 Hz, 1H), 7.09 (d, J= 8.3 Hz, 1H), 6.99 (d, J= 5.5 Hz, 1H), 6.77 - 6.66 (m, 2H), 5.08 (dq, J = 8.3, 6 .2 Hz, 1H), 4.73 (p,J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.77 (s, 3H), 3.17-3.05 (m ,1H), HRMS-ESI (m¿) 2.95 (p, J = 7.0 Hz, 1H), 2.32 (s, [M+H] calculated 3H), 1.50 (d, J= 7.2 Hz, 3H), for C26H34N2O7, 1.38 - 1.33 (m, 6H), 1.22 (d, J = 487.2439; found, 6.9 Hz, 3H), 1.11 ( d, J= 6 3 Hz X487.2423 3H). 13C NMR (126 MHz, CDCI3) δ 174.71, 172.49, 162.36, 159.43, 157.65, 146.58, 141.97, 137.67, 136.91, 134.03, 127 ,40, 115.92, 111.45,109,59,76,46,56,29, 55,12,48,15,39,14,33,95, 20,19,18,79,18,43,17 .63. 174 IF-2019-52232722-APN-ANP#INPI Page 347 of 408 II or r]·' IF-2019-52232722-APN-ANP#INPI 231 HRMS-ESI ( / 7½) [M+H]* calculated 1H NMR (500 MHz, CDCI3) δ 8.26 (d, J = 5.4 Hz, 1H), 8.22 (t, J = 7, 4 Hz, 1H), 7.22 - 7.03 (m, 4H), 6.93 (d, J =5.4 Hz, 1H), 5.73 (dd, / = 5.6,1.8 Hz, 2H), 5.16 (dq, / = 8.1, 6.3 Hz, 1H), 4.58-4.51 (m, 1H), 3.90 (s, 3H), 3.31 -3.22 (m, 1H), 2.37 (s, 3H), 2.06 (s, 3H), 1.31 (d, J = for C24H30N2O7, 459.2126; found, 459.2121 6, 2 Hz, 3H), 1.24 (d, / = 7.0 Hz, 3H). 1.03 (d, J =7.2 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 172.26,170.26,162,87,160.25, 145.68,143.94,142.57,141.57, 136.03,130.21,126.16,125.94, 109.49, 5.57 , 56.16, 48.08, 39.48, 20.87,19.84, 17.92,17.77,17.05. 232 111 HRMS-ESI (m / z) [M+Hf calculated for C23H27FN2O7, 463.1875; found, 463.1870 1H NMR (500 MHz, CDCI3) δ 8.33 (d, J = 7.4 Hz, 1H), 8.29 (d, J= 5.3 Hz, 1H), 7.20- 7.12 (m, 2H), 7.01 - 6.93 (m, 3H), 5.79 5.71 (m, 2H), 5.10-5.00 (m, 1H), 4.73 (p, J = 7.2 Hz, 1H), 3.92 (d, J = 2.0 Hz, 3H), 2.92 (p, / =7.1 Hz, 1H), 2.07 (d , / = 1.6 Hz, 3H), 1.50 (d. / = 7.1 Hz, 3H), 1.29 (dd, / = 7.0, 2.5 Hz, 3H), 1.08 (d, / = 6.3 Hz, 3H), 13C NMR (126 MHz, CDCI3) δ 172.37,170.29, 163.02,162.63, 160.68,160.30, 145.74,144.03, 142.51.138, 55, 138,52,129,32, 129,26,115,30,115,13, ​​109,59, 89,58,75,82,56,20,48,22. 44.12, 20.88, 18.39, 17.69, 17.39. 175 IF-2019-52232722-APN-ANP#INPI Page 349 of 408 or IF-2019-52232722-APN-ANP#INPI Page 3 233 HRMS-ESI (m / z) [M+H]* calculated for C25H32N2O8, 489.2231; found, 489.2220 1H NMR (500 MHz, CDCI3) δ 8.38 (d, J = 7.7 Hz, 1H), 8.29 (d, J = 5.3 Hz, 1H), 7.09 ( d, J=8.3 Hz, 1H), 6.96 (d, J=5.3 Hz, 1H), 6.79 - 6.62 (m, 2H), 5.76 (d, J = 2 .2 Hz, 2H), 5.17 - 5.05 (m, 1H), 4.75 (p, J = 7.2 Hz, 1H), 3.92 (s, 3H), 3.76 (s ,3H), 3.22-3.03 (m, 1H), 2.32 (s, 3H), 2.07 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H) , 1.23 (d, J = 6.9 Hz, 3H), 1.10 (d, J=6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 172.52,170.29,162.99,160.29, 157.63,145.74,144.02,142.57, 136.96,133.96,127.39,115.93, 111.48, 89.61 ,76,42, 56,19,55,11,48,23, 39,10, 20,88,20,21,18,51,18,21, 17,82. 234 IR (thin film) 3383, 2981, 1737.1679, 1505.1310, 1114, 1045, 732 cm'1 HRMS-ESI (m / z) [M+HJ* calculated for C25H30F3N2O6, 511.2050; found, 511.2048 1H NMR (400 MHz, CDCI3) δ 8.50 (d, J=7.4 Hz,1H), 8.34 (d, J=5.4 Hz, 1H), 7.64 ( dd,J = 8.0,1.3 Hz, 1H), 7.54-7.47 (m, 1H), 7.44 (d, J=7.8 Hz, 1H), 7.31 (t , J=7.5 Hz, 1H), 6.99 (d, J=5.4 Hz, 1H), 5.26-5.11 (m, 1H), 4.76 (p, J=7, 3 Hz, 1H), 3.89 (s, 3H), 3.34 (p, J = 6.6 Hz, 1H), 2.96 (hept, J = 7.0 Hz, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.36 (dd, J = 7.0,1.3 Hz, 6H), 1.28 (d, J = 6.8 Hz, 3H), 1 .10 (d, J = 6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.25. 176 IF-2019-52232722-APN-ANP#INPI Page 351 of 408 or IF-2019-52232722-APN-ANP#INPI Page 352 of 408 235 1H NMR (400 MHz, CDCIj) δ 8.47 (d, J = 8.1 Hz, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.42 (dd, J = 8.8, 5.4 Hz, 1H), 7.34 (dd, J = IR (film 9.2. 2.8 Hz, 1H), 7.21 (td, J = thin) HRMS-ESI (m / z ) I8.3'2.8 Hz·1H)· 7-00 (d, J = 5.5 3383, 2982, [M+H]* calculated |Ηζ·1H^' 5·13 <p·J~ 6 ·5Hz·1H). 1761.1738, for 4·75 <dq·J= 9.3,7.3 Hz, 1H), 1679.1500, CzsHz^NjOe 3.89 (s, 3H), 3.36 - 3.24 (m, 1312.1119 , 529,1956: found 1H^'2.95 <hept· J~ 7·° Hz·1H). 909,732 529 1954 ' 1-53 (d, J = 7.2 Hz, 3H), 1.36 cm'1 (dd.J = 7.0,1.5 Hz, 6H), 1.26 (d, J = 6.8 Hz, 3H). 1.11 (d, J = 6.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ J 58.80,-114.13. 236 1H NMR (400 MHz, CDCI3) δ 8.53 (d, J = 7.7 Hz, 1H), 8.32 (d, IR (film J = 5.4 Hz, 1H), 6.98 (d . J = 5.4 thin) Hz, 1H), 5.08 (qd, J = 6.5, 3.0 3383.2943 HRMS-ESI (m / z) Hz, 1H), 4.69 (dt, J =7.9, 7.0 Hz, 1763.1733,' tM+HJ «Aculated 1H), 3.89 (s, 3H), 3.02-2.87 1678.1504 for caH35N2O6, (m, 1H ), 1.74 (dddd, J = 19.4, 1310.1210,' 435·249°ί ha,lad°. 17.2. 9.8. 5.1 Hz, 3H), 1.671090.843, 435.2483 1.51 (m, 4H), 1.48 (d, J= 7.1 Hz, 731 cm'1 3H). 1.38 (d, J =7.0 Hz, 6H), 1.22 (d, J=6.4Hz,3H), 1.18- 1.02 (m, 3H), 0.94 (d, J= 6 .9Hz, |3H). 237 Λ 1H NMR (400 MHz, CDCI3) δ 18.52 (s, 1H), 8.34 (d, J = 5.4 Hz, R (1H film), 7.04 - 6.91 (m, 4H ), 5.60 thin) HRMS-ESI (m / z) pdp· 10.5· 6·3 Hz. 1H). 4.84 1382.2976, [M+H]* calculated 4·67 (m·1H)· 3·89 (s· 3H). 3.42 762.1734, for C^NíO» ,[dp-J = 10·6· 7.1 Hz, 1H), 2.95 678.1504.471.2490; found (hept·J = 7·° Ηζ·1H)· 2·41 (d. J 210.1079, 471 2488 ’ =2·5 Ηζ· 3H). 2.37 (s, 3H), 1.55 730 cm'1 Kdd·J = 14.2.7.1 Hz, 3H), 1.40 - 1.32 (m, 6H), 1.28 (d, J = 7 ,1 Hz, 3H), 1.03 (dd, J =6,2,3.0 Hz, I 3H)· 177 IF-2019-52232722-APN-ANP#INPI Page 353 of 408 J. IF-2019-52232722-APN-ANP#INPI Faginti 3 238 IR (thin film) 3384, 2977, 1762.1735, 1679.1505, 1211.1127, 861.731 cm'1 HRMS-ESI (m / z) [M+H]* calculated for CseH^FNaOe, 489.2395; found, 489.2399 1H NMR (400 MHz, CDCI3) δ 8.52 (d, J = 10.1 Hz. 1H), 8.34 (d, J= 5.4 Hz, 1H), 6.99 ( d,J = 5.4 Hz, 1H), 6.70 (ddd, J= 15.3, 9.4,2.7 Hz, 2H), 5.56 (dp, J = 10.4, 6, 3 Hz, 1H), 4.82-4.65 (m, 1H), 3.89 (s, 3H). 3.43 3.20 (m, 1H), 2.95 (hept, J = 7.0 Hz. 1H), 2.40 (d. J = 2.4 Hz, 3H), 2.35 (s, 3H) , 1.54 (dd,J= 13.5, 7.2 Hz, 3H), 1.36 (dd, J = 7.1, 1.6 Hz, 6H), 1.26 (dd, J = 7 ,2, 1.0 Hz. 3H). 1.02 (dd. J = 6.2, 2.9 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 118.50 (d, J= 25.8 Hz). 239 R (thin film) 3383, 2982, 1762, 1739, 1681, 1505, 1311, 1151, 1117, 772 cm1 HRMS-ESI (m / z) [M+H]+ calculated for C25H30F3N2O6, 511.2050; found, 511.2052 ’H NMR (400 MHz, CDCI3) δ 8.47 (d, J = 7.8 Hz, 1H). 8.33 (d, J = 5.4 Hz, 1H), 7.67 - 7.60 (m, 1H), 7.54 - 7.45 (m, 1H). 7.44 (d, J = 7.8 Hz, 1H), 7.34 - 7.27 (m, 1H), 6.99 (d, J= 5.5 Hz, 1H). 5.25-5.14 (m, 1H), 4.81 -4.69 (m, 1H), 3.89 (s, 3H), 3.403.25 (m, 1H), 2.96 (hept, J = 7, 0 Hz, 1H), 1.51 (d, J = 7.1 Hz. 3H). 1.37 (dd. J = 7.0. 1.8 Hz. 6H), 1.29 (d. J = 6.8 Hz, 3H), 1.09 (d. J = 6.3Hz, 3H). ”F NMR (376 MHz, CDCI3) δ 58.26. 178 IF-2019-52232722-APN-ANP#INPI Page 355 of 408 or IF-2019-52232722-APN-ANP#INPI or 240 IR (thin film) 3383.2982 1761.1740 1680.1500 1312.1120 909.732 cm*1 HRMS-ESI (m / z) [M+H]* calculated for C25H29F4N2O6, 529.1956; found 529.1958 1H NMR (400 MHz, CDCI3) δ 8.44 (d, J = 7.8 Hz, 1H), 8.33 (d, 7=5.4Hz, 1H),7.42(dd, J = 8.8, 5.4 Hz, 1H), 7.33 (dd, 7 = 9.2, 2.8 Hz, 1H),7.19(td, J = 8.3, 2.8 Hz , 1H), 7.00 (d,7 = 5.4 Hz, 1H), 5.14 (p, J= 6.5 Hz, 1H), 4.81-4.67 (m, 1H), 3 .90 (s, 3H), 3.36-3.22 (m, 1H), 2.96 (hept, 7 = 7.0Hz, 1H), 1.50 (d, 7 = 7.2 Hz, 3H ), 1.37 (dd, J= 7.0, 1.9 Hz, 6H), 1.28 (d,7 = 6.9 Hz, 3H), 1.11 (d, 7 = 6.3 Hz , 3H). 19F NMR (376 MHz, CDCI3) δ 58.80,-114.24. | 241 R (thin film) 3382, 2944, 1764, 1734, 680.1504, 210.1090, 1040, 916, 843.732 cm'1 HRMS-ESI (m / z) M+H]+ calculated Jara C23H35N2O6, 435.2490 ; found, 435.2491 1H NMR (400 MHz, CDCI3) δ 8.52 (s, 1H), 8.32 (d, 7 = 5.4 Hz, 1H), 6.98 (d, 7 = 5.4 Hz, 1H), 5.07 (qd, 7 = 6.5,3.0 Hz, 1H), 4.73 - 4.62 (m, 1H), 3.89 (s, 3H), 2.95 (hept, J = 7.0 Hz, 1H), .85-1.61 (m,2H), 1.61-1.50 m,2H), 1.47 (d, 7 = 7.1 Hz, 3H), .43-1.29 (m, 9H), 1.21 (d, 7 = 6.4 Hz, 3H), 1.17-1.01 (m, 3H), 0.93 (d, 7 = 6.9 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ ' 74.69, 172.36, 162.38, 159.45, 146.55, 142.04, 137.69, 109.56, 74.50, 56.28, 48.04, 43.14, 42.93,33.98,31,24,30.70, 25.13,25.01,18.82,18.71, 17.48, 12.50. 179 IF-2019-52232722-APN-ANP#INPI Page 357 of 408 IF-2019-52232722-APN-ANP#INPI or 242 IR (thin film) 3383, 2977 1762.1735 1679.1504 1210, 1081 914, 861, 731 cm'1 *H NMR (400 MHz, CDCfe) δ 8.49 (d, J= 8.4 Hz, 1H ), 8.34 (d, J= 5.5 Hz, 1H), 6.99 (d, J= 5.5 Hz, 1H), 6.70 (ddd, J= 17.0, 9.4, 3 .. 2.8 Hz, 2H), 5.57 (dq, J = 10.4, , r»R^'ESI WQ 6·4 Ηζ· Μ). 4.85 - 4.62 (m, 1H), . [M+HJ calculated 3.89 (s,3H), 3.36 (dp,J= 10 4 >, for 7.1 Hz, 1H), 2.95 (hept, J= 7.0 . CzeHMFNjOe, Hz , 1H), 2.40 (s, 3H). 2.35 is, 489.2395; found, 3H), 1.52 (d, J = 7.2 Hz, 3H),' 489.2399 1.36 (dd, J = 7.0,1.9 Hz, 6H), 1.26 (dd ,J = 7.2,1.0 Hz, 3H), 1.02 (d,J= 6.2 Hz,3H). 19F NMR (376 MHz, CDCI3) δ - 1 118.53. | 243 IR (thin film) 3383, 2977, 1763, 1735, 1679,1504, 1211,1080, 914, 731 cm1 1H NMR (400 MHz, CDCfe) δ 8.54 (d, J= 12.1 Hz, 1H) , 8.34 (d, J= 5.4 Hz, 1H), 7.04-6.94 , . (m. 4H), 5.60 (dp, J = 10.4, 6.3 V^S-ES! (m4) Hz· 1H)' 4·75 (ddcl. J = 14.6, 7.2. [ M+HJ calculated 3.5 Hz, 1H), 3.89 (s, 3H). 3.42 for C26H35N2O6, (dp. J= 10.6.7.1 Hz, 1H), 2.96 471.2490; found, (hept, J= 7.0 Hz, 1H), 2.41 (d, J 471.2495 = 2.5 Hz, 3H), 2.38 (s, 3H), 1.55 (dd, J = 14.2, 7.1 Hz, 3H), 1.36 (dd, J = 7.1, 1.7 Hz, 6H), 1.28 (d, J = 7.1 Hz, 3H), 1 .03 (dd, J = 6.2, 2.9 Hz, 3H). 244 R (thin film) J383, 2977, 761, 1735, 678, 1504, 309, 1209, 4 081, 1059, 731 cm'1 'H NMR (400 MHz, CDCfe) δ 8.49 (d, J= 9 .5 Hz, 1H), 8.34 (d, J = 5.4 Hz, 1H), 6.99 (d, J = 5.5 Hz, 1H), 6.82 - 6.61 (m, 2H), 5.56 ( dp, J= 10.4, 6.3 Hz, 1H), HRMS-ESI ( / 7½) 4.75 <Pd· J = 7.2,4.4 Hz, 1H), [M+HJ* calculated 1(s· $ H), 3.36 (dp, J= 10.3, I for 7.0 Hz, 1H), 2.95 (p. J = 7.0 Hz, C2eH34FN2O6, J H)' 2.40 <d·J ~ 2·4 Hz- 3H), 89.2395; found, (s. 3H), 1.54 (dd, J= 13.6, 489.2399 7.2 Hz, 3H), 1.36 (dd, J= 7.0. 1.8 Hz, 6H). 1.26 (dd. J= 7.2, 1.1 Hz,3H), 1.02 (dd.J= 6.2, 2.9 Hz, 3H). 19F NMR (376 MHz, CDCfe) δ _____________| 118.49 (d,J= 25.8 Hz). 180 IF-2019-52232722-APN-ANP#INPI Page 359 of 408 IF-2019-52232722-APN-ANP#INPI Pigini 245 IR (thin film) 3379.2986 1771.1736 1676.1508 1310.1149, 1116.1046, 732 cm'1 HRMS-ESI (m / z) [M+H]+ calculated for C23H26F3N2O6f 473.1737; found, 483.1733 1H NMR (400 MHz, CDCI3) δ 8.56 (d, J = 7.5 Hz, 1H), 8.35 (d, 5.5 Hz, 1H), 7.64 (dd, J = 8.0,1.4 Hz, 1H), 7.55-7.46 (m, 1H), 7.43 (d, J= 7.8 Hz, 1H), 7.35 - 7.28 (m, 1H) ), 7.01 (d, J= 5.5 Hz, 1H), 5.25 - 5.13 (m, 1H), 4.81 -4.70 (m, 1H), 3.91 (s, 3H), 3.43 - 3.29 (m. 1H), 2.40 (s, 3H), 1.55 (d, J= 7.2 Hz, 3H), 1.28 (d, J= 6 .8 Hz, 3H), 1.10 (d, J= 6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ - 58.25. | 246 IR (thin film) 3379, 2986, 1771,1737, 1677, 1500, 1312, 1154, 1123, 1045, 909, 732 cm'1 HRMS-ESI (m / z) M+H]* calculated for C23H25F4N2O6, 501 ,1643; found, 501.1642 1H NMR (400 MHz, CDCI3) δ I 8.61 - 8.44 (m, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.42 (dd, J = 8.8, 5.3 Hz. 1H), 7.34 (dd, J = 9.2, 2.9 Hz, 1H), 7.21 (td, J= 8.2,2.8 Hz , 1H), 7.02 (d, J= 5.5 Hz, 1H), 5.19 - 5.07 (m, 1H), 4.82 - 4.69 (m. 1H). 3.91 (s,3H), 3,373.23 (m, 1H). 2.41 (s, 3H), 1.54 (d, J= 7.2 Hz, 3H), 1.27 (d, J = 6.8 Hz. 3H). 1.11 (d, J= 6.2 Hz. 3H). 19F NMR (376 MHz, CDCI3) δ 58.80.-114.08. 181 IF-2019-52232722-APN-ANP#INPI Page 361 of 408 or IF-2019-52232722-APN-ANP#INPI Pigini 247 IR (thin film) 3379, 2946, 1771,1732, 1676, 1506, 1310, 1193, 1174, 1060, 906, 731 cm'1 HRMS-ESl (m / z) [M+H]* calculated for ¿21H31N2O6 , 407,2177; found, 407.2173 1H NMR (400 MHz, CDCI3) δ 8.58 (s, 1H), 8.33 (d, J=5.5 Hz, 1H), 7.00 (d, J=5.5 Hz, 1H), 5.09 (qd, J=6.5, 3.0 Hz, 1H), 4.77-4.62 (m, 1H), 3.90 (s, 3H), 2.40 (s, 3H), 1.83-1.68 (m, 3H), 1.59 (dddt, J= 19.6, 14.7.7.5, 3.1 Hz, 4H), 1.49 (d, J = 7.2 Hz, 3H), 1.38 (dddd, J = 13.6, 9.7, 6.8, 3.0 Hz, 1H), 1.22 (d, J = 6 .5 Hz, 3H), 1.18-1.02 (m, 2H), 0.95 (d, J = 6.8 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 172.30,168.88, 162.36,159.48, 146.65,141.67,137.52,109.73, 74.49, 56.28,48,23,43.34, 43.11 ,31.23, 30.75,25.16, 24.98,20.75,18.87,17.79, 12.49. 248 IR (thin film) 3378, 2980, 1770.1733, 1676.1506, 1310.1195, 1175, 1006, 907, 730 cm'1 HRMS-ESl (m / z) [M+H]* calculated for C24H31N2O6, 443.2177; found, 443.2176 1H NMR (400 MHz, CDCI3) δ 8.59 (d, J = 7.7 Hz, 1H), 8.35 (d, J=5.4 Hz, 1H), 7.07- 6.91 (m, 4H), 5.67-5.55 (m, 1H), 4,854.70 (m, 1H), 3.91 (s, 3H), 3.42 (dp, J= 10, 6.7.1 Hz, 1H), 2.41 (s, 3H), 1.56 (dd, J= 14.4, 7.1 Hz, 3H), 1.28 (d, J= 7.1 Hz, 3H), 1.04 (dd, J= 6.2, 2.8 Hz, 3H). 249 HRMS-ESl (m / z) [M+H]* calculated for C24H30FN2O6, 461.2082; found, 461.2080 1H NMR (400 MHz, CDCh) δ 8.57 (d, J= 8.7 Hz, 1H), 8.35 (d, J=5.5 Hz, 1H), 7.01 ( d, J=5.5 Hz, 1H), 6.70 (ddd, J= 15.2, 9.3, 2.5 Hz, 2H), 5.65 - 5.47 (m, 1H), 4 .81-4.64 (m,1H), 3.91 (s, 3H), 3.36 (dp, J= 10.5, 7.0 Hz, 1H), 2.40 (s, 6H), 2.35 (s, 3H), 1.55 (dd, J= 13.8,7.2 Hz, 3H), 1.26 (d,J = 7.2 Hz, 3H), 1.03 (dd , J= 6.2, 2.7 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 118.43. 182 IF-2019-52232722-APN-ANP#INPI Page 363 of 408 or IF-2019-52232722-APN-ANP#INPI Page 364 of 408 or 250 IR (thin film) HRMS-ESI (m / z) I3377.2985, [M+H]* calculated 1771.1737, for |1677.1507, C23H26F3N2O6, 1310.1149, 483.1737; found, 1116.771, 483.1735 731 cm'' 'H NMR (400 MHz, CDCI3) δ 8.54 (d, J= 7.8 Hz, 1H), 8.34 (d, 7= 5.4 Hz, 1H), 8.01 (d, J= 5.2 Hz, OH), 7.63 (dt, J= 8.0,1.7 Hz, 1H), 7.55-7.47 (m , 1H), 7.44 (d, 7 = 7.8Hz, 1H), 7.31 (dt, J= 9.6, 4.2 Hz, 1H), 7.01 (d,7=5.5 Hz, 1H), 5.28 - 5.12 (m, 1H), 4.75 (dqd, 7= 8.4, 7.2,1.3 Hz, 1H), 3.91 (s, 3H) , 3.41-3.28 (m, 1H), 2.41 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.29 (d, J = 6.8 Hz, 3H), 1.13-1.05 (m, 3H). 19F NMR (376 MHz, CDCI3) δ - 58.25. 251 IR (thin film) HRMS-ESI (m / z) I2985.1771.1 [M+H]* calculated 1738.1677, for ll500, 1312.1 C23H25F4N2O6, 1193.1154, 501.1643; found 1122.909, 501.1640 732 cm'' 'H NMR (400 MHz, CDCI3) δ 8.50 (d, J= 7.9 Hz, 1H), 8.34 (d, 5.4 Hz, 1H ), 7.43 (dd, J = 8.8, 5.3 Hz, 1H), 7.34 (dd, J = 9.2, 2.8 Hz, 1H), 7.20 (td, J = 8.2, 2.9 Hz, 1H), 7.02 (d, J = 5.5 Hz, 1H), 5.15 (h, J = 6.5 Hz, 1H), 4.74 (dq, 7 = 8.1, 7.1 Hz, 1H), 3.92 (s, 3H), 3.30 (p, J= 6.9 Hz, >H). 2.41 (s, 3H), 1.52 (d, 7 = 7.2 dz, 3H), 1.28 (d, 7= 6.8 Hz, 3H), 1.11 (d, 7 = 6 ,3Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.80, -114.19. —'----- 183 IF-2019-52232722-APN-ANP#INPI Page 365 of 408 or YO IF-2019-52232722-APN-ANP#INPI Pigini 366 do 10# o 252 IR (thin film) 3382, 2947, 1771.1732, 1676.1505, 1310.1199, 1174.1151, 1061, 906, 731 cm'1 Ή NMR (400 MHz, CDCI3) δ 8.58 (s, 1H ), 8.33 (d, J= 5.4 Hz, 1H), 7.00 (d, / = 5.4 Hz, 1H), 5.08 (qd, / = 6.4, 3.0 Hz , 1H), 4.75-4.63 (m. 1H). 3.91 (s. 3H), 2.40 (s.3H), 1.85-1.63, (m,4H), 1.63-1.51 (m, 2H), HRMS-ESI (m / z) 1.48 (d, / = 7.2 Hz, 3H) 1 45 [M+H] calculated 1.32 (m, 2H), 1.21 (d, / = 6.4 Hz, for C2ih3iN2O6 , 3H), 1.17 - 1.00 (m, 2H). 0.94 ' 407.2177; found, (d, / = 6.9 Hz, 3H) 407.2176 13C NMR (101 MHz, CDCI3) δ 172.27, 168.90, 162.40, 159.48, 146.66, 141.66, 137.53, 109.72, 74,58.56,28,48,07,43,13, 42,93,31,25,30,69,25,14, 25,01,20,75,18,69, 17.48, __12.50. 253 IR (film 3378^2979.1 1770.1733 calculated 1676,' 1506 for c24H3iN2Oe. 1195 175 443.2177; found. 1006.907,' 443·2170 730 cm-1 1H NMR (400 MHz, CDCI3) 8.59 (d, J = 8.8 Hz, 1H), 8.35 (d, / = 5.4 Hz, 1H), 7.08 - 6.92 (m, 4H). m, 1H), 4.76 (p, / = 7.3 Hz, 1H), 3.91 (s, 3H), 3.42 (dp, / = 10.5, 7.1 Hz, 1H), 2.41 (d, / =1.7Hz, 6H), 2.38 (s. 3H), 1.54 (d, / = 7.1 Hz,3H), 1.28 (d, / = 7, 2 Hz, 3H), 1.03 (d, I________ / = 6.2 Hz, 3H). 254 IR (thin film) HRMS-ESI (mi) 3379, 2980, [M+H]+ calculated I 1771.1733 , for 11676, 1507.1 C24H30FN2O6, 1 1174.1130, 461.2082; found, 1007.731 461.2082 cm-1 1H NMR (400 MHz, CDCI3) δ 8.55 (dd, J= 16.7, 7.9 Hz. 1H), 8.35 (d. / = 5.4 Hz, 1H), 7.01 (d, / = 5.5 Hz, 1H), 6.70 (ddd, / = 17, 0, 9.3, 2.7 Hz, 2H), 5.57 (dq, / =10.3, 6.1 Hz, 1H), 4,824.69 (m, 1H), 3.91 (s, 3H 3,). 36 (dp, / =10.5, 6.9 Hz, 1H). 2.40 (d, / = 2.6 Hz, 6H), 2.35 (s. 3H), 1.53 (d, / =7 .2 Hz, 3H). 49. 184 IF-2019-52232722-APN-ANP#INPI Page 367 of 408 255 IR (thin film) 3380, 2975 1770.173Í €1676.150 1310.1195 1175.1006 907.730 cm-' at 1H NMR (400 MHz, CDCb) δ 8.64 - 8.52 (m, 1H), 8 .35 (d, J= ), HRMS-ESl (mA) 5.4 Hz'1 H)' 7.07 “ 6·90 (m-4H)· I. [M+H]* calculated L5·68 ~ 5'53 <m· 1H)> 4.86-4.68 >. for C24H31N2O6 rm'3.91 (s·3H)< 3·42 (dp, J i. 443.2177; foundJf 1?·8· 7·1 Hz·1H). 2.42-2.39. 443 2176 (m·6H>·2·38 <s·3H). 1.56 (dd, J = 14.5, 7.1 Hz, 3H), 1.28 (d, J = I 7.1 Hz, 3H), 1.04 (dd. J = 6.2, ___| 2 ,8Hz, 3H). 256 IR (thin film) 3377.2981, 1771.1734, 1676, 1507, 1310, 1195, 1175, 1007, 908, 731 cm' I 'H NMR (400 MHz, CDCb) δ I 8.68 - 8.47 (m, 1H), 8.35 (d, J = I 5.4 Hz, 1H), 7.01 (d, J = 5.5 Hz, 1H), 6.70 (ddd, J = 14.7 , 9,4,2,4 HRMS-ESl (mA) Ηζ· 2H)> 5.θθ ~ 5.48 (m, 1H), [M+Hf calculated 4J73 <?dd·J = 8·8· 7.2, 5, 7 Hz, for I 1R)» 5.91 (d, J~ 1.6 Hz, 3H), I C24H30FN2O6. 3·36,(dp;J = 1 °·5· 7.0 Hz, 1H), 461.2082; found,2'4?(d> 2·8 Ηζ· 6H>·2·35 (s. 461.2084 3H)·1·55 (dd· J= 13.9. 7.2 Hz, 3H), 1.26 (d ,J = 7.1 Hz, 3H), 1.03 (dd, 6.2.2.7 Hz, 3H). 19F NMR (376 MHz, CDCb) δ 1 118.43,-118.49 NMR (400 MHz, CDCb) δ 8.46 (d, J = 7.4 Hz, 1H), 8.31 (d, J= 5.5 Hz, 1H), 7.20-7.10 (m 2H), 6.98 (d, < / = 5.5 Hz, 1H), 6.88-6.79 (m, 2H), 5.27 (dq, J = 7.7, 6.3 Hz, 1H), 4.61-4.51 HRMS-ESl (mA) 1H>· 3·88 (s. 3H) (s, [M+H]* calculated 1.3^). , 2.38 for C^Hm^Oz Ís' 3H)· 1.24 (d, J = 4.7 Hz, 3H), 145.1969; found, 1.22 (d' J= 3·8 Hz- 3H). 1.11 (d, 445.1949 13 ^=7.2Ηζ, 3H). „ 13C NMR (101 MHz, CDCb) δ 172.1, 168.9,162.3,159.4, 157.2,146.6,141.7,137.5, 131.2,128,1,127,3,120.5, 110.5,109.7,74, 9.56,3,55.4, 48.0, 37.4, 20.7,18.3,17.8, _________________16.6. 185 IF-2019-52232722-APN-ANP#INPI Page 369 of 408 IF-2019-52232722-APN-ANP#INPI 258 IR (thin film) 3377, 2980 2938, 1770 1732, 1674 1507.1310 1198.1174, 702 cm'1 'H NMR (500 MHz, CDCI3) δ 8.56 (s, 1H), 8.34 (d , J= 5.5 Hz, 1H), 7.32-7.27 (m, 2H), 7.247.16 (m, 3H), 7.01 (d, 4= 5.5 Hz, 1H), 5 .09 (dq, 4 = 7.7, 6.3 Hz, ur,..„ 1H), 4.77-4.67 (m, 1H), 3.91 , r»R^®'ESI (s - 3H) 2 96 - 2-8θ (m, 1H), [M+H] calculated 2.41 (s, 3H), 1.49 (d, 4= 7.2 Hz, for C22H27N2O6, 3H) , 1.30 (d, 4= 7.0 Hz, 3H) 415.1864; found, 1.10 (d, 4= 6.3 Hz, 3H) 415.1859 13C NMR (126 MHz, CDCI3) δ 172.3,169,0.162.4,159.4, 146.7,143.0,141.5,137.5, 128 ,4,127,8,126,7,109,7, 76,3, 56,3,48,1,45,0,20,8,18,7, 18,2,17,3. 259 IR (thin film) 3380, 2980, 2938.1770, 1734.1674, 1506.1193, ' 1173.1060, 800 cm'1 1H NMR (500 MHz, CDCI3) δ 8.56 (s, 1H), 8 .34 (d, 4= 5.4 Hz, 1H), 7.01 (d, 4=5.5 Hz, 1H), 6.61 (d, 4=3.5 Hz, 1H), 6.56 (dq, 4 = 3.4, 1.1 Hz, 1H), 5,074.98 (m, 1H), 4.77 -4.67 (m, HRMS-ESI (m / z) 1H), 3.91 (s, 3H), 3.20-3 11 [M+H] calculated (m, 1H), 2.42 (d, 4 = 1 1 Hz 3H) r. uPaA 2.40 (s, 3H), 1.49 (d, 4=7.2 Hz,' CziHjzNzOeS, 3H), 1.32 (d, 4=7.0 Hz 3H) 135.1584; found, 1.17 (d, 4 = 6.3 Hz 3H) ' 435.1581 ' 13C NMR (126 MHz, CDCI3) δ 172.2, 169.0, 162.4, 159.4, 146.7, 143.5, 141.5, 138.0, 137.5, 124.5, 124.1, 109.7, 75.9, 56.3,48,1,40,2,20,8,18, 7, ___________18,0, 17,3,15,3. 186 IF-2019-52232722-APN-ANP#INPI Page 371 of 408 IF-2019-52232722-APN-ANP#INPI Pigini ϋ 260 IR (thin film) 3381.2980 2940.1770 1733, 1675 1502, 1193 1175, 1150 731 cm'1 HRMS-ESI (m / z) , [M+H]* calculated , for , C23H28FN2O7, , 463.1875; found. 463.1874 'Η NMR (500 MHz, CDCI3) δ 8.54 (s,1H), 8.35 (d, J =5.4 Hz, 1H), 7.14-7.06 (m, 1H) , 7.01 (d, J = 5.5 Hz, 1H), 6.62 - 6.51 (m, 2H), 5.18-5.08 (m, 1H), 4,724.62 (m, 1H ), 3.92 (s, 3H), 3.79 (s, 3H), 3.42 - 3.31 (m, 1H), 2.41 (s, 3H), 1.46 (d, J = 7.2 Hz, 3H), 1.23 (d,J= 7.1 Hz, 3H), 1.13 (d, J =6.3 Hz, 3H). 19F NMR (471 MHz, CDCI3) δ 113.9--114.0 (m). | 261 IR (thin film) 2978, 2942, 1769.1712, 1602.1501, 1371, 1242, 1081.702 cm'1 HRMS-ESI (m / z) [M+H]* calculated for C21H23N2O6, 399.1551; found, 399.1549 'H NMR (500 MHz, CDCI3) δ 8.61 (d, J= 5.3 Hz, 1H), 7.24 7.17 (m, 2H), 7.17 -7.06 (m, 4H), 5.61 (q, J = 7.1 Hz, 1H), 5.16-5.06 (m, 1H), 4.06 (s, 3H), 2.93-2, 83 (m, 1H), 1.70 (d, J=7.1 Hz, 3H), 1.27 (d, J = 7.1 Hz, 3H), 1.04 (d, J= 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 168.2,158.7,154.2,149.1, 145.8, 142.5, 141.6, 131.5, 128.2, 128.0, 126.5, 111.2 ,76.5, 56.8,51,6,44,7,17.5,17.2, 14.0. J Il ' 262 R (thin film) ’942.1769, 713.1602, 501.1371 242, 1080, 731 cm’1 HRMS-ESI (m&) [M+H]* calculated for . C22H24FN2O7, — 47.1562; found, 447.1566 'H NMR (500 MHz, CDCI3) δ 8.60 (d, J= 5.2 Hz, 1H), 7.13 (d, J =5.3 Hz, 1H), 7.02 (dd, J = 8.5, 6.7 Hz, 1H), 6.59 - 6.50 (m, 2H), 5.56 (q, J= 7.1 Hz, 1H), 5.15 - 5.06 (m, 1H), 4.05 (s, 3H), 3.79 (s, 3H), 3.31 - 3.20 (m, 1H), .68 (d, J =7.0 Hz, 3H), 1.18 (d, J = 7.0 Hz, 3H), 1.16 (d, J= 6.3 Hz, 3H). 19FRMN(471 MHz, CDCI3)6113.9. 187 IF-2019-52232722-APN-ANP#INPI Page 373 of 408 IF-2019-52232722-APN-ANP#INPI 263 ESIMS m / z 427.2 KM+H)+] 1H NMR (400 MHz, CDCI3) δ 8.55 (d, J = 7.8 Hz, 1H), 8.35 (dd, J = 5.4 , 2.9 Hz, 1H), 7.23 7.05 (m, 4H), 7.01 (dd, J = 5.5, 2.2 Hz, 1H), 5.15 (dq, J = 8 .7, 6.2 Hz, 1H), 4.80 - 4.62 (m, 1H), 3.91 (d, J = 1.7 Hz, 3H), 3.353.02 (m,1H), 2 .41 (d, J = 1.8 Hz, 3H), 2.35 (s, 3H), 1.50 (t, J = 6.8 Hz, 3H), 1.25 (dd, J = 6, 9, 4.3 Hz, 3H), 1.11 (t, J = 5.9 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 172.39, 168.89, 159.49, 146.67, 141.80, 137.54, 135.55, 130.49, 126.39,126.30,126.23,109.75 , 56,28,48,19,48,09,39,75, 20.74, 19.96, 18.56,18.48, 18.25,17.58,17.46,-0.01. 264 ESIMS m / z 429.3 l(M+H)+] 1H NMR (400 MHz, CDCI3) δ 8.55 (d, J =7.6 Hz, 1H), 8.34 (d, J = 5 .4 Hz, 1H), 7.23-6.93 (m, 5H), 5.14 (dq, J = 8.4, 6.2 Hz, 1H), 4.73 (p, J = 7, 2 Hz, 1H),3.91 (s, 3H), 3.19 (dq, J= 8.4,6.9 Hz, 1H), 2.40 (s, 3H), 2.35 (s, 3H), 1.51 (d, J= 7.1 Hz, 3H), 1.25 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H) . 13C NMR (101 MHz, CDCI3) δ 172.39, 168.89, 162.39, 159.48, 146.67, 141.81, 141.66, 137.54, 135.51, 130.50, 126 .39, 126.27, 126.26, 109.74, 56.27,48.19, 39.81,20.74, 19.94, 18.73, 18.48, 17.46. 188 IF-2019-52232722-APN-ANP#INPI Page 375 of 408 Yo I J 265 'H NMR (400 MHz, CDCI3) δ 8.49 (s, 1H), 8.34 (dd, J = 5.4, 2.9 Hz, 1H), 7.22 - 7.06 (m, 4H) 6.99 (d, J = 5.4 Hz, 1H), 5.24 5.04 (m, 1H), 4.79 - 4.64 (m, 1H), 3.89 (d, J = 1.7 Hz, 3H), 3.18 (dq, J = 9.2, 6.9 Hz, 1H), 12.96 (p, J = 7.0 Hz, 1H), 2.35 (s , ESIMS / 7*457.5 11 37 Ί - 7'n' Μ2' lYM+Hi+i 3)» (ddt J - 7.0, 1.7 Hz, KM+H)+] 6H) 1 30 _ 1 18 (m 3H) 1 n (t J = 6.2 Hz. 3H). 13C NMR (101 MHz, CDCI3) δ 174.68,172.48, 162.41,159.47, 146.56,142.03,141.83,137.71, 135.55, 130.48,126.40, 126.29, 9 , 56.28,48.07, 39.77,33.97,19.96,18.81, J 18.56,18.26,17.60,-0.01. 1 266 Ή NMR (400 MHz, CDCI3) δ 8 49 (s, 1H), 8.33 (d, J= 5.4 Hz, 1H), 7.23 - 7.05 (m, 4H), 6, 99 (d, J= 5.5 Hz, 1H), 5.12 (dt, J= 8.4,6.2 Hz, 1H), 4.73 (p, J= 7.2 Hz, 1H), 3.89 (s, 3H), 3.38 - 3.09 (m, 1H), 2.95 (p, J= 7.0 Hz, 1H), 2.35 (s, 3H), 1.50 (d, J = 7.1 Hz, 3H), 1.36 ESIMS / 7* 457.4 (dd·J= 7·0· 1-1 Hz, 6H), 1.25 (d, i(M+ H)+] J= 6.9 Hz, 3H), 1.12 (d, J=6.2 Hz, 3H). 3C NMR (101 MHz, CDCI3) 56,28,48,17,39,81, 33,96,19,94,18,81,18,76, . _ ---1_________ 18,48,17,45, 189 IF-2019-52232722-APN-ANP#INPI Page 377 of 408 IF-2019-52232722-APN-ANP#INPI ¿*igini 37¾ of 108· 267 IR (thin film) 3087, 2984 1737.1513 1484, 1311 1151.1118 800, 771 cm'1 HRMS-ESI (m / z) [M+H]+calculated for C21H24F3N2O4S, 457.1403; found, 457.1399 'H NMR (400 MHz, CDCb) δ 12.93 (s, 1H), 10.74 (d, 7= 7.6 Hz, 1H), 8.00 (d, 7= 5, 1 Hz, 1H), 7.73-7.59 (m, 1H), 7.51 (t, 7= 7.7 Hz, 1H), 7.43 (d, 7= 7.8 Hz, 1H) , 7.33 (t, 7= 7.5 Hz, 1H), 6.89 (d, 7= 5.1 Hz, 1H), 5.30 5.18 (m, 1H), 5.14 (p , 7 = 7.2 Hz, 1H), 3.96 (s, 3H), 3.37 (p, 7 = 6.8 Hz, 1H), 1.69 (dd, 7 =7.2, 3, 2 Hz, 3H), 1.30 (d, 7 = 6.8 Hz, 3H), 1.14 (d, 7= 6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.23. 268 IR (thin film) 3086, 2984, 1735.1512, 1313, 1279, 1153, 1120, 909, 730 cm-1 HRMS-ESI (m / z) [M+H]* calculated for C21H23F4N2O4S, 475.1309; found, 475.1308 ’H NMR (400 MHz, CDCI3) δ 12.91 (s, 1H), 10.72 (d, 7 = 7.7 Hz, 1H). 8.00 (d, 7 = 5.1 Hz, 1H), 7.41 (dd, 7 = 8.7, 5.3 Hz, 1H), 7.36 (dd, 7= 9.1, 2, 8 Hz, 1H), 7.22 (td, 7 =8.2, 2.8 Hz, 1H), 6.90 (d, 7= 5.1 Hz, 1H), 5.16 (dp, 7= 21,6,6.9 Hz, 2H), 3.96 (s, 3H), 3.34 (p, 7 = 7.2 Hz, 1H), 1.68 (d, 7 = 7.2 Hz, 3H), 1.29 (d, 7= 6.8 Hz, 3H), 1.14 (d, 7= 6.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ 58.77, -113.84. 269 ​​R (thin film) 3128, 2947, 735.1511, 479, 1280, 200.1151, 985, 797 cm*1 HRMS-ESI (m / z) W+H]+ calculated for C19H29N2O4S, 381.1843; found, 381.1840 'H NMR (400 MHz, CDCI3) δ 12.94 (d, 7= 1.8 Hz, 1H), 10.76 (d, 7= 7.9 Hz, 1H), 7.98 (dd, 7= 5.1,1.4 Hz, 1H), 6.88 (d, 7 =5.1 Hz, 1H), 5.19-5.00 (m, 2H), 3.95 ( s, 3H), 1.85-1.69 (m. 2H), 1.68 -1.32 (m, 7H), 1.30 1.20 (m.4H), 1.20-1.01 (m, 3H), 0.96 (d, 7 = 6.8 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 188.94,171,20,157,16,149.30, 138.96,131.63, 109.05, 75.08, 56,26,52,28,43,32,43,13, 31 .22, 30.75, 25.15,24.98, 17.81, 17.23,12.49. 190 IF-2019-52232722-APN-ANP#INPI Page 379 of 408 or 270 1H NMR (400 MHz, CDCI3) δ 9.96 (d, J= 7.3 Hz, 1H), 8.34 (d, J = 5.5 Hz, 1H), 7.71 - 7.59 ( m, I 1H), 7.59-7.47 (m, 1H),7.44 HRMS-ESI (m / z) (d. J = 7.8 Hz, 1H), 7.39 - 7.28 [M+H] calculated (m, 1H), 7.00 (d, J = 5.5 Hz, 1H), for 5.28-5.15 (m, 2H), 3.91 (s, CasHjsFsNjOsS, 3H), 3.42-3.29 (m, 1H), 2.37 499.1509; found, (s, 3H), 1.64 (d, J= 7.2 Hz, 3H), 499.1508 1.30 (d, J = 6.8 Hz, 3H), 1.12 (d, J =6.3Hz, 3H). 19F NMR (376 MHz. CDCI3) δ 58.23. 271 1H NMR (400 MHz, CDCI3) δ 9.95 (d, J= 7.3 Hz, 1H), 8.34 (d, J= 5.4 Hz, 1H), 7.42 (dd, J = 8.8, 5.3 Hz, 1H), 7.35 (dd,J = HRMS-ESI (m / z) 9.2,2.8 Hz, 1H), 7.22 (td J = [M+ H] calculated 8.2, 2.8 Hz, 1H), 7.00 (d, J= 5.5 for Hz, 1H), 5.35-5.03 (m,2H),' 3.91 ( s,3H), 3.41 -3.21 (m, 517.1415; found, 1H), 2.37 (s, 3H), 1.64 (d, J= 7 1 517.1410 Hz, 3H) , 1.29 (d,J= 6.8 Hz,3H), 1.13 (d, J= 6.3 Hz, 3H). .9F NMR (376 MHz, CDCI3) δ I 58.78,-113.98. | 272 HRMS-ESI (m / z) [M+H]* calculated for C21H31N2O5S, 423.1948; found, 423.1944 1H NMR (400 MHz, CDCI3) δ 10.00 (d, J= 7.3 Hz, 1H), 8.33 (d, J= 5.4 Hz, 1H). 6.99 (d, J= 5.4 Hz, 1H), 5.24 - 5.06 (m, 2H). |3.91 (s, 3H). 2.36 (s. 3H), 1.83- 1.71 (m. 3H), 1.71 —1.54 (m, 6H), 1.50 (dtd, J= 14.3, 8.0, 3.3 Hz, 1H), 1.39 (dqd, J= 9.7,6.9, 3.0 Hz, 1H). 1.25 (d, J= 6.5 Hz, 3H), 1.20 - 1.02 (m, 2H). 0.96 (dd, J= 6.9,1.7 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 189.09,171.67,168.57,159.84, 146.29, 145.12, 136.88,109.21, 74.86, 56.41, 53.04,43.36, 43 ,13,31,22,30,75,25,17, 24,99,21,27,17,86,17,08, 12,46. 191 IF-2019-52232722-APN-ANP#INPI Page 381 of 408 IF-2019-52232722-APN-ANP#INPI or 273 IR (thin film) 2984.1739 1571, 1480 1310, 1150 1117.759 cm*1 'H NMR (400 MHz, CDCI3) δ 14.35 (s, 1H), 12.85 (d, J = 6.8 Hz , 1H), 7.91 (d, 7= 7.1 Hz, 1H), 7.64 (dd, 7=7.9,1.4 Hz, 1H), 7.51 (td, 7= 7, 6.1.3 Hz, 1H), HRMS-ESI (m / z) 7.44 (d, 7= 7.8 Hz, 1H), 7.32 (t, [M+Hf calculated 7 = 7.6 Hz, 1H), 6.79 (d, 7= 7.2 ' for Hz, 1H). 5.28-5.14 (m, 1H), C21H24F3N2O6, 4.73 (p, 7 = 7.1 Hz, 1H), 3.97 (s, '457.1581; found, 3H), 3.35 (tt, 7= 7.5, 3.8 Hz, 457.1583 1H), 1.62 (d, 7=7.2 Hz, 3H), 1.29 (d, 7 = 6.8 Hz, 3H ), 1.10 (d, 7 = 6.2Hz,3H). 19F NMR (376 MHz, CDCI3) δ - 1 58.22. | 274 IR (thin film) 2985, 1739, 1480.1313, 1153.1123, 909, 738 cm'1 1 'H NMR (400 MHz, CDCI3) δ 1 14.33 (s, 1H), 12.85 (d , 7= 6.9 Hz, 1H), 7.91 (d, 7 = 7.2 Hz, 1H), 7.44 (dd, 7= 8.8, 5.4 Hz, 1H), HRMS-ESI (m / z) I-38 (<“· J= 9.2, 2.8 Hz, 1H), (M+H]'calculated 2·® Hz, 1H), for 6·80 (d·J = 7·2 Hz, 1H), 5.23 - C21 H¡3F4N2Oe 5.09 <m. 1 HOUR). 4.73 (p, 7 = 7.2 Hz. 475J487; found,. <s'3Η>·3·41 ~3·25 475 1492 {rn· 1H).1·61 (d. 7 = 7.2 Hz. 3H). 1.27 (d, 7= 6.8 Hz, 3H). 1.11 (d, 7=6.3Hz.3H). .9F NMR (376 MHz, CDCI3) δ | 58.77,-114.03. | 275 i R (thin film) 2945.1733, 569.1479, 300.1212,: 152.1029, 757 cm'1 I 1H NMR (400 MHz, CDCI3) δ I 14.40 (s. 1H), 12, 75 (d, 7= 7.1,. Hz, 1H), 7.91 (d, 7 = 7.2 Hz. 1H). HRMS-ESI (m4) 6.79 (d. 7= 7.2 Hz, 1H), 5.10 [M+Hf calculated (qd, 7= 6.4, 3.0 Hz, 1H), 4.78- _ for C19H29N2O6, 4.63 (m, 1H), 3.97 (s, 3H), 1.85 181.2020; found, -1.68 (m, 2H), 1.68 -1.51 (m 381.2016 7H), 1.51 -1.44 (m, 1H), 1.44- 1.33 (m, 1H), 1.24 (d, 7= 6.4 Hz, 3H), 1.18 - 0.99 (m, 2H). 0.94 (d. 7 = 6.9 Hz, 3H). 192 IF-2019-52232722-APN-ANP#INPI Page 383 of 408 or 276 IR (thin film) 2978, 2937, 1735.1643, 1569, 1479, 1452.1211, 1154, 729, 702 cm’1 HRMS-ESI (m / z) [M+Hp calculated for C20H25N2O6, 389.1707; found, 389.1703 'H NMR (500 MHz, CDCfc) δ 14.39 (s, 1H), 12.82 (d, 7 = 6.9 Hz, 1H), 7.89 (d, 7 = 7, 2 Hz, 1H), 7.32-7.25 (m, 2H), 7.25-7.15 (m, 3H), 6.78 (d, 7 = 7.2 Hz, 1H), 5, 10 (dq, 7= 8.1, 6.3 Hz, 1H), 4.75— 4.64 (m, 1H), 3.97 (s, 3H), 2.96-2.86 (m, 1H), 1.56 (d, 7=7.2 Hz, 3H), 1.30 (d, 7 = 6.9 Hz, 3H), 1.12 (d, 7 =6.2 Hz, 3H) . 13C NMR (126 MHz, CDCI3) δ 171.1,165.5,152.5,149.3, 143.0,131.0,128.4, 127.8, 126.7, 123.7, 107.6, 76.5, 56.5 , 48.9, 45.0, 18.2, 17.9, 17.4. 277 IR (thin film) 2978, 2939, 1735, 1570, 1502, 1453. 1213.1152, 1031.952, 731 cm*1 HRMS-ESI (m / z) [M+Hp calculated for C2lH26FN2O7, 437.1719; found, 437.1727 1H NMR (500 MHz, CDCI3) δ 14.42 (s, 1H), 12.80 (d, 7=7.1 Hz, 1H), 7.89 (d, 7 = 7.2 Hz, 1H), 7.11 (dd, 7 =8.4, 6.7 Hz, 1H), 6.78 (d, 7 =7.1 Hz, 1H), 6.636.55 (m, 2H), 5.22-5.13 (m, 1H), 4.72-4.61 (m, 1H), 3.98 (s, 3H), 3.80 (s, 3H), 3.38 - 3, 29 (m, 1H), 1.51 (d, 7=7.2 Hz, 3H), 1.25 (d, 7 = 7.1 Hz, 3H), 1.13 (d, 7=6.3 Hz, 3H). 19F NMR (471 MHz, CDCI3) δ 113.9 (dt, 7= 11.2, 7.3 Hz). 193 IF-2019-52232722-APN-ANP#INPI Page 385 of 408 !ι IF-2019-52232722-APN-ANP#INPI or HRMS-ESI (m / z) [M+H]* calculated for C24H30N2O6, 443.2177; found 443.2186 'H NMR (500 MHz, CDCI3) δ 8.53 (d, J = 7.1 Hz, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.22 - 7.06 (m, 4H), 7.00 (d, J = 5.5 Hz, 1H), 5.14 (dq, J = 8.4, 6.3 Hz, 1H), 4.78 - 4 .68 (m, 1H), 3.90 (s, 3H), 3.18 (dt, J = 8.4,6.9 Hz, 1H), 2.74 (q, J = 7.5 Hz, 2H), 2.35 (s,3H), 1.51 (d,J = 7.1 Hz, 3H), 1.28 (t, J = 7.5 Hz, 3H), 1.25 (d, J= 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 172.43, 172.35,162,39,159.50, 146.60,141.81,141,71,137.61, 135.51,130.49,126.38,126 27 109.70.76,30.56 .28 ,48.16, ' 39.78, 30.93, 27.28,19.97,18.77, 18.49,17.47,8.81. | HRMS-ESI ( / 7½) [M+H]+calculated, for C25H32N2O6, 457.2333; found, 457.2343 H NMR (500 MHz, CDCI3) δ 8.5: (d, J = 6.1 Hz, 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.21-7 .06 (m, 4H), 6.99 (d, J = 5.5 Hz, 1H), 5.14 (dq J = 8.4, 6.2 Hz, 1H), 4.77 - 4.69 (m, 1H), 3.89 (s, 3H), 3.18 (dq, J = 8.4, 6.9 Hz, 1H), 2.68 (t, J = 7.5 Hz, 2H) , 2.35 (s,3H), 1.82 (h,J = 7.4Hz,2H), 1.50 (d,J= 7.1 Hz, 3H), 1.25 (d, J= 6 .8 Hz, 3H), 1.12 d, J = 6.2 Hz, 3H), 1.05 (t,J = 7.4 Hz, 3H). 2 I 3 13C NMR (126 MHz, CDCfe) δ 172.43,171.45, 162.37, 159.46, 146.60,141.81,141.76,137.58, 135.51, 130.49, 126.38,126 27 109, 67,76,28,56,25,48,15, ' 9.77, 35.79,19.96, 18.77, 18.48, 18.15, 17.46,13.60. 194 IF-2019-52232722-APN-ANP#INPI Page 387 of 408 IF-2019-52232722-APN-ANP#INPI or 280 ESIMSntó471 ([M+H]*) 1H NMR (400 MHz, CDCI3) δ 8.53 (s, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.22 - 7, 06 (m, 4H), 7.00 (d, J = 5.5 Hz, 1H), 5.13 (dq, J = 8.3,6.2 Hz, 1H), 4.85-4.67 (m, 1H), 3.90 (s, 3H), 3.18 (dq, J= 8.4,6.9 Hz, 1H), 2.80 - 2.67 (m, 2H), 2, 35 (s, 3H), 1.77 (p, J= 7.6 Hz, 2H), 1.48 (dd, J=17.8, 7.4 Hz, 5H), 1.25 (d, J = 6.9 Hz, 3H), 1.12 (d,J = 6.2 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H). 5 6.26 ,48.17, 39.80, 33.67, 26.64,22,22,19.96, 18.77,18.49,17.47,13.77. 281 ESlMSntó 455.4 ([M+H]*) 1H NMR (400 MHz, CDCI3) δ 8.52 (d,J = 8.0 Hz, 1H), 8.33 (d,J = 5.4 Hz , 1H), 7.22 - 7.05 (m, 4H), 6.99 (d, J=5.5Hz, 1H), 5.13 (dq, J = 8.3, 6.2 Hz, 1H ), 4.82 - 4.68 (m, 1H), 3.90 (s, 3H), 3.19 (dq, J = 8.4,6.9 Hz, 1H), 2.35 (s, 3H), 1.97 (tt,J= 8.0,4.6 Hz, 1H), 1.51 (d, J = 7.2 Hz, 3H), 1.32-1.21 (m, 5H ), 1.12 (d, J = 6.3 Hz, 3H), 1.07 (dq, J=7.5,4.0 Hz, 2H). 13C NMR (101 MHz, CDCI3) δ 172.49,172.45,162.36,159.53, 146.61,142.00,141.84,137.50, 135.52,130.51,126.41,126.29, -126.26,109.67, 60.39, 56.31, 48.13, 39.80, 21.04,19.96,18.83, 18.49,17,47,14,21,13.03, 9.26. 195 IF-2019-52232722-APN-ANP#INPI Page 389 of 408 or IF-2019-52232722-APN-ANP#INPI Page 390 of 408 'H NMR (400 MHz, CDCI3) δ 8.5E (d, 7 = 7.9 Hz, 1 Η), 8.40 (d, 7 = 5.5 Hz, 1H), 8.32-8.17 ( m, 2H), 7.67 — 7.57 (m, 1H), 7.50 (dd, J= 8.3,7.0 Hz, 2H), 7.20 - 7.08 (m, 4H) , 7.06 (d, J= 5.5 Hz, 1H), 5.11 (dq, J = 8.2, 6.2 Hz, 1H), 4.89 4.55 (m, 1H), 3 .90 (s, 3H), 3.23 3.03 (m, 1H), 2.34 (s, 3H), 1.47 282 ESIMSmfc491.4 (d,7 = 7.2Hz, 3H), 1, 23(d,7 = ([M+H]*) 6.9 Hz, 3H), 1.08 (d, 7= 6.2 Hz, 3H). 13C NMR (101 MHz, CDCI3) δ 172.51,164.53,162.25,159.68, 146.82, 141.85, 135.53, 133.47, 130.60,130.50,129.20,128.55, 8,126 ,25,109,77, 56,33,48,08,39,79,19,95,18,84, Illi | 18,47,17,46. J 1H NMR (500 MHz, CDCI3) δ 8.43 (d, 7 = 7.8 Hz, 1H), 8.28 (d, 7 = 5.3 Hz, 1H), 7.22 - 7.05 ( m, 4H), 6.94 (d, 7= 5.4 Hz, 1H), 5.78 (q, 7 = 6.4 Hz, 2H), 5.15 (dq, 7 =8.5, 6 .3 Hz, 1H), 4.75 (p, 7 = 7.2 Hz, ______ 1H), 3.89 (s, 3H), 3.25-3.15 (m, HRMS-ESI (m / z ) 1H), 2.55 (p, 7 = 7.0 Hz, 1H), 2.35 [M+H] calculated (s,3H), 1.53 (d, 7 = 7.2 Hz, 3H) 284 For C^NaOz, 1.26 (dd, 7 = 7.1, 5.9 Hz, 3H), 487.2439; found, 1.14 (dd, 7= 8.7, 6.6 Hz 9H)' 487.2450 13C NMR (126 MHz, CDCI3) δ 176.26,172.52,162.94, 160.27, 145.58,144,25.142 ,19,141,80, 135,51,130,50,126,37,126,26, I 109,50,89,96,76,30,56,13, 48,38,39,79,33,86,19,96,18, 69, Illi | 18,62,18,51,17,51. 196 IF-2019-52232722-APN-ANP#INPI Page 391 of 408 or IF-2019-52232722-APN-ANP#INPI Page 392 d< I !| 285 ESIMS mfr 413 ([M+HD1H NMR (400 MHz, CDCI3) δ 8.60 (d, . / = 5.3 Hz, 1H), 7.18 (d, J = 5.4 Hz, 1H), 7.14 (dd, J = 3.8,1.4 Hz, 2H), 7.08 - 6.99 (m, 2H), 5.60 (q, J=7.1 Hz, 1H), 5 .18 (dq, J = 8.2,6.2 Hz, 1H), 4.06 (s, 3H), 3.14 (dq, J= 8.3, 6.9 Hz, 1H), 2, 29 (s,3H), 1.71 (d, J =7.0 Hz, 3H), 1.22 (d, . / = 6.9 Hz, 3H), 1.07 (d, J = 6, 3 Hz, 3H) ”CMRN (101 MHz, CDCI3)6 168.34, 158.73, 154.19,149.12, 145.79,141,65,141,53,135.54, 131.44, 130.30, 126.41,126 ,23, 126,11,111,45, 56,84,51,51, 39,55,20,00,17,74,17,71,14,03. Cmpd No. - Compound Number Table3. Biological Tests Classification table for fungal _______________ pathogens % Control Classification >80 A £80 B Not tested C £0 D Table 4. Biological activity - PUCCRT and SEPTTR disease control in high volume applications High volume activity at 100 ppm* *Cmpd. No. *PUCCRT *SEPnR 1DP* 3DC* 1DP* 3DC* 116 A A B Γ A 197 IF-2019-52232722-APN-ANP#INPI Page 393 of 408 IF-2019-52232722-APN-ANP#INPI Page 1 rV o I—117 B B I B B __118 A A D B I I 119 A B D B I 120 B B D B I 121 A A D B 122 A A B B 123 A B D B |_124 B D D B 125 B D D B 126 A B D B 127 B B D B |_128 A A A A 129 A B B B 130 A A B B 31 A A B B 132 A A I A B 133 A B B B 134 B B Ί B B 135 B B B B 136 A B B B 137 A B B B 138 A A A B 139 B D B B 140 A B B B I 141 A B A B 142 A A A B 143 A D B B I 144 D B B B 145 B B B B 146 A B A B 147 A B Γ A B Γ~148 A B Γ A B Γ~ 149 D D I B B_J 150 D B B B 151 B D B B 152 A - ~B pB=- - B I 153 B B B B 154 D D B B 155 B B B B 156 D B I B B 157 B D I B B I 158 A A A B 159 A A I A A |160 B A B B 161 1 162 D D B B D D B B I 198 IF-2019-52232722-APN-ANP#INPI Page 395 of 408 or IF-2019-52232722-APN-ANP#INPI Page 163 B B B B 164 A A B A 165 A A A A 166 A A A A 167 A A A A 168 A A B A 169 A A A A 170 A A B B 171 A A B B 172 B A B B 173 A B B B 175 A A B B 176 A B D B 258 A A B B 259 A A B D 26 0 A B B B 267 A B B B 268 A B B B 269 B A B B 276 A B B B 277 B D B B * Cmpd. No. - Compound number 'PUCCRT - Wheat brown rust (Puccinia tritíciná). SEPTTR - Wheat leaf spot (Zymoseptoria tritici) * 1DP - 1-day protective * 3 DC - 3-day curative * ppm - Parts per million Table 5. Biological activity - PUCCRT and SEPTTR disease control in low volume applications Low volume activity at 121.5 g / ha*------------- *Cmpd No. 'PUCCRT 'SEPTTR 1DP* 3DC* 1DP* 3DC* 177 A A A A A 178 B B B B 179 A A B B 180 B B B B 234 B B B B 235 B B A A 236 B B B D 237 B B B B 199 IF-2019-52232722-APN-ANP#INPI Page 397 of 408 or IF-2019-52232722-APN-ANP#INPI Page 398 of 408 238 A B A A 239 D D B B 240 D D B B 241 D D B D 242 A B A A 243 B B B B 244 A B A A 245 A B A A 246 A A A A 247 B B B B 248 A B B A 249 A A A A 250 D B B B 251 B B B B 252 D B D B 3 A B B B 254 A A A A 255 A B B A 256 A A A A 257 B B B B 258 B A B A 259 B D B D 260 D D B D 261 B D B D 262 D D B B 263 B B B B 264 A A B B 265 B B B B B 266 B B B 275 B D D D 231 A B B 232 A __B _ D B 233 A B B B B 270 B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B 277 D B B B B B B B 'Cmpd. No. - Compound number 200 IF-2019-52232722-APN-ANP#INPI Page 399 of 408 IF-2019-52232722-APN-ANP#INPI Page 400 of 408 * PUCCRT - Wheat brown rust (Puccinia triticina) * SEPTTR - Wheat leaf spot (Zymoseptoria tritici) * 1DP - 1-day protector * 3DC - 3-day curative * g / ha - grams per hectare Table 6. Biological activity - Control of high volume diseases at 25 ppm PHAKPA* *Cmpd. No. 1DP* 3DC* 128 C A 158 c B 159 c A 175 A A 177 A A 178 A B 179 A A 180 A B 181 B D 182 B B 183 A B 184 A A 185 D D 186 B ​​B 187 A D 188 A B 189 A B 190 D D 191 B B 192 B D 193 B D 194 D D 195 B D 196 A B 197 D D 198 D D 199 D D 200 B B 201 B B 202 B D 203 A B 201 IF-2019-52232722-APN-ANP#INPI Page 401 of 408 IF-2019-52232722-APN-ANP#INPI Page 402 of 408 204 A A 205 A B 206 B D 207 B D 208 A D 209 A A 210 D D 211 B D 212 B B 213 A B 214 B B 215 B B 216 B D 217 B D 218 D B 219 D D 220 B B 221 D D 222 D D 223 D D 22 4 B D 225 D D 226 D B 227 B D 228 D D 229 D D 230 D D 231 B D 232 B D 233 A B 234 A A 235 A A 236 A _ D_ . 237 A A 238 A A 239 B B 240 B B 241 D D 242 A A 243 A A 244 A A 245 A A 246 A A 202 IF-2019-52232722-APN-ANP#INPI Page 403 of 408 IF-2019-52232722-APN-ANP#INPI Page 404 of 408 247 A B 248 A A 249 A , A 250 B B 251 A B 252 B B 253 A A 254 A A 255 A A 256 A A 257 B D 258 A A 259 B B 260 A B 261 B B 262 B B 263 A B 264 A A 265 A A 266 A A 270 A B 271 A A 272 A B 273 B B 274 B B 275 B B 276 D B 277 B B 284 A A 278 A A 279 A A 280 A A 281 A _ _A_ . 282 A A 285 A A .Cmpd. No. - Compound number PHAKPA- Asian soybean rust (Phakopsora pachyrtiizi) .1DP- 1 day protector *3DC - 3 day curative 203 IF-2019-52232722-APN-ANP#INPI Page 405 of 408 or Yo IF-2019-52232722-APN-ANP#INPI Page 406 of 4< either Table 7. Biological activity - Disease control in a 1DP* test at 100 ppm Cmpd. No.* ALTESO* CERCBE* COLLLA* LEPTNO* 263 B B D B 264 B A B A 266 B B D A 'Cmpd. No. - Compound number *ALTESO - Early burn of! tomato (Alternaria solani) ‘CERCBE – Sugar beet leaf spot (Cercospora beticola) COLLLA-Cucumber anthracnose (Glomerella lagenarium; Anamorph: Colletotrícum lagenarium) 'LEPTNO - Wheat glume spot (Parastagonospora nodorum) Table 8. Biological activity - Disease control in a 1DP* test at 100 ppm Cmpd. No.* PSPECU* PIRIOR* RHYNSE* UNCINE* 263 B B B A 264 B A B A 266 D A B A 'Cmpd. No. - Compound number *PSPECU - Cucumber downy mildew (Pseudoperonospora cubensis) 'PIRIOR- Anozus blight (Magnaporthe grísea; Anamorph: Piricularía oryzae) 'RHYNSE - Barley scald (Rhyncosporíum secalis) 'UNCINE - Powdery mildew of the grape (Uncinula necator) Ί DP - 1 day protector

Claims

1. A compound of Formula I (FORMULA I) characterized in that: Q is (FORMULAS); X is hydrogen or C(O)R 4 ; Z is N or N + O - and W is O; R 1 is hydrogen or alkyl, substituted with 0, 1 or multiple R 7 ; R 2 is methyl; R 3 is aryl or a saturated cyclic carbon chain, unsubstituted or substituted with 0, 1 or multiple R 7 ; R 4 is alkoxy or benzyloxy, each unsubstituted or substituted with 0, 1, or multiple R 7 ; R 5 is hydrogen, alkoxy, or halo, each unsubstituted or substituted with 0, 1, or multiple R 7 ; R 6 is hydrogen, -C(O)R 8 , or -CH2OC(O)R 8 ; R7 is hydrogen, alkyl, halo or alkoxy, each unsubstituted or substituted with 0, 1, or multiple R9; R8 is alkyl, alkoxy, or aryl, each unsubstituted or substituted with 0, 1, or multiple R7; R9 is hydrogen or halo; and R10 is hydrogen or alkyl, each substituted with 0, 1, or multiple R7, wherein the term “alkyl” refers to a branched, unbranched, or saturated cyclic carbon chain.11 Claims follow.