WO2017116954A1 - Picolinamides macrocycliques à utiliser en tant que fongicides - Google Patents

Picolinamides macrocycliques à utiliser en tant que fongicides Download PDF

Info

Publication number
WO2017116954A1
WO2017116954A1 PCT/US2016/068223 US2016068223W WO2017116954A1 WO 2017116954 A1 WO2017116954 A1 WO 2017116954A1 US 2016068223 W US2016068223 W US 2016068223W WO 2017116954 A1 WO2017116954 A1 WO 2017116954A1
Authority
WO
WIPO (PCT)
Prior art keywords
nmr
compounds
mhz
ddd
formula
Prior art date
Application number
PCT/US2016/068223
Other languages
English (en)
Inventor
Kevin G. Meyer
Chenglin Yao
Brian A. Loy
Original Assignee
Dow Agrosciences Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Publication of WO2017116954A1 publication Critical patent/WO2017116954A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
  • the present disclosure relates to macrocyclic picolinamides and their use as fungicides.
  • the compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
  • One embodiment of the present disclosure may include compounds of Formula I:
  • X is H or C(0)R 2 ;
  • Y is H, C(0)R 2 , or Q;
  • Ri is selected from the group consisting of ORs ;
  • R 2 is alkoxy, each optionally substituted with 0, 1 or multiple R 8 ;
  • R 3 is selected from the group consisting of hydrogen and alkoxy
  • R 4 is hydrogen, -C(0)R 6 , or -CH 2 OC(0)R 6 ;
  • R5 is hydrogen, alkyl, alkenyl, cycloalkyl, aryl, or -C(0)R 7 , each optionally substituted with 0, 1 or multiple R 8 ;
  • R 6 is alkyl or alkoxy, each optionally substituted with 0,1 or multiple R9;
  • R 7 is alkyl, optionally substituted with 0, 1, or multiple R 8 .
  • R 8 is alkyl, aryl, alkoxy, acyl, halo, each optionally substituted with 0, 1, or multiple R 9 ;
  • R9 is alkyl, alkoxy, acyl, halo, or haloalkyl.
  • Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.
  • Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.
  • 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.
  • alkenyl refers to a branched, unbranched 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.
  • alkynyl refers to a branched or unbranched carbon chain containing one or more triple bonds including, but not limited to, propynyl, butynyl and the like.
  • aryl refers to any aromatic, mono- or bi-cyclic, containing 0 heteroatoms.
  • heterocycle refers to any aromatic or non-aromatic ring, mono- or tricyclic, containing one or more heteroatoms
  • alkoxy refers to an -OR substituent.
  • hydroxyl refers to an -OH substituent.
  • arylalkoxy refers to -0(CH2) n Ar where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.
  • haloalkoxy refers to an -OR-X substituent, wherein X is CI, F, Br, or I, or any combination thereof.
  • haloalkyl refers to an alkyl, which is substituted with CI, F, I, or Br or any combination thereof.
  • halogen refers to one or more halogen atoms, defined as F, CI, Br, and I.
  • Formula (I) is read as also including salts or hydrates thereof.
  • Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, and hydroiodide.
  • Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.
  • composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
  • the compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds.
  • the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants.
  • the materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.
  • the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier.
  • Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment.
  • the formulations can be prepared according to procedures that are conventional in the agricultural chemical art.
  • the present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide.
  • formulations are applied as aqueous suspensions or emulsions.
  • Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates.
  • any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
  • Wettable powders which may 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.
  • 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 weight percent to about 75 weight percent.
  • the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like.
  • the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
  • Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate.
  • the compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers.
  • the concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions.
  • Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha.
  • Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2- ethoxyethanol.
  • Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers.
  • nonionic emulsifiers useful in preparing the emulsifiable concentrates include the 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 the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene.
  • Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts.
  • Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
  • Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of Methylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soy bean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; vegetable oils
  • Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases.
  • Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 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 can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
  • Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension.
  • Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above.
  • Other components such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.
  • the compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil.
  • Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance.
  • Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm.
  • a suitable solvent is a solvent in which the compound is substantially or completely soluble.
  • Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
  • Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
  • a suitable dusty agricultural carrier such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
  • the formulations may additionally contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism.
  • adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix.
  • the amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent.
  • Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9 - Cn
  • alkylpolyglycoside phosphated alcohol ethoxylate; natural primary alcohol (C12- C1 ⁇ 2) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99.
  • the formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
  • the formulations may optionally include combinations that contain other pesticidal compounds.
  • additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds.
  • the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use.
  • the compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 tol00:l.
  • the compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases.
  • the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s).
  • Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene- sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlor
  • ICIA0858 isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5- dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4- toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury
  • hydrochloride pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.
  • the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests.
  • the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s).
  • Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthr
  • chlorfenapyr chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin,
  • chlorphoxim chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin ⁇ , cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, deme
  • EPN epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate,
  • the compounds described herein may be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants.
  • the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s).
  • Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB;
  • P medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron,
  • Another embodiment of the present disclosure is a method for the control or prevention of fungal attack.
  • This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula I.
  • the compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity.
  • the compounds may be useful both in a protectant and/or an eradicant fashion.
  • the compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.
  • the compounds have broad ranges of activity against fungal pathogens.
  • exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Mycosphaerella graminicola; impect stage: Septoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine ⁇ Uncinula necator), barley scald (Rhynchosporium secalis), blast of rice ⁇ Magnaporthe grisea), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminisf.
  • the exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
  • the compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount.
  • disease-inhibiting and phytologically acceptable amount refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred.
  • concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like.
  • a suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m 2 ).
  • the compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
  • Compounds of Formula 1.2 can be prepared by the methods shown in Scheme 1, steps a - b.
  • Compounds of Formula 1.1 can be prepared from compounds of Formula 1.0, by treatment with chlorotriisopropylsilane in the presence of a base, such as imidazole, in an aprotic solvent such as dichloromethane (DCM), and at a temperature between 0 and 23 °C, as shown in step a.
  • a base such as imidazole
  • aprotic solvent such as dichloromethane (DCM)
  • Compounds of Formula 1.2 can be prepared from compounds of Formula 1.1, by treatment with a reducing agent, such as diisobutylaluminum hydride (DIBAL-H), in an aprotic solvent such as DCM, and at a temperature from about -78 and to about 23 °C, as shown in step b.
  • DIBAL-H diisobutylaluminum hydride
  • Compounds of Formula 2.1 can be prepared by the methods shown in Scheme 2, steps a - b.
  • Compounds of Formula 2.0 can be prepared from compounds of Formula 1.2, by treatment with (+)-Ipc 2 -allylborane, as described by Racherla, U. S.; Brown, H. C. J. Org. Chem. 1991, 56, 401-404, in a solvent such as diethylether at cryogenic temperatures, such as -78 °C, as shown in step a.
  • Compounds of Formula 2.1 can be prepared from compounds of Formula 1.2 by treatment with a base, such as sodium hydride, and benzyl bromide, in a solvent such as DMF, and at a temperature from about 0 and to about 23 °C, as shown in step b.
  • a base such as sodium hydride, and benzyl bromide
  • Compounds of Formula 3.1 can be prepared by the methods shown in Scheme 3, steps a - b .
  • Compounds of Formula 3.0 can be prepared from compounds of Formula 2.1 , by treatment with an oxidant, such as ozone, in an aprotic solvent, such as DCM, or in a mixture of solvents, such as methanol and DCM, at cryogenic temperatures, such as -78 °C, followed by treatment with a base, such as sodium borohydride, as shown in step a.
  • Compounds of Formula 3.1 can be prepared from compounds of Formula 3.0 by treatment with a desilylating agent, such as tetrabutylammonium fluoride (TBAF), in a solvent such as tetrahydrofuran (THF), at a temperature of about 0 °C to ambient temperature, as shown in step b.
  • a desilylating agent such as tetrabutylammonium fluoride (TBAF)
  • THF tetrahydrofuran
  • Compounds of Formula 4.1, where Y is C(0)iBu, herein referred to as Boc can be prepared by the method shown in Scheme 4, step a.
  • Compounds of Formula 4.1, where Y is Boc can be prepared from compounds of Formula 3.1, by treatment with compounds of Formula 4.0, where Y is as originally defined, in the presence of a catalyst, such as
  • step a (diethyloxonio)trifluoroborate, in a solvent such as DCM, at a temperature of about 0 °C, as shown in step a.
  • Compounds of Formula 5.0, where Y is Boc can be prepared by the method shown in Scheme 5, step a.
  • Compounds of Formula 5.0, where Y is Boc can be prepared from compounds of Formula 4.1, where Y is Boc, by treatment with a hydrolyzing agent, such as lithium hydroxide hydrate, in a solvent, such as THF, or in a solvent mixture, such as THF and water (2: 1), at ambient temperature, as shown in step a.
  • Compounds of Formula 6.0, where Y is Boc can be prepared by the method shown in Scheme 6, step a.
  • Compounds of Formula 6.0, where Y is Boc can be prepared from compounds of Formula 5.0, where Y is Boc, by treatment with a condensing agent, such as 2- methyl-6-nitrobenzoic anhydride, in the presence of a catalyst, such as N,N-dimethylpyridin-4- amine (DMAP), in a solvent such as DCM, at about ambient temperature, as shown in step a.
  • a condensing agent such as 2- methyl-6-nitrobenzoic anhydride
  • a catalyst such as N,N-dimethylpyridin-4- amine (DMAP)
  • DCM N,N-dimethylpyridin-4- amine
  • Compounds of Formula 7.0, where Y is Boc can be prepared by the method shown in Scheme 7, step a.
  • Compounds of Formula 7.0, where Y is Boc can be prepared from compounds of Formula 6.0, where Y is Boc, by treatment with hydrogen (H 2 ) in the presence of a palladium catalyst, such as palladium on carbon (Pd/C, 5 or 10 weight %), in a polar solvent such as ethyl acetate (EtOAc), at about ambient temperature, as shown in step a.
  • a palladium catalyst such as palladium on carbon (Pd/C, 5 or 10 weight %
  • EtOAc ethyl acetate
  • Compounds of Formula 8.1, where Y is Boc and Ri is as originally defined can be prepared by the methods shown in Scheme 8, steps a - b.
  • Compounds of Formula 8.0, where Y is Boc and Ri is as originally defined can be prepared from compounds of Formula 7.0, where Y is Boc, by treatment with a palladium catalyst, such as tris(dibenzylideneacetone)dipalladium(0) [Pd 2 (dba)3] , a ligand, such as l,l'-bis(diphenylphosphino)ferrocene (dppf), and an appropriate alkyl carbonate in a solvent such as THF, at a temperature of about 60 °C, as shown in step a.
  • a palladium catalyst such as tris(dibenzylideneacetone)dipalladium(0) [Pd 2 (dba)3]
  • a ligand such as l,l'-bis(diphenylphosphino)ferrocen
  • Compounds of Formula 8.1, where Y is Boc and Ri is as originally defined can be prepared from compounds of Formula 8.0, where Y is Boc and Ri is as originally defined, by treatment with H 2 in the presence of a palladium catalyst, such as Pd/C (5 or 10 weight %), in a polar solvent such as EtOAc, at about ambient temperature, as shown in step b.
  • a palladium catalyst such as Pd/C (5 or 10 weight %)
  • EtOAc a polar solvent
  • Compounds of Formula 9.0, where Y is Boc can be prepared by the method shown in Scheme 9, step a.
  • Compounds of Formula 9.0, where Y is Boc can be prepared from compounds of Formula 7.0, where Y is Boc, by treatment with a methylating reagent, such as trimethyloxonium tetrafluoroborate, and a proton scavenger, such as Ni,M,N8,N8- tetramethylnaphthalene-l,8-diamine, in a solvent such as DCM at about ambeint temperature, as shown in step a.
  • a methylating reagent such as trimethyloxonium tetrafluoroborate
  • a proton scavenger such as Ni,M,N8,N8- tetramethylnaphthalene-l,8-diamine
  • Compounds of Formula 10.0, where Y is Boc and Ri is as originally defined can be prepared by the method shown in Scheme 10, step a.
  • Compounds of Formula 10.0, where Y is Boc and Ri is as originally defined can be prepared from compounds of Formula 7.0, where Y is Boc, by treatment with a base, such as triethylamine, and an appropriate acyl chloride in a solvent such as DCM, at a temperature of about 0 °C to ambient temperature, as shown in step a.
  • Compounds of Formula 11.0, where Y is Boc and Ri is as originally defined can be prepared by the method shown in Scheme 11, step a.
  • Compounds of Formula 11.0, where Y is Boc and Ri is as originally defined can be prepared from compounds of Formula 7.0, where Y is Boc, by treatment with a triarylbismuth reagent, prepared according to the methods described by Hassan, A. et. al. Organometallics 1996, 15, 5613-5621, Moiseev, D. V. et al. J. Organomet. Chem.2005, 690, 3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett.
  • Compounds of Formula 12.1, where Y is Boc can be prepared by the methods shown in Scheme 12, steps a - b.
  • Compounds of Formula 12.0, where Y is Boc can be prepared from compounds of Formula 7.0, where Y is Boc, by treatment with methyl propiolate, and a catalyst, such as l,4-diazabicyclo[2.2.2]octane (DABCO), in a solvent such as DCM, at a temperature of about 0 °C, as shown in step a.
  • a catalyst such as l,4-diazabicyclo[2.2.2]octane (DABCO)
  • Compounds of Formula 12.1, where Y is Boc can be prepared from compounds of Formula 12.0, where Y is Boc, by treatment with H 2 in the presence of a palladium catalyst, such as Pd/C (5 or 10 weight %), in a polar solvent such as EtOAc, at about ambient temperature, as shown in step b.
  • a palladium catalyst such as Pd/C (5 or 10 weight %)
  • a polar solvent such as EtOAc
  • Compounds of Formula 13.2, where Y is Boc can be prepared by the methods shown in Scheme 13, steps a - c.
  • Compounds of Formula 13.0, where Y is Boc can be prepared from compounds of Formula 7.0, where Y is as originally defined, by treatment with but-3-yn-2- one, and a catalyst, such as DABCO, in a solvent such as DCM, at a temperature of about 0 °C, as shown in step a.
  • Compounds of Formula 13.1, where Y is Boc can be prepared from compounds of Formula 13.0, where Y is Boc, by treatment with H 2 in the presence of a palladium catalyst, such as Pd/C (5 or 10 weight %), in a polar solvent such as EtOAc, at about ambient temperature, as shown in step b.
  • Compounds of Formula 13.2, where Y is Bocefined can be prepared from compounds of Formula 13.1, where Y is as originally defined, by treatment with a fluorinating reagent, such as bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor®), in a solvent such as DCM at a temperature of about 0 °C to ambient temperature, as shown in step c.
  • a fluorinating reagent such as bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor®
  • Compounds of Formula 14.2, where Ri is as originally defined can be prepared by the methods shown in Scheme 14, steps a - b.
  • Compounds of Formula 14.1, where Ri is as originally defined can be prepared from compounds of Formula 14.0, where Y and Ri are as originally defined, by treatment with an acid, such as hydrogen chloride (HC1, 4 M in dioxane) or trifluoroacetic acid (TFAA), in a solvent such as DCM, at a temperature of about 0 °C to ambient temperature, as shown in step a.
  • an acid such as hydrogen chloride (HC1, 4 M in dioxane) or trifluoroacetic acid (TFAA)
  • a solvent such as DCM
  • Compounds of Formula 14.2, where Ri is as originally defined can be prepared from compounds of Formula 14.1, where Ri is as originally defined, by treatment with 3-hydroxy-4-methoxypicolinic acid in the presence of a base, such as N,N- diisopropylethylamine (DIE A), and a peptide coupling reagent, such as ((1H- benzo[d][l,2,3]triazol-l-yl)oxy)tri(pyrrolidin-l-yl)phosphonium hexafluorophosphate(V) (PyBOP), in an aprotic solvent such as DCM, at ambient temperature, as shown in step b.
  • a base such as N,N- diisopropylethylamine (DIE A)
  • DIE A N,N- diisopropylethylamine
  • a peptide coupling reagent such as ((1H- benzo[d][l,2,3]triazol-l-yl)oxy
  • Compounds of of Formula 15.0, wherein Ri is as originally defined can be prepared through the method shown in Scheme 15, steps a.
  • Compounds of Formula 15.0, wherein Ri is as orginally defined can be obtained from compounds of Formula 14.2, wherein Ri is as orginally defined and R 3 is acetyl, by treating with a base, such as a triethylamine, a catalyst, such as dimethylamino pyridine (DMAP), and acetyl chloride in an an aprotic solvent DCM at about ambient temperature, as shown in step a.
  • a base such as a triethylamine
  • a catalyst such as dimethylamino pyridine (DMAP)
  • acetyl chloride in an an aprotic solvent DCM at about ambient temperature
  • Compounds of Formula 15.0, wherein Ri is as orginally defined can be prepared from compounds of Formula 14.2, wherein Ri is as orginally defined and R 2 is methyl acetate, by treatment with a base, such as potassium carbonate, and bromomethyl acetate in a solvent such as acetone at about ambient temperature, as shown in step a.
  • a base such as potassium carbonate
  • bromomethyl acetate in a solvent such as acetone at about ambient temperature
  • Example 1 Preparation of (S)-ethyl 2-((triisopropylsilyl)oxy)propanoate.
  • the reaction mixture was poured into a separatory funnel and washed with H 2 0 (100 mL), saturated aqueous NaHC0 3 (100 mL), brine (100 mL), 1M HCl (100 mL), then brine (100 mL).
  • the organic layer was passed through a phase separator and concentrated to afford a clear, colorless oil.
  • Example 2 Preparation of (S)-2-((triisopropylsilyl)oxy)propanal.
  • Example 3 Preparation of (2S,3 ?)-2-((triisopropylsilyl)oxy)hex-5-en-3-ol.
  • Example 5 Preparation of (3 ?,4S)-3-(benzyloxy)-4-((triisopropylsilyl)oxy)pentan-l- ol.
  • Example 6 Preparation of (3 ?,4S)-3-(benzyloxy)pentane-l,4-diol.
  • Example 7 Preparation of (S)-methyl 3-(((3tf ,4S)-3-(benzyloxy)-4- hydroxypentyl)oxy)-2-((tert-butoxycarbonyl)amino)propanoate.
  • Example 8 Step 1 : Preparation of (5 -3-(((3R,45)-3-(benzyloxy)-4- hydroxypentyl)oxy)-2-((tert-butoxycarbonyl)amino)propanoic acid.
  • Example 8 Preparation of tert-butyl ((3S,8tf ,9S)-8-(benzyloxy)-9-methyl-2- oxo- 1 ,5-dioxonan-3-yl)carbamate.
  • Example 9 Preparation of tert-butyl ((3S,8tf ,9S)-8-hydroxy-9-methyl-2-oxo- 1 ,5- dioxonan-3-yl)carbamate.
  • Example 10A Preparation of tert-butyl ((3S,8tf ,9S)-8-methoxy-9-methyl-2- dioxonan-3-yl)carbamate.
  • Example 10B Preparation of (3S,6S,7 ?)-3-((tert-butoxycarbonyl)amino)-6-methyl-4- oxo- 1 ,5-dioxonan-7-yl isobutyrate.
  • tert-butyl ((3S,8tf ,9S)-8-hydroxy-9-methyl-2-oxo- 1 ,5-dioxonan-3- yl)carbamate (200.4 mg, 0.693 mmol) was dissolved in DCM (3.46 mL) and cooled to 0 °C in an ice bath. Triethylamine (434 ⁇ , 3.12 mmol) and DMAP (16.92 mg, 0.139 mmol) were added, followed by isobutyryl chloride (109 ⁇ , 1.039 mmol) via syringe over 30 sec. The reaction was then allowed to warm to rt and stirred for 4 h.
  • tert-butyl ((3S,8tf ,9S)-8-hydroxy-9-methyl-2-oxo- 1 ,5-dioxonan-3- yl)carbamate (201.0 mg, 0.695 mmol) was dissolved in DCM (3.47 mL). Pyridine (169 ⁇ , 2.084 mmol) was added, followed by cyclopentanecarbonyl chloride (127 ⁇ , 1.042 mmol) via syringe over 30 sec. The reaction was then stirred at rt for 4 h. After 4 h, TLC indicated consumption of starting material. The reaction was quenched with saturated aqueous NH 4 C1 (6 mL).
  • Example 10D Preparation of tert-butyl ((3S,8tf ,9S)-9-methyl-2-oxo-8-phenoxy- 1 ,5- dioxonan-3-yl)carbamate.
  • Example 10E, Step 1 Preparation of tert-butyl ((3S,8tf ,9S)-9-methyl-2-oxo-8-(((E)- 4,4,4-trifluorobut-2-en- 1 -yl)oxy)- 1 ,5-dioxonan-3-yl)carbamate.
  • the reaction mixture was heated to 60 °C and dropwise (E)-tert-butyl (4,4,4-trifluorobut-2-en-l-yl) carbonate (303 mg, 1.339 mmol) was then added via syringe. The reaction was allowed to stir at 60 °C for 30 min. After 30 min, TLC/UPLC indicated -50% consumption of starting material, and an additional aliquot (£)- tert-butyl (4,4,4-trifluorobut-2-en-l-yl) carbonate (303 mg, 1.339 mmol) was added, and the reaction was stirred for an additional 30 minutes. The reaction was cooled to rt and concentrated to afford an orange colored oil.
  • Example 10E, Step 2 Preparation of tert-butyl ((3S,8tf ,9S)-9-methyl-2-oxo-8-(4,4,4- trifluorobutoxy)- 1 ,5-dioxonan-3-yl)carbamate.
  • Example 10F, Step 1 Preparation of tert-butyl ((3S,8tf ,9S)-9-methyl-2-oxo-8-(((E)-3- oxobut- 1 -en- l-yl)oxy)- 1 ,5-dioxonan-3-yl)carbamate.
  • Example 10F, Step 2 Preparation of tert-butyl ((3S,8tf ,9S)-9-methyl-2-oxo-8-(3- oxobutoxy)- 1 ,5-dioxonan-3-yl)carbamate.
  • Example 10F, Step 3 Preparation of tort-butyl ((35,8R,95 -8-(3 ,3-difluorobutoxy)- 9-methyl-2-oxo- 1 ,5-dioxonan-3-yl)carbamate.
  • Example 11A, Step 1 Preparation of (3S,8tf ,9S)-9-methyl-2-oxo-8-phenoxy- 1 ,5- dioxonan-3-aminium chloride.
  • Example 11A, Step 2 Preparation of 3-hydroxy-4-methoxy-N-((3S,8tf ,9S)-9- methyl-2-oxo-8-phenoxy- 1 ,5-dioxonan-3-yl)picolinamide.
  • Example 11B, Step 1 Preparation of (3S,8tf ,9S)-3-airrino-9-methyl-8-(((E)-4,4,4- trifluorobut-2-en- l-yl)oxy)- 1 ,5-dioxonan-2-one.
  • tert-butyl ((3S,8 ?,9S)-9-methyl-2-oxo-8-(((E)-4,4,4-trifluorobut-2- en-l-yl)oxy)-l,5-dioxonan-3-yl)carbamate (142.0 mg, 0.357 mmol) was dissolved in DCM (1.6 mL) and cooled to 0 °C in an ice/water bath. After 5 min, trifluoroacetic acid (400 ⁇ , 5.19 mmol) was added dropwise via syringe over 30 sec. The resulting orange reaction was brought to rt via removal of the ice water bath and allowed to stir at rt for 2 h. After 2 h, TLC indicated
  • Example 11B, Step 2 Preparation of 3-hydroxy-4-methoxy-N-((3S,8tf ⁇ S ⁇ - methyl ⁇ -oxo-S- ⁇ E ⁇ -trifluorobut ⁇ -en-l-y ⁇ oxy ⁇
  • Example 12A Preparation of (3S,6S,7 ?)-3-(3-acetoxy-4-methoxypicolinamido)-6- methyl-4-oxo- 1 ,5-dioxonan-7-yl isobutyrate.
  • Example 12B Preparation of (3S,6S,7tf )-3-(3-(acetoxymethoxy)-4- methoxypicolinamido)-6-methyl-4-oxo- 1 ,5-dioxonan-7-yl isobutyrate.
  • Example A Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Mycosphaerella graminicola; Anamorph: Zymoseptoria tritici; Bayer code SEPTTR):
  • Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Septoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. When disease symptoms were fully expressed on the 1 st leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.
  • Example B Evaluation of Fungicidal Activity: Wheat Brown Rust ⁇ Puccinia triticina; Synonym: Puccinia reconditaf. sp. tritici; Bayer code PUCCRT):
  • Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22 °C with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24 °C for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des picolinamides macrocycliques de formule (I) et leur utilisation en tant que fongicides.
PCT/US2016/068223 2015-12-30 2016-12-22 Picolinamides macrocycliques à utiliser en tant que fongicides WO2017116954A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562273401P 2015-12-30 2015-12-30
US62/273,401 2015-12-30

Publications (1)

Publication Number Publication Date
WO2017116954A1 true WO2017116954A1 (fr) 2017-07-06

Family

ID=59225955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/068223 WO2017116954A1 (fr) 2015-12-30 2016-12-22 Picolinamides macrocycliques à utiliser en tant que fongicides

Country Status (1)

Country Link
WO (1) WO2017116954A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030022903A1 (en) * 1999-07-20 2003-01-30 Ricks Michael J. Fungicidal heterocyclic aromatic amides and their compositions, methods of use and preparation
US20130296371A1 (en) * 2012-05-07 2013-11-07 Dow Agrosciences Llc Macrocyclic picolinamides as fungicides
US20150094339A1 (en) * 2013-10-01 2015-04-02 Dow Agrosciences Llc Macrocyclic picolinamide compounds with fungicidal activity

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030022903A1 (en) * 1999-07-20 2003-01-30 Ricks Michael J. Fungicidal heterocyclic aromatic amides and their compositions, methods of use and preparation
US20130296371A1 (en) * 2012-05-07 2013-11-07 Dow Agrosciences Llc Macrocyclic picolinamides as fungicides
US20150094339A1 (en) * 2013-10-01 2015-04-02 Dow Agrosciences Llc Macrocyclic picolinamide compounds with fungicidal activity

Similar Documents

Publication Publication Date Title
EP3240773B9 (fr) Composés picolinamide à activité fongicide
EP3240419B1 (fr) Composés de picolinamide présentant une activité fongicide
EP3240413B1 (fr) Composés de picolinamide présentant une activité fongicide
US9549555B2 (en) Macrocyclic picolinamide compounds with fungicidal activity
US9549556B2 (en) Macrocyclic picolinamides as fungicides
US9686984B2 (en) Macrocyclic picolinamides as fungicides
EP3761790A1 (fr) Picolinamides en tant que fongicides
US20170183324A1 (en) Macrocyclic picolinamides compounds with fungicidal activity
WO2016109300A1 (fr) Picolinamides présentant une activité fongicide
WO2017116939A1 (fr) Picolinamides macrocycliques à utiliser en tant que fongicides
WO2017116954A1 (fr) Picolinamides macrocycliques à utiliser en tant que fongicides
WO2017116956A1 (fr) Picolinamides macrocycliques à utiliser en tant que fongicides
WO2016069370A1 (fr) Picolinamides macrocycliques à utiliser en tant que fongicides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16882413

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16882413

Country of ref document: EP

Kind code of ref document: A1