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WO2017116949A1 - Picolinamides macrocycliques à utiliser en tant que fongicides - Google Patents

Picolinamides macrocycliques à utiliser en tant que fongicides Download PDF

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Publication number
WO2017116949A1
WO2017116949A1 PCT/US2016/068215 US2016068215W WO2017116949A1 WO 2017116949 A1 WO2017116949 A1 WO 2017116949A1 US 2016068215 W US2016068215 W US 2016068215W WO 2017116949 A1 WO2017116949 A1 WO 2017116949A1
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Prior art keywords
compounds
nmr
methyl
mhz
formula
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PCT/US2016/068215
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English (en)
Inventor
Yu Lu
Kevin G. Meyer
Chenglin Yao
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Dow Agrosciences Llc
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Publication of WO2017116949A1 publication Critical patent/WO2017116949A1/fr

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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
    • 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
    • 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
    • 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
    • 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 resent 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 independently selected from the group consisting of alkyl, alkenyl, aryl, cycloalkyl, heterocycle, and C(0)Rs, each optionally substituted with 0, 1 or multiple
  • R 2 is alkyl or alkoxy, each optionally substituted with 0, 1, or multiple R5;
  • R3 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, alkoxy, aryl, arylalkoxy, cycloalkyl, halo, haloalkyl, or haloalkoxy;
  • R 6 is alkyl or alkoxy, each optionally substituted with 0, 1, or multiple R7;
  • R7 is hydrogen, alkyl, aryl, halo, acyloxy, alkenyl, alkoxy, heteroaryl, heterocycle, or thioalkyl, each optionally substituted withO, 1, or multiple R 8;
  • R 8 is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, aryl, or halo.
  • 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 and Ar refer to any aromatic ring, 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.
  • acyloxy refers to an -OC(0)R 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.
  • thioalkyl refers to an -SR substituent.
  • 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.
  • the formulations may additionally contain adjuvant surfactants to enhance deposition, wetting, and penetration of the compounds onto the target crop and organism. These 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, benzovindiflupyr benzylaminobenzene- sulfonate (BABS) salt, bicarbonates, biphenyl,
  • BABS benzylaminobenzene- sulfonate
  • pyrametostrobin pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxid
  • 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
  • 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; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beilubutamid, benazolin, be
  • 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; anamorph: Zymoseptoria 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 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. The exact 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.
  • a Grignard reagent such as RiMgX, where Ri is as originally defined and X is a halide, for example bromide or chloride, and copper (I) iodide (Cul) in a polar, aprotic solvent such as THF at cryogenic temperatures of about -78 °C, as shown in step a.
  • Compounds of Formula 1.2, where Ri is as originally defined can be obtained from compounds of Formula 1.1, where Ri is as originally defined, by treatment with a reducing agent such as LAH in a polar, aprotic solvent such as THF, at a reduced temperature of about 0 °C as depicted in step b.
  • Compounds of Formula 1.4, where Ri is as originally defined and R 2 is as originally defined, for example ie/t-butoxy or benzyloxy, can be obtained from compounds of Formula 1.2 by treating with a protected aziridine of Formula 1.3, wherein R 2 is as originally defined, for example (S)-l-ieri-butyl 2-methyl aziridine- 1,2- dicarboxylate or (S)-l -benzyl 2-methyl aziridine- 1,2-dicarboxylate, followed by treatment with a Lewis acid such as BF 3 Et2 in a halogenated solvent such as CH 2 C1 2 at reduced temperatures from about 0 °C to ambient temperature, as is depicted in step c.
  • a Lewis acid such as BF 3 Et2
  • a halogenated solvent such as CH 2 C1 2
  • Compounds of Formula 2.1, wherein Ri and R 2 are as originally defined can be prepared according to the methods outlined in Scheme 2, steps a - b.
  • Compounds of Formula 2.0, wherein Ri and R 2 are as originally defined can be prepared from compounds of Formula 1.4, by treating with a hydroxide base, such as lithium hydroxide (LiOH), in an aqueous solvent system, such as THF/water, at about 22 °C, as depicted in step a.
  • a hydroxide base such as lithium hydroxide (LiOH)
  • an aqueous solvent system such as THF/water
  • Compounds of formula 2.1, wherein Ri and R 2 are as originally defined, can be prepared by adding a solution of the compound of Formula 2.0 in a halogenated solvent such as CH 2 C1 2 or an aromatic solvent such as PhCH 3 to a mixture of a base, such as DMAP, and a mixed anhydride, such as 2-methyl-6-nitrobenzoic anhydride (MNBA), in either a halogenated solvent such as CH 2 C1 2 or an aromatic solvent such as PhCH 3 at a temperature between about 21 °C and about 60 °C over a period of 4 - 12 hours (h), as shown in step b.
  • a halogenated solvent such as CH 2 C1 2 or an aromatic solvent such as PhCH 3
  • a mixture of a base such as DMAP
  • MNBA 2-methyl-6-nitrobenzoic anhydride
  • Compounds of of Formula 3.2, wherein Ri is as originally defined can be prepared through the methods shown in Scheme 3, steps a - c.
  • Compounds of Formula 3.0, wherein Ri is as orginally defined can be obtained from compounds of Formula 2.1, wherein Ri is as orginally defined and R 2 is ie/t-butoxy, by treating with an acid, such as a solution of 4.0 Molar (M) hydrogen chloride (HC1) in dioxane, in an an aprotic solvent like CH 2 C1 2 at about 22 °C, as shown in step a.
  • an acid such as a solution of 4.0 Molar (M) hydrogen chloride (HC1) in dioxane
  • HC1 an aprotic solvent like CH 2 C1 2 at about 22 °C
  • Compounds of Formula 3.1, wherein Ri is as orginally defined can be prepared from compounds of Formula 2.1, wherein Ri is as orginally defined and R 2 is benzyloxy, by treating with H 2 in the presence of a palladium catalyst, for example palladium on carbon (Pd/C, 5 or 10 weight %), in a polar solvent like ethyl acetate (EtOAc) at about 22 °C, as shown in step b.
  • a palladium catalyst for example palladium on carbon (Pd/C, 5 or 10 weight %)
  • EtOAc ethyl acetate
  • Compounds of Formula 3.2, wherein Ri is as originally defined can be prepared from compounds of Formula 3.0 or Fomula 3.1, by treating with 3-hydroxy-4-methoxypicolinic acid in the presence of a base, such as N ⁇ V-diisopropylethylamine (DIPEA), and a peptide coupling reagent, such as benzotriazol-l-yl- oxytripyrrolidino-phosphonium hexafluorophosphate (PyBOP), in an aprotic solvent such as CH 2 C1 2 , as shown in step c.
  • DIPEA N ⁇ V-diisopropylethylamine
  • PyBOP a peptide coupling reagent
  • an aprotic solvent such as CH 2 C1 2
  • Compounds of of Formula 4.0, where Ri and R 3 are as originally defined can be prepared by the method shown in Scheme 4.
  • Compounds of Formula 4.0, where Ri and R 3 are as originally defined can be prepared from compounds of Formula 3.2, where Ri is as originally defined, by treatment with the appropriate alkyl halide with or without a reagent such as sodium iodide (Nal) and an alkali carbonate base such as sodium carbonate (Na2C0 3 ) or potassium carbonate (K2C0 3 ) in a solvent such as acetone, or by treatment with an acyl halide in the presence of an amine base, such as pyridine, Et 3 N, DMAP, or mixtures thereof in an aprotic solvent such as DCM, as shown in step a.
  • Example 1 Preparation of (S)-methyl -3-(((3R,45 -3-benzyl-4- hydroxypentyl)oxy)-2-(((benzyloxy)carbonyl)amino)propanoate:
  • Example 2 Step 1 : Preparation of (S)-3-(((3tf ,4S)-3-benzyl-4-hydroxypentyl)oxy)-2- (((benzyloxy)carbonyl)amino)propanoic acid:
  • Example 2 Preparation of benzyl ((3S, 8tf ,9S)-8-benzyl-9-methyl-2-oxo- 1 ,5- dioxonan-3-yl)carbamate:
  • Example 3 Preparation of (3S, 8tf ,9S)-8-ethyl-9-methyl-2-oxo- 1 ,5-dioxonan- 3-aminium chloride:
  • Example 3 Preparation of (3S, 8 ?,9S)-8-ethyl-9-methyl-2-oxo-l,5-dioxonan- 3-aminium chloride:
  • Example 3 Preparation of N-((3S, 8R.95 - 8-benzyl-9-methyl-2-oxo-l,5- dioxonan-3-yl)-3-hydroxy-4-methoxypicolinamide:
  • Example 4 Preparation of ((2-(((3S, 8tf ,9S)-8-benzyl-9-methyl-2-oxo- 1 ,5-dioxonan- 3-yl)carbamoyl)-4-methoxypyridin-3-yl)oxy)methyl acetate:
  • Example 5 Preparation of 2-(((3S, 8tf ,9S)-8-benzyl-9-methyl-2-oxo- 1 ,5-dioxonan-3- yl)carbamoyl)-4-methoxypyridin-3-yl) acetate:
  • 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.
  • Example C Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer code PHAKPA):
  • Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22 °C and 100 % relative humidity then transferred to a growth room at 23 °C for disease to develop. Disease severity was assessed on the sprayed leaves.

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Abstract

La présente invention concerne des picolinamides macrocycliques de formule (I) et leur utilisation en tant que fongicides.
PCT/US2016/068215 2015-12-30 2016-12-22 Picolinamides macrocycliques à utiliser en tant que fongicides WO2017116949A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10588318B2 (en) 2014-12-30 2020-03-17 Dow Agrosciences Llc Picolinamide compounds with fungicidal activity

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2012070015A1 (fr) * 2010-11-24 2012-05-31 Stemergie Biotechnology Sa Inhibiteurs de l'activité du complexe iii de la chaîne mitochondriale de transfert des électrons et utilisation de ceux-ci pour traiter des maladies
US20130296374A1 (en) * 2012-05-07 2013-11-07 Dow Agrosciences Llc Use of pro-fungicides of uk-2a for control of black sigatoka
US20150181868A1 (en) * 2013-12-26 2015-07-02 Dow Agrosciences Llc Use of macrocyclic picolinamides as fungicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012070015A1 (fr) * 2010-11-24 2012-05-31 Stemergie Biotechnology Sa Inhibiteurs de l'activité du complexe iii de la chaîne mitochondriale de transfert des électrons et utilisation de ceux-ci pour traiter des maladies
US20140051678A1 (en) * 2010-11-24 2014-02-20 Stemergie Biotechnology Sa Inhibitors of the activity of complex iii of the mitochondrial electron transport chain and use thereof for treating diseases
US20130296374A1 (en) * 2012-05-07 2013-11-07 Dow Agrosciences Llc Use of pro-fungicides of uk-2a for control of black sigatoka
US20150181868A1 (en) * 2013-12-26 2015-07-02 Dow Agrosciences Llc Use of macrocyclic picolinamides as fungicides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10588318B2 (en) 2014-12-30 2020-03-17 Dow Agrosciences Llc Picolinamide compounds with fungicidal activity
US10595531B2 (en) 2014-12-30 2020-03-24 Dow Agrosciences Llc Use of picolinamide compounds as fungicides
US11751568B2 (en) 2014-12-30 2023-09-12 Corteva Agriscience Llc Picolinamide compounds with fungicidal activity
US12114660B2 (en) 2014-12-30 2024-10-15 Corteva Agriscience Llc Picolinamide compounds with fungicidal activity

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