WO1998027080A1 - Chromones utiles en tant que fongicides - Google Patents

Chromones utiles en tant que fongicides Download PDF

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Publication number
WO1998027080A1
WO1998027080A1 PCT/GB1997/003368 GB9703368W WO9827080A1 WO 1998027080 A1 WO1998027080 A1 WO 1998027080A1 GB 9703368 W GB9703368 W GB 9703368W WO 9827080 A1 WO9827080 A1 WO 9827080A1
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Prior art keywords
mixture
optionally substituted
compound
same
different
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PCT/GB1997/003368
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English (en)
Inventor
Jacqueline Anne Macritchie
Mary Josephine O'mahony
Stephen David Lindell
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Agrevo Uk Limited
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Priority claimed from GBGB9626322.3A external-priority patent/GB9626322D0/en
Priority claimed from GBGB9707270.6A external-priority patent/GB9707270D0/en
Priority claimed from GBGB9707272.2A external-priority patent/GB9707272D0/en
Priority claimed from GBGB9707271.4A external-priority patent/GB9707271D0/en
Application filed by Agrevo Uk Limited filed Critical Agrevo Uk Limited
Priority to AU77382/98A priority Critical patent/AU7738298A/en
Publication of WO1998027080A1 publication Critical patent/WO1998027080A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • 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
    • A01N43/04—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 one hetero atom
    • A01N43/14—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 one 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
    • A01N43/34—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
    • A01N43/42—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 condensed with carbocyclic 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
    • C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans

Definitions

  • This invention relates to chromones useful as fungicides.
  • the invention provides the use as fungicides of compounds of formula
  • Z is O, S(O) n or NR, and a) P is WR 2 ; and Q is R 1 or W 2 R 2a or b) P is R a and Q is R ; and when Z is S(O) n or NR, and Q is W 2 R 2a ; P can be R 1 ;
  • W and W 2 which may be the same or different, are O, S(O) n , N(R 3 ), N(R 3 )N(R 4 ),
  • R 1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl or heterocyclyl group;
  • R, R 2 , R 2a , R 2b , R 3 and R 4 which may be the same or different, have the same meaning as R 1 , or are acyl, or any two adjacent R groups together with the atoms to which they are attached form an optionally substituted ring which may contain other hetero atoms;
  • R a and R* 5 which may be the same or different, have the same meaning as Ri
  • heterocyclyl groups being carbon linked or are cyano, nitro, COOR ' ' or
  • each X which may be the same as or different from any other X, is halogen, CN, O2, SF5, B(OH)2, trialkylsilyl or a group E, OE or SE where E is a group as defined hereinbefore for R a or is optionally substituted amino; or two adjacent groups X together with the atoms to which they are attached form an optionally substituted carbocyclic or heterocyclic ring; n is 0, 1 or 2; and p is 0 to 4. with the proviso that P and Q are not both hydrogen.
  • Any alkyl group present in the molecule is preferably of 1 to 10 carbon atoms, especially of 1 to 7 carbon atoms, and particularly of 1 to 5 carbon atoms, and may be straight or branched.
  • Any alkenyl or alkynyl group present in the molecule may be straight or branched, and is preferably of 2 to 7 carbon atoms, for example allyl, vinyl or propargyl.
  • Any cycloalkyl, cycloalkenyl or cycloalkynyl group present in the molecule is preferably of 3 to 7 carbon atoms, especially cyclopropyl, cyclopentyl, or cyclohexyl.
  • heterocyclyl includes both heteroaryl groups as described below and non- aromatic heterocyclyl groups.
  • Heteroaryl groups are generally 5- or 6-membered rings containing up to 4 hetero atoms selected from nitrogen, oxygen and sulfur, optionally fused to a benzene ring.
  • heteroaryl groups are those derived from thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1 ,3,4-oxadiazole, 1,3,4- thiadiazole, 1 ,2,4-oxadiazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, 1 ,2,3-triazole, tetrazole, benzo[b]thiophene, benzo[b]furan, indole, benzo[c]thiophene, benzo[c]furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzis
  • Non-aromatic heterocyclyl groups are generally 3, 5, 6 or 7-membered rings containing up to 3 hetero atoms from nitrogen, oxygen and sulfur, for example oxiranyl, thiiranyl, thiazolinyl, dioxolanyl, 1 ,3-benzoxazinyl, 1 ,3-benzothiazinyl, morpholino, pyrazoiinyl, sulfolanyl, dihydroquinazolinyl, piperidinyl, phthalimido, tetrahydrofuranyl, tetrahydropyranyl, pyrrolidinyl, indolinyl, 2-oxopyrrolidino, 2-oxobenzoxazolin-3-yl or tetrahydroazepinyl.
  • Substituents when present on any phenyl or heterocyclyl group may for example be halogen, CN, NO2, SF5, B(OH)2, trialkylsilyl, acyl, O-acyl or a group E, OE or S(O) n E, where E is as defined hereinbefore for R 3 or is acyl or optionally substituted amino; or two adjacent groups on the ring together with the atoms to which they are attached form a carbocyclic or heterocyclic ring, which may be similarly substituted.
  • acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids.
  • Examples of acyl groups are thus -COR 5 , -COOR 5 , -CLNR R6, -CON(R 5 )OR 6 , -COONR 5 R 6 , -CON(R 5 )NR 6 R 7 , -COSR 5 , -CSSR 5 , -S(O) q R 5 ,
  • R 5 , R 6 and R 7 which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted phenyl or optionally substituted heterocyclyl, or R 5 and R 6 , or R 6 and R 7 , together with the atom(s) to which they are attached can form a ring, q is 1 or 2 and L is O or S.
  • Amino groups may be substituted for example by one or two optionally substituted alkyl or acyl groups, or two substituents can form a ring, preferably a 5- to 7- membered ring, which may be substituted and may contain other hetero atoms, for example morpholine.
  • the invention also includes the compounds falling within formula I disclosed in the Examples.
  • the compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe graminis), vine powdery mildew (Uncinula necato ⁇ , vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides), rice sheath blight (Pelliculana sasakii), grey mould (Botrytis cinerea), damping off (Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab (Venturia inaequalis), glume blotch (Leptosphaeria nodorum).
  • Other fungi against which the compounds may be active include other powdery mildews, other rusts, and
  • the invention thus also provides a method of combating fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.
  • the invention also provides an agricultural composition
  • an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
  • composition of the invention may of course include more than one compound of the invention.
  • composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties.
  • additional active ingredients for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties.
  • the compound of the invention can be used in sequence with the other active ingredient.
  • the diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.
  • Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, e.g.
  • anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an
  • butyl-naphthalene sulfonate salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate.
  • amide sulfonates e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate.
  • Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols, such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, or ethoxylated acetylenic glycols.
  • a cationic surface-active agent examples include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
  • compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
  • An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
  • a dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
  • a granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.
  • Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
  • Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.
  • the concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1.0 per cent by weight, especially 0.0001 to 0.01 per cent by weight.
  • the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
  • the compound is generally applied to seeds, plants or their habitat.
  • the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds.
  • the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds.
  • a suitable application rate is within the range of from 5 to 1000 g per hectare, more preferably from 10 to 500 g per hectare.
  • the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure.
  • the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged.
  • the spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary.
  • a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
  • novel compounds of the invention can be prepared in various ways in known manner. Typical methods are shown in the following reaction schemes.
  • Y leaving group, e.g. halogen or tosyl.
  • R and X groups may be modified in known manner to give other desired values for these groups.
  • Pentanoyl chloride (19.4 ml) was added dropwise to 4-chlorophenol (20 g) in pyridine (100 ml) at 0°C The reaction mixture was stirred at room temperature for 1 hour. The mixture was evaporated under reduced pressure, the residue extracted with diethyl ether and the extract washed with water, dilute hydrochloric acid, aqueous sodium hydrogen carbonate, dried and evaporated to give 4-chlorophenyl pentanoate.
  • Aluminium trichloride (30.08 g) was added portionwise with stirring to this product (16.5 g) and the reaction mixture was heated at 165°C for 1 hour. The mixture was cooled and quenched with ice/hydrochloric acid (1N), extracted with diethyl ether and the extract washed with brine, dried over magnesium sulfate, filtered and evaporated to give 1-(5-chloro-2-hydroxyphenyl)-1-pentanone, as an oil.
  • Ethyl cyanoacetate (1.2 ml) was added to a stirred suspension of sodium hydride (0.44 g; 60% in oil) in dried tetrahydrofuran (100 ml). The mixture was stirred for 30 minutes and then the previous product (1 g) in dry tetrahydrofuran (25 ml) was added. The mixture was heated under reflux for 2 hours and then cooled and evaporated under reduced pressure. The residue was dissolved in water and acidified with acetic acid. The mixture was extracted with diethyl ether and the extract washed with water, dried over magnesium sulfate and evaporated under reduced pressure.
  • Butyl lithium (3.6 ml; 2.5M in hexane) was added to a suspension of copper bromide dimethyl sulfide (0.92 g) in dry diethyl ether at -20°C and the mixture cooled to -40°C.
  • a solution of the previous reaction product (0.97 g) in dry diethyl ether (50 ml) was the added dropwise to this solution.
  • the mixture was stirred at this temperature for 30 minutes and the quenched with aqueous saturated ammonium chloride.
  • the mixture was allowed to warm to room temperature, filtered and the filtrate washed with brine, dried and evaporated.
  • Example 6 Sodium hydride (0.53 g of 60% solution in oil) was added portionwise over 2 hours to a solution of 2',4'-dichloropropiophenone (2.03 g) and carbon disulfide (1.3 ml) in dry dimethylformamide (12 ml) and dry toluene (40 ml) at 5°C. The mixture was stirred at room temperature for one hour. Excess sodium hydride was quenched with 2-propanol and the mixture heated at 110°C for 1 1 hours. It was cooled, added to water (30 ml) and acetic acid (0.5 ml) added. The mixture was extracted with diethyl ether and the extract washed with water. The combined aqueous phases were acidified with hydrochloric acid, and the precipitate filtered and dried to give crude 7-chloro-4-hydroxy-3-methyl-2H-1-benzothiopyran-2-thione.
  • Methyl iodide (0.31 ml) was added to a solution of this compound (1.1 g) and potassium carbonate (0.69 g) in dry acetone (10 ml). The mixture was stirred for a short time at room temperature and the solvent evaporated under reduced pressure. The residue was partitioned between water and ethyl acetate and the aqueous layer extracted with ethyl acetate. The combined ethyl acetate extracts were washed with water and brine and dried over magnesium sulfate and evaporated under reduced pressure. The residue was recrystallised from ethyl acetate to give 7-chloro-3-methyl- 2-methylthio-4H-1-benzothiopyran-4-one, m.p. 156-7°C (Compound 6)
  • 1,4-dibromobenzene (20 g) and anhydrous aluminium chloride (15.8 g) at a temperature of 80°C.
  • the mixture was heated at 110°C for 5 hours and then left to stand overnight.
  • the mixture was poured into ice water (100 ml) and extracted with ethyl acetate. The extracts were washed with water and dilute brine, dried over magnesium sulfate, and evaporated under reduced pressure to give crude 2',5'-dibromopentanophenone.
  • Example 10 In a similar manner to that described in Example 8, compound 9 was reacted with butanol to give 6-bromo-2-butoxy-3-propyl-4H-1-benzothiopyran-4-one, m.p. 78-80°C. (Compound 10)
  • Example 11 In a similar manner to Example 6, 2',4',-dichloropropiophenone was reacted with phenyl isothiocyanate followed by methyl iodide to give 7-chloro-3-methyl- 2-methylthio-1-phenyl-4-quinolone, m.p. 200-2 °C. (Compound 11).
  • Valeryl chloride (8.7 ml) was added, dropwise, to a solution of methyl 5-bromoanthranilate (13.6 g) and triethylamine (10.3 ml) in dry dichloromethane (100 ml) at room temperature over 10 minutes. The mixture was filtered and the filtrate washed with 1M hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine and dried and evaporated under reduced pressure. The residue was allowed to stand and a solid recrystallised from a mixture of diisopropyl ether and cyclohexane to give methyl 5-bromo-N-valerylanthranilate, m.p. 53.5-5°C.
  • Example 13 Triethylamine (2.82 g) was added to solution of 2-acetyl-4-bromophenol (5 g). The mixture was cooled to 0 °C and 4-chlorobenzoyl chloride (4.07 g). added. The mixture was left at room temperature overnight under a nitrogen atmosphere. The mixture was quenched with water and the organic layer washed with 2N hydrochloric acid, aqueous sodium hydrogen carbonate, 2N hydrochloric acid and dried over magnesium sulfate and evaporated under reduced pressure. The residue was triturated with light petroleum (b.p. 40-60 °C) to give 2-acetyl-4-bromophenyl 4- chlorobenzoate, as an off white solid.
  • Potassium hydroxide pellets (1.2 g) was added to a solution of this compound (5.g) in dry pyridine (50 ml) maintained at 50 °C, The mixture was stirred at this temperature until all the starting material was consumed (determined by tic). The mixture was cooled to room temperature and added to acetic acid (300 ml; 20%). the precipitate was filtered, washed with water, dried and dissolved in dichloromethane. The solution was dried over magnesium sulfate and evaporated under reduced pressure to give 1-(5-bromo-2-hydroxyphenyl)-3-(4-chlorophenyl)-3-hydroxyprop-2-en-1-one, as a pale yellow solid.
  • Butyllithium (2.5 molar in hexane; 2.4 ml), was added to tetrahydrofuran (50 ml) at -70-80°C, followed by diisopropylamine (0.84 ml). The mixture was stirred at this temperature for 30 minutes. The previous product compound (1 g) was added and the mixture stirred for 30 minutes at -70 °C. Trimethyl borate (0.34 mi) was added and the mixture stirred at -78°C for 35 minutes. The mixture was then treated with acetic acid (0.27 g) and hydrogen peroxide (0.84 ml of 30%). The mixture was then allowed to warm to room temperature and stirred overnight under nitrogen.
  • This solution (now comprising 6-bromo-2-methylsulfonyl-4H-1-benzopyran-4-one) was added to a solution of sodium methoxide (7.35 g) in methanol (130 ml) and the mixture stirred at room temperature for 1 hour and then evaporated under reduced pressure. Water (50 ml) was added and the mixture extracted with dichloromethane. The extract was dried and evaporated under reduced pressure, to give crude 6- bromo-2-methoxy-4/-/-1-benzopyran-4-one.
  • Compounds are assessed for activity against one or more of the following:
  • Botrytis cinerea grey mould
  • Leptosphaeria nodorum glume blotch
  • Venturia inaequalis apple scab Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. Plants or plant parts were then inoculated with appropriate test pathogens and kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified

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  • 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)
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  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Composés représentés par la formule I (I) dans laquelle Z représente O, S(O)n ou NR et (a) P représente WR2 et Q représente R?1 ou W2R2a¿ ou (b) P représente Ra et Q représente Rb et, quand Z représente S(O)¿n? ou NR, et Q représente W?2R2a¿, P peut représenter R1; W et W2,qui peuvent être semblables ou différents, représentent O, S(O)¿n?, N(R?3), N(R3)N(R4), N(R3¿)O ou ON(R3); R1 représente hydrogène ou un groupe éventuellement substitué alkyle, alkényle, alkynyle, cycloalkyle, cycloalkényle, cycloalkynyle, phényle ou hétérocyclyle; R, R?2, R2a, R2b, R3 et R4¿, qui peuvent être semblables ou différents, possèdent la même signification que R1, ou représentent acyle ou deux groupes dans tous groupes R contigus et, avec les atomes auxquels ils sont fixés, constituent un noyau éventuellement substitué pouvant éventuellement contenir d'autres hétéroatomes; Ra et Rb qui peuvent être semblables ou différents, possèdent la même signification que R1 (groupes hétérocyclyle à liaison carbone) ou représentent cyano, nitro, COOR?1 ou COR1¿, chaque X, qui peut être semblable ou différent de tout autre X, représente halogène, CN, NO¿2?, SF5, B(OH)2, trialkylsilyle ou un groupe E, OE ou SE dans lequel E représente un groupe comme défini ci-dessus pour R?a¿ ou représente amino éventuellement substitué; ou deux groupes X contigus, avec les atomes auxquels ils sont fixés, constituent un noyau carbocyclique ou hétérocyclique éventuellement substitué; n est 0, 1 ou 2 et p est 0 à 4. Ces composés sont utiles en tant que fongicides.
PCT/GB1997/003368 1996-12-19 1997-12-18 Chromones utiles en tant que fongicides WO1998027080A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU77382/98A AU7738298A (en) 1996-12-19 1997-12-18 Chromones useful as fungicides

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
GBGB9626322.3A GB9626322D0 (en) 1996-12-19 1996-12-19 Heterocyclic fungicides
GB9626322.3 1996-12-19
GBGB9707270.6A GB9707270D0 (en) 1997-04-10 1997-04-10 Heterocyclic fungicides
GB9707272.2 1997-04-10
GBGB9707272.2A GB9707272D0 (en) 1997-04-10 1997-04-10 Heterocyclic fungicides
GB9707271.4 1997-04-10
GBGB9707271.4A GB9707271D0 (en) 1997-04-10 1997-04-10 Heterocyclic fungicides
GB9707270.6 1997-04-10

Publications (1)

Publication Number Publication Date
WO1998027080A1 true WO1998027080A1 (fr) 1998-06-25

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PCT/GB1997/003368 WO1998027080A1 (fr) 1996-12-19 1997-12-18 Chromones utiles en tant que fongicides

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AU (1) AU7738298A (fr)
WO (1) WO1998027080A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001122868A (ja) * 1999-08-18 2001-05-08 Toyama Chem Co Ltd クロモン誘導体またはその塩ならびにそれらを含有する抗真菌剤
WO2003010145A1 (fr) * 2001-07-20 2003-02-06 Bayer Cropscience Ag 4-hydroxy-quinolones substituees par biphenyle et leur utilisation comme pesticides et herbicides
EP1416799A1 (fr) * 2001-07-23 2004-05-12 Ramot at Tel Aviv University Ltd. Methodes et compositions de traitement des infections fongiques
US6812225B2 (en) 2001-01-16 2004-11-02 Astrazeneca Ab Therapeutic heterocyclic compounds
US7026314B2 (en) 2001-01-16 2006-04-11 Astrazeneca Ab Therapeutic chromone compounds
KR100916161B1 (ko) * 2007-02-21 2009-09-08 (주)바이오버드 평활근 세포 증식 억제제
US7635778B2 (en) * 2004-12-17 2009-12-22 Sabic Innovative Plastics Ip B.V. Composition, method of authenticating, methods of making authenticatable compositions, authenticatable articles made there from
WO2010080864A1 (fr) 2009-01-12 2010-07-15 Array Biopharma Inc. Composés contenant de la pipéridine et leurs utilisations
CN102675200A (zh) * 2012-05-16 2012-09-19 中国药科大学 一类具有抗肿瘤活性的2-苯基-4-喹诺酮化合物、其制备方法及用途
CN107556296A (zh) * 2017-09-06 2018-01-09 南京工业大学 一种2－羟基－3－氮杂环色酮类化合物及其合成方法和在抗真菌药物中的应用
CN110294730A (zh) * 2019-07-15 2019-10-01 浙江大学 一种二氟甲基硫化黄酮类化合物及其制备方法
US10479797B2 (en) 2016-06-06 2019-11-19 Arena Pharmaceuticals, Inc. Modulators of the beta-3 adrenergic receptor useful for the treatment or prevention of disorders related thereto
CN114989123A (zh) * 2022-05-18 2022-09-02 长江大学 黄酮-3-羧酸类化合物、含有该化合物的杀菌组合物及用途

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2173999A1 (fr) * 1972-02-08 1973-10-12 Thiemann Chem Pharm Fab
FR2208680A1 (fr) * 1972-12-04 1974-06-28 Warner Lambert Co
US3850966A (en) * 1973-05-14 1974-11-26 Warner Lambert Co 2-methyl-3-methylsulfonyl chromones
US4117149A (en) * 1975-09-12 1978-09-26 Pfizer Inc. 4-oxo-4h-benzopyrans as animal growth promotants
EP0000377A1 (fr) * 1977-07-13 1979-01-24 Bayer Ag Procédé de préparation de dérivés de chromone, nouveaux dérivés de chromone et leur utilisation comme agents protecteurs de plantes
GB1544048A (en) * 1976-06-16 1979-04-11 Erba Carlo Spa Substituted 2-vinyl-chromones
GB1544049A (en) * 1977-06-08 1979-04-11 Erba Carlo Spa Substituted 2-vinyl-chromones
JPS57185279A (en) * 1981-05-11 1982-11-15 Mitsui Toatsu Chem Inc Preparation of thiochromone-3-carboxylic acids
EP0080419A2 (fr) * 1981-11-25 1983-06-01 Lipha, Lyonnaise Industrielle Pharmaceutique Haloalkyl-8-4H-(1)-benzopyran-4-ones, et procédés de préparation
EP0114899A1 (fr) * 1982-12-28 1984-08-08 Eisai Co., Ltd. Dérivés de 2-méthalchromone et procédé pour leur préparation
EP0233105A1 (fr) * 1986-01-17 1987-08-19 Institut Pasteur Compositions thérapeutiques à base de dérivés de 3-alkoxyflavones et nouveaux dérivés de 3-alkoxyflavones
US5175151A (en) * 1990-09-07 1992-12-29 Schering Corporation Antiviral compounds and antihypertensive compounds
WO1997013762A1 (fr) * 1995-10-13 1997-04-17 Agrevo Uk Limited Fongicides heterocycliques

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2173999A1 (fr) * 1972-02-08 1973-10-12 Thiemann Chem Pharm Fab
FR2208680A1 (fr) * 1972-12-04 1974-06-28 Warner Lambert Co
US3850966A (en) * 1973-05-14 1974-11-26 Warner Lambert Co 2-methyl-3-methylsulfonyl chromones
US4117149A (en) * 1975-09-12 1978-09-26 Pfizer Inc. 4-oxo-4h-benzopyrans as animal growth promotants
GB1544048A (en) * 1976-06-16 1979-04-11 Erba Carlo Spa Substituted 2-vinyl-chromones
GB1544049A (en) * 1977-06-08 1979-04-11 Erba Carlo Spa Substituted 2-vinyl-chromones
EP0000377A1 (fr) * 1977-07-13 1979-01-24 Bayer Ag Procédé de préparation de dérivés de chromone, nouveaux dérivés de chromone et leur utilisation comme agents protecteurs de plantes
JPS57185279A (en) * 1981-05-11 1982-11-15 Mitsui Toatsu Chem Inc Preparation of thiochromone-3-carboxylic acids
EP0080419A2 (fr) * 1981-11-25 1983-06-01 Lipha, Lyonnaise Industrielle Pharmaceutique Haloalkyl-8-4H-(1)-benzopyran-4-ones, et procédés de préparation
EP0114899A1 (fr) * 1982-12-28 1984-08-08 Eisai Co., Ltd. Dérivés de 2-méthalchromone et procédé pour leur préparation
EP0233105A1 (fr) * 1986-01-17 1987-08-19 Institut Pasteur Compositions thérapeutiques à base de dérivés de 3-alkoxyflavones et nouveaux dérivés de 3-alkoxyflavones
US5175151A (en) * 1990-09-07 1992-12-29 Schering Corporation Antiviral compounds and antihypertensive compounds
WO1997013762A1 (fr) * 1995-10-13 1997-04-17 Agrevo Uk Limited Fongicides heterocycliques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 98, no. 23, 1983, Columbus, Ohio, US; abstract no. 198024a, page 634; XP002059001 *
G.ELLIS: "CHROMENES,CHROMANONES AND CHROMONES.", THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS, 1977, NEW-YORK, pages 947, XP002059000 *

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JP4647757B2 (ja) * 1999-08-18 2011-03-09 富山化学工業株式会社 クロモン誘導体またはその塩ならびにそれらを含有する抗真菌剤
JP2001122868A (ja) * 1999-08-18 2001-05-08 Toyama Chem Co Ltd クロモン誘導体またはその塩ならびにそれらを含有する抗真菌剤
US6812225B2 (en) 2001-01-16 2004-11-02 Astrazeneca Ab Therapeutic heterocyclic compounds
US7026314B2 (en) 2001-01-16 2006-04-11 Astrazeneca Ab Therapeutic chromone compounds
US7045514B2 (en) 2001-01-16 2006-05-16 Astrazeneca Ab Therapeutic heterocyclic compounds
US7285662B2 (en) 2001-01-16 2007-10-23 Astrazeneca Ab Therapeutic heterocyclic compounds
WO2003010145A1 (fr) * 2001-07-20 2003-02-06 Bayer Cropscience Ag 4-hydroxy-quinolones substituees par biphenyle et leur utilisation comme pesticides et herbicides
EP1416799A1 (fr) * 2001-07-23 2004-05-12 Ramot at Tel Aviv University Ltd. Methodes et compositions de traitement des infections fongiques
EP1416799A4 (fr) * 2001-07-23 2004-11-10 Univ Ramot Methodes et compositions de traitement des infections fongiques
US8178702B2 (en) 2004-12-17 2012-05-15 Sabic Innovative Plastics Ip B.V. Composition, method of authenticating, methods of making authenticatable compositions, authenticatable articles made there from
US7635778B2 (en) * 2004-12-17 2009-12-22 Sabic Innovative Plastics Ip B.V. Composition, method of authenticating, methods of making authenticatable compositions, authenticatable articles made there from
KR100916161B1 (ko) * 2007-02-21 2009-09-08 (주)바이오버드 평활근 세포 증식 억제제
WO2010080864A1 (fr) 2009-01-12 2010-07-15 Array Biopharma Inc. Composés contenant de la pipéridine et leurs utilisations
US8809538B2 (en) 2009-01-12 2014-08-19 Array Biopharma Inc. Piperidine-containing compounds and use thereof
CN102675200A (zh) * 2012-05-16 2012-09-19 中国药科大学 一类具有抗肿瘤活性的2-苯基-4-喹诺酮化合物、其制备方法及用途
US11560386B2 (en) 2016-06-06 2023-01-24 Arena Pharmaceuticals, Inc. Modulators of the beta-3 adrenergic receptor useful for the treatment or prevention of disorders related thereto
US10927123B2 (en) 2016-06-06 2021-02-23 Arena Pharmaceuticals, Inc. Modulators of the beta-3 adrenergic receptor useful for the treatment or prevention of disorders related thereto
US10479797B2 (en) 2016-06-06 2019-11-19 Arena Pharmaceuticals, Inc. Modulators of the beta-3 adrenergic receptor useful for the treatment or prevention of disorders related thereto
US10662200B2 (en) 2016-06-06 2020-05-26 Arena Pharmaceuticals, Inc. Modulators of the beta-3 adrenergic receptor useful for the treatment or prevention of disorders related thereto
CN107556296B (zh) * 2017-09-06 2020-10-02 南京工业大学 一种2-羟基-3-氮杂环色酮类化合物及其合成方法和在抗真菌药物中的应用
CN107556296A (zh) * 2017-09-06 2018-01-09 南京工业大学 一种2－羟基－3－氮杂环色酮类化合物及其合成方法和在抗真菌药物中的应用
CN110294730A (zh) * 2019-07-15 2019-10-01 浙江大学 一种二氟甲基硫化黄酮类化合物及其制备方法
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