WO2002064566A1 - Composes d'oxime o-ether et fongicides a usage agricole et horticole - Google Patents

Composes d'oxime o-ether et fongicides a usage agricole et horticole Download PDF

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Publication number
WO2002064566A1
WO2002064566A1 PCT/JP2002/001195 JP0201195W WO02064566A1 WO 2002064566 A1 WO2002064566 A1 WO 2002064566A1 JP 0201195 W JP0201195 W JP 0201195W WO 02064566 A1 WO02064566 A1 WO 02064566A1
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group
methyl
alkoxy
added
alkyl
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PCT/JP2002/001195
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English (en)
Japanese (ja)
Inventor
Yuki Nakagawa
Hiroshi Sano
Akira Mitani
Hiroshi Hamamura
Hisashi Tanigawa
Daisuke Ichinari
Takahiro Ando
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Nippon Soda Co.,Ltd.
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Priority to JP2002564499A priority Critical patent/JPWO2002064566A1/ja
Publication of WO2002064566A1 publication Critical patent/WO2002064566A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen 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

Definitions

  • Oxime 0-ether compounds and fungicides for agricultural and horticultural use Oxime 0-ether compounds and fungicides for agricultural and horticultural use
  • the present invention relates to a novel oxime 0-ether compound and a fungicide for agricultural and horticultural use containing the compound as an active ingredient.
  • Japanese Patent Application Laid-Open No. Hei 9-13047 describes that an oxam 0-ether compound containing a compound represented by the following structural formula is useful as a bactericide.
  • An object of the present invention is to provide a novel oxime 0-ether compound which can be advantageously synthesized industrially, has a certain effect, and is an excellent agricultural and horticultural fungicide with little phytotoxicity.
  • the present inventors have found that by introducing a functional group (R 2 ) having an electron-withdrawing property into the pyridine ring in the following formula [I], the control effect on agricultural and horticultural crop diseases can be improved as compared with the known compounds. improved, moreover found that phytotoxicity is reduced, and completed the present invention c That is, the present invention relates to the formula (I)
  • R 1 represents a hydrogen atom, an alkyl group, C 3 - 6 cycloalkyl group, 6 alkoxy group, C i ⁇ s alkylthio group, amino group, mono- or di-C ⁇ 1-6 Al Kiruamino group, C i ⁇ s Ashiruokishi group, C 1 - 6 alkoxy C alkyl group, C ⁇ 1-6 haloalkyl group, a human Dorokishi group or a halogen atom.
  • n represents an integer of 1 to 3, and when m is 2 or more, R 1 may be the same or different.
  • R 2 is Shiano group, a nitro group, formyl group, C alkylcarbonyl group, N over human Dorokishii amino C ⁇ ⁇ alkyl, N-C 1 - 6 Arukokishii amino C 1 - 6 Al kill group, a carboxyl group, C i ⁇ 6 alkoxycarbonyl group, a force Rubamoiru group, mono or di-C iota ⁇ 6 alkyl force Rubamoiru groups, C alkylsulfonyl groups, C alkylsulfinyl groups, C 2 ⁇ 6 alkenyl groups, C 2 ⁇ 6 alkynyl group or an Application Benefits C i ⁇ 6 alkylsilyl C 2 ⁇ 6 alkynyl group.
  • R 2 may be the same or different.
  • R 3 represents a hydrogen atom, C alkyl or C 3 ⁇ 6 cycloalkyl group.
  • R 4 and R 5 are the same or different and each represent a hydrogen atom or a C i- 6 alkyl group.
  • R 6 is, C i ⁇ s alkyl group, C 3 ⁇ 6 cycloalkyl group, C 2 ⁇ 6 alkenyl group, C 2 ⁇ 6 alkynyl group, Ci ⁇ 6 alkoxy group, C 3 ⁇ 6 cycloalkoxy group, C i 1-6 haloalkoxy group, C 1 - 6 alkoxy C alkoxy group, Alkoxy C alkoxy C alkoxy group, C 1 ⁇ 6 alkylcarbonyl O alkoxy group, ⁇ La alkyl group, Ararukiruokishi group, Ararukiruokishi C alkoxy group, C i ⁇ 6 alkoxy C alkyl group, (6 haloalkyl group, C 1 ⁇ 6 al
  • R 1 is a hydrogen atom
  • C- 6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers,
  • Ci- 6 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, t-butoxy,
  • C ⁇ 6 alkylthio groups such as methylthio, ethylthio, isopropylthio, and butylthio,
  • Ci to 6 acyloxy groups such as acetoxy, propionyloxy, and vivaloyloxy;
  • C alkoxy C alkyl groups such as methoxymethyl, methoxethyl, ethoxymethyl, propoxymethyl, butoxymethyl,
  • n represents an integer of 1 to 4.
  • R 1 may be the same or different.
  • R 2 represents a cyano group, a nitro group, a formyl group
  • C- 6 alkylcarbonyl groups such as methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropyl
  • N-hydroxyimino C alkyl groups such as N-hydroxyiminomethyl and N-hydroxyiminoethyl
  • N-Ci- 6 alkoxyimino C alkyl groups such as N-methoxyminomethyl, N-ethoxyiminomethyl, N-methoxymino-1-ethyl and N-ethoxymino-1-propyl;
  • a mono- or di-C 6 alkyl alkyl group such as methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, and t-butylcarbamoyl;
  • R 2 may be the same or different.
  • R 2 is preferably at the 4- or 6-position of the pyridyl.
  • R 3 is a hydrogen atom
  • C 1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers, or
  • Cyclopropyl, cyclopentyl, 1-methylcyclopentyl, hexahexyl Le represents one over good c 3 ⁇ 6 cycloalkyl group which may have a substituent cyclohexyl and methyl cyclohexane.
  • R 4 and R 5 are the same or different and are each a hydrogen atom or
  • R 6 is a C ⁇ - 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers,
  • C may have a substituent such as cyclopropoxy, cyclopentoxy, 1-methylcyclopentoxy, cyclohexyloxy, 1-methylcycloxy, etc.
  • C to C such as chloromethoxy, fluoromethoxy, promomethoxy, dichloromethoxy, difluoromethoxy, dibromomethoxy, trichloromethoxy, trifluoromethoxy, tripromethoxy, trichloroethoxy, tolufluoroethoxy, pentafluoroethoxy, etc. 6 haloalkoxy group,
  • C ⁇ to 6 alkoxy C ⁇ to 6 alkoxy groups such as methoxy methoxy, methoxy ethoxy, ethoxy methoxy, propoxy methoxy, butoxy methoxy, etc.
  • C ⁇ -6 alkyl carbonyloxy groups such as acetoxy, propionyloxy, and bivaloyloxy; Benzyl, para-nitrobenzyl, Lachlorbenzil, paramethoxybenzyl,
  • C aralkyloxy groups such as benzyloxy, paranitrobenzyloxy, parachlorobenzyloxy, paramethoxybenzyloxy, 1-phenethyloxy, 2-phenethyloxy, lamethoxy1-2-phenethyloxy,
  • Aralkyloxy C alkoxy groups such as benzyloxy ethoxy, para-nitro benzyl oxy ethoxy, para chloro benzyl oxy ethoxy, 1-phenyl oxy ethoxy, 2-phenyl ethoxy ethoxy, etc.
  • C alkoxy C alkyl groups such as methoxymethyl, methoxethyl, ethoxymethyl, propoxymethyl, butoxymethyl,
  • haloalkylsulfonyloxy groups such as chloromethylsulfonyloxy, fluoromethylsulfonyloxy, trifluoromethylsulfonyloxy, cyano, nitro, amino,
  • Mechiruami Bruno Echiruamino, Puropiruamino, Jimechiruami Roh, Jechirua Mi Roh, Jipuropiruamino, Jibuchiruamino, mono Moshiku such E chill isopropyl ⁇ Mino di C Bok 6 Arukiruamino group,
  • C-alkylcarbonylamino groups such as acetylamino, bivaloylamino, C-alkylthio groups such as methylthio, ethylthio, isopropylthio, hydroxy group, or
  • n When n is 2 or more, it may be an alkylene chain containing a hetero atom such as a dioxysilane ring to form a 5- to 7-membered condensed ring.
  • n represents an integer of 15; when n is 2 or more, R 6 is the same but different Is also good.
  • R 7 is a hydrogen atom, C 1 - 6 alkyl groups, C 3 - 6 cycloalkyl group, ( ⁇ 6 Haroa alkyl groups, C ⁇ 1-6 alkoxy C 1 to 6 alkyl groups, C 1 - 6 alkoxy C i - 6 alkoxy ( ⁇ 1-6 alkyl group, Ararukiru group, Ararukiruokishi C alkyl group, C i - 6 alkylcarbonyl group, an oxygen functional group represented by represents.] to C alkylsulfonyl group or a C 1 - 6 Haroaruki Rusuruhoniru group OB Compounds in which 7 is substituted at the ortho position of the benzene ring are particularly effective as agricultural and horticultural fungicides.
  • the compounds of the present invention are useful in a wide variety of filamentous fungi such as oomycetes (Oomycetes), ascomycetes (Ascomycetes), imperfect fungi (Deuteromycetesno, Basidiomycetes (B) Asidi omycetes) has excellent bactericidal activity, and has particularly excellent bactericidal activity against gray mold compared to the known compounds.
  • composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur during the cultivation of agricultural and horticultural crops including flowers, turf, and grass by seed treatment, foliage application, soil application, or water application. be able to.
  • Lactassy Leaf spot My cosphaerellaarachidis
  • Black rot My cosphaerellaberkeleyi
  • Cucumber powdery mildew S phaerothecafu 1 iginea
  • Blight wilt My cosphaerel 1 ame 1 onis
  • Bacterial rot S clerotiniasclerotior um
  • Gray Scab (CI adosporiumcuc um erin um) Tomato Gray mold (Botrytiscinerea)
  • Leaf spot (Coch1 ioboluss ativus) Eye spot disease (Pseudoccercosporar1 1-aherrpotrichhorids)
  • Crimson snow rot (Micron ect rieel l lanivialis) Rice blast (Pyricculala riaoraryzae)
  • Bentgrass Snow rot Bacterial sclerotium (Scl erotinii) Orchardgrass Powdery mildew (Erysipipegr aminis) Soybean purpura (Cercosporakikkucii)
  • Potato Tomato Blight (Phytopthorainfinfestestans) Prunus Downy Mildew (Pseuudoperonons sporacacubens ⁇ sj Grape Downy Disease (Pla s mo p a ra av i t i c o a.
  • It can be used for pest control.
  • the compound of the present invention is a drug having an excellent bactericidal effect not only on pathogenic bacteria sensitive to such drugs but also on resistant bacteria.
  • gray mold fungus B0 trytiscinerea
  • sugar beet brown spot Cercospora "betico 1a”
  • apple scab Venturia ⁇ naequalis
  • pear scabs Venturianashico 1a
  • the compound of the present invention is also effective against gray mold fungi (Botryti csinerea) showing resistance to dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione) as well as susceptible bacteria.
  • gray mold fungi Botryti csinerea
  • dicarboximide fungicides for example, vinclozolin, procymidone, iprodione
  • the compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater objects such as ship bottoms and fish nets.
  • the compound of the present invention can be produced as follows.
  • the compound represented by the formula (I) is a compound represented by the formula (II) and the compound represented by the formula (III) in the presence of a deacidifying agent such as a base, without a solvent, preferably in a solvent, It can be obtained by stirring at a reaction temperature of 0 to 150 ° C. for 10 minutes to 24 hours.
  • Solvents that can be used in this reaction include ketones such as acetone and 2-butanone, ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, alcohols such as methanol and ethanol, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide and water. These solvents can be used as a mixed solvent of two or more kinds.
  • the base examples include inorganic bases such as sodium hydroxide, hydroxylated lime, carbonated lime, sodium carbonate, sodium hydride, etc., alkali metal alkoxides such as sodium methylate and sodium ethylate, pyridine, Organic bases such as triethylamine, DBU and the like.
  • the compound represented by the formula [II], which is a starting material of the compound of the present invention, can be synthesized, for example, in the same manner as in the method described in JP-A-9-13477. Manufacturing method 2)
  • the compound represented by the formula [I] can be prepared by reacting a compound represented by the formula [IV] with a compound represented by the formula [V] or a salt thereof without a solvent, preferably in a solvent, at a reaction temperature of 0 to 15: 0. It can be obtained by stirring with C for 10 minutes to 24 hours.
  • Solvents that can be used in this reaction include alcohols such as ethanol and methanol, ethers such as getyl ether, tetrahydrofuran, and dioxane; cellosolves such as methyl sorb and ethyl sorb; and aromatics such as benzene and toluene.
  • Examples include hydrocarbons, acetic acid, N, N-dimethylformamide, dimethylsulfoxide and water. These solvents can be used as a mixed solvent of two or more kinds.
  • This reaction does not necessarily require the presence of a catalyst, but the addition of an acid or base may significantly accelerate the reaction.
  • the acid include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid, and bases such as sodium acetate.
  • the compound represented by the formula [IV] can be obtained by oxidizing the corresponding alcohol with an oxidizing agent such as manganese dioxide.
  • an oxidizing agent such as manganese dioxide.
  • the synthesis of the compound represented by the formula [IV] is described in Examples. Manufacturing method 3)
  • M represents a metal atom such as sodium, potassium, cesium, copper, and zinc; and an organic metal atom group such as trialkylsilyl and trialkyltin.
  • the compound represented by the formula (I) is a compound represented by the formula (VI) and the compound represented by R 2 M without a solvent, preferably in a solvent, at a reaction temperature of 0 to 150 ° C. It can be obtained by stirring for 10 minutes to 24 hours. Further, the presence of a catalyst such as bistriphenylphosphine palladium (II) chloride allows the reaction to proceed efficiently.
  • a catalyst such as bistriphenylphosphine palladium (II) chloride allows the reaction to proceed efficiently.
  • Solvents that can be used in this reaction include ketones such as acetone and 2-butanone, ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, chlorinated solvents such as dichloromethane and chloroform, methanol, Examples include alcohols such as ethanol, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, and water. Further, these solvents can be used as a mixed solvent of two or more kinds. Manufacturing method 4)
  • the compound represented by the formula [I, in which the 4-position of the compound represented by the formula [I] is substituted by a cyano group can also be produced as follows.
  • RRR 3 , R 4 .R 5 , and Ar represent the same meaning as described above.
  • 0 represents an integer of 1 to 3, and when o is 2 or 3, R 1 may be the same or different. When o is 1, R 2 may be the same or different.
  • the compound represented by the formula [I-11] in which the 4-position is substituted by a cyano group can be obtained by converting the compound represented by the formula [ ⁇ 1] to an appropriate aminosulfone Amination of the pyridine ring at the 1-position with phonic acids, followed by acetylation and methylation, leads to the compound of the formula ( ⁇ ), and further in the absence of solvent in the presence of a cyanating agent such as cyanogen hydride.
  • a cyanating agent such as cyanogen hydride.
  • it can be obtained by stirring in a solvent at a reaction temperature of 0 to 150 ° C for 10 minutes to 24 hours.
  • Solvents that can be used in this reaction include ethers such as getyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene and toluene; chlorine solvents such as dichloromethane and chloroform; alcohols such as methanol and ethanol. , Acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like. These solvents can be used as a mixed solvent of two or more kinds. Manufacturing method 5)
  • the compound represented by the formula [1-2] in which the 6-position is substituted with a cyano group can be produced as follows.
  • I 1 , R 2 , R 3 , R 4 , R 5 , and Ar represent the same meaning as described above.
  • o represents an integer of 1 to 3, and when o is 2 or 3, R 1 may be the same or different. When o is 1, R 2 may be the same or different.
  • the compound represented by the formula [1-2] in which the 6-position is substituted with a cyano group can be obtained by converting the compound represented by the formula [K] to a suitable oxidizing agent.
  • a suitable oxidizing agent such as trimethylsilyl cyanide in the absence of a solvent, preferably in a solvent, at a reaction temperature of 0 to 150 ° C for 10 minutes to 10 minutes. It can be obtained by stirring for 24 hours.
  • various derivatives can be synthesized by further chemically modifying the obtained product.
  • the chemical modification described here includes functional group conversion typified by the induction of an amino group by a reduction reaction of a dinitro group, and a functional group recognized as a protecting group in the field of organic synthesis such as a methoxymethyl group. Deprotection of the group, derivation of the resulting functional group such as hydroxyl group and amino group by alkylation and acylation, etc., and recognition as a leaving group in the field of organic synthesis such as halogen atom represented by S0 nogashira reaction. And induction using a reaction using a nucleophilic reagent from the functional group.
  • the salt of the compound [I] can be obtained by reacting [I] with an inorganic or organic acid in a suitable solvent.
  • the desired product can be obtained by performing ordinary post-treatment.
  • the structure of the compound of the present invention is determined from NMR, mass spectrum and the like.
  • the fungicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.
  • the compound of the present invention can be used in a pure form without adding other components, and can be in a form that can be taken by a pesticide for use as a pesticide, i.e., a wettable powder, a granule, a powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, floor pulls, wettable powders and the like.
  • Additives and carriers that can be added to pesticide preparations include solid powders, plant powders such as soybean flour, flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, etc.
  • Organic and inorganic compounds such as mineral fine powder such as clay, sodium benzoate, urea and sodium sulfate are used.
  • kerosene, xylene and petroleum-based aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trickle Luethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.
  • surfactants can be added as necessary to obtain a uniform and stable form in these preparations.
  • the surfactant that can be added include, for example, an alkyl phenyl ether to which polyoxetylene is added, an alkyl ether to which polyoxyethylene is added, a higher fatty acid ester to which polyoxetylene is added, and polyoxyethylene.
  • Nonionic surfactants such as sorbitan higher fatty acid esters to which ethylene is added, tristyryl phenyl ether to which polyoxyethylene is added, and sulfuric esters of alkylphenyl ether to which polyoxyethylene is added.
  • alkylbenzene sulfonate sulfate of higher alcohol
  • alkyl naphthalene sulfonate polycarboxylate
  • lignin sulfonate formaldehyde condensate of alkyl naphthalene sulfonate
  • isobutylene monomaleic anhydride Polymers and the like can be mentioned.
  • the amount of the active ingredient in the pesticide formulation is usually preferably from 0.01 to 90% by weight, more preferably from 0.05 to 85% by weight, based on the whole composition (formulation).
  • the obtained wettable powder, emulsion, flowable, aqueous solvent, and granule wettable powder are diluted to a predetermined concentration with water to form a suspension or emulsion, and the powder and granules are directly used as a plant. It is used in a method of spraying.
  • the formulated fungicide composition of the present invention is applied as it is or diluted with water or the like to plants, seeds, water surface or soil.
  • the application rate depends on the weather conditions, formulation, application time, application method, application place, disease to be controlled Although it varies depending on harm, target crops and the like, the amount of the active ingredient compound per hectare is usually 1 to: L 000 g, preferably 10 to 100 g.
  • the application concentration is 1-1 OOOppm, preferably 10-250ppm, In the case of granules and powders, they can be applied without dilution.
  • the compound of the present invention alone is sufficiently effective, but it can also be used in combination with one or more of various fungicides, insecticides, acaricides or synergists.
  • fungicides insecticides, acaricides, nematicides and plant growth regulators that can be used in combination with the compound of the present invention are shown below.
  • Copper agent basic copper chloride, basic copper sulfate, etc.
  • Sulfur agents Sulfur agents; thiuram, zineb, maneb, mancozeb, ziram, provevineb, polycarbonate, etc.
  • Organophosphorus agents IBP, EDDPP, trimethylphosphomethyl, pyrazophos, fosetyl and the like.
  • Benzimidazole agents thiophanate methyl, benomyl, carbendazim, thiabendazole and the like.
  • Diproloxymide iprodione, procymidone, vinclozolin, fluorimide, etc.
  • Carboxamide agents oxycarboxin, mepronil, flutranil, techlophthalam, trichloride, pencyclone and the like.
  • Asylalanine agent metalaxyl, oxazixil, furalaxyl and the like.
  • Methoxyacrylates cresoxime methyl, azoxystrobin, metominosto mouth bottles and the like.
  • Anilino pyrimidines andpurine, mepanipyrim, pyrimethanil, dibudinil and the like.
  • SBI agent triadimefon, triazimenol, bitertanol, microbutanyl, hexaconazole, propiconazole, triflumizole, prochloraz, perfurazoate, finarimol, pyribenzox, trifolin, flusilazol, etaconazole, diclobutrazol , Fluotrimazole, flutriafen, penconazole, diniconazole, imazalil, trimorph, fenpropimorph, pthiobate, epoxyconazole, metconazole, etc.
  • Antibiotics include voroxin, blasticidin S, kasugamycin, paridamycin, dihydrostreptomycin sulfate, and the like.
  • Pyrethroid insecticides Permethrin, Cypermethrin, Deltamethrin, Fumbrelet, Fenprono ,. Trin, pyrethrin, arrestrin, tetramethrin, resmethrin, dimesulin, propasulin, phenothrin, proctrin, fluvalinate, cyflutrin, cyhalothrin, flucitrinate, etofuline Proplox, cycloprotoline, trolamethrin, silafluophan, profenprox, atalinasulin.
  • Microbial pesticides such as B T and insect pathogenic viruses.
  • Nematicides penamiphos, phosthiazate, etc.
  • Plant growth regulator Plant growth regulator
  • the reaction mixture was extracted with getyl ether, and the organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
  • the crude product (0.37 g) obtained by the above method was dissolved in 10 ml of acetic acid, and 0.51 g (2.78 mmol) of 2,6-dimethoxybenzyloxyamine was added to the solution. Was added at room temperature and stirred for 1 hour.
  • the reaction mixture was neutralized by adding an aqueous solution of sodium hydrogen carbonate, and then extracted with ethyl acetate.
  • the precipitated crystals were collected by filtration, the whole amount of the obtained crystals was suspended in 1 OmL of water, and 4 g of a 10% aqueous sodium hydroxide solution was added at room temperature. After the solution was stirred at room temperature for 1 hour, it was extracted three times with 10 mL of methylene chloride, and the organic layers were combined and dried over magnesium sulfate. Magnesium sulfate After filtration of the palladium, 0.4 mL of acetic anhydride was added to the solution at room temperature, and the mixture was stirred at room temperature for 90 minutes.
  • the obtained 2-pyridone was dissolved in 4 ml of phosphorus oxychloride and stirred at 100 to 110 ° C for 6 hours. After cooling to room temperature, the reaction solution was poured into water, neutralized with saturated aqueous sodium hydrogen carbonate, and extracted with chloroform. This was dried over magnesium sulfate and concentrated under reduced pressure. The resulting reaction mixture was dissolved in 5 mL of THF, 4 mL of 2 N sulfuric acid was added, and the mixture was refluxed overnight while heating. After the reaction solution was cooled to room temperature, it was poured into water and neutralized with a 1N sodium hydroxide solution. After extraction with chloroform, the extract was dried over magnesium sulfate, and concentrated under reduced pressure.
  • Table 1 shows typical examples of the compounds of the present invention including the above Examples. The abbreviations in the table are Each has the following meaning.
  • Example 1 9 granules
  • Dioctyl sulfosuccinate sodium salt 1 part One part or more of potassium phosphate is well pulverized and mixed, water is added and kneaded well, and the mixture is granulated and dried to obtain granules having an active ingredient of 5%.
  • Example 20 Suspension
  • the above ingredients are mixed and wet-pulverized until the particle size becomes 3 micron or less.
  • Example 21 1 Granular wettable powder
  • Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents.
  • the control effect was determined by visually observing the diseased state of the test plant at the time of the survey, that is, the degree of growth of the fungus spots appearing on the leaves, stems and the like, and comparing the control effect with the untreated one.
  • Test Example 1 Test for controlling common bean gray mold
  • the flowers of the kidney beans (variety “Nagauzura”) cultivated in the seedling raising bucket were excised and immersed in a chemical solution prepared by adjusting the emulsion of the compound of the present invention to a concentration of 50 pm of the active ingredient. After immersion, it was air-dried at room temperature and spray-inoculated with Kinggen gray mold fungus (Botrytiscisinerea). The inoculated flowers were placed on untreated leaf leaves and kept in a high humidity constant temperature room (20 ° C) where light and dark were repeated every 12 hours for 7 days. The lesion diameter on the leaves was compared with that of untreated leaves, and the control value was determined. As a result, the following compounds showed excellent control values of 75% or more.
  • the compound numbers correspond to the compound numbers in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Pyridine Compounds (AREA)

Abstract

L'invention concerne des composés d'oxime O-éther représentés par la formule générale [1] ou des sels de ceux-ci, lesquels présentent une excellente activité fongicide et sont utiles en tant que fongicides destinés à être utilisés en agriculture et en horticulture, formule dans laquelle R1 représente hydrogène, alkyle C¿1-6?, cycloalkyle C3-6 ou analogue; m représente un nombre entier de 1 à 3; R?2¿ représente cyano, nitro, formyle ou analogue, R3 représente hydrogène, alkyle C¿1-6?, ou cycloalkyle C3-6; R?4 et R5¿ représente chacun hydrogène ou alkyle C¿1-6; R?6 représente alkyle C¿1-6?, cycloalkyle C3-6, alcényle C2-6, ou analogue; et n représente un nombre entier de 1 à 5.
PCT/JP2002/001195 2001-02-14 2002-02-13 Composes d'oxime o-ether et fongicides a usage agricole et horticole WO2002064566A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003087056A1 (fr) * 2002-04-15 2003-10-23 Nippon Soda Co.,Ltd. Nouveau compose oxime o-ether, procede de production, et bactericide agricole ou horticole
WO2003087058A1 (fr) * 2002-04-15 2003-10-23 Nippon Soda Co.,Ltd. Nouveau compose d'oxime o-ether, procede de production et bactericide agricole ou horticole
JP2009542776A (ja) * 2006-07-13 2009-12-03 バイエル・クロツプサイエンス・エス・アー 殺菌剤ヒドロキシモイル−テトラゾール誘導体
JP2011518207A (ja) * 2008-04-22 2011-06-23 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 殺真菌剤ヒドロキシモイル−ヘテロ環誘導体
WO2015199065A1 (fr) * 2014-06-24 2015-12-30 日本曹達株式会社 Compose pyridine et son utilisation
WO2019083008A1 (fr) * 2017-10-27 2019-05-02 住友化学株式会社 Composé pyridine, et composition de lutte contre des organismes nuisibles comprenant celui-ci

Citations (5)

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Publication number Priority date Publication date Assignee Title
EP0004754A2 (fr) * 1978-03-31 1979-10-17 Rhone-Poulenc Agrochimie Ethers de cétoximes à activité insecticide
EP0024888A2 (fr) * 1979-08-24 1981-03-11 Rhone-Poulenc Inc. Insecticides à base d'éthers de cétoxime
WO1993021157A2 (fr) * 1992-04-22 1993-10-28 Hoechst Schering Agrevo Gmbh (hetero)-aryle-alkyle-cetonoxime-o-ethers substitues acaricides, insecticides et nematocides, leur procede de fabrication, les agents qu'ils contiennent et leur utilisation comme produits antiparasites
JPH093047A (ja) * 1995-06-21 1997-01-07 Nippon Soda Co Ltd ケトンオキシムエーテル誘導体、その製造方法及び農園芸用殺菌剤
WO2001034568A1 (fr) * 1999-11-05 2001-05-17 Nippon Soda Co., Ltd. Composes oxime o-ether et fongicides utiles dans l'agriculture et l'horticulture

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0004754A2 (fr) * 1978-03-31 1979-10-17 Rhone-Poulenc Agrochimie Ethers de cétoximes à activité insecticide
EP0024888A2 (fr) * 1979-08-24 1981-03-11 Rhone-Poulenc Inc. Insecticides à base d'éthers de cétoxime
WO1993021157A2 (fr) * 1992-04-22 1993-10-28 Hoechst Schering Agrevo Gmbh (hetero)-aryle-alkyle-cetonoxime-o-ethers substitues acaricides, insecticides et nematocides, leur procede de fabrication, les agents qu'ils contiennent et leur utilisation comme produits antiparasites
JPH093047A (ja) * 1995-06-21 1997-01-07 Nippon Soda Co Ltd ケトンオキシムエーテル誘導体、その製造方法及び農園芸用殺菌剤
WO2001034568A1 (fr) * 1999-11-05 2001-05-17 Nippon Soda Co., Ltd. Composes oxime o-ether et fongicides utiles dans l'agriculture et l'horticulture

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003087056A1 (fr) * 2002-04-15 2003-10-23 Nippon Soda Co.,Ltd. Nouveau compose oxime o-ether, procede de production, et bactericide agricole ou horticole
WO2003087058A1 (fr) * 2002-04-15 2003-10-23 Nippon Soda Co.,Ltd. Nouveau compose d'oxime o-ether, procede de production et bactericide agricole ou horticole
JP2009542776A (ja) * 2006-07-13 2009-12-03 バイエル・クロツプサイエンス・エス・アー 殺菌剤ヒドロキシモイル−テトラゾール誘導体
JP2011518207A (ja) * 2008-04-22 2011-06-23 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 殺真菌剤ヒドロキシモイル−ヘテロ環誘導体
WO2015199065A1 (fr) * 2014-06-24 2015-12-30 日本曹達株式会社 Compose pyridine et son utilisation
JPWO2015199065A1 (ja) * 2014-06-24 2017-04-20 日本曹達株式会社 ピリジン化合物およびその用途
WO2019083008A1 (fr) * 2017-10-27 2019-05-02 住友化学株式会社 Composé pyridine, et composition de lutte contre des organismes nuisibles comprenant celui-ci

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