WO2009093637A1 - Composé amide et son utilisation - Google Patents

Composé amide et son utilisation Download PDF

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Publication number
WO2009093637A1
WO2009093637A1 PCT/JP2009/050941 JP2009050941W WO2009093637A1 WO 2009093637 A1 WO2009093637 A1 WO 2009093637A1 JP 2009050941 W JP2009050941 W JP 2009050941W WO 2009093637 A1 WO2009093637 A1 WO 2009093637A1
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WIPO (PCT)
Prior art keywords
methyl
naphthyridinecarboxamide
compound
fluoro
amide compound
Prior art date
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PCT/JP2009/050941
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English (en)
Japanese (ja)
Inventor
Mayumi Kubota
Hiroshi Sakaguchi
Yasuyuki Kandoh
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Sumitomo Chemical Company, Limited
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Publication of WO2009093637A1 publication Critical patent/WO2009093637A1/fr

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    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the straight chain (C1-C2 alkoxy) C2-C5 alkyl group represented by R 2 means a (C1-C2 alkoxy) C2-C5 alkyl group in which the carbon chain is not branched.
  • Examples of the linear C1-C6 alkyl group represented by R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • the straight chain (C1-C2 alkoxy) C2-C5 alkyl group includes 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group. Group, 5-methoxypentyl group and 5-ethoxypentyl group.
  • ethers such as tetrahydrofuran (hereinafter referred to as THF), ethylene glycol dimethyl ether, tert-butyl methyl ether (hereinafter referred to as MTBE), hexane, heptane, octane and the like.
  • Examples of the condensing agent used in the reaction include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as WSC) and carbodiimides such as 1,3-dicyclohexylcarbodiimide, (benzotriazole- 1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate (hereinafter referred to as BOP reagent) and the like.
  • WSC 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
  • BOP reagent 1,3-dicyclohexylcarbodiimide, (benzotriazole- 1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate
  • compound (III) is usually used in a proportion of 0.5 to 3 mol per mol of compound (II)
  • the reaction temperature is usually in the range of ⁇ 20 ° C. to 140 ° C.
  • the reaction time is usually in the range of 1 to 24 hours.
  • Examples thereof include halogenated hydrocarbons, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. Can be mentioned.
  • compound (III) is usually used in a proportion of 0.5 to 3 mol per mol of compound (IV), and base is usually used in a proportion of 1 to 5 mol per mol of compound (IV).
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound of the present invention can be produced by reacting compound (V) with compound (VI) in the presence of a base.
  • a base represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, or a p-toluenesulfonyloxy group.
  • the reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as THF, ethylene glycol dimethyl ether, and MTBE, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, nitriles such as acetonitrile, DMF, and the like. Acid amides, sulfoxides such as DMSO, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, water, and mixtures thereof.
  • ethers such as THF, ethylene glycol dimethyl ether, and MTBE
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as chlorobenzene
  • nitriles such as acetonitrile
  • DMF and the like.
  • the base used in the reaction examples include alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate, alkali metal hydroxides such as sodium hydroxide, alkali metal hydrides such as sodium hydride, and the like.
  • the compound (VI) is usually used in a proportion of 1 to 10 mol per mol of the compound (V), and the base is usually used in a proportion of 1 to 5 mol per mol of the compound (V).
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours. After completion of the reaction, when water is added to the reaction mixture, if a solid is precipitated, the compound of the present invention can be isolated by filtration.
  • the compound of the present invention can be isolated by extracting the mixture of the reaction mixture and water with an organic solvent, and drying and concentrating the organic layer. .
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • solvent used in the reaction examples include ethers such as THF, ethylene glycol dimethyl ether, and MTBE, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene.
  • ethers such as THF, ethylene glycol dimethyl ether, and MTBE
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • aromatic hydrocarbons such as toluene and xylene
  • chlorobenzene chlorobenzene.
  • Halogenated hydrocarbons esters such as butyl acetate and ethyl acetate
  • nitriles such as acetonitrile
  • acid amides such as DMF
  • sulfoxides such as DMSO
  • nitrogen-containing aromatic compounds such as pyridine, and mixtures thereof Can be mentioned.
  • Examples of the dehydrating condensing agent used in the reaction include WSC and carbodiimides such as 1,3-dicyclohexylcarbodiimide, BOP reagent and the like.
  • compound (VII) is usually used in a proportion of 0.5 to 3 mol per mol of compound (II), and a condensing agent is usually used in a proportion of 1 to 5 mol per mol of compound (II).
  • the reaction temperature is usually in the range of ⁇ 20 ° C. to 140 ° C.
  • the reaction time is usually in the range of 1 to 24 hours. After completion of the reaction, when water is added to the reaction mixture, if a solid is precipitated, the compound (V) can be isolated by filtration.
  • Examples thereof include halogenated hydrocarbons, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. Can be mentioned.
  • compound (VII) is usually used in a proportion of 0.5 to 1 mol per mol of compound (IV), and base is usually used in a proportion of 1 to 5 mol per mol of compound (IV).
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the present control agent contains the present compound and a carrier.
  • the carrier include a solid carrier, a liquid carrier, and a gas carrier.
  • the control agent of the present invention is usually further added with formulation adjuvants such as surfactants, sticking agents, dispersants, stabilizers, etc., wettable powder, wettable powder, flowable powder, granules, dry flowable powder, emulsion, It is formulated into aqueous liquids, oils, smokes, aerosols, microcapsules and the like.
  • the control agent of the present invention contains the compound of the present invention in a weight ratio of usually 0.1 to 99%, preferably 0.2 to 90%.
  • liquid carrier examples include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), fat Aromatic or alicyclic hydrocarbons (eg, n-hexane, cyclohexanone, kerosene), esters (eg, ethyl acetate, butyl acetate), nitriles (eg, acetonitrile, isobutylronitrile), ethers (eg, dioxane) , Diisopropyl ether), acid amides (for example, DMF, dimethylacetamide), and halogenated hydrocarbons (for example, dichloroethane, trichloroethylene, carbon tetrachloride).
  • alcohols eg, methanol,
  • surfactant examples include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyoxyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives. Etc.
  • formulation adjuvants include, for example, fixing agents, dispersants, thickeners, wetting agents, extenders, antioxidants, specifically casein, gelatin, polysaccharides (eg starch, arabic gum, cellulose derivatives, Alginic acid), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4) -Methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid or ester thereof, and the like.
  • fixants e.g starch, arabic gum, cellulose derivatives, Alginic acid
  • lignin derivatives bentonite
  • saccharides eg, synthetic water-soluble polymers
  • control agent for controlling plant diseases for example, treatment to grown plants such as foliage spraying, treatment to plant cultivation areas such as soil treatment, treatment to seeds such as seed disinfection Etc.
  • Cyclic amine bactericidal compounds benzimidazole bactericidal compounds such as carbendazim, benomyl, thiabendazole, thiophanate methyl; procymidone; ciprodini Pyrimethanyl; Dietofencarb; Thiuram; Fluazinam; Mancozeb; Iprodione; Vinclozoline; Chlorotalonyl; Captan; Mepanipyrim; Fenpiclonyl; Fludioxonil; Xylostrobin; pyraclostrobin; dimoxystrobin; pyribencarb; spiroxamine; quinoxyphene; fenhexamide; famoxadone; fenamidone; zoxamide; ethaboxam; Metolaphenone; fluopyran; bixafen; cyflufenamide and Kinajido and the like.
  • the control method of the present invention includes a step of treating an effective amount of the compound of the present invention with a plant or soil.
  • This invention control method is normally performed by processing this invention control agent to a plant or soil.
  • the amount of the present control agent used in the present control method varies depending on weather conditions, formulation form, application time, application method, application location, target disease, target crop, etc.
  • the amount of the invention compound is usually 1 to 500 g, preferably 2 to 200 g per 1000 m 2 .
  • Emulsions, wettable powders, suspensions and the like are usually diluted with water before use. In this case, the concentration of the compound of the present invention after dilution is usually 0.0005 to 2% by weight, preferably 0.005 to 1. % By weight.
  • Powders, granules and the like are usually applied as they are without dilution.
  • the amount of the compound of the present invention in the control agent of the present invention is usually applied in the range of 0.001 to 100 g, preferably 0.01 to 50 g per kg of seed.
  • the present control agent can be used as a plant disease control agent in farmland such as fields, paddy fields, lawns, orchards.
  • the control agent of the present invention can control diseases of the farmland in the farmland where the following “crop” and the like are cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, vegetables, solanaceous vegetables (eggplants, tomatoes, peppers, peppers, potatoes) Cucumber, pumpkin, zucchini, watermelon, melon, etc., cruciferous vegetables (radish, turnip, horseradish, kohlrabi, cabbage, cabbage, mustard, broccoli, cauliflower, etc.), asteraceae (burdock, Shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celeryaceae vegetables (carrot, parsley, celery, red pepper, etc.), red crustacean vegetables (spinach, chard, etc.) (Perilla, mint, basil ), Strawberry, sweet potato, yam, taro, etc., Bridegroom, Foliage plant, Fruit trees;
  • Fruit trees berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, oil palm etc.
  • Trees other than fruit trees tea, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black beet, black bean, moth, rat, pine , Spruce, yew), Jatropha etc.
  • Lawn Shiba (Nasis, Pleurotus, etc.), Bermudagrass (Neurodonidae, etc.), Bentgrass (Oleoptera, Hykonukagusa, Odonoptera, etc.), Bluegrass (Nagahagusa, Oosuzunokatabira, etc.), Fescue (Oonishi nokegusa, Drosophila, etc.) , Grass, etc.), ryegrass (rat, wheat, etc.), anemonefish, blue whale, etc. Others: flower buds, foliage plants, etc.
  • plants that have been given resistance by classical breeding methods include rapeseed, wheat, sunflower, and rice that are resistant to imidazolinone-based ALS-inhibiting herbicides such as imazetapil under the trade name Clearfield (registered trademark). Already sold. Similarly, there are soybeans that are resistant to sulfonylurea ALS-inhibiting herbicides such as thifensulfuron methyl by classical breeding methods, and are already sold under the trade name of STS soybeans. Similarly, SR corn and the like are examples of plants to which tolerance has been imparted to acetyl CoA carboxylase inhibitors such as trion oxime and aryloxyphenoxypropionic acid herbicides by classical breeding methods.
  • acetyl CoA carboxylase inhibitors such as trion oxime and aryloxyphenoxypropionic acid herbicides by classical breeding methods.
  • Plants tolerant to acetyl CoA carboxylase inhibitors have been identified as Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci. USA) 87, 7175-7179 (1990).
  • a mutant acetyl CoA carboxylase resistant to an acetyl CoA carboxylase inhibitor has been reported in Weed Science 53, 728-746 (2005).
  • a plant resistant to an acetyl-CoA carboxylase inhibitor can be produced by introducing a mutation into plant acetyl-CoA carboxylase or introducing a mutation associated with imparting resistance into the plant.
  • a base substitution mutation-introduced nucleic acid typified by chimera plastic technology (Gura T. 1999.
  • Examples of plants to which resistance has been imparted by gene recombination techniques include glyphosate-resistant corn, soybean, cotton, rapeseed, sugar beet varieties, and are already available under trade names such as Roundup Ready (RoundupReady (registered trademark)), Agriureture GT, etc. Sold.
  • RoundupReady registered trademark
  • Agriureture GT etc.
  • Sold there are corn, soybean, cotton and rapeseed varieties that are resistant to glufosinate by genetic recombination technology, and are already sold under trade names such as Liberty Link (registered trademark).
  • bromoxynyl-resistant cotton by gene recombination technology is already sold under the trade name BXN.
  • the above “plant” includes, for example, a plant that can synthesize a selective toxin or the like known in the genus Bacillus using a gene recombination technique.
  • Toxins expressed in such genetically modified plants include insecticidal proteins derived from Bacillus cereus and Bacillus popirie; Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C derived from Bacillus thuringiensis Insecticidal proteins such as ⁇ -endotoxin, VIP1, VIP2, VIP3 or VIP3A; nematode-derived insecticidal proteins; toxins produced by animals such as scorpion toxins, spider toxins, bee toxins or insect-specific neurotoxins; filamentous fungal toxins; plants Lectin; agglutinin; protease inhibitors such as trypsin inhibitor, serine protease inhibitor, patatin, cystatin
  • Ribosome inactivating protein RIP
  • steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyltransferase, cholesterol oxidase; ecdysone inhibitor; HMG-CoA reductase; sodium channel, calcium channel inhibitor, etc. Ion channel inhibitor; juvenile hormone esterase; diuretic hormone receptor; stilbene synthase; bibenzyl synthase; chitinase; glucanase and the like.
  • toxins expressed in such genetically modified plants Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34Ab or Cry35Ab and other ⁇ -endotoxin proteins, VIP1, VIP2, VIP3 or VIP3A etc.
  • insecticidal protein hybrid toxins partially defective toxins, and modified toxins.
  • Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant techniques.
  • Cry1Ab lacking a part Cry1Ab lacking a part of the amino acid sequence is known.
  • the modified toxin one or more amino acids of the natural toxin are substituted.
  • genetically modified plants that contain one or more insecticidal pest resistance genes and express one or more toxins are already known and some are commercially available.
  • these genetically modified plants include YieldGard (registered trademark) (a corn variety expressing Cry1Ab toxin), YieldGuard Rootworm (registered trademark) (a corn variety expressing Cry3Bb1 toxin), YieldGard Plus (registered trademark) (Cry1Ab and Cry3Bb1) Corn varieties that express toxin), Herculex I® (corn varieties that express phosphinothricin N-acetyltransferase (PAT) to confer resistance to Cry1Fa2 toxin and glufosinate), NuCOTN33B® ( Cotton varieties expressing Cry1Ac toxin), Bollgard I (registered trademark) (cotton varieties expressing Cry1Ac toxin), Bollgard II (registered trader) ) (Cotton varieties expressing Cry1Ac and Cry2
  • the “plant” includes those imparted with an ability to produce an anti-pathogenic substance having a selective action using a gene recombination technique.
  • anti-pathogenic substances PR proteins and the like are known (PRPs, EP-A-0 392 225).
  • PRPs PR proteins and the like are known (PRPs, EP-A-0 392 225).
  • Such anti-pathogenic substances and genetically modified plants that produce them are described in EP-A-0 392 225, WO 95/33818, EP-A-0 353 191 and the like.
  • anti-pathogenic substances expressed in such genetically modified plants include, for example, sodium channel inhibitors, calcium channel inhibitors (KP1, KP4, KP6 toxins produced by viruses, etc.).
  • Ion channel inhibitors include stilbene synthase; bibenzyl synthase; chitinase; glucanase; PR protein; peptide antibiotics, heterocyclic antibiotics, protein factors involved in plant disease resistance (called plant disease resistance genes, WO 03/000906)) and the like, and the like, and the like, and the like, which are produced by microorganisms.
  • plant disease resistance genes WO 03/000906
  • plant includes plants imparted with useful traits such as oil component modification and amino acid content enhancing traits using genetic recombination techniques.
  • useful traits such as oil component modification and amino acid content enhancing traits using genetic recombination techniques. Examples include VISTIVE (registered trademark) (low linolenic soybean with reduced linolenic content) or high-lysine (high-oil) corn (corn with increased lysine or oil content).
  • Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiot seedling (Gibberella fujikuroi); Wheat powdery mildew (Erysiphe graminis), red mold (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. recondita, P.
  • Monilinia mali apple rot (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), spotted leaf (Alternaria alternata apple pathotype), black rot (Venturia inaequalis), anthracnose (Glomerella cingulata); Pear black spot disease (Venturia nashicola, V. pirina), black spot disease (Alternaria alternata Japanese pear pathotype), red star disease (Gymnosporangium haraeanum); Peach ash scab (Monilinia fructicola), black scab (Cladosporium carpophilum), Phomopsis sp. (Phomopsis sp.);
  • Grapes black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola); Oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae); Colletotrichum lagenarium, powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.) Seedling blight (Pythium sp.); Tomato ring disease (Alternaria solani),
  • Sojae Sojae
  • rust Phakopsora pachyrhizi
  • Green Bean Anthracnose Coldnut black astringency (Cercospora personata), brown spot (Cercospora arachidicola), white silkworm (Sclerotium rolfsii); Pea powdery mildew (Erysiphe pisi); Potato summer plague (Alternaria solani), plague (Phytophthora infestans), half body wilt (Verticillium albo-atrum, V. dahliae, V.
  • a part represents a weight part.
  • Production Example 8 Add 0.19 g of cesium carbonate to a mixture of 0.15 g of N- (2-fluoro-3-hydroxyphenyl) methyl-2- [1,5] naphthyridinecarboxamide, 0.1 g of iodoethane and 3 ml of DMF, and stir at room temperature for 12 hours. did. A 15% aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate.
  • Reference production example 1 To a mixture of 0.30 g of [1,5] naphthyridine-2-carboxylic acid, 0.46 g of 2-fluoro-3-hydroxybenzylamine hydrobromide, 0.5 ml of pyridine and 5 ml of DMF, 0.43 g of WSC was added at room temperature. Stir for 8 hours. Water was added to the reaction mixture, and the mixture was concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography, so as to obtain 0.25 g of N- (2-fluoro-3-hydroxyphenyl) methyl-2- [1,5] naphthyridinecarboxamide.
  • Reference production example 2 A mixture of 0.42 g of 3-hydroxybenzylamine hydrochloride, 0.3 g of [1,5] naphthyridine-2-carboxylic acid, 0.43 g of WSC, 0.5 ml of pyridine and 5 ml of DMF was stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography, so as to obtain 0.29 g of N- (3-hydroxyphenyl) methyl-2- [1,5] naphthyridinecarboxamide.
  • Reference production example 3 A mixture of 20 g of 3-hydroxybenzaldehyde, 200 ml of 2-propanol, 16 g of pyridine and 15 g of hydroxylamine hydrochloride was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure. Water was added to the residue and extracted with ethyl acetate. The organic layer was washed successively with 5% hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give 26 g of 3-hydroxybenzaldehyde oxime.
  • Reference production example 4 4.5 g of 2-fluoro-3-methoxybenzyl alcohol, 2.9 ml of methanesulfonyl chloride and 50 ml of THF were mixed and stirred at 0 ° C. To the mixture, 6.0 ml of triethylamine was added and stirred at 0 ° C. for 30 minutes and then at room temperature for 2 hours. Ethyl acetate was added to the reaction mixture, followed by filtration through Celite (registered trademark). Water was added to the filtrate and extracted with ethyl acetate.
  • Reference production example 5 6.7 g of (2-fluoro-3-methoxyphenyl) methyl methanesulfonate, 5.3 g of potassium phthalimide and 60 ml of DMF were mixed and stirred at 70 ° C. for 4 hours. Thereafter, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, dilute hydrochloric acid and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with hexane to obtain 5.8 g of N- (2-fluoro-3-methoxyphenyl) methylphthalimide.
  • Reference production example 6 1.63 g of hydrazine monohydrate was added dropwise to a mixture of 7.7 g of N- (2-fluoro-3-methoxyphenyl) methylphthalimide and 30 ml of ethanol, and the mixture was heated to reflux for 4 hours. The reaction mixture was then cooled to room temperature. Water was added to the reaction mixture, and the mixture was concentrated under reduced pressure. Dilute hydrochloric acid was added to the residue and filtered. Ethyl acetate was added to the obtained filtrate, and a 15% aqueous sodium hydroxide solution was added to the aqueous layer until the pH reached 11. This liquid was separated into two layers.
  • Reference production example 11 69.4 g of [1,5] naphthyridine was dissolved in 700 ml of chloroform, 120 g of m-chloroperbenzoic acid was added at room temperature, and the mixture was stirred for 2 hours. To this mixture was added 12 g of m-chloroperbenzoic acid, and the mixture was further stirred at room temperature for 2 hours. The reaction mixture was subjected to silica gel column chromatography to obtain 73 g of [1,5] naphthyridine N-oxide.
  • Reference production example 12 73 g of [1,5] naphthyridine N-oxide and 76 g of 1,8-diazabicyclo [5.4.0] -7-undecene were dissolved in 700 ml of THF, and 52 g of trimethylsilylcyanide was added over 1 hour under ice cooling. It was dripped. It returned to room temperature over about 2 hours, and stirred for 15 hours. The reaction mixture was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain 38 g of 2-cyano [1,5] naphthyridine.
  • Reference production example 13 1.6 g of 2-cyano [1,5] naphthyridine was dissolved in 40 ml of 50% sulfuric acid aqueous solution and stirred for 4 hours while heating under reflux. The reaction mixture was ice-cooled, and 5N aqueous sodium hydroxide solution was added little by little to the reaction mixture, whereby crystals were precipitated. The crystals were collected by filtration and dried under reduced pressure to obtain 1.5 g of [1,5] naphthyridine-2-carboxylic acid.
  • Formulation Example 1 A wettable powder is obtained by thoroughly grinding and mixing 50 parts of any one of the compounds (1) to (21) of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate, and 45 parts of synthetic silicon hydroxide. .
  • Formulation Example 2 20 parts of any one of the compounds (1) to (21) of the present invention and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol and pulverized by a wet pulverization method. Thereafter, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, and further 10 parts of propylene glycol is added and stirred to obtain a flowable preparation.
  • Formulation Example 3 A powder is obtained by thoroughly pulverizing and mixing 2 parts of any one of the compounds (1) to (21) of the present invention, 88 parts of kaolin clay and 10 parts of talc.
  • Formulation Example 4 An emulsion is obtained by thoroughly mixing 5 parts of any one of the compounds (1) to (21) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.
  • Formulation Example 5 2 parts of any one of the compounds (1) to (21) of the present invention, 1 part of synthetic silicon hydroxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed well, and then water is added. Knead well and granulate dry to obtain granules.
  • Formulation Example 6 Mix 10 parts of any one of the compounds (1) to (21) of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water, and finely pulverize them by a wet pulverization method. To obtain a flowable formulation.
  • test examples show that the compounds of the present invention are useful for controlling plant diseases.
  • the control effect is obtained by visually observing the area of the lesion on the test plant at the time of the survey, and comparing the area of the lesion on the plant treated with the compound of the present invention and the area of the lesion on the untreated plant. evaluated.
  • Test example 1 A plastic pot was filled with sandy loam, cucumber (variety: Sagamihanjiro) was sown and grown in a greenhouse for 12 days.
  • Each of the compounds (1), (2), (5) to (9), (11), (13) to (16) and (18) to (21) of the present invention is converted into a flowable preparation according to Preparation Example 6. After that, it was diluted with water to a predetermined concentration (500 ppm) and sprayed on the foliage so as to adhere well to the cucumber leaf surface. After spraying, the plants were air-dried, and a spore-containing PDA medium of Botrytis cinerea was placed on the cucumber leaf surface. After inoculation, the lesion area was investigated after 5 days in a humid environment at 12 ° C. As a result, the lesion area in the plant treated with the compounds (1), (2), (5) to (9), (11), (13) to (16) and (18) to (21) of the present invention was It was 10% or less of the lesion area in an untreated plant.
  • Test example 2 A plastic pot was filled with sandy loam, cucumber (variety: Sagamihanjiro) was sown and grown in a greenhouse for 12 days.
  • Each of the compounds (1), (2), (5) to (9), (11) and (13) to (21) of the present invention is made into a flowable formulation according to Formulation Example 6, and then diluted with water to give The concentration (500 ppm) was applied, and the foliage was sprayed so that it sufficiently adhered to the cucumber leaf surface. After spraying, the plants were air-dried, and a mycelia-containing PDA medium of cucumber sclerotia bacterium was placed on the cucumber leaf surface. After the inoculation, the lesion area was examined after being placed at 18 ° C. under high humidity for 4 days.
  • the lesion area in the plant treated with the compounds (1), (2), (5) to (9), (11) and (13) to (21) of the present invention is the lesion area in the untreated plant. It was 10% or less of the area.
  • N- (2-methoxyphenyl) methyl-2- [1,5] naphthyridinecarboxamide (hereinafter referred to as a comparative compound) described in Bioorganic & Medicinal Chemistry Letters, 9, p.2583 (1999). (Indicated as (A).)
  • the same test was conducted using As a result, the lesion area on the plant treated with the comparative compound (A) was 76% or more of the lesion area in the untreated section.
  • N- (2-methoxyphenyl) methyl-2- [1,5] naphthyridinecarboxamide is a compound represented by the following formula (A).
  • Test example 3 A plastic pot was filled with floor soil, rice (variety: Nipponbare) was sown, and grown in a greenhouse for 12 days.
  • the present compounds (1), (5) to (7), (9), (13) and (18) were made into flowable preparations according to Preparation Example 6, and then diluted with water to a predetermined concentration (500 ppm).
  • the foliage was sprayed so as to adhere well to the leaf surface of the rice. After spraying, the plants were air-dried, and a pot having rice blast (Magnaporthe grisea) diseased leaves was left around the sprayed plants. All the rice plants were placed under high humidity only at night, and the lesion area was examined 5 days after the inoculation.
  • the lesion area in the plant treated with the compounds (1), (5) to (7), (9), (13) and (18) of the present invention was 10% of the lesion area in the untreated plant. It was the following.
  • Test example 4 A plastic pot was filled with sand loam, sown with cucumber (Sagamihanjiro), and grown in a greenhouse for 12 days. Thereafter, a spore-containing PDA medium of Botrytis cinerea was inoculated on the cucumber leaf surface, and then the compounds (1), (2), (7), (8) and (13) to (21) of the present invention. ) was made into a flowable formulation according to Formulation Example 6, diluted with water to a concentration of 200 ppm, and the spray solution was sprayed on the foliage so that it sufficiently adhered to the leaf surface of the cucumber. After spraying, the plants were air-dried and placed under high humidity at 12 ° C. for 2 days, and then the control effect was investigated.
  • the comparative compound (B) is a compound represented by the following formula (B) described in International Publication No. 2005/033079.
  • the compound of the present invention has an excellent controlling effect against plant diseases and is useful for controlling plant diseases.

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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)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Cette invention concerne un composé amide représenté par la formule (I), qui a une excellente activité de lutte contre les maladies végétales et est utile pour la lutte contre les maladies végétales. (I) [Dans la formule, R1 représente un atome d'hydrogène ou un atome de fluor ; et R2 représente un groupe alkyle C1-C6 linéaire ou un groupe alcoxy(C1-C2)alkyle C2-C5 linéaire].
PCT/JP2009/050941 2008-01-25 2009-01-22 Composé amide et son utilisation WO2009093637A1 (fr)

Applications Claiming Priority (6)

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JP2008-014903 2008-01-25
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JP2008014903 2008-01-25
JP2008-014902 2008-01-25
JP2008-014907 2008-01-25
JP2008014902 2008-01-25

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005033079A1 (fr) * 2003-09-30 2005-04-14 Eisai Co., Ltd. Agent antifongique a compose heterocyclique
WO2008126684A2 (fr) * 2007-03-22 2008-10-23 Sumitomo Chemical Company, Limited Composition agricole pour combattre ou prévenir des maladies des plantes causées par des microbes pathogènes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005033079A1 (fr) * 2003-09-30 2005-04-14 Eisai Co., Ltd. Agent antifongique a compose heterocyclique
WO2008126684A2 (fr) * 2007-03-22 2008-10-23 Sumitomo Chemical Company, Limited Composition agricole pour combattre ou prévenir des maladies des plantes causées par des microbes pathogènes

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