WO2003062222A1 - Carboxamides de pyrazole, intermediaires associes et pesticides contenant ces derniers en tant qu'ingredient actif - Google Patents

Carboxamides de pyrazole, intermediaires associes et pesticides contenant ces derniers en tant qu'ingredient actif Download PDF

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WO2003062222A1
WO2003062222A1 PCT/JP2003/000428 JP0300428W WO03062222A1 WO 2003062222 A1 WO2003062222 A1 WO 2003062222A1 JP 0300428 W JP0300428 W JP 0300428W WO 03062222 A1 WO03062222 A1 WO 03062222A1
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group
acid
compound
addition salt
acid addition
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PCT/JP2003/000428
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English (en)
Japanese (ja)
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Eiji Takizawa
Itaru Okada
Kazuhiko Kikutake
Toshiki Fukuchi
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Nihon Nohyaku Co., Ltd.
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Publication of WO2003062222A1 publication Critical patent/WO2003062222A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel pyrazolecarboxamides and a pesticidal composition containing these as an active ingredient.
  • novel pyrazolecarboxamides of the present invention are useful as agricultural and horticultural fungicides, insecticides and acaricides. Background art
  • N-benzylpyrazole-5-potoxolemide derivatives have insecticidal and acaricidal activity (see, for example, JP-A-64-25763).
  • the publication discloses the following compounds having insecticidal and acaricidal activity.
  • N_pyridylmethylpyrazole-15-carboxamide derivatives having a similar structure to the compound of the present invention include, for example, compounds of the present invention represented by the following general formula (I) as represented by the following structural formula (III) substituents corresponding to R 5 are those alkyl groups, insecticidal, acaricidal and disease are also disclosed as of having bactericidal activity represented by base and mildew (JP-2-62876 discloses the compound No. 34).
  • An object of the present invention is to provide a new substance which exhibits a high control effect against various pathogens and is effective for controlling pests such as insects and dapa, and which is particularly resistant to conventional insecticides.
  • An object of the present invention is to provide a highly safe substance which exhibits a high control effect against various pests showing the above, exhibits an effect even at a low dose, and has reduced problems such as residual toxicity and environmental pollution.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, novel pyrazolecarboxamides having a phenylpyridine skeleton and having a specific combination of substituents satisfy the above-mentioned requirements. It has been found that it has sterilizing, insecticidal and acaricidal activities, and has completed the present invention.
  • the present invention relates to a pyrazolecarboxamide compound represented by the following general formula (I) or an acid addition salt thereof.
  • R 1 represents an alkyl group of
  • R 2 represents an alkyl group, a haloalkyl group or a CCS in ⁇ Norekokishi group C 1 -C 5 a C 1 -C 5,
  • R 3 represents a hydrogen atom or an alkyl group ⁇ 3,
  • R 4 is ⁇ ⁇ 5 alkyl group, a haloalkyl group or a halogen atom -, provided that when m is 2 or more, R 4 may be the same or different, R 5 represents an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, a hydroxyl group, an acyloxy group, a halopropyloxy group, an alkylthio group, a formyl group,
  • Hi indicates an integer from 0 to 3
  • n an integer of 1 to 5
  • p 0 or 1
  • X represents a hydrogen atom, C ⁇ C 3 alkyl group, ⁇ 3 alkoxy group or a halogen atom.
  • the present invention relates to a phenylpyridylmethylamine compound represented by the following general formula (II) or an acid addition salt thereof.
  • R 3 , R 4 and m are as defined in the above general formula (I)
  • R 8 represents a haloalkoxy group.
  • the present invention relates to a composition
  • a composition comprising the above-mentioned pyrazolecarboxamide compound or an acid addition salt thereof, and an agricultural chemical adjuvant.
  • the present invention relates to the use of the above-mentioned pyrazolecarboxamide compound or its caro salt with acid as a pesticide.
  • the present invention relates to a method for controlling pests, which comprises contacting an effective amount of the pyrazolecarboxamide compound or an acid addition salt thereof with a pest.
  • examples of R 1 include a methyl group and an ethyl group , N-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, isopentyl, 2-ethylpropyl , neopentyl group, 2, 2-dimethylpropyl group, 2-methyl isobutyl group, cyclopropyl group, consequent opening heptyl group, such as consequent opening pentyl ( ⁇ ⁇ Ji 5 linear or branched alkyl group or a C Examples thereof include a cyclic alkyl group of 3 to C 5. Among them, R 1 is preferably a methyl group.
  • R 2 examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, —C 1 to C 5 straight chain such as methylbutyl group, isopentyl group, 2-ethylethyl pill group, neopentyl group, 2,2-dimethylpropyl group, 2-methylisobutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, etc.
  • a branched alkyl group or a C 3 -C 5 cyclic alkyl group fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, difluoroethyl Group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 21-fluoroethyl group, 2,2,2-trifluoroethyl group, 11- (trifluoromethyl) ethyl group, 1,1,2, 3,3,3-hexafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3 A straight-chain or branched-chain haloalkyl group such as 1,2,3,3,4,4,5,5,5-nonafluoropentyl group; ⁇ Methoxy group, ethoxy group, n -propoxy group, isopropoxy group, n-butoxy group, sec-butoxy
  • R 3 examples include a hydrogen atom; and a C i -c 3 linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Of these, a hydrogen atom is preferable as R 3 .
  • R 4 examples include methyl group, Echiru group, n- propyl group, an isopropyl group, n- heptyl group, sec- heptyl group, an isobutyl group, tert- butyl group, n- pentyl group, 2-methylbutyl group, 3 - Mechirupuchiru group, isopentyl group, 2-Echirupu port propyl group, a neopentyl group, 2, 2-dimethylpropyl group, a straight-chain or branched-chain alkyl group ⁇ 5 and 2-methyl isobutyl group; Furuoromechiru group, chloromethane ethyl group , Bromomethyl group, difluoromethyl group, difluoroethyl group, trifluorenemethyl group, trichloromethyl group, tribromomethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, and 1- (trifluor
  • R 5 examples include methyl group, Echiru group, n- propyl group, an isopropyl group, n- Buchinore group, sec- butyl group, an isobutyl group, tert- butyl group, n- Penchinore group, 2-methylbutyl group, 3 —Methylbutyl group, isopentyl group, 2-ethylpentyl group, neopentyl group, 2,2-dimethylpropyl group, 2-methylisobutyl group, etc., a linear or branched alkyl group of; fluoromethyl group, chloromethyl group, Bromomethyl group, difluoromethyl group, difluoroethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 1_ (trifluoromethylinoethyl) ethyl 1,1,2,
  • R 6 and R 7 may be the same or different and are each a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n_butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, isopentyl group, 2-ethylethyl pill group, neopentynole group, 2,2-dimethylpropyl group, 2 — Represents a C i Cs linear or branched alkyl group such as a methinoleisobutyl group); and two adjacent R 5 are taken together.
  • Contact Yopi alkylthio group is preferably a C i Cs, the alkoxyalkoxy group and Ashiruokishi group, what is good Masui c 2 to c 8.
  • An oral alkoxy group is preferred, and a trifluoromethoxy group or a difluoromethoxy group is particularly preferred.
  • the substitution position is preferably the 4-position.
  • Examples of X include a hydrogen atom; a C Cg linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; a methoxy group, an ethoxy group, an n-propoxy group, linear or branched alkoxy group having ⁇ 3 such as a propoxy group; a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.
  • X is preferably a hydrogen atom.
  • n is an integer of 0 to 3, and preferably 0 to 2.
  • m is 0, it means that R 4 does not exist.
  • n is an integer of 1 to 5, preferably 1 or 2.
  • p is 0 or 1, preferably 0.
  • p when p is 0, it means that there is no O binding to N.
  • the acid to be added to the compound represented by the general formula (I) is not particularly limited as long as it is an acid which can be added.
  • Carboxylic acids such as stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid and phthalic acid
  • sulfonic acids such as methanesulfonic acid, 1,3-propanedisulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonate
  • Inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
  • phenylpyridylmethylamine compound of the present invention represented by the general formula (II) (hereinafter abbreviated as a compound represented by the general formula (II)) and an acid addition salt thereof are described in the above pyrazole carboxy. It is a novel intermediate for producing amides and their acid addition salts.
  • the acid to be added to the compound represented by the general formula ( ⁇ ) is not particularly limited as long as it is an acid that can be added.
  • Carboxylic acids such as stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid and phthalic acid; methanesulfonic acid, 1,3 Sulfonic acids such as monopropanedisulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
  • the compound of the present invention represented by the general formula (I) is a novel compound and can be produced, for example, according to the following reaction formula.
  • the carboxylic acid chlorides (IV) and the phenylpyridylmethylamines (V) can be prepared in the presence or absence of a base, preferably using a solvent, at -10 to 50 ° C, preferably React at 0-25 ° C.
  • the reaction time is about several minutes to 10 hours, but the reaction is completed in a relatively short time.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • chloroform, dichloromethane Halogenated hydrocarbons such as water; esters such as methyl acetate and ethyl acetate; or polar solvents such as tetrahydrofuran, acetonitrile, dioxane, ⁇ , ⁇ -dimethylformamide, ⁇ ⁇ ⁇ -methylpyrrolidone, dimethyl sulfoxide, pyridine and the like. And the like.
  • the base examples include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and hydroxylated sodium; sodium carbonate, charcoal Inorganic bases such as alkali metal carbonates such as acid lime; and organic bases such as pyridine and triethylamine.
  • the solvent is distilled off under reduced pressure, and water is added.
  • Aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; extracted with esters such as ethyl acetate, washed with water, dilute hydrochloric acid and, if necessary, saturated saline It may be dried with a drying agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and the solvent may be distilled off under reduced pressure.
  • Carboxamides (VI) and phenylboronic acids (VII) are reacted in the presence or absence of a base or a transition metal catalyst, preferably using a solvent, at 0 to 150 ° C, preferably at room temperature to 120 ° C. .
  • the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • alcohols such as methanol, ethanol, and isopropanol
  • benzene Aromatic hydrocarbons such as toluene and xylene
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • halogenated hydrocarbons such as chloroform and dichloromethane
  • water esters such as methyl acetate and ethyl acetate
  • polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine and the like.
  • Examples of the leaving group include a chlorine atom, a bromine atom, an iodine atom, a methylsulfonyloxy group, a ⁇ -toluenesulfonyloxy group, and a trifluoromethylsulfonoxy group.
  • alkali metal hydrides such as sodium hydride
  • alkali metal hydroxides such as sodium hydroxide and hydroxylamide
  • inorganic bases such as alkali metal carbonates such as sodium carbonate and carbonic acid rim
  • organic bases such as pyridine and triethylamine.
  • transition metal catalyst examples include palladium compounds such as palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tris (dibenzylacetone) palladium, and bis (triphenylinolephosphine) nickelene.
  • palladium compounds such as palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tris (dibenzylacetone) palladium, and bis (triphenylinolephosphine) nickelene.
  • Nickel compounds such as chloride and tetrakis (triphen- ⁇ / phosphine) nickel can be exemplified.
  • the solvent is distilled off under reduced pressure, and water is added.
  • Aromatic hydrocarbons such as benzene, toluene and xylene insoluble in water; halogenated hydrocarbons such as chloroform and dichloromethane; extracted with esters such as ethyl acetate, washed with saturated saline, and then washed with anhydrous sodium sulfate and anhydrous It may be dried with a desiccant such as magnesium sulfate, and the solvent may be distilled off under reduced pressure.
  • the starting compound represented by the general formula (IV) can be synthesized, for example, by the method described in JP-A-64-25763. Most commercially available products of polyfluoroacids (VII) can be used.
  • the acid addition salt of pyrazolecarboxamides of the present invention can be produced by the following method.
  • the pyrazolecarboxamides (I) and the acid are reacted preferably at 15-50 ° C, preferably 0-25 ° C, using a solvent.
  • Organic acids and inorganic acids can be used as the acid.
  • organic acids include carboxylic acids such as acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecandioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid, and phthalic acid; Sulfonic acids such as acid, 1,3-propanedisulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, etc. be able to.
  • the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform, dichloromethane Water; esters such as ethyl acetate and methyl acetate; or polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide. be able to.
  • the solvent is distilled off under reduced pressure, and the crystals are separated by filtration to synthesize benzylamine inorganic acid salt and organic acid salt. This condition is sufficient, but if further purification is desired, high purity pyrazolecarpoxamidic acid addition salt can be synthesized by washing with the above-mentioned organic solvent.
  • the compound represented by the general formula (V) as a raw material can be synthesized by the following method.
  • R 4 , R 5 , m and n are as defined in the general formula (I).
  • the fluorocyanoviridines (VIII) are reacted with hydrogen in the presence of a metal catalyst, aqueous ammonia, preferably using a solvent at 0 to 100 ° C, preferably 25 to 50 ° C.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • Examples thereof include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, and xylene; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; or tetrahydrofuran, acetoetrile, dioxane, N, N-dimethyl ⁇
  • Examples include polar solvents such as formamide, N-methylpyrrolidone, dimethylsulfoxide, and pyridine.
  • the metal catalyst examples include Raney nickel, palladium carbon, platinum oxide and the like.
  • the target compound of the general formula (Va) can be isolated by filtering off the metal catalyst from the reaction mixture and distilling off the solvent under reduced pressure. Is obtained.
  • the product may be pure enough as it is, but if necessary, purified by distillation or column chromatography to obtain a pure product.
  • Vll (Va)
  • VIII The phenylcyanoviridines (VIII) are reacted with a metal hydride at a temperature of 178 to 150 ° C, preferably 1 to 78 to 100 ° C, preferably using a solvent.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform, dichloromethane Halogenated hydrocarbons, such as methyl acetate, ethyl acetate, etc .; And polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine and the like.
  • the metal hydride examples include sodium borohydride, lithium aluminum hydride and the like.
  • the target compound of the general formula (Va) can be isolated by post-treating the remaining metal hydride and then distilling off the solvent under reduced pressure, and represented by the general formula (Va) A compound is obtained.
  • the product may be sufficiently pure as it is, but if necessary, purified by distillation, column chromatography, or other means to obtain a pure product.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • alcohols such as methanol, ethanol, and isopropanol
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • acetone, methylethyl Ketones such as ketone and methylisobutyl ketone
  • halogenated hydrocarbons such as chloroform and dichloromethane
  • water esters such as methyl acetate and ethyl acetate
  • tetrahydrofuran, lycetonitrile dioxane, N, N-dimethylformamid
  • polar solvents such as N-methylpyrrolidone, dimethylsulfoxide and pyridine.
  • the metal catalyst examples include Raney nickel, palladium carbon, platinum oxide and the like.
  • the target compound of the general formula (V) can be isolated by filtering off the metal catalyst from the reaction mixture and then distilling off the solvent under reduced pressure. The compound represented by the general formula (V) A compound is obtained.
  • Phenylcyanopyridines (VIII) can be prepared by a known method, for example, the method described in Synthetic Communications, Vol. 11, page 513 (1981), by reacting the corresponding haloarenes and phenolic carboxylic acids with a transition metal catalyst and a base. By doing so, they can be synthesized.
  • the oximes (IX) can be synthesized by reacting the corresponding acetophenones with the corresponding hydroxysulfamines in the presence of carbonated lime by a known method.
  • R 3 , RR 5 , m and n are as defined in the above general formula (I), and Y is an acid.
  • the phenylpyridylmethylamines (V) and the acid are reacted, preferably in a solvent, at 15 to 50 ° C, preferably 0 to 25 ° C.
  • Organic acids and inorganic acids can be used as the acid.As the organic acids, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecandioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid
  • Carboxylic acids such as acid, benzoic acid and phthalic acid; methanesulfonic acid, 1,3-propanedisulfonic acid, p-toluene Examples thereof include sulfonic acids such as enesulfonic acid and dodecylbenzene sulfonic acid.
  • the inorganic acid examples include hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; chloroform, dichloromethane Water; esters such as ethyl acetate and methyl acetate; and polar solvents such as tetrahydrofuran, acetonitrile, dioxane, ⁇ , ⁇ -dimethylformamide, ⁇ -methylpyrrolidone, and dimethyl sulfoxide. be able to.
  • the solvent is distilled off under reduced pressure, and the crystals are separated by filtration to synthesize benzylamine inorganic acid salt and organic acid salt. This condition is sufficient, but if further purification is desired, high purity pyridylmethylamic acid adduct (X) can be synthesized by washing with the above-mentioned organic solvent.
  • the starting compound represented by the general formula (VI) can be synthesized by the following method.
  • the carboxylic acid chlorides (IV) and the pyridylmethylamines (XI) can be prepared in the presence or absence of a base, preferably using a solvent, at a temperature of 10 to 50 ° C, preferably 0 to 25 ° C. Let react.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; acetone, methylethyl Ketones such as norketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; or tetrahydrofuran, acetonitrile, dioxane, ⁇ , ⁇ -dimethylformamide, ⁇ — Polar solvents such as methylpyrrolidone, dimethylsulfoxide and pyridine.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • acetone methylethyl Ketones such as norketone and methyl isobutyl ketone
  • halogenated hydrocarbons such as chloroform and dichloromethane
  • the base examples include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and carbonated lithium; inorganic salts Amides such as pyridine and triethylamine;
  • the solvent is distilled off under reduced pressure, and water is added.
  • Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; extracted with esters such as ethyl acetate, washed with water, dilute hydrochloric acid and, if necessary, saturated saline It may be dried with a drying agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and the solvent may be distilled off under reduced pressure.
  • the compound represented by the general formula (I) has a high bactericidal effect against phytopathogenic fungi such as blast fungus, powdery mildew, rust fungus and mildew, and is an active ingredient of a fungicide for agricultural and horticultural use.
  • the compounds of the present invention may be used in the form of insects such as brown planthopper, brown beetle, brown beetle, etc., white-spotted plants such as black-tailed leafhopper and white-spotted pie, and aphids such as aphids such as red-spotted moss. , Lepidoptera such as Pleurotus japonicus, P.
  • insects of the order Orthoptera and high control activity against eggs and larvae of the order Acephalidaceae such as Nami-nada, Nisenamihada and Ran. It is also useful as an active ingredient for agricultural and horticultural insecticides and pesticides.
  • the phytopathogenic fungi, insects and mites to be controlled by the compound of the present invention are not limited to those exemplified above.
  • the compound represented by the general formula (I) When used as a fungicide, an insecticide, and / or an acaricide for agricultural and horticultural use, it may be used alone, but preferably used in the art. Used as agricultural and horticultural fungicides, insecticides, and Z or acaricides in the form of compositions made with the used pesticide adjuvants. These forms are not particularly limited, but are preferably in the form of emulsions, wettable powders, powders, flowables, fine granules, granules, tablets, oils, sprays, aerosols and the like. One or more compounds represented by the general formula (I) can be blended as an active ingredient.
  • Pesticide adjuvants used to produce the above agricultural and horticultural fungicides, insecticides, and / or acaricides include, for example, agricultural and horticultural fungicides, insecticides, and Z or acaricides. It can be used for the purpose of improving the effect, stabilizing, and improving the dispersibility.
  • pesticidal auxiliaries include carriers (diluents), spreading agents, emulsifiers, wetting agents, dispersants, disintegrants, and the like.
  • liquid carrier examples include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and daricol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and methyl.
  • aromatic hydrocarbons such as toluene and xylene
  • alcohols such as methanol, butanol and daricol
  • ketones such as acetone
  • amides such as dimethylformamide
  • sulfoxides such as dimethyl sulfoxide
  • methyl examples include naphthalene, cyclohexane, animal and vegetable oils, and fatty acids.
  • solid carrier examples include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like.
  • Usable surfactants can be used as emulsifiers and dispersants, such as higher alcohols such as sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether and lauryl betaine.
  • An ionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric ion surfactant or the like can be used.
  • a spreading agent such as polyoxyethylene phenol ether; polyoxyethylene radial phenyl ether; a wetting agent such as dialkyl sulfosuccinate; a fixing agent such as carboxymethyl cellulose and polyvinyl alcohol; lignin sulfonic acid Disintegrants such as sodium and sodium lauryl sulfate can be used.
  • the content of the effective ingredient in the agricultural and horticultural fungicide, insecticide, and / or acaricide of the present invention is selected from the range of 0.1 to 99.5%, and various conditions such as a formulation form, an application method and the like are used.
  • various conditions such as a formulation form, an application method and the like are used.
  • the preparations contain about 1 to 90% by weight, preferably 10 to 40% by weight, of the active ingredient.
  • an emulsion of a stock solution can be prepared by mixing a solvent and a surfactant with the above-mentioned compound as an active ingredient. It can be applied after dilution.
  • a stock solution by mixing the above active compound, a solid carrier, a surfactant and the like, and then dilute this stock solution to a predetermined concentration with water before use. it can.
  • the compound of the active ingredient, the solid carrier and the like can be mixed and applied as it is, and in the case of granules, the compound of the active ingredient, the solid carrier and a surfactant can be mixed and used.
  • each of the above-mentioned preparation forms is not limited to the above-mentioned method, and can be appropriately selected by those skilled in the art according to the kind of the active ingredient, the purpose of application, and the like.
  • the agricultural and horticultural fungicides, insecticides, and / or miticides of the present invention include, in addition to the compound of the present invention, an active ingredient, other fungicides, insecticides, acaricides, herbicides, insect growth regulators. Any active ingredient such as fertilizer, soil conditioner, etc. may be added.
  • the method for applying the agricultural and horticultural fungicide, the insecticide, and / or the acaricide of the present invention is not particularly limited. It can be applied by any method such as foliage application, water application, soil treatment, and seed treatment.
  • a solution having a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm can be used at an application rate of about 100 to 200 liters per 10 ares.
  • the application rate is usually 1 to 10 kg per 10 ares for granules with 5 to 15% of active ingredient.
  • Rukoto used in solution application rate of about 1 to 10 per liter 1 m 2 the concentration range of. 5 to 1000 ppm.
  • seed treatment about 10 to 100 ml of a solution in a concentration range of 10 to 1000 ppm per 1 kg of seed weight can be applied.
  • N- (6-chloro-2-pyridylmethyl) -1,3-dimethylvirazole-15-carboxamide (9.00 g)
  • 4-trifluoromethoxybenzeneboronic acid (10.5 g)
  • toluene 100 ml
  • dioxane 50 ml
  • a mixture of 2M sodium carbonate aqueous solution 50 ml
  • water 25 ml
  • tetrakistriphenylphosphine palladium 3.93 g
  • Powder '-2 parts by weight of the compound of the present invention, 93 parts by weight of clay (manufactured by Nippon Talc), and 5 parts by weight of Kalex Plex # 80 (white carbon, Shionogi & Co., Ltd., trade name) Pulverized to produce a powder containing 2% by weight of active ingredient.
  • the compound (III) disclosed in the above-mentioned JP-A-64-62876 and each of the compounds of the present invention were prepared in the same manner as in Preparation Example 3, and the preparation was diluted to a predetermined concentration with water.
  • the foliage was sprayed at a rate of 10 ml per pot to 1-2-wheat wheat (cultivar: Norin 61) grown in 6 cm pots. After air-drying with chemicals, spray inoculation with a spore suspension obtained from wheat leaves infected with wheat powdery mildew (Erysophe graminis), and then inoculate in a greenhouse? Left for ⁇ 10 days.
  • Each of the compounds of the present invention prepared in the same manner as in Preparation Example 3 was diluted to a predetermined concentration with water, and seedlings were grown in pots of 6 cm in diameter at the 1-2 leaf stage (cultivar: Norin 61 ) Was sprayed with foliage at a rate of 10 ml per pot. After air-drying with chemicals, spraying and spraying a spore suspension obtained by grinding wheat leaves infected with wheat leaf rot (Puccinia recondit), keeping in a wet room at 22 ° C for 15 hours, Left in the bath for 7 days.
  • Cabbage cut leaves (6 cm in diameter) were immersed in a water dilution of the insecticide of the present invention (wettable powder) produced according to the formulation of Formulation Example 1 for the compound of the present invention for 1 minute. After immersion, it was air-dried and placed in a plastic cup (7 cm in inside diameter). Five 3rd-stage insects of Lotus spruce were released into this cup (1 concentration, 2 repetitions). The larvae were kept in a constant temperature room at 25 ° C, and after 5 days from the release, the larvae were examined for viability and agony. The results are shown in Table 6 (in the table below, the compound numbers correspond to Nos in Table 11).
  • the miticide was prepared according to the formulation of Formulation Example 3 by using the compound (III) disclosed in Japanese Patent Application Laid-Open No. Sho 62-62876 and the various lignin compounds of the present invention, respectively, on the leaf with the spider mites. (Emulsion) was immersed (about 5 seconds) in water dilution (1 concentration, 2 repetitions).
  • the pyrazolecarboxamides of the present invention have an excellent control effect against bacterial strains, harmful insects and mites, and are excellent insecticides and acaricides for agriculture, forestry and epidemics. In addition, it is expected to be used as a pesticide for livestock, fisheries, and various kinds of pests in preservation and public health of various products.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne des composés représentés par la formule générale (I), utilisés dans la lutte contre les parasites et ayant une forte activité bactéricide sur divers micro-organismes pathogènes ainsi que de fortes activités insecticides et miticides. La présente invention se rapporte également à des pesticides contenant lesdits composés en tant qu'ingrédient actif ainsi qu'à des intermédiaires représentés par la formule générale (II), dans laquelle chaque substituant a la signification définie dans la description.
PCT/JP2003/000428 2002-01-21 2003-01-20 Carboxamides de pyrazole, intermediaires associes et pesticides contenant ces derniers en tant qu'ingredient actif WO2003062222A1 (fr)

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JP2002-011966 2002-01-21
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JP2002-281980 2002-09-26
JP2002281980A JP2003277362A (ja) 2002-01-21 2002-09-26 ピラゾールカルボキサミド類、その中間体およびこれを有効成分とする有害生物防除剤

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7429604B2 (en) 2004-06-15 2008-09-30 Bristol Myers Squibb Company Six-membered heterocycles useful as serine protease inhibitors
US8563474B2 (en) 2008-07-09 2013-10-22 Basf Se Pestcidal active mixtures comprising isoxazoline compounds I
US8597688B2 (en) 2008-07-09 2013-12-03 Basf Se Pesticidal mixtures comprising isoxazoline compounds II
US8633134B2 (en) 2008-12-23 2014-01-21 Basf Se Substituted amidine compounds for combating animal pests
US8722673B2 (en) 2008-12-23 2014-05-13 Basf Se Imine compounds for combating invertebrate pests
US8999889B2 (en) 2010-02-01 2015-04-07 Basf Se Substituted ketonic isoxazoline compounds and derivatives for combating animal pests
US9732051B2 (en) 2011-12-23 2017-08-15 Basf Se Isothiazoline compounds for combating invertebrate pests
WO2024206357A1 (fr) * 2023-03-29 2024-10-03 Merck Sharp & Dohme Llc Inhibiteurs d'il4i1 et procédés d'utilisation

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* Cited by examiner, † Cited by third party
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WO2005007627A1 (fr) * 2003-07-18 2005-01-27 Nihon Nohyaku Co., Ltd. Derive de phenylpyridine, produit intermediaire correspondant, et herbicide contenant ledit derive de phenylpyridine en tant qu'ingredient actif

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EP0329020A1 (fr) * 1988-02-16 1989-08-23 Mitsubishi Kasei Corporation Dérivés de pyrazole, procedés pour la préparation de ces composés, compositions insecticides, miticides et fongicides contenant ces dérivés comme ingrédients actifs
EP0365925A1 (fr) * 1988-10-14 1990-05-02 Mitsubishi Chemical Corporation Pyrazoles amidiques et insecticides et miticides les contenant
WO1997037990A1 (fr) * 1996-04-05 1997-10-16 Mitsubishi Chemical Corporation Pyrazoles et produits chimiques a usage agricole contenant ces composes comme ingredients actifs
WO1999046247A1 (fr) * 1998-03-11 1999-09-16 Mitsubishi Chemical Corporation Composes a base de pyrazole et produits chimiques agricoles renfermant ces composes en tant que principe actif
JP2001199984A (ja) * 2000-01-24 2001-07-24 Mitsubishi Chemicals Corp ピラゾール−５−カルボン酸アミド類、およびこれを有効成分とする殺虫、殺ダニ剤

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Publication number Priority date Publication date Assignee Title
EP0329020A1 (fr) * 1988-02-16 1989-08-23 Mitsubishi Kasei Corporation Dérivés de pyrazole, procedés pour la préparation de ces composés, compositions insecticides, miticides et fongicides contenant ces dérivés comme ingrédients actifs
EP0365925A1 (fr) * 1988-10-14 1990-05-02 Mitsubishi Chemical Corporation Pyrazoles amidiques et insecticides et miticides les contenant
WO1997037990A1 (fr) * 1996-04-05 1997-10-16 Mitsubishi Chemical Corporation Pyrazoles et produits chimiques a usage agricole contenant ces composes comme ingredients actifs
WO1999046247A1 (fr) * 1998-03-11 1999-09-16 Mitsubishi Chemical Corporation Composes a base de pyrazole et produits chimiques agricoles renfermant ces composes en tant que principe actif
JP2001199984A (ja) * 2000-01-24 2001-07-24 Mitsubishi Chemicals Corp ピラゾール−５−カルボン酸アミド類、およびこれを有効成分とする殺虫、殺ダニ剤

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7429604B2 (en) 2004-06-15 2008-09-30 Bristol Myers Squibb Company Six-membered heterocycles useful as serine protease inhibitors
US8563474B2 (en) 2008-07-09 2013-10-22 Basf Se Pestcidal active mixtures comprising isoxazoline compounds I
US8597688B2 (en) 2008-07-09 2013-12-03 Basf Se Pesticidal mixtures comprising isoxazoline compounds II
US9770029B2 (en) 2008-07-09 2017-09-26 Basf Se Pesticidal active mixtures comprising isoxazoline compounds I
US10231455B2 (en) 2008-07-09 2019-03-19 Basf Se Pesticidal active mixtures comprising isoxazoline compounds I
US10888094B2 (en) 2008-07-09 2021-01-12 Basf Se Pesticidal active mixtures comprising isoxazoline compounds I
US8633134B2 (en) 2008-12-23 2014-01-21 Basf Se Substituted amidine compounds for combating animal pests
US8722673B2 (en) 2008-12-23 2014-05-13 Basf Se Imine compounds for combating invertebrate pests
US8999889B2 (en) 2010-02-01 2015-04-07 Basf Se Substituted ketonic isoxazoline compounds and derivatives for combating animal pests
US9732051B2 (en) 2011-12-23 2017-08-15 Basf Se Isothiazoline compounds for combating invertebrate pests
WO2024206357A1 (fr) * 2023-03-29 2024-10-03 Merck Sharp & Dohme Llc Inhibiteurs d'il4i1 et procédés d'utilisation

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