WO1998030547A1 - Composes heterocycliques azotes, intermediaires pour leur elaboration, procede d'elaboration, et pesticides les contenant comme principe actif - Google Patents

Composes heterocycliques azotes, intermediaires pour leur elaboration, procede d'elaboration, et pesticides les contenant comme principe actif Download PDF

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WO1998030547A1
WO1998030547A1 PCT/JP1998/000084 JP9800084W WO9830547A1 WO 1998030547 A1 WO1998030547 A1 WO 1998030547A1 JP 9800084 W JP9800084 W JP 9800084W WO 9830547 A1 WO9830547 A1 WO 9830547A1
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group
substituent
carbon atoms
yield
tms
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PCT/JP1998/000084
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English (en)
Japanese (ja)
Inventor
Kenji Hirai
Tomoko Matsukawa
Jun Tokumura
Shinichiro Kochi
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Sagami Chemical Research Center
Kaken Pharmaceutical Co., Ltd.
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Priority to JP53075498A priority Critical patent/JP4162719B2/ja
Publication of WO1998030547A1 publication Critical patent/WO1998030547A1/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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms

Definitions

  • the present invention relates to a novel nitrogen-containing heterocyclic compound, an intermediate for producing the same, a method for producing them, and a pesticidal agent containing them as an active ingredient.
  • the present inventors have developed a novel insecticide that is safe against beneficial natural enemies such as spiders and has excellent insecticidal activity against insects and mites harmful to animals and plants.
  • the pyrazol derivative represented by the general formula (1) and the birazolinone derivative represented by the general formula (2) of the present invention are excellent insecticidal and miticidal agents.
  • the present invention was found to show activity and to provide a simple method for producing these compounds.
  • the present invention provides a novel nitrogen-containing heterocyclic compound having excellent insecticidal activity, an intermediate for producing the same, a method for producing them, and a pesticidal agent containing them as an active ingredient. . More specifically, the present invention provides a compound represented by the general formula (1):
  • R 1 represents a phenyl group which may have a substituent
  • R 2 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, Alkenyl group having 2 to 8 carbon atoms, alkynyl group having 2 to 8 carbon atoms, alkynyl group having 2 to 8 carbon atoms, A aralkyl group represented by the formulas 7 to 12, a rubamoyl group which may have a substituent, or an acyl group having a carbon number of 2 to 8.): a virazole derivative represented by the formula: and a general formula (2)
  • R z ′ is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, and a substituent
  • X represents a leaving group, and X is a leaving group
  • the present invention relates to a method for producing a birazolinone derivative represented by the formula:
  • the present invention relates to a pesticidal agent containing, as an active ingredient, a pyrazolinone derivative represented by the formula: BEST MODE FOR CARRYING OUT THE INVENTION
  • the substituent of the “phenyl group which may have a substituent” represented by R 1 includes a halogen atom, a cyano group, a nitro group, and a substituent.
  • substituents include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, and a hexyl group.
  • Examples thereof include a 2-fluorophenoxy group, a 4-fluorophenoxy group, a 4-trifluoromethylphenoxy group, and a 4-tbutylphenoxy group. Further, a plurality of these substituents may be present.
  • the alkyl group having 1 to 30 carbon atoms represented by R 2 and R 2 ′ includes a methyl group, an ethyl group, a propyl group, Examples thereof include isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, pentadecyl, pentadecyl, octadecyl and the like.
  • C 2-8 alkenyl groups include vinyl, aryl, crotyl, methallyl, 1-buten-3-yl, homoallyl, 2-pentenyl, 4-pentenyl, 2 -Hexenyl group, 4-heptenyl group, 7-octenyl group and the like can be exemplified, halogen atom, ditoxyl group, amino group, cyano group, alkoxy group having 1 to 4 carbon atoms, 1 to carbon atom 4 or more may be substituted with an alkoxycarbonyl group, a carboxyl group, a substituted aminocarbonyl group, a hydroxyl group, or the like.
  • alkynyl group having 2 to 8 carbon atoms examples include an ethynyl group, a propargyl group, a levyn-3-yl group, a 2-pentynyl group, and a 3-pentynyl group. May be substituted with one or more alkoxy groups, alkoxycarbonyl groups having 1 to 4 carbon atoms, carboxyl groups and the like.
  • aralkyl group having 7 to 12 carbon atoms include a benzyl group, a phenyl group, a / S-phenyl group, a cumyl group,
  • Examples thereof include a 3-phenylpropyl group and a naphthylmethyl group.
  • One or more may be substituted with a carboxyl group or the like.
  • Examples of the carbamoyl group which may have a substituent include N, N dimethylcarbamoyl, N, N-getylcarbamoyl, N-ethyl-N-cyclohexylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl And a substituted aminocarbonyl group such as a group.
  • Examples of the optionally substituted acetyl group having 2 to 8 carbon atoms include an acetyl group, a chloroacetyl group, a bromoacetyl group, a trifluoroacetyl group, a propionyl group, an ⁇ -chloropropionyl group, and a butanol.
  • substituted aminocarbonyl groups such as a dimethylcarbamoyl group, a getylcarbamoyl group, a morpholinocarbonyl group, a pyrrolidinocarbonyl group and a piperidinocarbonyl group can also be exemplified as the broadly-defined acyl group.
  • the leaving group X in the alkylating agent represented by the general formula (7) includes a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, a P-toluenesulfonyloxy group, a methanesulfonyloxy group.
  • a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, a P-toluenesulfonyloxy group, a methanesulfonyloxy group.
  • a sulfonyloxy group such as a silyl group and a trifluoromethanesulfonyloxy group
  • an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group.
  • Pest control in the present invention means control of particularly harmful pests. Therefore, the pesticidal agent of the present invention includes insecticides, acaricides, etc., and these pesticidal agents can be used in various forms at extremely low drug concentrations. Effective against pests.
  • the insect pests include Namihadani (Tetranychus urticae) N Mikanhatani (Pancmychus citri-), Nissena ⁇ ⁇ " ⁇ (Tetranychus cirmabarinus) ⁇ Kanzafu TeTetranychus kannzawai ⁇ Lingohadani Tet ranychus effetsis (Tet ranychus effetsis) ⁇ Kansani mite, Aculops pelekassi Naya ⁇ ⁇ ⁇ (Polvphagotar-sonemus latus) ⁇ Yuji (Brevipal pus obovatus) ⁇ Dried ticks (Tenuipolpus zruzhilashviliae) ⁇ Crow
  • Agricultural pests such as Lizzor beetles (Lissorhoptrus orzophilus), papilla japonica, Acaie spp., House flies, house cockroaches, fleas, lice, etc .; Storage pests, house pests such as termites, livestock pests such as mites, fleas, lice, etc., indoor dustiness such as acarid mites, Dermatophagoides pteronyssinus, and spider mites Two compounds, and the like.
  • the compound of the present invention can be produced by the method shown in the following reaction formula.
  • Step-1 is a step of reacting the hydrazine derivative (4) with 2-trifluoromethylacrylic acid to produce a carboxylic acid derivative (5).
  • the reaction can be performed in a solvent that does not harm the reaction, but proceeds even in a solvent-free solvent.
  • the solvent examples include aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, cyclobenzene, and dichlorobenzene; Ether solvents such as diisopropyl ether, tetrahydrofuran, dimethoxetane and 1,4-dioxane; halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, etc .; acetonitrile, propionitrile benzonitritol, etc.
  • aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, cyclobenzene, and dichlorobenzene
  • Nitril solvents such as N, N-dimethylformamide, N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, water, etc.
  • a mixed solvent can be used.
  • reaction proceeds sufficiently at room temperature, and the reaction time can be reduced by heating.
  • desired product can be obtained by usual post-treatment, and can also be used as a starting material for the next step without any isolation operation.
  • hydrazine derivative (4) for example, a salt such as a hydrochloride or a sulfate thereof can be used as it is in the reaction. In this case, it is more preferable to carry out the reaction in the presence of an equivalent or more of a base.
  • a base sodium carbonate, potassium carbonate, sodium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium hydride and the like can be used.
  • the reaction solvent the solvents exemplified above can be used, but the reaction can also be carried out by mixing an aqueous base solution and an organic solvent or in a two-phase solvent.
  • Step 12 is a step of cyclizing the carboxylic acid derivative (5) by an intramolecular amidation reaction to produce a birazolidinone derivative (3).
  • a carboxylic acid derivative (5) and a chloroformate such as methyl chloroformate, ethyl ethyl chloroformate, isobutyl chloroformate, etc.
  • Carboxylic acid chlorides such as bivaloyl diisovaleryl chloride, acid anhydrides such as acetic anhydride and trifluoroacetic anhydride, or phosphorus oxychloride diphenylphosphoric acid, etc., may be combined with triethylamine or N-methylmorpholine in some cases.
  • reaction in the presence of a base such as pyridine or pyridine to generate an acid anhydride in the system, whereby the intramolecular cyclization reaction proceeds and the desired virazolidinone derivative (3) can be obtained.
  • a base such as pyridine or pyridine
  • the reaction is preferably carried out in an organic solvent, and tetrahydrofuran, dimethyl ether, chloroform, dichloromethane and the like can be used.
  • the reaction temperature is not particularly limited, but it is usually preferable to carry out the reaction at a temperature selected from 130 ° C. to the solvent reflux temperature in terms of good yield.
  • N'-dicyclohexylcarpoimide DCC :
  • N, ⁇ '-diisopropylpropylcarpoimide DIPC
  • N-ethyl- N-ethyl-
  • carbodimids such as N '(3-dimethylaminopropyl) carbodimid hydrochloride ⁇ carbonyl diimidazole or the like as a coupling reagent
  • the desired bilazolidinone derivative (3) can be produced in good yield. it can.
  • the reaction may be performed in the presence of 1-oxybenzotriazole (H0BT).
  • H0BT 1-oxybenzotriazole
  • the reaction is preferably carried out in an organic solvent, and tetrahydrofuran, diethyl ether, chloroform, dichloromethane, ethyl acetate and the like can be used.
  • the reaction temperature it is usually preferable to carry out the reaction at a low temperature of about 0 ° C. to room temperature from the viewpoint of good yield.
  • Step one 3 by oxidatively dehydrogenated with bromine Birazorijinon derivative (3), the amount of c bromine is a step for preparing a Birazorino emissions derivative (6) is stoichiometrically material
  • the desired product can be obtained in good yield.
  • the reaction must be performed in a solvent, and any solvent that does not react with bromine can be used.
  • an ether solvent such as getyl ether, tetrahydrofuran, 1,4-dioxane or the like in terms of good yield.
  • the reaction is preferably carried out at a temperature of about 0 ° C. to about room temperature because the generation of by-products is small.
  • Step 14 comprises reacting the birazolinone derivative (6) with the alkylating agent (7) in the presence of a base to obtain a pyrazolin derivative ( ⁇ ) and a birazolinone derivative
  • Examples of the base include sodium hydroxide, sodium amide, sodium carbonate, sodium carbonate, sodium methoxide, sodium ethoxide-t-butoxide potassium, sodium hydroxide, potassium hydroxide, and other alkali metals.
  • Metal bases can be used. The amount of base used is
  • the desired product can be obtained in good yield.
  • the reaction is carried out in an organic solvent that does not hinder the progress of the reaction.
  • Solvents include getyl ether, tetrahydrofuran, dimethyloxetane, 1,4-dioxane, acetone, methylethyl ketone, acetonitrile, propionitrile, Toluene, xylene, N, N-dimethylformamide.
  • N-methylpyrrolidone, dimethyl sulfoxide and the like can be used (The reaction temperature is not particularly limited, but is selected from the range of o to ioo ° c.
  • a mixture of the pyrazole derivative ( ⁇ ) and the pyrazolinone derivative (2 ′) can be obtained by ordinary post-treatment, but these can be easily separated by using a silica gel column.
  • a developing solvent for the column for example, a mixed solvent of a polar solvent such as ethyl acetate, toluene, and chloroform and a non-polar solvent such as hexane and pennane is used so that the polarity suitable for the compound to be separated is obtained.
  • the desired product can be easily isolated by adjusting the composition ratio.
  • 2,5-Difluorophenylhydrazine (2,000 g, 13.9 leaked ol) and methylene chloride (30 mL) were put into an eggplant-shaped flask (100 cc) and dissolved.
  • ⁇ -trifluoromethylacrylic acid (2.14 g, 15.3 rol) under ice-cooling, the temperature was gradually raised to room temperature, and the mixture was stirred for 4.5 hours.
  • MSCM / e, relative intensity 286 (M + + 2 , 1.20), 285 (+ + 1, 12.09), 284 (M +, 100).
  • N- (4-Chloro-5-cyclopentyloxy 2-fluorophenyl) hydrazine (4.00 g, 16.4 gol ol) and methylene chloride (30 mL) were put into an eggplant-shaped flask (100cc) and dissolved.
  • ⁇ -trifluoromethylacrylic acid (2.52 g, 18. Ommol) under ice-cooling, and the temperature was gradually raised to room temperature, followed by stirring for 12 hours. After completion of the reaction, the reaction mixture was poured into 1N-hydrochloric acid (20 mL) and extracted with ethyl acetate (10 mL ⁇ 2).
  • Trifluoromethylpropionic acid (3. Tig, 13.6 mmol) and methylene chloride (30 mL) are put into an eggplant-shaped flask (100cc) and dissolved. Was. To this solution was added ⁇ , ⁇ '-dicylhexylcarbodiimide (3.09 g, 15.Ommol) under ice-cooling, and the temperature was gradually raised to room temperature, followed by stirring for 7 hours.
  • ⁇ '-Dicyclohexylurea was removed by celite filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product, which was recrystallized from geethylether, and further purified by a silica gel column (acetic acid). And purified by recrystallization from hexane to give 2- (2,5 difluorophenyl) 4-trifluoromethylvirazolidine-3-one. (4.96 g, 99.9% yield).
  • MSCm / e, relative strength 258 (M + +2, 1.21), 257 (M + ll, 14.82), 256 (M tens, 100).
  • reaction mixture was poured into 1N-hydrochloric acid (50 mL), extracted with ethyl acetate (20 mL ⁇ 3), and the organic layer was washed with water (20 mL) and 1N hydrochloric acid (20 mL ⁇ 2). After the organic layer was dried over anhydrous magnesium sulfate, the desiccant was removed, and the solvent was distilled off under reduced pressure.
  • MSCm / e, relative strength 375 (M + +5, 3.07), 374 ( ⁇ + +4, 2.96), 373 ( ⁇ + 3 18.56), 372 ( ⁇ 2 10.27), 371 ( ⁇ + + 1, 54.58), 370 ( ⁇ 9.26), 329 (100).
  • the organic layer was washed with 1N hydrochloric acid (20 mL x 2) and water (20 mL), dried over anhydrous magnesium sulfate, and dried to remove the desiccant. The solvent was removed and the solvent was distilled off under reduced pressure.
  • reaction mixture was poured into 1N-hydrochloric acid (50 mL), extracted with ethyl acetate (30 mLx2), and the organic layer was washed with 1N hydrochloric acid (10 mLx2) and water (10 mL), and dried over anhydrous magnesium sulfate. The desiccant was removed, and the solvent was distilled off under reduced pressure.
  • reaction mixture was poured into 1N-hydrochloric acid (50 mL), extracted with ethyl acetate (30 mLx2), and the organic layer was washed with 1N-hydrochloric acid (10 mLx2) and water (10 mL), and dried over anhydrous magnesium sulfate. Thereafter, the desiccant was removed and the solvent was distilled off under reduced pressure.
  • reaction mixture was poured into 1N-hydrochloric acid (50 mL), extracted with ethyl acetate (30 mLx2), the organic layer was washed with 1N-hydrochloric acid (20 mLx2) and water (20 mL), and dried over anhydrous magnesium sulfate. The desiccant was removed, and the solvent was distilled off under reduced pressure.
  • reaction mixture was poured into 1N-hydrochloric acid (50 mL), extracted with ethyl acetate (30 mLx2), and the organic layer was washed with 1N hydrochloric acid (20 mLx2) and water (20 mL), and then dried over anhydrous magnesium sulfate. Thereafter, the desiccant was removed and the solvent was distilled off under reduced pressure.
  • Example 1 By dehydrogenating the chloromethylpyrazolidine-3-one derivative with bromine, the corresponding 2-aryl-4-trifluoromethylpyrazolin-3-one derivatives were obtained. The yield, spectrum data, and the like are shown below as Example 1-1 15 to 120.
  • Example 1 Various aryl electrophiles were reacted by the same reaction procedure as in Example 1-22 using aryl-4 trifluoromethylbirazolin-3-one, and alkylation or acylation was performed. The corresponding 0-substituted and Z- or N-substituted respectively were obtained. The yield, spectrum data, and the like are shown below as Examples—123 to 160.
  • the pyrazole derivative wherein R 2 is represented by the general formula (1) is a hydrogen atom
  • R 2 is a hydrogen atom
  • the birazolinone derivative represented by the general formula (2) is a tautomer-its structure is thermodynamically more stable than that of the birazolinone derivative, and is observed as a birazolinone structure in various spectra.
  • these compounds are shown in Table 12 in which R 2 is a hydrogen atom.
  • the compound of the present invention when used as a pesticide, it can be used as it is, but in general, one or more kinds of extenders can be used as a mixture.
  • one or more kinds of extenders can be used as a mixture.
  • solid carrier Usually, as a bulking agent, solid carrier, solvent, surfactant And stabilizers, etc., and can be put to practical use in any dosage form such as hydrates, emulsions, powders, and flowables by conventional methods.
  • solid carriers examples include Kaolin clay, Attapulgite clay, Sericite clay, and No.
  • Mineral carriers such as ilofiraite clay, montmorillonite clay, zeolite, bentonite, acid clay, activated clay, serpentine, talc, and diatomaceous earth; inorganic salts such as sulfates, nitrates, and chlorides;
  • inorganic carriers such as synthetic carriers such as silica, and organic carriers such as sugars, starch, dextrin, wheat flour, corn flour, and wood flour.
  • the solvent examples include water, alcohols (isopropyl alcohol, butyl alcohol, benzyl alcohol, furfuryl alcohol, etc.), ketones (methylethyl ketone, cyclohexanone, isophorone, etc.), ethers ( Anisol, etc.), aliphatic and aromatic hydrocarbons (methylnaphthalene, dimethylnaphthalene, toluene, xylene, etc.), halogenated hydrocarbons (chlorobenzene, dichlorobenzene, etc.), acid amides (N-methylbirolidone, N , N-dimethylformamide, etc.), esters (butyl acetate, etc.), nitriles, etc., and one or a mixture of two or more thereof is used.
  • alcohols isopropyl alcohol, butyl alcohol, benzyl alcohol, furfuryl alcohol, etc.
  • ketones methylethyl ketone, cyclohexanone,
  • a surfactant may be used as a spreading agent, a dispersant, an emulsifier, a penetrant, a thickener, or a stabilizer.
  • surfactants include nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like.
  • polycarboxylates More specifically, polycarboxylates, polyoxyethylene alkylaryl ethers, and polycarboxylic acid surfactants Oxysorbitan alkylates, dialkylsulfosuccinate salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, ligninsulfonates, dinaphthylmethanedisulfonates, alkyl sulfates and the like. These surfactants are used as one type or as a mixture of two or more types depending on the application. Further, other auxiliary agents include carboxymethylcellulose, sodium alginate, propylene glycol, polyethylene glycol, xanthan gum, gum arabic and the like.
  • the compounding ratio of the active ingredient is appropriately selected according to need, but 0.01 to 30% (weight ratio) for powders or granules, 1 to 30% for emulsions, wettable powders or flowables. 80% (weight ratio) is appropriate.
  • emulsion, a wettable powder or a flowable formulation sprayed diluted with a predetermined amount of water, dust or granules can pesticidal as an active ingredient c the compounds of this invention which directly sprayed without dilution with water ⁇ means other active ingredients which do not inhibit the activity of the present active ingredient at the time of formulation or spraying if necessary, such as other insecticides, acaricides, herbicides, fungicides, plant growth regulators It is also possible to mix or use together with a synergist and the like.
  • the pest control agent of the present invention can exert excellent effects by methods such as soil treatment, foliage spraying treatment, and water surface treatment.
  • the amount of application varies depending on the application scene, application period, application method, control target, cultivated crop, type of application, etc., but the amount of active ingredient per hectare is usually in the range of 0.005 to 50 kg. It is.
  • a sponge moistened with water was placed in a 9 cm diameter petri dish, a mouth paper was placed on top of the sponge, and a bean leaf was placed. Twenty female female mites were inoculated on the leaves of kidney beans, and 24 hours later, unhealthy mites were removed.
  • the emulsion prepared according to Formulation Example 11 was diluted with water and sprayed with a spraying device so as to have a predetermined concentration (500 ppm) and a chemical solution adhesion amount (4. Omg / cm 2 ).
  • the petri dish was placed in a constant temperature room at 25 ° C, and the killing mite effect was evaluated 48 hours after spraying.
  • the ovicidal effect was evaluated by inoculating 20 female mites of the two-spotted mites under the same conditions, removing unhealthy mites after 24 hours, confirming oviposition, removing all female mites, and The emulsion prepared according to Example 11 was diluted with water, and sprayed with a spraying device so as to have the same concentration and the same amount of drug solution as in the killing mite test. One week after spraying, the ovicidal effect was determined. Each test was performed in duplicate, and the results are shown in Table-4. Table 1 4. Effects on Namihada two
  • a sponge moistened with water was placed in a 9-cm-diameter petri dish, a paper slip was placed on top of the sponge, and a 20-mm-diameter circular Satsuma mandarin leaf was placed with a leaf punch.
  • the mandarin leaf is inoculated with 10 female adult mites of the red mandarin, 24 hours Later, the unhealthy ticks were removed.
  • the hydrated ⁇ prepared according to Formulation Example 12 was diluted with water, and sprayed with a spraying device so as to have a predetermined concentration (500 ppm) and a chemical solution adhesion amount (4. Omg / cm 2 ).
  • the killing mite effect was determined 48 hours after spraying.
  • the ovicidal effect was evaluated by inoculating 10 female female mites under the same conditions, removing unhealthy mites after 24 hours, confirming oviposition, removing all female mites, and The wettable powder prepared according to -2 was diluted with water and sprayed with a spraying device so that the same concentration and the amount of the drug solution adhered to the test for killing mites were obtained.
  • the ovicidal effect was determined. Each test was performed in duplicate, and the results are shown in Table 1-5.
  • a wettable powder prepared according to Formulation Example 12 was diluted with water to a concentration of 500 ppm with the active ingredient.
  • the cut cabbage leaves (4 cm x 4 cm) were immersed in this aqueous solution for 30 seconds, air-dried, placed in a round polyethylene cup having a diameter of 5 cm, and five 3rd instar larvae were released.
  • the vessels were placed in a constant temperature room at 25 ° C, and 24 hours and 48 hours later, the life and death of the diamondback moth, the moulting inhibition and the presence of pupation after that were investigated, and the mortality rate until the pupa was formed was determined.
  • the test was performed in three consecutive sessions, and the results are shown in Table-6. Table 1 6. Effects on Conaga
  • the compound of the present invention has excellent insecticidal and acaricidal activity at a very low applied dose against many agricultural pests, sanitary pests and mites, and has almost no adverse effect on mammals, fish and beneficial insects. Absent. Therefore, the compound of the present invention can provide an effective pest control agent.

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  • Chemical & Material Sciences (AREA)
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Abstract

Composés hétérocycliques azotés (par exemple, dérivés de pyrazole ou de pyrazolinone), très efficaces comme principe actif des pesticides, notamment les insecticides et acaricides; intermédiaires pour leur élaboration et procédé d'élaboration. Les dérivés de pyrazole de formule générale (1) et/ou les dérivés de pyrazolinone de formule générale (2) peuvent être obtenus par réaction entre un composé de formule générale (6) et un agent d'alkylation, en présence d'une base, le composé de formule générale (6) étant préparé, par exemple, à partir d'un dérivé d'arylhydrazine et d'acide 2-trifluorométhylacrylique par addition et déshydrogénation oxydante.
PCT/JP1998/000084 1997-01-14 1998-01-13 Composes heterocycliques azotes, intermediaires pour leur elaboration, procede d'elaboration, et pesticides les contenant comme principe actif WO1998030547A1 (fr)

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JP53075498A JP4162719B2 (ja) 1997-01-14 1998-01-13 含窒素複素環化合物、それらの製造中間体、それらの製造方法及びそれらを有効成分として含有する有害生物防除剤

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5583751A (en) * 1978-12-18 1980-06-24 Nippon Nohyaku Co Ltd Pypazole derivative, its preparation, and herbicide containing the same
JPS6335563A (ja) * 1986-07-30 1988-02-16 バイエル・アクチエンゲゼルシヤフト ４−シアノ（ニトロ）−５−オキシ（チオ）−ピラゾ−ル誘導体
JPH07507265A (ja) * 1991-08-20 1995-08-10 コリア リサーチ インスティチュート オブ ケミカル テクノロジー ピラゾールを含むベンゾイルウレア誘導体、組成物及び用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5583751A (en) * 1978-12-18 1980-06-24 Nippon Nohyaku Co Ltd Pypazole derivative, its preparation, and herbicide containing the same
JPS6335563A (ja) * 1986-07-30 1988-02-16 バイエル・アクチエンゲゼルシヤフト ４−シアノ（ニトロ）−５−オキシ（チオ）−ピラゾ−ル誘導体
JPH07507265A (ja) * 1991-08-20 1995-08-10 コリア リサーチ インスティチュート オブ ケミカル テクノロジー ピラゾールを含むベンゾイルウレア誘導体、組成物及び用途

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