WO1994011340A1 - Hydrazone derivative - Google Patents

Hydrazone derivative Download PDF

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Publication number
WO1994011340A1
WO1994011340A1 PCT/JP1993/001648 JP9301648W WO9411340A1 WO 1994011340 A1 WO1994011340 A1 WO 1994011340A1 JP 9301648 W JP9301648 W JP 9301648W WO 9411340 A1 WO9411340 A1 WO 9411340A1
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WO
WIPO (PCT)
Prior art keywords
group
optionally substituted
substituted
alkyl group
hydrogen atom
Prior art date
Application number
PCT/JP1993/001648
Other languages
French (fr)
Japanese (ja)
Inventor
Takashi Kishimoto
Michihiko Matsuda
Renpei Hatano
Makio Yano
Jun Mitsui
Original Assignee
Nippon Soda Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to AU54337/94A priority Critical patent/AU5433794A/en
Publication of WO1994011340A1 publication Critical patent/WO1994011340A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-nitrogen bonds, e.g. azides, diazo-amino compounds, diazonium compounds, hydrazine derivatives
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/22—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having nitrogen atoms of amidino groups further bound to nitrogen atoms, e.g. hydrazidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/02—Compounds containing any of the groups, e.g. carbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/48—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • 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
    • C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/28—Nitrogen atoms
    • C07D295/32—Nitrogen atoms acylated with carboxylic or carbonic acids, or their nitrogen or sulfur analogues
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • the non-invention relates to a novel hydrazone derivative and a pesticide.
  • Background technology :
  • organophosphorus pesticides such as parathion and malazone
  • carbamate pesticides such as kylarvalyl and mesomil.
  • organophosphorus pesticides such as parathion and malazone
  • carbamate pesticides such as kylarvalyl and mesomil.
  • These insecticides have played an extremely important role in improving agricultural production.However, in recent years, the use of some of these insecticides has been restricted due to problems such as residual and accumulated environmental pollution, and resistant pests have been identified as a result of long-term use. What happened is coming out. Therefore, there is a demand for the development of a new drug that has excellent insecticidal properties against various pests including these resistant pests and can be used safely.
  • EP 50011 is known as a compound similar to the compound of the present invention, but its acaricidal activity is not necessarily sufficient.
  • An object of the present invention is to provide an agricultural chemical that can be synthesized industrially advantageously, has a certain effect, and can be used safely. Disclosure of the invention:
  • the present invention has the general formula (I)
  • X is a halogen atom, an optionally substituted alkyl group, Alkoxy group, cycloalkyloxy group which may be substituted, alkylsulfonyloxy group which may be substituted, alkylthio group which may be substituted or alkylsulfonyl group which may be substituted.
  • R represents a hydrogen atom or an optionally substituted alkyl group
  • R 2 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted alkoxycarbonyl group, A phenylcarboxy group which may be substituted or a phenylcarbamoyl group which may be substituted,
  • NR and R 2 may be taken together to form a 5- to 7-membered heterocyclic group containing N which may be substituted (provided that R and R 2 are further 1 to 2 Nitrogen or oxygen atoms),
  • R 3 represents a hydrogen atom or an optionally substituted alkyl group
  • R 4 represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group,
  • A represents a sulfur atom, an oxygen atom, an alkylene which may be substituted, alkylidene which may be substituted, carbonyl or N r 4 (where, r 4 is an alkyl group which may optionally be a hydrogen atom or a substitution. ),
  • n 0 or 1
  • Y represents an optionally substituted phenyl group or an optionally substituted pyridyl group.
  • examples of the group that substitutes alkyl or alkoxy include a halogen atom.
  • examples of the group for substituting fuunyl include a halogen atom, alkyl, haloalkyl, alkoxy, quino, loalkoxy, cycloalkyloxy and the like.
  • Examples of the group that substitutes the heterocyclic group include alkyl.
  • Examples of the group that substitutes a pyridyl group include a halogen atom.
  • the carbon number of alkyl and alkoxy is 1 to 6
  • the carbon number of cycloalkyl is 3 to 8
  • the carbon number of alkenyl and alkynyl is 2 to 6.
  • X, R,, R 2 , R 3 , R 4 , ⁇ , ⁇ , and ⁇ ⁇ have the same meanings as described above.
  • the reaction is carried out for 1 hour to several 10 hours in an organic solvent, if necessary, in the presence of an acid catalyst, at 0 ° C. to 200 ° C., and up to the boiling point of the solvent when a solvent is used.
  • the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, halogenated hydrocarbons such as carbon tetraform, carbon tetrachloride, and 1,2-dichloroethane, and tetrahydrofura.
  • ethers such as dioxane and dioxane.
  • R 5 and Re are the same or different and each represent a hydrogen atom, an optionally substituted alkyl group, and R 7 represents an optionally substituted alkyl group;
  • X, R 3 , A, n and Y have the same meaning as described above.
  • the reaction is carried out in an organic solvent, if desired, at 0 ° C. to 200 ° C. and, when a solvent is used, up to the boiling point of the solvent, for 1 hour to several 10 hours.
  • the solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and 1,2-dichloroethane, and tetrahydrocarbon.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • halogenated hydrocarbons such as chloroform, carbon tetrachloride, and 1,2-dichloroethane
  • Ethers such as drofuran and dioxane can be used.
  • the desired product can be obtained by performing ordinary post-treatment.
  • the structure of the compound of the present invention was determined from IR, NMR, MS and the like. BEST MODE FOR CARRYING OUT THE INVENTION
  • Example 1 4 'monochloro-2,2-dimethyl-2 -furanacetophenoxycarbonylhydrazone (Compound No. 4)
  • N C— N (CH 3 )
  • N C-NMe 2 mp
  • N C-thigh e 2
  • N CN e 2
  • the compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests, and the like, and has an insecticidal, nymphicidal, larvicidal and ovicidal action.
  • the following are typical examples.
  • Lepidopteran pests for example, Hasmonyoto, Totoga, Evening Managaga, Aomushi, Evening Managinaba, Konaga, Chino Kokakumonhamaki, Chiyamahamaki, Momoshinguiga, Nashihime Shinki, Mikanhamogiga, Chiya Nogamihoga Kameiga, Kobuno Meiga, Yo-Mouth Biancon Borra I, Ameri Kashiro Hitori, Sujimadarameiga, Heliotis, Helicoverpa, Agrotis, Iga, Kodlinga, Peta mimushi, etc.
  • Hemiptera pests such as peach aphids, evening aphids, Nisedai aphids, wheat bilee aphids, hosohelium stink bugs, stag beetles, stalks Coleoptera, Psyllides, Colorado beetle, Rice beetle, Coleoptera , Bean beetle, Burdock beetle, Diablotica, Tobacco beetle, Beetle bark beetle, Matsunomadara power beetle, Gomadara bee beetle, Agriotis genus, Nigyuyahoshten tou, Kokunusuto, Kota mizobushi, etc.
  • Pests of the eye e.g., fly, oak mouth flies, senchiniku flies, peri-mipa'e, mikanko mipa'e, corn flies, rice hammogliae, yellow flies, flies, flies, koga takaye, anetaishima power, shinahamadara Etc., insects of the order Thysanoptera, such as Thrips palmi Karny, Thrips japonicus, Hymenoptera, pests, such as C. elegans, C.
  • the compound of the present invention is an agent having an excellent insecticidal effect not only on susceptible strains, but also against pests of organic phosphorus agents, carbamates, pyrethroids, and resistant systems.
  • the pesticidal composition of the present invention contains a compound represented by the general formula [I] or a salt thereof as an active ingredient, and can be used as an active ingredient in a pure form.
  • the pesticide ie, wettable powder, water solvent, powder, emulsion, granule, flowable and the like.
  • solid additives such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, clay, etc.
  • Organic and inorganic compounds such as fine powder, sodium benzoate, urea and sodium sulfate are used.
  • liquid dosage forms vegetable oils, mineral oils, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, trichlor
  • ethylene, methyl isobutyl ketone, water, etc. as solvents.
  • a surfactant can be added if necessary to obtain a uniform and stable form.
  • the wettable powder, emulsion, aqueous solution, and flowable thus obtained are diluted to a predetermined concentration with water to form a suspension or emulsion, and powders and granules are sprayed on plants as they are. Used in.
  • the compound of the present invention alone is sufficiently effective, but it can also be used in combination with various insecticides, acaricides, nematicides, fungicides and synergists.
  • insecticides and acaricides that can be used by mixing with the compound of the present invention are shown below.
  • Organophosphorus and carbamate insecticides Phenthion, Phenyltrothion, Diazinone, Chlorpyrifos, ESP'Midothion, Phentoate, Dimethoate, Formothion, Marathon, Trichlorfon, Thiometone, Phosmet, Dichlorvos , Acetate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicion, cyano hos, isoxathion, pyridaphthion, hosalon, methidathion, sulprophos, chlorfenbimphos, tetracloth Lorubinphos, Dimethylbinphos, Propaphos, Isofenphos, Ethylthiomethone, Profenofos, Pyraclofos, Monocrotophos, Azinphosmethyl, Aldicarb, Mesomil, Thiodicarp, Carbofuran, Carbosulfan, Py
  • Example 5 wettable powder
  • Example 7 granules
  • the compound was diluted with water so that the compound concentration became 125 ppm.
  • the corn leaves were immersed in the chemical solution for 30 seconds, air-dried, and then put into a petri dish containing five Atoto 3rd instar larvae.
  • the glass lid was put on the container, and the mixture was placed in a constant temperature room at a temperature of 25 ° C and a humidity of 65%. Two iterations. The results are shown in Table 2.
  • N CH-N (CH 3 3) 2 HC 1

Abstract

A compound representd by general formula (I), a salt thereof, and a pest control agent, wherein: X represents halogen, alkyl, alkoxy, cycloalkyloxy, alkylsulfonyloxy, alkylthio or alkylsulfonyl; R1 represents hydrogen or alkyl; R2 represents hydrogen, alkyl, alkylcarbonyl, alkylcarbamoyl, alkoxycarbonyl, phenylcarbonyl or phenylcarbamoyl; or alternatively, R1 and R2 may be combined together to form =C(r1)Nr2r3, or NR1R2 may form a heterocycle; R3 represents hydrogen or alkyl; R4 represents alkyl, alkenyl or alkynyl; A represents S, O, alkylene, alkylidene, carbonyl or Nr4; n represents 0 or 1; and Y represents phenyl or pyridyl.

Description

明 細 書 ヒ ドラゾン誘導体 技術分野：  Description Hydrazone derivatives Technical fields:
未発明は、 新規なヒ ドラゾン誘導体及び有害生物防除剤に関する。 背景技術：  The non-invention relates to a novel hydrazone derivative and a pesticide. Background technology:
多年にわたる殺虫剤の研究開発によって多くの薬剤、 例えばパラチオン、 マラ ソ ン等の有機リ ン系殺虫剤、 力ルバリル、 メ ソミル等のカーバメー ト系殺虫剤な どが開発され実用化されて来た。 これら殺虫剤が農業の生産向上に果した役割は 極めて大きいが近年、 これらの殺虫剤の中には残留、 蓄積環境汚染等の問題から 使用が規制されたり、 長期使用の結果として抵抗性害虫を発生せしめたものが出 て来ている。 従って、 これら抵抗性害虫をはじめ各種害虫に卓越した殺虫特性を 有し、 安全に使用できる新規薬剤の開発が要望されている。  Over the years of research and development of insecticides, many drugs have been developed and put into practical use, for example, organophosphorus pesticides such as parathion and malazone, and carbamate pesticides such as kylarvalyl and mesomil. . These insecticides have played an extremely important role in improving agricultural production.However, in recent years, the use of some of these insecticides has been restricted due to problems such as residual and accumulated environmental pollution, and resistant pests have been identified as a result of long-term use. What happened is coming out. Therefore, there is a demand for the development of a new drug that has excellent insecticidal properties against various pests including these resistant pests and can be used safely.
本発明化合物と類似の化合物を開示したものとして E P 5 0 0 1 1 1が知ら れているが殺ダニ活性は必ずしも十分であるとは言えない。  EP 50011 is known as a compound similar to the compound of the present invention, but its acaricidal activity is not necessarily sufficient.
本発明の目的は工業的に有利に合成でき、 効果が確実で安全に使用できる農薬 を提供することである。 発明の開示 ：  An object of the present invention is to provide an agricultural chemical that can be synthesized industrially advantageously, has a certain effect, and can be used safely. Disclosure of the invention:
本発明は一般式 〔 I〕  The present invention has the general formula (I)
R
Figure imgf000003_0001
R
Figure imgf000003_0001
R R
N N
R K R K
〔式中、 Xはハロゲン原子、 置換されていてもよいアルキル基、 置換されていて もよ.いアルコキシ基、 置換されていてもよいシクロアルキルォキシ基、 置換され ていてもよいアルキルスルフォニルォキシ基、 置換されていてもよいアルキルチ ォ基または置換されていてもよいアルキルスルフォニル基を表し、 Wherein X is a halogen atom, an optionally substituted alkyl group, Alkoxy group, cycloalkyloxy group which may be substituted, alkylsulfonyloxy group which may be substituted, alkylthio group which may be substituted or alkylsulfonyl group which may be substituted. Represents
R , は水素原子または置換されていてもよいアルキル基を表し、  R, represents a hydrogen atom or an optionally substituted alkyl group,
R 2 は水素原子、 置換されていてもよいアルキル基、 置換されていてもよいァ ルキルカルボニル基、 置換されていてもよいアルキル力ルバモイル基、 置換され ていてもよいアルコキシカルボニル基、 置換されていてもよいフェニルカルボ二 ル基または置換されていてもよいフヱ二ルカルバモイル基を表し、 R 2 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted alkoxycarbonyl group, A phenylcarboxy group which may be substituted or a phenylcarbamoyl group which may be substituted,
また R , と R 2 が一緒になつて、 = C ( r , ) N r 2 r 3 (式中、 r , 、 r 2 、 r a は同一または相異なって水素原子または置換されていてもよいアルキル基 を表す。 ） を形成してもよく 、 The R, and R 2 is together such connexion, = C (r,) in N r 2 r 3 (wherein, r,, r 2, ra is an optionally hydrogen atom or a substituent the same or different alkyl Represents a group;) may be formed,
さ らに、 N R , R 2 は一緒になつて置換されていてもよい Nを含む 5〜 7員環 の複素環基を形成してもよく （但し R , R 2 はさ らに 1 ~ 2個の窒素原子または 酸素原子を含んでもよい） 、 Further, NR and R 2 may be taken together to form a 5- to 7-membered heterocyclic group containing N which may be substituted (provided that R and R 2 are further 1 to 2 Nitrogen or oxygen atoms),
R 3 は水素原子または置換されていてもよいアルキル基を表し、 R 3 represents a hydrogen atom or an optionally substituted alkyl group,
R 4 は置換されていてもよいアルキル基、 置換されていてもよいアルケニル基 または置換されていてもよいアルキニル基を表し、 R 4 represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group,
Aは硫黄原子、 酸素原子、 置換されていてもよいアルキレン、 置換されていて もよいアルキリデン、 カルボニルまたは N r 4 (式中、 r 4 は水素原子または置 換されていてもよいアルキルを表す。 ） を表し、 A represents a sulfur atom, an oxygen atom, an alkylene which may be substituted, alkylidene which may be substituted, carbonyl or N r 4 (where, r 4 is an alkyl group which may optionally be a hydrogen atom or a substitution. ),
nは 0 または 1 を表し、  n represents 0 or 1,
Yは置換されていてもよいフヱニル基または置換されていてもよいピリ ジル基 を表す。 〕  Y represents an optionally substituted phenyl group or an optionally substituted pyridyl group. ]
で表される化合物またはその塩及び有害生物防除剤である。 Or a salt thereof and a pesticide.
本発明において、 アルキル、 アルコシキを置換する基と しては、 例えばハロゲ ン原子などが挙げられる。 フユニルを置換する基と しては、 例えばハロゲン原子 、 アルキル、 ハロアルキル、 アルコキシ、 ノ、ロアルコキシ、 シクロアルキルォキ シなどが挙げられる。 複素環基を置換する基と しては例えばアルキルなどが挙げ られる。 ピリ ジル基を置換する基と しては、 例えばハロゲン原子などが挙げられ る。 また通常、 アルキル、 アルコキシの炭素数は 1 ~ 6であり、 シクロアルキル の炭素数は 3 ~ 8であり、 アルケニル、 アルキニルの炭素数は 2 ~ 6である。 本発明の化合物の製造方法は、 次の通りである。 In the present invention, examples of the group that substitutes alkyl or alkoxy include a halogen atom. Examples of the group for substituting fuunyl include a halogen atom, alkyl, haloalkyl, alkoxy, quino, loalkoxy, cycloalkyloxy and the like. Examples of the group that substitutes the heterocyclic group include alkyl. Examples of the group that substitutes a pyridyl group include a halogen atom. You. Usually, the carbon number of alkyl and alkoxy is 1 to 6, the carbon number of cycloalkyl is 3 to 8, and the carbon number of alkenyl and alkynyl is 2 to 6. The method for producing the compound of the present invention is as follows.
製造方法 1 Manufacturing method 1
R  R
R .  R.
(A) 一 Y + Η 2 Ν - Ν  (A) One Y + Η 2 Ν-Ν
X R 2  X R 2
R  R
グ R  R
o  o
( Α) „ 一 Υ (Α) „one Υ
Figure imgf000006_0001
Figure imgf000006_0001
R R
Ν Ν
R R R R
X、 R, 、 R2 、 R3 、 R4 、 Α、 η、 Υは前記と同じ意味を示す。 X, R,, R 2 , R 3 , R 4 , Α, η, and 示 す have the same meanings as described above.
反応は所望により有機溶媒中、 所望により酸触媒存在下、 0 °Cから 2 0 0 °C、 溶媒を用いる場合にはその溶媒の沸点までで、 1時間から数 1 0時間行われる。 溶媒と しては、 例えばベンゼン、 トルエン、 キシレン、 クロルベンゼン等の芳香 族炭化水素類、 クロ口ホルム、 四塩化炭素、 1 , 2—ジクロロェタ ン等のハロゲ ン化炭化水素類、 テ トラ ヒ ドロフラ ン、 ジォキサン等のエーテル類等が使用でき る。  The reaction is carried out for 1 hour to several 10 hours in an organic solvent, if necessary, in the presence of an acid catalyst, at 0 ° C. to 200 ° C., and up to the boiling point of the solvent when a solvent is used. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, halogenated hydrocarbons such as carbon tetraform, carbon tetrachloride, and 1,2-dichloroethane, and tetrahydrofura. And ethers such as dioxane and dioxane.
酸触媒と しては、 硫酸、 塩酸、 パラ トルエンスルフ ォ ン酸等が使用できる。 製造方法 2  As the acid catalyst, sulfuric acid, hydrochloric acid, paratoluenesulfonic acid and the like can be used. Manufacturing method 2
R3
Figure imgf000006_0002
R 3
Figure imgf000006_0002
R R
N H N H
R  R
(A) „ 一 Y (A)
Figure imgf000006_0003
Figure imgf000006_0003
R R 上記反応式において R5 、 Re は同一も しく は異なって、 水素原子、 置換され ていてもよいアルキル基、 R7 は置換されていてもよいアルキル基を示し、 X、 R3 、 、 A、 n、 Yは前記と同じ意味を示す。 RR In the above reaction formula, R 5 and Re are the same or different and each represent a hydrogen atom, an optionally substituted alkyl group, and R 7 represents an optionally substituted alkyl group; X, R 3 , A, n and Y have the same meaning as described above.
反応は所望により有機溶媒中、 0 °Cから 2 0 0 °C、 溶媒を用いる場合にはその 溶媒の沸点までで、 1 時間から数 1 0時間行われる。  The reaction is carried out in an organic solvent, if desired, at 0 ° C. to 200 ° C. and, when a solvent is used, up to the boiling point of the solvent, for 1 hour to several 10 hours.
溶媒と しては、 例えばベンゼン、 トルエン、 キシレン、 クロルベンゼン等の芳 香族炭化水素類、 クロ口ホルム、 四塩化炭素、 1 , 2 —ジクロロェタ ン等のハロ ゲン化炭化水素類、 テ トラ ヒ ドロフラン、 ジォキサン等のエーテル類等が使用で きる。  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and 1,2-dichloroethane, and tetrahydrocarbon. Ethers such as drofuran and dioxane can be used.
反応終了後は通常の後処理を行う ことにより目的物を得ることができる。 本発明化合物の構造は、 I R、 NMR、 MS等から決定した。 発明を実施するための最良の形態 ：  After completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention was determined from IR, NMR, MS and the like. BEST MODE FOR CARRYING OUT THE INVENTION
次に実施例を挙げ、 本発明を更に詳し く説明する。  Next, the present invention will be described in more detail by way of examples.
実施例 1 : 4 ' 一クロロー 2 , 2 —ジメチルー 2 —フ 二ルァセ ト フヱノ ン ェ トキシカルボニルヒ ドラゾン （化合物番号 4 ) Example 1: 4 'monochloro-2,2-dimethyl-2 -furanacetophenoxycarbonylhydrazone (Compound No. 4)
Figure imgf000007_0001
Figure imgf000007_0001
C H  C H
Figure imgf000007_0002
Figure imgf000007_0002
C H C H
N H C 0 E t 0. 8 gの 4 ' 一ク ロ口一 2 , 2— ジメ チル一 2—フエ二ルァセ 卜 フエ ノ ンに 、 0. 4 gのェチルカーバゼー 卜、 及び角虫媒量のパラ トルエンスルフ ォ ン酸を加 え、 1 2 0 °Cで 5時間攪拌した。 反応終了後、 混合物を室温にまで冷却し、 シリ 力ゲルカラムクロマ 卜グラフィ 一により分離精製して、 目的物である白色結晶の 4 ' 一 ク ロロー 2 , 2— ジメ チル— 2—フヱニルァセ トフヱ ノ ン エ トキシカル ボニルヒ ドラゾン 0. 8 gを得た。 m p 1 2 3— 1 2 4 °C 実施例 2 ： 4 ' 一 ク ロ口一 2 , 2— ジメ チル一 2—フエ二ルァセ ト フエ ノ ンヒ ド ラゾン （化合物番号 5 ) NHC 0 E t To 0.8 g of 4'-mono-1,2,2-dimethyl-12-phenylacetophenone, was added 0.4 g of ethylcarbazate and paratoluenesulfonate, a hornworm medium. In addition, the mixture was stirred at 120 ° C for 5 hours. After the completion of the reaction, the mixture was cooled to room temperature, separated and purified by silica gel column chromatography, and 4'-chloro-2,2-dimethyl-2-phenylphenylphenol of the target white crystals was obtained. 0.8 g of ethoxycarbonyl hydrazone was obtained. mp 1 2 3—1 2 4 ° C Example 2: 4'-Cross-mouth 1,2,2-Dimethyl-1-2-phenylacetophenonhydrazone (Compound No. 5)
Figure imgf000008_0001
Figure imgf000008_0001
C H  C H
Figure imgf000008_0002
Figure imgf000008_0002
N H  N H
1. 5 gの 4 ' _ク ロ口 _ 2， 2—ジメチルー 2—フエ二ルァセ 卜 フエ ノ ンに 、 1. 5 gのヒ ドラジン一水和物、 及び濃硫酸 1滴を加え、 8時間加熱還流した 。 反応終了後、 過剰のヒ ドラジン一水和物を減圧留去した後、 シリ カゲルカラム クロマ トグラフィ ーにより分離精製して、 目的物である白色結晶の 4 ' —クロ口 一 2 , 2 — ジメ チルー 2—フエニルァセ ト フエ ノ ン ヒ ドラゾン 0. 8 gを得た 。 mp l 3 7— 1 3 9。C 実施例 3 : 4 ' _ク ロロ _ 2 , 2—ジメ チル一 2—フエニルァセ ト フエ ノ ン N ' 一 { ( 1 ー ジメ チルァ ミ ノ ） ェチ リ デン } ヒ ドラゾン （化合物番号 1 4 ) To 1.5 g of 4 '_cloth_2,2-dimethyl-2-phenylacetophenonone, add 1.5 g of hydrazine monohydrate and 1 drop of concentrated sulfuric acid, and then 8 hours Heated to reflux. After the completion of the reaction, excess hydrazine monohydrate was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain 4'-chloro-1,2,2-dimethyl-2 —0.8 g of phenylacetophenonhydrazone was obtained. mp l 3 7—1 3 9. C Example 3: 4'_chloro_2,2-dimethyl-1--2-phenylphenylphenon N'-1-{(1-dimethylethylamino) ethylidene} hydrazone (Compound No. 14)
Figure imgf000009_0001
Figure imgf000009_0001
N H  N H
Figure imgf000009_0002
Figure imgf000009_0002
N = C— N ( C H 3) N = C— N (CH 3 )
C H C H
0. 9 gの 4 ' 一 ク ロロー 2 , 2— ジメ チルー 2—フヱニルァセ トフエ ノ ン ヒ ドラゾンに、 0. 5 3 gの N , N— ジメ チルァセ トア ミ ジン ジメ チルァセタ ールを加え、 1 2 0 °Cで 2時間反応させた。 反応終了後、 混合物を室温にまで冷 却し、 シリカゲルカラムクロマ トグラフィーにより分離精製して、 目的物である 白色結晶の 4 ' 一ク ロ口一 2 , 2— ジメ チルー 2—フエニルァセ トフエノ ン N ' ― { ( 1 — ジメ チルァ ミ ノ） ェチ リ デン} ヒ ドラゾン 1. 0 gを得た。 m p 1 2 2 - 1 2 5 °C 上記実施例を含め本発明化合物の代表例を第 1表に示す 第 1 表 To 0.9 g of 4'-one-chloro-2,2-dimethyl-2-hydrazone, add 0.53 g of N, N-dimethylacetamidine dimethylacetatar and add 1 2 The reaction was performed at 0 ° C for 2 hours. After the completion of the reaction, the mixture was cooled to room temperature, separated and purified by silica gel column chromatography, and the desired white crystals of 4'-one-mouthed 1,2,2-dimethyl-2-phenylphenylphenone N '-{(1 —dimethylamino) ethylidene} 1.0 g of hydrazone was obtained. mp 122-125 ° C. Representative examples of the compounds of the present invention including the above Examples are shown in Table 1. Table 1
Figure imgf000010_0001
第 1 表 （続き）
Figure imgf000010_0001
Table 1 (continued)
4-C1 NHCONHMe Me Me 0 4-C1 NHCONHMe Me Me 0
NHC0 C1 〃 〃 〃 〃 〃 mpNHC0 C1 〃 〃 〃 〃 〃 mp
〃 NHCONH ^ ^Cl 〃 〃 〃 〃 NHCONH ^ ^ Cl 〃 〃 〃
161-167 。C 161-167. C
N=C-NH e N = C-NH e
〃 1 〃 〃 〃 〃 Λ 〃 〃 1 〃 〃 〃 〃 Λ Λ 〃
Me  Me
N=C-NMe2 mpN = C-NMe 2 mp
〃 1 〃 〃 〃 〃 〃 〃 1 〃 〃 〃 〃 〃
Me. 122-125 °C mp Me. 122-125 ° C mp
〃 NHC02Et 〃 Et 〃 〃 〃 NHC0 2 Et 〃 Et 〃 〃
123-125 。C  123-125. C
〃 〃 CF3 〃 〃 〃 〃 〃 CF 3 〃 〃 〃
〃 〃 iPr 〃 〃 mp〃 〃 iPr 〃 〃 mp
〃 〃 〃 allyl 〃 〃 〃 〃 〃 〃 allyl 〃 〃 〃
118-120 。C  118-120. C
〃 〃 〃 CH2C≡CH 〃 〃 〃 〃 〃 〃 CH 2 C≡CH 〃 〃 〃
2-C1 Me 〃 〃 2-C1 Me 〃 〃
3-C1 〃 〃 〃 〃 〃 〃 第 1 表 （続き） 3-C1 〃 〃 〃 〃 〃 〃 Table 1 (continued)
4 - Me 匿 02Et Me Me ― 0 4-Me concealed 0 2 Et Me Me-0
4-CF3 mp 4-CF 3 mp
4-'Bu  4-'Bu
114-116 °C 114-116 ° C
22. 322.3
4-OMe N 1.5578 4-OMe N 1.5578
D  D
4-OCF3 mp 4-OCF3 mp
4-0'Pr  4-0'Pr
88-89 °C  88-89 ° C
4-0-^ 4-0- ^
4-F 4-F
rap rap
4-SMe  4-SMe
99 - 101 °C mp  99-101 ° C mp
4 - S02Me 4-S0 2 Me
139-140。C  139-140. C
4-0S02Me 第 1 表 （続き） 4-0S0 2 Me Table 1 (continued)
Figure imgf000013_0001
第 1 表 （続き）
Figure imgf000013_0001
Table 1 (continued)
4-C1 NHC02Et Me Me 一 0 4-C1 NHC0 2 Et Me Me 1 0
〃 〃 〃 〃 〃 〃 〃 〃 〃 〃
"i 0CF3 "i 0CF3
〃 〃 〃 〃 〃 〃 ' Pr Pr 〃 〃 〃 〃 〃 ' Pr
〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃
〃 〃 〃 CH2 1 〃 〃 〃 CH 2 1
C C
〃 〃 〃 II 〃 〃  〃 〃 〃 II 〃 〃
0  0
mp mp
〃 〃 〃 0 〃 〃 〃 〃 〃 0 〃 〃
106 - 108。C mp 106-108. C mp
〃 〃 〃 s 〃 〃 〃 〃 〃 s 〃 〃
100-103 °C 100-103 ° C
N N
〃 〃 〃 〃 〃  〃 〃 〃 〃 〃
H  H
N  N
〃 〃 〃 〃 1 〃 〃  〃 〃 〃 〃 1 〃 〃
Me  Me
N  N
〃 〃 〃 〃 1 〃 〃  〃 〃 〃 〃 1 〃 〃
iPr  iPr
N=C -腿 e2 N = C-thigh e 2
〃 〃 Et 0' 〃  〃 〃 Et 0 '〃
Me 第 1 表 （続き） Me Table 1 (continued)
N=C-N e2 N = CN e 2
4-C1 Me 0  4-C1 Me 0
Me  Me
〃 〃 allyl 〃 〃 〃 -0S02 e 〃 〃 Me 〃 〃 〃 〃 〃 allyl 〃 〃 〃 -0S0 2 e 〃 〃 Me 〃 〃 〃
4-CF3 〃 〃 〃 〃 〃 4-CF 3 〃 〃 〃 〃 〃
4-0CF3 〃 〃 〃 〃 〃 -S02Me 〃 〃 〃 〃 4-0CF 3 〃 〃 〃 〃 〃 -S0 2 Me 〃 〃 〃 〃
4-'Bu 〃 〃 〃 〃 〃 〃 4-'Bu 〃 〃 〃 〃 〃 〃
4-0'Pr 〃 〃 〃 〃 〃 4-0'Pr 〃 〃 〃 〃 〃
4- CI 〃 〃 〃 〃 〃 - )- Cl 4- CI 〃 〃 〃 〃 〃-)-Cl
〃 〃 〃 〃 -( )- CF3 〃 〃 〃 〃-()-CF 3
〃 〃 〃 〃 〃 -Q- tBu 〃 〃 〃 〃 〃 -Q- tBu
〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃
- 。i pr - i pr
〃 〃 〃 〃 〃 〃 — CF3 本発明化合物は農業上の有害生物、 衛生害虫、 貯殻害虫、 衣類害虫、 家屋害虫 等の防除に使用でき、 殺成虫、 殺若虫、 殺幼虫、 殺卵作用を有する。 その代表例 と して、 下記のものが挙げられる。 CF 〃 〃 〃 〃 〃 — CF 3 The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests, and the like, and has an insecticidal, nymphicidal, larvicidal and ovicidal action. The following are typical examples.
鱗翅目害虫、 例えば、 ハスモンョ トウ、 ョ トウガ、 夕マナャガ、 ァォムシ、 夕 マナギンゥヮバ、 コナガ、 チヤ ノ コカクモンハマキ、 チヤハマキ、 モモシンクイ ガ、 ナシヒメ シンクイ、 ミ カンハモグリガ、 チヤ ノホソガ、 キンモンホソガ、 マ イマィガ、 チヤ ドクガ、 二カメィガ、 コブノ メイガ、 ョ一口ビアンコーンボーラ 一、 アメ リ カシロ ヒ ト リ、 スジマダラメ イガ、 へリオティ ス属、 へリ コべルパ属 、 ァグロティ ス属、 ィガ、 コ ドリ ンガ、 ヮタァ力 ミ ムシ等、 半翅目害虫、 例えば 、 モモァカアブラムシ、 ヮ夕アブラムシ、 ニセダイ コ ンアブラムシ、 ムギク ビレ アブラムシ、 ホソヘリ カメムシ、 ァォクサカメ ムシ、 ャノネカイガラムシ、 クヮ コナカィガラムシ、 オンシッコナジラ ミ、 タパ'ココナジラ ミ 、 ナシキジラ ミ 、 ナ シグンバイムシ、 ト ビイロゥン力、 ヒメ ト ビゥ ン力、 セジロウンカ、 ツマグロョ コバイ等、 鞘翅目害虫、 例えば、 キスジノ ミハムシ、 ゥ リハムシ、 コロラ ドハム シ、 イネ ミ ズゾゥムシ、 コクゾゥムシ、 ァゾキゾゥムシ、 マメ コガネ、 ヒメ コガ ネ、 ジアブロティ カ属、 タバコシバンムシ、 ヒラタキクイムシ、 マツノマダラ力 ミ キリ、 ゴマダラカ ミ キリ、 ァグリオティ ス属、 ニジユウャホシテン トウ、 コク ヌス ト、 ヮタ ミ ゾゥムシ等、 双翅目害虫、 例えば、 ィェバエ、 ォォク口バエ、 セ ンチニクバエ、 ゥ リ ミパ'ェ、 ミ カンコ ミパ'ェ、 タネバエ、 イネハモグリバエ、 キ イロショ ウジヨ ウバエ、 サシバエ、 コガタァカイエ力、 ネッタイ シマ力、 シナハ マダラカ等、 総翅目害虫、 例えば、 ミ ナ ミ キイロアザミ ゥマ、 チヤ ノキイロアザ ミ ゥマ等、 膜翅目害虫、 例えば、 イエヒメア リ、 キイロスズメバチ、 力ブラハバ チ等、 直翅目害虫、 例えば、 チヤパネゴキブリ、 ヮモンゴキブリ、 .クロゴキブリ 、 卜ノサマバッ夕等、 等翅目害虫、 例えば、 イエシロアリ、 ャマ ト シロアリ等、 隠翅目害虫、 例えば、 ヒ トノ ミ等、 シラ ミ 目害虫、 例えば、 ヒ ト ジラ ミ等、 ダニ 類、 例えば、 ナミハダ二、 ニセナミハダ二、 カンザヮハダ二、 ミ カンハダニ、 リ ンゴハダ二、 ミ カンサビダニ、 リ ンゴサビダ二、 チヤ ノホコ リ ダニ、 ブレビパル パス属、 ェォテ トラニカス属、 ロビンネダニ、 ケナガコナダニ、 コナヒ ヨ ウ ヒダ 二、 ォゥシマダニ、 フタ トゲチマダニ等、 植物寄生性線虫類、 例えば、 サッマイ モネコブセンチユウ、 ネグサレセンチユウ、 ダイズシス トセンチユウ、 イネシン ガレセンチユウ、 マツノザィセンチユウ等。 Lepidopteran pests, for example, Hasmonyoto, Totoga, Evening Managaga, Aomushi, Evening Managinaba, Konaga, Chino Kokakumonhamaki, Chiyamahamaki, Momoshinguiga, Nashihime Shinki, Mikanhamogiga, Chiya Nogamihoga Kameiga, Kobuno Meiga, Yo-Mouth Biancon Borra I, Ameri Kashiro Hitori, Sujimadarameiga, Heliotis, Helicoverpa, Agrotis, Iga, Kodlinga, Peta mimushi, etc. , Hemiptera pests, such as peach aphids, evening aphids, Nisedai aphids, wheat bilee aphids, hosohelium stink bugs, stag beetles, stalks Coleoptera, Psyllides, Colorado beetle, Rice beetle, Coleoptera , Bean beetle, Burdock beetle, Diablotica, Tobacco beetle, Beetle bark beetle, Matsunomadara power beetle, Gomadara bee beetle, Agriotis genus, Nigyuyahoshten tou, Kokunusuto, Kota mizobushi, etc. Pests of the eye, e.g., fly, oak mouth flies, senchiniku flies, peri-mipa'e, mikanko mipa'e, corn flies, rice hammogliae, yellow flies, flies, flies, koga takaye, anetaishima power, shinahamadara Etc., insects of the order Thysanoptera, such as Thrips palmi Karny, Thrips japonicus, Hymenoptera, pests, such as C. elegans, C. elegans, Hachibana wasp, etc., Orthoptera pests, e.g., Japanese cockroach Pteridopsis cockroaches, Black cockroaches, Tonosamaba, etc., Isopterid pests, for example, House termites, Yamato termites, etc., Lepidopteran pests, for example, Dermatophagoides, Lice pests, for example, Lice lice Mites, for example, Namihadani, Nisenamihadani, Kansahadani, Mikanhadani, Lingohadani, Mikansabi mite, Lingosavidani, Chino nokoko red mite, Brevipalpas, Genus Tetranicas, Robinne mite Plants such as Hidani, Dermacentor Sex nematodes, for example, Sammai Monecobentienyu, Negusaresentiyu, Soybean ciscentiyu, Inesin Garesenichiyu, Matsunosaisenyu, etc.
又、 近年コナガ、 ゥン力、 ョコバイ、 アブラムシ等多く の害虫において有機リ ン剤、 カーバメー ト剤に対する抵抗性が発達し、 それら薬剤の効力不足問題を生 じており、 抵抗性系統の害虫にも有効な薬剤が望まれている。 本発明化合物は感 受性系統のみならず、 有機リ ン剤、 カーバメー ト剤、 ピレスロイ ド剤、 抵抗性系 統の害虫にも優れた殺虫効果を有する薬剤である。 本発明の有害生物防除剤は、 一般式 〔 I 〕 で表わされる化合物またはその塩を 有効成分と して含有するものであり、 有効成分化合物の純品のままでも使用でき るが、 通常、 一般の農薬のと り得る形態、 即ち、 水和剤、 水溶剤、 粉剤、 乳剤、 粒剤、 フロアブル等の形態で使用される。 添加剤及び担体と しては、 固型剤を目 的とする場合は、 大豆粉、 小麦粉等の植物性粉末、 珪藻土、 燐灰石、 石膏、 タル ク、 ベン 卜ナイ ト、 ク レイ等の鉱物性微粉末、 安息香酸ソーダ、 尿素、 芒硝等の 有機および無機化合物が使用される。  In addition, in recent years, many insect pests such as moth moth, pinworm, leafhopper and aphid have developed resistance to organic phosphorus agents and carbamates, which has led to a problem of insufficient efficacy of these agents. Also effective drugs are desired. The compound of the present invention is an agent having an excellent insecticidal effect not only on susceptible strains, but also against pests of organic phosphorus agents, carbamates, pyrethroids, and resistant systems. The pesticidal composition of the present invention contains a compound represented by the general formula [I] or a salt thereof as an active ingredient, and can be used as an active ingredient in a pure form. It is used in a form that can be taken by the pesticide, ie, wettable powder, water solvent, powder, emulsion, granule, flowable and the like. When solid additives are used as additives and carriers, vegetable powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, clay, etc. Organic and inorganic compounds such as fine powder, sodium benzoate, urea and sodium sulfate are used.
液体の剤型を目的とする場合は、 植物油、 鉱物油、 ケロシン、 キシレンおよび ソルベン トナフサ等の石油留分、 シクロへキサン、 シクロへキサノ ン、 ジメチル ホルムア ミ ド、 ジメチルスルホキシ ド、 ト リ クロルエチレン、 メチルイソブチル ケ ト ン、 水等を溶剤と して使用する。 これらの製剤において、 均一なかつ安定な 形態をとるために必要ならば界面活性剤を添加すること もできる。 このようにし て得られた水和剤、 乳剤、 水溶液、 フロアブル剤は水で所定の濃度に希釈して懸 濁液あるいは乳濁液と して、 粉剤、 粒剤はそのまま、 植物に散布する方法で使用 される。  For liquid dosage forms, vegetable oils, mineral oils, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, trichlor Use ethylene, methyl isobutyl ketone, water, etc. as solvents. In these preparations, a surfactant can be added if necessary to obtain a uniform and stable form. The wettable powder, emulsion, aqueous solution, and flowable thus obtained are diluted to a predetermined concentration with water to form a suspension or emulsion, and powders and granules are sprayed on plants as they are. Used in.
なお、 本発明化合物は単独でも十分有効であることはいうまでもないが、 各種 の殺虫剤、 殺ダニ剤、 殺線虫剤、 殺菌剤および共力剤と混合して使用することも できる。  It goes without saying that the compound of the present invention alone is sufficiently effective, but it can also be used in combination with various insecticides, acaricides, nematicides, fungicides and synergists.
本発明化合物と混合して使用できる殺虫剤、 殺ダニ剤などの代表例を以下に示 す。  Representative examples of insecticides and acaricides that can be used by mixing with the compound of the present invention are shown below.
有機燐およびカーバメー ト系殺虫剤 ： フェ ンチオン、 フエニ ト ロチオン、 ダイアジノ ン、 ク ロルピリ ホス、 E S P 'ミ ドチオン、 フェ ン トエー 卜、 ジメ 卜エー ト、 ホルモチオン、 マラ ソ ン、 ト リ ク ロルホン、 チオメ ト ン、 ホスメ ッ ト、 ジク ロルボス、 ァセフ ェー ト、 E P B P 、 メ チルパラチオン、 ォキシジメ ト ンメ チル、 ェチオン、 サ リ チオン、 シァノ ホ ス、 イ ソキサチオン、 ピリ ダフヱ ンチオン、 ホサロ ン、 メ チダチオン、 スルプロ ホス、 ク ロルフェ ンビンホス、 テ トラ ク ロルビンホス、 ジメ チルビンホス、 プロ パホス、 イ ソフェ ンホス、 ェチルチオメ ト ン、 プロフエ ノ ホス、 ピラ ク ロホス、 モノ ク ロ トホス、 ァジンホスメ チル、 アルディ カルブ、 メ ソ ミ ル、 チォジカルプ 、 カルボフラ ン、 カルボスルフ ァ ン、 ベンフラカルブ、 フラチォカルプ、 プロボ キスル、 B P M C M T M C M I P C、 力ルバリ ル、 ピリ ミ カーブ、 ェチオフ ェ ンカルプ、 フエ ノ キシカルプ、 カルタ ップ、 チオシク ラム、 ベンスルタ ッ プ等 ピレスロイ ド系殺虫剤 ： Organophosphorus and carbamate insecticides: Phenthion, Phenyltrothion, Diazinone, Chlorpyrifos, ESP'Midothion, Phentoate, Dimethoate, Formothion, Marathon, Trichlorfon, Thiometone, Phosmet, Dichlorvos , Acetate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicion, cyano hos, isoxathion, pyridaphthion, hosalon, methidathion, sulprophos, chlorfenbimphos, tetracloth Lorubinphos, Dimethylbinphos, Propaphos, Isofenphos, Ethylthiomethone, Profenofos, Pyraclofos, Monocrotophos, Azinphosmethyl, Aldicarb, Mesomil, Thiodicarp, Carbofuran, Carbosulfan, Pyrethroid insecticides such as benfracarb, flatiocarp, proboxil, BPMCMTMCMIPC, kylarvalyl, pirimicarb, ethioffenkalp, phenoxycarp, cartap, thiocyclam, bensultap, etc.
ペルメ ト リ ン、 シペルメ ト リ ン、 デルタメ ス リ ン、 フ ェ ン 'レ レー ト、 フェ ン プロハ" ト リ ン、 ピレ ト リ ン、 ア レス リ ン、 テ トラメ ス リ ン、 レスメ 卜 リ ン、 ジメ ス リ ン、 プロパス リ ン、 フ エ ノ ト リ ン、 プロ ト リ ン、 フルパ'リ ネー ト、 シフル 卜 リ ン、 シノヽ口 卜 リ ン、 フルシ ト リ ネ一 卜、 エ トフェ ンプロク ス、 シク ロプロ ト リ ン、 トロラメ ト リ ン、 シラフルォフェ ン、 プロフェ ンプロクス、 ァク リ ナス リ ン 等。  Permethrin, cypermethrin, deltamethrin, phen'late, femproha "trin, pyrethrin, areleslin, tetramethrin, resmetrine , Dimethrin, propasulin, phenothrin, protoline, full-palinate, cyfltrin, sino-glurin, full citrinette, etofen Proxox, cycloprotoline, trollamethrin, sirafluorfen, profenprox, acrinasrin, etc.
ベンゾィルゥ レア系その他の殺虫剤 ： Benzoyl Rare Other Insecticides:
ジフルべンズロ ン、 ク ロルフルァズ p ン、 へキサフルムロ ン、 ト リ フルムロ ン 、 テフルべンズロ ン、 フルフエ ノ クスロン、 フルシク ロ クスロ ン、 ブプロフエ ジ ン、 ピリ プロキシフェ ン、 メ トプレン、 ベンゾェピン、 ジァフェ ンチウロ ン、 ィ ミ ダク ロプリ ド、 フィ プロニル、 硫酸二コチン、 ロテノ ン、 メ タアルデヒ ド、 機 械油、 B Tや昆虫病原ウィルスなどの微生物農薬等。  Difluvenzuron, chlorfluazin, hexaflumuron, triflumuron, tefluvenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyphen, methoprene, benzepin, jafenthiuron , Imidacloprid, fipronil, dicotin sulfate, rotenone, metaaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.
殺線虫剤 ： Nematicide:
フエナ ミ ホス、 ホスチアゼ一 ト等。  Phenamiphos, phosthiazetate, etc.
殺ダニ剤 ： Acaricide:
ク ロルべンジ レー ト、 フエ二ソブロモレー 卜、 ジコホル、 ア ミ トラズ、 B P P S、 ベンゾメ ー ト、 へキシチアゾクス、 酸化フヱ ンブタスズ、 ポ リ ナクチン、 キ ノ メ チォネー ト、 C P C B S、 テ トラ ジホン、 アベルメ クチン、 ミ ルべメ クチン 、 ク ロフヱ ンテジン、 シへキサチン、 ピリ ダベン、 フヱ ンピロキシメ ー ト、 テブ フェ ンビラ ド、 ピリ ミ ジフェ ン、 フエ ノチォカルプ、 ジエノ ク ロル等。 Chlorbenzilate, fenisobromolate, dichofor, amitraz, BPP S, Benzomate, Hexitiazox, Fumbutatin oxide, Polinactin, Quinomethionate, CPCBS, Tetradiphone, Avermectin, Millbemectin, Clopententine, Cyhexatin, Pyridaven, Phmpiroximate, Tebufenvirad, Pyrimidiphene, Phenochocalp, Dienochlor, etc.
殺菌剤： Fungicide:
チオフ ァネー ト メ チル、 べノ ミ ル、 カルベンダゾール、 チアベンダゾール、 フ オルペッ ト、 チウラム、 ジラム、 ジネブ、 マンネブ、 ポ リ カーボネー ト、 I B P 、 E D D P、 フサライ ド、 プロべナゾール、 イ ソプロチオラ ン、 T P N、 キヤプ タ ン、 ポ リ オキシン、 ブラス トサイ ジン S、 カスガマイ シ ン、 ス ト レブ 卜マイ シ ン、 ノく 'リ ダマイ シン、 ト リ シクラゾール、 ピロキロ ン、 フエナジンォキシ ド、 メ プロニル、 フル ト ラニル、 ペンシク ロ ン、 ィプロジオン、 ヒメ キサゾール、 メ タ ラキシル、 ト リ フルミ ゾール、 ト リ ホ リ ン、 ト リ アジメ ホン、 ビテルタノ ール、 フエナ リモル、 プロ ピコナゾール、 シモキサニル、 プロク ロラズ、 ぺフラゾエー ト、 へキサコナゾール、 ミ ク ロブタニル、 ジク ロメ ジン、 テク 口フタラム、 プロ ビネブ、 ジチアノ ン、 ホセチル、 ビンク ロゾリ ン、 プロシ ミ ドン、 ォキサジキシ ル、 グァザチン、 プロパモカルプ塩酸塩、 フルアジナム、 ォキソ リニッ ク酸、 ヒ ドロキシィ ソキサゾール等。 次に製剤の実施例を示すが、 添加する担体、 界面活性剤等はこれらの実施例に 限定されるものではない。  Thiophanate methyl, benomyl, carbendazole, thiabendazole, phorpet, thiuram, ziram, zineb, maneb, polycarbonate, IBP, EDDP, fusaride, probenazole, isoprotiolane, TPN, Captan, Polyoxin, Blastocysin S, Kasugamycin, Streptomycin, Phosphorus ridamaisin, Tricyclazole, Pyrokirone, Phenadoxide, Mepronil, Furtranilil, Pensic Lon, iprodione, himexazole, metalaxyl, triflumizole, trifolin, triazimefone, bitertanol, fenarimol, propiconazole, simoxanil, prochloraz, difurazoate, hexaconazole, Micro pig Nil, dichlormidine, techmouth phthalam, provineb, dithianon, Josetyl, vincolozolin, procymidone, oxazixil, guazatine, propamocarp hydrochloride, fluazinam, oxolinic acid, hydroxyxoxazole. Next, examples of the preparation are shown, but the carrier, surfactant and the like to be added are not limited to these examples.
実施例 4 乳剤 Example 4 Emulsion
本発明化合物 2 0部  Compound of the present invention 20 parts
アルキルフエ二ルポ リ オキシエチレン 5部  Alkylphenyloxyethylene 5 parts
ジメ チルホルムア ミ ド 4 0部  Jim Chilholm Amid 40 0
キシ レン ' 3 5部  Xylene '3 5 parts
以上を混合溶解し、 使用に際し水で希釈して乳濁液として散布する。 実施例 5 水和剤  Mix and dissolve the above, dilute with water before use and spray as an emulsion. Example 5 wettable powder
本発明化合物 2 0部 高級アルコール硫酸エステル 5部 Compound of the present invention 20 parts Higher alcohol sulfate 5 parts
珪藻土 7 0部  Diatomaceous earth 70 parts
シ リ 力 5部  Series 5 parts
以上を混合して微粉に粉砕し、 使用に際し水で希釈して懸濁液と して散布する  Mix the above, pulverize into fine powder, dilute with water before use and spray as a suspension
実施例 6 粉剤 Example 6 Dust
本発明化合物 5部  5 parts of the compound of the present invention
タルク 9 4 . 7部  Talc 9 4.7 parts
シリ カ 0 . 3部  0.3 parts of silica
以上を混合粉砕し、 使用に際してはそのまま散布する。 実施例 7 粒剤  Mix and grind the above and spray as it is when using. Example 7 granules
本発明化合物 5部  5 parts of the compound of the present invention
ク レー 7 3部  Cray 7 3 copies
ベン トナイ ト 2 0部  Bentonite 20
ジォクチルスルホサク シネー 卜  Dioctyl Sulphosak Sineto
ナ ト リ ウム塩 1部  1 part of sodium salt
リ ン酸ナ ト リ ウム 1部  1 part of sodium phosphate
以上を造粒し、' 使用に際してはそのまま施用する。 産業上の利用可能性 ：  The above is granulated and applied as it is when used. Industrial applicability:
試験例 1 ァヮョ トウに対する効力 Test Example 1 Efficacy against aphalt
前記薬剤の実施例 5 に示された水和剤の処方に従い、 化合物濃度が 1 2 5 p p mになるように水で希釈した。 その薬液中に トウモロコシ葉を 3 0秒間浸漬し、 風乾後、 ァヮョ トウ 3令幼虫が 5頭入っているシャーレにその葉を入れた。 ガラ ス蓋をして温度 2 5 °C、 湿度 6 5 %の恒温室内に置き、 5 日後に殺虫率を調べた 。 2反復である。 結果を第 2表に示した。 化合物番号 5日後殺虫率 （％)According to the wettable powder formulation shown in Example 5 of the above drug, the compound was diluted with water so that the compound concentration became 125 ppm. The corn leaves were immersed in the chemical solution for 30 seconds, air-dried, and then put into a petri dish containing five Atoto 3rd instar larvae. The glass lid was put on the container, and the mixture was placed in a constant temperature room at a temperature of 25 ° C and a humidity of 65%. Two iterations. The results are shown in Table 2. Compound No. Insecticidation rate 5 days later (%)
3 0 0 3 0 0
4 0 0  4 0 0
4 0 0  4 0 0
5 0 0  5 0 0
7 0 0  7 0 0
9 0 0 対照化合物 A ' 4 0  9 0 0 Control compound A '40
*対照化合物 A * Control compound A
N = C H - N (C H33)ノ 2 H C 1
Figure imgf000021_0001
N = CH-N (CH 3 3) 2 HC 1
Figure imgf000021_0001
C H  C H
(ク ロルジメ ホルム） (Krolzime Holm)
試験例 2 ナミハダ二に対する効力 Test Example 2 Efficacy against Namihadaji
2寸鉢に播種したィ ンゲンの発芽後 7 ~ 1 0 日を経過した第 1本葉上に、 有機 燐剤抵抗性のナミハダ二の雌成虫を 1 7頭接種したのち、 前記薬剤の実施例 5 に 示された水和剤の処方に従がい、 化合物濃度が 1 2 5 p p mになるように水で希 釈した薬液を散布した。 温度 2 5 °C、 湿度 6 5 %の恒温室内に置き、 散布 4 曰後 に、 殺成虫率を調査した。 結果を第 3表に示した。  After inoculating 17 female adults of Nami-Nada two, which are organic phosphate-resistant, on the first true leaf 7 to 10 days after germination of green sowing seeds in 2-inch pots, According to the wettable powder formulation shown in Fig. 5, a chemical solution diluted with water was sprayed so that the compound concentration was 125 ppm. They were placed in a thermostatic chamber at a temperature of 25 ° C and a humidity of 65%, and after spraying 4, the insecticidal rates were investigated. The results are shown in Table 3.
化合物番号 4 日後殺虫率 （％) Compound No. Insecticidation rate after 4 days (%)
1 0 0  1 0 0
2 0 0  2 0 0
3 0 0  3 0 0
4 0 0  4 0 0
5 0 0  5 0 0
1 5 0 0  1 5 0 0
2 4 0 0  2 4 0 0
2 5 0 0  2 5 0 0
2 7 0 0  2 7 0 0
4 5 0 0  4 5 0 0
対照化合物 5 5  Control compound 5 5
*対照化合物 A * Control compound A
Figure imgf000022_0001
Figure imgf000022_0001
C H  C H

Claims

請 求 の 範 囲 一般式 〔 I〕 Scope of claim General formula (I)
R
Figure imgf000023_0001
R
Figure imgf000023_0001
R R
N N
R R R R
〔式中、 Xはハロゲン原子、 置換されていてもよいアルキル基、 置換されていて もよいアルコキシ基、 置換されていてもよいシクロアルキルォキシ基、 置換され ていてもよいアルキルスルフォニルォキシ基、 置換されていてもよいアルキルチ ォ基または置換されていてもよいアルキルスルフォニル基を表し、 [In the formula, X is a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, a cycloalkyloxy group which may be substituted, an alkylsulfonyloxy group which may be substituted. Represents an optionally substituted alkylthio group or an optionally substituted alkylsulfonyl group,
R , は水素原子または置換されていてもよいアルキル基を表し、  R, represents a hydrogen atom or an optionally substituted alkyl group,
R は水素原子、 置換されていてもよいアルキル基、 置換されていてもよいァ ルキルカルボニル基、 置換されていてもよいアルキル力ルバモイル基、 置換され ていてもよいアルコキシ力ルポ二ル基、 置換されていてもよいフヱニルカルボ二 ル基または置換されていてもよいフヱ二ルカルバモイル基を表し、  R is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkyl group, a substituted alkoxy group, an optionally substituted alkoxy group, A carboxy group which may be substituted or a carbamoyl group which may be substituted;
また R, と R2 が一緒になつて、 C r , ) !^ :^ !^ (式中、 r , 、 r 2 、 r は同一または相異なって水素原子または置換されていてもよいアルキル基 を表す。 ） を形成してもよく、 R, and R 2 together form C r,)! ^: ^! ^ (Wherein r,, r 2 , and r are the same or different and are each a hydrogen atom or an optionally substituted alkyl group ) May be formed,
さ らに、 NR, R2 が一緒になつて置換されていてもよい Nを含む 5 ~ 7員環 の複素環基を形成してもよく （但し R, R2 はさ らに 1 ~ 2個の窒素原子または 酸素原子を含んでもよい） 、 Further, NR and R 2 may be taken together to form a 5- to 7-membered heterocyclic group containing N which may be substituted (provided that R and R 2 are further 1 to 2 Nitrogen or oxygen atoms),
R3 は水素原子または置換されていてもよいアルキル基を表し、 R 3 represents a hydrogen atom or an optionally substituted alkyl group,
R4 は置換されていてもよいアルキル基、 置換されていてもよいアルケニル基 または置換されていてもよいアルキニル基を表し、 R 4 represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group,
Aは硫黄原子、 酸素原子、 置換されていてもよいアルキレン、 置換されていて もよいアルキリデン、 カルボニルまたは N r 4 (式中、 r 4 は水素原子または置 換されていてもよいアルキルを表す。 ） を表し、 A is a sulfur atom, an oxygen atom, an optionally substituted alkylene, an optionally substituted alkylidene, carbonyl or N r 4 (wherein r 4 is a hydrogen atom or Represents an alkyl which may be substituted. ),
nは 0または 1を表し、  n represents 0 or 1,
Yは置換されていてもよいフヱニル基または置換されていてもよいピリ ジル基 を表す。 〕  Y represents an optionally substituted phenyl group or an optionally substituted pyridyl group. ]
で表される化合物またはその塩。 Or a salt thereof.
2. 一般式 〔 I〕 2. General formula [I]
Figure imgf000024_0001
Figure imgf000024_0001
〔式中、 X、 R, 、 R2 、 R3 、 R4 、 A、 nおよび Yは前記と同じ意味を表す 。 〕 で表される化合物またはその塩の 1種または 2種以上を有効成分として含有 することを特徴とする有害生物防除剤。 [Wherein, X, R,, R 2 , R 3 , R 4 , A, n and Y represent the same meaning as described above.] ] A pesticidal composition comprising, as an active ingredient, one or more of the compounds represented by the following or a salt thereof.
PCT/JP1993/001648 1992-11-13 1993-11-11 Hydrazone derivative WO1994011340A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54337/94A AU5433794A (en) 1992-11-13 1993-11-11 Hydrazone derivative

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Application Number Priority Date Filing Date Title
JP4328828A JPH06157444A (en) 1992-11-13 1992-11-13 Hydrazone derivative and pest controlling agent
JP4/328828 1992-11-13

Publications (1)

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WO1994011340A1 true WO1994011340A1 (en) 1994-05-26

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AU (1) AU5433794A (en)
WO (1) WO1994011340A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001001781A1 (en) * 1999-07-05 2001-01-11 Basf Aktiengesellschaft Ant controllers and method for application thereof
JP2001072516A (en) * 1999-07-05 2001-03-21 Nippon Nohyaku Co Ltd Termite-proofing agent and its use
WO2002002515A1 (en) * 2000-06-30 2002-01-10 Agro-Kanesho Co., Ltd. Hydrazone derivatives effective in pest control or salts thereof
CN103641795A (en) * 2013-04-18 2014-03-19 南开大学 Acetophenone derivatives containing 1,2,3-thiadiazole and preparation method and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56128746A (en) * 1980-03-13 1981-10-08 Ricoh Co Ltd New hydrazone compound and its preparation
JPS6393761A (en) * 1986-07-17 1988-04-25 シエ−リング・アクチエンゲゼルシヤフト Substituted hydrazone, manufacture and vermicide
EP0500111A2 (en) * 1991-02-22 1992-08-26 Ishihara Sangyo Kaisha, Ltd. Hydrazone compounds, processes for their production, intermediates useful for their production and pesticidal compositions containing them

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56128746A (en) * 1980-03-13 1981-10-08 Ricoh Co Ltd New hydrazone compound and its preparation
JPS6393761A (en) * 1986-07-17 1988-04-25 シエ−リング・アクチエンゲゼルシヤフト Substituted hydrazone, manufacture and vermicide
EP0500111A2 (en) * 1991-02-22 1992-08-26 Ishihara Sangyo Kaisha, Ltd. Hydrazone compounds, processes for their production, intermediates useful for their production and pesticidal compositions containing them

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001001781A1 (en) * 1999-07-05 2001-01-11 Basf Aktiengesellschaft Ant controllers and method for application thereof
JP2001072516A (en) * 1999-07-05 2001-03-21 Nippon Nohyaku Co Ltd Termite-proofing agent and its use
JP4626731B2 (en) * 1999-07-05 2011-02-09 日本農薬株式会社 Anticide and method of use
WO2002002515A1 (en) * 2000-06-30 2002-01-10 Agro-Kanesho Co., Ltd. Hydrazone derivatives effective in pest control or salts thereof
CN103641795A (en) * 2013-04-18 2014-03-19 南开大学 Acetophenone derivatives containing 1,2,3-thiadiazole and preparation method and use thereof
CN103641795B (en) * 2013-04-18 2016-03-02 南开大学 One class contains acetophenone derivs of 1,2,3-thiadiazoles and its production and use

Also Published As

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AU5433794A (en) 1994-06-08
JPH06157444A (en) 1994-06-03

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