WO2010010959A1 - Ester compound and use thereof - Google Patents

Ester compound and use thereof Download PDF

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Publication number
WO2010010959A1
WO2010010959A1 PCT/JP2009/063308 JP2009063308W WO2010010959A1 WO 2010010959 A1 WO2010010959 A1 WO 2010010959A1 JP 2009063308 W JP2009063308 W JP 2009063308W WO 2010010959 A1 WO2010010959 A1 WO 2010010959A1
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Prior art keywords
compound
configuration
formulation
formula
cyclopropane ring
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PCT/JP2009/063308
Other languages
French (fr)
Inventor
Masayuki Mae
Tatsuya Mori
Noritada Matsuo
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Sumitomo Chemical Company, Limited
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Publication of WO2010010959A1 publication Critical patent/WO2010010959A1/en

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    • 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
    • C07C323/10—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 singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/16—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to an ester compound and use thereof.
  • JP-A Japanese Patent Application Laid-Open
  • 2004-2363 describes a certain kind of cyclopropanecarboxylates .
  • the present invention has an object of providing a novel compound having an excellent pest controlling effect.
  • the present inventors have intensively studied and resultantly found that a compound of the formula (1) has an excellent pest controlling effect, leading to the present invention.
  • the present invention provides an ester compound of the formula (1) :
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a methyl group, a 1-propenyl group, a 2- methyl-1-propenyl group or a 2-cyano-l-propenyl group (hereinafter referred to as the present compound)
  • a pest controlling composition comprising the present compound as an active ingredient
  • a pest controlling method comprising a step of applying an effective amount of the present compound to a pest or a habitat of the pest.
  • the present compound has an excellent pest controlling effect, thus, it is useful as an active ingredient of a pest controlling composition.
  • isomers are present ascribable to two asymmetric carbon atoms on a cyclopropane ring, and when R 2 is a substituent having a double bond, isomers ascribable to the double bond can present, and the present invention includes these isomers having a pest controlling activity.
  • the present compound includes, for example, the following compounds.
  • a compound of the formula (1) wherein R 1 represents a hydrogen atom and R 2 represents a 2-methyl-l-propenyl group, and the relative configuration of substituents at the 1- position and the 3-position on the cyclopropane ring is trans configuration;
  • a compound of the formula (1) wherein R 1 represents a hydrogen atom and R 2 represents a 2-methyl-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-
  • the present compound when used in a pest controlling composition, may be used in the form of isomer mixture of any ratio.
  • the isomer mixture includes, for example, the following compounds.
  • R 1 represents preferably a hydrogen atom.
  • R 2 represents preferably a 1- propenyl group, 2-methyl-l-propenyl group or 2-cyano-l- propenyl group, more preferably, a 2-methyl-l-propenyl group or 2-cyano-l-propenyl group, further preferably, a 2- methyl-1-propenyl group in which the relative configuration of a double bond is Z-configuration or a 2-cyano-l-propenyl group in which the relative configuration of a double bond is Z-configuration.
  • the absolute configuration at 1- position of the cyclopropane ring is preferably R- configuration .
  • the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration.
  • the present compound can be produced by reacting an alcohol compound of the formula (2)
  • the reactive derivative includes acid halides of the carboxylic acid compound of the formula (3), acid anhydrides of the carboxylic acid compound, or methyl esters of the carboxylic acid compound.
  • the acid halide includes acid chloride compounds and acid bromide compounds,
  • the reaction is carried out usually in a solvent in the presence of a condensing agent or base.
  • Examples of the solvent include hydrocarbons such as benzene, toluene or hexane, ethers such as diethyl ether, or tetrahydrofuran, and halogenated hydrocarbons such as chloroform, dichloromethane, or 1, 2-dichloroethane, chlorobenzene .
  • Examples of the condensing agent include dicyclohexylcarbodiimide and WSC (l-(3- dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) .
  • the base includes organic bases such as triethylamine, pyridine, N,N-diethylaniline, 4-dimethylaminopyridine, or diisopropylethylamine .
  • the reaction time is usually in the range of 5 minutes to 72 hours.
  • the reaction temperature is usually in the range of - 20°C to 100 0 C, and preferably in the range of -5°C to 100 0 C.
  • the reaction temperature is in the range of - ' 20 0 C to the boiling point of the solvent, preferably in the range of -5°C to the boiling point of the solvent, when the boiling point of the solvent to be used is lower than 100 0 C.
  • the molar ratio of the alcohol compound of the formula (2) to the carboxylic acid compound of the formula (3) or reactive derivative thereof can be arbitrarily selected, however, it is preferably equimolar or near ratio.
  • the condensing agent or base can be used usually at any proportion from 1 mol to excess amount, preferably 1 mol to 5 mol, with respect to 1 mol of the alcohol compound of the formula (2) .
  • the condensing agent or base is appropriately selected depending on the kind of .
  • the reaction mixture After completion of the reaction, the reaction mixture is filtrated and the filtrate is concentrated, alternatively, the reaction mixture is poured into water, then, usual post-treatment operations such as extraction with organic solvent, or concentration are performed, thus, the present compound can be obtained.
  • the resultant present compound can be purified by operations such as chromatography, or distillation.
  • the alcohol compound of the formula (2) is a compound described in JP-A No. 57-123146, and can be produced by a method described in this publication.
  • the carboxylic acid compound of the formula (3) is a commercially available product, or a compound described in JP-A No. 2000-63329, Agr. Biol. Chem. , 34, 1119 (1970), J. Chem. Soc. 1076 (1970), JP-A No. 47-43333, JP-A No. 49- 47531 and the like, alternatively, can be produced by methods described in these publications.
  • the pests on which the present compound manifests an effect include, for example, arthropods such as insects, or mites .
  • Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis and Plodia interpunctella, Noctuidae such as Spodoptera litura, Pseudaletia separate and Mamestra brassicae, Pieridae such as Pieris rapae crucivora, Tortricidae such as Adoxophyes spp., Carposinidae, Lyonetiidae, Lymantriidae, Autographa, Agrotis spp. such as Agrotis segetum and Agrotis ipsilon, Helicoverpa spp.,
  • Heliothis spp. Plutella xylostella, Parnara guttata, Tinea translucens, Tineola bisselliella, etc.
  • Culex spp. such as Culex pipiens pallens and Culex tritaeniorhynchus, Aedes spp. such as Aedes aegypti and Aedes albopictus, Anopheles spp. such as Anopheles sinensis, Chironomidae, Muscidae such as Musca domestica, Muscina stabulans and Fannia canicularis, Calliphoridae, Sarcophagidae, Anthomyiidae such as Delia platura and Delia antique, Tephritidae, Agromyzidae, Drosophilidae,
  • Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, etc.
  • Pediculus humanus Pthirus pubis, Pediculus capitis, Pediculus corporis, etc.
  • Delphacidae such as Laodelphax striatellus, Nilaparvata lugens and Sogatella furcifera
  • Deltocephalidae such as Nephotettix virescens and Nephotettix cincticeps
  • Aphididae Pentatomidae, Aleyrodidae, Coccoidea
  • Cimicidae such as Cimex lectularius, Tingidae, Psyllidae, etc.
  • Coleoptera Attagenus unicolor japonicus, Authrenus verbasci, Corn Rootworms such as Diabrotica virgifera and Diabrotica undecimpunctata howardi, Scarabaeidae such as Anomala cuprea and Anomala rufocuprea, Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, Anthonomus grandis grandis and Callosobruchus chinensis, Tenebrionidae such as Tenebrio molitor and Tribolium castaneum, Chrysomelidae such as Oulema oryzae, Phyllotreta striolata and Aulacophora femoralis, Anobiidae, Epilachna spp. such as Epilachna vigintioctopunctata, Lyctidae, Bostrychidae, Cerambycid
  • Orthoptera Gryllotalpidae, Acrididae, etc.
  • Acarina
  • Pyroglyphidae such as Dermatophagoides farinae and Dermatophagoides pteronyssinus, Acaridae such as Tyrophagus putrescentiae and Aleuroglyphus ovatus, Glycyphagidae such as Glycyphagus privatus, Glycyphagus domesticus and Glycyphagus destructor, Cheyletidae such as Cheyletus malaccensis and Cheyletus fortis, Tarsonemidae, Chortoglyphus spp., Oribatei, Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai, Panonychus citri and Panonychus ulmi, Ixodidae such as Haemaphysalis longiconis, Dermanyssidae such as Ornithonyssus sylviarum and Dermanyssus gallinae, etc.
  • the pest controlling composition of the present invention is usually a formulation.
  • the formulation form include an oil solution, an emulsifiable concentrate, a wettable powder, a flowable formulation (e.g., an aqueous suspension, or an aqueous emulsion) , a microcapsule, a dust, a granule, a tablet, an aerosol, a carbon dioxide formulation, a heat transpiration formulation (e.g., an insecticidal coil, an electric insecticidal mat, or a liquid absorbing core-type heat transpiration pesticide) , a piezo insecticidal formulation, a heat fumigant (e.g., a self combustion-type fumigant, a chemical reaction-type fumigant, or a porous ceramic plate fumigant) , an unheated transpiration formulation (e.g., a resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet)
  • formulations contain, depending on the formulation form, the present compound usually in an amount of 0.001 to 95% by weight of the total amount.
  • the formulation-forming method includes, for example, the following methods.
  • a method which comprises mixing the present compound with a solid carrier, liquid carrier, gaseous carrier, bait and the like, and if necessary, adding a surfactant or other formulation auxiliary substances and then processing.
  • a method which comprises impregnating the present compound in a base material [2] A method which comprises impregnating the present compound in a base material. [3] A method which comprises mixing the present compound and a base material, and then molding the resulting mixture.
  • the solid carrier for the formulation examples include fine powders or granules of clays (e.g., kaolin clay, diatomaceous earth, bentonite, Fubasami clay, or acid white clay) , synthetic hydrated silicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite, quartz, sulfur, active carbon, calcium carbonate, or hydrated silica) and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride, or urea); substances that are solid at room temperature (e.g., 2, 4, ⁇ -triisopropyl-1, 3, 5-trioxane, naphthalene, p- dichlorobenzene, camphor, or adamantine) ; and felt, fiber, fabric, knit, sheet, paper, thread, foam, porous material and multi-filament comprising one or more substances selected from the group consisting of wool, silk, cotton, hemp
  • liquid carrier examples include aromatic or aliphatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, or cyclohexane) , halogenated hydrocarbons (e.g., chlorobenzene, dichloromethane, dichloroethane, or trichloroethane) , alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, or ethylene glycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, or dioxane) , esters (e.g., ethyl
  • gaseous carrier examples include butane gas, chlorofluorocarbon, liquefied petroleum gas (LPG) , dimethyl ether and carbon dioxide.
  • surfactant examples include alkyl sulfate, alkyl sulfonate, alkylaryl sulfonate, alkylaryl ethers, polyoxyethylenated alkylaryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives .
  • other auxiliary agents for formulation include a binder, a dispersant and a stabilizer.
  • casein gelatin, polysaccharides (e.g., starch, gum arable, cellulose derivatives, or alginic acid) , lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (e.g., polyvinyl alcohol, or polyvinyl pyrrolidone) , polyacrylic acid, BHT (2, 6-di-tert-butyl-4-methylphenol) and BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3- tert-butyl-4-methoxyphenol) .
  • a base material for the insecticidal coil include a mixture of vegetable powder such as wood flour and lees powder, and a binder such as incense material powder, starch and gluten.
  • Examples of a base material for the electric insecticidal mat include a plate obtained by hardening cotton linter and a plate obtained by hardening fibrils of a mixture of cotton linter and pulp.
  • Examples of a base material for the self combustion- type fumigant include combustible exothermic agents such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood flour, thermal decomposition stimulants such as alkali metal salt, alkaline earth metal salt, dichromate and chromate, oxygen carriers such as potassium nitrate, combustion-supporting agents such as melamine and flour starch, extenders such as diatomaceous earth, and binders such as synthetic glue.
  • combustible exothermic agents such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood flour
  • thermal decomposition stimulants such as alkali metal salt, alkaline earth metal salt, dichromate and chromate
  • oxygen carriers such as potassium nitrate
  • combustion-supporting agents such as melamine and flour starch
  • extenders such as diatomaceous earth
  • binders such
  • Examples of a base material for the chemical reaction-type fumigant include exothermic agents such as alkali metal sulfide, polysulfide, hydrosulfide and calcium oxide, catalytic agents such as a carbonaceous material, iron carbide and active white clay, organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as strips of natural fiber and synthetic fiber.
  • exothermic agents such as alkali metal sulfide, polysulfide, hydrosulfide and calcium oxide
  • catalytic agents such as a carbonaceous material, iron carbide and active white clay
  • organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane
  • fillers such as strips of natural fiber and synthetic fiber.
  • Examples of a base material resin for resin transpiration formulations include polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene- ethyl methacrylate copolymer; ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers; polypropylene resins such as a propylene copolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polys
  • base material resins may be used alone or as a combination of two or more kinds. If necessary, a plasticizer such as phthalate (e.g., dimethyl phthalate, or dioctyl phthalate) , adipic acid esters and stearic acid may be added to these base materials.
  • phthalate e.g., dimethyl phthalate, or dioctyl phthalate
  • adipic acid esters and stearic acid may be added to these base materials.
  • the resin transpiration formulations can be prepared by mixing the present compound with the base material, kneading the mixture, followed by molding it by injection molding, extrusion molding or pressure molding.
  • the resultant resin transpiration formulations can be subjected to further molding or cutting procedure, if necessary, to be processed into a plate, film, tape, net or string shape. These resin formulations can be processed into animal collars, animal ear tags, sheet products, trap strings, gardening supports and other products.
  • Examples of a base material for the poison bait include food ingredients such as grain powder, vegetable oil, saccharide and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, accidental ingestion inhibitors for children and pets such as a chili powder; insect attraction fragrances such as cheese flavor, onion flavor and peanut oil.
  • the pest controlling method of the present invention comprises a step of applying an effective amount of the present compound to a pest or a habitat of the pest.
  • the present compound is usually applied, in the form of a pest controlling composition, to a pest or a habitat of the pest.
  • the application of the present compound can be carried out, for example, according to the following methods, and specific application methods can be appropriately selected depending on the form of the present compound, place to be used thereof, and the like.
  • the present compound or a pest controlling composition of the present invention is generally diluted so that the concentration of the present compound is 0.1 to 10000 ppm, and then sprayed.
  • both the application amount and the application concentration of the present compound can be appropriately selected depending on the form of the present compound, application time, application place, application method, the kind of pests, injury conditions and the like.
  • the present compound When the present compound is used for prevention of epidemics, its application amount is usually 0.0001 to 1000 mg/m 3 when applied in space, and 0.0001 to 1000 mg/m 2 when applied on plane.
  • a heat fumigant such as an insecticidal stick, electric insecticidal mat can be applied by volatilizing an active ingredient by heating according to its formulation form.
  • a unheated transpiration formulation such as resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet can be applied, for example, by placing as it is in a space to be applied, or placing the formulation under an influence of blowing air.
  • examples of the habitat of a pest include a closet, a Japanese cabinet, a Japanese chest, a cupboard, a toilet, a bathroom, a shed, a living room, a dining room, a garage and the interior of a car.
  • the present compound can be also applied to outdoor open space.
  • the present compound can be used on animals by a known method in the veterinary field, when used for controlling external parasites of livestock such as cow, horse, pig, sheep, goat, or chicken, or small animals such as dog, cat, rat, or mouse.
  • livestock such as cow, horse, pig, sheep, goat, or chicken
  • small animals such as dog, cat, rat, or mouse.
  • the present compounds when intended for systemic control, for example, table, feedstuff mixing, suppository and injection (intramuscular, subcutaneous, intravenous, intraperitoneal) are used for administration.
  • the present compounds are applied by such a method as spraying of oil or aqueous liquid, pour-on treatment, spot-on treatment, washing animal with a shampoo formulation, forming a resin transpiration formulation into collar or ear tag to be fixed on animal.
  • the amount of the present compound when administered to animal is usually in the range of 0.01 to 1000 mg with respect to 1 kg of body weight of animal.
  • the present compound can be used in admixture or together with other insecticides, acaricides, nematicides, soil pest controlling agents, bactericides, herbicides, plant growth regulators, repellents, synergists, fertilizers or soil improving agents.
  • insecticides, acaricides, nematicides, soil pest controlling agents, bactericides, herbicides, plant growth regulators, repellents, synergists, fertilizers or soil improving agents are not particularly restricted.
  • active ingredients of such insecticides and miticides include organophosphorus compounds such as fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulprofos, cyanophos, dioxabenzofos, dimethoate, phenthoate, malathion, trichlorphon, azinphosmethyl, monocrotophos, or e ' thion; carbamate compounds such as BPMC, benfuracarb, propoxur, carbosulfan, carbaryl, methomy1, ethiofencarb, aldicarb, oxamyl, or fenothiocarb; pyrethroid compounds such as ethofenprox, fenvalerate, esfenvalerate, fenpropathrin, cypermethrin, permethrin, cy
  • Examples of the active ingredient of the repellent include 3, 4-caranediol, N,N-diethyl-m-toluamide, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidine carboxylate, p-menthane-3, 8- diol and vegetable essential oils such as a hyssop oil.
  • Examples of the active ingredient of the synergist include bis- (2, 3, 3, 3-tetrachloropropyl) ether (S-421) , N- (2- ethylhexyl) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboxyimide (MGK-264) and ⁇ - [2- (2-butoxyethoxy) ethoxy] -4 , 5- methylenedioxy-2-propyltoluene (piperonyl butoxide) .
  • An emulsifiable concentration is obtained by dissolving 20 parts of any one of the present compounds (1) to (4) in 65 parts of xylene, adding 15 parts of Sorpol 3005X (registered trade name of Toho Chemical Co., Ltd.) thereto, and thoroughly mixing the mixture with stirring.
  • a wettable powder is obtained by adding 5 parts of Sorpol 3005X to 40 parts of any one of the present compounds (1) to (4), thoroughly mixing the mixture, adding 32 parts of Carplex #80 (synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.) and 23 parts of 300 mesh diatomaceous earth thereto, and mixing the mixture with stirring by a juice mixer.
  • Carplex #80 synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.
  • Tokuseal GUN synthetic hydrated silicon oxide, manufactured by Tokuyama Corp.
  • Reax 85A sodium ligninsulfonate, manufactured by West Vaco Chemicals
  • Bentonite Fuji bentonite, manufactured by Hojun Corp.
  • Shokozan A clay kaolin clay, manufactured by Shokozan Kogyosho
  • a thickening agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) in 56.3 parts of ion-exchanged water.
  • a microcapsule formulation is obtained by mixing 42.5 parts of the microcapsule slurry and 57.5 parts of the thickening agent solution.
  • a mixture of 10 parts of any one of the present compounds (1) to (4) and 10 parts of phenylxylylethane is added to 20 parts of a 10% aqueous solution of polyethylene glycol, followed by stirring with a homomixer to obtain an emulsion having a mean particle diameter of 3 ⁇ m.
  • a thickening agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) in 58.8 parts of ion-exchanged water.
  • a flowable formulation is obtained by mixing 40 parts of the above emulsion and 60 parts of the thickening agent solution.
  • Formulation Example 6 A dust is obtained by mixing 5 parts of any one of the present compounds (1) to (4), 3 parts of Carplex #80 (synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.), 0.3 part of PAP (a mixture of monoisopropyl phosphate and diisopropyl phosphate) and 91.7 parts of talc (300 mesh) with stirring by a juice mixer.
  • Carplex #80 synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.
  • PAP a mixture of monoisopropyl phosphate and diisopropyl phosphate
  • talc 300 mesh
  • An oil solution is obtained by dissolving 0.1 part of any one of the present compounds (1) to (4) in 10 parts of dichloromethane, and mixing the solution with 89.9 parts of deodorized kerosene.
  • Formulation Example 8 An oil aerosol is obtained by mixing and dissolving 1 part of any one of the present compounds (1) to (4), 5 parts of dichloromethane and 34 parts of deodorized kerosene, filling an aerosol vessel with the resultant solution, attaching a valve to the vessel, and charging the vessel with 60 parts of a propellent (liquefied petroleum gas) under pressure through the valve.
  • a propellent liquefied petroleum gas
  • An aqueous aerosol is obtained by mixing and dissolving 0.6 part of any one of the present compounds (1) to (4), 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier, registered trademark of Atlas Chemical Inc.), filling an aerosol vessel with the resultant solution and 50 parts of water, attaching a valve to the vessel, and charging the vessel with 40 parts of a propellent (liquefied petroleum gas) under pressure through the valve.
  • a propellent liquefied petroleum gas
  • An insecticidal coil is obtained by dissolving 0.3 g of any one of the present compounds (1) to (4) in 20 mL of acetone, uniformly mixing and stirring the solution and 99.7 g of a base material for an insecticidal coil (a mixture of an incense material powder, lees flour and wood flour in a ratio of 4:3:3), adding 100 mL of water thereto, thoroughly kneading the mixture, and molding and drying the mixture.
  • a base material for an insecticidal coil a mixture of an incense material powder, lees flour and wood flour in a ratio of 4:3:3
  • a part to be used for a liquid absorbing core-type heat transpiration device is obtained by dissolving 3 parts of any one of the present compounds (1) to (4) in 97 parts of deodorized kerosene, placing the resultant solution in a vessel made of vinyl chloride, and inserting a liquid- absorbing core into the vessel.
  • the liquid-absorbing core is prepared by solidifying an inorganic powder with a binder, followed by sintering it, upper part of which can be heated by a heater.
  • a heat fumigant is obtained by dissolving 100 mg of any one of the present compounds (1) to (4) in an appropriate amount of acetone, and impregnating a porous ceramic plate of 4.0 cm x 4.0 cm and 1.2 cm thick with the solution.
  • a room-temperature-volatilizing formulation is obtained by dissolving 100 ⁇ g of any one of the present compounds (1) to (4) in an appropriate amount of acetone, uniformly applying the solution onto a filter paper of 2 cm x 2 cm and 0.3 mm thick, and air-drying to remove acetone.
  • test examples show that the present compound is effective as an active ingredient of a pest controlling composition.
  • the present compound (2) 0.1 part, was dissolved in 10 parts of dichloromethane, and this was mixed with 89.9 parts of deodorized kerosene, to prepare a 0.1% oil formulation of the present compound (2) .
  • the same procedure as described above was carried out, except that the present compound (3) was used instead of the present compound (2), to prepare a 0.1% oil formulation of the present compound (3) .
  • Musca domestica adult insects were released in a cube chamber having a 70 cm side, and 0.7 ml of a 0.1% oil formulation of the present compound (2) was sprayed into the chamber under a pressure of 8.8xlO 4 Pa, by using a spray gun through a small window on the side surface of the chamber. Fifteen (15) minutes after spraying, Musca domestica adult insects were taken up into a clean cup (bottom diameter: 8.2 cm) in which an absorbent cotton containing 0.5% sugar water had been placed, and allowed to stand still until next day. The number of dead insects was counted 24 hours after standing still, and the insect death rate was calculated (repeated once) . The same test as described above was carried out also for the oil formulation of the present compound (3), and the insect death rate of Musca domestica adult insects was obtained. The results are shown in Table 1.
  • the present compound (1) 0.00625 parts, was dissolved in 10 parts of dichloromethane, and then mixed with 89.99375 parts of deodorized kerosene, to prepare a 0.00625% oil formulation.
  • Culex pipiens female adult insects were released in a cube chamber having a 70 cm side, and 0.7 ml of a 0.00625% oil formulation of the present compound (1) was sprayed into the chamber under a pressure of 8.8xlO 4 Pa using a spray gun through a small window on the side surface of the chamber.
  • Ten minutes after spraying Culex pipiens female adult insects were taken up into a clean cup (bottom diameter: 8.2 cm) in which an absorbent cotton containing 0.5% sugar water had been placed, and allowed to stand still until . next day.
  • the number of dead insects was counted 24 hours after standing still, and the insect death rate was calculated (repeated twice) .
  • the same test as described above was carried- out also for the oil formulation of the comparative compound (A) , and the insect death rate of Culex pipiens female adult insects was obtained.
  • the present compound (1) 0.025 parts, was dissolved in 10 parts of dichloromethane, and then mixed with 89.975 parts of deodorized kerosene, to prepare a 0.025% oil formulation.
  • comparative compound (B) compound described in JP-A No. 57-123146, hereinafter, referred to as comparative compound (B) of the following formula.
  • Musca domestica adult insects (each 5 males and females, total 10) were released in a cube chamber having a 70 cm side, and 0.7 ml of a 0.025% oil formulation of the present compound (1) was sprayed into the chamber under a pressure of 8.8xlO 4 Pa using a spray gun through a small window on the side surface of the chamber.
  • the number of knocked down insects was counted, as a result, 9.5 insects (average number after two repetitions) were knocked down with the oil formulation of the present compound (1) , and no insect was knocked down with the oil formulation of the comparative compound (B) .
  • the present compound has an excellent pest controlling effect, thus, it is useful as an active ingredient of a pest controlling composition.

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Abstract

An ester compound of the formula (1): wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a methyl group, a 1-propenyl group, a 2- methyl-1-propenyl group or a 2-cyano-l-propenyl group.

Description

DESCRIPTION ESTER COMPOUND AND USE THEREOF
Technical Field The present invention relates to an ester compound and use thereof.
Background Art
Conventionally, a lot of compounds have been developed to control pests, and put into practical use.
For example, Japanese Patent Application Laid-Open (JP-A) No. 2004-2363 describes a certain kind of cyclopropanecarboxylates .
Disclosure of the Invention
The present invention has an object of providing a novel compound having an excellent pest controlling effect.
The present inventors have intensively studied and resultantly found that a compound of the formula (1) has an excellent pest controlling effect, leading to the present invention.
That is, the present invention provides an ester compound of the formula (1) :
Figure imgf000002_0001
wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a methyl group, a 1-propenyl group, a 2- methyl-1-propenyl group or a 2-cyano-l-propenyl group (hereinafter referred to as the present compound) , a pest controlling composition comprising the present compound as an active ingredient, and a pest controlling method comprising a step of applying an effective amount of the present compound to a pest or a habitat of the pest.
The present compound has an excellent pest controlling effect, thus, it is useful as an active ingredient of a pest controlling composition.
Best Modes for Carrying Out the Invention
As the present compound, isomers are present ascribable to two asymmetric carbon atoms on a cyclopropane ring, and when R2 is a substituent having a double bond, isomers ascribable to the double bond can present, and the present invention includes these isomers having a pest controlling activity. The present compound includes, for example, the following compounds.
Figure imgf000003_0001
A compound of the formula (1) wherein R1 and R2 respectively represent a methyl group; A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a methyl group;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, and the absolute configuration at 1-position of the cyclopropane ring is R-configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, and the relative configuration of substituents at the 1- position and the 3-position on the cyclopropane ring is trans configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, and the relative configuration of substituents at the 1- position and the 3-position on the cyclopropane ring is cis configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, and the relative configuration of a double bond present in a substituent at 3-position of the cyclopropane ring is Z- configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is cis configuration; A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration, and the relative configuration of a double bond present in a substituent at 3-position of the cyclopropane ring is Z- configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is cis configuration, and the relative configuration of a double bond present in a substituent at 3-position of the cyclopropane ring is Z- configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-methyl-l-propenyl group;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-methyl-l-propenyl group, and the absolute configuration at 1-position of the cyclopropane ring is R-configuration; A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-methyl-l-propenyl group, and the relative configuration of substituents at the 1- position and the 3-position on the cyclopropane ring is trans configuration; A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-methyl-l-propenyl group, and the relative configuration of substituents at the 1- position and the 3-position on the cyclopropane ring is cis configuration; A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-methyl-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 2-methyl-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is cis configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, and the absolute configuration at 1-position of the cyclopropane ring is R-configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, and the relative configuration of a double bond present in a substituent at 3-position of the cyclopropane ring is Z- configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration; A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration, and the relative configuration of a double bond present in a substituent at 3-position of the cyclopropane ring is Z-configuration;
A compound of the formula (1) wherein R1 represents a hydrogen atom and R2 represents a 1-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration, and the relative configuration of a double bond present in a substituent at 3-position of the cyclopropane ring is Z-configuration;
The present compound, when used in a pest controlling composition, may be used in the form of isomer mixture of any ratio.
The isomer mixture includes, for example, the following compounds.
An isomer mixture 50 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;
An isomer mixture 80 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration; An isomer mixture 90 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 2-cyano-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;
An isomer mixture 50 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 2-methyl-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration; An isomer mixture 80 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 2-methyl-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;
An isomer mixture 90 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 2-methyl-l-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;
An isomer mixture 50 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 1-propenyl group, the
_ o _ absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration; An isomer mixture 80 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 1-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;
An isomer mixture 90 % or more of which is the compound of the formula (1) wherein R1 represents a hydrogen atom, R2 represents a 1-propenyl group, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;
In the formula (1), R1 represents preferably a hydrogen atom.
In the formula (1), R2 represents preferably a 1- propenyl group, 2-methyl-l-propenyl group or 2-cyano-l- propenyl group, more preferably, a 2-methyl-l-propenyl group or 2-cyano-l-propenyl group, further preferably, a 2- methyl-1-propenyl group in which the relative configuration of a double bond is Z-configuration or a 2-cyano-l-propenyl group in which the relative configuration of a double bond is Z-configuration.
In the formula (1) , the absolute configuration at 1- position of the cyclopropane ring is preferably R- configuration .
In the formula (1) , the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration.
The present compound can be produced by reacting an alcohol compound of the formula (2)
Figure imgf000011_0001
with a carboxylic acid compound of the formula (3)
Figure imgf000011_0002
(wherein R1 and R2 respectively represent the same meanings as described above) . or a reactive derivative of the carboxylic acid compound. The reactive derivative includes acid halides of the carboxylic acid compound of the formula (3), acid anhydrides of the carboxylic acid compound, or methyl esters of the carboxylic acid compound. The acid halide includes acid chloride compounds and acid bromide compounds,
The reaction is carried out usually in a solvent in the presence of a condensing agent or base.
Examples of the solvent include hydrocarbons such as benzene, toluene or hexane, ethers such as diethyl ether, or tetrahydrofuran, and halogenated hydrocarbons such as chloroform, dichloromethane, or 1, 2-dichloroethane, chlorobenzene . Examples of the condensing agent include dicyclohexylcarbodiimide and WSC (l-(3- dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) .
The base includes organic bases such as triethylamine, pyridine, N,N-diethylaniline, 4-dimethylaminopyridine, or diisopropylethylamine .
The reaction time is usually in the range of 5 minutes to 72 hours.
The reaction temperature is usually in the range of - 20°C to 1000C, and preferably in the range of -5°C to 1000C.
Here, the reaction temperature is in the range of - '200C to the boiling point of the solvent, preferably in the range of -5°C to the boiling point of the solvent, when the boiling point of the solvent to be used is lower than 1000C. In the reaction, the molar ratio of the alcohol compound of the formula (2) to the carboxylic acid compound of the formula (3) or reactive derivative thereof can be arbitrarily selected, however, it is preferably equimolar or near ratio. The condensing agent or base can be used usually at any proportion from 1 mol to excess amount, preferably 1 mol to 5 mol, with respect to 1 mol of the alcohol compound of the formula (2) .
The condensing agent or base is appropriately selected depending on the kind of . the carboxylic acid compound of the formula (3) or reactive derivative thereof.
After completion of the reaction, the reaction mixture is filtrated and the filtrate is concentrated, alternatively, the reaction mixture is poured into water, then, usual post-treatment operations such as extraction with organic solvent, or concentration are performed, thus, the present compound can be obtained. The resultant present compound can be purified by operations such as chromatography, or distillation. The alcohol compound of the formula (2) is a compound described in JP-A No. 57-123146, and can be produced by a method described in this publication.
The carboxylic acid compound of the formula (3) is a commercially available product, or a compound described in JP-A No. 2000-63329, Agr. Biol. Chem. , 34, 1119 (1970), J. Chem. Soc. 1076 (1970), JP-A No. 47-43333, JP-A No. 49- 47531 and the like, alternatively, can be produced by methods described in these publications.
The pests on which the present compound manifests an effect include, for example, arthropods such as insects, or mites .
Specific examples thereof are as follows.
Lepidoptera:
Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis and Plodia interpunctella, Noctuidae such as Spodoptera litura, Pseudaletia separate and Mamestra brassicae, Pieridae such as Pieris rapae crucivora, Tortricidae such as Adoxophyes spp., Carposinidae, Lyonetiidae, Lymantriidae, Autographa, Agrotis spp. such as Agrotis segetum and Agrotis ipsilon, Helicoverpa spp.,
Heliothis spp., Plutella xylostella, Parnara guttata, Tinea translucens, Tineola bisselliella, etc.
Diptera :
Culex spp. such as Culex pipiens pallens and Culex tritaeniorhynchus, Aedes spp. such as Aedes aegypti and Aedes albopictus, Anopheles spp. such as Anopheles sinensis, Chironomidae, Muscidae such as Musca domestica, Muscina stabulans and Fannia canicularis, Calliphoridae, Sarcophagidae, Anthomyiidae such as Delia platura and Delia antique, Tephritidae, Agromyzidae, Drosophilidae,
Psychodidae, Phoridae, Tabanidae, Simuliidae, Stomoxyidae, Ceratopogonidae, etc.
Blattaria:
Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, etc.
Hymenoptera:
Formicidae, Vespidae, Bethylidae, Tenthredinidae such as Athalia rosae ruficornis, etc. Siphonaptera:
Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, etc.
Anoplura:
Pediculus humanus, Pthirus pubis, Pediculus capitis, Pediculus corporis, etc.
Isoptera:
Reticulitermes speratus, Coptotermes formosanus, etc.
Hemiptera:
Delphacidae such as Laodelphax striatellus, Nilaparvata lugens and Sogatella furcifera, Deltocephalidae such as Nephotettix virescens and Nephotettix cincticeps, Aphididae, Pentatomidae, Aleyrodidae, Coccoidea, Cimicidae such as Cimex lectularius, Tingidae, Psyllidae, etc.
Coleoptera: Attagenus unicolor japonicus, Authrenus verbasci, Corn Rootworms such as Diabrotica virgifera and Diabrotica undecimpunctata howardi, Scarabaeidae such as Anomala cuprea and Anomala rufocuprea, Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, Anthonomus grandis grandis and Callosobruchus chinensis, Tenebrionidae such as Tenebrio molitor and Tribolium castaneum, Chrysomelidae such as Oulema oryzae, Phyllotreta striolata and Aulacophora femoralis, Anobiidae, Epilachna spp. such as Epilachna vigintioctopunctata, Lyctidae, Bostrychidae, Cerambycidae, Paederus fuscipes, etc. Thysanoptera :
Thrips palmi, Frankliniella occidentalis, Thrips hawaiiensis, etc. Orthoptera: Gryllotalpidae, Acrididae, etc. Acarina:
Pyroglyphidae such as Dermatophagoides farinae and Dermatophagoides pteronyssinus, Acaridae such as Tyrophagus putrescentiae and Aleuroglyphus ovatus, Glycyphagidae such as Glycyphagus privatus, Glycyphagus domesticus and Glycyphagus destructor, Cheyletidae such as Cheyletus malaccensis and Cheyletus fortis, Tarsonemidae, Chortoglyphus spp., Oribatei, Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai, Panonychus citri and Panonychus ulmi, Ixodidae such as Haemaphysalis longiconis, Dermanyssidae such as Ornithonyssus sylviarum and Dermanyssus gallinae, etc.
The pest controlling composition of the present invention is usually a formulation. Examples of the formulation form include an oil solution, an emulsifiable concentrate, a wettable powder, a flowable formulation (e.g., an aqueous suspension, or an aqueous emulsion) , a microcapsule, a dust, a granule, a tablet, an aerosol, a carbon dioxide formulation, a heat transpiration formulation (e.g., an insecticidal coil, an electric insecticidal mat, or a liquid absorbing core-type heat transpiration pesticide) , a piezo insecticidal formulation, a heat fumigant (e.g., a self combustion-type fumigant, a chemical reaction-type fumigant, or a porous ceramic plate fumigant) , an unheated transpiration formulation (e.g., a resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet) , an aerosol formulation (e.g., a fogging formulation), a direct contact formulation (e.g., a sheet-shaped contact formulation, a tape-shaped contact formulation, or a net-shaped contact formulation), an ULV formulation and a poison bait.
These formulations contain, depending on the formulation form, the present compound usually in an amount of 0.001 to 95% by weight of the total amount.
The formulation-forming method includes, for example, the following methods.
[1] A method which comprises mixing the present compound with a solid carrier, liquid carrier, gaseous carrier, bait and the like, and if necessary, adding a surfactant or other formulation auxiliary substances and then processing.
[2] A method which comprises impregnating the present compound in a base material. [3] A method which comprises mixing the present compound and a base material, and then molding the resulting mixture.
Examples of the solid carrier for the formulation include fine powders or granules of clays (e.g., kaolin clay, diatomaceous earth, bentonite, Fubasami clay, or acid white clay) , synthetic hydrated silicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite, quartz, sulfur, active carbon, calcium carbonate, or hydrated silica) and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride, or urea); substances that are solid at room temperature (e.g., 2, 4, β-triisopropyl-1, 3, 5-trioxane, naphthalene, p- dichlorobenzene, camphor, or adamantine) ; and felt, fiber, fabric, knit, sheet, paper, thread, foam, porous material and multi-filament comprising one or more substances selected from the group consisting of wool, silk, cotton, hemp, pulp, synthetic resins (e.g., polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene- ethyl methacrylate copolymer; ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers; polypropylene resins such as a propylene homopolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polystyrene; acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene resins; styrene elastomers such as a styrene-conjugated diene block copolymer and a hydrogenated styrene-conjugated diene block copolymer; fluorine resins; acrylic resins such as methyl polymethacrylate; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polycyclohexylene dimethylene terephthalate; or porous resins such as polycarbonate, polyacetal, polyacryl sulfone, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resins, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, foamed polypropylene and foamed ethylene) , glass, metal and ceramics .
Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, or cyclohexane) , halogenated hydrocarbons (e.g., chlorobenzene, dichloromethane, dichloroethane, or trichloroethane) , alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, or ethylene glycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, or dioxane) , esters (e.g., ethyl acetate, or butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone) , nitriles (e.g., acetonitrile, or isobutyronitrile) , sulfoxides (e.g., dimethyl sulfoxide), acid amides (e.g., N,N-dimethylformamide, N, N- dimethylacetamide, or N-methyl-pyrrolidone) , alkylidene carbonate (e.g., propylene carbonate), vegetable oils (e.g., soybean oil, or cottonseed oil), plant essential oils (e.g., orange oil, hyssop oil, or lemon oil), and water.
Examples of the gaseous carrier include butane gas, chlorofluorocarbon, liquefied petroleum gas (LPG) , dimethyl ether and carbon dioxide. Examples of the surfactant include alkyl sulfate, alkyl sulfonate, alkylaryl sulfonate, alkylaryl ethers, polyoxyethylenated alkylaryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives . Examples of the other auxiliary agents for formulation include a binder, a dispersant and a stabilizer. Specifically, there are, for example, casein, gelatin, polysaccharides (e.g., starch, gum arable, cellulose derivatives, or alginic acid) , lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (e.g., polyvinyl alcohol, or polyvinyl pyrrolidone) , polyacrylic acid, BHT (2, 6-di-tert-butyl-4-methylphenol) and BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3- tert-butyl-4-methoxyphenol) . Examples of a base material for the insecticidal coil include a mixture of vegetable powder such as wood flour and lees powder, and a binder such as incense material powder, starch and gluten.
Examples of a base material for the electric insecticidal mat include a plate obtained by hardening cotton linter and a plate obtained by hardening fibrils of a mixture of cotton linter and pulp.
Examples of a base material for the self combustion- type fumigant include combustible exothermic agents such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood flour, thermal decomposition stimulants such as alkali metal salt, alkaline earth metal salt, dichromate and chromate, oxygen carriers such as potassium nitrate, combustion-supporting agents such as melamine and flour starch, extenders such as diatomaceous earth, and binders such as synthetic glue.
Examples of a base material for the chemical reaction-type fumigant include exothermic agents such as alkali metal sulfide, polysulfide, hydrosulfide and calcium oxide, catalytic agents such as a carbonaceous material, iron carbide and active white clay, organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as strips of natural fiber and synthetic fiber.
Examples of a base material resin for resin transpiration formulations include polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene- ethyl methacrylate copolymer; ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers; polypropylene resins such as a propylene copolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; s acrylonitrile-butadiene-styrene resins; styrene elastomers such as a styrene-conjugated diene block copolymer and a hydrogenated styrene-conjugated diene block copolymer; fluorine resins; acrylic resins such as methyl polymethacrylate; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polycyclohexylene dimethylene terephthalate; polycarbonate, polyacetal, polyacryl sulfone, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride and polyurethane.
These base material resins may be used alone or as a combination of two or more kinds. If necessary, a plasticizer such as phthalate (e.g., dimethyl phthalate, or dioctyl phthalate) , adipic acid esters and stearic acid may be added to these base materials.
The resin transpiration formulations can be prepared by mixing the present compound with the base material, kneading the mixture, followed by molding it by injection molding, extrusion molding or pressure molding.
The resultant resin transpiration formulations can be subjected to further molding or cutting procedure, if necessary, to be processed into a plate, film, tape, net or string shape. These resin formulations can be processed into animal collars, animal ear tags, sheet products, trap strings, gardening supports and other products.
Examples of a base material for the poison bait include food ingredients such as grain powder, vegetable oil, saccharide and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, accidental ingestion inhibitors for children and pets such as a chili powder; insect attraction fragrances such as cheese flavor, onion flavor and peanut oil.
The pest controlling method of the present invention comprises a step of applying an effective amount of the present compound to a pest or a habitat of the pest.
In the controlling method, the present compound is usually applied, in the form of a pest controlling composition, to a pest or a habitat of the pest.
The application of the present compound can be carried out, for example, according to the following methods, and specific application methods can be appropriately selected depending on the form of the present compound, place to be used thereof, and the like.
(1) A method which comprises treating a pest or habitat of the pest with the present compound or the pest controlling composition of the present invention as it is. (2) A method which comprises diluting the present compound or the pest controlling composition of the present invention with a solvent such as water, and then spraying it on a pest or habitat of the pest.
In the method (2), the present compound or a pest controlling composition of the present invention is generally diluted so that the concentration of the present compound is 0.1 to 10000 ppm, and then sprayed.
(3) A method which comprises heating a pest controlling composition of the present invention at a habitat of the pest to volatilize the present compound.
In the method (3) , both the application amount and the application concentration of the present compound can be appropriately selected depending on the form of the present compound, application time, application place, application method, the kind of pests, injury conditions and the like.
When the present compound is used for prevention of epidemics, its application amount is usually 0.0001 to 1000 mg/m3 when applied in space, and 0.0001 to 1000 mg/m2 when applied on plane.
A heat fumigant such as an insecticidal stick, electric insecticidal mat can be applied by volatilizing an active ingredient by heating according to its formulation form. A unheated transpiration formulation such as resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet can be applied, for example, by placing as it is in a space to be applied, or placing the formulation under an influence of blowing air.
In the case where the present compound is applied for the purpose of prevention of epidemics, examples of the habitat of a pest include a closet, a Japanese cabinet, a Japanese chest, a cupboard, a toilet, a bathroom, a shed, a living room, a dining room, a garage and the interior of a car. The present compound can be also applied to outdoor open space.
The present compound can be used on animals by a known method in the veterinary field, when used for controlling external parasites of livestock such as cow, horse, pig, sheep, goat, or chicken, or small animals such as dog, cat, rat, or mouse.
As specific use methods, when intended for systemic control, for example, table, feedstuff mixing, suppository and injection (intramuscular, subcutaneous, intravenous, intraperitoneal) are used for administration. When intended for non-systemic control, for example, the present compounds are applied by such a method as spraying of oil or aqueous liquid, pour-on treatment, spot-on treatment, washing animal with a shampoo formulation, forming a resin transpiration formulation into collar or ear tag to be fixed on animal. The amount of the present compound when administered to animal is usually in the range of 0.01 to 1000 mg with respect to 1 kg of body weight of animal. The present compound can be used in admixture or together with other insecticides, acaricides, nematicides, soil pest controlling agents, bactericides, herbicides, plant growth regulators, repellents, synergists, fertilizers or soil improving agents. The kinds of the above-described insecticides, acaricides, nematicides, soil pest controlling agents, bactericides, herbicides, plant growth regulators, repellents, synergists, fertilizers and soil improving agents are not particularly restricted. Examples of active ingredients of such insecticides and miticides include organophosphorus compounds such as fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulprofos, cyanophos, dioxabenzofos, dimethoate, phenthoate, malathion, trichlorphon, azinphosmethyl, monocrotophos, or e'thion; carbamate compounds such as BPMC, benfuracarb, propoxur, carbosulfan, carbaryl, methomy1, ethiofencarb, aldicarb, oxamyl, or fenothiocarb; pyrethroid compounds such as ethofenprox, fenvalerate, esfenvalerate, fenpropathrin, cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprothrin, fluvalinate, bifenthrin, ' 2-methyl-2- (4- bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin, silafluofen, d-phenothrin, cyphenothrin, d- resmethrin, acrinathrin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, allethrin, d-furamethrin, prallethrin, imiprothrin, empenthrin, 5-(2- propynyl ) furfuryl 2,2,3, 3-tetramethylcyclopropane carboxylate, metofluthrin, profluthrin, and dimefluthrin; nitroimidazolidine derivatives, nitroguanidine derivatives such as clothianidin and dinotefuran, N- cyanoamidine derivatives such as acetamiprid, chlorinated hydrocarbon compounds such as endosulfan, γ-BHC, and 1- bis (chlorophenyl) -2,2, 2-trichloroethanol, benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron, and flufenoxuron, phenylpyrazole compounds, and metoxadiazone, bromopropylate, tetradifon, chinomethionat, pyridaben, fenpyroximate, diafenthiuron, tebufenpyrad, polynactin complexes (tetranactin, dinactin, trinactin) , pyrimidifen, milbemectin, abamectin, ivermectin, and azadirachtin. Examples of the active ingredient of the repellent include 3, 4-caranediol, N,N-diethyl-m-toluamide, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidine carboxylate, p-menthane-3, 8- diol and vegetable essential oils such as a hyssop oil. Examples of the active ingredient of the synergist include bis- (2, 3, 3, 3-tetrachloropropyl) ether (S-421) , N- (2- ethylhexyl) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboxyimide (MGK-264) and α- [2- (2-butoxyethoxy) ethoxy] -4 , 5- methylenedioxy-2-propyltoluene (piperonyl butoxide) .
EXAMPLES
The present invention will be illustrated further in detail by production examples, formulation examples and test examples, but the present invention is not limited to these examples.
First, production examples of the present compound are shown.
Production Example 1 Into a mixture of 145 mg of 4-methylthiomethyl- 2, 3, 5, 6-tetrafluorobenzyl alcohol, 130 mg of (IR) -trans-3- ((Z) -2-cyano-l-propenyl) -2, 2-dimethylcyclopropane carboxylic acid, 10 mg of 4-dimethylaminopyridine and 10 ml of anhydrous chloroform was added 156 mg of WSC, and the mixture was stirred at room temperature for 18 hours. Water was poured into the reaction mixture, and then extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, then, concentrated under reduced pressure condition, and the resulting residue was subjected to silica gel column chromatography, to obtain 150 mg of 4- methylthiomethyl-2, 3,5, 6-tetrafluorobenzyl= (IR) -trans-Z-3- (2-cyano-l-propenyl) -2, 2-dimethylcyclopropane carboxylate (hereinafter, referred to as the present compound (1) ) of the following formula.
(Present compound (D)
Figure imgf000027_0001
1H-NMR(CDCl3 ^MS) δ (ppm) : 1.20 (s, 3H) , 1.33 (s,3H) , 1.71 (d,lH, J=5.1Hz) , 1.95 (d,3H, J=I.5Hz) , 2.13 (s,3H) , 2.45-2.48 (m, IH) , 3.77 (s,3H) , 5.24 (s,2H) , 5.79 (dd, J=9.8, 1.5Hz)
Production Example 2
The same operation as in Production Example 1 was carried out except that (IR) -trans-3- (2-methyl-l-propenyl) - 2, 2-dimethylcyclopropane carboxylic acid was used instead of (IR) -trans-3- ( (Z) -2-cyano-l-propenyl) -2,2- dimethylcyclopropane carboxylic acid, to obtain 4- methylthiomethyl-2, 3, 5, 6-tetrafluorobenzyl= (IR) -trans-3- ((Z) -2-methyl-l-propenyl) -2, 2-dimethylcyclopropane carboxylate (hereinafter, referred to as the present compound (2)) of the following formula.
(Present compound (2))
Figure imgf000027_0002
1H-NMR(CDCl3^MS) δ (ppm) :1.13(s,3H) , 1.27 (s, 3H) , 1.39(d, IH, J=5.6 Hz), 1.70 (d, 3H, J=I .3 Hz),
1.71(d,3H, J=I.3Hz) , 2.08 (dd, IH, J=7.9, 5.6 Hz) , 2.13(s,3H), 3.77(s,2H), 4.88 (dt,lH, J=7.9,1.3 Hz) , 5.19 (d, IH, J=12.1 Hz) , 5.24 (d,lH, J=12.1 Hz)
Production Example 3
The same operation as in Production Example 1 was carried out except that (IR) -trans-3- ( (Z) -1-propenyl) -2, 2- dimethylcyclopropane carboxylic acid was used instead of (IR) -trans-3- ( (Z) -2-cyano-l-propenyl) -2, 2- dimethylcyclopropane carboxylic acid, to obtain 4- methylthiomethyl-2 ,3,5, 6-tetrafluorobenzyl= ( IR) -trans-3- ((Z) -1-propenyl ) -2 , 2-dimethylcyclopropane carboxylate (hereinafter, referred to as the present compound (3) ) of the following formula.
(Present compound (3) )
Figure imgf000028_0001
1H-NMR(CDCl3 ,TMS) δ (ppm) :1.14 (s, 3H) , 1.28 (s, 3H) , 1.4β (d,lH, J=5.3 Hz) , 1.67-1.73 (m, 3H) , 2.13 (d, 3H, J=O .8 Hz) , 2.18 (dd, lH, J=8.2, 5.3 Hz) , 3.77 (s, 3H) , 5.09-5.14 (m, IH) , 5.18-5.2β (m,2H) , 5.56-5.64 (m, IH)
Production Example 4
The same operation as in Production Example 1 is carried out except that 2, 2, 3, 3-tetramethylcyclopropane carboxylic acid was used instead of (IR) -trans-3- ( (Z) -2- cyano-1-propenyl) -2, 2-dimethylcyclopropane carboxylic acid, to obtain 4-methylthiomethyl-2, 3, 5, 6- tetrafluorobenzyl=2, 2,3, 3-tetramethylcyclopropane carboxylate (hereinafter, referred to as the present compound (4)) of the following formula.
(Present compound (4))
Figure imgf000029_0001
Next, Formulation Examples will be shown. Parts are by weight.
Formulation Example 1
An emulsifiable concentration is obtained by dissolving 20 parts of any one of the present compounds (1) to (4) in 65 parts of xylene, adding 15 parts of Sorpol 3005X (registered trade name of Toho Chemical Co., Ltd.) thereto, and thoroughly mixing the mixture with stirring.
Formulation Example 2
A wettable powder is obtained by adding 5 parts of Sorpol 3005X to 40 parts of any one of the present compounds (1) to (4), thoroughly mixing the mixture, adding 32 parts of Carplex #80 (synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.) and 23 parts of 300 mesh diatomaceous earth thereto, and mixing the mixture with stirring by a juice mixer. Formulation Example 3
A mixture of 1.5 parts of any one of the present compounds (1) to (4), 1 part of Tokuseal GUN (synthetic hydrated silicon oxide, manufactured by Tokuyama Corp.), 2 parts of Reax 85A (sodium ligninsulfonate, manufactured by West Vaco Chemicals), 30 parts of Bentonite Fuji (bentonite, manufactured by Hojun Corp.) and 65.5 parts of Shokozan A clay (kaolin clay, manufactured by Shokozan Kogyosho) are thoroughly ground, and water is added thereto. The mixture is then thoroughly kneaded, granulated with an extrusion granulator, and dried to obtain a 1.5% granule.
Formulation Example 4
Ten (10) parts of any one of the present compounds (1) to (4), 10 parts of phenylxylylethane and 0.5 part of Sumijul L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Ltd.) are mixed. The obtained mixture is added to 20 parts of a 10% aqueous solution of gum arable, followed by stirring with a homomixer to obtain an emulsion having a mean particle diameter of 20 μm. The emulsion is further mixed with 2 parts of ethylene glycol and the mixture is stirred in a warm bath at 60°C for 24 hours to obtain microcapsule slurry. Separately, a thickening agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) in 56.3 parts of ion-exchanged water. A microcapsule formulation is obtained by mixing 42.5 parts of the microcapsule slurry and 57.5 parts of the thickening agent solution. Formulation Example 5
A mixture of 10 parts of any one of the present compounds (1) to (4) and 10 parts of phenylxylylethane is added to 20 parts of a 10% aqueous solution of polyethylene glycol, followed by stirring with a homomixer to obtain an emulsion having a mean particle diameter of 3 μm. Separately, a thickening agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) in 58.8 parts of ion-exchanged water. A flowable formulation is obtained by mixing 40 parts of the above emulsion and 60 parts of the thickening agent solution.
Formulation Example 6 A dust is obtained by mixing 5 parts of any one of the present compounds (1) to (4), 3 parts of Carplex #80 (synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.), 0.3 part of PAP (a mixture of monoisopropyl phosphate and diisopropyl phosphate) and 91.7 parts of talc (300 mesh) with stirring by a juice mixer.
Formulation Example 7
An oil solution is obtained by dissolving 0.1 part of any one of the present compounds (1) to (4) in 10 parts of dichloromethane, and mixing the solution with 89.9 parts of deodorized kerosene.
Formulation Example 8 An oil aerosol is obtained by mixing and dissolving 1 part of any one of the present compounds (1) to (4), 5 parts of dichloromethane and 34 parts of deodorized kerosene, filling an aerosol vessel with the resultant solution, attaching a valve to the vessel, and charging the vessel with 60 parts of a propellent (liquefied petroleum gas) under pressure through the valve.
Formulation Example 9
An aqueous aerosol is obtained by mixing and dissolving 0.6 part of any one of the present compounds (1) to (4), 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier, registered trademark of Atlas Chemical Inc.), filling an aerosol vessel with the resultant solution and 50 parts of water, attaching a valve to the vessel, and charging the vessel with 40 parts of a propellent (liquefied petroleum gas) under pressure through the valve.
Formulation Example 10 An insecticidal coil is obtained by dissolving 0.3 g of any one of the present compounds (1) to (4) in 20 mL of acetone, uniformly mixing and stirring the solution and 99.7 g of a base material for an insecticidal coil (a mixture of an incense material powder, lees flour and wood flour in a ratio of 4:3:3), adding 100 mL of water thereto, thoroughly kneading the mixture, and molding and drying the mixture.
Formulation Example 11 An electric insecticidal mat is obtained by dissolving 0.8 g of any one of the present compounds (1) to
(4) and 0.4 g of piperonyl butoxide in acetone to obtain 10 mL of the solution, and uniformly impregnating, with 0.5 mL of the solution, a base material (in a plate form, obtained by hardening fibrils comprised of a mixture of cotton linter and pulp) for an electric insecticidal mat of 2.5 cm x 1.5 cm and 0.3 cm thick.
Formulation Example 12 A part to be used for a liquid absorbing core-type heat transpiration device is obtained by dissolving 3 parts of any one of the present compounds (1) to (4) in 97 parts of deodorized kerosene, placing the resultant solution in a vessel made of vinyl chloride, and inserting a liquid- absorbing core into the vessel. The liquid-absorbing core is prepared by solidifying an inorganic powder with a binder, followed by sintering it, upper part of which can be heated by a heater.
Formulation Example 13
A heat fumigant is obtained by dissolving 100 mg of any one of the present compounds (1) to (4) in an appropriate amount of acetone, and impregnating a porous ceramic plate of 4.0 cm x 4.0 cm and 1.2 cm thick with the solution.
Formulation Example 14
A room-temperature-volatilizing formulation is obtained by dissolving 100 μg of any one of the present compounds (1) to (4) in an appropriate amount of acetone, uniformly applying the solution onto a filter paper of 2 cm x 2 cm and 0.3 mm thick, and air-drying to remove acetone.
The following test examples show that the present compound is effective as an active ingredient of a pest controlling composition.
Test Example 1
The present compound (2), 0.1 part, was dissolved in 10 parts of dichloromethane, and this was mixed with 89.9 parts of deodorized kerosene, to prepare a 0.1% oil formulation of the present compound (2) . The same procedure as described above was carried out, except that the present compound (3) was used instead of the present compound (2), to prepare a 0.1% oil formulation of the present compound (3) .
Musca domestica adult insects were released in a cube chamber having a 70 cm side, and 0.7 ml of a 0.1% oil formulation of the present compound (2) was sprayed into the chamber under a pressure of 8.8xlO4 Pa, by using a spray gun through a small window on the side surface of the chamber. Fifteen (15) minutes after spraying, Musca domestica adult insects were taken up into a clean cup (bottom diameter: 8.2 cm) in which an absorbent cotton containing 0.5% sugar water had been placed, and allowed to stand still until next day. The number of dead insects was counted 24 hours after standing still, and the insect death rate was calculated (repeated once) . The same test as described above was carried out also for the oil formulation of the present compound (3), and the insect death rate of Musca domestica adult insects was obtained. The results are shown in Table 1.
Table 1
Figure imgf000035_0002
Test Example 2
The present compound (1), 0.00625 parts, was dissolved in 10 parts of dichloromethane, and then mixed with 89.99375 parts of deodorized kerosene, to prepare a 0.00625% oil formulation.
For comparison, a 0.00625% oil formulation was prepared by the same manner as above using 4-methoxymethyl- 2,3,5, 6-tetrafluorobenzyl= (IR) -trans-3- ( (Z) -2-cyano-l- propenyl) -2, 2-dimethylcyclopropane carboxylate (compound described in JP-A No. 2004-2363, hereinafter, referred to as comparative compound (A)) of the following formula.
Figure imgf000035_0001
Culex pipiens female adult insects were released in a cube chamber having a 70 cm side, and 0.7 ml of a 0.00625% oil formulation of the present compound (1) was sprayed into the chamber under a pressure of 8.8xlO4 Pa using a spray gun through a small window on the side surface of the chamber. Ten minutes after spraying, Culex pipiens female adult insects were taken up into a clean cup (bottom diameter: 8.2 cm) in which an absorbent cotton containing 0.5% sugar water had been placed, and allowed to stand still until . next day. The number of dead insects was counted 24 hours after standing still, and the insect death rate was calculated (repeated twice) . The same test as described above was carried- out also for the oil formulation of the comparative compound (A) , and the insect death rate of Culex pipiens female adult insects was obtained.
The results are shown in Table 2.
Table 2
Figure imgf000036_0001
Test Example 3
The present compound (1), 0.025 parts, was dissolved in 10 parts of dichloromethane, and then mixed with 89.975 parts of deodorized kerosene, to prepare a 0.025% oil formulation.
For comparison, a 0.025% oil formulation was prepared by the same manner as above using 4-methylthiomethyl-
2,3,5, β-tetrafluorobenzyl= (IR) -trans-3- ((Z) -2-chloro-3, 3, 3- trifluoro-1-propenyl) -2, 2-dimethylcyclopropane carboxylate
(compound described in JP-A No. 57-123146, hereinafter, referred to as comparative compound (B) ) of the following formula.
Figure imgf000037_0001
Musca domestica adult insects (each 5 males and females, total 10) were released in a cube chamber having a 70 cm side, and 0.7 ml of a 0.025% oil formulation of the present compound (1) was sprayed into the chamber under a pressure of 8.8xlO4 Pa using a spray gun through a small window on the side surface of the chamber. Three minutes after spraying, the number of knocked down insects was counted, as a result, 9.5 insects (average number after two repetitions) were knocked down with the oil formulation of the present compound (1) , and no insect was knocked down with the oil formulation of the comparative compound (B) .
Industrial Applicability
The present compound has an excellent pest controlling effect, thus, it is useful as an active ingredient of a pest controlling composition.

Claims

1. An ester compound of the formula (1) :
Figure imgf000039_0001
wherein R1 represents a hydrogen atom or a methyl group and R2 represents a methyl group, a 1-propenyl group, a 2- methyl-1-propenyl group or a 2-cyano-l-propenyl group.
2. A pest controlling composition comprising the ester compound as described in Claim 1 as an active ingredient.
3. A pest controlling method comprising a step of applying an effective amount of the ester compound as described in Claim 1 to a pest or the habitat of the pest.
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CN102781912A (en) * 2010-02-25 2012-11-14 住友化学株式会社 Ester compound and use thereof

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CN102822143B (en) * 2010-03-31 2015-04-22 住友化学株式会社 Pyrethrinoid - type esters as pesticides

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CN102770411A (en) * 2010-02-25 2012-11-07 住友化学株式会社 Ester compound and use thereof
CN102781912A (en) * 2010-02-25 2012-11-14 住友化学株式会社 Ester compound and use thereof

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