JPH08295677A - Ester compound and pest controlling agent containing the ester compound as active component - Google Patents

Abstract

PURPOSE: To obtain the new subject compound composed of a specific ester compound having a triazolone ring and a cyclopropane ring, capable of exhibiting excellent controlling effect on a pest such as an insect and a tick and useful as an active component of a pestcontrolling agent, etc. CONSTITUTION: This is a new ester compound having a triazol-3-one ring expressed by formula I (R<1> is methyl or H; R<2> is a propargyl or an allyl; R<3> is a 1-5C alkyl, a 1-5C haloalkyl or a 3-5C cycloalkyl; R<4> is a halogen or H) and a cyclopropane ring. This compound exhibits excellent controlling effect on a pest such as an insect and a tick and useful as an active component of a pest-controlling agent. This compound is obtained by reacting a carbon ring compound having a cyclopropane ring expressed by formula II with a triazolonylmethyl alcohol expressed by formula III in a solvent in the presence of a condensation agent such as dicyclohexylcarbodiimide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ester compound and a pest control agent containing the same as an active ingredient.

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Heretofore, some ester compounds have been used as an active ingredient of pest control agents, for example, JP-A-57-1587.
No. 65 publication. However, from the viewpoint of efficacy, these compounds are not always satisfactory as active ingredients of pest control agents.

[0002]

[Means for Solving the Problems] In view of the above situation, the present inventors have conducted extensive studies to find a compound having an excellent pest control effect, and as a result, the ester compound represented by the following general formula 2 is excellent. The present invention was completed by discovering that it has a pest controlling effect. That is, the present invention has the general formula

Embedded image [In the formula, R ¹ represents a methyl group or a hydrogen atom, and R ²
Represents a propargyl group or an allyl group, and R ³ represents C ₁
To C ₅ alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, etc.), C _{1 to} C ₅ haloalkyl groups (eg, 2,2,2)
-Trifluoro-1- (trifluoromethyl) ethyl group, 2,2,2-trifluoroethyl group, chloroethyl group, etc.) or C ₃ -C ₅ cycloalkyl group (cyclopropyl group, cyclobutyl group or cyclopentyl group) the stands, R ⁴ is a halogen atom (fluorine atom, chlorine atom,
Bromine atom) or a hydrogen atom. ] The ester compound (Hereinafter, it is described as this invention compound.) Shown by these, and the pest controlling agent which uses it as an active ingredient are provided.

[0003]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound of the present invention, R ² is preferably a propargyl group, R ³ is a C ₁ -C ₃ alkyl group (eg ethyl group), C _1- C ₃ haloalkyl group (eg 2,2,2
-Trifluoro-1- (trifluoromethyl) ethyl group, 2,2,2-trifluoroethyl group, etc.) or a cyclopropyl group is preferable, R ⁴ is preferably a halogen atom, and more preferably a fluorine atom, and R ¹ is methyl. When group, R ²
The position of bonding to the triazolone ring is preferably at the 4-position, and R ¹
When is a hydrogen atom, the bonding position of R ^{2 to} the triazolone ring is preferably the 2-position.

The compounds of the present invention include optical isomers (1R-cis / 1R) derived from asymmetric carbon atoms in the cyclopropane ring portion.
-Trans / 1S-cis / 1S-trans), COOR
Geometrical isomers derived from the bound double bonds ³ (E /
Z), and regioisomers of the alcohol moiety (R ² is bonded to the 4-position of the triazolone ring / R ² is bonded to the 2-position of the triazolone ring).
Of these, all optical isomers, geometrical isomers and positional isomers having pest controlling activity, and mixtures thereof in any ratio are included. In the compound of the present invention,
The cyclopropane ring moiety is (1R, cis) or (1R
S, cis) preferably has a configuration of, when cyclopropane ring moiety of the arrangement of the cis, those COOR ³ and cyclopropane about the double bond bound of COOR ³ is located in the cis [i.e., R ⁴ Is a halogen atom, (E), and when R ⁴ is a hydrogen atom, it has the configuration (Z). Regarding the alcohol moiety, R ² is preferably bonded to the 4-position of the triazolone ring.

The compound of the present invention can be produced, for example, by the following method. General formula 3

Embedded image [In the formula, R ³ and R ⁴ have the same meanings as described above. ]
A carboxylic acid compound or a reactive derivative thereof represented by the following formula:

[Chemical 4] [In the formula, R ¹ and R ² have the same meanings as described above. ]
The method of reacting with an alcohol compound represented by Examples of the reactive derivative of the carboxylic acid compound represented by the general formula 3 include acid halides and acid anhydrides, preferably acid chlorides.
When the carboxylic acid compound itself represented by the general formula 3 is reacted with the alcohol compound represented by the general formula 4, the reaction is usually dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl). ) In the presence of a dehydrating agent such as carbodiimide hydrochloride (WSC), dichloromethane, tetrahydrofuran (TH
F), benzene, toluene or the like in an organic solvent. An organic base such as pyridine, triethylamine, 4-dimethylaminopyridine or diisopropylethylamine can be coexistent in the reaction. The reaction temperature is usually in the range of -10 ° C to + 100 ° C or the boiling point of the organic solvent used, preferably 0 ° C to 30 ° C. The reaction between the carboxylic acid chloride of the carboxylic acid compound represented by the general formula 3 and the alcohol compound represented by the general formula 4 is usually dichloromethane, TH
In an organic solvent such as F, benzene, or toluene, pyridine,
It is carried out in the presence of an organic base such as triethylamine or 4-dimethylaminopyridine. The reaction temperature is usually in the range of -10 ° C to + 100 ° C or the boiling point of the organic solvent used, preferably 0 ° C to + 30 ° C. After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent, washing and concentration to isolate the desired compound of the present invention. If necessary, it may be further purified by a usual operation such as chromatography.

The carboxylic acid compound represented by the general formula 3 which is one of the intermediates in the production of the compound of the present invention is described in, for example, JP-A-57-126447 and European Patent No. 005.
It can be produced according to the methods described in JP-A No. 0534 and JP-A No. 1-156943. The alcohol compound represented by the general formula 4 which is the other intermediate in the production of the compound of the present invention can be produced according to the method described in, for example, JP-A-57-158765.

Examples of the compounds of the present invention are shown in Tables 1 and 2.

[Table 1]

[Table 2]

Examples of pests for which the compound of the present invention exerts a controlling effect include the following. Hemiptera Pests Planthoppers such as the brown leafhopper, the brown planthopper, and the white-backed planthopper, leafhoppers such as leafhoppers, green leafhoppers, leafhoppers, leafhoppers, stink bugs, whitefly bugs, insect insects, scale bugs ), Koga noimaiga, Nogameka moth, etc., Japanese common moth, Spodoptera litura, Spodoptera litura, Spodoptera litura, etc.
Amothis genus ( Agrothis spp.), Heliothis spp., Such as leafminers, hemlocks, mosquitoes, cabbage moths, tamanaga moths, etc. Aedes mosquitoes such as Aedes albopictus, Anopheles mosquitoes such as Aedes albopictus, Chironomid species, house flies, house flies, house flies such as house flies, blow flies, flesh flies, seed flies, onion flies, fruit flies, fruit flies, fruit flies, fruit flies and fruit flies Coleoptera insects such as western corn rootworm, southern corn rootworm, scarab beetle such as western corn rootworm, scarab beetle, scarab beetle, weevils such as weevils, rice weevil, etc. Mushidamashi, mealworm such as red flour beetle, Kisujinomihamushi, Chrysomelidae such as corn rootworm, beetles such, Epilachna genera such as the beetle, Epilachna vigintioctopunctata (Epilachna s
pp.), flat beetle, long-tailed beetle, long-tailed beetle, long-horned beetle, blue-footed stag beetle, etc.

Pteropteran pests German cockroaches, Black cockroaches, American cockroaches, Black cockroaches, Cockroaches, etc. Total pest insects Southern white thrips, Thrips thrips, Melanoptera pests Ants, wasps, etc. Orthoptera pests Kera, grasshoppers, etc. Conyptera pests Human fleas, etc. Liceidae pests Human lice, lice, etc. Pests pests etc. House dust mites House dust mites Hazardous mites such as mites, dust mites, tick mites, and house dust mites

When the compound of the present invention is used as an active ingredient of a pest control agent, it is usually mixed with a solid carrier, a liquid carrier, a gaseous carrier, a bait, or impregnated with a substrate such as mosquito coil or mat. If necessary, add surfactants and other auxiliaries for formulation to prepare oils, emulsions, wettable powders, flowable agents such as water suspensions / emulsions, granules, powders, aerosols, mosquito repellents. Heating and smoking agents such as incense sticks, electric mosquito repellent mats, and non-mats
Self-combustion type smoke agent / chemical reaction type smoke agent, heated smoke agent such as porous ceramic plate smoke agent, non-heat agent such as resin vaporizer / impregnated paper vaporizer, fuming agent such as fogging agent, ULV agent ,
It is used by formulating it in poison baits. In these formulations, the compound of the present invention is usually added as an active ingredient in a weight ratio of 0.001 to 95.
%contains. Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz, Fine powder or granules of sulfur, activated carbon, calcium carbonate, hydrated silica, etc., chemical fertilizers (ammonium sulphate, ammonium phosphide, ammonium nitrate, urea, ammonium salt, etc.) and the like, and examples of liquid carriers include water and alcohol. Kinds (methanol,
Ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (Ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.),
Acid amides (N, N-dimethylformamide, N, N-
Dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oil such as cottonseed oil, and the like, and examples of the gaseous carrier, that is, propellant include freon gas and butane gas. , LPG (liquefied petroleum gas),
Examples thereof include dimethyl ether and carbon dioxide gas. Examples of the surfactant include alkyl sulfate salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give.

Examples of formulation aids such as sticking agents and dispersants are casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginate sugars), lignin derivatives, bentonites, sugars, synthetic water-soluble polymers. (Polyvinyl alcohol, polyvinyl chloride, polyacrylic acid, etc.), and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like. Examples of the base material of the mosquito coil include incense mixture of vegetable powder such as wood powder and lees and binder such as tab powder, starch and glutein. Examples of the base material of the electric mosquito repellent mat include those obtained by hardening fibrils of cotton linter or a mixture of cotton linter and pulp into a plate shape. Examples of the base component of the self-burning smoke agent include a combustion exothermic agent such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, wood powder, alkali metal salt, alkaline earth metal salt, heavy Chromates, pyrolysis stimulants such as chromates, oxygen supplying agents such as potassium nitrate, combustion-supporting agents such as melamine and wheat starch, extenders such as diatomaceous earth, and binders such as synthetic sizing agents. As the base component of the chemical reaction type smoke agent, for example, an alkali metal sulfide, polysulfide, hydrosulfide, hydrous salt, heat generating agent such as calcium oxide, carbonaceous material, iron carbide, catalyst such as activated clay Agents, organic foaming agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, polystyrene, polyurethane, natural fiber pieces,
Examples include fillers such as synthetic fiber pieces. Examples of the base material of the non-heated transpiration agent include thermoplastic resin, filter paper, Japanese paper and the like. Examples of the base component of poison bait include bait components such as grain flour, vegetable oil, sugar, crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaseletic acid, preservatives such as dehydroacetic acid, and pepper powder. Examples include ingesting agents, cheese flavors, onion flavors, and peanut oil attractants. Formulations of flowable agents (suspension in water or emulsion in water) generally range from 1 to
75% compound 0.5 to 15% dispersant, 0.1 to 10%
Suspension aid (for example, a protective colloid or a compound imparting thixotropy), 0 to 10% of a suitable auxiliary agent (for example, defoaming agent, rust preventive, stabilizer, spreading agent, penetration aid) , Antifreeze agents, antibacterial agents, antifungal agents, etc.) and finely dispersed in water. It is also possible to use an oil in which the compound is hardly dissolved in place of water to prepare a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ester, polyvinyl alcohol and the like are used. Examples of the compound that imparts thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid, and the like.

The thus obtained preparation is used as it is or after diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with acaricide, nematicide, soil pest control agent, fungicide, herbicide, plant growth regulator, synergist, fertilizer and soil conditioner. Other insecticides and acaricides used include, for example, fenitrothion [O, O-dimethyl O- (3-methyl-4-
Nitrophenyl) phosphorothioate], fenthion [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl) phosphorothioate], diazinone [O, O-diethyl-O-2-isopropyl-6-methylpyrimidine-4. -Ylphosphorothioate], chlorpyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate], DDVP
[2,2-dichlorovinyl dimethyl phosphate] and other organic phosphorus compounds, BPMC [2-sec-butylphenylmethylcarbamate], propoxur [2-isopropoxyphenyl N-methylcarbamate] and other carbamate compounds,

Etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS) -α-
Cyano-3-phenoxybenzyl (RS) -2- (4-
Chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methylbutyrate], phenpropatrine [( RS) -α-
Cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS-cis, trans) -3- (2, 2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS-cis, trans) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxy] Rate], deltamethrin [(S) -α-cyano-3
-Phenoxybenzyl (1R-cis) -3- (2,2
-Dibromovinyl) -2,2-dimethylcyclopropanecarboxylate], 2-methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin [(1R-cis) 3 [(1 'RS) (1', 2 ', 2', 2'-tetrabromoethyl)]-2,2-dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester], silafluofene [4- Ethoxyphenyl {3- (4-fluoro-3-phenoxyphenyl) propyl} dimethylsilane] d-phenothrin [3-phenoxybenzyl (1R-cis, trans) -chrysanthemate], cyphenothrin [(RS) -α- Cyano-3-phenoxybenzyl (1R-cis, trans)-
Chrysanthemate], d-resmethrin [5-benzyl-3-furylmethyl (1R-cis, trans) -chrysanthemate], acrinathrin [(S) -α-cyano-
3-phenoxybenzyl (1R-cis (Z))-
(2,2-dimethyl-3- {3-oxo-3- (1,
1,1,3,3,3-hexafluoropropyloxy)
Propenyl} cyclopropanecarboxylate], cyfluthrin [(RS) -α-cyano-4-fluoro-3-
Phenoxybenzyl 3- (2,2-dichlorovinyl)
-2,2-Dimethylcyclopropanecarboxylate], lambda halothrin [(RS) -α-cyano-3-
Phenoxybenzyl (1RS-cis (Z))-3-
(2-chloro-3,3,3-trifluoroprop-1-
(Enyl) -2,2-dimethylcyclopropanecarboxylate], tefluthrin [2,3,5,6-tetrafluoro-4-methylbenzyl (1RS-cis (Z))-3
-(2-chloro-3,3,3-trifluoroprop-1
-Enyl) -2,2-dimethylcyclopropanecarboxylate], transfluthrin [2,3,5,6-tetrafluorobenzyl (1R-trans) -3- (2,
2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], plaresulin [(S) -2-methyl-4-oxo-3- (2-propynyl) -2-cyclopenten-1-yl (1R-cis , Trans) -chrysanthemate, d-allethrin [2-methyl-4-oxo-3- (2-propenyl) -2-cyclopentene-
Pyrethroid compounds such as 1-yl (1R-cis, trans) -chrysanthemate, d-tetramethrin [3,4,5,6-tetraphthalimidomethyl (1R-cis, trans) -chrysanthemate, imidacloprid [1- Nitroimidazolidine derivatives such as (6-chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-indeneamino], chlorfluazuron [1- (3,
5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl) -3-
(2,6-Difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl)
Urea], flufenoxuron [1- (4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl)
And benzoylphenylurea compounds such as urea.

When the compound of the present invention is used as an active ingredient of an agricultural pest control agent, its application amount is usually 0.1 to 500 g per 10 ares, and an emulsion, a wettable powder, a flowable agent, etc. are diluted with water. When applied, the application concentration is 0.1-
It is 1000ppm, and granules, powders, etc. are applied as it is without any dilution. When it is used as an active ingredient of a pest control agent for household and epidemic prevention, emulsions, wettable powders, flowable agents, etc. are diluted with water to 0.1 to 10,000 ppm and applied, and oil, aerosol, fumigant, and smoke are applied. For agents, evaporants, fumes, ULV, poison baits, etc., apply as they are.
The application amount and application concentration depend on the type of formulation, application time, application site, application method, pest type, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

[0015]

EXAMPLES The present invention will be described in more detail with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. Production Example 1 (E)-(1R, cis) -2,2-dimethyl-3- [2
-Fluoro-2- (ethoxycarbonyl) ethenyl] cyclopropane-1-carboxylic acid 4.576 g in dry benzene
Dissolve in 20 ml, 1.7 ml of thionyl chloride and catalytic amount of DMF
Was added and the reaction was carried out with heating under reflux for 2 hours. The reaction solution was concentrated under reduced pressure to obtain the corresponding carboxylic acid chloride. 5-Methyl-4-propargyl-2,4-dihydro-3H-1,2,4-triazol-3-one-2-ylmethyl alcohol 3.986 g, triethylamine 4.2 ml
And catalytic amount of 4-dimethylaminopyridine over dry TH
It was dissolved in 30 ml of F and cooled to 0 ° C. To the solution, 10 ml of a THF solution of carboxylic acid chloride prepared above was added dropwise, and then stirred at room temperature for 14 hours. The reaction solution was poured into saturated aqueous ammonium chloride and extracted with diethyl ether three times. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This was subjected to silica gel chromatography (developing solvent n-hexane: ethyl acetate = 3: 1 (v / v)) to give 5-methyl-4-propargyl-2,4-dihydro-3H-1,2,4-. Triazol-3-one-2-ylmethyl (E)-(1R, cis) -2,2-dimethyl-
6.39 g of 3- [2-fluoro-2- (ethoxycarbonyl) ethenyl] cyclopropane-1-carboxylate (the present compound (1)) was obtained. ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, 25
0Mz) δ value (ppm): 5.89 (q, 1H), 5.21 (dd, 2H), 4.44 (d, 2
H), 4.30 (q, 2H), 2.88 (brt, 1H), 2.37 (m, 1H),
2.36 (s, 3H), 1.91 (d, 1H), 1.36 (t, 3H), 1.26 (s,
3H), 1.25 (s, 3H) Production Example 2 (Z)-(1R, cis) -2,2-dimethyl-3- [2
-(Ethoxycarbonyl) ethenyl] cyclopropane-
Dissolve 0.183 g of 1-carboxylic acid in 8 ml of dry benzene,
Thionyl chloride (0.08 ml) and a catalytic amount of DMF were added, and the reaction was carried out while heating under reflux for 2 hours. The reaction solution was concentrated under reduced pressure to obtain the corresponding carboxylic acid chloride. 5-methyl-
4-propargyl-2,4-dihydro-3H-1,2,
4-Triazol-3-one-2-ylmethyl alcohol 0.188 g, triethylamine 0.23 ml and catalytic amount of 4
-Dissolve dimethylaminopyridine in 5 ml of dry THF
Cooled to ° C. 2 ml of a THF solution of carboxylic acid chloride prepared above was added dropwise to the solution, and then stirred at room temperature for 15 hours. The reaction solution was poured into saturated aqueous ammonium chloride and extracted with diethyl ether three times. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This was subjected to silica gel chromatography (developing solvent n-hexane: ethyl acetate = 3: 1 (v / v)) to give 5-methyl-4-propargyl-2,4-dihydro-3H-1,
2,4-triazol-3-one-2-ylmethyl
(Z)-(1R, cis) -2,2-dimethyl-3- [2
-(Ethoxycarbonyl) ethenyl] cyclopropane-
1-carboxylate (the present compound (2)) 0.287 g
I got ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, 27
0Mz) δ value (ppm): 6.60 (brt, 1H), 5.89 (d, 1H), 5.73 (d,
1H), 5.68 (d, 1H), 4.44 (d, 2H), 4.17 (q, 2H), 3.
28 (brt, 1H), 2.35 (brs, 1H), 2.35 (s, 3H), 1.91 (d,
1H), 1.30 (s, 3H), 1.29 (t, 3H), 1.26 (s, 3H)

Examples of the compounds of the present invention are shown below together with the compound numbers. (1) 5-Methyl-4-propargyl-2,4-dihydro-3H-1,2,4-triazol-3-one-2-
Ilmethyl (E)-(1R, cis) -2,2-dimethyl-3- [2-fluoro-2- (ethoxycarbonyl)
Ethenyl] cyclopropane-1-carboxylate (2) 5-methyl-4-propargyl-2,4-dihydro-3H-1,2,4-triazol-3-one-2-
Ilmethyl (Z)-(1R, cis) -2,2-dimethyl-3- [2- (ethoxycarbonyl) ethenyl] cyclopropane-1-carboxylate (3) 5-Methyl-4-propargyl-2,4- Dihydro-3H-1,2,4-triazol-3-one-2-
Ilmethyl (Z)-(1R, cis) -2,2-dimethyl-3- [3-oxo-3-{(2,2,2-trifluoro-1- (trifluoromethyl) ethoxy} -1-propenyl ] Cyclopropane-1-carboxylate (4) 2-propargyl-2,4-dihydro-3H-
1,2,4-triazol-3-on-4-ylmethyl (E)-(1R, cis) -2,2-dimethyl-3-
[2-fluoro-2- (ethoxycarbonyl) ethenyl] cyclopropane-1-carboxylate

Formulation examples are shown below. The parts are parts by weight, and the compounds of the present invention are represented by the above compound numbers. Formulation Example 1 Emulsion 20 parts of each of Compounds (1) to (4) was dissolved in 65 parts of xylene, 15 parts of emulsifier Sorpol 3005X (registered trademark of Toho Kagaku Co., Ltd.) was added, and well mixed by stirring to prepare a 20% emulsion To get Formulation Example 2 Wettable powder 40 parts of each of the compounds (1) to (4) and Solpol 3005X
Add 5 parts (above), mix well, and use Carplex #
32 parts of 80 (Shionogi registered trademark, synthetic silicon oxide hydroxide fine powder) and 23 parts of 300 mesh diatomaceous earth are added and mixed by stirring with a juice mixer to obtain each 40% wettable powder. Formulation Example 3 Granules 1.5 parts each of Compounds (1) to (4) and AGSORBLVM-MS
24/48 (fired montmorillonite manufactured by OIL DRI,
98.5 parts of granular carrier having a particle size of 24 to 48 mesh) and well mixed to obtain each 1.5% granule. Formulation Example 4 Microcapsules After mixing 10 parts of each of the compounds (1) to (4), 10 parts of phenylxylylethane and 0.5 part of Sumidule L-75 (tolylene diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.), Add to 20 parts of 10% aqueous solution of gum arabic and stir with a homomixer to obtain an emulsion having an average particle size of 20 μm. Next, 2 parts of ethylene glycol was added thereto, and the mixture was further reacted in a warm bath at 60 ° C. for 24 hours to obtain a microcapsule chiller. On the other hand, Zangsangam 0.
2 parts and 1.0 part of Veegum R (aluminum magnesium silicate manufactured by Sanyo Kasei) are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. Micro capsule thriller 4 above
2.5 parts and 57.5 parts thickener solution are mixed to give 10 parts each.
% To obtain microcapsules. Formulation Example 5 Flowable agent After mixing 10 parts of each of the compounds (1) to (4) and 10 parts of phenylxylylethane, the mixture was added to 20 parts of a 10% aqueous solution of polyethylene glycol and stirred with a homomixer to obtain average particles. An emulsion with a diameter of 3 μm is obtained. On the other hand, 0.2 parts of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate manufactured by Sanyo Kasei) are dispersed in 58.8 parts of ion-exchanged water to obtain a thickener solution. The emulsion 40
Parts and 60 parts thickener solution to mix to obtain each 10% flowable agent. Formulation Example 6 Powder 5 parts of each of Compounds (1) to (4) is added to Carplex # 8.
3 parts of 0 (the above), 0.3 parts of PAP and 91.7 parts of 300 mesh talc are added and mixed by stirring with a juice mixer to obtain each 5% powder.

Formulation Example 7 Oil agent 0.1 parts of each of the compounds (1) to (4) was added to dichloromethane 5
Dissolved in 9 parts of deodorized kerosene,
A 0.1% oil solution is obtained. Formulation Example 8 Oily aerosol 1 part of each of the compounds (1) to (4), 5 parts of dichloromethane and 34 parts of deodorizing kerosene are mixed and dissolved, filled in an aerosol container, and a valve part is attached, and then a propellant is passed through the valve part. 60 parts of (liquefied petroleum gas) is charged under pressure to obtain each oil-based aerosol. Formulation Example 9 Aqueous aerosol Compounds (1) to (4) each containing 0.6 part, xylene 5 parts, deodorizing kerosene 3.4 parts and an emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} were mixed and dissolved. things and,
50 parts of pure water is filled in an aerosol container, a valve portion is attached, and 40 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain each aqueous aerosol. Formulation Example 10 Mosquito coil Incense 0.3 g of each of the compounds (1) to (4) is dissolved in 20 ml of acetone, and a carrier for mosquito coil (tab powder: lees powder: wood powder 4:
Mix in a ratio of 3: 3) 99.7 g with stirring and mixing,
120 ml of water was added, and the mixture was thoroughly kneaded, molded and dried to obtain each mosquito coil. Formulation Example 11 Electric Mosquito Repellent Mat Acetone was added to 0.8 g of each of the compounds (1) to (4) and 0.4 g of piperonyl butoxide to dissolve them, and a total of 1 was obtained.
Make up to 0 ml. 0.5 ml of this solution is 2.5 cm × 1.5 cm, and the thickness is 0.5.
Each of the electric mosquito repellent matting agents is obtained by uniformly impregnating a 3 cm base material for electric mat (a fibril of a mixture of cotton linter and pulp is hardened into a plate shape). Formulation Example 12 Liquid Electric Mosquito Repellent Liquid Absorbent core (inorganic powder) in which 3 parts of each of Compounds (1) to (4) was dissolved in 97 parts of deodorized kerosene, placed in a vinyl chloride container, and the upper part of which could be heated by a heater. Each of the liquid electric mosquito repellents is obtained by solidifying with a binder and sintering. Formulation Example 13 Heat Smoke Agent Compounds (1) to (4) (100 mg) are each dissolved in an appropriate amount of acetone and impregnated into a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate, Get a heated smoker. Formulation Example 14 Normal temperature volatilizer 100 μg of each of the compounds (1) to (4) is dissolved in an appropriate amount of acetone, uniformly applied on a filter paper of 2 cm × 2 cm and 0.3 mm in thickness, and then air-dried with acetone. To obtain a room temperature transpiration agent. Formulation Example 15 Mite-proof sheet 1 Acetone solution of each of the compounds (1) to (4) was applied to a filter paper (1).
Impregnation is performed so that the amount becomes 1 g per m ² , and acetone is air-dried to obtain each mite-proof sheet.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of a pest controlling agent. The compounds of the present invention are shown by the above compound numbers, and the compounds used for comparison and control are shown by the compound symbols in Table 3.

[Table 3]

Test Example 1 Ten adult German cockroaches (5 males and 5 females) were placed in a polyethylene cup having a diameter of 9 cm and thinly coated with margarine on the wall surface.
, And cover with nylon mesh of 16 mesh,
It was installed at the bottom of an acrylic cylinder with an inner diameter of 10 cm and a height of 37 cm. 0.0 of the test compound obtained according to Formulation Example 7
0.6 ml of 03% oil solution was sprayed directly from the upper end of the cylinder at a pressure of 0.6 atm with a spray gun. After 1 minute, the number of knockdown insects of the test insects was examined (2 repetitions). The results are shown in Table 4.

[Table 4]

[0021] and the release, the 10 animals Culex female adults in the glass chamber of Test Example 2 70cm cubic (0.34 m ^3). 0.7 ml of 0.0125% oil solution of the test compound obtained according to Formulation Example 7 was sprayed into the chamber at a pressure of 0.8 atm with a spray gun. After 0.6 minutes, the number of knockdown worms of the test worms was examined (2 repetitions).
The results are shown in Table 5.

[Table 5]

[0022]

The compound of the present invention exhibits an excellent pest control effect.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroshi Kishida 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Mikako Nakamachi 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Yohji Takada 4-2-1 Takashi Takarazuka, Hyogo Prefecture Sumitomo Kagaku Kogyo Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula: [In the formula, R ¹ represents a methyl group or a hydrogen atom, and R ²
Represents a propargyl group or an allyl group, and R ³ represents C ₁
To C ₅ alkyl group, C _{1 to} C ₅ haloalkyl group or C _{3 to} C ₅ cycloalkyl group, and R ⁴ represents a halogen atom or a hydrogen atom. ] The ester compound shown by these. 2. A pest control agent comprising the ester compound according to claim 1 as an active ingredient.