JP2830349B2 - Carboxylic acid esters and their use as insecticides and acaricides - Google Patents

Description

The present invention relates to a novel carboxylic acid ester and its insecticide,
It relates to the use as an acaricide.

<Conventional technology> Until now, Japanese Patent Publication No. 55-42045 and Japanese Patent Application Laid-Open No. Sho 59-11874
No. 2, JP-A-61-280453, JP-A-57-11943, and JP-B-57-126447, it is known that certain carboxylic acid esters have insecticidal or acaricidal activity. I have.

<Problems to be Solved by the Invention> However, those compounds are not necessarily satisfactory enough in insecticidal and acaricidal activities.

<Means for solving the problem> In view of such circumstances, the present inventors, excellent insecticide,
As a result of various studies to develop compounds having acaricidal activity, the present inventors have found that the following carboxylic acid esters are excellent insecticidal and acaricidal compounds, and have reached the present invention.

That is, the present invention provides a compound represented by the general formula (I) [In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a methyl group, and R ² represents an alkyl group having 5 or less carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group or a haloalkyl group. (Hereinafter referred to as the compound of the present invention) and their use as insecticides and miticides.

The compounds of the present invention are: 1. Very active as fumigants, fumigants or transpirants.

2.High activity as oil or aerosol.

3. It acts very quickly on various pests and harmful mites, and has high insecticidal and acaricidal efficacy.

4. It is also effective against pests resistant to organophosphates or carbamates.

It has excellent characteristics such as.

Among the compounds of the present invention represented by the general formula (I), preferred are compounds wherein R ₂ is an alkyl group having 1 to 5 carbon atoms, a cyclopropyl group, an alkenyl group having 3 to 4 carbon atoms, and a compound having 3 to 4 carbon atoms. 4 represents an alkynyl group or a haloalkyl group having 1 to 4 carbon atoms. Of these, R ₁
Is more preferably a compound representing a hydrogen atom or a fluorine atom. Further particularly preferred compounds among these are those wherein R ₂ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
represents a tert-butyl group, a cyclopropyl group, an allyl group, a propargyl group, a 2-chloroethyl group or a 2-fluoroethyl group.

Among the above compounds, those in which R ₁ represents a hydrogen atom or a fluorine atom and R ₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group or a cyclopropyl group are most preferred. Next, specific examples of particularly preferable compounds among these compounds will be described.

The compound of the present invention has the formula (II) And a compound represented by the general formula (III) [Wherein, R ¹ and R ² represent the same meaning as described above, and Z represents a halogen atom. The carboxylic acid halide represented by the formula (I), usually, is reacted with the carboxylic acid chloride. The reaction is usually carried out in an inert solvent (eg, benzene, toluene, hexane, diethyl ether, etc.) in a base (eg, pyridine,
Triethylamine, etc.) at -30 to 100 ° C. for 30 minutes to 2
It takes 0 hours. The amount of the reagent used for the reaction is such that the carboxylic acid halide is usually 0.9 to 1.5 equivalents, preferably 0.95 to 1.1 equivalents, and the base is 1.0 to 2.0 equivalents, preferably 1 equivalent of the compound represented by the formula (II). Is 1.0 to 1.2 equivalents. After completion of the reaction, ordinary post-treatment such as extraction with an organic solvent is performed, and if necessary, purification is performed by an operation such as chromatography.

The compound of the present invention has various optical isomers and geometric isomers, and these isomers are also included in the present invention.

Table 1 shows examples of the compound of the present invention which can be produced by the above-mentioned production method.

Examples of pests and harmful mites to which the compound of the present invention exhibits excellent effects include the following.

Hemiptera pests Planthoppers such as brown planthoppers, brown planthoppers and brown planthoppers, leafhoppers such as leafhoppers and leafhoppers, aphids, stinkbugs, whiteflies, scale insects, scuttlebugs, hornworms, and other insects , Moths such as Noshimekokuga, Lotus armyworm, Armyworm,
Artemisia such as armyworm, white butterflies such as cabbage butterfly, antelopes such as kamakumamonhamaki, sink squid,
Hamoguriga acids, tussock such Uwaba acids, Kaburayaga, Agurotisu genus such as black cutworm (Agrothis spp.), Heliothis spp (Heliothis spp.), Plutella xylostella, clothes moth, webbing clothes moth, etc. Diptera Culex, Culex such as Culex, Aedes aegypti, Aedes albopictus Aedes, such as Aedes, Anopheles, such as Anopheles, Chironomidae, Musca domestica, Musca domestica, Musca domestica, blowfly, Phyllomorphidae, Anopheles, Flyfly, Drosophila, Drosophila, Flyfly, etc. Coleoptera pests, such as blackflies and flies, corn rootworms such as western corn rootworm, southern corn rootworm, etc.
Scarabaeids such as Scarabaeidae, weevils, weevils such as rice weevil, rice weevil, etc . ;
epilachna spp.), leaf beetle, long-spotted beetle, longhorn beetle, blue-spotted beetle, etc. Lepidopteran pests German cockroaches, black cockroaches, cockroaches,
Thrips and cockroaches, etc.Homoptera pests Thrips palmi, Thrips and others Hymenoptera pests Ants, wasps, wasps, etc. Orthoptera, moths, etc. Orthoptera pests Human fleas, etc. Louse pests, human lice, white lice, etc.Isopteran pests, Japanese termites, house termites, etc. Spider mites, spider mites, spider mite, Kanzawa spider mite, apple spider mite, etc. Ticks, ox tick, etc. The present compound exhibits particularly excellent insecticidal and acaricidal effects against the above-mentioned pests and harmful mites in fumigants, fumigants, vaporizers, oils, aerosols and the like against the above-mentioned pests and mites.

When the compound of the present invention is used as an active ingredient of insecticides and miticides, it is usually necessary to mix it with a solid carrier, liquid carrier, gaseous carrier, or bait, or impregnate it into a substrate such as a mosquito coil or mat. If present, add surfactants and other formulation auxiliaries to oils, emulsions, wettable powders, flowables such as suspensions and emulsions in water, granules, powders, aerosols and mosquito coils. Heating fumigants such as electric mosquito mats and no-mats, self-combustion type smokers, chemical reaction type smokers, heating fumigation agents such as electric heat type smokers, transpirants, fogging agents such as fogging, ULV
It is used by formulating it into agents, baits and the like.

In these preparations, the compound of the present invention as an active ingredient,
Usually, the content is 0.001 to 95% by weight.

Examples of solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide,
Bentonite, fubasami clay, acid clay, etc.), talc, ceramics, other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),
Fine powders or granular materials such as chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.) are listed.
For example, water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, etc.) Cyclohexane,
Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyl nitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N
-Dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethylsulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like. Butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers,
Examples include polyhydric alcohol esters and sugar alcohol derivatives.

Examples of adjuvants for preparations such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic,
Cellulose derivatives, alginic acid, etc.) Lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.)
Examples of stabilizers include PAP (acidic isopropyl phosphate) and BHT (2,6-di-tert-butyl-4-).
Methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant,
Fatty acids or esters thereof are listed.

The base material of the mosquito coil includes, for example, a mixture of a vegetable powder such as wood flour and lees flour and a binder such as tub flour, starch and glutin.

Examples of the base material of the electric mosquito collecting mat include those obtained by hardening fibrils of cotton linter or a mixture of cotton linter and pulp in a plate shape.

As a base material of the self-burning type smoke agent, for example, nitrate,
Combustion exothermic agents such as nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose, and wood flour; thermal decomposition stimulants such as alkali metal salts, alkaline earth metal salts, dichromate, and chromate; potassium nitrate Oxygen supply agents such as melamine, wheat starch and the like; extenders such as diatomaceous earth; binders such as synthetic paste;

Examples of the base material of the chemical reaction type smoke agent include exothermic agents such as sulfides, polysulfides, hydrosulfides, hydrated salts and calcium oxide of alkali metals, and catalyst agents such as carbonaceous materials, iron carbide and activated clay. And organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, polystyrene and polyurethane, and fillers such as natural fiber fragments and synthetic fiber fragments.

Examples of the base material of the electric heating type smoke agent include a porous ceramic plate, pulp, asbestos, and a porous glass material.

As bait bait, for example, cereal flour, vegetable essential oil,
Feed ingredients such as sugar and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, ingestion inhibitors such as pepper powder, cheese flavor, onion flavor, peanut oil, etc. Attractants and the like.

Formulations of flowables generally contain 1-75% of the compound in 0.1%.
5 to 15% of a dispersant, 0.1 to 10% of a suspending aid (for example, a protective colloid or a compound imparting thixotropic properties), 0
Fine water in water containing ~ 10% of suitable auxiliary agents (eg, antifoaming agent, rust inhibitor, stabilizer, spreading agent, penetration aid, antifreezing agent, antibacterial agent, fungicide, etc.) Obtained by dispersing. It is also possible to use an oil in which the compound hardly dissolves in place of water and use it as a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropic properties include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid and the like.
The preparation thus obtained is used as it is or diluted with water or the like. Also, mixed with other insecticides, acaricides, nematicides, soil pest control agents, repellents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners,
Or they can be used simultaneously without mixing.

When the compound of the present invention is used as an active ingredient of an agricultural pesticide, the application rate is usually 5 to 500 g per 10 ares, and when an emulsion, a wettable powder, a flowable, etc. are diluted with water and applied, The application concentration is 0.1 to 1000 ppm, and the granules, powders, etc. are applied as they are without dilution.

In addition, when used as an active ingredient of household and epidemic pesticides, emulsions, wettable powders, flowables, etc. are 0.1 to 10,000 pp with water.
Dilute to m and apply. Oils, aerosols, fumigants, smokers, transpirants, aerosols, ULV agents, poison baits, etc. are applied as they are.

All of these application rates and application concentrations depend on the type of formulation,
It depends on the situation such as application time, application place, application method, type of pest, degree of damage, etc., and can be increased or decreased without being concerned with the above range.

<Examples> Hereinafter, 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.

 First, Production Examples of the compound of the present invention will be shown.

Production Example 1 134 mg of 4-fluoro- (S) -3-hydroxy-4-hepten-1-yne and (1R) -cis-2,2-dimethyl-3-[(E) -2-ethoxy in 5 ml of dry toluene. Carbonyl-2-fluorovinyl] cyclopropane-1-carboxylic acid chloride (287 mg) was dissolved in pyridine 108 under ice cooling.
mg was added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 12 hours. The reaction solution was poured into 5 ml of cooled 5% hydrochloric acid, and the toluene layer was separated. The aqueous layer was extracted twice with diethyl ether, combined with the previous toluene layer, washed sequentially with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was treated by silica gel thin layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5),
290 mg of the desired compound [the present compound (1)] was obtained. ¹ H-NMR (CDCl ₃ solvent, TMS internal standard) 1.02 (t, 3H) 1.20 to 1.53 (m, 9H) 1.85 to 2.5 (m, 3H) 2.56 (d, 1H) 2.65 to 3.06 (m, 1H) 4.30 (Q, 2H) 5.20 (dt, 1H) 5.90 (dd, 1H) 6.31 (dd, 1H) ¹⁹ F-NMR (CDCl ³ solvent, CF ₃ COOH external standard) -48.53 (dd, 1F) -44.32 (d, 1F) Table 2 shows some of the compounds of the present invention produced according to the above production methods.

Next, production examples of insecticides and miticides containing the compound of the present invention as an active ingredient will be described. In the following formulation examples, parts represent parts by weight.

Lumber Example 1 Emulsion 10 parts of each of the present compounds (1) to (24)
And 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added and mixed well by stirring.
% Emulsion is obtained.

Formulation Example 2 wettable powder 20 parts of each of the compound (1), (19) or (21) of the present invention is composed of 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 20 parts of diatomaceous earth Add 54 parts to the mixture and stir and mix with a juice mixer to obtain a 20% wettable powder.

Formulation Example 3 Granules To 5 parts of each of the compounds (4), (20) and (24) of the present invention, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite, and 60 parts of clay are added, and sufficiently stirred and mixed. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 4 Dust One part of each of the present compound (6), (19) or (21) is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 part of PAP and 93.7 parts of clay are added thereto. And the mixture is stirred and mixed with a juice mixer, and acetone is removed by evaporation to obtain a 1% powder.

Formulation Example 5 Flowable agent 10 parts each of the present compound (8), (20) or (24) is added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol, and the mixture is stirred with a mixer to obtain a dispersant. To this, 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate are added, and 10 parts of propylene glycol are further added, followed by gentle stirring and mixing to obtain an emulsifier in 10% water.

Formulation Example 6 Oil Preparation 0.1 parts of each of the compounds (1) to (24) of the present invention was added to 99.9 of kerosene.
Mix to give 0.1% oil.

Formulation Example 7 Oily aerosol 0.2 of each of the present compound (1), (19) or (21)
Parts, 0.1 part of d-phenothrin and 59.7 parts of kerosene are mixed and dissolved, filled in an aerosol container, a valve part is attached, and 40 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to be oily. Get an aerosol.

Formulation Example 8 aqueous aerosol 0.3 of each of the present compound (4), (20) or (24)
Parts, d-phenothrin 0.2 parts, xylene 5 parts, kerosene 3.5
Part, emulsifier [Atmos 300 (trade name of Atlas Chemical Co.)] was mixed and dissolved and pure water (50 parts) was charged into an aerosol container, a valve was attached, and a propellant (liquefied petroleum gas) was passed through the valve. ) Pressurizing and filling 40 parts gives an aqueous aerosol.

Formulation Example 9 Mosquito coil incense 0.3 g of each of the present compounds (1) to (24) was added to acetone 20
dissolve in mlml, and add the carrier for mosquito coils (tab flour: lees flour: wood flour 4:
After mixing and mixing uniformly with 99.7 g, water 12
Add 0ml, knead well and mold and dry to obtain mosquito coil.

Formulation Example 10 Electric mosquito collecting mat Acetone is added to 0.4 g of each of the compounds (1) to (24) of the present invention and 0.4 g of piperonyl butoxide, and dissolved to make a total of 10 ml. 0.5 ml of this solution is 2.5 cm x 1.5 cm, thickness 0.3
The electric mosquito mat agent is obtained by uniformly impregnating an electric mat substrate (a fibril of a mixture of cotton linter and pulp solidified in a plate shape) of 1 cm.

Formulation Example 11 Heat-smoking agent 100 m of each of the present compounds (8), (20) and (24)
g is dissolved in an appropriate amount of acetone and impregnated into a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate to obtain a heated smoker.

Next, an insecticidal and acaricidal method using the compound of the present invention will be described in Test Examples. The compounds of the present invention are indicated by the compound numbers in Table 2, and the compounds used for comparison are indicated by the compound symbols in Table 3.

Test Example 1 2 ml of a 200-fold diluted solution (equivalent to 500 ppm) of the following emulsion of the compound of the present invention obtained in accordance with Formulation Example 1 with water was soaked in 13 g of artificial feed for common cutworm, and put into a polyethylene cup having a diameter of 11 cm. Ten larvae of the fourth cutworm of the cutworm, Spodoptera litura, were released, and after 6 days, the survival and death were examined to determine the mortality.
Repetition).

 The results are shown in Table 4.

Test Example 2 200-fold diluted water (equivalent to 500 ppm) of the emulsion of the following compound of the present invention and a control compound obtained according to Formulation Example 1 with water
Rice stalk (length about 12 cm) was immersed for 1 minute. After air-drying, rice stalks were placed in a test tube, and 10 adult resistant leafhoppers were released. One day later, survival and death were investigated, and the mortality was determined.
(2 repetitions).

 The results are shown in Table 5.

Test Example 3 The following test was performed using a mosquito coil containing 0.3% of the compound of the present invention and a control compound obtained according to Formulation Example 9.

1.5 g of each mosquito coil was ignited at both ends into a 183 cm (6.1 m ² ) peat grady chamber, and after burning for 10 minutes, 50 adult female Culex pipiens were released into the chamber and continued burning.

Twenty minutes after the release, the test insects were collected and fed with water, and one day later, the survival and death were investigated to determine the mortality.

 The results are shown in Table 6.

Test Example 4 10 adult German cockroaches (5 males and 5 females) were released into a polyethylene cup having a diameter of 9 cm, which was coated thinly on the wall with vaseline, and covered with a 16-mesh nylon ghost.
It was installed at the bottom of an acrylic cylinder with a height of 37 cm and a height of 37 cm.
0.6 ml of each 0.1% oil solution of the compound of the present invention and the control compound obtained according to Formulation Example 6 was sprayed directly from the upper end of the cylinder at a pressure of 0.6 atm with a spray gun. After 1 minute and 15 seconds, the number of knockdowns of the test insects was examined, and the knockdown insect rate was determined (two repetitions).

 The results are shown in Table 7.

Test Example 5 The following test was performed using the compound of the present invention obtained according to Formulation Example 9 and a mosquito coil containing 0.3% of a control compound.

1.5 g of each mosquito coil was ignited at both ends in a 183 cm square (6.1 m ² ) peat grading chamber, and after burning for 10 minutes, 50 house fly adults (male: female = 1: 1) were burned into this chamber. ) And continued burning.

Investigate the number of knockdown insects 20 minutes after release,
The knockdown insect rate was determined.

 The results are shown in Table 8.

Test Example 6 Each of the following compound of the present invention and a control compound was diluted to a predetermined concentration with acetone, and the diluted solution was uniformly applied to a 6 cm × 12 cm filter paper (dose: 200 mg / m ² ).

After air drying, the center of the filter paper was folded in two, and both ends were glued to form a bag. Dermatophago in the bag
ides farinae ) 20 animals were put together with the feed, the upper part of the bag was clipped, and the condition was maintained at a temperature of 25 ° C. and a humidity of 75%. One day later, the survival rate was examined to determine the mortality (two repetitions). .

 The results are shown in Table 9.

<Effects of the Invention> The compound of the present invention has high insecticidal and insecticidal properties against various pests and harmful mites, including lepidopteran pests, Hemiptera pests, lepidopteran pests, dipteran pests, and house dust mites. Show mite activity,
It is excellent also in the point of quick action, and can be used for various uses because of its extremely high activity as a fumigant or smoker.

Continuing from the front page (72) Inventor Noriotada Matsuo 4-2-1 Takashi, Takarazuka-shi, Hyogo Prefecture Within Sumitomo Chemical Co., Ltd. (72) Inventor Tohei Takagaki 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. In-company (72) Inventor Akiko Kakimizu 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Industries, Ltd. (56) References JP-A-49-132230 (JP, A) JP-A-59-118742 ( JP, A) JP-A-61-280453 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (1) General formula [In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a methyl group, and R ² represents an alkyl group having 5 or less carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group or a haloalkyl group. ] The carboxylic acid ester represented by these. Wherein R ¹ is hydrogen atom or fluorine atom, R ²
Is an alkyl group having 1 to 5 carbon atoms, a cyclopropyl group, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. Carboxylic esters. 3. An insecticide or acaricide comprising the carboxylic acid ester according to claim 1 as an active ingredient.