JPH0826908A - Smoking and heat-transpiring insecticide for killing fly and method for killing fly using the same - Google Patents

Abstract

PURPOSE:To satisfy insecticidal effect, safety, usability and producing property, etc., by selecting a 2,2,3,3-tetramethylcyclopropanecarboxylic acid ester having high vapor pressure and capable of improving insecticidal activity when used in a form of smoking and heat-transpiring insecticide as an optimum effective ingredient. CONSTITUTION:This smoking and heat-transpiring insecticide contains a propargylfurylmethyl alcohol ester compound of 2,2,3,3- tetramethylcyclopropanecarboxylic acid expressed by formula I (R is H or methyl) as an active ingredient. The insecticide obtained by including 0.3-1.2% active ingredient of formula I as an active ingredient and then processing in a form of incense is preferably used. 5-Propargyl-2-furylmethyl-2,2,3,3- tetramethylcyclopropanecarboxylate, etc., is preferably used as the compound of formula I. The compound of formula I is obtained by reacting 2,2,3,3- tetramethylcyclopropanecarboxylic acid or its reactive derivative with a propargylfurylmethyl alcohol of formula II or its reactive derivative.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula I:

[Chemical 9] (In the formula, R represents a hydrogen atom or a methyl group) 2,2,3,3-Tetramethylcyclopropanecarboxylic acid propargylfuryl methyl alcohol ester compound-containing smoldering and heating evaporation for slaughter The present invention relates to an insecticide and a fly-killing method using the insecticide.

[0002]

2. Description of the Related Art Insecticides for exterminating mosquitoes are generally mosquito coils, electric mosquito mats, and liquid electric mosquito smoked / heated transpiration insecticides. Although the demand is decreasing, its demand is still high. And, as its active ingredient, (±) -2-allyl-3-methyl-cyclopent-2-en-1-on-4-yl (+)-cis, trans-chrysanthate (hereinafter referred to as pinamine forte) ) Or its stereoisomer, for example, esbiothrin or esbiol, or (+)-2-propargyl-3-methyl-cyclopent-2-en-1-on-4-yl, (+)-cis, trans. -Chrysanthemart (hereinafter referred to as Etok), 5-propargyl-2-
Chrysanthemic acid ester compounds such as furylmethyl (+)-cis, trans-chrysanthate (hereinafter referred to as "flamethrin forte") are widely used.

On the other hand, as for flies, the number of flies is decreasing in urban areas, but there are opportunities to be more annoyed locally than in the past, such as around fishing villages, seafood processing plants, garbage processing plants, livestock houses, poultry houses, etc. Is increasing. Insecticides such as emulsions, oils, and powders are used to control the source of flies, and space aerosols are commonly used in general households to control adults.
It has the drawback of being transient and lacking in sustainability. Therefore, there has been an increasing demand for a smoldering / heated transpiration insecticide (incense stick, matte, liquid type) which is a space treatment agent and whose effect can last for several hours or longer.

By the way, the mosquito coil is a very rational insecticidal form because it retains spatial treatment with a single match in terms of time and has a constant effect until it burns out. During use, the active ingredient of mosquito coil is a few meters from the burning part where the burning temperature is about 800 ℃.
Although it volatilizes from a site near 200 to 250 ° C.,
Since smoke acts as a carrier, it is highly diffused and has a high insecticidal effect even in open situations. On the other hand, the temperature of the central part of the heat dissipation plate of the mat type heating evaporator is 160 to 180 ° C., and the temperature of the metal ring of the liquid heating evaporator is 120.
At ~ 140 ℃, it is lower than the active ingredient volatilization part of mosquito coil, and although matte and liquid types have slightly inferior diffusion power, it is a form suitable for use in closed rooms or in situations where smoke is disliked. .

The present inventor first tried to apply the chrysanthemic acid ester compound, which has been conventionally used for mosquito coil, mat, etc., in developing a smoked / heated transpiration insecticide in the form of incense stick. However, pinamine forte and ETOC had weak efficacy against flies, and even if the concentration of the active ingredient in the formulation was increased, sufficient insecticidal efficacy could not be obtained. The effect of Framethrinforte incense was confirmed,
It was necessary to further increase the efficacy, and there was a problem in terms of economy. The same was true for the matt or liquid-type heat-evaporated insecticides for fly sickness, with high concentrations of flamethrin forte showing the spore-killing effect, whereas pinamine forte and etok were ineffective even at high concentrations. The present inventor has also selected empentorin, which has the highest vapor pressure among commercially available pyrethroids, as an active ingredient, and has already developed a fly incense containing the same, but it is disadvantageous in cost and too volatile. Inevitably, the loss in the manufacturing drying process was unavoidable and was not always satisfactory. Therefore, the selection of the most suitable active ingredient for the smoky and heated transpiration insecticide for fly slaughter was an important issue.

[0006]

DISCLOSURE OF THE INVENTION The present invention selects the most suitable active ingredient for smoked and heat-transpiration insecticides for flies used in the form of incense sticks, mats and liquids.
It is an object of the present invention to provide a smoked / heated transpiration insecticide for fly sickness, which is excellent in all aspects such as usability and manufacturability, and a fly slaughter method using the same.

[0007]

In order to solve the above-mentioned problems, the present inventors have found that 2,2,3,3-tetramethylcyclopropanecarboxylic acid ester has a higher vapor pressure than the corresponding chrysanthemic acid ester. Focusing on the fact that the insecticidal activity can be improved when used in the form of a smoked / heated transpiration insecticide, the flametrin forte 2,2, which was found to be effective in the previous test, was used.
When a smoked / heat-evaporated insecticide containing a 3,3-tetramethylcyclopropanecarboxylic acid derivative (hereinafter, referred to as tephramethrin) was tested, it was confirmed that it showed a high fly-killing effect. As a result of further earnest studies, the present inventor has found that a propargylfurylmethyl alcohol ester compound of 2,2,3,3-tetramethylcyclopropanecarboxylic acid represented by the general formula I is specifically useful. They have found out the present invention and completed the present invention. That is, even with 2,2,3,3-tetramethylcyclopropanecarboxylic acid ester, for example, (+)-2-
Propargyl-3-methyl-cyclopent-2-ene-
1-on-4-yl and esters of 4-propargylbenzyl alcohol have a weak fly killing effect, and therefore smoked and heat-evaporated insecticides for fly killing that produce a high fly killing effect are propargyl furyl methyl alcohol and 2 , 2,3,3-tetramethylcyclopropanecarboxylic acid was found to be obtained for the first time using a compound in combination.

The invention of claim 1 is, as a means for solving the problems, as described above, as the active ingredient, the compound of the general formula I:

[Chemical 10] (In the formula, R represents a hydrogen atom or a methyl group) 2,2,3,3-Tetramethylcyclopropanecarboxylic acid propargylfurylmethyl alcohol ester compound for fly slaughter It relates to smoky and heat-transpiration insecticides.

The ester compound represented by the above-mentioned general formula I is a compound represented by the general formula II: 2,2,3,3-tetramethylcyclopropanecarboxylic acid or its reactive derivative according to a conventional method for ester synthesis.

[Chemical 11] It can be prepared by reacting with propargylfuryl methyl alcohol represented by the formula (wherein R represents a hydrogen atom or a methyl group) or a reactive derivative thereof. Examples of the reactive derivative of carboxylic acid include acid halide, acid anhydride, and alkali metal salt, while examples of the reactive derivative of alcohol include halide. The reaction is carried out in a suitable solvent, if necessary, optionally in the presence of an organic or inorganic base or acid as a deoxidizing agent or a catalyst, optionally under heating, and optionally in an inert atmosphere.

Among the compounds represented by the general formula I, the following compounds can be exemplified as those useful for the purpose of the present invention. In the present invention, of course, not only one kind but also two or more kinds may be mixed and used. (1) Compound 1 (teframethrin) The following formula:

[Chemical 12] 5-propargyl-2-furylmethyl 2, represented by
2,3,3-Tetramethylcyclopropanecarboxylate (2) Compound secondary formula:

[Chemical 13] 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate represented by the following formula (3):

Embedded image 5-propargyl-3-furylmethyl 2, represented by
2,3,3-Tetramethylcyclopropanecarboxylate In addition, teframethrin is disclosed in Japanese Patent Publication No. 46-4196, and an example as a mosquito coil is described therein. -No technical idea regarding the heat-transpiration insecticide is mentioned.

According to the invention of claim 2, in the constitution of claim 1, an ester compound of the general formula I is added as an active ingredient.
It is in the form of incense stick containing 3 to 1.2%.

According to the invention of claim 3, in the structure of claim 2, teframethrin is used as an active ingredient.

The invention of claim 4 uses the compound 2 as the active ingredient in the structure of claim 2.

The invention of claim 5 is one or two of phenolic stabilizers having at least two tert-butyl groups having a boiling point of 250 ° C. or higher in the constitution of any one of claims 2 to 4. The above is 0.5 to 3.
It is a mixture of 0 times the amount.

According to a sixth aspect of the present invention, in the constitution of the first aspect, a pulp mat having a thickness of 1.0 to 3.0 mm and a surface area of 7 to 15 cm ² contains 30 parts by weight of the ester compound of the general formula I as an active ingredient. ˜150 mg is impregnated and heated on a heat dissipation plate to evaporate the active ingredient into a mat form.

According to the invention of claim 7, in the structure of claim 6, teframethrin is used as an active ingredient.

The invention of claim 8 uses the compound 2 as an active ingredient in the structure of claim 6.

According to the invention of claim 9, in the constitution of any one of claims 6 to 8, one or more of pyrethroid synergist or higher fatty acid ester is used as an active ingredient as a volatilization regulator. The amount is 0.5 to 10 times as much.

The invention of claim 10 is the structure of any one of claims 6 to 9, wherein the phenolic stabilizer has at least two tert-butyl groups, or at least two tert-butyl groups. One or more hydroquinone stabilizers may be used in an amount of 0.1-1.
It is a mixture of 0 times the amount.

According to the invention of claim 11, in the constitution of claim 1, the ester compound of the general formula I as an active ingredient is
A plastic bottle is filled with a drug solution containing ˜6% and a solvent, and the upper part of the absorbent core partially immersed in the drug solution is heated to evaporate the active ingredient into a liquid form.

According to a twelfth aspect of the present invention, in the structure of the eleventh aspect, teframethrin is used as an active ingredient.

The invention of claim 13 uses the compound 2 as an active ingredient in the structure of claim 11.

The invention of claim 14 is the same as claims 11 to 1.
In the constitution of any one of 3 above, the solvent has a boiling point of 1
It uses an aliphatic hydrocarbon in the range of 80 to 350 ° C.

The invention of claim 15 is the same as claims 11 to 1.
In the constitution of any one of 3 above, water is contained as a solvent.

The present invention of claim 16 relates to a fly slaughter method comprising smoldering or heating to evaporate a smoldering / heat-evaporating insecticide for fly shaving containing an ester compound of the general formula I as an active ingredient.

The invention of claim 17 is, in the structure of claim 16, characterized in that the ester compound of the general formula I is contained as an active ingredient in an amount of 0.3 to 1.2%, in the form of an incense stick. It is a method of smoking.

The invention of claim 18 is the structure of claim 17, wherein teframethrin is used as an active ingredient.

The invention of claim 19 uses the compound 2 as an active ingredient in the structure of claim 17.

The invention of claim 20 is the structure of claim 16, wherein the thickness is 1.0 to 3.0 mm and the surface area is 7 to 15 cm.
² pulp quality mat, killing flies for smoldering-heating transpiration pesticide mat form was 30~150mg impregnated with ester compounds of general formula I as an active ingredient, evaporate the active ingredient by heating at the heat radiating board Is the way.

According to a twenty-first aspect of the invention, in the structure of the twentieth aspect, teframethrin is used as an active ingredient.

The invention of claim 22 uses the compound 2 as the active ingredient in the structure of claim 20.

A twenty-third aspect of the present invention is the composition of the sixteenth aspect, wherein a plastic solution is filled with a chemical solution containing 1 to 6% of the ester compound of the general formula I as an active ingredient and a solvent, and the chemical solution is absorbed. This is a method in which a liquid form of smoky and heat-transpiration insecticide for liquid syrup in which a part of the liquid core is immersed is attached to a heating evaporator, and the upper part of the liquid absorption core is heated to evaporate the active ingredient.

The invention of claim 24 is the structure of claim 23, in which teframethrin is used as an active ingredient.

The invention of claim 25 is the structure of claim 23, wherein the compound 2 is used as an active ingredient.

[0035]

According to the constitution of claim 1, since the ester compound of the general formula I has a high fly killing effect and the moderate volatility of this compound, it is effective not only for mosquitoes but also for flies for smoke fly burning and heat evaporation. An insecticide is provided. In addition, conventional pyrethroids, for example, pinamine, pinamine forte, bioallethrin, esbiothrin, esviol, etok, empentrin, or flamethrin forte may be appropriately mixed, and if necessary, pipette A synergist for pyrethroids such as ronyl butoxide, MGK-264, cinepyrine 500, S-421, Resen 384 may be added. Further, a bactericidal agent, a repellent, a deodorant, an aromatic agent, etc. may be appropriately added to give a multipurpose smoked / heat-evaporated insecticide.

According to the second aspect of the present invention, it is possible to obtain a smoked and heat-evaporated insecticide for fly sickle in the form of an incense stick that is excellent in fly killer efficacy and highly volatile. The content of the ester compound of the general formula I blended as an active ingredient is 0.3 to 1.2%, preferably 0.6 to 1.2%, more preferably 0.1.
It is 7 to 1.2%. When an incense is prepared by mixing the ester compound of the general formula I with other active ingredients such as flamethrin forte and empentrin, the total amount of the active ingredients is preferably 0.6 to 1.2%, and above all, 0.7-1.2% is more preferable.

After mixing the above-mentioned active ingredient with flame-retardant agents such as pyrethrum-extracted lees powder and wood flour, and binders (15-40% of the total amount) such as tab powder, starch and dextrin, a mixed powder is obtained. Then, water, a colorant, a fungicide, etc. are appropriately added and kneaded. Then, it is put into an extruder, molded into an incense stick form, and then dried to obtain the smoked / heated evaporation agent for fly slaughter of the present invention. Since the ester compound of the general formula I used in the present invention has a lower vapor pressure than that of empentrin, it also has an advantage that the active ingredient loss due to volatilization can be extremely reduced in the drying step during production.

According to the structure of claim 3, since tephramethrin, which is useful among the ester compounds of the general formula I, is used as the active ingredient, a smoker-burning / heat-evaporating agent having a superior incense form can be obtained. You can

According to the constitution of claim 4, since the compound 2 which is useful among the ester compounds of the general formula I is used as the active ingredient, the incense-like smoky-burning product with excellent incense form.
A heating transpiration agent can be obtained.

Generally, pyrethroid compounds, including ester compounds of general formula I, range from 0 to the active ingredient.
By blending 0.02 times the amount of dibutylhydroxytoluene, it can be stably stored for a long period of time in the original state. However, the stability in various formulations is
The stability of the active ingredient must be evaluated for each formulation, which varies significantly depending on the type of active ingredient, the type and amount of stabilizer selected. The stability of the ester compound of the general formula I in the incense form is slightly inferior to that of pinamine forte, but according to the constitution of claim 5, not only the stability over time but also the stability during smoking are significantly enhanced. Therefore, a high fly-killing effect can be achieved. As a result of various studies on the type and amount of the stabilizer, a phenolic stabilizer having a butyl group having at least two tert-butyl groups having a boiling point of 250 ° C. or higher was added to the ester compound of the general formula I at 0. It is preferable to blend in an amount of 0.5 to 3.0 times, on the other hand, for example, a mono-tert-butyl-phenol system such as 3-tert-butyl-4-hydroxyanisole or 2-tert-butyl-4-hydroxyanisole. Stabilizers have no effect,
Further, the effect was also low for amine-based stabilizers such as N, N'-diphenyl-p-phenylenediamine and phenyl-β-naphthylamine. It is considered that the reason why the boiling point is 250 ° C. or higher is effective because the ester compound of the general formula I as an active ingredient volatilizes from around 200 to 250 ° C., so that the stabilizer itself must not volatilize at this temperature. .

Examples of the stabilizer used in the invention of claim 5 include the followings but are not limited to them.

(1) 2,6-di-tert-butyl-
4-Methylphenol (BHT) [Stabilizer A] (2) 2,2'-Methylenebis (4-methyl-6-tert-butylphenol) [Stabilizer B] (3) 2,2'-Methylenebis (4-ethyl) -6-tert-butylphenol) [Stabilizer C] (4) 4,4'-butylidene bis (3-methyl-6-tert-butylphenol) [Stabilizer D] (5) 4,4'-thiobis (3-methyl) -6-tert-Butylphenol) [Stabilizer E] (6) 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4
-Methylphenyl acrylate [Stabilizer F] (7) 2,4-di-tert-butylphenyl 3,
5-di-tert-butyl-4-hydroxybenzoate [Stabilizer G]

In the constitution of claim 5, one or more of the above stabilizers are mixed in an amount of 0.5 to 3.0 times the amount of the ester compound of the general formula I. Various conventional stabilizers such as phosphite-based, amine-based and organic sulfur-based stabilizers may be mixed.

According to the structure of claim 6, it is possible to obtain a smoldering / heat-evaporated insecticide for fly sickle in the form of a mat, which is excellent in fly slaughter efficacy. The content of the ester compound of general formula I to be incorporated as an active ingredient is 30 to 150 mg per mat.
And preferably 40 to 150 mg. In addition to the active ingredient, a volatilization regulator, a stabilizer, a fragrance, a dye and the like are usually added, and a mat can be prepared according to a conventional method. The general formula I
Since the ester compound (1) has a higher volatility than pinamine forte or Etoc, it is not necessary to reduce the thickness of the mat, and the thickness can be appropriately selected.

According to the structure of claim 7, since tephramethrin, which is useful among the ester compounds of the general formula I, is used as an active ingredient, a mat-shaped smoldering / heating transpiration agent in a mat form having better performance can be obtained. You can

According to the structure of claim 8, since the compound 2 which is useful among the ester compounds of the general formula I is used as the active ingredient, a mat-shaped smoldering and heating transpiration agent in a mat form with better performance is obtained. be able to.

According to the structure of claim 9, one or more of the pyrethroid synergist or the higher fatty acid ester is blended as the volatilization regulator, so that the stable fly killer effect from the initial use to the final use can be obtained. Can be maintained.
As a synergist for pyrethroid, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2.
2.2] Oct-5-ene-2,3-dicarboximide (Cinepyrine 500), N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide (MGK-264), piperonyl butoxide and the like, while higher fatty acid esters include butyl stearate, isopropyl myristate, etc., but are not limited to these. is not.

According to the structure of the tenth aspect, since the stabilizer is further blended, the stability of the active ingredient and the dye over time, and the stability during mat heat evaporation can be enhanced. Since the dye is blended for the purpose of knowing the remaining level of the active ingredient at the time of use, it is required that it does not discolor during storage or use. As the phenolic stabilizer having at least two tert-butyl groups, those mentioned above are suitable,
Examples of the hydroquinone-based stabilizer having at least two tert-butyl groups include di-tert-butyl hydroquinone such as 2,5-di-tert-butyl-hydroquinone [stabilizer H]. .

According to the structure of claim 11, a long time (30
It is possible to obtain a liquid-type smoldering / heat-evaporating insecticide for liquid syrup that has no clogging of the absorbent core over a period of up to 60 days) and has an excellent slaughter effect. The content of the ester compound of general formula I incorporated as an active ingredient is 1 to 6%, preferably 2 to 6%. In addition to the active ingredient and solvent, if necessary, a fragrance, a volatilization regulator, a stabilizer and the like are mixed. As the volatilization adjuster and the stabilizer, those mentioned above can be used. The plastic bottle filled with the chemical liquid, the chemical liquid absorbent core is not limited at all, for example, as the liquid absorbent core, in addition to those obtained by solidifying an inorganic material with a sizing agent, those baked, or felt, cotton, A braid such as a non-woven fabric, or glass, inorganic fiber, plastic, wood, porous ceramic, porous evaporation layer, preferably, the periphery of which is covered with a holding material such as glass, inorganic fiber or plastic. You can

According to the twelfth aspect, since tephramethrin, which is useful among the ester compounds of the general formula I, is used as the active ingredient, it is possible to obtain a liquid form smoldering and heating transpiration agent for fly sickness with superior performance. You can

According to the thirteenth aspect, since the compound 2 which is useful among the ester compounds of the general formula I is used as the active ingredient, a liquid form smoldering and heating transpiration agent for fly sickness having a better performance is obtained. be able to.

According to the fourteenth aspect, the boiling point range of the solvent is suitable for the heat evaporation of the active ingredient, and a high fly sterilizing effect is exhibited, and the odor is small and it is toxicologically safe. Particularly, n-paraffin, isoparaffin, and naphthenic aliphatic hydrocarbons are preferable.

According to the fifteenth aspect, since water is used as the solvent, the danger of fire can be eliminated. In this case, various nonionic surfactants, preferably polyoxyalkylene alkyl ether solubilizers (referring to those capable of stabilizing the active ingredient in a clear state in water regardless of the presence or absence of micelle formation, In addition to the surfactant, it also includes a solvent that is compatible with water and oil).

According to the structure of claim 16, a smoldering / heat-evaporating insecticide containing an ester compound of the general formula I is smoked or heat-evaporated to provide a fly-killing method having a high fly-killing effect. To do.

According to the structure of claim 17, since the smoky-burning / heat-evaporating insecticide in the form of incense stick containing the ester compound of the general formula I is smoked, it has excellent fly-killing effect and diffusing power, and has a wide space. But it provides an effective method of killing flies.

According to the structure of claim 18, since tephramethrin, which is useful among the ester compounds of the general formula I, is used as the active ingredient, a more effective method of killing flies in the form of incense sticks is provided.

According to the structure of claim 19, since the compound 2 which is useful among the ester compounds of the general formula I is used as the active ingredient, a more effective fly killing method in the form of incense stick is provided.

According to the twentieth aspect of the present invention, since the smoldering / heat-evaporated insecticide for mat fly containing the ester compound of the general formula I is heat-evaporated, a closed room or
Provide a fly slaughter method suitable for use in a smoke dislike condition. The mat usually has a temperature of the central part of the heat sink of 160 to 18
Used by heating to 0 ° C.

According to the twenty-first aspect, since tephramethrin which is useful among the ester compounds of the general formula I is used as the active ingredient, a more effective fly killing method in the mat form is provided.

According to the twenty-second aspect, since the compound 2 which is useful among the ester compounds of the general formula I is used as the active ingredient, a more effective fly killing method in the mat form is provided.

According to the twenty-third aspect of the present invention, since the liquid form smoky and heat-evaporated insecticide containing the ester compound of the general formula I is vaporized by heat, it can be used in a closed room or under conditions where smoke is disliked. The present invention provides a method for killing flies that can maintain the efficacy of killing flies for a long period (30 to 60 days). Usually, it is housed in a heating evaporator, and the temperature of the metal ring is heated to 120 to 140 ° C. to evaporate the active ingredient. The structure and specifications of the heating evaporator are not limited at all, and any commonly available one can be used.

According to the twenty-fourth aspect, since tephramethrin, which is useful among the ester compounds of the general formula I, is used as the active ingredient, a more effective fly killing method in liquid form is provided.

According to the twenty-fifth aspect, since Compound 2 which is useful among the ester compounds of the general formula I is used as the active ingredient, a more effective method for killing fly by using liquid form is provided.

[0064]

EXAMPLES The present invention will be described in more detail with reference to Examples and Test Examples, but the present invention is not limited to these as long as the gist thereof is not exceeded.

Example 1 0.7 parts of tephramethrin and 0.7 part of stabilizer A (2,6-di-tert-butyl-4-methylphenol) were used as a base for incense sticks such as pyrethrum-extracted lees, wood flour and starch. The mixture was uniformly mixed with 98.6 parts of the material, kneaded by adding water, extruded and punched to obtain a smoked and heat-transpiration insecticide for insular sticks. Using this one roll (13 g) in a room of 6 tatami mats, the volatilization rate of the active ingredient was measured to be 75%, and it was possible to completely control flies and mosquitoes over a smoking time of 7 and a half hours.

Example 2 A compound 2 (5-propargyl-2-methyl-3) was added to a pulp mat having a thickness of 2.8 mm, a length of 22 mm and a width of 35 mm.
-Furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate) 80 mg, Cinepyrine 5
00 100 mg, stabilizer H (2,5-di-tert-butyl-hydroquinone) 10 mg, and diisopropylaminoanthraquinone 0.6 mg as a dye were impregnated to obtain a smoldering and heat-evaporating insecticide for fly sickness in the form of a mat.
This mat was stored in an aluminum film bag and stored at room temperature for 3 years. After opening, the mat was taken out, placed on the heat dissipation plate (center, about 170 ° C) of the heat vaporizer and used in a completely closed room. It was effective against mosquitoes and flies for 12 hours. . Further, with the passage of use time, the dye generally faded, and neither Compound 2 nor the dye had any problem in stability over time.

Example 3 45 m of n-paraffin solution having a tephramethrin concentration of 5%
1 was filled in a plastic bottle having an internal volume of 50 ml, and a liquid absorbent core with a holder (outer diameter 7.0 mm, length 75.5 mm) was driven therein. As the liquid-absorbing core, a bundle of polyester fibers coated with a silicone varnish on a braid of the same material was used to hold the periphery and the upper surface was heat-sealed. The n-paraffin has a boiling point in the range of 250 to 280 ° C. The obtained liquid type smoldering / heat-evaporating insecticide for fly sterilization was attached to a heat-evaporator having a metal ring temperature of 130 ° C., and electricity was applied. The amount of volatilization per day (12 hours) was about 1.5 ml over 30 days, and there was no clogging, and the high fly killing effect was maintained.

Test Example 1 According to Example 1, an incense stick-shaped smoky-burning / heat-evaporating insecticide in the form of incense stick was prepared and its stability over time (25
℃, 2 years storage), and the insecticidal efficacy against adult flies by the following cylindrical method. As for other components, in addition to the listed components, 28% by weight of starch, 0.2% by weight of sodium dehydroacetate, 25% by weight of the pyrethrum extracted lees, and wood flour were added to make the total amount 100%.
The stability over time was evaluated according to the following criteria, and the flies-killing effect was shown by the relative efficacy of the supine effect, with 1.0 as the incense of 1.0% by weight of empentrin. The stabilizers A, B, C or F used in this test are the compounds described above.・ ○; Recovery rate of active ingredient after storage for 2 years at 25 ℃ is 9
5% or more △: 25 ° C, recovery rate of active ingredient after storage for 2 years is 9
0 to 95% ・ ×; Recovery rate of active ingredient after storage at 25 ° C for 2 years is 9
0% or less (Cylindrical method) A plastic cylinder having an inner diameter of 20 cm and a height of 43 cm sandwiching rubber packings on the upper and lower sides is placed on a table with a height of 30 cm and a diameter of 5 cm is placed in the center of the lower disk. A circular hole is provided. Approximately 20 test flies are thrown into a cylinder, and an incense stick that has been ignited at one end is smoked from the circular hole of the lower disk. Smoke in the cylinder is 2 minutes. After the start of smoking, the number of supines with time is observed and the KT ₅₀ value is obtained.

[0069]

[Table 1]

[Table 2]

As a result of the test, teframethrin, compound 2,
The incense-shaped smoked and heat-evaporated insecticide containing the ester compound of the general formula I such as Compound 3 showed a higher fly-killing effect than the control pinamine forte incense. Further, by blending a phenolic stabilizer having at least two tert-butyl groups in an amount of 0.5 times or more with respect to the ester compound of the general formula I, the stability of these compounds over time is improved and the smoldering is improved. The time-killing effect was also enhanced. In the case of pinamine forte incense, 0.3% is effective against mosquitoes,
Even with 0.8% of the fly, the effect was low, and almost no effect of the stabilizer was observed. Furthermore, 2,
Even with an ester of 2,3,3-tetramethylcyclopropanecarboxylic acid, for example, the alcohol is (+)-2.
-Propargyl-3-methyl-cyclopent-2-en-1-on-4-yl and 4-propargylbenzyl alcohol had low fly killing effect. On the other hand, the incense stick containing the ester compound of the general formula I can realize an incense stick having a higher fly-killing effect, preferably by adding a specific stabilizer, and its practicality is extremely high. In the case of the empentryn incense as a control, there was a problem in that the volatility was too high to cause a loss during the drying step during production, but there was no problem in stability over time.

Test Example 2 According to Example 2, a mat-type smoldering and heat-evaporating insecticide for fly sickness was prepared according to the formulation shown in Table 2. Using a heating evaporator having a temperature of the central portion of the heat sink of about 168 ° C., the fly sterilization effect was evaluated by the following continuous aeration method. The stability over time was evaluated according to the same criteria as in Test Example 1, and the fly-killing effect was based on the fact that the fly-killing effect was 1.0.
The relative potency is shown with the potency of 1.0% by weight of incense. (Continuous aeration method) A cylinder made of plastic with an inner diameter of 20 cm and a height of 43 cm is stacked in two steps, and a cylinder with a 20 cm inner diameter and a height of 20 cm (the place where the test fly is put) is partitioned on the top and bottom with a 16 mesh wire mesh. Then, a cylinder having the same diameter and a height of 20 cm is placed. The four-tiered cylinders are placed on a table, and a heating evaporator is placed in the center of the table to evaporate. Then, about 20 test flies are released in the upper cylinder, and the number of supine turns is observed over time. After 20 minutes of exposure, all the test flies are transferred to a clean polyethylene container, 3% sugar water is given thereto, and the mortality is examined 24 hours after storage.

[0072]

[Table 3]

[Table 4]

[Table 5]

As a result of the test, teframethrin, compound 2,
Smoked and heat-transpiration insecticides in the form of mats containing an ester compound of general formula I such as compound 3 showed higher supine effect and lethality compared to the control pinamine forte and Etoc mat. . In the case of pinamine forte and etok, 40 mg to 10 mg is effective for mosquitoes, but for flies, even if the amount of the active ingredient is 150 mg, practical application is difficult at the level, and especially the supine effect is poor. It was Further, since pinamine forte and Etoc have a lower vapor pressure than the ester compound of the general formula I, increasing the content does not necessarily lead to the amount of transpiration, and only the residual amount of mat after use increases. Furthermore, even an ester of 2,2,3,3-tetramethylcyclopropanecarboxylic acid may be, for example, (±) -2-allyl-3-methyl-cyclopent-2-en-1-on-4-yl. The ester of (1) has a low fly sterilization effect, and therefore, it was revealed that the ester obtained by combining propargylfuryl methyl alcohol and 2,2,3,3-tetramethylcyclopropanecarboxylic acid is particularly useful. In order to increase the amount of transpiration of the control active ingredients (pinamine forte and ETOK), the thickness of the mat was changed to 1 mm (this test was 2.8 mm) and tested, but there was little improvement in efficacy. It was

Test Example 3 According to Example 3, a liquid form of smoldering and heat-transpiration insecticide for fly killing was prepared according to the formulation shown in Table 3. The metal ring was attached to a heating evaporator having a temperature of about 132 ° C., and the upper part of the liquid absorbing core was heated. Table 3 shows the evaluation of the flies-killing effect by the continuous aeration method shown in Test Example 2.

[0075]

[Table 6]

[Table 7]

As a result of the test, teframethrin, compound 2,
A liquid form of smoked and heat-evaporated insecticide for the fly containing the ester compound of the general formula I such as compound 3 has a higher upturning effect and a higher mortality rate than the control pinamine forte and Etoc liquid. Indicated. 2.6% to 0.7-1.3% for mosquitoes with pinamine forte and etok
However, even if the concentration of the active ingredient was 6%, the supine effect was inferior and the lethal effect was extremely low. Therefore, practical use could not be expected at all. In addition, it was difficult to further increase the concentration of pinamine forte or Etoc because the absorbent core was clogged during use. Therefore, the usefulness of the ester compound of the general formula I in the liquid form as a smoked / heat-evaporated insecticide for flies was confirmed.

[0077]

As described above, according to the invention of claim 1, the insecticidal efficacy and safety of not only mosquitoes but also flies,
It is possible to obtain a smoked / heat-evaporated insecticide for fly sickness, which is excellent in terms of usability and manufacturability.

According to the second to fourth aspects of the present invention, it is possible to obtain a smoked and heat-evaporated insecticide for fly sickle in the form of an incense stick that is excellent in fly scavenging effect and has high diffusibility.

According to the fifth aspect of the present invention, it is possible to obtain a smoked and heat-evaporated insecticide for fly sickle in the form of an incense stick, which is not only stable over time but also stable during smoking.

According to the inventions of claims 6 to 8, it is possible to obtain a smoldering / heat-evaporating insecticide for fly shavings in the form of a mat, which is excellent in fly scavenging effect.

According to the ninth aspect of the present invention, it is possible to obtain a smoldering and heat-evaporating insecticide for fly sickle in the form of a mat that maintains a stable fly scavenging effect from the beginning of use to the end of use.

According to the tenth aspect of the present invention, it is possible to obtain a smoldering / heat-evaporating insecticide in the form of a mat in which the stability of the active ingredient and the dye over time and the stability during heat-evaporation of the mat are enhanced. it can.

According to the eleventh to thirteenth aspects of the present invention, there is no liquid clogging of the absorbent core for a long period of time (30 to 60 days), and the liquid form of the smoky and heat-evaporating insecticide for fly killing is excellent in fly killing effect. The agent can be obtained.

According to the fourteenth aspect of the present invention, it is possible to obtain a liquid smoldering / heat-evaporating insecticide having a high fly sterilizing effect, a low odor, and a toxicologically safe liquid form.

According to the fifteenth aspect of the present invention, it is possible to obtain a liquid-type smoky-boiled / heat-evaporated insecticide for liquid syrup that eliminates the risk of fire.

According to the sixteenth aspect of the present invention, by using the ester compound of the general formula I as an active ingredient, it is possible to provide a fly-killing method having an excellent insecticidal effect not only on mosquitoes but also on flies.

According to the seventeenth to nineteenth aspects of the present invention, by smoking the smoked / heat-evaporated insecticide for insular sticks, the insecticidal effect and diffusing power are excellent, and the fly killing method is effective even in a wide space. Can be provided.

According to the twentieth to twenty-second aspects of the present invention, by heating and evaporating the smoky and heat-evaporated insecticide for mats in the form of a mat, it is suitable for use in a closed room or in a condition where smoke is disliked, and It is possible to provide a fly killing method with high fly killing efficacy.

According to a twenty-third aspect of the present invention, by heating and evaporating the liquid form of smoky and heat-evaporated insecticide for fly killing, in a closed room and under conditions where smoke is disliked,
It is possible to provide a fly slaughter method capable of maintaining the fly slaughter efficacy for a long period (30 to 60 days).

 ─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 6-120595 (32) Priority date Hei 6 (1994) May 10 (33) Priority claim country Japan (JP)

Claims (25)

[Claims] 1. An active ingredient represented by the general formula I: (In the formula, R represents a hydrogen atom or a methyl group) 2,2,3,3-Tetramethylcyclopropanecarboxylic acid propargylfurylmethyl alcohol ester compound for fly slaughter Smoked and heated transpiration insecticide. 2. The smoked and heated transpiration insecticide for fly sickle according to claim 1, wherein the active ingredient is represented by the general formula I: (Wherein R represents a hydrogen atom or a methyl group) contains 0.3 to 1.2% of a propargylfurylmethyl alcohol ester compound of 2,2,3,3-tetramethylcyclopropanecarboxylic acid represented by A smoked and heated transpiration insecticide for fly sickle, which is in the form of incense sticks. 3. The smoked and heat-evaporated insecticide for fly sickness according to claim 2, wherein the active ingredient is 5-propargyl-2-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate. Smoked and heated transpiration insecticide for fly sickle. 4. The smoked and heat-evaporated insecticide for fly sickness according to claim 2, wherein the active ingredient is 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxy. Smoked and heated transpiration insecticide for fly sick characterized by being a rat. 5. The smoked / heat-evaporated insecticide for fly killing according to any one of claims 2 to 4, which has a boiling point of 250.
One or two or more phenolic stabilizers having at least two tert-butyl groups at a temperature equal to or higher than 0.degree. Smoked and heated transpiration insecticide. 6. The smoked and heat-evaporated insecticide for fly killing according to claim 1, having a thickness of 1.0 to 3.0 mm and a surface area of 7-1.
In a 5 cm ² pulp mat, the active ingredient of the general formula I: (In the formula, R represents a hydrogen atom or a methyl group), which is impregnated with 30 to 150 mg of a propargylfurylmethyl alcohol ester compound of 2,2,3,3-tetramethylcyclopropanecarboxylic acid represented by A smoked and heat-evaporated insecticide for fly sickle, which is in the form of a mat that heats to evaporate the active ingredient. 7. The smoked and heat-evaporated insecticide for fly sickness according to claim 6, wherein the active ingredient is 5-propargyl-2-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate. Smoked and heated transpiration insecticide for fly sickle. 8. The smoked and heat-evaporated insecticide for fly sickness according to claim 6, wherein the active ingredient is 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxy. Smoked and heated transpiration insecticide for fly sick characterized by being a rat. 9. The smoked and heat-evaporated insecticide for fly killing according to claim 6, wherein the volatilization regulator is a synergist for pyrethroids, or one or two of higher fatty acid esters. 0.5 or more with respect to the active ingredient
Smoked and heated transpiration insecticide for fly sickle, characterized by containing 10 times the amount. 10. The smoked / heat-evaporated insecticide for fly sickle according to any one of claims 6 to 9, wherein at least two phenolic stabilizers having a tertiary butyl group or at least two stabilizers are used. One or more hydroquinone-based stabilizers having a tert-butyl group are blended in an amount of 0.1 to 1.0 times the amount of the active ingredient. . 11. The smoked and heat-evaporated insecticide for fly slaughter according to claim 1, wherein the formula I as an active ingredient: 1 to 6% of a propargylfuryl methyl alcohol ester compound of 2,2,3,3-tetramethylcyclopropanecarboxylic acid represented by the formula (wherein R represents a hydrogen atom or a methyl group) and a solvent. A smoked and heat-evaporated insecticide for fly sickle, characterized in that a liquid medicine is filled in a plastic bottle, and the upper part of an absorbent core partially immersed in the liquid medicine is heated to evaporate the active ingredient. 12. The smoked and heat-evaporated insecticide for fly sickness according to claim 11, wherein the active ingredient is 5-propargyl-2-.
A smoked / heat-evaporated insecticide for fly sickle, which is furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate. 13. The smoked and heat-evaporated insecticide for fly sickle according to claim 11, wherein the active ingredient is 5-propargyl-2-.
Methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate, which is a smoked and heat-evaporated insecticide for fly sickness. 14. The smoked and heat-evaporated insecticide for fly killing according to any one of claims 11 to 13, wherein an aliphatic hydrocarbon having a boiling point in the range of 180 to 350 ° C. is used as a solvent. Smoked and heated transpiration insecticide for fly sickle. 15. The smoldering and heat-evaporating insecticide for fly slaughter according to any one of claims 11 to 13, characterized in that it contains water as a solvent. Agent. 16. An active ingredient represented by the general formula I: embedded image (In the formula, R represents a hydrogen atom or a methyl group) 2,2,3,3-Tetramethylcyclopropanecarboxylic acid propargylfuryl methyl alcohol ester compound-containing smoldering and heating evaporation for slaughter Pesticide, smoked,
Alternatively, a fly slaughter method characterized by heating and evaporating. 17. The fly slaughter method according to claim 16, wherein
As an active ingredient, a general formula: (Wherein R represents a hydrogen atom or a methyl group) contains 0.3 to 1.2% of a 2,2,3,3-tetramethylcyclopropanecarboxylic acid propargylfurylmethyl alcohol ester compound. A method for killing flies, characterized by comprising smoking an incense-shaped smoky and heat-transpiration insecticide for flies. 18. The fly slaughter method according to claim 17,
The active ingredient is 5-propargyl-2-furylmethyl 2,
A method for killing flies, which is 2,3,3-tetramethylcyclopropanecarboxylate. 19. The fly killing method according to claim 17,
A method for killing flies, characterized in that the active ingredient is 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate. 20. The fly slaughter method according to claim 16,
A pulp mat having a thickness of 1.0 to 3.0 mm and a surface area of 7 to 15 cm ^{2 has} the general formula I: (In the formula, R represents a hydrogen atom or a methyl group) 2,3,3-tetramethylcyclopropanecarboxylic acid propargylfuryl methyl alcohol ester compound of 30 to 150 mg impregnated with a mat-form A method for killing flies, characterized in that a smoked and heat-evaporated insecticide for fly is heated on a radiator plate to evaporate the active ingredient. 21. The fly slaughter method according to claim 20,
The active ingredient is 5-propargyl-2-furylmethyl 2,
A method for killing flies, which is 2,3,3-tetramethylcyclopropanecarboxylate. 22. The fly slaughter method according to claim 20,
A method for killing flies, characterized in that the active ingredient is 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate. 23. The fly slaughter method according to claim 16,
Formula I as an active ingredient: 1 to 6% of a propargylfuryl methyl alcohol ester compound of 2,2,3,3-tetramethylcyclopropanecarboxylic acid represented by the formula (wherein R represents a hydrogen atom or a methyl group) and a solvent. A plastic bottle is filled with the drug solution, and a liquid form of smoldering / heated transpiration insecticide for liquid syrup in which a part of the liquid wick is immersed in this drug solution is attached to the heating evaporator, and the upper part of the liquid wick is heated. A method for killing flies, characterized in that the active ingredient is evaporated. 24. The fly slaughter method according to claim 23,
The active ingredient is 5-propargyl-2-furylmethyl 2,
A method for killing flies, which is 2,3,3-tetramethylcyclopropanecarboxylate. 25. The fly slaughter method according to claim 23,
A method for killing flies, characterized in that the active ingredient is 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate.