JPH0967215A - Insecticidal and pest controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an insecticidal and pest controlling agent capable of being applied in a wide range of organisms and certainly preventing deterioration of a pyrethroid compound by mixing a specific compound with a system containing a furan ring-containing pyrethroid compound as an effective ingredi ent. SOLUTION: In this insecticidal and pest controlling agent, 0.5-2.0 times amount of a maleimide compound of formula II (R4 is H, a 1-12C alkyl or a 3-6C cycloalkyl) is mixed with a pyrethroid compound of formula I (R2 is H or methyl; R2 is 2-methyl-1-propenyl when R1 is H or is methyl when R1 is methyl; R3 is H or methyl). As the compound of formula I, 5-propargy 12- furylmethyl chrysanthemate, 5-propargyl-2-furylmethyl 2,2,3,3- tetramethylcyclopropane carboxylate, etc., can be cited. As the maleimide compound, N-methylmaleimide, N-ethylmaleimide, etc., are preferable. The effective ingredients are transpired by adding water to the compounds of formula I and II, filling them in a plastic bottle, dipping a wick and heating the top of it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvements in insecticides and insect repellents containing a pyrethroid compound containing a furan ring as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION General Formula I

Embedded image (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂
Represents a 2-methyl-1-propenyl group when R ₁ is a hydrogen atom, and a methyl group when R ₁ is a methyl group. R ₃ represents a hydrogen atom or a methyl group. ) Is a pyrethroid compound that has excellent insecticidal and insecticidal efficacy and safety against humans and animals, and is a household insecticide and insect repellent such as mosquito coils, mosquito mats, liquid mosquito traps, aerosols, liquids, and insect repellents for clothing. It is widely used as the active ingredient of drugs. However, these compounds containing a furan ring are slightly inferior in chemical stability to light, oxygen, water, etc., as compared with other cyclopentenolone esters and other phenoxybenzyl ester-based pyrethroid compounds, and thus they are suitable for various preparations. Stabilization technology is required.

Conventionally, as a stabilizing method, 2, 6
-Mixing with an antioxidant such as ditertiary butyl-4-methylphenol (hereinafter referred to as BHT), mixing a paraphenylenediamine compound with a weakly basic substance [Japanese Patent Publication No. 55-50003], and using activated carbon [ Japanese Examined Sho 56
No. 29642] has been disclosed. Although these methods have achieved considerable results, there is still room for improvement in the presence of certain formulations, especially in the presence of water, and in situations where they are exposed to light or air for a long period of several months or more. .

[0004]

DISCLOSURE OF THE INVENTION The present invention seeks a more accurate and effective stabilizer for insecticides and insect repellents containing a pyrethroid compound containing a furan ring as an active ingredient, and finds a broader range of these pyrethroid compounds. It was made for the purpose of effective utilization.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted extensive studies, and as a result, by accurately blending a maleimide compound with a pyrethroid compound containing a furan ring, deterioration of the pyrethroid compound can be accurately achieved. The inventors have found that it can be prevented and completed the present invention.

That is, the invention of claim 1 has the general formula I as an active ingredient.

Embedded image (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂
Represents a 2-methyl-1-propenyl group when R ₁ is a hydrogen atom, and represents a methyl group when R ₁ is a methyl group. R ₃ represents a hydrogen atom or a methyl group. ) 1 type or 2 or more types of the pyrethroid compound shown by these, and is 0.05-about this active ingredient.
2.0 times the general formula II

Embedded image (In the formula, R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.) A insecticide or insect repellent compounded with a maleimide compound Is.

The pyrethroid compound represented by the general formula I used in the present invention includes 5-propargyl-2-furylmethyl chrysanthemate (hereinafter referred to as "flamethrin"), and 5-propargyl-2-furylmethyl 2,
2,3,3-Tetramethylcyclopropanecarboxylate (hereinafter referred to as teframethrin), 5-propargyl-2-methyl-3-furylmethyl chrysanthemate (hereinafter referred to as proparsulin), 5-propargyl-
2-Methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate (hereinafter referred to as compound A), 5-propargyl-3-furylmethyl
2,2,3,3-tetramethylcyclopropanecarboxylate (hereinafter, compound B) and the like can be mentioned. In addition,
It goes without saying that when there are optical or geometrical isomers based on the asymmetric carbon of the acid moiety, each of them and any mixture thereof are included.

The blending amount of the pyrethroid compound of the general formula I is appropriately determined depending on the dosage form, the field of application and the like. For example, in the case of a liquid mosquito repellent form, the total amount of drug solution is 0.5
In the form of insect repellent for clothing, it is suitable to impregnate a pulp mat with about 10 to 500 mg.

The insecticidal and insect repellent agents of the present invention include other insecticidal and insect repellent components such as allethrin, prarethrin, empentrin, resmethrin, pyrethroid compounds such as phtalthrin, phenothrin, permethrin and etofenprox, compounds such as silafluofen, fenitrothion. , An organic phosphorus agent such as DDVP, and a carbamate agent such as NAC or methoxadiazone may be appropriately mixed.

Examples of the maleimide compound represented by the general formula II used in the present invention include maleimide, N-methylmaleimide, N-ethylmaleimide, N
-Propylmaleimide, N-octylmaleimide, N-
Lauryl maleimide, N-cyclopentyl maleimide,
Examples thereof include, but are not limited to, N-cyclohexylmaleimide. In the present invention, one or more selected from these maleimide compounds are blended in an amount of 0.05 to 2.0 times the active ingredient of general formula I. If the amount is less than 0.05 times, the stabilizing effect is not sufficient. On the other hand, if the amount exceeds 2.0 times, the special effect is not enhanced and it is disadvantageous in terms of cost.

Further, the insecticide and insect repellent of the present invention may contain other type stabilizers such as BHT, 2,5-ditertiarybutylhydroquinone, 2,2'-methylenebis (4-methyl-6-), if necessary. (Tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 3-tert-butyl-4-hydroxyanisole, etc. may be added.

According to the invention of claim 2, in the constitution of claim 1, one or two kinds selected from flamethrin, teframethrin, and compound A are used as the active ingredient of the general formula I.

According to the invention of claim 3, in the constitution of claim 1 or 2, as the maleimide compound of the general formula II, particularly N-methylmaleimide, N-ethylmaleimide, and N
-One or two kinds selected from scirohexylmaleimide are used.

A fourth aspect of the present invention is an application of the configuration of the first aspect to an aqueous liquid mosquito repellent form containing a pyrethroid compound as an active ingredient, a maleimide compound, and water as a solvent.

According to the invention of claim 5, in the constitution of claim 4, one or two kinds selected from flamethrin and teframethrin are selected as the active ingredient of the general formula I, and as the maleimide compound of the general formula II, One or two kinds selected from N-methylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide are selected.

According to a sixth aspect of the present invention, the structure of the first aspect is applied to a form of an insect repellent agent for clothes, which is composed of a mat made of a chemical liquid impregnated pulp.

According to the invention of claim 7, in the constitution of claim 6, as the active ingredient of the general formula I, in particular, one or two selected from teframethrin and the compound A is selected to obtain a maleimide compound of the general formula II. , N-methylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide.

[0018]

According to the constitution of claim 1, the maleimide compound of the general formula II exhibits an appropriate stabilizing effect on the pyrethroid compound of the general formula I containing a furan ring under all conditions, and therefore is a very useful insecticide and insect repellent. Will be provided. Although there are many unclear points about the reason why the maleimide compound specifically exhibits a high stabilizing effect, it is considered that the furan ring portion is covered to prevent deterioration due to light, oxygen, water and the like.

The insecticidal and insect repellents of the present invention containing the pyrethroid compound of the general formula I have both high insecticidal and insect repellent efficacy and safety for humans and animals. Usually, preferably, a suitable carrier or other excipient is used. For example, it is prepared in a solid dosage form such as mosquito coil, mat, sheet or tablet, or a liquid dosage form such as emulsion, liquid, spray or aerosol. Then, although applied to the control of pests by a method according to each of these forms, the present invention is a conventional stabilizer, an aqueous liquid mosquito repellent leaving room for improvement in the stabilizing means, insect repellent for clothing, etc. In particular, the merit is great.

Typical examples of the carrier used in preparing a solid formulation include various mineral powders such as silicic acid, kaolin and talc, and various plant powders such as wood flour and wheat flour. . The volatility of the active ingredient can be controlled by using a sublimable carrier such as adamantane, cyclododecane, or triisopropyl trioxane, and the gel form can be obtained by using a gelling agent such as polyvinyl alcohol, alginic acid, and carrageenan. It can also be prepared. Furthermore, as the mat and sheet-shaped base material,
Pulp mat, paper, woven fabric, non-woven fabric or polyethylene, polypropylene, polyvinyl chloride, polyester,
Examples include plastic molded products such as ethylene vinyl acetate and porous glass materials.

On the other hand, in preparing the liquid form, a surfactant, a dispersant, various solvents, a propellant and the like can be used appropriately.

Further, the insecticidal and insect repellent of the present invention can be used as N-octylbicycloheptene dicarboximide (trade name MGK
-264), a mixture of N-octylbicycloheptene dicarboximide and an aryl sulfonate (trade name M
GK-5026), Cinepyrine 500, octachlorodipropyl ether, piperonyl butoxide and other synergists may be added, and the effect may be obtained by mixing other components such as a fragrance, a deodorant and a bactericide. An excellent multipurpose composition can be obtained, labor saving, and synergistic effect between drugs can be expected sufficiently.

According to the second aspect of the invention, since the pyrethroid compound of the general formula I is particularly useful, it is possible to obtain an insecticide or insect repellent having more practical utility.

According to the third aspect of the present invention, since the particularly useful maleimide compound of the general formula II is used, an insecticide or insect repellent having a more excellent stabilizing effect is provided.

According to the constitution of claim 4, the constitution of claim 1 is applied to an aqueous liquid mosquito repellent form, and an extremely useful insecticide or insect repellent is provided. That is, the excellent performance of the pyrethroid compound of the general formula I is imparted with a sufficient stabilizing effect including prevention of coloration of the drug solution during storage, and the utility is very high.
In preparing the aqueous liquid mosquito repellent, the above-mentioned general formula I
In addition to the active ingredient of the general formula II, the maleimide compound of the general formula II, and water as a solvent, a surfactant, preferably the general formula III

[Chemical 6] (Wherein, _{R 5} represents an alkyl group or phenyl group, having 1 to 8 carbon atoms, m and n is an integer of 0 to 6.
However, m + n ≧ 1. ) Is compounded. Among the surfactants of the general formula III, particularly preferable ones include diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether and the like.

Various liquid absorbent cores can be used as the absorbent core partially immersed in the aqueous chemical solution, but physical deterioration occurs due to dissolution, elution or swelling of the binder in the aqueous chemical solution. Those that do not exist, for example, those that consist of the fiber liquid absorption layer and the fiber braid that coats it, those that are formed by firing a mixture of inorganic powder, organic substance and inorganic binder, or polymer resin powder. Those obtained by baking or solidifying with a thermoplastic resin binder are suitable.

According to the structure of claim 5, since the hillethroid compound and the maleimide compound which are particularly useful in the composition of claim 4 are used, an insecticidal agent and an insect repellent in the form of an aqueous liquid mosquito repellent having higher performance can be obtained. be able to.

According to the constitution of claim 6, the constitution of claim 1 is applied to the form of an insect repellent for clothing, and an extremely useful insect repellent and insect repellent having excellent insect repellent and insect repellent effects for a long period of time are provided. In preparing the insect repellent form for clothing, it is common to impregnate a pulp mat with a chemical solution containing an active ingredient and a maleimide compound, and store this in a paper, non-woven fabric, or plastic case for use.

In the mixed composition containing the pyrethroid compound represented by the general formula I and empentrin, the former compound containing 0.3 times or more of empentrin inhibits discoloration and deterioration of empentrin on the copper metal. Moreover, it is very useful because it has a high synergistic effect in terms of insecticidal and insect repellent effects.

According to the constitution of claim 7, since the pyrethroid compound and the maleimide compound which are particularly useful in the constitution of claim 6 are used, it is possible to obtain an insect repellent in the form of an insect repellent for clothing, which has more excellent performance. You can

The insecticidal and insect repellent agents of the present invention thus obtained are used for flies, mosquitoes, cockroaches, at room temperature or under heating conditions.
It is highly effective against various indoor pests such as indoor dust mites and clothing pests, and it is also extremely useful as a pest control measure in archives and exhibition rooms.

[0032]

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 0.07 g of tephramethrin, 0.03 of empentrin
g, N-ethylmaleimide 0.02 g, BHT 0.0
A pulp mat having a thickness of 2 mm, a length of 22 mm and a width of 35 mm is impregnated with 05 g, a small amount of a fragrance, and 0.05 g of a glycol ether solvent, and the mat is housed in a plastic case and the insecticide of the present invention is in the form of an insecticide for clothing. , An insect repellent was obtained. The insecticide and insect repellent were stored together with the clothes in a semitransparent costume case placed near the window in the room. 8 months later,
The clothes were observed, but they had no effect on the clothes and had an excellent insect repellent effect.

Example 2 d-cis, trans-flamethrin 1.5% by weight, N-
Methyl maleimide 1.0% by weight, BHT 0.5% by weight,
50% by weight of diethylene glycol monobutyl ether,
And 45 ml of an aqueous drug solution containing purified water with an internal volume of 50 m
It was filled in a plastic bottle of 1 and loaded with a liquid absorbent core with a holder (outer diameter 7 mm, length 75.5 mm) to obtain the insecticide and insect repellent of the present invention in the form of an aqueous liquid mosquito. As the liquid absorbent core, the periphery of a bundle of polyester fibers is covered with a braid of the same material coated with silicone varnish,
The upper surface was heat-sealed. The obtained absorbent core-loaded chemical solution container was stored at 50 ° C. for one month, and the properties of the chemical solution were examined. As a result, the degree of coloration was very small compared to when the test was started. In addition, the temperature of the heating element is 130
It was attached to a heating evaporation device at ℃ and was energized. The volatilization amount per day (12 hours) was about 0.7 ml for 60 days without clogging, and high insecticidal efficacy was maintained.

Example 3 0.3 parts of d-trans-proparsulin and 0.5 parts of N-lauryl maleimide were uniformly mixed with 99.2 parts of a base material for incense stick such as pyrethrum extracted lees powder, wood powder and starch. After mixing, adding water and kneading, extruding and punching, a mosquito coil and insect repellent of the present invention was obtained. Using this one roll (13 g) in a room with 6 tatami mats, the volatilization rate of the active ingredient was measured to be 75%,
It was possible to completely control mosquitoes for a smoking time of 7 hours and a half.

Example 4 Compound A 80 mg, N-cyclohexylmaleimide 6
0 mg, 2,5-ditert-butylhydroquinone 10 mg, cinepyrine 500 100 mg, and diisopropylaminoanthraquinone 0.5 mg as a dye,
A 2.8 mm thick, 22 mm long, 35 mm wide mat made of pulp was impregnated to obtain the insecticidal and insect repellent agent of the present invention in the form of a mosquito repellent 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 flies and mosquitoes for 12 hours. . Further, with the passage of use time, the dye generally faded, and neither Compound A nor the dye had any problem in stability over time.

Test Example 1 A pulp mat (thickness: 2 mm, length: 22 mm, width: 35 mm) of each formulation shown in Table 1 prepared according to Example 1 was sealed and stored for half a year, and then the mat was taken out and had a diameter of 9 cm. It was put in a dish having a height of 2.1 cm. Similarly, 10 koga larvae were released on a petri dish with a diameter of 9 cm and a height of 2.1 cm, and 1
A 6-mesh wire mesh was sandwiched between and stacked on the drug-containing petri dish. That is, the koga larvae were exposed to only the chemical vapor and left for 24 hours to observe the knockdown state of the test insects. Furthermore, after the exposure, the test insects were transferred to another container, and the mortality rate after 24 hours was examined.
It was as shown in Table 1. A 1 cm × 2 cm piece of copper was placed in place of the larvae of Koga, and similarly, a 16-mesh wire net was sandwiched between the pieces, and the pieces were left in a thermostatic chamber at 60 ° C. After 3 days, the surface of each copper plate was observed to examine the effect of vapor on the metal. Further, the above mat was housed in a box-shaped plastic case having a height distance between the upper surface and the lower surface of about 8 mm, and the mat was wrapped with white cotton cloth as a sample. 80cm high, 100cm wide, 40c length with 4 fluorescent lamps
Table 1 also shows the results of observing the degree of coloration of the cotton cloth, which was placed in the m test m. In addition, the degree of coloring is indicated by − (nearly none) to ++ (thing in which coloring is recognized).

[0038]

[Table 1]

As a result of the test, the insecticide and insect repellent of the present invention was 2
After 4 hours, both the knockdown rate and the lethality rate of the carp were high, and the mixed composition with Empentrin was more excellent.
On the other hand, as shown in the control example, if the compounding ratio of the maleimide compound to the pyrethroid compound of the general formula I is 0.05 times or less, the stabilizing effect is insufficient,
On the other hand, even if the amount exceeds 2.0 times, the special effect is not enhanced, and there is no merit because it is disadvantageous in terms of cost. Among the maleimide compounds, the N-phenyl compound (Comparative Example 3) has a poor stabilizing effect, and the stabilizing effect disclosed by the present invention is
It was confirmed to be unique to the maleimide compound of the general formula II. Further, as shown in the control example, the effect on the metal was remarkably observed with empentrin alone (Control example 4), whereas the insecticidal and insect repellents of the present invention showed almost no abnormality, and It was also revealed that the pyrethroid compound suppresses the effect of empentrin on the metal.

Test Example 2 In accordance with Example 2, the insecticides and insect repellents of the present invention in the form of an aqueous liquid mosquito shown in Table 2 were prepared. The liquid absorbent core having the same specifications as in Example 2 was used, and the obtained liquid absorbent core-loaded chemical liquid container was used.
The solution was stored at 0 ° C for 1 month to examine the degree of coloration of the chemical solution, and was mounted on a commercially available heating evaporation device to examine the evaporation performance. For the evaluation of coloring, if the change in the color tone of Gardner is 1 or less, ○, 2
3 to 3 are indicated by Δ, and 4 or more are indicated by x. Evaporation performance is trapped in a column packed with silica gel at regular intervals,
After extraction of the active ingredient with acetone, gas chromatograph analysis was performed to determine the transpiration amount of the active ingredient per hour, and the table shows the relative ratio when the initial value of each active ingredient is 1.00.

[0041]

[Table 2]

As a result of the test, the insecticidal and insect repellents of the present invention showed that the degree of coloring over time of the aqueous chemical solution was suppressed to a level where there was almost no problem, and the transpiration performance was excellent. On the other hand, as shown in the control example, when the compounding ratio of the maleimide compound to the pyrethroid compound of the general formula I is 0.05 times or less, the stabilizing effect (coloring preventing effect) is insufficient, while 2. Even if the amount exceeds 0 times, the special effect is not enhanced and it is disadvantageous in terms of cost, which is not preferable. Further, among the maleimide compounds, the N-phenyl compound (Comparative Example 3) has a poor stabilizing effect, and like the case of Test Example 1, the maleimide compound of the general formula II is a pyrethroid compound of the general formula I containing a furan ring. It was clarified that it has a specific stabilizing effect on.

[0043]

As described above, in the insecticide and insect repellent of the present invention according to any one of claims 1 to 7, the maleimide compound of the general formula II is superior to the pyrethroid compound of the general formula I as an active ingredient. Since it has a stabilizing effect and has a high insecticidal and insecticidal effect with a high active ingredient and safety for humans and livestock, its practicality is extremely high.

Claims (7)

[Claims] 1. A compound represented by the general formula I as an active ingredient: (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂
Represents a 2-methyl-1-propenyl group when R ₁ is a hydrogen atom, and a methyl group when R ₁ is a methyl group. R ₃ represents a hydrogen atom or a methyl group. ) 1 type or 2 or more types of the pyrethroid compound shown by these, and is 0.05-about this active ingredient.
A 2.0-fold amount of the general formula II (In the formula, R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.) An insecticide characterized by being blended with a maleimide compound. Insect repellent. 2. The active ingredient is 5-propargyl-2-furylmethyl chrysanthemate, 5-propargyl-2-
One selected from furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate and 5-propargyl-2-methyl-3-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate or The insecticide and insect repellent according to claim 1, wherein the insecticide and the insect repellent are two kinds. 3. The insecticide or insect repellent according to claim 1, wherein the maleimide compound is one or two selected from N-methylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide. Agent. 4. A maleimide compound in an amount of 0.5 to 5.0% by weight of one or more pyrethroid compounds as an active ingredient, and 0.05 to 2.0 times the amount of the active ingredient.
And an aqueous liquid mosquito repellent form in which a chemical solution containing water as a solvent is filled in a plastic bottle, and the upper part of the absorbent core partially immersed in the chemical solution is heated to evaporate the active ingredient. The insecticide or insect repellent according to Item 1. 5. The active ingredient is 5-propargyl-2-furylmethyl chrysanthemate, and 5-propargyl-
2-furylmethyl 2,2,3,3-tetramethylcycloprobancarboxylate, which is one or two selected from maleimide compounds, and N-methylmaleimide, N-ethylmaleimide, and N-cyclohexyl. The insecticide and insect repellent according to claim 4, which is one or two selected from maleimide. 6. A pulp mat is provided with a chemical solution containing 10 to 500 mg of one or more pyrethroid compounds as active ingredients, and 0.05 to 2.0 times the maleimide compound with respect to the active ingredients. Impregnate this mat with paper,
The insecticide and insect repellent according to claim 1, which is in the form of a non-woven fabric or an insect repellent for clothing which is stored in a plastic case. 7. The active ingredients are 5-propargyl-2-furylmethyl 2,2,3,3-tetramethylcyclopropanecarboxylate, and 5-propargyl-2-methyl-3-furylmethyl 2,2,3. One or two selected from 3-tetramethylcyclopropanecarboxylate, and the maleimide compound is one or two selected from N-methylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide. The insecticidal and insect-repellent agent according to claim 6, which is present.