JP2006273863A - Fly and mosquito-repellent incense - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a practical fly and mosquito-repellent incense having excellent rate of diffusion in smoking and insecticidal efficacy. <P>SOLUTION: The fly and mosquito-repellent incense comprises 0.1-1.0 wt.% of one or a plurality of compounds selected from fluorine-substituted ester compounds of benzyl alcohol represented by general formula (I) as active ingredients, and preferably, additionally comprises one or a plurality of compounds of di-tertiary-butylphenol-based stabilizers with boiling point of 250°C or higher, with the proviso that in the formula, R<SB>1</SB>is a hydrogen atom or a methyl group, and when R<SB>1</SB>is a hydrogen atom, R<SB>2</SB>is a 3-methoxy-3-oxo-1-propenyl group, when R<SB>1</SB>is a methyl group, R<SB>2</SB>is also a methyl group, and X is a hydrogen atom, a fluorine atom, a methoxymethyl group or a propargyl group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to improvements in flies and mosquito coils.

Mosquito coils are familiar for more than 100 years as insecticides for combating mosquitoes, and their active ingredients are (±) -2-allyl- because of their heat transpiration and thermal stability. 3-methyl-cyclopent-2-en-1-one-4-yl (+)-cis, trans-chrysantemate (hereinafter referred to as pinamine forte) and its stereoisomers, such as esbiothrin and esviol The chrysanthemum ester compounds such as are widely used. On the other hand, the occurrence of flies is decreasing in urban areas, but there are more opportunities to suffer than before in fishing villages, seafood processing plants, garbage disposal sites, livestock barns, poultry houses, and the like. Insecticides such as emulsions, oils, and powders are used as countermeasures against flies. Spatial aerosols are widely used for adult insect control in general households, but have the disadvantage of being transient and lacking in sustainability. is there. Therefore, there is a demand for the development of an incense stick type that is a fly-removing incense stick, that is, a spatial treatment agent, has an effect that lasts for several hours, is more diffusive, and is effective even in an open scene.
Mosquito coils are a very reasonable form of insecticidal killing because they keep the spatial treatment in time with a single match and have constant potency until burned out. The active ingredient of the mosquito coil is volatilized from a site near 200 to 250 ° C. several mm away from the burning part, and this temperature is somewhat higher than the heating element temperature (120 to 170 ° C.) of the electric mosquito trap. In the conventional pinamine forte-containing incense stick, it is known that the volatilization rate of the active ingredient reaches 60 to 80% without adding a stabilizer, but the effect on the fly is weak, and the active ingredient concentration in the incense stick is reduced. It was difficult to apply it to the incense stick for fly removal even if it was up.

The present inventors have selected empentrin having the highest vapor pressure among commercially available pyrethroids as an active ingredient and have already developed a fly-removing incense stick (Patent No. 3001169), which is disadvantageous in terms of cost. The volatility was too high, and loss in the drying process during production was inevitable. Accordingly, the selection of an effective ingredient optimal for a fly-cranking incense is an important issue. For example, JP-A-10-203905 discloses 2-allyl-3-methyl-cyclopent-2-en-1-one-4. -Yl 2,2,3,3-tetramethylcyclopropanecarboxylate is disclosed as an active incense incense but is not always satisfactory.
Japanese Patent No. 3001169 JP-A-10-203905

  An object of the present invention is to provide a useful fly and a mosquito-repellent incense that contain an incense incense form and select an active ingredient that exhibits a higher insecticidal effect than a conventional pinaminforte incense against mosquitoes as well as flies. To do.

In order to solve the above-mentioned problems, the present inventors paid attention to the insecticidal efficacy of the compound represented by the general formula (I) against flies and that the vapor pressure is located between the empentrin and pinamine forte, An attempt was made to apply the compound represented by the general formula (I) to flies and mosquito coils. The compounds represented by the general formula (I) are disclosed in JP-A-57-165343, JP-B-62-48660 and JP-B-7-29989, in which mosquito coils are used as incense sticks. Examples have been described, but no technical idea regarding the fly-cranking incense is described. Thus, the fly-cranking incense containing the above-mentioned compound not only shows a high rodenticidal effect and is advantageous in terms of cost, but also the moderate volatility of the compound does not cause loss during production, and the use of the incense stick It was discovered that it is highly diffusive in time.
Furthermore, when the present inventors examined various stabilizers for the purpose of improving the volatilization performance of the compound, one or more di-tertiary butyl-phenol stabilizers having a boiling point of 250 ° C. or higher were used. , By adding 0.1 to 2.0 times the amount of the above-mentioned active ingredient, not only the stability over time but also the stability at the time of soot smoke can be remarkably enhanced, which can contribute to the improvement of volatilization performance The present invention has been completed.

（式中、Ｒ₁は水素原子又はメチル基であり、Ｒ₁が水素原子の場合、Ｒ₂は３−メトキシ−３−オキソ−１−プロペニル基を表し、Ｒ₁がメチル基の場合、Ｒ₂もメチル基を表す。また、Ｘは水素原子、フッ素原子、メトキシメチル基又はプロパルギル基を表す）で表されるフッ素置換ベンジルアルコールエステル化合物から選ばれた１種又は２種以上を、０．１〜１．０重量％含有するハエ及び蚊取り線香。
（２）一般式（Ｉ）のＲ₁が水素原子でＲ₂が３−メトキシ−３−オキソ−１−プロペニル基のフッ素置換ベンジルアルコールエステル化合物において、シクロプロパンカルボン酸部分が、１Ｒ，シス構造であり、二重結合がＺ配置を有する（１）に記載のハエ及び蚊取り線香。
（３）有効成分とともに、沸点が２５０℃以上のジ−ターシャリーブチル−フェノール系安定剤の１種又は２種以上を、前記有効成分に対して０．１〜２．０倍量配合した（１）又は（２）に記載のハエ及び蚊取り線香。
（４）共力剤として、ＭＧＫ−５０２６を含有することを特徴とする（１）又は（２）又は（３）に記載のハエ及び蚊取り線香。 That is, the present invention adopts the following configuration.
(1) General formula (I) as an active ingredient

(In the formula, R ₁ is a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents a 3-methoxy-3-oxo-1-propenyl group, and when R ₁ is a methyl group, ₂ represents a methyl group, and X represents a hydrogen atom, a fluorine atom, a methoxymethyl group or a propargyl group). Flies and mosquito coils containing 1 to 1.0% by weight.
(2) In the fluorine-substituted benzyl alcohol ester compound in which R _{1 in the} general formula (I) is a hydrogen atom and R ₂ is a 3-methoxy-3-oxo-1-propenyl group, the cyclopropanecarboxylic acid moiety is 1R, cis structure The fly and mosquito coil according to (1), wherein the double bond has a Z configuration.
(3) Along with the active ingredient, one or more di-tertiary butyl-phenol stabilizers having a boiling point of 250 ° C. or higher were blended in an amount of 0.1 to 2.0 times the active ingredient ( Flies and mosquito coils as described in 1) or (2).
(4) The fly and mosquito coil according to (1), (2) or (3), which contain MGK-5026 as a synergist.

  In the present invention, as an active ingredient, one or two or more selected from the compounds of the general formula (I) are selected, and preferably by adding a specific stabilizer, the volatilization rate at the time of smoke, and insecticide Provides highly practical flies and mosquito coils with excellent efficacy.

In the present invention, the compound of the general formula (I) is used as an active ingredient. Illustrative examples of compounds of general formula (I) are as follows.
Compound (A): 2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylate,
Compound (B): 2,3,4,5,6-pentafluorobenzyl-2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylate,
Compound (C): 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylate,
Compound (D): 4-propargyl-2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylate.
These compounds include stereoisomers based on the asymmetric carbon and double bond of the cyclopropanecarboxylic acid moiety, and any of active forms, racemates, and arbitrary mixtures are included in the present invention. Stereoisomers in which the propanecarboxylic acid moiety is a 1R, cis structure and the double bond has the Z configuration are preferred.
Compound (E): 2,3,5,6-tetrafluorobenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate,
Compound (F): 2,3,4,5,6-pentafluorobenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate,
Compound (G): 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate,
Compound (H): 4-propargyl-2,3,5,6-tetrafluorobenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate.
In addition, there is no stereoisomer in compound (E) thru | or compound (H).

The compound has a higher insecticidal effect on flies than pinamine forte, and is contained in the flies and mosquito coils in an amount of 0.1 to 1.0% by weight, preferably 0.2 to 0.9% by weight. If the amount is less than 0.1% by weight, the desired insecticidal effect cannot be obtained. On the other hand, if the amount exceeds 1.0% by weight, no significant increase in efficacy is observed.
Of course, conventional pyrethroids such as pinamine, pinamine forte, bioaresulin, esbiothrin, esviol, praretrin, empentrin, or transfluthrin may be appropriately mixed with the compound.

  The flies and mosquito coils of the present invention are characterized by the selection of the compound of the general formula (I), but it is preferable to blend a ditertiary butyl-phenol stabilizer having a boiling point of 250 ° C. or more as a stabilizer. For example, mono-tertiary butyl-phenolic stabilizers such as 3-tertiarybutyl-4-hydroxyanisole and 2-tertiarybutyl-4-hydroxyanisole are ineffective, and N, N′-diphenyl- The effect was also low for amine stabilizers such as P-phenylenediamine and phenyl-β-naphthylamine. The reason why the boiling point of 250 ° C. or higher is effective is that the pyrethroid of the active ingredient volatilizes from around 200 to 250 ° C., so that it is necessary that the stabilizer itself does not volatilize at this temperature.

Examples of the stabilizer used in the present invention include the following, but of course not limited thereto.
Stabilizer A: 2,6-di-tertiarybutyl-4-methylphenol (BHT),
Stabilizer B: 2,2′-methylenebis (4-methyl-6-tertiarybutylphenol),
Stabilizer C: 2,2′-methylenebis (4-ethyl-6-tertiarybutylphenol),
Stabilizer D: 4,4′-butylidenebis (3-methyl-6-tertiarybutylphenol),
Stabilizer E: 4,4′-thiobis (3-methyl-6-tertiarybutylphenol),
Stabilizer F: 2-tertiarybutyl-6- (3-tertiarybutyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate,
Stabilizer G: 2,4-di-tert-butylphenyl 3,5-di-tertiary butyl-4-hydroxybenzoate.

  In the present invention, one or more of the stabilizers are blended in an amount of 0.1 to 2.0 times the amount of one or more selected from the general formula (I). Various conventional stabilizers such as phosphite, amine, and organic sulfur may be mixed with this.

  The fly and the mosquito coil of the present invention may contain a synergist such as piperonyl butoxide, MGK-264, MGK-5026, S-421, and Leesen 384, if necessary, in the active ingredient composition. Furthermore, flame retardants such as insecticide chrysanthemum extract powder, wood powder, paste powder such as tab powder, starch, dextrin, gum arabic and CMC, malachite green as colorant, dehydroacetic acid as antifungal agent and 2,4-dinitro Flies and mosquito coils can be prepared according to a conventional method by adding phenol, other fine mineral powders, polyethylene glycol and the like as appropriate.

  According to the present invention, the compound of the general formula (I) is selected as an active ingredient, and preferably has an insecticidal effect higher than that of the conventional pinamine forte incense against mosquitoes as well as flies as well as a specific stabilizer. And provides extremely useful flies and mosquito coils.

  Next, the present invention will be described in more detail with reference to test examples and examples. However, the present invention is not limited to these examples unless it exceeds the gist.

Flies and mosquito coils were prepared according to the formulation shown in the following table, and the volatilization rate of the active ingredient during smoke and the insecticidal efficacy against adult flies were examined. Regarding the other components, in addition to the described components, starch was added in an amount of 20% by weight, sodium dehydroacetate 0.2% by weight, insecticidal chrysanthemum extract powder 15% by weight, and wood flour to make the total amount 100% by weight. The insecticidal efficacy was expressed as the relative efficacy of the knockdown effect, assuming that 1.2% by weight of pinamine forte incense was 1.0.

＊ 特開平１０−２０３９０５号公報開示の２−アリル−３−メチル−シクロペント−２−エン−１−オン−４−イル ２,２，３,３−テトラメチルシクロプロパンカルボキシレート

* 2-allyl-3-methyl-cyclopent-2-en-1-one-4-yl 2,2,3,3-tetramethylcyclopropanecarboxylate disclosed in JP-A-10-203905

As a result of the test, flies and mosquito coils containing the compound of the general formula (I), preferably a di-tertiary butyl-phenol-based stabilizer is added to the compound in an amount of 0.1 times or more by weight. The volatilization rate of the active ingredient at the time of smoke was improved, and it was confirmed that the insecticidal efficacy was higher than that of the pinamin forte incense stick (control incense stick).
On the other hand, in general, insecticides for controlling flies require a higher concentration than those for insecticides. For example, as in Comparative Example 2 and Comparative Example 3, empentrin and control compound P are useful as active ingredients for fly-scenting incense but are not always satisfactory because they require a high concentration. Further, as for pinamine forte-containing fly-scenting incense, as shown in Comparative Examples 4 to 6, even if the dosage is further increased, the insecticidal efficacy against flies is hardly enhanced, but for example, the compound A of the general formula (I) In the case of 0.1 to 1.0% by weight, the dose and the insecticidal efficacy were correlated, and it was confirmed that the physicochemical properties (especially vapor pressure) of the compound are suitable for the fly-scenting. In addition, the pinamine forte incense has almost no effect of adding a stabilizer, whereas the fly and mosquito-repellent incense of the present invention have a more excellent insecticidal activity against flies and mosquitoes by adding a specific stabilizer. Provided and its practicality is extremely high.

Base material for incense, such as pesticide chrysanthemum extract powder, wood flour, starch, 0.4 part of compound (A) and 0.3 part of stabilizer A (2,6-ditertiarybutyl-4-methylphenol) The mixture was uniformly mixed with 3 parts, and flies and mosquito coils were obtained by a known method. This volume (13 g) was used in a 6 tatami room, and the volatilization rate of the active ingredient was measured. As a result, it was 79%, and flies and mosquitoes were completely controlled over 7 hours and a half.

  Compound (B) 0.25 part, transfluthrin 0.2 part, stabilizer F [2-tertiarybutyl-6- (3-tertiarybutyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl Acrylate] 0.1 parts and MGK-264 0.3 parts were used to obtain flies and mosquito coils in accordance with Example 2. Flies and mosquito coils were placed in a hanging incense plate, and they were lowered to the waist and engaged in work in a barn where many flies occurred. However, the flies were not bothered for about 6 hours.

The flies and mosquito coils of the present invention have excellent volatilization rate at the time of smoking and insecticidal efficacy, and can be used as mosquito coils and are extremely practical, contributing to the development of the insecticide manufacturing industry.

Claims (4)

As an active ingredient, the general formula (I)

(In the formula, R ₁ is a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents a 3-methoxy-3-oxo-1-propenyl group, and when R ₁ is a methyl group, ₂ represents a methyl group, and X represents a hydrogen atom, a fluorine atom, a methoxymethyl group or a propargyl group). A fly and a mosquito-repelling incense, characterized by containing 1 to 1.0% by weight. In the fluorine-substituted benzyl alcohol ester compound in which R _{1 in the} general formula (I) is a hydrogen atom and R ₂ is a 3-methoxy-3-oxo-1-propenyl group, the cyclopropanecarboxylic acid moiety is 1R, cis structure, The fly and mosquito coil of claim 1 wherein the double bond has a Z configuration. Along with the active ingredient, one or more di-tertiary butyl-phenol stabilizers having a boiling point of 250 ° C. or higher are blended in an amount of 0.1 to 2.0 times the active ingredient. The flies and mosquito coils of claim 1 or 2. The fly and mosquito coil according to claim 1, 2 or 3, characterized by containing MGK-5026 as a synergist.