JP5231801B2 - Mosquitoes or fly incense sticks - Google Patents

Description

The present invention relates to a mosquito or fly-scavenging incense stick.

Mosquito coils are familiar for over 100 years as insecticides for combating mosquitoes. They are very reasonable because they maintain the spatial treatment in time with a single match and remain constant until burned out. Insecticidal form. In 1902, a spiral-type mosquito coil was invented in Japan, but the raw material was a mixed powder containing pesticide chrysanthemum dried flower powder (60-80%) and bamboo leaf powder (20-40%) as a binder. Thus, water was added to the mixture and kneaded to produce a spiral shape. Insecticidal chrysanthemum powder has been used for a long time as an insecticidal component, but it has been replaced by the industrialization of synthetic pyrethroid and allesrin, which has excellent thermal stability, and more recently, its optically active substance with high physiological activity is widely used all over the world. Has been.

Compared to organochlorine, organophosphorus, carbamate, and other synthetic insecticides, pyrethroids such as Alleslin are superior to insecticides and safe for warm-blooded animals, and are ideal as insecticides for household insecticides. However, the manufacturing process is complex and very expensive.
For this reason, it is very useful to save the amount of pyrethroid added by the addition of a potency enhancer (the compound itself has no insecticidal power, but enhances the insecticidal efficacy when blended with an insecticidal component) So far, in formulations such as oils, aerosols and powders, piperonyl butoxide, N- (2-ethylhexyl) -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide ( Hereinafter referred to as potency enhancer A), N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2,2,2] -oct-5-ene-2,3-dicarboximide, etc. It has often been used to mix enhancers with pyrethroids. There are many reports on the mechanism of the potentiator, for example, the body itself undergoes metabolic degradation to inhibit the oxidative detoxification metabolism of pyrethroids or promote the penetration of pyrethroids into the skin, acting on the nervous system It is known to increase the insecticidal efficacy of pyrethroids by making it easy to reach the point. However, it goes without saying that the mechanism of action of such an efficacy enhancer depends largely on the type of insect, and the efficacy enhancing effect of the efficacy enhancer is generally only about 10 to 20%.

In contrast, as a result of intensive studies on the action of certain compounding agents in the form of incense, the present inventors have newly discovered that efficacy enhancer A is specifically effective among the various efficacy enhancers. did. Patent Document 1 and Patent Document 2 disclose the usefulness of mosquito coils and have already filed an application (Japanese Patent Application No. 2006-308905) for clarifying the usefulness of flies . That is, in the incense stick form, the addition of potency enhancer A to several pyrethroids increases the insecticidal potency by a factor of 2-3, but this fact is only the mechanism of the conventional potency enhancer based on the above-described insect physiological mechanisms. In other reasons, the effect enhancer A contributed to increase the volatilization rate of the insecticidal component and increased the concentration of the insecticidal component in the air, or that the substance promoted the diffusion of the volatilized insecticidal component, etc. It was thought that the physical action also contributed.

In recent years, the occurrence of flies has decreased in urban areas, but there are more opportunities to suffer more than ever in the surroundings of fishing villages, seafood processing plants, garbage disposal sites, livestock barns, and poultry houses. As countermeasures, the demand for fly-cranking incense for space treatment is increasing, and there is a need for more effective efficacy enhancers including not only mosquito coiling incense but also fly-cranking incense.

The inventors of the present invention have made extensive studies aiming at further effective utilization of the efficacy enhancer A in the incense stick form, and efficacy enhancement agent A, that is, N- (2-ethylhexyl) -bicyclo [2,2,1]-. It was noted that the three-dimensional structure of hepta-5-ene-2,3-dicarboximide was composed of Exo type and Endo type. Efficacy enhancer A itself is already known, but there is no known document that mentions the efficacy enhancement effect by paying attention to Exo type and Endo type, and the present inventors work on the elucidation to complete the present invention. Has been reached.
Japanese Patent No. 3909717 Japanese Patent No. 3926836

The present invention investigates the effects of the Exo and Endo types of efficacy enhancer A on efficacy enhancement effects in mosquitoes or fly-scavenging incense containing efficacy enhancer A as an efficacy enhancer together with pyrethroids. It aims at providing the composition of the mosquito or the fly incense which adopted.

In order to achieve the above object, the present invention adopts the following configuration.
(1) N- (2-ethylhexyl) -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide has an Exo-type ratio of 30 to 40 % and an Endo-type ratio of 60 In the case of an efficacy enhancer having an Exo-type ratio of 0% and an Endo-type ratio of 100%, by blending 0.5% or more of an efficacy enhancer of ˜70% with respect to the amount of pyrethroid insecticide component Mosquito or fly-cranking incense that has enhanced insecticidal efficacy by pyrethroids compared to
(2) The mosquito or fly-harvesting incense according to (1) above, wherein the potency enhancer is mixed in an amount of 1.0 to 5.0 times the amount of the pyrethroid insecticide component.
(3) (Endo type) hymic anhydride is added with no organic solvent, or heated at 190 ° C. or higher with an organic solvent having a boiling point of 190 to 300 ° C. for 30 minutes or longer, allowed to cool, and then 2-ethylhexylamine alone, Alternatively, N- (2-ethylhexyl) -bicyclo [2,2,1] -hepta is obtained by adding 2-ethylhexylamine and water or an organic solvent having a boiling point of 110 to 150 ° C. and reacting at 95 to 160 ° C. for 30 minutes or more. Employing a method for producing an efficacy enhancer based on -5-ene-2,3-dicarboximide having an Exo-type ratio of 30 to 40 % and an Endo-type ratio of 60 to 70%. The mosquito or fly-removing incense stick according to any one of (1) and (2) above.
(4) The above (1), wherein the insecticidal component is 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate 2) The mosquito or fly-removing incense stick according to any one of (3).
(5) The insecticidal component is (S) -2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl (1R) -trans-chrysantemate, which is an isomer of praretrin. The mosquito or fly-removing incense stick according to any one of (1), (2) and (3) above.
(6) The mosquito according to any one of (1), (2), (3), (4), and (5) above, wherein the insecticidal object is either or both of Aedes aegypti and Aedes aegypti Flies catching incense.

The efficacy enhancer according to the present invention, when used in combination with pyrethroids in mosquitoes or fly-scenting incense, further enhances the insecticidal efficacy as compared to the conventional efficacy enhancer A, and is also excellent in terms of production supply and economy. It is extremely practical. Moreover, the manufacturing method is also easy and efficient, and its usefulness is extremely high.

The mosquito or fly-fighting incense stick of the present invention in which the efficacy enhancer is blended contains about 0.01 to 0.5% by mass of an insecticidal component in consideration of insecticidal efficacy against the target pests, economic efficiency, and the like. Such insecticidal components include allethrin, praretrin, pyrethrin, framethrin, transfluthrin, metfurthrin, empentrin, 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 2,2,3,3-tetramethylcyclopropane Various pyrethroid insecticide components such as carboxylate (hereinafter referred to as Compound A) or any isomers thereof are suitable, but not limited thereto.

The present invention relates to a three-dimensional structure of N- (2-ethylhexyl) -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide as a potentiating agent A in mosquitoes or fly-scenting incense sticks. It is characterized in that the composition ratio of Exo type and Endo type in is specified. That is, in the mosquito or the fly-scoring incense of the present invention, the potency enhancer A having an Exo-type ratio of 30 to 40 % is used.

As for the three-dimensional structure of the efficacy enhancer A, the following knowledge can be obtained from the literature, but so far no attention has been paid to the relationship with the action effect.
(1) A hymic anhydride [cis-5-norbornene-2,3-dicarboxylic anhydride] can be prepared by reacting with 2-ethyl-hexylamine in a solvent. According to a normal production method, (Endo type ) Potency enhancer A (Endo type) from hymic anhydride, and (Exo type) potency enhancer A from (Exo type) hymic anhydride.
(2) Regarding the raw material hymic anhydride, the Endo type is a commercial product and the Exo type is a custom-made product. Unless otherwise specified, the three-dimensional structure of the efficacy enhancer A is mainly the Endo type.

However, the present inventors considered that in the incense stick form, the three-dimensional structure of potency enhancer A might affect the potency enhancement mechanism, and conducted insecticidal potency tests on various combinations of Exo and Endo types. As a result, although the detailed reason is unknown, the Exo type has a higher insecticidal effect than the Endo type, and considering the economy and manufacturability, the ratio of 30% to 40 % is effective and preferable as the Exo type ratio. Is found. On the other hand, in the aerosol form, since a clear difference in insecticidal efficacy based on the Exo / Endo ratio cannot be observed, it is understood that the effect of the present invention is remarkable in the form of the incense stick. In the case of such a mosquito coil, the pharmacological basis that can exert its inherent effect is currently unknown, but this point is left to the future elucidation.
In addition, the compounding amount with respect to the amount of the insecticidal component of the efficacy enhancer A is suitably 0.5 times or more, and particularly preferably about 1.0 to 5.0 times.

Next, the manufacturing method of the efficacy enhancer mix | blended with the mosquito or the fly picking incense of this invention is described.
An inexpensive (Endo type) anhydrous hymic acid is used as a raw material, and the process is large. (1) Isomerization reaction of (Endo type) anhydrous hymic acid to (Exo type + Endo type), (2) Product Can be divided into a condensation reaction with 2-ethylhexylamine and (3) a distillation step of the potency enhancer A.

(1) (Endo-type) hymic anhydride is added with no organic solvent or heated at 190 ° C or higher for 30 minutes or more together with an organic solvent having a boiling point of 190 to 300 ° C to shift the Exo-type ratio to 30% or higher . When no organic solvent is added, a portion of the hymic anhydride may sublimate and adhere to the upper part of the container, but this also has no problem because isomerization has progressed. On the other hand, various organic solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, esters and ethers can be used as the organic solvent used in this step. However, in consideration of the next reaction and handling, kerosene is used. Is preferred. Usually, as the reaction time is lengthened, the ratio of Exo type tends to increase.

(2) After allowing to cool, 2-ethylhexylamine alone in the reaction product of (1), or when no organic solvent is added in the step of (1), 2-ethylhexylamine and water or a boiling point of 110 to 150 ° C An organic solvent (toluene, xylene, etc.) is added and reacted at 95-160 ° C. for 30 minutes or longer. The ratio of Exo and Endo does not change significantly during the reaction. Use of water, toluene, xylene and the like is effective for washing out the hymic acid anhydride adhering to the upper part of the reaction vessel for the progress of the reaction, and the process using water is particularly advantageous in terms of production safety. In addition, after completion | finish of reaction, if necessary, pH adjustment (5.5-7.0) of a reaction liquid is performed using soda ash, and it is made to transfer to a distillation apparatus.

(3) The distillation temperature of the efficacy enhancer A is 160 to 170 ° C./3 mmHg, and does not require any special equipment, and can be carried out by ordinary equipment.
It is also possible to carry out the isomerization reaction to (Exo type + Endo type) by directly heating the efficacy enhancer A to 210 ° C. or higher.

In the present invention, in addition to the insecticidal component and efficacy enhancer A, a binder, a flame retardant, and the like are blended to prepare a mosquito or fly-incense. In this case, the efficacy enhancing agent A is an effective insecticidal component. In many cases, the amount is 1.0 to 5.0 times the amount of ingredients.
Examples of the former binder include tab powder, starch, methyl cellulose, carboxymethyl cellulose, and the like. In addition, the latter flame retardants include insecticide chrysanthemum extract powder, fir, toga, cypress, tea, citrus, dried powder of fake acacia leaves, plant powders such as coconut shell powder, diatomaceous earth, clay, gemlite, kaolin, talc, etc. Mineral powder, or inorganic powder such as elementary ash.

Moreover, a pigment | dye, an antiseptic | preservative, a stabilizer, etc. may be contained as needed. Examples of the dye include malachite green, and typical examples of the preservative include acids such as sorbic acid, dehydroacetic acid, p-hydroxybenzoic acid, and salts thereof. Examples of the stabilizer include 2,6-di-tertiarybutyl-4-methylphenol (BHT) and 2,2′-methylenebis (4-ethyl-6-tertiarybutylphenol), but are not limited thereto. Not.
Furthermore, as long as the gist of the present invention is not hindered, a bactericidal agent, an antibacterial agent, a repellent, a fragrance, a deodorant and the like can be mixed to obtain a multipurpose composition having excellent efficacy.

In preparing mosquitoes or fly incense sticks, no special technique is required and a known production method can be employed. For example, water is added to a mixture of premix powder (a mixture of insecticide ingredients, efficacy enhancers, etc. as part of the flame retardant) and the remaining incense stick base material, and then kneaded. After molding by a punching machine, it can be dried to produce a mosquito coil or incense stick. Moreover, after molding using only the incense stick substrate, a liquid agent containing an active ingredient or the like may be sprayed or applied thereto.

The mosquitoes or fly-scoring incense obtained in the present invention are effective against mosquitoes such as Culex mosquito, Kogata mosquito, Aedes mosquito, Aedes aegypti, Anopheles, Chikaeka, etc. It is effective against sanitary pests such as cockroaches and indoor dust mites, and various pests such as chironomid and abu, and its practicality is extremely high.

In particular, when compound A (4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate) is selected as the active ingredient, so-called infection vector It has been confirmed that it is useful as a mosquito coil for controlling mosquitoes, and Japanese Patent Application No. 2006-304879 has already been filed for its basic structure, and the Patent No. 3926836 has been granted.

Further, as an active ingredient, compound B ((S) -2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl (1R) -trans-chrysantemate, which is a monoisomer of praretrin) Is particularly useful as a mosquito coil for controlling tropical infectious disease-borne mosquitoes, and a Japanese Patent Application No. 2007-061173 has already been filed for its basic structure.

Next, the present invention will be described in more detail based on specific examples.
[Reference example]

dl, d-T80-alleslin (0.27 parts) and Exo-type ratio 55% efficacy enhancer A (0.7 parts), incense base material 99.03 parts (alpha-starch and tab powder (Binder: 18 parts, insecticide chrysanthemum extracted powder: 25 parts, other wood flour, etc.), and after mixing with water containing colorant and preservative, kneaded, put into a plate sheet through an extruder, Punched into a spiral mold and dried to a moisture content of about 7 to 10% to produce a mosquito coil.

Compound A (0.15 part) and efficacy enhancer A (0.3 part) having an Exo-type ratio of 40% are mixed with an incense base material 99.55 parts (25 parts of oolong tea extract powder, 20 parts of coconut shell powder, wood After mixing uniformly with 30 parts of powder, mixed powder consisting of cocoon powder, starch, etc., water containing an antiseptic was added, and a fly picking incense was obtained by a known method.

(Endo type) 5.0 g of hymic acid anhydride was put into a reaction flask, heated at a reaction temperature of 195 ° C., and the heating time was adjusted to synthesize an potency enhancer A having an Exo / Endo type ratio shown in Table 1. Using the various mosquito coils prepared in accordance with the reference examples , the following insecticidal efficacy test was carried out against female adult mosquitoes.
[Field insecticidal efficacy testing of a room of 25m ^3]
After releasing 100 adult female mosquitoes in a closed 25 m ³ room, a test mosquito coil (prepared according to the reference example ) was placed in the center of the room. The female mosquitoes that were exposed for 2 hours and fallen over time were counted, and the KT ₅₀ value was determined.

As a result of each test, the mosquito coils with the efficacy enhancer A of the present invention having an Exo-type ratio of 30 to 40 % (Endo-type ratio of 60 to 70%) and pyrethroids are not mixed with the efficacy enhancer A. (Comparative Example 1 and Comparative Example 4) and even when the potency enhancer A is blended, the incense in which the Exo type ratio is less than 30% [Comparative Example 2 (all Endo type), Comparative Example 3 (Exo type 20%) Compared with Comparative Example 5 (Exo type 20%)], the KT ₅₀ value was very low, and the rapid efficacy was remarkably enhanced. In addition, as the Exo-type ratio exceeded 30% to 40%, the insecticidal efficacy was enhanced.

(Endo type) 5.0 g of hymic anhydride is put in a reaction flask, heated at a reaction temperature of 195 ° C., and the heating time is adjusted to synthesize the potency enhancer A of Exo / Endo type ratio shown in Table 2. Using the various mosquito coils prepared in accordance with the reference examples , the following insecticidal efficacy test was carried out against Aedes aegypti female adults.
[Field insecticidal efficacy testing of a room of 25m ^3]
After releasing 100 adult female Aedes aegypti in a closed 25 m ³ room, an ignited test mosquito coil (prepared according to the reference example ) was placed in the center of the room. The number of female Aedes aegypti that had been exposed for 2 hours and fallen over time was counted, and the KT ₅₀ value was determined.

As a result of each test, the mosquito coil in which the efficacy enhancer A of the present invention having an Exo-type ratio of 30 to 40 % (Endo-type ratio of 60 to 70%) and Compound A or Compound B is added to the efficacy enhancer A Even when blended with incense sticks (Comparative Example 1 and Comparative Example 3) and potency enhancer A, all of the incense sticks were also carried out against Aedes aegypti compared to Endo type incense sticks (Comparative Examples 2 and 4). As in Example 2 , the KT ₅₀ value was very low and the rapid efficacy was significantly enhanced.

(Endo type) 5.0 g of hymic anhydride is put in a reaction flask, heated at a reaction temperature of 195 ° C., and the heating time is adjusted to synthesize the potency enhancer A of the Exo / Endo type ratio shown in Table 3. And the insecticidal efficacy test with respect to the following housefly female adults was conducted using the various incense sticks prepared according to Example 1 .
[Field insecticidal efficacy testing of a room of 25m ^3]
After releasing 100 adult house flies in a closed 25 m ³ room, a test fly-collecting incense (prepared according to Example 1 ) was placed in the center of the room. The adult housefly that had been exposed for 3 hours and fell down over time was counted, and the KT ₅₀ value was determined.

As a result of each test, similar to the insecticidal efficacy test related to the mosquito coil incense in Example 2 , the fly-type incense stick has an Exo-type ratio of 30 to 40 % (Endo-type ratio of 60 to 70%) in the pyrethroid. By compounding the efficacy enhancer A of the invention, the rapid efficacy was remarkably enhanced.
Therefore, in the incense stick form, the usefulness of using the potency enhancer A having an Exo-type ratio of 30 to 40 % is clear.

For comparison, tests in aerosol form were performed as follows.
House flies (about 25 female adults per group) were released into a 60 cm cubic (0.216 m ³ ) glass chamber, and the test aerosol insecticide shown in Table 3 (stock solution 120 mL + propellant gas 180 mL) was sprayed for 1 second. After exposure for 10 minutes, the number of supine worms with the passage of time was recorded, and the KT ₅₀ value was determined. The results are shown in Table 4.

As shown in Table 4, no clear difference in insecticidal efficacy based on the Exo / Endo ratio was observed in the aerosol form in which efficacy enhancer A was added to pyrethroid, and the effect of the present invention was characteristic in the incense stick form. .

The present invention can be used in the field of manufacturing mosquitoes or fly incense sticks.

Claims (6)

N- (2-ethylhexyl) -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide has an Exo-type ratio of 30 to 40% and an Endo-type ratio of 60 to 70%. By adding 0.5 times or more of the efficacy enhancer to the amount of the pyrethroid insecticide component, the Exo ratio is 0% and the Endo ratio is 100% compared to the efficacy enhancer. Mosquitoes or fly-scavenging incense that enhances the insecticidal efficacy of pyrethroids.   The mosquito or fly-harvesting incense according to claim 1, wherein the potency enhancer is added in an amount of 1.0 to 5.0 times the amount of the pyrethroid insecticide component. (Endo-type) hymic anhydride is added with no organic solvent, or heated with an organic solvent having a boiling point of 190 to 300 ° C. at 190 ° C. or higher for 30 minutes or longer, and after cooling, 2-ethylhexylamine alone, or 2- N- (2-ethylhexyl) -bicyclo [2,2,1] -hepta-5 is prepared by adding ethylhexylamine and water or an organic solvent having a boiling point of 110 to 150 ° C. and reacting at 95 to 160 ° C. for 30 minutes or more. It is en-2,3-dicarboximide, and the method for producing an efficacy enhancer based on an Exo-type ratio of 30 to 40% and an Endo-type ratio of 60 to 70% is adopted. The mosquito or the fly-taking incense according to any one of claims 1 and 2. The insecticidal component is 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate. The mosquito or fly-removing incense stick according to claim 1. The insecticidal component is (S) -2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl (1R) -trans-chrysantemate, which is an isomer of praretrin. The mosquito or the fly-removing incense stick according to any one of claims 1, 2, and 3. The mosquito or the fly-removing incense stick according to any one of claims 1, 2, 3, 4, and 5, wherein the insecticidal target is both Aedes aegypti and Aedes mosquitoes.