JPH0543410A - Insecticidal, vermin-proofing and repelling agent dissipating at ordinary temperature and containing carboxylic acid ester derivative and insecticidal, vermin-proofing and repelling method using the same - Google Patents

Abstract

PURPOSE:To provide an insecticidal, vermin-proofing and repelling agent dissipating at ordinary temperature, containing a cyclopropanecarboxylic acid ester derivative and having high insecticidal, vermin-proofing and repelling effect, low toxicity to warm-blooded animal and high chemical stability, etc. CONSTITUTION:The objective agent contains, as an active component, a compound of formula (R1 and R2 are methyl, Cl, halomethyl or methoxy; R is 2- methyl-3-allyl-2-cyclopenten-4-on-1-ol, 2methyl-3-propargyl-2-cyclopenten-4-on-1-ol or 5-propargyl-2-methyl-3-furylmethyl alcohol), e.g. 2-methyl-3-allyl-2cyclopenten-4- on-1-yl-2,2,3,3-tetramethylcyclopropane carboxylate. The compound is expected to be widely applicable to fly, mosquito, cockroach, house dust mites, etc., as well as clothes vermin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature volatile insecticide, insect repellent and repellent, and an insecticide, insect repellent and repellent method using the same.

[0002]

2. Description of the Related Art Conventionally, paradichlorobenzene, naphthalene, and camphor have been generally used as insect repellents. However, as room temperature volatile pyrethroids were developed, some of them were put into practical use. Unlike ordinary insect repellents, these room temperature volatile pyrethroids have the following characteristics. I. Not only insecticidal but also insecticidal. B. To exert an effect against pests in a very small amount. C. Low toxicity to warm-blooded animals. D. There is no unpleasant odor typical of conventional insect repellents. From this, it is expected that not only insect repellents for clothing but also insecticides such as flies, mosquitoes, cockroaches, and indoor dust mites, insect repellents, and repellents are used. A compound having an ethynyl group at the position has a drawback that it is chemically unstable and easily decomposes or polymerizes under the influence of a metal (particularly a copper compound).

[0003]

DISCLOSURE OF THE INVENTION The present invention is highly insecticidal, insect repellent, and repellant in view of the carcinogenicity of paradichlorobenzene and the instability of the present room temperature volatile pyrethroid with respect to metals. Room temperature volatile insecticides and insect repellents that can satisfy all requirements such as efficacy, low toxicity to warm-blooded animals, and chemical stability (not easily affected by metals).
It was made for the purpose of developing a repellent.

[0004]

To achieve the above object, the present invention provides a compound of formula I

[Chemical 3] (In the formula, R ₁ and R ₂ are the same or different and each represent a methyl group, a chloro atom, a halomethyl group or a methoxy group. R is 2-methyl-3-allyl-2-cyclopenten-4-one-1. -Ol, 2-methyl-3-propargyl-2-
Represents either cyclopenten-4-one-1-ol or 5-propargyl-2-methyl-3-furylmethyl alcohol. ) The present invention relates to a room temperature volatile insecticide, an insect repellent, and a repellent containing a carboxylic acid ester derivative represented by (4), and an insecticide, an insect repellent, and a repellent method using the same.

In the present invention, the compounds of the formula I are already known, but only those intended for hygiene pests and unpleasant pest control applications for spraying and heating fumigation are disclosed, such as insect repellents. There is no disclosure of the application to a room temperature volatile insecticide, insect repellent and repellent. However, the present inventors have paid attention to the volatility of the acid and alcohol constituting the formula I, and tested combinations of this with various acids. As a result, the pyrethroid of the formula I was found to be a volatile pyrethroid that has been put to practical use. It was found that while maintaining the characteristics of, it is suitable for this purpose. That is, the present invention is a room temperature volatile insecticide,
In the field of insect repellent and repellent, especially in the field of insect repellent for clothing, paradichlorobenzene, which has many problems in terms of safety for humans and animals,
Since an ideal room temperature volatile active ingredient that replaces naphthalene or the like is provided, its practical advantages are enormous.

Examples of the compound used as the active ingredient in the present invention are as follows. Compound 1

[Chemical 4] 2-Methyl-3-allyl-2-cyclopenten-4-one-1-yl 2,2,3,3-tetramethylcyclopropanecarboxylate n _D ²⁰ 1.4976 Compound 2

[Chemical 5] 2-Methyl-3-allyl-2-cyclopenten-4-one-1-yl 2,2,3-trimethyl-3-chlorocyclopropanecarboxylate n _D ²⁰ 1.4865 Compound 3

[Chemical 6] 2-Methyl-3-allyl-2-cyclopenten-4-one-1-yl 2,2-dimethyl-3,3-dichlorocyclopropanecarboxylate n _D ²⁰ 1.4903 Compound 4

[Chemical 7] 2-Methyl-3-allyl-2-cyclopenten-4-one-1-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n _D ²⁰ 1.4920 Compound 5

[Chemical 8] 2-Methyl-3-allyl-2-cyclopenten-4-one-1-yl 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate n _D ²⁰ 1.4891 Compound 6

[Chemical 9] 2-Methyl-3-propargyl-2-cyclopentene-
4-on-1-yl 2,2,3,3-tetramethylcyclopropanecarboxylate Melting point 62-63 ° C. Compound 7

[Chemical 10] 2-Methyl-3-propargyl-2-cyclopentene-
4-on-1-yl 2,2,3-trimethyl-3-chlorocyclopropanecarboxylate n _D ²⁰ 1.4927 Compound 8

[Chemical 11] 2-Methyl-3-propargyl-2-cyclopentene-
4-on-1-yl 2,2-dimethyl-3,3-dichlorocyclopropanecarboxylate n _D ²⁰ 1.4955 Compound 9

[Chemical formula 12] 2-Methyl-3-propargyl-2-cyclopentene-
4-on-1-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate Compound 10

[Chemical 13] 2-Methyl-3-propargyl-2-cyclopentene-
4-on-1-yl 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate n _D ²⁰ 1.4863 Compound 11

[Chemical 14] 5-propargyl-2-methyl-3-furylmethyl
2,2,3,3-Tetramethylcyclopropanecarboxylate n _D ²⁰ 1.4914 Compound 12

[Chemical 15] 5-propargyl-2-methyl-3-furylmethyl
2,2,3-Trimethyl-3-chlorocyclopropanecarboxylate n _D ²⁰ 1.4882 Compound 13

[Chemical 16] 5-propargyl-2-methyl-3-furylmethyl
2,2-Dimethyl-3,3-dichlorocyclopropanecarboxylate n _D ²⁰ 1.4916 Compound 14

[Chemical 17] 5-propargyl-2-methyl-3-furylmethyl
2,2,3-Trimethyl-3-trifluoromethylcyclopropanecarboxylate n _D ²⁰ 1.4940 Compound 15

[Chemical 18] 5-propargyl-2-methyl-3-furylmethyl
2,2,3-Trimethyl-3-methoxycyclopropanecarboxylate n _D ²⁰ 1.4928

The above-mentioned compound is represented by the following formula II according to the general method for producing an ester.

[Chemical 19] (In the formula, R ₁ and R ₂ are the same or different and each represent a methyl group, a chlorine atom, a halomethyl group or a methoxy group.) And 2-methyl-3- Allyl-2-cyclopenten-4-one-1
-Ol, 2-methyl-3-propargyl-2-cyclopenten-4-one-1-ol, 5-propargyl-
It can be prepared by reacting any alcohol of 2-methyl-3-furylmethyl alcohol or a reactive derivative thereof. Examples of the reactive derivative of carboxylic acid include acid halide, acid anhydride, lower alkyl ester, alkali metal salt, and the like, while examples of reactive derivative of alcohol include halide.
The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizing agent or catalyst, and optionally with heating. In the compound of formula I, R ₁ , R
_{When 2} are different substituents, optical isomers exist, and in the alcohol portion of compound 1 to compound 10, an asymmetric carbon exists, and optical isomers based on this exist, but these single and Mixtures, any of which are included in the present invention.
Although only the trifluoromethyl group is illustrated as a specific example of the halomethyl group, it also includes a fluoromethyl group, a difluoromethyl group, and the like.

Next, synthetic examples of the compounds used in the present invention are shown.

[0009]

[Synthesis Example 1] 3.2 g of 2,2,3,3-tetramethylcyclopropanecarboxylic acid chloride was dried with benzene 15.
It is dissolved in ml and 2-methyl-3-allyl-2-
A solution of 3.0 g of cyclopenten-4-one-1-ol dissolved in 20 ml of dry benzene was added, and further 3 ml of dry pyridine was added as a condensing agent to precipitate crystals of pyridine hydrochloride. After sealing and leaving at room temperature overnight, the crystals of pyridine hydrochloride were filtered off, the benzene solution was dried with sodium sulfate, and benzene was distilled off under reduced pressure to give 2-methyl-3-allyl-
2-cyclopenten-4-one-1-yl 2,2
4.4 g of 3,3-tetramethylcyclopropanecarboxylate (Compound 6) was obtained.

[0010]

[Synthesis Example 2] 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylic acid (4.0 g) and 5-propargyl-2-methyl-3-furylmethyl alcohol (3.0 g) were dissolved in benzene (50 ml), 6.4 g of dicyclohexylcarbodiimide was added and left tightly sealed overnight. The next day, the mixture was refluxed for 4 hours to complete the reaction, and after cooling, the precipitated dicyclohexylurea was filtered off. The oily substance obtained by concentrating the filtrate was allowed to flow down a 100 g silica gel column to give 5-propargyl-2-methyl-3-furylmethyl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate. (Compound 14) 5.3
g was obtained.

The compound of the present invention is a liquid or a solid at room temperature and is generally easily dissolved in an organic solvent. These compounds have higher volatility than conventional pyrethroids, and since they also exert repellent effects at low concentrations, insecticides used at room temperature,
It is useful as an insect repellent and repellent, and is expected to be widely applied to clothing pests, flies, mosquitoes, cockroaches and indoor dust mites. The room temperature volatile insecticide, insect repellent, and repellent of the present invention may be used as the active ingredient compound as it is, but usually, preferably a suitable carrier or other excipient is used, for example, powder, tablet. , A mat, a sheet, or the like, or a liquid formulation such as an emulsion, a spray, or an aerosol, and is applied to control pests by a method according to each of these forms.

Typical examples of the carrier used for preparing the 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 compound of the present invention can be adjusted by using a sublimable carrier such as adamantane, cyclododecane, or triisopropyl-trioxane, and polyvinyl alcohol, alginic acid, a gelling agent such as carrageenan can be used. It can also be prepared in the form. Further, as the mat or sheet-like 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.

Further, the compound of the present invention may be added to N-octylbicycloheptene dicarboximide (trade name: MGK-26).
4), a mixture of N-octylbicycloheptene dicarboximide and an aryl sulfonate (trade name MGK-
5026), Cinepyrine 500, octachlorodipropyl ether, piperonyl butoxide, and other synergists may be added. Although the compound of the present invention has excellent chemical stability to metals, 2,6-ditertiarybutyl-4-methylphenol (BHT), Yoshinox 4
Addition of a phenol-based or amine-based antioxidant such as 25,2,6-ditertiarybutylphenol is useful for increasing the stability of the compound of the present invention over time.

In addition, other insecticides such as fenitrothion, DDVP, organophosphorus agents such as diazinon, NAC,
Carbamate agents such as MTMC, BPMC, PHC, pyrethrins, allethrins, phtalthrin, phenothrin,
By mixing conventional pyrethroid insecticides such as permethrin and empentrin, or fragrances, deodorants, fungicides, etc., a versatile composition with excellent potency can be obtained, labor saving, and expected synergistic effects between drugs. It is possible.

The room-temperature volatile insecticide, insect repellent, and repellent of the present invention thus obtained are applied to clothing storage furniture such as chests of drawers and clothing boxes, and are highly effective against clothing pests such as squid, koga, scabbard beetle, and stag beetle. In addition to exterminating effects, flies, mosquitoes, lice in pet huts such as dogs and cats,
Control of ticks, prevention of invasion of harmful insects in electric products and electronic devices, or extremely useful for preventing insects in a library, exhibition room, etc., the present invention does not need to use a heating device in this way, It provides a practical insecticidal, insecticidal and repellent method that can be used at room temperature.

In order to further clarify that the preparation provided by the present invention is excellent, the following Examples and test results of effects are shown.

[0017]

Example 1 0.03 g of Compound 1 of the present invention, 0.15 g of cinepyrine 500, dibutylhydroquinone (D
0.01 g of BHQ) was soaked in a cardboard sheet having a thickness of 2 mm, a length of 35 mm and a width of 22 mm to obtain an insect repellent mat for clothing.

[0018]

Example 2 0.3 g of the compound 2 of the present invention, 0.0 perfume
1 g of thickness was soaked in a cardboard sheet having a thickness of 1 mm, a length of 60 mm and a width of 80 mm to obtain an insect repellent mat for clothing.

[0019]

Example 3 Mixture of trimethylene norbornane and adamantane (mixing ratio; former: latter = 8: 2 (parts by weight)) 1
1 part by weight of the compound 3 of the present invention was mixed with 00 parts by weight to obtain an insect repellent for clothing.

[0020]

Example 4 Using ethylene-vinyl acetate copolymer and chlorinated polyethylene as a sustained release controller,
Compound 4 of the present invention was kneaded at 0.5% and then molded to obtain an insect-repellent / repellent net having a thread thickness of 0.3 mm and a mesh size of 3 mm.

[0021]

Example 5 A solution of 0.25 g of Compound 5 of the present invention to which kerosene was added to 100 ml was placed in a pressure resistant container, 200 ml of a mixed gas of liquefied petroleum gas and dimethyl ether was added, and a spray valve was attached to the insecticidal and insect repellent aerosol. Got

[0022]

Test Example 1 Insecticidal Test by Evaporation 1 ml of an acetone solution containing a predetermined amount of a test compound was dropped on a petri dish having a diameter of 9 cm and a height of 2.1 cm, and acetone was air-dried to form a dry film. Similarly diameter 9
Ten koigami larvae were released on a petri dish having a height of 2.1 cm and a height of 2.1 cm, a 16-mesh wire net was placed on the top surface, and the bottom surface of the drug-treated petri dish was placed on top of this. That is, the knock-down situation of the test insects was observed by letting the adult koigami be exposed to the chemical vapor only for 24 hours. Furthermore, after the exposure, the test insects were transferred to another container, and the mortality rate after 24 hours was examined. The results are shown in Table 1.

[0023]

[Table 1] In Table 1 above, the reference compound pyrethroid A has the following formula (A)

[Chemical 20] It is a commercially available pyrethroid having a room temperature volatility.

As a result of the test, the compound of the present invention showed a high knockdown effect and mortality against the larvae of the dressing insect, Koga, and was superior to the commercially available room temperature volatile pyrethroid A.

[0025]

Test Example 2 Practical Test by Evaporation The insect repellent mat for clothing prepared in Example 2 was housed in a plastic case and hung in a chest of 600 l. Immediately after the start of the test and after 6 months, 10 first-instar larvae of squid
Place a glass ring with a diameter of 4 cm and a width of 2 cm (both sides covered with woolen cloth) in the closet, and after 1 day, 2
When the mortality of insects was observed after 7 days, it was as shown in Table 2.

[0026]

[Table 2] In the table, pyrethroid A is a commercially available pyrethroid represented by the formula (A).

As a result of the test, the compound of the present invention shows an insecticidal and insecticidal effect superior to that of the control compound pyrethroid A against mosquito larvae of the insect pest of clothing, and its volatility and efficacy are optimum as insecticides and insecticides for clothing. It was confirmed. It was similarly effective against other clothing pests such as Pleurotus cornucopia, Pleurotus sp. Insecticides and insect repellents for clothing have a very long period of larvae of the clothing pests that are the target, and larvae are present almost all the year regardless of the seasons, and there is little opportunity to be noticed, so long-lasting effect is maintained. It is very different from conventional pesticides in that it requires active ingredients that That is, although the control compound allethrin is widely used as an active ingredient of a sanitary pest control agent in terms of basic efficacy upon contact, it is more widely used as an active ingredient of a sanitary pest control agent, but it is poor in volatility and long-term stability and is an insect repellent for clothing. Does not meet the conditions as. As described above, when developing insecticides and insect repellents for clothing, it is necessary to test them under actual use conditions in which clothing pests inhabit, and to comprehensively evaluate the mortality of clothing pests and the food damage prevention effect.

[0028]

[Test Example 3] Stability test against metal After a few drops of the reagent reagent were dropped onto the center of a copper plate measuring 2 cm x 5 cm, the copper plate was placed in a glass pot and
It was left in a constant temperature room at 0 ° C. After 3 days, the surface of each copper plate was observed, and the results were as shown in Table 3.

[0029]

[Table 3]

As a result of the test, unlike the control pyrethroid A, the compound of the present invention does not undergo alteration by acting with a metal, and is used not only in the closet but also in various usage scenes such as mechanical equipment and exhibition rooms. It was confirmed that it could be used without problems. Combined with the insecticidal efficacy test, the compound of the present invention is effective,
The stability against metals and the practicality thereof are extremely higher than those of the commercially available pyrethroid A.

[0031]

[Example 6] When the insect repellent and repellent net obtained in Example 4 was hung at the entrance of a kennel and used, it was effective in suppressing the invasion of flying insects such as mosquitoes and gnats and maintaining the health of dogs. there were.

[0032]

Example 7 The insect-repellent mat obtained in Example 1 was put in a display case accommodating a large number of old documents at a rate of 2 pieces / 50 l. Even after 1 year, there was no stain due to clothes pests, stains, etc., and invasion of cockroaches etc. could be prevented.

[0033]

[Example 8] The insect repellent mat obtained in Example 2 was left to hang from the ceiling of a garbage collection place (a shed of about 20 m ³ ) where flies are densely hung in 4 places, and after 3 days, almost no flies fly. I can't see it anymore.

[0034]

The compounds of formula I used in the present invention have volatility at room temperature and have high insecticidal, insecticidal, repellent effects, low toxicity to warm-blooded animals, and chemical stability (influence of metals). Ordinary temperature volatile insecticides, insect repellents and repellents, and insecticidal, insect repellent and repellent methods using the same.

Continued Front Page (72) Nobuyuki Nishida Inventor Nobuyuki Nishida 4-10-26- 105 Himejima, Nishiyodogawa-ku, Osaka-shi, Osaka

Claims (2)

[Claims] 1. The following formula I: (In the formula, R ₁ and R ₂ are the same or different and each represent a methyl group, a chloro atom, a halomethyl group or a methoxy group. R is 2-methyl-3-allyl-2-cyclopenten-4-one-1. -Ol, 2-methyl-3-propargyl-2-
Represents either cyclopenten-4-one-1-ol or 5-propargyl-2-methyl-3-furylmethyl alcohol. ) A volatile ester insecticide, insect repellent and repellent characterized by containing a carboxylic acid ester derivative represented by 2. The following formula I: (In the formula, R ₁ and R ₂ are the same or different and each represent a methyl group, a chloro atom, a halomethyl group or a methoxy group. R is 2-methyl-3-allyl-2-cyclopenten-4-one-1. -Ol, 2-methyl-3-propargyl-2-
Represents either cyclopenten-4-one-1-ol or 5-propargyl-2-methyl-3-furylmethyl alcohol. ) The insecticidal, insect-repellent and repellent method, which comprises volatilizing the carboxylic acid ester derivative represented by (4) at room temperature.