JPH059103A - Carboxylic ester derivative-containing insecticide/insect-proofing agent for clothes - Google Patents

Abstract

(57) [Summary] [Structure] General formula (In the formula, R represents any one of formula 2, formula 3, and formula 4.) An insecticide or insect repellent for clothing, which comprises the carboxylic acid ester derivative represented by the formula. [Effect] The compound of the general formula 1 used in the present invention has volatility at room temperature, and an insecticidal or insect repellent containing the same has a high insecticidal or insecticidal effect against clothing pests, while warm-blooded animals. It has low toxicity, is less susceptible to the effects of metals, and has excellent chemical stability.

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 pyrethroid suitable as an active ingredient for insecticides and insect repellents for clothes pests such as squid.

[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. These room temperature volatile pyrethroids have the following characteristics, unlike conventional insect repellents. I. Not only insecticidal effect but also insecticidal effect. 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 its application will be expanded, but for compounds having an ethynyl group at the α-position of the chain alcohol part, it is chemically unstable and the influence of metals (particularly copper compounds) is expected. It has the drawback that it is susceptible to decomposition or polymerization upon reception.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the present situation in which carcinogenicity of paradichlorobenzene is a problem.
Satisfies all the requirements for insecticides and insect repellents used to control clothes pests such as mosquito, such as high insecticidal effect, insecticidal effect, low toxicity to warm-blooded animals, and chemical stability (not easily affected by metals) It was made for the purpose of making it happen.

[0004]

In order to achieve the above object, the present invention relates to an insecticidal or insect repellent for clothing containing a carboxylic acid ester derivative represented by the general formula (1).

[0005]

In the present invention, the alcohol component (2-methyl-3-allyl-2-cyclopenten-4-one-1-ol, 2-methyl-3-propargyl-2-cyclopentene-4-) constituting the general formula 1 is used. On-1-all, 5
-Propargyl-2-furylmethyl alcohol) is already known, but in combination with chrysanthemic acid, dichlorovinyl chrysanthemic acid, etc., only those intended for sanitary pests and unpleasant pest control applications are disclosed, and insect repellents are disclosed. There is no disclosure of application to agents. However, the inventors of the present invention focused on the volatility of the acid constituting the general formula 1 and tested the combination of this with the alcohol moiety.
It was found that the pyrethroid of (1) retains the characteristics of the practically used volatile pyrethroid and is suitable for this purpose. That is, the present invention, in the field of clothing insect control, in terms of safety for humans and animals, paradichlorobenzene, which is problematic, provides an ideal room temperature volatile active ingredient that replaces naphthalene, etc. There is something.

The compounds used as active ingredients in the present invention are as follows.

[Chemical 7] 2-Methyl-3-allyl-2-cyclopenten-4-one-1-yl 2,2

[Chemical 8] 2-Methyl-3-propargyl-2-cyclopentene-
4-on-1-yl 2,2,3,3-tetramethylcyclopropanecarboxylate m. p. 62-63 ° C

[Chemical 9] 5-propargyl-2-furylmethyl 2,2,3,3
-Tetramethylcyclo

According to the general method for producing an ester, the above-mentioned compound is 2,2,3,3-tetramethylcyclopropanecarboxylic acid represented by the formula 5 or its reactive derivative, and the compound represented by the formula 6 (wherein R is Can be prepared by reacting with an alcohol represented by the general formula (2), (3) or (4) 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.
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. The alcohol moiety represented by Chemical formulas 2 and 3 has an asymmetric carbon atom and optical isomers based on the asymmetric carbon atom. Of course, these compounds alone and as a mixture are included in the present invention.

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 overnight standing at room temperature, the crystals of pyridine hydrochloride were filtered off, the benzene solution was dried over sodium sulfate, and benzene was distilled off under reduced pressure to give 2-methyl-3-allyl-2-cyclopentene- 4-on-1-yl 2,
4.4 g of 2,3,3-tetramethylcyclopropanecarboxylate was obtained.

[0010]

Synthesis Example 2 2.8 g of 2,2,3,3-tetramethylcyclopropanecarboxylic acid and 2-methyl-3-propargyl-2-cyclopenten-4-one-1-ol 3.
0 g was dissolved in 50 ml of benzene, 6.4 g of dicyclohexylcarboximide was added, and the mixture was left tightly sealed overnight. The next day, the mixture was heated under reflux 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 on 100 g of a silica gel column to give 2-methyl-3-propargyl-2-cyclopenten-4-one-1-yl 2,2,3,3-.
Tetramethylcyclopropanecarboxylate 4.0 g
Got

The compounds of the present invention are liquid or solid at room temperature and are generally easily soluble in organic solvents. These compounds are
It has a characteristic that it has a higher volatility than conventional pyrethroids, and it is a particularly excellent effect when used as a so-called clothing insecticide or insect repellent that is volatilized by a suitable heating element or evaporation promoter or at room temperature. Is obtained. Since the compound of the present invention also exerts a repellent effect at low concentrations, it can be expected to have a wide range of insecticidal and insecticidal effects against clothing pests. Examples of the suitable heating element here include an electric heater and a chemical heating element (for example, a composition containing sodium sulfide and carbon, a composition containing salt, iron, carbon, a hydrated salt of sodium metasilicate, quicklime, etc.). , Heat is generated by contacting these with water or air)
Examples of the evaporation promoting aid include sublimable substances such as adamantane, cyclododecane, and trimethylene norbornane. The carrier used for clothing insecticides and insect repellents is not particularly limited, but examples include pulp mats, woven fabrics, non-woven fabrics, plastic molded products such as polyethylene and polypropylene, and porous glass materials. You can

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 compounds of the present invention have excellent chemical stability to metals, they are phenolic compounds or amines such as 2,6-ditertiarybutyl-4-methylphenol (BHT) and 2,6-ditertiarybutylphenol. Adding an antioxidant such as a system 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,
A multi-purpose composition with excellent potency can be obtained by mixing conventional pyrethroid insecticides such as permethrin and empentrin, or fragrances, deodorants, etc., which can be expected labor saving labor and sufficient synergistic effect between drugs. Is.

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

[0016]

Example 1 Compound of the present invention: 0.03 g of chemical compound, 0.15 g of cinepyrine 500, and 0.01 g of dibutylhydroquinone (DBHQ) were impregnated into a thick paper sheet having a thickness of 2 mm, a length of 35 mm, and a width of 22 mm to prevent insects for clothing. Get the mat.

[0017]

Example 2 0.3 g of the compound of the present invention, 0.
01 g is impregnated into 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.

[0018]

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 9 of the present invention is mixed with 00 parts by weight to obtain an insect repellent for clothing.

Test Example 1 Insecticidal test by transpiration The insecticidal mat for clothing prepared in Example 2 was placed in a plastic case and hung in a chest of 600 l. Immediately after and 6 months after the start of the test, 10 larvae of the first moth
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 one day later, 2
When the mortality of insects was observed after 7 days, it was as shown in Table 1.

[0020]

[Table 1]

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 clothing insects, and its volatility and efficacy are optimum as an insecticide and insecticide for clothing. It was confirmed. It was similarly effective against other clothing insect 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 exist almost all year round regardless of the four seasons, and there is little opportunity to be noticed, so long-lasting effects are 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.

Test Example 2 Stability Test Against Metals After a few drops of the reagent reagent were dropped onto the central portion of a copper plate measuring 2 cm × 5 cm, the copper plate was placed in a glass pot, and 6
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 2.

[0023]

[Table 2]

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.

[0025]

EFFECTS OF THE INVENTION The compound of the general formula 1 used in the present invention has volatility at room temperature and has a high insecticidal and insecticidal effect, low toxicity to warm-blooded animals, and chemical stability (hard to be influenced by metals. Insecticides and mosquito repellents for clothing.

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 10]

Claims (1)

Claim: What is claimed is: 1. A carboxylic acid ester derivative represented by the general formula (1) (wherein R represents any one of formulas 2, 3, and 4). An insecticide and insect repellent for clothing, characterized by.