JP3204420B2 - Insecticides and insect repellents containing polyfluorobenzyl ketone derivatives, and insecticidal and insect repellent methods using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a normal-temperature volatile polyfluorobenzyl ketone derivative suitable as an active ingredient of various insect pests, especially insect pests for clothing pests such as iga and insect repellents.

[0002]

2. Description of the Related Art Conventionally, para-dichlorobenzene, naphthalene, and camphor have been generally used as insect repellents. However, when a normal-temperature-volatile pyrethroid was developed, a part thereof was put into practical use. These room temperature volatile pyrethroids are different from conventional insect repellents and have the following features. I. Show insecticidal effect as well as insect repellent effect. B. To be effective against pests in a very small amount. C. No unpleasant odor peculiar to conventional insect repellents. Therefore, compounds having an ethynyl group at the α-position of the chain alcohol, such as empentrin, are chemically unstable and are affected by metals (particularly copper compounds). There is a drawback that it is liable to be decomposed or polymerized in response to heat. Also, pentafluorobenzyl alcohol ester derivatives have been noted for their high insecticidal and insect repellent effects, but have a problem of high toxicity to warm-blooded animals.

[0003]

SUMMARY OF THE INVENTION In view of the carcinogenicity of paradichlorobenzene and the current situation where problems of conventional pyrethroids have been pointed out, the present invention relates to sanitary pests such as flies and mosquitoes and clothing pests such as iga. The purpose of insecticides and insect repellents used for controlling insects is to satisfy all requirements such as high insecticidal and insect repellent effects, low toxicity to warm-blooded animals, and chemical stability (less susceptible to metals). It was done.

[0004]

In order to achieve the above object, the present invention provides an insecticide and an insect repellent containing a polyfluorobenzylketone derivative represented by the general formula I, and an insecticide and an insect repellent using the same. Related.

[0005]

In the present invention, R ₁ represents a hydrogen atom or a methyl group; R ₂ represents a methyl group when R ₁ is a methyl group; and R ₂ represents a methyl group when R ₁ is a hydrogen atom. 1
-Represents a propenyl group or a 2,2-dichlorovinyl group. R ₃ represents a hydrogen atom or a fluorine atom. The polyfluorobenzyl ketone derivative represented by ()) is a novel compound. The present inventors have focused on the insecticidal activity and volatility of the polyfluorobenzyl ketone represented by the general formula I, and conducted an efficacy test. It has been found that the compound has excellent chemical stability and low toxicity to warm-blooded animals, and is suitable for this purpose. That is, the present invention, particularly in the field of clothing insect repellent, paradichlorobenzene, naphthalene, which has many problems in terms of safety and chemical stability for humans and livestock,
Since it provides an ideal room-temperature volatilizable active ingredient replacing conventional volatilizable pyrethroids and the like, its practical merits are great.

The following are examples of compounds used as active ingredients in the present invention. Compound 1

Embedded image 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropyl-2 Compound 2

Embedded image 2,2,3,3-tetramethylcyclopropyl-2 ',
3 ', 4', 5 ', 6 Compound 3

Embedded image 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropyl-2 ', Compound 4

Embedded image 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropyl-2 Compound 5

Embedded image 2,2,3,3-tetramethylcyclopropyl-2 ',
3 ', 5', 6'-te Compound 6

Embedded image 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropyl-2 ',

The above-mentioned compound can be prepared, for example, by the following formula II according to a general method for producing ketones.

Embedded image (Wherein, R ₃ represents a hydrogen atom or a fluorine atom; X represents a halogen atom.) A Grignard reagent obtained by reacting a polyfluorobenzyl halide represented by the following formula with a magnesium metal:

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methyl group when R ₁ is a methyl group, and a 2-methyl-1-propenyl group, and 2,2- when R ₁ is a hydrogen atom. Represents a dichlorovinyl group, and Y represents a halogen atom.). The reaction is carried out in a suitable solvent, if necessary, in the presence of a metal salt or a metal complex catalyst, if necessary, with cooling. In the compound of the formula I, when R ₁ is a hydrogen atom, optical and geometric isomers based on the steric structure of the acid moiety exist, and these alone and in mixtures are encompassed in the present invention.

Next, a synthesis example of the compound used in the present invention will be described.

[0009]

[Synthesis Example 1] Metal magnesium 0.8 in a three-necked flask
g, 20 ml of anhydrous ether and a piece of iodine,
After adding a few drops of 2,3,4,5,6-pentafluorobenzyl bromide, the reaction was started by heating to 40 ° C.
While stirring at this temperature, 8.35 g of 2,3,4,5,6-pentafluorobenzyl bromide was added to anhydrous ether 2
The solution dissolved in 0 ml was dropped over about 30 minutes. After refluxing for another hour, the flask was cooled with ice, 0.1 g of cuprous chloride was added, and 5.97 g of 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid chloride was dried. What was dissolved in 10 ml of ether was gradually dropped and stirred. After stirring overnight, the reaction solution was poured into 5% hydrochloric acid and extracted twice with ether. The organic layer was washed with an aqueous sodium carbonate solution and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography to give 2,2-dimethyl-3.
-(2-methyl-1-propenyl) cyclopropyl-
7.5 g of 2 ', 3', 4 ', 5', 6'-pentafluorobenzyl ketone (compound 1) was obtained.

[0010]

[Synthesis Example 2] Metal magnesium 0.8 in a three-necked flask
g, 20 ml of anhydrous tetrahydrofuran and a piece of iodine were added, a few drops of 2,3,4,5,6-pentafluorobenzyl bromide were added, and the mixture was heated to 40 ° C. to start the reaction. 2,3,4,5,6 while stirring at this temperature
A solution of 8.35 g of pentafluorobenzyl bromide in 20 ml of anhydrous tetrahydrofuran was added dropwise over about 30 minutes. After refluxing for an additional hour, the flask was ice-cooled, 0.1 g of cuprous chloride was added, and 5.12 of 2,2,3,3-tetramethylcyclopropanecarboxylic acid chloride was added.
g in 10 ml of anhydrous tetrahydrofuran was gradually added dropwise and stirred. After stirring overnight, the reaction solution was poured into 5% hydrochloric acid and extracted twice with ether. The organic layer was washed with an aqueous sodium carbonate solution and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography to give 2,2,3,3-tetramethylcyclopropyl-2 ', 3', 4 ', 5',
5. 6'-pentafluorobenzyl ketone (compound 2)
8 g were obtained.

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 the characteristic of high volatility compared to conventional pyrethroids, and is particularly excellent when used as a so-called transpiration insecticidal, which is volatilized by a suitable heating element or transpiration promoting aid or at room temperature, as an insect repellent. Is obtained. Since the compound of the present invention also exerts a repellent effect at a low concentration, it can be expected to have a wide range of insecticidal and insecticidal effects against sanitary pests such as flies, mosquitoes, cockroaches, indoor dust mites, and clothing pests. Examples of the suitable heating element include an electric heater and a chemical heating element (for example, a composition composed of sodium sulfide and carbon, a composition composed of salt, iron, carbon, a hydrous salt of sodium metasilicate, quick lime, etc.). When water or air is brought into contact with these substances, heat is generated.), And as the evaporation aid, sublimable substances such as adamantane, cyclododecane, trimethylene norbornane and the like can be mentioned. In addition, the insecticide for transpiration, the carrier used for the insect repellent is not particularly limited,
For example, pulp mat, woven fabric, non-woven fabric, polyethylene,
Plastic molded articles such as polypropylene, porous glass materials, and the like can be given.

The compound of the present invention may be added to N-octylbicycloheptenedicarboximide (trade name: MGK-26).
4), a mixture of N-octylbicycloheptenedicarboximide and an aryl sulfonate (trade name: MGK-
5026), a synergist such as sinepirin 500, octachlorodipropyl ether, piperonyl butoxide may be added.

Also, other insecticides such as organophosphorus agents such as fenitrothion, DDVP and diazinon, NAC,
MTMC, BPMC, carbamates such as PHC, pyrethrin, allethrin, phthalthrine, phenothrin,
By mixing conventional pyrethroid insecticides such as permethrin and empentrin, or fragrances, deodorants, bactericides, etc., a multipurpose composition with excellent efficacy can be obtained, labor savings and a synergistic effect between drugs are also expected. It can be done.

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

[0015]

Example 1 0.3 g of the compound (1) of the present invention and 0.1% of a fragrance were added.
01 g was 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.

[0016]

Example 2 0.03 g of the compound (2) of the present invention, 0.15 g of sinepiline 500 and 0.01 g of dibutylhydroquinone (DBHQ) were impregnated in a cardboard sheet having a thickness of 2 mm, a length of 35 mm and a width of 22 mm to prevent insects. I got a mat.

[0017]

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 added to 00 parts by weight to obtain an insect repellent for clothing.

[0018]

Test Example 1 Efficacy Test by Transpiration The insect repellent mat for clothing prepared in Example 1 was housed in a plastic case, and suspended in a 600-liter closet. Immediately after the start of the test and 6 months later, the first instar larva of iga 10
A glass ring of 4 cm in diameter and 2 cm in width (covered on both sides with a wool cloth) in which the animals were released was placed in a closet.
After 1 day, 7 days later, the mortality was observed, as shown in Table 1.

[0019]

[Table 1] In the above Table 1, the control compound pyrethroid A is represented by the following formula (A)

Embedded image Is a commercially available pyrethroid.

As a result of the test, the compound of the present invention showed an insecticidal and insecticidal effect more than the control compound pyrethroid A against the harmful larva of clothing pests, and its volatility and efficacy are most suitable as insecticides and insecticides for clothing. It was confirmed that. It was similarly effective against other clothing pests such as burrowing beetle, pitted beetle, kioga and zyutanga, and sanitary pests such as flies and mosquitoes.

[0021]

Test Example 2 Stability Test for Metal A few drops of a reagent agent were dropped on the center of a copper plate having a size of 2 cm × 5 cm, and the copper plate was placed in a glass pot.
It was left in a constant temperature room at 0 ° C. Three days later, the surface of each copper plate was observed.

[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, unlike the control pyrethroid A, does not deteriorate due to the action of metal, and is used not only in a closet but also in various use scenes such as equipment and exhibition rooms. It was confirmed that it could be used without any problems.

[0023]

The compound of the general formula I used in the present invention has normal volatility, high insecticidal and insect repellent effects, low toxicity to warm-blooded animals, and chemical stability (less susceptible to metals). And insecticides and insect repellents having the same.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A01N 35/02

Claims (2)

(57) [Claims] 1. The following formula 1 (Wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methyl group when R ₁ is a methyl group, and a 2-methyl-1-propenyl group, and 2,2- when R ₁ is a hydrogen atom. An insecticide or insect repellent, which comprises a polyfluorobenzylketone derivative represented by any one of a dichlorovinyl group and R ₃ represents a hydrogen atom or a fluorine atom. 2. The following formula I (Wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methyl group when R ₁ is a methyl group, and a 2-methyl-1-propenyl group, and 2,2- when R ₁ is a hydrogen atom. Wherein R ₃ represents a hydrogen atom or a fluorine atom.) A polyfluorobenzyl ketone derivative represented by the formula: