JPH02275809A - Insecticidal and miticidal method - Google Patents

Abstract

PURPOSE:To perform insecticidal and miticidal treatment in high initial effect and long-term sustained action by evaporating a specific insecticidal and miticidal agent under mild heating condition. CONSTITUTION:1-Ethynyl-2-pethyl-2-pentenyl 3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropanecarboxylate of formula is adsorbed to a proper carrier and evaporated under mild heating, i.e. heating at 50 to 100 deg.C. The evaporation effect can be increased by the addition of a sublimable substance such as adamantane and cyclododecane and the effect can be promoted by the mixed use of a synergist for pyrethroid. Furthermore, the effect can be stabilized by the addition of an antioxidant and an ultraviolet absorber. An especially excellent effect can be attained by the present method against hygienic vermin and disagreeable vermin living in a house.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is based on the formula (I) 1-ethynyl-2-methyl-2-pentenyl 8-(2,2-dichloroethenyl)-2,2 -dimethylcyclopropanecarboxylate (hereinafter referred to as compound (I)
). ) is evaporated under mild heating conditions.

<Prior art> Many insecticidal and acaricidal methods using insecticides and acaricides are known, but little is known about insecticidal and acaricidal methods that involve evaporating pyrethroid compounds under mild heating conditions. However, only a method using 1-ethynyl-2-methyl-2-pentenyl chrysanthemate is described in JP-A-56-75411 and the like.

<Problem to be solved by the invention> However, these insecticidal and acaricidal methods are not necessarily fully satisfactory, as they are not sufficiently effective or have problems with the sustainability of their efficacy over a long period of time. .

Means for Solving the Problems> The present inventors have developed an insecticidal and acaricidal method that transpires a compound under mild heating conditions, rather than methods that may cause burns such as smoke caused by combustion or transpiration caused by high-temperature heating. After careful consideration, we selected the following from among the countless known insecticides and acaricides:
In particular, they discovered compound (I) and completed the present invention.

Although it is stated in Japanese Patent Publication No. 55-42045 that the compound CI) has insecticidal and acaricidal activity, the present inventors have determined that the compound is suitable for an insecticidal and acaricidal method in which the compound is evaporated under mild heating conditions. It was discovered that this compound has both high initial effect and long-term sustainability, leading to the present invention.

・The weak heating conditions mentioned here are those that can be easily obtained using a chemical heating element such as a hand warmer or a heating element such as an electric heater.
This is under a temperature condition of 60°C to too'c.

The method of the present invention is effective against various types of pests and resident mites, but is particularly effective against sanitary pests, wood pests, food pests, unpleasant indoor pests, and the like. Among them, it is particularly effective against sanitary pests and unpleasant indoor pests.

Specific pests to be controlled are listed below.

Lepidopteran pests such as the snail moth, Diptera pests Culex, Anopheles mosquitoes, Aedes mosquitoes, house flies, insect flies, Chironomid flies, chironomids, black flies, nymphae, black flies, horseflies, stable flies Isocoleopteran pests such as the black weevil, red bean weevil, white beetle, grasshopper beetles, and rattle beetles such as the green beetle, the Japanese cockroach, etc. Reticopteran pests such as the German cockroach, black cockroach, American cockroach, brown cockroach, orbaceous cockroach, etc. Hymenoptera pests such as ants, ant beetles, etc. History of Hymenoptera Pests Human Flea Pests Pests Pests of the Pyramidium Human Flea, Isoptera Pests Pests Such as Pubic Lice Yamato Termite, House Termite etc. Acarinae Pest Mites, House dust mites such as house dust mites, black mites, house dust mites etc. When compound CI) is evaporated to kill insects or mites, compound CI) is usually adsorbed onto a suitable carrier before use.

Examples of adsorption carriers include papers such as filter paper and cardboard, valves, resins such as polyethylene, polypropylene, and vinyl chloride, ceramics, asbestos, glass fibers, carbon fibers, chemical fibers, natural fibers, nonwoven fabrics, and porous polymer films. Compound C
These carriers on which I) has been adsorbed can be used in any desired dosage form.

Note that the transpiration effect can be further enhanced by adding a sublimable substance such as adamantane, cyclododecane, or trimethylnorbornane as a transpiration-promoting aid.

In addition, α-[2-(2-butoxyethoxy)ethoxy]-4゜5-methylenedioxy-2-propyltoluene (hyheronyl butoxide), which is a synergist for pyrethroids,
N-(2-ethylhexyl)bicyclo(2,2,1)but-5-ene-2,8-dicarboximide (MGK
-264), octachlorodiisopropyl ether (S
-421), cinepirin 500, and other known synergists effective against allethrins and pyrethrins to enhance the efficacy.

In addition, by adding and using antioxidants and ultraviolet absorbers to increase stability against light, heat, oxidation, etc.
The efficacy can be stabilized. As an antioxidant,
For example, 2.2'-methylenebis(6-tert-butyl-4-ethylphenol), 2.6-tert-butyl-4-methylphenol (BHT), 2.6-tert-butylphenol, 2.2' -methylenebis(6-tert-butyl-4-methylphenol),
4.4-methylenebis(2,6-tert-butylphenol), 4.4'-butylidenebis(5-tert-butylphenol)
t-butyl-8-methylphenol), 4.4-thiobis(6-tert-butyl-8-methylphenol),
Examples of ultraviolet absorbers include phenol derivatives such as BHT, bisphenol derivatives or aryls such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, and condensates of phenetidine and acetone. Examples include amines and benzophenone compounds.

Also, allylaminoanthraquinone, l,4-diisopropylaminoandraquinone, 1゜4-diaminoanthraquinone, 1,4-dibutylaminoanthraquinone, l
- A pigment such as amino-4-anilinoanthraquinone and a fragrance for the transpiration composition may be used in combination.

When adsorbing compound (I) onto a carrier, fatty acid esters such as isopropyl myristate, isopropyl palmitate, and hexyl laurate, organic acids such as isopropyl alcohol, and deodorized kerosene are used as additives to reduce viscosity and facilitate impregnation. A solvent can be used if necessary.

The carrier adsorbed with compound CI) obtained as above can be used by evaporation under mild heating conditions, and can be used indoors, in storage, closets, warehouses, vehicles, ships, airplanes, stores, livestock sheds, etc. It exhibits particularly excellent insecticidal and acaricidal effects when installed in relatively closed areas such as inside drainage ditches and sewage ditches, but it is also sufficiently effective at killing insects and mites in more open areas such as outdoors. Can kill mites.

When heating the carrier on which compound (I) has been adsorbed, a heating element such as a petroleum benzine type warmer, a chemical reaction exothermic type warmer, a heater whose heating temperature is adjusted to 50 to 100°C, an incandescent lamp, a fluorescent lamp, etc. Lighting equipment such as electric lights and oil lamps can be used. In addition, heaters for electric mosquito repellent mats that are normally sold on the market are heated to about 160°C (no mat) (a part of the porous liquid-absorbing core is immersed in an insecticidal liquid, and the core absorbs the insecticidal liquid. The heater for the insect killing device (which heats the upper part of the insecticide) generates heat at about 180 to 160°C, but it can also be used in the present invention by appropriately modifying the electric resistance, the material of the heat generating part, the thermostat settings, etc.

A specific method of using a heating element includes, for example, a method in which a carrier adsorbed with compound CI) is made into a mat shape of an appropriate size to match the heating element, and this is placed on the heating element. , a no-mat method.

In addition, methods of using a body warmer or the like that utilize the heat of chemical reaction include mixing compound CI) into a heat generating agent or adsorbing compound (I) to the packaging material outside the heating element. .

Specific methods for using electric lights such as incandescent lamps and fluorescent lamps, and lighting equipment such as oil lamps as heating elements include, for example, applying compound CI) to the glass surface of the lamp or a part of the lighting equipment. Another method is to place a carrier adsorbed with compound (I) on or near the glass surface of a lamp and utilize conductive heat or radiant heat from the lamp.

In the insecticidal and acaricidal method of the present invention, when compound (I) is used, the amount to be used includes the concentration used, the type of preparation, the method of use, the timing of use, the temperature, humidity, the place and area of use,
The amount of the active ingredient of compound (I) is usually 0.1q~ per space, although it varies greatly depending on conditions such as the opening/closing status of the space used, the presence or absence of wind and airflow, the type and habitat of target pests and harmful mites, etc. 50II, preferably! η〜22
That's about it. However, these amounts can be increased or decreased depending on changes in the conditions of use described above, without regard to this range.

In the insecticidal and acaricidal method of the present invention, by stirring the air using artificial or natural wind from an electric fan such as an electric fan, an air conditioner, etc. and generating an air current, insecticide and acaricidal can be carried out over a wider area. I can do it.

In addition, compound (I) can be synthesized by the method described in Japanese Patent Publication No. 55-42045. Also,
As shown in Table 1, compound CI) has optical isomers due to the asymmetric carbon atoms on the alcohol side and acid side, and geometric isomers due to the cyclopropane ring on the acid side. Among these, CI) -A, ( :I)-B and CI)-C
is more effective.

Table 1 <Examples of Actual Cells> The present invention will be explained in more detail below using formulation examples and test examples, but the present invention is not limited to these examples.

First, a formulation example will be shown.

Formulation Example 1 Compound (I) 80 I19 was dissolved in an appropriate amount of acetone and impregnated into a 4 cm x 4 cm, 0.14 cm thick valve plate, and the acetone was air-dried to obtain a mild heating type transpiration agent. Ta. By fixing this to the surface of a petroleum benzene type body warmer that generates heat at 50 to 70°C, a mild heating type insecticidal and acaricidal device was obtained.

Formulation Example 2 Compound (I) 50q and BHT20q were dissolved in an appropriate amount of acetone and impregnated on one side of a nonwoven fabric, and then the acetone was air-dried to obtain a mild heating type transpiration agent. By using this as the outermost bag of a heating element that generates heat at 50 to 70° C. by utilizing oxidation heat, a mild heating type insecticidal and acaricidal device was obtained.

Formulation Example 8 Compound (I) 80 q, octachlorodiisopropyl ether 40W9 and BHT8019 were dissolved in an appropriate amount of hexane, and a 8 cm x 8 eaIs thickness of 0.1 was prepared.
A weak heating type transpiration agent was obtained by impregnating a valve plate of 1.5 cm in diameter.

A heating element (e.g. body warmer) that heats this to 50-70℃
By pasting it on one side of the paper, a mild heating type insecticidal and acaricidal device was obtained.

Formulation Example 4 Compound CI) 0.4N and piperonyl butoxide 0.4N.
2F was commonly understood as acetone, and the total amount was 10 m. 0.5 cm of this solution was placed in a 2.5 cm x 1.5 cm, thickness 0
, 8 cytg of a base material for an electric mat (fibrils of a mixture of cotton linters and bulbs solidified into a plate shape) was uniformly impregnated to obtain a mild heating type transpiration agent. In addition, the heater part of the mat is 50 to io'c.
By fixing it to an electric mat heater that generates heat, a mildly heated insecticidal and mite killing device was obtained.

Formulation Example 5 A mild heat-type insecticide is produced by immersing the lower part of a porous liquid-absorbing core with a diameter of 0.9 cm and a length 7 side in an insecticidal solution containing Compound (I) l 00 q as deodorized kerosene IO-. ,
Obtained acaricide. This liquid-absorbing wick and insecticidal liquid were fixed to a no-mat heater in which a part of the heater generates heat to go-too degrees Celsius, and the upper surface of the liquid-absorbing wick could be heated, thereby obtaining a mild heating type insecticidal and mite killing device. .

Formulation Example 6 Compound CI) 50k,2,2-methylenebis(6-t
ert-butyl-4-ethylphenol) 101q 25 Mg of isopropyl myristate and kerosene 654 were mixed to obtain a homogeneous solution. This solution was mixed with 2.5 m×1.
A weak heating type transpiration agent was obtained by uniformly impregnating a 5 m long electric mat base material (fibrils of a mixture of cotton linters and bulbs solidified into a plate shape) with a thickness of 0.11 mm. By fixing the mat to an electric mat heater, in which a portion of the heater generates heat at 50 to 100°C, a mild heating type insecticidal and mite killing device was obtained.

Formulation Example 7 Compound CI) 50c uniformly containing 500 Ill
A transparent vinyl chloride sheet with m x 9 wounds and a thickness of 0.23,
By wrapping and fixing it around the surface of a household fluorescent lamp (for 100V, 20W), a mild heating type insecticide and acaricide can be obtained. Attach this lamp to a household fluorescent light stand,
By applying electricity and heating the vinyl sheet, it can be used as a mild heating type insecticidal and acaricidal device.

Formulation Example 8 Compound (I) 0. I and BHTo, 05F are impregnated into 2 g of diatomaceous earth to obtain a mild heating type transpiration agent.

This diatomaceous earth is uniformly mixed in an exothermic agent that generates heat to 50 to 100° C. by utilizing oxidation heat, and the mixture is packed in a Japanese paper bag to obtain a mildly heated insecticidal and acaricidal device.

Formulation Example 9 Compound CI) 50 ■, piperonyl butoxide 101
After dissolving 11g and 50IIIg of dibutylhydroquinone in an appropriate amount of acetone and impregnating one side of the nonwoven fabric, the acetone is air-dried to obtain a mildly heated transpiration agent. This is used as an inner bag for filling an exothermic agent that generates heat to 70 to 100° C. by utilizing oxidation heat, and the outside is covered with a cotton bag to obtain a mild heating type insecticidal and acaricidal device.

Next, a test example will be shown. In the following examples, compound (I) is indicated by the compound symbol in Table 1, and the compound used for comparison is indicated by the compound symbol in Table 2.

It was placed at the center of the bottom of Table 2, and 20 adult C8MA house flies (male/+=1/l) were released into the chamber. At this time,
The temperature of the heating element of the above-mentioned mild heating type insecticidal and acaricidal equipment is 50~
It was 70"C.

After 80 minutes, the test insects were transferred to a separate container and given water and food.
The survival rate was determined after 24 hours and the mortality rate was determined (2 repetitions).
.

The results are shown in Table 8.

Table 8 Test Example 1 A mildly heated insecticidal and acaricidal device obtained according to Formulation Example 2 (the dose of the active ingredient is 50 m/bag) was added to 0.84 i (70 m/bag).
Test Example 2 in a glass chamber for σ cubic) A mild heating type insecticidal and acaricidal device obtained according to Formulation Example 4 (
However, the following test was conducted using the active ingredient (dose of 10jIF/matsu).

50 adult female Culex mosquitoes were released6, 1 FF/(1
Install the above equipment at the center of the bottom of a beet gradation chamber (88cy++ cubic), and set the heater temperature to 90±1.
Electricity was applied so that the temperature reached 0°C.

The knockdown insects were investigated after 10 minutes had elapsed, and the knockdown insect rate was determined (2 repetitions).

The results are shown in Table 4.

Table 4: 0 tick equipment (active ingredient dose: 8011g/mat)
．． It was installed at the center of the bottom of an 84i (703 cubic) glass chamber.

Dermatophagoides
Two glass petri dishes (diameter 9 squares, height 2 m) containing 20 animals (E. farinae) and feed were placed at diagonal positions at the bottom two corners of the glass chamber.

At this time, the temperature of the heating element of the mild heating type insecticidal and acaricidal device was 60±10°C.

After 120 minutes, we checked whether the mites were alive or dead, and calculated the rate of dead and bitter mites (
2 repetitions).

The results are shown in Table 5.

Table 5 Test Example 8 Weak heating type insecticidal and acaricidal test example 4 obtained according to Formulation Example 8 A mild heating type insecticidal and acaricidal device obtained according to Formulation Example 5 was heated to 0.84n? The specimen was placed at the center of the bottom of a (70 cm cubic) glass chamber, and 20 adult German cockroaches (male/male = 1:1) were released into the chamber. At this time, the temperature of the heating element of the above-mentioned mild heating type insecticidal and acaricidal device is approximately 100
“It was C.

The number of knockdowns after 80 minutes was investigated and the knockdown rate was determined (2 repetitions).

The results are shown in Table 6.

Table 6 Test Example 5 A mildly heated insecticidal and acaricidal device obtained according to Formulation Example 6 was placed at the center of the bottom of a stainless steel cylinder with a diameter of 20 Cl1 s and a height of 806 nm, and electricity was applied until the heater temperature reached 50°.
I set it to be C. Diameter 4-1 height 12cr! g
Into a glass tube, 10 female Culex mosquitoes were placed, and two test tubes with both ends covered with nylon net (16 mesh) were fixed vertically using a pedestal in the center of the upper end of the cylinder. The updraft was allowed to pass through the tube. Twenty minutes after the test tube was installed, the test insects were collected together with the tube, and sugar water was given to the test insects. After 24 hours, the survival rate was determined to determine the mortality rate.

Even after collecting the test insects, the insecticide and acaricide devices continued to be energized and maintained at 50°C. 5 hours and 1 day after the start of electricity supply,
After 2 days and 4 days, the insecticidal test was repeated using adult female A. larvae placed in a glass tube using the same procedure as above, and each time the mortality rate after 24 hours was determined to investigate the residual effectiveness. .

The results are shown in Table 7.

Table 7 Reference Production Example (Compound (I)-A) Dissolve 0.5Of (is)-1-ethynyl-2-methyl-2-bentenol (Japanese Patent Publication No. 68-52615) in dry toluene, and dissolve 0.5Of of pyridine. added. Add (1R)-trans-8-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid chloride (the corresponding carboxylic acid is
898) was added and stirred overnight at room temperature. Water was added to the reaction solution, and the mixture was extracted with toluene.

The organic layer was washed successively with dilute hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and dried over anhydrous sodium sulfate. After filtering and concentrating, the residue was subjected to silica gel chromatography (f8 bathing medium; hexane:Sakuichi=1O:1)
The compound CI)-A, i.e. (IS)-1, was purified by
-ethynyl-2-methyl-2-pentenyl(1R)-trans-8-(2,2-dichloroethenyl)-2,2-
dimethylcyclopropanecarboxylic) 1.05F (
A yield of 83%) was obtained.

n2o" 1.5068 [α]24=-7.2° (dimethyl ether, C=0
．． 53) <Effects of the Invention> The insecticidal and acaricidal methods of the present invention are effective against various pests including sanitary pests and unpleasant indoor pests, not only in relatively closed places but also in more open places such as outdoors. It can be effectively used in any location.

Claims (4)

[Claims] (1) 1-ethynyl-2-methyl-2-pentenyl 8-
An insecticidal and acaricidal method characterized by transpiring (2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate under mild heating conditions. (2) 1-ethynyl-2-methyl-2-pentenyl 8-
An insecticidal and acaricidal method characterized by transpiring (2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate at 50°C to 100°C. (3) (1S)-1-ethynyl-2-methyl-2-pentenyl (1R)-trans-8-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate under mild heating conditions. An insecticidal and acaricidal method characterized by transpiration. (4) (1S)-1-ethynyl-2-methyl-2-pentenyl (1R)-trans-8-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate at 50°C to 100°C Insecticide characterized by transpiration with
Mite killing method.