CH677717A5 - - Google Patents

Description

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

CH 677 717 A5

description

The invention relates to a method for controlling insects and / or mites, wetGhes comprises the evaporation of the active ingredient without heating.

Although various insecticidal and / or acaricidal agents are known to date, organophosphorus insecticides such as dichlorvos ((CH30) 2P (0) 0CH = CCl2) are isolated examples of agents for a method for controlling insects and / or mites where the active ingredient is actually evaporated without heating. As the only example of the use of a pyrethroid compound, an insecticide with low toxicity, a method is known in practice in which (1-ethynyl-2-methyl-2-pentenyl) chrysanthemum is used to control pests in clothing.

If it is in a relatively small space, such as a chest of drawers or a drawer, (1-ethynyl-2-methyl-2-pentenyl) chrysanthemum shows the corresponding effect. However, as long as it is not used in a fairly large amount, this agent is not necessarily effective for pest control in extensive rooms, such as rooms, pantries, cupboards, warehouses, vehicles, ships, airplanes, stores, cattle houses, stables, drainage systems or sewers. This agent should also be used in large quantities to achieve a long-term effect.

Vaporizing the active ingredient by intensive heating is sometimes useful for increasing its effectiveness. However, saving energy is advisable to protect the environment. If an active ingredient can be evaporated without heating, it is possible to save valuable energy. Furthermore, dangers such as burns or fire, caused by the heating element or the heat generator to evaporate the active substance, can be prevented.

The invention is therefore based on the object of providing a method for controlling insects and / or mites both in extensive and relatively closed spaces and in open spaces, which comprises the vaporization of an active ingredient without heating.

This problem is solved by the surprising finding that 3- (2,2-dichloroethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid 1-ethynyl-2-methyl-2-pentenyl ester (compound I) of the formula

C2H5

CH,

V_c / o

/ \ »H CH-O-C-CH- v

# / \

H3C CH3

ycn = cci2

• .CH

CD

HC1

provides the best result among numerous and well-known insecticides and acaricides.

The insecticidal and acaricidal activity of compound I is described in JP-B 5 542 045. It has now surprisingly been found that mere evaporation of this compound without heating leads to a high initial activity against insects and / or mites and that it lasts for a long period of time.

The term "without heating" used here means ordinary temperature (without heating or cooling), namely a temperature up to 30 ° C, but above 0 ° C.

The method of the present invention is effective against various insect pests and mites. Above all, it is effective against disease-borne vermin, wood pests and vermin in food and in the household. It is particularly effective against infectious and household pests.

Specific examples of insect pests and mites to which the method of the present invention can be applied are described below.

- Lepidoptera:

Plodia interpunctella (dried fruit moth)

- Diptera:

Culex spp. (common mosquito), Anopheles spp. (Malaria mosquitoes), Aedes spp., Muscidae (houseflies), Drosophiiidae (fruit flies), Psychodidae (butterfly mosquitoes), Chironomidae (swarm mosquitoes), Calllphoridae (blow flies), Sarcophagidae (flesh flies), Simuliidae (Stingflies mosquitoes), Tabidae mosquitoes (Tabida mosquitoes), Tabida mosquitoes (Tabida mosquitoes), Tabida mosquitoes (Tabida mosquitoes), Tabida mosquitoes (Tabida mosquitoes), Tabida mosquitoes (Tabida mosquitoes) Biting flies)

- Coleoptera:

Sitophilus zeamais (corn beetle), Callosobruchus chinensis (bean beetle), Tribollum castaneum (red flour beetle), Anoblldae (knock and beetle beetle), Lyctidae (wood flour beetle), Paederus fuscipes

- Dictyoptera:

Blattella germanica (German cockroach), Periplaneta fuiiginosa (smoky brown cockroach), Periplaneta americana (American cockroach), Periplaneta brunnea (brown cockroach), Blatta orientalis (cockroach)

2nd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

OH 677 717 A5

- Hymenoptera:

Formicidae (ants), Bethylidae (Bethylid wasps)

-Siphonaptera:

Pulex iritans

-Anopiura:

Pedicuius humanus capitis (head louse), Pthirus pubis (crab louse)

- Isoptera:

Reticulitermes speratus, Coptotermes formosanus (Formosa termites)

-Acarina:

House dust and food mites, e.g. Acaridae, Pyroglyphidae and Cheyletidae, Ixodidae, e.g. Boophilus microplus and Dermanyssidae.

A carrier is not absolutely necessary to control insects and / or mites by evaporating Compound I. However, compound I is usually used after application to a suitable carrier.

Specific examples of adsorbent carriers used for this purpose are filter paper, cardboard, cellulose, resins such as e.g. Polyethylene, polypropylene or polyvinyl chloride, ceramics, asbestos, glass fibers, carbon fibers, chemical fibers, natural fibers, nonwovens (cotton linters), porous polymer films, porous glass materials or metal disks (e.g. aluminum shells). These carriers with the compound I applied can be used in any embodiment. If synthetic resins are used as carriers, their formability can be improved by adding a plasticizer (e.g. dioctyl phthalate).

However, a carrier is not always necessary. If an object made of the materials described above is present in a room with insects and / or mites to be controlled, it is sufficient to apply compound I to this object.

The effectiveness of the evaporation can be further increased by adding easily sublimable materials, such as adamantane, cyclododecane or trimethylnorbornane, as an aid to promoting evaporation.

It is also possible to improve the effectiveness by using compound I in a mixture with known synergists which are active together with allethrin and pyrethrins. Specific examples of pyrethroid synergists are a- [2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluo [(piponylbutoxide), N- (2-ethylhexyl) bicyclo [2.2, 1] hepta-5-en-2,3-dicarboxyimide (MGK-264®), octachlorodi-isopropyl ether (S-421®) or Synepirin-500®.

The effectiveness of Compound 1 can be improved when used in conjunction with antioxidants and ultraviolet absorbers to increase the stability to light, heat and oxidation. Specific examples of antioxidants are 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert. -butylphenol, 2,2'-methylenebis (6-tert-butyl-4-methyl-phenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis ( 6-tert-butyl-3-methylphenol), 4,4'-thiobls (6-tert-butyl-3-methylphenol) and dibutylhydroquinone (DBH). Specific examples of ultraviolet absorbers are phenol derivatives such as e.g. BHT, bisphenol derivatives, arylamines, e.g. Condensation products between phenyl-a-naphthylamine, phenyl-β-naphthylamine or phenetidine and acetone and finally benzophenone compounds.

Compound 1 can be mixed with dyes, e.g. Allylaminoanthraquinone, 1,4-diisopropyla-minoanthraquinone, 1,4-diaminoanthraquinone, 1,4-dibutylaminoanthraquinone or 1-amino-4-anilinòan thrachinone and fragrances can be used for vaporizable compositions.

If necessary, additives such as fatty acid esters (e.g. isopropyl myristate, isopropyl palmitate and hexyl laurate) or organic solvents (e.g. isopropanol and deodorized kerosene) can be used to apply the compound I to a carrier in order to reduce the viscosity and facilitate impregnation.

The carrier with the applied Compound I described above can then be used by evaporating Compound I without heating. The result is a high level of insecticidal and / or acaricidal activity, not only if it is in a small but also in a larger room (e.g. room, pantry, cupboard, warehouse, vehicle, ship, plane, storage, cattle shed, stable, drainage system or Sewer) is used.

In the process of the present invention, the amount of Compound I to be used is not critical. It should be determined taking many factors into account. These are e.g. Concentration of compound I, method of preparation, type and time of use, ambient temperature and humidity, type and size of the room, whether the room is open or not, whether natural or artificial air currents exist in the room or not, the type of insects or mites to be controlled and spreading the insects or mites. However, compound I is usually used in amounts of 1 mg / m3 to 500 g / m3, preferably from 10 mg / m3 to 5 g / m3. This is only a rough guide, and Compound I can also be used outside of this area as needed.

The insecticidal and / or acaricidal effectiveness of the method of the present invention can be improved by an artificial draft of a motorized fan (e.g. electric fan) or air conditioning or by natural wind, so that the method in a larger

3rd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

CH677717 A5

Space can be applied.

Compound I can e.g. according to the method described in JP-B55-42 045. Because of the asymmetric carbon atoms in the alcohol and acid moiety there are optical isomers of compound I. There are also geometric isomers of the cyclopropane ring of the acid unit. Some of them are shown in Table I. Of these isomers, compounds I-A, I-B and I-C are more effective than the other isomers.

Table I

connection

Configuration of the

Configuration of the

Alcohol unit

Acid unit I-A

S

1 R-trans t-B

S

1RS-trans

I-C

RS

1 R-trans

1-D

RS

1RS-cis l-E

RS

1 RS-cis, trans

The following reference example, the manufacturing and experimental examples serve to illustrate the present invention and are not intended to limit the scope thereof.

Reference example

Connection I-A is established as follows:

0.50 g (1S) -1-ethynyl-2-methyl-2-pentenol (described in JP-B-63-52 615) is dissolved in dry toluene and 0.50 g pyridine is added. 0.90 g of (1 R) -trans-3- (2,2-dich! Ora-thenyl) -2,2-dimethylglycopropanecarboxylic acid chloride (the corresponding carboxylic acid is described, for example, in JP-A-62-253 398 described). The solution obtained is stirred overnight at room temperature. After adding water, the reaction mixture is extracted with toluene. The organic phase is washed successively with dilute aqueous hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution. The phase is then dried over anhydrous sodium sulfate. The dried phase is filtered and concentrated to a residue. After purification of the residue by chromatography on a silica gel column (eluent: hexane / ethyl acetate, 10/1), 1.05 g of (1R) -trans-3- (2,2-dichloroethenyl) -2,2-dimethyl- cyclopropanecarboxylic acid (1S) -1-ethynyl-2-methyl-2-pentenyl ester (compound IA) in a yield of 83%.

n2 ° j5: 1.5063

[a] 24; -7.2 ° (dirnethyl ether, c = 0.53).

Manufacturing example 1

100 mg of compound I are dissolved in a suitable amount of acetone. The solution is evenly distributed on filter paper with an area of 10 cm2 and a thickness of 0.3 cm. To remove the acetone, the paper is air dried and a composition is obtained from which the active ingredient can be evaporated without heating (hereinafter referred to as a non-heating vaporization).

Manufacturing example 2

200 mg of compound I and 100 mg of BHT are dissolved in a suitable amount of acetone. The solution is applied evenly to filter paper with an area of 10 cm x 15 cm and a thickness of 0.3 cm. To remove the acetone, the paper is air-dried and a preparation that can be vaporized without heating is obtained.

Manufacture example 3

600 mg of compound I are dissolved in a suitable amount of acetone, which is absorbed evenly by a filter paper of size 10 cm × 15 cm. To remove the acetone, the paper is air-dried and a preparation that can be vaporized without heating is obtained.

4th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

CH 677 717 A5

Manufacturing example 4

200 mg of compound I are dissolved in a suitable amount of acetone. The solution is filled into an aluminum bowl with an inner diameter of 9 cm so that the solution is evenly distributed on the bottom. To remove the acetone, it is dried in air and a preparation which can be vaporized without heating is obtained.

Manufacturing example 5

250 mg of compound I and 250 mg of polyethylene glycol are dissolved in a suitable amount of acetone. A carrier fabric for electric smoking mats (a disc formed from a mixture of fibers made of cotton linters and cellulose) with a size of 10 cm x 30 cm and a thickness of 0.28 cm is evenly impregnated with this solution. To remove the acetone, the mat is air-dried and a preparation that can be vaporized without heating is obtained.

Manufacturing example 6

65 parts by weight of powdered PVC are mixed with 30 parts by weight of the plasticizer dioctyl phthalate. The mixture is melted at 150 ° C. This thermoplastic resin is mixed with 5 parts by weight of compound I, and the resulting mixture is thoroughly kneaded in a closed system. The kneaded mixture is injection molded into a 5 cm x 6.5 cm disc and 0.5 cm thick and cooled to obtain a preparation that can be vaporized without heating.

In the following experimental examples, the compounds of the invention are designated according to Table I; the comparison compounds are designated in accordance with Table II.

Table II

connection

Chemical name

Remarks

(A)

[(RS) -3-AIIyI-2-methyl-4-oxocycIopent-

Bioallethrin

2-enyl] (1 R) -trans-chrysanthemate

(B)

[(RS) -1-ethynyl-2-methyl-2-pentene

Empenthrin

nyl] (1R) -cis, frans chrysanthemum

(C)

(2,2-dichlorovinyl) dimethyl phosphate

Dichlorvos

Experimental example 1

The following test is carried out with an aluminum shell from preparation example 4. The amount of active ingredient is adjusted to 0.005 mg / aluminum dish.

20 female houseflies (Musca domestica, CSMA strain) are placed in a polyethylene container (diameter 9 cm, height 4.5 cm). Then the upper part of the container is covered with a nylon mesh with a mesh size of 1 mm. The container is closed with the aluminum shell described above, so that the treated surface of the shell faces the inside of the container. The nylon net serves to avoid direct contact of the insects with the treated surface. After 120 minutes at 27 ° C, the aluminum shell is removed and water and food are given to the insects. After 24 hours, the dead and live animals are counted to determine mortality (two repetitions).

Table III shows the results.

Table III

connection

Mortality (%)

l-A

100

I-B

100

I-C

100

(A)

0

(B)

2.5

(O)

5

untreated

2.5

5

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

CH677 717 A5

Experimental example 2

A filter paper according to production example 1 is used, but the amount of active ingredient is 3.4 mg / filter. This becomes free-floating in a glass chamber of 0.34 m3 (70 cm cubes) with a thread that is 10 cm from the middle of the ceiling of the glass chamber hanging down, attached. The amount of active ingredient is 10 mg / m3; the room temperature is 25 ° C.

After 30 minutes, 20 adult female common mosquitoes (Culex pipiens pallens) are added to the chamber. 60 minutes later, the insects destroyed are counted to determine the appropriate percentage (two repetitions).

Table IV shows the results.

Table IV

Connection destroyed (%)

l-A

100

I-B

100

I-C

100

(A)

0

(B)

55

(C)

65

untreated

0

Experimental example 3

A preparation on filter paper according to Production Example 3 is cut into six equal parts with a size of 5 cm x 5 cm (amount of active ingredient 100 mg / filter paper piece).

20 adult Tyrophagus putrescentrae are placed in a petri dish with a diameter of 9 cm and a hell of 2 cm together with food. The opening of the petri dish is covered with a nylon mesh with a mesh size of 1 mm. The piece of filter paper mentioned above is placed on the nylon mesh and the petri dish is closed with another petri dish of the same size. The arrangement thus obtained is left to stand at room temperature (30 ° C.) and a humidity of 75%. After 24 hours, the dead and live animals are counted to determine mortality (two repetitions).

Table V shows the results.

Table V

connection

Mortality (%)

i-A

100

I-B

100

l-c

100

untreated

7.5

Experimental example 4

An experiment to determine the residual effectiveness is carried out with a carrier fabric for smoking mats according to Production Example 5 (amount of active ingredient 250 mg / mat).

In a peer-grady chamber of 6.1 m3 (183 cm cubes), the mat is suspended freely with a 20 cm long thread that hangs from the middle of the ceiling. The mat is left in this position for 9 hours at room temperature (25 ° C). The amount of active substance is 41 mg / cm3. 9 hours later, 100 adult houseflies (Musca domestica) are placed in the chamber. The number of houseflies destroyed in 30 minutes is counted to determine the corresponding percentage.

After the experiment, the mat is removed from the chamber and suspended with a thread floating in a cardboard chess egg (30 cm x 28 cm x 36 cm). The box is left in a room at 25 ° C.

The same experiment is repeated with the mats stored in the corrugated cardboard boxes 1, 3, 5, 8 and 12 weeks after the initial experiment.

Table VI shows the results.

6

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

CH677717A5

Table VI

Connection destroyed (%)

to start after after after after

1 week 3 weeks 5 weeks 8 weeks 12 weeks l-A

~ L

o o

100

100

100

100

100

(A)

0

3rd

1

3rd

2nd

2nd

(B)

100

100

100

80

42

22

(C)

100

100

76

44

19th

3rd

untreated

0

2nd

T

3rd

0

1

Claims (5)

Claims 1. A method for controlling insects and / or mites, characterized in that 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid-1-ethynyl-2-methyl-2-pentenyiester is evaporated without heating. 2. The method according to claim 1, characterized in that the isomer (1 R) -trans-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid- (1 S) -1 -äthinyI-2-methyi -2-pentenyiester is used. 3. The method according to claim 1, characterized in that the isomer (1 RS) -trans-3- (2,2-di-chloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid- (1S) -1-ethynyl-2-methyl- 2-pentenyl ester is used. 4. The method according to claim 1, characterized in that the isomer (1 R) -trans-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid (1RS) -1-äthinyi 2-methyl-2 -pentenyiester is used. 5. The method according to any one of claims 1 to 4, characterized in that the temperature is 0 ° C to 30 ° C. 7