DK174607B1 - Use of pesticides and methods of controlling cockroaches - Google Patents

Description

DK 174607 B1

The present invention relates to a novel use of pest control agents and methods for controlling cockroaches using the (S) - (+) enantiomer of hydroprene.

Hydroprene is ethyl (2E, 4E) -3,7 / l-trimethyl-2,4-dodecadienoate. It is known to have juvenile hormone activity on insects, e.g., cockroaches such as Blattella germanica (see, e.g., J. Econ. Entom 68, 1975, p.

46-48).

10 In the hydroprene, there is an asymmetric carbon atom at C-7, and accordingly there are R and S enantiomers of the compound. In J. Agric. Food Chem. 26, 1978. pp. 542-550, comparative juvenile hormone activity tests are described with (S) - (+) hydroprene, (FO - (-) - hydroprene and its racemic mixture on Aedes 15 aegyptl, Galleria meilonella, Tenebrio molitor, Musca domestica and Heliothls virescens These tests showed that the (S) - (*) enantiomer exhibited about twice as much activity on these insect species as the racemic mixture.

20 Surprisingly, it has now been found that (S) - (+) hydroprene exhibits an unexpectedly superior juvenile hormone activity on cockroaches relative to racemic hydroprene.

Thus, one aspect of the invention is a method of controlling 25 cockroaches, wherein a method of placing a cockroach propagation inhibitory amount of (S) - (+) hydroprene at the site affected by this population. In this context, the term "(S) - (+) -hydroprene" means.

30 hydroprene, which contains substantially more than 50% by weight of the (S) - (+) enantiomer. The hydroprene used according to the invention is preferably comprised mainly of (S) - (+) hydroprene. Preferably, the hydroprene contains less than 10% by weight, preferably less than 5% by weight of the (R) enantiomer, and is preferably substantially free of the (R) enantiomer (i.e., contains less than 2% by weight of the (R) enantiomer).

In another aspect, the invention relates to the use of a pest control agent containing: a) (S) -C ") - hydroprene, b) a diluent and c) when the diluent is a solvent, at least one adjuvant selected from a propellant, a surfactant, and a thickener for controlling cockroaches.

In the present context, the term "diluent" refers to a liquid or solid agriculturally acceptable material which can be added to the active ingredient to bring it into a mold for easier or improved application. It comprises carriers and solvents and may be, for example, calcium carbonate, talc, clay, diatomaceous earth, resins (e.g. polyvinyl chloride, polyester urethane, ethylene urethane, ethylene vinyl acetate, polypropylene and polyethylene), xylene, a petroleum solvent (including nigroin, benzene, a hydrocarbon such as pentane, hexane, octane), an alkanol such as isopropanol, a chlorinated hydrocarbon (e.g., CH 2 Cl 2, CCl 3 CH 3), a glycol monoalkyl ether, water and the like.

20

The term "propellant" means an agriculturally acceptable liquid gas which, in itself, exerts a pressure in a container provided with a valve and comprising a pest control agent which forces the contents out of the container when the valve is actuated.

25

The term "surfactant" refers to an agriculturally acceptable material which discloses the pesticide emulsifiers, dispersibility, wettability, dispersibility or other surface modifying properties.

30

The term "thickening agent" refers to a material which increases the viscosity of a liquid.

(S) - (*) - Hydroprene can be prepared in a manner known per se from the racemate or by synthesis from an optically active starting material.

3 DK 174607 B1 (S) - (+) - Hydroprene exhibits a unique combination of properties over other juvenile hormone active substances, which makes it remarkably effective as a cockroach population control agent.

5

It is persistent in the environments where cockroaches reside. It is sufficiently volatile to migrate from one surface to another, thereby penetrating the habitats of the cockroaches, distributing therein and remaining accessible to the cockroaches located there.

Furthermore, the (S) - (+) - hydroprene is effective in inducing sterility in cockroaches and also has other juvenile hormone active properties. This property is essential for effective cockroach eradication. Finally, the (S) - (+) - hydroprene has a high activity level. Its improved activity in relation to racemic hydroprene means that it is much more economical to use and cause less pollution of food and human habitation than the racemic mixture.

In this regard, substantially pure (S) - (+) - hydroprene has been found to combat in the laboratory the propagation of the German 20 cockroach at distribution levels as low as a few tenths of micrograms per gram. m2. Higher distribution levels may be needed ten! control of other cockroaches such as the American cockroach (Periplaneta americana) and the Oriental cockroach (Blatta orientalis). When used in practice, higher distribution levels are also used than in the laboratory. Thus, depending on the nature of the habitat surfaces, cockroach species, application method, etc., the level of distribution of (S) - (+) hydroprene in the practical application is conveniently in the range of 0.3-40 mg / m2, preferably 3-30 mg / m2.

30 (S) - (*) - Hydroprene is typically applied in a form of composition suitable for use in cockroach control. Examples of compositions suitable for such use include aerosols (in aerosol dispensers or atomizers), cockroach baits, cockroach powders, emulsifiable concentrates, spray for immediate use, ultra-low volume spray, odor plates and cockroach strips, gradually releasing the active substance; such preparations can be obtained in the usual manner. The preparation is suitably applied to cockroach habitats, which include human housing, food storage or manufacturing sites, and industrial plants.

For use of (S) - (+) - hydroprene in aerosol form, the active ingredient is conveniently formulated together with an inert, volatile solvent and a propellant.

Examples of suitable volatile solvents are chlorinated alkanes such as methylene chloride or 1,1,1-trichloroethane.

10

Examples of suitable propellants are low boiling alkanes such as propane or butane or fluorinated hydrocarbons.

For use of the (S) - (*) hydroprene in spray form, for example as an emulsifiable concentrate or spray for immediate use, the active ingredient is conveniently formulated together with an emulsifier and solvent.

Examples of suitable emulsifiers are sorbitol, fatty acid esters, 20 polyethoxyated fatty acid esters of alcohols or phenols, and calcium dodecyl benzoate.

Examples of suitable solvents are aromatic hydrocarbons such as xylene.

25

Solid compositions such as powders or powders include (S) - (*) - hydroprene and a solid support.

Examples of suitable solid supports are calcium carbonate, diatomaceous earth and 30 clays.

(S) - (+) - Hydroprene can also be applied in solid form by evaporation from a solid support, for example in the form of odor plates and strips, especially the latter. Such formulations contain (S) - (+) -hydroprene, a polymer and preferably a plasticizer.

5 DK 174607 B1

Examples of suitable polymers (resins) are polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylics, nylon, especially polyvinyl chloride.

For use of the (S) - (*) hydroprene in bait form, the active ingredient is suitably formulated with a foodstuff. Suitable foodstuffs for use in such baits are cornmeal, dog food and corn syrup.

10 (S) - (+) - The hydroprene can also be used in microencapsulated form. Such microcapsules are conveniently of the gelatin or nylon type; Suitably, compositions comprising microcapsules contain a thickener such as xanthan gum.

(S) - {+) - The hydroprene compositions may contain conventional additives such as UV stabilizers, heat stabilizers, antioxidants and pigments. They may also contain conventional insecticides such as organophosphates and pyrethroids to provide an initial decline in a portion of the cockroach population or other insects at the site of application. They are manufactured in a manner known per se. Suitable compositions usually comprise 0.01-80% by weight (S) - (+) - hydroprene.

Aerosols suitably comprise 0.01-10% by weight of emulsifiable 2g concentrates and ultra-low volume spray 0.3-80% by weight, immediate use 0.5-10% by weight, and cockroach bell chemo or strips 1-15% by weight (S) - ( +) hydroprene.

The invention is illustrated in more detail by the following examples. Parts are 30 parts by weight.

6 DK 174607 B1

Formulation Example

1. Aerosol

ABC

5 (S) - (*) - Hydroprene (100%) 0.021 0.064 0.1 CH 2 Cl 2 17.646 16.936 16.9 CC13-CH3 54.333 55 55

Propane / isobutane up to 483 kN / m2 28 28 28 2. Emulsifiable concentrate 10 (S) - (+) -Hydroprene (100%) 10

Antioxidant (butylated hydroxytoluene) 0.2

Emulsifier (polyoxyethylene sorbitol ester) 30.8

Solvent (aliphatic hydrocarbon) 59.0 3. Spray for immediate use (S) - (*) - Hydroprene (100%) 0.4

Water 91.86

Antioxidant (butylated hydroxytoluene) 0.44 Emulsifier (polyoxyethylene sorbitol ester) 2.0

Chelating agent (NaEDTA) 5.0

Buffering agent (citric acid) 0.3 4. Bait 25 (S) - (+) - Hydroprene (100%) 1.0 CH 2 Cl 2 5.0

Corn flour 94.0 DK 174607 B1 7 5. Powder (S) - (+) -Hydroprene (100%) 10/0

Ethylene glycol 4.5

Antioxidant (butylated hydroxytoluene) 0.5 5 Silica 85 T est 1

Atomizers containing 15 and 45 mg (S) - (*) hydroprene, respectively, formulated according to Formulation Examples 1A and 1B respectively, are discharged into an atomization chamber of 85 mJ. At the time of discharge 10, the chamber contained cigarette paper and three different test substrates (treated vinyl tiles, glass and unpainted veneer) spaced 1.8, 2.7 and 3.7 m from the nebulizer. This mist was allowed to settle for 20 minutes and the paper and substrates were removed. The papers were extracted and the extracts analyzed to determine the amount of (S) - (+) hydroprene (in µg / cm 2 substrate) deposited at the three distances. The deposits are in the ozone range of 0.005-0.053 µg / cm 2.

After removal from the chamber, the treated test substrates are placed in a laboratory under ambient conditions. Within 1 hour of the removal, 10-12 German cockroaches in the fifth or sixth stage are closed with each of the treated substrate surfaces. Feed, water and hiding place are provided.

The containers are inspected daily for the first ten days. At study times, feed and water are supplemented as needed. All 25 cockroaches that change skin to the adult stage are removed and sacrificed during the first ten test days (cockroaches in the last ten days of the last stage before skin change are not sensitive to juvenile active substances).

After day ten, the vessels are examined every seventeenth day and 30 following status information is noted.

8 DK 174607 B1

Total number of surviving cockroaches.

Each cockroach's adult or nymphal status.

Gender of all adult cockroaches.

Possible juvenile hormone effect on adult cockroaches.

5 Eggs to be worn.

The viability of dropped eggs.

Proven F. | progeny.

The final reading is made. week 12 after the ten-day period after treatment.

10 Based on these readings, the treatments for the total juvenile hormone effects are scored.

The (S) -hydroprene total juvenile hormone response is significantly better than the standard racemic mixture used. More substantially, the results of the readings on the total number of 15 F ^ nymphs and F ^ nymphs obtained per female cockroach, which has had the opportunity to mate and have cubs, that the (S) - (+) -hydroprene propagating activity of ca. seven times higher than the racemic mix.

Test 2 20 Serial dilutions of (S) - (+) hydroprene or racemic hydroprene in acetone are applied to glass and veneer plates by dripping the solution onto the plates from a cannula. The plates are used as floors in test cages.

Each cage is provided with hiding places, water and feed and 50 German cockroaches in the fourth stage. The cages are kept at 27 ° C, 16 hours light cycle 25 and 50% relative humidity for approx. Two months. The control efficacy is judged on the basis of morphological effects and 100% inhibition / reproduction. In these tests, the (S) - (*) hydroprene gave 100% control of propagation at a distribution of 0.1 µg / cm 2, whereas the lowest distribution which gave 100% control of propagation with racemic hydroprene, were 10 µg / cm2 on glass and 1 µg / cm2 on veneer.

Claims (11)

Use of a pesticide containing 5 a) (S) - (+) - hydroprene, b) a diluent and c) when the diluent is a solvent, at least one adjuvant selected from a propellant, a surfactant and a thickening agent. remedy, 10 for fighting cockroaches. Use according to claim 1, characterized in that the agent comprises 0.01-80% by weight (S) - (+) - hydroprene. 15 Use according to claim 1 or 2, wherein the agent is in aerosol form. Use according to claim 1 or 2, 20 wherein the agent is in spray form. Use according to claim 1 or 2, wherein the agent is in solid form. Use according to claim 5, wherein the agent is in the form of a bait. Use according to claim 5, wherein the diluent of the agent is a polymer and further comprises a plasticizer. Method for controlling cockroaches, characterized in that a cockroach propagation inhibiting amount of (S) - (+) - hydroprene is applied at the site affected by 35 cockroaches. DK 174607 B1 Process according to claim 8, characterized in that the distribution of (S) - (+) -hydroprene at the site is in the range 0.3-40 mg / m2. Process according to claim 8 or 9, characterized in that the (S) - (+) - hydroprene is applied in aerosol or spray form. Process according to claim 8 or 9, 10, characterized in that the (S) - (+) hydroprene is applied by evaporation from a solid support.