DE2448452A1 - PESTICIDES AGENTS - Google Patents

Description

PATENT ANWALTSBÜRO TlEDTKE - BüHLING · "KlNNE TEL. (089) 53 96 53-56 TELEX: 524845 tlpat CABLE ADDRESS: Germanlapatant Munich

8000 Munich 2

Bavariaring 4

P.O. Box 202403, October 10, 197

SOCIETE NATIONALE DES PETROLES D'-AQUITAINE Courbevoie, France

Pesticides

The invention relates to new pesticides and compositions containing them and their use.

In particular, the invention relates to a systemic pesticide containing both phosphorus and sulfur contains.

Compounds with systemic effects that can be given to warm-blooded animals without being toxic to the organism and which at the same time are capable of damaging insects and their larvae living on (or in) the body of these animals

609816/1087

* Z-

to destroy are extremely sought after at the moment. Products, which meet these three requirements are rare.

In the literature, sulfur and phosphorus containing compounds are considered to have a systemic effect and described as gifted insecticidal properties. Law

however, these compounds often show strong insecticidal activity also toxicity to warm blooded animals that is too severe to be applied.

It has now been found that the 0,0-dialkyl-S-mercaptoethyl-dithiophosphate the general formula

P - SCH ₉ -CH ₅ SH (I)

_R / ll

¹ s

in which R and R ^, which are generally the same, are alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl or isopropyl mean a particularly interesting pesticide (especially insecticidal and acaricidal) have an effect. In addition, they show a systemic effect against Warm-blooded animals and can be absorbed through the skin by the animal without danger. You have a very strong one pesticidal activity and are ingested by warm-blooded animals Doses not toxic.

R and R ^ are preferably each methyl or ethyl, especially methyl.

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Of the compounds of the general formula (I) mentioned above, this is 0,0-dimethyl-S- [2-mercaptoethyl] dithiophosphate especially interesting. As shown in the examples, it has a systemic effect on Animals and an insecticidal effectiveness against mosquitoes that is stronger than that of three recognized systemic insecticides of known effectiveness; Furthermore, it is with doses that are used for the destruction of the Pests must be ingested by the animal, non-toxic.

The present invention thus also encompasses a method of controlling harmful insects at a location where which is affected by these or could be affected. This procedure involves the use of a certain amount Amount of a compound corresponding to the above formula (I) at the point where the harmful insects are to be controlled should be.

The invention finally comprises a pesticidal agent containing (at least) one compound of the above formula (I) and in particular a solid composition of a pesticide which contains the compound together with a solid carrier, a liquid pesticidal composition which contains the compound together with a carrier liquid that by a boiling in the temperature interval 130-270 ⁰ C hydrocarbon

f; Π 9 ^e '■ P / 1 Γ Β 7

is formed, a pesticidal composition containing the compound and a surfactant and a pesticidal agent that contains the compound along with another pesticide. The invention further includes sterilized pharmaceutical composition for the veterinary field which contains the compound with a for the

t-

Contains a pharmaceutically acceptable carrier and a pharmaceutical composition for the veterinary field Veterinary sector, which contains the connection with another veterinary pharmaceutical product and finally an animal feedable product containing the compound.

The composition can be made by mixing the ingredients. It may contain for example 0.01 to 85 wt.% Of the compound. For some applications, the compositions are originally prepared in the form of concentrates, for example with 0.5 to Φ % by weight of the compound, and these are generally diluted with water or a hydrocarbon, usually with water for spray application, to such an extent that the concentration of the compound is 0.01 to 5% by weight.

The compound can be used in the form of an effective functional derivative. So the connection can be easy are acetylated with modification of the SH group by:

609816/1087

- SC - CH,

for example with the help of acetic anhydride and pyridine.

The compound can be made into a composition according to conventional formulations for different applications are processed. These compositions normally contain a surfactant and / or one Carrier. The carrier can be a liquid, for example water (which can be used, for example, to dilute a Concentrate is used). In addition, when water is used as a carrier in a concentrate, an organic Solvent be present as a carrier, although this is not usually to be used. A water Concentrate containing a carrier may advantageously * also contain a surface-active agent.

A liquid other than water, for example an organic solvent, usually a water-immiscible solvent, for example a hydrocarbon which ^{boils between 130 and 270 °} C. and in which the compound is dissolved or suspended, can serve as the carrier. A concentrate containing organic solvent also suitably contains a surfactant such that the concentrate acts as an auto-emulsifiable oil when water is added.

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The carrier can be a solid which should be finely divided. Examples of suitable solids are clay, sand, mica, chalk, attapulgite, diatomaceous earth, perlite and sepiolite (meerschaum) as well as synthetic ones solid carriers such as silica, silicates and lignosulfonates (e.g. Na, K, Ca and ammonium lignosulfonates). The access

The composition can be in the form of tablets or granules.

Water-soluble or water-dispersible wettable powders can be prepared by adding a surface-active agent to the compound (with or without a carrier). The term "surface-active agent" is used here Used in a broad sense and includes materials that are different from emulsifiers, dispersants and wetting agents. Such agents are well known in the pesticide art. The applied Surfactants can include anionic agents such as soaps of fatty sulfate esters such as Sodium dodecyl sulfate, sodium octadecyl sulfate and sodium cetyl sulfate, fatty-aromatic sulfonates such as alkylbenzenesulfonate or butylnaphthalene sulfonate as well as more complicated ones Sulphonates of fatty acids such as the (amide) condensation product of oleic acid and N-methyltaurine or sodium sulph onate of dioctyl succinate.

R09816 / 10S7

The surface-active agents can also include nonionic agents such as, for example, condensation products of fatty acids, fatty alcohols or fat-substituted ones Phenols with ethylene oxide or fatty esters and ethers of sugars or polyhydric alcohols or products that starting from the latter can be obtained by condensation with ethylene oxide or as block copolymers of ethylene oxide and propylene oxide known products.

The surfactants can also include cationic agents such as cetyltrimethylammonium bromide.

Preferred surface-active agents include fatty alkyl sulfates, alkyl aryl sulfonates, fatty alkyl ethoxylates, sulfated fatty alkyl ethoxylates, dialkyl sulfosuccinate esters, the (amide) condensation product of oleic acid and N-methyltaurine, lignin, sulfonate salts, sulfonated naphthalene-formaldehyde condensates and sulfonated urea-formaldehyde condensates.

The compositions can have an "adhesive" coating e.g. from vinyl resin or casein, which can prolong the remaining activity.

The compound can be used with other pesticides, for example with a systemic one for the treatment of animals

fi 0 9 S * ■ e / 1 0 8 7

or non-systemic insecticide or mixed with an acaricide.

The compound is useful for controlling pests, in particular, harmful insects which the Attack crops, attack animals, or pose a public health hazard. The connection can at a location already infested by pests or to reduce or prevent future infestation administered or applied.

The connection can be used in plants, soils, lands, swampy or watery areas, animals, buildings and furniture; Surfaces such as walls and floors, in feed preparations, in storage facilities such as buildings and ships and other places or places that are attacked by pests can be applied.

Administration to animals, e.g. to domestic cattle, sheep, Pigs, horses, dogs and cats can be taken orally or parenterally (through the skin or by injection) for example in Form of sterilized veterinary pharmaceutical compositions containing the compound in association with a suitable veterinary pharmaceutical carrier. It can be in the form of tablets or granules or grains or mixed with drinking water or animal feed administered.

609818/1087

The preparations for adding to drinking water can contain surface active agents to ensure a solution or contain sufficient dispersion.

The preparations for addition to the feed can contain carriers that are physiologically acceptable to the animals, such as talc, chalk, Contain plaster of paris or earth with or without surfactants.

The connection can be impregnated or coated of grains or granules, for example of gypsum granules, are prepared with the compound.

The compound can be used with other veterinary pharmaceuticals Products are mixed. For internal use in animals, the dosage is of course from Factors such as toxicity to the animals, the particular treatment desired, the animal treated and the one used Depend on connection. In general, however, the dose is 2 to 250 mg and preferably 10 to 100 mg of the Compound per kilogram of body weight. A single dose may be sufficient, otherwise administration will stop if necessary, repeated. For larger mammals, a dose of about 1 to 10 g can be used.

However, the external application of the

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- Io -

binding in animals either by spraying or wetting; compositions are used that for example 0.01 to 0.5% by weight of the compound.

What is particularly interesting about these compounds is that they are "systemic". They are also absorbed through the skin. The compounds according to the invention can therefore be used advantageously by simply pouring a composition on the back of the animals which contains, for example, 5 to 10 % of the compound dissolved in a liquid hydrocarbon carrier boiling between 130 and 270 ^° C.

For the "topical treatment" of larger mammals, 5 to 50 g of the compound can be used per animal.

The compound can also be used to control pests, especially parasites, which the crops, for example grain, spoil and it is then generally applied at a dose of 0.1 to 5 kg per hectare. So it can be applied to a place where a plant should develop or it is applied immediately after the plant has developed. Preferred treated plants are cereals, cotton, Sugar beet, fruits and vegetables or legumes.

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The compounds according to the invention are also used to control pests, in particular harmful insects, that pose a public health hazard. They are then generally in a Dose of 50 to 1000mg of the compound per square meter of surface, for example in buildings or moving Goods or furniture or in a dose of 0.1 to 10 mg per cubic meter in the atmosphere.

The compounds according to the invention and especially the Ο, Ο-dimethyl-S-mercaptoethyl-dithiophosphate are from of particular interest when used as systemic insecticides in animals, for example to control ticks Domestic cattle are used. The compound of the invention also has systemic insecticidal activity against the larvae of horseflies and ectoparasites such as mosquitoes. The treatment of livestock on a farm, in particular domestic cattle, is preferred.

The compound is also against common flies, Aphidae or aphids, spiders and moths or mites (mites) effective.

The invention is illustrated below with the aid of Examples described.

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Examples 1 to 4

3-week-old mice weighing between 10 and 20 g were administered orally with 0,0-dimethyl-S-mercaptoethyl dithiophosphate (Experiment No. 1) and that treated in a dose corresponding to 100 mg of compound per kg of body weight. the Mice were then hindered from moving and each time something went into the interior of a tube formed by a copper grid larger than the mouse - brought, which was closed at both ends with a clamp.

The tubes containing the individual mice were then placed in 150 mm cubic glass cages. In time intervals from 1 and 6 hours after the treatment of the mice were 20 mosquitoes (Aedes aegypti), which had previously been 48 hours to had been given no food whatsoever on water and had been very lightly anesthetized by carbon dioxide gas, in Each cage inserted and allowed to satiate on the mouse for 1 hour. The mosquitoes were then removed from the cage, observed for 24 hours and the number of dead animals noted. Analog experiments were performed on mice treated with the two most widely used conventional systemic insecticides namely 0,0-dimethyl-0- (2,4,5-trichlorophenyl) -phosphorothioate, also called "Fenchlorphos" or "Ronnel" (experiment No. 2) and 4-tert-butyl-2-chlorρhenyl-methyl-phosphoramide, also known as "Crufomate" or * Ruelene "(Ver

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examined No.3) were treated as well with a known insecticide of related structure represented by a mixture of O, O _r dimethyl-S - (- and 0 -) - 2- (äthylthioäthyl) phosphorothioate as "Demetonmethyl I and II ^w or "Metasystox" (Experiment No. 4) is formed in a dose of 100 mg / kg. The percentage of mosquitoes killed was calculated for each treatment.

In the attached table are: The designation of each Compound, the time after the mice were treated that the mosquitoes were admitted to the mice and the percentage the mortality of the mosquitoes. This table enables the effectiveness of the compound to be compared with connections 2, 3 and 4.

Compound 1 according to the invention is a systemic product because it is still active 6 hours later (50 %) and it is effective because it can kill 96% of mosquitoes or "cuterebra larvae".

Compound 2 is much less systemic and less effective.
Compound 3 is not systemic and only weakly effective.

Compound 4 is toxic at the dose used.

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Time (hrs)

Mosquito mortality

1 6

96 40

1 6

20 5

1 6

10 0

toxic to mice

CD O CO 03

Trial tested connection no.

0,0-dimethyl-S-mercaptoethyldithiophosphate (according to the invention)

O, O-Dimethy1-0- (2,4,5-trichlorophenyl) thiophosphate "Fenchlorphos" or ⁿ Ronnel ^M

4-tert-butyl-2-chloropheny1-

methylphosphoramide

"Crufornate" or ^B Ruelene ^w

Mixture of O, O-dimethyl-S-

(and-0 -) - 2- (ethylthioethyl) -

thiophosphate

^M Demeton-methyl I and II "or,

^M Metasystox ^M

Claims (14)

Claims Q. Thiophosphate-based pesticidal agents characterized by a solid or liquid carrier with 0,0-dialkyl-S-mercaptoethyl-dithiophosphate the general formula RO P - SCH ₂ -CH ₂ SH R ₁ O in which R and R ₁ are generally the same and are formed by alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl or isopropyl. 2. Pesticidal agent according to claim 1, characterized in that the dithiophosphate is 0,0-dimethyl-S-mercaptoethyl-dithiophosphate is present. 3. Pesticidal agent according to claim 1 or 2, characterized in that the liquid carrier is formed by a hydrocarbon boiling ^{between 130 and 270 ° C.} 4. Festicides Ilittel according to claim 1 or 2, characterized in that the solid carrier by clay, sand, Mica, chalk, attapulgite, diatomaceous earth, perlite, sepiolite, silicic acid, silicates or lignosulfonates are formed will. β Π 9 R 16/1087 5. Pesticidal agent according to one of the preceding claims, characterized in that the composition additionally contains another pesticide and / or a veterinary pharmaceutical compound, 6. Pesticidal agent according to one of the preceding claims, characterized in that the pesticidal composition is to be fed to animals. Product added is. 7. Pesticidal agent according to one of the preceding claims, characterized in that the content of dialkyl mercaptoethyldithiophosphate makes up from 0.01 to 85% by weight of the composition and is in particular from 0.01 to 5 % . 8. Pesticidal agent according to one of the preceding claims Claims, characterized in that the dialkyl mercaptoethyl dithiophosphate is in the form of its acetyl derivative. 9. Pesticidal agent according to one of the preceding claims, characterized by a content of one ionic surfactants and especially soaps or fatty sulfate esters or a non-ionic surfactant Agents such as the condensation products of fatty acids, fatty alcohols or fatty phenols with ethylene oxide or on cationic surfactants such as B π ° ' ^: ' ί ^; / 1 Π 8 7 Cetyltrimethylammonium bromide. 10. Use of the pesticidal agent according to one of the preceding claims for the protection of animals in particular Domestic animals and especially cattle against insects and larvae, characterized in that the animals have a non-toxic Dose of the pesticidal agent is administered. 11. Use according to claim 10, characterized in that the pesticidal agent for combating mosquitoes, cuterebra larvae, ticks or horseflies are used, which settle in particular on herds of cattle. 12. Use according to claim 10, characterized in that the pesticidal agent is added to the feed or drinking water will. 13. Use according to claim 10, characterized in that the pesticidal agent to the animals parenterally or via the Skin is administered. 14. Use of the pesticidal agent according to any one of claims 1 to 9 for the protection and treatment of crops, Areas or rooms, swampy or watery terrain or the atmosphere against insects and larvae through atomization of the pesticidal agent on the infected area. 609816/1087