DE1567030A1 - Insecticides - Google Patents

Description

The invention relates to insecticidal agents containing a synergistic mixture of organic compounds Carbamates as an active ingredient.

It is known that numerous mono- or disubstituted aryl esters of carbamic acid have good properties as insecticides. One of the most active among of these compounds is oCnaphthyl-I-methylcarbamate.

In addition, the applicant has previously shown that certain phenyl esters of carbamic acid, in which the Phenyl nucleus in meta position carries an acyl group, are very useful insecticides; they are much more active than the carbamic acid derivatives previously known for this purpose, in particular cK-naphthyl-N-methylcarbamate (see Franz. Patent application PV 932 596 of April 25, 1963).

009826/2030

\ ■ It has now been found that is obtained upon mixing of o (naphthyl-.N-methylcarbamate with at least one Metaacylphenylcarbamat an insecticide, which activity is significantly higher than that of the known constituents individually. It is in particular also significantly higher than that of concerned metaacylphenylcarbamate alone, which in turn far exceeds the effectiveness of the öf-naphthyl-N-methyl-carbamate.

The insecticides according to the invention consist of a mixture of O ^ -naphthyl-N-methylcarbamate with at least one Metaacylphenylcarbamate, which latter the following general Formula has:

N - 000 -

where Hj and Eg, which can be equal or different, either for one hydrogen atom each or for one lower hydrogen atom each Alkyl radical and It, stand for a lower alkyl radical, while a hydrogen atom or an electronegative group, preferably a halogen atom, and the number η 1, 2 or 3 can mean.

009826/2030

Examples of compounds according to the above formula include: m-acetylphenyl carbamate, m-propionylphenyl carbamate and m ~ butyrylphenyl carbamate; m- (CX-methylacetylJ-phenylcarbamate; m-acetyl-p-chlorophenylcarbamate; m-acetylphenyl-E-methylcarbamate, m-acetylphenyl-NN-dimethylcarbamate, m-acetylphenyl-N-lT-diethylcarbamate and m-acetylphenyl -dibutylcarbamate; m-acetylphenyl-I ¹ T-ID. ethyl-N-ethyl carbamate and m-acetylphenyl-Si-methyl-N-isopropyl carbamate.

The mutual share of the. Carbamates in dea. Means according to the invention can vary within very wide limits, i.e. the means can basically 99 to 1 part C ^ -Naphthyl-N-methylcarbamate to 1 to 99 parts by weight of acylphenylcarbamate contain.

Because of their particularly good synergistic effect however, mixtures are preferred which are based on 90 to 25 parts of c * -saphthyl-N-methylcarbamate Contain 10 to 75 parts of m-acylphhenyl carbamate. When using m-acetylphenyl-N-methylcarbamate leaves For example, a very good synergistic effect is achieved even with 10 parts of this compound (A) per 90 parts of O (-haphthylli-methylcarbamate) (B) determine. If the proportion of the product identified above with A is increased to 25 parts, for example 3e 75 parts B so the effectiveness of compound A alone, which in turn is already more active than connection B alone,

009826/2030

still exceeded. If the ratio is 50 to 75 parts or more A to 50 to 25 parts or less B, the synergy is even more evident and the effectiveness of the mixture is two to three times higher than that of the product when used alone in the same dosage.

The insecticidal mixtures according to the invention can be used in can be used in various forms, for example as a powder, as a suspension in an inert liquid, as a solution or as an emulsion.

They can be applied by evaporation or spraying or by impregnating the substances to be protected with a solution of the mixture in an appropriate solvent. Aromatic hydrocarbons, for example, serve as solvents, such as benzene, toluene, xylene or decalin; Chlorinated hydrocarbons, such as carbon tetrachloride or perohllorethylene; Esters or ethers, such as alkyl acetates or propionates, dioxane or tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, Oyclohexanone, etc.

The solutions used for combating insects according to Invention contain practically 0.5 to 20, preferably 1 to weight percent mixture of active ingredients.

009826/2030

BAD OFHOlNAt

If necessary, it is von Torteil, if one uses the means \ tx ^ iim \ a \ o ^ s- £ OT; m ^ T ^ -scA ^ t, - ^ ο ^ θΐ «lie MuLsIcm QlP. contains common surfactant. They have also been used in the form of a water-wettable powder in which the active ingredient is applied to a carrier such as talc, kaolin, silica gel, etc. and then impregnated with a suitable surface-active agent in an amount of 0.05 to 5% proven. Such powder mixtures, which generally contain 10 to 95% by weight of active ingredient, can also be used in the dry state without admixing a wetting agent and not diluted with water.

Generally speaking, the active ingredients according to the invention can be used in the form of preparations containing, 0.5 to 99 »5 $ of the active ingredient mixture and the rest from one or more inert substances such as solvents, liquid dispersion media, water, powdery inorganic substances Consisting of fillers, surface active agents, etc.

The invention is explained in more detail with the aid of the examples. The insecticidal effectiveness of Oi-Naphthyl-lime thylcarbamate alone or that of one of the methylacylphenylcarbamates according to formula I, namely the m-acylphenyl-U-methylcarbamate, compared with the effectiveness of a mixture of both substances.

009826/2030

example 1

In closed test vessels (Petridosen) were Ac e to nib * solutions of oWtfaphthyl-n-methylcarbamate (B), of m-acetylphenyl-N-methylcarbamate (A) and very finely divided by a mixture of these Oarbatnaten. From each of these products a series of 5 test vessels was provided, all of which contain the same amount of the agent to be tested, i.

25 mg per m surface contained. Another test vessel (petridose), in which no orbamate had been filled, was withheld as a comparison object. Ημη test insects of the species

Oalandra granaria introduced, namely 100 male and 100 female animals; at regular intervals were the dead insects counted. Each mess was made five times at the The concentration given below is repeated, with the result being Mean value from the 5th experiments was used.

The content of the carbamates (A) and (B) was up to each 100 parts by weight mixture:

A: 10 parts A: 25 parts A: 50 parts Ai75 parts

W: 90 "W: 75" W: 50 "W: 25"

009826/2030 BAD ORlGfNAiT

The results can be seen from the curves in FIGS. 1 and 2, although only partially for the sake of clarity were entered.

In FIG. 1, the ordinate in percent shows the actually observed mortality of the Calandrae and the abscissa shows the number of hours during which the animals were in contact with the insecticide investigated. The curves (a) (b) correspond to dosages of 25 mg / m of m-acetylphenyl-N-methylcarbamate and C 1-4 -naphthyl-M-methylcarbamate. Curve (c) corresponds to a mixture of 25 parts by weight A and 75 parts by weight B and curves (d) and (d ₂ ), which are combined into a single curve (d), correspond to mixtures of 25 parts by weight .-parts A and 25 parts by weight B, as well as from 50 parts by weight A and 50 parts by weight B. The dosage used corresponds to that which was used when determining curves (a) and (b) , ie it amounts to 25 mg of active ingredient per m ^{2 of} surface area.

The curves (d.) And (dp) are in the drawing summed up, because the result of these two insecticide mixtures effectiveness achieved was essentially the same. The figure still contains the curve (t) that corresponds to the comparative experiment corresponds and represents a straight line which practically coincides with the axis of abscissa.

009826/2030

BAD ORfGJNAl.

The curves show that with the same dosage of active ingredient, the mixtures of o ^ -naphthyl-N-niethylcarbamate and m-acetylphenyl-N-methylcarbamate are effective, which is much greater than that of the more effective of these two orbamates.

If, for example, after 48 hours the mortality for the (X-naphthyl-N-methylcarbamate reaches about 26% and for the m-acetylphenyl-N-methylcarbamate QO% , it is 95% for the mixtures of 75% E and 25> « and the $ 100 mortality peak has been reached for 3 hours for the other mixtures represented by curve (d).

In order to particularly illustrate the synergistic effect brought about by the orbamate mixtures to be used according to the invention, Pig. 2 shows the effectiveness of various mixtures again compared to that of the two carbamates alone.? Ig. 2 shows a section along the line xy in £ ⁿ ig. 1, ie the exposure time is uniformly 45 minutes. The ordinate here also means the mortality in % , the abscissa the corresponding proportions (0-100) of m-acetylphenyl-N-methyloarbamate (A) or o <-Naph, thylli-methylcarbamate

009828/2030

BAD LOCAL

The line of the theoretically calculated effectiveness of the mixtures from (A) and (B) would represent, with the curves (f ₁ ) and (fg), which correspond to the actually observed values for the effectiveness of the respective mixtures, then the phenomenon of synergy jumps clearly in the eyes. The synergy area (S) enclosed by curves (f.) And (f ^) and by straight line (e) is _; as Pig.2 shows, very large.

Example 2

The test conditions corresponded exactly to Example 1, only that instead of the m-acetylphenyl-N-methylcarbamate used there (A) now m-propionylphenyl-li-methylcarbamate (A ') was used.

The tested mixtures of (A ') and (B) correspond in weight composition to Example 1. The results go from Fig. 3 and Pig. 4 emerges.

In Fig. 3 (same coordinates as in Fig. 1) the curves (a *), and (b ') correspond to dosages of 25 gM ^ m-propionylphenyl or (X-naphthyl-N-carbamate. The curve (c ¹ ) corresponds to a mixture of 25 parts by weight A 'plus 75 parts by weight Bj, curve (d') corresponds to 75 parts A '+ 25 parts B; curve (e') corresponds to 50 parts A '+ 50 parts B. The dosage

is 25 mg of active ingredient mixture per 1 m.

009826/2030

BATH ORIGINAL

The curves show that the effectiveness of the mixtures is always significantly higher than that of the unmixed Carbamates.

The synergistic effect can be seen particularly clearly from FIG. 4, which corresponds to Pig.2 in Example 1. Here, too, the large synergy area (S ') becomes clear, which is indicated by the straight line (f) - which corresponds to the theoretical effectiveness of the mixtures of A' and B - and the curves g, and go (mortality rates actually observed for the mixtures of A ' ^f and B) is enclosed.

Claims

009826/2030

BADORLGiNAL

Claims (6)

'i? at entan s'prü'Ch e 1. Insecticidal agents containing c ^ -Iaphthy 1 -lira ethyl carbamate as an active ingredient, characterized by an "additional content of at least one metaacyl carbamate the general formula where iL and ji _2J, which can be identical or different, either represent 3s a hydrogen atom or each represent a lower alkyl radical and Α- * represents a lower alkyl radical, while X represents a hydrogen atom or an electronegative group, preferably a halogen atom and the number η 1 , Can mean 2 or 3. . 2. Insecticidal agent according to claim 1, characterized in that the weight ratio between the two active ingredients present in a synergistic mixture is between 99: 1 and 1:99. 3. Insecticidal agents according to claim 1 and 2, characterized in that that the metaacyl carbamate is m-acetylphenyl-U-methyloarbamate is available. 009826/2030 ORIGINAL INSPECTED I 3D '/ UJU 4. Insecticidal agent according to claim 3, characterized in that 75 to 10 parts by weight of m-acetylphenyl-N-methylcarbataate meet .Every 25 to 90 parts by weight of flC-japhthyl-li-methylcarbamate. 5. Insecticidal agents according to claims / i and 2, characterized in that to 25 to 90 parts by weight i \ -liaphthyl-E-methylcarbamate 75 to 10 parts by weight of tn-propionylphenyl-I-methylcarbamate meet. 6. insecticidal agent according to claim 5, characterized in that on, 25 to 90 parts by weight C 1-4 Haphthyl-III-methylcarbamate 75 to 10 parts by weight of m-propionylphenyl-xl-methylcarbamate meet. 009826/2030 BATH ORIGINAL Emptied