FR2713890A1 - Synergistic insecticidal compsn. contg. pyrethroid and aniline derivs. - Google Patents

Abstract

Insecticidal compsn. comprises (i) one of the aniline derivs. (I) N-dichlorofluoromethylthio-N'N'-dimethyl-N-phenylsulphamide; N-(3,5-dichlorophenyl)- 1,2-dimethylcyclopropane-1,2-dicarboximide and 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (Ia); and (ii) a pyrethroid (II). (II) Is chosen from (a) alpha-cyano-3-phenoxybenzyl esters of 3-(2,2-dichlorovinyl-, 2,2-dibromovinyl-, or 2-chloro-3,3,3-trifluoropropenyl)- 2,2-dimethylcyclopropane carboxylic acid; (b) 2,2,3,3- tetramethylcyclopropane carboxylic acid or 2-(4-chlorophenyl)-3-methylbutyric acid; (c) 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether; and (d) 2-methyl-biphenyl-3-ylmethyl 3-(2-chloro-3,3,3-trifluoroprop-1-enyl- 2,2-dimethyl-cyclopropane carboxylate or 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylacyclopropane carboxylate.

Description

INSECTICIDE COMPOSITION CONTAINING A DERIVATIVE

  ANILINE AND A PYRETHROID COMPOUND.

  The subject of the present invention is an insecticide composition

  containing an aniline derivative and a pyrethroid compound.

  To date, many insecticides have been developed which have been used in practice for the elimination of Alevrodidae. However recently insects have quickly acquired resistance to

  various insecticides, which significantly reduced their activity.

  Therefore a need arose for new insecticides

  exhibiting excellent activity with respect to these insects.

  An object of the invention is to provide an insecticidal composition for eliminating these insects, this composition comprising a derivative

  aniline fungicide and a pyrethroid compound.

  The composition according to the invention exhibits excellent insecticidal activity with regard to harmful insects, in particular with regard to

  Alevrodidae as a result of a synergistic action.

  The invention therefore provides an insecticidal composition (hereinafter called

  after "the present composition") comprising as active materials: (a) an aniline derivative chosen from the group consisting of

  N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide (compound A-

  1, common name: dichlofluanide), N- (3,5-dichlorophenyl) -1,2-dimethyl-

  cyclopropane-1-2-dicarboximide (compound A-2, not common:

  procymidon) and 3- (3-5-dichlorophenyl) -5-methyl-5-vinyl-

  1,3-oxazolidine-2,4-dione (compound A-3); and (b) a pyrethroid compound selected from the group consisting of

  3- (2,2-dichlorovinyl) -2,2-dimethylcyclo-propanecarboxylate a-cyano-

3-phenoxybenzyl (compound B-1),

  3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclo-propane-

  α-cyano-3-phenoxybenzyl carboxylate (compound B-2),

  a-cyano-3-phenoxy- 2,2,3,3-tetramethylcyclopropanecarboxylate

  benzyl (compound B-3), acano-3-phenoxy-benzyl 2- (4-chlorophenyl) -3-methylbutyrate (compound B-4),

  2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzylether (compound B-

, common name: etofenprox),

  3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate

  3-phenoxybenzyl (compound B-6), 3- (2-chloro-3,3,3trifluoroprop-1-enyl) -2,2-dimethylcy-clopropane-2-methylbiphenyl-3-ylmethyl carboxylate (compound B-7) and the

  3- (2,2-dichlorovinyl) -2,2-dimethylcy-clopropanecarboxylate

phenoxy-benzyl (compound B-8).

  The compounds of the present invention may sometimes have stereoisomers and geometric isomers and these isomers, as well

  that their mixtures are part of the invention.

  Examples of the isomers are given below with the numbers

attributed to them.

  (RS) -3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (compound A-3a, common name: bincrozorin), pair of enantiomers

  (1R-cis) S and (1S) -cis R du 3- (2,2-dichlorovinyl) -2,2-dimethylcyclo-

  α-cyano-3-phenoxybenzyl propanecarboxylate (compound B-la, name

  common: alphametrin), mixture (1: 1) of (Z) - (1R, 3S), S-ester and (Z) -

  (lS, 3S), R-ester of 3- (2-chloro-3,3,3-trifluoroprop-l-enyl) -2,2-dimethyl-

  α-cyano-3-phenoxy-benzyl cyclopropanecarboxylate (compound B-2a,

  common name: lambdacyhalothrin), 2,2,3,3-tetramethylcyclo-

  (RS) -a-cyano-3-phenoxybenzyl propanecarboxylate (compound B-3a, common name fenpropathrin), (RS) -2- (4-chlorophenyl-3-methyl-butyrate (RS) a-cyano-3- phenoxybenzyl (compound B-4a, common name:

  fenvalerate), (1 R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethyl-cyclopropane-

  (S) -a-cyano-3-phenoxybenzyl carboxylate (compound B-6a, name

  common: deltamethrin) and 3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -

  (2-methyl-biphenyl-3-yl) methyl 2,2-dimethylcyclopropanecarboxylate

  (compound B-7a, common name: bifenthrin).

  The active ingredients of the invention, for example the compounds A-1, A-2 and A-3, are described in Farmchemicals Handbook 1991 (published

  by Meistel Publishing Company), respectively in C131, C288 and C322.

  The compounds B-la, B-2a, B-3a, B-4a, B-5a, B-6a and B-7a are described in Farmchemicals Handbook 1991, respectively in C134,

C175, C137, C138, C308, C97 and C44.

  Examples of harmful insects eliminated by the present composition include the following Hemiptera: Aphids (Aphidoidea) such as Mvzus persicae, Aphis gossyvpii, Alevrodidae such as Bemisia tabaci, Trialeurodes vaporariorum, etc. Thrips (Thysanoptera): Thrips such as Scirtothrips dorsalis, Thrips palmi, etc. Lepidoptera: Arctiidae such as Plutella xvlostella, budworms (Tortricidae) such as Adoxophves spp., Adoxophves orana, leafminers (Lvonetiidae) such as Phvllocnistics citrella, etc. Mites: Spider mites (tetranvchidae) such as Tetranvchus urticae, Tetranvchus kanzawai, Panonychus citri, Panonvchus ulmi, etc. Examples of the crops to which the present composition is applied include agricultural / horticultural crops, such as those of fruit trees, vegetables, cotton fields,

  flowers and ornamental plants, and others.

  According to the invention, the aniline derivative (a) and the pyrethroid compound (b) used as active materials, can be used as such without mixing with another component, but, normally, they are mixed with various supports, such as '' a solid support, a liquid support, a gaseous support, etc. and, where appropriate, with surface-active agents and auxiliary formulating agents as additives to present them in the form of emulsifiable concentrates, wettable powders, fluid compositions (for example a suspension in water , an emulsion in water, etc.), powder, aerosols, very low volume compositions (ULV) and others. In addition, the various

  active ingredients can be formulated in advance in the forms below

  top in varying concentrations, then mixed, or can be diluted with water to obtain chemical solutions

respective, then mixed.

  These compositions normally contain the aniline derivative (a) and the pyrethroid compound (b), as active ingredients, in a mixing ratio by weight of 50: 1 to 1: 1. The total proportion of active ingredients in the composition is normally 0.1 to 95% by weight. Examples of solid supports used for the composition include fine powders or clay granules (for example kaolinic clay, diatomaceous earth, hydrated synthetic silicon oxide, bentonite, Fubasami clay, acid clay , etc.), talcs, ceramics and other minerals (e.g. sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), industrial fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea,

  ammonium chloride, etc.) and others.

  Examples of a liquid carrier include water, alcohols (e.g. methanol, ethanol, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g. benzene , toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (e.g. hexane, cyclohexane, kerosene, diesel, etc.), esters (e.g. acetate d ethyl, butyl acetate, etc.), nitriles (e.g. acetonitrile, isobutyronitrile, etc.), ethers (e.g. diisopropyl ether, dioxane, etc.), amides ( for example N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (for example dichloroethane, trichloroethane, carbon tetrachloride, etc.) dimethyl sulfoxide, vegetable oils (for example l soybean oil, cottonseed oil, etc.)

and others.

  Examples of the gaseous support, i.e., spray agent, include Freon gas, butane gas, liquefied petroleum gas, dimethyl ether, carbon dioxide gas and the like. Examples of surfactants include alkyl sulfates, alkyl sulfonate salts, alkylarylsulfonates, alkylaryl ethers, their polyoxyethylene derivatives, polyethylene glycol ethers, polyalcohol esters, derivatives of

sugar alcohols and others.

  Examples of auxiliary agents to the compositions include fixing agents and dispersing agents, such as casein, gelatin, polysaccharides (for example starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, water-soluble synthetic polymers (e.g. polyvinyl alcohol,

  polyvinylpyrrolidone, polyacrylic acids, etc.) and others.

  Examples of stabilizers include PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA

  (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-

  methoxyphenol), vegetable oils, mineral oils, agents

  surfactants, fatty acids or their esters, and the like.

  The fluid compositions (suspension in water or emulsion in water) can be obtained by fine dispersion of 1 to 75% by weight of the active materials in water containing 0.5 to 15% by weight of an agent dispersant, 0.1 to 10% by weight of a suspension aid (for example a protective colloid, a compound conferring thixotropic properties, etc.) and 0 to 10% by weight of a suitable auxiliary agent (for example a antifoam, antirust, stabilizer, spreading agent, penetration aid, antifreeze agent, antibacterial agent, antifungal substance, etc.). It is also possible to prepare a suspension in an oil using an oil in which the compound is practically not dissolved in place of water. As protective colloid, it is possible to use, for example, gelatin, casein, gum arabic, a cellulose ether, polyvinyl alcohol and others. Examples of the compound conferring thixotropic properties include bentonite, aluminum silicate

  and magnesium, xanthan gum, polyacrylic acid and the like.

  The present composition can be made more stable by the addition of antioxidants or UV absorbents, such as phenol derivatives (for example BHT and BHA), bisphenol derivatives or arylamines (for example phenyl-a condensates -naphthylamine, phenyl-f3naphthylamine and phenetidine with acetone, etc.) or

  stabilizers such as benzophenone derivatives.

  The compositions thus obtained can be used as

  that they have been prepared or after dilution, for example with water.

  They can also be used after mixing with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, baits

  for animals, etc. or be used as a mixture between them.

  The application dose of the present composition, expressed in active ingredients, is normally around 5 to 1000 g, preferably

about 50 to 300 g per 10 ares.

  Emulsifiable concentrates, wettable powders and flowable compositions are normally diluted with water at a concentration of from about 100 ppm to about 3000 ppm, preferably from about 500 ppm to about 2000 ppm. Powders, aerosols and

  very low volume compositions are used as prepared.

  The application dose and the concentration of these compositions can be variable, that is to say possibly be increased or decreased depending on the nature of the active material, the type of composition, the time, the place and the method of application, the type of Alevrodidae,

  the extent of the damage and others.

Examples:

  The following preparation examples and test examples illustrate the invention in more detail, but are not intended to limit its scope. In the preparation examples, all

the "parts" are by weight.

  Preparation example 1 Emulsifiable concentrates 10 parts of a compound A-1, A-2 or A-3a are mixed with 10 parts of a compound B-la, B-2a, B-3a, B-4a, B- 5, B-6a or B-7a and the mixture is dissolved in 30 parts of xylene and 30 parts of dimethylformamide. To the solution obtained, 14 parts of polyoxyethylenated styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and sufficiently mixed with

  stirring to obtain emulsifiable concentrates at 20%.

  Preparation example 2 Wettable powders 10 parts of a compound A-1, A-2 or A-3a are mixed with 10 parts of a compound B-la, B-2a, B- 3a, B-4a, B- 5, B-6a or B-7a and add it to a mixture of 4 parts of sodium lauryl sulphate, 2 parts of calcium ligninsulfonate, 2 parts of hydrated synthetic silicon oxide in fine powder and 54 parts of diatomaceous earth , then mixed with stirring using a household mixer to obtain wettable powders at 20%. Preparation example 3 Granular wettable powders 10 parts of a compound A-1, A-2 or A-3a are mixed with 10 parts of a compound B-la, B-2a, B-3a, B-4a, B -5, B-6a or B-7a. We

  add 10 parts of a formaldehyde condensate to the mixture

  sodium naphthalenesulfonate, 1.5, parts of sodium alkylnaphthalenesulfonate, and ASP-400P (kaolin clay sold by Engelhard Co.) to obtain 100 parts of mixture, which is sufficiently mixed and finely ground with a grinder pneumatic. The ground product is introduced into a granulation turbine having a diameter of 40 cm and granules are formed by spraying approximately parts of distilled water (per 100 parts of powder) at 45 rpm, using a manual sprayer. The granules obtained are dried using a fluidized bed drier (50 ° C; 20 min) and passed through sieves of about 1.2 and about 0.5 mm mesh size.

  (14 to 30 mesh) to obtain 20% granular wettable powders.

  Preparation example 4 Powders 1.0 parts of a compound A-1, A-2 or A-3a are mixed with 1.0 part of a compound B-la, B-2a, B-3a, B-4a , B-5, B-6a or B-7a and the mixture is dissolved in an appropriate amount of acetone. To the solution obtained, add 5 parts of hydrated synthetic silicon oxide in fine powder, 0.3 parts of PAP and 92.7 parts of clay, and mix sufficiently with stirring using a household mixer, then expel acetone by evaporation to obtain

powders at 2.0%.

  Preparation example 5 Fluid compositions 10 parts of a compound A-1, A-2 or A-3a are mixed with 10 parts of a compound B-la, B-2a, B- 3a, B-4a, B- 5, B-6a or B-7a and the mixture is added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol and the mixture is stirred to obtain a dispersion. To the dispersion obtained, 30 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum and magnesium silicate are added and, in addition, 10 parts of propylene glycol are added and mixed. gently with agitation for

  obtain fluid compositions at 20%.

  Preparation example 6 Oil-based aerosols 0.5 parts of a compound A-1, A-2 or A-3a are mixed, 0.5 part of a compound B-la, B- 2a, B-3a, B-4a, B-5, B-6a or B-7a and 10 parts of trichloroethane and the mixture is dissolved in 59 parts of deodorized kerosene then an aerosol container is filled with this solution. Then, the container is fitted with a valve by which 30 parts of a propellant (liquefied petroleum gas) are introduced under

  pressure to obtain oily-based aerosols.

  Preparation example 7 Water-based aerosols An aerosol container is filled with 50 parts of pure water and with a mixture of 0.5 parts of a compound A-1, A-2 or A-3a, 0.5 parts of '' a compound B-la, B-2a, B-3a, B-4a, B-5, B-6a or B-7a, 5 parts of xylene, 3.0 parts of deodorized kerosene and 1 part of an emulsifier [ATMOS 300 (registered trademark of Atlas Chemical Co.)]. Then, the container is fitted with a valve by which 40 parts of a propellant (liquefied petroleum gas) are introduced under pressure so as to obtain

water-based aerosols.

  Preparation example 8 Smoke-producing compositions by heating 50 mg of a compound A-1, A-2 or A-3a and 50 mg of a compound B-1a, B-2a, B-3a, B-4a are dissolved. BS, B-6a or B-7a in an appropriate amount of acetone and a porous ceramic plate, measuring 4.0 cm x 4.0 cm x 1.2 cm, is impregnated with the solution obtained for

obtain a smoke composition.

  The following examples of tests make it possible to show that the present composition exhibits an excellent insecticidal activity due to a synergistic action compared to the case where the

  aniline derivative (a) or the pyrethroid compound (b).

  The aniline derivative used for comparison is designated by the following symbol: Compound C-1: 3- (3,5-dichlorophenyl) -N- isopropyl-2,4-dioxo-

  imidazolidine-l-carboximide (common name: iprodion).

  Examples of tests The emulsifiable concentrates prepared using the compounds B-la (Fastac 10EC, manufactured by Shell International Chemical Co.), B-2a (Karate 2.5EC, manufactured by ICI Agro) are diluted with water. Chemicals Co.), B-3a (Rody-10EC, manufactured by Sumitomo Chemical Co. Ltd;), B-5 (Trebon 20EC, manufactured by Kumiai Chemical Industry Co. Ltd.), B-6a (Decis 2.5EC, manufactured by Roussel Uclaf Co.), and wettable powders prepared using the compounds A-1 (Euparen 50 WP, manufactured by Nihon Tokushu Noyaku Co. Ltd.), A-2 (Procymidon 50 WP, manufactured by Hokko Chemical Industry Co. Ltd.), A-3a (Ronilan 50 WP, manufactured by Sankyo Co. Ltd.), B-7a (Telstar 2WP, manufactured by Nissan Co. Ltd.) and C1 (Rovral 50 WP, manufactured by Takeda Yakuhin Co . Ltd.), then the diluted solutions obtained are mixed so that the solutions

  of tests have predetermined concentrations of active ingredients.

  Cabbages (at the 4-5 leaf stage) are sprayed with 30 ml of the above chemical test compositions, these being planted in polyethylene pots. After air drying, the sheets are cut and each sheet is placed in a plastic tray (diameter: 9 cm; depth: 2 cm). Then, we have, in the tray, 50 to 100

  Bemisia tabaci adults. The tray is kept in a room at 25 C.

  After 24 hours, the mortality is determined (with triplicate tests).

  The results are shown in Tables 1 and 2.

  Next, the theoretical insecticide rate (%) and the synergistic effect index (%) were calculated using the following equations, respectively. [Equation 1] Theoretical insecticide rate (%) = A + 1 (100 - a) x B} / 100 [Equation 2] Synergy effect index (%) = {insecticide rate (%) / theoretical insecticide rate (% )} x 100 o A is an insecticide rate (%) of the compound A-1, A-2, A-3a or C-1 and B is an insecticide rate (%) of the compound B-la, B-2a, B -3a, B-5, B-6a

or B-7a.

Table 1

  Concentration Rate Rate Effect index Active ingredients of the active synergistic insecticide insecticide (ppm) (%) theoretical (%) (%) A-3a + B-3a 500 + 100 49.4 6.3 784

A-3a 500 1.8 - -

  B-3a 100 4.6 No treatment - 2.2 il

Table 2

  Materials Concentration Rate Rate Index of active effect of the insecticide insecticide material with active synergy (ppm) (%) theoretical (%) (%) A-1 + B- la 1000 + 100 46.6 3.1 1 503 A -1 + B-2a 1000 + 25 87.2 12.9 676 A-1 + B-3a 1000 + 100 98.2 12.4 792

A-1 + B-5 1,000 + 200 97.7 47.3 207

  A-1 + B-6a 1,000 + 25 66.9 4.1 1,632 A-1 + B-7a 1,000 + 20 96.8 19.9 486 A- 2 + B-3a 500 + 100 76.0 16.8 452

A-2 + B-5,500 + 200 91.4 60.2 152

A-2 + B-7a 500 + 20 79.0 26.1 303

C-1 + B-3a 500 + 100 6.6 - -

A-1 1,000 0.8 - -

A-2,500 1.4 - -

B-la 100 2.3 - -

B-2a 25 16.3 - -

B-3a 100 15.6 - -

B-5 200 59.6 - -

B-6a 25 5.2 - -

B-7a 20 25.1 - -

C-1,500 1.5 - -

No treatment - 0.9 - -

r

Claims (13)

  1. Insecticidal composition characterized in that it comprises, as active materials: (a) an aniline derivative chosen from the group consisting of N-dichlorofluoromethylthio-N ', N'-dimethyl-Nphenylsulfamide, N - (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1, 2-dicarboximide and 3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-1,3oxazolidine-2,4-dione; and (b) a pyrethroid compound selected from the group consisting of   3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate a-cyano-   3-phenoxybenzyl, 3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethyl-   α-cyano-3-phenoxybenzyl cyclopropanecarboxylate, 2,2,3,3-tetra-   α-cyano-3-phenoxybenzyl methylcyclopropanecarboxylate, 2- (4chlorophenyl) -3-α-cyano-3-phenoxybenzyl methylbutyrate, 2- (4ethoxyphenyl) -2-methylpropyl-3-phenoxybenzylether,   3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate a-cyano-   3-phenoxybenzyl, 3- (2-chloro-3,3,3-trifluoro-prop-1-enyl) -2,2-   2-methyl-biphenyl-3-ylmethyl dimethyl-cyclopropanecarboxylate and 3-phenoxy-benzyl 3- (2,2-dichlorovinyl) -2,2-dimethyl-cyclopropanecarboxylate. 2. Insecticidal composition according to claim 1, characterized by   the fact that said aniline derivative is N-dichlorofluoromethylthio- N ', N'-dimethyl-N-phenylsulfamide.   3. Insecticidal composition according to claim 1, characterized by   the fact that said aniline derivative is N- (3,5-dichlorophenyl) -   1,2-dimethylcyclopropane-1,2-dicarboximide. 4. Insecticidal composition according to claim 1, characterized by   the fact that said aniline derivative is 3- (3,5-dichlorophenyl) -5methyl-   -vinyl-1,3-oxazolidine-2,4-dione. 5. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-   α-cyano-3-phenoxybenzyl carboxylate.   6. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is a-cyano- 2,2,3,3-tetramethylcyclopropanecarboxylate   3-phenoxybenzyl. 7. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is 3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethyl-   α-cyano-3-phenoxybenzyl cyclopropane-carboxylate.   8. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is 2- (4-chlorophenyl) -3-methylbutyrate a-cyano-   3-phenoxybenzyl. 9. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxy-   benzyl ether. 10. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is 3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane-   α-cyano-3-phenoxybenzyl carboxylate.   11. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid is 3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethyl-   2-methylbiphenyl-3-ylmethyl cyclopropane-carboxylate.   12. Insecticidal composition according to any one of   Claims 1 to 4, characterized in that the said compound   pyrethroid r is 3- (2,2-dichlorovinyl) -2,2-dimethylcyclo-   3-phenoxybenzyl propanecarboxylate.   13. A method of eliminating harmful insects, characterized in that it comprises the application of a composition according to one   any of claims 1 to 12 on the premises where harmful insects.