DD257382A5 - INSECTICIDAL COMPOSITION WITH MORE THAN AN ACTIVE SUBSTANCE - Google Patents

Abstract

According to the invention, an insecticidal composition having more than one active ingredient is provided which comprises, as active ingredient, a synthetic pyrethroid of the general formula (I) (wherein X is chlorine or bromine) in an amount of 0.001 to 99% by mass of the eight possible isomers, at least 95% of a 55:45 to 25:75 mixture of the enantiomeric pairs I a: I b, wherein I a is 1RcisS 1ScisR and I b is 1RtransS 1StransR, is mixed with an activator if desired and / or with an additive in an amount of up to 100%, preferably an antioxidant, stabilizer, wetting agent, emulsifier, dispersing agent, antifoaming agent, disintegrating agent, carrier agent and / or filling agent. The advantage of the insecticidal composition according to the invention is that it is less toxic to warm-blooded animals and useful parasites and therefore less harmful to the environment. Formula (I)

Description

Field of application of the invention

The invention relates to insecticidal compositions having more than one active ingredient and their use.

Characteristic of the known technical solutions

In this patent specification, the spatial configuration of the substituents related to the chiral carbon atom denoted by "" is denoted by "S" and "R", respectively. The designations "eis" and "trans" denote the position of the substituents. attached to the carbon atom "3" of the cyclopropane ring, which is related to the spatial configuration of the substituents of carbon atom "1." The absolute spatial configuration of the substituent attached to the carbon atom "1" is denoted by the prefix "1 R" and "1", respectively "1 S" denotes.

In the patent specification, the various enantiomers and enantiomeric pairs are designated by the following abbreviations:

la mixture of 1 RcisS and 1 ScisR

Ib mixture of 1 RtransS and 1 StransR

Ic mixture of 1 RcisR and 1 ScisS

Id mixture of 1 RtransR and 1 StransS

If 1 RcisS

Ig 1 RtransS

lh IScisR

Ii 1 StRans

Of the compounds of general formula I.

/

GOOCH I

CU

the following are commercially available: - "Cypermethrin" of Formula II

comprising all isomers;

- "Alphamethrin" of formula II, which has only the isomers 1 RcisS and 1 ScisR;

- "deltamethrin" of formula III

KX

^ COOCH!

which has only the 1 RcisS isomer.

In terms of their insecticidal activity, the choice of possible isomers is due to the experimental fact that certain isomers - especially in experiments with Musca domestica species - have proven to be highly and excellently toxic to certain insects, and there has been an apparent trend to market the most active isomers or to synthesize them (Pest, etc., 7,273 ... [1976]).

It is known that the pyrethroid of the formula II (which is known under the generic name "cypermethrin") belongs to the valuable family of synthetic pyrethroids and is useful as an insecticide (HU-PS 170 866). Phenoxybenzaldehyde cyanohydrin can be prepared with cyclopropanecarboxylic acid chloride in the presence of a base (Pestic., Sci., 6.537, [1975]) .The product thus obtained consists of eight stereoisomers, ie, a mixture of four enantiomeric pairs. Mixture of trans- and cis-cyclopropanecarboxylic acid chlorides is used, then the mixture contains 18 to 19% of enantiomer pairs, 21 to 22% of enantiomer pairs, 26 to 27% of enantiomer pair I b and 33 to 34% of enantiomer Pair I d.

In the prior art, the stereoisomers of cypermethrin show different biological activity. It is generally believed that the activity of molecules containing cis-cyclopropanecarboxylic acid is better than that of the corresponding trans derivatives (Pest, Sci., 7,273 [1976]).

In comparative biological assays of various pyrethroids (Pest, Sci., 9, 112-116 [1978]), the cis and trans stereoisomers - including the cypermethrin stereoisomer pairs - were evaluated together.

The comparative experiments were performed with Musca domestica L and Phaedon cochleariae Fab species. From the chloro derivatives of the trans isomers, the activity data of 1 RtransS (Ig) and 1 RtransR were presented. These data show that while the 1 RtransS isomer has strong activity, the 1 RtransR isomer is significantly less active (after the experiment, the bioresmethrin (100) related activity is 1400 and 81 respectively in Musca domestica and 2200, respectively. 110 in Phaedon cochleariae). It was further demonstrated that the activity of a mixture of both isomers tested was less than the calculated value. Thus, the isomers showed rather antagonism rather than the expected synergism, and the value of antagonism was 1.42 and 1.46 in the housefly or horseradish leaf beetle. Because of these experiments and publications, trans-isomers and mixtures thereof have lost much of their biological interest, and research has focused on the active cis derivatives and mixtures thereof. These led to the development of alphamethrin (isomeric mixture of 1 RcisS and 1 ScisR [la] of the chlorinated derivatives) and of decamethrin (which contains the only 1 RcisS isomer [If] of the bromo derivatives).

For this reason, various procedures are known for the preparation of mixtures enriched in cis isomers of known cypermethrin-isomer mixtures.

Object of the invention

With the invention, the deficiency of the prior art should be eliminated.

Explanation of the essence of the invention

According to one aspect of the present invention, there is provided an insecticidal composition having more than one active ingredient which comprises, as an active ingredient, a synthetic pyrethroid represented by the general formula I (wherein X represents chlorine or bromine) in an amount of 0.001 to 99 mass% the eight possible isomers at least 95% of a 55:45 to 25:75 mixture of the enantiomer pairs la: lb, where la 1 is RcisS + 1 ScisR and Ib 1 is RtransS + 1 StransR - optionally with an activator and / or an additive in an amount of up to 100% by mass, preferably an antioxidant, stabilizer, wetting agent, emulsifier, dispersant, antifoaming agent, diluent, carrier and / or filler.

The invention is based on the finding that the isomer mixture I a + I b has valuable and advantageous biological properties. These properties are surprising and unforeseeable, although extensive research has already been carried out in the field of pyrethroids of general formula I and a number of publications and patents have appeared.

It is also known that mixtures enriched in cis isomers can be prepared by crystallization from solutions containing other isomers (CA 95, 1981, KOKAI No. 57755/81). A substantially pure 1: 1 mixture of TRcisS and 1 ScisR isomers can be separated by the use of suitable solvents from a mixture also containing the other cis isomers (British Patent 2,064,528). The isomer mixture I a is described as being very active.

Specifically, so-called "high-cis" syntheses have been elaborated for the preparation of cis-cyclopropanecarboxylic acid intermediates containing cis isomers beyond a certain limit (over 50%), but these processes have been quite expensive (Angew. Chem. I e 24,996 [1985]).,

The invention is based on the finding that when using a combination of the 1 RtransS isomer I g (which is the most active trans isomer of the compounds of formula II) and the 1 StransR isomer I i (which under the less active isomers of the remaining seven isomers) no characteristic antagonism characteristic of the previously published isomer pairs can be observed.

Rather, a synergistic effect beyond the additive effect of the pure I g and I i isomers, when used as such.

The above knowledge has created a new way of selecting the isomers of synthetic pyrethroids to develop a new type of drug with excellent properties. The new active ingredient has several advantages over the previously known isomer selections:

- lower toxicity in warm-blooded animals and humans;

- a more economical manufacturing process;

- less damage caused to beneficial parasites and bees.

The novel compositions containing the isomer mixture Ib are described and claimed in our co-pending patent application, application file reference.

The invention is based on the further recognition that the biological order of biological activity previously found in the individual isomers and the already known rules described for the isomer pairs are not absolutely valid for other isomer pairs.

Therefore, an attempt was made to compare and simultaneously test the 1 RtransS + 1 StransR enantiomer pair Ib-which was determined to be active as a result of the experiments - with other isomers. The comparison has shown that the synergism observed between the members of the enantiomeric pair Ib (i.e., Ig and Ii) does not occur between the members of the corresponding cis-enantiomeric pair Ia (i.e., If and Ih).

The invention is based on the further finding that, while of the 1 RcisS (If) and 1 RtransS (Ig) isomers, in general, the If isomer is the more active, the biological activity of the enantiomeric pair Ia and Ib in some species is precisely that . Has partly resulted.

As a result of the above facts, it has surprisingly been found that when the enantiomeric pairs Ia and Ib are used simultaneously, a synergistic effect is observed, i. the effect of the combination is stronger than the additive effect of both enantiomer pairs when used as such.

It has been found that the synergistic biological effect of mixtures of Ia + Ib is not limited to those mixtures in which Ib is more active than Ia. Thus, the use of two enantiomer pairs in potato beetles (Leptinotarsa decemlineata) results in significant synergism. These results are set forth in detail in the examples. Based on the above findings, a new selection was made from the already known isomer mixtures, and this resulted in the novel composition of the invention.

In addition to the synergistic effect, the composition according to the invention has a number of other advantages, and for this reason it is an excellent product. It is very important that the compositions of the invention are less toxic to mammals than the heretofore known compositions having a similar efficiency. This is clearly evidenced by the so-called selectivity index (5 17 and 747, respectively), which is the quotient of approximate LD ₅₀ values which are local in rats (280 and 355 mg / kg) and in house flies (0.54 and 0.48 mg / kg, respectively). This selectivity index is at la 50 / 0.45 = 111.

The synergistic effect is also seen with mites (see biological example 19), therefore the compositions are also useful as acaricidal agents. The compositions of the invention have low toxicity to bees and do not harm useful parasites and entomophages (biological examples 25 and 26). The advantageous properties are based on the repulsive effect, preferably the duration of action and the suitable, the drug inherent activity.

By virtue of the abovementioned properties, it is possible to use the mixture of the enantiomer pairs according to the invention for integrated crop protection technology (IPM = integrated pest control).

The economic advantages of the compositions of the invention are at least as important as the biological efficiency. The preparation of a pure cis-enantiomeric pair Ia requires very expensive synthetic methods or is associated with the loss of the trans components that are formed in the reaction mixture. In contrast, the invention allows the use of virtually all components I a and I b from the reaction mixture formed by the most economical syntheses. (The efficiency of course depends on the respective syntheses used and the ratio of the components I a and I b of the mixture).

The insecticidal compositions of the invention containing isomer pairs Ia and Ib mixed with known additives may be formulated in forms suitable for direct use. The composition of the present invention may be ULV (ultra-low volume) compositions, sprays, dispersible powders, granules, surface active or other powders, durable emulsions, etc. The compositions are suitable for the pesticidal treatment of vegetables, vineyards, orchards, cereal fields and other large crops. Due to their low toxicity, the compositions of the present invention are particularly useful in the control of flying insects and pests that live in housings or walls of stalls, or in the treatment of pasture.

Another aspect of the invention relates to the use of the insecticidal compositions. It is preferred to use the compositions under field conditions in an amount of from 2 to 25 g of active ingredient per hectare. The insecticidal compositions of the invention may contain, in addition to isomer pairs I a and I b, activators and other synergists, e.g. Piperonyl butoxide. The additives increase the efficiency of the active substance without increasing the toxicity to warm-blooded animals.

According to a preferred embodiment, dispersible granules are provided which contain from 1 to 99% by weight of active compound mixed with from 99 to 1% by weight of suitable additives. As the additive, for example, 0.1 to 1% by mass of anionic and / or nonionic surfactants, such as alkali salts of alkylarylsulfonic acids, alkali salts of condensation products of alkylarylsulfonic acids and formaldehyde, alkylaryl glycol ethers, sulfated long-chain alcohols, polyethylene oxides, sulfated fatty alcohols, fatty acid polyglycol esters and various other commercial surfactants.

The insecticidal compositions of the invention may also be formulated in the form of concentrates, preferably containing from 5 to 50% by weight of the active ingredient mixed with from 50 to 95% by weight of additives which allow the formation of a durable emulsion when the emulsion concentrate, with or without water is emulsified.

As the additive, 1 to 20% by mass of a surfactant and / or 0.1 to 5% by mass of a stabilizer can be used, and the mixture can be preferably made up to 100% with an organic solvent. As the surfactant, the use of a mixture of anionic and nonionic surfactants is preferred. The following surfactants may preferably be used: calcium salts of alkylarylsulfonic acids, mono- and diesters of phosphoric acid, nonyl and tributhenol polyglycol ethers, adducts of fatty alcohols and ethylene oxide, fatty acid polyglycol esters, ethylene oxide-propylene oxide block polymers, etc.

The solvents used may preferably be mixtures of aromatic hydrocarbons (for example xylenes), cyclohexanol, butanol, methyl ethyl ketone, isopropanol and the like.

The compositions according to the invention may also contain other synergists which make it possible to reduce the amount of active ingredient. For this purpose, it is preferable to use piperonyl butoxide. A process for the preparation of an insecticidal active ingredient which comprises, of the eight possible isomers of synthetic pyrethroids of general formula I (wherein X is chlorine or bromine) substantially only a 55:45 to 25:75 mixture of enantiomeric pairs I a: Ib in which la 1 RcisS and IScisRist and Ib 1 RtransS and iStransRist - has the following steps: a) From a mixture which, in addition to the isomer pairs I a + I, also other possible isomers and / or the isomer pairs I a + Ib in a ratio other than the desired value, preparing a saturated solution with a protic or apolar aprotic inert organic solvent, seeding the solution with a 55:45 to 25:75 mixture of enantiomer pairs la + Ib existing seed crystal and isolation of at a temperature between 3O ⁰ C and -30 ⁰ C precipitating crystals; or

b) inoculating a melt of a mixture containing, in addition to the isomer pairs I a + I b, other isomers and / or the isomer pairs Ia + I b in a ratio other than the required value, with one from a 55:45 to 25: 75 mixture of enantiomer pairs la and Ib existing seed crystal at a lying between 10 ° C and 60 ⁰ C temperature, leaving the solution to crystallize at a temperature between 30 ⁰ C and -1O ⁰ C and, if desired, suspending the on this mixture obtained in a protic or apolar aprotic inert organic solvent at a temperature between -1O ⁰ C and -2O ⁰ C and isolating the precipitated crystals; or

c) addition of an enantiomer pair I a or I b to a solution or melt of a mixture other than the isomer pairs

I a + I b contain other isomers and / or the isomer pairs la + I b in a ratio other than the required value, in an amount such that the solution or the melt contains the isomers in a ratio of 55:45 to 25:75 and, if desired, crystallization according to variant a) or b); or

d) Mixing of the enantiomeric pairs Ia and I at the desired ratio if desired in the presence of a protic or apolar aprotic organic solvent - homogenizing the mixture and crystallizing - if desired after the inoculation step according to variant a).

According to variant a) of the inventive method ₁₀ alcohol may preferably be a C ^ hydrocarbon, chlorinated Ci-e hydrocarbon, Ci-s-dialkyl ether or CI_ be used as organic solvent. The solvents may be straight-chain or branched-chain or cyclic and alicyclic.

It is preferred to carry out seeding with a seed crystal in the presence of an antioxidant - especially tertiary butylhydroxytoluene or 2,2,4-trimethylquinoline - and to use ethanol, isopropanol, petroleum ether or hexane as the solvent.

The crystallization can preferably be carried out with gentle cooling.

In a preferred embodiment of the process, a mixture of 60% trans and 40% cis-cypermethrin enantiomer pairs (18.2% I a, 26.8% I b, 21.8% I c and 33.2% I d, hereinafter referred to as I e) used as starting material.

The mixture is dissolved in isopropanol and the solution is made with seed crystals consisting of a mixture of Ia and Ib in the presence of 0.01% of 2,2,4-trimethylquinoline or tertiary butylhydroxytoluene. A crystalline product is recovered in an absolute yield of 35 to 40%, melting at 63.5 to 65 ⁰ C, having enantiomeric pairs I a and I b in a ratio of 40:60, and enantiomeric pairs I c and contains I d as an impurity in an amount of 5%. The products thus obtained can be recrystallized as described above. Thus, the mixture of enantiomeric pairs I a and I b can be prepared with greater than 99% purity.

Similar results can be obtained by recrystallization of mixtures with a different cis / trans ratio.

The cypermethrins used as starting material can be prepared by esterification of the mixture of cyclopropanecarboxylic acids with a suitable cis / trans ratio.

The following table gives the melting points of mixtures with different cis / trans ratio.

Ia / l b 25:75 30:70 40:60 50:50 55:45

F.P. ° C 67-71.5 65-68 63.5-65 60.5-62 61.5-64

The practicality of the crystallization step in the desired direction necessarily depends on the purity of the cypermethrin mixture used as the starting material. If the content of the active ingredient is less than 95%, the yields decrease. Tar-like impurities can even inhibit crystallization.

The crystallization of the mixture of the enantiomeric pairs I a and I b can also be carried out without a solvent. Thus, cypermethrin of composition Ie can be inoculated with crystals consisting of Ia and Ib. In a refrigerator, the precipitation of the mixture of I a and I b takes place within one week. The crystals are isolated by adding chilled to -20 ⁰ C ethanol to the mixture and by filtering the crystals.

The mixture of the enantiomeric pairs la + I b can also be prepared so that I a and I b are mixed and / or different amounts of which are crystallized or that a mixture of la and Ib or a calculated amount of Ib are mixed or crystallized ,

The biological effectiveness of the products according to the invention is tested in various types of insects. In the experimental procedures, the effect of the reference standard and known methods - e.g. obtained by chromatographic separation or by chromatographic separation of cypermethrins prepared from chiral acids - prepared stereoisomers.

The insecticidal compositions according to the invention are harmless to the environment and can be used, above all, in households and stables for controlling flying insects and pests that live in secret, and also for bathing domestic animals and for treating pastures.

embodiments

Further details of the invention will become apparent from the following chemical and biological examples, without limiting the scope of the examples.

Chemical Examples Example 1

100 g cypermethrin (which after gas chromatography consists of a mixture of 18.2% Ia, 21.8% Ic, 26.8% Ib and 33.2% Id), 0.2 g of potassium hydroxide and 0.2 g of tertiary 2,6-dibutyl -4-methylphenol are dissolved in 2000 ml of isopropanol with stirring at 45, ^{0 0} C. The solution is slowly cooled to 30 ⁰ C, clarified with charcoal and filtered at 30 ⁰ C. The colorless solution is seeded with a group consisting of 60% of Ib and 40% of la crystal, and the mixture is stirred for 24 hours at -1O ⁰ C. The precipitated product is filtered, washed with isopropanol and dried under vacuum. This gives 36.02 g of a snow-white crystalline product. Melting point 62 to 65 ⁰ C (uncorrected value). After GC and TLC analysis, the product contains 37% Ia and 58% Ib isomers. Yield: 76% (based on the content of la + Ib isomer of cypermethrin starting material). la isomer Rf = 0.25; Ib isomer R _f = 0.20.

After recrystallization from isopropanol, 32 g of product are recovered as first crops. Melting point: 63.5 to 65, O ⁰ C; the product consists of 39.5% la and 59.5% lb.

NMR (CDCl ₃ ) 8 (ppm): 1.05-2.45 m (8H); 5.6, d, j = 8Hz (= CH trans 0.6H); 6.14, d, J = 8Hz (= CH ice 0.4H); 6.35, d, (1H); 6,85-7,6Om, (9H).

Example 2

100 g of cypermethrin (27.8% Ia, 21.8% Ib, 32.1% Ie and 18.2% Id), 0.2 g of potassium hydroxide and 0.2 g of tertiary 2,6-dibutyl-4-methylphenol are dissolved in 2000 ml of isopropanol dissolved at 45 ⁰ C with stirring. The solution is clarified with activated charcoal and filtered at 30 ⁰ C. The colorless solution is seeded with a consisting of 20% Ib and 80% la seed and stirred for 36 hours at -1O ⁰ C. The precipitated product is filtered, washed with isopropanol and dried under vacuum. This gives 30 g of snow-white crystalline product, m.p. 66-73 ° C. After gas chromatography, the product contains 77% Ia + 19% Ib, purity 96% (TLC see Example 1). After recrystallization from isopropanol are obtained as the first generation 26.5 g snow-white crystalline product, melting point 70 to 73 ⁰ C containing 81.5% la + 18% Ib (GC analysis). IR (KBr) vc _{= 0} : 1730cm " ¹

NMR (CDCl ₃ ) O (PPm): 1.05-2.45 m (8H); 5.60, d, J = 8Hz (= CHtransO, 2H); 6.14, d, J = 8Hz (= CH ice 0.8H); 6.35, d (ArCH 1 H); 6,85-7,6Om (9H).

Example 3

100 g of colorless, transparent oily Cypermethrin (18.2% la, 21.8% Ic, 26.8% Ib and 33.2% Id) are inoculated with a seed crystal consisting of 60% Ib and 40% la, and the solution becomes allowed to crystallize at 7 ° C for one week. The mixture is poured into 100 ml of a 1: suspended 1 mixture of isopropanol and diisopropyl ether and filtered at -15 ⁰ C. The crystals are washed with isopropanol and dried under vacuum. This yields 40.1 g of white crystalline product containing 37.5% Ia and 59% Ib. Melting point 62.5-65 ⁰ C. Yield 86%. After recrystallization from isopropanol are obtained as the first generation 36g snow-white crystalline product, melting point 63.5 to 65 ⁰ C, which consists of 40% la and 60% Ib (GC). The IR and NMR data are identical to those mentioned in Example 1.

Example 4

100 g of cypermethrin (18.2% la, 21.8% Ic, 26.8% Ib, 33.2% Id) and 0.05 g of tertiary 2,6-dibutyl-4-methylphenol are stirred with constant stirring at ^{0 0} C in Dissolve 100 ml of diisopropyl ether, and the solution is clarified with 2 g of activated carbon. The solution is filtered and seeded at -15 ° C with a consisting of 60% Ib and 40% la seed crystal. The mixture is left to crystallize for 72 hours, the crystals are filtered, washed with diisopropyl ether and isopropanol and dried. Thereby 38 g of a snow-white crystalline product with a melting point of 62 to 65 ⁰ C are obtained, which contains 37.5% la and 58% Ib. After recrystallization from isopropanol are obtained as a first generation 35g snow-white crystalline product, melting point 63.5 to 65 ⁰ C, in which the ratio of la: lb isomers is 40:60. The physical constants are identical to those given in Example 1.

Example 5

10 g samples of the product obtained according to Example 2 (ratio of 1: 1b isomers = 4: 1) are mixed with 4.60 g, 6 g, 10 g, 16.67 g and 22.0 g of pure seed crystals of Ib, respectively obtained mixtures are recrystallized according to the description in Example 1 each from a 10-fold amount of isopropanol. The composition and melting point of the products thus obtained are included in the following table.

la: lb Mp CC) 55:45 61.5 to 64 5: 5 60.5 to 62 4: 6 63.5 to 65 3: 7 65-68 25:75 67 to 71.5

Examples

10 g samples of pure crystalline isomer pair 1a are mixed with 8.20 g, 10.00 g and 15.00 g pure crystalline isomer pairs, respectively, and the mixtures are homogenized. The crystal mixtures obtained thereby contain the substances la + Ib in a ratio of 55: 45.50: 50 and 40:60, respectively. Melting point 61.5 to 64 ° C, 60.5 to 62 ° C and 63.5 to 65 ⁰ C.

Example 7

10 g samples of the pure crystalline isomer pair Ia are dissolved in a 10-fold amount of isopropanol, and to each sample are added 23.34 g and 30.0 g of pure crystalline isomer pair Ib, respectively. The solutions are allowed to crystallize. The precipitated white crystalline products (melting point 65 to 68 ⁰ C and 67 to 71.5 ⁰ C) contain the la: Ib isomers in a ratio of 30:70 and 25:75. The product thus obtained can be formulated as a plant protection product and is a useful insecticidal active ingredient.

Example S

To 166.2 g of perlite (d _max = 120μ, ηη) 0.8 g of synthetic silica (Aerosil 300) are placed in a high speed vortex stirrer. 20 g of a cypermethrin mixture of the enantiomer pairs la: lb = 4: 6 and 2 g of fatty alcohol polyglycol ether are added, so that the mixture is uniformly homogenized. The powder mixture is first in a mechanical mill and then

milled in an air-flow mill, whereupon 5 g of octylphenol polyglycol ether (EO = 20) and 2 g of sulphosuccinate are added in a high-speed stirrer. The resulting powdered surface-active powder mixture (WP) is subjected to a suspension stability test. Network time = 23 seconds; Floatability = 89% (standard WHO method).

Example 9

3g of a mixture of cypermethrin enantiomer-pairs la: lb = 3: 7 and 0.3 g of fatty alcohol polyglycol ether are placed in a homogenizer on talc (d _{m "ax} = 15 / xm) and with a buffer of 0.8 g synthetic silicic acid (Aerosil 200 and 193.9 g of potassium and sodium phosphate are adjusted to a pH of 6.5. To the mixture, 1 g of dioctylsulfosuccinate and 1 g of fatty alcohol polyglycol ether sulfonate are added with stirring, and the mixture is ground to an average particle size of 20μΓη a thin, flowable powder mixture is obtained.

Example 10

5 g of a mixture of cypermethrin enantiomer pairs la: Ib = 55:45 are dissolved in a mixture of 21.25 g of xylene and 42.5 g of n-propanol with slow stirring. To the solution, a mixture of 4g of ethoxylated aikylphenol + calcium linear alkylaryl sulfonate salt and a mixture of 6g of ethoxylated amine + alkali salt of linear alkylaryl sulfonate are added with stirring until all the materials are completely dissolved, after which 21.25g of water are added. As a result, a transparent solution is obtained whose properties are maintained at a temperature lying between ^{0 0} C and 50 ⁰ C for a long time. The solution may optionally be diluted with water in any amount to form an emulsion having a droplet size of 0.8 to 1.5 ^ m.

Example 11

5 g of a mixture of the cypermethrin enantiomer pairs la: Ib = 25:75 are dissolved in a mixture of 75 g of xylene and 10 g of an aliphatic oil, followed by a mixture (7.5 g) of ethoxylated aikylphenol + calcium salt of linear alkylarylsulfonate and also a mixture (2.5g) of ethoxylated fatty acid + linear alkylaryl sulfonate salt with slow stirring. When measured by the CIPAC method, the emulsion concentrate is still stable after 170 hours.

Example 12

In a mechanical granulator, a 50:50 mixture of the cypermethrin enantiomeric pairs Ia and Ib are mixed with 1,500 g of polycarboxylate alkali salt, 500 g of sodium dodecylbenzenesulfonate, 500 g of sucrose and 7200 g of china clay. The powder mixture is mixed with 8300 g of water using a high shear agitator (v = 10 m / s) and spray dried. The distribution of the particle size is as follows: 0.1 to 0.4 mm = 95%. The floatability is 98% (according to the WHO method).

Example 13

Emulsifiable concentrates (EC) are prepared by mixing the following ingredients:

10EC component component Quantity, kg / kg Isomer-pairela: lb = 40:60 Isomer-pairela: lb = 40:60 0.105 cyclohexanol cyclohexanol 0,290 Atlox3386B Atlox3386B 0,020 Atlox3400B Atlox3400B 0,045 Odorless mineral oil Odorless mineral oil 0,540 5EC Quantity, kg / kg 0,050 0,290 0,020 0,045 0.595

Biological Examples Example 14

Table 1 shows the activity of various stereoisomers of cypermethrin in the housefly (Muscadomestica). The experiment is carried out as follows:

The active ingredient is dissolved in a 1: 2 mixture of oil and acetone; Filter paper sheets (Whatman No. 1, diameter 9 cm) are impregnated with the solutions of the corresponding stereoisomers or enantiomer pairs. The acetone may evaporate, after which the insects are placed on the filter paper sheets placed in Petri dishes. For each dose, three replicates are performed and 15 insects are added to each Petri dish. After 24 hours, the percentage mortality is determined. The corrected percent mortality is calculated using Abbot's formula.

Table 1

Cypermethrin stereoisomer

0.04

Dose (mg / filter paper) 0.11 0.33

Mortality after 24 h (%)

1.00

If 68 la 44 ig 48 ib 32 la: lb = 40:60 41

93 84 68 62 81

100 100 100 100 100 100 83 100 100 95 100 100 100 100 100

According to this experiment, the activity of the mixture la + Ib corresponds to that of the pure isomer Ia.

Example 15

From Table 2 it can be seen that the enhanced activity shown in Example 14 is due to the synergistic effect of the trans isomer in Tribolium confusum.

Table 2

active substance

Dose (mg / sheet)

0.11 0.33 1.00

Mortality after 24 h,%

3.00

IScisR (lh) 0 1 RcisS (If) 80 la 22 IStransR (li) 0 IRtransS (lg) 70 ib 64 la: lb = 40:60 61

38 80 100 100 100 100 65 94 100 0 71 90 92 100 100 89 100 100 89 100 100

In Example 18 it is shown in other insect species that the enantiomeric pair Ib according to the invention is more active than Ia. The increased activity is evident not only in mortality after 24 h, but also in the fact that the toxic effect occurs more quickly.

Example 16

Table 3 shows the insecticidal activity of mixtures of enantiomeric pairs Ia and Ib in different proportions in American rice beetles (Tribolium confusum). As a test method, that explained in Example 14 was used.

Table 3

la: lb

0.02

Dose (mg / filter paper)

0.06 0.25

Mortality after 24h,%

1.00

10: 0

5: 5

4: 6

3: 7

12:10

0 0

14

20

14 43 53 81 46

54 • 100 100 100 100 100 100 100 100 100

The above data clearly demonstrates the synergism between enantiomeric pairs Ia and Ib.

Example 17 '

According to a further realization of the invention, when mixtures of the enantiomeric pairs Ia and Ib are combined with conventional pyrethroid synergists (e.g., piperonyl butoxide, NIA 16388, etc.), the enhancement of activity

exceeds the normal value (see Example 16).

Table 4 shows the activity against potato beetles.

The test procedure is as follows:

The test substances are dissolved in 2-ethoxyethanol (cellosolve). A 0.3-ju.l drop of the solution is applied to the abdominal area of the imago. The treatment is carried out with the help of two parallel experiments and 10 insects for each dose. The

Mortality is determined after 48 hours.

Table 4

active substance

0.05

Dose (^ g / beetle)

0,10 0,20

Mortality after 24 h,%

la

ib

la: lb = 4: 6 la: lb = 3: 7 deltamethrin cypermethrin

55 25 60 65 60 20

75 75 70 75 75 45

Synergism can be observed between the enantiomer pairs la and Ib, although la is more active than Ib in Imagos of potato beetles. Mixtures of enantiomeric pairs Ia and Ib have the same activity as deltamethrin.

Example 18

The comparative test of la, Ib and a 40:60 mixture of la: Ib is made with bean beetles (Acanthoscelidesobtectus), American rice flour beetles (Tribolium confusum), houseflies (Musca domestica) and sheep flies (?) (Lucillia sericata). The procedure described in Example 14 is used. The results are summarized in Table 5.

Table 5

species enantiomers 0.02 0.07 Dose (mg / filter paper) 0.67 95 2.0 6.0 Pair 0.22 Mortality,% 100 10 37 63 100 100 100 A. Obtectus la 32 55 87 100 100 100 (Imago) ib 30 55 90 100 100 100 la: lb = 4: 6 0 18 51 100 100 100 T. confusum la 14 73 100 100 100 100 (Imago) ib 16 80 100 100 100 100 la: lb = 4: 6 36 63 88 100 100 100 M. domestica la 0 18 67 57 100 100 (Imago) ib 25 45 85 75 100 100 ia: lb = 4: 6 0 30 29 75 60 65 L sericata la 22 55 70 100 100 (Imago) ib 18 50 60 100 100 la: lb = 4: 6

Example 19

Determination of the activity of stereoisomer pairs as a function of time in American rice flour beetles

(T.confusum).

Imagos of American rice flour beetles (T. confusum) are seeded in Petri dishes according to the procedure described in Example 14. Three parallel experiments are carried out for each dose and 15 animals are used for each parallel experiment. At each time the insects lying on its back are counted and the percentage results are shown in Table 6.

Table 6

Stereoisomer pairs and enantiomer pairs

exposi Dose (mg / filter paper) 0.33 0 1.00 3, OC TION 0.11 % of the toxic symptoms 0 duration pointing insects 0 (Minutes) 0 0 0 0 30 0 0 0 8th 60 0 5 0 67 120 0 40 0 88 180 0 61 48 64 30 0 0 84 100 60 0 0 100 100 120 39 14 100 100 180 0 49 0 33 30 0 16 88 60 0 66 100 120 10 100 100 180

Continuation of Table 6

Stereoisomer pairs and enantiomer pairs

exposi Dose (mg / filter paper) 0.33 0 1.00 (3.0 TION 0.11 % of the toxic symptoms 0 duration pointing insects 0 (Minutes) 0 0 ' 0 15 30 0 0 0 70 60 0 34 0 100 120 0 70 0 100 180 0 84 15 68 30 18 0 98 100 60 30 21 100 100 120 34 100 100 100 180 0 100 47 61 30 0 0 82 100 60 28 85 100 100 120 56 100 100 100 180 0 100 50 55 30 15 85 100 60 30 , 100 100 120 55 100 100 180

la: lb = 4: 6

Example 20

Imagos of American rice flour beetles (T. confusum) are treated analogously in Example 14. The synergist used is piperonyl butoxide at a dose of 0.5 mg / filter paper.

Table 7

Cypermethrin stereoisomer

0.4

Dose (mg / filter paper) o, t 0.2 0.1 Mortality after 24 h,% 0 53 12 0 58 16 18 90 57 43 95 75

la 96 la + PBO 100 la + lb 100 la + Ib + PBO 100

It will be noted that the mixture of enantiomers Ia and Ib can be synergized to a greater extent than enantiomer Ia (Ia: Ib = 4: 6).

Example 21

The active ingredients are dissolved in 2-ethoxyethanol and the solutions are applied in the form of O, 2- / nl droplets to the back of white bear spinners (Hyphantria cunea) at the L ₇ -L ₈ -learv stage. The treated insects are placed on strawberry leaves in Petri dishes. The test is performed in two parallel experiments for each dose and with 10 insects for each dose. The killed beetles are counted after 24 hours, and the percentage mortality rate is calculated. The results are summarized in Table 8.

Table 8

active substance

0.023

Dose (^ g / larva) 0 " 0.047 0.094 Mortality after 24 h,% 80 60 65 70 15 30 65 50. 55 50 10 25

la 40 ib 10 la: lb = 4: 6 40 cypermethrin 0

Example 22

Leaves already infected by mites (Tetranychus urticae) are injected under the Potter hood. After 24 hours, the mortality on the treated leaves was compared to the control.

Table 9

active substance

approximate LD50 (ppm)

la

ib

la: lb = 4: 6

cypermethrin

deltamethrin

0.056 0.340 0.060 0.120 0.185

-11 - £ 01

Example 23

The öEC formulations prepared according to Example 13 are diluted with water 5Ox, 100x, 20Ox, 400x, 80Ox and 160Ox and 0.5 ml cans are sprayed onto glass plates. After drying, 10 L decemlineata lmagos are placed on each glass plate and the insects are covered with Petri dishes. The experiments are carried out using 6 dose levels and in 3 parallel trials for each dose. The killed insects are counted after 48 hours. The results are included in Table 10.

Table 10

5EC 160Ox 80Ox dilution 100x 5Ox 97 formulation 40Ox 20Ox 93 - 0 27 Mortality,% 87 100 la •O 33 53 63 80 83 la: lb = 4: 6 7 35 53 73 83 deltamethrin 0 17 53 67 67 cypermethrin 33 50

Example 24

In an analogous manner to Example 23, glass plates are sprayed with the 5EC formulations prepared according to Example 13. After drying, place 10 Imagos of Beanbug (Acanthoscelidesobtectus) on each plate and cover the insects with Petri dishes. The killed insects are counted after 24 hours. The test is performed at 6 dose levels, performing 3 parallel experiments per dose. The results are summarized in Table 1.

tables

5EC 160Ox 80Ox dilution 10Ox 5Ox formulation 40Ox 200x 0 13 Mortality,% 50 70 la 10 17 27 33 53 70 la: lb = 4: 6 7 13 30 37 57 75 deltamethrin 0 3 20 37 45 60 cypermethrin 10 20

Example 25

15 bean plants infected with green peach aphids (Myzus persicae) at the age of 6 days are grown in each pot. After a period of 12 days, strongly and uniformly infected plants are selected and injected until draining with freshly prepared from the formulations of Example 13 emulsions. The treatments are performed with three dose levels (active ingredient 2.5, 5 and 10 ppm), and four parallel experiments are carried out (one pot per parallel experiment). On the second, fourth and eighth days after the treatment, the aphids are brushed off the plants on a white paper with a soft brush, and the living insects are counted. The results are included in Table 12.

Table 12

5EC concentration Average number 8th formulations (Ppm) of aphids per pot Days after treatment 2 4

la: lb = 4: 6

deltamethrin

2.5 5.0

10.0 2.5 5.0

10.0 2.5 5.0

10.0

83 245 29 90 17 30 71 251 32 82 11 21 47 137 19 29 11 23 2780 4120

control

Example 26

Potted tomato plants are sprayed with a suspension prepared from the active ingredient and a mixture of acetone and water. The treated plants are placed in an isolation room and infected with larvae of Leptinotarsa decemlineara in the L ₃ stage. The percentage of paralyzed larvae that fall off the plants is determined after 6 hours. The results are shown in Table 13.

Table 13

concentration la la: lb = 4: 6 (Ppm) % paralyzed larvae 1000 100 100 200 100 100 40 46 75 8th 18 60

Example 27

The treatments are carried out on a parcel of 25 m ² , which is heavily infested by potato beetles. 10 plants per plot are specially marked, on which the Colorado beetles have been counted before. (During the determination of the number of pests, only adults of the second generation of the summer are considered, because at the time of the experiment the ratio of larvae in the stages L ₃ and L4 is negligible). The treatment is carried out on a 25 m ² parcel at a dose of 10 g of active ingredient / ha in the form of aqueous suspensions of the formulations according to Example 10, and three parallel experiments are carried out. The test is evaluated by counting the live insects on the labeled plants. The average values of the three parallel experiments are listed in Table 14.

Table 14

5ME Average number of live

Formulation insects / 10 plants

Time passed since the treatment

(in days)

0 1 3 9 9 la 171 11 4 25 la: lb = 4: 6 213 8th 10 22 deltamethrin 181 7 179 19 control 211 206 183

Example 28

Residual contact test with adult animals of Aphidinus matricariae. Adult animals of M. matricariae are contacted with remnants of the active ingredients applied freshly to glass plates forming cages, and then the surviving animals are counted.

Treatment: Test product (s) and control treated with water.

Repetitions: at least3. Lot size (net): 1 cage.

Parasites of known age (24 hours) are used.

The products are applied to each of the glass plates at a concentration of 5.1 ppm.

10 female animals of A. matricariae are placed in each cage and fed with honey as food. The number of females surviving the exposure is determined after 1, 2 and 24 hours in independent experiments. The total number of survivors is calculated for each cage. The results are included in Table 15.

Table 15

5 ppm 1h concentration 5h Mortality,% 100 1 ppm 1h 90 24 hours 100 100 100 50 96 Ia 100 20 63 la: lb = 4: 6 100 85 deltamethrin

Example 29

Direct contact test with pupae of A. matricariae.

Adult dolls of A. matricariae on pepper leaves in Petri dishes receive a direct spray with the active ingredients. Paprika leaves infected with parasite pupae are used two or three days before emergence. The leaves are placed on moistened filter paper in a plastic Petri dish.

Treatment application: see example 28.

Leaf pieces are placed on the bottom of clean Petri dishes after treatment. The trays are stored in a climatic chamber at a temperature of 20 ° C, 70% relative humidity and a light-dark cycle of 16 to 8 hours. Surviving dolls hatch after 2 to 3 days, the number of hatched and dead dolls is counted. The results are included in Table 16.

Table 16

Active substance concentration

30 ppm 10 ppm 5 ppm 1 ppm

Mortality,%

lb: la = 6: 4 14.3 0 0 0

Deltamethrin 75.0 33.0 0 0

la 77.0 12.5 0 0

Control 0 0 0 0

Claims (5)

-1- 257 38Z claims: 1. Insecticidal composition with more than one active ingredient, characterized in that it contains as active ingredient a synthetic pyrethroid of the general formula ^ (wherein X is chlorine or bromine) in an amount of 0.001 to 99% by mass - of the eight possible isomers at least 95% of a 55:45 to 25:75 mixture of the enantiomer pairs la: lb, in which la 1 RcisS + 1 ScisR and Ib 1 RtransS + 1 StransR is mixed on request with an activator and / or with an additive in an amount up to 100%, preferably an antioxidant, stabilizer, wetting agent, emulsifier, dispersing agent, antifoam, Diluent, carrier and / or filler contains. 2. Insecticidal composition according to claim 1, characterized in that it contains as active ingredient a 40:60 mixture of la: lb. 3. Insecticidal composition according to claim 1, characterized in that it contains as active ingredient a 30:70 mixture of la: lb. 4. Insecticidal composition according to claim 1, characterized in that it contains as active ingredient a 50:50 mixture of Ia: Ib. 5. Use of an insecticidal composition with more than one active ingredient according to claim 1, characterized in that it is used for controlling insect pests in a dose of 2.0 to 25 g of active ingredient per hectare.