CS254994B2 - Synergetic insecticide and method of its efficient component production - Google Patents

Description

The invention relates to an insecticidal than one pyrethroid of formula I

4 as well as a process for the preparation of these active substances.

In the description of the present invention, the spatial configuration of the substituents relative to the chiral carbon atom designated by the letter "ar" is characterized by the letters "S", respectively. "R".

The terms "cis" and "trans", respectively, refer to the position of the substituents that are attached to the carbon atom "3" of the cyclopropane ring in relation to the spatial configuration of the carbon atom substituents "1" of the cyclopropane ring. The absolute spatial configuration of the substituents that is attached to the carbon atom "1" of the cyclopropane ring is indicated by the prefix "1 (R) ^U and" 1 (S) ".

In this specification, various enantiomers and pairs of enantiomers are designated by the following abbreviations:

Ia mixture of 1 (R) -cis (S) and 1 (S) -cis (R) 1b mixture of 1 (R) -trans (S) and (S) -trans (R) Ic mixture of 1 (RJ-cis (R) ) and 1 (S) -cis (S) 1d mixture of 1 (R) -trans (R) and (S) -trans (S) If 1 (R) -cis (S) Ig 1 (R) -trans (S) )

Ih 1 (S) - cis (R) 1 (S) - trans (R).

Pyrethroids of the formula I (known under the generic name "Cypermethin") are known to belong to a valuable group of synthetic pyrethroids and are useful as insecticides (cf. Hungarian patent specification 170 866). These compounds can be prepared by reacting m-phenoxybenzaldehyde cyanohydrin with cyclopropanecarboxylic acid chloride in the presence of a base [cf. Fist. Sci. 6, 537 et al. (1975)]. The product thus obtained contains eight stereoisomers, i.e. a mixture of four pairs of enantiomers.

When mixtures of cyclopropanecarboxylic acid chlorides with a ratio of 60 to 40 isomers are used, the mixture contains 18 to 19% pairs of enantiomers Ia, 21 to 22% pairs of enantiomers Ic, 26 to 27% pairs of enantiomers 1b and 33 to 34% pairs enantiomers Id.

It is already known that stereoisomers of Cypermethrin have different biological activity. In general, the activity of molecules containing the cis-isomers of cyclopropanecarboxylic acid has been shown to be higher than that of the corresponding trans-derivatives [cf. Fist. Sci. 7, 273 (1976)].

In comparative biological tests of various pyrethroids [cf. Fist. Sci. 9, 112-116 (1978)], the cis- and trans-stereoisomers - including the stereoisomeric pairs of Cypermethrin - were evaluated together.

Comparative tests were performed on house fly (Musea domestica L.) and leaf beetle [Phaedon cochleariae Fab.). As for the chloro derivatives, data on the effect of the 1 (R) -trans (S) (Ig) and 1 (R) -trans (R) isomers have been reported from the trans isomers.

The data shown shows that while the 1 (R) -trans (S) -isomer has strong potency, the • 1 (R) -trans (R) -isomer is significantly less potent [as in the potency test using Bioresmetrin as the standard (100). the efficacy values are 1 400 and 81 (in the housefly test) and 2 200 and 110 (in the leaf beetle test)].

It was further described that the efficacy of the mixture of both tested isomers was lower than the calculated value. It is clear from the above that the isomers exhibit antagonism rather than the expected synergism and the degree of antagonism is 1.42 in the case of housefly or 1.46 in the case of Colorado beetle.

Based on the results of these tests and literature data, trans-isomers and mixtures thereof have become of biological interest and research has focused on active cis-derivatives and mixtures thereof. This led to the development of Alphametrin (an isomeric mixture of the l (R) -cis (S) and l (S) -cis (R) (Ia) chloro derivatives) and Decametrine (which consists only of the l (R) -cis (S) -isomer ( If) bromo derivative).

Similar data was given below for the bromo derivative. For Colorado beetle the antagonism is 1.48.

The present invention provides a synergistic insecticidal composition comprising more than one active ingredient, characterized in that it contains as active ingredient from 0.001 to 99% by weight of the synthetic pyrethroids of formula I

of the eight possible isomers, only the enantiomeric pair Ib is present, i.e. a mixture of 1 (R) -trans (S) and (S) -trans (R), optionally in admixture with at least one activator and auxiliary components, in particular an antioxidant, stabilizer % surfactant, wetting agent, emulsifier, dispersant, antifoam, diluent and / or filler in an amount of up to 100 wt.

According to a preferred embodiment of the present invention, the synergistic insecticidal composition comprises a mixture of isomers Ib having a purity of at least 95%.

This mixture of isomers is a new crystalline substance whose physicochemical properties are shown in the examples.

The invention is based on. recognizing that the isomeric mixture Ib has valuable and advantageous biological properties. These properties are surprising and unexpected, although research has already been carried out in the field of pyrethroids of the general formula I and a number of publications and patents have been published.

The invention is based on the discovery that when using the combination of the 1 (R) -trans (S) -isomer (Ig 1, (which is the most potent trans-isomer of compounds of formula I) and the (S) -trans (R) -isomer (J 1) ), which ranks among the less active isomers of the remaining seven isomers), no antagonistic properties characteristic of previously published isomeric feathers were observed.

In addition, there is a synergistic effect compared to the additive effect of the pure Ig and ^T i isomers when used alone.

The above finding allows a new way of selecting isomers of synthetic pyrethroids to obtain a new active ingredient with superior properties.

This new active ingredient has a number of advantages over previously known isomers, such as:

- lower toxicity to warm-blooded and human;

- more economical preparation;

- minor damage to useful parasites and bees.

The significance and critical advantage of the mixture of the Ib isomers of the present invention is that it is not the cause of allergic and skin diseases as generally observed using the corresponding cis-isomers of Cypermethrin with similar efficacy.

The synergistic efficacy of the components of the mixture of isomers Ib is much more surprising since similar synergism does not occur between the components of the mixture of isomers Ia.

Furthermore, the present invention relates to a method for producing said novel isomeric pair. According to a particularly important aspect of the present invention, the invention relates to a process for producing an isomeric pair of Ib Cypermethrin, which allows highly economical preparation of an active ingredient having the same degree of activity as the active ingredient previously available only through a very expensive isolation process for pure and uniform cis-isomer.

The present invention provides a synergistic insecticidal composition comprising more than one active ingredient and environmentally friendly in an amount of from 0.001 to 99% by weight of the synthetic pyrethroids of Formula I, of which eight possible isomers contain only the enantiomeric pair Ib, i.e. a mixture of isomers 1 (R) -trans (S) and 1 (S) -trans (R), optionally in admixture with at least one activator and auxiliary agent, in particular an antioxidant, stabilizer, wetting agent, emulsifier, dispersant, anti-foaming agent, diluent and / or filler in an amount up to 100 wt.

According to another aspect, the present invention provides an isomeric mixture of Ib having a purity of at least 95% containing an enantiomeric pair of 1 (R) -trans (S) and 1 (S) -trans (R) of formula I.

^; The physical constants of said enantiomeric pair are as follows:

IR (KBr): _.delta . _O

735 cm ¹ .

NMR Spectrum (CDCl3): • S (ppm):

1.22, 1.27 [С (СНз) 21,

1.69 (d, 1H, Cl).

2.32 (m, 1H, C 3),

5.6 (d, 1H, Si),

6.39 (s, 1H, .alpha.-proton).

Said pure enantiomeric pair is a white crystalline material which, to the best of our knowledge, has not been described so far.

The melting point of the 1: 1 mixture of isomers is 81.0 to 81.5 ° C. It should be noted that the Ig .alpha. Isomeric pair components themselves

Ο ο They are not crystalline substances. Accordingly, in addition to the biological and economic advantages, the combination of the present invention facilitates the production method, the preparation method, the storage and the treatment method.

The isomeric pair 1b of the present invention is also more advantageous than the known combinations in terms of side effects. The novel isomeric pair of the present invention has very low bee toxicity and does not harm useful entamophages and parasites (cf. biological examples 4 and 5). These properties are due to the repellent effect, the preferred persistence and the inherent activity of the active ingredient.

The above-mentioned advantageous properties make it possible to use the insecticidal composition according to the invention in integrated plant protection (IPM).

The present invention is based on another finding that the enantiomeric pair of the invention has substantially the same insecticidal activity as the enantiomeric pair 1a, but is substantially less toxic to warm-blooded. This is clearly evidenced by the so-called selectivity index (7,800), which is the ratio of the approximate LD 50 values measured in rats (5,000 mg / kg) and house fly (0.64 mg / kg). This selectivity index for enantiomeric pair la is 50 / 0.45 = 111.

Isomeric pair 1b is less toxic to parasites than isomeric pair 1a, which is particularly important. For this reason, the insecticidal composition of the present invention can be used more safely, since at the edge of the treated area and after treatment (i.e., the area treated with a low concentration of active agent), parasites and bees are not killed. The repellent effect of the isomeric pair 1b is also extremely good.

The insecticidal compositions of the present invention comprising the isomeric pair 1b in admixture with known ingredients may be formulated for ready-to-use forms.

The compositions of the invention may be concentrates, i.e., ultra-low-volume (ULV) formulations, sprays, dispersible powders, granules, wettable or other powders, emulsions, etc.

These compositions are suitable for the pesticide treatment of vegetable, garden, cereal and other large-area crops. Due to their low toxicity, the compositions according to the invention are particularly suitable for combating flying insects and pests with a hidden way of life, in stables and also for bathing domestic animals and for treating pastures.

As mentioned above, the present invention also relates to the use of insecticidal compositions as defined above. It is preferred to use the formulations under field conditions with application of 2 to 25 g of active ingredient per ha.

The insecticidal compositions of the present invention may contain, in addition to the pairs of isomers 1b, activators and other synergistically active ingredients, for example piperonyl butoxide. Said additives increase the efficacy of the active ingredient without increasing the warm-blooded toxicity.

According to a preferred embodiment of the present invention, the insecticidal compositions are used in the form of a dispersible granulate containing 1 to 99% by weight of the active ingredient in admixture with 99 to 1% by weight of a suitable additive. For example, 0.1 to 1% by weight of anionic and / or nonionic surfactants such as alkali metal alkylarylsulfonic acid salts, alkali metal formaldehyde salt of alkylarylsulfonic acid and alkali metal formaldehyde, alkylaryl polyglycol ethers, long chain sulfated alcohols, , polyethylene oxides of sulfated fatty alcohols, fatty acid polyglycol esters, and various other commercially useful surfactants.

The insecticidal compositions of the present invention may also be prepared in the form of concentrates containing preferably 5 to 50% by weight of the active ingredient in admixture with 50 to 95% by weight of additives which allow the preparation of a stable emulsion when the emulsion concentrate is emulsified in water or in the presence of water. .

Further, 1 to 20% by weight, surfactant and / or 0.1 to 5% by weight of a stabilizer can be used as additives and the mixture is preferably added to 100% by weight with an organic solvent.

It is preferred to use as a surfactant mixtures of anionic and non-ionic surfactants having a hydrophilic-lipophilic balance value of 8 to 14. The surfactants preferably used are:

calcium salts of alkylarylsulfonic acids, phosphoric acid mono- and diesters, nonyl- and tributylphenol polyglycol ethers, adducts of fatty alcohol with ethylene oxide, polyglycol esters of fatty acids, block polymers of ethylene oxide with propylene oxide, etc.

The solvents used are preferably mixtures of aromatic hydrocarbons (e.g. xylenes), cyclohexanol, butanol, methyl ethyl ketone, isopropyl alcohol, etc.

The compositions of the present invention may also contain other synergistically active ingredients that allow the amount of active ingredient to be reduced. Piperone / butoxide may be used advantageously for this purpose.

The present invention further provides a process for the preparation of an insecticidally active ingredient comprising, out of the eight possible isomers of the compounds of formula I, only a few enantiomers of 1 (R) -trans (S) 4-1 (S) -trans (R) (1b) from mixtures containing also other isomers of other compounds.

The enrichment of mixtures of Cypermethrin with isomers that are likely to have greater potency is described in several patents. According to the patent [C. A. Vol. 95; (1981), Japanese Patent Publication KOKAI No. 57,755/81], with a crystalline isomeric mixture of Cypermethrin containing 86.9% of the isomer Ic,

9.5% of the isomers Ia and 5.6% of the mixture of isomers Ib-i-Id are prepared by seeding a mixture containing

53.5% of the Ic isomers, 38.7% of the Ia · and 7.8% of the mixture of the Ib - | - Id isomers. In this case, it was expected that the biological activity of the compounds remaining in the mother liquor would be higher.

The preparation of pairs of cis-isomers or substances enriched in pairs of cis-isomers is also the subject of other known processes. According to the known method, the mixture of pairs of enantiomers Ia and Ic is subjected to epimerization in order to convert the enantiomeric pair Ic into the enantiomeric pair Ia · and to produce the known Alphametrin, respectively. Decametrin by Asymmetric Transformation [Chem. and Ind., March 19, (1985), pp. 199-204; European Patent Publication No. 0 067 461; Netherlands Patent Specification No. '888,431, cf. Derwent 76,766 D).

However, there are no data in the prior art about methods which would lead to the preparation of trans-isomers.

Accordingly, the present invention provides a process for preparing a mixture of Ib isomers consisting only of pairs of 1 (R) -trans (S) and (S) -trans (R) enantiomers, i.e. containing only two isomers of the eight possible isomers of a compound of Formula I, from the mixture containing also other isomers of formula I, which comprises:

a) prepare a saturated solution in a protic or apolar aprotic inert organic solvent from a mixture containing the desired isomers in a mixture with other possible isomers, which solution is seeded with a crystal consisting of a pair of enantiomers 1 (R ') - trans (S) hl (S) -trans ( R), and the precipitated crystals are isolated at a temperature between -30 and -30 ° C; or bj seeding a melt of a mixture containing the desired isomers in admixture with other possible isomers at a temperature of between 10 and 60 ° C with a seed crystal of a pair of enantiomers of 1 (R) trans (S) 4 1 (S) trans (R); at a temperature between 30 and -10 ° C, and optionally the mixture so obtained is suspended in a protic or apolar aprotic organic solvent at temperatures between -10 and -20 ° C and the precipitated crystals are isolated; or be

c) dissolving the mixture containing the trans-isomers in a secondary or tertiary organic amine of 4 to 9 carbon atoms as the base, optionally with the addition of an organic solvent, and inoculating the solution thus obtained with the isomer of the 1 (R) -trans (S) -] - 1 (S) -trans (R) and then the precipitated crystals are filtered off.

According to variants a) and c) of the process according to the invention, it is advantageous to work with 1 to 12 carbon atoms, 1 to 6 carbon atoms of chlorinated hydrocarbons, 1 to 5 carbon atoms dialkyl ethers or 1-alcohols. to 10: carbon atoms as organic solvent. The solvents may be straight or branched, cyclic or alicyclic;

It is further preferred to carry out the seeding with a seed crystal in the presence of an antioxidant, in particular tert-butylhydroxytoluene or 2,2,4-trimethylquinoline, and using ethanol, isopropyl alcohol, petroleum ether or hexane as solvent.

Said reaction variants may be particularly economically employed if the overall production process also comprises: the use and preparation of isomers of formula I other than isomers Ib.

If the preparation of synthetic Gypermethrin is feasible and if the aim of the process according to the invention is to prepare only a mixture of trans-isomers using one of the esterification processes, variant c) is particularly suitable for the economical preparation of pairs of isomers Ib by the process according to the invention. According to said variant c),? namely, it converts the complete amount of the mixture of trans-isomers into the desired enantiomeric pair Ib.

In the process according to variant c), the organic amine base used is largely:

triethylamine, morpholine, pyrrolidine, piperidine, di-propylamine, ephedrine or sec-butylamine.

A precondition for the feasibility of the process according to variant c) is to obtain a ^! · The transport of high purity seed crystals with a purity above 95% and a melting point above 80 from the non-crystalline pure isomers li and Id. This allows for deliberate direct asymmetric transformation.

The dissolution of the mixture in the amine can preferably be carried out in the presence of an organic solvent. The solvents mentioned in the case of variant a) can be used for this purpose.

Option a) comprises dissolving a mixture of trans-isomers of Cypermethrin containing the isomers 1 (R) -trans (Sj, 1 (S) -trans (R), 1 (R) -trans (R) and 1). (S) -trans (S) in triethylamine. Crystalline starting materials are dissolved at a temperature between ⁷ 40 ° C and 70 ° C and the resulting solution can be filtered, the oily mixture of cypermethrin can be equally well · dissolve at the ^temperature: room temperature.

Crystallization of pairs of 1 (R) -trans (S) 4 ~ 1 (S) -trans (R) isomers can be accomplished by seeding the solution at room temperature

5 4 9 9 4 crystals of a mixture of isomer 1 (R) trans (S) and 1 (S) -trans (R) in µm; 1: 1 (recommended number: 99.8%), then <m: 92%. between 0 ° C and 20 ^° C, optionally wdmm. The segregated crystals are separated by filtration through centrifugation and the pitch liquor adhering to the crystal surface is washed with an alkanron (preferably a solution of cycloalkane type, in particular pmimether). The combined mother liquors were completely quenched. The rat procedure is repeated. Asynmlrmhá ir; the muse is preferably blasted into a dry inert pl; and; (Nitrogen abrasion).

Cond i '·:. ·' Иmúmmho przi · ψ · η sine isomers J (R'-iim.m (3j; S · ÍruisfRj having a purity of about 95% may ^рг; р. R <? Uat 80% yield in another embodiment, it may be increased from 9 ° to 99.9% by further crystallization from alcohol, in particular from iso-propyl-alcohol.

When the base serves as a solvent, it is preferable to use aroin as the base with a content of not more than 0 to 0.4%. Pollution -rm ^f -i trímsrómmerů Cypermetlirinu that having used as starting material, the yield of cis Isomers-vat decreases.

Insecticidal compositions according to the invention lohoto IE harmless to the environment and can ^{Posza> /:} t Murni: in dmnácaostech and stables. k heals against lot insects and pests with a hidden way of life. n also favors the pet food jukcž i to treat n mlvim

Longer details. Lohot-a vmálezu. are included in the following nails. which illustrate a process for the manufacture of an active ingredient and further in examples which illustrate biological effects. For example, these do not restrict η '·' ¹ 'in' - 'in any way.

Examples of suitable methods for preparing the active ingredients also include other possible methods for preparing the pair of enantiomer Ib. ti. Chromatographic method and onimetry. They do not, however, constitute an object of the present invention. however, they represent other preferred methods for preparing a new pair of Tb enantiomers.

Examples illustrating the preparation of active ingredients:

He did.

.10 g of a mixture of Snoggy containing 182 percent of the Ia isomers. 21.8% Tc isomers,

26.8% of the isomers Ib and 33.2% of the isomers Id are dissolved in 5П of a mixture of n-hexane π tetrahdrofuran in a ratio. 99: 5. The solution obtained is chromatographed on a column of 500 g of silica gel. A mixture of n-hexane and tetrahydrofuran in a ratio of 95: 5 is used as eluent and 25 ml is collected. Fractions with a P ₄ value of 0.2. TLC (n-hexamine / tettrahydrofurants as solvent system). Combined fractions were evaporated in vacuo. Evaporation gave 2.9 g of a residue which was dissolved in 29 ml of ethanol at 45 ° C. C and the resulting solution was allowed to crystallize at 0 DEG C. ^q precipitated product is filtered, washed twice with 10 ml of ice cold ethanol and dried in vacuo. This afforded 2.6 g of white crystalline product, mp 30.2 C.

Climatector's analytical data:

R, - 0.2 (krtoclin. G, solvent system: mixture of n-hexane and tetrahydrofuran)

IR spectrum (KBr technique):

c c - 0 - 1 735 cm ¹

No spectrum (deuterochloroform, -5 in ppm):

1.22, 1.27 [C (S) 2],

1.69 (cl, 1H, Cl);

2.32 (m, 1H, C1), [delta] (d, CI), 6.39 (s, 1H, (Z-proton)).

Example 2

10 10 g of a crystalline mixture of Cypermeih.rin trans isomers (containing 53.9% of the isomers i (R) -trans (R) and 1 (S) -trans (S) and 43.3% Ig isomers (according to gas chromatography) 19 parts of anhydrous triethylamine are added, the mixture is heated under nitrogen and stirring at 60 ° C, then the engraving solution is filtered and the filtrate is cooled to 30 ° C. The clear colorless solution thus obtained is seeded with a mixture of isomers Ib in 1: 1, cooled to room temperature and allowed to crystallize for one day, then cold filtered and dried at room temperature to give 8.4 g of a snow-white crystalline product. According to gas chromatography, the product contains 95% of a mixture of the desired isomers Ib in a ratio of 1: 1. The mother liquor is evaporated, repeating the above steps to give 1.05 g of a white crystalline solid as a second crop. o mp 79-80 C. ^U

The product was recrystallized from 50 ml of isopropanol. 8.5 g of a snow-white crystalline product with a melting point of 80.5 DEG C. are obtained in the first step. Active ingredient content 98%. Further recrystallization yielded 7.5 g of crystalline product, m.p. 81.5 ° C. Active substance content above

99.5%.

IR spectrum (KBr technique):

h = o - 1 735 cm ¹

NMR spectrum (CDCl 3, δ in ppm):

1.22, 1.27 [С (СНз) 2],

1.69 (d, 1H, Cl).

2.32 (m, 1H, C 3),

5.6 (d, 1H),

6.39 (s, 1H, α-β photon).

Example 3

100 g of a crude oil mixture of Cypermethrin trans isomers (containing 48% of 1 (RJ-trans (R) and (S) -trans (S) isomers and 47% of isomer 1b (according to gas chromatography) is dissolved in 150 ml of anhydrous triethylamine and 0.2 g of tert-butyl-hydroxytoluene with stirring, and the solution is then quickly filtered, seeded, crystallized twice and recrystallized in an analogous manner to that described in Example 2. 82 g of a snow-white pair of isomers 1b are obtained as crystals and temperature. 80 DEG-80.5 DEG C. The active substance content is 97.5%.

Example 4 g of an oily mixture of trans-isomers of Cypermethrin [containing 85% of the isomers 1 (R) trans - ((R) and 1 (S) -trans (S) and 14% of the isomers 1b)] are dissolved in 15 ml of anhydrous triethylamine at room temperature, crystallized in the same manner as described in Example 2. In this way, 8 g of a snow-white crystalline product which is a mixture of isomers 1b are obtained. M.p. 79-80.5 ^° C.

Example 5 g of crystalline trans-Cypermethrin [containing 52% of the 1 (R) -trans (R) and (S) -trains (S) isomers and 47% of the IbJ isomers are dissolved in 15 ml of tri- at 50 ° C. of n-propylamine. The solution is filtered, cooled to 30 ° C and seeded with a crystal consisting of a 1: 1 mixture of isomers 1b. The mixture is then left to crystallize for 48 hours. 8.2 g of a snow-white crystalline product, m.p. 78 DEG-80 DEG C., are thus obtained. Purity (by gas chromatography analysis): 95%.

Example 6

The procedure was as in Example 5 except that 15 ml of tributylamine was used as the base. 7.5 g of a snow-white crystalline pair of isomers 1b are thus obtained. Mp 77-79 ° C. Purity 93%.

Example 7

The procedure was as in Example 5 except that 15 ml of triisopropylamine was used as the base. 7.5 g of a snow-white crystalline pair of isomers 1b are thus obtained.

Mp 78-80 ° C. Product purity

95.5%.

Example

The procedure was as in Example 5 except that 15 ml of diisopropylamine was used as the base. 8.0 g of a snow-white crystalline pair of isomers 1b are thus obtained. Mp 78-80 ° C. Product purity 95.5 percent.

Example 9 g of trans isomers of Cypermethrin (containing 48% of isomers 1 (R) -trans (S) and 1 (SJ-trans (R) and 49% of pairs of isomers 1b)) are dissolved in 50 ml of isopropyl alcohol with stirring and heating, 2 ml of aqueous ammonium hydroxide solution (specific gravity 0.880 g / ml) are added, the solution is seeded with isomer 1b crystals, stirred for 24 hours at 20 ° C, cooled to 0-5 ° C and stirring is continued. The suspension is filtered, the product is washed with isopropanol and petroleum ether and dried to give 6 g of a white crystalline pair of isomers 1b (1: 1), m.p. 78 ^DEG- 79 ^DEG C. Purity 92% (by gas chromatography) The second crop is recovered from the mother liquor

1.5 g of white crystalline product. Mp 78-79 ° C. The compound obtained as the second crop is identical to the crystals obtained as the first crop.

Example 10 g of trans-Cypermethrin (containing 54% of the isomers 1 (R) -trans (S) and (S) -trans (R) and 45% of the isomers 1b) are dissolved in 100 ml of petroleum ether (b.p. 60-80 ^{° C).} C), then 1 ml of a 0.5 M sodium carbonate solution and a 1: 1 (v / v) mixture of water and methanol containing 10% (w / v) tetrabutylammonium bromide are added, and this solution is seeded with the crystal of Example 2, The crystals were washed with petroleum ether and dried to give 6.8 g of a white crystalline pair of isomers 1b, mp 78-80 ° C, purity 95% (by gas chromatography).

Example 11 g of crystalline trans-Cypermethrin [containing 52% of the isomers 1 (R) -trans (S) and (S) -trans (R) and 47% of the isomers 1 (R) -trans (R) and (S) -trans (S)] is dissolved in 100 ml of petroleum ether at 50-60 ° C. 0.02 g of 2,6-di-tert-butyl-4-methylphenol are added to the solution. After filtration, the filtrate was seeded at 30 ° C with 1: 1 isomer 1: 1 isomer crystals. Crystallization was performed as described above. 3.8 g of a snow-white crystalline pair of isomers 1b (1: 1) are thus obtained. Mp 77-79 ° C. Purity 93%. Recrystallization from pe *

1.5 g of trolether are obtained, m.p.

80.5 mesh The crystalline mother liquor is epimerized in a particularly pure form.

Example 12. 10 g of crystalline trans Cypermethrin [containing 45% of the 1 (R) -trans (S) and 1 (S) -trans-R] isomers and 53% of the 1 (R) -trans (R) and 1 (S) isomers troro (S) is dissolved in 75 ml of isopropyl-alkanol at 50 to 60 ° C. The solution was further processed in a manner analogous to that described in Example 11. This gave 3.6 g of a snow-white crystalline pair of isons. According to the gas chrpniatoугоне is mmom mixture, with a ratio: 1 94%. The melting temperature is 80 °. Further recrystallization is performed as described in the example

2. A product having an active ingredient content of more than 99% is thus obtained. The crystalline mother liquor is opimerized in a separate bond.

Example .13

To the millimeter mmbmBcm was added the mother rim of Example 11 (the solution enriched in isomers is further added 1 g of basic icmtomic resin [Dosvex type, 2X4 rnesh (serval) I. The heterogeneous suspension was stirred at 40 ° C. After 1.2 hours, the mixture is filtered and the residue is washed twice with 1 ml of isopropyl alcohol each, and according to gas chromatography, the solution contains 41% pairs of isomers Jb and 46% pairs of isomers Id, and the solution is evaporated and crystallized as described in Example 1.1.

Example 14

The procedure is carried out in the usual manner as described in Example ‘3, except that iptarol ether is used as the solvent. According to gas chromatography, the solution contains 39% of the isomers Ih and 56% of the isomers 1 (Rj-trans) and 1 ()) krons (S).

EXAMPLE 15 g of a colorless olefin powder (containing 30% of isomer 1b, 31% of isomer 1d, 18% of isomer Ia, and 21% of isomer Icl) are seeded with seed crystals of a 1: 1 mixture of isomers Jb and then left to mix. crystallize after 1 week at 7 [deg.] C. The viscous oil obtained is cooled to a temperature ^{, the} C1 proom is suspended in 10 ml of a 1: 1 mixture of isopropyl alcohol and diisopropylether, the suspension is cooled by mist. The crystals obtained are washed with 5 ml of ice / isopropyl alcohol and dried at room temperature to give 2 g of white crystalline product 1b, m.p. 78-80 ^° C. According to gas chromatography, the purity of the product was 96%.

Recrystallization from 13 ml of hexane gave 2.25 g of a snow-white crystalline product. Melting point 80-81 ° C. The active ingredient content is 99%.

EXAMPLE 16 g of Cypermethrin (containing 30% of isomers 1b, 31% of isomers Id, 18% of isomers Ja and 21% of isomers Ic) are dissolved in 100 ml of warm isopropyl alcohol and 0.02 g of 2,5-cii is added to the obtained solution. tert-butyl-4-methylphenol. The solution is clarified by the addition of 0.2 g of activated carbon, filtered while hot and the filtrate is seeded at 30 ° at 1 ° 1 with a 1: 1 isomer 1 seed mixture. The mixture is crystallized for 24 hours at 10 ° C, 43 hours at 0 ° C and finally 24 hours at -5 ° C (crystallization is carried out to prevent the product from precipitating in oily form). The crystals are filtered off cold, washed with isopropanol and dried at room temperature. 2.6 g of a snow-white crystalline pair of isomers 1b (1: 1) are thus obtained. Melting point 78-80 ° C, 95% purity. Recrystallization from hexane gave 2.3 g of a snow-white crystalline product. Melting point 80-81 ° C. The active ingredient content is 53%.

Examples illustrating the composition and preparation of the compositions of the invention:

Example 17

Emulsifiable concentrates (ЕС) are prepared by mixing the following components:

Emulsifiable concentrate (10 ЕС)

Component Quantity kg / kg pair of isomers 1b0.105 cyclohexanol 0.290

Atlox 3,386 В0.020

Atlox 3,400 В0,045 mineral oil (odorless) 0,540

Emulsifiable concentrate (5 ЕС)

Component

Amount kg / kg pair of isomers 1b0.050 cyclohexanol 0.290

Atlox 3,386 В0.020

Atlox 3,400 В0,014 mineral oil (odorless) 0,595

Formulations based on emulsifiable concentrates (5 ЕС) at a rate of 20 g of active ingredient per hectare afford the same protection against potato leaf beetle (Leptinotarsa decemlineata) as agents of the same composition, but containing the isomers Ia (Aliphametrine) as active ingredient.

Example 18

A solution of 1.5 g pairs of Ib isomers and 1.5 g of fatty alcohol polyglycol ether is homogenized in a powder homogenizer with 30 g of synthetic silicic acid (Wessalon S), 60 g of talc (pH 7.1), 5 g of sucrose, 35 g dodecylbenzenesulfonic acid. A thin flowing powder is obtained in this way.

Example 1 a d 19.

g of pairs of Ib isomers are diluted with 2 g of ethanol. This solution is mixed in a powder homogenizer with 5 g of lignin sulphonic acid calcium salt, 5 g of nonylphenyl polyglycol ether (20 ethylene oxide units) and 70 g of calcium carbonate. The mixture thus obtained is then ground on an Alpine 100 mill. The wettability according to the CIPAC method is 81%. The wetting time is 18 seconds.

Examples illustrating biological activity:

Example 20

In this test, the effects of pairs of enantiomers Ia and Ib on bean beetle (Acanthoscelides obtectus), darkling beetle (Tribolium confusum) and buzzard (Lucilia sericata) were compared. The results of the tests show that the pair of enantiomers Ib is more potent than the pair of enantiomers Ia.

The results of this test are summarized in Table 1 below.

Table 1

Species of insects tested pair of enantiomers 0.02 0.07 Dose (mg / bowl) 6.0 0.22 mortal 0.67 liters in% 2,0 Acanthoscelides Ia .10 37 63 100 ALIGN! 100 ALIGN! 100 ALIGN! obtectus (imago) [0057] Ib 32 55 87 100 ALIGN! 100 ALIGN! 100 ALIGN! Tribolium confusum Ia 0 18 51 100 ALIGN! 100 ALIGN! 100 ALIGN! (imago) [0057] Ib 14 73 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! Lucilia sericata Ia 0 30 29 57 60 65 (imago) [0057] Ib 22nd 55 70 75 100 ALIGN! 100 ALIGN!

The test is performed as follows:

The stereoisomers are dissolved in a 1: 2 mixture of mineral oil and acetone and impregnated with filter rolls (Whatman No. 1, 9 cm diameter) with an appropriate portion of the active ingredient solution. The acetone is then evaporated and the test insects are placed on filter paper discs, which are placed together with the insects in petri dishes. For each dose of test compound, 3 parallel experiments were carried out and 15 specimens of test insects were placed in each Petri dish. Mortality was measured after 24 hours.

The corrected percent mortality is calculated according to the Abott formula.

In the previous table and in the following tables, the dose of active ingredient is given in mg / / dish. This is understood to mean the dose of active ingredient which has been impregnated with a filter paper disc inserted into the dish.

Example 21

The results shown in Table 2 below demonstrate synergism between the stereoisomers of the ip pair of enantiomers Ib. This test is performed using a darkling beetle as a test insect (Tribolium confusum). Using different dosages of the active ingredient, the following effects were obtained with the contact effect:

Table 2

Active ingredient Dose (mg / bowl)

0.11 0.33 1.00 3.00 mortality in% l (S) -trans (R) 0 0 71 90 l (R) -trans (S) (lg) 80 94 100 ALIGN! 100 ALIGN! a pair of enantiomers Ib 90 100 ALIGN! 100 ALIGN! 100 ALIGN!

5 4 98 4

This assay was performed according to the same method as described in Example 20.

Example 22

The following Table 3 summarizes the LD 50 values for the Ig and If isomers and for the pair of Ib isomers. These data were measured after local treatment.

Table 3

Stereoisomers of Cypermethrin

LDso (^ g / insect specimen) Tribolium confusum measured expected-factor value weighted synergism value mu

LDoo (, ag / insect specimen) Musea domestica measured expectant-value value bath synergishodnota mu

Ig 1 (R) -trans (S) -l 1 (S) -trans (R) Ib

73.6 - - 13.4 ——

1291.8 - - 141.9 ——

51.9 139.3 2.68 12.8 24.51.92

The above data demonstrate synergism between trans-isoinery of both types.

The tests were performed as follows:

(a) House fly test (Musea domestica)

The active ingredients are dissolved in 2-ethoxyethanol and 0.3 μΐ solution droplets are applied to the dorsal cuticle of the female flies of 3-5 days old. For each dose, 10 specimens of test insects are used and 2 parallel experiments are performed. The tests are carried out for 5 different doses of active substance, ranging from 0 ° C to 100%. After treatment, specimens of test insects are placed in glass vials. Mortality was measured after 24 hours. The data are converted to log 10 doses and mortality by the probit method. LD 50 and confidence limit values are calculated by linear regression analysis of log probit values. The expected values needed to calculate the synergism are obtained using the harmonic average. The synergism factor is the ratio of expected values to measured values.

(b) Test for darkling (Tribolium confusum)

The active ingredients are dissolved in 2-ethoxyethanol and 0.3 µl of solution droplets are applied to the abdominal portion of the experimental insect ages of 1 to 2 weeks of age. The treatment is performed in two parallel experiments using 20 specimens of test insect per dose. The tests are carried out for 5 different doses of active substance, ranging from 0% to 100%.

The evaluation and determination of LD 50 values and synergistic factors are performed in the same manner as described above under a).

Example 23

Aphidinus matricariae adults test - residual protective effect

The tests are carried out in glass containers onto the walls of which the active substance is applied. Adult Aphidinus matricariae are exposed to residues of this active ingredient and the number of surviving insect specimens is determined.

The treatment is carried out with the active substances to be tested and with water (control experiment).

Each experiment is repeated at least three times. The size of the treated area is represented by the area of the interior of the glass container.

Parasites of known age (24 hours) are used.

The products to be tested are applied to the interior of the glass container at a concentration of 5 and 1 ppm. ,

Ten female Aphidinus matricariae specimens and honey as food are placed in each of the glass containers. After 1, 5 and 24 hours, the number of surviving specimens was determined in independent experiments. The total number of surviving specimens for each vessel was determined. The results are shown in Table 4.

Table 4

Active substance Concentration 5 ppm 1 PPm 1 h 1 h 5 h 24 h la 100 ALIGN! 100 ALIGN! 100 ALIGN! 96 lb 100 ALIGN! 0 75 88 control 0 0 0 1.5

Example 24

Direct contact effect on pupae of Aphidinus matricariae

Adult pupae of Aphidinus matricariae on pepper leaves are placed in petri dishes and sprayed with active ingredients. Pepper leaves are used that have pupae in the stage 2 to 3 days before hatching. The leaves are placed on a moistened filter paper in a plastic petri dish.

Table 5

The treatment is carried out in the same manner as in Example 23.

The leaf pieces are transferred after treatment to the bottom of transparent Petri dishes. The dishes are stored in an air-conditioned room at 20 ^° C, 70% relative humidity and a daily cycle of 16 hours light and 8 hours dark. Surviving pupae hatch after 2 to 3 days. The number of live and killed specimens of the test insects is determined.

The results of this test are shown in Table 5 below.

lb61.0

Deltamethrin75.0 control0

Concentration (ppm)

51 Mortality in%

00

33,0 oo

00

Example 25 The active ingredients are dissolved in 2-ethoxyethanol and 0.3 μΐ of solution droplets are applied to the abdominal portion of the leaf beetle image of Leptinotarsa decemlineata. The treatment is performed using two paT and b at 1 k and 6

Cypermethrin enantiomers 0.05 lb0

Cypermethrin0

Example 26

The image of the darkling beetle (Tribolium confusum) was treated as described in Example 20 and mortality was determined in% after 24 hours. Ralel experiments were added to the active compounds, using 10 specimens of test insects per dose of active compound. After treatment, the insects are placed in petri dishes and mortality is determined after 48 hours. The results are shown in Table 6 below.

Dose (^ g / insect specimen)

0,10 0,200,40 mortality in% after 24 hours

7585

4575 piperonyl butoxide (hereinafter referred to as PBO) in an amount of 0.5 mg / dish. The results of this assay are shown in Table 7 below. From these results, it can be seen that the pair of enantiomers 1b can be synergized to a greater extent than the isomeric pair 1a.

Table 7

Effective Dose (mg / bowl) component 0.4 0.2 0.1 0.05 mortality in% after 24 hours 0,025

la 96 53 la + PBO 100 ALIGN! 58 [0057] Ib 100 ALIGN! 85 Ib + PBO 100 ALIGN! 91

Example 27

The active ingredients are dissolved in 2-ethoxyethanol and the solutions obtained are applied as 0.2 μΐ droplets to the back of larvae of Hyphantria cenea larvae in the 7th to 8th stages. The treated larvae are placed on strawberry leaves and placed in petri dishes.

00

00

100 ALIGN!

399

The test is performed for 5 different doses of active ingredient. Two parallel experiments were performed and 10 test insects were used per dose. After 24 hours, killed insect specimens are counted and mortality is calculated in%. The results are summarized in Table 8 below.

Table 8

Stereoisomers

Cypermethrin 0.023

Dose ( ₄ µg / larva)

0.047 0.094 0.1.88 0.375 Mortality in% after 24 hours

Ib 10 15

Cypermethrin 0 0

Example 28

The emulsion concentrates (5%) prepared according to Example 17 are diluted with 50X, 100X, 200X, 400X, 800X and 1600X with water and 0.5 ml of each of these emulsions is sprayed onto a glass plate. After drying, spray 30 70 80

50 75 metal layers are placed on each plate with 10 images of potato beetle (Leptinotarsa decemlineata) and the insects are covered. All assays are performed using 6 doses and 3 parallel experiments for each dose. The killed insects are counted after 48 hours. The results are summarized in Table 9 below.

Table 9

Emulsion concentrate (5 ЕС) 1 600 X 800 X Diluted 400 X 200 X mortality in percent 100 X 50 X Cypermethrin 0 17 33 50 67 83 [0057] Ib 0 13 37 57 87 100 ALIGN!

Example 29

Test of insecticidal effect on bean-throat imago (Acanthoscelides obtectus)

The killed insects are counted after 24 hours and the molarity in percent is calculated.

The test results are shown in Table 10.

Table 10

Emulsion concentrate (5 ЕС) 1 600 X 800 X Diluted 400 X 200 X mortality in% 100 X 50 X Cypermethrin 0 3 10 20 May 43 60 [0057] Ib 3 10 20 May 37 53 67

Claims (7)

Synergic insecticidal composition, characterized in that it contains as active ingredient from 0.001 to 99% by weight of a synthetic pyrethroid of the formula I, of which only a few enantiomers Ib are present, i.e. a mixture of 1 (R) -trans (S) and (S) -trans (R) isomers, optionally in admixture with at least one activator and adjuvants, in particular antioxidants, stabilizers, wetting agents, emulsifiers, dispersants, antifoams, diluents and / or fillers in amounts up to 100 ° / o wt. 2. A process for preparing a mixture of isomers Ib consisting only of pairs of enantiomers 1 (RJ-trans (S) and l (S) -trans (R)), i.e. containing only two isomers of the eight possible isomers of the compound of formula I (П) other isomers of formula (I) characterized in that they are: a) prepare a saturated solution in a protic or apolar inert organic solvent from a mixture containing the desired isomers in admixture with other possible isomers, which solution is seeded with a crystal consisting of a pair of enantiomers of 1 (R) -trans (S) -J- (1 (S) - trans (R), and the precipitated crystals are isolated at a temperature between -f-30 and -30 ° C, or b) seeding the melt of the mixture containing the desired isomers in admixture with other possible isomers at a temperature between 10 and 60 ° C with a seed crystal of a pair of enantiomers of 1 (R) -trans (S) + 1 (S) -trans (R); crystallize at a temperature between 30 and -10 ° C. and optionally the suspension thus obtained is suspended in a protic or apolar aprotic solvent at temperatures between -10 and -20 ° C and the precipitated crystals are isolated, or c) dissolving the mixture containing the trans-isomers in a secondary or tertiary organic amine of 4 to 9 carbon atoms as the base, optionally with the addition of an organic solvent, and inoculating the solution thus obtained with the isomer 1 (R) -trans (S) a1 ( S) -trans (R) and then the precipitated crystals are filtered off. 3. The method according to item 2 of variant a) or (c), characterized in that the organic solvent used is a hydrocarbon of 1 to 12 carbon atoms, a chlorinated hydrocarbon of 1 to 6 carbon atoms, a dialkyl ether of 1 to 5 carbon atoms in alkyl radicals or an alcohol of 1 to 10 carbon atoms, these solvents may be straight or branched chain and may be cyclic or alicyclic. 4. The process according to claim 2, wherein the seed crystal seeding is carried out in the presence of an antioxidant, preferably tert-butylhydroxytoluene or 2,2,4-trimethylquinoline and using ethanol, isopropyl alcohol or hexane as the solvent. 5. The process according to claim 2, characterized in that the solvent used is an alkane of 4 to 10 carbon atoms, a cycloalkane of 5 to 10 carbon atoms, an alkanol of 1 to 8 carbon atoms and / or a cycloalkanol of 5 to 8 carbon atoms. carbon atoms or mixtures thereof, preferably hexane, petroleum ether, cyclohexane, methanol, ethanol or isopropyl alcohol. 6. The process according to claim 2 of variant a), characterized in that it is used as a solvent 2B uses methanol, ethanol or isopropyl alcohol. 7. The process of claim 2, wherein the organic amine base is triethylamine, morpholine, pyrrolidine, piperidine, diisopropylamine, ephedrine, or sec-butylamine.