LT3529B - Process for preparation of cypermethrine isomers - Google Patents

Abstract

1. Technical Result Increase in stability of the composition. 2. Essence A stable arthropodicidal composition containing stabilizer and as active ingredient cypermethrine of the formula (I) CH O Cl CO2 CH Cl  wherein carbon atoms indicated by 1,3 and  stand a chiral carbon atom and the wavy line indicates cis or trans configuration related to the cyclopropane ring – which contains at least 95% of 1R trans S and 1S trans R (Ib) isomer pair, or mixture of 1R cis S and 1S cis R (Ia) and the isomer pair (Ib) of the ratio (Ia):(Ib) = 55:45-25:75, or the isomer pair Ia or Ib and as a stabilizer non-volatile carboxylic acids of pK1=1-5 such as phtalic acid, succinic acid, tetraric acid, maleic acid, fumaric acid, malonic acid or once or several times substituted alkylated derivatives thereof and/or oxalic acid. 3. Field of Application Organic chemistry. 5 Tables.

Description

The present invention relates to 0 (-cyano-3-phenoxybenzyl-3- (2,2-dichloro vinyl) -2,2-dimethylcyclopropabcarboxylate (hereinafter cypermethrin) of formula (I):

for the preparation of enantiomers (mirror isomers) of a given isomer ratio using an asymmetric transformation.

In the present invention, the spatial configuration of the substituents with respect to the chiral carbon atom (denoted by the formula) is characterized by the symbols S and R. The terms go and trans are used to denote the position of the 3 carbon atoms on the cyclopropane ring and the absolute spatial configuration of the substituent denoted by IR and 1S. The following abbreviations are used to designate the various enantiomers and their pairs:

A mixture of Ia lRcisS and IScisR; alphamethrin (Fastac),

Ib IRtransS and IStransR (Transmix),

A mixture of Ic lRcisR and IScisS,

Id IRtransR and IStransS blend, lf lRcisS,

Ih IScisR,

II IStransR,

Ia + Ib Asymmetryin (Chinmix).

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-2EN 3529 B

The present invention relates to the following cypermethrin of formula (I):

mixtures of isomers containing at least 95 pairs of isomers of IRtransS and IStransR (Ib) or only a mixture of the pairs of lRcisS and IScisR (Ia) and (Ib) in the ratio of (Ia) :( Ib) = 55: 4- 5 to 25:75, obtained by a second order asymmetric transformation in the presence of an amino-type base and a solvent, from a mixture of cypermethrin isomers containing, in addition to the (Ib) isomeric pair, a cis -isomeric pair and other trans isomers, or (Ia) + (Ib) pair of isomers in an undesirable ratio; this method is realized as follows:

(a) undergoes a chemical reaction between 0 and 90% by weight of the mixture of isomers in the form of an oil or crystalline compound of formula I having a purity of at least 90% by weight in the trans isomers or eis / trans isomers of 65:35 to 15:85; At 25 ° G, in a system containing up to 0.5% moisture with 0.1-0.5 parts by weight of triethylamine or 0.0005-0.01 parts by weight of 1,5-diazabicyclo / 4,3,0 / non- 5-ene (DBN) or 1,5-diazabicyclo / 5,4,0 / undecene (DBU) (based on the weight of the initial mixture of isomers) under vigorous stirring and in the presence of propanol at the saturation point of the desired mixture of isomers, adding propanol to the mixture an epimerization reaction and, if necessary, triethylamine such that the ratio of propanol to cypermethrin at the end of the reaction is 0.5 to 2 parts by weight, and if necessary, gradually cooling the reaction mixture to isolate the product;

b) after the reaction, the isolated crystalline mass is treated with an aqueous acid solution and / or dissolved in an organic, water-immiscible solvent at 0-70 ° C, or melted without addition of solvent at 60-70 ° G and washed with an aqueous acid solution; the organic layer is washed with water, which may optionally contain salts or acids, and / or the crude material is recrystallized from a solvent containing the organic acid;

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-3EN 3529 B

c) adding an aldehyde as a cyano-binding agent to the process sequence processing section;

(d) the sequence of operations is carried out continuously in several reactors, forming a chain of reactors connected in series of 2 to 10 reactors, which can be refrigerated and heated and have mixers. The reactor temperature is controlled within the temperature range of +30 - -25 ° C, maintaining a maximum temperature difference of 10 ° G in the adjacent reactors; initially adding to the reactor 1 part by weight of the desired crystalline material and, if necessary, up to 0.4 parts by weight of base; the mixture is diluted in each reactor with additional 0.4 parts by weight of protic solvent, if necessary. The addition of 1 part by weight of the crude isomer mixture of the crude Formula 1 compound to the reactors 1, if necessary, adds an additional base amount to give 0.4 parts by weight and, if necessary, adds up to 0 , 4 parts by weight of a protic solvent; the mixture is stirred and all or part of the reaction mixture is introduced into the second and further reactors, whereupon the addition of protic solvent and base and mixing are repeated several times, if necessary. The crude cypermethrin is added to the first reactor continuously or in portions, together with up to 0.4 parts by weight of protic solvent and / or base s. After passing the reaction mixture through the reactor circuit, where the above treatment is carried out, the crystals are isolated, if necessary, from the resulting crystalline suspension at the end of the reactor chain.

The aforementioned isomers of cypermethrin are insecticides with valuable biological properties (EP 205 010 and EP 208 758).

Using known methods, the required mixture of isomers is isolated by crystallization of a mixture of cypermethrin isomers.

Crystallization is carried out in the presence of a base causing epimerization of the O-carbon atom, and the undesired isomers can in theory be converted into the desired product. In organic chemistry this method is called asymmetric second order transformation ·

According to the above procedure, which is suitable exclusively for the cis-isomers, the (la) isomer is obtained from a mixture of cis-permethrin. The starting material was suspended in 1.5 to 3.0 times the volume of triethylamine or dissolved by heating and (la) w · υ i: · ιi ι was added to the solution.

ILI1II UIIIIH .IIIIIJUIIKIIJJ -4I III! III Jilllll crystals for the formation of crystallization centers having the 1: 1 ratio of lRcisS and IScisR isomers and the solution or suspension were slowly crystallized with gradual freezing. 90-95% purity la was obtained with a yield of about 80% (EP 6746 and 109113).

An analogous method for obtaining lb from cypermethrin containing the trans isomers of lb and Id has been published by epimerization with an organic or inorganic base or by epimerization, if necessary, in an organic solvent such as petroleum ether and in the presence of 2,6-di-tert. -butyl-4-methylphenol as an antioxidant at 30-60 ° C (EP 215 010).

According to a later publication, la, lb and Iat-Ib were obtained by treating an initial suspension of isomers in a hydrocarbon base and a catalyst which was substantially dissolved in a suspension selected from quaternary ammonium and phosphorus compounds and crown ether. The suspension was stirred at a temperature suitable for the transformation and the resulting isomers were isolated. The formation of a benzoin ester as a by-product was reduced by adding to the suspension an aldehyde acceptor such as metabisulfite and / or a catalyst, tetraalkylammonium halide, dissolved in an aprotic solvent such as organic nitrile. Solid inorganic bases or their aqueous solutions were used. Sodium cyanide is the preferred base (PCT publication VJO 88/10249).

the disadvantage of this route is the significant degradation of cypermethrin under the recommended reaction conditions, e.g. benzoine-

CL

Formation of CL (II).

The proposed molecule-acceptor helps prevent only the formation of benzoin derivatives and not the degradation of cypermethrin. Another disadvantage of the process is the release of cyanide as a by-product of decomposition. The treatment of a reaction mixture consisting of several layers also complicates the reliable operation of this critical reaction.

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-5I 111 »III» 11 its industrial realization. Perhaps this is why the numerous examples in this publication do not yield the yield results. The increased difficulties encountered in mixtures containing the la and lb isomers are evident from EP 67461, which describes the preparation of a pair of la isomers by transforming a mixture of (Ia-f-Ic) isomers with triethylamine. . According to this publication, when the starting material contains 6 or 10% impurities of the trans isomers, the yield of la is reduced to 63 or 36% When the amount of the trans isomer is higher, no crystallization of la can be expected and no more the isolation of the mixture (Ia + Ib). .

According to the known method, the pure (Ia-Hb) mixture can be obtained by selectively crystallizing sufficiently pure cypermethrin, selecting the right conditions, the right solvent, the right temperature and adding pure crystals for the formation of crystallization centers. The process takes several weeks. In this way, the mixture of Ia + Ib can be obtained in 80% yield, based on the amount of Ia + Ib isomeric pair present in the starting cypermethrin. The disadvantage of this route is that other, biologically less valuable stereoisomers of cypermethrin remain unused (EP 208 758).

Industrial production of pure isomeric products (containing more than 97 active substances) remains problematic to date. By the way, mixtures containing la have an irritating effect on the skin causing severe allergies and it is therefore desirable to simplify the treatment.

According to the present invention, the epimerization is to be carried out in a system containing up to 0.5% moisture. According to our results, the catalytic amount of water may already influence the formation of the benzoine derivatives of formula II. Unlike the previous methods, we do not bind the products of the uprising, but we try to avoid the degradation of hydrolytic cypermethrin. '

According to the present invention, the industrial process can be carried out by combining the components a), b) and c), and optionally d). This process produces stable pure products, is simple to perform, safe and acceptable from the point of view of health.

The components of the process are further specified as follows:

Part (a) of the process of the present invention is based on the fact that, in order to successfully carry out the asymmetric second-order transformation, the critical factor for maintaining the speed of the epimerization and crystallization processes that have begun is not only the choice of the appropriate base, »· ι. i i a · ιι ι

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-6ENG 3529 B but also the amount of propanol to be added to the epimerization reaction at the required temperature. It has been observed that by adding a suitable crystallization solvent, such as isopropanol, to the mixture of oily cypermethrin isomers, the solvent dissolves to a certain extent in cypermethrin, and then, upon reaching the so-called saturation or equilibrium value, the mixture rapidly turns into an emulsion. Upon further addition of the solvent, the resulting emulsion is gradually converted to the true thii-pal. The same phenomenon is observed when a suitable solvent for crystallization has a base. According to our observations, asymmetric transformation can be accomplished more rapidly in saturation or equilibrium conditions. To the best of our knowledge, no such observation regarding asymmetric transformation has been published. The rate of transformation decreases with the amount of material formed, but can be increased by the addition of propanol (propanol selectively promotes crystallization of Ia and Ib). This process is further promoted by cooling the mixture.

However, such saturation or equilibrium conditions are of short duration and therefore the composition of the resulting product is affected by small deviations. If the temperature is raised from 14-15 ° G to 20 ° C during the preparation of the mixture of isomers Ia: Ib «4: 6, the yield is significantly reduced and an increase in the Ib pair of enantiomers can be observed instead of the thermodynamically more likely pair of Ia enantiomers (86 ° G). The same can be achieved by consciously increasing the amount of solvent. The process of the present invention allows the preparation of a product that differs from the initial cis: trans composition of cypermethrin by as much as 30% by weight, and the product having the desired isomer ratio can be isolated. The starting material can be used in the form of an oil as well as crystalline mixtures of cypermethrin isomers. Using a crystalline starting material, the epimerization reaction can be performed faster even if the process is not continuous.

The preparation of some of the isomerically important pairs of Ia: Ib is described below.

To obtain mixtures having an isomer ratio of Ia: Ib = = 40:60, a mixture of cypermethrin isomers (Ia ++ Ic) = 35-45, (Ib-hld) = 50-60% by weight is used as starting material and the reaction is carried out for 4-10 days, depending on quantity, at 3-16 ° q,

I IU ;; l. · Ι, Κ! The inoculum is then added for a period of 1-5 days at -0 ° C with a cypermethrin: triethylamine: propanol ratio of 1: 0.2-0.3: 1-1.5-Isopropanol preferably starting on the second day and continue until day 5.

For a mixture of Ia: Ib = 50:50% by weight, the starting material is a mixture of (Ia-hLcJ = 40-55, (IbTId) = 45-55% by weight) and isomerization is carried out for 1-10 days.

If a mixture of isomers Ia: Ib = 25-30: 75:70% by weight is required then a mixture of IaJ-Ic = 35-45 and Ibl-Id = 50-60% by weight is used as starting material. The asymmetric transformation and isolation is performed in 1-5 days at 25 ° C.

If cypermethrin in oil form is used as the starting material, it is desirable to cool the reaction mixture below 0 ° C and recrystallize the small amount of (Ic + Id) pair of isomers in the isolated product may be further reduced by washing the filtered crystalline final product. Washing may be used solvents such as hexane, heptane, petroleum ether, preferably ethanol and / or isopropanol or mixtures of these solvents with acids, such as acetic acid, phthalic acid, maleic acid, fumaric and malonic species _and štys, may be used, the alkylated malonic acid.

The asymmetric transformation can be performed in the presence of both isopropanol and n-propanol.

An important feature of this process is that the reaction mixture is gradually cooled below 0 ° C, preferably below (-10) to (-25) ° G, during the last third reaction time.

We have found that a small amount of a gas such as nitrogenous impurities is involved in the epimerization of the final product. Such epimerization can also be caused by impurities present in the solvent added or by any of the other reagents involved in the preparation, or by impurities present with the added materials during the preparation of the preparation. Iliustruojančiose examples shown in the tables as possible to prevent unwanted epimerisation at a certain time by adding an acid (shown by adding a small amount of triethylamine) and how to stabilize the products- * ^BLI ''·>'*"' ^{1 1} i uuuiiaiu muLAii IDL no -3-

Studies have shown that b) is needed in our way.

According to component b) of the present invention, the reaction mixture may be acidified or the base in the crystalline suspension may be bound using aqueous solutions of 0.1 to 5% by weight of acid, preferably hydrochloric, formic, phthalic, toilet, rumar or alkylated, or maleic acid optionally containing a cyano-binding reagent.

The water-immiscible solvent, preferably hexane, cyclonexane, petroleum ether, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, benzene, toluene or xylene, may be used to extract the crystalline suspension. The extract is preferably washed with water or water saturated with sodium chloride and / or 0.1% by weight aqueous solution of mineral or organic acid, preferably hydrochloric, acetic phthalic, milled, alkylated, fumaric or maleic acid.

The product may be recrystallized using a non-polar or protic solvent, preferably hexane, heptane, petroleum ether, methanol, ethanol, isopropanol or mixtures thereof with an acid, preferably maleic, fumaric, malonic or alkylated malonic acid.

At the end of the op erations, the product is obtained in the form of crystals, melt, or solution. The product isomer ratio remains stable after 12 months.

If the reaction is carried out under anhydrous conditions, the above degradation of cypermethrin can be avoided. Decomposition also reduces the amount of cyanide in the reaction mixture.

However, a slight degree of degradation is possible in the reaction mixture during long treatment under industrial conditions. Therefore, as part of our invention c), we ensure that the occurrence of free cyanide does not cause safety problems. Whenever small amounts of free cyanide can be generated by acidification of the medium, aldehyde is added to the reaction mixture as a stable cyanogen-binding reagent. To avoid the release of cyanide into the air, it is preferable to use formaldehyde. The resulting nitrile of cyanoglycic acid in the waste mixture can be hydrolyzed to glycolic acid simply by heating, and the resulting mixture can be processed without any risk.

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-9EN 3529 B

The second-order asymmetric transformation is a heterogeneous equilibrium reaction consisting of two steps. The determination of the kinetics of such reactions is possible only experimentally. In our case, the process becomes even more complicated as the concentration changes with the addition of solvent as the crystallization proceeds and the temperature of the epimerization can be increased and then lowered as the process proceeds. In order to determine whether the kinetics of the process reX t action allows the use of a theoretically cassicidal reactor, a reaction sequence was established. The reaction can be described with unmistakable second-order kinetics, which means that utilizing a continuous or near-continuous reactor circuit can increase the throughput and, accordingly, the degree of transformation achieved per unit time.

Component (d) of our invention is based on the recognition that based on the second order reaction kinetics of asymmetric transformation of cypermethrin, the process can be more successfully accomplished using a continuous or near-continuous reactor chain. The reaction can be carried out continuously or almost continuously. In the first case, the materials are added or removed continuously, and in the second, the materials are inserted in such a way that the reactor circuit operates continuously. Several reactor circuits may be arranged parallel to each other. It is best to use trans-junctions in the reactor circuit, because then recirculation or bypassing is possible. The advantage of the method is that it is possible to increase the efficiency by using several batch reactors as well as the degree of transformation. The resulting material can be processed continuously - This prevents decomposition or aggregation bound by the process stoppage. The desired transformation can be achieved in a shorter amount of time per unit quantity of material and thus reduce the risk of material degradation. The temperature of the equipment must remain constant to avoid energy loss.

The present invention provides stable arthropodic compositions comprising as active ingredient a mixture of cypermethrin isomers of the formula I containing at least 95% by weight of the IRcisS and IScisR (la) enantiomeric pairs and enantiomers IRtransS and IStransR (lb) in the ratio Ia: Ib = 55: + 5 - 25:75, or a pair of la or lb isomers and a stabilizer in an amount of 0.001-0.1% by weight of the active ingredient, tartaric acid or acidic n iii · i.imu n ιιιιι · .ι · .ΐΐ.

-10LT 3529 B blend, preferably non-volatile carboxylic acids having pK ^ = 1-5 such as phthalic, succinic, tartaric, maleic, fumaric, malonic, or mono- or polyalkylated derivatives thereof and / or oxalic acid.

In the realization of component (d) according to the invention, it is expedient to use an initial reaction mixture comprising: 50-80% by weight of cypermethrin, 1-50% by weight of propanol, 10-20% by weight of triethylamine or 0.0002-0. 01% by weight DBN or DBUTE It is also appropriate to ensure that the final reaction mixture, after asymmetric transformation, has concentrations of 25-4-5% by weight of cypermethrin, 45-75% by weight of propanol, 4-14% by weight of triethylamine or 0.0002-. 0.004% by weight

DBN or DBU.

In a continuous process, the reaction mixture must have a flow rate of 50 to 150 g / h / liter of reactor system volume.

Stabilized solutions or products containing cypermethrin isomers, together with the above-mentioned stabilizing acids, may be used in formulations containing additives for use in pesticides for agricultural, industrial, veterinary, human health and / or hygienic purposes (see eg EP 208,758). Care must be taken to avoid additives which may impair the stabilizing effect of the acids, especially the bases, or to include them in the determination of the amount of acid used. Solvents should be selected accordingly.

Other details of our invention are illustrated by the following examples.

Analysis of the used and isolated materials was performed by high performance liquid chromatography. (See Analythical Methods for Pesticide and Plant Growth Regulators: XIII, Ed. By G. Zweig and J. Sherma, Acad. Press, 1984).

example

Preparation of a 40:60 mixture of IRc i s S and IScisR (Ia) and IRtransS and IStransR (lb) Enantiomeric Pairs from Cypermethrin

100 g of crystalline cypermethrin having a purity of 90% by weight (melting point: 38-43 ° G), isomer ratio: Ia - 18.1 weight lb - 23.1 weight ¢, lc - 23.5 weight Id - 34, 3% by weight) suspended in a mixture of 21.7 g of triethylamine and 23.5 g of isopropanol in a magnetic stirrer. Mass il ί .i and i

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-11EN 3529 B solution is stirred for 24 hours at 16 ° C. The gradually thickening suspension is diluted 4 times with the addition of

31.5 g of isopropanol every 24 hours. The mixture was then stirred for another 24 hours at 0 ° C. The slurry was filtered, washed with 39.3 g of isopropanol, 31.5 g of isopropanol containing 0.25% by weight of acetic acid, and another 23.5 g of isopropanol and dried under vacuum at room temperature. 87 g of snow-white crystals are obtained.

melt mp: 62-63 ° C.

Isomer ratio: Ia = 38.0% by weight, lb = 59.3% by weight,

Ic = 1.2 wt%, Id = 0.4 wt%.

Purity: 93.9% by weight.

The filtrate was evaporated and the process described above was repeated using a mixture of the product (13.5 g) and 13.0 g of isopropanol / 2.88 g of triethylamine to give another 7 g of a snow-white crystalline material.

melt temp. 62-65 ° G.

Ratio of isomers: Ia = 48% by weight, lb 48.2% by weight,

Ic = 1 wt%, Id = 0.4 wt%.

Purity: 97.6% by weight.

example

Preparation of a 40:60 mixture of TOCsS and IScisR (Ia) and IRtransS and IStransR (lb) from cypermethrin

The reaction is carried out according to the procedure described in Example 1, except that the crystalline cypermethrin is replaced by 100 g of cypermethrin in the form of a thick oil (purity: 95.6% by weight; isomer composition:

Ia = 17.6% by weight, lb = 22.6% by weight, Ic = 22.9% by weight, Id 32.4% by weight), and the reaction is carried out at 11G. A total of 91 g (91%) of the snow-white crystalline product is obtained in steps I and II.

Lyd. mp: 62-64 ° C.

Composition of isomers: Ia = 38.1% by weight, lb = 58.1% by weight,

Ic = 1.1% by weight, Id »0.7% by weight.

Purity: 98 weight ¢.

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-12EN 3529 Example B

Preparation of a mixture of cis and IScisR (Ia) and IRtransS and IStransR (lb) 5O: bO from cypermethrin

This mixture may be prepared according to the method described in Example 1, using only 100 g of crystalline cypermethrin as the starting material (purity: 98% by weight; Ia = 22.3% by weight, Ib: 20.4% by weight, Ic: 26.6% by weight). Id = 28.7% w / w). A total of 9b g of snow-white crystalline product was obtained from steps I-mo and ΙΙ-ro.

melt mp: 54.5-65.5 ° G.

Composition of isomers: Ia = 48.2% by weight, Ib = 48.4% by weight 0, Ic = 1.1% by weight, Id = 0.6% by weight.

Purity: 98.3% by weight.

example

Preparation of cRiSis and IScisR (Ia) and IRtransS and IStrans (Ib) from Cypermethrin at 25 ° C

Starting material is the same as in Example 1, only epimerization is carried out at 25 ° C to give 52.1 g of snow-whiteCrystalline material.

Lyd. mp: 65-68 ° G.

Composition of isomers: Ia = 28.8% by weight, Ib = 67.3% by weight, Ic = 0.8% by weight, Id = 0.3% by weight.

Purity: 97.2% by weight.

example

Preparation of INSc and IScisR (Ia) and IRtransS and IStransR (Ib) from · Cypermethrin using DBN

The starting material is the same as in Example 1, except that triethylamine is replaced by 0.1 g of DBN and in steps I and II of the process, a total of 95 g of white crystalline product is obtained.

melt mp: 62-64 ° G.

Composition of isomers: Ia = 39.4% by weight, Ib = 57.4% by weight

Ic = 1.2 wt%, Id = 0.8 wt%.

Purity: 98.8% by weight.

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EN 3529 Β Example

Preparation of a 40:60 mixture of iRcisS and IScisR (Ia) and IRtransS and IStransR (Ib) from n-propanol

The apparatus, comprising a magnetic stirrer, a thermometer and two openings, is supplemented with 100 g of cypermethrin in oil (purity: 91.4% by weight; Ia: 16.6% by weight, Ib: 21.5% by weight,

Ic = 21.8 wt%, Id = 31.5 wt%). The substance is mixed with

14.5 g of triethylamine and 24.1 g of n-propanol for 4 days at 10-12 ° G. During this time, the suspension is diluted 24 hours later with a mixture of 14.5 g of triethylamine and 16 g of n-propanol, and the dilution is repeated 3 times every 24 hours with 24.1 g of n-propanol. After the last portion of the solvent is added, the reaction temperature is lowered to 5 ° C and stirred for a further 24 hours. The precipitated crystals are filtered off, washed with impurities as described in Example ir, and dried. The first step yields 82 g of a snow-white crystalline material.

Lyd. 62-63 ° C Composition of isomers: Ia = 38.0% by weight, Ib = 60.0% by weight,

Ic «1.0 wt $>, Id = 0.5 wt%.

Purity: 99.5 weight

After evaporation of the filtrate, the mixture is crystallized as described in Example 1.

example

Add 3000 kg of cypermethrin in oil form (purity: 92% by weight, composition: (Ia + -Ic) = 42% by weight ¢, (Ibf-Id) = 50) in a 3000L unit with controlled refrigeration, steam heating and a propeller type mixer 180 kg anhydrous isopropanol (water content: max. 0.2% by weight),

180 kg of anhydrous triethylamine (water content: max. 0.2 wt.%) And the mixture is dissolved by stirring. If necessary, 1 kg of crystalline cypermethrin (Ie = 38 wt.%, Ib »58 wt.%) May be added to form crystallization centers at 25 ° C. For the transformation, the solution is stirred for 18 hours at 3-7 ° C and 228 kg anhydrous isopropanol is added to the crystalline mixture, and the mixture is again stirred for 24 hours at 3-7 ° G, 96 kg anhydrous isopropanol is added and stirred for another 24 hours at 3-7 ° C. , added n it.ι:, .ι · ι; ιι

ILIJI · .111111 111Ι ·. · Ι

An additional 96 Kg of anhydrous isopropanol is added and the mixture is stirred for 168 hours at 3-7 ° G.

The reaction mixture was then cooled to ΐκΐ 0 - (-5) ° C and stirred for 96 hours. The resulting crystalline suspension, divided into 4 equal portions, is filtered through a suction filter using nitrogen - 120 kg of the crystalline mass is washed with anhydrous isopropanol, filtered off, the turbid precipitated by adding 4% by weight of acetic acid-isopropanol solution and filtered under nitrogen. The obtained crystals were dried for 12 hours by heating at 40-45 ° C and stirring under vacuum with a shovel-type bag. 500 Kg of asymmetry is obtained. Its composition according to the chromatographic data is: Ia = 38.2% by weight, ib <58.3% by weight, Ic = 0.6% by weight, Id = 0.8% by weight.

Purity: 97.9 weight sample

Proceed as described in Example 1, only a disk-type mixer is used, and after the third dilution, 48 hours later, the suspension is diluted a fourth time. The mixture is stirred for 48 hours at 0 ° C and diluted with a further 40 ml (3175 g) of isopropanol. The mixture was then cooled and stirred for 48 hours at -5 ° C and 72 hours at -10 ° C. According to the procedure of Example 1, 90 g of snow-white crystalline material are obtained.

melt mp: 62.5 ° C.

Composition of isomers: Ia = 39.0 wt%, Ib = 59.5 wt% Ic = 0.6 wt%, Id = 0.2 wt%.

Example 9

Proceed as in Example 1, using 0.1 g of DBU instead of triethylamine. In steps I and II, a total of 94 g of snow-white crystalline material is obtained.

melt mp: 62.5-64 ° C.

Composition of isomers: Ia = 39.6% by weight, Ib = 57.2% by weight,

Ic = 1.2 wt. 0, Id = 0.9 wt

Purity: 98.9 Weight »ΙΕΙΙ i:; Ι. · Ι; ΙΗ I I Jllll I linu iUUIIILHtil I« III IJ1IJI

-15EN 3529 Example B

Seven 750-liter reactors, equipped with refrigerators and mixers, are connected in a circuit. The first reactor is cooled to 0 ° C, the second reactor to 8 ° G and the rest to 14, 15, 10, 0 and -10 ° C. To the reactors are added 100 g of 95% crystalline 2,2-dimethyl-3- (2,2-dichloro-vinyl) -cyclopropanecarboxylic acid <x-cyano- (m-phenoxybenzyl) e steric (cypermethrin) lRcisS and IScisR (Ia) and IRtransS and IStransR (Ib) ison mixture at a ratio of Ia: Ib = 40: 60- To the first and second reactors are also added 50 ml of isopropanol and 30 ml of triethylamine, and to the third reactor 40, to the fourth reactor-120 and to the fifth reactor 120 , sixth to 160 ml and seventh to 200 ml isopropanol. With vigorous stirring, the mixture is thermostated. To the first reactor was added 100 g of cypermethrin, 94% medium purity oil, containing all the eis and trans isomers in a ratio 41:59, and 30 ml of isopropanol. The mixtures are stirred continuously and after 12 hours 30 ml of triethylamine are added to the first reactor. Half of the diluted mixture is injected into a second reactor and cypermethrin and isopropanol are again added to the first reactor. After 12 hours, the mixture is diluted with 30 ml of triethylamine in the first reactor, and half of the mixture in the second reactor is injected into the third reactor and half of the mixture in the first reactor is transferred to the second reactor. Thereafter, 100 g of cypermethrin and 30 ml of isopropanol are again added to the first reactor and, after stirring for 12 hours, the mixture of the first reactor is diluted with 30 ml of triethylamine and the mixture of the third reactor is diluted with 40 ml of isopropanol and reactor to third reactor and from first reactor to second reactor.

After repeating the addition of cypermethrin and isopropanol after 12 hours of stirring and transfer, 30 ml of triethylamine are added to the first reactor and 40 ml of isopropanol to reactors 3, 4, 5, 6 and 7. Half of the mixture is passed from one reactor to the next, and the material at the end of the reactor chain passes through the filter. The entire sequence of operations is repeated every 12 hours. The filtered material containing 0.1% w / w formaldehyde is washed with isopropanol containing 0.5% acetic acid and dried at room temperature. Each time 85 g of snow is obtained ® · ΕΊ Η.Ι. II I JIEI1II ISIU MILU | JJJMI

-16EN 3529 B White Crystalline Material.

Purity: 97% by weight. The material contains 53.5 a pair of la isomers and 58.5% of a pair of Ib isomers.

melt temp. : 63 ° CI yield (calculated on starting material): 85%.

example

The seven 750 ml reactors, which have refrigerators and mixers, are connected in a circuit. The temperature of the first reactor is maintained at 20 ° G, the second reactor at 25 ° C> the third reactor at 25 ° C, and the remaining reactors are cooled so that each reactor is 5 ° C lower than the reactor upstream. 100 g of a pair of Ib isomers containing at least 95% of the crystalline end product are added to the reactors and 30 ml of triethylamine and 30 ml of isopropanol are added to the first and second reactors. An additional 40 ml isopropanol is added to the third reactor, 80 to the fourth reactor, 120 to the fifth reactor, 180 to the sixth reactor and 200 ml to the seventh reactor. The mixtures are thermostated with vigorous stirring and then 100 g of an oil containing all trans isomers, cypermethrin having an average purity of 94 or fused cypermethrin and 30 ml of isopropanol are added to the first reactor. After stirring for 12 hours, 20 ml of triethylamine are added to the first reactor. Half of the diluted mixture is transferred to the second reactor and cypermethrin and isopropanol are added again to the first. After 12 hours, the mixture in the first reactor is diluted with 30 ml of triethylamine, half of the mixture in the second reactor goes to the third reactor and half of the contents of the third reactor to the fourth reactor. Then, 100 g of cypermethrin and 30 ml of isopropanol are again added to the first reactor. After stirring for 12 hours, the contents of the first reactor are diluted with 30 ml of triethylamine and the third with 40 ml of isopropanol. Half of the contents of the third reactor passes to the fourth reactor, as well as from the second to the third and from the first to the second. After repeating the addition of cypermethrin and isopropanol and stirring for 12 hours, the contents of the first reactor are diluted with 30 ml of triethylamine and the contents of reactors 3, 4, 5, 6 and 7 are diluted with 40 ml of isopropanol. the product passes through the filter- The whole sequence of operations is repeated every «sei i: .1.1111 ι: 111111 IUIU 11Ι1ΙΙ · 1 ·.! Ι: Ι

-17LT 3529 B hours to desired time. The filtered material, containing 0.05% by weight of formaldehyde, is washed with isopropanol containing, each time, 85 g of a snow-white crystalline product containing 98% of a pair of Ia isomers.

Lyd. temp. : 80 ° G.

example

The process can be carried out according to the procedure described in Example 10 except that the starting material is cypermethrin containing 1: 1 cis-trans isomers and 1: 1 crystals of at least 95 Ia and Ib is used to form crystallization centers. 85 g of snow-white crystalline material.

Purity: 97% Isomer ratio: Ia to Ib 48: 49L.p. mp: 65 ° C.

example

The process can be carried out according to the procedure described in Examples 10-13, except that the product obtained at the end of the reactor chain containing 0.2% by weight of formaldehyde is acidified with 2% by weight aqueous hydrochloric acid and extracted with 500 ml of heptane. The hot extract is washed with 50 ml of 1% hydrochloric acid solution, 100 ml of water and 100 ml of saturated sodium chloride solution, and the mixture is crystallized by gradual freezing to -5 [deg.] C. The crystallization is filtered off and dried. 87 g of a white crystalline product are obtained each time.

Purity: 98.5% Isomer ratio: Ia: Ib = 39.0: 59.5Melt. mp: 65.5 ° C14 Example

The process can be carried out according to the procedure described in Example 10, except that the material obtained at the end of the reactor chain containing 0.3% by weight of formaldehyde is acidified with 2% by weight of hydrochloric acid. The mixture is extracted with dichloroethane and the organic layer is washed with 50 ml of 1% hydrochloric acid and twice with

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-13EN 3529 B

100 ml of water, evaporated, dissolved in double methanol and crystallized by gradual cooling to -5 ° G. Each time, 86 g of a snow-white crystalline product were obtained.

Purity: 98 ¢.

Isomer ratio: Ia; Ib = 39:59. melt mp: 63 ° G.

example

The process can be carried out according to the procedure described in Example 10 except that the product obtained at the end of the reactor chain is neutralized with 2% hydrochloric acid, extracted with ethyl acetate and the organic layer is washed 5 times with 50 ml of 0.5% aqueous phthalic acid solution. 1% by weight of formaldehyde. After evaporation of the solvent, the product is dissolved in two volumes of methanol containing 2% by weight of phthalic acid and crystallized by gradual freezing to -5 ° C. The crystals are filtered off and dried. 86 g of a snow-white crystalline product are obtained.

Purity: 98

Isomei ratio: Ia: Ib - 39: 59.

The composition of the isomers remains unchanged after 12 months storage. temp. : 63 ° C16 sample

The process can be carried out according to the procedure described in Example 10, except that at the beginning of the process, a crystalline 99.5% purity cypermethrin having eis and trans isomers in a ratio of 4: 6 is added to the reactor chain. The material is transferred to another reactor every 24 hours. The reactor chain end slurry is acidified with an aqueous solution of 0.4% w / w formaldehyde and 2% w / w hydrochloric acid and extracted with 500 ml (433 g) xylene and washed with 50 ml 2% w / w aqueous phthalic acid and 100 ml (1%). ) maleic acid solution. This yields 535 g of a Ghinmix solution containing 6.9% isomeric pair Ia, 10.6% isomeric pair lb, 0.35% isomeric pair Ic and 0.28% isomeric pair Id.

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The processes can be carried out according to the procedures described in Example 10, characterized in that the material obtained at the glycan end of the reactors is acidified with an aqueous solution containing 2% hydrochloric acid and 0.4% w / w formaldehyde. The mixture was extracted with 400 ml of petroleum ether (100-120) while heating to 60 ° C. The organic layer is washed with an aqueous solution containing 0.1% by weight of formaldehyde and 0.1% by weight of hydrochloric acid, followed by 50 ml of a solution of 1% by weight of hydrochloric acid and 0.1% by weight of formalin, 50 ml of water and 50 ml aqueous solution containing 5% by weight of diethylmalonic acid. The organic layer was separated and the solution crystallized by slow cooling. After filtration and drying, 88 g of a snow-white crystalline mixture of Ia: Ib = = 59.0: 59.5 isomers are obtained.

Purity: 98 Lp. temp. ; 65 ° 018 Example

The processes can be carried out according to the procedures described in Example 17, except that, after washing with a solution of malonic acid, the final treatment step is washed with 50 ml of water and the organic layer is separated. To the solutions are added 0.2 ml of isopropanol containing 0.04 g of maleic acid. The mixture is crystallized by slow cooling. Filtration and drying gave 87 g of a white crystalline product containing a mixture of Ia: Ib = 39.0: 59.5 isomers.

Purity: 98.5 melting point temp .: 64-66 ° GIsomer ratio remains unchanged after 12 months storage. ' p a v y z d y s

Stability test

A mixture of crystalline 99.9% pure cypermethrin isomers containing 1 g of 40% by weight of the Ia isomer pair and 1 g of 60% by weight of the Ib isomeric pair is dissolved in 2 ml of toluene and diluted with 8 ml of anhydrous ethanol. Similar solutions are prepared from pairs of Ia and Ib isomers, respectively. the following acids are added to the samples for analysis, as shown in the following table— Layers, dissolved in anhydrous ethanol (10% by volume) and 10 volumes of «τι I S.I · Ι; Ι! Ι I i millll» IIU UUIMtHJ I Ιΐ: · ΙΙ! .HIIUI

-20LT 3529 Bio% triethylamine in anhydrous ethanol. The solutions are stored at room temperature and after one week the isomeric composition of the substance is determined.

The results are summarized in the tables below.

table

Y = Ia + Ib X = Ic · + Id

Acid Acid- Triethylamine solution quantity, composition those s 0 ml. .0.01 ml 0, 1 ml 1 ml t XI. H ' X Y X Y X Y and A Y las, ml (%) (%) (%) (%) (¢) (%) (¢ 0) - 0 0 99.9 50 49.9 47 45 40 43 Phthalic acid 1 0 99.9 0 99.9 0 99.9 50 49.9 Phthalic acid 2 0 99.9 0 99.9 0 99.9 5 94.9 Malic acid 1 0 99.9 0 99.9 0 99.9 3 96.9 Malic acid 2 0 99.9 0 99.9 0 99.9 0 99.9 Malic acid- 0.1  0 99.9 0 99.9 5 94.9 50 49.9 tis Malonic acid 1 0 99.9 0 99.9 0 99.9 0 99.9 Furoaric acid 1 0 99.9 0 99.9 0 99.9 3 96.9 Fumaric acid 2 0 99.9 0 99.9 0 99.9 0 99.9 Oxalic acid 1 0 99.9 0 99.9 0 99.9 2 97.9 Oxalic acid 2 0 99.9 0 99.9 0 99.9 0 99.9 p-Toluolsul- acid 1 0 99.9 0 99.9 0 99.9 49.9 50 p-Toluolsul- acid 2 0 99.9 0 99.9 0 99.9 2 97.9

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-21EN 3529 Table B ϊ '= lb X'- ld

Acid Ml of acid solution Content and composition of triethylamine solution 0 ml 0.01 ml 0.1 ml 1 ml X ' (%) f ¹ (%) X ' (0) Y ' X ' (%) Ί ' X ^z (%) Y ^z (%) - 0 0 99.9 50.1 49.8 4 6 45.8 41 42 Phthalic acid st 2 0 99.9 0 99.9 4.9 95.1 Maleino acid 2 0 99.9 0 99.9 0 99.9 0 99.9 The acid of grace 1 0 99.9 0 99.9 0 99.9 0 99.9 Fumaric acid 2 0 99.9 0 99.9 0 99.9 0 99.9

table

Y = la X = Ic

Acid Acid- those s Trie tilamin solution quantity, composition solution, las, ml 0 ml 0.01 ml 0.1 ml 1 ml X M Y ^{z /} (%) X (%) Y ^zz (%) X Y ^zZ X (%) (¢) - 0 0 99.9 50.4 49.2 48 43 41 42 Phthalic acid 2 0 99.9 0 99.9 0 99.9 6th 94.2 Maleino acid 2 0 99.9 0 99.9 0 99.9 0 99.9 Nice acid 1 0 99.9 0 99.9 0 99.9 0 99.9 Fumaro acid 2 0 99.9 0 99.9 0 99.9 0 99.9 Oxal acid 1 0 99.9 0 99.9 0 99.9 2.2 97.1 Oxal acid 2 0 99.9 0 99.9 0 99.9 0 99.9

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-22EN 3529 Example B

Stability test

Dissolve 1 g of the product obtained according to the procedure described in Example 18 in 2 ml of toluene and dilute with 8 ml of anhydrous ethanol and add 10% by volume of triethylamine solution. The solution is kept at room temperature for 1 week, after which the isomeric composition is determined.

X = Ic + Id, Y = la + lb Isomers Content of triethylamine solution (ml) 0 0, 01 0, 02 0, 05 0.1 0.2 X (%) 2 2 2 20th 48 47 Y (%) 96 96 96 78 49.5 48 Figure 21 y z d y s 200 g of reaction : mixture Kris talin suspensions, formed at the end of this reaction according to 10 in the example described in the

placed in a unit having a heater, a mixer and a bottom device for removing material. While stirring, the mixture is acidified with an aqueous solution of 2% by weight hydrochloric acid and 0.2% by weight of formaldehyde to pH = 2. After stirring for 15 minutes, the pH of the solution is checked and the crystalline suspension is melted to 60 ° C. After stirring for 15 minutes, the oily cypermethrin is precipitated and separated. The warm product is dissolved in 150 ml of isopropanol containing 1% by weight of maleic acid and crystallized by slow cooling with the addition of crystallization centers. The precipitated snow-white crystals are filtered off, washed with 50 ml of glacial isopropanol containing 1% by weight of maleic acid and dried. 56 g of a snow-white crystalline product are obtained.

melt 62.5-63 ° C Purity: 97%.

Isomer ratio: Ia: Ib = 38.5: 58.5 Yield: 88% starting material.

-23 «ιιη ι iii example

The process performed according to the procedure described in Example 10 is only 1000 times larger. Materials are charged and discharged continuously.

The following material flows shall be used:

Reactor queue Material flow to reactor (kg / h) Material flow from reactor (kg / h) ciperme rubbing early reactor trie tilamine isophthalic acid 1 8.33 0 1.83 2.0 12.16 2 0 ' 12.16 0 ' 0 12.16 3 0 12.16 0 2.6 14.76 4 0 14.76 0 2.6 17.36 5 0 17.7 6 0 2.6 19.96 6th 0 19.96 0 2.6 22.56 7th 0 22.56 0 2.6 25.16

The daily average yield is 171.0 kg of the product described in Example 10.

example

The process can be carried out as described in Example 22, only trans-cypermethrin is taken as starting material and crystalline material containing 93% of the lb isomers is added to each reactor. The mixture is thermostated at the temperature set forth in Example 11 and the triethylamine is fed to the second reactor at 1.83 kg / h. at flow rate to increase the crystallization potential in Unit 1. This gives 173.2 kg of a snow-white crystalline product containing 98.1% of a lb pair of isomers melting at 80.5 ° G.

example

Add 0.8 g of 'synthetic silicic acid (Aerosil 300) to 166.2 g of perlite (d - 120 m) in a homogenizing high speed blender. To the mixture is added 20 g of cypermethrin having an enantiomeric pore ratio of Ia: Ib = 4: 6, 0, 04 # fumaric acid and 2 g of fatty alcohol polyglycol ether to form a homogeneous mixture. The powder mixture is ground first

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-24EN 3529 B in a mechanical mill and then in an air stream mill- Then 5 g of octylphenol polyglycol ether (EO = 20) and 2 g of sulfosuccinate are added to the high speed blender. The wettable powder mixture (WP) suspension thus obtained is tested for stability. Wet time = 23 seconds; flotation activity = 89% (standard V / HO method).

Example 1 g of a mixture of cypermethrin enantiomeric pairs of Ia: Ib = 55: 45 and 0.1 O malonic acid are dissolved in a mixture of 21.25 g of xylene and 42.5 g of n-propanol with slow stirring. While stirring, a mixture of 4 g of ethoxylated alkylphenol + calcium n-alkylarylsulfonate and 6 g of ethoxyalkylated amino + alkali metal n-alkylarylsulfonate is added until complete dissolution, followed by addition of 21.25 g of water. This produces a clear solution which retains its properties over a long period of time at a temperature between 0 and 50 ° C. If necessary, the solution may be diluted with water in any ratio; an emulsion with a droplet size of 0.8-1.5 ^ m is formed.

example g of a mixture of pore enantiomers of cypermethrin in the ratio Ia * .Ib «= 25:75 and 0.002 g of diethylmalonic acid are dissolved in a mixture of 75 g of xylene and 10 g of aliphatic oil, followed by the slow addition of a mixture of 75 g of ethoxylated alkylphenol + calcium -alkarylsulfonate, and a mixture (2.5 g) of ethoxylated fatty acid + n-alkylarylsulfonate. Measurements by CIPAC show that the emulsion concentrate remains stable for 170 hours.

example

The emulsifiable concentrates (EC) are obtained by mixing the following components:

EG

The component Quantity, Pair of isomers Ia: Ib = 40:60 0.105 Diethylmalonic acid 0, 00005 Cyclohexanol 0, 290 Atlox 3386 B 0, 020 Atloz 3400 3 Odorless - mineral oil 0, 045 0, 54 0

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The component

Pair of isomers Ia: Ib = 40:60

Diethylmalonic acid

Cyclohexanol

Atlox 3386 3

Atlox 3400 B

An odorless example of mineral oil

Emulsifiable concentrates (EC) in component s:

^{'10 EG}

The component

A pair of isomers lb

Diethylmalonic acid

Cyclohexanol

Atlox 3386 B

Atlox 3400 B

Odorless mineral oil

EC

The component

A pair of isomers lb

Diethylmalonic acid

Cyclohexanol

Atlox 3386 'B

Atlox 3400 B

Colorless mineral oil example g

somas addition, 5 carbonate mill Alpine ^f as 81%;

Quantity, kg / kg

0, 050 0, 00005 0, 290 0, 020 0, 045 0,595 are obtained by mixing these

Quantity, kg / kg

0.105 0, 00005 0.290 0, 020 0, 045 0.540

Quantity, kg / kg

0, 050 0.00005 0, 290 0, 020 0, 045 0.595 pair of isomers lb is diluted with 0.02 g maleic acid, g nonylphenylpolyglycol ether powder in homogenizer.

In a 10C type mill. By wetting time = g ethanol. A solution of 5 g of calcium lignosulfone (E0 = 20) and 70 g of calcium was thus obtained with CIPAC flotation activity for 18 seconds.

Claims (14)

DEFINITION OF INVENTION ^(I) d. , belong to chiraa showing eis or in which the carbon atoms designated 1, 3 and the linear carbon atom and the curved lines are trans configuration with respect to the cyclopropane ring are the isomers of the isomers having at least 95% IRtransS of the theoretically possible 8 cypermethrin isomers; IStransR (Ib) isomeric pairs, or is a mixture of only the RacisS ii · IScisR (Ia) and (Ib) isomeric pairs in the ratio (Ia) :( Ib) 55:45 - 25:75 from a mixture of cypermethrin isomers without (Ib) ) isomers, both eis and other trans isomers, or a pair of Ia + Ib isomers in an undesirable ratio using a second-order asymmetric transformation in the presence of an amino base and a solvent, (a) Reaction of the isomers in the form of an oil or crystalline compound of formula (I) having a purity of at least 90% by weight with a minimum of 60% by weight of trans isomers or cisir trans isomers in the range 65:35 to 15:85 temperature, in a system containing up to 0.5 5? moisture, with triethylamine in a total amount of 0.1 to 0.5 parts by weight, or with 1,5-disabicyclo / 4,3, O / non-5-ene (DBN) or 1,5-diazabicyclo / 5 , 4, O / undecene (DBU) in an amount of 0.0005 to 0.01 parts by weight based on the initial weight of the mixture of isomers under vigorous stirring and in the presence of propanol, initiating the reaction in the saturation of the various liquid phases produced during the transformation reaction , by adding propanol and, if necessary, triethylamine, to the mixture, by means of an epimerization reaction such that the ratio of propanol to cypermethrin is 0.5 to 2 parts by weight at the end of the reaction, and the crystalline product is gradually released if necessary. ι ΐΕ.πιι -27EN 3529 B by reaction mixture, and b) After the transformation reaction, the isolated crystalline mass is treated with an aqueous acid solution and / or dissolved in an organic, immiscible water solvent at 0-70 ° G, the aroa is melted without the addition of solvent at 60-70 ° G and the organic layer is washed washed with water containing salts or acids, as appropriate, and / or recrystallized from a solvent containing organic acid, and (c) adding the aldehyde as a cyano-binding agent in the processing step of the sequence of operations or, if necessary, d) continuous sequence of operations in several reactors, forming a chain of reactions, connecting two to ten reactors having refrigerators, mixers and heaters in series and sequentially assembling them; reactor temperature controlled in the range of f-30 to -25 ° G with a maximum temperature difference of 10 ° G; adding 1 part by weight of crystals of the final product to the reactors and, if necessary, up to 0.4 parts by weight of base and, if necessary, mixing each mixture with an additional amount of solvent up to 0.4 parts by weight; adding to the first reactor 1 part by weight of at least 90% by weight of a mixture of isomers of the compound of formula I and optionally adding up to 0.4 parts by weight of base and, if necessary, up to 0.4 parts by weight of a protic solvent; mixing the mixture and transferring all or part of the mixture to the second and subsequent reactors; adding a protic solvent and a base and mixing repeatedly if necessary; adding crude cypermethrin and up to 0.4 parts by weight of protic solvent and / or base to the first reactor, either continuously or in portions; after passing the reaction mixture through the reactor chain, where the treatment described above is carried out, the crystals are isolated if necessary from the resulting crystalline suspension at the end of the reactor chain. 2. A process according to claim 1, wherein the asymmetric transformation is carried out in the presence of isopropanol or n-propanol. 3- The process according to lp-, wherein in the third reaction period the reaction mixture is gradually cooled to below 0 ° C, preferably to -10 to -25 ° C. -28EN 3529 B 4. A process for preparing a mixture of 1? -Isomers of la: lb = 40:60, wherein the starting material is lRcisS + IScisR + lRcish. + IScisS (ra f lc) = 35-45 wt.% IRtransS + IStransR -t lStransS. + IRtransR (lb + - Id) = = 50-65 wt.% Mixture of isomers and the ratio of pyrethroico: triethylamino: isopropanol of formula (I) is 1: 0.2-0.3: 1-1.5, and the reaction time in the batch process is 4-10 days at 3-16 ° G and 1-5 days at 0 ° 0. 5- Method according to p. for a mixture of isomers Ie. : Ib - 50:50 except that the starting material used is a mixture of (la + lc) = 45-55% (lb -f- Id) = 45-55% by weight of isomers. 6. The method of p. for the mixture of isomers la: lb - 25-30: 75-70, except that the starting material used is (Is. + lc) - 35-45% by weight, (lb + Id) - 50-55% by weight of the isomeric mixture, and the reaction is carried out and the product is isolated at 25 G 7. A method according to claim 1, wherein the material is fed and discharged continuously or intermittently. 8. Method according to p. b) an alkali, wherein solvents such as petroleum ether, hexane, heptane, ethanol, isopropanol, and mixtures thereof with acids such as acetic, phthalic, maleic, fumaric, malonic and alkylated malonic acids are used to remove impurities in the filtered material. 9- Method according to p. b) the part comprising using aqueous solutions of 0.1 to 5% by weight of acids, preferably salt, formic, phthalic, malonic, fumaric, maleic and / or alkylated malonic, to acidify the reaction mixture or to treat the crystal suspension, wherein - in need, there is a cyano-binding substance 10. A process according to claim 1 (b), wherein the crystalline suspension is extracted with a water-immiscible organic solvent, preferably hexane, cyclohexane, heptane, petroleum ether, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, benzene. or xylol. -29II IIIJ U J III I u m ;, biiiui 11. A process according to claim 10 wherein the extract is washed with water, water saturated with sodium chloride and / or 0.1-5% by weight of mineral or organic acid, preferably salt, vinegar, phthalate, milled, alkylated milled, fumar or maleic in aqueous solution containing a cyano-binding agent if necessary. 12. Method according to p. (c) a portion, other than the use of formaldehyde as a cyanide binder 15. The method of p. b) a part, wherein the recrystallization of the product uses a non-polar or protic solvent, preferably hexane, heptane, petroleum ether, methanol, ethanol, isopropanol or a mixture thereof with an acid such as acetic, maleic, fumaric, malonic and / or alkylated malonic acid. 14. Stabilized arthropodic compositions containing as active ingredient cypermethrin s of formula (1) in which 1, 3 and # belong to the Viral carbon atom and the curved line shows the eis or trans configuration with respect to the cyclopropane ring having at least 95% by weight. a mixture of isomers of lhcisS and IScisR (la) and lhtransS and IStransh (lb) enantiomers in a weight ratio of Ia: Ib = 55:45 - 25:75 or a pair of la or lb isomers, except that, as a stabilizer, is from 0.001 to 0.1% by weight, based on the active ingredient, of an acid or mixture of acids, preferably of this non-volatile carbonic acid, having a pK- ^ = 1-5, such as phthalic, amber, tartaric, maleic, fumaric, pleasant or their derivatives with one or more substituents on the chain such as their alkylated derivatives and / or oxalic acid. 15-The process according to claim 1 (b), wherein the initial reaction mixture is at a concentration of 50-SO0 of cypermethrin, 1-50% of 0 propanol, 10-20% by weight of triethylamine or 0.0002-0.02. % by weight of DBN or DBU, and the concentration of the final reaction mixture obtained from the transformation is as follows: 25-45% by weight of cypermethrin, 45-75% by weight of propanol, 4-14% by weight of triethylamine or 0.0002-0.003% by weight of DBN or DBU where the flow rate of the reaction mixture is between 50 and 150 g / h / liter of reactor volume.