HU210098B - Process for producing isomeric mixtures of cypermethrin and stabilised insecticidal compositions and concentrates containing the mixtures - Google Patents

Abstract

The invention relates to the process for preparation of cypermetrine isomers mixtures of formula Iwherein 1,3, and α-marked carbon atoms refer to chiralic carbon atom, and waved line indicates to cis or trans configuration relative to cyclopropane nucleus, which contains at least 95% of isomer pairs: IR trans S and IS trans R (Ib) or only IR cis S and IS cis R (Ia) mixture and the (Ib) isomer pair in the ratio of (Ia):(Ib)=55:45 - 25:75, obtained by type 2 asimmetric transformations, in the pressence of an amine base and protonic solvent between O°C and +25°C from the starting cypermetrine isomers mixture, having at least 90% wt % purity, containing and other cis or trans isomers, following after (Ib) pair of isomers or Ia+Ib pairs of isomers in undesired ratio.The process is carried out continuously in several conse cutive reactors. The cristals are formed at the end of reactors chain, which optional are separated from crystalls suspension.

Description

Scope of the description: 12 pages (including 2 sheets)

HU 210 098 Β preferably in the presence of an alkanol with a second grade asymmetric transformation from 0-25 ° C from a starting cypermethrin isomer mixture of at least 90% purity, which is a cis isomer or cis and other transisomers in the isomeric pair Ib, or isomer pair Ia: Ib; contains an undesirable ratio such that

a.) the reaction is carried out in several reactors such that a

2 to 10 refrigerated and heated mixer reactors are connected in series to a reactor chain, the adjacent elements (+) 30 - (-) within a temperature range of 25 ° C to a temperature difference of up to 10 ° C, 1 part by weight of the desired product crystal upon start-up; and optionally, 0.0010.4 parts by weight of a protic solvent and / or 0.0010.4 parts by weight of base, the mixtures are optionally diluted in the reactor with additional amounts of 0.001-0.4 parts by weight of protic solvent and then into the first reactor. 1 part by weight of at least 90% pure isomeric mixture of the formula I, and optionally an additional 0.001 to 0.4 parts by weight of base and optionally 0.001 to 0.4 parts by weight of protic solvent, the mixture is stirred, the reaction mixture or part thereof with the second one. and then released to the next reactor, where the protic solvent and base feed and stir repeatedly repeatedly repeatedly adding crude cypermethrin to the first reactor repeatedly or intermittently, optionally 0.01 to 5% by weight of the decomposition and by-product admixture, 0.001 to 0.4 parts by weight of solvent and / or base, while the reaction mixture is added. each reactor passes through the above treatment in a row and at the end of the reactor chain the crystals are isolated from the lowered reaction mixture,

b. ) neutralizing the base optionally present in the reaction mixture leaving the last reactor and / or on the surface of the crystalline product with acid and / or recrystallizing the crystals from an acid-containing solvent and / or digesting the crystalline suspension in the presence of an aqueous acid at 60-70 ° C;

c. ) is extracted with the crystalline organic solvent at 0-70 ° C and the extract obtained is washed with acidic salts or water containing acid and optionally washed with water.

d. ) Aldehyde is added as the cyanating agent at the processing stage of the system.

The present invention relates to a (0-cyano-3-phenoxybenzyl) -3- (2,2-dichloro-vinyl) -2,2-dimethylcyclopropanecarboxylate (free or R-ISO cypermethrine) of the formula (I) having a specific isomer ratio. hereinafter referred to as "cypermethrin", for the preparation of enantiomeric mixtures by asymmetric transformation, as well as for concentrates and compositions containing them.

Compared to the chiral carbon atom labeled with α in the present specification, the substituent spacing is characterized by S and R. The term "cis" and "trans" denote the placement of substituents on the carbon at the 3 carbon atoms of the cyclopropane ring;

The following abbreviations are used to denote the various enantiomers or enantiomeric pairs, if applicable:

1R IRisS and 1ScisR mixture of alpha-ether (Fastac) 1b IRt and trans (Transmix)

Ic is a mixture of RisR and lSIS

Id is a mixture of IRtrans and IST

If IR is trans

Ih lScisR

ICtransRa + lb asymmetrine (Chinmix) t% in the description is always% by weight.

SUMMARY OF THE INVENTION The present invention provides a continuous process for the cypermethrin of formula (I), wherein the carbon atoms of 1,3 and α are chiral carbon, the wavy line denotes the cis or trans spacing relative to the cyclopan ring for the preparation of isomeric mixtures which are at least 95 of the possible 8 isomers of cypermethrin. % or only the isomer pair IrisS and 1ScisR (Ia) or only the IRtransS and IStrasR (1b) isomeric pair or only the mixture of Ia: Ib = 55: 45-25: 75, tertiary amine base and protic solvent, preferably in the presence of an alkanol with a second asymmetric transformation at 025 ° C from a starting cypermethrin isomer mixture of at least 90% purity which, in addition to the isomeric pair la, has a different cis isomer or a cis and / or other trans isomer in the isomer pair Ib, or an isomeric pair Ia: Ib; comprising reacting the reaction in a plurality of reactors k to form a reactor chain in series by cooling the heated and heated mixing reactors 2-10, the adjacent elements (+) 30 - (-) within a temperature range of 25 ° C to a temperature difference of up to 10 ° C, one at each of the reactor elements 1 part by weight of the desired product crystal and optionally 0.001-0.4 parts by weight of protic solvent and / or 0.001-0.4 parts by weight of the base are optionally added to the reactor in addition to 0.001-0.4 parts by weight of the protic solvent. and then adding to the first reactor 1 mass unit of at least 90% pure crude isomer of formula (I), and optionally an additional 0.001-0.4 parts by weight of base and optionally 0.0010.4 parts by weight of protic solvent, the mixture being stirred and the reaction mixture stirred. or part of it a

HU 210 098 Β second and then into the next reactor, where the protic solvent and base feed and stirring are repeatedly repeated several times while the raw cypermethrin is added continuously or intermittently to the first reactor, the component is 0.01 to 5% by weight of the decomposition and by-product. -binding additive, 0.001-0.4 parts by weight of solvent and / or base, while the reaction mixture passes through the above treatment in all reactors and the crystals are isolated from the lowered reaction mixture at the end of the reactor chain;

b. ) neutralizing the base optionally present in the reaction mixture leaving the last reactor and / or on the surface of the crystalline product with acid and / or recrystallizing the crystals from the acid-containing solvent and / or digesting the crystal suspension in the presence of an aqueous acid at 60-70 'C;

c. ) is extracted with the crystalline organic solvent at 0-70 ° C and the extract is washed with optionally acidic salts or water containing acid, and

d. ) Aldehyde is added to the processing section of the system as a cyanide binding agent.

The above isomers of cypermethrin are insecticidal agents with very favorable biological properties. The preparation of the isomeric pair Ia is described in U.S. Patent Nos. 184,783,185,176,186,407,186,406. in Hungarian, the preparation of the 1b isomer pair is described in 198,373 Hungarian, the above mixture of la + lb in 198612 and 199390. Hungarian patents were known.

The prior art preparations can be briefly described as separating the desired isomer mixture by crystallization from a cypermethrin isomer mixture. By carrying out the crystallization in the presence of a base capable of inducing the epimerization of the alpha carbon atom, unwanted isomers can be transformed, so that in principle, the entire starting isomer mixture can be converted to the desired product. The process is known as Asymmetric Transformation II in Organic Chemistry. It is important to note, however, that their implementation requires special circumstances after the preparation of mixtures of isomers (la, lb, or la and lb).

No. 888,336. Belgian and No. 67,461. In accordance with the procedures described in European Patent Specifications, for the preparation of la, it is practically based on a mixture of cis cypermethers. The starting material is warmly dissolved in 1.5 to 3-fold triethylamine, then seeded with 1: 1 (Ia) seed crystals containing 1RcSS and 1ScisR and the solution is slowly cooled to slowly crystallize. Thus, 90% to 95% pure la isomeric pair is obtained in 80% yield.

Act 198 373 is similar. also in the case of the process described for the preparation of 1b in the Hungarian patent, except that the crystallization of the isomer pair 1b is preferable to the isomeric pair I previously described, it is not necessary to start strictly from the cypermethrin containing only trans isomers and the purity of both the yield and the extractable material can be increased. solvents, e.g. using isopropanol.

No. 199 390 The process of Patent No. 5,102,195 allowed direct preparation of at least 95% and 70: 45-25: 75 isomeric mixtures of the la and lb isomers by asymmetric transformation of the order II, with the total amount of cypermethrin containing 8 isomers being 0.25 to 0.35 times. Crystallization with (-) 25 ° C - (+) 25 ° C for 7 days at room temperature was carried out with a mixture of triethylamine and 1.5 to 2.5-fold propanol, and then the product was isolated by filtration and washed free of contamination.

However, the production of isomeric products (containing more than 97% active ingredient) under industrial conditions still posed a number of problems. Particularly due to the skin irritant, individual allergic effects of Ia-containing mixtures, processing requires a closed system of special devices. Due to these possible clogging up, the rinsing of the filter hub can not be safely performed to remove the base traces. In addition, the special filter washer-field targeting machines also significantly limit production from the capacity side. Increasing the volume of the tank reactor is difficult due to decomposition and rubbing problems. Obviously, instead of intermittent manufacturing, one should strive for a process that can be carried out continuously. A partial solution is the use of multiple synchronous tank reactors, since a system adapted to the capacity of the filter device would require the use of 7-14 small reactors due to the long (7 day) reaction time.

Asymmetric transformation II is a two-step heterogeneous equilibrium reaction. The apparent kinetics of such a reaction can only be determined experimentally. In our case, the process is also fundamentally complicated by further dilution of the changing concentration as the crystallization progresses, and by raising the process, and then reducing the "reaction temperature". Thus, in order to clarify whether the process's apparent kinetics in principle allows the use of cascade reactor lines, the apparent regularity of the reaction was determined. We have found that the process can be described by seemingly second-order kinetics, which also means that the use of a continuous or quasi-continuous reactor line can significantly increase the capacity, or. Conversion below the time unit.

The essence of the present invention is the recognition that the process of kinetic kinetic asymmetric transformation of cypermethrin makes the process more advantageous in a continuous or non-continuous manner. using a quasi-continuous cascade reactor.

It is also within the scope of the present invention to use antioxidants in the reaction to suppress the decomposition of the compound of formula (I), e.g. BHTt [2,6- (dicertiary butyl) -4-methylphenol].

It has been further found that some of the oxo compounds are selectively reactive, e.g. the purity of the final product can be further improved by the use of the carbicarbide as these (due to the hydrolytic decomposition of the molecule) with aldehyde, or. they react with the continuously increasing benzoine of formula (II) and mel3

On the one hand, the formation of slurry products can be reduced, and on the other hand they can be washed in the form of eye-carbazone. Decreasing the decomposition also reduces the free cyan content of the reaction mixture from the other side.

The cyanide risk can be further reduced by using dilute acids containing additional additives to neutralize the cyanide present in order to neutralize the reaction mixture. This is a low-chain aldehyde, or formaldehyde may be used. For neutralization or for for washing, the solvent used in the propanol, so as to avoid loss of material, is to use a large amount of dilute aqueous solution containing 0.1 to 5% by weight of acid and optionally formaldehyde. As an acid, the mineral is effectively neutralizing the base. organic acids, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen sulfate, and the like. formic acid, phthalic acid, malonic acid, maleic acid, etc. will be discussed. Because of the aforementioned basic sensitivity of the product, it is preferable to use slightly acidic conditions in the washing steps and recrystallizations. The product obtained under these conditions can be stored for a long time under the influence of the acid traces contained therein. It is preferred to use acids which are readily soluble in the product, crystallized or dried. Such is e.g. phthalic acid, malonic acid, or its alkylated derivatives, maleic acid, fumaric acid, tartaric acid, and the like. The stabilizing effect of these is exemplified. Listed additives; The beneficial effect of antioxidant, aldehyde binder, cyanide and acid stabilizer has not yet been published. Their use makes it possible to produce a final product of a quality that provides a product suitable for direct molding by solvent extraction.

The reaction can be carried out continuously and continuously. In the first case, the feeds and material pickup are carried out continuously, while in the second case, the feed is carried out so that the reactor chain operates without interruption. In parallel, several reactor chains can be formed. It is preferable to use linkages in the reactor chain to allow recirculation or "by pass" execution. The extraordinary advantage of this method is that its production capacity can be multiplied compared to similar tank reactors and at the same time the conversion conversion can be improved. The resulting product can be processed continuously so that the decomposition due to the job can be avoided. thrombosis. The desired conversion is available in less time per unit of material. The individual devices can be tempered to a constant temperature, which, while being technologically more advantageous, saves energy. Operations can be routinely performed, which increases the safety of production. The process can be automated easily. It is very positive that after the reactor line contains a large amount of seed crystals, the conversion can be carried out with lower quality starting cypermethrin, while the quality of the final product will be constant. It can also be said that the buffer capacity of the reactor chain can be positively enforced.

The following examples illustrate our process. Used or used recovered materials were analyzed by HPLC (see Analytical Methodes Forum Pesticides and Plant Growth Regulators: XIII Ed by Zweig and J. Sherma, Academic Press 1984).

Example 1

2,2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester η cis S and IS cis R (Ia) and IR trans S and continuous preparation of IS trans R (Ib) 1a: 1b = 4: 6 isomer from cypermethrin containing all stereoisomers.

Seven series of 750 ml refrigerated mixer reactors each. The first reactor is cooled to 0 ° C, the second reactor is cooled to 8 ° C, and the other reactors are individually cooled to 14, 15, 10, 0 and -10 °. The reactors are charged with 100-100 g of crystalline 2,2-dimethyl-3-ylcarboxylic acid (R) cis S and IS cis R (la) as well as IR trans S and IS trans R (Ia: Ib = 40:60 and at least 95%). - (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl ester (cypermethrin). Furthermore, 30 ml of isopropanol and 30 ml of triethylamine are charged to the first and second reactors, followed by addition of 30 ml of triethylamine. In addition to the third reactor, 40 isopropanol is added to the fourth reactor, 80 to the fourth reactor, 160 to the sixth reactor, and 200 ml to the sixth reactor. The mixtures are thermostated with vigorous stirring and then 100 g of all cis and trans isomers are introduced into the first reactor. : 59% by weight of an average 94% pure cypermethrin with 94% pure isopropanol, and the mixtures are continuously stirred, and after 30 hours, 30 ml of triethylamine are added to the reactor. repeating the measurement of cypermethrin and isopropanol in the first reactor. After 12 hours, the first reactor mixture is diluted with 30 ml of triethylamine and half of the second reactor mixture is transferred to the third reactor.

Then, 100 g of cypermethrin and 30 ml of isopropyl alcohol are again added to the first reactor. After 12 hours of stirring, the first reactor was diluted with 30 ml of triethylamine, the third reactor was diluted with 40 ml of isopropanol and reactor 3 was reacted into reactor 4 or reactor. Half of the blends from 3rd to 1rd from reactor 2 to reactor 2.

By repeating the measurements of cypermethrin and isopropanol, 122 hours of stirring followed by the progress of the material, the first reactor with 30 ml of triethylamine, after dilution of the third, fourth, fifth, sixth and seventh reactors with 40 ml of isopropanol, half of the reactors in the next reactor, respectively. the material obtained at the end of the reactor chain is passed to a filter and the sequence is repeated for 12 hours at any time. The filtered material was washed with 0.5% (w / w) acetic acid in isopropanol and dried at room temperature. Occasionally, 85 g of snow-white crystalline material are obtained. Purity 97% containing the isomer pair la in 38.5% is 58.5% of the Ib isomer pair. 63 ° C. Yield 85% of the amount of material introduced.

EN 210 098

Example 2

Preparation of 2,2-dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl ester IR cis S and IS cis R (la) from a mixture of cis cypermethrin stereoisomers.

Seven series of 750 ml refrigerated mixer reactors each. The first reactor was heated to 20 ° C, the second reactor was heated to 25 ° C, the third reactor was heated to 25 ° C, the fourth reactor was heated to 20 ° C, and the other reactors were subjected to a temperature difference of 5 ° C relative to the previous one. cooled to lower temperature. The crystalline final product containing at least 95% of isomer pair (Ia) was charged to the reactors, and 30-30 ml of triethylamine and 30 to 30 ml of isopropanol were added to the first and second reactors, followed by a further 40 in the third reactor, 80 in the fourth reactor. reactor 120, isopropanol 160, and 200 ml isopropanol. The mixtures were thermostated by continuous intensive stirring, and 100 g of oil cypermethrin or cypermethrin melt containing 30% total cis and trans isomers were added to the first reactor and 30 ml isopropanol was added. After stirring for 12 hours, 30 ml of triethylamine are charged to the first reactor. Half of the diluted mixture is discharged into the next reactor and the measurement of cypermethrin and isopropanol is repeated in the first reactor. After 12 hours, the first reactor mixture was diluted with 30 ml of triethylamine and half of the second reactor mixture was transferred to the third reactor and half of its first content into the second reactor. Then, 100 g of cypermethrin and 30 ml of isopropyl alcohol are again added to the first reactor. After 12 hours of stirring, the first reactor was diluted with 30 ml of triethylamine, the third reactor was diluted with 40 ml of isopropanol and reactor 3 was reacted into reactor 4 or reactor. Half of the mixture is transferred from reactor 2 to reactor 3 and from the first reactor to reactor 2.

Repeating the measurements of cypermethrin and isopropanol, the first reactor was reacted with 30 ml of triethylamine after dilution of reactors 3, 4, 5, 6 and 7 with 40 ml of isopropanol, according to the 12-hour agitation and the advance of the material, as described above. half to the next reactor, or the material obtained at the end of the reactor chain is passed to a filter and the sequence is repeated for 12 hours at any time. The filtered material was washed with 0.5% (w / w) phthalic acid isopropanol and dried at room temperature. Occasionally, 85 g of snow-white crystalline material are obtained, containing 98% of the isomer pair la. 82 ° C.

Example 3

Preparation of 2,2-dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl ester IR trans S and IS trans R (Ib).

The procedure described in the second example is followed by starting with a crystal containing at least 95% of the isomer pair Ib and starting from a cypermethrin containing trans isomers. 85 g of snow-white crystalline material are sometimes obtained as described. Purity 98%. 80 ° C.

Example 4

2.2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester IR cis S and IS cis R (Ia) and IR trans S and IS trans Preparation of R (Ib) Ia: Ib = 1: 1 Isomer Mixture.

The first example is carried out with the exception that the apparatus is started with crystals containing at least 95% and 1: 1 isomers of la and Ib, and starting from cis-trans isomers containing 1: 1 cypermethrin. 85 g of snow-white crystalline material are sometimes obtained as described.

Purity: 97% la and Ib isomer ratio 48:49.

65 ° C.

Example 5

2.2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropane-carbinic acid α-cyano (m-phenoxybenzyl ester IR cis S and IS cis R (la) and IR trans S and IS trans Preparation of R (Ib) Iblb - 4: 6.

The same procedure as in Example 1 was followed, except that the material discharged at the end of the reactor chain was neutralized with 2% hydrochloric acid in 500 ml of heptane, heated to 65 ° C, extracted with 50 ml of 1% (w / w) hydrochloric acid in 100 ml of water and 100 ml. with saturated brine, and then gradually crystallized to -5 ° C. The precipitated material was filtered and dried. Occasionally, 87 g of white crystalline material are obtained. Purity: 98.5%, Isomer: Ia: Ib = 39.0: 59.5. Melting point: 65.5 ° C.

Example 6

2.2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester IR cis S and IS cis R (la), and IR trans S and IS trans R (Ib) Ia.bb = 4: 6 isomer mixture.

The first example was carried out with the exception that the material at the end of the reactor chain was neutralized with 2% hydrochloric acid, extracted with dichloroethane, washed with 50 ml of 1% hydrochloric acid and twice with 100 ml of water, evaporated and then twice with methanol. dissolve hot and gradually crystallize at -5 ° C. Occasionally, 86 g of snow-white crystalline material are obtained. Purity: 98%. Isomer ratio: Ia: Ib = 39:59 mp: 63 ° C.

Example 7

2.2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester IR cis S and IS cis R (la) as well as IR trans S and IS trans R (Ib) Ia. Preparation of Ib = 4: 6 isomer mixture.

The first example was carried out with the exception that the material at the end of the reactor chain was neutralized with 2% hydrochloric acid, extracted with ethyl acetate, and the organic phase was washed five times with 50 ml of 0.5% aqueous phthalic acid solution, and then evaporated twice. Dissolve 2% in phthalic acid in methanol and slowly crystallize at -5 ° C. The crystals were filtered and dried. Occasionally, 86 g of snow-white crystalline material are obtained. Purity: 98%.

EN 210 098

Isomer ratio: Ia: Ib = 39:59

Melting point: 63 'C.

Example 8

2.2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester IR cis S and IS cis R (la), and IR trans S and IS Preparation of trans R (Ib) Iab = 4: 6 isomer mixture.

As in the previous example, except that after starting the reactor line, crystalline cypermethrin containing cis: trans isomers of 99.5% purity was used, at which 11% of the semicarbazide hydrochloric acid salt and 0.1% were added to avoid side reactions. % BHT (2,6-di-tert-butyl 4-methylphenol) was added and the material was transported every 24 hours. The suspension at the end of the reactor line was neutralized with 2% aqueous hydrochloric acid. Extract with 500 ml (433 g) of xylene, wash with 50 ml of 2% aqueous phthalic acid solution and once with 100 ml of 1% maleic acid solution. Thus, a solution containing 535 g of Chinmix constituents containing the isomer pair la in 6.9% of the Ib isomer was 10.6%, the Ic isomer pair was 0.35% and the isomer pair ld was 0.28%.

Example 9

2.2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester IR cis S and IS cis R (la), and IR trans S and IS trans R (Ib) Ia.bb = 4: 6 isomer mixture.

The first example was carried out with the exception that the material discharged at the end of the reactor chain was neutralized with an aqueous solution containing 2% hydrochloric acid and 0.4% formaldehyde, and the mixture was heated to 60 ° C with 400 ml of petroleum ether (100 ml). extracted. The organic phase was washed with an aqueous solution containing 0.11% formaldehyde and 11% hydrochloric acid (100 ml) and the washings were repeated with 50 ml of water and 1% aqueous diethyl malonic acid solution in 11% hydrochloric acid and 0.11% formaldehyde. and the solution is slowly cooled down to crystallize. After filtration and plowing, 88 g of snow-white crystalline material are obtained.

Purity: 98%

Isomer ratio: Ia: Ib = 39.0: 59.5

Melting point: 65 ° C.

Example 10

2,2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (3-phenoxy-benzyl) -terl cis S and IS cis R (Ia) and IR trans S and IS trans R (Ib) Ia: bb = 4: 6 isomer mixture.

As in the ninth example, except that the washing with the last malonic acid solution was washed with 50 ml of water and the organic phase was separated. To the solution was added isopropanol (0.2 ml, 0.04 g), and crystallized slowly. Filtration and drying gave 87 g of white crystalline material. Purity: 98.5%

Isomer ratio: 39.0: 59.5

Melting point: 64-66'C.

Example 11

Investigation of Stability of Cypermethrin Ia: Ib = 4: 6 Isomer Mixture

1-1 g of the isomer pair la was 40% of the 99.9% pure crystalline cypermethrin isomer mixture containing 60% of Ib isomer each was dissolved in 2 ml of toluene and diluted with 8 ml of anhydrous ethyl alcohol. Samples were mixed with 10% v / v anhydrous ethyl alcohol and 10% triethylamine in anhydrous ethyl alcohol according to the table below, allowed to stand at room temperature and tested for isomeric composition after 1 week. Y = la + Ib, X = Ic + b

Tables: A. Ftalic acid

Amount of phthalic acid solution Amount of triethylamine solution, composition 0 ml 0.01 ml - 0.1 ml 1 ml X (%) Y (%) X (%) Y (%) X (%) Y (%) X (%) Y (%) 0 ml 0 99.9 50 49.9 47 45 40 43 0.01 ml 0 99.9 5 99.9 50 49.9 45 47 0.1 ml 0 99.9 0 99.9 10 89.9 47 49.9 1 ml 0 99.9 0 99.9 0 99.9 50 49.9 2 ml 0 99.9 0 99.9 0 99.9 5 94.9

B maleic acid

amount of maleic acid solution Amount of triethylamine solution, composition OML 0.01 mi 0.1 ml 1 ml X (%) Y (%) X (%) Y (%) X (%) Y (%) X (%) Y (%) 0 ml 0 99.9 50 49.9 47 45 40 43 0.01 mi 0 99.9 0 94.9 50 49.9 44 46 0.1 ml 0 99.9 0 99.9 0 99.9 49.1 49.0 1 ml 0 99.9 0 99.9 0 99.9 3 96.9

EN 210 098

amount of maleic acid solution Amount of triethylamine solution, composition | 2 ml 0 99.9 j 0 99.9 i 0 j 99.9 0 99.9 j

C. malonic acid

amount of malonic acid solution Amount of triethylamine solution, composition 0 ml 0.01 ml 0.1 ml 1 ml X (%) Y (%) X (%) Y (%) X (%) Y (%) X (%) Y (%) 0 ml 0 99.9 50 49.9 47 45 40 43 0.01 ml 0 99.9 0 94.9 50 49.9 44 46 0.1 ml 0 99.9 0 99.9 5 94.9 50 49.9 1 ml 0 99.9 0 99.9 0 99.9 0 99.9 2 ml 0 99.9 0 99.9 0 99.9 0 99.9

D. Fumaric Acid

amount of fumaric acid solution Amount of triethylamine solution, composition 0 ml 0.01 ml 0.1 ml 1 ml X (%) Y (%) X (%) Y (%) X (%) Y (%) X (%) Y (%) OML 0 99.9 50 49.9 47 45 40 43 0.01 ml 0 99.9 5 94.9 49.9 50 43 45 0.1 ml 0 99.9 0 99.9 5 94.9 49.9 50 1 ml 0 99.9 0 99.9 0 99.9 3 96.9 2 ml 0 99.9 0 99.9 0 99.9 0 99.9

E. oxalic acid

amount of oxalic acid solution Amount of triethylamine solution, composition 0 ml 0.01 ml 0.1 ml 1 ml X (%) Y (%) X (%) Y (%) X (%) Y (%) X (%) Y (%) OML 0 99.9 50 49.9 47 45 40 43 0.01 ml 0 99.9 3 96.9 50 49.9 47 48 0.1 ml 0 99.9 0 99.9 0 99.9 49 48 1 ml 0 99.9 0 99.9 0 99.9 2 97.9 2 ml 0 99.9 0 99.9 0 99.9 0 99.9

E p-toluenesulfonic acid

Amount of p-toluenesulfonic acid solution Amount of triethylamine solution, composition 0 ml 0.0 ml 0.1 mi 1 ml X (%) Y (%) X (%) Y (%) X (%) Y (%) X (%) Y (%) OML 0 99.9 50 49.9 47 45 40 43 0.01 ml 0 99.9 40 59.9 50 49.9 46 46 0.1 ml 0 99.9 5 94.9 3 96.9 45 48 1 ml 0 99.9 0 99.9 0 99.9 49.9 50 2 ml 0 99.9 0 99.9 0 99.9 2 99.9

Example 12 was diluted with zero and 10% v / v triethylamine solution

The results obtained in the procedures described in Example 10 were added. The solutions were allowed to stand at room temperature for 1 week at room temperature and then tested for 1-1 g of the isomer of Example 10, dissolved in 2 compositions.

in toluene, then the solution is 8 to 8 ml of anhydrous ethanol X = Ic + Id, Y = la + Ib

isomer Amount of triethylamine solution (ml) 0 0.01 0.02 0.05 0.1 0.2 X (%) 2 2 2 20 48 47 Y (%) 96 96 96 78 49.5 48

EN 210 098

Example 13

Preparation of the isomers of cypermethrin Ia: 1b = 4: 6 from the mixture containing all the stereoisomers 200 g of the reaction mixture from Reactor 7 obtained in the first example was passed into a bottom-cooled, heated, stirring apparatus and with constant stirring of 2% hydrochloric acid and 0%. Acidified to pH 2 with an aqueous solution containing 2% formaldehyde. After stirring for 15 minutes, the pH of the mixture was checked and then heated to 60 ° C, the crystalline suspension was melted into an emulsion. After stirring for 15 minutes, the oily cypermethrin was sedimented and separated. The warm material was taken up in 150 ml of isopropanol containing 1% maleic acid and slowly cooled after crystallization. The precipitated snow-white crystals were filtered and washed with 50 ml of ice-cold 1% maleic acid in isopropanol solution and dried. 56 g of snow-white crystalline material are obtained. 62.563 ° C

Purity: 97.0%.

Isomer ratio Ia: Ib = 38.5-58.5

Yield 88% of the yield.

Example 14

2,2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid α-cyano (m-phenoxybenzyl) ester η cis S and IS cis R (Ia) and IR trans S and continuous preparation of IS trans R (Ib) la.Ib = 4: 6 isomer from cypermethrin containing all the stereoisomers using 1, 0, 5J-diazabicyclononene base.

Seven series of 750 ml refrigerated mixer reactors each. The first reactor is cooled to 0 ° C, the second reactor is cooled to 8 'C, the other reactors are cooled individually at 14, 15, 10, 0 and -10' C. The reactors are charged with 100-100 g of crystalline 2,2-dimethyl-3-ylcarboxylic acid (R) cis S and IS cis R (la) as well as IR trans S and IS trans R (Ia: Ib = 40:60 and at least 95%). - (2 ', 2'-dichloro-vinyl) -cyclopropanecarboxylic acid a-cyano (m-phenoxybenzyl) ester (cypermethrin). In addition, 40 ml of isopropanol and [1,5,5] diazabicyclonone (hereinafter DBN) are added to the first and second reactors, followed by a further 40 into the fourth reactor, 80 to the fourth reactor, 120 to the sixth reactor, and 160 to the sixth reactor. 200 ml of isopropanol were added to the seventh reactor. The mixtures were thermostated with vigorous stirring and 100 g of total cis-cypermethrin containing 40% by weight of total cis and trans isomers were added to the first reactor and 40 ml of isopropanol were added. The mixtures were stirred continuously, and after 12 hours 0.1 g of DBN was added to the first reactor. Half of the mixture thus obtained is discharged into the next reactor, and the addition of cypermethrin and isopropanol to the first reactor is repeated. After 12 hours, the mixture of the first reactor is mixed with 0.1 g of DBN and half of the second reactor mixture is transferred to the third reactor. 100 g of cypermethrin and 40 ml of isopropanol are then re-weighed into the first reactor. After 12 hours of stirring, the first reactor is mixed with 0.1 g of DBN, the third reactor is diluted with 40 ml of isopropanol and reactor 3 is reacted into reactor 4 or reactor. 2nd to 3rd and

Half of the mixture is released from reactor 1 to reactor 2. By repeating the measurements of cypermethrin and isopropanol according to the 12-hour stirring and then, as the material progressed, the first reactor with 0.1 g of DBN after dilution of the third, fourth, fifth, sixth and seventh reactors with 40 ml of isopropanol, half of the reactors in the following. reactor or the material obtained at the end of the reactor chain is passed to a filter and the sequence is repeated for 12 hours at any time. The filtered material was washed with 0.5% (w / w) acetic acid in isopropanol and dried at room temperature. Occasionally, 86 g of snow-white crystalline material are obtained.

Purity 97% containing the isomer pair la in 39.5% is 57.5% of the Ib isomer pair. M.p .: 63.5 'C. Yield 86% of the substance added.

Example 15

As described in Example 1 of the application, except that 30 ml of isopropanol are added to the first reactor instead of 30 ml of triethylamine and 30 ml of isopropanol. The process is then carried out as described in the first example, with the triethylamine measurement always being carried out in the second reactor. Occasionally, 83 g of snow-white crystalline material were obtained at the end of the reactor chain. Purity 97% containing the isomer pair la, 39, and 58% of the isomer pair Ib. Mp 63-64 ° C. Yield: 83% by weight of the substance introduced.

Example 16

As described in Example 1 of the application, except that in the first reactor, only 40 ml of triethylamine was added to 30 ml of triethylamine and 30 ml of isopropanol. The process is carried out as described in the first example to give the product specified therein.

Example 17 (WP Formulation)

166.2 g of perlite (d _max = 120 gm), 0.8 g of silicic acid (AEROSIL 300) are mixed in a fluidization fast mixer. While stirring, 20 g of the enantiomeric mixture of Ia.Tb = 39:59 stabilized with maleic acid of Example 10 was added and a mixture of 2 g of fatty alcohol polyglycol was added to uniformly homogenize the mixture. The powder mixture was ground in a mechanical blast followed by an air blast followed by the addition of 5 g of octylphenyl polyglycol ether (EO = 20) and 2 g of sulfosuccinate in a rapid mixer. The resulting wettable powder mixture (WP) is subjected to a suspension stability test. Moisture time 23 sec, float 89% (standard WHO) method).

EXAMPLE 18 (EC Formulation) The cis-cermethrin enantiomer mixture Ia: Ib = 38.5: 58.5 prepared in Example 13 was dissolved in a mixture of 75 g of xylene and 10 g of aliphatic oil, followed by slow stirring with 7.5 g of ethoxylated alkylphenol + linear alkylarylsulfonate calcium salt and 2.5 g of ethoxylated

HU 210 098 Β fatty acid and linear alkyl arylsulfonate salt. The emulsion concentrate obtained is stable after 170 hours as measured by the CIPAC method.

Claims (13)

PATENT CLAIMS A continuous process for the preparation of isomeric mixtures of cypermethrin of formula (I) wherein the carbon atoms 1,3 and a represent a chiral carbon atom, and the wavy line represents a cis or trans position relative to the cyclopan ring, which is theoretically at least 95% of its 8 isomers. or containing only the isomeric pair of irisSIS and lScisR (Ia) or only the mixture of IRtransS and iStrisR (lb) or only a mixture thereof of Ia: Ib = 55: 45-25: 75, in the presence of a tertiary amine base and a protic solvent, preferably alkanol A second type of asymmetric transformation from 0 to 25 ° C of a mixture of starting cypermethrin isomers of purity of at least 90%, containing an undesired ratio of the cis and other trans isomers of the Ia pair of isomers or the Ia: Ib pair of isomers, characterized in that the. ) the reaction is carried out in a plurality of reactors, the reactor chain being cooled and heated to form a reactor chain in series, the adjacent elements being set within a temperature range of (+) 30 - (-) 25 ° C to a maximum of 10 ° C. the reactor elements are initially loaded with 1 part by weight of the desired final temperature crystal and optionally 0.001 to 0.4 parts by weight of protic solvent and / or 0.001 to 0.4 parts by weight of base, optionally in addition to the amount of material added to the previous reactor. 0.4 parts by weight of protic solvent is added, and the first reactor is charged with 1 part by weight of a crude isomeric mixture of formula (I) of at least 90% purity, optionally from 0.001 to 0.4 parts by weight of base and optionally from 0.001 to 0.4 parts by weight of protic solvent. the mixture is stirred, the reaction mixture or a portion thereof is second and then sequentially followed feed into a feeder reactor, wherein the protic solvent and base addition and mixing are optionally repeated several times while the crude cypermethrin, optionally 0.01-5% by weight decomposition and by-product binder, 0.001-0-0% is added continuously or intermittently to the first reactor. , 4 parts by weight of solvent and / or base as the reaction mixture passes through each of the reactors in series with the above treatment and at the end of the reactor chain the crystals are isolated from the reaction mixture, b. ) neutralizing the base optionally present in the reaction mixture leaving the last reactor and / or on the surface of the crystalline product with acid and / or recrystallizing the crystals from an acid-containing solvent and / or digesting the crystal slurry in the presence of aqueous acid at 60-70 ° C; c. ) is extracted with the crystalline organic solvent at 0-70 [deg.] C. and the resulting extract is washed, optionally, with water containing acidic salts or acid, and d. ) as a cyanogen scavenger, aldehyde is added during the processing step of the system. The process according to claim 1, wherein the feed and removal of the materials are performed continuously so that the reactor line is operated continuously. The process according to claim 1, wherein the feeding and withdrawing of the materials is done in batches so that the reactor line is operated continuously. Process according to claim 1, characterized in that the base is a secondary and / or tertiary amine base containing one or more nitrogen atoms containing from 2 to 12 carbon atoms, preferably triethylamine. Process according to claim 1 or 2, characterized in that the protic solvent is a C2-C4 primary or secondary alcohol or a mixture thereof, preferably propanol. 6. A process according to claim 1, characterized in that the solvent for removing impurities in the filtered material is petroleum ether, hexane, heptane, ethanol, isopropanol and their acids, preferably acetic acid, phthalic acid, maleic acid, fumaric acid or malonic acid or alkylated malonic acid. mixtures thereof. 7. A process according to claim 1, characterized in that the reaction mixture is optionally containing from 0.1 to 5% by weight of aqueous acid, optionally containing hydrochloric acid, formic acid, phthalic acid, malonic acid or alkylated malonic acid or maleic acid. It is neutralized. 8. A process according to claim 1, wherein the extraction solvent is a water immiscible organic solvent, preferably hexane, cyclohexane, heptane, petroleum ether, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate. acetate, benzene, toluene or xylene. 9. A process according to claim 1, characterized in that the extract of the product is water, water saturated with common salt and / or an aqueous mineral or organic acid with a concentration of 0.1 to 5% by weight, optionally containing hydrochloric acid, acetic acid, phthalic acid, malonic acid, alkylated malonic acid, fumaric acid or maleic acid or p-toluenesulfonic acid. 10. An element of process d) according to claim 1, characterized in that aldehyde, preferably formaldehyde, is used as the cyanogen scavenger. 11. A process according to claim 1, characterized in that the product is crystallized with an apolar, aprotic and / or protic solvent, preferably hexane, heptane, petroleum ether, methanol, ethanol, isopropanol, or with acids, preferably acetic acid, maleic acid. , fumaric or malonic or alkylated malonic or p-toluenesulfonic acid. 12. The stabilized insecticidal composition containing the crystalline isomeric mixture obtained according to claim 1, wherein the stabilizer is preferably 0.001 to 0.1% by weight of an acid or a mixture of acids. The carboxylic acids of the non-volatile pK] = 1-5 include phthalic, succinic, tartaric, maleic, fumaric, malonic, oxalic or p-toluenesulfonic acids. 13. A stabilized insecticidal active compound concentrate containing the isomeric mixture obtained according to claim 1, wherein the stabilizer is preferably 0.001-0.1% by weight of acid or mixture of acids, preferably non-volatile carboxylic acids having a pK1 = 1-5 strength. Contains phthalic, amber, tartaric, maleic, furan, oxalmalon or p-toluenesulfonic acids.