CS270009B1 - The method of dividing the geometrical and transient levels of 2/2-diaethyl-3- [2, 2-indalhalinyl / cyclopropanecarboxylic acid kyaalines - Google Patents

Abstract

A method for preparing staroleoaarnic 2;2-dimethyl-3-/2;2-dihalovyl/cyclopropanecarboxylic acids of the general formula I, where X represents halogen/ and starting in the toa/ and acting on this aaes at a temperature of -50 to *100 °C with an aromatic compound of the general formula II/ where Y represents a group -CH-CH-/ -O-j —S— or -NH- and A represents hydrogen/ methyl or a halogen atom/ optionally in an inert solvent/ until a crystalline addition compound of the general formula XXX is precipitated /lRcia-I/ . /lScie-I/ . /11// (III) containing an aromatic compound of the general formula II/ where Y and A are as defined above/ cla-ethereoisoaers of the acid of the general formula 1/ where X is as defined above, the absolute configuration of 1Rols(1Roia-I) and 1Scla(ISoia-I) in an equimolar ratio/ while the remaining ethereoisoaers of the acid of the general formula 1/ where X is as defined above/ remain dissolved in the reaction mixture and chemically unchanged. Esters of the acid of the general formula 1/ where X is as defined above in the cla configuration are more effective insecticides than the corresponding esters of the acids of the general formula 1/ where X has the above definition in the trans configuration.

Description

The invention relates to the method of further! geometric cle- and trans- isomers of dihalovinylcyclopropanecarboxylic acids of general formula 1, wherein X represents a halogen atom.

It is known that certain cysteine esters of formula 1; who X has the meaning given above are effective insecticides, the acid-containing esters of the formula I in the cle configuration being generally more effective! than matching! kyeolin ethers of formula I in the trans configuration. Some methods are also known which allow the resolution of the cis and tranMeomers of an acid of formula X; which the train is not entirely satisfactory from a technical point of view.

A known separation process is the traction cryetalizaco cie-trane etoreoieomorni mixtures of an acid of the general formula I. From the published data (see e.g. Coll. Czech. Chon. Cornaun. 24, 2230, 19591 OE 1 570 557 / y, it is clear that this process is difficult and unprofitable. Another known process is the traction precipitation from solutions of the salts of the ethoformomers of the acid of the formula I, which X has the meaning given above (e.g. EP 0003060, EP 00110875 /, whereby only a partial separation of cis- and tran-etorooisomers occurs. 30 also shows the traction distillation of cis- and tran-etheromers of the acidic acid of the general formula X / see EE 199 725, Co. U.S. Pat. No. 199,725, in which only the partial separation of ether isomers also occurs. According to published data, both traction overflow and doetilac require additional cleaning,;

e.g., fractional crystallization.

The disadvantages of the prior art are that the mixture of geometric cis- and tran-isomers of an acid of formula Xf wherein X is halogen, is treated at -50 to * 100 ° C with an aromatic compound of formula XX, wherein Y is -CH »CH-, oxygen, * sulfur or -NH-group o A represents hydrogen; methyl or halogen, optionally in an inert solvent, the cryetallic addition compound of formula XXI * (IRcie-I) precipitating from the fractional emulsion. / IScis-I /. (11) (1X1), containing an aromatic compound of formula XX, wherein A and Y are as defined above, and the cisol isoisomers of kyeolin of formula i; who X my meaning given; the aboolute configuration of IRcie (1Rcle-X) and the absolute configuration of Scie (1Scie-I) in the okiaolar ratio, while the remaining kyeolin isomers of formula I, which X is as defined above, remain dissolved in the reaction mixture and chemically unchanged. Addition compound of formula XIi; where X, * A and Y in the general formulas X o XX have the meanings given above, are separated from the fractional emol by decantation, filtration or centrifugation. It can be decomposed into the racemic glycerol of the formula I, which X is as defined above, and the aromatic compound of the formula II, which Y and A are as defined above, by the action of heat in the temperature range 25 to 100 ° C, optionally under reduced pressure. up to 150 Pa. X is a separation of the cis- and tran-aethereoic acids of the general formula I, in which X is as defined above, ee thus using crystalline editing compounds which are selectively formed from the cie-; not the age in the trane-etorooisomers of the kyeolin of formula I, which X is as defined above, the use of aromatic aromatic compounds of formula II; who A and Y have the meanings given above. In order to form a cryetal adduct, it is necessary for the presence of the two optical antipodes of the cis-kyeolin of the general formula X; who X has the meaning given above, because his survival always corresponds to the general formula III, where X; A and Y in formulas I and II are as defined above. Crystalline adducts with a different etorooisomeric yield of the acid component I, which X is as defined above, are not formed by the action of an aromatic ducin of formula II, which A and Y are as defined above.

This circumstance can be advantageously used to separate the racemic form of the cis-kyeolin of the general formula If X is as defined above from the ced- and trans-ether groups of the acid of the formula I, X having the meaning given above. In the process of the invention, the storeoisomers IRcle-I and ISole-X are precipitated in the form of a crystalline addition compound of formula IXX, wherein X, A and Y in formulas X and XX are as defined above, in which they are present in an equimolar ratio. The duconin addition can be separated from the remaining kyeolin ethers of the general formula Xf which X has the meaning given above by methods known per se, for example by filtration or centrifugation.

CS 270 009 81

The essence of the invention and the methods of its use are further elucidated in the following examples, which in no way limit the scope of the invention in any way.

Example 1

Separation of cis- and tran-storeoisomeric permethrinic acid (1} X-Cl) using a thiophene editing compound (11 »Y« -S-); A «H /

9.93 g of racemic permethrin acid containing 82% of the cis- and 18% of the trans-isomer was dissolved hot in 30 ml of thiophene and then the reaction mixture was cooled with ice. The precipitated crystals were filtered off with suction, washed with chilled thiophene and dried. 9.59 g of the adduct of the general formula III were obtained, which corresponds to 98% of the cis-isomer in the starting mixture. Thermal decomposition (100 ° C) in vacuo gave 7.98 g of cis-permsthrin acid, containing more than 2% of trans-isomer.

Example 2

Separation of the cis- and trans-athereoisomerO of permathrin acid (1 »Χ · 01) by means of an adduct with furan / II» Y-O-; A-H /

2.98 g of racemic permethrinic acid containing 90% of cis- and 10% of trans-acid were dissolved in 4 ml of ether, the solution was cooled in January and 1.1 ml of furan were added. After 1/2 hour, the crystalline product was filtered off with suction and washed with cooled ether-furan (2 L). 1.07 g of adduct of the general formula (IIIi) were obtained, corresponding to 34% of the cis-isomer in the starting mixture. According to gas chromatography, the crystalline adduct contains only traces of trans acid.

Example 3

Separation of cis- and trans-permothrinic acid (Ij X-Cl) by adduct e 2-methylfuran

4.3 g of racemic cie- and trans-permethrinic acid (Θ2 t 18) were dissolved in 8.5 ml of 2-methylfuran and cooled with ice. 2.46 g of a crystalline adduct of the general formula III, ¹ corresponding to 68% of the cis-isomer in the starting athereoisomeric mixture, were obtained. According to gas chromatography, the adduct contains less than 2% trans-acid.

Example 4

Separation of cis- and trans-permothrinic acid / 1 ». X-Cl / with the help of an adduct with benzene

A, 10.4 g of racemic permethrinic acid containing 72% cis- and 28% trans-fluorine (NMR) was dissolved hot in benzene (41.5 ml). After spontaneous cooling to room temperature, the mixture was cooled with ice. 8.40 g of adduct of general formula III were obtained; which corresponds to 94.5% of the cie-isomer present in the starting mixture. B. 10-88 g of permethrin acid containing 30% of the trans-isomer were treated in a similar manner. In the presence of 43.5 ml of benzene, 6.7 g (96% of theory) of a crystalline adduct of the formula III are obtained, containing, according to NMR, traces of the trans-isomer.

Claims (2)

BACKGROUND OF THE INVENTION A process for the separation of mixtures of geometric targets and the trans isomer of 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acids of the general formula I, in which X represents a halogen atom, characterized in that the trans-stereoisomer A of an acid of formula I wherein X is halogen; ee pAsobi at a temperature of -50 to * 100 ° C with an aromatic compound of general formula II; wherein Y is -CH-CH-; -0-. -S- or -NH- and A is hydrogen, methyl or halogen, optionally in an inert solvent, to precipitate a crystalline addition compound of formula III (IRcie-I). / IScia-I /. / 11 / / 111 / CS 270 009 B1 composed of 1 equivalent of an aromatic compound of formula II; wherein Y and A are as defined above; 1 equivalent of the acid sterooleaer of the acid of formula i; who X has the meaning given above; in the absolute configuration IRcie (1Rcle-I) and 1 equivalent of cie-storooiaoaoru cyeelines of formula i; wherein X is as defined above; in the absolute configuration IScio (IScia-I), while the remaining stereoisomers of the acid of formula I; who X and E are as defined above, remain dissolved in the reaction mixture chemically unchanged by a crystalline addition compound of formula III, wherein X 1, Y and A in formulas I and II are as defined above; ee separates the keelins of the formula I from the tranetethooroolymers in the annual mixture by documentation; filtration or centrifugation. 2, The method of item 1; characterized by that; a crystalline editing compound of formula IIIJ which X; Y and A in the general formulas I and II have the meanings given above, they decompose into the aromatic cis-kyeolin of the eyebrow formula i; who X has the meaning given above; and an aromatic compound of formula II; who Y and A have the meanings given above, by the action of heat, optionally under reduced printing to 1150 Po; in the temperature range 25 to 100 ° C,