PL126741B1 - Method for producing (s)-2-(4-chlorophenyl)-isovalerate(s) of alpha-cyano-3-phenoxybenzyl - Google Patents

Description

The present invention relates to a process for the preparation of (S) -2- (4-hloTOiphenyl) is -phenoxybenzyl by isomerization of α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenylMzovalerate on an asymmetric carbon atom of the 3-phenoxybenzyl radical) and the isolation of (S) -2- (4-chlorophenyl) isovalerate (S) -a-cyano-3-phenoxybenzyl from (S) -2- (4-chlorophenyl) isovalerate (R, S) -a-cyano- 3-phenoxybenzyl. Α-cyano-3-phenoxybenzyl 2- (4-chlorophenyl) isovalerate, a compound of Formula I, showing low toxicity to mammals and a broad spectrum of insecticidal activity [as described in a published Japanese application (Patent (OPI) No. 26425/74 or in U.S. Patent No. 3,996,244] has two asymmetric carbon atoms in the molecule and exists in the form of four optical isomers. In the following description, 2- (4-chlorophenyl) ) .alpha.-cyano-3-phenoxybenzyl isovalerate of the formula (I) will be called "phenvalerate", (S) -2- (4-chlorophenyl) isovalerate (R, S) -a-cyano-3-phenox y-benzyl "phenvalerate A", <E) -2- (4-chlorophenyl) isovalerate (S) -a-cyano-3-phenoxybenzyl phenvalerate Aa ", (S) -2- (4-chlorophenyl) iso- (R) -a-cyano-3-phenoxybenzyl valerate "fenvalerate A0, (R) -2- (4-chlorophenic)) (S) -a-cyano-3-phenoxybenzyl isovalerate" fenvalerate | iem Bo " and (R) -2- (4-chlorolenyl) isovalerate (R) -a-cyano-3-phenoxybenzyl "BP * fenvalerate". 10 The ratio of the absolute configuration of the asymmetric carbon atom in the acid radical to the insecticidal activity of the ester has been explained, and the preparation of (S) -2- (4-chlorophenyl) isovalric acid, from which the ester with higher insecticidal activity is obtained, is known. [Miyakado et al., Agr. Bio. Chem., 39, 267 (1975)]. Miyakado et al., In the above-cited reference, describe a method of resolving the optical isomers of α-isopropylphenylacetic acid and the insecticidal activity of phenylacetic acid esters with an optically active acid radical. The ratio of the absolute configuration of the asymmetric carbon atom in the alcohol radical to the insecticidal activity is described in Published Japanese Patent Application No. 135013/76, which also describes the preparation of esters with an optically active alcohol radical. Published Japanese Patent Application No. 99071/76 (corresponding to U.S. Patent No. 825507, filed on August 17, 1977) describes the preparation of an isomer of phenvalerate with an optically active alcohol radical by chromatography of the phenvalerate. A on a silica gel column, giving separation of A phenvalerate into Aa fenvalerate and A0 fenvalerate. In the manner described in the aforementioned Japanese Patent Application No. 135013/76, 3-phenoximandelic acid obtained by separating the optical isomers of 3-phenoxy mandelic acid is passed through the optically active 25s 126 741 4. These methods give good results on a laboratory scale, but are not suitable for use on an industrial scale. Aa phenvalerate is an excellent compound, having an insecticidal activity about four times the insecticidal activity of racemic phenvalerate (e.g. as described in the Jailer application). U.S. Patent No. 99071/76, corresponding to U.S. Patent Serial No. 825,507, filed on August 17, 1977). Method of producing (S) -2- (chlorophenyl) isovalerate (S) -a-cyano-3-phenoxybenzyl according to the invention consists in that (S) -2- (4-chlorophenyl) isovalerate (S) -a-cyano-3-phenoxybenzyl is crystallized from the solution of (S) -2- (R, S) -a-cyano-3-phenoxybenzyl (4-chloropheryl) isovalerate, in a solvent, in the presence of a basic substance as a catalyst, adding a seed of (S) -2- (4-chlorophenyl) isovalerate (S) crystals -a-cyano-3-phenoxybenzyl. A lower alcohol such as methanol, ethanol or mixed alcohol is used as a solvent. Znane solvents containing methanol or ethanol; aliphatic, cycloaliphatic or a mixture of aromatic and aliphatic hydrocarbons, or a mixture of cycloaliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and methylcyclohexane or a mixture of pentane, hexane or nemane , toluene or xylene, or 1,5-diazabicyclo [4.3.0] -nonene-5. Methanol is the most preferred solvent. The basic catalyst is used from a wide range of basic substances such as nitrogen bases, phosphorus bases, strong bases and basic ion exchange resins. Specific examples of suitable basic substances are ammonia, aliphatic amines such as methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, diethylamine, di-n-propylamine, di-n-butylamine, triethylamine, triethylamine, propylamine, tri-n-butylamine and ethanottoamine, aromatic amines, such as aniline, 1-naphthylamine and 2-naphthylamine, quaternary ammonium salts, such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetra-n-propylammonium hydroxide, heterocyclic compounds such as pyridine, quinoline, pyrrolidine and piperidine, phosphorus bases such as triphenylphophthyl and tri-n-butycrophtha, strong bases such as alkali metal and alkaline earth metal hydroxides (e.g. sodium hydroxide or potassium hydroxide), alcoholates alkali metals or alkaline earth metals (e.g. sodium methylate or sodium ethylate), alkali metal or alkaline earth metal amides (e.g. sodium amide or magnesium amide), metal hydrides calories or alkaline earth metals (e.g. sodium hydride, potassium hydride or lithium aluminum hydride) and basic ion exchange resins. Suitable commercially available base-type ion-exchange resins are fJX) WEX 2x8 * '[product trade name of Dow Chemical Company, a strongly basic ion exchange resin of a styrene-divinylbenzene copolymer with quaternary ammonium groups (-NRj + + CH)], 5 "AMBERLITE 1H-45 (trade name of the product of Rohm & Haas Company, a weak base ionitic resin in which the interchangeable groups are the groups _N (R) f? -NH [trade name of the product Rohm & Haas Combo pany, a weakly basic ion exchange resin (MR type) in which the groups exchangeable are -N (CH,) t], "AMBERLIST A-21" [Rohm & Haas Company trade name, a weak base ion exchange resin (MR type), whose interchangeable groups are groups —N (CH *) S, useful in aqueous solutions] and "AMBERLIST A-27" [trade name for the product of Rohm & Haas Company, # strongly basic ion exchange resin (OH type) , in which the exchangeable groups are groups of formula 2, useful in non-aqueous solutions]. From the point of view of ease of removal of the catalyst and after the isomerization reaction, substances substantially insoluble in the above-described solvents are preferred, in particular ion exchange resins of the basic type. It should be understood that the basic catalysts are not limited to the materials listed above and other substances may also be used without departing from the spirit and scope of the invention. The addition of a seed of the crystal is not necessary, but in commercial operation it is desirable for the crystallization to proceed smoothly. The use of a seed in a continuous industrial operation on an industrial scale is not necessary because the crystals remain in the reactor. In studies of the process of producing an isomer of fenvalerate having an optically active alcohol radical, it was found that the addition of a seed crystals of Aa phenvalerate, Bp fenvalerate or a mixture thereof into a solution of phenvalerate A selectively causes only Aa phenvalerate to crystallize. As in the case of pyrethral type esters, the crystallization of the above compound is not influenced at all by the properties of racemic phenvalerate, which is an oil with high viscosity, Fenvalerate Aa: mp 57, »° C, [a] g - = 11.2 ° (in CHClf, c = 6.5) Fenvalerate B (3: melting point 59. * ° C, [a] * - + 12.5 ° (in CHCl * c «3.8) For example, 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid a-cyano-3-pheiioxybenzyl ester, in which is an ester of the pyrotroid type derived from With an alcoholic compound as in the above compound, the d-trans (IR, 3S) isomer of the acid radical and the (S), (B) or racemic alcohol radical does not crystallize. However, a 1: 1 mixture (by weight) of the ester of the d-trans configuration of the acid radical and the (R) configuration of the alcohol radical with the ester of the 1-trans (1S, 3R) configuration, the acid radical and the (S) configuration of the alcohol radical (mp 75.0-76.8 ° C) and a 1: 1 mixture (by weight) of an eether of the d-trans configuration of the acid radical and the (S) configuration of the alcohol radical with the ester of the 1-trans configuration of the acid radical and the configuration ( R) of the alcohol radical (mp 78.5-80 ° C) was obtained in a crystalline form. It has also been found that in the case of α-ethynyl-3-phenoxybenzyl 1- (4-chlorophenyl) isovalerate, which is a pyrethroid ester with a structure very similar to that of the compound in question, a mixture of esters with a racemic acid radical and a racemic alcohol radical (mp 46-47 ° C), a mixture of two of their diastereoisomers (each of them racemic) and an ester with an optically active acid radical are crystalline at room temperature. During recrystallization of the mixture of esters with the racemic acid radical and the racemic alcohol radical from hexane, mainly the diastereoisomer having a melting point of 87-88 ° C. and a very low insecticidal activity crystallizes. The ester recovered from non-opaque 4ugu is a diastereoisomer (mp 51-52 ° C) having a higher insecticidal activity. However, in the case of the above treatment of the ester with an optically active acid radical (mp 61-4J2 ° C) no selective crystallization of the diastereoisomer is observed In the case of allethrin (alletronyl chrysanthemate), a long known synthetic ester of the pyrethroid type, present in the form of four diastereoisomers, only "crystalline buttrin", a diastereoisomer composed of an ester with a d-trans acid radical and an alcohol radical. 1 and the ether of the 1-trans acid radical and the alcohol radical of the d-configuration are known in crystalline form [e.g., M. Matsui and I Yamamoto, Nature! Occuring Insecticides, M. Jacobson & DGGrosby Eds., P. 3fc —42, Marcel Dekker, Inc., New York (1971)]. The ethereal crystalline forms of "crystalline allethrin" do not crystallize. The above facts indicate that it is not possible to predict which isomers optical isomers or their mixtures will be obtained as crystals, and it cannot be predicted whether this optical isomer can be selectively crystallized from its mixture with other optical isomers. The effective use of the mother liquor obtained as a by-product in the preparation of fenvalerate from an optically active alcohol radical, and it has been found that when dissolving an optically active alcohol-containing phenvalerate in a non-equilibrium (R) (S) in a protic solvent or solvent mixture containing a protic solvent, and preferably adding or dissolving a basic catalyst, in the solvent and the subsequent addition of the basic catalyst, the asymmetric carbon atom of the alcohol radical is rapidly isomerized. As a rule, it was assumed that the mandelonitrile ester as described above is unstable in a protic solvent or in the presence of a basic catalyst and that the bond cleavage occurs ester or nitrile decomposition. However, it has now been found that mainly isomerization takes place in the above-described ester. The isomerization of an optically active aliphatic nitrile in the presence of a basic catalyst has already been reported [e.g. in J. Am. Chem Soc. 86, p. 5457 (1964)]. However, the ester isomerization as described above in solution has not been described so far. It has also been found that by adding a basic catalyst to the Aa phenvalerate solution, crystallization of Aa phenvalerate and isomerization of Aa phenvalerate and Aa phenvalerate can be carried out simultaneously. obtained in high yield. When the base used as catalyst releases the optically active fenvalerate, a solvent is not always necessary. The use of aromatic hydrocarbons alone and a-cetonitrile alone in the process according to the invention does not give good results, since they dissolve Aa fenvalerate to a very large extent. Methanol and ethanol are the preferred lower alcohols with methanol being most preferred. If methanol is used, its water content should preferably be limited to less than $ • / *. Favorable results are not obtained with isopropanol or hydrated isopropanol. The appropriate concentration of A-phenvalerate in the solution is from about 1 to about 90 * / t The preferred concentration is 20 to 7 in terms of the yield of crystals obtained and the rate of crystallization. In the process according to the invention, the catalyst can be added to the solution containing the M-isomerized phenvalerate A, or the solution containing phenvalerate A can be passed through a column filled with the catalyst. The suitable isomerization temperature is that at which the ester does not degrade significantly. The rate of isomerization is faster at higher temperatures. Preferably, the isomerization is carried out at a temperature from about -50 ° C to the boiling point of the solvent, and in particular from -20 to +150 ° C. The optically active fenvalerate may have any value in the (S) / (R) ratio of the radical Of the above bases, ammonia and amine are preferred from the standpoint of crystal yield and the like, ammonia and triethylamine are most preferred. A suitable amount of catalyst is about 0.01 to about 100, preferably 0.7 to 50 * / molar t with respect to phenvalerate A. A suitable isomerization temperature is about -50 to about + 50 ° C, in terms of crystal yield and crystallization rate. The preferred isomerization temperature is -30 to + 15 ° C. It is desirable, but not necessary, to mix the solution during iso-o .. merization. The invention is illustrated by the following non-limiting examples. Unless otherwise stated, all parts, percentages and ratios are by weight. 126 741 In the following examples, the (R) isomer of an alcohol radical (A0 fenvalerate) and the (S) isomer of this radical (Aa phenvalerate) were analyzed for the following methods. gas chromatography under the following conditions: kclum: 1G% silicone DC - QF-1 3 mm 0 = 3.0 mm (carrier Chromosorb A -DMCS) column temperatures: 245 ° C evaporator temperature: 250 ° C nitrogen pressure: 1.96 10 * kPa Under the above conditions, the retention time of the (S) isomer, i.e. Aa phenvalerate, is about 43 minutes, and the retention time of the (R) isomer, i.e., Ap phenvalerate, is about 38 minutes. retention time, i.e. that the retention time of the ester with the alcohol radical of the (S) configuration, i.e. Ba phenvalerate, is the same as that of A0 fenvalerate, and the retention time of the ester of the (R) configuration of the alcohol radical, i.e. Bp fenvalerate, the same as Aa fenvalerate. So when present in used m fenvalerate A of the ester of the (R) configuration of the acid radical overlap each other and their surfaces are approximately proportional to the quantitative fraction. The optical purity of the acid radical of phenvalerate A was determined as follows: the phenvalerate A was hydrogenated in ethanol using platinum oxide as a catalyst, and the (S) -2- (4-chlorophenyl) isovaleric acid obtained is converted into the acid chloride with thionyl chloride. The acid chloride was converted into the 1-menthol ester with the aid of 1-menthol. Gas chromatography determines the quantitative ratio of the two diastereoisomers, and the result is the optical purity of the acid radical. Example 1 The starting material is fenvalerate A, which according to gas chromatography contains 50.5% of the (R) isomer and 49 5% of the (S) isomer of the alcohol radical and the optical purity of the acid radical of 92.8% (unless otherwise stated, the same starting material is used in the other examples). 5.0 g of the starting material is dissolved in 5.0 g of ethyl alcohol and 1 mg of (S) -2- (4-chlorophenyl) isovalerate (S) -a-cyano-3-phenoxybenzyl crystals are added as seed. The mixture is kept for 4 days at -6 ° C, then the precipitated crystals are filtered off. Sediment on the hopper three. rinsed times with 2 ml of cold ethanol (0-5 ° C). The yield of the crystals (mp 57.9 ° C.) is 1.27 g. Gas chromatography analysis shows that the crystals of the (R) isomer and the (S) isomer contain 4% and 96% of the alcohol radical respectively. The corresponding values for the ester remaining in the feed are 65.5% and 34.5%. Example n. The procedure is as for pesticide I, except that 5.5 g of mixture 1 is used instead of ethyl alcohol: 5 (by weight) of benzene with n-hexane. The yield of the crystals is 0.62 g. The analysis of the crystals shows the content of the (R) isomer of the alcohol radical as 2.7% and 97.3% of the (S) isomer. Example III. The procedure is as in Example I, except that 6 g of methyl alcohol are used instead of ethyl alcohol. The yield of the crystals is 1.78 g. The analysis of the crystals shows the content of the (R) and (S) isomers of the alcohol radical, respectively 4.5% and 95.5%. Example IV. 5.18 g of Aa fenvalerate are dissolved in 5.2 g of methanol and 1 mg of Aa fenvalerate is added to the solution as seed. 10 The whole is stirred over the day at 2 to 4 ° C, then drained off the precipitated crystals. The filter cake is washed with two 3 ml portions of cold hexane (0-5 ° C). The yield of the crystals is 1.48%. (28.6 wt.% Based on the starting phenvalerate A). The analysis of the crystals shows the content of the alcohol radical (R) and (S) isomers of 3.4% and 96.6%, respectively. The corresponding values for the fenvalerate A recovered from the feed are 68.5% and 31.5%. EXAMPLE 5 0.35 g of a basic ion exchange resin (DOWEX 2 × 8) is added to the flow obtained in Example 1 as a catalyst. The shanine is kept at 70 ° C within 6 hours. The solution is then cooled to room temperature and a sample is analyzed by gas chromatography. The (R) and (S) isomers of the alcohol ester radical are found to be 51.8% and 48.2%, respectively. The catalyst is filtered off under reduced pressure to a total weight of the solution of 7.5 g. 1 mg of Aa phenvalerate crystals are added to the concentrate as seed and allowed to stir for 3 days at -5 ° C. The precipitated crystals are then drained off. The sediment deposited on the filter is washed three times with 0.5 g of cold ethyl alcohol (0-5 ° C). The crystal yield is 0.46 g. Gas chromatography shows the participation of the (R) and (S) isomers of the alcohol ester radical, respectively 3 , 9% and 96.1%. 40 Example VI. An ethanolic ester solution of the composition described in Example V (concentration 10%, total amount of solution 30 g) is passed through a glass column filled with 100 ml of basic ion exchange resin (AMBERLITE IR-45), acting as catalyst, in ethanol. . The passage of the solution takes 5 hours. The column is then eluted with 30 g of fresh ethyl alcohol for 3 hours. The spills are pooled and a sample of the combined spills is analyzed by gas chromatography. The combined effluents contain the (R) and (S) isomer of the alcohol ester radical at 55.3% and 44.7% respectively. The effluents are concentrated under reduced pressure to a total solution weight of 10 g. To concentrate 55 is added 4.2 g of fresh phenvalerate A, and then the mixture is heated to dissolve the phenvalerate A. The resulting solution is cooled to room temperature and 10 mg of Aa phenvalerate crystals are added as seed. The mixture is left standing at -6 ° C for 2 days. The lost crystals drain off. The precipitate deposited on the filter paper is washed twice with 1.0 g of cold ethanol (0-5 ° C). The yield of the crystals is 1.02 g, and the proportion of the (R) and (S) isomers of the C5 alcohol radical of the ester is 3.9% and 96.1%, respectively. 126 741 Example VII. 5.0 g of Aa phenvalerate are dissolved in 5.5 g of a 1: 5 (by weight) mixture of benzene and n-hexane and 1 mg of Aa phenvalerate crystals are added as stsiew. The mixture is left to sprinkle for 4 days at -6 ° C. The lost crystals drain off. The sediment deposited on the filter is washed three times with 2 ml of cold n-hexane. The crystal yield is 0.62 g. The analysis shows the participation of the (R) and (S) isomers of the alcohol ester radical 2, W # and 07% / t, respectively. 0.35 g of a strongly basic ion exchange resin (AMBERLIST A-27, OH type) is added to the feed as a catalyst and the mixture is kept for 6 hours at 60 ° C. The solution is then cooled to room temperature, and a sample of it is analyzed by gas chromatography. The proportion of the (R) and (S) isomers of the alcohol ester radical is 52.8% and 47.2% respectively. The catalyst is filtered off and the solvent is evaporated off under reduced pressure, bringing the solution to a total weight of 10 g. 1 mg of Aa phenvalerate is added to the concentrate as seed, and the mixture is left to stand at -5 ° for 3 days. C. The lost crystals drain off. The precipitate deposited on the filter is washed three times with 0.5 g of cold hexane (0-5 ° C.). The yield of • crystals is 0.28 g. The analysis shows the participation of the (R) and (S) isomers of the alcohol ester radical 3.9 * / f and 96.1 * / t, respectively. Example VIII. An ester solution with the composition as the first filter in Example VII in a mixture of benzene and n-hexane (concentration 1 (M, total solution 30 g) is passed through a glass column filled with 100 ml of strongly basic ion exchanger (AMBERLIST A -27, OH type), which acts as a catalyst, in benzene. The flow of the solution takes 5 hours. The column is eluted with 90 g of fresh benzene in 3 hours. The leaks are combined and a sample of the combined effluents is analyzed by chromatography. It shows the contribution of the (R) and (S) isomers of the alcoholic ester, respectively 53.3% and 46.7%, respectively. From the combined effluents, the solvent is distilled off under reduced pressure, and the residue is added to 3.5 g of a 1: 5 (by weight) mixture of benzene with 'n-hexane. The mixture is kept at 40 ° C until the residue is dissolved in the benzene-n-hexane mixture. The resulting solution is cooled to room temperature and seed is added to the mixture. 10 mg of crystals of Aa phenvalerate. The mixture leaves a s For 4 days at -6 ° C, then filter the precipitated crystals. The precipitate deposited on the filter paper is washed twice with 1.0 g of cold hexane (0-5 ° C.). The yield of the crystals is 0.35 g. The analysis of the crystals shows the presence of the (R) and (S) isomers of the alcohol ester radical in amounts of 3% and 96.1% respectively. Example IX. 5.82 g of Aa fenvalerate is dissolved in 11.6 g of methanol and 1 mg of Aa fenvalerate crystals are added as seed. Further, 120 mg of triethylamine are added as a catalyst and the whole is cut for 2 days at 2 to 4 ° C. The precipitated crystals are filtered off. The precipitate deposited on the filter is washed twice with 5 ml of cold hexane (0-5 ° C.). The yield of the crystals is 4.61 g (79.3 Vt by weight with respect to the phenvalerate A used). The analysis of the crystals shows the participation of the (R) and (S) isomers of the alcohol ester radical 1.4Vt and 98.6V§, respectively. For the fenvalerate A recovered from the slurry the corresponding values are 51.0 Cf /% and 49.0% / r. Example X.6.78 g of fenvalerate A are dissolved in 6.8 g of methanol and the seed is added to 1 mg of Aa fenvalerate crystals. 68 mg of triethylamine are then added as a catalyst and the mixture is stirred for 24 hours at 2 to 4 ° C. The lost crystals drain off. The precipitate deposited on the filter is washed twice with 5 ml of cold hexane (0-5 ° C.). The yield in the crystals is 5.91 g (87.2% by weight, based on the phenvalerate A used). The analysis of the crystals shows the participation of the (R) and (S) isomers of the alcohol ester radical 2.0% and 98.0% respectively. Example XI. 7.22 g of Aa fenvalerate is dissolved in 7.2 g of methanol and 1 mg of Aa fenvalerate crystals are added as seed. Then 43 mg of n-propylamine are added as a catalyst and the whole is stirred at 2 to 4 ° C overnight. The lost crystals are filtered off and the precipitate deposited on the filter is washed twice with 5 ml of cold hexane (0-5 ° C). The yield of the crystals is 5.57 g (77% by weight with respect to the phenvalerate A used). The analysis of the crystals shows the participation of the (R) and (S) isomers of the alcoholic ester radical 4.4e / t and 95.6% / t, respectively. Example XII. 6.49 g of Aa fenvalerate is dissolved in 6.5 g of methanol and 1 mg of Aa fenvalerate crystals are added as seed. Then 47 mg of diethylamine is added as a catalyst and the mixture is stirred for 24 hours at 2 to 4 ° C. The precipitated crystals are filtered off, and the precipitate deposited on the filter is washed twice with 5 ml of cold hexane (0-5 ° C). The yield of the crystals is 4.84 g (74.6% / t by weight with respect to the phenvalerate A used). The analysis of the crystals shows the participation of the (R) and (S) isomers of the alcohol ester radical, respectively 2.3% and 97.7%. Example XIII. 7.36 g of Aa fenvalerate are dissolved in 7.4 g of ethanol and 1 mg of Aa fenvalerate crystals are added as seed. Then 74 mg of triethylamine are added as a catalyst and the whole is stirred at 2 to 4 ° C for 24 hours. The precipitated crystals are then filtered off and washed three times in a filter with ml of cold hexane (0-5 ° C). The yield in the crystals is 3.04 g (41.3% by weight with respect to the phenvalerate A used). The analysis of the crystals shows the participation of isomers of the alcoholic ester radical (R) in and (S) 4.0% / t and 96.0 P / #, respectively. Example XIV. 7.70 g of Aa fenvalerate are dissolved in 7.7 g of methanol and 1 mg of Aa phenvalerate crystals are added as seed. Then 200 mg of triphenylphosphine are added as a catalyst and the whole is stirred at 2 to 4 ° C overnight. The precipitated crystals are filtered off and washed on the filter with two 3 ml portions of cold hexane (0-5 ° C). The yield of the crystals is 3.60 g (4BJ & k by weight with respect to the fenvaluate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester of 3.4% and 96.6%, respectively. Example XV. 6.64 g of Aa phenvalerate are dissolved in 6.6 g of methanol and 1 mg of Aa phenvalerate crystals are added as seed. Then 62 mg of aniline is added as a catalyst and the whole is mixed at 2 to 4 ° C for 24 hours. The precipitated crystals are filtered off and washed twice in the filter with cold hexane (0-6 ° C.). The yield of the crystals is 2.99 g (45.1% by weight, based on the phenvalerate A used). The analysis of the crystals shows the relationship of the (R) and (S) isomers of the alcohol radical. Example XVI. 7.85 g of Aa fenvalerate is dissolved in 7.2 g of methanol and 1 mg of Aa fenvalerate crystals are added as seed. Then 0.71 g of a 10% methanolic solution of tetramethylammonium hydroxide was added as a catalyst, and the mixture was stirred for 24 hours at 2 to 4 ° C. The precipitated crystals are filtered off and washed on the filter with three 3 ml portions of cold hexane (0-5 °). The yield of the crystals is 4.05 g (51.0% by weight, based on the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radicals 3.8% and 96.2%, respectively. Example XVII. 40.00 g of fenvalerate A are dissolved in 80 g of methanol and 1 mg of Aa phenvalerate crystals are added as seed. Then, 2.00 g of triethylamine are added as a catalyst and the whole is stirred at -6 ° C overnight. The precipitated crystals are filtered off and washed on the filter with two 20 ml portions of cold methanol (0-5 ° C. The yield of the crystals is 33.36 g (83.4% by weight with respect to the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical, respectively 2.3% and 97.7%. Example 18.40.00 g of fenvalerate A are dissolved in 40 g of methanol and 1 mg of crystals of Aa fenvalerate are added as seed. Then 0.40 g of triethylamine is added as a catalyst and the whole is mixed for 3 days in -6 ° C. The recovered crystals are filtered off and washed on the filter with two 20 ml portions of cold methanol (0-5 ° C). The yield of the crystals is 35.82 g (89.6% by weight based on the phenvalerate used) A). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical, 2.5% and 97.5%, respectively. Example 19.10.00 g of fenvalerate A It is dissolved in 10 g of methanol and 1 mg of Aa phenvalerate crystals are added as seed. Subsequently, 0.10 g of pyridine was added to the catalyst and the mixture was stirred at -6 ° C for 24 hours. The precipitated crystals are filtered off and washed on the filter with two. 5 ml of cold methanol (0-5 ° C.) each. The yield of the crystals is 4.36 g (43.6% by weight with respect to the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical, respectively 3.0% and 97.6%. Example XX. 10.00 g of Aa fenvalerate are dissolved in 20 g of methanol and 1 mg of Aa fenvalerate crystals are added as seed. Subsequently, 20 g of 40% aqueous methylamine solution is added as a catalyst and the calpsc is stirred for 24 hours at -6 ° C. The precipitated crystals are filtered off and washed on the filter with two 5 ml portions of cold methanol (0-5 ° C). The yield of the crystals is 8.52 g (85.2% with respect to the db of the used phenvalerate A). The crystal analysis shows 2.3% and 97.7% share of the (R) and (S) isomers of the alcohol ester radical, respectively. io Example XXI. 40.00 g of Aa phenvalerate are dissolved in methanol and 1 mg of Aa phenvalerate crystals are added as a seed. Subsequently, 0.48 g of a 28% aqueous ammonia solution was added as the catalyst, and the mixture was stirred for 24 hours at -6 ° C. The precipitated crystals are filtered off and washed on a filter with two 20 ml portions of cold methanol (0-5 ° C). The yield of the crystals is 33.20 g (83.0% by weight, based on the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical, respectively 2.3% and 97.7%. Example XXII. 10.00 g of Aa fenvalerate is dissolved in 10 g of methanol and 1 mg of Aa phenvalerate crystals are added as seed. Then 0.10 g of ethylene diamine is added as a catalyst and the whole is stirred at -6 ° C overnight. The precipitated crystals are filtered off and washed on the filter with two 5 ml portions of cold methanol (0-5 ° C). The yield of the crystals is 8.12 g (81.2% by weight with respect to the phenvalerate A used). Analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical 2.0% and 97.4%, respectively. Example XXIII. 100.00 g of Aa fenvalerate is dissolved in 200 g of methanol and 4 mg of Aa phenvalerate crystals are added as seed. Then 3.00 g of triethylamine are added as a catalyst and the whole is stirred for 24 hours at -13 ° C. The precipitated crystals are filtered off and washed on the filter with two 50 ml portions of cold methanol (0-5 ° C). . The yield of the crystals is 84.21 g (84.2% by weight with respect to the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol radical of the ester, 3.0% and 97.0%, respectively. Example XXIV. 10.00 g of Aa fenvalerate is dissolved in 10 g of methanol and 1 mg of Aa phenvalerate crystals are added as seed. Na- M stepsteps As catalyst, 0.10 g of triethylamine is added and the whole is stirred for 24 hours at 12 ° C. The precipitated crystals are filtered off and washed on the filter with two 5 ml portions of cold methanol (* -5 ° C). The yield of the crystals is 7.43 g (74.3% by weight with respect to the phenylenate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical 1.2% and 98.8%, respectively. Example XXV. 40.00 g of A M fenvalerate are dissolved in 60 g of methanol and 10 mg of Aa phenvalerate crystals are added as seed. 1.95 g of a methanolic ammonia solution (ammonia content & 3% by weight) are then added as a catalyst and the mixture is stirred for 24 hours at -6 ° C. The precipitated crystalline product drains 40126741 1 * 14 phenvalerate Aa. Subsequently, 0.8 g of triethylamine was added as a catalyst and the whole was stirred at -6 ° C for 24 hours. The precipitated crystals are filtered off and washed on the filter paper with two 20 ml portions of cold methanol (0-5 ° C). The yield of the crystals is 21.36 g (53.4 Vt by weight with respect to the phenvalerate A used). The analysis of the crystals shows 2.5% and 07.5% of the (R) and (S) isomers of the alcohol ester radical, respectively. in Example XXXI. The procedure described in Example XVII is repeated. After one day, about 10% of the suspension was added to the swarm with 400 g of Aa phenvalerate in 600 g of methane, which was cooled to -6 ° C. Then 8.0 g of triethylamine are added as a catalyst and the whole is stirred at -6 ° C for the day. The precipitated crystals are filtered off and washed on the filter paper with two 200 ml portions of cold methanol (0-5 ° C). The yield of the crystals is 381.9 g (86.8% by weight, based on the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical, respectively 2.4% and 97.69%. Example XXXII. 40.00 g of Aa fenvalerate is dissolved in 60 g of methanol and 10 mg of Aa fenvalerate crystals are added as seed. Then 0.12 g of 5-diazabicyclo {4.3.0 i of nonene-5 is added and the whole is stirred for 24 hours at 0 ° C. The precipitated crystals are filtered off and washed on the filter with two 20 ml portions of cold methanol 30 (0 -5 ° C). The yield of the crystals is 32.35 g (30.9% by weight with respect to the phenvalerate A used). The crystal analysis shows 3.2% and 96.8% proportion of the (R) and (S) isomers of the alcohol ester radical, respectively. 35 Example XXXIII. 40.00 g of Aa phenvalerate are dissolved in a mixture of 5 g of toluene, 35 g of heptane and 20 g of methanol, 10 mg of Aa phenvalerate crystals and 4.8 g of triethylamine are added and the whole is stirred at -6 ° C overnight. The precipitated crystals are filtered off and washed on the filter with two 20 ml portions of cold methanol (0-5 ° C. The yield of the crystals is 23.72 g (59.3% by weight with respect to the denveranate A used). The analysis of the crystals shows the contribution of the isotter (R) and (S) of the alcohol radical of the ester, respectively., **, and 08.4%. The scope of the invention is not limited to the described embodiments. A number of changes and modifications can be made and modification, without departing from its concept and scope, and the filter is washed with two 20 ml portions of cold methanol (0-5% C). The yield of crystals is 34.56 g (86.4% by weight with respect to the used of phenvalerate A) 3 The analysis of the crystals shows the content of the (R) and (S) isomers of the alcohol ester radical, respectively 2.3% and 97.7%. Example XXVI. 40.00 g of fenvalerate A are dissolved in 80 g of inetyleyklohelttan and as a seed 10 mg of Aa phenvalerate crystals are added. Then 0.8 g of methanolic ammonia solution is added as the catalyst (ammonia content 8.3% by weight) and mixes all day at -6 ° C. The precipitated crystals are filtered off and washed on the filter with two 20 ml portions of cold methylcyclohexam (0.5 ° C.). The yield of the crystals is 31.40 g (78.5% by weight based on the phenvalerate A used). The crystal analysis shows 1.4% and 98.6% of the (R) and (S) isomers of the alcohol ester radical, respectively. Example XXVII. 40.00 g of Aa phenvalerate is dissolved in a mixture of 10 g of toluene and 70 g of heptane and 10 mg of Aa phenvalerate crystals are added as seed. Then, as the catalyst, 9.8 g of methanolic ammonia solution (ammonia content 8.3% by weight) are added and the mixture is stirred at -6 ° C for 24 hours. The precipitated crystals are filtered off and washed on the filter with two 20 ml portions of cold heptane (0-5 ° C). The yield of the crystals is 31.72 g (79.3% by weight based on the phenvalerate A used). The analysis of the crystals shows the proportion of the (R) and (S) isomers of the alcohol ester radical, respectively 2.2% and 97.8%. Example XXVIII. 40.00 g of fenvalerate A are dissolved in 60 g of methanol and 10 mg of Aa fenvalerate crystals are added as seed. Then a solution of 38 mg of sodium hydroxide in g of methanol is added as a catalyst and the mixture is stirred at -6 ° C for 24 hours. The precipitated crystals are filtered off and washed on the filter paper with two 20 ml portions of cold methanol (0-5 ° C.). The yield of the crystals is 23.84 g (59.6% by weight with respect to the phenvalerate A used). The analysis of the crystals shows the participation of the (R) and (S) isomers of the alcohol ester radical, respectively 2.8% and 97.2%. Example XXIX. 40.00 g of Aa phenvalerate are dissolved in 60 g of methanol and 10 mg of Aa phenvalerate crystals are added. Then, a solution of 47 mg of sodium cyanide in 2 mg of methanol is added as a catalyst and the whole is stirred at -6 ° C overnight. The precipitated crystals are filtered off and washed on the filter with two 10 ml portions of cold methanol (0-5 ° C). . The yield of the crystals is 22.8 g (57.2% by weight, based on the phenvalerate A used). The crystal analysis shows 2.2% and 97.8% proportion of the (R) and (S) isomers of the alcohol ester radical, respectively. Example XXX. 40.00 g of fenvalerate A [with the composition of the alcohol radical 51.0% of the (R) isomer and 48.0% of the (S) isomer and the optical purity of the acid radical 82.0%] are dissolved in 60 g of 1 methanol and as a seed adds 10 mg of a crystal. Claims 1. A method of producing (S) -2- (4-cMorophenic) -isovalerate (S) -a-cyano-3-fencfcsybenzyl, including those mentioned (S) -2- (4- (S) -ecyano-3-phenoxybenzyl chlorophenic) isovalerate is crystallized from a solution of (R, S) -a-cyano-3-phenoxybenzyl -z- <4-chloroienyl) isovalerate in a solvent in the presence of a basic substance as of the catalyst by adding a seed of (S) -2- (4-chlerienyl) isovalerate (S) -a-cyano-3-phenoxybenzyhi crystals and releasing crystalline (S) -2- (4-chlorophenyio) isovalerate (S) -a -cyano-3-phenoxybenzyhi from the mother liquor. 2. The method according to claim 1, is based on the fact that a lower alcohol or a mixture of solvents containing a lower alcohol is used as the solvent. 3. The method according to p. The process of claim 2, wherein the solvent is methanol, ethanol or a mixture of solvents containing methanol or ethanol. 4. The method according to p. The process of claim 1, wherein the solvent is an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon or a solvent mixture containing an aliphatic hydrocarbon or a cycloaliphatic hydrocarbon. 5. The method according to p. The process of claim 4, wherein the solvent is one of the compounds pentane, hexane and heptane. 6. A method according to claim The method of claim 4, wherein the solvent is a mixture of (a) a solvent selected from the group consisting of pentane, hexane and heptane with (b) a solvent from the group consisting of benzene, toluene and xylene. 7. The method according to claim 15 A process as claimed in claim 4, characterized in that cyclohexane and / or methylcyclohexane are used as the solvent. 8. The method according to p. A process as claimed in claim 1, characterized in that the basic substance is a nitrogen or phosphor base. 9. The method according to p. The process as claimed in claim 8, characterized in that ammonia or organic amine is used as the nitrogen base. 10. The method according to claim The method of claim 1, wherein the basic substance is one of the compounds of the group consisting of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkaline earth metal alkoxide, an alkali metal amide, an alkaline earth metal amide, an alkali metal hydride, and a metal hydride. an alkaline earth thallium and a basic ion exchange resin, preferably an alkali metal hydroxide or an alkaline earth metal hydroxide. - @ e <* PATTERN 1 -N <3 PATTERN 2 Composition: B.Z. ttok: Prt «mniaPougrtfkzntUPreL OfcnalOOzl PL

Claims (10)

Claims 1. The method of producing (S) -2- (4-cMorophenic) -isovalerate (S) -a-cyano-3-fencfcsybenzyl, including the mentioned (S) -2- (4-chlorophenic) (S) -ecyano-3-phenoxybenzyl isovalerate is crystallized from a solution of (R, S) -a-cyano-3-phenoxybenzyl isovalerate in a solvent in the presence of a basic substance as a catalyst by adding a seed crystals of (S) -2- (4-chleroienyl) isovalerate (S) -a-cyano-3-phenoxybenzyhi and gives off crystalline (S) -2- (4-chlorophenyio) isovalerate (S) -a-cyano-3 -phenoxybenzyhi from the mother liquor. 2. The method according to claim 1, is based on the fact that a lower alcohol or a mixture of solvents containing a lower alcohol is used as the solvent. 3. The method according to p. The process of claim 2, wherein the solvent is methanol, ethanol or a mixture of solvents containing methanol or ethanol. 4. The method according to p. The process of claim 1, wherein the solvent is an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon or a solvent mixture containing an aliphatic hydrocarbon or a cycloaliphatic hydrocarbon. 5. The method according to p. The process of claim 4, wherein the solvent is one of the compounds pentane, hexane and heptane. 6. A method according to claim The method of claim 4, wherein the solvent is a mixture of (a) a solvent selected from the group consisting of pentane, hexane and heptane with (b) a solvent from the group consisting of benzene, toluene and xylene. 10 15 7. The method according to p. A process as claimed in claim 4, characterized in that cyclohexane and / or methylcyclohexane are used as the solvent. 8. The method according to p. A process as claimed in claim 1, characterized in that the basic substance is a nitrogen or phosphor base. 9. The method according to p. The process as claimed in claim 8, characterized in that ammonia or organic amine is used as the nitrogen base. 10. The method according to claim The method of claim 1, wherein the basic substance is one of the compounds of the group consisting of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkaline earth metal alkoxide, an alkali metal amide, an alkaline earth metal amide, an alkali metal hydride, and a metal hydride. an alkaline earth thallium and a basic ion exchange resin, preferably an alkali metal hydroxide or an alkaline earth metal hydroxide. - @ e <* PATTERN 1 -N <3 PATTERN 2 Composition: B.Z. ttok: Prt «mniaPougrtfkzntUPreL OfcnalOOzl PL