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    • 专利摘要:
    A process for the preparation of an ester of chiral (A) acid with a racemic (R,S) alpha -cyano-3-phenoxybenzyl alcohol (B) by reacting an ester of chiral (A) acid with alpha -cyano-3-phenoxybenzyl alcohol of the formula <IMAGE> B in its optically active (R) form or (S) form or a mixture of esters of said (R) alcohol and (S) alcohol in non-equimolecular proportions with a base selected from the group consisting of ammonia, primary, secondary and tertiary amines, quaternary ammonium compounds, liquid amines of high molecular weight and a catalytic amount of a strong base in at least one solvent for the starting esters and in which the ester of racemic alcohol is soluble and recovering from the resulting solution the ester of chiral (A) acid with racemic (R,S) alcohol.
    公开号:SU1200848A3
    申请号:SU772476520
    申请日:1977-04-22
    公开日:1985-12-23
    发明作者:Варнан Жюлиан；Прос-Марешаль Жак；Коске Филипп
    申请人:Руссель Юклаф (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of cis- or trans-cyclopropanecarboxylic acid esters (chiral acid) and racemic 6i-cyano-3-phenoxybenzyl alcohol, which are used as agricultural pesticides or herbicides.  A method of producing esters of cis or trans-cyclopropane-carboxylic acids and racemic alcohol of ob-cyano-3-phenoxybenzyl alcohol is known, which consists in that cis or trans-cyclopropanecarboxylic acid of formula U 3-phenoxybenzyl alcohol ij.  In the resulting racemate, the active component which has been used is the chiral acid ester and the α-cyano-3-phenoxybenzyl alcohol of configuration (S), and the inactive isomer (R) does not find use.  The purpose of the invention is the utilization of the cis- or trans-cyclopropanecarboxylic acid ester and o-cyano-3-phenoxybenzyl alcohol of configuration (R).  This goal is achieved according to the method of obtaining esters of cis or trans-cyclopropanecarboxylic acids and racemic alcohol cyano-3-phenoxybenzyl alcohol of the general formula where Na is chlorine or bromine by treating the ester of cis or trans-cyclopropanecarboxylic acid-LO1 and oi -cyano-3-phenoxybenzyl alcohol of configuration (R) or a mixture of this ester with cis- or trans-cyclopropanecarboxylic acid ester and o (, - cyano-3-phenoxybenzyl alcohol of configuration (S) containing 69.5-83% of isomer (R) and 17-30.5% isomer (S), based agent selected from the group is an aqueous solution of gilrok 48 sy ammonium or sodium, or tetrabutylammonium, or triztilamine, or n butylamine, or piperidine, or pyrrolidine, or sodium ethylate in an organic solvent selected from the group acetone, monoaromatic hydrocarbon, dimethyl sulfoxide, dimethylformamide, dioxane, tetrahydrofuran, at 0-20 ° C.  The proposed compounds are obtained in quantitative yield.  Under the conditions of the proposed method, &quot; d-cyanated carbanion and H are formed under the action of a base.  Protonization under the action of the latter leads to the formation in equimolecular amounts of two stereoisomers — an alcohol ester (S) and an alcohol ester (R), a configuration, t. e.  to the racemate. In the proposed method, the inversion of the configuration of the alcohol part of the molecule takes place.  In order to achieve the completeness of the process, it is necessary that the initial reagents are soluble in the reaction medium, therefore, the solvents are chosen taking into account. tom fulfillment of such condition.  The racemate in the future with the aim of isolating S-isomer can be separated under conditions of fractional crystallization.  Example 1  Preparation of racemic alcohol ester from OC-cyan-3-phenoxybenzyl ester of (R) 2,2-dimethyl-3R- (2,2-dibpo-vinyl) cyclopropane-1R-carboxylic acid.  I g 1X -cyano-3-phenoxybenzyl ester of (R) 2,2-dimethyl-ZR- (2,2-dibromovinyl) -cyclogophopan-lR-carboxylic acid, (OS) d 30.5 ° (C 1%, benzene ) and ((yd). p -25.5 ° (C 1%, chloroform), dissolved in 2.5 cm of acetone, 0.16 g of triztilamine was added, stirred for 15 hours at 20 s, concentrated to dryness under reduced pressure, and 1 g was obtained. (R, S) 2,2-dimethyl-3R- (2, 2-dibromovinyl) -cyclopropane-lR-carboxylic acid cyano-3-phenoxybenzyl ester, (((y) jj + 13.5 (C%, benzene), which by chromatography on silica gel with elution with a mixture of petroleum ether (h. Kip, 35-70 ° C, and isopropyl ether (8-2), gives two identical spots, of which o are; sho with Rip 0.7 corresponds to complex alcohol ester (R).  and the other with PF 0.64 - alcohol ester (S).  Example 2 Preparation of racemic alcohol ester from o-cyano-3-phenoxybenzyl, (R) 2,2-dimethyl-Z- (2,2-dibrovinyl) cyclopropane-1R-carboxylic acid ester.  Similar to example 1, but acetone is replaced by benzene.  The racemic alcohol ester of the same quality as in Procedure 1 is isolated in the same yield.  Example 3  Preparation of the racemic alcohol ester is derived from c-cyano-3-phenoxy-benzyl ester of (R) 2,2-dimethyl-3- (2,2-dibromo vinyl) cyclopropane-1R-carboxylic acid.  Similar to example 1, but acetone is replaced by dioxane.  With the same yield, the ester of racemic alcohol of the same quality as in measure 1 was isolated.  Example A.  Preparation of racemic alcohol ester from (vi-cyano-3-phenoxybenzyl ester (R) 2,2-dimetshl-ZR- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid.  Similar to example 1, but acetone is replaced by tetrahydrofuran.  An ester of racemic alcohol of the same quality as in Example 1 is obtained in the same yield.  Example 5  The preparation of the racemic alcohol ester is based on the od-cyano-3-phenoxybenzyl ester of (R) 2,2-dimethyl-3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid.  In 2.5 cm of dimethylformamide, g of cyano-3-phenoxybenzyl ester of (R) 2,2-dimethyl-ZR- (2,2-dibromovinyl) cyclopropane-R-carboxylic acid is dissolved, 0.16 g is added. triethylamine, stirred for 15 hours at 20 ° C, water was added, extracted with methylene chloride, the chloromethylene solution was washed with water, dried, the erOj was concentrated to dryness and 1 g of cyano-3-phenoxybenzyl ether (R, S) 2.2 was obtained -dimethyl-3R- (2,2-dibromovinyl) cyclopropane -1 -1 R-carboxylic acid, (. ) j, + 13.5 (C%, benzene), showing as a result of the same chromatography as in Example 1, the same spots with the same Rm.  Example 6  Preparation of the racemic alcohol compound from t-cyano-3-phenoxybenzyl ester of (R) 2,2-dimethyl-3K- (2,2-dibromovinyl) cyclopropane-IR-carboxylic acid.  Similar to example 5, but dimethylformamide is replaced by dimethylsulfrxide. The racemic alcohol ester of the same quality is obtained in the same yield as in Example 5, Example 7.  Preparation of racemic alcohol ester from C; -cyano-3-phenoxybenzyl ester, (R). 2,2-dimethyl-ЗЬ- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid.  The process is carried out analogously to example 1, replacing 0.16 g of triethylamine 0.14 g of Mrrfolin. An ester of racemic alcohol is obtained with the same extract and of the same quality as in example 1.  Example 8  Preparation of the ester alcohol ester starting from "; cyano-3-phenoxybenzyl (R) 2,2-dimethyl-3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid ester.  The process is carried out in benzene as in Example 2; replacing 0.16 g of triethylamine with 0.135 g of piperidine.  An ester of racemic alcohol is obtained with the same yield and the same quality as in Example 1.  Example 9  Preparation of the racemic alcohol ester from the (y; cyano-3-phenoxybenzyl (R) 2,2-dimethyl-3R- (2,2-dibromovinyl) ester) cyclopropane-1R-carboxylic acid.  The process is carried out in benzene as in Example 2, replacing 0.16 g of triethylmine with 0.11 g of pyrrolidine.  A false ester of racemic alcohol is obtained in the same yield and quality, as in Example 1.  Example 10  Preparation of racemic alcohol ester of isod from 6i-cyano-3-phenoxybenzyl R) 2,2-dimethyl-3R- (2,2-dibropyl) cyclopropane-1R-carboxylic acid ester.  They work in acetone in the same way as the prior 1, but they replace 0.16 g of triethylmine with 0–15 cm of an aqueous solution of ammonium hydroxide.  Get complex firm racemic alcohol with the same extract and the same quality as n in example 1.  Example 11  Preparation of the racemate alcohol ester from C-cyano-3-phenoxy-benzyl ester of (R) 2,2-dimethyl-3R- (2,2-dibromo-vinyl) cyclopropane-R-carboxylic acid.  Dioxane was operated as in Example 3, but 0.16 g of triethylamine was replaced with 0.008 g of sodium hydroxide.  An ester of racemic alcohol is obtained in the same yield} i of the same quality as in Example 1.  Example 12  The preparation of the racemic alcohol ester was based on 06-cyano 3-phenoxybenzyl (R) 2,2-dimethyl-3H- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid ester.  The tetrahydrofuran is operated analogously to Example 4, but 0.16 g of triethylamine is replaced with 0.015 g of sodium ethoxide.  The ester of racemic alcohol is obtained in the same yield and quality as in Example 1, Example 13, Preparation of the ester of racemic alcohol is taken from a mixture of 5 g (v; -cyano-3-phenoxybenzyl (R) ester 2 , 2-dimethyl-3R- (2,2-dibromovinyl) cyclopropane-1R, -carboxylic acid and 1 go-cyano-3-phenoxybenzyl (S) ester of 2,2-di methyl-3R- (2,2- dibromovinyl) cycloprop-1R-carboxylic acid, and.  Obtaining a mixture of ester of alcohol (R) and ester of alcohol (S) in the ratio of 5-1. Dissolve 10 g of w-cyan-3-phenoxy benzyl (R, S) ester of 2,2-dnmethyl-3R- (2.2 -dibromovinyl | cyclopropane-1R-carboxylic acid (ij, +13.5 (1%, beneol, 20 cm of methanol, stirred for 20 hours at 20 ° C; extract by suction of the precipitate formed, washed, dried, and 4 are obtained g "6-cyano-3-phenoxybenzyl (S) ester of 2,2-dimethyl-3R- (2,2-dibromovinyl cyclopropane-H-carbonic acid, t. pl, 100c, (“i) p +60.5 (s.  1%, benzene) or (about) |, ° + 25 ° (C 1%, chloroform), concentrate the mother liquors to dryness under reduced pressure and obtain 6 g of a mixture consisting of 5 g of 0 (;, - cyano-3- phenoxybenzyl (R) ester of 2,2-dime- (2,2-dibromovinyl) cyclopropane-1 R-carboxylic acid and 1 gsb-cyano-3-phenoxybenzyl (S) ester of 2,2-dimethyl-3R- (2.2 -dibromovinyl) cyclopropane-R-carboxylic acid (mixture M), b, Preparation of a raremic alcohol ester from a mixture of an ester of alcohol (R) and an ester of alcohol (S).  Mixture M is dissolved in 20 cm of benzene, 1 g of triethylamine is added, stirred for 18 hours at 20 ° C, concentrated to dryness by distillation under reduced pressure, and 6 g of oi-cyano-3-phenoxybenzyl (R, S) are obtained. 2,2-dimethyl-ЗR- (2,2-dibromovinyl) cyclopropane-1R carboxylic acid ester of the same quality as in Example 1, (wasp) +13.5 (with 1% benzene and two identical spots on the chromatographic method, Example 14, Preparation of a racemic alcohol ester starting from a mixture of 5 rji-cyano-3-phenoxy-benzyl (R) 2,2-dimesh-1-3R- (2 2-dibromovinyl) cyclopropan-1R-carbono ester acid and 1 g of about-cyane-3-phenoxybenzyl (S) ester of 2,2-dimethyl-3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid.  A mixture of alcohol ester (R) and alcohol ester (S) is prepared as in example 13a. The process is carried out analogously to example 136, replacing 1 g of triethylamine with 0.9 g of pyrrolidine, and preparing the ester of racemic alcohol with the same yield and the same quality, as in example 13.  Example 15 Preparation of racemic acid starting from (x; cyano-3-phenoxybenzyl (R) 2,2-dimethyl-3R- (2,2-dichloroivinyl cyclopropane-1R-carboxylic acid) ester.  1 g of o-cyano-3-phenoxybenzyl (R) 2,2-dimethyl-3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylic acid ester is dissolved in 2.7 cm of diconane, 0.1-3 g of triethylamine, stir the solution for 15 hours at 20, concentrate to dryness under reduced pressure and obtain 1 gob-cyano-3-phenoxybenzyl (R, S) ester 2,2-dimethyl-3R- (2.2 -dichlorovinyl) -cyclopropane-1P-carboxylic acid.  (a :) +16 {About 1%, benzene.  This compound is after chromatography on silica gel and eluted with petroleum ether (m. Kip, 35-75 ° C) and isopropyl gives two equal spots, one of which with Rm 0.68 corresponds to an ester of alcohol (R), and the other with Kf 0.62 to an ester of alcohol (S).  Example 16 Preparation of a racemic alcohol ester from o6-cyano-3-phenoxybenzyl (S) 2,2-dimethyl-WE (2,2-dichlorovinyl) cyclopropane-1R-carboxylic acid ester.  Starting from 1 g of 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1R-carboxylic acid oi-cyano-3-phenoxy-benzyl ester of 2,2-dimethyl-ZK, (C, (oi) +66 ( C 1%, benzene) and acting analogously to example 15, I get 1 g of (y-cyano-3-phenoxybenzyl (R, S) ester 2,2-dimethyl-3K- (2,2-dichlorovinyl) cyclopropan-1 R-carbon acids of the same quality as in example 15.  Example 17  but.  Preparation of racemic alcohol ester starting from a mixture of 10 g of Ob-cyano-3-phenob of sibenzyl (R) 2,2-dimethyl-3R - (2,2-dichlorovinyl) cyclopropane-1R -carboxylic acid and 4.4 g9 - cyano-3-phenoxybenzyl (S) 2,2-dimethyl-3- (2,2-dichlorovinyl cyclopropane-1 R-carboxylic acid) ester, 20 g of methanol-3-phenoxy-benzine 1 (R , S) 2j2-dimethyl-ZR- (2,2-dichlorovinyl) cyclopropane-1R-carboxylic acid ester {) in IB. C (1%, benzene), stirred for 24 hours at 0, extract the precipitate by suction, wash it, dry and obtain 5,6 rtjj-cyano-3-phenoxybenzene (S) ether 2,2-dimethyl- RR (2,2-dichlorovinyl) cyclopropane-IR-carboxylic acid, t. mp, 60 ° C, ((v:) | +66 (C 1%, benzene), concentrate the mother liquors to dryness and obtain 14.4 g of a mixture consisting of 10 g of about-cyano-3-phenoxybenzyl (R) ether 2,2-di methyl-ZN- (2,2-dichlorovinyl) cycloprop-1K-carboxylic acid 4.4g-cyano-3-phenoxybenzyl (S) ester 2,2-dimethyl-3R- (2,2-dichlorovinyl j cycle lopropane-R-carboxylic acid (mixture M,).  b.  Preparation of a racemic alcohol ester from a mixture of an alcohol ester (R) and an alcohol ester (S), 488 Mixture M, dissolved in 40 cm of dihydrogen, 2 g of triethylamine added, stirred for 20 hours at 20 C is concentrated to dryness under reduced pressure and 14.4 go cyano-3-phenoxybenzyl (R, S) 2,2-dimethyl-3R- (2,2-dichlorovinyl) -cyclopropane-1R-carboxylic acid ester is obtained, (o) n-16 ° (with 1% benzene).  This compound, which is chromatographed on silica gel and eluted with a mixture of petroleum ether (m, bale, 35–75 ° C) and isopropyl ether (8–2), leads to equal spots, one of which is RCJ, 0, 68 with RO, 0.68 corresponds to the complex eff (R), and the other with R 0.62 py alcohol ester alcohol (S).  Example 18  Preparation of racemic alcohol ester  d is-cyano-3-phenoxybenzyl (S) ester of 2,2-dimethyl-ZR-C2,2-dibromovinyl) cyclopropane-1R-carboxylic acid, 1 g of 0-cyano-3-phenoxybenzyl (s) ester 2, 2- dimethyl-ze- (dibromovinyl) | cyclopropane-1R-carboxylic acid, (o /) + 60.5 ° (c 1%, benzene), (f ° + 25 ° (C 1%, chloroform), t. square .  , dissolved in 2.5 cm of acetone, 0.16 g of triethylamine is added, the solution is stirred for 15 hours at 20 ° C, concentrated to dryness under reduced pressure, and 1 g of Oi-cyano-3-f-noxibenzyl (R, S) is obtained 2,2-Dimethyl-ЗR- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid ester, (o) ° +13.5 (with 1% benzene).  This compound is after chromatography on silica gel and eluted with petroleum ether t. kip  35-75 c) and isopropyl ether Gw in a ratio of 8-2) gives two identical spots, one of which with Rf 0.7 corresponds to the ester of alcohol (R), and the other with Rm 0.64 - to the ester of alcohol (S) the same quality as the ester of racemic alcohol obtained in example 1.  Example J 9.  Preparation of the racemic ester ester from the ci-cyano-3-phenoxybenzyl (S) ester of 2,2-dimethyl-3H-C2,2-dibromovinyl) -cyclopropan-1R-Kap6o new acid.  Based on 1 g of the alcohol ester (S) following Example 2, the racemic alcohol ester of the same quality as in Example 1 was isolated in the same yield.  Example 20 Preparation of ester starting from oi-cyano-3-phenoxybenzyl (S) ester 2 (2-dimethyl LC (2 J 2-dibromovinyl) cyclopropane-lR-carboxylic acid.  Based on 1 g of alcohol ester (S), following Example 3, the ester of racemic alcohol of the same quality as in Example 1, Example 21, Preparation of racemic alcohol ester starting from a; -cyano-3-phenoxybenzyl (S) ester 2 2-dimethyl-3- (2 5 2-dibropinyl cyclopropane-R-carboxylic acid.  Based on 1 g of the ester of alcohol (S), operation is similar to Example 4, the ester of racemic alcohol of the same quality is obtained with the same yield as in Example 1, Example 22.  Preparation of racemic alcohol ester is based on (X.  -cyano-3-phenoxybenzyl ester (S) 2,2-dimethyl-3K- (2,2-dibromo vinyl) cyclopropane-1R carboxylic acid.  In 2.5 cm of dimethylformamide, 1 g of 0-cyano-3-phenoxybenzyl (S) ester of 2,2-dimethyl-WH- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid is added to 1 g 0.16 g of triethylamine, stirred for 15 hours at 20 (water is added, extracted with methylene chloride, the chloromethylene solution is washed with water, dried, and concentrated to dryness to give 1 roi-cyano-3-phenoxybenzyl (R, S) ether 2, 2 dimethyl-3R (2, 2-di-bromovinyl) cyclopropane-1R-carboxylic acid of the same quality as in example 1.  Example 23  Preparation of the racemic alcohol ester from the cyano-3-phenoxybenzyl (S) 2,2-dimethyl-3R (2,2-dibromoynyl) cyclopropane-1R-carboxylic acid ester, Based on 1 g of the alcohol ester (3 ) 5 following Example 6, the same quality of racemic alcohol ester of the same quality as in Example 1, Example 24 is obtained.  Preparation of racemic alcohol ester from vin with {, -aiano-3-phenoxybenzyl (S) 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropan-1R-carboxylic acid ester.  Based on 1 g of alcohol ester (S), following Example 7, a racemic alcohol ester is obtained in the same yield and quality as in Example 1, Example 25, Preparation of a racemic alcohol ester starting from -cyano-3- phenoxybenzyl (S) ester of 2, 2-dimethyl-CK- (2, 2-dibpo-vinyl) cyclopropane-1 R-carboxylic acid.  Based on 1 g of the alcohol ester (S), operating as in Example 8, a racemic alcohol ester is obtained in the same yield and quality as in Example 26.  Preparation of racemic alcohol ester from the ixi-cyano-3-phenoxybenzyl (S) 2,2-dimethyl-3R- (2,2-dibromovinyl) cyclopropan-1R-carboxylic acid ester.  Based on 1 g of the alcohol ester (S), operating as in Example 9, a racemic alcohol ester is obtained in the same yield and quality as in Example 1.  Example 27 Preparation of a racemic alcohol ester starting from (y; -cyano-3-phenoxy-benzyl (S) ester 2,2-dimethyl-3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid.  Based on 1 g of the alcohol ester (S) 5 as in Example 10, the ester of the racemic alcohol is obtained in the same yield and quality as in Example 1, Example 28, Preparation of the ester of racemic alcohol starting from SL-Piano 3-phenoxybenzyl (S) ester of 2,2-dimethyl-3R- (2,2-dibromvinyl) cyclopropane-1 R-carboxylic acid.  Based on I g of alcohol ester (S). act similarly to prier 11, get ester of racemic alcohol with the same output of the same quality as in example 1.  Example 29  The preparation of the racemic alcohol ester is derived from about-cyano-3-phenoxy-benzyl (S) ester of 1 R, cis-2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acid.  ot-cyano-3-phenoxybenzyl (S) ester, 1R, 2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carbox acid, (((+58 4%, toluene) , add 0.785 cm of n-butylamine, stir for 72 hours at 20 ° C, concentrate to dryness under reduced pressure, and give 10 g of residue, which is purified by chromatography on silica gel, eluting with benzene. Thus, 9.1 g are obtained (U-cyano-3-phenoxybenzyl (R, S) ether 1R, cic :: - 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic cx lots, ((x;) +7 , 5 ° (with 4%, toluene).  Example 30  Preparation of racemic alcohol ester from 0-cyano-3-phenoxy-benzyl (S) 1R ester, cis-2,2-dime yl-3- (2, -dibromovinyl) cyclopropane-1-carboxylic acid.  10 Oi-cyano-3-phenoxybenzyl (S) ether 1R, cis-2,2-dimethyl-3- (2,2-di bromo vinyl) cyclopropane -1 -carboxylic acid, (((x :) o ° +58 ± 1 (C 4%, then 48 luol), 1 g of tetrabutylammonium hydroxide is added, stirred for 24 hours, concentrated to dryness by distillation under reduced pressure, 10.2 g of residue are obtained, which is chromatographed on silica gel, eloured with toluene and 8.9 g of "; -cyano-3-phenoxybenzyl (R, S) ester 1R, cis-2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acid, (o , i) ° +7.5 (with 4%, toluene), Example 31.  Preparation of racemic alcohol ester. starting from fti-cyano-3-phenoxybenzene 1 OWN (S) 1R ester, cis-2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acid.  3 g of 30 cm of benzene dissolved 10 g of 0-cyano-3-phenoxybenzyl (S) 1R ester, cis-2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acid, () ° + 58 + 1® (with 4%, toluene), add 10 g of Amberlite 1A, stir 72 h, concentrate to dryness under reduced pressure, chromatograph on silica gel,.  zyluiru toluene, and get 9 g (x; -cyano-3-phenoxybenzyl (R, S) ether 1R, cis-2,2-dimethyl-3- (2,2-di bromo vinyl) cyclopropane-1-esarbonovoy-tion slots, (8 (;) М + 7.5 ° (with 4%, tow.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING CIS- OR TRANS-CYCLOPROPANOCARBOXYLIC ACIDS AND RACEEMIC ¢ 6-CYANO-3-PHENOXYBENZYL ALCOHOL of the general formula where R is chloro or bromo, characterized in that, for the purpose of utilization of trans-cyclopropane & ester —Cyano-3-phenoxybenzyl alcohol of configuration (R), the latter or its mixture with ester of cis or trans-cyclopropanecarboxylic acid and β-cyano-3-phenoxybenzyl alcohol of configuration (S) containing 69.5-83% of the isomer (R) and 1730.5% of the isomer (S) are treated with the main agent selected from the group of an aqueous solution of ammonium or sodium hydroxide, or tetrabutylammonium, or triethylamine, or n-butylamine, or piperidine, or pyrrolidine ^ or sodium ethylate, in an organic solvent selected from the group acetone, monoaromatic hydrocarbon, dimethyl sulfoxide, dimethylformamide, dioxan , tetrahydrofuran, at 0-20 6 С,>
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    SE446725B|1986-10-06|
    DK176977A|1977-10-24|
    DE2718038A1|1977-11-17|
    IE45383B1|1982-08-11|
    BE853866A|1977-10-24|
    CA1078864A|1980-06-03|
    NL179280C|1986-08-18|
    DK171105B1|1996-06-10|
    CH620890A5|1980-12-31|
    GB1582594A|1981-01-14|
    US4151195A|1979-04-24|
    SE7704517L|1977-10-24|
    NL7704520A|1977-10-25|
    FR2348901B1|1983-01-28|
    AU510903B2|1980-07-17|
    ES458109A1|1978-03-16|
    ZA772465B|1978-06-28|
    JPS6127384B2|1986-06-25|
    LU77185A1|1977-11-22|
    DE2718038C2|1984-06-07|
    IT1082199B|1985-05-21|
    AU2458577A|1978-11-02|
    IE45383L|1977-10-23|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7612093A|FR2348901B1|1976-04-23|1976-04-23|
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