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    • 专利摘要:
    A process for the preparation of an ester of chiral (A) acid with an optically active (S) alpha -cyano-3-phenoxybenzyl alcohol 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 a racemic (R,S) mixture or a mixture of esters of said (R) alcohol and (S) alcohol in non-equimolecular proportions designated herein as "ester (R+S)" with a base selected from the group consisting of ammonium hydroxide, primary, secondary and tertiary amines, quaternary ammonium compounds, liquid amines of high molecular weight, ion exchange resins of a basic character and a catalytic amount of a strong base in at least one solvent in which the ester of the (R) alcohol is soluble and in which the ester of the (S) alcohol is insoluble and recovering from the resulting medium the chiral (A) acid ester of the (S) alcohol which is insoluble.
    公开号:SU990082A3
    申请号:SU772481551
    申请日:1977-04-22
    公开日:1983-01-15
    发明作者:Варнан Жюлиан；Прос-Марешаль Жак；Коске Филипп
    申请人:Руссель-Юклаф (Фирма)；
    IPC主号:
    专利说明:

    la, in an amount from catalytic up to 20% by weight of the starting ester at 0-20 ° C and the separation of the target product from the solution.
    This method allows to achieve the yield of the target product up to 80-90%, as a result of which the unproductive consumption of the initial reagent sharply decreases, since during the reaction the constituent ester of the alcohol residue R undergoes an almost quantitative (above 90%) conversion of racer S - -, - j chiral acid A isoacioe j
    | -r (gsh% itg cG
    f gpujp L + ether residues jg
    SfomSopeg base Example 1. The transformation of R1-o.-Cyano-3-phenoxybenzyl ester of 2, 2-dimethyl-3H- (2,2-dibromovinyl) -cyclic propane-1-carboxylic acid into tS -Y-cyano-3-phenoxybenzyl 2,2-dimethyl 3R- (2,2-di6romvinyl) -cyclopropane-1 carboxylic acid ester. . 1 g of R-c-cyano-3-phenoxy-5-benzyl ester of 2,2-dimesh-1-WN- (2,2-dibromovinyl) cyclopropan-1J-carboxylic acid) is introduced into 2.5 cm of isopropanol 1.50 (from 1% benzene ) or Col-l f, 5 ° (with 1%, chloroform), and 0.15 cm of an aqueous solution of ammonium hydroxide is added over Tew, shaken for 18 hours at 20 ° C, the precipitate is sucked off, washed, dried and 0.9 g of 2,2-dimethyl-3R- (2,2-dibromovinyl) cyclopropane-lR-carboxy-acid of S-cyano-3-phenoxybenzyl ester of 0-g are obtained, m.p. 100 ° С, 60, 5 ° (with 1%, benzene) + 25 ° (s 1%, chloroform) .. Calculated,%: C 52.3; H 3.79 / N 2.77; Br 31.63. C22H190zNBg2 / 502.2 / Found,% t C 52.2; H 4.0, N 2.7; Br 31.5 .. Example 2. Transformation of 2,2-dimethyl-3R- (2,2-dibromvin1: 1l A-cyano-3-phenoxybenzyl ester) cyclopropane-1y-carboxylic acid into C3-e-cyano-3 2,2-dimethyl 3R- (2,2-dibromoinyl) cyclopropane-1R-carboxylic acid α-phenoxybenzyl ester Starting from 1 g of ester tR under the conditions of Example 1, but using 0.30 cm of an aqueous solution of oxide hydrate ammonium get 0.9 ester alcohol CSI of the same quality as in example 1. P r and I m p. 3. The transformation of R O1-cyano-3-phenoxy-Senelovo ether
    The configuration in the ES due to the formation of C5 cyano-3-phenoxybenzyl ester chiral (A) drops out of the reaction mixture (see diagram) and the waste as an R-configuration ester, remaining in solution, is insignificant.
    At the same time, if in the used solvent system both esters remain soluble, the amount proceeds to be recissed. Reaction Scheme:
    1 Raising 2, 2-dimethyl-ZR- (2,2-dibromovinyl) -cyclopropan-lR carboxylic acid in tS 3-o1-cyano-3-phenoxybenzyl 2,2-dimethyl-3R- (2,2-dibromovinyl) ester -cyclopropane-lR-carboxylic acid. . Starting from 1 g of tR3 alcohol ester under the conditions of Example 1, but replacing ammonium oxide hydrate with 0.16 g of triethylamine, 0.87 g of C5 alcohol ester of the same quality as Example 1 is obtained. Example 4. Conversion of IR } -ei-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-3 - (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid in the S -Y-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2,2-dibromovinyl) cyclopropane-1R-carboxylic acid. Starting from 1 g of alcohol ester 3 under the conditions of Example 1, but replacing ammonium oxide hydrate with 0.32 g of triethylamine, 0.9 g of alcohol ester LSI is obtained, of the same quality as in Example 1. Example 5. Conversion of R 3-o {.- cyano-3-phenoxybenzyl 2,2-dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid in S 3-o1.-cyano-3-phenoxybenzyl ester 2,2 -dimethyl-3R- {2,2-dibromovinyl) cyclopropane-1R carboxylic acid. i Starting from 1 g of alcohol ester to 3 under the conditions of Example 1, but replacing ammonium hydroxide with 0.11 g of pyrrolidine, 0.80 g of alcohol ester of tS of the same quality as in Example 1 is obtained. Example b. Conversion of t R -el-cyane-3-phenoxybeneyl ester of 2,2-dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-R-carboxylic acid to S D-o (-cyano-3-phenoxybenzyl ester 2,2 -dimethyl 3R- (2,2-dibromovinyl) -cyclopropan-lR-carboxylic acid .. Starting from 1 g of ester R 3 under the conditions of example 1, but replacing ammonium hydroxide O, 13 g, morpholine and paste Khiva over 96 at 20 ° C, get 0.9 g of ester of alcohol S of the same quality as in example 1. Example 7 4 Conversion of H -o-cyano-3-phenoxy-benzyl ester of 2,2-dimeyl-3V -12,2-dibromovinyl) -cyclopropane-1B-carboxylic acid The notes in the Cs J-ci-cyano-3-phenoxybenzyl 2,2-dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-lR-carboxylic sour you. Starting from 1 g of alcohol ester R under the conditions of example 1, but replacing ammonium hydroxide with 0.008 sodium hydroxide, 0.85 g of alcohol ester fs is obtained, the same quality as in Example 1. Example 8. RJ transformation -s-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-3B- (2,2-dibromovinyl) -cyclopropane-1B-carboxylic acid S 3-o.-cyano-3-phenoxybenzyl ester 2,2-dimethyl- 3ft- {2,2-dibromovinyl) -cyclopropane-lR-carboxylic acid. Starting from 1 g of ester of R3 under the conditions of Example 1, but replacing 2.5 cm of isopropanol with 2.5 cm of butanol, 0.80 g of alcohol ester tS of the same quality as in Example 1 is obtained. Example 9. The transformation of R -ot-diano-Z-phenoxybenzyl ester of 2,2-dimethyl-3 R- (2,2-dibromovinyl) -cylopropan-lR-carboxol acid to Cs-c-cyano-3-phenoxybenzyl ester 2,2- dimethyl-3 R- (2,2-dibromovinyl) -cylopropane-1J-carboxylic acid. Starting from 1 g of tR alcohol ester, under the conditions of Example 1, but replacing 2.5 cm of isopropanol with 2.5 cm of tert-butanol, 0.85 of a complex alcohol S of the same quality as in Example 1 is obtained. Example 10. Conversion R-aL-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-3 R- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid in C5-o1-cyano-3-phenoxybenzyl ester of 2,2-dimethyl- ZR- {2,2-dibromovinyl) -cyclopropan-11 -carboxylic acid. In a mixture of 2 cm-acetonitrile and 0.5 cm of water, 1 g of alcohol ester R is dissolved, 0.25 cm of an aqueous solution of ammonium hydroxide is added, the mixture is shaken for 18 hours at 20 ° C, the precipitate formed is sucked off, acetyl nitrile containing 25% water, drying and get 0.87 g of ester of alcohol tS of the same quality as in example 1. Example 11. The transformation of fRJ-ei-cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-3R- (2I2-dibromovinyl) I -cyclopropane-1H-carboxylic acid in fS -o-cyano-3-phenoxybenzyl ester of 2.2- dimethyl-ZR- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid.: Starting from 1 g of ester alcohol a3g under the conditions of example 9, consumed 2.5 cm of tert-butanol, but replacing ammonium hydroxide 0.16 g three ethylamine, get 0.8 g of ester of alcohol Cs jToro the same quality as in example 1. Example 12. Conversion of-oC-cyano-Z-phenoxybenzyl ester 2,2-dimethyl-S- (2,2-dibromovinyl) -cyclopropan-1 R-carb new acid tS D-ei-cyano-3-phenoxybenzyl 2,2-dimethyl-ZR- (2,2-dibromovinyl) cyclopropane-1 R-carboxylic acid. Starting with 1 g of an alcohol ester R under the conditions of Example 8 when consumed. 2.5 cm of butanol, but the ammonium hydroxide ammonium hydroxide is 0.11 g of pyrroldine; 0.8 g of alcohol ester Sj of the same quality as in Example 1. Example 13. Conversion of R, S —oL-cyano-3- 2,2-Dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid phenoxybenzyl ester in S -o-cyano-3-phenoxybenzyl 2,2-dimethyl-3R- (2,2-dibrominyl) -cyclopropane-1P-carboxylic acid. 105 g of CR.S 3-C-cyano-3-phenoxy-benzyl ester of 2,2-dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-1-carboxylic acid Co-Sv - 1%, chloroform), and Cof3 + 14 (with 1% benzene) is dissolved in 262.5 dM isopropanol. To the solution was added 15 cm of an aqueous solution of ammonium hydroxide, shaken for 18 hours at 20 ° (b), the resulting residue was separated by suction, washed with 105 cm of iso-, propanol, dried, and 95.1 g of S 3-O1-cyano were obtained -3-phenoxybenzyl 2,2-dimethyl-3R- {2,2-dibroquinyl) cyclopropane-1R-carboxylic acid ester. M.p. 100®C, + 60.5 ° (with 1%, benzene) of the same quality as in Example 1. Example 14. Conversion of tR.S-oh-cyano-3-phenoxybenzyl ester 2, 2-dimethyl- 3R- (2 2-Dibromovinyl) -cyclopropane-1H-carboxylic acid in 2,2-dimethyl-3R-{2,2-bromovinyl) -cyclopropane-1B-carboxylic acid s 3-o1-cyano-3-phenoxybenzyl ester, B 2 , 5 cm of isopropanol injected 1 g of ester of racemic alcohol
     1, Sj, 0.30 cm of an aqueous solution of ammonium hydroxide is added, shaken for 20 hours at 20 ° C, the precipitate is separated by suction, washed with 1 cm of isopropanol, dried, and 0.9 g of alcohol S is obtained. ., as in example 1.
    Example 15. The transformation of t, R | S -oL-cyano-Z-phenoxybenzyl ether. 2,2-Dimethyl-ZR- (2,2-dibromovinyl) -cyclopropane-1K-carboxylic acid in Cs -o cyano-3-phenoxybenzyl ester 2,2-dimethyl-3H-12,2-dibromovyl) -cyclopropane- 1K-car6onic acid ™ - 3
    1 g is introduced into 2.5 cm of isopropanol.
    ester of racemic alcohol LR, S, 0.16 g of triethylamine is added, shaken for 15 hours at 20 ° C, the resulting precipitate is separated by suction, washed with 1 cm of isopropanol (Dried and get 0.87 g of ester SJ of the same alcohol quality, as in example 1.
    Example 16. The transformation of K75 -o; - 2,2-dimethyl-WH- (2,2-dibromovinyl) -cyclopropane-1H-carboxylic acid cyano-3-phenoxybenzyl ester into J-cyano-3-phenoxybenzyl ester s 2,2-dimethyl-3B- (2 2-dibromovinyl) -cyclopropane-1R-carboxylic acid.
    1 g of the ester of racemic alcohol CR, S3 is added to 2.5 cm of isopropanol, 0.32 g of triethylamine is added, the mixture is shaken at 20 ° C for 15 hours, the precipitate is separated by suction, washed with 1 cm of isopropanol, dried and obtained 0.9 g of ester alcohol tS of the same quality as in example 1.
    Example 17, the Conversion of R, 5 l-dL-cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-3K- (2,2-dibromovinyl) -diklopropan-1R-carboxylic acid in 5-o.-cyano-13-phenoxybenzyl 2,2-dimethyl-3H- (2,2-dibromovinyl).-cyclopropane-lR-carboxylic acid ester,
    1 g is introduced into 2.5 cm of isopropanol. racemic alcohol ester R, S, add 0.32 g of triethylamine, shake for 15 hours at 20 ° C, separate the precipitate by suction, wash it with 1 cm of isopropanol, and dry to obtain; 0.9 g of ester alcohol CS3 are of the same quality as in example 1,
    Example 18. Conversion, 5 -Y-cyano-4-phenoxybenzene ester of 2,2-dimethyl-ZR-2,2-dibromvinyl) -cyclopropane-1R-carboxylic acid to 23 with-cyano-3-phenoxybenzyl ester 2,2 -dimethyl-3R- (2,2-dibromovinyl) -cyclopropan-1 R-carboxylic acid.
    1 g of ester of racemic alcohol is introduced into 2.5 cm3 of isopropanol. 0.13 g of morpholine is added, (shake for 96 hours at, the precipitate is separated by suction, washed with 1 cm3 of isopropanol, and dried to give 0.9 g ester alcohol CS of the same quality as in example 1.
    Example 19. Conversion of t R, S} -, o1-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-3 R- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid to Cs3 Cyano-3-phenoxybenzyl ester 2, 2-dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-1 R-carboxylic acid.
    2.5 cm isopropanol injected with 1 g of, 2,25-dimethyl-3R- (2,2-dibromovinyl) -cyclopropane-1 of R-carboxylic acid, 5U-o1-cyano-3-phenoxybenzyl ester, 0.008 g of sodium hydroxide is added, shaken 18 h at 20 ° C, the precipitate formed is isolated with suction, washed with 1 cm of isopropanol, dried and obtained 0.85 g of alcohol of ester quality, as in Example 1.
    Example 20. Conversion With R, S J-ct-cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2,2-dibromovinyl) -cyclopropan-1 R-cad bonsic acid in S; 3-o-cyano 2,2-Dimethyl-3 R- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid -3-phenoxybenzyl alcohol.
    1 g of tRpS ester of racemic alcohol is dissolved in a mixture of 1 cm of acetonitrile and 0.5, 0.15 cm of an aqueous solution of ammonium hydroxide is added, shaken for 17 hours, the precipitate is separated by suction, washed with acetonitrile containing 25% water, dried and get 0.87 g of ester alcohol CS of the same quality as in example 1..
    Example 21. The transformation of a mixture of t R And-o-Cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2,2-dibromovinyl) -cyclopropan-1 R-carboxylic acid and ES n-ot-cyano-Z- 2,2-dimethyl-3 phenoxybenzyl ester. R- (2,2-dibromovinyl) -cyclopropan-1 R-carboxylic acid containing more than 50 wt.% alcohol ester f ..
    but). Obtaining a mixture of complex ester alcohol B} and alcohol and Cs. Introduced 10. g. B, 5-c1-cyano-3-phenoxybenzyl 2,2-dimethyl-3R-t2, 2-dibromovInyl) cyclopropane-lR-carboxylic acid 0 ° -1 ° (with 1% chloroform) and NiP + 14 ° (with 1% benzene) in 20 cm of isopropanol, shaken for 18 hours at 20 ° C, the precipitate formed is sucked off, washed with 10 cm of isopropanol, dried and 4 g of complex is obtained.
    alcohol ester, m.p. HY- (with 1% benzene).
    The filtrate and washings are combined and a solution is obtained which contains 5 g-J-o1-cyano-3-phenoxy-benzyl fir 2.2-dimethyl-3- (2,2-dibromovinyl) -cyclo-propan-1R-carboxylic acid and 1 g C83- "1-cyano-3-phenoxybeneyl ester 2., 2-dimethyl-ZR- (2 2-dibromovinyl) -cyclopropan-1 R-cabonic acid.
    b). The transformation of a mixture of complex. alcohol ester CRJH ester alcohol S 3 ester alcohol S.
    To solution. L is added 0.8 cm3 of an aqueous solution of ammonium hydroxide, shaken for 20 hours, the precipitate is isolated by suction, washed with 5 cm of propanol, dried, and 4.5 g of Csj-d-cyano-3-phenoxybenzyl ester 2 are obtained , 2-dimethyl-3 R- (2,2-Dibromovinyl) -cyclopropane-lR-carboxylic acid. M.p. , roij | «+ 60 ° (with 1%, benzene) of the same quality, in example 1. or 13.
    Example 22. Conversion of Rjf-cC-cyano-Z-phenoxybenzyl ester-2, 2-dimethyl-ZR- (2,2-dichlorovinyl) -cyclopropan-lR-carboxon acid to Us-c-cyano-3-phenoxybenzyl ester. 2,2-Dimethyl-ZR- (2,2-dichlorovINIL) -cyclopropane-lR-carboxylic acid.
    but). Obtaining ester alcohol structure R.
    10 g of the ester of racemic alcohol tR..i ° + 16.5 ° Vc 10% | benzene) are subjected to chromatography on silica gel, spilled with a mixture of petroleum ether (mp 40–70 C) and isopropyl ether (85-15), to give are 3 g of C L-S-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-ZR- {2,2-dichloro, vinyl) -dipropane-lR-carboxic acid foLj2 (-) 31, (with 1% benzene ) or d3-21.5 ° (with 1%, chloroform).
    b). Conversion of the CS structure to an alcohol ester.
    To 60 g of R j-ot-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-3R- (2,2-dichlorovinyl) -cyclopropane-lR-carboxylic acid -31 1c 1%, benzene) or (- 21, 5 (with 1% chloroform), prepared under the conditions described in paragraph a), is added 120 cm of isopropanol, and then 9 cm of an aqueous solution of ammonium hydroxide, cooled to 0 ° C, shaken for 48 hours at OC, isolated the precipitate formed is sucked washed
    30 cm of isopropanol at l (-) 20C, cy-shat and get 48i, 5 J-cyano-3-phenoxybenzyl O 2,2-dimethyl-3R- {2,2-dichlorovinyl) -cyclopropane-lR-carboxylic acid ester. TP pl 6 OC
    tci.l | j 1%, benol) or
    ten
    and.
    1% chloroform
    +34
    Example 23. The transformation of 1 R, S3-h) -cyano-3-phenoxybenzyl ester; 2,2-dimethyl-WH- (2,2-dichlorovInil) -cyclopropane-lR-carboxylic acid in tS -1-cyano-3- 2,2-Dimethyl-3R-f2,2-dichlorovinyl) -cyclopropane-1R-phenolic acid phenoxybenzyl ester
    To 600 g of the ester of the racemic alcohol CR.S +16.5 (with 10% benzene, add 1200 cmtnzopropanol, and then injected into the resulting solution 90 cm {aqueous solution of ammonium hydroxide, cooled to, shaken for 48 hours at this temperature, aspirated from the precipitate, washed it in 300 cm - isopropanol at C-), dried and get 485 g of 53-o1-cyano-3-phenoxy-benzyl ether, 2,2-dimethyl-R- (2,2-dichlorovinyl) - cy.klopropan-1 R-carboxylic acid. T. pl. 6 0 ° С 01
     +660 (with 1%, b; anzol) or +34 (with 1%, chloroform).
    Calculated,%: C, 63.48; H, 4.60; N 3.36; CJ 17.03.
    C22 H-DOMS 12 / 416.28.
    NID,%: C 63.7; H 4.6; N 3.4, I 17.1 ....
    example 24. Transformation | R, S -oi-cis-3-phenoxybenzyl 2,2-dimeTyl-3V-12, 2-dibromovinyl) -cyclopropan-lR-carboxylic acid in Sj-ot-cyano-Z-phenoxybenzyl 2,2-dimethyl-ester ZR- (2,2-dibromovinyl) -cyclopropane-lR-carboxylic acid.
    10 g of jГR, S ;; dissolve; t-cyano-3-. -phenoxybenzyl 2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropane-1R-1-t-baseone acid, fdL3 0 °, -1 (with 1% chloroform) and Co.32o + 14 ° (with 1% , benzene) in 25 cm of isopropanol, 0.8 g of diisopropylamine is added, shaken for 6 hours at and then 2 hours at 0 ° C, the precipitate is sucked off, crystallized in 2 volumes of isopropanol, and 8.04 rCsJ-ot-cyano are obtained -Z-phenoxybenzyl 2,2-dimethyl-3R- (2, 2-dibromovinyl) -cyclopropane-lR-carboxylic acid ester. Cot} + 57 ° (with 4%, toluene).
    Example 25. Conversion of CR-, S J-oL-cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclo-propane-lR-carboxyl acid to CS 3-c6-cyano-3- 2,2-Dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropane-lR-carboxylic acid phenoxybenzyl ester.
    Under the conditions of example 24, but embedded within 48 hours with, the same product yield of the same quality is obtained as in example 24.
    Example 26. The transformation of RtSJ-oL-cyano-3-phenoxybeneyl fir 2,2-dimethyl-3- (2,2-dibromvil) -cyclopropane-lR-carboxylic acid in f S -c "cyano-3-phenoxybeneyl ether 2, 2-dimethyl-3- (2,2-dibromovinyl) -cyclopropane-lR-carboxylic acid.
    Under the conditions of Example 24, but using isopropanol containing 3.5% voi and shaking 8 hours at 20.degree. C., 8.16 g of SJ-oi-cyano-3-phenoxybeneyl ether are obtained. 2, 2-dimethyl- HK- (2, 2-dibromovinyl) -cyclopropane-1R-carboxylic acid Coij |, +56.5 ° (with 4%, toluene),
    Example 27. Conversion of R, 5-a1-cyano-3-phenoxybenzyl ester 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropane-lR-carboxylic acid to S L-Cyg-cyano-Z-phenoxybenzyl ester 2, 2-dimethyl-ZR-12-, 2-dibromovinyl) -cyclopropane-1K-carboxylic acid.
    10 g of R, S J-oi-cyano-3-phenoxybenzyl 2,2-dimethyl-3R- (2, 2-dibromovinyl) -cyclo-nponaH-1R-carboxylic acid Wj) o are dissolved
     0 ° -1 ° (with 1%, chloroform;) and Cot3p
     4-14 ° (from 1%, benzene in 25 cm of isopropanol, 1.39 g of piperidine is added, shaken for 18 hours at 20 ° C, the precipitate is sucked off, washed with isopropanol, dried and 8.6 g of SJ-ct are obtained - cyano-3-phenoxybenzyl 2,2-dimethyl-3R-i-2, 2-2-dibromovinyl) -cyclopropane-lR-carboxylic acid, identical with the product obtained in examples 24-25.
    | h,
    Example 28. The transformation of R, S -C1-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid s J-oi-cyano-Z-phenoxybenzyl ester 2,2-Dimethyl-R- (2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid,
    Under the conditions of Example 27, but replacing 1.39 g of piperidine with 1.66 g of diisopropylamine, and starting from the 10th ester of RS alcohol, 8.85 g of ester S of the same quality as in Examples 24-27 are obtained. .
    Example 29. Conversion of CR, S) -o-cyano-3-phenoxy-benzyl ester of 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropane-1 R-carboxylic acid to t S -o-cyano-3- 2,2-dimethyl-3-R- (2, 2-dibromovinyl) -cyclopropan-1 R-Kap phenoxybenzyl ester;
    Under the conditions of Example 27, but replacing piperidine with 2.7 g of ephedrine, it is stirred for 24 hours at and starting from 10 g of ester of R.S. alcohol, 8.7 g of ester of alcohol SJ are obtained.
    the same quality as in examples 24-28.
    Example 30. The transformation of R, S J-ot-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropane-1R-carboxylic acid in S J-ci-cyano-Z-phenoxybenzyl
    2,2-Dimethyl-3R- (2, 2-dibromo-vinyl) -cyclopropane-1R-carboxylic acid ester.
    Analogously to Example 24, but replacing 0.8 g of diisopropylamine with 4.4 g of triethylenediamine. After 72 hours of shaking, 7.5 g of ester alcohol fsj of the same quality as in Examples 24-29 are obtained.
    Example 31. The transformation of R, S Z-N-cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2, 2-dibromo. Vinyl) -cyclopropan-1R-carbonoBOY
    acids in C S 3 -O-cyano-3-phenoxybenzyl 2,2-dimethyl-3R- {2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid ester.
    10 g of alcohol ester R, 5
    dissolved in 25 cm. isopropanol, 0.23 g of potassium tertiary butylate is added, shaken for 18 h and 7.7 g of ester alcohol CS3 of the same quality as in Examples 24-30 are obtained.
    Example 32. Transformation tR S J-ci-cyano-3-phenoxybenzyl ester of 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropane-1 R-carboxylic
    acids in Cs -o-cyano-3-phenoxy-benzyl ester 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropane-1R-carboxylic acid.
    According to Example 31, but replaced
    0.23 g of potassium tert.-butylate 0.34 g of sodium isopropylate and stirring
    24h when, get 7.3 g of ester alcohol S j the same quality as in examples 24-31.
    Example 33. Transformation
    tR, S-cyano-3-phenoxybenzyl ester of 2,2-methyl-3R- (2, 2-dibromovinyl) -cyclopropane-1R-carboxylic acid in CS 3-c6-cyano-3-phenoxybenzyl ester of 2,2-dimethyl- 3R- {2,2-dibromovinyl) -cyclopropane-1K-carboxylic acid.
    10 g of I, S -Y-cyano-3-phenoxyben zyl ester, 2,2-dimethyl-ZR- (2, 2-dibromovinyl) -cyclopropan-1 of R-carboxylic acid o1z | 0 ° - (2) 1 ° (with 1%, chloroform) and +14 (with 1%, benzene) in
    25 cm of isopropanol containing 3.5% water is added 0.84 g of benzylamine,
    stirred for 23 hours at, the precipitate formed is filtered off with suction, it is crystallized in 2 volumes of isopropanol and 8.25 g are obtained (α-cyano-3-fe-1 I noxibenzyl ester 2,2-dimethyl-g
    ji3R- (2, 2-dibromovinyl) -cyclopro13 pan-1L-carboxylic acid +57 (with 4%, lofiyon. Prper 34, Conversion of CR S N-Cyano-3-phenoxybenzyl ester 2,2-dimethyl-3K- I2,2-dabrmvinyl) -cyclopropane-1k-carboxylic. acids in S (2,2-dimethyl-3K- (2,2-dibromovinyl) cyclopropane S-6-6-phenoxybazyl ester; -1R-carboxylic acid; 10 g Cft.Sjs 25 cm of ester is dissolved. Isopropanol is added 1 , 20 g of n-butylamine, shaken for 24 hours while the precipitate formed is filtered off with suction, washed and dried, and 9.0 g of ester of alcohol Cs 3 of the same quality as in Examples 24-33 are obtained. 35, g Conversion of 2,2-dimethyl-AY (2, 2-dibromovinyl) -cyclopropan-1H-carboxylic acid C R-S o-cyano-3-phenoisibenzyl sulphate ester into t S oC-cyano-Z-phenoxybenzyl 2,2-dimethyl-3R-2, 2-dabromvinip) -c new ester Clopropane-1K-carboxylic acid, Under the conditions of Example 33, but using 1.20 g of secondary butylamine t or 1-methylpropyl aiNBiH), and shaking 24 hours at 20 ° C, 9.1 g of alcohol ester are obtained {Sjioro qualities, as in examples 24-34, Example 36, the Transformation of C Z-S-Cyano-Z-phenoxybenzyl ester of 2,2-dimethyl-ZK-12, 2-; schromvinyl) -CYCLOPROP &amp; H-1 R-carbsanes Acids in ts J-ot-cyano-3-phenoxybenzyl 2,2-dimethyl-3B- (2,2-dibrominyl) -cyclopropane-1R-carboxylic acid. Under the conditions of 31, but replacing 0.23 g of tert, potassium butylate with 0.64 cm of 40% aqueous solution of the hydroxide of fabutylammonium, after 24 h, shaking at 8.4 g of ester alcohol tSX of the same quality, as in examples 24-35. Example 37. Conversion of 2,2-dimethyl-3R-I2,2-dibromovinyl) -cyclopropan-1R-carboxylic acid -dL-diano-Z-phenoxybenzyl ester of 2,2-dimethyl-3R-I2,2-dibromovinyl) -cyclopropane-1R-carboxylic acid to ester 2.2 -dimethyl-3R-12,2-dibromovyl) -cyclopropane 1R-carboxylic acid. 10 g of CR, S3 alcohol ester is dissolved in 25 cm of isopropanol, 10 g of AMBERLIT resin (RA 400 styrene-divinyl benzene styrene polymer) added, 20/50 mesh size, which is pre-washed with diluted to 1/3 perchloric acid, water to neutral Wednesday 1n. sodium hydroxide solution, and then with water, shaken for 24 hours at 20 ° C, the precipitate is sucked off (a mixture of resin and ester I of alcohol ts}}, methylene chloride is added, shaken, filtered, the concentrate is concentrated and the mixture is dried 7.8 g of ester alcohol ester, of the same quality as in Examples 24-36, Example 38, Conversion t R, S - "A-cyano-3-phenoxy-benzyl ester 2,2-dimethyl-3R- (2 , 2-dibromovinyl) -cyclopropane-1-carboxylic acid in C3.} O-Cyano-3-phenoxybenz1Sulfur ester of 2,2-dimethyl-3R- (2., 2-dibromovinyl) -cyclopropane-lR-carboxylic acid,. B the conditions of example 37, but 10 g of AMBERLIT 1R 45 resin (time | Mer in mesh, 20/50.), after shaking for 72 hours at 20 ° C, 8.1 g of alcohol ester of t S of the same quality as the products are obtained, , obtained in 24-37 cimers, Example 4, Transformation t RS of J-ot-cyano-3-phenoxybenzyl 2,2-dimethyl-3R- (2, 2-dibromovinyl) -cyclopropan-1R- ester carboxylic acid in ts 3-bA-cia-but-3-phenoxybenzyl 2,2-dimethyl-3ft- (2,2-dibromovinyl) -cyclopropane-1K-carboxylic acid ester. Analogously to Example 37, but using 10 g of DOVEX A resin (1x8 (mesh size 200/400), which is a highly alkaline anion exchange resin, with an active trimethyl enemylammonium group after 72 hours of shaking at 20, get an alcohol ester tSl, the same quality as the quality of the products obtained in examples 24-38, Example 40, the Conversion of R, S -OC With cyano-3-phenoxybenzyl ester of 2,2-dimethyl-SV- (2, 2-dibromovinyl) - cyclopropane-1K-carboxylic acid in Is 3-e-cyano-3-phenoxybenzyl 2,2-dimethyl-3K- (2,2-dibromoyl) -cyclopropane-1R-ka ester rboic acid. Analogously to example 37, but consumed 10 g of liquid Amberlite L A1 (high molecular weight amines of the company ROM e XAAZ viscosity 7 cP at. 25 s), after 72 h shaking nojj; 8.9 g of alcohol ester t S of the same quality as the quality of the products obtained in examples 24-39. Example 41, Conversion K, $ 2- (3,1-phenoxybenzyl ester of 2,2-dimethyl-W3- (2, 2-dibromovinyl) -cyclopropan-lR-carboxylic acid in CS -eii-cyano-3-phenoxybenzyl ester, 2,2-dimethyl-3K- (2,2-dibromovinyl U-cyclopropane-1R-carboxylic acid, under conditions analogous to example 37, but 3.75 g of liquid upotr AMVERLITA A2, having a viscosity of 18 cps at after 18 hours shaking at 20 ° C to give 8.1 g of the ester alcohol IS J of the same quality. “The quality of the products obtained in the example, pax 24-40.
    Example 42 Conversion of 2,2,3-dimethyl-3 R-12,2-dibromvin Il) cyclopropane-1K carboxylic acid C R, S 3- / -Cyano-3-phenoxybeneyl ester of 2,253-e1-cyano-3-phenoxybenzyl 2,2-dimethyl-3- (2,2-dibroivinyl) -cyclopropane-1L-carboxylic acid ester ..
    Under the conditions of Example 27, but replacing the isopropanol with isopropanol containing 3.5% water, and after shaking for 24 hours at 20 ° C, 8.95 g of tS ester is obtained.
    权利要求:
    Claims (1)
    [1]
    1. Elliott M.Synthetic InsectIcld with a new oreles of activity. Nature, 248, 1974, p. 711 (prototype).
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    优先权:
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