Optically active N-.alpha.-fluoroacryloylamino acid polymers for the resolution of racemates

• US 5,292,924 A
• Filed: 11/13/1992
• Issued: 03/08/1994
• Est. Priority Date: 07/03/1990
• Status: Expired due to Term

• Current Assignee: Daicel Chemical Industries Limited
• Original Assignee: Bayer AG
• Inventors: Grosser, Rolf, Arlt, Dieter, Lange, Walter, Bielefeldt, Dietmar, Bomer, Bruno
• Primary Examiner(s): Rizzo, Nicholas S.
• Assistant Examiner(s): GUPTA, YOGENDRA N
• Application Number:
  US07/976,246
• Time in Patent Office: 480 Days
• Field of Search: 560/38, 560/39, 560/40, 560/41, 560/43, 560/121, 560/122, 560/123, 560/155, 560/170, 564/152, 564/155, 564/156, 564/160, 540/608, 546/225, 546/245, 548/530, 558/14, 558/254, 526/245, 526/248
• US Class Current: 560/41
• CPC Class Codes: B01D 15/3833 Chiral chromatography
• CPC Class Codes: B01J 20/261 obtained by reactions only involving carbon to carbon unsaturated bonds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F
• CPC Class Codes: B01J 20/265 modified or post-treated polymers polymer carriers or substrates subjected to further impregnating or coating B01J20/3208
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 20/29 Chiral phases
• CPC Class Codes: B01J 20/327 Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: C07C 233/49 having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 2602/42 the bicyclo ring system containing seven carbon atoms
• CPC Class Codes: C08F 20/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide

Abstract

α-Fluoro-substituted N-acryloylamino acid derivatives of the formula ##STR1## are used to make polymers optionally for chromatographic resolution of racemates into their enantiomers. The fluorine atom improves performance in many instances.

Claims

1. An optically active polymer containing at least 40 mol % of structural units of the formula (V) ##STR10## in which R₁ represents a straight-chain or branched C₁ -C₈ -alkyl, a C₇ -C₁₂ -aralkyl, a C₃ -C₁₀ -cycloalkyl, a C₆ -C₁₄ -aryl or a furyl, thienyl or pyridyl radical, which are unsubstituted or substituted by benzyloxycarbonyl, alkoxycarbonyl of up to 6 C atoms, hydroxyl, alkyl, cycloalkyl or alkoxy each having up to 6 C atoms, halogen, phenoxy, benzoxy, acylamino of up to 8 C atoms or by carbonylalkoxy of up to 6 C atoms,

R₃ represents hydrogen or C₁ -C₄ -alkyl or together with R₁ forms a tri- or tetramethylene group,

X is oxygen or an NR group, in which

R₄ represents hydrogen or straight-chain or branched C₁ -C₄ -alkyl or together with R₂ and the nitrogen atom forms a 5- or 6-membered ring which is unsubstituted or substituted by an alkoxycarbonyl group of up to 6 carbon atoms or by one or two alkyl groups each having 1 to 4 carbon atoms, and

R₂ represents a straight-chain or branched C₁ -C₂₂ -alkyl, C₇ -C₁₂ -aralkyl, C₃ -C₁₀ -cycloalkyl, C₆ -C₁₄ -aryl or a terpenyl radical, each of which is unsubstituted or substituted by halogen, alkyl or alkoxy each having to 4 C atoms.

2. An optically active polymer according to claim 1 in the form of a crosslinked insoluble or swellable bead polymer or in a form in which it is bound to a finely divided organic support material.

3. A polymer according to claim 1, wherein ##STR11##

4. A polymer according to claim 1, wherein ##STR12##

5. A polymer according to claim 1, wherein ##STR13##

6. A polymer according to claim 1, wherein ##STR14##

7. A polymer according to claim 1, wherein

X is NR₄ and

R₄ represents hydrogen or straight chain or branched C₁ -C₄ -alkyl.

8. A polymer according to claim 1, wherein

X is NR₄ and

R₄ represents hydrogen or straight chain or branched C₁ -C₄ -alkyl or together with R₂ and the nitrogen atom forms a 6-membered ring which is unsubstituted or substituted by an alkoxycarbonyl group of up to 6 carbon atoms or by one or two alkyl groups each having 1 to 4 carbon atoms.

9. A method of resolving a mixture of optical isomers which comprises contacting said mixture with an adsorbent comprising an optically active polymer according to claim 1 thereby to adsorb said mixture, and separately eluting from said adsorbent the individual isomers of said mixture.