Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds

• US 5,198,429 A
• Filed: 12/03/1990
• Issued: 03/30/1993
• Est. Priority Date: 03/30/1988
• Status: Expired

• Current Assignee: Eagle Machinery Company
• Original Assignee: Eagle Machinery Company
• Inventors: Wenz, Gerhard, von der Bey, Eva, Konig, Wilfried, Lutz, Sabine
• Primary Examiner(s): GRIFFIN, RONALD
• Application Number:
  US07/585,117
• Time in Patent Office: 848 Days
• Field of Search: 536/103, 514/58, 435/280, 562/401, 210/632, 210/634, 210/635, 210/636
• US Class Current: 514/58
• CPC Class Codes: C07B 57/00 Separation of optically-active compounds
• CPC Class Codes: C08B 37/0012 Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof

Abstract

Substituted cyclodextrins of the general formula ##STR1## in which R² and R⁶ mean straight-chain or branched alkyl or alkenyl groups with 1 to 8 carbon atoms or cycloalkyl groups with 5 to 8 carbon atoms which can be the same or different, and

R³ represents a straight-chain or branched alkyl or alkenyl group, which can be the same or different to the residues R² and R⁶, with 1 to 8 carbon atoms or a cycloalkyl group with 5 to 8 carbon atoms, or

an acyl group with an optionally substituted, saturated or olefinically unsaturated aliphatic or cycloaliphatic or with an aromatic hydrocarbon residue with 1 to 8 carbon atoms, and

n=6 or 7,

a process for their production, and a process for the separation of chiral organic compounds by chromatographic separation processes in which the substituted cyclodextrins are used as stationary phase.

Claims

1. A substituted cyclodextrin of the formula ##STR3## in which R², R³ and R⁶ each independently is an alkyl or alkenyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, or

R³ may be an acyl group having 1 to 8 carbon atoms or an acyl group substituted with an aromatic hydrocarbon radical or a saturated or olefinically unsaturated aliphatic or cycloaliphatic radical having 1 to 8 carbon atoms, and n is 6 or 7,

with the exclusion of those compounds wherein R² =R³ =R⁶ =methyl, n=6 or 7, R² =R³ =R⁶ =ethyl, n=7, R² =R⁶ =allyl, R³ =methyl, n=7, R² =R⁶ =prop-1-enyl, R³ =methyl, n=7, R² =R⁶ =methyl, R³ =n-butyl, n=7, R² =R⁶ =methyl, R³ =benzoyl, n=7 and R² =R³ =alkyl or acyl, R⁶ =C>

4-alkyl.

2. A substituted cyclodextrin according to claim 1, wherein the alkyl and/or acyl groups have 3 to 6 carbon atoms.

3. A substituted cyclodextrin according to claim 1, wherein R², R³ and R⁶ are alkyl or alkenyl groups with 3 to 6 carbon atoms or R³ may be an acetyl group.

4. A substituted cyclodextrin according to claim 1, wherein R² and R⁶ each is a n-pentyl-group and R³ is an acetyl group.

5. A process for the production of a substituted cyclodextrin according to claim 1, which comprises dissolving an α

- or β

-cyclodextrin in an anhydrous solvent, adding a pulverized alkali hydroxide, and reacting the cyclodextrin with an alkyl halide.

6. A process according to claim 5, including the further step of reacting the product with an acylating agent in an anhydrous solvent containing an amine.

7. A process according to claim 5 wherein the anhydrous solvent is aprotic.

8. A process according to claim 6 wherein the anhydrous solvent is aprotic.

9. A process according to claim 16, 17, or 8 wherein the reactions are carried out under inert gas.

10. In the chromatographic separation of individual chiral organic compounds from a mixture by contacting the mixture with a stationary phase, the improvement which comprises employing as the stationary phase a substituted cyclodextrin according to claim 1.

11. A separation process according to claim 10, wherein the contact is made with the chiral organic compounds in gas phase.

12. A separation process according to claim 10, wherein the chiral organic compounds are enantiomers.

13. A separation process according to claim 12, wherein the enantiomers are selected from the group consisting of alcohols, polyols, 1,5-anhydro-alditols, hydroxy esters, aldols, lactones, spiro-acetals, amines, amino-alcohols, amino-acid esters and a trifluoroacetylation product of any of the foregoing.

14. A separation process according to claim 13, wherein the enantiomers are polyols selected from the group consisting of diols, polyols containing more than two hydroxy groups and monosaccharides.

15. A separation process according to claim 14, wherein the enantionmers are methylglycosides.