USRE36092E - Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds - Google Patents

Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds Download PDF

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USRE36092E
USRE36092E US08/526,141 US52614195A USRE36092E US RE36092 E USRE36092 E US RE36092E US 52614195 A US52614195 A US 52614195A US RE36092 E USRE36092 E US RE36092E
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carbon atoms
methyl
group
process according
cyclodextrin
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Wilfried Konig
Gerhard Wenz
Sabine Lutz
Eva von der Bey
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Macherey-Nagel & Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B57/00—Separation of optically-active compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—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

Definitions

  • the present invention relates to substituted cyolodextrins, to a process for their production, and to a process for the separation of chiral organic compounds by chromatographic separation processes, particularly gas chromatography, using the substituted cyclodextrins as stationary phase.
  • Substituted cyclodextrins are known, for example, from DE-OS 37 10 569, which is no prior publication, which describes the production of ultrathin films from these cyclodextrin compounds or an inclusion compound on the basis of the cyclodextrin compounds. These ultrathin films can be used, for example, as protective film for compounds which are sensitive to light and oxygen, or as carrier in chromatography.
  • Triethyl- ⁇ -cyclodextrin is described in Journal of Pharmaceutical Sciences (1987, 660).
  • Such a separation is almuost exclusively limited to enantiomers with amide, carbamate, oxime, or hydroxyl groups.
  • intermolecular hydrogen bridge bonds are built so that diastereomeric associates between chiral separation phase and chiral substrates are formed.
  • the enantiomers to be separated were mostly converted into derivatives with amide or carbamoyl functions.
  • R 2 and R 6 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
  • R 3 represents a straight-chain or branched alkyl or alkenyl group, which can be the same or different to the residues R 2 and R 6 , with 1 to 8 carbon atoms
  • 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
  • R 6 C> 4 -alkyl
  • a further solution. of the problem underlying the present invention is the provision of a process for the chromatographic separation of chiral compounds, particularly of enantiomers.
  • the substituted cyclodextrins according to the present invention permit a separation of enantiomers which is mainly caused by inclusion effects at the macrocyclic chiral cyclodextrins, and which--due to the separation mechanism which, compared to the separation phases according to the prior art, is completely different--can be employed even for tho se enantiomers not being able to form hydrogen bridges and therefore could not be separated on the chiral separating phases used until now.
  • the compounds according to the present invention on the one hand have the advantage of having a very high temperature stability of more than 200° C., on the other hand, the separation mechanism which--compared to the separation phases known until now--is different in most cases permits the conversion into very readily volatile derivatives, such as trifiuoroacetylated compounds, which in case of correspondingly low temperatures are cluted from the column.
  • substituted cyclodextrins consisting of 6 or 7 glucose rings and having as substituents R 2 , R 3 and R 6 the n-pentyl-group or as substituent R 3 the acetyl group and as R 2 and R 6 n-pentyl groups.
  • the products according to the present invention are produced in that at first ⁇ - or ⁇ -cyclodextrin is dissolved in an anhydrous solvent and reacted with an alkyl halide under addition of powdered alkali hydroxide.
  • This reaction stage can be conducted in such a way that optionally either the hydroxyl groups in 2 or 6-position or the three hydroxyl groups being in 2-, 3-, and 6-position are alkylated.
  • the 2,6-di-O-alkylated intermediate product is optionally isolated and reacted in an anhydrous solvent with an acylating agent, preferably an acid anhydride or an acid chloride, under the addition of a tertiary amine.
  • an acylating agent preferably an acid anhydride or an acid chloride
  • the crude products respectively obtained can be purified by column chromatography and isolated in pure form.
  • the characterization was carried out by 1 H- and 13 C-nuclear resonance spectroscopy, respectively, and by chemical degradation with subsequent analysis of the degradation products by combined gas chromatography and mass spectrometry according to P. MischnickLubbecke, W. A. Konig and M. Radeloff, Starch/Starke 39 (1987) 425.
  • Coating of the separating capillary columns with the substituted cyclodextrins according to the present invention is carried out according to W. A. Konig and K. Ernst, J. Chromatogr. 280 (1983) 135.
  • the capillaries filled with the separating phases according to the present invention are particularly suitable for the separation of, for example, enantiomers of diols, polyols, monosaccharides, methylglycosides, 1,5-anhydroalditols, hydroxy esters, alcohols, aldols, lactones, spiro acetals, amino alcohols, amines, amino-acid esters, and other chiral compounds which, if necessary, are trifluoroacetylated with trifluoroacetic acid anhydride in dichloromethane according to known processes and thus can be converted into volatile derivatives suitable for gas-chromatography.
  • FIGS. 1 to 10 demonstrate exemplary separations of enantiomers on the separating phases hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin (FIGS. 1 to 5 and 9), hexakis(2,6-di-O-pentyl-3-O-acetyl)- ⁇ -cyclodextrin (FIG. 10) and heptakis(2,6-di-O-pentyl-3-O-acetyl)- ⁇ -cyclodextrin (FIGS. 6 to 8), respectively.
  • the Figures clearly show the even baseline of the chromatograms and the excellent separation efficiency of the separating columns filled with the substituted cyclodextrins according to the present invention.
  • FIG. 1 Separation of enantiomers of a mixture of racemic diols after trifluoroacetylation, 40 m-glass capillary with hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin; 48° C., 5 min. isothermal, then 2°/min.
  • FIG. 2 Separation of enantiomers of isopropylidene glycerol after trifluoroacetylation. 40 m-glass capillary with hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin; 70° C.
  • FIG. 3 Separation of enantiomers of glyceric acid and tarric acid after esterification with methanolic HCl and trifluoroacetylation; 40 m-glass capillary with hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin; 90° C.
  • FIG. 4 Separation of enantiomers of D- and L-glucose after trifluoroacetylation. 40 m-hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin-glass-capillary; 115° C.
  • FIG. 5 Separation of enantiomers of 2-chloro-1-phenylethanol and 2-bromo-1-phenylethanol after trifluoroacetylation. 40 m-glass capillary with hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin, 110° C.
  • FIG. 6 Separation of enantiomers of amines and amino alcohols after trifluoroacetylation. R-enantiomers are eluted first. 45 m-glass capillary with heptakis(2,6-di-O-pentyl-3-O-acetyl)- ⁇ -cyclodextrin; 140° C., 2°/min.
  • FIG. 7 Separation of enantiomers of chiral pharmaceuticals (amphetamine, mexiletin, pholedrine, tranylcypromine). 45 m-glass capillary with heptakis(2,6-di-O-pentyl-3-O-acetyl)- ⁇ -cyclodextrin; 175° C.
  • FIG. 8 Separation of enantiomers of ⁇ -amino butyric acid, ⁇ -amino butyric acid, and ⁇ -aminoisobutyric acid after esterification with methanolic HCl and trifluoroacetylation.
  • FIG. 9 Separation of enantiomers of spiro-acetals. 40 m-glass capillary with hexakis(2,3,6-tri-O-pentyl)- ⁇ -cyclodextrin; 100° C.
  • FIG. 10 Separation of enantiomers of ⁇ -lactones, 38 m-glass capillary with hexakis(3-O-acetyl-2,6-di-O-pentyl)- ⁇ -cyclodextrin; 150° C.
  • Sedimentation of a white precipitate indicates the start of the reaction.
  • 18.5 g (120 mmol) n-pentylbromide and 4.8 g (120 mmol) sodium hydroxide are each added daily.
  • the reaction mixture is poured on 1.5 l water and extracted twice with 500 ml t-butyl-methyl ether.
  • the combined ether phases are washed with water and conc. solution of sodium chloride and are concentrated under vacuum.
  • the residue, a yellow oil is dried under vacuum (0.05 torr) at 70° C. for 16 hours.
  • the volumes of the fractions to some extent depend on the water content of the silica gel. After distilling off the solvent from fraction II and drying under vacuum (0.05 torr) at 70° C., 7.42 g of the pure product in form of a colorless glass are obtained.
  • the crude product so obtained is dissolved in 300 ml tetrahydrofuran (Fluka, dried over sodium/benzophenone) under protective gas (nitrogen). This solution is added to 4.3 g (180 mmol) sodium hydride (Fluka, 80% suspension in mineral oil). Adherent mineral oil is removed by washing the sodium hydride with tetrahydrofuran.
  • n-pentyl bromide Fluka
  • reaction mixture is poured on 500 ml water, and the tetrahydrofuran is distilled off.
  • the residue is extracted twice with 200 ml t-butyl-methyl ether each.
  • the unified ether phases are washed with water and conc. solution of sodium chloride and boiled down under vacuum. The yellow, oily residue is dried under vacuum (0.05 torr) at 70° C. for 16 hours.
  • the crude product is fractionated by column chromatography over 500 g silica gel Si6O (Merck, 40-63 ⁇ m).
  • silica gel Si6O Merck, 40-63 ⁇ m
  • solvent petroleum ether boiling range 60°-95° C.
  • t-butyl-methyl ether blending ratio 85:15 (v/v).
  • the following fractions are obtained:
  • Heptakis(2,6-di-O-pentyl-3-acetyl)- ⁇ -cyclodextrin 1.06 g (0.5 mmol) heptakis(2,6-di-O-pentyl)- ⁇ -cycludextrin (produced according to the direction of Exanple 2) are dissolved with 21 mg (0.175 mmol) 4-dimethylamino pyridine (Merck) in 5 ml CH 2 Cl 2 (Aldrich; dried by distillation over diphosphorus pentaoxide) over nitrogen as protective gas.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
US08/526,141 1988-03-30 1989-03-25 Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds Expired - Lifetime USRE36092E (en)

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US08/526,141 USRE36092E (en) 1988-03-30 1989-03-25 Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds

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DE3810737A DE3810737A1 (de) 1988-03-30 1988-03-30 Substituierte cyclodextrine
DE3810737.6 1988-03-30
PCT/EP1989/000332 WO1989009235A1 (en) 1988-03-30 1989-03-25 Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds
US07/585,117 US5198429A (en) 1988-03-30 1989-03-25 Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds
US08/526,141 USRE36092E (en) 1988-03-30 1989-03-25 Substituted cyclodextrins and process for chromatographic separation of chiral organic compounds
US18936193A 1993-12-30 1993-12-30

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DE4009621A1 (de) * 1990-03-26 1991-10-02 Henkel Kgaa (alpha) -cyanacrylatklebstoffzusammensetzungen
EP0494967A4 (en) * 1990-08-08 1993-03-17 Advanced Separation Technologies, Inc. Chiral separation media
US5491223A (en) * 1991-02-28 1996-02-13 Daicel Chemical Industries, Ltd. Polysaccharide derivative and separating agent
US5959089A (en) * 1993-07-19 1999-09-28 Hannessian; Stephen Amino-cyclodextrin syntheses
CA2100820C (en) * 1993-07-19 1999-11-02 Stephen Hanessian Amino-cyclodextrin and related structures
EP0748247B1 (en) * 1994-02-22 2012-06-20 The Curators Of The University Of Missouri Macrocyclic antibiotics as separation agents
DE4414128A1 (de) * 1994-04-22 1995-10-26 Consortium Elektrochem Ind Teilweise acylierte beta-Cyclodextrine
US5985772A (en) 1994-06-23 1999-11-16 Cellresin Technologies, Llc Packaging system comprising cellulosic web with a permeant barrier or contaminant trap
US5928745A (en) * 1994-06-23 1999-07-27 Cellresin Technologies, Llc Thermoplastic fuel tank having reduced fuel vapor emissions
US5492947A (en) 1994-06-23 1996-02-20 Aspen Research Corporation Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative
US5776842A (en) 1994-06-23 1998-07-07 Cellresin Technologies, Llc Cellulosic web with a contaminant barrier or trap
FR2741079B1 (fr) * 1995-11-13 1997-12-26 Oreal Nouveaux composes, derives de cyclodextrine et leur utilisation, notamment en cosmetique
US5882565A (en) 1995-12-11 1999-03-16 Cellresin Technologies, Llc Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative
JP3865436B2 (ja) * 1996-07-11 2007-01-10 塩水港精糖株式会社 分岐シクロデキストリンの製造方法
FR2755123B1 (fr) * 1996-10-28 1998-11-20 Commissariat Energie Atomique Purification de l'eau au moyen de cyclodextrines
KR100435426B1 (ko) * 1996-11-29 2004-08-16 주식회사 포스코 구조 이성질체의 분리에 유용한 6-디메틸옥틸실릴-2,3-디에틸-베타-시클로덱스트린 및 그 제조방법
KR100411289B1 (ko) * 1996-11-29 2004-02-14 주식회사 포스코 회전장애 이성질체의 분리에 유용한 6-알릴디메틸실릴-2,3-디에 틸-베타-시클로덱스트린 및 그 제조방법
US6017458A (en) * 1997-08-27 2000-01-25 National University Of Singapore Separating materials for chromatography and electrophoresis applications comprising regiodefined functionalised cyclodextrins chemically bonded to a support via urethane functionalities
FR2767834B1 (fr) * 1997-08-29 1999-12-03 Inst Francais Du Petrole Mono et di-derives de cyclodextrines, leurs synthese et purification et leur utilisation en support
US6391862B1 (en) * 1997-10-14 2002-05-21 The Texas A&M University System Chiral resolving agents for enantioseparations
JP2002517521A (ja) * 1998-05-29 2002-06-18 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ アシル化アルキル化シクロデキストリン誘導体及びその薬物担体としての使用
US20040129640A9 (en) * 2002-01-18 2004-07-08 National University Of Singapore Materials comprising polymers or oligomers of saccharides chemically bonded to a support useful for chromatography and electrophoresis applications
US7589233B2 (en) * 2003-07-29 2009-09-15 Signature R&D Holdings, Llc L-Threonine derivatives of high therapeutic index
CN103406113B (zh) * 2013-07-11 2015-02-25 哈尔滨工程大学 固载化型β-环糊精衍生物类手性固定相的制备方法
CH710884A1 (de) * 2015-03-17 2016-09-30 Zhaw Zurich Univ For Applied Sciences Icbc Inst For Chemistry & Biological Chemistry Verfahren zur gaschromatographischen Trennung eines Enantiomerengemisches.
CN106824141B (zh) * 2015-12-04 2020-11-24 中国科学院大连化学物理研究所 一种环糊精色谱固定相的制备方法

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US5198429A (en) 1993-03-30
EP0407412B1 (de) 1993-07-14
DE3810737A1 (de) 1989-10-12
JPH03505337A (ja) 1991-11-21
WO1989009235A1 (en) 1989-10-05
DE58904919D1 (de) 1993-08-19
EP0407412A1 (de) 1991-01-16

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